Sucrose

Sucrose
Properties and Applications
Sucrose
Properties and Applications
Edited by
M. MA THLOUTHI
Faculte des Sciences
Universite de Reims Champagne-Ardenne
and
P. REISER
CEDUS
Paris
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
First edition 1995
1995 Springer Science+Business Media Dordrecht

Originally published by Chapman & Hali in 1995
Softcover reprint of the hardcover 1st edition 1995
Typeset in 1O/12pt Times by Cambrian Typesetters, Frimley, Surrey
ISBN 978-1-4613-6150-3
ISBN 978-1-4615-2676-6 (eBook)
DOI 10.1007/978-1-4615-2676-6
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Preface
This book has as its origin the wish of the sugar profession in France, as
represented by CEDUS (Centre d'etude et de documentation du sucre), to
gather together the widespread information on sucrose into a single
source-a volume directed at researchers, producers and users of sucrose,
which would also provide useful background material for students. The
idea received an enthusiastic response from all the authors invited to
contribute to this work, who are known not only for their expertise in the
field but also for their enthusiasm for the subject.
Although sucrose is often described as a unique commodity with the
advantages of high purity, low price, ready availability and optimum
sweetness, and although it is used as a model for the study of carbohydrates
and biological molecules, our knowledge of its properties has advanced
only slightly in recent years. Most industrialists and researchers still use
data known for more than 60 years. The recent literature on sucrose, which
is relatively abundant, consists either of repetitions of what has already
been published, or of sophisticated computations rather distant from
everyday concern.
This situation is not new. In the preface to his excellent handbook,
Principles of Sugar Technology (1953), Pieter Honig states: "There is only
one way in which the sugar industry can make real progress, and that is by
systematic research and by collecting facts in a critical and objective way.
This is the only real foundation on which improvements can be made."
This statement is still true. In writing this book, we have tried to collect
data, to consider the most important properties of sucrose in detail, and to
provide a new insight into recent aspects of sugar studies and applications.
After a short discussion of the economic aspects of sucrose, recent
studies of sucrose structure in its crystalline form and in aqueous solution
using modern tools like 13C NMR are presented, along with calculations of
molecular mechanics. Chapter 3 provides an overview of sucrose crystallization, starting with a basic understanding of the driving force in the
crystallization processes, viz. supersaturation of solution, and ending with
a new and promising technology which is even environmentally compatible:
the cooling crystallization of raw juices. In chapter 4 the structure and
practical aspects of amorphous sugar are considered. Amorphous sucrose
may be found both at high temperatures and below OCC, and its study
proves to be informative as a model for most amorphous food systems.
Following the discussions of crystalline and amorphous sucrose, its
vi
PREFACE
solution properties are treated in the subsequent four chapters. In chapter

5, solubility-one of the most important properties for both research and
industrial work-is detailed, with particular emphasis on the most recent
equations for the calculation of solubility as a function of temperature and
in the presence of other saccharides. Rheological properties are covered in
chapter 6, which discusses the equations available for the calculation of
viscosity as a function of concentration or temperature, and the effect of
viscosity on molasses formation and exhaustion and on the running of
industrial machinery. Methods of analysis of sucrose in syrups and liquid
sugars are described in chapter 7, and a critical compilation of the most
important physical properties of sucrose and sucrose solutions is presented
in chapter 8.
Applications of sucrose are dealt with in the last four chapters. Some of
the properties of sucrose, mainly due to hydration, taste and high purity,
are important for food technology and are described in chapter 9. The
compatibility of sucrose with other food ingredients and the enhancements
of food flavour are covered in chapter 10. Chapter 11 is devoted to the use
of sucrose as a raw material for chemical and enzymatic reactions. This
opens the door for the possible diversification of the sugar industry, which
is the real challenge for the near future. Finally, new technology for the
drying of fruits and vegetables, based on one of the numerous interesting
properties of sucrose, namely osmotic pressure, is described in chapter 12.
We do not claim to cover all aspects of the properties and applications of
sucrose, because of the ubiquity of this molecule and the diversity of
information currently available. We only wish to stimulate further the
interest of sugar scientists and technologists and to ensure that none of
their fervour is lost.
M. Mathlouthi
P. Reiser
Contributors
Professor G.G. Birch
Department of Food Science and Technology,

University of Reading, Reading RG6 2BX,
UK
Dr Z. Bubnik
Institute of Chemical Technology, Technika

1905, 16628 Prague 6, Czech Republic
Dr M.A. Clarke
Sugar Processing Research Institute, Inc., 1100

Robert E. Lee Blvd, New Orleans, LA 70124,
USA
Mr J. Genotelle
Ingenieur Arts et Manufacture, 5 Rue Frevillele-Vingt, 92310 Sevres, France
Dr S. Guilbert
CIRAD, 24 Avenue du Val de Montferrand,

B.P. 5035, 34032 Montpellier, France
Dr M.A. Godshall
Sugar Processing Research Institute, Inc., 1100

Robert E. Lee Blvd, New Orleans, LA 70124,
USA
Professor P. Kadlec
Institute of Chemical Technology, Technika

1905, 16628 Prague 6, Czech Republic
Dr R. Khan
POLYBios, LBT, Area di Ricerca, Padriciano

99, 34012 Trieste, Italy
Dr J.P. Lescure
S.N.F.S. Services Techniques, 369, Rue Jules

Guesde, B.P. 39, 59651 Villeneuve d'Ascq
Cedex, France
Professor G. Mantovani
Universita di Ferrara, Dipartimento di Chimica,

Via L. Borsari 46, 44100 Ferrara, Italy
Professor M. Mathlouthi
Laboratoire de Chimie Physique Industrielle,

Faculte des Sciences, Universite de Reims
Champagne-Ardenne, B.P. 347, 51602 Reims
Cedex, France
Dr S. Perez
INRA Rue de la Geraudiere, BP 527, 44072

Nantes Cedex, France
viii
CONTRIBUTORS
Dr A.L. Raoult-Wack
CIRAD, 24 Avenue du Val de Montferrand,

B.P. 5035, 34032 Montpellier, France
Mr P. Reiser
Ingenieur, CEDUS, 30 rue de Lubeck, 75116

Paris, France
Dr G. Rios
University of Montpellier 11,3402 Montpellier,

France
Professor G. Vaccari
Universita di Ferrara, Dipartimento di Chimica,

Via L. Borsari 46, 44100 Ferrara, Italy
Professor A.J. Vlitos
World Sugar Research Organisation, University

of Reading Innovation Center, Philip Lyle
Building, PO Box 68, Reading RG6 2BX, UK
Contents
1 Economical aspects of sugar

A.I. VLITOS
1.1 Introduction
1.2 Nutritional and energetic aspects
1.3 Sugar in world trade: statistical data
1.4 Conclusion
Bibliography
2 The structure of sucrose in the crystal and in solution

S. PEREZ
2.1 Introduction
2.2 Nomenclature
2.3 Structural characteristics of crystalline sucrose
2.3.1 Conformation of sucrose
2.3.2 Hydrogen bonding in crystalline sucrose
2.3.3 Packing features of crystalline sucrose and relation to morphology
2.3.4 Solid-state cross-polarization magic angle spinning NMR
spectroscopy of sucrose
2.4 Exploration of sucrose conformations by computational methods
2.4.1 Conformational variability of the fructofuranose ring
2.4.2 Conformational variability of the sucrosyllinkage
2.5 The solution conformations of sucrose
2.5.1 High-resolution NMR spectroscopy
2.5.2 Chiro-optical measurements
2.6 Conclusions and perspectives
Acknowledgements
References
3 Sucrose crystallisation
G. VACCARI and G. MANTOVANI
3.1 Introduction
3.2 Morphology
3.2.1 Single crystal
3.2.2 Twins
3.2.3 Conglomerates
3.2.4 Effect of impurities
3.3 Solubility
3.3.1 Pure solution
3.3.2 Impure solution
3.4 Crystallisation
3.4.1 Nucleation
3.4.2 Crystal growth
1
1
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2
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CONTENTS
3.5 Crystallisation technique

3.5.1 Evaporation crystallisation
3.5.2 Cooling crystallisation
3.6 Crystal quality
3.6.1 Inclusions
3.6.2 Colour of the crystals
3.7 Conclusions
References
58
60
63
66
69
70
71
72
Amorphous sugar
M. MATHLOUTHI
75
4.1 Introduction
4.2 Structure of amorphous sucrose
4.2.1 Order and disorder in concentrated amorphous solution
4.2.2 Structure of freeze-dried and spray-dried sucrose
4.2.3 Dry-milled and extruded sucrose
4.3 Thermal properties of amorphous sugar
4.3.1 Behaviour of concentrated amorphous solutions
4.3.2 Glass transition of amorphous solid sucrose
4.4 Rearrangement in amorphous sugar
4.4.1 Moisture dependence of the amorphous-crystalline transformation
4.4.2 Temperature dependence of amorphous sugar transformation
4.5 Practical importance of amorphous sugar
4.5.1 Structure modification of sugar and the shelf-life of food products
4.5.2 Agglomeration, caking and the stability of crystalline sugar
4.6 Conclusion
References
75
76
76
80
82
84
85
86
89
89
91
94
95
95
97
97
5 Sucrose solubility
z. BUBNIK and P. KADLEC
5.1 Introduction
5.2 Expression of concentration and composition of sucrose solutions
5.2.1 Relationships for expression of concentration of sucrose
in pure and impure water solutions
5.3 Sucrose solubility in water
5.3.1 Effect of temperature on the sucrose solubility
5.3.2 Phase equilibrium diagram for the system sucrose-water
5.3.3 Supersaturated solutions
5.4 Sucrose solubility in impure sugar solution and other solvents
5.4.1 Three-component triangle diagram
5.4.2 Influence of beet and cane non-sugars on the solubility of sucrose
solutions in technical sugar solutions
5.4.3 Equation for solubility of sucrose in impure solutions
5.5 Solubility of sucrose in other solvents
5.5.1 Ternary systems: sucrose-water-organic liquid solvent
5.6 Solubility of some saccharides
5.7 Conclusion
List of symbols
References
6 Rheological properties of sucrose solutions and suspensions

M. MATHLOUTHI and J. GENOTELLE
6.1 Introduction
6.2 Theoretical basis of viscosity relations
101
101
101
103
105
105
107
108
110
110
114
115
118
118
118
121
123
124
126
126
127
CONTENTS
6.2.1 Einstein's equation

6.2.2 Viscosity--{;oncentration relations
6.2.3 Viscosity-temperature relations
6.2.4 Results and interpretation
6.3 Viscosity of impure solutions
6.3.1 Relations applicable to homogeneous phases
6.3.2 Relations applicable to heterogeneous phases
6.4 Methods for determining viscosity and flow properties
6.4.1 Laboratory methods
6.4.2 Factory methods
6.5 Applications
6.5.1 Effect of viscosity on crystallization
6.5.2 Effect of viscosity on molasses formation and exhaustion
6.5.3 Effect of viscosity on machines running
6.6 Conclusion
References
7 Analysis of sucrose solutions

J.P. LESCURE
7.1 Introduction
7.2 Sucrose identification by vibrational spectroscopy
7.2.1 Infrared
7.2.2 Raman spectroscopy
7.2.3 NMR spectroscopy
7.3 Methods of titration of sucrose
7.3.1 Physical methods
7.3.2 Refractometry
7.3.3 Polarography
7.3.4 NIR spectrophotometry
7.3.5 Isotope dilution
7.4 Chemical methods of analysis
7.4.1 Reducing sugars
7.4.2 Chromatography
7.5 Enzymatic methods
7.5.1 Methods description
7.5.2 Situation of enzymatic methods
7.6 Determination of the syrups quality
7.6.1 Purity
7.6.2 Ash
7.6.3 Colour
7.6.4 S02
7.6.5 Heavy metals
7.7 Microbiology
7.8 Standards and regulations
7.8.1 Codex Alimentarius
7.8.2 The European Regulation 79/796
7.8.3 Pharmacopoeia
7.8.4 Sugar regulation
References
8 Physical properties
P. REISER, G.G. BIRCH and M. MATHLOUTHI
8.1 Introduction
8.2 Properties of the crystal
Xl
127
128
132
135
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186
186
186
xii
CONTENTS
8.2.1 X-ray crystallinity

8.2.2 Melting point
8.2.3 Density
8.2.4 Compressibility
8.2.5 Granulometry
8.2.6 Electrical properties
8.2.7 Specific heat
8.3 Properties of amorphous sucrose
8.3.1 Density
8.3.2 Specific heat
8.3.3 Glass transition, recrystallization and melting
8.3.4 13C NMR spectra of amorphous sucrose
8.4 Aqueous solutions
8.4.1 Concentration units
8.4.2 Solubility
8.4.3 Density of sucrose solutions
8.4.4 Density and apparent specific volume
8.4.5 Refractive index
8.4.6 Polarimetry
8.4.7 Thermal properties of aqueous sucrose solutions
8.4.8 Increase in volume
8.4.9 Boiling point
8.4.10 Freezing point
8.4.11 Water activity
8.4.12 Osmotic pressure
8.4.13 Surface tension
8.4.14 Viscosity of sucrose solutions
References
Technological value of sucrose in food products

M.A. CLARKE
9.1 Introduction
9.1.1 Sources, production and consumption of sucrose
9.1.2 Comparative sweetness of sugar
9.2 Chemical properties of sucrose
9.2.1 Purity
9.2.2 Solution reactions: inversion, degradation, Maillard and
browning reactions
9.2.3 Sensory properties
9.2.4 Color
9.2.5 Antioxidant properties
9.3 Physical properties of sucrose
9.3.1 Colligative properties
9.4 Applications: effects of sucrose in food processing
9.4.1 Breads
9.4.2 Cakes
9.4.3 Cookies and sweet biscuits
9.4.4 Icings and frostings
9.4.5 Beverages
9.4.6 Jams, jellies and preserves
9.4.7 Confectionery
9.4.8 Dairy products
9.4.9 Ready-to-eat breakfast cereals
9.4.10 Meats
9.4.11 Frozen and tinned vegetables
9.5 Biochemical properties of sucrose
References
187
187
188
188
188
188
189
190
190
190
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191
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200
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231
232
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240
241
242
243
243
243
243
244
244
244
244
245
246
CONTENTS
10
Role of sucrose in retention of aroma and enhancing the flavor

offoods
M.A. GODSHALL
10.1 Introduction
10.2 Sucrose and the other basic tastes
10.2.1 Interactions with salty taste
10.2.2 Interaction with bitter taste
10.2.3 Interaction with acid-sour taste
10.2.4 Interaction with other sweeteners
10.3 Retention of aromas
10.3.1 Fixing volatiles with sucrose
10.3.2 Co-crystallization
10.3.3 Headspace effects-aromas in solution
10.4 Modifying the taste of sucrose
10.4.1 Enhancing the sweetness of sucrose
10.4.2 Hydrocolloids and perception of sweetness
10.4.3 Temperature effects on sweet perception
10.4.4 Masking the sweetness of sucrose
10.4.5 Interaction of sucrose-color-flavor
10.4.6 Iron-sucrose interactions
10.5 Effect of sucrose in selected food systems
10.5.1 Coffee
10.5.2 Fatty systems
10.5.3 Chocolate confectionery
10.5.4 Fruit flavors
10.5.5 Effect of crystal size on mouthfeel in confections
10.5.6 Sucrose and cake crumb, crust and quality
References
11
Sucrose: its potential as a raw material for food

ingredients and for chemicals
R. KHAN
11.1 Introduction
11.2 Chemical reactivity
11.2.1 Reactivity towards tritylation reaction
11.2.2 Cyclic acetalation reactions
11.2.3 Selective esterification
11.2.4 SN 2 displacement reactions
11.3 Enzymic reactions
11.3.1 Lipase-catalysed acylation reactions
11.3.2 Selective deacylation reaction
11.4 Food ingredients
11.4.1 High-intensity sweetners
11.4.2 Emulsifiers and surface active compounds
11.4.3 Low-calorie fat
11.4.4 Non-cariogenic, reduced calorie, low-intensity sweetners
11.4.5 Bulking ingredients
11.5 Chemicals from sucrose
11.5.1 Synthetic polymers based on sucrose
11.5.2 Detergents
References
Xlii
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CONTENTS
XtV
12
Sucrose and osmotic dehydration

A.L. RAOULT-WACK, G. RIOS and S. GUILBERT
12.1 Introduction
12.2 General presentation of osmotic dehydration
12.3 Operating variables related to the sucrose concentrated solution
12.4 Influence of sucrose impregnation on the end-product quality
12.5 Control of the sucrose concentrated solution
12.6 Conclusion
References
Index
279
279
279
282
284
286
287
288
291
1 Economical aspects of sugar

A. J. VLITOS
1.1 Introduction
Sugar is a major commodity in world trade. Although competition from

alternative sweeteners and starch-derived isoglucose is substantial, over
100 million tons of sugar have been produced worldwide annually in recent
years. Approximately a similar amount is consumed. Unlike many other
foods, sugar can be produced in the temperate zones as well as in the
tropics and subtropics. It is, in every sense, an 'international' commodity
with a well-established infrastructure. Sugar-beet accounts for most of the
sugar produced and consumed in Europe, although cane sugar is still
imported from the so-called Lome Convention nations (Africa, Caribbean,
Fiji, etc.). Sugar-cane is still the major source of sugar in Africa, South
America, Asia, Hawaii, Florida, Louisiana, Fiji, Mauritius and in the
Caribbean islands. In North America, other than Florida, Louisiana and
Texas, sugar-beet is the leading sugar-producing crop. The lead producer
of sugar in the world is now the European Community (Ee).
Although mechanisation of agricultural operations is quite common in
areas producing sugar-beet, sugar-cane cultivation relies more heavily on
hand-labour especially in Third World nations. However, notable exceptions are Australia, Hawaii, Florida, Louisiana and Texas where mechanised sugar-cane cultivation is the rule rather than the exception. The
question which often arises is which country is the most efficient producer
of sugar in the world, and whether sugar-cane represents the more efficient
source? The answer is that Australia is probably the most efficient
producer of sugar (in economic terms) from sugar-cane and France the
most efficient producer from sugar-beet. The level of efficiency is roughly
equal.
1.2 Nutritional and energetic aspects
Nutritional trends will play a role in future markets for sugar. Since
overconsumption of fats is now considered a more serious health hazard
than overconsumption of carbohydrates, many food processors will find it
more convenient to replace fats with sugars in many foods. The physical
M. Mathlouthi et al. (eds.), Sucrose

Springer Science+Business Media Dordrecht 1995
SUCROSE
and chemical properties of sugar are still considered vital in adding bulk
and taste to certain foods (i.e. fibre) which otherwise would prove bland
and unappetising. Thus, the markets for sugar both for non-food and for
food uses are likely to remain buoyant in the long term. One of the
important reasons for the continued popularity of sugar both for food and
other uses is its relatively low and stable price and the ability of suppliers to
respond to market demand rapidly and reliably. The infrastructure built to
supply sugar to the market is second to none worldwide. Production,
storage, shipping and packaging of sugar have been developed to the very
high level of efficiency demanded by an international commodity of
commerce and trade.
An important economic aspect of sugar production has to do with the
utilisation of by-products and with the use of sugar and its by-products,
molasses, to produce ethanol (a liquid fuel) and other chemicals. In Brazil
the production of ethanol as a liquid fuel represents a major market for
sugar; this alternative use for sugar is likely to become increasingly
important in nations lacking fuels but which have a capacity to produce
sugar crops.
It should be noted that the photosynthetic efficiency of sugar cane and of
sugar beet offers hope that in future more nations will become aware of the
potential value of these crops as sources of renewable energy supplies and
as sources of products presently relying on petroleum and other fossil fuels.
The economics of sugar-based chemical products will change as supplies of
fossil fuels become scarce and more expensive. Environmental pressures
may also favour, in the long term, the use of sucrochemicals which may be
more biodegradable and less damaging to the environment than traditional
products.
1.3 Sugar in world trade: statistical data

To demonstrate more quantitatively the economic aspect of sugar
production a series of figures follow, showing the world production of
sugar-beet and sugar-cane on a scale rivalled by very few other food crops.
The following data reproduced from the United States Department of
Agriculture's Economic Research service demonstrate the scale of sugar's
economic prominence in world trade. As mentioned above, world
consumption and production (Figure 1.1) roughly keep pace, but from
1990 to 1993 production outpaced consumption. This situation is likely to
change in 1994 given shortfalls of production in Cuba and elsewhere.
Consumption in some parts of the world is increasing as may be noted from
the data in Figure 1.2. Consumption in Asia is rising and is likely to
continue in the future. It is also interesting to note the relatively high
consumption in Eastern Europe from 1988 to 1991 (Figure 1.3). This is
ECONOMICAL ASPECfS OF SUGAR
Millio n m etnt: tons, raw va lue

120
115
110
105
100
95
90
.982/83
86/87
84/85
90/91
88/89
92/93'
Marketing year
'Forecast.
Figure 1.1 World production (---) and consumption (- - -).

Million metric tons, raw value
40 - , - - - - - - - - - - - - - - - - - - - - - - ,
30
20
10
o
1982 83
84
85
86
87
88
89
90
Year
Figure 1.2 Consumption in Asia.
91
92
SUCROSE
(d)
10
15
20
25
Million metric tons, raw value

Figure 1.3 Consumption in selected regions (average of 1988-1991 marketing years).
(a) North America; (b) Latin America (includes Central America, Caribbean and South
America (excluding Mexico) ); (c) Western Europe; (d) Eastern Europe (includes former
Soviet Union); (e) Africa; (f) Middle East.
likely to continue and may accelerate. Of special interest is the projected

consumption of sugar in the People's Republic of China (Figure 1.4) which
is approaching that of the US. Of course, on a per capita basis, US
consumption is much greater than that in the People's Republic of China as
may be noted in Figure 1.5. Table 1.1 lists consumption in the EC and
other major consuming nations.
Sugar and its pricing often confuses laymen. The world price is much
lower than the prices in the USA and other nations and the differences in
price are often quite large as seen in Figure 1.6. Similarly, there are
differences between 'world refined' and 'raw sugar' prices (Figure 1.7).
Price indices for refined beet and cane sugar in the USA are reflected in
Figure 1.8 where it will be noted that the refined cane sugar index was
much greater than that for refined beet sugars. Similarly, the differences in
sugar price (retail, wholesale refined and domestic raws in the USA) can
vary considerably (Figure 1.9). Of particular relevance in assessing
ECONOMICAL ASPECTS OF SUGAR
Million metric tons. raw value
16
Former Soviet Union
14
--
---
,/
-,
,/
12
"
-----'
India
i0
",.,--
"
.'
--
--- - . ---'
~U.:S=-.~_.-==-=::::-:=
;;;>
,~
8
6
China __ - -
Me xico
o
1982/83
'Forecast
84/85
86/87
88/89
90/ 91
Marketing year
Figure 1.4 Projected consumption in China compared to other nations.
Table 1.1
nations
Sugar consumption (metric tons X 106 ) in the EC and other major consuming
Country or area
Former Soviet Union'
EC I
India
United States
China
Brazil
Mexico
Japan
Indonesia
Pakistan
Others
World total
'Includes 12 former USSR republics, excludes Baltic states.
IIncludes unified Germany, excludes French overseas.
1990-91
1991-92
13.04
12.82
12.32
7.96
7.50
7.09
4.26
2.79
2.42
2.40
12.5
12.8
13.1
8.0
7.6
7.2
4.3
2.8
2.5
2.5
37.57
110.17
39.0
112.8
(f)
10
20
30
40
50
60
Kilograms refined
Figure 1.5 Consumption of sugar (per capita) - world and selected areas. (a) World; (b)
China; (c) India; (d) US; (e) EC) (f) Cuba.
Cents/lb.
25
20
./
./
./
-, .....
--
----
86
88
15
10
1982
84
90
92
Year
Figure 1.6 World and US sugar prices. (- - -) USA: Contract no. 14 New York. (--) the
world: Contract no. 11 Stowed Caribbean ports.
Cents/lb.
\
16
12
\
\.
o
1982
90
88
86
84
92
Year
Figure 1.7 World refined and raw sugar prices. (--) Refined: London daily price, Europe.
(- - -) raw: price no. 11 Caribbean.
June 1982
140
100
130
120
110
100
1983 84
85
86
87
88
89
90
91
92
Year
Figure 1.8 US produced price index for refined beet (.) and cane sugar C,w).
SUCROSE
Cents lib.
50
40
Retail
30
Wholesale refined
... / \
1.1/ - ,
1""
20
11
21 /- ./ - \
I "
,-~/_-~/
.. - .... -- ... _ .... __ ..
... ----- .... - ...
...... / '
......
,-------
Domestic row, N.Y. spot
31
10
o
1982
84
88
86
90
92
Yea r
Figure 1.9 US sugar prices. 1, US average; 2, midwest; 3, starting June 1985 prices are for
nearly futures.
Cents/lb .. dry weight
35
Sug or. refined
25
.. --, ,----...
',-~' / '
-- ...................
:..:_/
" , . , '"
..- ......
15
HFCS-55 ,.--
~ __
',
..............
'
'
HFCS-42
o
1,982
84
86
88
90
92
Year
Figure 1.10 Wholesale prices for HFCs and sugar - US midwest market.
ECONOMICAL ASPECTS OF SUGAR
19112
160
= 100
150
110
130 ,
90
1903 84
85
86
87
88
89
90
91
92
Year
Figure 1.11 US consumer price index for (~) sugar and (.) selected sweetener-containing
products.
competition to sugar from other isoglucose or high fructose corn syrups

(HFCS-55 and -42) are the relative prices compared with refined sugar. It
may be seen in Figure 1.10 that price advantages are presently in favour of
both HFCS-55 and HFCS-42. A US consumer price index for sugar and
selected sweetener-containing products is reproduced in Figure 1.11. It is
interesting to note that from 1983 to the present sweetener-containing
products have maintained a much higher price index than sugar and
artificial sweeteners.
1.4 Conclusion
Sugar is a major commodity in world trade. An infrastructure has been
built over the past 100 years to maintain production, shipping and storage
of sugar to keep pace with consumption and in some years to outpace
consumption. In the foreseeable future, sugar will continue to be in
demand both for food and non-food uses. It is a food commodity produced
at relatively low cost in temperate, subtropical and tropical areas of the
10
SUCROSE
world and as a regenerable source of energy represents an important

economic asset.
Bibliography
ISO (1992) International Sugar Organisation Sugar Yearbook, ISO, London, UK.
USDA (1993) Sugar and Sweetener Situation and Outlook Report. Economic Research
Service. United States Department of Agriculture, Washington DC.
2 The structure of sucrose in the crystal and in

solution
s.
PEREZ
2.1 Introduction
The term 'structure' defines the arrangement of all the parts of a whole.
For a molecule, this requires the identification and the relative spatial
orientation of all the constituting atoms. Needless to stress that such a
knowledge is of fundamental importance for the basic understanding of the
molecular properties and functions. The evolution of the concept of
structure has been parallel to the progress in structural chemistry.
Obviously, the first constitutional representation of sucrose, advanced by
Tollens in 1883 (Tollens, 1883), represented the synthesis from the most
advanced tools available at the time. It took, however, 10 years before
Fischer came up with the correct formulation for sucrose as a glucofuranosyl fructofuranoside (Fischer, 1893). This was followed by several
key discoveries including the representations given by Haworth (1929),
Pigman (1948), Morrison and Boyd (1959). In a recent review about the
evolution of the structural representation of sucrose, Lichenthaler et al.
(1991) covered with elegance some of the major facts of the structural
representations of sucrose including those provided by modern computer
graphics.
In many chemical, biological and technological processes, the threedimensional structure of a molecule may be of considerable significance.
At the present time, there are two main experimental methods available
for determining three-dimensional structures, at the atomic level: X-ray
crystallography of single crystals and nuclear magnetic resonance (NMR)
spectroscopy of solutes. In the crystalline state, the descriptor 'structure'
has a static connotation. A crystal structure analysis will provide accurate
description of the individual three-dimensional arrangement. In the liquid
state, the descriptor 'structure' is associated to a statistical one-dimensional
probability. Therefore, a dynamic rather than a static description must be
sought, especially when geometries are changing rapidly. Hence, the term
'structure' must also encompass the dynamic fluctuations that the
molecule may undergo.
The present chapter describes the essential concepts and tools which
may be required to apprehend fully the current state of knowledge about
12
SUCROSE
the structures and the different levels of structural organizations of

sucrose. It is the author's hope that these tools will also be useful to the
reader to decipher the structural works and modifications that will deal
with such a unique molecule.
2.2 Nomenclature
Most monosaccharides exist in the form of heterocyclic rings or cyclic
hemiacetals, such as five-membered furanoses or six-membered pyranoses.
The centre of chirality generated by hemiacetal ring closure is called the
anomeric centre which is the only carbon bound to two oxygen atoms. It is
labelled C-1, and the others are numbered sequentially around the ring.
The two stereoisomers are referred to as anomers, designated a or fJ
according to the configurational relationship between the anomeric centre
and a specified anomeric reference atom. The D or L designation of the
configuration refers to the position of the hydroxyl group on the
asymmetric carbon farthest from the C-1, i. e. the C-5 of hexoses and the C4 of pentoses.
The official name of sucrose, according to the IUPAC-IUB Commission
of Biochemical nomenclature is fJ-D-fructofuranosyl-a-D-glucopyranoside.
It is abbreviated to fJ-D-Fruf-(2-1)-a-D-Glcp. The numbering of the atoms
is shown in Figure 2.1. A disaccharide is a compound in which two
Figure 2.1 Sucrose and its atomic labels of interest. = 0-5g - C-Ig - O-Ig - C-2f.1jJ = C-Ig
- 0- Ig - C-2f - 0-5f. OJ g = 0-5g - C-5g - C-6g - 0-6g. OJr = 0-5f - C-5f - C-6f - 0-6f. Xr = 0-5f
- C-2f - C-lf - O-If.
THE STRUCTURE OF SUCROSE
13
monosaccharide units are joined by a glycosidic linkage, i.e. the anomeric

centre is always linked to the hydroxyl of another sugar. It can be regarded
as formed by the reaction of one glycosidic (anomeric) hydroxyl group with
another hydroxyl group liberating one water molecule. When there is no
hemiacetal group free, the resulting disaccharide is known as a nonreducing disaccharide. This is the case for sucrose.
The conformation of a molecule is best described by angular rotations
about bonds which are given by torsion angles. A torsion angle in the
sequence of atoms A-B-C-D is measured by the angle which the bond AB makes with the bond C-D when projected down B-C. The angle is 0
when the bonds A-B and C-D are eclipsed (or cis), whereas it is 180 when
the bonds A-B and C-D are trans; it is counted positive when C-D is
rotated clockwise with respect to A-B.
The conformations about the glycosidic linkage bonds are described by
the following torsion angles:
ct> = 0-5g - C-1g - 0-lg - C-2f
'\jJ
= C-1g -
0-lg - C-2f - 0-5f
The orientation of the three hydroxymethyl groups are described by the

torsion angles, wg , Wf and Xf:
= 0-5g - C-5g - C-6g - 0-6g

= 0-5f - C-5f - C-6f - 0-6f
Xf = 0-5f - C-2f - C-lf - O-lf
Wg
Wf
The orientations of the 0-6g, 0-6f and O-lf primary hydroxyl groups are
referred to as either gauche-gauche (GG), gauche-trans (GT) or transgauche (TG) depending on whether the values of the above torsion angles
are closest to -60, 60 and 180. The sign of the torsion angles is defined in
agreement with the IUPAC-IUB Commission of Biochemical Nomenclature (1971).
2.3 Structural characteristics of crystalline sucrose
In 1947, an X-ray determination of the structure of sucrose sodium
bromide dihydrate (Beevers and Cochran, 1947) confirmed the chemically
assigned relative configuration of the asymmetric carbons of the molecule.
The X-ray determination of the structure of sucrose was performed by
Beevers et al. (1952) but for technical reasons the accuracy of the
determination was not satisfactory. Subsequently, Brown and Levy (1963),
carried out a highly precise refinement using neutron diffraction which
allowed a thorough description of the essential structural features offered
by crystalline sucrose. Because of the scale of the computational problem
at the time, the refinement of the structure was not continued to complete
14
SUCROSE
Table 2.1 Crystal data of sucrose as revealed by neutron and X-ray diffraction
Neutron
10.8633
8.7050
7.7585
102.945
X-ray
(5)
(4)
(4)
(6)
10.8648
8.7028
7.7578
102.956
(15)
(12)
(11)
(15)
715
Space group
d(calc)
1.590 Mgm-3
convergence. Ten years later were published, in a back to back fashion,

two further refinements of the structure of sucrose. The first refinement by
Brown and Levy (1973) was performed using neutrons at a wavelength of
1.078 A, whereas the refinement was based on X-ray data collected using
Moka at 0.71069 A (Hanson et at., 1973). These works gave unit cell
parameters and space group symmetry in good agreement (see Table 2.1).
Whereas X-ray diffraction determines the maxima of electron density
distribution, neutron diffraction determines nuclear atomic coordinates.
Except for hydrogen or deuterium atoms, the difference between the
nuclear positions and the electron density peaks is noticeable only in very
high precision structure analysis. Differences in bond lengths from X-ray
(d x ) and neutron diffraction (d N) analysis of the same crystal structure of
sucrose are small for dx-<iN for C-OH bonds (0.0048 (12) A), whereas for
C-H and O-H bonds the differences appear to be much larger and
significant, i.e. -0.13(1) A and -0.17(2) A. Therefore, for the rest of the
presentation, the fractional coordinates determined from the neutron
diffraction data will be used. The location of the coordinates of the 45
atoms of sucrose in its crystalline unit cell was determined with such a high
accuracy because the number of experimental structure factors used was
2813.
2.3.1 Conformation of sucrose
From this set of fractional coordinates bond lengths can be readily
computed, as can valence angles and torsional angles of interest. The
torsion angles of interest are reported in Table 2.2, whereas a molecular
representation of sucrose in its crystalline conformation is shown in Figure
2.2. The glucose residue adopts a 4C j conformation, whereas that of the
fructofuranose residue is a 4T) twist (<p = 265.2, q = 0.353) (Cremer and
15
Table 2.2 Torsion angles C) of interest for crystalline sucrose

Torsion angles about the glycosidic linkage
0-5g - C-Ig - 0-lg - C-2f
107.8
H-Ig - C-1g - 0-lg - C-2f
-8.0
C-Ig - 0-lg - C-2f - 0-5f
-44.7
C-1g - O-Ig - C-2f - C-If
73.7
-159.8
C-Ig - O-Ig - C-2f - C-3f
Endocyciic torsion angles
0-5g - C-1g - C-2g - C-3g
C-1g - C-2g - C-3g - C-4g
C-2g - C-3g - C-4g - C-5g
C-3g - C-4g - C-5g - 0-5g
C-4g - C-5g - 0-5g - C-I g
C-5g - 0-5g - C-Ig - C-2g
55.0
-56.0
56.3
-54.9
55.2
-55.0
0-5f C-2f C-3f C-4f C-5f -
C-4f
C-5f
0-5f
C-2f
C-3f
-31.2
161.6
-27.3
8.0
14.7
Exocyciic torsion angles

C-5g - 0-5g - C-Ig - 0-lg
0-lg - C-1g - C-2g - 0-2g
0-2g - C-2g - C-3g - 0-3g
0-3g - C-3g - C-4g - 0-4g
0-4g - C-4g - C-5g - C-6g
0-5g - C-5g - C-6g - 0-6g
C-4g - C-5g - C-6g - 0-6g
67.7
54.7
62.8
-64.3
64.6
-56.4
64.3
C-5f - 0-5f - C-2f - 0-lg

0-5f - C-2f - C-If - O-If
C-3f - C-2f - C-If - O-If
0-lg - C-2f - C-If - O-If
0-2f - C-2f - C-3f - 0-3f
0-3f - C-3f - C-4f - 0-4f
0-5f - C-5f - C-6f - 0-6f
C-4f - C-5f - C-6f - 0-6f
-102.4
171.3
-72.1
50.6
-157.5
-78.4
-69.5
49.3
C-2f C-3f C-4f C-5f 0-5f -
C-3f C-4f C-5f 0-5f C-2f -
Figure 2.2 Representations of sucrose in its crystalline conformation; the intramolecular

hydrogen bonds are shown as dashed lines.
Pople, 1975). The orientations of the primary hydroxyl groups are gauchegauche for both OJ g and OJf and is trans-gauche for Xf' They all correspond to
low-energy arrangements usually observed in crystal structures of carbohydrates. It should also be noted that sucrose has overlapping sequences of
C-O bonds that cause anomeric and exo-anomeric effects C-5g - 0-5g - CIg - 0-lg - C-2f - 0-5f - C-5f.
16
SUCROSE
2.3.2 Hydrogen bonding in crystalline sucrose

The description of the crystalline structure of sucrose cannot be made
without considering the influence of hydrogen bonding. A hydrogen bond
is the attractive force that arises between the donor covalently pair X-H
and other non-covalently nearest neighbour electronegative acceptor
atoms A, A', ... The hydrogen bonding in the crystalline state is known
from crystal structure analysis of almost 100 mono-, di-, tri- and
tetrasaccharides, amino acids, and many peptides (Jeffrey and Saenger,
1991). General rules have been assessed along with general hydrogen
bonding patterns. Chief among them are the occurrences of two- threeand four-centre hydrogen bonds. The two-centre hydrogen bond scheme:
X-H ... A; is by far the most common, but there is strong evidence that
the three-centred bonds occur frequently. A systematic study of the threecentre hydrogen bond in carbohydrate crystal structures indicated a wide
range of situations going from the almost symmetrical cases with r-r ~ 2.1
A, 8-8 ~ 135 to very unsymmetrical configurations where r-r' ~ 0.6 A
and 8-8' ~ 70. The occurrence of four-centre hydrogen bonding is by
far less frequent. Its geometrical definition requires only that X-H , .. A,
X-H .. , A' and X-H .. , A" angles are greater than 90,
Starting from the set of fractional coordinates and using the neighbouring
Table 2.3 Description of the hydrogen bonds in crystalline sucrose
O-H
H ... 0 0 ... 0 O-H ... OCO)
Intramolecular hydrogen bond

O-If-H ... 0-2g
1,000
1,000
0-6f-H ... 0-5g
0.974
0.972
1.851
1.895
2.781
2.850
158.6
167.1
Putative intramolecular hydrogen bond

0-3f-H ... 0-lg
1,000
O-If-H ... 0-lg
1,000
0.969
0.974
2.506
2.440
2.744
2.772
93.6
100.0
Intermolecular hydrogen bond

0-2g-H ... 0-6f
1,001
0-3g-H ... 0-3f
II, 001
II,1 -1 1
0-6g-H . , . 0-3g
0-3f-H ... 0-4f
II, 000
0.972
0.959
0.956
0.969
1.892
1.907
1.921
1.908
2.855
2.862
2.848
2.864
170.2
172.8
162.9
168.5
1,00-1
0.976
1.760
2.716
165.4
0.912
2.309
2.534
2.539
2.838
2.879
3.373
116.6
103.0
152.1
O-H ... O
Symmetry
operations'
0-4f-H ... O-If

0-4g
0-2f
HO-3g
0-6g
1,010
1,000
II, 1 0 1
'The symmetry transformations generate the coordinates of the acceptor oxygen atoms from
the basic coordinates taken from the work of Brown and Levy (1973). The first digit
represents either (I) the symmetry operation x,y,z, or (II) the symmetry operation -x,
112+y, -z. The last three digits specify a lattice translation along a, band c.
17
molecules derived from combinations of space group symmetry and unit

cell symmetry operations the set of intra- and intermolecular hydrogen
bonds can be unravelled. All the oxygen atoms in the molecule are
involved in hydrogen bonding. The crystalline structure is characterized by
an unusually large number of weak hydrogen bonds (see Table 2.3). A
schematic representation of the hydrogen bond features found in crystalline
sucrose is shown in Figure 2.3(a).
The two inter-residue intramolecular hydrogen bonds, O-lf-H ... O-2g
(a)
0-5--~----H--D -6f----1..--H--1) -2g

/1/2.85
1.90
1.89
5>~:~5 /<')
H:V
165 /
0-6g-H
:
~63'\
2.54
0-4g
O-If
, 1.92
O-Ig
&1.76
15~O_~g~_O_3f~_O_4f-.
_6~/
17 "
2.53
1.91
~:
I
I
0-2f
1.91
2.51
O-Ig
Figure 2.3 (a) Schematic representation of the hydrogen bond features found in crystalline
sucrose. (b) The four-centre hydrogen bond network in crystalline sucrose.
18
SUCROSE
and 0-6f-H ... 0-5g, are both from the fructofuranose to the glucopyranose residue. As a consequence, the ring oxygens lie on the same side
of the midline of the molecule. These bonds are arranged in an eightmembered ring fashion including (i) the minor intramolecular component
of a three-centre bond from the glucose primary hydroxyl group 0-6g-H to
the ring oxygen 0-5g; and (ii) 0-5g accepts two hydrogen bonds, one intra,
the other inter-residue.
The intermolecular hydrogen bonding involves an unusual four-centre
bond. A four-centre hydrogen bond is defined as one in which the proton
makes three first neighbour contacts to potential hydrogen bond acceptor
atoms in the forward direction with respect to the donor X-H bond. The
glucose 0-4g-H displays such a four-centres feature as shown in Figure
2.3(b). The 0-4g-H of the glucopyranose residue forms two intermolecular
bonds, to the fructofuranose ring oxygen 0-2f, and the glucopyranose 0-6g
and an intramolecular hydrogen bond to 0-3g. All the OH ... 0 angles
are greater than 90. Two of these bonds form an unusual triangle with the
two-centre bond from 0-6g-H to 0-3g-H.
2.3.3 Packing features of crystalline sucrose and relation to morphology
In order to arrive at a full understanding of the packing arrangement, the

intermolecular energy between a given molecule (i.e. the reference
Table 2.4 Description of the packing features in crystalline sucrose
Ref.
Symmetry
operation
Number
'short
contacts"
H-bonds
H, 1 -1 I
H, I 0 I
122
122
0-6g-H
0-4g-H
0-3
0-6
-5.20
-5.20
H,O -I I
H, 001
92
92
0-3g-H
0-3f
-5.14
-5.14
1,00 I
1,00 -1
85
85
0-2g-H
0-4f-H
0-6g
O-If
-6.01
-6.01
H, 0 -10
H, 000
69
69
0-3f-H ... 0-4f
-3.60
-3.60
1,0 -10
1,01 0
49
49
0-4g-H ... 0-5f
-2.21
-2.21
H,I -10
H, 1 00
24
24
~
Energy
(kcal mol")
-0.73
-0.73
'The symmetry transformations generate the coordinates of the acceptor oxygen atoms from
the basic coordinates taken from the work of Brown and Levy (1973). The first digit
represents either (I) the symmetry operation x,y,z, or (H) the symmetry operation -x,
1/2+y, -z. The last three digits specify a lattice translation along a, band c.
19
molecule) and all its neighbours is evaluated by taking into account the
intermolecular hydrogen bonds as well as the non-bonded interactions.
The results obtained from a packing analysis of sucrose are given in Table
2.4. In the molecular arrangements found in the crystal structure of
sucrose, the packing is highly dense, since each molecule is surrounded by
12 neighbours; this of course is in agreement with the high density of 1.59
of the crystals. All these 12 neighbours occur in pairs but only some give
rise to strong intermolecular associations. From these, preferred molecular
layers can be defined. The strongest layer arises from a combination of the
two-fold screw symmetry and a translational symmetry. The two-fold screw
axis element is parallel to the b axis, and it generates a chain where the
molecules are very tightly interacting. The interactions involve intermolecular hydrogen bonds and many van der Waals contacts which express the
complementarity of the molecular shapes in contact (Figure 2.4(a. On
(a)
(b)
(<) ' ' ' ' ' ' ' '
."t:.
,~'
(d)
Figure 2.4 (a) The molecular chain around the two-fold screw axis in crystalline sucrose.
Projection of the crystal structure of sucrose normal to: (b) the a crystallographic axis; (c) the
b crystallographic axis; (d) the c crystallographic axis.
20
SUCROSE
the basis of energy this chain may be viewed as a 'nuclei' for further
arrangements during the crystal growth. Associating such chains through a
simple translation in the (1 0 1) direction makes molecular layers having a
high density of atoms. The lateral cohesion between these layers is
achieved by a simple translation. For this reason there is no cancelling of
the intrinsic polarity arising from a given molecule first and the molecular
chain, second. Therefore, an overall polarity is maintained at the threedimensional level of each sucrose crystal. Figures 2.4(b)-(d) are projections
of the crystalline structure of sucrose normal to the a, band c axis,
respectively.
2.3.4 Solid-state cross polarization magic angle spinning NMR

spectroscopy of sucrose
NMR chemical shifts are extremely sensitive to the electronic environment
of the nuclei. They provide probes for identifying chemical structures. IH
and l3C NMR are the most common methods used for the structural
elucidation of organic molecules in solution. Technical advances of
multiple-pulse and spin-enhancement methods have extended the application of NMR spectroscopy to solids. On crystalline powder samples it is
possible to measure the isotropic equivalent chemical shifts experimentally,
using magic angle spinning (MAS). One commonly applied method is BC
cross-polarization (CP-MAS), since this method addresses the effect of
crystal environment on the electronic structure around the carbon nucleus.
In principle, the comparison between solution and solid-state NMR
spectroscopy provides a probe for studying the effect of solvation and
crystal lattice on the molecular structure.
Sucrose is one of the rare cases for which solid-state NMR and crystal
structure analysis have been performed on the same molecule. The solidstate l3C (CP-MAS) of partially deuterated crystalline samples of sucrose
has been reported (Pfeffer et al., 1990) and its assignment compared with
the solution spectra (Figure 2.5). From this work it appears that there are
some resonances whose relative chemical shift positions do not correspond
to each other. The resonance at C-lf is observed at a much lower field in
the solid state (6 = 67.9) than in solution. As for resonances at C-6g and
C-6f they are both found at higher fields in the solid state. In addition, C-3f
resonance is out of place relative to its position in solution (6 84.4 versus
6 77.5, respectively). These differences are not unexpected since the
electronic surrounding of each atom differs on going from the solid state to
the solution. They may be due to different conformations of the three
primary hydroxyl groups in the solid and solution, as well as a change in the
puckering of the fructofuranosyl moiety.
21

C-Sg
C.3g\, C-2g
C-lg
C-2f
'l/
C-st
C-4g
c~t
C_3tC-4t
Cl'
C~
90
I
100
70
I
80
60
C-4g
C-lg
C-4t
C-2g
C-3t
C-6t
Clt
100
90
80
70
C~g
60
Figure 2.5 Solid-state 13CP-MAS NMR spectra of sucrose, along with the corresponding
resonances as recorded in the solution state.
2.4 Exploration of sucrose conformations by computational methods
Conformational analyses of sucrose have been attempted in many instances

using methods based on atoms or electrons. Electron-based modelling or
molecular orbital methods fall into two classes: the ab initio method which
includes all electrons and requires only minimal parametrization and the
semi-empirical methods. Their application is still limited to somehow small
molecules which can be considered as analogue to carbohydrates. One of
the most recent applications in the field deals with a tetrahydropyrantetrahydrofuran analogue of sucrose (Van Alsenoy et at., 1994). The semiempirical methods include only the valence electrons, and must therefore
be calibrated extensively. Although requiring significant computing resources, calculations can be performed on molecules of the size of sucrose
using such a program as PCILO (Perturbation Configuration Interaction
using Localized Orbitals; Diner et at., 1969). Atom-based methods (also
called molecular mechanics), predict the properties of molecules in the
ground state by a system wherein atoms are connected by 'springs'
(represented by potential energy functions such as simple harmonic
22
SUCROSE
oscillators). When calibrated (i.e. parametrized) on related model molecules, molecular mechanics often gives good structures and energies for
carbohydrates. The molecular mechanics program, MM3 (Allinger et al.,
1989) which includes tools to deal with exo-anomeric effect and hydrogen
bonding has been used to investigate many neutral disaccharides.
Although MM3 has special functions to accommodate the anomeric
sequences, the effect of overlapping anomeric sequences of sucrose, have
not been included in the parametrization. Disaccharide computations are
usually performed in the space of glycosidic torsion angles and tV where
the residues can adjust internally at each increment. These calculations,
so-called 'flexible' or 'relaxed residue' analysis, are complicated by the
existence of a very large number of local minima on the multi-dimensional
potential energy surface, especially those connecting with pendant groups
such as primary and secondary hydroxyl groups. Despite their inherent
difficulties, these methods are gradually replacing the previously used
methods which treated each residue with a fixed rigid geometry and were
assessing the space available to the molecule by rotations about the
glycosidic torsion angles and tV.
2.4.1 Conformational variability of the fructofuranose ring

The energy surface for fructofuranose (Figure 2.6) calculated in the space
of puckering parameters (, q) has been calculated with MM3 (Allinger et
ai., 1989). These calculations account for the influence of the conformation
of both the primary and the secondary hydroxyl groups. The map agrees
well with the experimental data, showing all crystallographically observed
conformations to have energies within 2 kcal mol- 1 of the lowest energy
structure. All but one of the 20 structures are located in the large
'northern' minimum. Observed shapes range from the 2E to the 4Ts form,
spanning five northern conformations. Conversion between the northern
and southern minima is possible by either western or eastern routes.
2.4.2 Conformational variability of the sucrosyllinkage

The relative orientations of the fructofuranose and glucopyranose rings of
sucrose were first modelled using the HSEA (Hard Sphere Exo-anomeric
Effect; Thogersen et al., 1982) program. That work, starting with the
crystalline conformation, predicted a structure very close to that of the
starting sucrose structure. At that time, it was concluded (Bock and
Lemieux, 1982) that sucrose was conformationally rigid, partly as a result
of the two intramolecular inter-residue hydrogen bonds: O-lf-H ... 0-2g
and 0-6f-H . . . 0-5g. Subsequent work with the PFOS (Potential
Function for Oligosaccharide Structures) program (Tvaroska and Perez,
1986) yielded five local minima and suggested that the glucopyranose-
23
3~52T
10
~Eo
o
E2J
3
Figure 2.6 Conformational wheel for a fructofuranose. The conformations of the fructofuranose ring are described as deviations from an improbable structure in which all atoms are
co-planar. In any case three atoms always describe a plane, so possible low energy shapes will
have either one or two atoms out of plane. The structures in which only one atom deviates are
called envelopes (E), with the deviant atom either subscripted or superscripted to show the
direction of its deviation from the plane. When two atoms are out of plane, they lie on
opposite sides of the ring and the shape is described as a twist (7). Altogether there are 20 such
characteristics E and T shapes which can be placed on a circle called a 'conformational wheel'.
Such a representation allows to follow the path of conformational interconversion that avoids
all-planar structures. To describe structures in which the two deviant atoms are not equally
displace from the plane of the ring, the Creme-Pople puckering parameter <j> is used, along
with the parameter q which defines the amplitude of puckering. For a particular structure, q
can be shown as the length along the radius of the conformational wheel, with an all-planar
structure residing at the centre.
fructofuranose linkage can assume several different and well distinct

conformations (Herve du Penhoat et ai., 1991). The first 'relaxed-residue'
modelling study of sucrose (Tran and Brady, 1990a, b) was done with the
computer program CHARMM (Brooks et ai., 1983) using parameters
appropriate for carbohydrates (Ha et ai., 1988). Three low-energy regions
were found to contain five local minima. A recent study with another force
field (PIMM88) (Lichtenthaler et ai., 1992) gave comparable results. The
conformational behaviour of sucrose has been analysed with MM3, using
slightly different sets of parameters (French and Dowd, 1993; Perez et ai.,
1993).
24
SUCROSE
0
V
co
0
0
to
0
to
!&
25
The relaxed-residue potential energy surface of sucrose using MM3 with

16 structures (arising from different combinations of side group orientations) is shown in Figure 2.7. In agreement with the results obtained for the
'rigid residue' approximation (Herve du Penhoat et ai., 1991) and the
'relaxed residue' modelling of sucrose (French and Dowd, 1993; Perez et
ai., 1993) there is a limited conformational flexibility for the torsion
angle (40-140) compared with the 'IjJ torsion which covers all, or almost
all, the angular range from -240 to 120. Such a behaviour is typical of
disaccharides having axial-equatorial linkages. Nevertheless, a reason for
the 'IjJ rotation to be more facile is that the fructofuranose ring can easily
deform. Relaxing the geometries in modelling studies does not drastically
alter the location of minima, but it lowers or removes the barriers among
minima found with 'rigid' residues and it lowers the relative energies of the
remaining alternate minima. Three low-energy domains are found on this
map. The larger domain is located around = 80 and 'IjJ = -60 contains
the global energy minimum Sl ( = 110.0, 'IjJ = -60 (GT-GT-TG).
Another low-energy conformer, S2, occurs at = 70 and 'IjJ = 90 (GTGT- TG). The crystalline conformation of sucrose (S*) is found at the
periphery of this domain. The two other low-energy domains have energies
2-3 kcal mol-1 higher. Typical low-energy representatives are S3 and S4
which occur respectively at = 75 and 'IjJ = 170 (GT-GG-TG) and =
90 and 'IjJ = 55 (GT-GT-TG). The scheme of intramolecular hydrogen
bonds found in crystalline sucrose (O-lf-H ... 0-2g and 0-6f-H ... 05g) is not present in any of the low-energy conformers described hereupon.
Actually, only Sl displays a hydrogen bond based on 0-2g and O-lf but
with an inversion of the donor-acceptor scheme. As for S3 family of
conformers, several inter-residue hydrogen bonds can be formed such as
O-lf-H ... 0-5g, O-lf-H ... 0-6g, and 0-2g-H ... 0-6f; their occurrences were already proposed by Tran and Brady (1990a, b). The S4
conformers are characterized by a 0-6g ... 0-3f hydrogen bond which
could exhibit a 'flip-flop' in its donor-acceptor scheme.
There are intermediate conformations of the interresidue linkage which
permit the formation of an intramolecular hydrogen bond. However,
Figure 2.7 Adiabatic map of sucrose, along with the molecular representations of the four
low energy conformers. The conformational energy map for sucrose has been made with
MM3(92) with a dielectric constant" = 4. The map shows the lowest relative energy at each
10 increments from one of the 16 starting models. The lower axis corresponds to the rotation
about the C-1g - 0-lg bond (torsion angle <1 of glucose, which is axial. The vertical axis
corresponds to the rotation about C-2 - 0-lg bond (torsion angle "IjJ) of fructose which is
pseudo-equatorial. Iso-energy contours are drawn at increment of 1 kcallmol with respect to
the lowest energy conformation at 51; the outer limit is at 10 kcal/mol. The coding of grey
goes from dark grey for the lowest energy area, to light grey for conformations having an
energy higher than 10 kcallmol. At a given energy value, greater rotation is permitted about
the "IjJ torsion angle. The conformation observed in the crystal structure of sucrose is shown
by '. For each representative of the low energy conformers (51-54) a molecular drawing is
shown. They are inserted into an electrostatic potential molecular surface as obtained by
MNDO calculations.
26
SUCROSE
numerous low-energy conformations do not allow the formation of any

such stabilizing features. This is actually found in the crystal structure of
numerous other sucrosyl-containing molecules. A survey of all the sucrose
moieties in crystalline oligosaccharides (French and Dowd, 1993; Perez et
al., 1993) yields a 40 range in the <j> torsion angle as well as a 90 range in
'4'. These numerical data from crystal structure determinations provide
essential references for investigating the behaviour of the molecule in
solution (Jeffrey, 1973).
2.5 The solution conformations of sucrose
Average properties, such as those measured by NMR spectroscopy, chirooptical methods, infrared and Ramam spectroscopy, can be calculated
using an ensemble representation derived from the calculated potential
energy surfaces by standard mechanical methods.
2.5.1 High-resolution NMR spectroscopy
Internal flexibility displayed at the glycosidic linkage, as well as at the

primary hydroxyl groups is clearly evident from calculations of molecular
structures using the different protocols described in the previous section.
But it is only recently that such a feature has been integrated in the
interpretation of the solution conformations of sucrose as inferred from
high-resolution NMR spectroscopy. In the past decade, there has been an
upsurge in the application of NMR in the assessment of molecular
conformations in solutions. Basically, two types of effects can be put to
work: those transmitted through bonds (such scalar effects as coupling
constants) and those transmitted through space (dipolar effects, such as in
the case of nuclear overhauser enhancements, NOE). If the distance
dependence is assumed, as in the case of NOE, through space effects may
be used to estimate internuclear distances. Determining three-dimensional
structures and conformations of carbohydrate molecules from NMR
solution is a rather complex process, and this field still needs to be firmly
established (Carver, 1991; Meyer et al., 1993; Perez, 1993). Until recently,
almost all applications of NOE to conformational analysis of carbohydrates
has assumed, explicitly or implicitly, monoconformational behaviour, i.e.
the occurrence of a single conformation in solution. Bock and Lemieux
(1982) argued, supported by modelling using the HSEA method and
detailed 13C, T 1 and NOE measurements, that the overall conformation of
sucrose is approximately the same in water and in dimethyl sulfoxide
(DMSO) solutions, and this conformation is similar to that observed in the
crystalline state. These conclusions were supported by analysis of 13C
NMR spin-lattice relaxation times of aqueous sucrose over a range of
concentrations and temperatures (McCain and Markley, 1986a, b). Based
on IH NMR measurements in DMSO, (Christofides and Davies, 1985;
27
Davies and Christofides, 1987) it was suggested the occurrence of a

competition between two hydrogen bonds, i.e. O-lf-H ... 0-2g and 0-3fH ... 0-2g. This later hydrogen bond can only exist in the area of =
100 and 'IjJ = -160. Obviously such a scheme of dual hydrogen bonds
cannot be envisaged for explaining the experimental data in DMSO.
A reinvestigation of the conformational behaviour of sucrose and its 2deoxy-analogue in diluted aqueous solution was performed with the full
consideration of internal flexibility of the molecules. For both molecules
IH steady-state NOE and NOESY data were measured along with the
long-range 13C_1 H coupling constants (Herve du Penhoat et al., 1991). The
conformational equilibrium between the many low-energy conformers was
described using the data derived form energy calculations using the PFOS
approach. Typically, the overall population was made of several thousands
of conformers. For each predicted low-energy conformer, the theoretical
steady-state method and the 3J C _ H data were correlated with the glycosidic
torsion angles. Agreement between experimental and theoretical data
could not be reached by any single conformation model, and only
conformational averaging about all the potential energy surface can
reproduce the experimental data. The inclusion of hydrogen bonding in the
force field did not affect the statistical weight of calculated NOE, and the
similar values of observed NOEs for sucrose and the 2-deoxy analogue
argue against the importance of hydrogen bonding in sucrose conformation
in aqueous diluted solution. The lack of conformational rigidity of sucrose
was confirmed by an independent investigation (Poppe and Van Halbeck,
1992) using several temperatures and magnetic field strengths. Some
intriguing questions remain to be solved about the type of motion that
sucrose undergoes in solution, such as the rate of internal motions
compared to the overall tumbling rate of the molecule and compared to the
dynamics of water molecules.
2.5.2 Chiro-optical measurements

Optical rotation has long been used to study the conformation of
carbohydrates. A model based on interacting oscillators has recently been
extended to the calculations of disaccharides. The calculations refer to
molecules in vacuum, but a solvent correction can be applied. Optical
rotations are calculated for the linkage geometry representing energetically
favoured regions of the <1>, 'IjJ space. The statistically averaged optical
rotation of a disaccharide can be calculated using the energy surface with
the detailed conformational dependence of the disaccharide on optical
rotation. Sucrose has been the subject of a recent investigation (Stevens
and Duda, 1991) where a rigid-residue conformational study was used to
assess the low-energy conformers. It was concluded that the furanose ring
form which predominates in solution has the phase angle located in the
northern conformer ranging from 4 over 4T5 to 5' The optical rotation of
28
SUCROSE
sucrose was best accounted for in terms of an equilibrium mixture of two

linkage conformers, one being similar to the crystalline structure and the
other one representing another energy minimum having the 0-3f ... 02g intramolecular hydrogen bond.
2.6 Conclusions and perspectives
The aim of the present chapter was to describe the three-dimensional
structures that sucrose can display. Many experimental and theoretical
characterizations of differeiif levels of structural investigations have been
reported. In order to help rationalize the body of fragmented evidences,
computational molecular modelling was used thereby providing a continuous depiction of the molecular behaviour of sucrose. Modelling is
particularly useful for sucrose which is less obvious than structures of other
disaccharides. This is because sucrose has a flexible fructofuranose ring
linked to the fairly rigid glucopyranose ring. This flexibility is enhanced by
the presence of three primary hydroxyl groups, one of which is next to the
glycosidic linkage.
Experimental and theoretical works agree and show the sucrose linkage
to be nearly as flexible as any other disaccharide linkage. A survey of all
the sucrosyl moieties in crystalline oligosaccharides yields a 40 range in the
<j> torsion angle as well as a 90 range in 'ljI. In its crystalline conformation,
the sucrose molecules 'uses' most of its conformational degrees of freedom
to pack in a highly dense fashion.
As intra- and intermolecular hydrogen bonding in the solid state is
influenced by packing effects, it cannot be expected that the fixed overall
shape is retained in solution. Somehow conclusively, a 13C CP-MAS
analysis of crystalline sucrose indicated that the three primary hydroxyl
groups could have different bond rotamers distributions in the solid and in
the liquid states. They can indeed satisfy their hydrogen bonding with
protic solvents. Recent NMR studies in water have provided further
evidences indicating that the intramolecular hydrogen bonds were not
permanently maintained (Herve du Penhoat et ai., 1991). The conformational behaviour could be best described as a dynamical average of several
interconverting conformers in solution at least in the case of diluted
solution. Of course the population of low-energy conformers may vary
significantly as a function of the concentration, temperature and the nature
of the solvent. In DMSO solution, it is believed that two main low-energy
conformations are prevailing, which occur with a 2:1 equilibrium.
Mathlouthi and collaborators (Mathlouthi and Luu, 1980; Mathlouthi et
ai., 1980) observed a concentration dependence of Raman frequencies
assigned to the CHz groups of the C-lf and C-6f hydroxymethyl groups of
sucrose. They interpreted this observation as indicating that both intra-
29
molecular hydrogen bonds exist at high concentration, but are successively

broken upon dilution, with a single hydrogen bond persisting at intermediate concentration. The disappearance of the O-If ... 0-2g hydrogen
bond, at low concentration, may be accompanied by a change in glycosidic
linkage conformation. A concentration dependence in the low-angle X-ray
diffraction behaviour of sucrose solution was suggested to be compatible
with such model. Infrared data on solution, quenched melt, and freezedried samples and CPMAS 13C NMR data on freeze-dried samples were
also analysed on the basis of such a model (Mathlouthi, 1981; Mathlouthi et
al., 1986). It is clear that all these data are consistent with the lack of
conformational rigidity of sucrose as inferred from the extensive set of
theoretical characterizations.
Pioneering work on the field of sweet-taste chemoreception (Shallenberger and Acree, 1967; Kier, 1967; Shallenberger et al., 1969) proposed
that there should be complementarity between a hydrogen bond donor,
AH, and acceptor, B, on both receptor and sweetener molecules. The
distance between AH and B should be between 2.5 and 4.0 A. This
tripartite AH-B-X theory originated from a consideration of the crystalline
conformation of sucrose. It is worth mentioning that the occurrence of such
a glucophoric feature can also be identified on many of the lowest energy
conformations that sucrose can adopt. Besides, such a criterion is satisfied
by almost every sugar and many amino acids in many ways irrespective of
the property of the sugar molecule. There must be other stereochemical
requirements based on molecular shape and the electrostatic potential
associated with that shape that must be involved in the elicitation of
sweetness (Jeffrey, 1993). Actually, the wealth of significant information
provided by elucidating and analysing crystalline complexes between
protein and carbohydrates has shown that all the potential sources of
conformational flexibility may be utilized by the carbohydrate molecule to
mould itself to fit the protein combining site and to allow further
interactions with the neighbouring protein surface.
It has been suggested that hydrogen bonding, displaying both cooperativity and polarizability could play an important role in molecular
recognition (Jeffrey, 1993). Electrostatic information could be transmitted
in the vicinity of a receptor site. The transfer of electrostatic information
through polarization of the hydrogen bonded water structure at the
receptor site could be effective in several ways such as guiding the
sweetener molecule on to the receptor site in the correct orientation. In
perspective the necessary structural characterizations of the structures of
sucrose in water solutions are underlined. While the role of water structure
in sweet taste chemoreception has been examined (Mathlouthi et al., 1993)
no detailed investigation of the electrostatic potential has been performed
yet. Not only do we need molecular descriptions of the preferred
30
SUCROSE
conformations that sucrose can adopt once solvated, but also the
perturbation that the structure of water undergoes in presence of such
solute.
Acknowledgements
The author wishes to thank the many collaborators who have contributed
to the exploration of some of the aspects of structural sucrochemistry
presented in this chapter; in particular, Florence Casset, Soizic Cros, Soren
Engelsen, Catherine Herve du Penhoat, Stephan Houdier, Anne Imberty
and Christophe Meyer.
References
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for hydrocarbons. J. Am. Chem. Soc., 111,8551-8566.
Beevers, e.A. and Cochran, W. (1947) Proc. Royal Soc. London, Ser. A., 190,257.
Beevers, e.A., McDonald, T.R.R., Robertson, J.H. and Stern, F. (1952) Acta Crystallogr.,
5, 68~90.
Bock, K. and Lemieux, R.U. (1982) The conformational properties of sucrose in aqueous
solution: intramolecular hydrogen-bonding. Carbohydr. Res., 100,63-74.
Brooks, C.L., Bruccoleri, R.E., Olafson, B.D., States, D.J., Swaminathan, S. and
Karplus, M. (1983) CHARMM: A program for macromolecular energy, minimization and
dynamics calculations. J. Compo Chem., 4, 187-217.
Brown, G.M. and Levy, H.A. (1963) Sucrose: Precise determination of crystal and
molecular structure by neutron diffraction. Science, 141,921-923.
Brown, G.M. and Levy, H.A. (1973) Further determination of the structure of sucrose
based on neutron-diffraction data. Acta Crystallogr., B29, 790-797.
Carver, J.P. (1991) Experimental structure determination of oligosaccharides. Curro Opinion
Struct. Bioi., 1,716-722.
Christofides, C. and Davies, D.B. (1985) Co-operative and competitive hydrogen bonding in
sucrose determined by SIMPLE 'H N.M.R. spectroscopy. J. Chem. Soc., Chem.
Commun., 1533-1534.
Cremer, D. and Pople, J.A. (1975) A general definition of ring puckering coordinates. J.
Am. Chem. Soc., 97, 1354-1358.
Davies, D.B. and Christofides, e. (1987) Comparison of intramolecular hydrogen-bonding
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Carbohydr. Res., 163, 269-274.
Diner, S., Malrieu, J.P., Jordan, F. and Gilbert, M. (1969) Localized bond orbitals and the
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Fischer, E. (1893) Ber. Deutsch Chem. Ges., 26, 2400-2412.
French, A.D. and Dowd, M.K. (1993) Exploration of disaccharide conformations by
molecular mechanics. J. Mol. Struct. (Theochem), 286, 183-201.
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for molecular mechanics of carbohydrate. Carbohydr. Res., 180,207-221.
Hanson, J.e., Sieker, L.e. and Jensen, L.H. (1973) Sucrose: X-ray refinement and
comparison with neutron refinement. Acta Crystallogr., B29, 797-808.
Haworth, W.N. (1929) The Constitution of Sugars. Arnold and Co., London, UK, pp. 70-71.
Herve du Penhoat, e., Imberty, A., Roques, N., Michon, V., Mentech, J., Descotes, G. and
Perez, S. (1991) Conformational behaviour of sucrose and its deoxy analogue in water as
determined by NMR and molecular modelling. J. Am. Chem. Soc., 113,3720-3727.
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IUPAC-IUB Commission of Biochemical Nomenclature (1971) Arch. Biochem. Biophys.,

145,405-421.
Jeffrey, G.A. (1973) Conformational studies in the solid state: Extrapolation to molecules in
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Jeffrey, G.A. (1993) Hydrogen bonding with sugars and the role of hydrogen bonding in
molecular recognition. In Sweet-Taste Chemoreception (eds Mathlouthi, M., Kanters, J.A.
and Birch, G.). Elsevier Applied Science, London, UK, pp. 1-10.
Jeffrey, G.A. and Saenger, W. (1991) Hydrogen Bonding in Biological Structures. SpringerVerlag, Berlin, Germany.
Kier, L.B.A. (1967) A molecular theory of sweet taste. 1. Pharm. Sci., 61,1394-1397.
Lichtenthaler, F.W., Immel, S. and Kreis, U. (1991) Evolution of the structural representation of sucrose. Starch/Starke, 43, 121-132.
Lichtenthaler, F.W., Immel, S., Martin, D. and Miiller, V. (1992) Some disaccharidederived building blocks of potential industrial utility. Starch/Starke, 44, 445-456.
Mathlouthi, M. (1981) X-ray diffraction study of the molecular association in aqueous
solution of o-fructose, o-glucose, and sucrose. Carbohydr. Res., 91,113-123.
Mathlouthi, M. and Luu, D.V. (1980) Laser-Raman spectra of o-glucose and sucrose in
solution. Carbohydr. Res., 81, 203-212.
Mathlouthi, M., Luu, c., Meffroy-Biget, A.M. and Luu, D.V. (1980) Laser-Raman study
of solute-solvent interactions in aqueous solutions of o-fructose, o-glucose, and sucrose.
Mathlouthi, M. Cholli, A.L. and Koenig, J.L. (1986) Spectroscopic study of the structure of
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M., Kanters, J.A. and Birch, G.). Elsevier Applied Science, London, UK, pp. 141-174.
McCain, D.C. and Markley, J.L. (1986a) The solution conformation of sucrose: Concentration and temperature dependence. Carbohydr. Res., 152,73-80.
McCain, D.C. and Markley, J.L. (1986b) Rotational spectral density functions for aqueous
sucrose: Experimental determination using l3C NMR. J. Am. Chem. Soc., 108,4259-4264.
Meyer, C., Perez, S., Herve du Penhoat, C. and Michon, V. (1993) Conformational analysis
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MA, USA, p. 789.
Perez, S. (1993) Theoretical aspects of oligosaccharide conformation. Current Opinion Struct.
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Perez, S., Meyer, c., Imberty, A. and French, A.D. (1993) Molecular features and
conformational flexibility of sucrose. In Sweet- Taste Chemoreception (eds Mathlouthi, M.,
Kanters, J.A. and Birch, G.). Elsevier Applied Science, London, UK, pp. 55-73.
Pfeffer, P.E., Odier, L. and Dudley, R.L. (1990). Assignment of l3C CPMAS NMR spectra
of crystalline methyl jl-o-glucopyranoside and sucrose using deuterium labelling and
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Pigman, W.W. (1948) Chemistry of Carbohydrates. Academic Press, New York, USA,
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Poppe, L. and Van Halbeek, H. (1992) The rigidity of sucrose: Just an illusion? J. Am. Chem.
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Shallenberger, R.S. and Acree, T.E. (1967) Molecular theory of sweet taste, Nature, 216,
480-482.
Shallenberger, R.S., Acree, T.E. and Lee, c.Y. (1969) Sweet taste of 0- and L-sugars and
amino-acids and the steric nature of their chemo-receptor site. Nature, 221, 555-556.
Stevens, E.S. and Duda, C.A. (1991) Solution conformation of sucrose from optical
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Thogersen, H., Lemieux, R.U., Bock, K. and Meyer, B. (1982) Further justification for the
exo-anomeric effect. Conformational analysis based on nuclear magnetic resonance
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32
SUCROSE
Tran, V.H. and Brady, l.W. (1990a) Disaccharide conformational flexibility. I. An

adiabatic potential energy map for sucrose. Biopolymers, 29,961-976.
Tran, V.H. and Brady, l.W. (1990b) Disaccharide conformational flexibility. II. Molecular
dynamics simulations of sucrose. Biopolymers, 29, 977-997.
Tvaroska, I. and Perez, S. (1986) On the conformational energy calculations of oligosaccharides. Carbohydr. Res., 149, 389-410.
Van Alsenoy, C., French, A.D., Cao, M., Newton, S.Q. and Schafer, L. (1994) Ab initio
and molecular mechanics studies of the distorted sucrose linkage in raffinose. (Submitted
for publication)
3 Sucrose crystallisation
G. VACCARI and G. MANTOVANI
3.1 Introduction
One of the main characteristics of commercial sugar is its high purity

(>99.9%) which is comparable to that of the purest organic substances
which are produced on an industrial scale. To obtain such a product, both
from beet or cane, rather complex processing schemes are followed which
depend on the quality and quantity of non-sucrose compounds present in
the solution at the end of the extraction stage. Before reaching the
crystallisation stage, the solution leaving the extractor is usually subjected
to various purification steps in order to eliminate as many non-sucrose
compounds (non-sugar) as possible. Nevertheless, a remarkable amount of
such compounds remains in solution so that it will be the crystallisation
process which will complete the purification operation by obtaining crystals
which, normally through recrystallisation process, give a commercial
product with the desired characteristics.
The scope of the present chapter is to give some basic ideas on the
crystallisation process and to correlate the presence of non-sucrose
compounds and crystallisation management with the characteristics of the
final product. For a better understanding of the phenomena occurring
during crystallisation, we mention some basic concepts about sucrose
molecules and sugar solutions even though this subject is widely researched
and described in detail in other chapters of this book.
The sucrose molecule has eight hydroxyl groups which can be involved in
hydrogen bond formation. In sufficiently diluted aqueous solutions all the
hydroxyl groups form hydrogen bonds with water molecules. If the
concentration increases, the great flexibility of the bond joining the two
glucose and fructose molecules promotes the formation of a structure
presenting, at first, only an intramolecular bond and then two intermolecular bonds (Mathlouthi, 1981). If sucrose concentration in the solution
increases, aggregation phenomena occur between sucrose molecules which
promote step by step the formation of aggregates which will create the
stable three-dimensional nucleus (see below) (Schliephake, 1963).
For crystal formation, the various hydroxyl groups of the sucrose
molecule are available for hydrogen bonding. Even if the two intramolecular hydrogen bonds are not taken into consideration, it must be pointed

34
SUCROSE
out that one of the hydroxyl groups cannot be involved in the formation of
hydrogen bonds in the single crystal for steric reasons. On the other hand,
such a group plays a determining role in twin formation (see below)
(Aquilano et al., 1983; Mantovani et al., 1983).
3.2 Morphology
3.2.1 Single crystal

Vavrinecz (1965) described in detail the sucrose crystal morphology
considered as all the faces which determine the sucrose external habit.
Sucrose belongs to the sphenoidic class of the monoclinic crystal system
and is characterised by 15 simple forms whose relative positions are shown in
Figure 3.1(a). The eight most important faces are shown in Figure 3.1(b).
The crystal is polar along the binary b-axis belonging to space group P2 1
and its faces are in general identified via the Miller's indices or through
conventional letters (see Figure 3.1).
The relative development of the different faces, depending upon the
different growth rate, determines the exterior shape of the crystal. In
particular, the most rapid faces tend to disappear from the final
morphology where we can find, in general, the eight faces mentioned
above. In pure solution the faces of the right pole (+b) grow more rapidly
than those of the left pole (-b). As far as the development along the three
crystallographic axes is concerned, the crystal becomes more elongated
along the b-axis although we have to take into account that, in pure
i (503)
q (011)
0(111) ..
)\:I
f-k-
c (001)
q' (011)
d (101)
0' (111)
P (110)
f (210)
U
a (100)
............... p' (110)
f (210)
"-"'.
w (111)
w' (111)
C
(a)
Lb
r (101)
(b)
Figure 3.1 (a) Sucrose crystal showing all the 15 forms. (b) The eight most important faces.
(The Miller's indexes of the different faces are indicated in parentheses.)(After Vavrinecz,
1965.)
SUCROSE CRYSTALLISATION
35
solution also, the different faces grow, and then also the elongation along
the three axes, depends upon temperature and supersaturation (see below).
The presence of impurities in the mother liquor can then deeply modify the
exterior shape of the crystal.
The way sucrose molecules are packed inside the crystal has been
studied since the 1960s (Mantovani et al., 1967; Smythe, 1967, 1971). More
recent investigations (Aquilano et al., 1983), which were based on the
study of the formation of periodic bond chains (PBCs), allowed this subject
to be analysed thoroughly by defining more carefully the crystal morphological aspect (Figure 3.2).
By means of such analysis it is possible to define the F (flat), S (stepped)
or K (kinked) character of the different faces (Hartman and Perdok, 1955).
Without going into detail on such items we can point out that S, and in
particular K, faces tend to disappear from the crystal morphology since
they are more rapid than F faces. This is the reason why only eight out of
the 15 forms described above are present in the crystal: six of such faces are
F faces (a, p, p', C, r, q) and two (0, d) have an S character. The presence
of these two last faces in the final morphology, and in particular the d
faces, is to be related to the effect of the solvent which stabilises the faces
themselves (Aquilano et al., 1986).
3.2.2 Twins
The hydroxyl group which, as mentioned above, is not involved in the
hydrogen bond formation of the single crystal becomes essential in the twin
Figure 3.2 Projection of sucrose crystal structure along the c-axis. At the centre of the crystal
is drawn the projection of one of the PBes. (From Aquilano et al. (1983), reproduced with
permission.)
36
SUCROSE
formation. The twins are composed of two single crystals, the relative
position of which is rational and constant from the crystallographic point of
view. According to Vavrinecz (1965) they are formed by rotating one of
the single crystals 180 around the c-axis to obtain junction with the other
single crystal which remains in its original position. Also, according to
Vavrinecz (1965), we can distinguish three types of twin crystals:
0
(1) twin crystals which have their left poles turned towards each other
while the right poles point outwards (Figure 3.3(a;
(2) twin crystals which have their right poles grown together while the
left poles are pointing outwards (Figure 3.3(b; and
(3) twin crystals which represent a transition between the two above
types where both single crystals are placed behind each other and
are grown together along the a face (Figure 3.3(c.
From the crystallographic point of view (Mantovani et al., 1983) only twins
of type (1) can grow in pure solution; the growth of twins of types (2) and
(3) is to be ascribed to the presence in the solution of impurities which
modify the morphology of twins of type (1). From the technological point
of view, the presence of twins represents a negative aspect either relating
to strictly technological problems or crystal quality. Moreover, twins tend
to be larger in comparison to single crystals not only because they originate
from the junction between two crystals but also because they present, at
the two poles of the b-axis, two couples of pi faces (which grow more
rapidly in comparison with p faces). Further, in the zone of junction
between the two crystals, growth centres are activated (dislocations) which
favour the crystal growth along the c-axis. Consequently, larger crystals are
obtained compared to single crystals, with constant growth conditions (see
Figure 3.4), which worsen the sugar commercial quality.
Moreover, the junction zone between the two single crystals becomes a
weak point from the mechanical point of view. Therefore, the two crystals
can separate after growth, generating fragments which are technologically
noxious. Again, in the junction zone between the two crystals, mother
liquor can be retained and hardly eliminated through the usual crystals
washing inside the centrifuge, so even worsening the final crystal quality.
The formation of twins is strictly related to solution supersaturation; the
higher the supersaturation the higher the probability of twins' formation.
3.2.3 Conglomerates
Whereas the junction of two crystals forming twins obeys well-defined
crystallographic rules, the formation of conglomerates during the crystallisation process is due to a completely random junction of two or more
single crystals growing together (Figure 3.5).
Although the formation of conglomerates has not been completely
37
c (001)
I,
.. .
......
/
a (100)
d (101)
p' (110)
"'r (101)
(a)
c (001)
d (101 )
..............
\. ........
P (110)
V--
a (100)
r (101)
(b)
(c)
Figure 3.3 Twins of sucrose crystals. (a) Twin of type (1); (b) twin of type (2); (c) twin of
type (3). (After Vavrinecz, 1965.)
38
SUCROSE
Figure 3.4 Single and twin crystals present in the same crop.
Figure 3.5 Conglomerates present in commercial sugar.
explained, it seems that it can be related to the crystallisation conditions

(Pot, 1980; Kuijvenhoven, 1983). High supersaturations, which in their
turn favour high growth rate and spontaneous nucleation phenomena,
certainly promote the formation of conglomerates. Even the traditional
crystallisation in the pans, which promotes local supersaturations, favours
the formation of conglomerates. Other important parameters are seed
characteristics, stirring, crystallisation duration and crystal size. In particular it may be noted that the number of conglomerates is lower for better
39
seed characteristics, higher stirring, lower crystallisation duration and

smaller crystal size. Of course, the negative consequences on sugar
characteristics, quoted above with regard to the twins, become more
serious in the case of conglomerates, in particular, as far as crystal washing
during centrifugation is concerned.
3.2.4 Effect of impurities
Omitting, at this moment, the effect of impurities on the solution
characteristics, and in particular on sucrose solubility, we take into
consideration the possibility of interaction between such impurities and the
different crystal faces. If such impurities modify the relative growth rates of
the different faces, the crystal habit is also modified. Such modifications
can be such that certain faces, which normally are not present, can appear.
Powers (1970) pointed out that, if structural affinity with a single face
exists, or there is the possibility of bond formation, the molecule of
impurity can statistically remain on the surface for a period of time. If the
local conditions are favourable, a localised layer of impurity molecules can
develop, so hindering further attachment of sucrose molecules from
solution; in such a case we can observe an even drastic decrease of the
growth rate of the face itself up to its total blocking. If, soon after, the local
conditions change, the layer-by-Iayer growth of sucrose molecules can start
again overgrowing the impurity layer. On the other hand, if the interaction
between the impurity and the layer is weak, the weakly adsorbed impurity
molecule can be easily removed by the sucrose molecule coming from the
mother liquor phase. In this case there is competition between impurity
and sucrose molecules, also influenced by temperature, which causes a
modification of the growth rate of the face itself.
Before going into details on the specific effect of particular impurities on
sucrose crystal morphology, we consider the different morphologies of
sugar crystals originating from cane or beet processing. Obviously, if it is
refined sugar, the morphological differences are unimportant because in
both cases the concentration of impurities in the final growth solutions is
very low. On the contrary, if we consider raw sugar, and in particular the
one coming from low-grade boiling, crystals originating from beet
processing are morphologically very different from the ones coming from
cane processing. Furthermore, if db is the ratio between the crystal
elongation along c- and b-axes (see Figure 3.1), such a ratio for beet raw
sugar is lower than 1, whereas it is higher than 1 for cane raw sugar. In
other words, the impurities as a whole present in beet juices favour the
elongation of crystals along b-axis whereas in the case of cane raw sugar the
impurities as a whole favour the elongation along the c-axis. We have to
take into account that high concentrations of raffinose in beet juices and of
mono-, oligo- or polysaccharides in cane juices remarkably intensify such
40
SUCROSE
(a)
(b)
Figure 3.6 Morphological characteristics of raw sugar originating from (a) beet, and
(b) cane processing.
elongation along b- and c-axes, respectively. In Figure 3.6 cane and beet
raw sugars are compared.
In order to analyse the specific role of the different impurities as habit
modifiers, they can be subdivided into the following four groups:
(a)
(b)
(c)
(d)
monosaccharides,
oligosaccharides,
polysaccharides, and
inorganic non-sugars.
41
It is understandable that impurities relating to the groups (a), (b) and (c)
can interact with some sucrose crystal faces since they are, at least
partially, formed by structural units which belong to the sucrose molecule. In
fact (see Figure 3.2) the various faces of the sucrose crystal present at their
surface, under peculiar steric conditions, glucose or fructose units.
Depending on the number and strength of bonds established by the
different sugars with the various sucrose crystal faces, we can observe
poisoning phenomena of some faces also at low impurity concentration
(i.e. raffinose). Moreover, we can observe competition effects with sucrose
molecules at high impurity concentrations (i.e. monosaccharides).
3.2.4.1 Monosaccharides. Van Hook (1983a, 1988) studied carefully the

effect of glucose, fructose and invert (this he considered as an equimolecular
sum between glucose and fructose) on sucrose crystal morphology. He
pointed out that the most evident effects are observed at high concentrations of monosaccharides (100-200 g per 100 g water). Such concentrations
characterise cane processing juices and, in particular, low-grade boiling
products.
Vaccari et al. (1990, 1991a) taking as a starting point the peculiar
morphology observed in cane crystals (Figure 3.7), which show, together
with an elongation along c-axis, the appearance of rare faces on the right
pole and a peculiar D shape, studied deeply the influence of glucose and
fructose on sucrose crystallisation, drawing the following conclusions:
the most significant effects were observed at the highest concentration
of the impurities;
glucose interferes in particular with the left pole so far as to
completely block the p faces growth;
fructose interferes in particular with the right pole drastically slowing
down the growth of the 0' and q' faces (which, in general, are not
observed in the crystal), whose size becomes particularly important;
and
the combined effects of glucose and fructose causes an unusual crystal
form as shown in Figure 3.8.
Such results were interpreted by Aquilano et at. (1990) as a competition
mechanism in the surface absorption between the monosaccharides and
sucrose molecules. Such a mechanism becomes as much remarkable as the
impurities concentration becomes higher.
3.2.4.2 Oligosaccharides. With the general term oligosaccharides we

mean molecules of sugars formed by three or more monosaccharide units.
The most important from the processing point of view are the ones present
in the raw material and, in particular, raffinose (present in beet) and the
three kestoses and theanderose (present in cane). We can see in Figure 3.9
42
SUCROSE
Figure 3.7 Cane sucrose crystal showing the characteristic D shape.
r------------'"
I
....... _........
~.~."! .
.. "
c
: I
: I
: I
.. b
: I
:~
1}
;;iii>
/
Figure 3.8 Schematic drawing of the morphological change of sucrose crystal grown in the
presence of high concentrations of glucose and fructose.
43
.
~
GALACTOSE
GLUCOSE
FRUCTOSE
FRUCTOSE
FRUCTOSE
FRUCTOSE
FRUCTOSE
(raffinose)
CD
GLUCOSE
FRUCTOSE
(1 - Kestose)
GLUCOSE FRUCTOSE
GLUCOSE
(sucrose)
FRUCTOSE
(6 - Kestose)
FRUCTOSE
GLUCOSE
(Neo-Kestose)
GLUCOSE
GLUTOSE
(Theanderose)
Figure 3.9 Composition of the main oligosaccharides.
that such compounds are made by a molecule of monosaccharide

(galactose, fructose or glucose) bonded to a sucrose molecule. It is
therefore understandable, at least qualitatively, that there is the possibility
of an interaction between such molecules and that of the sucrose
crystal faces so modifying their growth morphology.
Although many papers have been published (see the references in Morel
du Boil, 1991, 1992) about the effect of oligosaccharides on the elongation
along the c-axis of crystals originating from cane processing, this subject
has been not studied yet in depth from the structural point of view as was
done for raffinose. The macroscopic effect of this trisaccharide, which
promotes the formation of very elongated crystals along the b-axis (Figure
3.10), has been carefully studied by Vim Hook (1981a,b, 1983). Taking into
account that such morphological changes can be observed even at
relatively low impurity concentrations, it could be supposed that, unlike
what occurs in the presence of glucose and fructose, some particular crystal
faces were selectively poisoned.
A complete review on the influence of raffinose on sucrose crystal
44
SUCROSE
Figure 3.10 Sucrose crystal grown in the presence of raffinose. (From Vaccari et al. (1986),
reproduced with permission.)
kinetics and morphology has been published by Vaccari et al. (1986). It is

pointed out that p' faces growth is completely blocked whereas no slowing
down effect can be observed on the p faces. Relating to the other faces,
there is a rapid disappearance of the d face morphology (the growth rate of
which is not influenced by the presence of raffinose), a slowing down of the
c faces and a drastic blocking of the a and r face growth. The final
morphology then becomes very simplified and crystals obtained grow
only along the -b-axis so presenting a needle-shape aspect as shown in
Figure 3.10.
From the technological point of view, these facts can cause big problems
which can be summarised as follows:
decrease, as a whole, of the crystal growth rate in the presence of a
high concentration of the trisaccharide such as can occur in the
Steffen plants for molasses desugarisation (Hartmann, 1974);
fragmentation of the thin crystals grown and the possibility that a part
of these fragments pass through the liners of the centrifuge.
We can incidentally point out that raffinose can cause a relatively unusual
phenomenon-'tapering'-which promotes the peculiar morphology shown
in Figure 3.11. Such a phenomenon has been studied utilising the interferometric holography, and the relevant results have been discussed
(Bedarida et al., 1988).
Another rather surprising effect caused by the presence of raffinose in
the growth solution is the change of the type (1) twins into types (3) and
(2). Such a phenomenon (Mantovani et al., 1983), presented as a scheme in
Figure 3.12, is directly promoted by the blocking of p' and a faces which
favours the overlapping of the a faces from p faces.
3.2.4.3 Polysaccharides. The presence of polysaccharides, and in
particular dextrans (glucose polymers), is particularly important in cane
processing. Many researchers have studied the morphological effects due
45
r-
Figure 3.11 Sucrose crystal tapering effect caused by the presence of raffinose in the growth
solution.
p'l~t
Ip,
p'
~
p'
P~p
a
Figure 3.12 Morphology modification of sucrose twins type (I) in the presence of raffinose
in the growth solution.
to the presence of such polymers (Bruijn, 1966; Kamoda et ai., 1968;

Sutherland, 1968; Leonard and Richard 1969; Sutherland et ai., 1969;
Imrie and Tilbury 1972; Covacevich and Richard, 1974) and, although the
conclusions are often conflicting, there is agreement that such compounds
play an important role. The reason for possible discrepancies can be due to
the different experimental conditions, different characteristics of the
polymers (i.e. molecular weight), and eventual synergistic effects which
46
SUCROSE
Figure 3.13 Sucrose crystal, grown in the presence of dextrans, elongated along the c-axis.
(From Mantovani et al. (1993), reproduced with permission.)
will be discussed below. What can be observed is an elongation along the caxis which can give crystals with a particularly high db ratio.
As in the case of raffinose, these drastic morphological effects have
detrimental influence from the technological point of view. In fact, the
elongation along the c-axis is not to be considered as an increase in the
growth rate along this axis but as a decrease of the growth rate of both p
and pi faces along the b-axis. Sucrose crystal grown in the presence of high
concentrations of dextrans are shown in Figure 3.13.
3.2.4.4 Inorganic non-sugars. Although it is rather difficult to suppose a

direct interaction between inorganic compounds and the different faces of
the sucrose crystal, many authors have studied this subject not always
reaching coincident results. However, the most studied effect concerns the
anomalous development of the d face of crystals grown in the presence of
potassium chloride (Aquilano et al., 1986, 1987). This phenomenon is
explained through an epitactic effect between one of the potassium
chloride crystal faces and the sucrose crystal d face. Sucrose crystal grown
in the presence of potassium chloride is shown in Figure 3.14.
47
Figure 3.14 Sucrose crystal, grown in the presence of potassium chloride, showing a large d
face.
The simultaneous presence of a big number of compounds in the

industrial growth solutions can cause crystal morphological modifications
which cannot be ascribed to only one of such substances, either
carbohydrates with a low or high molecular weight, or different organic or
inorganic compounds. In fact, negative or positive synergistic effects can
occur so that such impurities can help to enhance a certain habit
modification or limit the effect that each of them, being alone, can exert on
the final crystal shape. This fact can, at least within certain limits, justify
the apparently conflicting effects described by different researchers on the
grounds of tests carried out on crystals grown from industrial solutions.
3.3 Solubility
Although this subject has been covered in chapter 5 of this book, we would
like to discuss some points with the aim of relating them to the following
paragraph concerning nucleation and crystal growth. Sucrose is included
among the compounds presenting high solubility in water and such a
solubility is highly influenced by the presence of both organic and inorganic
compounds which are normally present in industrial solutions. To deal with
the problems related to nucleation and growth it is extremely important to
know the solubility curve as a function of temperature and how such a
curve can vary in the presence of other compounds in the solution which, in
the following, will be generically named 'non-sugars'.
48
SUCROSE
S/W
6
5,5
5
4,5
I
I
I
I
I
I
4
LABILE
3,5
~------
3
2,5
UNSATURATED
2'----"-----'--L---'-----'-_.L---'-----'-_.L---'-----'----l
30 35 40 45 50 55 60 65 70 75 80 85 90
Temp.oC
Figure 3.15 Schematic sucrose solubility diagram. Solid line, ft
ft = (s/w)/(s/w),at ,oln'
= 1.00; dotted line, ft = 1.35.
3.3.1 Pure solution
A schematic sucrose solubility diagram in water is shown in Figure 3.15

where the supersaturation zone is subdivided into the parts related to
nucleation and growth (see below). It is pointed out that, starting from an
unsaturated solution, it is possible to enter the supersaturation zone via
isothermal evaporation (line 1) or simple cooling (line 2) or adiabatic
evaporation (line 3). In this last case, cooling is promoted by water
evaporation under vacuum. This solubility curve can be shifted to lower or
higher SIW ratio values (S, sugar; W, water) depending on the presence of
non-sugars in the solution.
3.3.2 Impure solution
The effect of non-sugars on sucrose solubility depends on both their type

and concentration. In the case of traditional beet processing, a low nonsugar concentration in the solution (purity >90%), causes a sucrose
solubility decrease: when the NIW ratio increases (N, non-sugar; W,
water) sucrose solubility linearly increases. Figure 3.16 shows the solubility
curve calculated according to Gmt data (curve A) (Vavrinecz, 1978-79)
bearing in mind that the trend of such a curve can vary depending on the
49
(S/W) impure solution

1,4
(S/W) pure solution
1,3
1,2
1,1
0,9
0,8 L -_ _---JL-_ _---l
0,5
---l..
1,5
"'-'-
--...L
2,5
N/W
Figure 3.16 Effect of non-sugar composition and concentration on the saturation function.
non-sugar composition. In particular, curve B shows the trend of the

solubility curve for Quentin molasses (Vavrinecz, 1978-79) where sodium
and potassium ions have been partially replaced by magnesium ions. Curve
C shows the saturation function concerning a raw juice direct crystallisation
via the elimination of the whole traditional purification process as will be
described below (Vaccari et al., 1993a). The big effect exerted on sucrose
solubility by both the non-sugar concentration and composition is quite
clear.
By moving from beet to cane processing, it is clear that the change of the
non-sugar composition can promote sucrose solubility variation. Taking
into account the high percentage of invert which more and more increases
in the cane sugar juices, a special attention has been devoted to this
peculiar non-sugar (or, better, non-sucrose) on sucrose solubility
(Vavrinecz, 1978-79). Figure 3.17 emphasises how sucrose solubility
progressively decreases when invert concentration increases.
3.4 Crystallisation
3.4.1 Nucleation
We have already pointed out (see section 3.1) that in sufficiently
concentrated solution there is formation of aggregates among sucrose
50
SUCROSE
(8/W) impure solution

(8/W) pure solution
1.0
'.
.: .
'::.
70C
....
':.<;;:'::::':'::::':. ~
':.'.
'.'
'::'"
'. 40
' .. 30
'<:.
25
. 23
. 20
0.7'----------------10.0
to
Invert
Water
Figure 3.17 Sucrose solubility variation in the presence of invert. (after Vavrinecz, 1978-79.)
molecules. By reference to Figure 3.15, as we enter the supersaturation zone

there is an even higher probability that these aggregates reach such
dimensions to originate a stable three-dimensional nucleus which, increasing, will form the sucrose crystal. From the thermodynamic point of
view, the stable three-dimensional nucleus is formed only if a certain
energy barrier is overcome so that the process can go on towards the crystal
formation. Without going into detail of the theoretical discussion (Mullin,
1972) we can remember that, in the formation of a nucleus, there is a
request of energy for the surface formation, whereas a part of energy is
released by molecules owing to the decrease of the molecular motion
caused by transition from solution to crystalline state (crystallisation is, as
is known, an exothermic process). The total energetic balance as a function
of the molecules aggregate dimension has the trend depicted in Figure 3.18
where the critical radius rc and critical free energy !1Gc are pointed out.
If the dimension of the molecules aggregate is less than rc the aggregate
will tend to collapse so releasing sucrose molecules, whereas if it is more
51
Free Energy 6. G
+
--------------------_.,-~-~--
Radius
01---=::::=----------------1--------'.-----+
dissolution
regrowth
Figure 3.18 Total free energy variation in the nucleation process.
than r c the process will go on towards the progressive increase of the

nucleus dimension, that is the crystal formation occurs. The probability
that aggregates present in the solution reach the critical radius dimensions
will be as much higher as the solution supersaturation. If supersaturation is
named 13, and defined as the ratio of sucrose/water of the solution and
sucrose/water in saturated solution at the same temperature, the following
has been shown (Van Hook, 1959; Mullin, 1972; Maurandi, 1981):
rc = A/(T X In f3)
(3.1)
where A is a constant depending on the interface tension and molecular

volume and T the absolute temperature. From equation (3.1) we can
observe that the critical radius is as much smaller as temperature and
supersaturation are higher. Moreover, the critical free energy value can be
obtained through the following formula:
(3.2)
where B is a coefficient again depending on the interface tension and
molecular volume. We can observe that the dependence of I:!.Gc on
temperature and supersaturation is still more important compared with
critical nucleus radius.
The nucleation rate J, e.g. the number of nuclei formed per unit time
52
SUCROSE
and unit volume, which can be expressed via a type Arrhenius equation,
becomes:
J = K X exp - (C/(T3 X (In fJ)2))
(3.3)
where K and C are constants. It can be observed that the nucleation rate is
as much higher as higher are temperature and supersaturation.
What is reported above relates to pure solutions which do not contain
crystals or other solid impurities able to favour nucleation by lowering the
energy barrier leading to the stable nuclei formation. In such a case,
nucleation (indicated as heterogeneous nucleation) can occur under softer
supersaturation conditions as shown in Figure 3.19.
It should be remembered that nucleation rate cannot increase to infinity
with supersaturation increase. In fact, beyond a certain fJ value, the
solution viscosity can reach such values that the system assumes a glassy
character so drastically decreasing the nucleation rate.
With regard to Figure 3.15, it should be taken into account that the
presence of non-sugar in the solution will shift not only the saturation
curve, as pointed out above, but also the nucleation zone. In particular,
increasing the non-sugar concentration (and consequently decreasing the
solution purity quotient) the metastable zone will spread so moving away
Nucleation rate
heterogeneous
nucleation
homogeneous
nucleation
Supersaturation
Figure 3.19 Nucleation rate variation as a function of supersaturation for homogeneous and
heterogeneous nucleation.
53
from the saturation curve up to the nucleation zone. In other words, in the
presence of higher concentrations of non-sugar, more drastic supersaturation conditions will be necessary in order that the spontaneous nucleation
phenomenon can occur (Maurandi, 1981).
3.4.2 Crystal growth
3.4.2.1 Pure solution. The growth process of crystals from solution in
general, and of sucrose crystal in particular, is a very complex one. The
solute molecules, which in solution can be more or less hydrated or
aggregated, must have the possibility, as already pointed out, of placing
themselves on the crystal surface. Here they must be free to move and
suitably orientated to be able to find a suitable position where they may be
fixed after having lost their hydration water.
Bearing in mind the complexity of this subject, it is understandable that
it has been studied from different points of view with the aim of explaining
its various steps. It is well known that the surface diffusion theory has been
studied through the two-dimensional nucleation mechanism (Kossel, 1934)
and dislocations, which led to the Burton, Cabrera and Frank (BCF)
theory (Burton et al., 1951), the more complex Gilmer, Gez and Cabrera
theory (Gilmer et al., 1971) and the volume diffusion growth mechanism
elaborated by Chernov (Chernov, 1961). Bennema (1968) studied these
theories also using data of sucrose crystal growth. However, the study of
the crystallisation process as a whole is here limited by referring to the
diffusion process theory (Smythe, 1971; Mullin, 1972).
If dm is the amount of sucrose which crystallises in the time dt and e and
CO are the concentration of supersaturated and saturated solutions,
respectively, the growth rate can be given by a general equation such as
dm/dt = K A (e - eot
(3.4)
where A is the total surface of the crystals and K is the kinetic coefficient of
the crystallisation total process. If R is the specific growth rate and a the
relative supersaturation as (cleO - 1), equation (3.4) can be written as
follows:
R
= (dm/dt)
(VA)
= K'a
(3.5)
where K' = K (eot. Taking this into account the whole process can be
regarded as the sequence of two principal steps: the first of which
(diffusion process) transfers molecules from the bulk solution to the
crystals surface and the second one concerns the insertion of molecules into
the surface (reaction process). By reference to Figure 3.20, we can divide
equation (3.4) into the following ones which concern the two subsequent
steps, respectively:
54
SUCROSE
R = k d (C - C')
R=kr(c'-coy
diffusion process
reaction process
(3.6)
(3.7)
where k d and k r are the coefficient of mass transfer by diffusion and the
rate constant for the surface reaction, respectively; c' is the sucrose
concentration at the crystal-solution interface and z is the order of the
surface reaction process. In the simplest case where z = 1, we can
eliminate the term c' in equations (3.6) and (3.7) so obtaining the following
expression:
(3.8)
which, if compared with equation (3.4) where n = 1, points out that the
overall crystal growth coefficient K depends upon the two constants k d and
k r Since the two diffusion and reaction processes occur in series it is
obvious that the slower controls the total growth rate. This fact means that
if k r k d the overall growth process is ruled by surface reaction whereas
if k d k r it is the diffusion process which rules the whole process. These
two extreme situations can be obtained under particular conditions of
growth temperature or solution stirring (Maurandi et ai., 1988).
With regard to the growth temperature it has been widely shown that at
low temperature it is the surface reaction which dominates, whereas at high
temperature it is the volume diffusion which prevails. If we would like to
experimentally determine the values of k r and k d , it is sufficient to calculate
the K value of the overall process at low and high temperatures,
c
diffusion
c
CRYSTAL
c'
reaction
stagnant
film
.Q
~
CCD
o
bulk of solution
crystal/solution
interface
Figure 3.20 A model representation of concentration driving force for a two-step

crystallisation process.
55
respectively. Taking into account that the k i coefficients are related to

temperature through a normal Arrhenius relationship:
(3.9)
k i = Z exp - (E/R1)
where E i is the activation energy, R is the gas constant, T is the absolute

temperature and Z is a constant, we can calculate the activation energy of
the surface reaction (at low temperature) and the diffusion process (at high
temperature). In Figure 3.21 the data of activation energy reported by Van
Hook (1981a) for surface reaction, volume diffusion and the overall
process, are shown.
As regards solution stirring, we have to take into account that k d = D/b
where D is the diffusion coefficient and b the thickness of the boundary
layer around the crystal where mass transfer occurs only by diffusion (see
Figure 3.20). The value of b can be obtained bearing in mind the
expression involving the Sherwood (Sh), Schmidt (Sc) and Reynolds (Re)
numbers (Mullin, 1972; Maurandi, 1989)
Sh = 2/3 Re l / 2 Sc 1l3
(3.10)
where Sh = Lib; Sc = 1']/Q D; Re = u L Q/1']; L is crystal size; 1'] is

the viscosity coefficient of the solution; Q is the density of the solution; D
is the diffusion coefficient of the growth unit in the solution; b is the
thickness of the boundary layer; and u is the crystal-solution relative rate.
K Joule/mole
80
(a)
60
(c)
40
20
(b)
C
OL..---------'--------'------L..------.-J.+
o
20
40
60
80
Figure 3.21 Activation energy for (a) surface reaction; (b) volume diffusion; and (c) overall
process. (After Van Hook, 1981a).
56
SUCROSE
By obtaining the value of () we have
() = 3/2
X L I/2 X (T]/Q)1/6 X D 1I3 /U 1/2
(3.11)
From equation (3.11) we can observe that the boundary layer thickness
decreases with the increase of u, that is of the solution stirring, so causing
the increase of k d value. For sufficiently high values of solution stirring, the
k d value becomes much greater in comparison with the value of k r and the
overall process will be ruled by the surface reaction and then K = k r . In
Figure 3.22 the variation of the growth rate R as a function of the relative
motion crystals/solution is shown: for sufficiently high values of stirring the
k r value can be calculated and then, taking into account the relationship
among K, k r and k d , the k d value under different crystallisation conditions,
can be obtained.
What was described above relates to the simplest case where z of
equation (3.7) = 1 and, consequently, the value of n in the general
equations (3.4) and (3.5) = 1. For z values higher than 1, the expression of
the rate equation becomes obviously more complicated so that the
variation of R with supersaturation is of parabolic type at low supersaturation and becomes linear at high supersaturation values as shown in Figure
3.23.
Moreover, we have to bear in mind that for solutions having high
viscosity, such as concentrated sucrose solutions with high impurities
contents, k d varies with the solution viscosity which, in turn, depends upon
growth rate
stirring
Figure 3.22 Effect of stirring on crystal growth rate.
57
growth rate
supersaturation
Figure 3.23 Growth rate as a function of supersaturation if z > 1.
the supersaturation; therefore, the R value can reach a maximum and then
decrease at sufficiently high supersaturation values (Smythe, 1971;
Maurandi et al., 1988).
3.4.2.2 Impure solutions. The presence of organic or inorganic impurities in the growth solution promotes a decrease of the overall growth
rate of crystals together with the change of their morphology. With regard
to this latter aspect, we have previously observed that certain impurities
can poison certain faces slowing down their growth until their complete
blocking. This obviously corresponds to a decrease of the overall growth
rate of the crystal. However, even if the impurity is not involved in a direct
interaction with the crystal faces, it can play an important role in the crystal
growth by modifying the solution characteristics and, in particular, its
viscosity. This is without taking into account the effect of the impurity on
sucrose solubility as quoted above.
We have already pointed out (see section 3.4.2.1) that the diffusion
constant k d depends on the diffusion coefficient through the relationship k d
= Dlo. The diffusion coefficient is, in turn, related to the solution
viscosity, l), through the Stokes-Einstein equation (Mullin, 1972):
D = A X (TIl))
(3.12)
where A is a constant and T is the absolute temperature. If viscosity

increases, the diffusion constant, and consequently k d , decrease.
As previously reported for pure solutions (Mathlouthi and Kasprzyk,
58
SUCROSE
1984) viscosity varies with both temperature and supersaturation,

decreasing if T increases and increasing if 0 increases. In particular,
concerning supersaturation (0), viscosity exponentially increases at constant temperature according to the following relationship:
l]
=a
exp j3 (0
+ 1)
(3.13)
Therefore, we can infer that k d decreases if supersaturation increases

according to
k d = B exp - (j3 (0
+ 1
(3.14)
where B is a coefficient depending on temperature and boundary layer

thickness which, in turn, as previously mentioned, depends upon the
relative crystal-solution rate and, consequently, the magma stirring
conditions.
In the presence of impurities, in particular for solutions having a low
purity quotient, the relationships between viscosity, concentration and
temperature become consequently more complicated. Many researchers
have studied this problem (see the references in Mathlouthi and Kasprzyk,
1984) taking into account the importance it has also from the technological
point of view (see also chapter 6). Without going into such details which
can be known through the data in the literature, we can sum up by
emphasising that impurities cause a decrease of the growth rate as a whole.
This decrease becomes particularly drastic for the low purity quotient of
juices as pointed out in Figure 3.24 (Nakhmanovich and Zelikman, 1928;
Van Hook, 1959; Maurandi et al., 1988).
Obviously, the presence of impurities also affects the crystallisation
process activation energy and, in particular, the diffusion process activation
energy (equation (3.9. It was shown (Maurandi et al., 1982, 1984; Van
Hook, 1983b) that impurities exert an effect which is analogous to the one
exerted by an increase of temperature: a concentration increase promotes
an increase of the volume diffusion influence on the overall crystal growth
process.
3.5 Crystallisation technique

All the points discussed above from the theoretical point of view have to be
taken into consideration in the sugar factory where the main goal is to
produce the maximum amount of sugar to be put in the bags. Of course,
theory must fit with practical situations encountered in both beet and cane
processing.
If we consider again the sucrose solubility curve shown in Figure 3.25,
we have to point out that, from the industrial point of view, we must avoid
concentrating the solution (line 1) up to the spontaneous nuclei formation.
59
Growth rate (91m 2 min.)
70
75
80
85
90
95
100
Purity
Figure 3.24 Sucrose crystallisation rate variation as a function of juice purity. Values of /3:
(.) 1.03; (+) 1.06; (*) 1.09; and (.) 1.12.
In fact, we must avoid the creation of an uncontrolled number of seeds so

that it is impossible to predict the final crystals size. Therefore, after having
reached the zone A we add a predetermined amount of nuclei having fixed
sizes. Such nuclei, obtained by grinding the sugar itself, are suspended in
an organic solvent before addition to the supersaturated solution. After
this addition, crystals can grow either constantly remaining within the zone
A by supplying undersaturated solution (evaporation crystallisation) or
through a real cooling process (cooling crystallisation). So described, this
operation seems very simple; on the contrary, the process is very
complicated taking into account the high number of variables which
gradually modify the physico-chemical parameters to be observed and the
necessity of obtaining a final crystal product having well-defined characteristics.
As for physical variables, we have to consider that, during crystallisation,
the following parameters vary: mother liquor purity quotient; solubility;
crystallisation rate; crystals surface; supersaturation; solution viscosity;
crystallisation temperature; ebullioscopic rise; crystal to solution ratio;
mother liquor Brix; magma Brix.
The physico-mechanical limits are determined by considering that the
crystals to mother liquor ratio cannot be increased beyond a certain value
because the step following crystallisation is the physical separation of
60
SUCROSE
S/W
:
temperature
Figure 3.25 Sucrose solubility curve showing the course to be followed in industrial
crystallisation.
crystals from mother liquor through centrifugation. Moreover, the time

allowed for crystallisation cannot be too long, in particular at high
temperatures, either for energetic and plant engineering reasons or in
order to maintain the solution chemical characteristics, and, in particular,
its colour. As regards the final crystal characteristics to be obtained, we
have to bear in mind that, though crystallisation by itself is an effective
purification process, further recrystallisation steps can be needed after
dissolution of the crystals so carrying out, directly or indirectly, a true
raffination process.
3.5. J Evaporation crystallisation

In Figure 3.25 the course to be followed for an evaporation crystallisation
is tentatively shown from the general point of view. Under particular
vacuum conditions, in order to avoid too high ebullition temperatures, the
solution concentration is increased following the line 1. Then, the suitable
amount of seed is added after having reached the metastable zone.
However, this point should not be too close to the nucleation area in order
to avoid false grain formation and not too close to the saturation curve so
61
that there is a sufficient concentration range (c - CO) to allow a relatively

high growth rate (see equation (3.8)).
If we know the seed average size, which can be supposed spherical and
having a volume v, and the density d of the sucrose crystal (1.55 g/cm 3 ) , we
can obtain the average weight (P = v X d) of each seed and then, knowing
the total amount of seeds, we can calculate the number of seeds. After the
addition of seed and the starting of crystallisation, the supersaturation has
to be maintained around the point A by eliminating at the same time water
through evaporation and feeding undersaturated solution. During this
process we observe the following.
crystal growth so that the crystals total area A progressively increases;
solution purity quotient decrease due to the non-sugar (N) concentration increase and the consequent decrease of the SIN ratio;
solution viscosity increase;
specific growth rate R decreases on the grounds of that described in
the section 3.4.2.2;
ebullition temperature increase;
magma Brix increase; and
crystals to solution ratio increase.
The amount, M, of sucrose (g/min) crystallised at a certain step of the
crystallisation process under certain operation conditions of temperature,
supersaturation, juice purity and stirring, can be calculated by (Maurandi,
1975)
M=RXA
(3.15)
where R and A are the growth rate (g/m 2 min) and crystals' total area (m 2 )
at that moment, respectively.
The total area, A, can be given by A = s X n where n is the number of
crystals previously calculated in the seeding step (by supposing that neither
new nuclei formation nor crystals dissolution occur), and s is the average
area of each crystal. Such area can be calculated by the following
relationship:
s = 412 m 2 / 3
(3.16)
where 4.12 is the statistical shape factor (Bubnik and Kadlec, 1992) and m
is the average weight of each crystal given by the ratio between the amount
of sugar crystallised and the total number of crystals. Taking into account
that during crystallisation, which involves a progressive purity quotient
decrease, the growth rate decreases and the surface increases, we can
follow the variation of M through the progressive quotient decrease. Such
a curve presents a maximum and can be utilised for calculating the growth
average rate of M (g/min) during the whole crystallisation process. A curve
calculated using the data processed by Maurandi (1975) is shown in Figure
3.26.
62
SUCROSE
A (m 2)
R (g/m 2 min) ; M (g/min)
M
6
OL---------'-------------l...-----------*
75
80
85
. 90
P unty
Figure 3.26 Variation of the amount of crystallised sugar (g/min) as a function of the solution
purity quotient variation during crystallisation.
The value of M can be utilised for the calculation of the crystallisation

time given by the ratio between the amount of sugar to be crystallised and
the average rate of M calculated as described above. It is obvious that the
average value of M will be as much smaller, and then the crystallisation
time as much longer, as much lower is the purity quotient of the juice to be
crystallised (low R values) and as much smaller is the crystals number. In
fact, crystallised sugar being the same, the lower the crystals number, the
higher the individual size of each crystal and the lower the total area A.
Coming back to the point A depicted in Figure 3.25, we have to take into
account that during crystallisation the saturation curve as well as the
metastable zone area might vary. Of course, this fact causes a further
difficulty if we have to maintain certain supersaturation and crystal growth
rate conditions. At this point the problem is how we can prolong the
crystallisation process by eliminating water through evaporation and
adding undersaturated solution. The key is the crystals to solution ratio
which cannot overcome certain values related to the mother liquor
viscosity characteristics and magma consistency. At the time scheduled for
ending the crystallisation process, at first the solution feeding and then
evaporation are interrupted; the final magma is then discharged at the
prefixed Brix value into the cooling crystallisers where, following line 2,
crystals will further grow up to point B. In the case of low boiling, the
cooling step can be prolonged for 40-50 h. Under particular conditions of
solution viscosity (low boiling), before centrifuging magma it can be
63
necessary to increase slowly temperature along the line 3, always

remaining within the supersaturation zone up to the point C corresponding
to the centrifugation step.
Depending on the purity characteristics of the juice to be submitted to
the first crystallisation step as well as the plant engineering choices which
can be done also depending on the final sugar characteristics to be
obtained, the mother liquor, after the first crystallisation stage, is then
submitted to a second or eventually a third crystallisation before producing
molasses.
Figure 3.27 shows a scheme in three stages giving white sugar as the first
product whereas sugar of second and third products is dissolved. On the
ground of what was discussed above, it is quite understandable that the
crystallisation time increases moving from first to second and third
crystallisations (the ratios are about 1:3:9), whereas, due to the viscosity
increase of the mother liquor, the crystal to solution ratio decreases from
the first (about 1) to the low boiling crystallisation (about 0.6).
Obviously, in the cane sugar crystallisation, the basic ideas remain the
ones discussed above even if, due to the different characteristics of the
mother liquor, the sugar end schemes can vary. In general, cane sugar
factories produce raw sugar which is converted into white sugar in the
refineries where, after affination, dissolution and purification, the sugar is
recrystallised through various crystallisation steps (Figure 3.28).
3.5.2 Cooling crystallisation

Whereas during the evaporation crystallisation most of the sugar is
crystallised at nearly a constant temperature by maintaining constant
supersaturation conditions through solvent evaporation, in cooling crystallisation a different sucrose solubility variation in function of temperature is
utilised. In the case of the true cooling crystallisation, that is without water
evaporation, the maximum amount of sugar to be obtained is given by the
solubility difference between temperatures at the starting and the end of
crystallisation. By reference to Figure 3.25, it is then necessary that the
cooling range be as large as possible including the high temperatures range
where the solubility variation is greater. Also in this case, we need to
carefully follow the variation of the operation parameters which normally
occur during crystallisation both for avoiding nucleation phenomena and
maintaining the crystallisation rate within the programmed conditions. In
fact, the rate of cooling should be adjusted taking into account the
following:
the growth kinetics tend to decrease both due to the temperature
decrease and progressive decrease of the mother liquor purity
quotient;
AFFINATION
,~
MELTING
I
I-
3rd CRYSTALLISATION
mother liquor
2nd CRYSTALLISATION
II
mother liquor
1st CR YSTALLISATION
Figure 3.27 Crystallisation scheme in three stages.
2nd raw sugar
I SI raw sugar
THICK JUICE
MOLASSES
WHITE SUGAR
c::
oCIl
t'1
::c
(")
til
.j::..
0\
MOLASSES
LOW BOILING
refinery raw sugar
3rd CRYSTALLISATION
PURIFICATION
MELTING
AFFINATION
Figure 3.28 Crystallisation scheme of a cane sugar refinery.
mother liquor
mother liquor
RAW SUGAR
REFINED SUGAR
c::
CIl
VI
0\
-l
oZ
;l>
Vi
t""
t""
CIl
-<
~
'"
(j
tT1
CIl
'o"
(j
66
SUCROSE
the crystal surface progressively increases with the growing of the

crystals; and
viscosity is influenced by two conflicting factors: temperature decrease
promotes viscosity increase whereas the progressive decrease of the
S/W ratio, due to the crystallisation process, tends to decrease
viscosity.
Also in this case we can draw a profile of the variation of the sucrose
amount M crystallised in the unit time along the range of the mother liquor
purity quotient variation, that is along the cooling range. We can then
calculate the average value of M and determine the cooling time.
However, we have to take into consideration that for optimising the
growth conditions, we need to vary the cooling rate during the whole
crystallisation process.
Crystallisation through cooling only, starting from traditional thick
juices, has been studied both in the laboratory (Mantovani et at., 1988) and
on pilot plant (Vaccari et at., 1988). The authors started from the point that
the soft conditions which can be maintained during cooling crystallisation
can allow crystals of commercial quality to be obtained even starting from
particularly coloured juices.
A cooling crystallisation scheme in three stages has been proposed which
is shown in Figure 3.29.
Recently, the subject has been reconsidered by Schliephake et at. (1992)
who have pointed out the advantages of the multiple-stage cooling
crystallisation also from the point of view of the energy saving. Recently
again, the cooling crystallisation principle has been applied to the direct
crystallisation of raw juice such as eliminating any type of purification
process (Vaccari et at., 1991b,c, 1992, 1993b). The basic scheme shown in
Figure 3.30 has been verified at the level of pilot plant and further studies
are in course in order to evaluate the industrial applicability of the process.
The simultaneous presence of evaporation crystallisation and cooling
crystallisation can be found in the so-called continuous crystallisation
systems (Austmeyer, 1986; Schliephake et at., 1987) and in the MET plants
(Maurandi et at., 1986). In this case, the main goal does not concern crystal
quality but rather the crystallisation process rapidity.
3.6 Crystal quality

From the commercial point of view, sugar crystal quality is determined
both by internal and external crystal characteristics. Whereas the internal
characteristics depend on both the crystallisation conditions and solution
quality, external characteristics mainly depend upon the efficiency of the
washing conditions during centrifugation step and storage conditions.
MOLASSES
...
3rd COOLING
CRYSTALLISATION
CONCENTRATION
mother liquor
2nd COOLING
CRYSTALLISATION
CONCENTRATION
1st COOLING
CRYSTALLISAnON
mother liquor
Figure 3.29 Basic scheme of a cooling crystallisation process in three stages.
mother liquor
LOW BOILING
AFFINATION
raw sugar
MELTING
CONCENTRATION
THICK JUICE
WHITE SUGAR
c::
('"')
2j
-l
;I>
Cii
;I>
L'
L'
-l
V>
-<:
:<l
('"')
tTl
V>
:<l
V>
"
2nd COOLING
CRYSTALLISATION
MOLASSES
mother liquor
CONCENTRATION
if
mother liquor
1st COOLING
CRYSTALLISATION
CONCENTRATION
RAW JUICE
Figure 3.30 Basic scheme of the direct crystallisation of raw juice.
2nd RAW SUGAR
1st RAW SUGAR
REFINED SUGAR
CRYSTALLISATION
FILTRATION
MELTING
"
AFFINATION
l
VJ
tTl
VJ
'"
(j
c:
000
69
3.6.1 Inclusions
The crystal internal characteristics can be conditioned by the presence of
impurities inside the crystal lattice. These impurities can be coloured or
colourless and they can have high or low molecular weights. Taking into
account that the presence of such substances can be very important related
to the crystal quality and, in particular, colour and ash content, it is clear
that such parameters have been deeply studied often yielding conflicting
results.
One point supported by a number of researchers emphasises that certain
compounds, which are coloured and have a high molecular weight, can be
bonded to the sucrose molecules at the different crystal faces so more or
less uniformly finding a place inside the sucrose crystal. On the contrary,
other authors ascribe major importance to the phenomenon of physical
capture of mother liquor microdroplets (sometimes also macrodroplets)
inside the crystal. The presence of such microdroplets (inclusions) has been
widely studied using photography by Powers (1970). It is clear that, if such
inclusions are made by mother liquor containing impurities, and in
particular coloured ones, they affect crystal quality.
The interpretation put forward by Powers mainly relates to the etch pits
formation which occur inside the crystallisers during the evaporation. In
fact, due to the stirring, crystals reaching a zone at higher temperature
(near heating surfaces) where the solution is undersaturated, tend to
dissolve so creating on their surface small or big cavities which are filled
with mother liquor. The latter becomes included when crystals, moving by
stirring to a no more undersaturated zone, rapidly grow so healing their
surface. However, recently it has been pointed out that the capture of
mother liquor can be simply caused by particular growth kinetics
conditions which, by destabilising the crystal surface, can create hollows
able to capture solution (Mantovani et at., 1985a).
Taking into account that the various crystal faces have different growth
rates it has been proposed, and then experimentally confirmed, that the
most rapid faces can include mother liquor more rapidly than the other
ones independently of the crystals originating from beet or cane processing
(Mantovani et at., 1985b, 1986). In particular, in the case of beet sugar
crystals, which grow more rapidly along the +b-axis direction, the pi faces
are involved in the capture of mother liquor (Figure 3.31(a)). As far as
cane sugar crystal is concerned, which is elongated along the c-axis as
already mentioned, it is along this direction that the phenomenon
preferentially occurs (Figure 3.31(b.
The capture of mother liquour can be limited through a control of the
growth kinetics conditions and, in particular, taking care of supersaturation.
70
SUCROSE
(a)
(b)
Figure 3.31 Coloured inclusions in crystals grown from (a) beet; and (b) cane juices.
3.6.2 Colour of the crystals

This parameter is obviously related to the previous section but we need to
take into account the contribution given to the whole colour by the layer of
mother liquor surrounding the crystals. The washing carried out in the
centrifuge by water and/or vapour might minimise such a problem;
however, the higher the washing the higher the amount of sugar dissolved.
On the other hand, even if the washing is prolonged, the quality of sugar
remains constant due to the presence of colouring matter inside the crystal
71
(3)
(b)
-----... re-entrant angle
Figure 3.32 Re-entrant angles in (a) twins; and (b) conglomerates.
lattice (Shore et aI., 1984). Moreover, the presence of conglomerates and

twins, irregular crystal size and mother liquor viscosity remarkably affect
the washing effect (Broughton, 1986; Van der Poel et al., 1986):
In particular, the presence of re-entry angles, which can occur both in
twins and conglomerates (Figure 3.32), makes difficult the elimination of
mother liquor even dissolving a high amount of sugar. In this case, we can
only avoid the formation of such crystals by adopting suitable growth
conditions.
Crystals having very high size heterogeneity can cause packing phenomena inside the centrifuge basket slowing down the washing water flow
and creating preferential channels so that the massecuite is only partially
washed. Also in this case the problem should be solved in advance which
means during the crystallisation process in order to avoid false grain
formation. The mother liquor viscosity increases by moving from high
purity syrups crystallisation to low boiling. As is known, for the latter the
washing during centrifugation is scarcely useful so that an artificial magma
is normally prepared by mixing sugar with a saturated solution having a
fixed purity. Such a magma is then again centrifuged and the crystals
washed as pointed out in Figure 3.27. Also in raw sugar refining (Figure
3.28) the mother liquor layer outside the crystal is at first eliminated
through the preparation and centrifugation of an artificial magma.
3.7 Conclusions
From the preceding pages of this account it can be inferred how complex
are the problems involved in crystallisation. Taking into account that the
72
SUCROSE
latter basically is a purification process, the study in depth of its various

aspects becomes fundamental relating with the final product quality. On
the other hand, it needs to be borne in mind that, when all is said and done,
the final sugar characteristics must fit the customer's requirements.
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energies from pure and impure solutions. Zuckerindustrie, 109, 734-739.
Maurandi, V., Paganelli, B. and Rossi, A. (1986) Sucrose crystal growth after the vacuum
pans. Zuckerindustrie, 111,55-58.
Maurandi, V., Mantovani, G. and Vaccari, G. (1988) Kinetic studies on low grade boiling.
Sugar Technol. Rev., 14, 29-118.
Morel du Boil, P.G. (1991) The role of oligosaccharides in crystal elongation. Proceedings of
the South African Sugar Technologists' Association, Mount Edgecombe, Natal, South
Africa, pp. 171-178.
Morel du Boil, P.G. (1992) Theanderose-a contributor to c-axis elongation in cane sugar
processing. Int. Sugar J., 94,90-94.
Mullin, J.W. (1972) Crystallization. Butterworths, London, UK.
Nakhmanovich M.T. and Zelikman T.F. (1928) Methods of determining the speed of
crystallization. Sakharnaya Prornyshlennost, 6, 32-53.
Pot, A. (1980) Industrial sucrose crystallization. PhD thesis, Delft University of Technology,
Delft, The Netherlands.
Powers, H.E.C. (1970) Sucrose crystal: inclusion and structure. Sugar Technol. Rev., 1,85190.
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Schliephake, K., Austmeyer, K.E. and Hempelmann, R. (1987) Crystallization of higherpurity massecuites by cooling. Zuckerindustrie, 112, 269-273.
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2 Technical prospects for crystallization. Zuckerindustrie, 117,549-556.
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74
SUCROSE
Vaccari, G., Mantovani, G. and Sgualdino, G. (1988) The CCC system of continous cooling
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Amorphous sugar
M. MATHLOUTHI
4.1 Introduction
The crystallinity of a substance depends on the method of measurement
(Weyl and Marboe, 1962). When the crystals are too small their
crystallinity is hidden from the X-rays. It may sometimes be detected by
electron or neutron diffraction. However, the microcrystalline state is an
unsteady state. It is just a non-equilibrium stage testifying the continuity
between the crystalline and amorphous states. Amorphous means without
shape. It refers to a visual observation. For the information on noncrystallinity to be complete, the technique revealing this will be discussed,
i.e. X-ray amorphous.
What characterizes amorphous solids in contrast to the liquids is their
departure from equilibrium. They have very long relaxation times and may
remain almost indefinitely in a metastable state. Amorphous is not
synonymous with 'absence of order'. There is always a certain structure
which depends on the way the glassy or amorphous solid was prepared.
While only one crystal structure of sucrose is known from X-ray (Hanson et
al., 1973) or neutron diffraction (Brown and Levy, 1973), whatever the
conditions of crystallization the information on the amorphous state may
not be obtained from a single method, and almost each technique of
preparation leads to a different type of organization.
Amorphous sugar can result from dry-milling, the quenching of the melt,
the rapid drying of solutions (spray-drying), the freeze-concentration of
aqueous solutions and their freeze-drying as well as from the boiling or the
extrusion of highly concentrated solutions followed by cooling. It may be
described as glassy, vitreous, rubbery or concentrated amorphous system.
The characterization of its structure can be derived from the interpretation
of the broad one or two bands diffuse X-ray diffractogram, the vibrational
spectra, the viscosity and the thermal behaviour manifested by temperatures and concentrations typical of glass transition, recrystallization,
collapse and melting. Most of these physical and structural properties of
amorphous sugar are moisture dependent.
Water content and water activity together with temperature are
determining factors of the mobility and reorganization of sucrose molecules

76
SUCROSE
in the amorphous matrix. These factors are at the ongm of stickiness,

caking and recrystallization of amorphous sugar. Such an instability is
difficult to predict even though critical values of water activity, viscosity or
glass transition temperatures were proposed (White and Cakebread, 1966)
for structure transitions of different products containing amorphous
sugars. The stability of amorphous sugar in foods and pharmaceuticals is of
practical and economical importance. It affects quality attributes of foods
such as texture, aroma retention and shelf-life. In particular, the stability
of crystalline sugar, the duration of curing and the prevention of caking
require molecular interactions in the concentrated film of syrup around the
crystals to be controlled (Bressan and Mathlouthi, 1994).
Determination of crystallinity and molecular structure of amorphous
sugar are considered here. The interaction of non-crystalline sucrose with
water and the thermal properties including glass transition and recrystallization are also reviewed. The applications of amorphous sugar, undesirable
(caking, stickiness) or desirable (fondant, fudges) are also described.
4.2 Structure of amorphous sucrose

Depending on the method of preparation, amorphous sucrose may be
considered as a supercooled liquid (in the case of quenched melt, drymilled or extruded sucrose) or a supersaturated solution, sometimes called
concentrated amorphous solution (CAS) for freeze-concentrated and, to
some extent, freeze-dried samples (Bellows and King, 1973). Thermodynamic conditions of crystallization of such media are filled up whereas
the kinetics requirements are far from being obtained. Both supercooled
and supersaturated non-equilibrium states correspond to non-crystalline
sucrose. They differ in the amount of moisture, generally higher for
concentrated amorphous solution, and in the degree of order of such
complex structures.
4.2.1 Order and disorder in concentrated amorphous solution

Highly supersaturated solutions of sucrose are relatively easy to obtain
either by freeze-concentration or by boiling. Discussion of the solutesolvent interactions in these metastable systems may be informative on the
phase transitions that may occur under varying temperature conditions. It
was remarked that a certain continuity exists between amorphous and
crystalline states. Likewise, there is a linkage between the structures of
dilute and concentrated solutions including concentrated amorphous
solutions and freeze-dried sucrose which is just a freeze-concentrated
sample from which water (ice) was removed by sublimation.
Thus, it is of relevance to recall the solute-solvent interactions in
AMORPHOUS SUGAR
77
aqueous solutions of sucrose at different concentrations. Several experimental evidences (Mathlouthi, 1980; Hooft et al., 1993; Perez et al., 1993)
showed that the structure of the sucrose molecule in dilute aqueous
solution is not that of a hard sphere with two intramolecular H-bonds. It is
highly hydrated, lacking intramolecular hydrogen bonds and inducing a
long-range order of the bulk water sometimes called 'structure maker
effect' (Walrafen, 1966). As the concentration is increased, the flexibility
(Mathlouthi, 1981) around the glycosidic bond allows the establishment of
an intramolecular bond at intermediate concentrations and two intramolecular bonds at high concentrations. The limits of dilute, intermediate and
high concentrations may roughly be situated at one-third of saturation,
two-thirds and saturation concentration, respectively, i.e. 22.3, 44.6 and
66.8% (w/w). Below a concentration of 22.3% (w/w) no inter- or
intramolecular interactions are found. The organization of sucrose
molecules is comparable to that of the quenched melt as may be derived
from Fourier-transform infrared (FT-IR) spectra (Mathlouthi et al., 1986).
A better resolution of IR bands in the 1200-1800 cm- I region was observed
for freeze-dried and concentrated solutions and assigned to a higher degree
of order in these media (see Figure 4.1). The absence of order in dilute
solutions and their comparison with the glassy molten state is known from
a classical work on crystallization (Tammann, 1926).
Most of the work on physico-chemical properties of sucrose in water has
dealt with dilute solutions, or for nucleation and growth of crystals, with
supersaturated solutions. Factor analysis of the FT-IR spectra of sucrose
solutions of 10, 23, 33, 40, 50, 66 and 70% (w/w) permitted differentiation
of at least two species of sucrose molecules, one with intramolecular bonds
and a relatively higher order comparable with the crystal and the other of
lower order comparable with the quenched melt (Mathlouthi et al., 1986).
The concentration 40% (w/w) sucrose in water was found either from
viscosity measurements (Schneider et al., 1963) or NMR results
(Richardson et al., 1987) to correspond to a transition from solvated
(sucrose-water association) to the associated state (sucrose-sucrose
association). The change of behaviour of sucrose solutions at around 40%
(w/w) was also demonstrated (Mathlouthi et al., 1980) from the ratio of
intensities of Raman bands characteristic of the sugar (6(CH z on the
one hand and of water (b(HzO)) on the other. The evolution of this ratio
in terms of mass concentration displays a discontinuity at 30-40%.
Prior to crystallization, the existence of swarms of sucrose molecules,
called protonuclei, in the apparently homogeneous solution was demonstrated (Tikhomiroff, 1965) by means of various techniques (density,
viscosity, thin-layer chromatography and interferometry). Thus, its seems
that the degree of order (sucrose-sucrose association) increases as the
concentration increases. Depending on the thermal history of the
concentrated solution (freezing or boiling) and the rate of cooling or
78
SUCROSE
1400
1100
V
I
800
Cm-;
1400
,k
800
Cm-'
Figure 4.1 FT-TR spectra of sucrose solutions with (a) 22, (b) 66, and (c) 70% (w/w)
concentration and (a) vitreous, (b) lyophilized and (c) crystalline, sucrose.
heating, the molecular interactions in concentrated sucrose solutions are

different and so is the structure of the amorphous product.
The freezing of a sucrose solution may be considered as a way of
removing water from the solution. The rate of cooling influences the size
and orientation of ice crystals. A rapid deep-freezing may increase the
amount of supercooled unfrozen water. The overall structure of the freezedried product depends on the freezing step (Flink, 1983). The concentration
in concentrated amorphous solution (CAS) obtained by freezing is not
homogeneous (Luyet and Rasmussen, 1968). It is generally high (above
80%) situated in the metastable region (supersaturation >1.35). No
AMORPHOUS SUGAR
79
nucleation or crystal growth of sucrose can occur and the hydrates found in
concentrated solutions at low temperatures are only short-lived agglomerates of sucrose and water molecules locally associated with a certain order
(Young and Jones, 1949; Steinbach, 1977). These associates are more
comparable to the swarms described by Tikhomirof than to stable
crystalline species as is known for a-D-glucose, monohydrate or other
carbohydrate hydrates.
The structure of the concentrated frozen solution is responsible for
accidents like the collapse during the freeze-drying of sucrose. The
mobility of water and sucrose molecules when temperature is raised may
lead to a dense glazed film in the surface which hinders the mass transfer
and affects the porosity of lyophilized sugar. These temperature-dependent
transformations will be discussed further below.
Apart from freezing, concentrated amorphous solution may be obtained
by boiling. The glassy state is, therefore, favoured by a rapid cooling which
contributes to increase the viscosity and by the presence of other molecular
species like glucose, fructose, maltodextrins, or gelatine as is the case for
confectionery products. The structure of such a medium may be considered
as a supersaturated viscous solution. Supersaturation in boiled sweets is
extremely high, above the range where nucleation and growth of sucrose
crystals are possible. Nevertheless, small crystals are found (Lewis, 1990)
in confectionery products either because of a poor formulation or during
the storage. The size of crystals plays a major role in the textural properties
and quality of the product (Hartel and Shastry, 1991). However, the
instability of the grained confections is not only due to supersaturation. It
is also dependent on viscosity, temperature, agitation and the composition
in non-sucrose solids. The effect of each of these parameters on the
structure of the product especially as concerns the rate of nucleation and
growth of crystals was only approached qualitatively (Hartel and Shastry,
1991) except for a detailed study of the rates of progress of sucrose
nucleation in sugar glasses with varied amounts of dextrose, fructose and
water (Herrington and Branfield, 1984). Even in these glasses, the
determining factor seems to be the availability of water which allows or not
the transition from viscous to viscoelastic or rigid behaviour. A viscous
phase was always present between the glassy and crystalline layers
(Herrington and Branfield, 1984). The 'threshold' water content and
possibility of crystallization was found (Herrington and Branfield, 1984) to
depend on the type of additive. In particular, a very slow rate of
crystallization was found with fructose, which may be due to the increased
solubility of sucrose in sucrose-fructose-water systems (Kelly, 1954), or to
the higher affinity of fructose for water. Although water is only present at
very low amounts (2-6%) in sugar glasses, its interactions with the
different solutes and its mobility are at the origin of the structure and the
stability of the product.
80
SUCROSE
4.2.2 Structure of freeze-dried and spray-dried sucrose
Because of the difficulty of obtaining a reproducible glassy structure by

melting or evaporation of concentrated solution, freeze-dried sucrose was
very often taken as a reference of the amorphous state. However,
amorphous sugar is difficult to produce by lyophilization. A very rapid
cooling in liquid nitrogen of individualized drops of sugar solution running
from a burette is necessary to obtain a non-crystalline sample by freezedrying (Carstensen and Van Scoik, 1990). The lyophilized drops were 'xray amorphous' with a large specific surface area (3.9 m2/g) which
increased their reactivity with water vapour. As already mentioned, the
structure of freeze-dried sucrose depends on the method of measurement.
X-ray diffraction permitted (Mathlouthi, 1973) differentiation of lyophilized sucrose from quenched melt glassy sucrose and to show their
departure from the crystalline state (see Figure 4.2). However, it is known
(Legrand, 1967) that diffuse X-ray diffractograms may be obtained with a
10
'0
(a)
(b)
'0
15
14
"
13
1.2
1t
10
0
8
Figure 4.2 X-ray diffractograms of (a) lyophilized, (b) crystalline and (c) vitreous sucrose.
AMORPHOUS SUGAR
81
small number of small crystalline particles. Application of radiation with

shorter wavelengths than X-rays, i.e. electron diffraction, was found
(Mathlouthi, 1973) to be more sensitive to the detection of crystallinity in
freeze-dried sucrose. Although lyophilized sugar is mainly amorphous, the
presence in its lamellar non-crystalline structure (see Figure 4.3) of zones
containing microcrystals was ascertained by scanning electron microscopy
and electron diffraction (Figure 4.4). The microcrystalline state of freezedried sucrose is responsible for its instability (Mathlouthi, 1973, 1975).
Indeed its recrystallization in presence of water vapour or after annealing
in the freeze-drier has as its origin the presence of microcrystals in the
amorphous bulk. The morphology and structure of divided solids were
found to depend on the temperature and pressure of dehydration
Figure 4.3 Scanning electron microphotograph of lyophilized amorphous lamellar sucrose.
Figure 4.4 Microcrystals found in lyophilized sucrose and their electron diffractogram.
82
SUCROSE
(Rouquerol, 1964). Maintaining the freeze-dried sucrose in the freezedrier and applying heat was found to increase its crystallinity. The
crystalline sample obtained after an annealing may be more or less porous
depending on the heat applied.
Amorphous sugar can also be obtained by spray-drying. Its crystallization
was obtained (Palmer et al., 1956) either by exposure to humid air (RH =
32%) or more rapidly by exposure to humid air and seeding with 5% fine
crystals. Rapid air-drying of sucrose generally takes place at such high rates
of water removal that the solution quickly reaches a high concentration.
Under such conditions, the molecular association needed for crystalline
structure is not obtained and the product remains in the glassy state (Flink,
1983). Spray-drying and drum-drying mainly concern lactose in whey or
milk and generally lead to amorphous lactose except if a pre-crystallization
step was applied.
4.2.3 Dry-milled and extruded sucrose

Milling of crystalline sugar was found (Weichert, 1976) to produce
amorphous sugar. The amorphization was attributed (Weichert, 1976) to
an increase of temperature up to 2000C for less than a microsecond, which
provokes the melting of a layer of sucrose molecules at the fracture area.
The structure of dry-milled sucrose was derived directly from the
microphotographs or indirectly from water vapour sorption and the heat of
solution (Roth, 1976). However, as the origin of the transformation orderdisorder during the milling is the melting of superficial layers in the crystal,
it may be of relevance to control the crystallinity of the glassy molten
sugar. This was achieved using X-ray (Mathlouthi, 1973), FT-IR and CPMAS (cross-polarization magic angle spinning) 13C NMR spectra
(Mathlouthi et al., 1986) of the amorphous quenched melt sample as
compared to lyophilized sugar on the one hand and to the crystalline
sucrose on the other. The spectrum of the quenched melt was found
(Mathlouthi et al., 1986) to be more comparable to the dilute solution than
to the solid freeze-dried sample. The effect of heat on the melted sugar was
to break inter- and intramolecular hydrogen bonds. While the structure of
crystalline sugar is stabilized by hydrogen bonds, giving narrow resonance
lines in the 13C NMR spectrum, excessive line-broadening in the spectrum
of freeze-dried and molten sucrose makes it difficult to distinguish them on
the basis of this technique (see Figure 4.5). The use of differential thermal
analysis seems more appropriate for the differentiation of the two solid
amorphous states. As may be seen in Figure 4.6, the thermogram of the
freeze-dried sample involves a peak of recrystallization at 110C and a
melting endotherm at 180C like the crystalline sugar, beside the glass
transition at about 60C. The glassy molten sample shows an important
glass transition endotherm at 60C followed by a devitrification and a
83
AMORPHOUS SUGAR
(a)
(b)
(c)
120
100
80
60
Figure 4.5 CP-MAS l3C NMR spectra of (a) vitreous, (b) lyophilized and (c) crystalline
sucrose.
staggered endothermic transformation which probably has as its origin an

increase of fluidity rather than a clear melting. Such a mobility of sugar
molecules depends on temperature, moisture and composition of the glass.
Hence, for the dry-milled sugar, the few molecules thick layer which melts
by crystal breakage clumps as a glassy sugar which recrystallizes in the
presence of humid air.
The traces of moisture are very likely at the origin of the discrepancies
between glass transitions temperatures found for small carbohydrates
(Levine and Slade, 1988; Finegold et al., 1989; Ollett and Parker, 1990). In
boiled sweets and extruded sugar (Tabouret, 1977), the temperatures are
84
SUCROSE
(a)
(c)
20
60
100
140
180 'C
Figure 4.6 Differential thermograms of (a) crystalline, (b) lyophilized and (c) vitreous
sucrose.
as high as 13o-200C in the extruder under pressure. In these conditions

both the dissolution and the melting may be put forward to explain the
formation of the glassy state. Indeed, about 2-7% water remains in the
extruded sugar. The dissolution of sucrose in presence of dextrose and
10% water at 130C was reproduced (Tabouret, 1977) in the laboratory
and given as an argument for the decrystallization of sucrose in a glucose
syrup (DE = 36-39) after extrusion. Therefore, the border between
supercooled liquid (molten glass) and extremely supersaturated solutions is
ill defined as concerns the nature of the amorphous sugar when traces of
water (2-7%) are present.
4.3 Thermal properties of amorphous sugar

The change in mechanical properties of the glassy sugar are determined by
use of different techniques amid which differential scanning calorimetry
seems the more appropriate to account for the mobility of molecules
during the glass transition. This structure modification invariably occurs
below the freezing point and is accompanied by an important change in
physical properties like viscosity, specific heat, entropy and specific
volume. The question whether glass transition is a kinetic phenomenon,
AMORPHOUS SUGAR
85
mainly dependent on viscosity and relaxation times or a thermodynamic

process better accounted for by thermodynamic properties like entropies,
heat contents and volumes, was not clearly answered in the early studies
(Kauzman, 1948). It was elucidated later by Gibbs (1971) who demonstrated
that the flattening of the E-T, H-T, S-T and V-T curves derives from the
fact that the number of configurations available in the glass transition
region is small, which gives small entropies in polymeric glasses. Then,
both the kinetic and thermodynamic approaches are valid and are
supported by the dearth of configurations in the activated state corresponding to the non equilibrium glassy structure. Thermal changes of noncrystalline sucrose were investigated either for CAS or for the amorphous
solid.
4.3.1 Behaviour of concentrated amorphous soiutions

Aqueous carbohydrate solutions are known to exhibit a non-equilibrium
freezing behaviour. The sucrose-water system was taken (MacKenzie,
1977) as a model system for biological media and carefully studied during
the cooling and rewarming by use of differential thermal analysis.
Depending on the concentration of sucrose solution and the rate of
warming, different thermal events are observed (MacKenzie, 1977).
Among these are glass transition, antemelting, incipient melting, devitrification (recrystallization of ice) and an equilibrium melting, respectively,
characterized by the temperatures Tg , Tam, Tim, Td and Tm' The
supplemented phase diagram of sucrose-water system was established
(MacKenzie, 1977). The crystallization of sucrose was never observed in
these studies nor in ours (Mathlouthi, 1973). The eutectic point is just an
extrapolated intersection of sucrose solubility curve and ice melting curve
and has no real experimental existence. Investigating the thermal
behaviour of the sucrose-water system reveals the existence of a sucrose
concentration above which ice cannot be formed (MacKenzie, 1977;
Maltini, 1977). This maximally freeze-concentrated solution was found
(Maltini, 1977) at 67-72% of soluble solids. It was recently determined to
be 81.2% sucrose (C'g) and shown by a novel experimental approach to
occur at a temperature (T'g) of -40C (Ablett et ai., 1992).
The discrepancies between the values of C' g' the maximally freezeconcentrated sucrose solution, were discussed (Ablett et ai., 1992; Slade
and Levine, 1994). The method of calculation of C'g based on the
determination of the amount of ice from the melting peak area using the
latent heat of ice at OC seems to underestimate this amount and also C' g'
A consensus was proposed by Karel et ai. (1994) for a value of 80 5% for
all small carbohydrates. For the author, it seems logical to relate results
from different origins. A wealth of data (Allen et ai., 1979; Akhumov,
1975; Suggett, 1976; Franks, 1977; Culp, 1981) exists concerning the
86
SUCROSE
hydration numbers of sugars. Therefore, taking a hydration number, n =

5, for sucrose and supposing these five molecules are unfrozen leads to a
concentration of 79.17% which might be C' g for sucrose. A hydration
number of three for glucose leads to a value of C'g = 76.92%. These values
lie within the range of 80 5% proposed by Karel et al. (1993). At low
temperatures all thermal events concern water rather than sugar. It is
beyond the scope of this chapter to discuss the structure of water in
supercooled systems. As concerns sucrose, it may be noticed that whereas
the removal of water by heat allows very high concentrations (above 95%
to be reached), the cooling has a limit in disassociating water from sugar.
This limit is C'g = 80%, which corresponds to n = 5. Moreover, although
the thermodynamic conditions of crystallization are reached (the solution
is supersaturated), sucrose does not crystallize. This is due to the kinetic
hindrance with viscosity reaching the critical threshold of 10 12 Pa s and to
the impossibility of establishing direct sucrose-sucrose bonds, the sugar
molecules being fully hydrated. However, if we consider, the sucrose
molecule hydrated with five molecules of water as the real solute species,
the maximally freeze concentration (79.17% (w/w)) becomes a saturation
solution, with regard to the hydrated solute, a pseudo-equilibrium rather
than a non-equilibrium. In these conditions, one can derive from previous
phase diagrams (MacKenzie, 1977; Roos and Karel, 1991; Ablett et al.,
1992) a new one that may be reconciled with classical (Van Hook, 1961)
solubility and supersolubility curves delimiting the undersaturation,
metastable and labile zones of crystallization of sucrose (see Figure 4.7).
Our hypothesis of a pseudo-equilibrium of hydration reached by freezeconcentration was evoked by Roos and Karel (Roos and Karel, 1991) as an
unknown alternative to the kinetic inhibition of crystallization. The
parallelism between solubility and supersolubility curves and the almost
constant value for supersaturation (0 = (C/Csat ) = 1.35) along the
supersolubility curve together with the correspondence of the glass
transition of 'amorphous sugar' T g = 60C with the supersolubility of the
fully hydrated sucrose are further arguments for the existence of the
pseudo-equilibrium state. This state of organization of sucrose-water
solutions constitutes the limit for a supersaturated or supercooled system
to cross before reaching the equilibrium conditions.
4.3.2 Glass transition of amorphous solid sucrose

The continuity between the behaviour of concentrated amorphous solutions
and non-crystalline solid sucrose may be observed from the continuity in
Tg-supersolubility curve (see Figure 4.7). The glass transition temperature
of amorphous sugar was found (Roos and Karel, 1990) to depend on the
moisture content. It decreases on increasing water content. Water plays its
role of plasticizer. A small amount of moisture (1 %) provokes a decrease
87
AMORPHOUS SUGAR
Toe
60
UNDERSATURATION
Zone
20
LABILE
Zone
,,
,,
,,
\
\
\
\
\
60
Figure 4.7 Phase diagram of sucrose-water binary system showing (- - - -) the ice-melting
curve; (E) the hypothetical eutectic point and the maximally concentrated amorphous
solution with C'g = 80% and T'g = -40C.
of about 20c e of the Tg value of the freeze-dried sample (Roos and Karel,
1990). Increased amounts of moisture decrease the glass transition
temperature below room temperature and provoke stickiness, collapse and
recrystallization. The glass transition temperature seems to be a good
indicator of the transitions that may occur in an amorphous sugar, like
collapse, stickiness and caking during storage.
88
SUCROSE
Application of equation (4.1) originally reported by Gordon and Taylor

(1952) to fit the prediction of glass transition temperature, T g , in binary
polymer mixtures, was found (Roos, 1993) suitable for water-small
carbohydrates mixtures:
WI T g ,
WI
+ kW2 T g ,
+ kW2
(4.1)
where WI and W2 are weight fractions of solute and water, respectively, T g "
and T g , the Tg values for solute and water.
With T g, = -135e and using the experimental values of T g , Roos
(1993) obtained a linear expression of k:
k = 0.0293 T g
+ 3.61
(4.2)
The value of k = 4.7 0.2 obtained (Roos, 1993) for sucrose solutions
(65-80%) permitted (Roos and Karel, 1991) the establishment of a state
diagram for amorphous sucrose with experimental results fitting with those
calculated.
The glass transition (Tg ) and melting (Tm) temperatures were often
related, despite the fact that glass transformation is a kinetic process and
melting a thermodynamic process. An empirical relation, called the 'twothirds' rule (Tg = 2/3 T m), was verified (Sanditov, 1976) from the relative
change in volume around glass transition supposed constant and the
difference between the coefficients of thermal expansion at T g . Values of
TglT m = 0.69-0.70 were obtained for mannose, glucose and galactose and
interpreted as a sign of a constant change in specific volume during the
glass-crystal transition. This 'two-thirds' rule is more or less in agreement
with the Tm/Tg values given in more recent work (Roos, 1993) to be
constant around 1.40. In particular, for sucrose a Tm/Tg ratio = 1.38 and a
melting point at 187e (460 K) yields a T g of 60.3e which is in agreement
with experimental results.
The change in specific volume and other temperature dependent
modifications show that the liquid-glass transformation is a relaxation
process. The jump in specific heat, dielectric constant and other coefficients
at T g tend to compare the glass transition with a second-order phase
transition. Another noticeable change at the glass point is that of viscosity.
A large increase in viscosity at Tg which reaches 10 12 Pa s was found by
extrapolation of experimental data (Parks et al., 1934). Values of Tg were
also derived from empirical relations such as the Vogel-Tamman-Fulcher
(VTF) (Angell et al., 1982) or Williams-Landel-Ferry (WLF) (Williams et
al., 1955) equations. Their validity and departure from DSe experimental
results were discussed (Parks et al., 1934; Slade and Levine, 1994). The
structural reasons for the large increase in viscosity at T g for associated
liquids like water-sugar systems may be explained by use of the theory of
AMORPHOUS SUGAR
89
rate processes (Glasstone et at., 1941) applied to liquids with free volumes.
Indeed, for a molecule to flow, it is necessary that it jumps from one hole
to another. For this it has to acquire a certain activation energy. Such an
activation energy is much higher for associated liquids than for other
analogous substances because, in addition to the normal work required to
make a hole, it is necessary to break the hydrogen bonds surrounding the
molecule. Increasing the temperature above T g provokes a rapid decrease
in viscosity which lead to the collapse, stickiness and recrystallization of
sucrose especially in presence of traces of water.
4.4 Rearrangement in amorphous sugar

Glass transition, collapse and sticky point temperatures were reported
(Levine and Slade, 1986; Roos and Karel, 1990) to be closely related. The
dissimilarities of collapse and glass transition as proposed by To and Flink
(1978a) were criticized by Levine and Slade (1986, 1989). The irreversibility
of the collapse of a freeze-dried product was considered as a macroscopic
event having a morphological effect (loss of porosity) while at molecular
level the phenomenon is reversible. Although a certain continuity exists
between concentrated amorphous solution and amorphous dry sugar the
reversibility at T g might concern water rather than sugar. Both the flexibility
around the glycosidic bond and diffusion leading to a possible homogenous
nucleation above T g and in dry amorphous sucrose plead in favour of an
irreversibility at a molecular level of the rearrangement (collapse , stickiness).
The structure modifications in non-crystalline sucrose mainly depend on
moisture, temperature and the composition of the medium.
4.4.1 Moisture dependence of the amorphous-<.:rystaliine transformation
The early studies (Makower and Dye, 1956; Palmer et at., 1956) of
amorphous sucrose submitted to relative humidities ranging from 4.6 to
33.6% at 25C showed that above 20% RH amorphous sucrose recrystallizes (in a reasonable time) after adsorption and desorption of water. A
characteristic kinetics of water vapour adsorption and desorption was
observed and since this earlier work the observation was repeated for other
oligosaccharides (Guilbot and Drapron, 1969), for dry-milled sucrose
(Roth, 1976) and lyophilized sucrose (Mathlouthi, 1973). We report our
results in Figure 4.8. They show an increase in sample weight exposed to 38
and 44% RH followed by a decrease and a stabilization. Analysis of these
samples by X-rays confirms the recrystallization after desorption of water
vapour. The quenched melt glassy sucrose exposed to the same atmospheres remained amorphous and its adsorption of water was much lower
90
SUCROSE
than that of the lyophilized sugar (Mathlouthi, 1973). The rapid recrystallization of freeze-dried sucrose after sorption and desorption of water was
attributed to its microcrystalline structure (Mathlouthi, 1973). Particular
attention was paid to the nucleation kinetics during the disorder-{)rder
transformation of amorphous sucrose (Van Scoik and Carstensen, 1990).
A retarding effect on nucleation was observed with additives like gelatine,
raffinose, invert sugar, fructose and other carbohydrates. These additives
have in common their hydrophilicity and their binding of water which
prevents availability of this solvent and lowers its plasticizing effect.
Increasing the temperature from 23 to 40C for an amorphous sample
exposed to 33% RH decreases the lag time (time to reach maximum
adsorption) from 240 to 10 h. The amorphous material was supposed to
change from anhydrous amorphate to hydrous amorphate form in a first
step upon adsorption of water. This allows molecules to change from
improper orientations and distances to proper orientations and improper
distances. Then, the sucrose molecules achieve their bringing together
(proper intermolecular distances) before crystallization (Carstensen and
Scoik, 1990).
water intake %
o
hours
-2
20
40
60
80
100
120
Figure 4.8 Kinetics of water adsorption and desorption by freeze-dried sucrose submitted to
different relative humidities at 20C. Relative humidities: (.) 20%, (D) 27%, (T) 38% and
(e) 44%.
AMORPHOUS SUGAR
91
It seems, however, difficult by the use only of visual, microphotography

and X-ray techniques (Van Scoik and Carstensen, 1990) to ascertain the
clear differentiation of nucleation from crystallization. As already mentioned, the degree of order depends on the method of observation. 'X-ray
amorphous' sucrose may be crystalline to electron diffraction. The 'X-ray
crystallinity' of amorphous sucrose mixed with waxy maize starch and
submitted to varied water activity values was found (Chinacoti and
Steinberg, 1986) to be extremely slow or inhibited when a wet mixture was
submitted to desorption between 0.33 and 0.84 aw . This might be due to
the mobility of water (Chinacoti, 1993) which depends on the physical
state of sucrose and a certain competition for water between ingredients.
In presence of other polysaccharidic components, the recrystallization of
amorphous sucrose, in humidified freeze-dried model systems, was always
delayed when compared to that of pure sucrose (Iglesias and Chirife,
1978).
4.4.2 Temperature dependence of amorphous sugar transformation

Increasing the temperature of non-crystalline sucrose provokes an increase
in mobility of molecules especially in presence of water. Such a mobility
leads to the collapse behaviour either in concentrated amorphous solutions
at temperatures above T g ' or in freeze-dried and spray-dried sugar at
higher temperatures. Rewarming of the CAS was used as an annealing
treatment to favour the recrystallization of ice. If all crystallizable water is
not transformed into ice, it will recrystallize during the freeze-drying to
form very fine crystals which melt below the melting point of the sample
and provoke a 'collapse' during the lyophilization (Flink, 1983). Such a
collapse yields a non-porous freeze-dried sugar which is partially crystalline
and partially sticky. This miscarried freeze-drying is comparable to other
defects that happen during the dehydration and storage of amorphous
sugar.
The collapse of freeze-dried sugar was found (To and Flink, 1978b) to
occur over a range of temperature (20-40C), which corresponds to the
observed (Roos and Karel, 1990) T g when moisture was increased from 0
to 1%. The reported values of Tg for amorphous sugar varied from 72 to
40C probably because the unavoidable traces of humidity in the samples.
This especially occurs because during the drying process, a rapid removal
of water from the surface originates in the formation of a glassy dried layer
over a viscous concentrated solution. Mobility of water in this solution
during the storage provokes stickiness and caking of the sugar.
Annealing of CAS at a temperature slightly above the glass transition,
called homogeneous nucleation (Tn) or crystallization (Tc) or antemelting
(Tam) and equal to -32C proved to be efficient in preventing the collapse
during lyophilization. Likewise, a thermal treatment of 'annealing' of the
92
SUCROSE
dry amorphous sugar was applied (Mathlouthi, 1973) at different temperatures above 60C, the Tg value of freeze-dried sucrose. Such a treatment
was achieved in the freeze-drier for 3-10 h. Analysis of crystallinity of the
freeze-dried annealed samples was made by X-ray diffraction. The results
Figure 4.9 X-ray diffractograms of freeze-dried sucrose submitted to different treatments of

annealing: (a) 3 h at 60C; (b) 8 h at 80C; (c) 3 h at 95C; and (d) 2 h at 120C.
93
AMORPHOUS SUGAR
are reported in Figure 4.9. They show that with thermal treatment at 60C the
Tg temperature did not improve crystallinity of the sample, whereas by
heating for 3 h at 120C the recrystallization temperature yielded a sample
completely crystalline. The samples treated at 80 and 95C show an
increased degree of crystallinity as temperature is increased. The same
kind of information was obtained from the FT-IR spectra (in the region
2800-3800 cm- I ) of freeze-dried sucrose submitted to temperatures
between 60 and 120C (see Figure 4.10).
Recrystallization was also obtained after sorption and desorption of
water. Comparison of the X-ray diffractograms (see Figure 4.11) of the
lyophilized samples recrystallized after sorption of water at 20C and
annealing at 120C show slight differences in the intensities of peaks at
characteristic angles (12-138, 9-108 and 6-78). Comparison of the
rate of dissolution of the two samples showed that the annealed sucrose
which kept a certain porosity dissolves more rapidly than the sample
recrystallized after sorption of water vapour which was a little bit sticky
(Mathlouthi, 1973).
3400
3200
2800 Cm-1
Figure 4.10 Ff-IR spectra of freeze-dried sucroses submitted 1 h to annealing at different

temperatures: (a) 60C; (b) 80C; (c) 100C; and (d) 120C.
94
SUCROSE
14
12
(3)
J'-"
,W
J''.j
JJ
10
(b)
----,--r,---,.....---r,--,---rj--..--...,,--.-----.,
-rj
15
13
II
()
Figure 4.11 Comparison of the X-ray diffractograms of freeze-dried sucrose recrystallized

after annealing at 120C (a) and after sorption of water vapour (b).
4.5 Practical importance of amorphous sugar

The non-crystalline state of the organization of sucrose in foods and
confectionery may have important consequences as concerns their stability
and shelf-life. It may also alter the taste, the texture and aroma retention in
these products. Adsorption of water and increase in temperature are
generally at the origin of phase transitions that may occur in foods
AMORPHOUS SUGAR
95
containing amorphous sugar. The presence of other compounds, especially

polyols and carbohydrates that may share water with sucrose, constitutes
an additional factor of instability.
4.5.1 Structure modification of sugar and the shelf-life of food products
The transformation of amorphous sugar may be either a softening, giving a
viscous solution in which major defects are stickiness, collapse and a loss of
flavour, or a recrystallization which can be detrimental to the quality of
boiled sweets, ice creams or porous dehydrated foods. The viscosity at the
sticky point of a powder composed of maItodextrin, sucrose and fructose
was measured (Wallack and Judson King, 1988) and found equal to the
predicted (according to the Frenkel model) value of 106 _108 Pa s. It was
concluded that increasing the particle size decreases the surface powder
energy, hence the predicted viscosity and can prevent stickiness (Wallack
and Judson King, 1988). Collapse and stickiness are related. They generally
occur at glass transition temperature Tg The effect of viscosity on the
stability of fondants was discussed (Cakebread, 1972). It is needed in this
case that an adequate proportion of corn syrup be added to sucrose
solution, so that viscosity is increased enough to maintain fine grains in
suspension for a long time. Shelf-life of confectionery also needs that
equilibrium relative humidity be maintained below 80% to ensure safety
from risk of microbial spoilage. Change in structure, such as a recrystallization of sugar, may lead to a loss of flavour, a decrease in viscosity and an
increase in water activity which may cause the degradation of the product.
Fudges are other sweets appreciated for their smoothness and fineness of
grain. They have in common with chocolate that the grain should have
a size not larger than 25 !-tm. It was noticed (Niediek, 1991) that the higher
the amount of amorphous sugar in chocolate, the higher its water content
and its aroma retention. Probably because its large specific area,
amorphous sugar adsorbs large amounts of volatiles, whether they are
hydrophilic or hydrophobic (Niediek, 1988). Aroma retention was found
to increase when the pressure is increased. For amorphous sucrose and
amorphous lactose the heat of adsorption of volatile compounds is greater
than that of evaporation. However, the loss of structure of amorphous
sugar provokes a loss of volatile whether this collapse is caused by moisture
uptake or heating (Flink, 1983). Flavour enhancement by sucrose in
selected food systems is detailed in Chapter 10 of this book.
4.5.2 Agglomeration, caking and the stability of crystalline sugar
Amorphous sugar is in a metastable state. It is very hygroscopic. Its
tendency to adsorb water even at low water activities (below 0.20 a w )
predisposes it to caking, agglomeration and the loss of free-flowing ability.
96
SUCROSE
This high reactivity with water is manifested in the exothermal heat of

solution (Van Hook, 1981) (-8.8 cal/g for glassy slightly caramelized or
lyophilized sucrose) while the heat of solution (Culp, 1946) of crystalline
sucrose is 4.73 cal/g. Depending on the kind of amorphous sugar, the heat
of solution may vary. The 'cotton candy' amorphous sugar was exothermal
to the extent of 11 cal/g but this fell rapidly upon exposing to air (Van
Hook, 1981). The flowability and tendency to stick and cake concerns
a number of powders like instantanized soluble coffee, dehydrated fruit
juices and powdered sucrose. This behaviour depends on water
activity, size of particles and temperature. These parameters determine
the packaging and shelf-life of the powders. Considering the scope
of this book, particular interest is given to the storage of powdered
sucrose and sugar lumps.
Either for crystalline sugar or for the cubes, a more or less long period of
curing is necessary to prevent such accidents as the caking of powdered
sugar in the bags or the silo or the sticking of cubes to the carton package.
This period may last as long as 5 days for packaged cubes being ventilated
with air at 25-30C. The origin of caking and instability of crystalline sugar
is very likely the non-equilibrium behaviour of the film surrounding the
crystals. Investigation of this behaviour resulted (Bressan and Mathlouthi,
1994) in the proposition of a thermal treatment of sugar at 60C prior to
moistening, moulding and drying of the cubes and ventilating them with air
at ambient temperature. What complicates the problem of the stability of
crystalline sugar is a tendency in the factories to dry at high temperatures
(above 80C) with large rates of air. This treatment rapidly yields a glassy
layer at the surface of the crystal under which remains a layer of
supersaturated solution in contact with the crystal. Recrystallization of the
supersaturated solution together with the dissolution of the glass imply
diffusion phenomena of water and sucrose which may be accelerated in
presence of humidity in the air or impurities in the amorphous layer. Such
rearrangements always lead to equilibrium, which means that the
crystallizable sugar recrystallizes by incorporation to the existing crystals
and a saturated solution remains at a level of moisture of about 0.02%
(w/w). However, reaching this equilibrium requires that the heat of
crystallization and the water released be evacuated. If a suitable aeration
with fresh air having a dew point far below storage temperature is
achieved, then the risks of caking, agglomeration and stickiness are
reduced. As was already noticed, the high reactivity with water especially
for microcrystalline sucrose may lead to a spontaneous recrystallization
and the agglomeration of the powders. Caking may be inhibited by addition
of very finely divided highly hygroscopic powders (Irani et ai., 1959) such
as starch or tricalcium phosphate which adsorb water and prevent sucrose
recrystallization. The effectiveness of anticaking agents depends on the
size of particles and on relative humidity.
AMORPHOUS SUGAR
97
4.6 Conclusion
Amorphous sugar is present as a thin layer at the surface of crystalline
sugar. It may also be produced by melting, spray-drying, freeze-drying or
concentration of solutions either by heating or cooling. Understanding of
the modifications of its structure especially around the glass transition
temperature requires that the interactions between water and sucrose be
elucidated. A physico-chemical parameter which seems to be determining
as concerns the mobility of molecules and the rearrangements of structure
is viscosity. Likewise, hydration water, specific area and the heat of
solution are informative on the reactivity of amorphous sugar with water.
Such a reactivity is manifested by a characteristic sorption and desorption
behaviour when water activity is increased. The preponderance of water,
even when it is present as traces, suggests the continuity between
amorphous solid and aqueous solution. Amorphous sugar is present in
number of food products. Its structure is a determining factor for such
properties as the texture, flavour and shelf-life of these products.
Powdered sugar involves at its surf:lce an amorphous thin layer (glassy and/
or supersaturated solution). Controlling the kinetic and thermodynamic
conditions of recrystallization in the thin layer during the drying and
cooling processes may be favourable to the stability and reduction of the
duration of curing.
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Tikhomiroff, N. (1965) Association moleculaire au cours de la periode de precristallisation
des solutions aqueuses sursaturees de saccharose. Indust. Alim. Agric. (Paris), 82,755-772.
100
SUCROSE
To, E.C. and Flink, J.M. (1978a) 'Collapse' a structural transitIOn in freeze-dried
carbohydrates II. Effect of solute composition. 1. Food Technol., 13,567-581.
To, E.C. and Flink, J.M. (1978b) 'Collapse' a structural transition in freeze-dried
carbohydrates, III. Perequisite of recrystallization. 1. Food Technol., 13,583-594.
Van Hook, A. (1961) Crystallization, Theory and Practice. Reinhold, New York, USA.
Van Hook, A. (1981) Growth of sucrose crystals, a review. Sugar Technol. Rev., 8, 41.
Van Scoik, K.G. and Carstensen, J.T. (1990) Nucleation phenomena in amorphous sucrose
systems. Int. J. Pharm., 58, 185-196.
Wallack, D.A. and Judson King, C. (1988) Sticking and agglomeration of hygroscopic
amorphous carbohydrate and food powders. Biotechnol. Prog., 4, 31-35.
Walrafen, G.E. (1966) Raman spectra studies of the effect of urea and sucrose on water
structure. 1. Chern. Phys., 44, 3726-3726.
Weichert, R. (1976) Untersuchungen zur temperatur an der bruchspitze. Thesis, Karlsruhe,
Germany.
Weyl, W.A. and Marboe, E.C. (1962) The Constitution of Glasses, A Dynamic Interpretation,
Vol. 1: Fundamentals of the Structure Inorganic Liquids and Solids. Interscience Publishers,
New York, USA, pp. 118-127.
White, G.W. and Cakebread, S.H. (1966) The glassy state in certain sugar containing
products. J. Food Technol., I, 73-82.
Williams, M.L., Landel, R.F. and Ferry, J.D. (1955) The temperature dependence of
relaxation mechanisms in amorphous polymers and other glass forming liquids. J. Am.
Chern. Soc., 77, 3701-3706.
Young, F.E. and Jones, F.T. (1949) Sucrose hydrates, the sucrose-water phase diagram. 1.
Phys. Chern., 53, 1334-1350.
Sucrose solubility
Z. BUBNIK and P. KADLEC
5.1 Introduction
Sucrose solubility means the concentration of sucrose in a saturated
solution which is in equilibrium with sucrose in the solid state. Solubility of
sucrose in water is of fundamental importance in defining the supersaturation, or driving force of sucrose crystal growth. Solubility of sucrose in
mixtures of water with different organic solvents has important uses in
some branches of the chemical and pharmaceutical industries, in analytics,
etc. It is especially the case for ethanol, methanol, propyleneglycol,
glycerol, acetone and pyridine.
A molecule of sucrose has eight hydroxyl groups, three hydrophilic
oxygen atoms (bound in a circle) and 14 hydrogen atoms. This enables the
formation of hydrogen bonds with water molecules, hydration of sucrose
molecules and therefore easy dissolution of sucrose in water. In nonaqueous solvents, sucrose solubility is significantly lower than in water and
sucrose does not dissolve in non-polar solvents. Sucrose shows much
higher values of solubility in ammonia, dimethylsulphoxide, aminoethanol
and methylamine. Lower values exist for sulphur dioxide, formic and
acetic acid, dimethylformamide, pyridine, glycol, methanol, ethanol and
dioxan.
Solubility of sucrose is influenced by temperature and by the amount and
type of other dissolved molecules (impurities, non-sugars). Only a few of
the impurities do not affect sucrose solubility or decrease it. Most
impurities increase solubility. This is especially true of non-sugars which
remain in sugar juices after their purification by standard procedures of
sugar technology.
5.2 Expression of concentration and composition of sucrose solutions
Concentration of sugar solutions is expressed in different ways depending
on current application. Among the usual ways we can count weight percent
(formerly Brix), mass and mole fraction, weight, sucrose to water ratio,
molality, molar concentration and partial density. The cited quantities are
defined for pure and impure solutions in the following text.

0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Dry
substance,
DS(%)
0
0.0526
0.1111
0.1765
0.2500
0.3333
0.4286
0.5385
0.6667
0.8182
1.0000
1.2220
1.5000
1.8570
2.3330
3.0000
4.0000
5.6670
9.0000
19.0000
SW
(g sucrose per
g water)
0
0.1538
0.3246
0.5155
0.7304
0.9738
1.252
1.573
1.948
2.390
2.921
3.571
4.382
5.425
6.817
8.764
11.69
16.55
26.29
55.51
-
0
50.89
103.80
158.90
216.20
275.90
338.10
403.00
470.60
541.20
614.80
691.70
772.00
855.80
943.20
1034.50
1129.80
1229.10
1332.50
1440.10
1551.90
19.00
9.00
5.67
4.00
3.00
2.33
1.86
1.50
1.22
1.00
0.82
0.67
0.54
0.43
0.33
0.25
0.18
0.11
0.05
0.00
Cm
(mol sucrose
per kg water)
(g sucrose per
litre solution)
WS
(g water per
g sucrose)
Table 5.1 Sucrose concentration expressed in different units (at 20C)
0
0.1487
0.3033
0.4641
0.6316
0.8060
0.9878
1.177
1.375
1.581
1.796
2.021
2.255
2.500
2.756
3.022
3.301
3.591
3.893
4.207
4.534
CM
(mol sucrose
per kg solution)
0
0.00276
0.00581
0.00919
0.01298
0.01723
0.02204
0.02754
0.03387
0.04125
0.04996
0.06039
0.07311
0.08897
0.1093
0.1363
0.1738
0.2296
0.3212
0.4998
1.oo
1.0000
XM
Molar fraction
(mol per mol)
trl
'"
'"
'"c::
(j
0
N
......
103
SUCROSE SOLUBILITY
The values of the concentration of pure sucrose solutions are expressed

using the suitable equations and reported in Table 5.1. As seen in Table 5.1,
the evolution of the values deriving from the various expressions is
significantly different, especially for concentrated solutions. Usage of
weight percent deforms the correct idea about the ratio between the
quantity of moles of sucrose and water. Application of weight percent is
advantageous for technical practice, e.g. for balance calculations. This unit
is not always suitable for expressing physico-chemical parameters which
generally are simple functions of molality or mole fractions.
Activity of the dissolved species should be substituted to concentration
in the relations used for accurate physico-chemical calculations. Activity,
a, is expressed as a product of concentration C m (mol sucrose per kg water)
and activity coefficient fm:
(5.1)
a = fm X C m
According to eli and Valter (1967) it is possible to calculate activity

coefficient, fm, from the following relationship:
log fm = 0.06105 X Cm
X C~ - 0.000124 X
em
+ 0.01203
C;, - 0.002343
(5.2)
Equation (5.2) is valid for C m < 5.8 mol/kg (i.e. 66.7%).
5.2.1 Relationships for expression of concentration of sucrose in pure

and impure water solutions
These relationships are listed and defined below:
(a) Sucrose content is the weight percent of sucrose in the solution, S
(%).
(b) Mass fraction X w (g sucrose per g solution)
X
S
100
=-
(5.3)
(c) Sucrose to water ratio, SW (g sucrose per g water)

For pure solutions:
S
SW=-100 - S
(5.4)
For impure solutions:

S
SW=--100 - DS
where DS is dry substance (%)
(5.5)
104
SUCROSE
(d) Water to sucrose ratio, WS (g water per g sucrose)

For pure solutions:
100-S
WS=-S
(5.6)
100-DS
WS=--S
(5.7)
(e) Concentration, c (g sucrose per litre solution), partial density
S X Q
c=---
(5.8)
100
(f)
where Q is the specific gravity (kglm

(kg/m 3) of the sucrose solution.
Molality, Cm (mol sucrose per kg water)
For pure solutions:
1000 X S
C m = (100 _ S) X M
(5.9)
1000 X S
= (100 -
(5.10)
DS) X M s
where M s is sucrose molecular weight (342.30 glmoI)

g/moI)
(g) Molar concentration C M (mol sucrose per litre solution)
S X Q
100
(5.11)
Ms
(h) Molar fraction, X M

For pure solutions: mol sucrose per (mol sucrose
S
(100 - S)
+ mol
water)
Ms
S
(100 - S) X Ms
(5.12)
+-Mw
For impure solutions: mol sucrose per (mol sucrose

+ mol non-sucrose)
+ mol water
S
(100 - DS) X M s
XM =---------------S
1
DS - S
(100 - DS) X Ms
+--+-----Mw
(100 - DS) X M NS
(5.13)
105
SUCROSE SOLUBILITY
where M s is the sucrose molecular weight (342.30 g/mol); M w is

the water molecular weight (18.016 g/mol); and MNS is the nonsucrose molecular weight.
Remark: Kadlec and Sarka (1977) and Kadlec and Hyndnik
(1979) have presented for beet non-sugars an average value for
non-sucrose molecular weight M NS = 114 g/mol which corresponds
approximately to one-third of the molecular weight of sucrose.
Average value M NS = 205 g/mol was experimentally found for
non-sugars contained in cane solutions (Kadlec and Hyndrak,
1979). It corresponds in this case to about three-fifths of sucrose
molecular weight.
5.3 Sucrose solubility in water

5.3.1 Effect of temperature on the sucrose solubility
As stated in the introduction, sucrose is very soluble in water because of its

structure. The solubility increases significantly with temperature. This
dependence is called the solubility curve and can be generally described by
the equation of the reaction isochore for ideal systems. It was found that
sucrose solutions do not comply to ideal systems and therefore different
empirical equations were suggested for the dependence of solubility on
temperature. They fit with experimental data. It is especially the case for
polynomial functions. The fitting was made with a number of the published
experimental data (Herzfeld, 1892a, b; Grut, 1937-38); Taylor, 1948;
Charles, 1960; Smelik and Vasatko, 1970a, b, 1971,1972).
Vavrinecz (1962) carried out a critical comparison of several functional
equations (results of 25 authors) and showed that the power series
equation of the fourth degree gave the best results:
DS = 64.447 + 0.08222 X t + 1.6169 X 10-3 X
X 10-6 X ~ - 4.63 X 10-8 X t4
f2 - 1.558
(5.14)
where OS is dry substance (in the case of pure sucrose water solutions the
values of OS equal that of sucrose content S(%)) and t is temperature (0C).
Using this equation the mean probable error in the evaluation of
solubility is only 0.05%. The equation is valid in a range of temperatures
from -13 to 100C and was adopted by the 15th Session of ICUMSA
(Heitz, 1974).
At the same time the equation according to Charles (1960) was
recommended which is valid in the range of temperature from 0 to 86C.
OS = 64.397
X 1Q-6 X ~
+ 0.07251
+ 2.0569
10-3 X f2 - 9.035
(5.15)
106
SUCROSE
For the calculations which do not require high accuracy a simple

equation can be applied expressing the linear dependence of the water to
sucrose ratio, WSsat,pure, on the temperature.
WSsat,pure = a
(b - t)
(5.16)
By the modification of equation (5.16) we can obtain the relations for

further, more frequent quantities - the sucrose to water ratio, SWsat,pure,
and dry substance content, OSsat.pure, of saturated solutions.
SWsat,pure
=b-
OSsat,pure
(5.17)
100
(5.18)
B - t
For the range of technically important temperatures from 30 to 80C the

coefficients of equations (5.17) and (5.18) were evaluated for the data
according to Vavrinecz (1962) and Charles (1960) shown in Table 5.2.
In the above temperature range the agreement of the values of solubility
calculated from equations (5.14) and (5.18) (for Vavrinecz's values) also
from equations (5.15) and (5.18) (for Charles's data) is very good. The
standard deviation of calculated values for dry substances according to
both types of equations is only 0.048% for Vavrinecz's data and 0.033% for
Charles's values.
For temperatures above 100C the data are importantly different and
inaccurate especially in earlier studies. Therefore, the study of Smelik et al.
(1970-72) was selected because it fits best with the equations of Vavrinecz
and Charles and it permits by extrapolation to reach the sucrose melting
point:
os =
71.0615 + 5.3625
10-2
X t
+ 6.55303
10--4
(5.19)
Equation (5.19) is valid for the temperatures ranging from 100 to 125C.
Table 5.3 was calculated using equations (5.14) and (5.19) where the
sucrose solubility is expressed by dry substance content and the ratio of
sucrose to water. The values above 125C were obtained by extrapolation
and therefore have a limited validity.
Table 5.2 Evaluation of the coefficients shown in equations
(5.17) and (5.18)
Coefficient
b
A
B
Vavrinecz (1962)
Charles (1960)
0.0039102
148.86
255.74
404.60
0.0039682
147.78
252.01
399.78
107
SUCROSE SOLUBILITY
Table 5.3 Solubility of sucrose in water
eC)
g sucrose per
g water
Dry
substance,
DS(%)
Molar
fraction, X M
(mol per mol)
-10
-5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
105
110
115
120
125
130
1.7615
1.7837
1.8127
1.8489
1.8926
1.9443
2.0047
2.0741
2.1535
2.2435
2.3450
2.4589
2.5863
2.7282
2.8857
3.0598
3.2515
3.4616
3.6901
3.9368
4.2003
4.4775
4.7637
5.0335
5.4499
5.9347
6.5062
7.1895
8.0211
63.79
64.08
64.45
64.90
65.43
66.04
66.72
67.47
68.29
69.17
70.10
71.09
72.12
73.18
74.26
75.37
76.48
77.59
78.68
79.74
80.77
81.74
82.65
83.43
84.50
85.58
86.68
87.79
88.91
0.08484
0.08582
0.08710
0.08868
0.09059
0.09283
0.09544
0.09842
0.10180
0.10561
0.10986
0.11459
0.11981
0.12556
0.13185
0.13871
0.14613
0.15411
0.16263
0.17164
0.18104
0.19071
0.20046
0.20944
0.22290
0.23801
0.25508
0.27452
0.29685
Temperature
5.3.2 Phase equilibrium diagram for the system sucrose-water
The sucrose solubility in water is graphically expressed in Figure 5.1 in the

form of a simplified phase diagram of sucrose-water. The curves of sucrose
solubility and ice solidification which theoretically intersect in the eutectic
point are shown in Figure 5.1. Above these curves there exist undersaturated solutions. The solubility curve begins in the point of sucrose melting
(186C), separates undersaturated sucrose solutions from the two-phase
system saturated solution-solid sucrose and finishes in the eutectic point
(-13.9C). The solidification curve illustrates the equilibrium between the
saturated solution and solid phase of the solvent, i.e. the ice. Under the
temperature of the eutectic point ice continues to form whereas sucrose
concentrates in concentrated amorphous solutions.
The solidification curve can be described by the following equation
108
SUCROSE
200
1 :,'-T-l:-T---;:~;:::;~::::;-r--,
,
MELTIHG POINT
'----r--+;
--+--+-.
,
i
180
180
~--~
-~
140
I
I
r-
-+--i--+-
-+--+----+
I
!
i
-.L..-L_L_+--i-'==::::+===+=::::'::::~-I-,L-1
80
i
80 ----;-
-=r~~-~t::r-:~;:~r.:_
i --r-T-"-r'I~IlOSE+~E I j_.--t---
20 '---",
-40+--....'--+---t-'--+-!--t-!--+---t---+-'--+---l
20
10
30
40
50
80
70
80
90
100
SUCI'O" S (%)
Figure 5.1 Phase equilibrium diagram sucrose-water.
which was evaluated by Bubnik et al. (1994) on the basis of the data of
Weast (1976-77) and Washburn et ai. (1927):
tfpd
= 0.05176 X DS
DS 3 + 7.552
10-
+ 1.327
DS
10-3
DS 2
2.416
10-5
(5.20)
where t fpd is the temperature of the freezing point depression of pure

sucrose solution (OC) and DS is the dry substance (%).
The values calculated by means of equation (5.20) are shown in
Table 5.4. The values for other saccharides - glucose, fructose, lactose
and maltose (Washburn et al., 1927; Weast, 1876/77) - are presented for
comparison in chapter 8.
5.3.3 Supersaturateq. solutions
If we evaporate or cool a saturated solution, a supersaturated solution
easily appears where the sucrose concentration is higher than that
corresponding to the saturation state. This state keeps for quite a long time
in the absence of a solid phase although it is a thermodynamically instable
state. It is caused by the increase in viscosity and by limitation of
movement of the molecules. This worsens the conditions for formation of
stable crystal nuclei. Creation of supersaturated solution is a condition for
separating the solid phase from the solution.
109
SUCROSE SOLUBILITY
Table 5.4 Freezing point depression of sucrose solutions

g sucrose per 100 g solution
Freezing point depression Cc)
1.00
2.00
3.00
4.00
5.00
0.05
0.11
0.17
0.23
0.29
6.00
7.00
8.00
9.00
10.00
0.35
0.42
0.49
0.56
0.63
11.00
12.00
13.00
14.00
15.00
0.71
0.79
0.87
0.95
1.03
16.00
17.00
18.00
19.00
20.00
1.21
1.30
1.40
1.49
22.00
24.00
26.00
28.00
30.00
32.00
34.00
36.00
38.00
40.00
1.70
1.92
2.16
2.42
2.71
3.02
3.35
3.72
4.13
4.58
42.00
44.00
46.00
48.00
50.00
5.07
5.62
6.22
6.88
7.6\
52.00
54.00
56.00
58.00
60.00
8.40
9.28
10.24
11.30
12.45
62.00
64.00
66.00
68.00
70.00
13.71
15.09
16.58
18.21
19.97
1.12
110
SUCROSE
The amount of supersaturation can be expressed by means of the

coefficient of supersaturation SS(1) which expresses the ratio between the
given sucrose concentration in the solution, SW (g sucrose per g water),
and concentration of the saturated solution, SWsat , at the same temperature.
SS
SW
SWsat,pure
(5.21)
Table 5.5 shows dry substance contents of supersaturated solutions for

the values of supersaturation usual 10 the technical practice
(SS = 1.0-1.30).
5.4 Sucrose solubility in impure sugar solution and other solvents
5.4.1 Three-component triangle diagram
Adding a third component into the binary system sucrose-water is better

illustrated graphically by use of a diagram in the shape of an isosceles
triangle. Each of the three corners of the triangle represents a pure
component (i.e. component concentration equal to 100%) while the
concentration of this component equals zero at the opposite side. The tieline of the two vertices represents a mixture of the two given components
and every point inside the triangle gives the composition of the mixtures of
all three components. The diagram can be expressed for one temperature
(isothermal diagram) or for a certain range of temperatures (polythermal
diagram). The relative proportions among the components used to be
expressed in weight percent or in molar fractions.
The system sucrose-fructose-water shown in Figure 5.2 can be given as
an example. The grid lines are also constructed in the figure to make the
reading of the values from the diagram easier. The figure comprises a scale
of sucrose concentration as well. The tie-line of the points AC represents a
solution saturated with sucrose while the curve BC shows a solution
saturated with fructose. The point C is called a triple point and the solution
is saturated with both components. The vertices of the triangle and the
points A, Band C divide the triangle surface into four areas. The surface
WACB (W is the vertex of the triangle with water concentration 100%)
represents a solution non-saturated by none of the compounds. In the
space limited by the points SAC (S is the vertex with sucrose concentration
100%) the mixture of crystalline sucrose with the solution saturated by
sucrose is found while among the points FBC (F is the vertex with a
fructose concentration of 100%) there is the mixture of crystalline fructose
and a solution saturated by fructose. The mixture of saturated solution
with crystalline sucrose as well as fructose is found in the area among the
points SCF.
1.00
63.8
64.1
64.4
64.9
65.4
66.0
66.7
67.5
68.3
69.2
70.1
71.1
72.1
73.2
74.3
75.4
76.5
77.6
78.7
79.7
80.8
81.7
82.7
-10
-5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Temperature
CC)
64.2
64.5
64.9
65.3
65.9
66.5
67.2
67.9
68.7
69.6
70.5
71.5
72.5
73.6
74.6
75.7
76.8
77.9
79.0
80.1
81.1
82.0
82.9
1.02
64.7
65.0
65.3
65.8
66.3
66.9
67.6
68.3
69.1
70.0
70.9
71.9
72.9
73.9
75.0
76.1
77.2
78.3
79.3
80.4
81.4
82.3
83.2
1.04
65.1
65.4
65.8
66.2
66.7
67.3
68.0
68.7
69.5
70.4
71.3
72.3
73.3
74.3
75.4
76.4
77.5
78.6
79.6
80.7
81.7
82.6
83.5
1.06
65.5
65.8
66.2
66.6
67.1
67.7
68.4
69.1
69.9
70.8
71.7
72.6
73.6
74.7
75.7
76.8
77.8
78.9
79.9
81.0
81.9
82.9
83.7
1.08
66.0
66.2
66.6
67.0
67.6
68.1
68.8
69.5
70.3
71.2
72.1
73.0
74.0
75.0
76.0
77.1
78.2
79.2
80.2
81.2
82.2
83.1
84.0
1.10
66.4
66.6
67.0
67.4
67.9
68.5
69.2
69.9
70.7
71.5
72.4
73.4
74.3
75.3
76.4
77.4
78.5
79.5
80.5
81.5
82.5
83.4
84.2
1.12
66.8
67.0
67.4
67.8
68.3
68.9
69.6
70.3
71.1
71.9
72.8
73.7
74.7
75.7
76.7
77.7
78.8
79.8
80.8
81.8
82.7
83.6
84.4
1.14
67.1
67.4
67.8
68.2
68.7
69.3
69.9
70.6
71.4
72.2
73.1
74.0
75.0
76.0
77.0
78.0
79.0
80.1
81.1
82.0
83.0
83.9
84.7
1.16
67.5
67.8
68.1
68.6
69.1
69.6
70.3
71.0
71.8
72.6
73.5
74.4
75.3
76.3
77.3
78.3
79.3
80.3
81.3
82.3
83.2
84.1
84.9
1.18
Supersaturation coefficient SS (1)
67.9
68.2
68.5
68.9
69.4
70.0
70.6
71.3
72.1
72.9
73.8
74.7
75.6
76.6
77.6
78.6
79.6
80.6
81.6
82.5
83.4
84.3
85.1
1.20
Table 5.5 Supersaturated solutions of sucrose in water: dry substance, DS(%) of supersaturated solutions
68.2
68.5
68.9
69.3
69.8
70.3
71.0
71.7
72.4
73.2
74.1
75.0
75.9
76.9
77.9
78.9
79.9
80.9
81.8
82.8
83.7
84.5
85.3
1.22
68.6
68.9
69.2
69.6
70.1
70.7
71.3
72.0
72.8
73.6
74.4
75.3
76.2
77.2
78.2
79.1
80.1
81.1
82.1
83.0
83.9
84.7
85.5
1.24
68.9
69.2
69.5
70.0
70.5
71.0
71.6
72.3
73.1
73.9
74.7
75.6
76.5
77.5
78.4
79.4
80.4
81.3
82.3
83.2
84.1
84.9
85.7
1.26
69.3
69.5
69.9
70.3
70.8
71.3
72.0
72.6
73.4
74.2
75.0
75.9
76.8
77.7
78.7
79.7
80.6
81.6
82.5
83.4
84.3
85.1
85.9
1.28
69.6
69.9
70.2
70.6
71.1
71.7
72.3
72.9
73.7
74.5
75.3
76.2
77.1
78.0
79.0
79.9
80.9
81.8
82.8
83.7
84.5
85.3
86.1
1.30
r.n
c::
......
......
......
t=
c::c::I
r'
r.n
tTl
'0r.n"
(")
112
SUCROSE
WATER
100
SUCROSE
80
40
o
FRUCTOSE
Figure 5.2 Triangle diagram of the system sucrose-fructose-water at 30C.
An example of reading of the composition of a three-component mixture

from the triangle diagram using the cited system of the grid lines is shown
in Figure 5.2 for a mixture characterized by the point P. We proceed as
follows: the lines parallel to the sides of the triangle are drawn starting
from the point P. These lines express the constant value of component
concentration whose crystalline state (i.e. concentration 100%) is described'
by the opposite vertex, e.g. the parallel line X1-X2 expresses the constant
sucrose concentration. In the point where the parallel lines intersect the
sides of the triangle (i.e. the points Xl and X2; Y1 and Y2; Zl and Z2), we
read the concentrations of all the three components. In this case the
following composition corresponds to the solution in the point P: sucrose
15%, fructose 35% and water 50%.
Further, we present similar three-component diagrams for the systems
where the third component of the system sucrose-water are glucose (Figure
5.3) and sodium chloride (Figure 5.4) according to Kelly (1954, 1959).
Fructose, glucose and NaCI belong to the typical compounds accompanying sucrose in its impure solutions and characterize a certain group of nonsugars (see section 5.4.2).
The selected data describing solubility of sucrose in water in the
presence of another compound are given for the system sucrose-invert
sugar-water according to Lyle (1950) (Table 5.6) (equimolar mixture of
113
SUCROSE SOLUBILITY
WATER
o~------------,~------------,
20 ..
----.---------*
60
: ., --"7:,.-.-+'~-jt-~;~.~
100
>< --,/ -/!f':'\""""~:-i
~-+---'T. . ,~.-...;..-._.- \.....\....;'- _...+--...:;....../-'_\"4-""_;'_\";;\'f-';'_/_.:.;v_--lI

100
60
20
40
60
SUCROSE
GLUCOSE
Figure 5.3 Triangle diagram of the system sucrose-glucose-water at 30C.
WATER
0,------------.,.--------------,
-*-----------20+-----
40 --.--..----I:---+-----j~-:.::--~-----_l
60
-I:
- }:..,,r---.+.-..- +----';!,..-
--i;
-.-._\:
100 r--+--'T--'i---+--:.t---';'---+--+-....:.r~:::::..lI
100
80
80
40
20
o
SUCROSE
N.CI
Figure 5.4 Triangle diagram of the system sucrose-NaCi-water at 30C.
114
SUCROSE
Table 5.6 Solubility of sucrose in the presence of invert sugar

Temperature
(0C)
40
45
50
55
60
65
Solubility of sucrose (g per g water) at concentration of invert sugar

(g per g water)
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
2.05
2.16
2.27
2.38
2.50
2.61
2.00
2.11
2.22
2.33
2.45
2.56
1.95
2.06
2.17
2.28
2.40
2.51
1.91
2.02
2.13
2.24
2.36
2.47
1.87
1.98
2.09
2.20
2.32
2.43
1.83
1.95
2.06
2.18
2.29
2.41
1.80
1.91
2.03
2.14
2.26
2.37
1.77
1.88
2.00
2.12
2.23
2.35
1.75
1.86
1.98
2.10
2.22
2.33
1.72
1.84
1.96
2.08
2.20
2.32
Table 5.7 Solubility of sucrose in the presence of raffinose

Temperature
Dry substance of sugar solution DS(%)

at concentration of raffinose (g per 100 g solution)
CC)
0
30
35
40
45
50
55
60
65
70
68.3
69.2
70.1
71.1
72.1
73.2
74.3
75.4
76.5
68.1
69.0
69.9
70.9
72.0
73.1
74.2
75.3
76.5
67.8
68.7
69.7
70.7
71.8
72.9
74.1
75.2
76.4
67.5
68.4
69.4
70.5
71.6
72.7
73.9
75.1
76.3
67.1
68.1
69.1
70.2
71.3
72.5
73.7
74.9
76.1
66.7
67.7
68.8
69.9
71.0
72.2
73.4
74.7
75.9
66.2
67.3
68.4
69.5
70.7
71.9
73.1
74.4
75.7
glucose and fructose is understood as invert sugar), and sucrose-raffinosewater according to Liang et al. (1988) (Table 5.7).
5.4.2 Influence of beet and cane non-sugars on the solubility of sucrose

in technical sugar solutions
The complicated situation found for sucrose solubility in impure sugar
solutions becomes particularly important in the lower purity of syrups and
molasses, where the influences of the quality and amount of non-sucrose.
Sucrose solubility in impure solutions has already been studied by many
investigators but no equation providing a general application for all kinds
of molasses and impure solutions was found.
According to Vavrinecz (1978-79) the compounds present in impure
aqueous sucrose solutions can be divided into four groups.
(a) Substances which are influenced neither by water nor by sucrose insoluble materials and carbohydrates (e.g. fructose) which do not
immobilize water.
115
SUCROSE SOLUBILITY
(b) Substances which bind water - glucose, glucose-containing mixtures

(starch syrups), maltose, raffinose and other carbohydrates which
have water of crystallization, inorganic salts with high amounts of
water of crystallization and no direct combination with sucrose (e.g.
MgS0 4 )
(c) Substances which bind sucrose - alkali hydroxides and alkali salts of
weaker acids (e.g. potassium carbonate and potassium acetate).
Most of the substances in this group also bind a certain amount of
water.
(d) Substances which bind water as well as sucrose - e.g. KCI and NaCI
(group of the most positive melassigenic compounds).
5.4.3 Equation for solubility of sucrose in impure solutions

The influence of impurities on sucrose solubility can be expressed as the
saturation coefficient, SC(l):
SC
SWsat,lmp
.
(5.22)
SWsat,pure
where SWsat,imp is the sucrose to water ratio in saturated impure solution (g

sucrose per g water); and SWsat,pure is the sucrose to water ratio in
saturated pure solution (g sucrose per g water).
The saturation coefficient, SC, was studied by a number of researchers.
Through the combined efforts of Wiklund (1955), Wagnerowski et al.
(1961, 1962) and Vavrinecz (1978-79) a correlation was developed
between the saturation coefficient SC(l) and the non-sucrose to water
ratio, NSW (g non-sucrose per g water). This relationship is expressed by
the following equation:
SC = a X NSW
+ b + (l-b)
e-exNSW
(5.23)
where a, b, c are coefficients depending on the quality of non-sucrose.

Vavrinecz (1978-79) summarized in his review the results of the
investigation of sucrose solubility in impure solutions and computed values
of the coefficients a, band c for each of the groups of examined data. The
values of the coefficients varied in a very large range: a = 0.20-0.43, b =
0.43--0.83 and c = 1.36-2.85, the average values are a = 0.292, b = 0.691
and c = 1.80.
The computed curve according to the average values a,b,c and to some
results of various authors is shown in Figure 5.5. The differences between
curves do not allow an unambiguous application of the solubility values. In
addition, the results of some authors show that the course of curve
according to equation (5.23) is not independent on the temperature and
consequently the choice of the solubility data is further made difficult.
116
SUCROSE
--,..
fI)
Gl
lE
Gl
o
S
~
1.1 +---+----H7L-?'-7L-+-+---+----I
1ii
fI)
v
0.9+---+---+---+---+---+----1
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Nonsucrose/water ratio NSW (1)
Figure 5.5 Dependence of saturation coefficient on the non-sucrose to water ratio. Data
taken from O. measured values by Orazi (1938); W, Wagnerowski (1961,1962); B, Bubnfk
and Kadlec (1982, 1988); G, Grut (1937-38); R, Reinefeld (1979); Y, average values by
Yavrinecz (1978-79).
The composItIOn of different products and intermediate products in

sugar technology can be schematically and simply illustrated by means of a
triangle diagram which describes the system sucrose-water-non-sugars
(see Figure 5.6.). The straight lines going through the vertex of a triangle
with water concentration 100% express the constant ratio between sucrose
content S (%) and non-sugars NS (%) and it is possible to calculate the
purity Q (%) from these ratios.
Bubnik and Kadlec (1992) carried out the evaluation of the status quo
with the following results.
(a) If the exact solubility data are required, it is necessary to determine
the solubility by means of experimentation (crystallization or
dissolution), especially for the low purity solutions.
(b) If the analytical composition is known (content of K, Na, Ca, Mg
and others), it is possible to apply some of the more complicated
equations, which include the influence of some main non-sugars on
the solubility (e.g. Schneider et al., 1961; Reinefeld et al., 1979).
(c) If only the rough values for the technical use are required, it is of
practical interest to choose some large groups of data, which were
determined with sufficient accuracy, the sugar-beet being cultivated
in similar conditions and the examined impure solutions produced
117
SUCROSE SOLUBILITY
100,----------...=.=----:::--:-:=..,..-:-::-::-::-::----,
95
~ - - . white sugar
raw sugar.---;'
syrupC
9 0 \
85
80
75
70
65
:~
:~
Q=65%
Purity
"
'\!
'X syrup A
jV ':j(
"tltolasse~/ J 'V\... 'X/\
""" ~" ..JV\ ~_~thickJulce
Q=56 %
"'"
'\
"--' , ... ]~
~0)E-JII!t.~<--
~~~
---1
'\ rawiuice
1\ j '\ ~ j
j\ l
40
1\/ \ J j\iW.
'\ '\ '\ '\ \
35
'\1\ '\/ '\ J
~ J'Y:. .1\1 I \thin Juic e
30
I I \ ! 1\ J '\
I\~ / \ '\ j
25
1\ '\/\ 'V '\ j '\ '\IV "'0:~J ,/\ i
20
1\ I j \ "IV j \ '\ j\1 j \ J"'ci- ~i\", i
15
/ \ / . / \ I 1\/\ 'V\/ '\1\/\/ 'V\ ~ ~
10
I V \ \ ! \ \!V IV\ ./\/\/\ .IV' j\~
~ -f-/....l\Jf-.'...,\.1'--'(-/_\+.1.....:/>(-'...,\.1'--'(-\/_'\-./""':\>(--1/'-I'-Of\'/'_'\+./...,\f---OT
/''-\-Of./_!\+(-'\./>(--1'--'(-~....3!
NS 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100yJ
Figure 5.6 Triangle diagram of the system sucrose-water-non-sucrose for impure sugar
solutions.
by classical technology (no Quentin process, etc.). As a typical case

it is possible to take the work of Gmt (1937, 1937-38).
The dependence of the saturation coefficient SC (Gmt, 1937-38) on the
non-sucrose to water ratio NSW can be described very precisely by the
following equations.
(a) According to Vavrinecz (1978-79) equation (5.23) with coefficients:
a = 0.178, b = 0.820 and c = 2.1
(b) According to Bubnfk and Kadlec (1992):
for NSW < 0.864 SC = 1 - 0.1387

+ 0.1606 X (NSW)2
NSW
for NSW > 0.864 SC = 1 + 0.1659 X (NSW - 0.864)
(5.24)
(5.25)
If we substitute the value of the saturation coefficient SC from the

equations (5.23) or (5.24) and (5.25) into the equation (5.22), we can
calculate the solubility of sucrose in the form of the sucrose to water ratio,
SWsat,imp (g sucrose per g water). We obtain the value of the sucrose
solubility in water SWsat,pure (g sucrose per g water) from equations (5.14)
or (5.15).
118
SUCROSE
Using the equations cited, the tables of sucrose solubility in impure sugar
solutions were calculated (Bubnfk and Kadlec, 1992; Bubnfk et al., 1994)
with the solubility expressed (see Table 5.8) by the sucrose to water ratio,
SWsat,imp (g sucrose per g water) and also by the dry substance content DS
(%) (see Table 5.9). The tables are convenient for technical use, especially
in the sugar industry, where it is of practical interest to have simple
tables with a limited validity. Table 5.9 is presented for the temperature
range 4G-90C and purity 55-100%. The values under 30C and over 80C
and purity under 60% were obtained by means of approximation and have
only a partial validity.
5.5 Solubility of sucrose in other solvents
The sucrose solubility in nonaqueous solvents is generally significantly
lower than in water and sucrose does not dissolve in non-polar solvents.
Some more important values of solubility are shown by sucrose (Dobrzycki,
1984) in condensed ammonia (72% sucrose in solution), dimethylsulphoxide (42%) and methylamine (more than 25%). Liquid sulphur
dioxide shows lower values, also formic and acetic acid, dimethylformamide, pyridine (approx. 6%), propyleneglycol, glycerol (7%),
methanol, ethanol, acetone and dioxane.
5.5.1 Ternary systems: sucrose-water-organic liquid solvent
Similarly to the three-component diagram sucrose-water-non-sucrose we

can graphically illustrate the ternary system sucrose-water-solvent by a
triangle diagram. We present as an example the diagram for the system
sucrose-water-acetone at 30C according to Verhaar (1940) (see Figure
5.7). This figure shows that two liquid phases (Ll and L2), at a given
temperature, exist at equilibrium.
Other important ternary systems are described in Table 5.10 for the
system sucrose-ethanol-water (Schiwek and Kolber, 1985), Table 5.11 for
the system sucrose-propyleneglycol-water (Fey et al., 1951) and Table 5.12
for the system sucrose-glycerol-water (Segur and Miner, 1953).
5.6 Solubility of some saccharides

Solubility of sucrose was compared with other usual saccharides. This
comparison is summarized and the basic data of solubility of glucose,
fructose, invert sugar, maltose, lactose and raffinose in water are reported
in chapter 8.
For the calculation of the dependence of solubility of the cited
2.01
1.97
1.95
1.94
1.97
2.01
2.08
2.19
2.34
20
2.07
2.04
2.02
2.01
2.04
2.09
2.17
2.28
2.45
25
2.15
2.12
2.09
2.09
2.12
2.18
2.27
2.40
2.59
30
2.24
2.20
2.18
2.17
2.22
2.28
2.38
2.53
2.75
35
2.35
2.30
2.28
2.27
2.33
2.40
2.52
2.69
2.93
40
2.46
2.41
2.39
2.38
2.45
2.54
2.67
2.87
3.15
45
2.59
2.53
2.51
2.51
2.59
2.70
2.85
3.08
3.41
50
100
95
90
85
80
75
70
65
60
55
Purity,
Q(%)
66.7
67.5
68.4
69.6
70.9
72.4
74.2
76.2
78.5
81.0
20
30
68.3
69.0
69.9
71.1
72.4
73.9
75.7
77.7
80.0
82.5
25
67.5
68.2
69.1
70.3
71.6
73.1
74.9
76.9
79.2
81.7
69.2
69.9
70.8
71.9
73.2
74.8
76.5
78.6
80.8
83.3
35
2.89
2.82
2.80
2.80
2.94
3.08
3.30
3.61
4.08
60
3.06
2.99
2.96
2.98
3.14
3.32
3.58
3.95
4.51
65
3.25
3.18
3.15
3.17
3.38
3.59
3.90
4.35
5.03
70
70.1
70.8
71.7
72.8
74.1
75.6
77.4
79.5
81.8
84.2
40
71.1
71.7
72.6
73.7
75.0
76.6
78.4
80.4
82.7
85.1
45
72.1
72.7
73.6
74.7
76.0
77.6
79.4
81.4
83.7
86.1
50
60
74.3
74.8
75.7
76.7
78.1
79.7
81.5
83.5
85.8
88.1
55
73.2
73.8
74.6
75.7
77.0
78.6
80.4
82.5
84.7
87.1
75.4
75.9
76.7
77.8
79.1
80.7
82.6
84.6
86.8
89.1
65
76.5
77.0
77.8
78.9
80.2
81.8
83.7
85.7
87.9
90.1
70
Dry substance of saturated impure solutions at temperature, tCC)
2.73
2.67
2.64
2.65
2.75
2.88
3.06
3.32
3.71
55
77.6
78.1
78.8
79.9
81.3
82.9
84.8
86.8
88.9
91.1
75
3.46
3.38
3.35
3.38
3.64
3.90
4.27
4.81
5.66
75
Sucrose to water ratio, SW (g sucrose per g water) for temperature, t (OC)
Table 5.9 Dry substance of saturated impure sugar solutions DS (%)
100
95
90
85
75
70
65
60
55
Purity,
Q(%)
Table 5.8 Sucrose to water ratio in saturated impure sugar solutions, SW (g sucrose per g water)
78.7
79.1
79.9
81.0
82.4
84.0
85.9
87.8
89.9
92.1
80
3.69
3.60
3.58
3.62
3.94
4.25
4.70
5.36
6.43
80
90
80.8
81.1
81.9
83.0
84.4
86.1
87.9
89.9
91.9
94.0
79.7
80.1
80.9
82.0
83.4
85.1
86.9
88.9
90.9
93.1
4.20
4.09
4.07
4.15
4.64
5.09
5.76
6.79
8.56
90
85
3.94
3.83
3.82
3.88
4.27
4.65
5.19
6.02
7.38
85
rJ'J
c:::
......
......
\0
r:
a:I
c:::
t"'"
rJ'J
tl'1
rJ'J
:>:l
(")
120
SUCROSE
Table 5.10 Solubility of sucrose in ethanol-water solutions (g sucrose per 100 g solution)
Temperature,
t
eq
15
20
25
30
35
40
45
50
55
60
65
70
Ethanol concentration (g ethanol per 100 g solution)

0
12
16
20
66.04
66.72
67.47
68.29
69.17
70.10
71.09
72.12
73.18
74.26
75.37
76.48
62.07
63.00
63.96
64.96
65.99
67.04
68.13
69.25
70.41
71.59
72.80
74.05
58.10
59.09
60.12
61.18
62.26
63.38
64.52
65.70
66.90
68.14
69.41
70.70
54.15
55.20
56.27
57.37
58.50
59.65
60.83
62.03
63.26
64.52
65.80
67.11
50.21
51.31
52.43
53.56
54.71
55.88
57.06
58.27
59.49
60.73
61.98
63.25
46.28
47.43
48.58
49.74
50.90
52.06
53.23
54.41
55.99
56.77
57.96
59.15
SUCROSE
100,-----------......,...------------,
80
eo
40 +-.-..--.-...-.. --.-~- .....-..-...;;:.. --.--+(....-\_
20
o*-~~-,;~....:.r'---+--+-+-+-+"";::""-lf
80
o
20
40
eo
WATER
Figure 5.7 Triangle diagram of the system sucrose-water-acetone.
saccharides on the temperature, Bubnik et ai. (1994) evaluated the

equations as follows:
(5.26)
where DS is dry substance of saturated solution (%), t is temperature CC),
and ao ... a4 are coefficients.
121
SUCROSE SOLUBILITY
Table 5.11 Solubility of sucrose in propyleneglycol-water solution (at temperature 25C)

Propyleneglycol
in water
(% w/w)
Sucrose
g per 100 ml solution
g per 100 g solution
84.4
75.7
52.2
39.4
24.5
4.8
2.0
64.4
58.8
42.7
33.5
21.8
4.5
1.9
o (water)
25
50
62
75
95
99
Table 5.12 Solubility of sucrose in glycerol-water solution

Glycerol Sucrose solubility (g per 100 ml solution) Sucrose solubility (g per 100 g solution)
at different temperatures (OC)
at different temperatures (OC)
in water
(% w/w)
25
15
15
35
25
35
o (water)
25
50
75
82
95
99.95
87.4
73.2
54.6
28.6
20.1
5.8
84.4
78.2
38.0
32.4
25.5
12.6
7.2
92.3
82.2
63.7
38.1
29.0
16.6
66.0
55.9
42.4
22.7
15.9
4.6
64.4
59.4
44.8
25.4
20.0
9.9
5.7
69.2
61.9
48.7
29.5
23.3
13.0
The difference between original data and that calculated according to

equation (5.26) is lower than 0.1% for glucose and fructose, 0.1% for
invert sugar (average value), 0.2% for lactose and raffinose and 0.3% for
maltose (average value).
The values of the coefficients for various saccharides are given in the
following survey together with the reference and the range of validity (see
Table 5.13).
5.7 Conclusion
Solubility of sucrose in water and non-aqueous solvents belongs to its basic
properties and influences significantly technological processes. Solubility
of sucrose in impure aqueous sugar solutions is especially important. These
are treated during industrial sugar production in the sugar factories. The
content as well as composition of the admixtures (i.e. non-sugars) issuing
from the natural raw material (sugar-beet or sugar-cane) influence
significantly solubility of sucrose and therefore white sugar extraction. The
influence of non-sugars on the solubility is in a tight bond with molasses
122
SUCROSE
Table 5.13 Coefficients of equation (5.26) based on previously published data

au
al
Glucose
32.2725
0.73964
(Honig, 1953) for o-50C
Glucose
33.6227
1.20103
(Corn Refiners Association, 1975), for
Fructose
77.1708
-0.122121
(Bates et ai., 1942) for 2o-55C
Invert
50.846
0.40579
(Honig, 1953) o-50C
Maltose
35.911
0.32528
(Washburn et ai., 1927) o-97C
Lactose
10.8294
0.135663
Lactose
-32.597
1.58966
(Roetman and Burna, 1974) 8o-200C
Raffinose
6.6676
0.089312
a2
-1.2121
10-
a3
a4
-1.1655 X 10-2 5.11882 X 10-5

0
50-91C
2
1.42655 x 10- -2.0944 X 10-4 0.01515 X 10-6
2.0930 X 10-2 --6.6613 X 10-4
3.1532 X 10-3
6.660 x 10-<>
2.74441
6.34667 x 10-3 -2.2804
10-5
10-5
9.5174 X 1~
-8.2194 x 10-3
0.011045
1.7030
10-8 1.5575
10- 10
formation and is quantitatively expressed by means of melassigenic

coefficients. Many authors have been therefore dealing with studies of the
relations between non-sugars composition in beet and extraction (or
solubility). Even nowadays these questions are being intensively studied.
Solubility is also a very important value for crystallization processes
where it determines the rate of supersaturation of the solutions and so also
the value of crystallization rate. The solubility increases significantly with
the temperature which is manifested at higher temperatures, commonly
used in industrial crystallization, by high content of dry solids and high
viscosity of mother syrups.
The values of sucrose solubility in water are known with a sufficient
accuracy. For impure solutions it is possible to use either some of the
published figures or, when accurate data are needed, to carry out
experimental determination. The sucrose solubility is experimentally
determined through reaching the saturation state. The most frequent are
the crystallization experiment with a supersaturated solution, sucrose
being dissolved in an undersaturated solution at the given temperature
(e.g. the so-called Polish test) or an increasing temperature of a
supersaturated solution (saturoscopic method).
Sucrose solubility in non-aqueous solvents is much lower. It is used, for
example, in pharmaceutical production, in analytics (e.g. moisture
determination of crystalline sucrose - pyridine and ethanolamine,
dispersion medium for measurement of crystals - glycerol, etc.).
Solubility in ternary mixtures sucrose-water-solvent (e.g. ethanol or
acetone) is also important.
SUCROSE SOLUBILITY
123
List of symbols
a
a,b,c
aO,al,aZ,a3,a4
A,B
C
Ms
Mw
NS
NSW
Q
S
SC
SS
SW
SWsat
SWsat,pUTe
SWsat,imp
WS
WSsat,pUTe
Activity (mol sucrose per kg water)

Coefficients
Coefficients
Coefficients
Concentration (g sucrose per litre solution), partial
specific gravity
Molality (mol sucrose per kg water)
Molar concentration (mol sucrose per litre solution)
Dry substance (%)
Activity coefficient (1)
Non-sucrose molecular weight (sugar-beet non-sucrose
114 g/mol, sugar-cane non-sucrose 205 g/mol)
Sucrose molecular weight (342.30 g/mol)
Water molecular weight (18.016 g/mol)
Non-sucrose (non-sugars, impurity) (%)
Non-sucrose/water ratio (g non-sucrose/g water)
Purity (%)
Sucrose content (%)
Saturation coefficient (1)
Coefficient of supersaturation (1)
Sucrose to water ratio (g sucrose per g water)
Sucrose to water ratio (g sucrose per g water) of the
saturated sucrose solution
saturated pure sucrose solution
saturated impure sucrose solution
Temperature (0C)
Temperature of freezing point depression of sucrose
solution CC)
Water to sucrose ratio (g water per g sucrose)
Water to sucrose ratio (g water per g sucrose) of the
saturated pure sucrose solution
Molar fraction (mol sucrose per mol
sucrose + non-sucrose + water)
Mass fraction (g sucrose per g solution)
Specific gravity (density) (kg/m 3 ) of sucrose solution
124
SUCROSE
References
Bates, F.J. et al. (1942) Polarimetry, Saccharimetry and Sugars, Circular NBS No C440,
Washington, DC, USA.
Bubnik, Z. and Kadlec, P. (1988) Krystalizacni rychlost sacharosy, Dil II [Growth rate of
sucrose crystals, Part II]. Listy Cukrov., 104, 201.
Bubnik, Z. and Kadlec, P. (1992) Solubility of sucrose in impure sugar solutions. Zuckerind.,
117,619--625.
Bubnik, Z., Kadlec, P., Bruhns, M. and Urban, D. (1994) Handbook of Sugars. Chemical
and Physical Data of Sugar Manufacture and Processing. A Bartens, Berlin, Germany.
Charles, D.E. (1960) Solubility of pure sucrose in water. Int. Sugar J., 62, 126.
Ciz, K. and Valter, V. (1967) Roztoky sacharosy [Solutions of sucrose]. In Zdklady
cukrovarnictvi (dil IV) [Sugar Technology, Vol. IV] (ed. Bretschneider, R.) SNTL,
Prague, Czech Republic, p. 53.
Corn Refiners Association (1975) Critical Data Tables (3rd edn).
Dobrzycki, J. (1984) Chemiczne Podstavy Technologii Cukru [Chemical Principles of Sugar
Technology]. Wyd. Naukowo-Techniczne, Warszawa, Poland, p. 254.
Fey, M.W., Weil, C.M. and Segur, J.B. (1951) Solubility of sucrose in aqueous glycerol and
propyleneglycol. Ind. Eng. Chern. Ind., 43, 1435-1436.
Grut, E.W. (1947) Untersuchung von Ubersattigung und Viskositat in Kuhlmaischen fUr
Erst-Product. Cbl. Zuckerind., 45, 345.
Grut, E.W. (1937-38) Setfeni 0 pfesyceni a viskozite v refrizerantech pro prvni produkt
[Investigation of saturation and viscosity by cooling crystallization of A-product]. Dil II.
Rozpustnost sacharosy v Ciste vode [Part II. Solubility of sucrose in pure water]. Listy
Cukrov., 56, 53-55. Dil III. Rozpustnost sacharosy v neCistych roztocich [Part III.
Solubility of sucrose in impure sucrose solutions]. Listy Cukrov., 56, 62--64.
Heitz, F. (1974) Crystallizing qualities of sugar solutions. Proceedings of the 16th Session
ICUMSA, Subject 25, Ankara, Turkey, p. 353.
Herzfeld, A. (1892a) Uber die L6slichkeit des Zuckers in Wasser, Wessen und Ursache der
Melassebildung im Algemeinen Einfluss der Raffinose darauf im besonderen. Z. Ver.
Rubenzucker-Industrie, 42, 174.
Herzfeld, A. (1892b) Die Loslichkeit des Zuckers in Wasser. Z. Ver. Rubenzucker-Industrie,
42,232.
Honig, P. (ed.) (1953) Principles of Sugar Technology (Vol. 1). Elsevier, Amsterdam, The
Netherlands, p. 84.
Kadlec, P. and Sarka, E. (1977) Molami hmotnost necuknY v melase [Molar weight of
nonsucroses in molasses]. Listy Cukrov., 93, 131.
Kadlec, P. and Hyndrak, P. (1979) Ebuliometricke stanoveni molami hmotnosti necukn.l'
[Ebuliometric method for determination of molar weight of nonsucroses]. Listy Cukrov.,
95, 13.
Kelly, F.H.e. (1954) Principles of Sugar Technology (Vol. II). Elsevier, Amsterdam, The
Netherlands, p. 103.
Kelly, F.H.e. (1959) The solubility of sucrose in impure solutions. In Principles of Sugar
Technology (Vol. 11) (ed. Honig, P.). Elsevier, Amsterdam, The Netherlands, p. 96.
Liang, B., Hartel, R.W. and Berglund, K.A. (1988) Solubility of sucrose in water in the
presence of raffinose. Int. Sugar 1., 90, 25-28.
Lyle, O. (1957) Technology for Sugar Refinery Workers. London, UK.
Orazi, G. (1938) La solubilita dello zucchero nelle soluzioni impure (Coefficiente di
saturazione). Ind. Sacch. Ital., 31, 401.
Reinefeld, E., Emmerich, A., Fantar, N. and Gerlach, M. (1979) Grundlagen zur
Verbesserung der Melasseerschopfung. Zuckerind., 104, 599.
Roetman, K. and Burna, T.J. (1974) Neth. Milk Dairy J., 28, 155.
Schiweck, H. and Kolber, A. (1985) Zur Frage der Optimalen Ausbildung der Zuckerkruste
bei Krustenpralinen. Susswaren Technik Wirtschaft, 19, 273.
Schneider, F., Emmerich, A., Reinefeld, E., Walter, E. and Keirn, W. (1961) Auswirkung
der Nichtzuckerstoffe der Rube, insbesondere auf die Melassebildung. 1. Beziehung
SUCROSE SOLUBILITY
125.
zwischen Nichtzuckerzusammensetzung und Entzuckerungsgrad von Melassen. Zucker, 14,

208.
Segur, J.B. and Miner, C.S. (1953) J. Agric. Food Chern., 1,567-568.
Smelik, A., Vasatko, J., Dandar, A. and Matejova, J. (1970--72) Die Loslichkeit der
Saccharose [Solubility of Sucrose). I. Mitteilung (1970a) Bewertung der Untersuchungsergebnisse tiber die LOslichkeit der Saccharose in Wasser, Zucker, 23, 133. II. Mitteilung
(1970b) Ouadratische Gleichungen fUr die Loslichkeit der Saccharose, Zucker, 23, 595. Ill.
Mitteilung (1971) Die Bewertung der Messungen der Saccharoseloslichkeit in Wasser mit
Hilfe der Ausgeglichenen Ouadratischen Modelfunktion, Zucker, 24, 138. IV. Mitteilung
(1972) Loslichkeit der wasserfreien Saccharose und theoretische Approximation der
Loslichkeit des Hemipentahydrates der Saccharose in Wasser, Zucker, 25, 89.
Taylor, M. (1948) The solubility of pure sucrose in water at high temperatures. Int. Sugar J.,
50,292.
Vavrinecz, G. (1962) Neue Tabelle tiber die Loslichkeit reiner Saccharose in Wasser. Z.
Zuckerind., 12, 481.
Vavrinecz, G. (1978-79) The formation and composition of beet molasses. Sugar Technol.
Rev., 6,117.
Verhaar, G. (1940) Arch. Suikerind. Ned. en Ned.-Indie. In Principles of Sugar Technology
(Vol. II) (ed. Honig, P.). Elsevier, Amsterdam, The Netherlands, p. 110.
Wagnerowski, K., Dabrowska, D. and Dabrowski, C. (1961) 0 ilosciowych stosunkach
skladnik6w melasu rzeczywistego, Gaz. Cukrown., 63, 97.
Wagnerowski, K., Dabrowska, D. and Dabrowski, C. (1962) Probleme der Melasseerschopfung, Z. Zuckerind., 12, 664.
Washburn, E.W., West, c.J., Dorsey, N.E., Bichowsky, F.R. and Klemenc, A. (1927)
International Critical Tables (Vol. II). McGraw-Hili, New York, USA.
Weast, R.C. (ed.) (197~77) CRC Handbook of Chemistry and Physics (57th edn). Chemical
Rubber Co., Cleveland.
Wiklund, O. (1955) Molektilverbindungen zwischen Saccharose und Salzen. Ein Beitrag zur
Beleuchtung des Mechanismus der Melassebildung. Zucker, 8, 266.
6 Rheological properties of sucrose solutions

and suspensIOns
M. MATHLOUTHI and J. GENOTELLE
6.1 Introduction
Viscosity of sugar solutions is informative on the transport properties of
the sucrose molecule in the aqueous medium. For this reason, it is a
physical property particularly important in crystallization studies. Viscosity
is affected by temperature, concentration of solute and of suspended
matter. Slight amounts of impurities, especially macromolecules, provoke
an appreciable increase in viscosity and a change in the rheological
behaviour of concentrated sucrose solutions. As stressed in an earlier
review (Mathlouthi and Kasprzyk, 1984) theory is a good guide to practice
and the solving of the day-to-day problems posed in a sugar factory such as
the flow in pipes, cooling of crystallizers, centrifugation or molasses
exhaustion, require that rheological properties of syrups, molasses and
massecuites be taken into account.
The rheological behaviour of sugar solutions and suspensions is derived
from the rate of deformation or rate of flow obtained when a force is
applied to the sample. When the relation between the shear stress (force
applied per unit area) and the shear rate (velocity gradient resulting from
the application of shear stress) is linear, the fluid is said to be Newtonian.
This is the case for pure sucrose solutions at all temperatures and
concentrations experimented. When the increase in shear stress gives more
than a proportional increase in shear rate, with the curve beginning at the
origin, the flow behaviour is pseudo-plastic. It is also described as a shearthinning behaviour. The apparent viscosity decreases in this type of flow
with increasing shear rates, eventually reaching a constant value at high
shear rates. At low shear rates, a pseudo-plastic fluid may exhibit a nearly
linear variation of shear stress in function of shear rate. This is called a
'Newtonian regime' (Bourne, 1982). It illustrates the necessity of avoiding
the single-point measurements and the danger of restriction of measurements to low shear rates. Pseudo-plasticity is found for low-grade
massecuites (Kaga, 1961) while the rheological behaviour of molasses may
be Newtonian or pseudo-plastic depending on their composition. Cane
sugar molasses, because of the concentration of soluble colloids, exhibits a

RHEOLOGICAL PROPERTIES OF SUCROSE
127
pseudo-plastic behaviour (Smolnik and Delavier, 1972). If no highmolecular-weight macromolecules or gas blisters are found in molasses, its
behaviour remains Newtonian (Schneider et ai., 1967).
Another non-Newtonian flow behaviour less common in sugar solutions
and suspensions is the dilatant or shear-thickening phenomenon. It
corresponds to an increase in apparent viscosity with increasing shear rate.
Viscosity of the two-phase system constituted by massecuites is not easy to
measure. It is dependent on different factors such as the crystal content,
size and shape of crystals, concentration and composition of mother liquor
as well as the type of viscometer (rotating cylinder or pipeline viscometer).
However, massecuites at the usual conditions of temperature, concentration
and crystal content keep their fluidity. They do not behave like plastics
which do not flow until a minimum stress is reached.
We now present the theoretical basis of viscosity relations used for pure
sucrose solutions as well as the practical approach of prediction of viscosity
and flow behaviour for industrial sugar solutions and suspensions. Methods
of measurements used in the laboratory and the factory are reviewed and
their validity for the different types of samples commented on. Interpretation
of viscosity data is made at a molecular level to show the role of solvent
association to sucrose as well as solute-solute interactions or the role of
impurities on the rheological behaviour of impure solutions. This information is applied to the understanding of the role of viscosity in sugar
factory processes.
6.2 Theoretical basis of viscosity relations

6.2.1 Einstein's equation
One of the earliest attempts to use hydrodynamics equations to calculate
the molecular dimensions of a spherical solute in dilute solution is due to
Einstein (1906). This was applied to sucrose solutions. At very high
dilution in a fluid strictly Newtonian, Einstein showed that the relative
viscosity of a very dilute suspension of rigid spherical uncharged particles
in a continuous liquid medium is given by a relation which, in the first
order, gives
II
llrel = - - = 1 + 2.5<1>
llo
(6.1)
where II and llo are, respectively, the absolute viscosities of solution and
solvent and the volume fraction occupied by the solute.
Application of this relation requires that the solute molecules are large
compared with a molecule of the solvent and that they are far enough
128
SUCROSE
apart. Using Landolt and Bornstein tables, Einstein calculated ll/llo =

1.0245 (at 20e) for a 1% aqueous sucrose solution and found that 1 g of
sucrose dissolved in water has the same effect on the viscosity as small
suspended rigid spheres of total volume 0.98 cm 3 ( = 0.024512.5). As the
specific volume of 1% sucrose solution is 0.61 cm 3 g-l, the difference is
ascribed to the fact that sugar molecules limit the mobility of water and
that the dissolved sugar molecule behaves in hydrodynamics relations as a
hydrated molecule having a volume of 0.98 X 342 N cm-3 with 342 being
the molecular weight of sucrose and N the Avogadro number.
The calculation of hydrodynamic radius (P) of the sucrose molecule by
use of equation (6.1) and the Kirchhoff-Stokes-Einstein relation giving the
diffusion coefficient (D):
D = RT/6rtllNP
(6.2)
was made. It results in the following data:
P = 0.49
N = 6.56
10--6 mm
23
X 10
The Avogadro number is given with a relatively low error (5%) while the
hydrodynamic radius of sucrose is 20% higher than the value obtained
from crystallographic data (Pc = 4.04 A). The difference between
hydrodynamic radius (4.9 A) and crystallographic radius (4.04 A) permits
calculation of a hydration number of 5.3 water per sucrose molecule which
is in good agreement with the value generally admitted (Akhumov, 1981;
Culp, 1982). Most of equations used for polymer solutions in infinitely
dilute state are comparable to Einstein's relation (equation (6.1. They
are at the basis of the empirical relations used in the sugar industry.
6.2.2 Viscosity-concentration relations

The calculations of Einstein were made for a spherical particle. In fact, the
shape of the sucrose molecule is far from spherical. To account for this
parameter and for the deformation of the solvent by the solute, Simha
(1940) introduced a shape factor in Einstein's equation:
llrel = 1
+ v<l>
(6.3)
where v is the axial ratio for ellipsoids. It was calculated for discs and rods.
Extension of Einstein's relation to the second order (Simha, 1952) gives
_ll_ _ 1 = 2.5<1>
llo
+ 12.6<1>~
(6.4)
were <1>2 is the mole fraction of solute (<1>2 = (v2c2)/m2, where V2 is the
molar volume of solute, m2 its molecular weight and C2 the concentration).
129
Replacing
<1>2
by its value and dividing by
11 - 110
11oC2
C2
= 2.5(~) + 12.6 (
m2
gives
(6.5)
V2 )2 C2
m2
Equation (6.5) is comparable to the Huggins (1942) equation:

- 110
-11 - = [11] + k'[11Fc+
(6.6)
...
where
11 - 110
lim
C
110c
is the intrinsic viscosity. The parameters [11] and k' (Huggins constant) are
generally used to characterize the size and solute-solvent interactions in
polymer solutions. The application of a triple extrapolation procedure
permitted an increased accuracy in the determination of intrinsic viscosity
[11] of sugars and sweeteners (Mathlouthi et ai., 1993). Beside extrapolation
of equation (6.6) two other functions are extrapolated towards zero (see
Figure 6.1). These functions are
2.8
2.6
2.4
2 ~_~_~_"'--_"-_~_~----'
o
2
4
3
5
6
7
Figure 6.1 Triple extrapolation of (0) reduced specific viscosity, (+) inherent viscosity and
(*) reduced differential viscosity in function of concentrations c (g % mt) to obtain intrinsic
viscosity [TIl.
130
SUCROSE
the inherent viscosity given by the relation of Kraemer (1938):
1
T]
2
T]inh = -In ( - ) = [T]] - f3[T]] C+ ...
C
T]o
(6.7)
the reduced differential viscosity (Meffroy-Biget and Unanue, 1977):
T]diff
T] - T]o = [T]] + (m + b - 1)[T]Fc+ ...

T]
C
(6.8)
Another equation frequently used in the literature for sugar solutions is

that of Jones and Dole (1929):
T]rcl
T]
= -- = 1 +
T]o
Bc + Dc 2 +
..
(6.9)
B + Dc+ . ..
(6.10)
which may be written
T]sp
T] - T]o
T]oc
-------=
where B is comparable to [T]] in the Huggins equation (6.6). B is expressed

in litres mol-I and the concentration c in mol litre-I, T] and T]o being,
respectively, the viscosity of solution and solvent and c the concentration.
The Jones and Dole equation is comparable to the Einstein-Simha
relation:
T]r = 1 + v</> + C</>2 + . . .
(6.11)
where </> is the volume fraction occupied by the hydrated solute (</> =
(cM 2 ~)/1000) and v a coefficient accounting for the shape of solute (v =
2.5 for spherical particles). Comparison of equations (6.10) and (6.11)
permits likening of B to a parameter accounting for the size of hydrated
solute called Bsizc ' For spherical particles:
Bsizc
2.5 M2V~
1000
(6.12)
M2 being the molecular weight of solute and ~ its apparent specific

volume.
The experimental coefficient B is an overall hydrodynamic volume. It is
expressed as the sum of two components one due to the size and shape of
solute (B sizc ) and the other originating from its effect on solvent structure
(Bs,ruc,urc) :
B = Bsizc + Bs,ruc,urc
(6.13)
Another relation between relative viscosity and concentration is due to

Vand (1948):
In lJr
k\c
+ '2
(k 2
k l )C2
131
(6.14)
1 - Qc
where k l is a shape factor for single spheres and k 2 a shape factor for
collision doublets, '2 a collision time constant, Q a hydrodynamic
interaction constant and c the concentration.
The two first terms of equation (6.14) multiplied by (1 - Qc) and
neglecting Q2C2 gives
In lJr = klc
+ k\Q + '2 (k 2 -
k l ) c2 +
...
(6.15)
This relation is comparable to equation (6.7). Such a comparison permits

one to deduce that k\ = [lJ] and
Q
f3 = (~-
'2(k 2 - k j )
k1
For a sucrose molecule taken as a model of solute with an ellipsoidal shape

having an axial ratio alb = 1.84, Vand (1948) obtained the values of k l =
2.75, k 2 = 3.175, Q = 0.60 and '2 ranging from 2.089 at ooe to 1.489 at
100C. He could also deduce hydration numbers of 10.54 at ooe and 2.45 at
100C.
The model of Vand (1948) was adapted by Robinson and Stokes (1959)
for the study of dilute solutions of small molecules. They found a hydration
number of 7.7 water per sucrose molecule at 20C which is in good
agreement with previous results. Furuse (1969) applied a relation inspired
from the work of Vand (1948) to describe the viscometric behaviour of
water-sugar and water-glycerine solutions:
lJr =
+ 0.5<1>2
(6.16)
1 - <1>2
where has the same meaning as in equation (6.1).

Reviewing the equations expressing the viscosity of dilute sucrose
solution as a function of concentration reveals their similarity with the
relations applied to dilute solutions of polymers. This is the case for the
equation used by Inhat et ai. (1968) to calculate the hydration numbers of
different saccharides from their hydrodynamic volume, which is comparable
to equation (6.6) of Huggins (1942). Among the other viscosity-eoncentration relations, that of Kaganov (1949) seems particularly adapted to sugar
solutions:
(6.17a)
where N is molar concentration,
be written as follows:
al
and b l constants; equation (6.rt7a) may

(6.17b)
132
SUCROSE
In this form, Kaganov's relation is comparable to that of Arrhenius (1916):

(6.17c)
in which Staudinger (1932) showed that k is comparable to intnnslc
viscosity [TJ]' c being the concentration. Equation (6.17a) was applied
(Genotelle, 1978) to the calculation of the viscosity of sugar solutions in the
range of concentrations (0-85% (w/w)) and temperatures between 10 and
80C. This relation is also suitable for molasses and run-offs providing that
a calibration taking into account the effect of non-sucrose is made.
Wagnerowski (1976) has published a relation taking into account both
the concentration and the temperature of sucrose solutions:
log TJ
=N
4120
- - - 11.75) - 2.10
t + 91
(6.18)
when TJ is viscosity in poises; t is temperature in C and N is the mole

fraction of sucrose (N= B/( 1900-18B) ); B being the concentration in Brix.
For pure sucrose solutions, most ofthe equations found in the literature are
derived from Einstein, Huggins or Kraemer's relations. Hence, Moulik
(1968) adapted Einstein's equation (equation (6.1)) to the calculation of
the viscosity of concentrated solutions. To take into account the shapes of
sugar molecules which are not spherical, Moulik and Khan (1977) applied a
modified Vand's equation (equation (6.14)) and declared it to be a
universal equation valid for electrolytes and non-electrolytes in concentrated solutions. Burianek (1956) proposed an equation for the viscosity of
industrial sugar syrups which is comparable to Kraemer (1938), see
equation (6.7).
6.2.3 Viscosity-temperature relations
The viscosity of a liquid was considered as a rate process and treated by the
molecular kinetic theory (Glasstone et al., 1941). Indeed, viscosity involves
a velocity gradient in its definition. If two layers of molecules in a liquid at
a distance l from each other are submitted to a force F, then the viscosity
coefficient TJ describing the resistance to the displacement of one layer
past the other is defined as
Fxl
TJ= ~v
(6.19)
where ~ v is the difference in velocity of the two layers. The viscous flow of
the liquid implies that molecules jump from one equilibrium position to
another. For this movement to occur it is needed that the system passes
over a potential energy barrier (Glasstone et al., 1941). Considering an
activation energy for the viscous flow Evisc> viscosity was expressed in
function of temperature using an Arrhenius relation:
133
(6.20)
II = BeEvisdRT
where B is a constant, R the gas constant and T absolute temperature.

An equation comparable to equation (6.20) was used by Andrade (1930)
and found valid for different liquids:
II = aV 1/ 3 eb / T
(6.21)
where a and b are constants and V the molar volume of liquid. The
occurrence of molar volume in viscosity relations originates from the
importance in the fluidity of liquids of the free volume theory of Eyring. If
V is the molar volume of liquid and V s that of solid, the difference (V - V s)
is due to holes in the structure of the liquid. It was found proportional to
fluidity (lIll) and viscosity expressed as
C
(6.22)
ll= - V- V s
where C is a constant.
An equation comparable to equation (6.22) was proposed by Hildebrand
(1971): II = c/(V - Vo) where c and II have the same significance as in
equation (6.22), V being the molal volume of liquid and V o the molal
volume at which fluidity is zero. Hildebrand and Lamoreaux (1973)
expressed the fluidity <p as a linear function of the relative molar
expansion V - Vo)/Vo):
1
<p = -= B
(6.23)
II
The parameters B = V de and V 0 are obtained from the extrapolation of the

plots of <p against V, which are linear over a wide range of temperatures.
Equation (6.23) implies that no 'solid-like' clustering takes place in the
liquid (Hildebrand and Lamoreaux, 1973; Hildebrand, 1978).
Although the 'hole' or free volume concept was established for pure
simple liquids, it was applied to aqueous sugar solution (Soesanto and
Williams, 1981) in the region of temperatures and concentrations where
glassy behaviour is approached. The treatment of amorphous sugar
systems was inspired from that of amorphous synthetic polymers using the
well-known WLF equation (Williams et ai., 1955):
log
Ct
Cz
(T - Tg )
+ (T -
Tg )
(6.24)
where II is viscosity of amorphous system, Q its density at temperature T

above glass transition, llg and Qg being the viscosity and density at Tg the
glass transition temperature taken as reference. Cl and Cz are coefficients
that describe the relaxation process (here viscosity) at T > Tg ; CI is
134
SUCROSE
proportional to inverse of free volume of the system at T g and C2 is the ratio

of free volume at Tg over the expansion coefficient of the free volume.
From experimental data on synthetic amorphous polymers, Williams et
al. (1955) extracted the values of universal constants CI and C2 (Cl = 17.44;
C2 = 51.6). Thus, the WLF equation is often used in the following form:
log
(1]/1]g)
= - 17.44 (T-Tg )/[51.6
+ (T-Tg )]
(6.25)
The application of equation (6.25) to amorphous food polymers,

oligomers and monomers, especially carbohydrates was recently reviewed
(Slade and Levine, 1994). The good fitting between experimental data for
sucrose-fructose mixtures at temperatures more than 20C above T g and
concentrations above 90% (w/w) with the calculated data using the WLF
equation (6.25) are among the earliest applications of the WLF relation to
sugar solutions (Soesanto and Williams, 1981). Prediction of the viscosity
of undercooled melts of glucose and fructose was also found to fit with
experimental results (Ollett and Parker, 1990). As the amorphous state of
sugar has a practical importance (see chapter 4), it is of relevance to find a
tool for prediction of its mobility transformation (viscosity) from glass
transition temperature easily determined by differential calorimetry.
Plotting log 1] against liT by analogy with Arrhenius equation was
criticized by Hildebrand (1978). Interpretation of log 1] as an 'activation
energy', implies the presence of quasi-lattice structures opposed to the flow
in the liquid. This is a major difference between Eyring (Glasstone et al.,
1941) and Hildebrand's theories. Although Arrhenius type equations
expressing viscosity as a function of temperature are less accurate for
amorphous concentrated solutions than the WLF model, many empirical
equations used to describe experimental viscosity-temperature data both
for aqueous solutions and supercooled sugar melts are found in the
literature. Among these are the Vogel-Tammann-Fulcher (VTF) equation
(Angell et al., 1982):
1]
= A exp (B(T-To ))
(6.26)
and the power-low equation (Hill and Dissado, 1982):

(6.27)
where To and T' g are reference temperatures, A, B, A and r constants.
The sucrose literature involves some of these relations of the Arrhenius
type like Kaganov's equation (1949) (1] = AebN1I) where A and bare
constants, N the concentration and T the temperature, and the relations
proposed by Pidoux (1961) and Barber (1966).
Doolittle (1954) expressed viscosity as a function of free volume using an
Arrhenius equation:
f
1]
= A exp (B VjV r)
(6.28)
135
where A and B are constants V f = V - Va, V f being the free volume, V the
specific volume and Va the volume occupied at OK (absolute zero)
obtained by extrapolation of a V - T plot. Using a modified Arrhenius
equation and Doolittle's relation (6.28), Miller (1963) found that such a
model is applicable even to associated liquids like water if non-bound
water is taken as the free volume. The Eyring theory was adopted by
Thomas (1965) who found an empirical relation in which the ratio of the
activation energy of viscous flow to the energy of vaporization at the same
temperature is in good correlation with the size, shape and polarity of
the solute molecule. The viscous flow does not seem to rupture hydrogen
bonds in associated liquids (Thomas, 1965). The absolute reaction-rate
theory of Eyring was found to fit for both Newtonian and non-Newtonian
flow and to agree with Einstein's equation (Utsugi and Ree, 1971).
Dynamic viscosity of pure sucrose solutions as well as diffusion and
molecular structure of these solutions were interpreted using the free
volume theory (Erszterle, 1990). Free volume was found to decrease
linearly with sucrose concentration in undersaturated solution and to
diminish with increasing supersaturation in supersaturated solutions.
Equations were proposed for viscosity in both regions of saturation and the
computed values compared to experimental results (Erszterle, 1990).

6.2.4.1 Dilute solutions. The values of intrinsic viscosity [ll] Huggins
constant (k') and the B coefficients of sucrose and the monosaccharides (Dglucose and D-fructose) constituting it are listed in Table 6.1. Intrinsic
viscosity accounts for the hydrodynamic volume of solute and k' for the
interactions between solute and solvent. To interpret these viscometric
constants two other characteristics of sugars in dilute aqueous solutions,
the apparent specific volume and h, the hydration number derived from
the apparent molar volume B coefficient (Mathlouthi et al., 1993), are given
in Table 6.2.
Comparison of intrinsic viscosity [ll] to apparent specific volume V~
comes to compare a hydrodynamic to a static volume. Likewise, k'
Table 6.1 Intrinsic viscosity [ll] and Huggins constant k' for o-glucose, o-fructose and
sucrose (25C)
Sugar
o-Glucose
o-Fructose
Sucrose
[ll]
(em) g-I)
k'
2.38
2.28
2.41
0.89
0.84
0.95
136
SUCROSE
Table 6.2 Apparent specific volume (ASY) and hydration number for o-glucose, o-fructose
and sucrose (25C)
Sugar
o-Glucose
o-Fructose
Sucrose
h
(water per mole of sugar)
0.62
0.61
0.62
3.45
2.87
6.63
-----~----
-~-
-u-
-----~-----
Scheme 6.1 Schematic representation of the flow of a hydrated solute showing the
hydration water).
deformation of force lines around the solute
describes a dynamic hydration whereas h measures a static hydration. k'

accounts for the effect of the flowing solute molecule on the bulk water at a
certain distance beyond the primary hydration shell given by h the number
of molecules of water bound to the sugar and affecting its kinetics
properties (viscosity, diffusion ... ) (see Scheme 6.1).
The solution properties listed in Tables 6.1 and 6.2 were found helpful in
interpreting the ease of accession of sugars to the receptor site of the taste
bud (Mathlouthi et al., 1993). Pauling (1946) has stressed the fact that the
sizes and shapes of molecules are of great significance in determining their
physiological behaviour.
6.2.4.2 Concentrated solutions. The standard values of viscosity of
sucrose solutions adopted by ICUMSA are the data tabulated at the
National Bureau of Standards (NBS) by Swindells et al. (1958) supplemented by the viscosity table for concentrated pure sucrose solutions
(75-85Brix and 5-80C) published by Schneider et al. (1963). These data
are reported in chapter 8.
137
Analysis of the NBS-Schneider results was performed by Genotelle

(1978). An empirical relation was found to fit with a good accuracy ( 1 %)
with these results. A temperature function (<p = (30-t)/(91 + t) ) valid for
water was corrected as a function of concentration. This relation is
log II = 22.46 N - 0.114
+ <p
(1.1
+ 43.1
N1.2S)
(6.29)
where N = (BI1900 -18 B) is the mole fraction of sucrose B being Brix and
<p = (30 - t)/(91 + t), t being the temperature. The good fitting between
viscosities obtained from equation (6.29) and NBS-Schneider results are
illustrated in Table 6.3.
Table 6.3 Comparison of experimental and calculated values of viscosity of pure sucrose
solution (mPa s)
Temperature (0C)
% MS
10
20
30
40
50
60
70
80
Ref.'
B=O
1.30
1.27
1.00
0.97
0.80
0.77
0.65
0.63
0.55
0.54
0.47
0.47
0.41
0.41
0.36
0.37
I
3
20
2.64
2.71
1.95
1.97
1.49
1.51
1.18
1.20
0.97
0.99
0.81
0.83
0.68
0.72
0.68
0.72
I
3
30
4.49
4.70
3.19
3.26
2.37
2.40
1.83
1.86
1.47
1.49
1.20
1.23
1.00
1.04
0.85
0.90
1
3
40
9.17
9.76
6.17
6.35
4.37
4.44
3.24
3.28
2.49
2.53
1.97
2.01
1.60
1.65
1.32
1.39
I
3
50
25.2
26.8
15.4
15.8
10.1
10.2
6.99
7.03
5.07
5.11
3.81
3.87
2.94
3.04
2.34
2.45
I
3
60
III
118
58.5
59.7
33.8
33.8
21.0
20.9
14.0
13.8
9.66
9.66
6.98
7.06
5.20
5.35
I
3
65
313
330
147
149
77.3
76.9
44.4
43.8
27.5
27.1
17.9
17.8
12.4
12.4
8.81
8.94
I
3
70
1206
1250
482
485
222
220
114
113
64.4
63.4
39.0
38.5
25.0
24.9
16.8
16.9
I
3
75
7402
7478
2328
2340
885
889
389
391
193
193
105
105
61.4
61.4
38.3
38.3
I and 2
3
80
93300
93000
20700
21250
6280
6195
2250
2180
855
890
394
409
203
207
114
114
2
3
85
4.21.106
4.18.10 6
541000
579000
111000
111100
30000
27450
7000
8270
2740
2920
1170
1174
598
525
2
3
'Experimental values taken from: 1, Swindells et al. (1958); 2, Schneider et al. (1963).
Calculated values from: 3, Genotelle (1978).
138
SUCROSE
6.3 Viscosity of impure solutions

Most of results reported in the literature show that pure sucrose solutions
as well as industrial run-offs, syrups and molasses have a Newtonian
behaviour in the whole range of concentrations and temperatures practised
in sugar factories. However, it happens that, in presence of macromolecular
impurities (dextrans, pectins ... ), the rheological behaviour becomes
pseudo-plastic or viscoelastic. Each of the constitutents of the non-sucrose
in technical sugar solutions, because of its specific association with water,
may exert a specific influence on the viscosity of sucrose solutions. Most of
the equations proposed to predict the viscosity of impure solutions are
empirical adaptations of the relations described above for pure sucrose
solutions.
6.3.1 Relations applicable to homogeneous phases

One of the earliest relations used in sugar factories is that of Kaganov
(1949). This relation was adapted by Silina (1953) to draw a nomogram
permitting estimation of the viscosity of molasses at different temperatures
and concentrations providing that the viscosity is known at a certain
concentration and temperature.
The availability of mathematical relations for the calculation of viscosity
is needed in the sugar factories, especially as the means of rapid
computation are widespread and the usefulness of rheology is recognized
both for simulation research programs and for process control.
Wagnerowski (1976) proposed, for the Polish molasses, an equation
comparable to equation (6.18) where only the coefficients are modified:
2440
log II = N ( - - - 6.66) - 1.70
t + 63
(6.30)
where N = B/(1900-18 B) is the mole fraction of sucrose, B being the

apparent % of dry matter (refractometric 1/1Brix). For intermediate
products between molasses and pure sucrose solutions, Wagnerowski used
a relation derived from equations (6.18) and (6.30) taking into account the
purity of product. It may be noticed that N is calculated supposing that
molecular weight of apparent dry matter is equivalent to that of sucrose.
Although this is far from being true, equation (6.30) proves to be useful for
the Polish molasses.
The application of equation (6.29) was extended to all industrial beetsugar solutions (Genotelle, 1978). The dry matter content expressed by
'Brix' was corrected considering the effect of non-sucrose on its measured
value and the effect of the composition of impure solutions on the specific
viscosity. This yielded the following formula:
139
10g'YJ = 22.46 N-2.114
 (1.1
43.1 A X N1.2s)
(6.31)
with N = (BJ(1900-18 B o )); B o = B a (k + (1 - k) X PllOO), = (30 - t)1

(91 + t) and A = 0.85 + 0.15PllOO, Band P are, respectively, the % of dry
substance and the purity of product; k being a coefficient of calibration
obtained from an experimental value of the viscosity of molasses.
The flow behaviour of cane molasses was found non-Newtonian (Kanga
and Raja Rao, 1978) fitting with a power law model of equation expressing
the wall shear stress Cw as a function of the dimensions of tube and the
pressure drop:
Cw =
D!!.P
---=k'
4L
8V
(6.32)
( _ ) nt
where D and L are diameter and length of the tube, !!.P the pressure drop
along the tube, V the velocity of fluid, k' is the flow consistency and n', a
behaviour index (k' = ke E1RT) where E is the activation energy of flow and
T the absolute temperature. k' and n' were calculated from the application
of equation (6.32) to molasses and the results found useful for the design of
pipes.
6.3.2 Relations applicable to heterogeneous phases

The fluids flowing in the crystallization station of a sugar factory are
heterogeneous in nature (mixtures of syrups and crystals) called massecuites.
The rheological behaviour of the massecuites is different from that of
concentrated homogeneous solutions. The mathematical treatment of such
mixtures is complex and most of the relations given in order to predict the
viscosity (or consistency) of massecuites are empirical. They tend to find a
correlation between the viscosity of molasses and that of massecuites. Silina
(1953) studied the viscosity of beet low-grade massecuites. She found that
this parameter obey's Poiscuille's law and is proportional to the mothermolasses viscosity. She also found a relationship between the percentage of
crystals in the massecuites and the ratio of viscosities of massescuites and
molasses. These results are summarized in Table 6.4.
Viscosity of beet molasses and massecuites were extensively studied by
Wagnerowski (1983). He proposed a modified Silin equation to express the
relation between the viscosity of massecuites and that of mother liquor:
log
'YJMC
- = 0.01326 X
'YJEM
B MC
85
85 - Cr
1)
(6.33)
where 'YJMC and 'YJEM are the viscosities of a massecuite and its mother
liquor; B MC being the % dry substance of massecuite and Cr the % of
crystals. A relation was established for Polish beet massecuites with 42% of
140
SUCROSE
Table 6.4 Ratio of massecuites to molasses viscosities T]MClT]mol

as a function of crystal content
Crystals % massecuite
30
4.35
6.58
11.24
14.50
19.25
26.3
35.7
35
40
42
44
46
48
crystals at a given temperature (8); the optimal cooling temperature being

(8 op!) (Wagenerowski, 1983):
log
T]MC(e)
40
8op! -
12.5
+ 0.3158
+ 10~
- 0.267
130
log-8 + 50
(6.34)
This empirical formula is important for mastering the process of lowgrade crystallization.
More recently (Broadfoot and Miller, 1990), found that the nonNewtonian behaviour of massecuites and molasses can be adequately
described using a 'Power law' model:
(6.35)
where 't is shear stress at the interface of fluid and the shear producing
element, K is the consistency, and Yis the shear rate and n the flow index.
The viscosity, fl, of the massecuites and molasses which generally show a
pseudo-plastic behaviour is derived from equation (35) and expressed by
(6.36)
where Yeorr is the corrected shear rate at the interface. For pseudo-plastic
material n varies between 0 and 1 and shows an increase in pseudoplasticity as it goes away from unity. The range of shear rates usually found
in sugar factories lies between 0.1 and 10 S-1 (Broadfoot and Miller, 1990).
The influence of temperature T on the consistency K of massecuites was
expressed by an exponential relation (K = Ae-mt ) (Diaz Garcia, 1977). The
same author established from this relation and other empirical formula of
consistency taking into account the crystal content, nomograms predicting
the influence of temperature and crystal content on the viscosity of
massecuites.
141

The rheological behaviour of molasses and massecuites depends on their
composition. Cane sugar molasses were found to exhibit pseudo-plasticity
mainly due to soluble colloids (gums) (Smolnik and Delavier, 1972)
whereas beet molasses have shown a viscoelastic behaviour (Devillers and
Phelizot, 1971).
6.3.3.1 Homogenous phases. Different factors affect the viscosity of

molasses. Among these are the increase in concentration and the
composition of inorganic and organic non-sugars.
6.3.3.1.1 Effect of inorganic non-sugars. The concentration of cations
and anions in low-grade products greatly affects the solubility of sucrose.
The influence of non-sugars on sucrose solubility is estimated by use of an
empirical relation and a laboratory test called the 'Polish test' very helpful
in beet sugar factories (Wagnerowski, 1983). Another parameter influenced
by non-sugars is the concentration of molasses and run-offs. The
measured value of % DS is far more from the true value (obtained by
desiccation in an oven or by Karl Fischer titration) the more the non-sugar
amount is high. These discrepancies are of major importance in comparing
the viscosities of pure and impure solutions. The proportion and nature of
cations determines the reasons for viscosity increase in impure
solutions. Their effect augments as follows: K+ < Na+ < Ca2 + < Mg2 +. It is
combined to that of anions which show increasing influence: N0 3-<CI-<
glutamate < lactate. The global effect is linked to the importance of
hydration of sucrose and non-sugars as well as the possible formation of
sucrose-eations adducts. The effect of cations added to pure sucrose
solutions was investigated both for their basic molecular association
interest (Misra and Misra, 1977; Mohanty et al., 1981) and for the factory
concern (Breitung, 1956; Khalikovskii, 1965). The effect of some cations
and anions on the viscosity of saturated sucrose solutions at 40C is
illustrated in Figure 6.2. It should be noticed that Mg 2 +associated with Ciprovokes an increase in the viscosity of saturated sucrose solution more
than ll-fold. This is especially interesting as Mg 2 + is exchanged against
Na+ and K+ in an ion exchange process (Quentin process) to improve
molasses exhaustion.
6.3.3.1.2 Effect of organic non-sugars. The non-Newtonian flow of
molasses is mainly due to the presence of organic macromolecules
(dextrans, gums). Macromolecular components of cane molasses were
obtained after dialysis of the dilute syrup (Cortis-Jones et al., 1963). The
fraction having the highest effect on molasses viscosity is composed of
polysaccharides. The dextran of bacterial (Leuconostoc mesenteroides)
origin has the major effect. The increase in viscosity under the effect of
142
SUCROSE
10
6
4
2
o
o
K+ Na+ Ca++ Mg+ + Betaine Invert
Figure 6.2 Effect of some anions and cations as well as of betaine and invert on the viscosity
of sucrose solutions at 40C. (Tl,lTls) is the ratio of impure to pure saturated solution.
(Adapted from Breitung (1956).)
dextrans (Geronimos and Greenfield, 1978) was investigated and a

mathematical relation of viscosity as a function of dextran concentration
proposed. The pseudo-plasticity induced by dextrans in pure sugar solution
was less important than in molasses. In cane sugar molasses, the pseudoplastic behaviour was much more correlated with temperature than with
concentration (Smolnik and Delavier, 1972).
Another class of organic additives used to decrease molasses' viscosity is
that of surface active agents. This topic has been reviewed (Berger, 1976).
It was reported that several surfactants are efficient in reducing viscosity
and enhancing crystal yields. However, the dosage of surfactants seems to
be critical in obtaining the optimum viscosity.
6.3.3.2 Heterogeneous phases.
The rheological behaviour of massecuites

was found pseudo-plastic at low shear rates and approaching the
143
Newtonian flow at higher shear rates (Ness, 1979). Results of determination

of massecuites viscosity depend on the method of measurement. The
pipeflow method was offered as an alternative to the rotating cylinder
method (ICUMSA, 1990) for determining the rheological properties of
molasses and massecuites was found to depend on the tube dimensions.
Wall effects which are at the origin of discrepancies of the results are
minimized with a large LID ratio (Ness, 1980).
The viscosity of massecuites depends on the crystal content, crystal size
and shape as well as on the size distribution of crystals and the viscosity of
molasses (Rouillard and Koenig, 1980). The effect of crystal content was
determined by Silina (1953) (see Table 6.3). They were found comparable
to more recent data (Rouillard and Koenig, 1980). Another approach
consisting in calculating the velocity of flow of crystals in a massecuite
considered as a fluidized bed permitted Kelly (1957) to calculate the crystal
content in which massecuite loses fluidity. It was even established that
crystals are more compressed in massecuite than in granulated dry sugar
(Kot et ai., 1968).
Another source of heterogeneity is the entrapped gas in molasses and
massecuites. Wagnerowski and Dabrowski (1965) evaluated that the
incorporation of 20 ml of gas per g of molasses provokes the doubling of its
viscosity. The effect of entrapped gas was also found to increase the
pseudo-plastic behaviour (lower value of n in equation (6.35)) and the
consistency of molasses (higher value of K). The entrapped gas may have
as its origin in beet molasses a fermentation which occurs in immature or
frozen beets (Wagnerowski et ai., 1961).
6.4 Methods for determining viscosity and flow properties
Various types of viscometers and empirical devices for determining the

rheological properties of sucrose solutions, molasses and massecuites were
used in laboratories and in the factories. The principles of measurement
encountered may be classified as follows:
flow time in a capillary tube;
rate of fall of a calibrated sphere in the viscous medium;
torque required to rotate a solid body at a definite angular velocity in a
viscous sample;
damping effect of a medium on a thin plate vibrating in the medium;
and
rate of flow under pressure through orifices and pipelines.
The different methods are grouped, depending on the interest in their
use, as laboratory or factory methods.
144
SUCROSE
6.4. J Laboratory methods

6.4.1.1 Capillary viscometers. These viscometers measure the time
necessary for a given volume to flow through a capillary. If l is the length of
capillary, r its radius and P the pressure difference under which a
Newtonian liquid flows, the friction force per unit surface is equal to the
product of viscosity, lJ, by the gradient of velocity dv/dr (Champetier and
Monnerie, 1973) for a laminar flow, we have
dv
Pr
dr
2lJl
-=-
(6.37)
Intergration of equation (6.37) yields a parabolic expression:

V
22
=-(R - , )
4lJl
(6.38)
From equation (6.38) and the volume Q of liquid flowing in the time t,
an expression of viscosity is derived:
lJ
rrR 4
= -Pt
8Ql
(6.39)
This value of viscosity is only valid for laminar flow. Absolute viscosity is
derived from equation (6.39). What is measured is the time t necessary for
a volume Q to flow in a vertical capillary. Writing equation (6.39) as t = f
(lJ) is known as the Poiseuille law:
8Ql
t =
:rtr4 p
lJ
(6.40)
Corrections must be made to account for the convergence and

divergence of streamlines respectively at the inlet and outlet of capillary
(Couette correction) and considering the fact that a part of the pressure P
is used to communicate the kinetic energy to the liquid instead of
vanquishing the friction forces. Corrections were discussed in detail for
capillary viscometers used for polymers (Vanwazer et al., 1963; Champetier
and Monnerie, 1973). Capillary viscometers are generally used for dilute
solutions to determine intrinsic viscosity. Their dimensions and conditions
of utilization were previously (Mathlouthi and Kasprzyk, 1984) commented.
Results obtained with an Ubbelhode capillary viscometer are listed in
Table 6.1 for sucrose, glucose and fructose.
6.4.1.2 Rotating viscometers (Couette type). Viscosity depends on shear

rate. It is necessary to vary this rate to measure viscosity of sugar solutions
and suspensions with rotating viscometers and coaxial cylinders. The
studied sample is placed in the space between the two coaxial cylinders.
145
One of the cylinders rotates at an angular velocity (w), the other is fixed.
The torque (C) resisting to shear stress is measured on the axis of one of
the cylinders (the rotating one). To each velocity (w) corresponds a shear
rate (y). Variation of shear rate may be obtained continuously or
discontinuously. Shear stress values (0) are proportional to torque values.
Viscosity derives from the ratio of shear stress to shear rate (TJ = 0/ y);
TJ is expressed in Pa s; 0 in Pa and y in S-I.
6.4.1.3 Falling-ball viscometers. This measurement is based on Stokes law.

When the movement of a falling sphere takes place under gravity with a
velocity v, the friction force F exerted on the sphere with a radius R in a
liquid of viscosity TJ is
F
=-Jt
R 3 (Q - Qo)g
(6.41)
where Q and Qo are specific gravities of the sphere and the liquid,
respectively. In steady state conditions viscosity 'TJ is expressed by
'TJ=
2gR 2
(Q -
9v
Qo)
(6.42)
However, corrections should be made to take into account the influence

of the proximity of the walls. Moreover, the falling ball is not suitable to
measure the viscosity of very viscous and dark liquids like molasses. This is
the reason why it was recommended by ICUMSA (1990) to delete it as a
suitable alternative method for measuring the viscosity of molasses.
6.4.2 Factory methods

Industrial viscosity measurements are generally derived from laboratory
methods and adapted to the specific problems posed by the flow of the
products. The use of viscometers to control crystallization was reported in
a review of automatic pan boiling (Knovl and Moller, 1976).
6.4.2.1 Rotating viscometers. The viscometers most used in the sugar

industry are the Couette type viscometers. The theory is the same as
described above. However, it is recommended that the geometry of the
measuring system, particularly the ratio of the diameter of the spindle to
the diameter of the coaxial cylinder reservoir, should be defined and the
extent of its influence on the parameters of the Power law (equation (6.35))
determined (ICUMSA, 1990). The rotating cylinder viscometers were
found satisfactory and adopted as the official method by ICUMSA (1978).
The range of viscosities covered by these viscometers is wide (10-3 to 105 Pa s).
Their accuracy may be tested using silicone standards with known absolute
viscosities (Kitterman, 1974).
146
SUCROSE
Beside the analysis of viscosity of molasses, run-offs and syrups, the

rotating body viscometers were also applied to control low-grade cyrstallization stations. The cooling of massecuite and dilution before centrifugation may be monitored by use of a rotating viscometer. It is needed that
set values be regularly checked with a laboratory measurement and that
the rotating body be rinsed from time to time to avoid the formation of
crystal crusts.
6.4.2.2 Pipeflow viscometers. Instruments employing the principle for the

rate of flow of a fluid under pressure through a pipeline can measure a wide
range of viscosities (10-2 to 10 10 Pa s). This principle is comparable to that
of the capillary viscometer. Comparison of pipeflow to rotating viscometer
in determining low-grade cane massecuites viscosity was made (Ness,
1983). The shear stress Tw and shear rate Yw at the wall of pipeflow
viscometer were derived from experimental data. The viscosity of the
massecuite is given by
l)
Tw
= --with
Yw
Tw
DI1P
4L
and
where D and L are, respectively, the diameter and length of the tube, 11 P
the air pressure applied, V the average flow velocity, n 1 the slope of the
loglog plot of T w versus 8V/D. Applying the power law, this plot Tw is
linear and n J is a constant written as n (Ness, 1983). The flow index n was
found independent of the tube dimensions and the consistency dependent
on D and L.
6.4.2.3 Other viscometers. Viscosity measurements for factory, laboratory or process control do not need to be as accurate as research results.
However, one should be aware of the importance of performing the
measurements at the good shear rate. For pseudo-plastic products, a single
viscosity value is useless. A more complete information is provided by the
rheological behaviour obtained in a wide shear range or from consistency
and behaviour index derived from the Power law. Among the instruments
utilizable for massecuites are the orifice and vibrating viscometers. The
flow properties were investigated for massecuites by measuring the head
loss across an orifice at a given flow rate (Maudarbocus, 1980). The
obtained results were comparable to that of the pipeflow viscometer. In the
vibrating instruments, the rate of damping of vibration of a probe is
measured. The probe may be a metallic strip or a sphere immersed in the
147
liquid or the massecuite. The viscosity of massecuites measured by an

ultrasound viscometer was found to be less influenced by the crystals
content than that obtained with a rotating viscosity (Ahari et al., 1967).
The use of viscosity-eonsistency instruments was analysed and the
problems posed by automatic control of crystallization especially for the
effect of crystal content on rotating viscometers discussed (Schliephake
and Austmeyer, 1975).
6.5 Applications
The viscosity of sucrose solutions is important for more than one purpose.
Viscosity of pure solutions may be used to calibrate viscometers. In the sugar
factory, the rheological characteristics of syrups and masscuites play a
major role during the boiling and the crystallizing processes. It is a limiting
factor for the workability of low-grade masscuites and hence for the yield
of sugar extracted.
6.5.1 Effect of viscosity on crystallization
Crystal growth in a supersaturated solution may be roughly divided in two

steps:
(1) a diffusion step consisting in the transfer of more or less hydrated
sucrose molecules from the bulk solution to the vicinity of the
crystal; and
(2) an integration step consisting in incorporating the vicinal molecules
in the crystal lattice after disassociation of hydration water.
The rates of the two steps are different depending on temperature. For
temperatures above 40C commonly applied in sugar factories, diffusion is
the limiting step. As diffusion coefficient is inversely proportional to
viscosity, the rate of growth (R c ) may be expressed by
R c = K (0 - 1)1'Yl
(6.43)
where 0 is supersaturation and 'Yl viscosity, K being a constant. It appears

from equation (6.43) that at a constant supersaturation an increase in
viscosity provokes a decrease in growth rate. However, the role of viscosity
in crystal growth seems controversial. For Van Hook (1981) the limiting
parameter is the orientation and incorporation of molecules to the faces of
the crystal rather than viscosity. An other argument is that certain colloids
(acacia gums, pectins and starch) increase tremendously the viscosity of
sugar solutions but have no effect on crystal growth (Van Hook, 1952).
This argument was criticized by Silin (1958) who considers that colloids act
148
SUCROSE
as screens for sugar molecules. They increase viscosity but do not limit
diffusion and crystallization rate.
It is to be noted that for the same concentration in dry matter, viscosity
increases rapidly when the purity is lowered for saturated solutions
(Maurandi, 1971). On the other hand, viscosity dependence on temperature
does not follow the same behaviour for high and low purity products. This
is observed in Figure 6.3. For purities close to 100%, viscosity decreases as
temperature is increased above 80-90C. However, for lower purities, it
may be observed (see Figure 6.3) that viscosity reaches a minimum, and
this minimum takes place at lower temperatures for lower purities. The
optimum is situated at 40C for molasses, which is the usual end of cooling
of low-grade massecuites. Therefore, it seems wrong to work at very high
temperatures in low-grade boiling. This corresponds to lower crystallization
rates and lower crystal yields. For first strike boilers, the temperature is a
Log 11
- ---
0.8
"
,/
0.6
0.4
0.2
P:90
40
60
80
'C
100
Figure 6.3 Variation of viscosity as a function of purity and temperature. (- - -) b = 1.05;

( - - ) 0 = 1.0.
149
compromise between the crystalIization rate (favoured at high temperatures) and the crystals yield (higher at low temperature). In general, the
optimum is situated at 80C.
6.5.2 Effect of viscosity on molasses formation and exhaustion

The growth of sucrose crystals in low purity media such as molasses is
considerably reduced under the effect of an increasing viscosity whereas
the limit of exhaustion only depends on temperature, concentration in nonsugars and the specific effect of the non-sugars on solubility. This effect is
expressed by the equation relating the solubility coefficient (K sat ) to nonsugars expressed as the ratio of non-sugars to water content (NS/W): (K sat
= a (NS/W) + b). This expression is at the basis of the 'Polish test' of
control of molasses exhaustion. Although the Mg2 + ion is known to
enhance viscosity as compared to (Na+ and K+) it proves to be a good
means of molasses exhaustion because of a favourable effect at Mg2 + on
the saturation coefficient Ksat . Apart from increasing the viscosity, the ion
exchange yields a higher apparent refractometric Brix although the
exchange of cations decreases the weight of dry matter. PracticalIy the
ratio of actual to apparent non-sugars is 0.89 for Quentin products against
0.93 for usual molasses. Sucrose solubility is decreased because of the
important hydration of sucrose and Mg 2 +, which leads to a decrease in the
slope of the saturation coefficient (Ksat = a (NS/W) + b). As an example,
the characteristics, especially viscosity, of molasses brought to saturation at
50C are compared with the same molasses after 60% of ion exchange
(Quentin), without any change in water content (Table 6.5).
From these data, it is observed that the ion exchange provokes an
important increase (X2.5) of viscosity. After crystallization of sucrose in
the Quentin molasses to reach saturation, at constant NS/w ratio, its
characteristics become: apparent Brix = 85.7%; a = 1.0, purity = 52.3%
and 'Y) = 3500 mPa s. It is noticeable that the increase in viscosity due to
Mg 2 + is practicalIy compensated by a better exhaustion of molasses, which
Table 6.5 Comparison of molasses before and after ion exchange (Quentin)
Parameters
Polish test coefficients
a
b
Viscosity of a test sample (8 = 85, T = 45C)
Apparent refractometric Brix
Apparent purity
NSIW
Supersaturation
Viscosity
Initial
Quentin
0.28
0.68
3000 mPa s
86.5%
58.0%
2.70
1.0
0.17
0.72
5000 mPa S
87.4%
59.0%
2.85
1.31
10200 mPa s
4000 mPa s
150
SUCROSE
occurs after bringing the molasses at saturation to a lower viscosity.

However, it is difficult to estimate the real gain in yield because the routine
analysis gives apparent values which are not comparable for treated and
non-treated molasses.
Wagnerowski (1983) thinks that viscosity is not a fundamental parameter
in optimizing molasses exhaustion. He recommends to reduce the viscosity
of massecuites by reducing the crystal contents with a preliminary
centrifugation of low-grade massecuites. It is theoretically possible to
reduce the purity of molasses by lowering the temperature. However, this
needs a very long time and the viscosity reaches very high values beyond
the limits of the equipment. Practically, a 'standard' viscosity of molasses
was defined by Silin (1958) with the following characteristics (Brix = 82; T
= 40C, 'YJ = 4400 mPa s), which corresponds to a limit of mother liquor
viscosity in the centrifuges = 7000 mPa s. These values are now pushed
beyond these limits because of improvement of materials power. Taking
into account both the results of Polish test and reference viscosity a graph
was drawn (see Figure 6.4) to give an overall view of the effect of the
conditions of work on molasses exhaustion. For example, the purity of
85
:!>
' so
:!>
'~
\Q
\~
80
,,
,
\
\0
\
,,
0"01.05
55 L.r------.-----r--~-r---~~
3.5
3
2
2.5
lSI.
Figure 6.4 Effect of work conditions on molasses exhaustion. For a standard viscosity at
50C,1] = 300 Pa.s, the Polish coefficients being a = 0.30 and b = 0.70. From the NSIW ratio
it is possible to deduce saturation, viscosity and purity of molasses.
molasses is about 58% for T

Pa s); (see Figure 6.4).
151
= 50C, 0 = 1.05 and T] = 10 000 mPa s (1000
6.5.3 Effect of viscosity on machines running

Sizing of pumps, pipes and flow orifices is calculated in function of the flow
rate and the viscosity of product so that head losses are limited to
acceptable values. For concentrated sugar solutions like syrups, run-offs,
molasses and massecuites an important margin of security is needed
because the fluctuations of viscosity may limit the flow. For low-grade
products the compacity of massecuites may reach values as high as 1000 Pa s.
An on-line control of viscosity limits this value to 300 Pa s at the inlet of
pumps. The efficiency of separation centrifugals which is at the basis of raw
sugar quality needs that mother liquor viscosity is limited to about 10 Pa s
for discontinuous machines and 30 Pa s for the continuous ones.
The rheological properties of technical sugar solutions have been taken
into account for the calculations of the diameters of pipes and orifices and
for the conditions of work in crystallizers and centrifuges (Blanc, 1970;
Gebler and Ciz, 1979). It was shown that the factors governing the laminar
flow of massecuites across circular or rectangular apertures are derived
from viscosity measurements and equations.
6.6 Conclusion
Viscosity of sugar solutions is important both from the basic and practical
point of views. The mathematical treatment of viscosity shows the
complexity of the problem. This is due to the solvation and molecular
association in pure sucrose solutions. In presence of impurities or crystals
in suspension it is necessary to apply empirical relations. Most of the
equations applied either to pure or impure solutions are derived from
polymer science studies. The values of the viscosity of pure sucrose solutions
have been measured for a long time and adopted as a means of calibration of
viscometers. However, the rheological properties of run-offs, molasses and
massecuites need to be known accurately so that a good method (rotating or
pipeflow viscometer) be adopted and that the measurements be performed
in the good shear rate range. Although viscosity is a limiting factor to
diffusion, the real effect in low-grade products depends on the nature of
each non-sugar component and needs to be elucidated at the molecular
level. Hydrodynamic problems posed by friction in pipes, pumps and
centrifugals as well as crystallization rates can be better investigated by use
of rheological characteristics of technical sugar solutions.
152
SUCROSE
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Analysis of sucrose solutions

J.P. LESCURE
7.1 Introduction
The role of the analyst is to give the possessor or the user of a product or a
substance quick and precise answers to any question related to its
characterization, its dosage and its technological value. In this chapter, we
intend to gather elements which may serve this purpose for all types of
high-sucrose solutions, from technical sugar solutions to liquid sugars or
processed products. This paper will also deal with issues of quality, from
the point of view of both norms and regulations.
Sucrose and other carbohydrates can be easily distinguished, either by
taste or by means of easily developed physical and chemical reactions. The
taste of sucrose is always taken as the reference taste. Its quality of taste
provides sweetness, smoothness and mouthfeel that are difficult to
duplicate.
Chemical characterization of sucrose may use colorimetric reactions,
oxidation-reduction properties, or chromatographic separations. The
process can be performed on sucrose solutions directly, on a product dried
in an oven at atmospheric pressure (130 2C), in the case of sucrose
solutions, or under a reduced pressure of 3.4 kPa (34 mbar), in the case of
a reducing-sugar-enriched mixture.
For colorimetric reactions, the most common reactions are performed in
the presence of sulphuric acid. Dehydration reactions occur after hydrolysis
by warm drying, leading to the formation of deoxyulose, which yield to 5hydroxymethyl-2-furaldehyde (HMF), as well as further degradations of
no interest here.
Colorants in the visible wavelength can be easily obtained from
chromogenic HMF, whose absorption band in the ultraviolet range is quite
strong at about 280 nm. The so-called Molisch reaction is the most usual
one: the addition of a newly prepared solution of a-naphthol and
concentrated sulphuric acid leads to the formation of a highly characteristic
violet-red ring. In the presence of sulphuric acid, it is also possible to add
other chromophoric radicals that shift the absorption towards visible
wavelengths, for instance, orcinol at 420 nm, anthrone at 585 nm and
phenol at 480 nm. These reactions, which are not highly selective, are
common to all sugars. They are widely used in biology for the titration of

156
SUCROSE
total sugars. They are still commonly used to reveal stains after sugar
separation by thin-layer chromatography.
Sucrose does not have a free carbonyl group in its molecule and does not
give any of the reactions specific to reducing sugars. More particularly, it
does not react with a hot copper solution in an alkaline medium. After acid
hydrolysis, the glucose-fructose mixture easily reacts with a boiling copper
solution and gives a red-orange cuprous oxide precipitate.
This behaviour is quite typical of a non-reducing oligoside. It is an
effective indicator of the presence of sucrose, that can be easily confirmed
through thin-layer chromatography or spectral analysis.
Thin-layer separation of sugars can be carried out on various supports:
cellulose, silica gel, magnesium silicate, kieselguhr, with the use of
adequate eluent. Many operation methods can be found in the literature
published sometime ago, such as the bibliographical review by Berger and
Borodkin (1967), or the monograph on thin-layer chromatography
published by Stahl (1969).
As already mentioned, sugar characterization involves colorimetric
reactions. Several specific colorants have been specially developed,
particularly a mixture of aniline and diphenylamine in a phosphoric acid
medium recommended by Berger and Borodkin (1967) in order to avoid
the interference of heterolevulosane I and II found in non-refined sugar
remelts. The European Pharmacopoeia (Anon., 1992) is still using a thinlayer chromatography technique on a silica gel support. The eluent is a
mixture of water/methanol/acetic acid/ethylene chloride (10:15:25:50).
Colour is developed with thymol in sulphuric acid at BOC.
The current development of gas chromatography and of high-performance liquid chromatography (HPLC) , which allow precise quantitative
dosage, has resulted in a more restricted use of thin-layer chromatography.
The latter serves mainly for identification purposes. It should be noted,
however, that Poole and Poole (1994) have reviewed the most recent
developments of this technique.
7.2 Sucrose identification by vibrational spectroscopy

Spectroscopic techniques basically result from the interaction of a radiation,
generally an electromagnetic radiation with matter. Although vibrational
spectroscopy requires specific laboratory equipment rather than mere
routine equipment, it is highly valued for its fast and accurate identification
of unknown substances. It is capable of rapidly generating highly
characteristic data which constitute a real fingerprint of the product.
157
ANALYSIS OF SUCROSE SOLUTIONS
7.2. I Infrared
Infrared spectroscopy has been greatly modified by the advent of powerful

computers and of Michelson's interferometer. It has been possible for the
last 30 years to record in a few minutes Fourier-transform infrared (Ff-IR)
spectra, which give a far better resolution than traditional grating and
prism devices. As an example Figure 7.1 shows an Ff-IR spectrum of
crystallized sucrose in the 4000-400 cm- 1 frequency range.
Information provided by this spectrum is essentially the same as that
provided by traditional infrared. Early work by Barker et al. (1954)
focused on a- and j3-anomers' characteristic bands and in pyranoidic
monosaccharides observed at 844 cm- l and 890 em-I. Shallenberger and
Birch (1975) have shown the narrow bands due to free OH groups at
3600 cm- 1 and that due to OH group linked by hydrogen bonds around
3400 em-I.
In spite of a wide range of water absorption in this area, multiple
correlations allow quick titration of sucrose in the near-infrared (NIR).
Recent developments of this technique are examined in the section
concerning sucrose titration. Comparative studies of vitreous state and
concentrated sucrose solutions were made by Mathlouthi et al. (1986) in
the range 1200-800 em-I, where water absorption is far more reduced
4000
2000
400
Figure 7.1 Ff-IR spectrum of crystallized sucrose in the (4000-400 em-I) wavenumber range.
(By courtesy of M. Mathlouthi, University of Reims, France.)
158
SUCROSE
(Figure 7.2). Dupuy et al. (1993) have shown how, in the middle infrared,
sample preparation may alter the actual performance.
(3)
1111
III
(b)
4111
2010
181
Figure 7.2 FT-IR spectra of aqueous solution (65% w/w) of sucrose (a) in the wavenumber
range (18Q0--800 em-I) and of maximally concentrated (85% w/w) amorphous solution; (b) in
the wavenumber range (400-800 em-I). (By courtesy of M. Mathlouthi, University of Reims,
France.)
159
As concerns identification, it should be noted to what extent operation

conditions can modify the infrared spectrum aspect. It is advisable to
conduct a comparison with a standard sample of pure product in the same
conditions. Maximum absorption levels should be observed at the same
frequencies.
7.2.2 Raman spectroscopy

The use of high energy permitted accurate data lasers with sucrose solutions
to be obtained. Mathlouthi and Luu (1980) have studied the structure of
a concentrated sucrose solution (W = 60%), and have constructed a table
of characteristic frequency bands with corresponding intensities (Table
7.1). This table could be extremely useful for identification purposes.
Nguyen Quy Dao et al. (1992) have mentioned applications of the laser
Raman technique, coupled with optical fibres, tested for the on-line
control of sugar solutions in the foodstuffs industry (fruit juices).
7.2.3 NMR spectroscopy

Proton spectroscopy was applied to sucrose by Lemieux and Stevens
(1966). The spectrum reveals the anomer proton, bound to the carbon
Table 7.1 Raman spectroscopy: Assignment of frequencies observed in aqueous solution
(according to Mathlouthi and Dang Vinh Luu (1980*
v (em-I)
1628
1456
1366
1340
1266
1130
1110
1064
920
836
746
640
600
548
528
470
456
416
374
16.4
33.6
45.7
37.8
25
68
60
89
25
100b
21
35.7
31.4
60.7
69
38
36.4
17.8
40
0.56
0.93
0.67
0.72
0.71
0.53
0.20
0.31
0.34
0.10
0.38
0.24
0.45
0.25
0.17
0.10
0.23
0.84
0.25
Attributions
b(HOH)
b(CH 2 )
w(CH 2 )
r(CH 2 )
1:(CH 2 )
b(COH)
v(C-O)endo
v(C-O)exo
b(C-H)
v(C-C)
b( CCO )endo(Fru)
b( CCO )exo(Fru)
b(OC0 1)
b(CCO)endo(GIc)
b(CCO)exo(GIc)
b(CCC)(Fru)
b(CCC)(GIc)
b(O-H-O)
b(COC)
*Key: /, = relative intensity; Q,

depolarization ratio; endo, = endocydic; exo, =
exocydic; Fru, = D-fructosyl moiety; b, = taken as reference; GIc, = D-glucosyl moiety; b, =
bending; w, = wagging; r, = rocking; 1:, = twisting; and v, = stretching.
160
SUCROSE
located between two oxygen atoms, the resonance doublet of which clearly
decoupled as compared with the other protons bound to other carbons of
the rings or to the hydroxymethyl groups of sucrose.
It should be noted that Lowman and Maciel (1979) have used Fourier
transform H NMR to determine sucrose content in beet press juice, based
on time decay of water resonance in presence of Cr(III). Different authors
(Mathlouthi et al., 1986; Grabka, 1993) have investigated the 13C NMR
spectrum of sucrose.
7.3 Methods of titration of sucrose
The following section gives a survey of the various techniques used to dose
sucrose or sucrose equivalent in technical or purified sugar solutions,
especially those which are marketed under the name of 'liquid sugars', or
more or less highly inverted sugar solutions. These techniques will mainly
be used for high-sucrose processed products. They involve either physical
or chemical properties of sucrose and reducing sugars, or biological
reactions.
7.3. I Physical methods
7.3. 1. I
Polarimetry
7.3.1.1.1 Saccharimetric scale. The rotatory power due to molecule

asymmetry is high for sugars, especially for sucrose. Considering Biot's
laws obeyed by a substance for a given radiation, rotation is proportional
to the path length and to the concentration of this solution.
Hence
[alA =
defines the substance's specific rotation for the radiation considered. [a] is
commonly expressed in degrees and tenths of degrees, the length I in
decimeters and the concentration c in g/cm 3 .
However, sucrose polarimetric titration is of such importance in the
sugar industry, and in trade and customs controls, that it has become
necessary to set up an operation method and a measuring instrument scale
in order to directly obtain the strength w for 100 g of analysed product.
The principle is based on the use of a strictly defined mass m o of the
substance to be analysed, the so-called 'normal weight' (or previously
'typical head'). This mass is always dissolved in the same volume of water
Yo, and rotation measurements are performed using a tube of constant
161
length, 10 , It is agreed that the rotatory power of sugar has a constant value
which does not depend on concentration. The measuring instrument is
scaled so as to directly give the strength w for 100 g of the analysed
solution. This is the basis of the International Sugar Scale. It is the result of
parallel efforts in different countries that led to the introduction of a single
scale. The various stages can be summarized as follows:
In Germany, Wentzke (1842-1843) attempted to determine a scale

using a solution with a relative density of 1.100 with respect to water at
17SC. This scale, based on old units, let to a 'normal weight' close to
26.003 g in vacuo and to a specific rotation for sucrose:
[aHJ5 = 66.685
In France, an attempt was made to define the value of 100 on the scale
using the rotation performed by the yellow doublet of sodium,
through a I-mm-thick quartz sheet at 20C. The corresponding
'normal weight' was determined after numerous investigations and
was finally fixed by the administration at 16.29 g weighed in air against
brass counterweights, and at 16.30 g weighted under vacuum. The
corresponding specific rotation of sucrose was:
[alba = 66.41
The lack of accuracy of these purely physical definitions led ICUMSA to
abandon them, during its first meeting in 1897, and to define a common
international scale based on an apparent 'normal weight' of 26 g, weighed
in air against brass counterweights, dissolved in 100.00 cm 3 of water, the
solution being observed at 20C using a 2 dm tube.
Pure sucrose sets the value 100 on the scale. The difficulty lies in
preparing a solution from a sufficiently purified sugar in order to determine
the corresponding angle with precision. To take into account advances in
the chemical and metrologic fields, ICUMSA redefined the angle at
the value of 100 on the scale in 1904, 1932, and finally reached the 1986
agreement resulting from extremely accurate and concording measurements
performed by the Physikalisch-Technische Bundesanstalt (PTB) ,
Brunswick, Germany, and by the Bureau of Standards, USA. Moreover,
in order to avoid any sort of confusion with the former values, it was
decided to change the notation of the international unit from oS to oZ.
The definition of the value 100 on the scale is currently as follows.
'Normal sugar solution' is defined as 26.016 g of pure sugar, weighed in
vacuum and dissolved in 100.00 cm 3 of pure water at 20.00C. This
corresponds to a solution of 26.0000 g of sugar weighed in air in normal
conditions (101.3 kPA pressure, 20C, and 50% relative humidity), in
100.000 cm 3 at 20.00C.
The value 1000 Z on the international sugar scale corresponds to the
162
SUCROSE
optical rotation of the normal sugar solution as defined, at the wavelength

of the green rays of the isotope 198Hg (A. = 546.2271 nm in vacuum, at
20.00C through a 200-mm-long tube).
In these standard conditions, the rotation angle is
[a]
20.OOC
546.2271
= 40.777 0.001
The following relation is used to determine the value 1000 Z at wavelengths

other than 546.2271 nm:
=a+
aO.S462271
where A. is the wavelength and a = -0.001 7982; b

+0.006 557 36; and d = + 0.000010 382 5.
Hence, for filtered sodium D-line:
[a]
20.ooC
589.4400
+-:;:s
= +0.276531 8; c =
34.626 0.001
In such conditions specific rotation for sodium D-line is expressed as

follows
100.34.426
= 66.59
=
2.26.000
if weighing is performed in air, or
=
100.34.426
2.26.016
= 66.55
if weighing is performed in vacuo.

Quartz-standards are defined according to this scale
It should be noted, however, that in current laboratory practice, the
accuracy of the saccharimeters cannot generally reach international
standards. In current practice, it is possible to use instruments with
standards established prior to 1986; the shift from the former S scale to the
Z scale can be easily made by cutting down the result by 0.029%.
Polarization is one of the most accurate measurements performed in the
laboratory. In order to preserve this accuracy, it is necessary to proceed as
cautiously as possible following the adequate laboratory practice as defined
by Schneider (1979). Here are some of the main principles:
Equipment must be carefully checked. Tubes need to fulfil the
ICUMSA requirements: they must be closed by strictly parallel cover
glasses, and should not produce any polarization when filled with
water and submitted to a gradual rotation of 180 around their axis.
163
Gauged glassware should be strictly standardized with distilled water.

In most cases, defecation is unnecessary as sugar solutions are clear
enough. It would otherwise be necessary to perform defecation with basic
lead acetate, in the proportion of 1 cm 3 of basic lead acetate of density to
1.24 0.01 of water, for 100 cm 3 . For more detailed information, readers
are referred to the ICUMSA (Anon. 1994a) methods.
Hygiene and environment concerns have prompted the study of other
defecants, but basic lead acetate is the only one to be currently recognized
worldwide.
Measurements are only valid if no other polarizing substance is present.
Otherwise double polarization may be necessary.
7.3.1.1.2 Double polarization. The method is based on the following
principle: when a sugar solution contains active substances other than
sucrose, the result given by the saccharimeter is faulty.
(7.1)
where W is the solution strength and no the variation due to the presence of
other polarizing substances.
In theory, it is possible to perform a selective hydrolysis of sucrose in
order to transform into an equimolar mixture of glucose and fructose. The
direction of polarization changes because the negative rotation of fructose
is higher than the glucose one (this operation is called accordingly
'inversion').
After inversion, the result read on the saccharimeter can be written as
follows:
nz
= --x
100
W+ no
(7.2)
where R denotes the result read after complete inversion of the normal
weight of pure sucrose in 100 cm 3 .
Interference is suppressed by difference and the strength is given by the
following relation:
W=
100
(nJ nz)
100 - R
(7.3)
(100 - R) is called Clerget's divisor, after the name of the first man who
developed this technique in 1849.
7.3.1.1.3 Techniques of double polarization. In order to be universal,
relation should meet several conditions that are unfortunately not always
filled:
164
SUCROSE
(1) It is based on the assumption that the specific rotation [a] does not
depend on temperature and concentration. Now, the saccharimetric
scale is an approximation close enough to titrate pure sucrose
solutions, variations due to concentration are much higher for invert
sugars, which are also much more sensitive to temperature.
(2) Selective hydrolysis of sucrose is extremely difficult to carry out: in
an acid medium, the other oligosides can be more or less hydrolysed;
through enzymatic processes it is possible to obtain a more or less
complete hydrolysis of raffinose and kestoses.
The following methods are noteworthy:
(a) Dutton's (1979) method of double polarization, and enzymatic
process corrected by a separated chromatography titration of
raffinose and kestoses.
(b) The Clerget (1849) method is broadly used in France for conventional dosage of sugar in molasses. This method uses the former
French normal weight, namely, 16.27 g. When polarization is
performed with a saccharimenter at 26 g, recorded results have to
be corrected accordingly, that is, multiplied by the coefficient
26/16.27. At 20C, the value of Clerget's divisor is then 134 or, more
generally, at a different temperature t (in 0C):
w=
100 X (n ! - nz)
X
144 - 1/2 X I
26
16.27
(7.4)
(c) The Clerget-Herzfeld (Herzfeld, 1888) method uses the international half-weight. Hence the formula becomes
200 X (n! - nz)
W=-----142.66 - 1/2 X t
(7.5)
(d) The American Custom Laboratory Methods (Anon., 1942),

provide more elaborate temperature corrections and makes it
possible, in theory, to measure sucrose and raffinose.
These all are conventional methods. Hence, operation requirements have
to be strictly applied and calculations must be done using the Clerget
divisor specific to each method.
7.3.2 Refractometry
The biunivoque relation between the refractive index of pure sucrose
solution and its concentration can be used to titrate sucrose in aqueous
solutions.
Many instruments are graduated as saccharimetric scales and give
directly the strength W of the solution for 100 g (in the sugar industry, this
165
magnitude is usually expressed in degrees Brix (OBx) on the Brix scale lBx
= 1% of dry substances (DS). (This denotation is for internal use only, it
does not have a legal value in the European Union.) For practical use of
refractometry, readers are referred to chapter 8. Tables are to be read at
20C. Potential corrections depend on type of device used.
In 1936, Landt (1936) published correction tables for the lo-30C range
which are still valid for measurements made in the air.
With a dipping refractometer, air is not taken into account, and
Rosenbruch (1978) published specific tables for temperatures ranging from
10 to 40C. These corrections can be applied at 546 nm (green ray of
mercury) as well as at 589 nm (doublet of sodium).
Development of computers has increased calculation speed, and the use
of tables is gradually declining. Rosenhauer's (1966) equations can be used
to determine the strength of solutions with up to 85% sucrose for solutions
prepared in air in standard conditions (101.325 kPa, 20C and 50% relative
humidity).
Pair
= ao
T~e c~efficients
In
+ aj
X n
X n
+ a3
X n
+ a4
X n
values are a function of the wavelength used to determine
au:
Mercury greenline,
546 nm
ao - 0.337
+ 0.861
az - 0.834
a3 + 0.362
a4 - 0.593
al
+ az
500
909
048
171
099
359
872
354
461
058
X
X
X
X
X
Doublet of sodium,
589 nm
105
105
105
105
104
- 0.355 515
330
- 0.891 061
- 0.389 665
- 0.642 726
+ 0.914
999
824
027
844
227
X
X
X
X
X
lOS
105
lOS
lOS
104
Several instruments are available today which can automatically determine

the strength and display it on a digital dial. Temperature correction is
usually integrated.
Many marketed syrups are blends which contain varying proportions of
invert sugars. De Whalley (1935) proposed the following formula of linear
correction, taking into account the level of invert sugar present in a
solution which concentration W is expressed for 100 g:
Wp
= W r + 0.022
Wi
where Wp denotes the corrected concentration in % DS and W r denotes

the apparent refractometric concentration similating the product to
sucrose. This formula was recorded in the EEC regulation 79/797/ (EEC,
1979).
Rosenbruch (1986) wrote a more accurate third degree polynomial
correction formula, which allows good accuracy even with highly inverted
solutions:
166
SUCROSE
t!. W
= (A + B X W r + C X W/ + D X W,3) X Wi + E X W?
= 6.222 X 103 ; B = 2.372 5 X 10-4; C = -1.8165 X 1O--{); D =
where A
1.8906 x1O-8 ; and E = 2.328 X 10-5 .
This method of correction of the refractometric concentration was
officially confirmed through a series of interlab tests organized by the
Brunswick Institute (Rosenbruch, 1990).
It can be simplified for poorly inverted solutions as follows:
= (A + B 1 X
103 and B 1 = 2.251
t!. W
W v ) X Wi
where Al = 5.830 X
X 10-4.
Use of refractometry in measuring the apparent purity of solutions is
further developed in this chapter. Refractometry is widely used, not only
for the control of marketed solutions, but increasingly for on-line
measurements with sensors whose reliability is constantly improving
(Burzawa et al., 1990).
7.3.3 Polarography
Polarography is a particular application of the oxidation-reduction studies
which were carried out using intensity-potential curves. Originally, the
technique was developed in relation to systems using mercury drops
electrode. Similar methods employing solid electrode use the same
methodology, and are often designated by more specific terms
'voltamperometry', 'pulsed amperometry', etc. Various polarographic
methods were proposed. Amid these are the lowering of the maximum
potential due to oxygen for pure sugar titration using the surface tension
properties of refined sugar solutions, or the oxidation of carbonyl
groups.
Polyachenko (1956) developed a polarographic method for the titration
of fructose in invert solutions. Shul'man (1958) has introduced a technique
for dosing both sucrose and fructose. Glucose cannot be detected, as it is
entirely dissimulated by the fructose wave.
These techniques would not be of much interest if not for the recent
development of a pulsed amperometric method for the polarographic
analysis of OH groups by absorption on a gold electrode. This highly
sensitive technique is used in chromatographic detection, as will be seen in
the section on HPLC.
7.3.4 NIR spectrophotometry
This technique has considerably developed since the mid-1980s. Its
principle is quite simple and is gaining notoriety (McClure, 1994). A
monochromatic beam of light runs through a sample laid in a measurement
cell. Part of the energy is absorbed, and the rest is reflected. The reflected
167
light is integrated in an Ulbricht sphere and undergoes analysis. By

selecting a few specific wavelengths, the instrument can be standardized on
the basis of similar products previously analysed and selected to cover the
entire range of products components to be a multilinear relation. The
accuracy of the analysis depends on the choice of wavelengths, and on the
extent to which the data collected for sampling is representative.
In current laboratory practice, the result is rapidly achieved from the
experimentally established regression. Although, as previously mentioned,
the infrared spectrum is not very selective in such conditions, this
technique yields good results, e.g. the correlation coefficient r between the
laboratory and the automatic measurement ranges from 0.994 to 0.999 for
the dry substance content, expressed in percentage (Brix scale), of the
more or less pure processed products, from syrup to molasses. Regarding
sucrose analysis (from polarization), r is suitable for high purity products (r
= 0.996), although it is affected by the nature of impurities.
Using molasses collected from several French sugar refineries, the IRIS
laboratory obtained a correlation coefficient of 0.92 using three wavelengths. In better targeted collections, taken from a single factory,
Burzawa et ai. (1991) and Vaccari et ai. (1987) obtained far better
correlations, around or higher than 0.990. Vaccari et ai. (1990) also showed
that performance deteriorates rapidly when molasses are collected in two
different sites and cross-tested. Specialized literature gives several
examples of on-line control using this technique (Vaccari et al., 1987, 1990;
Burzawa et al., 1990). Readers are reminded that NIR spectroscopy was
selected for the automatization of the crystallization plant of the sugar
refinery in Bucy-le-long, France.
The operation has been quite successful for the last few years. This
technique could be easily adjusted to other applications, especially
downstream in the fabrication process, and in sucrose solutions development.
7.3.5 Isotope dilution
This technique consists in adding a known quantity of radioactive 14C_

sucrose to the solution to be analysed. Sucrose is then extracted from the
solution and purified regardless of its origin. It is an internal standardization method involving the comparison of the radioactivity of the final
product with that of the radioactive sucrose added to the sample.
Various purification methods have been developed by Horning and
Hirschmi.iller (1959) in Germany, and by Sibley et al. (1965) in the US.
These methods are considered as reference methods, and are not suitable
for routine laboratory control.
168
SUCROSE
7.4 Chemical methods of analysis
In spite of their high degree of accuracy, physical methods such as

polarimetry, refractometry, and densimetry can only be used for the
titration of pure sucrose solutions. If solutions are more complex, with the
presence of reducing sugars, colorants or flavour enhancers, chemical
methods can be employed to determine sugar content, and especially
sucrose. These methods involve reducing-sugar titration.
7.4.1 Reducing sugars

These methods are based on the reducing properties of free carbonyl group
in reducing sugars reacted with a copper solution in alkaline medium. As
total alkaline degradation of the reducing sugars cannot be easily avoided
in the course of titration, it is important to respect all operation details in
order to achieve good reproducibility. Sucrose interferes slightly in these
titrations and they must be corrected accordingly.
It should be noted that the simplest methodology, gravimetric separation
and weighing of cuprous oxide, as described by Saillard (1923), is no longer
in use.
The methods officially recognized by ICUMSA and quoted in regulations or standards documents together with the Luff-Schoorl method are
reviewed in the following survey:
(a) Knight and Allen (Anon., 1994b): to be applied for very low
concentrations (0.002-0.017%) only. It uses back-titration of the
excess of copper solution after hot precipitation of the cuprous
oxide by means of an EDTA solution.
(b) The Berlin Institute's Method (Anon., 1994c): to be applied to
solutions or products whose reducing sugars-content does not
exceed 10%; the characteristic of this method is the use of a Muller
solution prepared with carbonate instead of sodium hydroxide in
Fehling's solution. It is based on the following principle: the
cuprous oxide formed by the reduction of copper salts is oxidized by
an excessive addition of iodine, the latter being subsequently backtitrated by sodium thiosulfate. The result has to be corrected in
order to account for water blank, blank on a cold solution and
sucrose interference. Gfner (Schneider, 1979) has introduced
another method based on the same principle that only differs in
terms of operation instructions.
(c) Lane and Eynon (Anon., 1994d): this method has the widest
application. It is suitable from 0.1 g of reducing sugar for 100 cm 3 of
solution. Beyond 0.8 g for 100 cm3 , work should be performed after
169
dilution. The method consists of performing the titration of a known

quantity of Fehling's solution, at boiling temperature, using the
sugar solution in the burette. The final stage of titration is revealed
by total decoloration. The end-point can be improved by the
addition of methylene blue, which then turns from the normal form
(blue) into the reduced one (decolorized). The ICUMSA currently
recommends a constant volume method. In the presence of sucrose,
correction is provided by the tables.
(d) Luff-Schoorl (Anon., 1994e): this method was introduced in various
European regulations (EEC, 1971, 1979), expecially as regards
feed. Instead of the Fehling's solution, it uses an alkaline solution of
copper sulfate and hot sodium citrate in standardized conditions.
Back-titration is carried out through reduction, in an alkaline
solution, of the excess of copper salts by potassium iodide. Iodine is
titrated by sodium thiosulphate after the medium is acidified.
7.4.2 Chromatography
In spite of the development and the economic significance of the analytical
techniques mentioned so far, we cannot but acknowledge the huge
difficulties faced by analysts in the past for mixtures of sugars with similar
physical and chemical properties.
Chromatographic techniques are still greatly praised by specialized
laboratories. They have made it possible to finely separate sugars with
similar characteristics by bringing into play partition coefficients between
the mobile phase that drives the mixture to be analysed, and the stationary
phase. These techniques are constantly improving. Theory of chromatography is beyond the scope of this chapter but it will only be dealt with
application to the sugar analysis.
Gas-liquid chromatography was the first technique that yielded a quick
and specific dosage of sucrose in sugar compounds using another method
than polarization. It was mostly developed in the 1970s.
7.4.2.1 Gas-liquid chromatography. The most widely used form of this
technique is based on a partition coefficient between the mobile phase and
an immobilized liquid which soaks a fixed support. This is the reason why
it is denoted by the abbreviation GLC (gas-liquid chromatography).
In spite of their light molecular weight, sugars are not sublimable mainly
because of their instability at high temperature and of hydrogen bonds with
hydroxyl groups. However, it is easy to obtain silylated derivatives which
are, despite a heavier molecular weight, easily volatile and far more stable
than sugars at high working temperatures.
Devillers et al. (1974) have published a technique which was developed
and used at the time to establish a mass balance in sugar factories based on
170
SUCROSE
sucrose. The technique was improved through the use of capillary columns
and it is still used for the dosage of raffinose.
All other described techniques (Karr and Norman, 1974; Wong Sak Hoi,
1980) present various drawbacks:
(1) long preparation time of samples;
(2) preparation of the silylated derivate requires complete drying of
sample in an oven where degradations may occur; and
(3) reducing sugars polymorphism often leads to three different peaks.
Schiiffler and Morel du Boil (1984) developed a silylation technique in a
humid environment using a reagent in excess (hexamethylenedisilazane or
HMDS) which reacts on water (Figure 7.3). The reaction takes place with
trifluoracetic acid. Silylation occurs very quickly (10 mn in a water-bath
thermostated at 80a C ultrasonically homogenized). International interlab
tests showed that the technique was highly reproducible. It was awarded
official status (ICUMSA, 1986). In the Republic of South Africa, it is
used in the official analysis of sugar cane juice, but it has proved to be less
accurate in the case of non-purified beet juice. According to Oikawa
(1990), this lack of precision is due to protein interference.
As regards the analysis of reducing sugars, Schiiffler and Morel du Boil
(1984) have proposed reducing the number of one-doublet peaks, by
performing an oximation just before silylation. This method is elegant but
it is hardly used, especially in situations where the sugar mixture is a
complex one.
G
F
Figure 7.3 GC chromatograms according to the Schaffler method: left, sucrose syrup; right,
molasses; G, glucose; F, fructose; S, sucrose; X, internal standard xylose. (By courtesy of G.
Deruy, IRIS, France.)
171
The use of HPLC is therefore strongly recommended for the analysis of

sugar mixtures.
7.4.2.2 HPLC. HPLC is a method widely used in many areas. As it has

been thoroughly described in the specialized literature, this paper will only
outline it briefly. An eluent liquid is injected into a separative column
using a pump with constant flow (the regularity of the flow, especially the
absence of pulsations, is the touchstone of the technique; excellent sucker
pumps, generally with double barrels, can be found in the market). At the
end of the column, the liquid goes through a detection device, which is
connected to an electronic appliance designed to amplify, record and
integrate the signals. The column is generally fitted with small size particles
(from 10 to several dozen !-lm), made up of a support, often chemically
bonded, which constitutes the stationary phase; the best separations are
performed with perfectly spherical particles of very small diameter.
It is most important that the flow inside the device is not disturbed in
order to avoid an anomaly in the detected signals. The analysed sample is
therefore introduced through a specific valve which, in a normal position,
allows for the direct flow of the eluent and an 'injection' position allows
for the integration in the circuit of a sampling ring of constant volume
(10-20 !-lm) filled with the product to be analysed. In order to avoid
anomalies, the gas must be removed from the eluent before use.
It should be noted that different possibilities may be added to the basic
device as described below:
The column can be thermostated at temperatures different from the
ambient temperature, especially in order to reduce the viscosity of the
eluant liquid.
The eluant can be modified in a pre-programmed way, it is then
referred to as the elution gradient.
Lastly, a chromophore group can be injected so as to enhance the
detection at the end of the separative column, the so-called postcolumn coloration.
By combining the three factors involved in both the separation and the
selective measurement of the analyte under study, i.e. nature of the
stationary phase, composition of the eluant and detection technique,
various analytic techniques have been developed. They are summarized in
Table 7.2.
The accuracy of the method depends on the technical possibilities of
peaks separation, on reproducibility and on the ageing of the separative
column, and above all on the complexity of the product.
Thus, in 1990, in the course of assessing intercomparison-based
methods, Lescure (1990) had the following results (Table 7.3) on the
various products processed from beet sugar.
172
SUCROSE
Table 7.2 High-performance liquid chromatography: Review of the various combinations

usable for the HPLC analysis
Nature of the
stationary phase
Principle of
separation
Eluent
Particularities
Silica
Water or water Bad separation, improved with

+ amine
amine
CI8 bonded silica Decreasing

(or reverse phase) polarity
Water
Separation
by increasing molecular weights
unseparated glucose and fructose
Bonded silica: NH 2 By difference in

(amine)
polarity
Acetonitrile/
water: 80/20
Separation
by increasing molecular weights
overlapping glucose and fructose
Problem
Schiff's basis formation
Cation exchange
resin form: Na,
Ca, Pb
Ligand exchange, Water + metal Separation

in the reverse order of molecular
absorption/
acetates
weight
desorption
bad separation of osides
Anion exchange
resin
pK. of the
0.1 M NaOH
'alcohol' groups solution
Very good separation and very high

sensitivity
Table 7.3 High-performance liquid chromatography: Assessment of

relative accuracy (CV%) for HPLC and polarization methods of
analysis of sucrose in different sugar products (Lescure, 1990)
Products
Polarization'
Sucrose analysis by
HPLC', separation of Ca 2 +
cation exchange column
Brei
Syrup
Molasses
0.7
1.6
0.8
1.3
0.4
1.1
'Methods: polarization, ICUMSA method

ICUMSA method GS8--1. (Anon., 1994).
GS1/2/3,
HPLC,
Using the same method applied to the collection of cane and beet
molasses, Schaffler (1990) obtained a repeatability variation coefficient
CV r = 0.58 and a reproducibility coefficient of CV r = 1.82. With a similar
method, the ISO (1993) obtained a repeatability variation coefficient
ranging from 0.65 to 3.1 for glucose titration (dextrose). It should be noted
that in this case, the technique at work is slightly more complex, as a
deionization is needed to suppress the refractometric interference of the
salts present in these solutions. Deruy and Lescure (1988) published a
detection technique through post-column coloration using para-aminobenzoic hydrazide (HAB) , which is extremely selective. Bugner and
173
Feinberg (1990) demonstrated that the reproducibility deteriorates when

products are dosed in complex systems such as finished products (biscuits,
beverage, desserts, etc.): the reproducibility CV varies considerably
according to the difficulty of extraction and the analyte concentration.
Recent studies have shown the great opportunities offered by pulsed
amperometric detection, after sugar separation on anionic resin.
Bichsel (1990) and later Peschet and Giacalone (1991) have dosed traces
of reducing sugars and higher glycosides (raffinose and kestose) in a
sucrose syrup. Figure 7.4 illustrates the separation achieved in the IRIS
laboratory by Deruy using this technique.
Before concluding this chapter, it seems appropriate to give a survey of
the industrial applications of chromatography (see Guerain et al., 1986;
Buttler et al., 1993). It is mainly applied to on-line control of various
distilling procedures, but it might well be used in the control of other types
of processing.
7.5 Enzymatic methods
The principle of these methods is extensively described in the specialized
literature, especially in Bergmeyer's work (1974). Only specific reactions
will be described.
7.5.1 Methods description

As a general rule, dosage concerns reducing sugars, glucose and fructose,
although sucrose can be easily hydrolysed through the action of /3fructofuranosidase at pH 4.5.
Sucrose
~
~
/3- Fructofuranosidase
Glucose
+ Fructose
Its concentration is calculated through the titration of glucose which is

present before and after hydrolysis. Several methods are possible:
(a) Kinetic method (Devillers et al., 1975)
~
Gluconic acid
Glucose oxidase
+ H2 0 2
Hydrogen peroxide thus formed is used with peroxidase to oxidize

the 4-aminophenazone:
H20 2
+ 4-aminophenazone
+ phenol
(reduced form)
H 20
+ 4-phenylaminophenazone
(oxidized form)
174
(a)
SUCROSE
A
(b)
GF
Figure 7.4 HPLC chromatograms with Carbopac ACI column (pulsed amperometry
detection). (a) Mixture of sugars: A, arabinose; G, glucose; F, fructose; L, lactose; S,
sucrose; R. raffinose; and M, maltose. (b) Molasses: G, glucose; F, fructose; S, sucrose; R,
raffinose. (By courtesy of G. Deruy, IRIS, France.)
175
The reaction elicits a colorant which is measured at 505 nm. This

technique is suitable for automatic analysis using a continuous flow
instrument and yields excellent results with beet sugar.
Some authors have expressed doubts regarding the use of this
technique with cane sugar. In this case, the sucrose molecule is
associated with kestoses, trisaccharidic compounds resulting from
the condensation of a furanosyl moiety on one of the three
hydroxymethyl groups of sucrose. Kestoses, in trace amounts,
interfere in sucrose titration through an enzymatic process and are
more frequent in cane than in beet.
(b) 'End point' manual titration of reducing sugars: it uses another
reaction with hexokinase in presence of ATP (adenosine triphosphate), and glucose-6-phosphate dehydrogenase with NAPD
(nicotinamide adenine dinucleotide phosphate).
GlucoseATP
~
Glucose-6-phosphate + ADP
Glucose-6-phosphate
~
Gluconate-6-phosphate
+ APD
+ NADP + H+
Glucose-6-phosphate dehydrogenase
The reaction is shifted to the right by use of a buffer of pH 7.6 which

recombines the freed protons.
Fructose also reacts with ATP and gives
Fructose
+ ATP
Fructose-6-phosphate
Hexokinase
+ ADP
When phosphoglucose-isomerase is added, the reaction can be

written:
Fructose-6-phosphate
Glucose-6-phosphate
Phosphoglucose isomerase
and is to be analysed as before.

NADPH is dosed by ultraviolet spectophotometry, either at 340 or at
334 nm, according to the type of instrument used. Its concentration is
proportional to the increase in absorbance induced by the reaction.
These reactions use a costly reagent as the enzymes need to be prepared
in an extremely pure form in order to retain their specificity. Generally
speaking, products are provided by the specialized firms Boehringer or
Sigma. Other firms, such as Leeds & Northrup, Yellow Springs, and
Tacussel, sell fixed enzyme reactors. These reactors always combine a
reaction column or chamber with an amperometric device coupled up with
an exploitation system designed to give a quantitative response after
standardization. This equipment has been mainly designed for medical
applications and is used mostly for sucrose dosage. Yellow Springs also
combines invertase and fixed enzymes, and sells a special version of the
equipment for the direct dosage of sucrose.
176
SUCROSE
Immobilized enzymes are also used in the so-called FIA technique (flow
injection analysis) as described by Bengtsson and Tjebbes (1991). In this
continuous flow technique, a pump injects a transport solution which may
contain one or several reagents. Samples are injected at regular intervals
through a by-pass valve similar to the injection device used in liquid
chromatography. Secondary reagents can be injected at the end of the
reaction.
The scheme used by Bengtsson for sucrose titration is shown on Figure
7.5.
The first fixed enzymes reactor contains mutarotase, glucose oxidase and
catalase. It makes it possible to eliminate glucose before sucrose
hydrolysis. The second one contains the same reagents as in the Devillers
method, although in a fixed form. The other similarity with the Devillers
method is the injection of a colorant which reacts with hydrogen peroxide
and is detected by a colorimeter. The recorded height of the peaks is
proportional to the concentration of sucrose.
7.5.2 Situation of enzymatic methods

The ICUMSA only investigated final stage enzymatic dosages of glucose
and fructose in 1982. At the time, reproducibility was not thought good
enough to lead to an official recommendation. It should be noted that
continuous flow methods have developed considerably, and have been
compared to traditional polarization methods. The methods are used to
characterize the technological value of beets in various countries around
the world (France, Austria, Spain and Morocco with the Devillers method,
and Sweden with the BengtssonlFlA method).
The practical difficulties involved in organizing interlaboratory testing
using homogenous equipment across the world is the only factor standing
in the way of their official recognition.
7.6 Determination of the syrups quality
7.6.1 Purity
Sugar syrup analysis also aims at characterizing extraneous elements which
might be present, most often in trace amounts.
It should be recalled that percentage is frequently used for the ratio of
sucrose to dry substances. This also leads to the definition of the notion of
non-sugar, namely, all dissolved substances other than sugar:
(non sugar) = (dry substances) - (sugar)
It is possible to dose dry substances with great precision (oven method or

Karl Fischer method) but the methods are too time-consuming for current
HP 1000
Computer
Sucrose reactor
~VV'-
Detector
Figure 7.5 Flow diagram in an FIA (flow injection analysis) device. (After Bengtsson and Tjebbes (1991).)
Injector
glucose - f - "killer"
Pump
er
-....I
-....I
zVJ
o
rc:
::l
o
VJ
trl
~
VJ
(")
VJ
Vi
o
..,.,
oo(
VJ
>
Z
>
r-
178
SUCROSE
laboratory practice. It is therefore necessary to resort to refractometric or

densimetric determination. Dry substances are assimilated to sucrose. The
margin of error is narrower in refractometry than in densimetry. The usual
denotation is refractometric or densimetric apparent purity.
It is understood, however, that, whereas the notion of purity is very
important with regards to process control or to estimate a crystallization
yield in the prescribed manner, it is of little importance regarding
marketed solutions made of highly purified sugars, always purer than
99.7%. Users should then try to quantify certain categories of impurities
more specifically inasmuch as their presence is not wanted, in particular
mineral salts, which are globally dosed in the form of ash or colour.
7.6.2 Ash
As some ions are volatile, chlorides in particular, they are replaced by ion
sulphate. Sulphates have a greater stability at high temperatures and fix
fewer carbon particles. A double sulphatation is performed. Operation
instructions are given by the ICUMSA (Anon., 1994g). Use 15-35 g of
syrup in a platinum dish. First, 8 cm 3 of 1.84 g/cm 3 sulphuric acid is added,
followed by calcination at 550C until the apparent disappearance of
carbon. A few drops of concentrated sulphuric acid are added again,
followed by a second calcination at 650C. Resulting ash must be flaky and
should not adhere to the dish.
In fact, this method remains delicate and lacks precision for white sugars
or syrups prepared with white sugar. The indirect conductimetric method is
far more reproducible and is therefore preferable. It works on the principle
of the proportionality between conductivity and the concentration of
dissolved salts. Solutions with 28% (m/mH) concentration are used as
conductivity then reaches its maximum and is less affected by concentration.
C28 conductivity at 20C is expressed in r-tS/cm. Conductrimetric ash is
conventionally expressed for 100 g by
conductimetric ash = 6 and 10-4 X Czs
(C28 denotes measured conductivity, the index 28 indicates that work is

performed on a sugar solution at 28% m/mH).
Diluting water used should be of very low conductivity 2 r-tS/cm) and
the value of C 28 has to be corrected in order to eliminate water
conductivity:
e28 =
C read - 0.35 X Cwater
For more details, readers are referred to the ICUMSA methods (Anon.,
1994g).
The colour point used by the European Union is written as follows:
1 point = 3.13
C28
179
7.6.3 Colour
Measurement is made by absorption spectrophometry at 420 nm on a sugar

solution at 50 g DS for 100 g of solution.
The measure is expressed in ICVMSA units (IV) = (100 X E 42 J(L X w
X d) where l is the length of cell, E 420 is the solution absorbancy, w is the
concentration in grams for 100 g (OBx), and d is the apparent density.
The solution is filtered beforehand to avoid the interference of
suspended matter.
It should be noted that a sucrose solution can never be a true solution, as
understood in chemistry. There is always a diffraction of light by
microparticles (seed of crystallization). Results vary slightly according to
the device used, in function of their respective configuration. This method
has been published by the ICVMSA (1994a).
In the European Vnion, the colour point is often written as follows:
1 point = 7.5 IV
Other impurities are taken into account in the regulations. The CODEX
has set maximum concentration in the products delivered for human
consumption. The problem is to dose the traces in the sugar solution.
7.6.4 S02
The rosaniline method is the ICVMSA (1994b) official method. Spectrophometry at 560 nm is used to measure the colour of the suphite/rosalinine
compound formed after reaction with a formaldehyde solution. The
addition order of reagents has to be strictly followed to ensure the suitable
and reproducible development of colour. Standardization starts with a
freshly prepared range.
Rosaniline (or decolorated fuschine) is considered dangerous for the
health. This is the reason why it is currently replaced by the ICVMSA
(Anon., 1994c) method developed by the Boehringer firm. Sulphite
oxidase forms hydrogen peroxide which is reduced by NADH peroxidase
and gives colourless NAD+ at 340 nm in presence of sodium hydroxide.
The result is obtained by measuring the difference in absorbancy.
7.6.5 Heavy metals
Atomic absorption spectrophotometric methods are the most widely used

today.
The ICVMSA has adapted some methods for use with arsenic and lead
although it continues to use colorimetric methods for lead, copper, arsenic,
and iron.
180
SUCROSE
The AOAC (1990) has proposed atomic absorption spectrophotometric

methods.
7.7 Microbiology
Contamination by pathogen strains is hardly a major risk, as shown by the

investigation led by Gireaudot-Liepmann and Catteau (1992). When
pathogen strains (e.g. Proteus mirabilis, Salmonella typhimurium,
Escherichia coli pathogen strain, Escherichia coli ATCC 10537, Salmonella
montevideo, Pseudomonas aeruginosa) are introduced into a liquid sugar
(marketed product taken during processing), whatever regeneration
process in used to avoid osmotic shocks, a decrease in the number of viable
bacteria can be observed with time, and they completely disappear after an
18 h stabilization period. Bacteria which develop or resist in a concentrated
sugar solution are thus more osmophilic, and noxious for applications or
the preservation of products containing insufficiently sterilized syrups,
although they are far less dangerous than the pathogen strains mentioned
above. In particular moulds and yeasts may develop on the surface and
gradually contaminate the whole mass through convection movements. It
is also necessary to count total mesophilic germs (incubation at 30C), total
thermophilic aerobic germs, flat-sour germs, and HzS producing anaerobic
thermophilic germs.
It should be recalled that 'flat-sour' germs can turn glucose into acid, and
that they are characterized by a lowering of pH level, as shown by the
purple bromocresol (PBC) indicator which turns from violet to yellow in
the form of a halo around the colonies. HzS producers are easily identified
by adding iron citrate in the solution which turns black as a result of
sulphide formation under the action of microorganisms.
Besides general recommendations on foodstuffs hygiene, there are no
regulatory norms in the field of microbiology. Guarantees are determined
by mutual agreement between supplier and the buyer, though it is of
common practice to adhere to norms set by American traders.
(a) National Canners' Association (1970) standards: They mainly
concern crystallized sugar and are to be performed on five samples.
They set the following limits:
less than 150 total thermophilic germs for 10 g in a sample, and
on average fewer than 125 germs for 10 g in the 5 samples,
less than 75 'flat-sour' germs for 10 g in a sample, and on
average fewer than 50 germs for 10 g in the 5 samples.
(b) National Soft Drink Association Norms (American Bottlers of
Carbonated Beverages, 1962): They are more specific to liquid
181
sugars and are to be performed on 20 samples. They set the

following limits:
on average fewer than 100 germs for 10 g of dry equivalent,
only one sample can exceed 200 germs and it is not to be
included in the overall average if all the other samplings
analysed on the same day fulfil the previous requirement,
less than 10 yeasts for 10 g of dry equivalent, only one sample
can exceed 18 and it is not to be included in the overall average
if all the other samplings analysed on the same day fulfil the
previous requirement,
less than 10 moulds for 10 g of dry equivalent, on average, only
one sample can exceed 18 and it is not to be included in the
overall average if all the other samplings analysed on the same
day fulfil the previous requirement.
Most of the bacteriological methods of analysis which may be applied to
sugars are described in the specialized literature, particularly in IRIS
(Anon., 1984) and ICUMSA (Anon., 1994).
7.8 Standards and regulations

Unlike products to be processed that are traded by mutual agreement
under the responsibility of contracting parties, foodstuffs ready for
consumption have to conform to a number of rules established by
International Organizations in view of protecting consumer's health.
Quality standards for sugars in the CODEX Alimentarius are set by the
FAO (Food and Agriculture Organization), which is the United Nations'
Special Commission on Food and Agriculture, and the World Health
Organization. The European Regulation 79/796 (EEC, 1979) is enforceable
after transposition in the national legislations of all European states.
Sugar is also used in pharmacology for preparations and specialties.
Pharmacology is concerned with and has the duty of averting all sorts of
risks. It established regulatory rules for its own use that are gradually
becoming international through the efforts towards harmonization of the
main pharmacopoeia, that is, European, American and Japanese.
In all market organizations, decision-making authorities set a number of
rules in order to determine qualities and quantities that are to be taken into
account, e.g. such as the disposition of the sugar regulation which is
enforceable in all member-states of the European Union.
Besides what they have primarily been designated for, these documents
are often used as reference tests in many ordinary transactions. Although
the survey cannot be exhaustive owing to frequent updatings in this area,
182
SUCROSE
the following section is an attempt to underline the main qualitative norms

and the analysis methods recommended by decision-making authorities.
7.8.1 Codex Alimentarius
It does not include industrial norms specific to liquid sugar. By analogy
with the dispositions concerning crystallized sugars, it should be noted that
liquid sugars have to respect the limits set for traces of contaminating
agents, namely:
conductimetric ash: less than 0.1 g per 100 g of dry substances,

colour: less than 150 ICUMSA units,
S02: less than 20 mg/kg of dry substance,
arsenic: less than 1 mg/kg of dry substance,
copper: less than 2 mg/kg of dry substance, and
lead: less than 0.5 mg/kg of dry substance.
The Codex also draws attention to the fact that sugars must comply with
the general rules on foodstuffs regarding:
pesticide residues,
hygienic rules, particularly as regards microbiology and parasites, as
well as products proceeding from microorganisms and liable to be
damaging to health.
As the Codex does not have a specific analysis method for sugar, it
recommends the ICUMSA methods for invert sugars, conductimetric ash,
colour, and S02, and the AOAC methods for arsenic and copper titration.
7.8.2 The European Regulation 79/796
Unlike the Codex, the European Regulation describes a number of
categories: liquid sugar, white liquid sugar, inverted white liquid sugar,
invert sugar syrup, invert white sugar syrup. Dry substance content should
be determined by refractometry on the basis of Rosenhauer's equation and
with de Whalley's correction in the case of reducing sugars. Invert sugars
should be determined according to the Luff-Schoorl method, however a
dispensation is allowed for if states opt for the Lane and Eynon method
with constant volume.
7.8.3 Pharmacopoeia
According to the latest trends, sulfated ash is to be replaced with
conductimetric ash following the pharmacopoeia's own procedure, that is
to say, at 25C instead of 20C for the ICUMSA. Levels of invert sugars
should not exceed 0.04 g for 100 g and sulphites 15 ppm. For the
183
pharmacopoeia's own methods, users are referred to reference works in

the countries concerned.
7.8.4 Sugar regulation

Regulating the total sugar in a sugar syrup, the regulations in force in the
member states of the European Union provide for the application of the
chemical method according to Lane and Eynon on an inverted solution
according to Clerget-Herzfeld. The total content is converted into sucrose
after multiplication by 0.95.
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'Bottlers' Granulated and Liquid SURar.
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Physical properties
P. REISER, G.G. BIRCH and
M. MATHLOUTHI
8.1 Introduction
Although the physical properties of sucrose have been studied for nearly
two centuries, there is a need to gather the numerous information
dispersed in different sources in the same book. The tables included in this
chapter are a critical selection of data published in the sugar literature and
are by no means an exhaustive compilation of all the knowledge in the
field. The three forms under which sucrose may be found in the laboratory
or the factory are the crystalline, amorphous and aqueous solution. This is
also the order of presentation of the physical properties selected and
estimated of certain utility to the reader. Some of the properties
(solubility, viscosity) reported here are more thoroughly developed in
other chapters of the book. Sucrose is one of the purest chemicals available
at a low price and this is probably the reason why it has been always used as
a standard for calibration of densimeters, viscosimeters, refractometers,
polarimeters, etc. Although the modern computers offer huge possibilities
of modeling and rapid computation, nothing can replace experimental
work. That is why most of data listed in the following tables have as their
origin experimental determinations.
8.2 Properties of the crystal

Sucrose crystallizes as an anhydrous monoclinic crystal. It belongs to space
group P2 1 Its structure was one of the earliest to be precisely determined
by neutron diffraction (Brown and Levy, 1963) and further refined using
X-ray (Hanson et al., 1973) and neutron diffraction (Brown and Levy,
1973) data. Structural characteristics of crystalline sucrose (see chapter 2)
and crystallization aspects (see chapter 3) including morphology and effect
of impurities are given elsewhere in this book. The data reported here are
intended to complement information given in the other chapters or to
cover aspects of practical interest.

187
PHYSICAL PROPERTIES
8.2. J X-ray crystallinity

The crystal data are reported in chapter 2, the Miller indexes of the
different faces of the sucrose crystal in chapter 3 and X-ray diffractogram
in chapter 4 of this book. However, from a practical point of view, it is
relevant, having a white powder looking like sugar and wishing to check if
it is crystalline sucrose to have a tool for verification of the X-ray
diffractogram. This is achieved through ASTM (American Society for
Testing Materials) card index reported in Table 8.1.
8.2.2 Melting point

Melting point is another means of ascertaining the nature of a substance.
Unfortunately, most of the carbohydrates decompose or dehydrate at
temperatures very close to their melting point. The presence of impurities,
moisture or small amounts of non-crystalline sucrose may modify the
result. The generally admitted melting point is 186C, although values
ranging from 182 to 192C were reported even in recent literature (Roos,
1993).
Table 8.1 ASTM index card for sucrose crystal'
dA
4.70
3.59
7.54
10.58
//1 1
100
100
70
16
dA
//1 1
hkl
dA
lilt
10.59
7.54
6.95
6.69
5.71
5.43
5.27
4.70
4.52
4.36
4.25
4.03
3.93
3.78
3.68
3.59
3.52
3.44
3.36
3.24
16
70
40
60
34
12
12
100
63
30
33
40
12
20
15
100
40
7
10
14
100
001
101
110
011
111
200
111
210
020
211
120
201
021
121
211
300
3.15
2.876
2.794
2.735
2.670
2.578
2.513
2.479
2.408
2.343
2.301
2.254
2.178
2.068
1.898
1.850
1.794
1.694
1.670
1.639
12
30
20
14
12
7
10
11
10
22
8
14
9
10
5
7
7
1
2
3
'dA, interplanar distance in A; 1Il relative intensity; hkl, Miller indexes.
C 1zH 22 0
11
Sucrose
188
SUCROSE
8.2.3 Density
The density of sucrose crystal may be derived from crystallographic data
(see chapter 2). It has been measured at 15C by Plato since 1901 and the
value found (Q = 1587.9 kg/m 3 ) is still valid for practical purposes.
Dependence of the density Q of crystallized sucrose on temperature (t)
was calculated (Ciz and Valter, 1967) using the following equation:
Q=
1 + 1.116
Qzo
X
104
(t - 20)
with reference value given by Helderman (1927): Qzo
= 1588.4 kg/m 3 .
8.2.4 Compressibility
The cubic compressibility coefficients (k) of sucrose crystals were
determined (Bridgman, 1933) using the following relation:
k=a+bXP
The constants a and b are given in Table 8.2 in the intervals of pressure P
(0 = 12 X 105 kPa) and temperature (3Q-75C).
8.2.5 Granulometry
Crystallized sugar is commercially available with various grain sizes
adapted to different food applications. Weight, surface area and volume of
sugar crystals of different mesh or screen openings are listed in Table 8.3.
Bubnik and Kadlec (1993) obtained similar results when computing surface
area and number of crystals as a function of linear dimension.
8.2.6 Electrical properties

Sucrose crystals were reported to be triboluminescent, i.e. they emit light
upon fracture (Hirschmiiller, 1953). Because of the polar character of the
sucrose molecule, and the dipole-dipole interaction nature of the hydrogen
Table 8.2 Cubic compressibility coefficient (k) of sucrose crystals
(From Bridgman, 1933)*
Temperature
("C)
30
75
Pressure
(x 105 Pa)
(x 105 Pat!
b
(x 105 Pat2
0-12000
0-12000
6.930 X 10-6
7.486 X 10-6
-161.1 X 10- 12
-184.2 X 10- 12
k = a + b x p. a and b are constants, p is pressure (105 Pa), k [(10 5

Pat!) may be calculated by means of the values in the table.
189
PHYSICAL PROPERTIES
Table 8.3 Calculated weight, surface area, and volume of sugar crystals (from Pancoast and
Junk, 1973)
Mesh
5
6
7
8
9
10
12
14
16
20
24
28
32
35
42
48
60
65
80
100
115
150
170
200
250
270
325
Screen
opening
(mm)
Weight of
crystals
(mg)
Number of
crystals
per mg
Surface area
of crystal
(mm 2 )
Volume
of crystal
(mm 3 )
Surface areal
mg of crystal
(mm 2 )
3.962
3.327
2.794
2.362
1.981
1.651
1.397
1.168
0.991
0.833
0.701
0.589
0.495
0.417
0.351
0.295
0.246
0.208
0.175
0.147
0.124
0.104
0.088
0.074
0.061
0.053
0.043
69.1
40.9
24.2
14.6
8.65
5.00
3.02
1.77
1.08
0.642
0.382
0.227
0.134
0.0805
0.0479
0.0285
0.0165
0.00999
0.00595
0.00352
0.00212
0.00125
0.000755
0.000450
0.000252
0.000165
0.000088
0.014
0.024
0.041
0.068
0.012
0.200
0.330
0.560
0.930
1.560
2.620
4.400
7.460
12.400
20.900
35.100
60.600
100.00
168.00
284.00
472.00
800.00
1320.0
2220.0
3970.0
6060.0
11400.0
69.5
49.0
34.5
24.7
17.4
12.1
8.63
6.03
4.34
3.08
2.17
1.54
1.08
0.768
0.545
0.385
0.267
0.191
0.135
0.0957
0.0681
0.0479
0.0342
0.0242
0.0165
0.0124
0.00817
43.6
20.7
15.2
9.25
5.45
3.16
1.91
1.12
0.681
0.405
0.241
0.143
0.0845
0.0508
0.0302
0.0180
0.0104
0.0063
0.00375
0.0222
0.00134
0.000788
0.000476
0.000284
0.000159
0.000104
0.0000555
1.004
1.200
1.426
1.690
2.010
2.420
2.860
3.410
4.020
4.790
5.680
6.790
8.060
9.540
11.40
13.50
16.20
19.10
22.70
27.20
32.10
38.30
45.30
53.70
65.50
75.10
93.00
bonding in the crystal, sucrose crystals possess a dipole moment and

dielectric constant. Dipole moment was reported (Landt, 1934) to be equal
to 3.1 X 10- 18 C m and dielectric constant CT = 3:5-3.85 depending on
orientation (Narayana, 1950). According to Pavlik (1939) a piezoelectric
effect (emission of electricity when pressure is exerted) has been observed
on sucrose crystals. However, no electrical conductivity value was reported
for sucrose as it is a non-conducting material.
8.2.7 Specific heat
The specific heats (Cp in kJ/kg K) of crystalline sucrose in a temperature

range from 0 to 100C are given in Table 8.13 with the values reported by
Lyle (1957) for aqueous solutions. Cp was also calculated for sucrose
crystals using equation of Anderson et al. (1950):
Cp = 1.1269
+ 4.524
1O-3 .t
+ 6.24
1O--{)
.f-
and the computed values found different from Lyle's results.
190
SUCROSE
8.3 Properties of amorphous sucrose

Occurrence and practical importance of amorphous sugar are described in
chapter 4 as well as its structure and some of its thermal properties.
8.3.1 Density
Because of its structure, it is easily understandable that the density of

amorphous sucrose is lower than that of the crystal. Although different
structures and packing of the molecules may be obtained from the different
methods of amorphization of sucrose and consequently density may also
vary, the value of 1507.7 kg/m 3 reported by Plato (1901) can be given as an
example.
8.3.2 Specific heat
The specific heat of amorphous sucrose was found to be about 1.432 kJ/kg
K between 22 and 25C.
8.3.3 Glass transition, recrystallization and melting
Differential scanning calorimetry (DSC) was used (Roos and Karel, 1990)
to determine the glass transition (Tg ), recrystallization (Tc ) by moisture
sorption and melting (Tm) of the rearranged amorphous sucrose after
submission to different equilibrium relative humidities. The values of T g ,
Tc and T m are listed Table 8.4.
8.3.4
/3C
NMR spectra of amorphous sucrose
As already mentioned (see chapter 4) the structure of amorphous sucrose

depends on the method of preparation. Tentative assignments of CP-MAS
Table 8.4 Glass-transition temperatures (Tg standard deviation) for amorphous sucrose
equilibrated to varying equilibrium relative humidities in the surrounding air (from Roos and
Karel, 1990)
Water activity'
0.00
0.11
0.23
0.33
H 2 0 (g/100 g)
Tg (0C)
0.0
1.4
3.8
4.7
56.6 3.4
37.4 8.0
27.9 2.4
t
12.6 0.9
Tc (0C)
104.4
83.7
75.1
57.4
2.3
7.6
4.1
1.2
Tm (0C)
183.5
172.1
165.0
1.2
4.2
2.1
'Water activity at 25C, obtained with P205 (0.00) and saturated solutions of LiCi (0.11),
CH 3 COOK (0.23) and MgCI 2 (0.33).
tMoisture content allows crystallization at room temperature.
191
PHYSICAL PROPERTIES
Table 8.5 Tentative assignments DC chemical shifts (ppm downfield from Me4Si) for sucrose
in various physical states (from Mathlouthi et al., 1986; Jones et al., 1979)
Freeze-dried
Quenched melt
Crystalline
D 2 0 Solution
Assignments
104.7
93.4
102.6
93.5
83.1
82.0
73.9
73.2
104.5
92.8
82.2
77.3
74.8
73.4
73.3
71.9
70.0
63.2
62.2
61.0
C-2'
C-I
C-5'
C-3'
C-4'
C-3
C-5
C-2
C-4
C-6'
C-I'
C-6
104.7
93.4
82.4
81.35
73.6
73.7
65.3
61.3
65.0
61.8
72.1
68.2
66.3
61.5
60.2
(cross-polarization magic angle spinning) BC NMR spectra chemical shifts

of amorphous, crystalline and aqueous sucrose solutions were proposed
(Jones et al., 1979; Mathlouthi et al., 1986). They are reported in Table 8.5.
8.4 Aqueous solutions
The physical properties of sucrose solutions are important both for

laboratory studies (structure, nucleation and crystal growth), industrial
practice (beverage, confectionery, candying) and molecular biology
investigations (to produce the suitable gradient for separation of biological
materials). Therefore, the information listed in the following tables might
meet more than the interest of the sugar profession only.
8.4. J Concentration units
Although the subject is treated in detail in chapter 5 and Table 5.1 is given
for sucrose concentrations expressed in different units with 5% dry matter
increment, it may be of relevance to complement chapter 5 with a table
giving the different values of concentration with 1% dry matter increment.
(see Table 8.6). Data reported in Table 8.6 are computed using equations
(5.4), (5.6), (5.8), (5.9), (5.11), and (5.12).
8.4.2 Solubility
One of the most important properties of sucrose is its high solubility in
water. Solubility in pure water and impure solutions is essential in
determining the saturation conditions in boiling and crystallizing the sugar
in cane or beet sugar factories. Tables of solubility exist for more than one
Table 8.6 Expression of various sucrose concentrations at 200 e

Dry
substance
DS(%)
SW
WS
C
Cm
(g sucrose (g water (g sucrose (mol sucrose
per g water) per g
per litre per kg water)
sucrose) solution)
Cm
(mol sucrose
per kg
solution)
Molar
fraction,
X m (mol
per mol)
0
1
2
3
4
5
6
7
8
9
0
0.0101
0.0204
0.0309
0.0417
0.0526
0.0638
0.0753
0.0870
0.0989
99.00
49.00
32.33
24.00
19.00
15.67
13.29
11.50
10.11
0
10.02
20.12
30.30
40.55
50.89
61.31
71.81
82.39
93.06
0
0.02951
0.05963
0.09036
0.1217
0.1538
0.1865
0.2199
0.2540
0.2889
0
0.02927
0.05878
0.08851
0.1185
0.1487
0.1791
0.2098
0.2407
0.2719
0
0.00053
0.00107
0.00162
0.00219
0.00276
0.00335
0.00394
0.00455
0.00517
10
11
12
13
14
15
16
17
18
19
0.1111
0.1236
0.1364
0.1494
0.1628
0.1765
0.1905
0.2048
0.2195
0.2346
9.00
8.09
7.33
6.69
6.14
5.67
5.25
4.88
4.56
4.26
103.80
114.60
125.60
136.60
147.70
158.90
170.20
181.50
193.00
204.50
0.3246
0.3611
0.3984
0.4365
0.4756
0.5155
0.5565
0.5984
0.6413
0.6853
0.3933
0.3349
0.3668
0.3990
0.4314
0.4641
0.4971
0.5303
0.5638
0.5976
0.00581
0.00646
0.00712
0.00780
0.00849
0.00919
0.00992
0.01066
0.01141
0.01218
20
21
22
23
24
25
26
27
28
29
0.2500
0.2658
0.2821
0.2987
0.3158
0.3333
0.3514
0.3699
0.3889
0.4085
4.00
3.76
3.55
3.35
3.17
3.00
2.85
2.70
2.57
2.45
216.20
227.90
239.80
251.70
263.80
275.90
288.10
300.50
312.90
325.50
0.7304
0.7766
0.8240
0.8726
0.9226
0.9738
1.026
1.081
1.136
1.193
0.6316
0.6659
0.7005
0.7354
0.7706
0.8060
0.8418
0.8778
0.9142
0.9508
0.01298
0.01379
0.01461
0.01546
0.01633
0.01723
0.01814
0.01908
0.02004
0.02103
30
31
32
33
34
35
36
37
38
39
0.4286
0.4493
0.4706
0.4925
0.5152
0.5385
0.5625
0.5873
0.6129
0.6393
2.33
2.23
2.13
2.03
1.94
1.86
1.78
1.70
1.63
1.56
338.10
350.90
363.70
376.70
389.80
403.00
416.30
429.70
443.20
456.80
1.252
1.313
1.375
1.439
1.505
1.573
1.643
1.716
1.791
1.868
0.9878
1.025
1.063
1.100
1.139
1.177
1.216
1.255
1.295
1.335
0.02204
0.02308
0.02415
0.02525
0.02637
0.02754
0.02873
0.02996
0.03122
0.03253
40
41
42
43
44
45
46
47
48
49
0.6667
0.6949
0.7241
0.7544
0.7857
0.8182
0.8519
0.8868
0.9231
0.9608
1.50
1.44
1.38
1.33
1.27
1.22
1.17
1.13
1.08
1.04
470.60
484.50
498.50
512.60
526.80
541.20
555.70
570.30
585.00
599.80
1.948
2.030
2.116
2.204
2.295
2.390
2.489
2.591
2.697
2.807
1.387
1.415
1.456
1.497
1.539
1.581
1.623
1.666
1.709
1.752
0.03387
0.03525
0.03668
0.03816
0.03968
0.04125
0.04287
0.04455
0.04629
0.04809
Table 8.6 Continued
Dry
substance
DS(%)
Cm
WS
C
SW
(g sucrose (g water (g sucrose (mol sucrose
per litre per kg water)
per g water) per g
sucrose) solution)
Cm
(mol sucrose
per kg
solution)
Molar
fraction,
X m (mol
per mol)
50
51
52
53
54
55
56
57
58
59
1.0000
1.0410
1.0830
1.1280
1.1740
1.2220
1.2730
1.3260
1.3810
1.4390
1.00
0.96
0.92
0.89
0.85
0.82
0.79
0.75
0.72
0.69
614.80
629.90
645.20
660.60
676.10
691.70
707.50
723.40
739.40
755.60
2.921
3.041
3.165
3.294
3.429
3.571
3.718
3.873
4.034
4.204
1.796
1.840
1.885
1.930
1.975
2.021
2.067
2.113
2.160
2.208
0.04996
0.05189
0.05390
0.05598
0.05814
0.06039
0.06273
0.06516
0.06770
0.07035
60
61
62
63
64
65
66
67
68
69
1.5000
1.5640
1.6320
1.7030
1.7780
1.8570
1.9410
2.0300
2.1250
2.2260
0.67
0.64
0.61
0.59
0.56
0.54
0.52
0.49
0.47
0.45
772.00
788.40
805.10
821.80
838.70
855.80
873.00
890.30
907.80
925.40
4.382
4.569
4.767
4.974
5.194
5.425
5.671
5.931
6.208
6.503
2.255
2.303
2.352
2.401
2.450
2.500
2.550
2.601
2.652
2.704
0.07311
0.07600
0.07902
0.08218
0.08549
0.08897
0.09262
0.09646
0.1005
0.1048
70
71
72
73
74
75
76
77
78
79
2.3330
2.4480
2.5710
2.7040
2.8460
3.0000
3.1270
3.3480
3.5450
3.7620
0.43
0.41
0.39
0.37
0.35
0.33
0.32
0.30
0.28
0.27
943.20
961.20
979.30
997.60
1016.00
1034.50
1053.30
1072.20
1091.20
1110.40
6.817
7.152
7.512
7.899
8.315
8.764
9.251
9.780
10.36
10.99
2.756
2.808
2.861
2.914
2.968
3.022
3.077
3.132
3.188
3.244
0.1093
0.1141
0.1191
0.1245
0.1302
0.1363
0.1428
0.1497
0.1571
0.1652
80
81
82
83
84
85
86
87
88
89
4.2630
4.5560
4.8820
5.2500
5.6670
6.1430
6.6920
7.3330
8.0910
4.OO
0.25
0.23
0.22
0.20
0.19
0.18
0.16
0.15
0.14
0.12
1129.80
1149.30
1169.00
1188.80
1208.90
1229.10
1249.40
1269.90
1290.60
1311.50
11.69
12.45
13.31
14.26
15.34
16.55
17.95
19.55
21.42
23.64
3.301
3.358
3.415
3.473
3.532
3.591
3.650
3.710
3.770
3.831
0.1738
0.1831
0.1933
0.2043
0.2163
0.2296
0.2442
0.2603
0.2783
0.2985
9.OO
0.11
0.10
0.Q9
0.08
0.06
0.05
0.04
0.03
0.02
0.01
0.00
1332.50
1353.70
1375.00
1396.50
1418.20
1440.10
1462.10
1484.30
1506.70
1529.20
1551.90
26.29
29.54
33.60
38.81
45.77
55.51
70.11
94.46
143.15
289.22
3.893
3.955
4.017
4.080
4.143
4.207
4.271
4.336
4.402
4.467
4.534
0.3212
0.3471
0.3768
0.4113
0.4517
0.4998
0.5579
0.6297
0.7204
0.8389
1.0000
90
91
92
93
94
95
96
97
98
99
100
10.1100
11.5000
13.2900
15.6700
19.OO
24.0000
32.3300
49.0000
99.0000
194
SUCROSE
century (Herzfeld, 1892). The subject is thoroughly treated in chapter 5.

To complement Table 5.2 which gives solubility of sucrose in water each
SoC, we report in Table 8.7 the solubility for unit increments of
temperature. The equations which fit with experimental data and which
were used to calculate solubility in each of the ranges of temperature -13
to 100C (Charles, 1960; Vavrinecz, 1962); 100-125C (Smelik et ai., 1972)
and above 125C (extrapolation by Bubnik and Kadlec) were discussed in
chapter 5. The solubility of some mono- and disaccharides of common use
in the food industry may be of relevance to include in a book on sucrose
solutions. This is given in Table 8.8.
Table 8.7 Solubility of sucrose in water

Temperature (0C)
g sucrose per g water
Dry substance (%)
Molar fraction
(mol per mol)
-13
-12
-11
-10
1.7513
1.7544
1.7578
1.7615
63.65
63.69
63.74
63.79
0.08439
0.08453
0.08468
0.08484
-9
-8
-7
-6
-5
1.7654
1.7696
1.7740
1.7787
1.7837
63.84
63.89
63.95
64.01
64.08
0.08502
0.08520
0.08540
0.08560
0.08582
-4
-3
-2
-1
0
1.7889
1.7945
1.8003
1.8063
1.8127
64.14
64.21
64.29
64.37
64.45
0.08805
0.08630
0.08655
0.08682
0.08710
1
2
3
4
5
1.8194
1.8263
1.8335
1.8410
1.8489
64.53
64.62
64.71
64.80
64.90
0.08739
0.08769
0.08801
0.08834
0.08868
6
7
8
9
10
1.8570
1.8654
1.8742
1.8832
1.8926
65.00
65.10
65.21
65.32
65.43
0.08903
0.08940
0.08978
0.09018
0.09059
11
12
13
14
15
1.9023
1.9123
1.9226
1.9333
1.9443
65.54
65.66
65.78
65.91
66.04
0.09101
0.09144
0.09189
0.09236
0.09283
195
PHYSICAL PROPERTIES
Table 8.7 Continued
Dry substance (%)
Molar fraction
(mol per mol)
16
17
18
19
20
1.9557
1.9674
1.9795
1.9919
2.0047
66.17
66.30
66.44
66.58
66.72
0.09333
0.09383
0.09435
0.09489
0.09544
21
22
23
24
25
2.0178
2.0313
2.0452
2.0595
2.0741
66.86
67.01
67.16
67.31
67.47
0.09600
0.09659
0.09718
0.09779
0.09842
26
27
28
29
30
2.0892
2.1047
2.1205
2.1368
2.1535
67.63
67.79
67.95
68.12
68.29
0.09907
0.09973
0.10040
0.10109
0.10180
31
32
33
34
35
2.1706
2.1882
2.2062
2.2246
2.2435
68.46
68.63
68.81
68.99
69.17
0.10253
0.10327
0.10403
0.10481
0.10561
36
37
38
39
40
2.2629
2.2827
2.3030
2.3237
2.3450
69.35
69.54
69.72
69.91
70.10
0.10642
0.10726
0.10811
0.10897
0.10986
41
42
43
44
45
2.3668
2.3890
2.4118
2.4351
2.4589
70.30
70.49
70.69
70.89
71.09
0.11077
0.11169
0.11264
0.11360
0.11459
46
47
48
49
50
2.4833
2.5082
2.5337
2.5597
2.5863
71.29
71.50
71.70
71.91
72.12
0.11559
0.11662
0.11766
0.11873
0.11981
51
52
53
54
55
2.6135
2.6413
2.6696
2.6686
2.7282
72.33
72.54
72.75
72.96
73.18
0.12092
0.12205
0.12320
0.12437
0.12556
56
57
58
59
60
2.7584
2.7893
2.8207
2.8529
2.8857
73.39
73.61
73.83
74.05
74.26
0.12677
0.12801
0.12927
0.13055
0.13185
Temperature Cc)
196
SUCROSE
Table 8.7 Continued
Temperature (OC)
Dry substance (%)
Molar fraction
(mol per mol)
61
62
63
64
65
2.9191
2.9533
2.9881
3.0236
3.0598
74.48
74.70
74.93
65.15
75.37
0.13318
0.13453
0.13590
0.13729
0.13871
66
67
68
69
70
3.0967
3.1344
3.1727
3.2118
3.2515
75.59
75.81
76.03
76.26
76.48
0.14014
0.14161
0.14309
0.14460
0.14613
71
72
73
74
75
3.2921
3.3333
3.3753
3.4181
3.4616
76.70
76.92
77.14
77.37
77.59
0.14768
0.14925
0.15085
0.15247
0.15411
76
77
78
79
80
3.5058
3.5508
3.5965
3.6429
3.6901
77.81
78.03
78.24
78.46
78.68
0.15577
0.15746
0.15916
0.16089
0.16263
81
82
83
84
85
3.736
3.7867
3.836
3.8861
3.9368
78.89
79.11
79.32
79.53
79.74
0.16440
0.16618
0.16798
0.16980
0.17164
86
87
88
89
90
3.9883
4.0403
4.093
4.1463
4.2003
79.95
80.16
80.37
80.57
80.77
0.17349
0.17536
0.17724
0.17914
0.18104
91
92
93
94
95
4.2547
4.3097
4.6652
4.4211
4.4775
80.97
81.17
81.36
81.55
81.74
0.18296
0.18489
0.18683
0.18877
0.19071
96
97
98
99
100
4.5342
4.5912
4.6485
4.7060
4.7637
81.93
82.11
82.30
82.47
82.65
0.19267
0.19462
0.19657
0.19852
0.20046
101
102
103
104
105
4.7405
4.8108
4.8830
4.9572
5.0335
82.58
82.79
83.00
83.21
83.43
0.19968
0.20204
0.20446
0.20692
0.20944
197
PHYSICAL PROPERTIES
Table 8.7 Continued
Dry substance (%)
Molar fraction
(mol per mol)
106
107
108
109
110
5.1120
5.1928
5.2760
5.3617
5.4499
83.64
83.85
84.07
84.28
84.50
0.21201
0.21464
0.21734
0.22009
0.22290
111
112
113
114
115
5.5409
5.6347
5.7316
5.8315
5.9347
84.71
84.93
85.14
85.36
85.58
0.22578
0.22873
0.23175
0.23485
0.23801
116
117
118
119
120
6.0414
6.1517
6.2658
6.3839
6.5062
85.80
86.02
86.24
86.46
86.68
0.24126
0.24459
0.24800
0.25150
0.25508
121
122
123
124
125
6.6329
6.7644
6.9007
7.0424
7.1895
86.90
87.12
87.34
87.57
87.79
0.25877
0.26255
0.26643
0.27042
0.27452
126
127
128
129
130
7.3426
7.5019
7.6678
7.8407
8.0211
88.01
88.24
88.46
88.69
88.91
0.27874
0.28307
0.28753
0.29212
0.29685
Temperature CC)
Table 8.8 Solubility of some saccharides in water
Dry substance DS (%) of saturated solutions

Temperature
(0C)
0
1
2
3
4
5
6
7
8
9
Glucose
32.3
33.0
33.8
34.5
35.2
36.0
36.7
37.4
38.2
38.9
Fructose
Invert
sugar
Maltose
Lactose
Raffinose
50.8
51.3
51.7
52.2
52.8
53.3
53.9
54.5
55.1
55.8
35.9
36.2
36.6
36.9
37.3
37.6
38.0
38.3
38.7
39.1
10.8
11.0
11.1
11.3
11.5
11.7
11.9
12.1
12.3
12.5
6.7
6.8
6.9
7.1
7.3
7.5
7.8
8.2
8.6
9.1
198
SUCROSE
Table 8.8 Continued

Temperature
(0C)
Glucose
Fructose
Invert
sugar
Maltose
Lactose
Raffinose
56.4
57.1
57.7
58.4
59.1
59.7
60.4
61.1
61.7
62.4
39.5
39.8
40.2
40.6
41.0
41.4
41.9
42.3
42.7
43.1
12.8
13.1
13.3
13.6
13.9
14.2
14.5
14.9
15.2
15.5
9.6
10.3
11.0
11.8
12.7
13.7
14.8
16.1
17.4
18.9
20.5
22.2
24.1
26.1
28.3
30.7
10
11
12
13
14
15
16
17
18
19
39.7
40.4
41.1
41.9
42.6
43.4
44.1
44.8
45.6
46.3
20
21
22
23
24
25
26
27
28
29
47.1
47.8
48.5
49.3
50.0
50.8
51.5
52.2
53.0
53.7
78.9
79.2
79.4
79.7
79.9
80.2
80.4
80.7
81.0
81.3
63.1
63.7
64.4
65.0
65.6
66.3
66.9
67.5
68.1
68.7
43.6
44.0
44.4
44.9
45.3
45.8
46.2
46.7
47.2
47.6
15.9
16.3
16.6
17.0
17.4
17.8
18.2
18.7
19.1
19.5
30
31
32
33
34
35
36
37
38
39
54.5
55.2
55.9
56.7
57.4
58.1
58.9
59.6
60.4
61.1
81.5
81.8
82.1
82.4
82.7
82.9
83.2
83.5
83.8
84.1
69.3
69.8
70.4
71.0
71.6
72.1
72.7
73.3
73.8
74.4
48.1
48.6
49.1
49.5
50.0
50.5
51.0
51.5
52.0
52.5
20.0
20.5
20.9
21.4
21.9
22.4
22.9
23.4
23.9
24.4
40
41
42
43
44
45
46
47
48
49
61.8
62.6
63.3
64.1
64.8
65.5
66.3
67.0
67.7
68.5
84.3
84.6
84.9
85.2
85.4
85.7
85.9
86.2
86.4
86.7
75.0
75.6
76.2
76.8
77.4
78.1
78.8
79.5
80.2
81.0
53.0
53.5
54.0
54.6
55.1
55.6
56.1
56.7
57.2
57.7
25.0
25.5
26.0
26.6
27.1
27.7
28.3
28.9
29.4
30.0
50
51
52
53
54
55
56
69.2
71.4
71.8
72.2
72.6
72.9
73.3
86.9
87.2
87.4
87.6
87.9
88.1
58.2
58.8
59.3
59.9
60.4
61.0
61.5
30.6
31.2
31.8
32.5
33.1
33.7
34.3
199
PHYSICAL PROPERTIES
Table 8.8 Continued

Temperature
(0C)
Glucose
Fructose
Invert
sugar
Maltose
Lactose
57
58
59
73.7
74. I
74.4
62. I
62.6
63.2
35.0
35.6
36.2
60
61
62
63
64
65
66
67
68
69
74.8
75.1
75.5
75.8
76.2
76.5
76.8
77.2
77.5
77.8
63.7
64.3
64.8
65.4
66.0
66.5
67.1
67.7
68.3
68.8
36.9
37.5
38.2
38.9
39.5
40.2
40.9
41.6
42.2
42.9
70
71
72
73
74
75
76
77
78
79
78.1
78.5
78.8
79.1
79.4
79.7
80.1
80.4
80.7
81.0
69.4
70.0
70.6
71.1
71.7
72.3
72.9
73.5
74.1
74.6
43.6
44.3
45.0
45.7
46.4
47.1
47.8
48.5
49.2
49.9
80
81
82
83
84
85
86
87
88
89
81.3
71.6
82.0
82.3
82.6
82.9
83.3
83.6
83.9
84.3
75.2
75.8
76.4
77.0
77.6
78.2
78.8
79.4
80.0
80.6
50.6
51.3
51.9
52.5
53.0
53.6
54.2
54.7
55.2
55.8
90
91
92
93
94
95
96
97
98
99
100
84.6
85.0
81.2
81.8
82.4
83.0
83.6
84.2
84.8
85.4
86.0
86.6
87.2
56.3
56.8
57.3
57.8
58.3
58.8
59.3
59.8
60.3
60.7
61.2
Raffinose
200
SUCROSE
8.4.3 Density of sucrose solutions
The density of sucrose solutions is generally used in sugar technology and

in the sugar trade to measure the concentration of dissolved substances.
Since the non-sucrose impurities present in technical sugar solutions affect
the density in the same way as sucrose, density can be used as an
approximate method for determination of dry substance content. The density
tables for sucrose have existed for nearly one century (Plato, 1900) and are
still used as reference marks in brewery. ICUMSA recommended in its
16th session (1978) that density should be determined at 20C related to
water at 4C (weight corrected to vacuum) by means by hydrometers or
pycnometers, the latter giving more accurate results.
Following the recommendations adopted by ICUMSA in 1982, new
measurements of density were performed by Wagenbreth et al. (1988)
using Kell's (1975) relation of determination of water density Qw (kg/m 3 )
when temperature t (0C) is varied:
(999.83952 + 16.952577 X t - 7.9905127 X 10-3 X (2
- 46.241757 X 1O--{) X P + 105.84601 X 10-9 X t4 - 281.03006
X lO- IZ X ~)/ (1 + 16.887236 X 10-3 X t)
Qw =
A polynomial including Qw giving the density Q of sucrose solutions as a

function of mass concentration c (g sucrose % g of solution) at 20C and
temperature t (0C) was adopted by ICUMSA (1990) to replace Plato's
table:
z
3
Q = Qw + atcZ + a3c3 + (blc + bzc + b 3c ) X (t - 20)
z
+ (CIC + czc + C3C3) X (t - 20)Z + (d,c + dzc Z) X (t - 20?
+ elc(t -
20)4
Coefficients.= 385.850 74
Gz = -13.03435
G3 = -3.6663
G,
d,= -5.110
dz =
1.580
10-5
X 10-5
= -0.459244
b z = 7.5699 X
hi
b3
6.2667
e,
1.986
lO- z
lO- z
6.0198 X 10-3
3
Cz = -1.3008 X 10C3 = -4.907 X 10-4
CI
10-7
The values of density derived from this polynomial are listed in Table 8.9
with Q in kg/m 3 , c in g sucrose % g of solution and t in C.
8.4.4 Density and apparent specific volume
Theoretically the density (or mass per unit volume) represents the packing
characteristics of solute molecules among water molecules, which depends
on the molecular structure of both. Moreover, since water is 'structured',
201
PHYSICAL PROPERTIES
Table 8.9 Density Q (kg m-3 ) of aqueous sucrose solution as a function of the mass fraction
w (%) and temperature CC) (from ICUMSA, 1990)
Temperature CC)
w(%)
5
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
10
20
30
40
50
60
70
80
999.70
1019.56
1040.15
1061.48
1083.58
1106.47
1130.19
1154.76
1180.22
1206.58
1233.87
1262.11
1291.31
1321.46
1352.55
1384.58
1417.50
1451.30
998.20
1017.79
1038.10
1059.15
1080.97
1103.59
1127.03
1151.33
1176.51
1202.01
1220.64
1257.64
1286.61
1316.56
1347.49
1379.36
1412.20
1445.90
995.64
1015.03
1035.13
1055.97
1077.58
1099.98
1123.20
1147.28
1172.25
1198.16
1224.98
1252.79
1281.59
1311.38
1342.16
1373.98
1406.70
1440.50
992.21
1011.44
1031.38
1052.06
1073.50
1095.74
1118.80
1142.71
1167.52
1193.25
1219.93
1247.59
1276.25
1305.93
1336.63
1366.36
1401.10
1434.80
988.03
1007.14
1026.97
1047.51
1068.83
1090.94
1113.86
1137.65
1162.33
1187.94
1214.50
1242.05
1270.61
1300.21
1330.84
1362.52
1395.2
1429.00
983.19
1002.20
1021.93
1042.39
1063.60
1085.61
1108.44
1132.13
1158.71
1182.23
1208.70
1236.18
1264.67
1294.21
1324.80
1356.46
1389.2
1422.90
977.78
996.70
1016.34
1036.72
1057.85
1079.78
1102.54
1126.16
1150.88
1176.14
1202.56
1220.99
1258.45
1287.96
1318.55
1350.21
1383.0
1416.80
971.76
990.65
1010.23
1030.56
1061.63
1073.50
1096.21
1119.79
1144.27
1169.70
1196.11
1223.53
1251.99
1281.52
1312.13
1343.83
1376.60
1410.60
the interaction between solute and solvent is extremely complex. Electrostrictive forces counterbalance displacement of water molecules so that
water molecules, in general, have good packing characteristics. In other
words, sugars dissolved in water show higher densities (up to 1.5 g/cm 3 )
than many other organic compounds. Sucrose is no exception to this rule
and, in fact, sucrose has a slightly higher density than many other sugars
which emphasizes its good compatibility with water structure. The
interaction between sucrose and water, giving rise to the solute-solvent
effects, is largely due to hydrogen bonds. These have a lifetime of about
10-9 s and occur at specific loci in the sucrose molecule. Generally
equatorial hydroxyl groups are more easily hydrated than axial hydroxyl
groups but such effects are modified by the interplay between the hydroxyl
groups of the sucrose molecule itself, i.e. intramolecular hydrogen
bonding.
Apparent molar volume <j>(V~) of the sugar can be calculated using the
density of solution and that of water:
<j>(V~)
= M
x(_l_ - ~)
QI
/W2
Q2
with QI density of solution, Q2 density of water, WI mass fraction of water,

W2 mass fraction of solute and M molecular weight of solute. The partial
molar volume is apparent molar volume at infinite dilution. The
corresponding specific volumes are obtained by dividing molar volumes by
202
SUCROSE
molecular weight of the solute. These offer the advantage of comparing the
characteristics of substances on a mass basis. The apparent molar volumes
of dissaccharides are about twice those of monosaccharides and trisaccharides about thrice, etc.... However, the apparent specific volumes of most
sugars are all within 0.6O--D.63 cm 3/g. Increase in temperature causes a
corresponding increase in apparent specific volume which is presumably
related to a diminution in the overall number of hydrogen bonds.
Apparent molar volumes (AMV in cm 3/mol) are good experimental
indicators of the effective size of sugar molecules (see Table 8.10). Of
particular importance in taste chemoreception is the apparent specific
volume (ASV in cm 3/g) which is a measure of the packing ability of a
particular form of solute conformation in water (Shamil et ai., 1987). This
parameter was useful to discriminate basic tastes. Sweet substances
generally fit into the range 0.51-0.71 cm 3/g and sucrose, the optimum
sweetener, is situated in the center of the sweet range (0.61 cm 3/g).
8.4.5 Refractive index

Like densimetry, refractometry is a rapid method for determining total
solids in aqueous sucrose solutions. The principle of the method is recalled in
chapter 7 (in this book). The 20th Session of ICUMSA (1990) officially
adopted formulae and tables recommended in the 17th Session (1978)
which give the Refractive Index in vacuo for aqueous sucrose solutions
with concentrations ranging from 0 to 85% at temperatures between 15 and
30C, and wavelengths from 546.1 to 589.3 nm.
For practical purposes, Table 8.11 reports the Refractive Index of
aqueous sucrose solutions prepared in standard air at 20C and concentrations ranging from 0 to 85% for a wavelength of 589.3 nm (ICUMSA,
1979).
Temperature variations may seriously affect the reliability of refractometer readings and negative (1G-19C) or positive (21-30C) corrections to
refractometer readings have been published (Pearson, 1976; ICUMSA,
Table 8.10 Apparent molar and specific volumes of sugars at 20C and
5% (w/v) (From ShamjI, 1988; Lopez-Chavez, 1993)
Sugar
Glucose
Frucrose
Mannose
Galactose
Sucrose
Trehalose
Maltose
Lactose
Apparent molar volume

(cm 3/mol)
Apparent specific volume

(cm 3/g)
111.2
108.1
0.6178
0.6006
0.6178
0.6100
0.6120
0.6080
0.6161
0.6179
111.2
109.8
209.5
208.6
210.9
211.5
349527
354087
352659
354243
355840
1.349371
1.350930
1.352501
1.354084
1.355679
11
1.357287
1.358907
1.360539
1.362185
1.363842
1.365513
1.367197
1.368894
1.370604
1.372328
16
17
18
19
20
21
22
23
24
25
15
14
12
13
341903
343404
34917
346442
347978
1.341753
1.343253
1.344765
1.34289
1.347824
6
7
8
9
10
365681
368366
369064
370776
372501
357448
359070
360703
362350
364009
334564
336009
337466
338933
340412
1.334420
1.335864
1.337320
1.338786
1.340264
1
2
3
4
5
333129
0.1
1.332986
0.0
Sucrose g/100 g
365849
367535
369235
370948
372674
357610
359232
360867
362515
364176
349682
351243
352817
354492
356000
342052
343555
34509
346595
348133
334708
336154
337612
339081
340561
33272
0.2
366017
367705
369406
371120
372847
357772
359395
361032
362681
364342
349838
351400
352975
354561
356160
342202
343706
345221
346748
348287
334852
336300
337758
339228
340709
333415
0.3
366185
367874
369576
371292
373021
357933
359558
361196
362846
364509
349993
351557
3533133
354721
356321
342352
343857
345373
346902
348442
334996
336445
337905
339376
340858
333558
0.4
366354
368044
369747
371464
373194
358095
359722
361360
363014
364676
350149
351714
353291
354880
356482
342502
344008
345526
347055
348596
335141
336590
330851
339524
341007
333702
0.5
0.6
366522
368214
3699518
371637
373368
358257
359885
361525
363178
364843
350305
351871
353449
355040
356642
342652
344159
345678
347209
348751
335285
336736
338198
339671
341156
333845
Table 8.11 Refractive index of pure sucrose solutions at 20C and 589 nm (Data from ICUMSA, 1979)
366691
368384
370090
371809
373542
358420
360048
361690
363344
365011
350461
352029
353608
355199
356803
342802
344311
345831
347362
348906
335430
336882
338345
339819
341305
333989
0.7
366859
368554
370261
371982
373716
358582
360212
361854
363510
365178
350617
354186
353767
355359
356964
342952
344462
345983
347516
349061
335574
337028
338492
339967
341454
334132
0.8
367028
368724
370432
372155
373890
358744
360376
362019
363676
365346
350774
352343
353925
355519
357126
343103
344614
346136
347670
349216
335719
337174
338639
340116
341604
334276
0.9
(,;.)
en
tT1
::l
tT1
:<l
0...,
:<l
...,
t"""
n
;I>
::r::
-<
en
...,
374239
375991
377756
379536
381329
383137
384958
386794
388644
390509
392388
394283
396192
398116
400055
1.374065
1.375815
1.377579
1.379357
1.381149
1.382955
1.384775
1.386610
1.388459
1.390322
1.392200
1.394092
1.396000
1.397922
1.399860
1.401813
1.403781
1.405764
1.407763
1.409777
1.411807
1.413853
1.415915
1.417993
1.420087
1.422197
1.424323
1.426466
1.424625
1.430800
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
412215
414265
416230
418411
420508
422621
424750
426896
429059
431238
422409
424537
426681
428842
431019
402205
404176
406163
408165
410182
392577
394473
396383
398309
100249
383318
385141
386978
388830
390696
374414
376167
377934
379715
381509
0.2
412011
414059
416122
418202
420297
402009
403978
405963
407964
409980
0.1
Sucrose gl100 g
0.0
Table 8.11 Continued
422833
424964
427112
429276
431456
412420
414470
416537
418620
420718
402401
404374
406362
408366
410385
392766
394663
396575
398502
400444
383500
385324
387163
389016
390884
374588
376343
378111
379893
381689
0.3
423046
425178
427328
429493
431675
412624
414676
416744
418829
420929
402598
404572
406562
408567
410588
392955
394854
396767
398696
4000639
383682
385507
387348
389202
391071
374763
376519
378289
380072
381870
0.4
423258
425393
427543
429711
431894
412828
414882
416952
419038
421140
402795
404770
406762
408768
410790
393144
395044
396959
398889
400834
383863
385691
387532
389388
391259
374938
376695
378467
380251
382050
0.5
423471
425607
427759
429928
432114
413033
415089
417160
419247
421351
402992
404969
406961
408970
410994
393334
395235
397152
399083
401030
384046
385874
387717
389575
391447
375113
376872
378644
380431
382231
0.6
423684
425821
427975
430146
432033
413238
415295
417368
419457
421562
403189
405167
407162
409171
411197
393523
395426
397344
399277
401225
384228
386058
387902
389761
391635
375288
377049
378822
380610
382412
0.7
423897
426036
428192
430364
432553
413433
415502
417576
419667
421774
403386
405366
407362
409373
411400
393713
395617
397537
399471
401421
384410
386242
388088
389948
391823
375464
377225
379001
382593
382593
0.8
424110
426251
42408
430582
432773
413648
415708
417785
419877
421985
403583
405565
407562
409575
411604
393903
395809
397730
399666
401617
384593
386426
388273
390135
392011
375639
377402
379179
382774
382774
0.9
VJ
tTl
VJ
;<l
("')
c::
N
0
1.444204
1.446497
1.448807
1.451134
1.453478
1.455839
1.458217
1.460613
1.463026
1.465456
1.467903
1.470368
1.472850
1.475349
1.477866
1.480400
1.482951
1.485520
1.488105
1.490708
1.493328
1.495966
1.498620
1.501292
1.503980
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
60
1.432993
1.435201
1.437427
1.439669
1.411928
56
57
58
59
493591
496230
498887
501560
480654
483207
485777
488365
490970
468149
470616
473099
475600
478119
456076
458456
460854
463268
465700
444432
446727
449039
453667
453713
433213
435423
437650
439894
442155
493855
496495
499153
501828
480909
483463
486035
488625
491231
468395
470863
473349
475851
478371
456313
458695
461094
463511
465944
444661
446957
449271
451601
453949
433433
435645
437874
440119
442382
494118
496760
499420
502096
481163
483720
486294
488884
491493
468641
471111
473598
476103
478624
456551
458934
461335
463753
466188
444890
447188
449503
451835
454184
433653
435867
438098
440345
442609
494381
497026
499687
502365
481418
483976
486552
489144
491754
468887
471359
473848
476354
478878
456788
459174
461576
463996
466433
445119
447419
449736
452069
454420
433874
436089
438322
440571
442836
494645
497291
499954
502634
481673
484233
486810
489405
492016
469134
471607
474098
476606
479131
457026
459413
461817
464239
466678
445348
447650
449968
452304
454656
434095
436312
438546
440796
443064
494909
497556
500221
502903
481929
484490
487069
489665
492278
469380
471855
474348
476857
479384
457264
472059
462059
464482
466922
445578
447881
450201
452538
454893
434316
463534
438770
441022
443292
495173
497822
500488
503172
482184
484747
487328
489926
492541
469627
472104
474598
477109
479638
457502
459893
462300
464725
467167
445807
448112
450434
452773
455129
434537
436757
438994
441248
443519
495437
498088
500576
503441
482440
485005
487587
490186
492803
469874
472352
474848
477361
479892
457740
460133
462542
464969
467413
446037
448343
450667
453008
455365
434758
436980
439219
441475
443747
495701
498354
501024
503711
482695
485262
487846
490447
493066
470121
472601
475099
477645
480146
457979
460373
462784
465212
467658
446267
448575
450900
453243
455602
434980
437203
439444
441701
443976
Ul
N
0
[J)
tTl
:!
tTl
::<:l
."
::<:l
."
t'"'
;l>
-<
[J)
r;
:I:
."
206
SUCROSE
1979). These corrections are given in Table 8.12 between 15 and 30C. The
presence of extraneous saccharides in technical sugar solutions also
reduces the accuracy of refractometers. For mixtures in aqueous sucrose
solutions and invert sugar, a formula for the correction of refractometric to
dry substance was proposed (ICUMSA, 1990).
8.4.6 Polarimetry
When a beam of plane polarized light is passed through optically active
(chiral) solute such as a mono- or a disaccharide, it is bent to the right or
left, depending on the overall chiral properties of the solute (Shallenberger,
1985). In practice, this is done in a polarimeter (saccharimeter in the sugar
industry).
Sucrose differs from reducing sugars in that its specific rotation remains
constant over time whereas reducing sugars exhibit mutarotation, i.e.
change in rotation due to the establishment of a tautomeric equilibrium
over a particular period. This property allows sucrose to be sensitively
identified and it is indeed a dependable parameter for assessing its purity.
Application of polarimetry to sugar products is based on the determination of a ratio of optical rotation between the same and an aqueous sucrose
solution with reference concentration, i.e. the 'normal sugar solution'. The
basic conditions of polarimetry (the so-called 'International Sugar Scale')
and the existing method of measurement are extensively described in
chapter 7.
The new reference, lOooZ corresponding to
[a]
20.00C
546.2271
= 40.777C,
has been valid since 1 July, 1988. Saccharimeter scales and quartz control
plates calibrated with the former reference, lOooS for
[a]
20000C
589.4400
= 40.765C
'
can still be used providing that the values obtained are reduced by 0.029%.
Taking into account the new reference, the specific rotation value (in for a
concentration in g/cm 3 and length of the tube in dm, the wavelength being
that of spectrally filtered yellow sodium light D-line 589.4400 nm at 20e)
is, for sucrose weighed in standard air: [alJo = 66.590C.
8.4.7 Thermal properties of aqueous sucrose solutions
8.4.7.1 Specific heat. Specific heat is the amount of heat required to raise
one degree the temperature of a unit weight of solution. As shown in Table
8.13, the specific heat of sucrose solutions (in kJ/kg K) is lower than that of
0.Q7
0.14
0.22
0.29
0.37
0.45
0.53
0.61
0.69
0.78
Add to the measured value

21
0.06 0.07
22
0.13 0.14
23
0.20 0.21
24
0.27 0.28
25
0.34 0.35
26
0.42 0.43
27
0.50 0.51
28
0.58 0.59
29
0.66 0.67
0.74 0.75
30
0.Q7
0.14
0.21
0.29
0.36
0.44
0.52
0.60
0.68
0.77
0.33
0.27
0.20
0.14
0.Q7
Subtract from the measured value

15
0.29 0.31
0.32
16
0.24 0.25 0.26
17
0.18 0.19 0.20
18
0.12 0.13 0.13
19
0.06 0.06 0.Q7
15
10
CC)
Temperature
0.07
0.15
0.22
0.30
0.38
0.46
0.54
0.62
0.70
0.79
0.34
0.28
0.21
0.14
0.07
20
0.07
0.15
0.23
0.30
0.38
0.46
0.55
0.63
0.71
0.80
0.35
0.28
0.21
0.14
0.Q7
25
0.08
0.15
0.23
0.31
0.39
0.47
0.55
0.64
0.72
0.81
0.36
0.29
0.22
0.15
0.Q7
30
0.08
0.15
0.23
0.31
0.39
0.47
0.56
0.64
0.73
0.81
0.37
0.30
0.22
0.15
0.08
35
0.08
0.16
0.23
0.31
0.40
0.48
0.56
0.64
0.73
0.81
0.37
0.30
0.23
0.15
0.08
40
0.08
0.16
0.24
0.32
0.40
0.48
0.56
0.65
0.73
0.82
0.38
0.30
0.23
0.15
0.08
45
0.08
0.16
0.24
0.32
0.40
0.48
0.56
0.65
0.73
0.81
0.38
0.31
0.23
0.15
0.08
50
Sucrose (g/100 g of solution)
0.08
0.16
0.24
0.32
0.40
0.48
0.56
0.64
0.73
0.81
0.38
0.31
0.23
0.15
0.08
55
0.08
0.16
0.24
0.32
0.40
0.48
0.56
0.64
0.72
0.81
0.38
0.31
0.23
0.15
0.08
60
0.08
0.16
0.23
0.31
0.39
0.47
0.55
0.64
0.72
0.80
0.38
0.31
0.23
0.15
0.08
65
0.08
0.15
0.23
0.31
0.39
0.47
0.55
0.63
0.71
0.79
0.38
0.31
0.23
0.15
0.08
70
0.08
0.15
0.23
0.31
0.39
0.46
0.54
0.62
0.70
0.78
0.38
0.30
0.23
0.15
0.08
75
0.08
0.15
0.23
0.30
0.38
0.46
0.53
0.61
0.69
0.77
0.37
0.30
0.23
0.15
0.08
80
0.07
0.15
0.22
0.30
0.37
0.45
0.52
0.60
0.68
0.75
0.37
0.30
0.22
0.15
0.07
85
Table 8.12 Temperature corrections between 15 and 30C for refractive index determined at 589 nm (reference temperature = 20C) (Data from
ICUMSA,1989)
""-<
[/J
""tT1
'..,til"
'""0"
ri
>
1""
[/J
:I:
208
SUCROSE
Table 8.13 Specific heat (kJ/kg K) of sucrose and its solutions (From Lyle, 1957)
Temperature Water
(0C)
0
10
20
30
40
50
60
70
80
90
100
4.187
4.187
4.191
4.195
4.199
4.204
4.212
4.216
4.224
4.233
4.241
Concentration of sucrose solutions (g/ 100 g of solution)

10
20
30
40
50
60
70
80
90
3.936
3.936
3.936
3.977
3.977
3.977
3.977
3.977
3.977
4.019
4.019
3.684
3.684
3.726
3.726
3.726
3.768
3.768
3.810
3.810
3.810
3.852
3.433
3.475
3.475
3.517
3.517
3.559
3.559
3.601
3.601
3.643
3.643
3.182
3.224
3.224
3.266
3.308
3.349
3.349
3.391
3.433
3.475
3.475
2.931
2.973
3.014
3.056
3.098
3.140
3.140
3.182
3.224
3.266
3.308
2.680
2.721
2.763
2.805
2.847
2.889
2.973
3.014
3.056
3.098
3.140
2.428
2.470
2.554
2.596
2.638
2.680
2.763
2.805
2.847
2.889
2.973
2.177
2.219
2.303
2.345
2.428
2.470
2.554
2.596
2.680
2.721
2.763
1.926
2.010
2.052
2.135
2.219
2.261
2.345
2.386
2.470
2.554
2.596
Sucrose
crystal
1.164
1.202
1.235
1.269
1.306
1.340
1.172
1.411
1.444
1.478
1.516
water. These values may be defined as the ratio of the thermal capacity of
sucrose to that of water and they are of practical interest in heat transfer
calculations for food processes.
8.4.7.2 Heat of solution. When crystallized sucrose is dissolved in water,

thermal energy is absorbed and the temperature decreases. Depending on
temperature, size of crystal and the degree of crystallinity, the dissolution
of sucrose may be more or less endothermic. Van Hook (1981) reported
that fine granulated sucrose shows an endothermal effect of 16.7 0.8 Jig
when 5.0 g of sucrose are dissolved in 50 g of water at room temperature.
Other data quoted from the thesis of Roth (1976) are 4.75 0.26 kJ/mol for
crystalline sucrose, which is in good agreement with the values of 4.73 kJI
mol given by Culp (1946). Freshly milled sugar has a heat of solution of
3.52 0.9 kJ/mol; a recrystallized sample after adsorption of water by
amorphous sugar is endothermal to the extent of 3.86 0.16 kJ/mol while
amorphous sugar shows an exothermic effect to the extent of -16.9 kJ/mol
(Roth, 1976).
8.4.7.3 Heat of dilution. The heat of dilution is the amount of heat
evolved when a sucrose solution is diluted with water. Values obtained by
Vallender and Perman (1931) when 1 g of water is added to different
concentrations of sucrose at different temperatures are reported in Table
8.14.
8.4.7.4 Heat of crystallization. Kilmartin and Van Hook (1950) reported
that the enthalpy of crystallization (heat content of crystallized sucrose and
saturated sucrose solution minus heat content of supersaturated solution)
is, respectively, 10.47 kJ/mol and 32.66 kJ/mol at 30 and 57C. More
209
PHYSICAL PROPERTIES
Table 8.14 Heats of dilution (1) of sucrose solutions at different temperatures (0C) and for
various concentrations (gll00 g of solution) (From Vallender and Perman, 1931)
Temperature (OC)
Concentration (g/100 g of solution)
Heat of dillution per g of

water added (1)
58.94
56.98
55.03
51.27
49.4
47.39
45.31
2.22
1.80
1.59
1.17
1.05
0.75
0.63
63.39
61.82
60.32
56.51
55.05
53.62
52.2
47.79
46.49
41.20
40.07
34.84
30.18
25.88
22.39
18.99
7.03
6.36
5.82
4.98
4.44
3.85
3.60
2.72
2.39
1.67
1.55
1.09
0.88
0.54
0.35
0.28
40
66.75
63.96
62.43
60.81
59.26
57.75
56.26
54.8
47.03
45.78
38.24
37.02
34.48
31.66
28.66
23.86
18.93
10.38
8.12
6.99
6.2
5.82
5.57
4.9
4.69
2.93
2.68
1.88
1.67
1.42
1.09
0.96
0.71
0.50
60
67.97
66.23
64.59
63.23
63.07
61.77
59.78
58.90
56.67
9.04
8.37
7.62
7.33
7.24
6.82
6.41
5.99
5.28
20
210
SUCROSE

Temperature (OC)
Concentration (g/IOO g of solution)
Heat of dillution per g of

water added (1)
53.83
52.50
51.24
49.99
47.14
44.60
41.95
39.38
36.91
33.24
28.72
4.90
4.61
4.31
4.02
3.39
3.06
2.47
2.26
2.01
68.79
66.35
63.94
61.59
59.33
50.67
48.82
43.83
42.23
36.10
29.91
23.52
8.46
7.83
7.33
6.87
6.20
4.77
4.10
3.31
3.06
2.26
1.55
0.80
80
1.51
1.17
Table 8.15 Heat required to vaporize water with heat available from crystallization for 100 g
of solution. (From Nicol, 1973)
Heat available from crystallization
Sucrose (g per
100 g of solution)
86
87
88
89
90
91
92
93
Heat required, latent

heat of vaporization
(kJ)
31.6
29.4
27.1
24.9
22.6
20.3
18.1
15.8
~H
at nooe
(kJ)
16.2
16.4
16.6
16.7
~H
at 120C
(kJ)
20.9
21.1
21.3
21.6
21.8
~H
at l300e
(kJ)
26.9
27.3
27.6
27.9
recently, Nicol (1973) investigating the dehydration of sugar solutions

found that in some cases the heat available from crystallization is sufficient
to allow vaporization of water. This is reported in Table 8.15.
211
PHYSICAL PROPERTIES
8.4.8 Increase in volume

When sucrose is dissolved in water at a constant temperature, an expansion
of volume occurs. Increase in volume (in 10-3 m 3 ) at 20 e for aqueous
sucrose solutions at different final concentrations (1-70% w/w) is given in
Table 8.16. The data are adapted from Spengler et al., 1938; Bates and
Associates, 1942b; Norrish, 1967.
0
8.4.9 Boiling point

Because of its particular importance in sugar technology and other
processes like confectionery, much attention has been paid to boiling point
of pure and impure sugar solutions (Bates and Associates, 1942b; Norrish,
1967; Nicol, 1968; Spengler et al., 1938; Vavrinecz, 1973; Sheng, 1990).
Table 8.16 Increase in volume when sucrose is dissolved in water at 20C (From Bates and
Associates 1942a)
Resultant solution
kg of sucrose added
in 1 m 3 of water
11.99
23.98
35.97
47.97
59.96
71.95
83.94
95.93
107.92
119.92
239.83
359.75
479.66
599.58
719.49
839.41
959.32
1079.24
1199.15
1319.07
1438.99
1558.90
1678.82
1798.73
1918.65
2038.56
2158.48
2278.39
2398.31
Sucrose in g/loo g
of solution
Specific gravity
(d2~~8
Increase in volume
(10- 3 m3 )
1.1862
2.3443
3.4760
4.5816
5.6622
6.7186
7.7515
8.7619
9.7503
10.7175
19.3602
26.4772
32.4399
37.5080
41.8688
45.6606
48.9881
51.9316
54.5539
56.9049
59.0246
60.9456
62.6945
64.2935
65.7611
67.1128
68.3618
69.5194
70.5953
1.0028
1.0074
1.0118
1.0620
1.0205
1.0247
1.0289
1.0331
1.0371
1.0411
1.0781
1.1104
1.1387
1.1638
1.1861
1.2061
1.2240
1.2403
1.2550
1.2684
1.2807
1.2920
1.3024
1.3121
1.3210
1.3292
1.3370
1.3442
1.3509
0.027
0.057
0.083
0.110
0.140
0.167
0.197
0.223
0.254
0.280
0.560
0.844
1.124
1.412
1.696
1.980
2.268
2.552
2.840
3.127
3.415
3.703
3.994
4.282
4.570
4.857
5.149
5.437
5.728
212
SUCROSE
Table 8.17 Boiling point elevation of sucrose solutions at
atmospheric pressure (from Bates and Associates, 1942b)
g sucrose per
100 g of water
50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850
900
950
1000
1050
1100
1150
1200
1250
1300
1350
1400
1450
1500
1550
1600
g sucrose per
100 g of solution
Boiling point
elevation Cq
33.33
50.00
60.00
66.67
71.43
75.00
77.78
80.00
81.82
83.33
84.62
85.71
86.67
87.50
88.24
88.89
89.47
90.00
90.48
90.91
91.30
91.67
92.00
92.31
92.59
92.86
93.10
93.33
93.55
93.75
93.94
94.12
0.74
1.79
2.98
4.25
5.57
6.88
8.18
9.44
10.65
11.81
12.93
13.98
14.98
15.93
16.84
17.69
18.51
19.27
20.01
20.70
21.36
21.99
22.58
23.16
23.70
24.22
24.71
25.18
25.64
26.07
26.49
26.88
Boiling point elevation (BPE) is defined as the difference between the

boiling temperature of sugar solution and that of water at the same
absolute pressure. BPE is pressure and concentration dependent. Values
of BPE are reported in Table 8.17 for atmospheric pressure according to
Bates and Associates (1942b).
Under vacuum, BPE may be calculated using a formula proposed by
Hugot (1987): BPE = 0.25 X DS X (30 + DS) X [1 - 0.54h/(229 - h))/
(103.6 - DS), where DS is the % dry substance and h the vacuum in
mmHg.
8.4.10 Freezing point

Like other polyhydroxycompounds, sucrose depresses the freezing point of
water far below Oe. Depending on initial concentration, it may even
213
PHYSICAL PROPERTIES
prevent a non negligible amount of water from freezing. The maximum

freeze concentrated amorphous sucrose solution was discussed in chapter
4 of this book. The freezing point depression together with amorphization
of a fraction of ice confer to sucrose a cryoprotectant ability. This property
is not only due to the specific hydration and structure maker effect water
organization below OC, but also to surface interactions between frozen
proteins and cells.
Values of freezing point depression of sucrose and other saccharides
(fructose, glucose, lactose and maltose) are reported in Table 8.18
according to Bubnik and Kadlec (chapter 5).
Approximate estimation of freezing point depression can be obtained
using the formula given by Hoynak and Bollenback (1966): freezing point
(CO) = -(5.DS)/(85-DS) with DS (dry substance) in g % g of solution.
8.4.11 Water activity
When sucrose is dissolved in water, entropy is decreased as water
molecules become organized under the effect of the sugar. Water
molecules are less free to escape into the vapour phase and this is at the
origin of vapor pressure depression. As water activity is by definition the
ratio of the vapour pressure of solution and solvent (a w = PI Po), and by
convention a w = 1.0 for water, the increase in sucrose concentration
provokes a decrease in a w . This parameter is of practical use in the food
industry and sucrose is known as a good water activity depressor, playing in
this case a role of preservative for foods sensitive to bacterial spoilage.
Water activity of sucrose solutions above 50% (w/w) are reported
according to Norrish (1967) in Table 8.19.
Norrish (1966) also established a relation applicable for confectionery
syrups between water activity and the composition of the syrup:
In
aw
= In
Xl
+ [(-K z )lIZ
X Xz
+ (-K3 )lIZ
X X3
+ ... F
where Xl is the molar fraction of water; Xz, X3 are the molar fractions of
solutes 2,3; K z, K 3 are the activity coefficients of solutes 2,3; K = -2.6 for
sucrose; Kvaries from -2.4 to 0.9 for glucose syrups with DE ranging from
90 to 33, respectively.
8.4.12 Osmotic pressure
Osmotic pressure is another property of sucrose linked to its solute-solvent
interactions in water. It is closely related to water activity by the relation.
= -
RxT
--_- X In A w
V
where n is osmotic pressure, V the partial molar volume of water, Rand T
are gas constant and absolute temperature, respectively.
Table 8.18 Freezing point depression CC) of sucrose and other saccharides solutions
g solute/loo g solution
Anhydrous
solute
Freezing point depression (0C)
Hydrated
solute
Sucrose
Fructose*
Glucose
Lactose
Maltose
1.00
2.00
3.00
4.00
5.00
1.05
2.11
3.16
4.21
5.26
0.05
0.11
0.17
0.23
0.29
0.10
0.21
0.32
0.43
0.54
0.08
0.18
0.28
0.38
0.50
0.06
0.11
0.17
0.23
0.29
0.06
0.11
0.17
0.23
0.29
6.00
7.00
8.00
9.00
10.00
6.32
7.37
8.42
9.47
10.53
0.35
0.42
0.49
0.56
0.63
0.66
0.78
0.90
1.03
1.16
0.62
0.74
0.87
1.01
1.15
0.35
0.42
0.50
0.35
0.42
0.48
0.55
0.62
11.00
12.00
13.00
14.00
15.00
11.58
12.68
13.68
14.74
15.79
0.71
0.79
0.87
0.95
1.03
1.29
1.43
1.57
1.71
1.86
1.29
1.44
1.59
1.74
1.90
0.69
0.77
0.84
0.92
1.00
16.00
17.00
18.00
19.00
20.00
16.84
17.89
18.95
20.00
21.05
1.12
1.21
1.30
1.40
1.49
2.01
2.16
2.32
2.48
2.64
2.06
2.22
2.38
2.55
2.71
1.08
1.17
1.25
1.34
1.43
22.00
24.00
26.00
28.00
30.00
23.16
25.26
27.37
29.47
31.58
1.70
1.92
2.16
2.42
2.71
3.05
3.43
3.82
4.20
3.05
3.39
3.74
4.09
4.45
1.64
1.85
2.08
2.34
2.62
32.00
34.00
36.00
38.00
40.00
33.68
35.79
37.89
40.00
42.10
3.02
3.35
3.72
4.13
4.58
4.81
5.18
5.56
5.94
6.35
2.93
3.25
3.60
3.99
4.41
42.00
44.00
46.00
48.00
50.00
44.21
46.31
48.44
50.54
52.65
5.07
5.62
6.22
6.88
7.61
6.76
7.20
7.65
8.14
8.65
4.88
5.35
52.00
54.00
56.00
58.00
60.00
54.76
56.86
58.97
61.07
63.18
8.40
9.28
10.24
11.30
12.45
62.00
64.00
66.00
68.00
70.00
65.29
67.39
69.50
71.60
73.71
13.71
15.09
16.58
18.21
19.97
*Hydrated solute column not shown for fructose.
Water
activity
0.936
0.935
0.935
0.935
0.933
0.933
0.932
0.932
0.931
0.929
0.929
0.929
0.927
0.927
0.927
0.926
0.926
0.925
0.924
0.924
0.923
0.922
0.922
0.921
0.920
Sucrose by
weight (%)
50.0
50.2
50.4
50.6
50.8
51.0
51.2
51.4
51.6
51.8
52.0
52.2
52.4
52.6
52.8
53.0
53.2
53.4
53.6
53.8
54.0
54.2
54.4
54.6
54.8
62.0
62.2
62.4
62.6
62.8
61.0
61.2
61.4
61.6
61.8
60.0
60.2
60.4
60.6
60.8
59.0
59.2
59.4
59.6
59.8
58.0
58.2
58.4
58.6
58.8
Sucrose by
weight (%)
0.887
0.886
0.886
0.884
0.882
0.894
0.891
0.890
0.889
0.888
0.898
0.897
0.896
0.895
0.894
0.902
0.901
0.901
0.900
0.899
0.907
0.906
0.905
0.904
0.903
Water
activity
70.0
70.2
70.4
70.6
70.8
69.0
69.2
69.4
69.6
69.8
68.0
68.2
68.4
68.6
68.8
67.0
67.2
67.4
67.6
67.8
66.0
66.2
66.4
66.6
66.8
Sucrose by
weight (%)
0.829
0.827
0.823
0.823
0.821
0.838
0.836
0.835
0.833
0.831
0.846
0.845
0.842
0.842
0.840
0.854
0.853
0.851
0.850
0.848
0.862
0.860
0.859
0.857
0.856
Water
activity
78.0
78.2
78.4
78.6
78.8
77.0
77.2
77.4
77.6
77.8
76.0
76.2
76.4
76.6
76.8
75.0
75.2
75.4
75.6
75.8
74.0
74.2
74.4
74.6
74.8
Sucrose by
weight (%)
Table 8.19 Activity of water in aqueous sucrose solutions (From Norrish, 1967)
84.0
84.2
84.4
84.6
84.8
85.0
85.2
85.4
85.6
85.8
86.0
86.2
86.4
86.6
86.8
0.743
0.740
0.739
0.735
0.732
0.727
0.723
0.720
0.716
0.713
83.0
83.2
83.4
83:6
83.8
82.0
82.2
82.4
82.6
82.8
Sucrose by
weight (%)
0.759
0.756
0.752
0.746
0.746
0.773
0.770
0.767
0.763
0.762
0.786
0.783
0.781
0.778
0.775
Water
activity
0.529
0.522
0.516
0.507
0.500
0.562
0.555
0.549
0.542
0.535
0.592
0.586
0.580
0.574
0.568
0.620
0.614
0.609
0.603
0.598
0.645
0.640
0.635
0.630
0.625
Water
activity
0.213
0.203
0.193
0.182
0.172
0.161
0.151
0.141
0.131
0.122
94.0
94.2
94.4
94.6
94.8
0.266
0.256
0.245
0.235
0.224
92.0
92.2
92.4
92.6
92.8
93.0
93.2
93.4
93.6
93.8
0.317
0.314
0.297
0.287
0.276
0.366
0.356
0.347
0.337
0.327
Water
activity
91.0
91.2
91.4
91.6
91.8
90.0
90.2
90.4
90.6
90.8
Sucrose by
weight (%)
"tl
VI
......
tv
CIl
ttl
ttl
"tl
'0"
'::l"
"tl
r'
:>
(=i
...:
CIl
:t
64.0
64.2
64.4
64.6
64.8
0.915
0.915
0.914
0.913
0.912
0.911
0.911
0.910
0.909
0.908
56.0
56.2
56.4
56.6
56.8
57.0
57.2
57.4
57.6
57.8
65.0
65.2
65.4
65.6
65.8
63.0
63.2
63.4
63.6
63.8
Sucrose by
weight (%)
0.919
0.919
0.918
0.917
0.916
Water
activity
55.0
55.2
55.4
55.6
55.8
Sucrose by
weight (%)
0.869
0.867
0.866
0.865
0.863
73.0
73.2
73.4
73.6
73.8
72.0
72.2
72.4
72.6
72.8
71.0
71.2
71.4
71.6
71.8
0.881
0.880
0.878
0.878
0.876
0.875
0.874
0.872
0.871
0.870
Sucrose by
weight (%)
Water
activity
0.798
0.795
0.793
0.791
0.788
0.810
0.807
0.803
0.802
0.800
0.819
0.817
0.815
0.813
0.811
Water
activity
81.0
81.2
81.4
81.6
81.8
80.0
80.2
80.4
80.6
80.8
79.0
79.2
79.4
79.6
79.8
Sucrose by
weight (%)
0.668
0.664
0.659
0.654
0.650
0.689
0.685
0.681
0.677
0.672
0.709
0.705
0.701
0.697
0.693
Water
activity
89.0
89.2
89.4
89.6
89.8
88.0
88.2
88.4
88.6
88.8
87.0
87.2
87.4
87.6
87.8
Sucrose by
weight (%)
0.411
0.402
0.393
0.384
0.375
0.454
0.445
0.437
0.429
0.420
0.493
0.485
0.478
0.470
0.462
Water
activity
97.0
97.2
97.4
97.6
97.8
96.0
96.2
96.4
96.6
96.8
95.0
95.2
95.4
95.6
95.8
Sucrose by
weight (%)
0.033
0.029
0.024
0.020
0.016
0.068
0.061
0.054
0.047
0.040
0.112
0.103
0.094
0.085
0.077
Water
activity
.....-
tv
{/)
trl
{/)
:o:l
("")
c:::
0\
217
PHYSICAL PROPERTIES
Osmotic pressure of sucrose solutions in atmospheres for concentrations

in molalities (mol/kg water) ranging from 0.1 to 1.0 are reported in Table
8.20 according to Heyrovska (1987).
8.4.13 Surface tension

This parameter accounts for the cohesion of water molecules in the liquid
state. Sucrose molecules, because of their compatible packing in water,
slightly enhance the air interfacial tension of water, usually called surface
tension. The values of surface tension (mN/m) of sucrose solution at room
temperature for concentrations ranging between 0 and 65% were adapted
from Landt (1934). They are given in Table 8.21.
8.4.14 Viscosity of sucrose solutions

Although the theory of viscosity is detailed in chapter 6 of this book, only
few data are given in that chapter. The authors (Mathlouthi and Genotelle)
preferred to focus on practical aspects such as empirical relations for the
calculation of viscosity or the control of molasses exhaustion rather than
the listing of the values of viscosity. These data are reported for pure
sucrose solutions in Table 8.22 according to ICUMSA (1979).
Table 8.20 Osmotic pressure of aqueous

sucrose solutions at 25C (From Heyrovska,
1987)
Sucrose
(g/100 g of water)
3
6
9
12
15
18
21
24
27
30
33
36
Osmotic pressure
(x 105 Pa)
2.17
4.56
6.95
9.33
11.72
14.11
16.49
18.89
21.27
23.66
26.05
28.43
Table 8.21 Surface tension (N/m) at 21C at

various sucrose concentrations (g/100 g of
solution) (From Landt, 1934)
Concentration
(g/I00 g of solution)
0
5
10
15
20
25
30
35
40
45
50
55
60
65
Surface tension
(N/m)
72.68
72.91
73.51
74.10
74.70
75.30
75.89
76.49
n08
77.68
78.27
78.87
79.46
80.06
2.373
2.504
2.645
2.799
2.967
3.150
3.353
3.573
3.815
4.082
4.375
4.701
5.063
5.467
3.187
3.376
3.581
3.806
4.052
4.323
4.621
4.950
5.315
5.718
6.167
6.71
7.234
7.867
4.487
4.772
5.084
5.428
5.808
6.230
6.693
7.212
7.791
8.436
9.166
9.992
10.93
11.98
6.692
7.148
7.653
8.214
8.841
9.543
10.31
11.19
12.17
13.27
14.55
16.00
17.67
19.58
30
31
32
33
34
35
36
37
38
39
40
41
42
43
1.493
1.555
1.622
1.692
1.769
1.852
1.941
2.037
2.140
2.251
1.945
2.031
2.124
2.224
2.331
2.447
2.573
2.708
2.855
3.015
30
20
2.642
2.768
2.904
30.50
3.208
3.380
3.565
3.767
3.986
4.225
10
3.782
3.977
4.187
4.415
4.661
4.931
5.223
5.542
5.889
6.271
20
21
22
23
24
25
26
27
28
29
Sucrose (gil 00 g
of solution)'
3.241
3.461
3.706
3.977
1.833
1.927
2.029
2.141
2.260
2.390
2.532
2.687
2.856
3.039
1.184
1.231
1.281
1.333
1.390
1.451
1.516
1.587
1.663
1.744
40
Temperature eC)
Table 8.22 Viscosity (mPa s) of pure sucrose solutions (From ICUMSA, 1979)'
2.49
2.65
2.82
3.01
1.47
1.54
1.61
1.69
1.78
1.87
1.98
2.09
2.21
2.35
0.97
1.00
1.04
1.09
1.13
1.17
1.22
1.28
1.34
1.40
50
1.97
2.08
2.21
2.35
1.20
1.25
1.31
1.37
1.44
1.51
1.59
1.67
1.76
1.86
0.81
0.84
0.87
0.90
0.93
0.97
1.01
1.05
1.10
1.14
60
1.60
1.68
1.77
1.88
1.00
1.04
1.09
1.14
1.19
1.25
1.31
1.37
1.44
1.52
0.68
0.71
0.73
0.76
0.79
0.82
0.85
0.88
0.92
0.96
70
1.32
1.39
1.46
1.54
0.85
0.88
0.92
0.96
1.00
1.05
1.10
1. 15
1.20
1.26
0.59
0.61
0.63
0.65
0.67
0.70
0.72
0.75
0.78
0.81
80
......
C/l
tTl
C/l
'"
(j
c::
00
235.7
291.6
364.6
461.6
591.5
767.7
1013
1355
1846
2561
44.74
51.29
59.11
68.51
79.92
93.86
111.0
132.3
159.0
192.5
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
21.76
24.29
27.22
30.60
34.56
39.22
44
45
46
47
48
49
110.9
133.8
163.0
200.4
249.0
313.1
398.5
513.7
672.1
982.5
25.21
28.48
32.34
36.91
42.38
48.90
56.79
66.39
78.51
92.70
13.18
14.55
16.11
17.91
19.98
22.39
58.49
69.16
82.42
99.08
120.1
147.2
182.2
227.8
288.5
370.1
15.43
17.24
19.34
21.79
24.68
28.07
32.12
36.95
48.78
49.84
8.579
9.383
10.30
11.33
12.51
13.87
33.82
39.32
46.02
54.27
64.48
77.29
93.45
114.1
140.7
175.6
10.11
11.18
12.41
13.84
15.49
17.42
19.68
22.35
25.51
29.28
5.917
6.421
6.988
7.628
8.350
9.171
21.04
24.11
27.80
32.26
37.69
44.36
52.51
62.94
75.97
92.58
6.991
7.669
8.439
9.321
10.34
11.50
12.86
14.44
16.29
18.46
4.277
4.611
4.983
5.400
5.868
6.395
14.0
15.8
17.9
20.5
23.7
27.5
32.1
37.7
44.7
53.3
5.07
5.52
6.03
6.61
7.27
8.02
8.88
9.88
11.1
12.4
3.22
3.46
3.71
4.00
4.32
4.68
9.66
10.9
12.2
13.8
15.7
17.9
20.6
23.9
27.9
32.9
3.81
4.12
4.47
4.87
5.30
5.81
6.38
7.04
7.80
8.65
2.50
2.66
2.85
3.05
3.28
3.53
6.98
7.75
8.63
9.68
10.9
12.4
14.1
16.1
18.4
21.4
2.94
3.17
3.42
3.70
4.01
4.36
4.76
5.20
5.72
6.30
1.99
2.11
2.25
2.40
2.56
2.74
5.20
5.74
6.35
7.05
7.87
8.81
9.93
11.3
12.8
14.7
2.34
2.50
2.69
2.89
3.12
3.37
3.66
3.98
4.34
4.75
1.63
1.71
1.82
1.93
2.05
2.19
'-0
......
til
VJ
:;I:l
..,tTl
."
:;I:l
."
r'
:>
is
-<
VJ
:I:
."
93300
178000
351000
750000
1.7 X 106
4.21 X 106
9.44 X 106
1206
1658
2329
3340
4906
7402
11400
18200
30700
52500
10
20700
35700
64700
123000
250000
54100
3.18 X 106
481.6
636.3
854.9
1170
1631
2328
3390
5010
7870
12400
20
2250
3450
5550
9230
16200
30000
53100
114.0
142.0
178.9
228.5
296.0
389.5
535
735
1050
1500
221.6
283.4
367.6
484.3
648.5
884.8
1270
1800
2680
4100
6280
10100
17100
30200
55000
111000
206000
40
30
Temperature (0C)
394
547
773
1140
1720
2740
4230
39.0
46.6
56.1
68.4
84.1
105
131
170
221
292
64.4
78.4
96.5
121
152
193
247
324
441
603
855
1240
1860
2880
1700
8000
13100
60
50
203
272
373
519
773
1170
1710
25.0
29.4
34.9
41.7
50.3
61.4
76.7
95.5
122
156
70
114
151
204
283
404
598
857
16.8
19.5
22.8
26.9
32.0
38.3
45.9
56.2
70.5
88.5
80
'The values up to 75 g sucrose/100 g of solution derive from Swindells et al. (1958). Above 75 gllOO g. the data are those of Schneider et al. (1963).
'Weights corrected to vacuum.
80
81
82
83
84
85
86
3628
5253
7792
11876
18639
30207
70
71
72
73
74
75
76
77
78
79
Sucrose (gil 00 g
of solution)'
'"tT1
;<l
(j
'"
C
N
N
0
PHYSICAL PROPERTIES
221
References
Anderson, G.L., Higbie, H. and SIegman, G. (1950) J. Am. Chern. Soc., 72, 3798.
Bates, F.J. and Associates (1942a) Nat. Bur. of Standards, Circular C440, Washington, DC,
SA, p. 642.
Bates, F.J. and Associates (1942b) Nat. But. of Standards, Circular C440, Washington, DC,
USA, p. 365, 694.
Bridgman, P.W. (1933), Proc. Am. Acad. Arts Sci., 68, 27.
Brown, G.M., Levy, H.A. (1963) Science, 141,921-923.
Brown, G.M. and Levy, H.A. (1973) Sucrose: precise determination of crystal and
molecular structure by neutron diffraction. Acta Crystallogr., 829, 790-797.
Bubnik, Z. and Kadlec, P. (1992) Zuckerind., 117,345-350.
Charles, D.F. (1960) Solubility of pure sucrose in water. Int. SugarJ., 62,126-131.
Ciz, K. and Valter, V. (1967) Properties of sucrose. In: Sugar Technology (ed.
Bretschneider, R.). SNTL Pub., Prague, Czech Republic, p. 33.
Culp, E.e. (1946) Heat of solution: sucrose in water. Sugar, 41 (2),44,46.
Hanson, J.e., Sieker, L.e. and Jensen, L.H. (1973) Acta Crystallogr., 829, 790-797.
Helderman, W. (1927) Z. Phys. Chern., 130,396.
Herzfeld, A. (1892) Z. Ver. Rubenzuckerind., 42,181.
Heyrovska, R. (1987) The physical chemistry of aqueous solutions of sucrose. In Abstracts of
Lectures and Posters of the 8th Int. Symposium on Solute-Solvent Interactions (eds
Barthel, J. and Schmeer, G). Univ. Regensburg, pp. 106-109.
Hirschmiiller, H. (1953) Physical properties of sucrose. In Principles of Sugar Technology
(Ed. Honig, P). Elsevier Pub., Amsterdam, L. The Netherlands, pp. 19-72.
Hoynak, P.S. and Bollenback, G.N. (1966) This is Liquid Sugar (nnd edn). Refined Syrups
& Sugars Inc., New York, USA, p. 242.
Hugot, E. (1987) La Sucrerie de Cannes (JIJrd edn). Lavoisier Pub., Paris, France.
ICUMSA (1978) 17th Session, Montreal, S.12, Refractive Index, pp. 166-174.
ICUMSA (1979) Sugar Analysis, General Methods, ICUMSA Pub., Peterborough, UK.
ICUMSA (1982) 18th Session, Dublin, S.7, Density. ICUMSA Pub., Peterborough, UK,
pp.84-86.
ICUMSA (1990) 20th Session, Colorado Springs, S.II, Density. ICUMSA, Spieweck, F.,
265-270
Jones, A.J., Hamish, P. and MacPhail, A.K. (1979) Sucrose: an assignment of the I3C
NMR parameters by selective decoupling. Aust. 1. Chern., 32, 2763-2766.
Kell, G.S. (1975) J. Chern. Engng. Data, 20, 97
Kilmartin, E.J. and Van Hook, A. (1950) Sugar, 45,34.
Landt, E. (1934) Naturwiss" 22, 809.
Lopez-Chavez, A (1993) Solution properties and tastes of polyols. PhD thesis, Reading
Univ., Reading, UK.
Lyle, O. (1957) Technology for Sugar Refinery Workers. Chapman & Hall Pub., London,
UK, p. 629.
Mathlouthi, M., Cholli, A.L. and Koenig, J.L. (1986) Spectroscopic study of the structure
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Narayana, R. (1950) Current sciences, 19, 276.
Nicol, W.M. (1968) Boiling point elevation of pure sucrose solutions. Int. Sugar J., 70, 199202.
Nicol, W.M. (1973) Sucrose dehydration by heat of crystallization. In Advances in
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Pancoast, H. and Junk, W. (1973) Handbook of Sugar, 1st Ed., AVI.
Pavlik, B. (1939) Z. Kristallogr., Kristallgeom., Kristallphys. Chern., 100,414.
Pearson, D. (1976) The Chemical Analysis of Food. Churchill Livingstone, Edinburgh, UK.
222
SUCROSE
Plato, F. (1900) Wiss. Abh. Kaisel., Normal Aichung Kommission, 2, Springer Verlag,
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Swindells, 1.F., Snyder, C.F., Hardy, R.C. and Golden, P.E. (1958) Viscosities of sucrose
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Vallender, R.B., and Perman, E.P. (1931) Trans. Faraday Soc., 27,124.
Van Hook, A. (1981) Growth of sucrose crystals. Sugar Techno!. Rev., 8, 41-79.
Vavrinecz, G. (1962) Z. Zuckerind., 12,481.
Vavrinecz, G. (1973) Z. Zuckerind., 23, 10.
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Mitteilungen, 98, 198.
Technological value of sucrose in food products

M.A. CLARKE
9.1 Introduction
The technological value of sucrose in food products is the value of sucrose
as a component in foods and food products that results from the unique
combination of physical and chemical, including sensory, properties found
in the sucrose molecule: common table sugar. In this chapter, production
and consumption figures on sucrose will be presented; utilization amounts
in food categories and beverages will be outlined. Subsequent sections will
detail and describe the physical and chemical properties of sucrose that, in
their unusual multiplicity and strength, combine to give sucrose its
versatility as a universal sweetener.
Early biotechnology, beginning perhaps thousands of years Be, was
based on sucrose in certain plants especially for fermentation reactions;
these will be reviewed in light of current sucrose-based fermentations in
industry today. The applications section of this chapter will list various
food types in which sucrose is used, and will outline the functions of
sucrose in these foods, thereby providing examples of the technological
value of sucrose.
9.1.1 Sources, production and consumption of sucrose

Sucrose, regular table sugar, is usually derived from sugar-cane or sugarbeet, the former grown in the tropics or semitropics, the latter in cooler or
temperate climates, both yielding sucrose at between 10 and 15% weight of
the plant. Crop production and sucrose manufacture are described
extensively in the literature (Meade and Chen, 1985; Clarke and Godshall,
1988; McGinnis, 1987). Juice extracted from the crop plant is purified and
concentrated to syrup; sucrose is crystallized and removed from the syrupcrystal mixture; the residual dark, heavy syrupy material is molasses or
treacle. White sugars are crystallized from very light colored syrups; brown
sugars from dark colored syrups. Syrups intermediate in the process are
sometimes sold as special dark syrups for food or beverage manufacture; a
light colored partially inverted syrup (medium invert syrup) is frequently
used in confectionery, canning, beverages and baking. High test molasses

224
SUCROSE
(cane juice molasses) is cane juice concentrated by evaporation without

purification; it is finding increasing use in food manufacture.
Production and consumption of both sugar-cane and sugar-beet sourced
sucrose are listed, on a regional basis for the past several years, in Table
9.1 (Licht, 1993). Ratio of cane:beet sourced sugar is indicated in the same
table.
Category of consumption, or type of usage, figures are not available on a
global basis. Consumption categories for the US are listed in Table 9.2
(Anon., 1993). Production of starch-based glucose syrups, though an
important (>50%) market factor in the US, totals less than 10% of sugar
production, worldwide.
9.1.2 Comparative sweetness of sugar

Sweetness of sugar is discussed from the theoretical and food science points
of view in chapters 2 and 10. Comparative sweetness of several
Table 9.1 Production, consumption and source of sucrose by region' (From Licht, 1993)
1991-92
Region
1992-93
Production Consumption % Cane Production Consumption % Cane

Western Europe
Eastern Europe
Africa
North and Central
America
South America
Asia
Oceania
Total
19.8
10.0
7.6
17.3
16.2
9.3
20.6
9.8
6.7
17.2
15.4
9.5
20.6
15.2
38.6
3.4
16.5
12.3
38.7
1.1
19.4
16.1
34.0
4.9
16.6
12.8
40.3
1.1
115.8
111.4
111.5
112.9
63.5
65.2
'In 1 000 000 tons, raw value, from September to August.

Table 9.2 Usage of sugars by category in the US, calendar year, 1000 tons (From Anon.,
1993)
Bakery, cereal
Confectionery, chocolate
Ice cream, dairy
Beverages
Canned, frozen foods
All other food
Non-food
Wholesale and institutional
Retail
1991
1632
1276
439
204
332
623
89
2177
1182
1992
1719
1246
429
164
315
649
69
2205
1230
Total'
8063
8259
'May not add up because some small categories are not included.
VALUE OF SUCROSE IN FOOD PRODUCTS
225
Table 9.3 Carbohydrate - sweetness ratings (From

Yalpani, 1992)
Carbohydrate
Sucrose
Glucose
Fructose
Galactose
Maltose
Lactose
50% Invert
90% HFCS*
42% HFCS
95 DE corn syrup'
42 DE corn syrup
Brown sugar
Honey
Malt syrup
Sweetness
100
75-80
175
32
40
20
120-130
120-160
100-110
75-80
40-50
85-90
95-105
25-30
Also
Maltitol
Lactitol
Isomalt
Xylitol
Sorbitol
Mannitol
Neosugar
*HFCS is high fructose corn syrup.

'DE is dextrose equivalent (in
starches).
90
30-39
28-45
100
60
40
40-60
hydrolysed
carbohydrate sweeteners in various forms is listed in Table 9.3 (Yalpani,

1992). Sweetness is influenced by form (solid or solution), concentration in
solution and temperature and by many subjecive factors, e.g. color of
sample tested.
Choice of sweetener in a food product depends not only on sweetness
and cost, but on a combination of chemical and physical properties
affecting texture, color and color development, moisture content, storage
factors, and packaging quality. The following sections of this chapter will
discuss the chemical and physical properties of sucrose and their effect on
foods. These properties are listed in Table 9.4.
9.2 Chemical properties of sucrose
9.2.1 Purity
The purity of sucrose, generally available at over 99.9% purity with the
major non-sugar present being water, provides a relatively low cost
226
SUCROSE
Table 9.4 Physical and chemical properties of sucrose

Physical
Chemical
Bulk density
Colligative properties
Crystallinity
Dielectric constant
Osmotic pressure
Solubility
Vapour pressure
Viscosity
Water activity
Antioxidant
Color
Fermentation
Flavor
Flavor enhancement
Purity
Sensory properties
Sweetness
Table 9.5 Microbiological specifications for sugars
(1)
Canners standards
Flat sour spores:
Average not more than 50 spores/lO g
Maximum 75 spores/l0 g
Thermophilic anaerobic spores
Shall be present in not more than 60% in five samples
Sulfite spoilage bacteria
Shall be present in not more than 40% in five samples and in anyone sample to
the extent of not more than 5 spores/lO g
(2)
Carbonated beverage
Not more than
200 mesophilic bacteria/lO g
10 yeast/lO g
10 molds/l0 g
(3)
'Bottlers' liquid sugar

Shall not contain more than:
100 mesophilic bacteria/lO g (dry sugar)
10 yeast/lO g (dry sugar)
10 molds/l0 g (dry sugar)
ingredient with consistent chemical, physical and microbiological characteristics for the food and beverage industry. In Table 9.5 are outlined
microbiological specifications, in the USA, for sugars for various uses.
9.2.2 Solution reactions: inversion, degradation, Maillard and browning
reactions
The principal reactions of sucrose, in food manufacture or preparation,
occur as reactions in solution. Although the medium or substrate may
appear to be a solid, e.g. bread dough, cake mixture, the sugars
undergoing reactions are in solution form, dissolved in water. Reactions
are outlined in Table 9.6.
227
Table 9.6 Solution chemistry of sucrose

(1) Sucrose hydrolysis to glucose and fructose (invert)
(2) Glucose and fructose reaction types
(a) Acidic - HMF formation
(b) Alkaline - Lactic acid formation
- Transformations, rearrangements
(c) Acid and alkaline - Maillard reactions to form colors and flavors, condensations
The hydrolysis of sucrose, called 'inversion,' to an equimolar mixture of

glucose and fructose, called 'invert sugar' or 'invert' (because of the
inversion from positive to negative, upon hydrolysis, of the polarimetric
measurement used to quantify the sugars), is the initial reaction for most of
the important reaction sequences of monosaccharides in food chemistry.
Inversion can occur from low pH up to about pH 8.5. Subsequent
reactions, which occur also in all syrups of glucose and/or fructose are, as
outlned in Table 9.6:
(a) Reactions in acidic medium, outlined in Figure 9.1 (Monte and
Magna, 1981-82), which lead to formation of 5-hydroxymethyl
furfural (HMF). HMF rapidly decomposes into dark-colored compounds, with off-flavors.
(b) Reactions in alkaline medium, outlined in Figure 9.2, include lactic
acid formation by chemical means (rather than by fermentation),
and the rearrangement of glucose to a mixture of mannose and
fructose, which is often responsible for the reported presence of
fructose and mannose in food products that contain, in actuality,
only glucose. An alkaline environment during extraction or hydrolysis procedures can cause the transformation of glucose to a
mixture of mannose and fructose by this mechanism.
(c) Maillard reactions: the reaction of a reducing sugar with an uamino group to form a condensation product that can subsequently
polymerize into dark-colored compounds, is the basis of the
'browning reaction' observed during baking and cooking processes.
Alternate pathways of color, or melanoidin, formation after the
initial Maillard reaction are shown in Figure 9.3 (Monte and Magna,
1981-82).
(d) Thermal degradation of sucrose and caramel formation. The
thermal decomposition of solid sucrose may be the exception to the
rule that the common food-related reactions occur in water
solution; however, moisture absorption by sucrose as it is heated
can account for some thermal degradation along pathways of
solution reactions. Multiple reactions, some anhydrous, some
involving water are involved in the formation of the complex
228
SUCROSE
H-C=O
I
H-C-OH
I
HO-C-H
I
H-C-OH
I
H-C-OH
I
CH20H
D-GLUCOSE
H-C-OH
"I
C-OH
HO-C-H
I
H-C-OH
I
H-C-OH
I
CH 20H
1,2-ENOL
H-C=O
I
C-OH
" H
9H-C-OH
I
H-9- 0H
CH 20H
1l
3-DEOXYALDOSE-2-ENE
rearrangement
H-C=O
I
C=O
"I
H-C-H
H-C-OH
I
H-C-OH
,
CH 20H
3-DEOXY-D-GLUCO
-SULOSE
H-C=o
I
C=O
I
H-C
"I
C-H
H-C-OH
I
CH 20H
cyclization
5-HYDROXYMETHYL
FURFURAL
HEXOSULOSE-3-ENE
Figure 9.1 Formation of HMF from glucose. (From Monte and Magna (1981-82),
mixture known as 'caramel'; these have been reviewed by Godshall

(1986, 1988)
An outline of some of the reactions involved in thermal degradation
shown in Figure 9.4.
IS
229
H-C-OH
"I
C-OH
HO-C-H
I
H-C-OH
I
H-C-OH
I
CH 20H
H-C=O
I
H-C-OH
I
CH 20H
l,2-ENEOL
GLYCERALDEHYDE
H-C-OH
"
C-OH
I
CH20H
TRIOSE ENEDIOL
PYRUVALDEHYDE
HYDRATE
'il'1JiJ~ 1!.@/lJINV ~ &JlNqgVIJIJ"~I!.&J~IN~
W~IJIJ ~IX~IJIJ~'il'~OIJlJ 1N~~ININ~IJIJ@~INJIEIJIJ'il'
HO-9=O
H-C-OH
I
CH a
DL-LACTIC ACID
H-C=O
I
HO-C-H
I
HO-C-H
I
H-C-OH
I
H-C-OH
I
CH 20H
D-MANNOSE
9 H20H
C=O
I
HO-9- H
H-C-OH
I
H-C-OH
I
CH 20H
H-C-OH
"
C-OH
I
HO-C-H
I
H-C-OH
I
H-C-OH
I
CH 20H
ENEDIOL
D-FRUCTOSE
H-C=O
I
H-C-OH
I
HO-C-H
I
H-C-OH
I
H-C-OH
I
CH 20H
D-GLUCOSE
Figure 9.2 Reactions in alkaline solution. (From Monte and Magna (1981-82), reproduced
with permission.)
230
SUCROSE
Aldose + Amino acids
N-Substituted clycosylamine
Pathway I
N-Substituted l-amino-l-deoxy-2-ketose
Pathway 2
3-Deoxyhexonone
intermediates
5-(Hydroxymethyl)2-Furaldehyde
Methyl dicarbonyl
intermediates
+ Amines
Reductones
dicarbonyls
Pigments or melanoidins
Figure 9.3 Pathways of melanoidin formation. (From Monte and Magna (1981-82),
9.2.3 Sensory properties

The sweetness of simple carbohydrates is, of course, their outstanding
characteristic property. Sweetness, and these sugars, are major aids to
palatability, at comparatively low cost.
Considerable discussion has been recently devoted to elucidating and
explaining sweetness (Mathlouthi et ai., 1993). Although final conclusions
are still in debate, it is clear that the human response to the sweetness of
sucrose differs from response to other sweet compounds. The relative
231
~
F~_
6L..(6
OH
H2C - - - O
H+
CH20H
~
o
~
CH20H
OH
H+
~H -
f Sucrose-OH
1
HOH 2 C
non-specific
degradation
~ ~O~OH.CH20H
\--Y'
OH
vv
HO
\:~L
( -O-Sucrose
-CH 20H
OH
Figure 9.4 Mechanism of thermal degradation of sugars.
sweetness, compared to sucrose, of glucose is less than sucrose and of

fructose is more, depending on the form (solid or solution), degree of
cooking and concentration of the monosaccharide. Sweetness data from
Table 9.3 are further amplified in Table 9.7; flavor enhancement and
effects of sucrose on flavor extension and suppression are discussed by
Godshall in the same article (Godshall, 1988) (see also chapter 10).
Other sensory properties of sucrose are related to its ability to form a
variety of crystal sizes, and to its bulk density, viscosity and solubility
properties.
9.2.4 Color
Although sucrose, glucose and fructose are themselves white crystalline
materials, they are in part responsible for most of the yellow-to-brown
colors developed in baked and processed foods. Reactions responsible for
color formation include the following discussed above;
thermal degradation of sugars, with condensation at low pH and
caramel formation;
alkaline degradation of fructose, with subsequent condensation; and
232
SUCROSE
Table 9.7 Sweetness and flavor of selected carbohydrates in solution
Carbohydrate
Monosaccharides
Glucose
Fructose
Disaccharides
Sucrose
Maltose (malt sugar, maltobiose)
Lactose (milk sugar)
Palatinose (isomaltulose, Iylose)
Leucrose (glucose-I, 5-fructose)
Polyols (sugar alcohols, hydrogenated sugars)
Xylitol
Sorbitol (hydrogenated glucose) syrupy
Maltitol (hydrogenated maltose)
Mannitol
Lactitol (hydrogenated lactose)
Mixtures and syrups
Lycasin 80/55 (hydrogenated glucose syrup)
Palatinit (Isomalt; I: 1 mix of glu-sorbitol
+ glu-mannitol)
HFCS (high fructose corn syrup)
Invert syrup
Maltodextrin (DE < 20)
Neosugar (fructo-oligosaccharides)
Sweetness
61,70
130-180
100
43,50
40, 26, 15-30
50
50
100, 85-120
50,63,70
68
40,65
30-40
75
45
100-160
105
0+
46--60
Flavor character
Sweet, bitter side taste
Pure sweet, fruity
Pure sweet
Sweet, syrupy
Faint sweet, fruity
Pure sweet, masks bitter
Pure sweet
Sweet, cooling
Sweet, cooling
Sweet
Sweet
Clean, sweet
Sweet
Pure sweet
Sweet
Sweet
Bland to faintly sweet
Sweet
Maillard reactions with primary amines and subsequent melanoidin

formation.
9.2.5 Antioxidant properties

Sucrose has been reported to exhibit antioxidant properties in preventing
deterioration of flavor in canned fruit, and of rancidity in cookies. Sugar
solutions can inhibit rust formation on iron (relative to water) (Nicol,
1991). The lowering of water activity by sucrose may be in part responsible
for these observations. An extract of non-sugars in molasses has also been
found to exhibit an antioxidant effect on whole grain products (Clarke,
1991).
9.3 Physical properties of sucrose
9.3.1 Colligative properties

Freezing point depression, boiling point elevation, osmolality and effect on
water activity are all affected by the concentration of sugar in a product.
233
Freezing-point depression is an important property in ice creams, frozen

desserts and sauces, and in freeze-dried foods. The effect of sucrose and
glucose on freezing point depression is shown in Figure 9.5 (Best, 1992).
All colligative properties are affected by the number of molecules present
in a given quantity, rather than by the weight of the quantity. Figure 9.6
shows the effect of several sweeteners at varying concentrations on the
freezing point of a frozen dessert (Smith, 1990). Glucose and fructose,
having about twice the number of molecules per gram (or other weight)
that sucrose does, have a greater effect on freezing point depression and
other colligative properties than does sucrose. This property must be
combined with sweetness and viscosity properties in sweetener selection
for frozen foods.
The reduced vapor pressure caused by the sugars in solution has a
significant effect on increasing the boiling point of solutions as shown in
Figure 9.7 (Jun'( and Pancoast, 1980). Boiling point elevation is important
in candy manufacture, and in sauces and condiments that may be added to
a mixture to be cooked or processed. Boiling point elevation for sucrose
concentrations used in confectionery manufacture is reported in Table 8.18
(see chapter 8). The increase in boiling point allows higher cooking
temperatures and subsequent slower formation of very small crystals on
cooling (Flanyak, 1991).
The high osmotic pressure generated by sucrose in solution (see chapter
8, Table 8.21) is an important factor in preservation of foods, and
prevention of microbial contamination (Flanyak, 1991) (Honig, 1953).
High concentrations of sugars decrease the water activity and lower the
equilibrium relative humidity, leaving insufficient water available to
32
LL
0
+-'
Q.
OJ 31
'N
Q)
Q)
.....
LL
30
+------,~----r---r_--___r_
10
15
20
Solution concentration (% solids)

Figure 9.5 Freezing poinl depression of sucrose and glucose. (From Best (1992), reproduced
by permission.)
234
SUCROSE
oo
-80
100
Sweetener Concentration Percent (w/w)

Figure 9.6 Freezing points of various concentrations of sweetners used in frozen dessert
manufacture. CSS, corn syrup solids; DE, dextrose equivalent; DS, disaccharides; FRU,
fructose; MD, maltodextrins; MS, monosaccharides. (From Smith (1990), reproduced with
permission. )
B.PoE
30
25
20
15
10
5
70
75
80
85
90
%0050
Figure 9.7 Boiling point elevation (BPE) by sucrose and 50% invert (for invert the values are
uncorrected for barometer or possible superaturation factors.). (From Junk and Pancoast
(1980), reproduced by permission.)
235
VALUE OF SUCROSE IN FOOD PRODUcrS
sustain viable microorganisms. In acidic media, such as jams and

preserves, sucrose inverts to glucose and fructose thereby increasing the
molal concentration of sugars per weight, and the lowering effect on water
activity.
The equilibrium relative humidity (ERH) , a measure of water activity, is
the ratio of the vapor pressure of atmosphere at a sugar crystal to the vapor
pressure of water at the same temperature, or, it can be considered as the
relative atmospheric humidity at which the sugar is in equilibrium with the
air. There are three ways in which water is associated with a sucrose
crystal:
Free water (surface water) - varies with surface humidity and composition of
syrup film on crystal
Bound water - converts to free water during conditioning
Inherent water - moisture pockets in crystal. From 0.01 % for 0.5 mm crystals
to 0.4% for 3--4 mm crystals.
After sugar is crystallized, some of the bound water diffuses out of the
crystal and into the air during the conditioning process, when ambient air is
circulated through the sugar. If conditioning is insufficient, the water does
not leave the sugar crystal and causes stickiness and subsequent caking or
hardening of the sugar (Nicol, 1979). Figure 9.8 shows the difference in
humidity isotherms for sugar of different grain size. The availability of
sucrose in large, uniformly sized crystals is an important property in
preparation of dry mixes, for their stability and keeping properties.
Fructose and glucose are also available in crystalline form, but only in
smaller crystal sizes which, combined with their tendency to hygroscopicity,
\Wcter content
Ii
/f/
.-
~-------~--
--
~.-.-._.-._.-
/i
/,/
.,./
......-.---r---r---.....--,.---.......--..,.,...-_.,......--.--_ERH
10
30
50
70
90
Figure 9.8 Water vapor sorption isotherms (20C) of white granulated sugar of different
quality: ( - - ) poorer quality, smaller grain; (- - - -) intermediate; and (_._._) better
quality, larger grain.
236
SUCROSE
decrease their effectiveness on keeping qualities of dry mixes. The purity

of large, uniform crystals of sucrose is an important factor in maintaining
flavor properties of mixes.
Equilibrium relative humidity factors are important for flow properties,
and for resistance to infection by microorganisms. From Figure 9.8, it may
be seen that the equilibrium water content of sugar remains much the same
over the 20-70% relative humidity range; therefore, sugar is normally free
flowing in most temperate climates. Table 9.8 shows the minimum ERH at
which microorganisms can grow; it is apparent that concentrated solutions
of sugar, as in jams, jellies and preserves, do not have sufficient available
moisture to permit growth of microorganisms (Nicol, 1979), this is one way
in which sugars can act as a preservative. Equilibrium moisture absorption
of sucrose is shown in Table 9.9, compared to other commercial sweeteners
and carbohydrates (Yalpani, 1992).
9.3. J. J Solubility. The solubility of carbohydrate solid sweeteners is
shown in Figure 9.9. Sucrose is intermediate in solubility between glucose
and fructose. Rate of solution depends on particle size, rate of agitation,
Table 9.8 Minimum ERH allowing microorganism
growth (From Nicol, 1979)
ERH(%)
Type of microorganism
Common bacteria
Common yeasts
Common molds
Halophilic bacteria
Xerophilic molds
Osmotolerant yeasts
91
88
80
75
65
60
Table 9.9 Equilibrium moisture absorption of sucrose compared with other sweeteners (From
Yalpani, 1992)
Sweetener
Moisture absorption (%)

60% RH*
Sucrose, cryst.
Glucose, cryst.
Fructose, cryst.
Invert sugar
Maltose, solid
Lactose, anhydr.
Raffinose, anhydr.
*RH, relative humidity at 20C.
100% RH*
1h
9 days
25 days
0.04
0.07
0.38
0.19
0.80
0.54
0.74
0.03
0.07
0.63
5.1
7.0
18.4
14.5
73.4
76.6
18.4
1.4
15.9
1.2
12.9
237
gsugar %gsolution
90
70
50
30
20
ltD
60
temperature
Figure 9.9 Solubility of some sugars. (From Nicol (1979), reproduced by permission.)
and degree of undersaturation. The high degree of solubility is essential in

preparation of tinned fruits, jams, jellies, preserves and syrups. Mixtures
of sugars can give a higher dissolved solids concentration than an individual
sugar, another important factor for low water activity in jams, syrups and
preserves, where the sucrose-invert mixture is the usual combination. The
hygroscopic nature of sugars is related to their solubility: the high degree of
solubility of crystalline fructose correlates with its high degree of hygroscopicity or rate of water absorption. Crystalline fructose is frequently
mixed with sucrose, to prevent too much water pickup and inadvertent
solubilization of the fructose sweetener in storage or in dry mixes. Further
information on solubility is found in chapter 5.
9.3.1.2 Viscosity. This property is discussed in detail in chapter 6. The

viscosity of solutions of simple carbohydrates varies with their concentration
(Honig, 1953; Nicol, 1991); viscosity of their pure solutions is generally
Newtonian. Sucrose is intermediate in viscosity between the very high
viscosity of glucose syrups and the high fructose syrups: one reason for the
very high, almost plastic viscosity of glucose syrups is their content of
unhydrolyzed starch and dextrin molecules. These compounds are at lower
concentrations in the more highly processed high fructose syrups.
Comparative viscosities of sucrose and fructose are shown in Table 9.10
(Yalpani, 1992).
238
SUCROSE
Table 9.10 Viscosities of sucrose and fructose at 20C (Yalpani, 1992)
Concentration (w/w%)
Viscosity (cps)
Sucrose
20
30
40
50
60
70
1.9
3.2
6.2
15.0
58.0
480.0
Fructose
1.8
2.9
5.6
11.0
34.0
170.0
Table 9.11 Bulk density of sugars (From Junk and Pancoast, 1980)
Sugar type
Typical values
kg/m 3
16/ft 3
Confectioners AA
Sanding
Manufacturer's or fine
833-881
801-833
785-833
52-55
50-52
49-52
Granulated'
Bottler's or standard granulated
Baker's special
Sifted powdered
Compacted powdered
Agglomerated
Soft (brown)-compacted
769-817
785-849
384-481
609-721
320-384
833-993
48-51
49-53
24-30
38-45
20-24
52--{)2
'Maximum value of bulk density for granulated sugar occurs at grain size 0.2 mm, and is
93 kg/m 3 (no conglomerates).
9.3.1.3 Bulk density. The large, uniform particle size of sucrose makes it
an ideal carrier for trace ingredients, e.g. color, flavor, as well as a diluent
and bulking agent. These properties, combined with its solubility, have
made sucrose a popular ingredient in dry mixes. Bulk densities of typical
sugar are listed in Table 9.11 (Junk and Pancoast, 1980). Table 9.12 shows
related information on sieve analysis of these typical commercial grades
also variety of granulations (McGinnis, 1987).
The humectancy properties of sucrose, or its resistance to change in
water absorption as referred to above, give sucrose-containing dry mixes
desirable keeping qualities. The humectant properties of sucrose also mean
that cakes, breads, and cookies made with sucrose show good resistance to
drying out, and stay fresher longer.
The moisture and bulking properties of sugar, particularly sucrose,
affect the physical structure of baked products, cereals and confectionery
by three principal means.
mu
C
680
27
668
19
Mean aperture - coefficient of variance

MA 1271 660
CV
22
21
18.0
49.2
24.0
5.0
0.7
9.3
49.2
37.6
Percentage finer than last screen reported above

3.9
0.1
0.3
3.8
5.7
59.1
27.1
7.3
0.5
5.0
55.0
34.0
5.3
0.0661 1680
0.0469 1190
0.0331 840
0.0232 590
0.0165 420
0.0117 297
0.0083 210
0.0059 149
0.0041 105
74
0.0029
44
0.0017
Inch
Openings
0
625
21
0.8
3.1
31.6
56.7
7.8
Coarse granulated
11.3
59.8
25.6
3.2
12
16
20
30
40
50
70
100
140
200
325
Meshes
per inch
USBS sieve size
Large
crystal
specials
553
16
0.2
0.0
13.4
72.7
11.8
1.9
480
20
0.6
0.0
5.5
44.5
37.0
10.5
1.9
420
26
1.6
1.3
18.4
37.4
29.1
12.2
325
32
2.4
0.3
11.9
39.1
32.6
13.7
Manufacturers
Fine
granulated
granulated
312
31
6.0
0.0
9.3
39.2
33.5
13.0
300
32
5.0
0.0
3.0
36.0
41.0
15.0
Extra-fine
granulated
Table 9.12 Comparative sieve analysis of various grain sizes and brands (From McGinnis, 1987)
275
28
3.0
5.0
45.0
37.0
10.0
210
27
3.0
1.5
48.5
35.5
12.0
Bakers
special
165
28
6.8
30.4
40.8
22.0
0.5
1.8
9.2
34.2
0.0
3.7 0.1
9.3 1.1
Powdered
26.5 54.4 87.099.8
17.3
37.1
19.1
Crushed
grain
t"'
\0
V.l
IV
rJJ
(')
..,c:::
0
0
:<l
."
0
0
0
"J1
tT1
rJJ
:<l
(')
c:::
"J1
rJJ
tT1
c:::
<
240
SUCROSE
(1) The effect of sugars on gelatinization of starch in a mixture. Sugar

delays onset of gelatinization to higher temperature, allowing a
baked product more time to rise (Nicol, 1970).
(2) The effect of sugars on denaturation of protein, related to the water
binding capacity of sugar and its ability to stabilize protein foam, as
in meringues and egg white leavened, fat-free, cakes.
(3) The ability of sucrose to disperse its particles (in some cases,
amorphous particles) throughout fat-phase confections, e.g.
chocolate, to maintain bulk, even distribution of flavor, and stability
to moisture and to microbial infection. The fact that sucrose can
adapt the rheological properties of chocolate to the non-Newtonian
flow characteristics that permit layering is vital for chocolate
manufacture. The finer the particle size of the sugar, the more
viscous the chocolate melt, for any given fat content (see Table
9.12).
9.3.1.4 Dielectric constant. The dielectric constants of sucrose and

monosaccharides are much higher than those of complex carbohydrates,
lipids, proteins, or other major food components as shown in Tables 9.13
(Malmberg and Maryott, 1950) and 9.14 (Shukla and Misra, 1990). Dielectric
constant is one physical property of a food that affects its heating by
microwave radiation. Because sucrose has, additionally, the special
property of forming a permanent dipole when hydrogen is bonded with
water, it is an especially suitable ingredient for formulation of microwaveable foods. It can be used to increase rate of heating, to allow surface
heating only, or to formulate browning and crisping conditions (Shukla and
Misra, 1990).
9.4 Applications: effects of sucrose in food processing
The following section will describe the effects that the chemical and
physical properties of sucrose, as outlined above, show in the various
baked goods, confectionery and other foods in which sucrose plays an
important role, nutritionally, and otherwise.
9.4.1 Breads
Sugars provide the base for yeast fermentation and rising of bread. Sucrose
increases the gelatinization temperature of starch and allow higher rising.
Browning reactions, including Maillard reactions and other forms of nonenzymatic browning, create the color of the product, and increase the
bread flavor. Humectancy characteristics increase moisture retention and
shelf life.
241
Table 9.13 Dielectric activity of major food constituents

at microwave frequencies (From Shukla and Misra, 1990)
Food constituents
Relative activity
Bound water
Free water
Protein
Lipid
Triglycerides
Phospholipids
Complex carbohydrates: starch
Monosaccharides
Associated electrolytes
Ions
Low
High
Low
Low
Medium
Low
High
Low
High
Table 9.14 Dielectric constants of aqueous dextrose and sucrose solutions (From Malmberg
and Maryott, 1950)
Dielectric constant at
20C
25C
30C
80.38
79.17
76.76
75.64
68.82
65.56
61.91
70.76
74.43
71.90
69.13
66.05
62.57
58.64
Glucose (wI %)
0
5
10
15
20
30
40
50
72.13
68.73
64.90
78.54
77.37
76.14
74.80
73.43
70.46
67.11
63.39
Sucrose (wI %)
0
10
20
30
40
50
60
80.38
78.04
75.45
72.64
69.45
65.88
61.80
78.54
76.19
73.65
70.86
67.72
64.20
60.19
76.56
73.11
9.4.2 Cakes
Cakes, in the USA, are of three main types: pound cakes, with little
chemical leavening, which contain 25-35% by weight sugar; layer cakes,
leavened with baking powder or soda, which contain 23-30% sugars; and
sponge or chiffon cakes, with egg as principal leavening, which contain 3037% sugars. Angel food cakes, leavened by egg whites only, contains 42%
sugar by weight. Sucrose is the required sweetener for most cakes to enable
air incorporation, through creaming with fat and maintaining air bubbles,
242
SUCROSE
and also for elevation of starch gelatinization temperature, and for

preservation and shelf-life because of humeclancy factors. Some 10-15%
of sucrose can be replaced by glucose and/or fructose in syrup form (with
adjustment to liquid content) to produce cakes with slightly less volume
and sweetness, and a heavy crust.
A comparison of a standard cake made with and without sugar is shown
in Table 9.15. The cake made without sugar did not rise and was dry and
tasteless (Tsang and Clarke, 1988). A slice from the cake without sugar
contained some 25% more calories than a similarly sized slice from the
cake with sugar, because of the smaller size and concentration of fat in the
sugarless cake.
One recent development in this area is the developing market in the
USA for fat-free, or lowered fat, cakes and sweet breads, with formulations containing higher levels of sugar and oligosaccharides to supply bulk
substitute for the missing fat.
9.4.3 Cookies and sweet biscuits

Sucrose contributes flavor, taste, color, texture and tenderness to cookies,
as in cakes and breads, and adds to shelf life. The type of sugar used can
affect the crumb structure, spread and softness of the cookie. Brown sugars
and molasses soften the crumbs, and extend shelf-life. Glucose and
fructose produce more crust color at lower temperatures than sucrose;
lactose, a disaccharide in milk products, has the effect of maintaining crust
color. Coarser granulated sugar will produce a crisper cookie, and the
spread of the cookie increases as sucrose levels are increased, or grain size
decreased. The recently popular combination cookie with crisp crust and
soft interior can be made by combining an inner dough made with
monosaccharides and an outer dough made with sucrose. Over several
days, moisture migrates from the outer shell to the inner dough creating
the combination texture cookie.
Table 9.15 Comparison of cakes made with and without sugar (Tsang and Clarke, 1988)
100 g of cake
made with sugar
100 g of cake
made without sugar
25
23
20
29
33
Butter or margarine (g)

Sugar (g)
Eggs (g)
Flour + spices (g)
Cream (g)
Total (g)
Energy (kcaltl00 g)
Content (same size slices)
3
100
26
37
4
100
408 kcal = 5 slices

c. 82 kcal
414 kcal = 3-4 slices

104-138 kcal
'Ingredients other than sugar were identical.
243
9.4.4 Icings and frostings

Sugars are essential in these products for flavor, taste, texture - depending
on grain size of the sugar - and appearance. The purity and consistent
composition of sucrose are important to the simple water-sugar icings most
commonly used on baked goods.
9.4.5 Beverages
Sugar provides sweetness, flavor and mouthfeel in carbonated soft drinks,
and in simulated juice-type beverages. Low microbial level, and low levels
of turbidity and non-sugars are important to protect the flavor and
appearance of the beverage. High fructose corn syrup is used instead of
sucrose in almost all nutritively sweetened soft drinks in the USA, because
HFCS is much cheaper than sucrose in the USA.
9.4.6 Jams, jellies and preserves

The preservation effect, resulting from lowered water activity and high
osmotic pressure, is important here to maintain texture of fruit and to
prevent microbial contamination. The properties of sweetness and flavor
are also significant. Visual appearance of clear jellies and preserves is
another factor: some sweeteners, other than sucrose, cause haziness in
jellies. Inversion of sucrose, or use of invert syrups, prevents crystallization
in these products.
9.4.7 Confectionery
In chocolate products, sucrose is preferred because of its range of grain size
(see Table 9.12), solubility, dispersant ability in fat, stability bulk and
texture. The rheological properties contributed by sucrose to the fat
mixture are paramount to the flow and solid formation behavior of
chocolate. Sucrose has the ability to pass through an amorphous,
microcrystalline form, at about 160C (see chapter 4) which aids in the
refining and tempering of chocolate. In milk chocolate, Maillard reactions
between reducing sugars and milk protein contribute to the 'caramel'
flavor. In non-chocolate confectionery, such as hard, boiled sweets or
candy, the high viscosity of sugar solutions, and the solubility of sugars
which allow them to remain in supersaturated solution, and provide a
stable syrup phase (Flanyak, 1991; Jeffrey, 1993) are of significance.
Resistance to microbial infection is another key point. The addition of the
more difficultly crystalline glucose allows preparation of a hard sweet with a
glossy texture, with no crystalline sucrose.
Gel-type sweets, both pectin and starch, require sugars for their bulk,
244
SUCROSE
sweetness and flavor, and viscosity to support the gel structure. Caramels,
toffees and fudges require Maillard reaction products from reducing sugars
and milk (or other) proteins to produce the desired flavors.
9.4.8 Dairy products

Simple sugars give the necessary freezing point lowering to maintain
texture and product quality in ice creams and frozen desserts. Too Iowa
freezing point means too little water may be frozen: an icy texture can
develop (Smith, 1990). Sucrose provides good dispersion among fats in ice
creams, and increases viscosity in lower fat products. Sugars are used for
sweetness, flavor, preservation (high osmotic pressure) and texture in
sweetened condensed milk. Flavor, sweetness and texture are added by
sugars to yogurt products. Again, sugars are not fat substitutes, but are
finding use in lowered fat products to increase bulk, flavor and texture or
tenderness.
9.4.9 Ready-to-eat breakfast cereals

Sugars added to cereals contribute flavor, color (browning characteristics)
and sweetness, but also give important textural modifications. Sugars are
added to doughs at levels from 6 to 25%. Sugars act as binders, and can act
to increase crispness, spread, and surface porosity in much the same way as
in baked cookies. The greatest use of sugar in ready-to-eat cereals is as a
surface coating; the solubility and crystallization properties permit clear or
frosted coatings that can serve as flavor or additive carriers, and that
increase the shelf-life of the cereal. Content of invert sugar must be
controlled to prevent stickiness.
9.4.10 Meats
Sugar is often added in small quantities to cured, dried or preserved meats,
especially to pork products. The purposes of the sugars are: as a
preservative, to lower water activity, and as a flavor enhancer, to contrast
with salt and extend the meat flavor. Sugar is added at a level below 1%,
contributing less than 1 g carbohydrate (or 4 kcal) to 100 g raw slab or
sliced bacon with a total of 665 kcal (USDA, 1991).
9.4.11 Frozen and tinned vegetables

Sugars are sometimes added in small (sub-percent) levels to cooked tinned
and frozen vegetables to enhance flavor and help preserve color and
texture. A well-known example is the addition of sugar to baked beans: the
245
flavor and preservative effects of added sugar are significant to anyone who
has tasted plain boiled or baked navy or pea beans without sauce, and the
regular baked beans in sauce. The addition of sugar-containing sauce
causes a maximum increase of 0.8 g carbohydrate (or 3.2 kcal) per 100 g of
baked beans (USDA, 1991).
9.5 Biochemical properties of sucrose
This section should perhaps more properly be called a brief summary of
fermentation reactions of sucrose. The microbiological reactions of sucrose
that are important in food processing have been listed, as specifications, in
Table 9.5. The ability of sucrose to serve as a feedstock for microorganisms
that can convert sucrose chemically, through enzymic reactions, to a
variety of food and organic chemicals, including foods and fuels, makes
sucrose a most facile and versatile substrate for fermentation.
Sucrose in cane juice and molasses has been known as a feedstock for
fermentation to ethyl alcohol for at least 4000 years: two types of fermented
liquors from sugarcane sources are mentioned in the ancient India:-t texts,
the Vedas (Paturau, 1989).
The production of ethanol, for industrial and/or fuel use, by fermentation
with some species of the yeast Saccharomyces cerevisiae family is common
at raw sugar factories everywhere except in the US: molasses is generally
the fermenation substrate. The enormous ethanol fuel program in Brazil
requires more substrate than could be provided by residual backstrap
molasses alone, and so some cane is grown for production of juice for
fermentation. A general practice at cane sugar factories in Sao Paulo state
is to take one crop of crystals (first or A strike) from the evaporated juice
and use the residual syrup, which contains two to three times the sucrose
levels of final molasses, for fermentation. These mills produce sugar and
alcohol only, producing no molasses.
Production of beverage alcohol and rum, the latter still an art as much as
a science in some countries, is general in sugarcane growing areas, with
most rum produced from molasses and a very small percentage of specialty
rums produced from cane juice. In some areas, beverage alcohol (or cane
spirits) or neutral flavor is produced to be sold as is or used as a basis for
other (non-rum) liquors. Many descriptions of fermentation and rum
production are to be found in the literature (Clarke and Godshall, 1988;
Paturau, 1989).
Fermentations similar to these for ethyl alcohol production also produce
industrial CO 2 , often at distilleries or breweries in conjunction with the
major product. Liquid CO 2 is used extensively in carbonated beverages.
Some other fermentation processes that use molasses (or sucrose or
glucose) as a feedstock, and the type of microorganisms commonly
246
SUCROSE
Table 9.16 Microorganisms used in common fermentations and the fermations products
Product
Common microorganism
Acetic acid and vinegar

Butanol-acetone
Dextran
Lactic acid
Citric acid
Glycerol
Bakers yeast
Feed yeasts
L-Lysine
Itaconic acid
Acetobacter aceti
Clostridium acetobutolycum
Leuconostoc mesenteroides or dextranicum
Lactobacillus delbruckii
Aspergillus niger
Saccharomyces ellipsoideus
Saccharomyces cerevisiae
Torulopsis uti/is
Corynebacterium glutamicus
Brevibacterium spp. Aspergillus terreus
employed, are listed in Table 9.16 (Paturau, 1989). There are many
variations on these basic fermentations.
References
Anon. (1993) Sugar and Sweetener Situation and Outlook Report. USDA Economic Research
Service.
Best, D. (1992) Working with sweeteners. Prepared Foods, January, 50-52.
Clarke, M.A. (1991) Non-sucrose carbohydrates. In Handbook of Sweeteners (eds Marie, S.
and Piggott, J.R.). Blackie, London, UK.
Clarke, M.A. and Godshall, M.A. (1988) Chemistry and Processing of Sugarbeet and
Sugarcane. Elsevier, Amsterdam, The Netherlands.
Flanyak, J.R. (1991) Effects of sucrose in confectionery processes. The Manufacturing
Confectioner, October, 61-66.
Godshall, M.A. (1986) Flavors from beet and cane sugar products. Proc. Sugar Proc. Res.,
pp.210-228
Godshall, M.A. (1988) The role of carbohydrates in flavor development. Food Technol.,
November, 71-78.
Honig, P. (1953) Principles of Sugar Technology (Vol. 1). Elsevier, London, UK.
Jeffrey, M.S. (1993) Key functional properties of sucrose in chocolate and sugar
confectionery. Food Technol., January, 141-144.
Junk, W.R. and Pancoast, H.M. (1980) Handbook of Sugars. AVI Publishing Co., Westport,
CT, USA.
Licht, F.O. (1993) World Sugar Statistics (54th edn). F.O. Licht, Ratzeburg, Germany.
Malmberg, c.G. and Maryott, A.A. (1950) Dielectric constant of solutions. J. Res. Nat. Bur.
Standards, 45, 299-307
Mathlouthi, M., Birch, G.G. and Kanters, J.A. (1993) Sweet Taste Chemoreception. Elsevier
Applied Science, London, UK.
McGinnis, R.A. (1987) Beet Sugar Technology (3rd edn). Beet Sugar Development
Foundation, Denver, CO, USA.
Meade, G.P. and Chen, J.c.P. eds. (1985) Cane Sugar Handbook (11th edn). WileyInterscience, New York, USA.
Monte, W.C. and Magna, J.A. (1981-82) Flavor chemistry of sucrose. Sugar Techno/. Rev.,
8,181-204.
Nicol, W.M. (1979) Sucrose and food technology. In Sugar, Science and Technology (eds Birch,
G.G. and Parker, K.J.). Applied Science Publishers, Ltd, London, UK, pp. 211-230.
Nicol, W.M. (1979) Sucrose and food technology. In Sugar, Science and Technology (eds Birch,
G.G. and Parker, K.J.). Applied Science Publishers, Ltd, London, UK, pp. 211-230.
247
Paturau, J .M. (1989). Byproducts of the Cane Sugar Industry (3rd edn). Elsevier Sugar Series
No. 11, Amsterdam, The Netherlands.
Shukla, T.P. and Misra, D.K. (1990) Sugar in microwave cooking. In. Sugar: A User's Guide
to Sucrose (eds Pennington, N.L. and Baker, C.S.). AVI Publishing House, New York,
USA.
Smith, D.E. (1990) Sugar in dairy products. In Sugar: A User's Guide to Sucrose. (eds
Pennington, N.L. and Baker, C.W.). AVI Publishing House, New York, USA.NY, 331 pp.
Tsang, W.S.C. and Clarke, M.A. (1988) Chemistry in sugar food processing. In Chemistry
and Processing of Sugarbeet and Sugarcane (eds Clarke, M.A. and Godshall, M.A.).
Elsevier, Amsterdam, The Netherlands.
USDA (1991) Handbook (No.8). Composition of Foods. USDA, Washington, DC, USA.
Yalpani, M. (1992) Personal communication. Alpha-Beta Technology, Boston, MA, USA.
10 Role of sucrose in retention of aroma

and enhancing the flavor of foods
M.A. GODSHALL
10.1 Introduction
Sucrose interacts with food ingredients and in processed foods in many
different ways. The major flavor function of sucrose is, certainly, to
sweeten food, but sucrose also influences the flavor quality of foods in
diverse other ways.
Anecdotal and hearsay claims are made about the interaction of sucrose
with the flavor of foods, many of these in advertising copy for competing
ingredients. An example of this is the following statement that appeared in
the October 1993 issue of Food Engineering (Dillon, 1993) touting another
sweetener: ' ... sucrose often overshadows fruit and spicy flavors'. Is this
true or untrue, and how do we find out? As we will find, later in this
chapter, that statement is not true.
The home cook has known for generations that a small amount of
sucrose will enhance the flavor of vegetables, meats and other foods that
are not normally sweet. These cooks have found that sucrose added in a
subthreshold concentration (below the sweet detection level) will improve
the overall flavor.
Commercial food processors have recognized the same phenomenon,
and add sucrose (and sometimes other sweeteners) in small quantities to
enhance and improve the flavor of many canned and processed meats,
condiments and vegetables.
10.2 Sucrose and the other basic tastes
Four basic taste sensations are recognized in sensory studies - sweet, sour,
salty and bitter. A fifth sensation, known as 'umami' is recognized by
Japanese workers, but it is not yet well enough defined in the literature to
be considered a basic taste. Tastes differ from flavors or aromas in that a
'taste' is sensed on the tongue and can still be identified when the nose is
closed off. Aromatics or volatiles are sensed with the olfactory apparatus
and are very numerous, encompassing literally hundreds of sensations.
'Flavor' is the term that encompasses the entire sensory experience of a

ROLE OF SUCROSE IN AROMA AND FLAVOR OF FOODS
249
food, and includes such elements as individual aromas and basic tastes as
well as other sensations, such as texture and chemical stimulation.
In general, bitter, acid and salty tastes are suppressed in the presence of
sucrose, but the sweet taste of sucrose is not suppressed as much except at
high concentrations of the other tastants. The ability of sucrose to suppress
the other basic tastes, especially bitter and sour tastes, is responsible for
much of sugar's ability to 'round out' or 'smooth' the flavor of foods. All
taste-taste interactions are concentration dependent.
10.2.1 Interactions with salty taste
A low concentration of sodium chloride enhances the sweetness of sucrose,

and a high salt concentration depresses sweet taste. Sucrose, on the other
hand, depresses saltiness at all concentrations of sucrose (Kroeze, 1978;
Gillette, 1985; DeGraff and Fritjers, 1989). Other salts, i.e. alkaline
acetates and butyrates, also enhance the sweetness of disaccharides
(Unilever NV, 1980). Moskowitz (1972) suggests that mixtures of sweet
and salt develop an unblended or 'clashing' taste when the taste intensities
are in a similar range because the two taste modalities are attempting to
dominate the taste perception.
10.2.2 Interaction with bitter taste
Some current theories on sweetness receptors postulate that a close

relationship exists between sweet and bitter taste receptors. Structurefunction studies have shown that some carbohydrates possess both bitter
and sweet molecular regions, and may, therfore, be able to span both types
of receptors. As a consequence, the interactions between sucrose and
bitter substances are complex and interesting.
Many bitter foods (chocolate, coffee, tea, alcohol) are traditionally
sweetened. Sucrose imparts 'balance' to bitter foods (Busch-Stockfisch and
Domke, 1991). Sucrose moderates (suppresses) the bitterness of caffeine
and coffee, but these do not suppress the sweetness of sucrose as much
(Calvino et al., 1990).
10.2.3 Interaction with acid-sour taste
Sucrose effectively decreases the acidity of sour compounds. Hoppe

showed that the sourness of citric acid undergoes an exponential decrease
with increased sucrose concentration (Hoppe, 1981). An optimum sugaracid blend of 8% sucrose and 1.11 % citric acid was recommended for
maximizing beverage flavors (McBride and Johnson, 1987). These
researchers noted a compression pattern in that increasing concentrations
250
SUCROSE
of sugar and acid exerted a diminishingly small effect. In sugar-acid

solution of changing intensity, sugar clearly suppresses the intensity of
acid, but only the highest concentration of citric acid unequivocally
suppresses sweetness. In fact, sucrose is felt to suppress or moderate the
'unpleasantness' of acids more so than it can that of sodium chloride
(Frank and Archambo, 1986).
Moskowitz (1972) has suggested that there is a compatibility between
sucrose and both bitter and sour tastes, and that a blended flavor may
develop in almost all mixture proportions of sucrose-bitter and sucrosesour.
It is interesting to note that there is a report that carbonation did not
affect sweetness in a sucrose sweetened beverage at sucrose concentrations
ranging from 2 to 16% (Yau and McDaniel, 1992). The personal
observation of the author is that a soft drink tastes sweeter once it has lost
its carbonation and gone 'flat'.
10.2.4 Interaction with other sweeteners

The threshold concentration of sucrose is around 0.2-0.5% in aqueous
solution. Moderate interactive effects occur between sucrose and other
carbohydrate sweeteners (Moskowitz, 1974). A study by Van Der Heijden
et ai. (1983), showed that sucrose taste intensity is enhanced in increasing
order by xylitol, fructose and glucose; in turn, sucrose strongly enhances
the sweetness of xylitol and fructose, but not glucose. Stone and Oliver
(1969) found that a synergistic effect (i.e. the mixture is sweeter than
would be expected from simple addition of the sweetness of the individual
mixture components) of about 20-25% occurred with glucose-sucrose
mixtures. The interaction is more pronounced at low concentrations; for
example, sucrose and fructose are strongly synergistic at 10% concentration, but only slightly synergistic at 20 and 30% (Partanen, 1988). Sucrose
and glucose are also synergistic at 10% concentration, but becomes
increasingly more suppressive as concentrations are increased (Partanen,
1988). Along the same lines, sucrose and corn syrup tend to be suppressive
(Partanen, 1988). These relationships should be kept in mind when
formulating products that contain mixtures of natural sweeteners.
With regard to the interaction of sucrose with high-intensity sweeteners,
Kamen (1959) showed that sucrose and calcium cyclamate are synergistic
at intermediate concentrations of sucrose (to correspond to 5.79% sucrose
and 14.63% sucrose), but not interactive at lower (2.31 % sucrose) or higher
(37 .07% sucrose) concentrations.
Sucrose is generally highly synergistic with high-intensity sweeteners,
showing synergistic sweetness increases of 11% for mixtures with aspartame,
14% with acesulfame, 15% for cyclamate, and 19% for saccharin (Frank et
ai., 1989a). Results such as these suggest that combinations of sucrose with
251
intense sweeteners may be beneficial in cutting down on some of the

unpleasant bitter side-tastes that some of the intense sweeteners possess.
10.3 Retention of aromas
Flavor and aroma retention during the processing of dry food is of great
importance. Food systems are extremely complex, and in order to
understand some of the dynamics of ingredient and processing interactions,
model systems are often used to simplify the factors. The literature
abounds with studies of model systems that use different sets of
carbohydrates and polymers, different volatiles, and different processing
conditions to try to understand the dynamics of flavor retention in food
processing. Sucrose is often included in these studies.
Factors that affect the retention of volatiles in foods include such diverse
elements as:
type of drying system,

chemical nature of the volatile,
chemical nature of the non-volatile components,
concentration of each starting material,
time of drying
temperatures of processing, and
beginning and ending moisture content.
Model studies, in general, have shown that sucrose is effective in retaining

volatiles in dehydrated foods. Table lO.l, adapted from Flink and Karel
(1970), shows that the order of volatile retention in a freeze-dried system
was sucrose> maltose;:::: lactose> glucose dextran-lO, for five volatile
Table 10.1 Retention of volatiles in freeze-dried model systems (Adapted from Flink and
Karel, 1970)
Organic volatiles
Acetone
Methyl acetate
2-Propanol
n-Butanol
tert-Butanol
Volatile retention in systems' containing the specified

non-volatile solute (g/I00 g solids)
Glucose
Maltose
Sucrose
Lactose
Dextran-l0
0.99
0.67
2.11
1.26
1.93
2.01
2.29
2.71
2.27
3.10
2.30
2.51
3.02
2.83
3.27
1.83
2.20
2.71
2.50
3.15
0.03
0.04
0.30
0.70
2.96
All systems had the initial composition (% by weight): non-volatile solute: 18.8; organic
volatile: 0.75; water: 80.45.
252
SUCROSE
compounds. Voilley et al. (1977) showed that sucrose retained acetone,

octanoic acid and l-octanol more so than glucose or fructose; and that
retention of volatiles increased with sucrose concentration but not for
fructose concentration. Part of this effect was attributed to the ability of
sucrose to retain the integrity of the microstructure. Similar findings for
sucrose were reported by Sugisawa et al. (1973) - sucrose (and maltose)
retained more of five alcohols and one ester than did levoglucosan, DE 20
maltodextrin and gum arabic in a freeze-dried model system.
In a model system containing sucrose and pregelatinized starch frozen at
different temperatures prior to microwave freeze-drying, the retention of
1-decanal and D-limonene was enhanced by the presence of sucrose (Chen
etal., 1993).
Dry sucrose binds on the order of 100 mmol/g each of ethanol, acetone
and propionic acid, a quantity felt to correspond to penetration of one to
two monolayers on the crystal surface (Rasmussen and Maier, 1974). Of
the disaccharides, lactose, which possesses various crystalline and
amorphous forms, is more efficient than sucrose for adsorbing large
quantities of volatiles in the dry state, but lacks many of the other desirable
qualities of sucrose (Ehler et al., 1979). Carbohydrates that are capable of
forming inclusion compounds with flavor compounds, such as the
cyclodextrins and starch, also adsorb volatiles more efficiently than
sucrose.
10.3.1 Fixing volatiles with sucrose
During the 1970s, General Foods submitted a series of patents for fixing
volatile flavors in sucrose, using acetaldehyde as the model compound
(Earle et al., 1972; Mitchell and Stahl, 1974; Mitchell, 1975; Chall et al.,
1979; Malizia and Mitchell, 1979; Anon., 1980; Pitchon et al., 1980).
Fixation occurred at levels of 0.1-0.5 wt%. Acetaldehyde was used as a
flavor enhancer, providing a clean taste in dry gelatine dessert mixes.
Several different techniques were used, but all exploited the ability of
sucrose to encapsulate volatiles in microregions by dehydration of a melt.
10.3.2 Co-crystallization
An American sugar producer has developed a process known as cocrystallization, in which rapid agitation of a supersaturated sugar solution
results in aggregates of microsized crystals as cooling proceeds (Chen et al.,
1988; Awad and Chen, 1993). The resulting structure is an open, lacy
agglomerate well-suited to the incorporation of other flavors. A secondary
flavor ingredient can be added to the supersaturated syrup, resulting in an
oxidatively stable, encapsulated flavor mixture. This process greatly
enhances the ability of sucrose to act as a flavor carrier, and has been
253
demonstrated with such ingredients as peanut butter, orange juice,

chocolate, and essential oils.
10.3.3 Headspace effects - aromas in solution
Headspace analysis refers to the determination of the equilibrium
concentration of volatiles above a sample. Headspace analysis is significant
because it will give an objective measurement of constituents that
contribute to the aroma of a food. Ideally, headspace analysis can be
supplemented and/or correlated with human sniffer panels, although little
of this type of work is actually carried out.
The influence of a major solute, such as sucrose, on the volatility of
flavor compounds depends on many factors, and can give contradictory
results. In general, one finds that the partition coefficient of a volatile
substance in solution increases with addition of a solute, due to a saltingout effect. However, sometimes other competing effects, such as intermolecular associations or even complexation between the volatile and the
solute, may decrease volatility (King, 1983). Therefore, up to a certain
point, the aroma of a beverage could, theoretically, be intensified by
increasing the volatility of its trace aroma constituents by increasing the
sucrose content.
The volatility of compounds is, in fact, strongly influenced by increasing
sucrose concentration. Massaldi and King (1973) noted that increasing
sucrose concentration increased volatility of n-hexylacetate and decreased
that of D-limonene and n-butylbenzene. Nawar (1971) found that acetone
volatility progressively increased and 2-heptanone and heptanal volatility
progressively decreased in 20, 40 and 60% sucrose solutions. In a study
that compared odor analysis and GC headspace analysis, Ebeler et al.
(1988) showed that while 5, 20, and 40% sucrose solutions did increase the
headspace of menthone and isoamyl acetate, the panelists could not
distinguish a significant difference in aroma, even though they could
distinguish different concentrations of added volatiles in the range of
1.25-20 ppm.
Marinos-Kouris and Saravacos (1975) have published the activity
coefficients of nine organic compounds in 0, 20, 40, and 60% sucrose
solutions. These are shown in Figure 10.1. Table 10.2 shows the relative
volatilities of organic compounds in various concentrations of sucrose
(Marinos-Kouris and Saravacos, 1975). What is noteworthy in this data is
that there is relatively little difference in the volatility of most compounds
in water (0% sucrose) and in 15% sucrose, which is about the maximum
concentration one would find in a beverage. Volatilities increase at a much
faster rate after that.
254
SUCROSE
ethyl
acetate
102 f---+-----",...L+-----",..L--t-----I
10
F----=--t----+---+--i
20
60
40
102 0~--2..J.0---4..L0---6LO----l
0/0 sucrose
% sucrose
Figure 10.1 Activity coefficients of organic aroma compounds in aqueous solutions (25C).
(From Marinos-Kouris and Saravacos (1975), reproduced with permission.)
Table 10.2 Relative volatilities of organic compounds in aqueous sucrose solution at 25C
(From Marinos-Kouris and Saravacos, 1975)
% Sucrose concentration
Volatile compound
15
Methyl anthranilate
Methanol
Ethanol
n-Propanol
n-Butanol
N-Amyl alcohol
n-Hexanol
I-Butanone
3-Pentanone
Ethyl acetate
Ethyl butyrate
1.02
8.3
8.6
9.5
14.1
23.0
31.0
76.0
77.0
225
643
1.27
8.9
9.0
10.0
15.0
24.7
36.0
96.0
85.0
265
855
35
2.15
9.8
lOA
12.0
21.0
41.8
62.0
112.0
121.0
368
1620
60
4.96
14.5
16.7
18.5
43.6
105.0
195.0
181.0
272.0
986
6500
255
10.4 Modifying the taste of sucrose

The effect of the basic tastes on sucrose has already been discussed.
Several compounds/ingredients also have the ability to either enhance or
diminish the taste of sucrose in food. From a psychological perspective, we
also find the phenomenon that the perceived sweet flavor is affected by the
color of a food.
10.4.1 Enhancing the sweetness of sucrose
Maltol (2-methyl-3-hydroxy-pyran-4-one) is probably the best known

flavoring ingredient with the ability to enhance the sweetness of sucrose.
Concentrations of 5-75 ppm were reported to enhance the sweetness of
sucrose to such an extent that up to 15% of the sucrose could be eliminated
(Bouchard et al., 1968; Johnson, 1976). This effect is probably due to the
sweet aroma of maltol, which can confuse inexperienced tasters (Bingham
et al., 1990). This study also found that a subthreshold concentration of
maltol (15 ppm) in sweetened lemonade did not significantly affect the
sweet taste. Results such as these, that seem contradictory, indicate that
the influence of maltol on sweetness perception is olfactory rather than
gustatory, and depends on the concentration of malto\.
Furaneol (2,5-dimethyl-3-hydroxy-4-oxo-4,5-dihydrofuran) is also
reported to enhance the sweetness of sucrose, such that a syrup containing
9% sucrose and 12 ppm furaneol was judged by a taste panel to be as sweet
as a syrup containing 10% sucrose (Pickenhagen and Ohloff, 1975).
Both maltol and furaneol can be classified as caramel-type molecules,
which result from the degradation of carbohydrates. The presence of
caramel compounds in brown sugar may account for the fact that brown
sugar is often perceived as sweeter than regular white granulated sugar,
even though it is of a lower purity (approx 90% versus 99%) (Godshall et
al., 1984).
An extract of the licorice plant (Glycyrrhiza glabra) , glycyrrhizin, has a
sweet taste 50 times sweeter than sucrose. A derivative, ammonium
glycyrrizinate, is reported to potentiate sweetness and has a strongly
synergistic effect with sucrose (MacAndrews & Forbes Company, 1966).
This compound is commercially available in the US under the name
Magnasweet.
Ethanol also enhances the sweetness of sucrose (Martin and Pangborn,
1970). For example, a solution of 8% sucrose in 10% ethanol was judged to
be as sweet as an aqueous solution of 10% sucrose. Similarly, 7% sucrose
in 20% ethanol appeared to be as sweet as a 10% sucrose solution.
256
SUCROSE
10.4.2 Hydrocolloids and perception of sweetness

Gums and thickeners play an important role in many sweetened foods, and
some of these have a pronounced effect on the sweetness of sucrose. In
general, hydrocolloids decrease sweetness of sucrose, with a significant
portion of the effect being attributed to viscosity. However, viscosity is not
the only determinant, as the type of hydrocolloid also has an effect, as for
example, in a study by Paulus and Haas (1980), guar gum was found to
more significantly decrease sweetness than tara seed gum, carob seed gum,
and methyl cellulose, which had the least effect. In the same study, it was
found that an increase of 1.5-2.5 times as much sucrose would be necessary
to induce the same sweetness in a solution of 1000 cPs viscosity when
compared to one of 1 cP. It should be noted, however, that in this study,
very low concentrations of sucrose were used, to determine the effect on
threshold values.
At higher concentrations of sucrose, it was found that guar gum reduced
sucrose sweetness about 25% (Launay and Pasquet, 1982). Pangborn et al.
(1973) concluded that the sweetness intensity of sucrose begins to be
significantly depressed when the viscosity of the medium exceeds 12-16 cPo
Vaisey et al. (1969) found that gums with less viscosity drop as shear rates
increase, such as guar and carboxymethylcellulose, tend to mask sweetness
perception more.
The take-home message to these types of findings is that care must be
taken when changing the thickeners and stabilizers in a product recipe,
since the sucrose taste profile may change noticeably.
10.4.3 Temperature effects on sweet perception

Temperature generally affects the basic tastes in a similar manner - at
approximately physiological temperatures (32-38), the sensitivity to sweet
taste is maximum (Shimizu et al., 1959). At both low temperatures
(5-1OC) and high temperatures (4Q-60C), sweetness of sucrose decreases
(Paulus and Reisch, 1980). However, fructose solutions taste significantly
sweeter than sucrose at 5C but the reverse is true at 60C, with fructose
showing a marked decrease in sweetness with increases in temperature
(Fricker and Gutschmidt, 1974). Data such as these suggest that foods and
beverages that are to be served warm or hot may require more sucrose and
other taste substances to produce the desired taste intensity; also that
sucrose would be preferable than fructose as a sweetener in warm
beverages.
10.4.4 Masking the sweetness of sucrose

Arylalkanoic acids, in particular, 3,4-dimethoxyphenylacetic acid, can
reduce the sweetness of sucrose by up to 80% when incorporated into
257
recipes (Lindley, 1984). Another compound, the sodium salt of paramethoxypropanoic acid (common name, lactisole), commercially available
under the trade name Cypha, can be used in products at the 15-100 ppm
level to reduce the perception of sweetness, while not changing the
quantity of sucrose used (LaBell, 1989).
Triterpene saponins in the leaves of Gymnema sylvestre and Ziziphus
jujuba will inhibit the sweet taste of sucrose for up to 1 h for Gymnema
and about 15 min for Ziziphus (Adams, 1985). Gymnema extracts reduced
the sweetness of all concentrations of sweet solutions by an average of 77%
(Frank et al., 1992). The surfactant sodium dodecyl sulfate (not a food
ingredient) also inhibits the perception of sweet taste, suggesting that
surfactant properties of these inhibitors play a role. However, the
surfactants glycerol monostearate and lecithin increase both intensity and
persistence of sweet taste, so generalizations should be avoided
(Ogunmoyela and Birch, 1982).
10.4.5 Interaction of sucrose-eolor-flavor

Studies have shown that color has a strong effect on the perception of
flavor, especially of fruit-flavored beverages (Kotyla and Clydesdale,
1978). Sweetness perception can be strongly affected by the type of color,
especially red color. Johnson and Clydesdale (1982) showed that the
perception of sweetness in a dark red solution was 2-10% higher than in a
light red solution, even though the sucrose concentration in the dark red
solution was actually 1% lower than in the light red solution. They also
showed that perceived sweetness increased approximately 2-12% as red
color intensity increased at the same time that a constant 4% sucrose
concentration was maintained (Johnson et al., 1983).
While red color enhances sweetness, yellow color can cause a decrease
of as much as 2% in perceived sweetness (Kotyla, 1978). Green color also
is often equated with lower perceived sweetness. Roth et al. (1988)
conclude that: 'the psychophysical relationship between sweetness and
color is complex and related to the concentration of sucrose, color
intensity, and pleasantness effects'.
10.4.6 Iron-sucrose interactions

Sucrose, in common with other food carbohydrates, interacts with iron
salts in various ways that can significantly affect flavor. The taste of both
ferric and ferrous iron salts is masked by complexing with sugar at high pH
(above 7.5) and is enhanced at low pH (below 5.5) (Cross et al., 1985).
Table 10.3 compares various food carbohydrates for their effect on the
flavor threshold of iron salts. In a study on the effect of fortifying a
beverage with various types of iron salts and sweetened with various
carbohydrates, sucrose gave overall more acceptable scores than fructose,
258
SUCROSE
Table 10.3 Threshold concentration of iron salts (From Cross et al., 1985)
Threshold concentration
Iron salt
Ferrous sulfate
Ferric ammoniumcitrate
Carbohydrate
(equivalent to
5% w/v Fructose)
Low pH
pH 5.5)
High pH
(>pH 7.5)
2.1
6.8
25.7
13.6
42.6
39.9
330.0
26.2
None
Sorbitol
Glucose
Lactose
Maltose
Fructose
Sucrose
0.1
0.2
0.3
0.4
0.5
None
Sorbitol
Glucose
Lactose
Maltose
Fructose
Sucrose
7.7
2.5
4.2
2.6
6.1
3.7
3.9
I.5
45.0
168.1
134.0
64.0
140.0
97.0
248.7
glucose, sorbitol, maltose, and lactose, in its ability to mask the flavor of
ferric ammonium citrate, ferric nitrate, and ferrous sulfate (Cross and
Kearlsey, 1986). No sugar was effective in masking the flavor of the fourth
salt, ferric chloride. Interactions such as these have important implications
in iron-fortification of foods.
10.5 Effect of sucrose in selected food systems
10.5.1 Coffee
As noted above, caffeine bitterness is more suppressed by sucrose than
sucrose sweet taste is inhibited by caffeine. As sucrose concentration
increases, it also slightly inhibits coffee flavor; this would suggest that there
is an optimum amount of sucrose for coffee sweetening (Calvino et ai.,
1990). International interlaboratory taste tests have also suggested that
some countries prefer higher levels of sugar in their coffee than others
(Lundgren et ai., 1978).
Addition of sugar to freeze-dried coffee extract was found to increase its
storage stability in terms of flavor, aroma, and acidity (Nogueira de
Moares Pitombo et ai., 1987).
10.5.2 Fatty systems

Fatty flavor is enhanced by sucrose in all but the highest fat formulations
(36% or greater) (Pangborn and Tunaley, 1988), a fact which should be
kept in mind when formulating low-fat foods, since these often lack the
259
desirable full flavor of the original food. Part of the effect of sucrose in
enhancing fatty flavor was attributed to its effect on increasing viscosity
and mouthfeel (Wiet et al., 1993). Reformulating fatty foods into low-fat
versions must take into account not only the effect of the sweetener on
flavor, but also the effect of gums and hydrocolloids added for bulking, as
discussed in an earlier section.
10.5.3 Chocolate confectionery

Sucrose is the major ingredient in chocolate, comprising up to 50% of its
total weight. Studies have shown that sucrose in uniquely suited to use in
chocolate, which requires a dry sweetener with low hygroscopicity (Martin,
1987). Sucrose also shows superior flavor-taste interactions over sweeteners
such as fructose or sorbitol, as well as improved texture (Ogunmoyela and
Birch, 1984). The sweet taste of sucrose in cocoa can be intensified and
persist longer by the addition of surfactants such as glycerol monostearate
and lecithin (Ogunmoyela and Birch, 1982). At the same time, added
surfactants could decrease overall chocolate flavor, a less than desirable
result (Birch and Ogunmoyela, 1980).
Niediek (1975, 1981) has made extensive studies on the effect of
'amorphous' sugar (finely ground or powdered sugar) on chocolate taste
quality, and finds that the increased sorption properties of sucrose in the
amorphous state can lead to off-flavors in chocolate if great care is not
taken. Niediek (1975, 1981) also makes the interesting observation that
powdered or ground sugar always has a distinctly different taste from
granular sugar.
10.5.4 Fruit flavors

Sucrose either does not affect fruity flavor (for example, sucrose did not
change the fruity flavor perception of either orange or strawberry flavor in
a study by Wiseman and McDaniel (1991)) or enhances it. Usually, as
sucrose level increases, the perception of fruity flavor also increases, as
studies have shown enhancement of several fruit and berry flavors (Valdes
et al., 1956; Von Sydow et al., 1974; Bonnans and Noble, 1993). Therefore,
the statement quoted at the beginning of this article is shown to be
untrue - sucrose does not mask fruit flavors.
Fruit flavors can also be interactive with sucrose and enhance the
perception of sweetness in sucrose solutions as is seen with strawberry
flavor (Frank et al., 1989b).
10.5.5 Effect of crystal size on mouthfeel in confections

Sucrose contributes to texture in many foods, but nowhere is its texturizing
function more important than in grained confections, such as creams,
260
SUCROSE
chocolates, and fondants. The term 'mouthfeel' refers to the texture of a

food in the mouth, and in confections, the size of the sucrose crystal is of
paramount importance to the overall flavor quality. The human palate
recognizes particles in the size range of 20-40 !-tm as smooth and creamy. If
the particles (i.e. sugar crystals) are any larger, the confection is perceived
as grainy and of low quality (Jeffrey, 1993).
10.5.6 Sucrose and cake crumb, crust and quality

Attempts to replace sucrose in bakery items, such as cakes, routinely show
the superiority of sucrose in development of texture, flavor and appearance.
In one such study, the interior of cakes (crumb) as well as cake crusts made
with various sweeteners were judged. Sucrose was superior for the interior,
followed in decreasing order of acceptability by HFCS (high fructose corn
syrup), fructose, fructose-glucose, and glucose (Thompson et al., 1980).
Sucrose also resulted in highly acceptable crust flavor, followed, in
decreasing order, by fructose, fructose-glucose, and HFCS. Sucrose has
also been shown to be superior to fructose in sugar cookies and white cake,
when substituted at the 100% level (Hardy et al., 1979). The study
referenced above also illustrates another point: although fructose is
considerably sweeter than sucrose in solution, it does not always show this
property in cooked or baked systems (Godshall, 1990).
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sourness. J. Food Sci., 57(6), 1412-1416.
11
Sucrose: Its potential as a raw material for food

ingredients and for chemicals
R. KHAN
11.1 Introduction
In Europe, sucrose (sugar) is isolated from sugar-beet (Beta vulgaris) and

accounts for nearly 40% of the total world production which in 1992
exceeded 110 million tonnes. The remaining 60% of the world production
is manufactured from sugar-cane (Saccharum officinarum), grown in the
tropics.
Structurally and functionally, sucrose is a unique organic molecule and is
the most abundant of all sugars. In the past three decades, the progress
towards the understanding of the chemistry, structure, physical and
functional properties of the sucrose molecule has been rapid. In 1965 there
were only about 15 well-characterised sucrose derivatives and today there
are more than three hundred well-identified sucrose compounds described
in the carbohydrate literature.
This chapter will begin with a discussion on some of the fundamental
chemical aspects of sucrose, in particular the results which have made a
significant contribution towards the understanding of the structure and
reactivity of the molecule. The discussion will then concentrate on some of
the actual and potential commercial developments concerning food
ingredients. In this area, sucrose-based products such as high-intensity
sweeteners, low-calorie fats, bulking ingredients, low-intensity reducedcalorie sweeteners, and emulsifiers and surface active agents will be
described. Finally, some recent developments in sucrochemistry leading to
interesting chemicals will be presented.

POTENTIAL FOR FOOD INGREDIENTS AND CHEMICALS
265
Sucrose (1), j3-D-fructofuranosyl a-D-glucopyranoside, is a non-reducing

disaccharide, and the numbering of the carbon position in the molecule is
as shown in the structure. It contains eight hydroxyl groups, three of which
are primary (C-6, 6', I') and the remaining five are secondary (C-2, 3, 3',
4, 4'). The primary hydroxyl groups react preferentially, in particular the
hydroxyl groups at 6 and 6' positions (James et ai., 1989).
11.2 Chemical reactivity
11.2.1 Reactivity towards trityiation reaction
Treatment of sucrose with four molar equivalents of chlorotriphenylmethane (trityl) in pyridine gave, after acetylation and chromatography, 6,1' ,6'-tri- (2) and 6,6'-di- (3) O-tritylsucroses in 50 and 30%,
respectively (Hough et ai., 1972). Compound 2 is an intermediate in the
synthesis of sucralose (Hough et ai., 1979), a high-intensity sweetener
developed and marketed by Tate & Lyle pic and Johnson & Johnson of the
USA. Detritylation of 2 with aqueous acetic acid followed by acetyl
migration from C-4 to C-6 gave 4, which on chlorination with thionyl
chloride, pyridine and trichloroethane gave, after deacetylation, 4,1' ,6'trichloro-4,I' ,6' -trideoxygaiactosucrose (5, sucralose).
11.2.2 Cyclic acetaiation reactions
The most significant development in the chemistry of sucrose has been the
synthesis of cyclic actetals which had defied preparation, despite many
2 R = Ac, R' = Tr [-C(C6HS)31

3 R=R'=Ac
266
SUCROSE
attempts, until 1974. The first synthesis of 4,6-0-benzylidenesucrose

(Khan, 1974) (6,35% yield) was achieved from the reaction of sucrose with
a,a-dibromotoluene in pyridine. Since then many new novel acetalating
reagents have been used to give a variety of sucrose acetals. Treatment of
sucrose with 2,2-dimethoxypropane, N,N-dimethylformamide and
toluene-p-sulphonic acid gave 4,6-0-isopropylidene (7) (Khan et at., 1978)
and 4,6: l' ,2-di-O-isopropylidene (8) (Khan et at., 1975). The unique eightmembered 2,1'-cyclic acetal bridges the two rings in sucrose, is more
stable to acid than the 4,6-acetal linkage and has been effective in
providing access to selective reactions at 2 and l' positions in sucrose.
t("
A
C.H, 0
OH
0t(
MX
CHzOH
~
HO
CHzOH
OH
..
OH
OH
OH
CHzOH
0
~H'OH
HO
OH
X~\~HO
~
CHzOH
OH
Me/\
Me
8
The diphenylsililene cyclic acetals of sucrose were synthesised by using

2,2-dimethoxydiphenylsilane, N,N-dimethylformamide and toluene-psulphonic acid to give the 2,1'- and 2,1':6,6'-di-O-(diphenylsilylene)
derivatives in 45 and 10% yield, respectively (Jenner and Khan, 1980).
JJ.2.3 Selective esterification
The selective esterification reactions of sucrose have recently been

reviewed (James et at., 1989). 6-0-Acetylsucrose (9) has been synthesised
in 40% yield by direct acetylation of sucrose with acetic anhydride in
pyridine at -40C followed by column chromatography. This compound
has been chlorinated to give sucralose. The concept of the direct protection of
the 6-0H group of sucrose and then selective chlorination of the C-4,1' ,6'
267
positions has led to an economic process for the production of sucralose

(Khan and Mufti, 1982).
4,6-Cyclic orthoester derivatives of sucrose are intermediates for the
synthesis of 6-0-acylsucroses which are valuable compounds for the
synthesis of sucralose. Garegg et at. (1988) have described the use of this
approach in their elegant synthesis of 6-0-acetyl-2,3,4-tri-0-s)-3methylpentanoyl) sucrose, a precursor of tobacco flavour.
Treatment of sucrose with trimethylorthoacetate, N,N,-dimethylformamide and toluene-p-sulphonic acid followed by acid hydrolysis gave
the 6-0-acetylsucrose (9) as the major and the 4-0-acetylsucrose as the
minor component which underwent acetyl migration from C-4 to C-6,
when treated with an organic base such as t-butylamine in N,Ndimethylformamide to give sucrose 6-acetate (Simpson, 1987). When the
kinetic
reagent
2,2-dimethoxyethene
was
used,
4,6-0-(1methoxyethyledene) sucrose (10), the intermediate for compound 9, was
obtained in near quantitative yield (Khan et at., 1992).
0t(
t( ~CH'OH .x o~CHZ
CHZOAC
OH
HO
CHzOH
Me
OH
HO
HO
OH
OH
CHzOH
OH
OH
10
The reactivity of sucrose towards pivaloyl (2,2-dimethylpropionyl)

chloride has been thoroughly investigated (Chowdhary et at., 1984). The
'reactivity profile' of sucrose towards pivaloylation has been shown to be
significantly different from other acid halides. For example, reaction of
sucrose with four molar equivalent of toluene-p-sulphonyl chloride in
pyridine revealed, based on product isolation, the reactivity order of 0-60-6'>0-1'>0-2. Whereas a reactivity order for the pivaloylation
reaction, under similar reaction conditions, was observed to be: 0-6 = 0-6'
>0-1'>0-4. Two divergent routes to sucrose octapivalate by way of this
reaction have been suggested, each due to different reactivities of the
partially pivalated derivatives towards further acylation:
(a) 6,6'-OH>l'-OH>4'-OH>2-0H>4-0H>3-0H
(b) 6,6'-OH>l'-OH>3'-OH>3-0H>4'-OH>2-0H and 4-0H
268
SUCROSE
11.2.4 SN2 displacement reactions

The first SN2 displacement reaction at C-2 posItion in sucrose and in
methyl a-o-glucopyranoside was achieved during the study of sulphuryl
chloride reaction with sucrose (Khan et al., 1980).
The formation of a transition state at C-2 to allow an SN2 displacement
reaction in methyl a-o-glucopyranoside was considered to be not possible
because of the unfavourable dipole-dipole interactions due to the ring
oxygen and the C-l oxygen. However, when methyl 3-O-benzoyl-4,6-0benzylidene-a-o-glucopyranoside 2-chlorosulphate was treated with
lithium chloride in hexamethylphosphoric triamide it gave, with inversion
of configuration at C-2, the corresponding 2-chloro-manno derivative.
Similar treatment of the sucrose hexaacetate 2,I'-bis (chlorosulphate) (11)
with lithium chloride led to the 2,1'-manno derivative (12). Since then
there have appeared many reports in the carbohydrate literature to support
that an SN2 displacement reaction in an alkyl a-o-glucopyranoside is
possible.
II
12
11.3 Enzymic reactions
11.3.1 Lipase-catalysed acylation reactions

Enzymic acylation reactions offer considerable promise in the synthesis of
specific ester derivatives of sucrose. For example, reaction of sucrose with
an activated alkyl ester in N,N-dimethylformamide in the presence of
subtilisin gave l'-O-acylsucrose, which on further treatment with an
activated fatty acid ester in acetone in the presence of lipase Chromobacterium viscosum afforded the I' ,6-diester derivative (Rive et al., 1988;
Carrea et al., 1989).
6-0-Acetyl-(9) and 4' ,6-di-O-acetyl-sucrose, important intermediates
for sucralose, have been synthesised from sucrose using lipases. Treatment
of sucrose with isopropenylacetate in pyridine in the presence of Lipase P
Amano gave, after chromatography, 9 (33%) and the 4' ,6-diacetate (8%).
The latter compound has been obtained in 47% yield by the prolong
treatment, and has been converted to sucralose (5) (Dordick et al., 1992).
269
11.3.2 Selective deacylation reaction

Partially esterified derivatives of sucrose have been prepared using
enzymes. Enzymatic hydrolysis of sucrose octa-acetate (13) in a phosphate
or citrate buffer has led to a series of compounds such as sucrose
heptaacetate 4'-hydroxy, sucrose heptacetate 4-hydroxy, and sucrose tetraacetate 4,1' ,6' ,4'-tetrahydroxy (Bornemann et al., 1992) (14). Compound
14 has been enzymically transformed to the 4'-butyrate derivative 15,
which on chlorination followed by deacylation gave sucralose (Dordick et
al., 1992) (5).
14
13
15
The hydrolysis of sucrose octa-acetate (13) with lipase Candida

cylindracea has been reported to cause deacetylation selectively, unlike
chemical deesterification reactions, in the pyranose moiety to give
2,3,6,1' ,3' ,4' ,6'-hepta-, 2,3,4,1',3',4' ,6'-hepta-, 2,3,1',3',4' ,6'-hexa-,
2,6,1' ,3',4' ,6' -hexa-, and 2,1' ,3',4' ,6'-penta- O-acetylsucroses (Gng et al.,
1993).
11.4 Food ingredients
The recent chemical and biotechnological advances and the resulting

commercial opportunities have influenced the business strategy of the
sugar industry. Most of the big sugar companies have now extended their
interests beyond sugar into starch, high fructose corn syrup, synthetic and
270
SUCROSE
natural high-intensity sweeteners, and other related food and chemical

products. Some of these opportunities which sucrose presents will be
discussed.
11.4.1 High-intensity sweeteners
There are a number of high-inensity sweeteners based on sucrose but all of

them are halodeoxy derivatives (Hough and Khan, 1989). 4,1',6'Trichloro-4,1' ,6'-trideoxygalactosucrose (5) with the trade name 'sucralose'
is 650 times the sweetness of sucrose. It is being developed and
marketed by Tate & Lyle pic and Johnson & Johnson of the USA.
Sucralose has been approved for use in food in Canada, Australia and
Russia and is awaiting approval as a food and drink additive by the Food
and Drug Administration (FDA) of the USA and other health authorities
all over the world.
Sucralose is readily soluble in water (28% w/w, at 20oq, non-cariogenic,
tastes like sucrose, and is heat stable. The relatively good sweetness quality
and its heat stability will be of particular value in cooking and baking
applications. The market potential of sucralose can be assessed on the basis
of the market size for aspartame which in 1985 was roughly US$700
million. It is of interest to note that aspartame, unlike sucralose, is not
stable to heat which excludes it from such markets as baking and cooking.
11.4.2 Emulsifiers and surface active compounds
Purified, food grade, sucrose fatty acid esters are being commercially
produced in Japan by Mitsubishi Kasei Food Corporation, Tokyo, and Dai
!chi Kogyo Seiyaku, Kyoto. These esters are approved by the FDA for
food applications.
The degree of fatty acid esterification in the sucrose molecule determines
its functional properties, for example, an average degree of esterification
of two will impart the mixture emulsifying characteristics and one ester
group per sucrose molecule will give the compound surface active
properties (Parker et al., 1976). Sucrose esters are used in Japan in
processed food for such functions as emulsification, and crystallisation
inhibition, wheat flour improvers and lubrication. Sucrose monolaurate
has been shown to inhibit the growth of Escherichia coli and other bacteria
(Ando et al., 1983) with obvious advantages in food and drink products.
11.4.3 Low-calorie fat
Sucrose polyesters developed by Procter and Gamble under the brand

name 'Olestra' are neither absorbed nor hydrolysed by pancreatic lipases
and are therefore classed as low-calorie fats (Mattson and Volpenheim,
271
1968). In addition, these products appear to reduce the level of cholesterol

in humans. The polyesters containing six to eight fatty acid esters per
sucrose molecule are prepared by a solventless transesterification process.
Sucrose is treated with ethyl ester of fatty acids in the presence of sodium
methoxide between 100-180C for 14 h. The unreacted fatty acid esters
and lower substituted sucrose esters are removed by enzymic hydrolysis
with lipase. Sucrose polyesters containing five or more fatty acid esters are
resistant to lipases.
'Olestra' has yet to be approved by the FDA for human consumption.
11.4.4 Non-cariogenic, reduced calorie, low-intensity sweeteners

n.4.4.1 Isomaltulose and [somalt. Isomaltulose (Palatinose) and Isomalt (Palatinit) are marketed as reduced calorie and non-cariogenic food
ingredients. An efficient enzymic process for the production of isomaltulose, 6-0-( a-D-glucopyranosyl)-D-fructose, was first developed by
Tate & Lyle (Buck and Cheetham, 1979). Isomaltulose is produced on an
industrial scale from sucrose using immobilised a-glucosyl transferase
from Protaminobacter rubrum. In Japan, palatinose is used as a noncariogenic sweetener. In Germany, the Sudzucker company also produces
isomaltulose using a similar technology.
Isomaltulose is a free-flowing, non-hygroscopic, crystalline (m.p.
123-124C) material. Its sweetness intensity is 42% that of sucrose.
Isomaltulose is hydrolysed and absorbed in the small intestine and, like
sucrose, has as energetic value of 4 kcal/g. It is not utilised by the microbial
flora of the mouth and consequently no organic acids or polysaccharides
are formed. Hence, it has been considered as a non-cariogenic sweetener.
Its annual production is roughly 10 000 tonnes/year.
Isomaltulose is converted on a commercial scale to Isomalt (Palatinit) by
a process which involves: catalytic hydrogenation (Raney-nickel catalyst),
filtration and ion-exchange treatment to remove the catalyst, evaporation,
and crystallisation to give a mixture of 6-0-( a-D-glucopyranosyl)-Dsorbitol and 6-0-(a-D-glucopyranosyl)-o-mannitol (Schiweck et al., 1991).
Isomalt crystallises from water as dihydrate (m.p. 145-150C). It has a
neutral sweetness as compared with sucrose which has round and balance
sweetness. The caloric value of isomalt is 2 kcal/g. It is claimed to be a noncariogenic and a suitable sweetener for diabetics.
11.4.4.2 Leucrose. Leucrose, 5-0-(a-D-glucopyranosyl)-fJ-D-fructo-pyranose (m.p. 156--158C), is a keto-disaccharide. It appears to be a general
secondary product of dextran-producing strains of bacteria. Pfeifer
& Langen of Germany have developed a commercial process for the
272
SUCROSE
production of leucrose which involves the following: extraction of the

enzyme dextransucrase from Leuconostoc mesenteroides bacteria, treatment with a 65% aqueous solution of sucrose and fructose (1:2, w/w) at
25C, separation of the product from fructose by ion-exchange column
chromatography, and crystallisation as leucrose monohydrate (Schwengers,
1991).
The structure of leucrose has been confirmed by 1 Hand 13C NMR
(Kamerling et at., 1972; De Bruyn et at., 1975) and by X-ray crystallography
(Thiem et at., 1989).
The sweetness intensity of leucrose is half of that of sucrose. It is
considerably more stable towards acid hydrolysis than sucrose. Towards
enzymes such as sucrase, isomaltase and glucoamylase the hydrolysis is
approximately 54% slower than sucrose but the rate is still fast enough to
ensure that no leucrose enters the large intestine. It is not broken down by
microbial flora of the mouth and therefore it is considered to be a noncariogenic sweetener.
The higher cost of production of leucrose will not permit its use as a
substitute for sucrose in the low price segment of the market. However, it
can be used in speciality low-calorie food products, such as a replacement
of high-calorie fat in chocolates or as an ingredient in non-cariogenic food
for children.
1I.4.4.3 Fructootigosaccharides. Meioligo, the trade name in Asia

(formerly Neosugar), also called Actilight in Europe is a mixture of Dglucose, sucrose, and fructooligosaccharides (FOS) with one (1-kestose),
two (nystose) and three fructofuranosyl residues linked by way offi-(1~2)
bonds to the fructosyl moiety of sucrose (Hikada, 1982; Fuji and Komoto,
1991). The production process for Neosugar involves the microbial
fermentation of sucrose using a fungal fructosyltransferase enzyme from
Aspergillus niger.
Neosugar is claimed to be a non-cariogenic and reduced-calorie
sweetener promoting bifidogenus flora. Nystose, a trisaccharide and a
component of Neosugar has been shown not to provide D-glucose and Dfructose to the body which makes it a potential candidate for a bulk
sweetener in diets for diabetic patients.
Neosugar is commercially produced by Meiji Seika Company of
Japan. In Europe, it is being developed by a joint venture with Eridania
Beghin-Say, Beghin Meiji Industries. In America, although not yet
approved as a food additive, it is still being developed jointly by Meiji
Seika and Golden Technologies Company.
273
11.4.5 Bulking ingredients

Sucrose, in addition to its sweetness, provides such important functional
properties as viscosity, mouthfeel, flavour profile, and humectancy. If
high-intensity sweeteners, which lack the bulking properties of sucrose, are
to be used in the formulation of low-calorie food and drink products they
would require a low-calorie bulking ingredient. A low-calorie bulking
agent which can satisfactorily replace sucrose does not exist. Currently,
there is interest in oligo- and polysaccharides based on sucrose and fructose
as they are claimed to be reduced calorie and non-cariogenic sweeteners
and/or bulking materials. Some of these products which are derived from
sucrose will be discussed in this section.
11.4.5.1 Polyfructans. Polyfructans are polymers of fructose that occur

in nature in two general forms characterised by the types of their glycosidic
linkages. Inulin, found in Jerusalem artichoke, chicory and many plants of
the compositae family have ft-1,2-linked fructofuranose molecules and is
not very soluble in water. The second type, known as levans or fructans,
hasft-(2~6) glycosidic linkages, with some branching through the CH zO-1
position in the fructofuranose residues. Fructans are produced by
microbial processes but have also been shown to occur in various grasses
and some plants. They are known in sugar industry as microbial products
that indicate sucrose loss and filtration problems in the beet sugar factory.
They are associated with deteriorated beet and with frozen and thawed
beet.
Microbial synthesis of a homogeneous polysaccharide containing fructose
with f3-(2~6) fructose backbone from sucrose by a strain of Bacillus
polymyxa (NRRL B-18475) has been achieved in >80% yield (Clarke et
al., 1991). The structure of the polysaccharide has been established by
NMR, and also by conventional techniques. It has been demonstrated that
the polysaccharide has ft-(2~6) backbone with up to 12% branching
through ft-(1~2) linkage. The X-ray crystal structure revealed that the
polymer is amorphous in nature.
The polysaccharide is non-hygroscopic in solid form, soluble in water,
and is readily hydrolysed at high temperatures and acid pH to fructose. It is
not hydrolysed by amylase, dextranase or glucanases. Some degree of
hydrolysis has been achieved using crude pullulanase or Gramanase.
11.4.5.2 Fructoglucans. Acid-catalysed thermal polymerisation of
sucrose has been described to give a fructoglucan polymer in about 30%
yield (Manley-Harris and Richards, 1993). The reaction is similar to the
one used for the preparation of 'polydextrose', a low-calorie bulking
ingredient manufactured from D-glucose. Treatment of anhydrous,
amorphous, acidified (1 % citric acid) sucrose under different temperature
274
SUCROSE
and pressure conditions afforded, after precIpItation by ethanol from

aqueous solution, the desired fructoglucan.
The structure of the polymer has been established by methylation
analysis, gas-liquid chromatography-mass spectrometry and gel permeation chromatography. The polymer is highly branched and of low
molecular weight, with the o-glucose and o-fructose ratio in about 2: 1. The
average degree of polymerisation for the major portion is about 25. The
reducing end groups include some o-glucopyranose linked at the 6position, plus possibly L-glucosan and dianhydrofructose. The fructose
residues are mostly in furanose form and are mostly in the internal part of
the molecule generally linked through the I-position. The internal 0glucose residues are predominantly in pyranose form and are mostly linked
through the 6-position, also providing 2-, 3-, and 4-position for cross
linkages.
There is commercial opportunity for carbohydrate-based polymers with
reduced calorie, provided that the sensory and functional properties and
cost are comparable to those of sucrose.
11.5 Chemicals from sucrose
Sucrose is used on a relatively large scale in countries like Brazil, India and
Pakistan for the production of industrial ethanol and chemicals therefrom,
such as acetic acid and acetic anhydride. Similarly, the use of sugar in the
production of commercially important microbial polysaccharides such as
xanthan gum, gellan and alginates has already been demonstrated
(Buchholz and Buttersack, 1988).
In this chapter, the discussion will be limited to the applications of
sucrose in the production of polymers or polymer intermediates, surfactants, and additives for detergent powders.
11.5.1 Synthetic polymers based on sucrose

11.5.1.1 Polyurethanes. The non-reducing and polyhydroxy functionalities of sucrose make it suitable for conversion to polyfunctional polyols for
polyurethane manufacture (Frisch and Kresta, 1977; Fuzesi, 1977; Meath
and Booth, 1977). Sucrose is not directly used as polyol in polyurethane
manufacture because it gives brittle foams. Thus sucrose is first etherified
with polyhydroxypropyl group in order to confer miscibility with diisocyanate and fluorocarbon blowing agent and to provide the molecular
spacing necessary to impart such useful structural characteristics as
strength and flexibility to the finished foam.
The use of sucrose in polyurethanes provides one of its most important
275
large-scale outlets in the chemical industry. In Europe, during 1984 and

1985, roughly 9400 tonnes of sucrose was used in the manufacture of
polyurethane foams (Khan and Jones, 1988).
11.5.1.2 Reactive sucrose derivatives. A series of reactive sucrose

derivatives as intermediates to a variety of different polymers has recently
been reported. They are still only a chemical curiosity and their
commercial potential has yet to be established.
New sucrose derivatives with reactive esters and ethers have been
synthesised. These derivatives are neither well defined nor are they single
compounds. Invariably, they are mixtures of isomers with average degrees
of substitution. However, they have led to interesting polymers or polymer
intermediates such as sucrose methylacrylate gels, chelating resins, sucrose
derivatives with carbonic acid amide groups or N-methylated groups as
condensation components for formaldehyde, sucrose derivatives with
photoactive groups, and sucrose derivatives with primary amino groups
and their fatty acid amides (Gruber and Greber, 1991).
Monomethylacryloyl and vinylbenzyl derivatives of sucrose have been
prepared as intermediates for polymers (Sachinvala et ai., 1991) and
preparation of a range of copolymers of styrene and O-methylacryloylsucrose has been described (Jhurry et ai., 1992). Reactive intermediates, 40- and 6-0-monoacryloyl derivatives have been synthesised by selective
acid-catalysed hydrolysis of 4,6-0-(1-ethoxy-2-propenylidene) sucrose.
Polymerisation and copolymerisation with styrene has been reported
(Fanton et ai., 1993).
11.5.2 Detergents
11.5.2.1 Surfactants. Sucrose mono-fatty acid esters have applications in
detergents, cosmetics, and pharmaceutical formulations. These esters are
produced in Japan on a commercial scale. The reaction of sucrose with a
triglyceride or a methyl ester of a fatty acid has normally been carried out
in an aprotic solvent in the presence of a basic catalyst. In a solventless
process, sucrose is heated with stirring with tallow in the presence of
potassium carbonate at 140C to afford a mixture containing roughly 27%
of sucrose monoesters, 3% of the higher esters and mono-, di-, and
triglycerides, and 30% of soaps. The crude mixture exhibits excellent
surface active properties (Parker et ai., 1976).
Major industrial applications for non-toxic and biocompatible sucrosebased surfactants can be visualised in the detergent industry, in the area of
cosmetics, and in food and feed formulations. The market for low-cost
biodegradable surfactants in the treatment of oil spills is also considerable.
276
SUCROSE
1l.5.2.2 Bleaching boosters. Sodium perborate is generally used as a

bleaching agent in detergent formulations. However, in order to perform
well at temperatures as low as 40C it requires an activator such as
tetra-acetyl ethylene diamine. The activator, an organic compound with at
least one acyl group, reacts with the perhydroxy ion of the bleaching agent
in order to release the required peroxyacid.
It has been demonstrated that, instead of tetra-acetyl ethylene diamine,
sucrose polyacetate can be used as an effective bleaching booster in
detergent formulations (Mentech et al., 1993).
11.5.2.3 Detergent builders. Environmentally friendly detergent builders
have commercial potential. Sodium tripolyphosphate which is the best
metal ion chelator is unfriendly to the environment. Citric acid and its
sodium salt are biocompatible and have found application in liquid
detergent formulations.
Carbohydrate based products such as oxidised starches, gluconic acid,
glucaric acid, and sucronic acid are interesting materials as detergent
builders or co-builders (to support and enhance the performance of
zeolites). However, the present cost of production of these materials is too
high to be commercially attractive.
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Fuzesi, S. (1977) Sucrose-based rigid l'fethanes in furniture applications. Am. Chem. Soc.
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Garegg, P.J., Oscarson, S. and Ritzen, H. (1988) Partially esterified sucrose derivatives:
synthesis of 6-0-acetyl-2,3,4-tri-O-[(s)-3-methylpentanoyl] sucrose, a naturally occurring
flavour precursor of tobacco. Carbohydr. Res., 181,89-96.
Gruber, H. and Greber, G. (1991) Reactive sucrose derivatives. In Carbohydrates as
Organic Raw Materials (ed Lichtenthaler, F.W.). VCH, Weinheim, Germany, pp. 95-116.
Hikada, H. (1982) Neosugar - manufacturing and properties. Proceedings of 1st Neosugar
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Hough, L. and Khan, R. (1989) Enhancement of sweetness of sucrose by conversion into
chlorodeoxy derivatives. In Progress in Sweeteners (ed Grenby, T.H.). Elsevier Applied
Sciences, London, UK, pp. 97-120.
Hough, L., Mufti, K.S. and Khan, R. (1972) 6,6'-Di-O-trityl-sucrose, Carbohydr. Res., 21,
144-147.
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167.
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SUCROSE
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12
Sucrose and osmotic dehydration

A.L. RAOULT-WACK, G. RIOS and S. GUILBERT
12.1 Introduction
The osmotic dehydration process, previously reviewed by Ponting et ai.
(1966), Le Maguer (1988), and Raoult-Wack et ai. (1992), consists of
soaking moisture-rich foods in concentrated solution, which creates two
cross mass transfers (Ponting et ai., 1966; Karel, 1975; Hawkes and Flink,
1978).
(1) An important water outflow, from product to solution. The food
product may lose up to 70% of water (g water/lOO g initial product)
at moderate temperature (3G-50oq, away from oxygen, and without
phase change, within a time duration of 1-3 h.
(2) A solute transfer, from solution to product. It is thus possible to
insert the desired amount of preserving agent, any solute of
nutritional interest, or sensory quality improver into the product.
Hence, this technique appears to be all the more promising, in that it
makes it possible to achieve a formulation of a food item without any
damage to its integrity, which can be called 'direct formulation'
(Raoult-Wack et ai., 1992).
A product's own solutes leaching may also be observed (Ponting et ai.,
1966; Ponting, 1973; Dixon and len, 1977; Lerici et ai., 1977; Adambounou
and Castaigne, 1983; Heng et ai., 1990; Vial et ai., 1990). Although in low
quantity, this loss is essential regarding the final product's organoleptic
(acidity for instance) and nutritional qualities (mainly vitaminic and
mineral). In most cases, the lower the leaching, the better the quality. In
some cases however, leaching is expected, for instance to improve the
sensory qualities of plum wine by reducing excessive acidity and astringency
(Vyas et ai., 1989; Moutounet et ai., 1991).
12.2 General presentation of osmotic dehydration

The dewatering effect is usually conceived as an osmosis phenomenon
through the cell semi-permeable (i.e. water permeable/solute repellent)
membranes. This is the reason why such processes have often been called
280
SUCROSE
'osmotic' dehydration (Ponting et ai., 1966). Proof has been given that
semi-permeable membranes are not a necessary condition for high water
loss, with only marginal sugar pickup (Raoult et ai., 1989; Raoult-Wack et
ai., 1991a). This result is all the more interesting since one must often work
with items in which tissue structures have been damaged by ripening or
chemical or heat pretreatments, or freezing. Therefore, it was suggested to
refer to such processes as 'dewatering and impregnation soaking processes'.
(DIS) (Wack et ai., 1992). The mass transfer is schematically represented
in Figure 12.1.
Most applications deal with fruits and vegetables in sucrose or other
sugar solutions (dextrose, lactose, corn syrups). But solutions of sodium
chloride, sorbitol, glycerin, ethanol, polyols and other water activity
lowering agents may also be used, frequently blended with sucrose
(Hawkes and Flink, 1978; Contreras and Smyrl, 1981; Darbonne, and
Bain, 1991). The solutes used should be neither toxic nor expensive and
should be highly soluble in order to give highly concentrated solutions, but,
if possible, not strongly viscous. They should also be compatible with the
physico-chemical (pH, structure, etc.) and organoleptic (favor) food
characteristics. These agents, usually called water activity lowering agents,
and their properties were reviewed by Guilbert (1992).
Soaking of fruits in concentrated sucrose solutions has traditionally been
used for candying (Campi, 1985), and semi-candying (Ponting et ai., 1966;
Heng et ai., 1990). Candying consists in favouring the penetration of
sucrose into the product. This is achieved by preliminary tissue processing,
such as chemical or heat treatments (e.g. blanching), and the implementation of a low concentration difference between the product and the
solution. The semi-candying process has been more recently developed. It
consists of adding a final warm-air-drying to a candying phase which is
reduced by a half compared with a classical candying. This process has
been used for 'dried fruit' production, particularly in South-East Asiatic
countries (Wack, 1990).
concentrated solution
...................
product
...................
.................... ,
...
.............
.....................
........................ ,
........................
....................... ,
...........
..
... .......................,
A
WATER
...
..................
.........
.......... ,
.................... ,
... .................... . ..
............... ""A . . . .
SOLUTE(S)
product's own solutes
.........................
..............
.................... .....
..............
...
..
..
...............................
:::::::::::::::
......................
...................
...
........
............... ... .
~----
(minerals. sugars. organic acids...)
.;:;::::::::
Figure 12.1 Schematic drawing of mass transfer in soaking processes.
SUCROSE AND OSMOTIC DEHYDRATION
281
Recently, there has been increasing interest in soaking treatments of

food items in highly concentrated solutions, in order to simultaneously
achieve a significant dewatering and a controlled formulation of the solid
food, provided that adequate control of mass transfer is achieved. Water
loss and solute gain kinetics depend on the natural tissue properties
(possibly affected by heat or chemical pretreatments, of freezing) and
operating variables, such as specific surface area of food pieces, temperature, time duration, mode of phase contacting, concentration and
composition of the solution. To date, most studies have been carried out at
atmospheric pressure. However, recent publications deal with the effect of
pressure on mass transfer (particularly water loss) in fruit (Shi and Fito,
1993a, b). In this chapter, particular attention will be devoted to the
process variables related to the concentrated solution, i.e. concentration
and composition, at atmospheric pressure (section 12.3).
The soaking process does not generally produce stable products. It has
to be used as a preprocessing step before a complementary processing,
such as drying, smoking, pasteurizing, canning, freezing, frying, or
addition of preservative agents. Various combinations were reviewed by
Raoult-Wack et al. (1992). Drying is the most widely used complementary
process, generally leading to 'intermediate moisture foods', or dried foods,
intended to be directly eaten out of hand (snacks, etc.) or to be
incorporated in industrial cooked dishes, pastry, breakfast cereals, dairy
products (yogurts, ice creams), or to be rehydrated.
The interest for the introduction of an osmotic dehydration preprocessing
into a conventional stabilizing process mainly relies on the particularly
good nutritional (vitaminic and mineral) and organoleptic qualities
(aroma, colour, texture) of the final product (Ponting et al., 1966). These
characteristics are to be ascribed notably to moderate operating temperatures (Ponting, 1973; Uzuegbu and Ukaka, 1987), lower loss of volatile
components (Ponting, 1973; Bongirwar and Sreenivasan, 1977; Jezek and
Smyrl, 1980) (since the process is operated in liquid phase) and above all to
the effects (direct or indirect) related to the introduced solute (section
12.4).
Introducing an osmotic dehydration preliminary step into the conventional stabilizing process may also lead to substantial energy savings
(Lenart and Lewicki, 1988; Collignan et al., 1992; Lewicki and Lenart,
1992). In fact the product is processed in liquid phase, giving generally
good heat and mass exchange coefficients, and water is removed from the
product without phase change (Bolin et al., 1983). Globally, a DIS
preliminary step decreases time of convection drying necessary to obtain
water activity between 0.6 and 0.8 (intermediate moisture food) (Lenart,
1988), and also the water load to the drier, or the freezer to other
dehydrating systems (Huxsoll, 1982). Hence, an osmotic dehydration step
combined with convection drying can increase the throughput of the drying
282
SUCROSE
production line. The throughput can be increased four fold if the dryer
surface is fixed; under a regular industrial production conditions, an energy
cost reduction of 40-50% can be foreseen (Lenart and Lewicki, 1988).
However, the evaluation of the economical interest of osmotic dehydration
must take into account the costs related to the concentrated solution. From
this point of view, the management of total amount of concentrated
solutions employed may constitute a key factor to the process viability (see
section 12.5).
12.3 Operating variables related to the sucrose concentrated solution

The objective here is to show how the control of operating variables
directly related to the concentrated solution, in the particular case of
sucrose, makes it possible to widen the range of possible applications of
osmotic dehydration.
Osmotic dehydration is generally favoured by the implementation of
highly concentrated solutions (50-75 g of solute/lOO g solution) and small
pieces of food (e.g. 1 or 2 cm 3 ). In most common operating conditions,
mass transfer mainly occurs during the first 2 h for water loss, and during
the first 30 min for solute gain. Then, mass transfer rates become
progressively lower and water loss stops whereas solute gain goes on
increasing regularly. Hence, the product tends to gain back weight, and
long time duration provides solute-rich products (Karel, 1975). Figure 12.2
represents water loss and solute gain observed after a 3 h of processing, on
a model food (agar gel) immersed and agitated in sucrose solutions of
various concentrations: 20,30,40,50,60 or 67% w/w (Raoult-Wack et al.,
1991a). This figure clearly underlines the key role of the concentration of
the soaking solution. Controlling concentration allows definition of an
'impregnation' situation, when solute gain is greater than water loss, which
is the case of candying or semi-candying, and a 'dewatering' situation in the
opposite case. Hence, a wide range of applications may be achieved,
characterized by various water loss to solute gain ratios.
The composition of the concentrated solution is another key factor of
osmotic dehydration . Solutes may be used as dewatering and/or impregnating
agents, and these requirements are generally conflicting. For instance,
impregnation is favoured by low-molecular-weight solutes whereas dewatering is enhanced by high-molecular-weight solutes (Raoult-Wack et
al., 1992). Therefore, the use of blends comprised to two solutes or more
have been proposed, which may provide respective advantages of each
solute (Islam and Flink, 1982; Lenart and Flink, 1984a). The prediction of
the effect of one given blend is not easy, due to solute interactions. Hence,
it is often necessary to define by experiment which blend of solutes is the
best suited to a given product. As an illustration, sucrose has often been
283
WL, SG (gliOO g initial product)
Figure 12.2 Evolution of (.) water loss and (e) sucrose gain obtained at t = 180 min as a
function of the initial concentration difference between the model food and the solution
(50C). (From Raoult-Wack et al. (1991a), reproduced by permission of Marcel Dekker Inc.)
used together with other solutes in mixed blends, for instance salt/sucrose
(50/10 or 45/15 g of each per 100 g solution), for vegetable processing
(Islam and Flink, 1982; Lenart and Flink, 1984a).
More recently, sucrose-salt blends were used, to achieve simultaneous
dewatering and salting of lean and fat fish (Collignan and Raoult-Wack,
1992; Collignan et al., 1992). It was shown that a high dewatering effect
could be obtained, due to the high concentration levels implemented with
mixed blends as compared to binary salt solutions (traditionally used),
which was reinforced by sucrose-salt interactions. Moreover, sucrose-salt
interactions proved to hinder salt entrance. As an illustration, Figure 12.3
gives the response surface for salt gain (noted StG, expressed in g/100 g
initial product) as a function of salt concentration (noted Cst, expressed in
g/litre water) and sucrose concentration (noted Csu, expressed in g/litre
water), in the case of cod fillets soaked in salt-sucrose solution (at 10C,
for 4 h 54 min). Figure 12.3 shows that in the range of low sucrose
concentrations, salt gain increases linearly as a function of salt concentration. For high sucrose concentration, salt gain is independent from salt
concentration and remains low.
This recent advance made it possible to improve traditional processing of
fish in that (1) the traditional salting/drying sequence could be reduced
thanks to one single dewatering and impregnation soaking process, and
(2) it is possible to obtain low salt content dried fish, with minimal sucrose
content (Collignan and Raoult-Wack, 1994).
284
SUCROSE
StG(g/100g
product)
initial
9.5
7.125
4.75
2.375
350
262.5
175
87.5
Cst (gIl water)
Csu (gIl water)

Figure 12.3 Osmotic dehydration of cod fillets soaked in salt-sucrose solution (lOOC, 4 h 54
min): response surface StG = f(Cst, Csu). (From Collignan and Raoult-Wack (1992),
reproduced by permission.)
12.4 Influence of sucrose impregnation on the end-product quality
The solute is inserted into the product during the soaking treatment has
both direct and indirect effects on the end-product quality. In fact, it is
responsible for direct modifications of the organoleptic quality of the
processed product, but also influences the product behaviour during
osmotic dehydration and further processing or storage. As an example of
direct modifications, the presence of the introduced sucrose in the product
was found to increase the sugar to acid ratio (Dixon and Jen, 1977),
improve the texture (Lerici et at., 1983; Torregiani et at., 1988; Paoletti et
at., 1990) and the stability of the pigments during drying and storage
(Collignan and Raoult-Wack, 1994). It is thus possible to limit the
introduction of S02 into reactive products (Ponting, 1966; Dixon et at.,
1976; Crivelli et at., 1989). The presence of the introduced solute may also
enhance the product suitability to rehydration (Mazza, 1983), and have a
protective effect on natural tissue structure during further drying, freezing,
or freeze-drying, by limiting collapse and cellular disruption (Lee et ai.,
1967; Bolin and Huxoll, 1993).
The influence of the introduced solute on the product behaviour also
285
depends on the solute distribution within the product, and the physical
state of the impregnated food. During the soaking treatment of a model gel
or a raw plant tissue in sucrose solutions, solute remains located in a 2 or
3 mm depth superficial layer in the product (Bolin et ai., 1983; Lenart and
Flink, 1984b; Raoult-Wack et ai., 1991c; Marcotte and Le Magner, 1991,
1992), e.g. during 8 h in the case of potatoes soaked in 60% w/w sucrose
solution at 20c C (Lenart and Flink, 1984b), whereas water loss occurs
deeply in the product. According to some authors, sucrose entrance would
be limited to extracellular spaces (Hawkes and Flink, 1978; Bolin et ai.,
1983). Microscopic observations confirmed that sucrose can diffuse
through the cell wall, and then stays in the space between the wall and the
membrane (Isse and Schubert, 1992). The formation of this concentrated
layer can be a key factor to control mass transfer during osmotic
dehydration, in the sense of favouring water loss and limiting solute
impregnation (Raoult-Wack et ai., 1991a, b). Moreover, this layer may
also reduce hydrosoluble solute losses, such as ascorbic acid (Vial et ai.,
1990) or fructose (Saurel, 1993). The tissue impregnation, and particularly
the presence of the concentrated sucrose layer, may also influence the
product behaviour during the complementary processing. As an illustration,
it has been widely observed that drying rates are lower after an osmotic
treatment, but the behaviour of solute-impregnated products during airdrying is not yet fully understood (Lenart and Flink, 1984a; Lenart and
Lewicki, 1988; Collignan et ai., 1992).
The physical state of the food solids (mainly polymer matrix, own
sugars, and impregnating sugars) is of particular importance for aroma
retention and for textural and chemical changes during final drying and
storage. During relatively rapid drying of foods which have been
previously subjected to osmotic dehydration, amorphous sugars are
generally formed, due to high initial solid content, high viscosity and
presence of other compounds with anticrystallizing properties (such as
organic acids and polymers). During storage, crystallization rate of sugars
in the product is determined by (1) crystallization characteristics of sugars,
and (2) temperature and moisture content.
Since it is possible, to a certain extent, to 'formulate' the food and
particularly the food surface by osmotic dehydration, the balance between
various sugars with desired crystallization characteristics can be adjusted.
For example, a soft texture can be obtained by adding sugars or other
ingredients such as glucose, invert sugar or maltodextrins, which delays or
prevents crystallization. This technique has currently been used in the
candying and semi-candying industry. On the contrary, a surface impregnation with sucrose will favor surface crystallization, thus decreasing, for the
same water activity, the product stickiness, and giving a product with a
crisp surface and a soft internal part.
For a given composition and water content, the physical state of foods is
286
SUCROSE
related to temperature, above the glass transition temperature (Tg ) (see

chapter 4). For this temperature range - typically from Tg to (Tg +
100 K) - the WLF equation (Williams et aI., 1955) gives a good description
of the dependence of the viscosity of food solids on [T - Tg ] (Solsanto and
Williams, 1981), and hence of transitions and transformations related to the
mobility of sugar molecules, such as crystallization, collapse and stickiness
(Levine and Slade, 1989; Roos and Karel, 1993). The dependence on time
is exponential and as a result, there is a rapid rate of transition when (T Tg ) is large (Roos and Karel, 1993). It is generally the case for pre-soaked
products, which are moderately dried (to reach a final water content
ranging from 12 to 16%, which corresponds to water activities 0.55 to
0.65), in order to get a soft texture.
The main evolution observed during storage is sugar crystallization,
which occurs faster in hermetically sealed containers, at constant moisture
content, than in open containers or in relatively permeable packaging
materials, when the water activity of product remains constant or decreases
(Vuataz, 1988). This can be attributed to the release of water (which occurs
during crystallization at constant water content) and related increase of (T
- T g ) of the amorphous portion of the material, which causes acceleration
of crystallization (Roos and Karel, 1993).
12.5 Control management of the sucrose concentrated solution

Optimization of the concentrated sucrose solution has two main objectives:
the reduction of syrup volumes involved and control of recycling of syrup.
During the soaking process, the concentrated solution undergoes composition changes related to the produce evolution, which looses water and
solutes, and gains sucrose from the solution. For osmotic dehydration
processes characterized by high water loss, the most important change is
the dilution of the concentrated solution; however, changes related to
product's leaching (colour, acids, sugar, minerals, vitamins) should not be
neglected since they may influence the product quality.
Most laboratory studies are carried out with a large excess of solution
volume, so as to ensure negligible variations of the solution composition,
which makes the interpretation and modelling easier. The weight ratio,
solution to product, is generally between 10 and 20. However, as far as
industrial applications are concerned, this ratio has obviously to be as low
as possible to decrease production costs. The influence of the weight ratio
solution to product (experimental values; 2, 6 or 20) on the process
performances was recently studied by Saurel (1993) on model gel cubes
soaked in sucrose solution. This study showed that it is possible to act on
temperature or concentration in order to compensate the dilution of the
concentrated solution, when a low ratio was used.
287
Giroux (1992) studied the automation of a continuous device for osmotic

dehydration. Results showed that on-line measurements of the electrical
conductivity and density of the concentrated sucrose solution allow indirect
control of mass transfer (water loss and solute gain) within the soaked
product. Such a control is possible only when the ratio of solution to
product is low enough to provide significant changes in solution composition.
Recycling the solution is actually the second stage of osmotic dehydration.
In the case of binary sucrose solution, recycling can be achieved by
reconcentration. As far as energy savings are concerned, this stage is not
limiting as it could take advantage from the performing evaporation
techniques like multi-effect evaporators or mechanical steam recompression
(Huxsoll, 1982; Bolin et al., 1983). It may be pointed out that to some
extent, the concept of multiple effect dehydration is indirectly applied to
the piece-form product, as noticed by Huxsoll (1982). Solution recycling
may also be achieved through addition of dry sugar (O'Mahony et al.,
1986), provided that further industrial valorization of concentrated sugar
solutions (e.g. for candies, or table syrup) is possible. In the case of mixed
blends, recycling is more complex, since the respective proportions of each
solute should be respected.
12.6 Conclusion
Sucrose can be used, alone or blended with other solutes in concentrated
solutions, to simultaneously achieve dewatering and direct formulation of
water-rich foods by 'osmotic dehydration', before any complementary
processing. The control of the combined process, and hence the quality
(stability, and organoleptic characteristics) of the end-product, appear to
be tightly related to the control of the total amount of sucrose inserted in
the food, its distribution within the foods, as well as its physical state.
These parameters are mainly influenced by the composition and concentration of the soaking solution. Moreover, on-line measurements on the
soaking solution can provide indirect continuous control of mass transfer
between the product and the solution.
Recent trends in the field of osmotic dehydration consist of using mixed
solutions, which makes it possible to widen up the application range of the
process to vegetable and animal products, whereas it was formerly limited
to semi-candying of fruit. These trends are enhancing the need for further
understanding and control of the soaking solution properties, mainly
determined by composition, solute interactions, and concentration.
288
SUCROSE
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SUCROSE
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Index
activity coefficient 103

agglomeration 95
amorphous quenched melt 92
amorphous solid sucrose
glass transition of 86-8
rearrangement in 89
specific heat of 190
amorphous sucrose
density of 190
properties of 190
amorphous sugar 75, 97
thermal properties of 84
amorphous sugar transformation
moisture dependence of 89
temperature dependence of 91
antioxidant properties 232
apparent specific volume 200, 202
aqueous solutions 191
aroma retention 251
Arrhenius 134
ash 178
B coefficients 135
bacteriological methods 181
Berlin Institute's Method 168
beverages 243
bleaching boosters 276
boiled sweets 95
boiling point 211
breads 240
breakfast cereals 244
bulk density 238
bulking ingredients 273
cake 241
crumb 260
crust 260
caking 95
cations 141
chemical reactivity 265
chocolate confectionery 259
chromatography 169
:r.as-liquid 169
I C NMR spectra
190
co-crystallisation 252
Codex Alimentarius 182
coffee 258
colour 179, 231
commodity 1,9
compressibility 188
computational methods 21
concentrated amorphous solution 78
behaviour of 85
disorder in 76
order in 76-7
concentrated solutions 136
concentration units 191
conductivity 178
confectionery 95, 243
conformation 13-14
solution 26
conformational flexibility 25, 27
conformational variability 22
conglomerates 36, 38
consumption 2, 4
control management 286
convection drying 281
cookies 242
crystal
colour 70
quality 66, 69
size 259
surface 66
crystalline sugar
stability of 95
crystallinity 75
crystallisation 56-{)3
cooling 63, 66
evaporation 60
process 33, 61-2
rate 59
technique 58
temperature 59
time 62-3
cubes 96
cyclic acetalation 265
dairy products 244
deacylation reaction 269
density 188
detergent builders 276
detergents 275
dextran 142
dextrans 46
dielectric constant 240
differential thermal analysis
dilute solutions 135
domestic raws 4
85
292
INDEX
Einstein 128
equation 127, 132
relation 128
electrical properties 188
emulsifiers 270
energetic aspects 1
energy, renewable 2
enzymatic methods 173, 176
enzymic reactions 268
equilibrium relative humidity (ERH)
235--6
esterification 266
European Regulation 79/796 182
fatty systems 258
fixing volatiles 252
flow behaviour 127, 139
fondants 95
food ingredients 269
food processing 240
free volume 134-5
freeze-dried sugar
collapse of 91
freezing point 212-3
fructoglucans 273
fructo-oligosaccharides (FOS)
fruit flavour 259
furaneol 255
jams 243
jellies 243
Jones and Dole equation
272
glass transition 85, 190

glassy molten sample 82
glassy state 79
granulometry 188
growth 53-7
crystal 53, 57
rate 56
headspace effects 253
heat of crystallisation 208
heat of dilution 208
heat of solution 208
heavy metals 179
heterogeneous phases 142
relations 139
high fructose corn syrups 9
high-intensity sweeteners 270
high performance liquid chromatography
(HPLC) 171-2
Hildebrand 133
homogeneous phases
relations 138
Huggins constant 135
hydrocolloids 256
hydrogen bonding 16
icings and frostings 243
immobilised enzymes 176
impure solution 48
solubility 110, 114, 115
impurities 39,40,41,69
effect of 39
inclusions 69
increase of volume 211
infrared 157
Fourier-tranform (Ff-IR) 157
near (NIR) 157
spectroscopy 157
spectrum 159
inorganic compounds 47
inorganic non-sugars 46
instability 76
interaction 250
iron-sucrose 257
sucrose-eolour-flavour 257
International Sugar Scale 161
inversion 163
isoglucose 9
isotope dilution 167
130
Knight and Allen. 168

laboratory methods 144
Lane and Eynon 168
liquid, fluidity of 133
low-calorie fat 270
low-intensity sweeteners 271
Luff-Schoorl 169
macromolecules
components 141
organic 141
Maillard reactions 227
massecuites 139, 140, 143
meats 244
melting point 187
microbiology 180
microcystalline structure 90,91
microorganisms 180
mobility of water 91
modifying taste 255
molasses 140, 150
exhaustion 149, 150
Quentin 149
standard viscosity of 150
monoclinic crystal 186
monosaccharides 41
morphology 34
crystal 34, 35
mouthfeel 259
Neosugar 272
INDEX
neutron 14
neutron diffraction 13
NIR spectrophotometry 166
NIR spectroscopy 167
NMR spectroscopy 20, 159
NMR spectrum 82
nomenclature 12
nonaqueous solvent
solubility in 118
nucleation 49, 51, 52, 53
rate 51
nucleus 50, 51
radius 51
nutritional aspects
oligosaccharides 41, 43
optical rotation 27
orientations 15
orifices lSI
osmotic dehydration 279,281
osmotic pressure 213,217
packing 18, 19
pharmacopaeia 182, 183
phase equilibrium diagram 107, 108
pipes lSI
poisoning 41
polarimetry 206
polarisation 162, 163, 164
polarography 166
polyfructans 273
polysaccharides 44
polyurethanes 274
potassium chloride 46
powdered sugar
caking of 96
storage of 96
power law 139
preserves 243
price 4, 9
pseudo-plastic 140
pulsed amperometric detection 173
pure solution 48
purity 176, 178
raffinose 44
Raman spectroscopy 159
reactive sucrose derivatives 275
recrystallisation 89, 90, 93
reducing sugars 168
Refractive Index 202
refractometry 164, 165, 166
regulations 181
rheological behaviour 126, 127, 139, 141
saccharides 120, 121
solubility of 118
salt-sucrose solution 283
293
saturation coefficient 115, 117

sensory properties 230
shape
ellipsoidal 131
factor 131
shear rate 126
shear stress 126
shelf-life 95
silylation technique 170
SN2 displacement 268
S02 179
soaking process 281
soaking treatments 281
solubility 47,48,49, 122
sucrose 48, 49
solution reactions 226
specific heat 189
specific rotation 161
stability 76
standards 181
statistical data 2
structure 11, 76, 77
sucralose 270
production of 267
synthesis of 267
sucrose
biochemical properties of 245
chemical characterisation of 155
chemicals from 274
consumption of 223-4
density of solutions 200
dry-milled 82
extruded 82
freeze-dried 80, 81, 82
impregnation 284, 285
methods of titration of 160
molecule 33
physical properties of 186, 232
polyesters 270, 271
production of 223
radioactive 167
solubility 101, 105, 106, 121, 191, 194
sources of 223
spray-dried 80, 82
technological value of 223
titration 175
sucrose solution
composition of 101
concentration of 101, 103, 104
freezing of 78
sucrose-salt blends 283
sucrose-water system
thermal behaviour of 85
sugar
dry-milled 83
extruded 83, 84
hydration numbers of 86
sugar glasses 79
294
INDEX
sugar solutions
viscosity of 151
supersaturated solutions 108
supersolubility 86
surface active compounds 270
surface tension 217
sweet perception 256
sweet-taste chemoreception 29
sweetness 224, 225
sweetness masking 256
synergistic effect 250
synthetic polymers 274
taste
acid-sour 249
basic 248
bitter 249
salty 249
temperature 104, 105, 106
ternary system 118
thermal degradation 227
thermal properties 206
thermal treatment 93
thin-layer chromatography 156
thin-layer separation 156
three-component mixture 112
three-component triangle diagram
three-dimensional structures 28
tissue impregnation 285
trade I
twins 35
crystals 36
110
vegetables 244
vibrational spectroscopy 156
viscometers
capillary 144
Couette type 145
falling-ball 145
orifice 146
pipeflow 146
rotating 144
vibrating 146
viscosity 58, 126, 131, 237
dependence on temperature 148
effect of 147, 149, 151
impure solutions 138
inherent 130
intrinsic 129, 132, 135
massecuites 143
of molasses 150
reduced differential 130
reference 150
relations 127
role of 147
of sucrose solutions 217
of sugar solutions 151
viscosity-eoncentration relations 128, 131
viscosity-temperature relations 132
washing 71, 91, 213
WLF equation 134
X-ray 13, 14
crystallinity 187

Sucrose - Properties and Applications

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Sucrose - Properties and Applications

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Properties and Applications

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

First edition 1995

1995 Springer Science+Business Media Dordrecht

Typeset in 1O/12pt Times by Cambrian Typesetters, Frimley, Surrey

Printed on permanent acid-free text paper, manufactured in accordance

solution properties are treated in the subsequent four chapters. In chapter

Professor G.G. Birch

Department of Food Science and Technology,

Institute of Chemical Technology, Technika

Sugar Processing Research Institute, Inc., 1100

Ingenieur Arts et Manufacture, 5 Rue Frevillele-Vingt, 92310 Sevres, France

CIRAD, 24 Avenue du Val de Montferrand,

Sugar Processing Research Institute, Inc., 1100

Institute of Chemical Technology, Technika

POLYBios, LBT, Area di Ricerca, Padriciano

S.N.F.S. Services Techniques, 369, Rue Jules

Universita di Ferrara, Dipartimento di Chimica,

Laboratoire de Chimie Physique Industrielle,

INRA Rue de la Geraudiere, BP 527, 44072

CIRAD, 24 Avenue du Val de Montferrand,

Ingenieur, CEDUS, 30 rue de Lubeck, 75116

University of Montpellier 11,3402 Montpellier,

Universita di Ferrara, Dipartimento di Chimica,

Professor A.J. Vlitos

World Sugar Research Organisation, University

1 Economical aspects of sugar

2 The structure of sucrose in the crystal and in solution

3.5 Crystallisation technique

6 Rheological properties of sucrose solutions and suspensions

6.2.1 Einstein's equation

7 Analysis of sucrose solutions

8.2.1 X-ray crystallinity

Technological value of sucrose in food products

Role of sucrose in retention of aroma and enhancing the flavor

Sucrose: its potential as a raw material for food

Sucrose and osmotic dehydration

1 Economical aspects of sugar

Sugar is a major commodity in world trade. Although competition from

M. Mathlouthi et al. (eds.), Sucrose

1.3 Sugar in world trade: statistical data

ECONOMICAL ASPECfS OF SUGAR

Millio n m etnt: tons, raw va lue

Figure 1.1 World production (---) and consumption (- - -).

Million metric tons, raw value

likely to continue and may accelerate. Of special interest is the projected

ECONOMICAL ASPECTS OF SUGAR

Million metric tons. raw value

Figure 1.4 Projected consumption in China compared to other nations.

.. - .... -- ... _ .... __ ..

... ----- .... - ...

Domestic row, N.Y. spot

Cents/lb .. dry weight

Sug or. refined

ECONOMICAL ASPECTS OF SUGAR

competition to sugar from other isoglucose or high fructose corn syrups

world and as a regenerable source of energy represents an important

2 The structure of sucrose in the crystal and in

the structures and the different levels of structural organizations of

THE STRUCTURE OF SUCROSE

monosaccharide units are joined by a glycosidic linkage, i.e. the anomeric

0-lg - C-2f - 0-5f