Fuel 142 (2015) 94101

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Express method for total content assessment of aromatic hydrocarbons

and oxygen in nished gasolines by refractometry and densimetry
Vyacheslav F. Nikolaev a,b,, Ilmir I. Tabrisov b, Anatoly I. Penkovsky c, Rasima B. Sultanova b
a
Laboratory of Chemistry and Petroleum Geochemistry, A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientic Center of the Russian Academy of Sciences,
420088, Arbuzov St., 8, Kazan, Russia
b
Department of Technology of Basic Organic and Petrochemical Synthesis, Kazan National Research Technological University, 420045, K. Marx St., 68, Kazan, Russia
c
Department of Analytical Instruments, Central Design Bureau Photon, 420075, Lipatov St., 37, Kazan, Russia

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Boundary conditions are established,

Finished gasoline, total aromatics, oxygen, rapid refracto-densimetric test method, unbalanced gasoline,
adulteration.
0,351
0,349

Normal-80
0,347
0,345

sRLL

matching gasoline Euro 4, 5 by total

aromatics and oxygen.
 Method for the development of a new
ASTM standard is proposed.
 The method can be implemented in
the onboard quality gasolines
analyzer with the output result on a
car dashboard.

Regular-92

0,343

RI=1,0545

0,341

Premium-95

0,339
0,337

RI=1,0522
sR LL =0,3373

0,335

1,04 1,042 1,044 1,046 1,048 1,05 1,052 1,054 1,056 1,058 1,06

RI

a r t i c l e

i n f o

Article history:
Received 1 March 2014
Received in revised form 26 September
2014
Accepted 15 October 2014
Available online 6 November 2014
Keywords:
Index of refraction
Density
Oxygenate
CottonMouton effect
Adulteration

a b s t r a c t
This paper presents routine refracto-densimetric indicators which may be used to identify unbalanced
automobile gasoline and falsications (surrogates). These criteria are supposed to reduce considerably
the amount of testing via standard chromatographic and spectroscopic methods. Refracto-densimetric
method for controlling the limiting weight content of oxygen is based on substantial difference between
specic refractions of oxygenates and hydrocarbon gasoline components. Application of the refractive
intercept which is additive in the volume fractions of components and constant for different homologous
series of hydrocarbons allowed to establish its maximum value, the excess of which identies a gasoline
with a high content of aromatic hydrocarbons. In addition, the excess of refractive intercept of certain
limit value can also indicate the possible presence of conjugated diolens in gasoline and bicyclic arenes.
2014 Elsevier Ltd. All rights reserved.

Corresponding author at: Laboratory of Chemistry and Petroleum Geochemistry, A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientic Center of the
Russian Academy of Sciences, 420088, Arbuzov St., 8, Kazan, Russia.
http://dx.doi.org/10.1016/j.fuel.2014.10.042
0016-2361/ 2014 Elsevier Ltd. All rights reserved.

V.F. Nikolaev et al. / Fuel 142 (2015) 94101

1. Introduction
The focus of monitoring light petroleum products, in particular
the motor gasolines, is in the quantitative determination of various
groups of hydrocarbons. In motor gasolines, besides the products
of direct distillation of crude oil and products of secondary processes of its processing (catalytic cracking, reforming process,
etc.), there are oxygenates added during the compounding of commercial gasoline in order to increase the octane number and the
complete combustion.
The arsenal of modern methods for determining the composition of petroleum products is very wide [16]. Since petroleum
products are multicomponent mixtures, many physical methods
in the study of such mixtures require special approaches, both in
staging the experiment, and in its subsequent interpretation. In
some cases, when assessing the quality of petroleum products, it
is convenient to use the integral (i.e. non-spectroscopic and nonchromatographic) physical methods, in which a particular property
of a substance or mixture is represented as a numerical (integral)
value. These methods can be referred to, in particular, as magnetic
birefringence (CottonMouton effect) [79], refractometry [10],
tensiometry, viscosimetry, densimetry [11] and dielectrometry
[12]. The sensitivity of each method to a particular group of compounds (hydrocarbons) allows on combining them (using together)
to determine the content of mixtures, to evaluate their performance properties and their identication. The need to develop
the methods of rapid identication of petroleum products is dictated by the fact that the volume of counterfeit products, especially
in the motor fuels market, remains signicant [1316]. It is generally known that one way of falsication of motor fuels is replacement of components to cheaper and environmentally hazardous
ones, which leads to signicant deterioration in performance properties of fuels, and to increased carbonization, thereby to resource
reduction of the engine.
The problem of improving the quality of motor fuel is of particular importance also due to the fact that the constantly increasing
requirements of international standards for environmental
properties of fuels [17], which makes the development of methods
for rapid identication of petroleum products an extremely urgent
task. Implementation of such control methods is of extreme interest both for fuel inspection, customs and immediate consumers,
because these methods allow to detect counterfeits and doubtful
quality gasolines subjected to subsequent verication by the standard methods recommended by fuel standards Euro-4 and Euro-5.
Important quality parameters of conventional gasolines are the
total content of aromatic hydrocarbons limited by fuel standards
Euro-4 and Euro-5 with the value not greater than 35 vol%, and
the total oxygen content not more than 2.7 wt%. In order to make
these parameters standards a series of spectroscopic and chromatographic ASTM-methods were recommended. Increased content of aromatic hydrocarbons results in incomplete combustion
of the fuel, to the growth of soot formation and as a consequence,
to increased toxicity of emissions into atmosphere. In turn, the
increased oxygen content (more than 2.7 wt%), due to the presence
of oxygenates (dialkyl ethers and lower aliphatic alcohols) in gasolines, leads to the increase of toxic aldehydes and ketones content
in combustion products, to the reduction of the heat of fuel
combustion, to increased fuel consumption, to delamination of
gasoline in contacting with moisture, to swelling of non-metallic
parts of fuel supply pipe. Possibility of the routine assessment of
the quality of gasoline on the total content of aromatic hydrocarbons will also allow to identify gasoline with a high content of conjugated diolens and with unacceptable in gasoline bicyclic arenes
(e.g. naphthalene and its derivatives), added to surrogate fuels to
increase the octane number. The presence of the latter in gasoline

95

results in increased gum-and soot formation and low stability of

the performance of fuels at long-time storage.
This paper shows that the use of refracto-densimetric method
allows not only to carry out the prompt semi-quantitative analysis
of light petroleum products, but also to present the results of this
analysis in the form of easily understood visual form. This visibility
is ensured by measuring only two physico-chemical properties of
gasoline index of refraction nD20 (hereinafter simply n) of the
sample at 20 C on the yellow D-line Na (k = 589 nm) and its density at 20 C d20 (further d), as well as by the use of derivatives of
these two characteristics refractive intercept RI (Eq. (1)) [18]:

RI n  d=2;

specic LorentzLorenz refraction sRLL (Eq. (2)) [10]

sRLL n2  1=n2 2  d

and specic refraction of GladstoneDale sRGD (Eq. (3)) [19]:

sRGD n  1=d:

Refractive intercept RI is additive on the volume fractions of

components (Eq. (4)) [20]:

RImix

k
X
RIi v i RI1 v 1 RI2 v 2 . . . RIk v k

i1

which follows from the additivity of the index of refraction of the

mixture nmix on the volume fractions of components vi (Eq. (5))
[10,21,22] (Rvi = 1):

nmix

k
X
ni v i n1 v 1 n2 v 2 . . . nk v k

i1

and additivity of mixture density dmix (Eq. (6)):

dmix

k
X
di v i d1 v 1 d2 v 2 . . . dk v k ;

i1

where k number of components in the mixture. This rule holds

with good accuracy for hydrocarbon mixtures and with somewhat
less accuracy for mixtures, if one of the components is a lower aliphatic alcohol. Specic LorentzLorenz refraction sRLL and GladstoneDale sRGD are additive with respect to the weight fractions
of components wi (Eq. (7)):

sRmix

k
X
sRi wi sR1 w1 sR2 w2 . . . sRk wk :

i1

It should be noted that if weight fractions of the components wi

(Rwi 1) are used in the study, then to describe the dependence of
the density of the mixture dmix on the content it is necessary to use
the Eq. (8):

1=dmix

k
X
wi =di w1 =d1 w2 =d2 . . . wk =dk :

i1

The given dependences Eqs. (5), (6) and (8) are derived from
supposition that the mixture volume equal to the sum of volumes
of the starting components, which is performed for hydrocarbon
mixtures with a sufciently high accuracy. In case of deviations
of dependencies Eqs. (5)(8) from linearity in terms of volume or
weight fractions of the components of the binary (or pseudobinary)
mixture using these equations in software refracto-densimetric
analyzers, there can be used different approximating equations
that best describe the properties of mixtures in a wide range of
compositions. Among these dependencies:
Hyperbolic equation (Eq. (9)) [10]:

c1 =c2 1  c2 =c2 Kqmix  q2 =q1  qmix ;

96

V.F. Nikolaev et al. / Fuel 142 (2015) 94101

where qi, qmix physico-chemical properties of the starting individual components and the mixture, for example, index of
refraction n, density d or its inverse value 1/d, specic refraction
sR or refractive intercept RI, c1 and c2 volume v1, v2, weight w1,
w2 or the molar x1, x2 fractions of components, respectively
(c1 = 1  c2), K parameter obtained by statistical processing
of data array ciqi;
Korzheniovsky equation (Eq. (10)) (cited by [10])

c1 =c2 m 1  c2 =c2 m Kqmix  q2 =q1  qmix ;

10

where K and m model parameters for a particular mixture;

RedlichKister equation (Eq. (11)) [23]

qmix  q1 c1  q2 c2 c1 c2 

m
X
Ai c1  c2 i ;

11

i0

where Ai coefcients for a particular binary mixture, m

selectable polynomial degree;
Model of Hwang (Eq. (12)) [24]:

qmix  q1 c1  q2 c2 c1 c2 B0 B1 c31 B2 c32 ;

12

where B0, B1, B2 parameters, constant for a specic binary

mixture;
Nonstoichiometric model of competing van der Waals interactions (Eq. (13)) [2528]:

qmix  q1 c1  q2 c2 A2 c2 expB2 c2 A12 c1 c2 A1 c1 expB1 c1 ;

13
where A1, A2, A12, B1, B2 parameters for a specic binary
mixture (c1 = 1  c2);
Model of the balance of contributions of imaginary endo- and
exotherms (Eq. (14)) [2932]:

qmix  q1 c1  q2 c2 K 1 cl1 cp2 K 2 cr1 cs2 ;

14

where K1, K2, l, p, r, s adjustable parameters. First approximations for the coefcients K1 and K2 during iterations are chosen
equal in absolute value but opposite in sign, and for the exponents l, p, r, s the rst approximation is taken to be equal 1. These
expressions can be used in solving problems related to the definition of the binary (pseudobinary) mixture on any of physico-chemical properties qmix and properties of the initial
components q1 and q2.

The paper presents the results of a study of about 500 samples

of commercial gasolines Normal-80, Regular-92 and Premium-95,
obtained during the Month of Republican control of the quality
of fuels in 201112. The index of refraction nD20 was taken on a
hand-held (portable) refractometer IRF-470 (CDB Photon, Kazan)
with accuracy 0.00025. To prevent the evaporation of light fractions after injecting gasoline quickly close the top cover of refractometer, wait for 1015 s, so that the sample acquires the
temperature of refractometer. The index of refraction measurements are conducted three times, and then not the average, but
the minimum value of the three measurements of the index of
refraction are selected. This is a conservative estimate to eliminate
bias caused from evaporation.
Densities of motor gasoline were determined by oil laboratory
of Republican Inspection for Quality Control of fuels using hydrometer GOST-R 51069-97 at 15 C, which then were by us recalculated
to 20 C as related to Eq. (15) [33]:
20

15

 5b;

where b temperature correction equal to 0.00086.

v aromatics 0:934BIN 0:021

15

16

Magneto-optical method for determining the total content of

aromatic hydrocarbons in gasolines on the installation Mobin
(IPL-456) would be more preferable if these settings were not
uncommon.
3. Results and discussion
3.1. Refractometric criterion of oxygenates exceedance in gasolines
and oxygen content of 2.7 wt%
Since this normative of fuel standards Euro-4 and Euro-5 weight
fraction of oxygen was used, then as refractometric criterion there
was used specic LorentzLorenz refraction sRLL, additive exactly
in weight fractions of components and dened in Eq. (2). For calculation of minimum sRLL value, below which there is a high probability of exceedance in gasoline oxygen content, we used data on
methanol (MeOH), as well as on most common oxygenates: ethanol (EtOH), isopropyl alcohol (i-PrOH), tert-butyl alcohol (t-BuOH),
isobutyl alcohol (i-BuOH), methyl tert-butyl ether (MTBE), ethyl
tert-butyl ether (ETBE), methyl tertiary amyl ether (MTAE), diisopropyl ether (DIPE) and some higher dialkyl ethers (Table 1). Since
in different oxygenates the fraction of oxygen wO/oxygenate varies
(Table 1), then their maximum permissible weight fraction wmax
in gasoline, providing the oxygen content of 2.7 wt%, will also be
different (Eq. (17)):

wmax 0:027=wO=oxygenate

2. Experimental procedure

Heptanetolueneisobutyl alcohol mixtures, modeling gasolines, were prepared from reagents qualied as pure according
to the Russian standards TU 2631-023-44493179-98, TU 2631007-44493179, and GOST 6016-77, respectively.
Index of refraction nD20 measurements of ternary mixtures were
performed on IRF-23 refractometer, densities d20 were determined
pycnometrically at 20 C. For additional control of gasoline to the
total content of aromatic hydrocarbons by the method of magnetic
birefringence (CottonMouton effect) on the installation MOBIN
(IPL-456) described in [7,8,11], magneto-optical benzene index
(BIN) representing the ratio of the gasoline magnetic birefringence
(CottonMouton constant) to the magnetic birefringence of benzene determined under the same conditions (t = 20 C, HeNe laser
k = 632.8 nm) was measured. Magneto-optical benzene index BIN
is associated with the volume fraction of aromatic hydrocarbons
varomatics in gasolines by Eq. (16)

17

where 0.027 limit of oxygen in gasoline (2.7 wt%), expressed in

weight fractions, wO/oxygenate weight fraction of oxygen in oxygenate, calculated as wO/oxygenate = 15.9994/Moxygenate (15.9994
weight of gram-atom of oxygen, Moxygenate weight of oxygenate
gram-mole).
Since specic LorentzLorenz refraction sRLL and Gladstone
Dale sRGD have not only additivity in mixtures, but also structural
additivity at the molecular level, assuming that the specic refraction of the alkyl part of one to another oxygenate is approximately
constant (strictly speaking, it is not so), we can write the Eq. (18)

sRoxygenate sRalkyl walkyl=oxygenate sRO wO=oxygenate

sRalkyl 1  wO=oxygenate sRO wO=oxygenate
sRalkyl  sRalkyl  sRO wO=oxygenate ;

18

where walkyl/oxygenate, wO/oxygenate weight fractions of the alkyl and

oxygen in the molecule of the oxygenate, respectively (walkyl/oxygenate + wO/oxygenate = 1), sRalkyl specic refraction alkyl fraction of
oxygenate (or alkyl part and hydroxyl hydrogen, if aliphatic alcohol
is used as an oxygenate), sRO specic oxygen refraction. Fig. 1
shows the dependence of specic LorentzLorenz refraction sRLL(-

97

V.F. Nikolaev et al. / Fuel 142 (2015) 94101

Table 1
Refractometric characteristics of lower alcohols and dialkyl ethers [34] and their maximum weight fractions wmax(oxygenate), supplying the oxygen content of 2.7 wt%.
Oxygenate

nD20

d20

Moxygenate

wO/oxygenate

wmax

sRLL

sRGD

RI

MeOH
EtOH
i-PrOH
tert-BuOH
i-BuOH
MTBE
ETBE
MTAE
DIPE
Dibutyl ether
Dipentyl ether
Diisopentyl ether
Dihexyl ether
Diheptyl ether
Dioctyl ether

1.3288
1.3611
1.3776
1.3878
1.3970
1.3690
1.3794
1.3891
1.3679
1.3992
1.4119
1.4085
1.4204
1.4275
1.4327

0.7914
0.7893
0.7855
0.7887
0.8021
0.7405
0.7465
0.7672
0.7241
0.7689
0.7833
0.7770
0.7936
0.8008
0.8063

32.0
46.1
60.1
74.1
74.1
88.1
102.2
102.2
102.2
130.2
158.3
158.3
186.3
214.4
242.4

0.500
0.347
0.266
0.216
0.216
0.182
0.157
0.157
0.157
0.123
0.101
0.101
0.086
0.075
0.066

0.0540
0.0778
0.1014
0.1250
0.1250
0.1487
0.1725
0.1725
0.1725
0.2197
0.2671
0.2671
0.3144
0.3618
0.4091

0.2569
0.2804
0.2932
0.2991
0.3002
0.3047
0.3099
0.3083
0.3108
0.3147
0.3176
0.3178
0.3191
0.3209
0.3221

0.4155
0.4575
0.4807
0.4917
0.4950
0.4983
0.5083
0.5071
0.5081
0.5192
0.5259
0.5257
0.5297
0.5338
0.5366

0.9331
0.9665
0.9849
0.9935
0.9960
0.9988
1.0062
1.0055
1.0059
1.0148
1.0203
1.0200
1.0236
1.0271
1.0296

0.35

y = -0,151x + 0,3327
0.33

sRLL

0.31

0.29

0.27

0.25
0

0.1

0.2

0.3

0.4

0.5

0.6

wO/oxygenate
Fig. 1. Dependence of specic LorentzLorenz refraction sRLL(oxygenate) of dialkyl
ethers and lower aliphatic alcohols versus weight fraction of oxygen wO/oxygenate
(data from methanol CH4O to dioctyl ether C16H34O).

aromatic sRLL(toluene) = 0.3375, parafnic sRLL(heptane) = 0.3449

and olenic sRLL(hexene-1) = 0.3471 hydrocarbons main components of gasolines. Thus, the addition of oxygenate to hydrocarbon
(gasoline) in terms of refractometry and densimetry looks exactly
the same as if we increased the size of the alkyl parts in oxygenate.
This fact makes refractometry an excellent method of oxygen content control in gasoline without having to identify individually
each of the oxygenates, as is done in the chromatographic determination of the total oxygen content. Simultaneous presence of several different oxygenates in gasoline is also not an aggravating
circumstance for refracto-densimetry. Furthermore, since there is
currently a trend to use oxygenates with a relatively large volume
of a hydrocarbon part (C6 and higher), then implementation of
additivity rule of specic refraction sRLL of the mixture on specic
refractions of components (sRLL)i and their weight fractions wi
becomes still stricter. Fig. 2 shows the dependence of specic LorentzLorenz refraction sRLL(oxygenate) on molecular weight of
oxygenate.

sRLL oxygenate 0:332714  2:41504=MR

oxygenate) on weight fraction of oxygen wO/oxygenate. To show the
generality of this dependence in a wide range of weight fraction
of oxygen wO/oxygenate in Fig. 1 there are also shows the data for
the higher dialkyl ethers, which, of course, are not used as oxygenate additives to gasoline.
In analytical form, the obtained dependences are presented by
Eqs. (19)(21):

As might be expected, the constant terms of Eqs. (19) and (22)

are equal in value. Specic refraction sR of binary mixture,
consisting of oxygenate and hydrocarbon component woxygenate
whydrocarb 1, can be given by Eq. (23):

sRhydrocarb  sRhydrocarb  sRoxygenate woxygenate

19

sRGD oxygenate 0:552853  0:27645  wO=oxygenate

r  0:998; s0:0019

20

23

The boundary value of the specic refraction of the

compounded gasoline corresponding to the content of 2.7 wt% of
oxygen (Table 2) is calculated using the limiting weight fraction
wmax of particular oxygenate (Table 1), its specic refraction

RIoxygenate 1:04175  0:218674  wO=oxygenate

r  0:998; s0:0016

22

sRmix sRoxygenate woxygenate sRhydrocarb whydrocarb

sRLL oxygenate 0:332714  0:15094  wO=oxygenate

r  0:999; s0:0008

 0:999; s0:00077

0.33

21
sRoxygenate

0.31

The above correlations indicate that these refractometric characteristics are quite sensitive to the oxygen content in the oxygenate and can be used in the development of refracto-densimetric
rapid method to control the oxygen content in gasolines. Free
terms of Eqs. (19)(21) represent the average specic refractions
sRLL(alkyl), sRGD(alkyl) and the average refractive intercept RI(alkyl)
hydrocarbon fraction of oxygenate. Moreover, the specic Lorentz
Lorenz refraction sRLL(alkyl) of the hydrocarbon fraction in (19)
turns out to be equal 0.3327 that is within the range of specic
refractions naphthene hydrocarbons sRLL(cyclohexane) = 0.3295,

0.29
0.27
0.25
0

50

100

150

200

250

Moxygenate
Fig. 2. Dependence of specic LorentzLorenz refraction sRLL(oxygenate) versus the
molecular weight of oxygenate.

98

V.F. Nikolaev et al. / Fuel 142 (2015) 94101

Table 2
Calculated specic LorentzLorenz refractions sRLL of hydrocarbonoxygenate mixtures with the content of the latter in the mixture in the amount wmax, providing 2.7 wt% of
oxygen.
Hydrocarbon component

sRhydrocarb

Hexane
Heptane
Hexene-1/heptane (18/82)
i-Octane
Cyclohexane/heptane (1/4)
Toluene/heptane (35/65)
Catalytic (ally cracked) gasoline
sRAVR =

0.3467
0.3449
0.3453
0.3438
0.3416
0.3426
0.3388
0.3434

sRmix (hydrocarbon/oxygenate) at wmax

MeOH

EtOH

i-PrOH

t-BuOH

i-BuOH

MTBE

ETBE

MTAE

DIPE

0.3419
0.3402
0.3405
0.3391
0.3370
0.3380
0.3344
0.3387

0.3416
0.3399
0.3403
0.3388
0.3368
0.3377
0.3343
0.3385

0.3413
0.3397
0.3400
0.3386
0.3367
0.3376
0.3342
0.3383

0.3408
0.3392
0.3395
0.3382
0.3363
0.3371
0.3338
0.3378

0.3409
0.3393
0.3397
0.3383
0.3364
0.3373
0.3340
0.3380

0.3405
0.3389
0.3393
0.3380
0.3361
0.3370
0.3337
0.3376

0.3404
0.3389
0.3392
0.3379
0.3361
0.3370
0.3338
0.3376

0.3401
0.3386
0.3389
0.3377
0.3358
0.3367
0.3336
0.3373

0.3405
0.3390
0.3394
0.3381
0.3363
0.3371
0.3340
0.3378

Table 3
Refractive intercepts of different homologous series of hydrocarbons [18].
Hydrocarbons

Refractive intercept RI

Parafnic
Saturated monocyclic (naphthenes)
Monoolens
Diolens
Conjugated diolens
Aromatic monocyclic
Naphthalenes

1.0458
1.0395
1.0521
1.0613
1.0809
1.0626
1.1082

sRLL(oxygenate), specic refractions of different hydrocarbons,

their mixtures and gasoline of catalytic cracking, which is the basic
component of at the compounding of motor gasoline.
The bottom line of Table 2 shows the average column rank values (on oxygenates) of specic LorentzLorenz refraction sRLL mixtures, containing 2.7 wt% of oxygen. It can be seen that the specic
refractions of mixtures of hydrocarbons and dialkyl ethers and
lower alcohols fall within the interval sRLL = 0.3373  0.3387. The
same interval for GladstoneDale specic refractions makes up
sRGD = 0.5563  0.5583. For oxygenates MTBE and ETBE the boundary values of specic refractions coincide and are equal to
sRLL = 0.3376 and sRGD = 0.5565. Thus, gasolines having a value of
the specic refraction sRLL < 0.3373 (or sRGD < 0.5563), should be
attributed to the gasolines with a higher oxygen content (or oxygenates), which shall be conrmed by subsequent studies by arbitration chromatographic or infrared spectroscopic methods [3
5,35].
3.2. Method for detecting gasolines with high content of aromatic
hydrocarbons, conjugated diolens and bicyclic arenes
There are a number of analytical methods for assessing the content of these components [13,6]. Negative effect of olens on the
quality of fuel is discussed in [36]. The proposed refracto-densimetric gasoline control method with the indicated components,
which strictly speaking, cannot be considered analytical, still

makes it easy to identify gasoline with a high content of these

groups of hydrocarbons. To calculate the upper limit of refractive
intercept RI (1) by aromatic hydrocarbons additivity rule was used
for volume fractions of its components (Eq. (4)). The upper boundary of refractive intercept of gasolines corresponding to the limiting volume fraction of aromatic hydrocarbons varomatics = 0.35 in
motor gasoline, can be estimated in several ways depending on
the availability of a priori information about gasoline [37]. The
main components of gasoline are parafnic, naphthenic, aromatic
hydrocarbons and oxygenates, provided by dialkyl ethers and
lower aliphatic alcohols, and unsaturated compounds olenic
hydrocarbons. Refractive intercept of these components [18] is
given in Tables 3 and 1.
Calculation of the refractive intercept RIgasoline, exceeding of
which would indicate a high content of aromatic hydrocarbons
varene > 0.35 (>35 vol%), was conducted by Eq. (13):

RIgasoline 0:2RInaphtene 0:8RIparaff v paraff=napht

RIaromatics v aromatics RIoxygenate v oxygenate
RIolefine v olefins ;

24

where RIi refractive intercepts of gasoline i-component from

Tables 1 and 3. Thus, there should be performed normalization
equation v paraff=napht v aromatics v oxygenate v olefins 1. As the input
data there were used refractive intercepts for four basic hydrocarbon components of commercial gasolines (Table 3) and for ethyltert-butyl ether (Table 1),
It is evident from the data of Table 4 that the routine method for
controlling motor gasoline on the total content of aromatic hydrocarbons becomes available. The use of the boundary value
RI = 1.0522 seems reasonable, since the presence of diolens, especially conjugated diolens certainly reduces the quality of gasoline
though the norms of Euro-4 and Euro-5 and do not differentiate the
species composition of olen fraction in gasolines. The found
boundary value RI can simultaneously detect surrogates of fuels
containing naphthalene and its derivatives, refractive intercept
which makes up RI = 1.1082. Indirectly, high refractive intercept
may indicate also on heavy fractional composition of gasoline.

Table 4
Limiting values of refractive intercepts RI of gasolines containing 35 vol% of aromatic hydrocarbons depending on the composition of parafnnaphthenic and olen parts and on
the presence of oxygenate.
Characteristics of non-aromatic gasoline components

Without olens
Monoolens (18 vol%)
Or diolens (18 vol%)
Or conjugated diolens (18 vol%)

With limiting content of oxygenate

Composition of parafnnaphthenic fraction of
gasolines

Without oxygenate
Composition of parafnnaphthenic fraction of
gasolines

Parafns/naphthenes 4/1

Parafns

Parafns/naphthenes 4/1

Parafns

1.0451
1.0465
1.0481
1.0517

1.0457
1.0469
1.0485
1.0521

1.0509
1.0522
1.0539
1.0565

1.0517
1.0528
1.0545
1.0580

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V.F. Nikolaev et al. / Fuel 142 (2015) 94101

0.3500

1,06

1,055

5
1,05

RI

4
3

1,045

EURO- 4, 5

Conditioned mixtures
0.3400

increased
carbonization,
incomplete
combustion,
unbalanced
gasoline

0.3300

sRLL

gum formation and low stability of the

performance of gasoline at long-time
storage

0.3200

sRLL=0,3376

High oxygen
wO/mixture>0,027

High both
parameters

0.3100

2
RI=1,0517

0.3000

1,04

toxic emissions of aldehydes and ketones, low enthalpy

of combustion, tendency to delamination

0.2900
0.990

0,1

0,2

0,3

0,4

0,5

Visually dependence of boundary magnitudes of a refractive

intercept on a volume fraction of aromatics and the nature of not
aromatic part of gasolines is demonstrated in Fig. 3.
At Fig. 3 drawing the magnitudes resulted in the Tables 1 and 3
and the following equations were used:

Line 3
Line 4
Line 5

1.020

1.030

1.040

1.050

1.060

1.070

0,6

Fig. 3. Dependence of calculated boundaries of refractive intercept RI of the

gasolines corresponding to fuel standards Euro-4 and Euro-5 on the total aromatics,
oxygenate and composition of parafnnaphthenic and olenic parts.

Line 2

1.010

RI

RI = 0.15  1.0062 + (1  0.15  varomatics)

 (1.0458  0.8 + 1.0395  0.2) + 1.0626  varomatics.
RI = (1.0458  0.8 + 1.0395  0.2)
 (1  varomatics) + 1.0626  varomatics.
RI = 0.18  1.0521 + (1  0.18  varomatics)
 (1.0458  0.8 + 1.0395  0.2) + 1.0626  varomatics.
RI = 0.18  1.0613 + (1  0.18  varomatics)
 (1.0458  0.8 + 1.0395  0.2) + 1.0626  varomatics.
RI = 0.18  1.0809 + (1  0.18  varomatics)
 (1.0458  0.8 + 1.0395  0.2) + 1.0626  varomatics.

The eld of the gasolines (Fig. 3) corresponding to standards

Euro-4 and Euro-5, is bounded by three bold lines.
3.3. Experimental verication of the obtained boundary values sR and
RI
To check the acceptability of the proposed approach and the
boundary values of the calculations on specic refraction sRLL and
refractive intercept RI there were prepared 65 three component
mixtures of heptanetolueneisobutanol with variation of weight
fraction intervals of each component wi = 0  1. As a boundary
value of refractive intercept there was used the value RI = 1.0517,
since it is known for certain that mixtures do not contain olens.
The accuracy of differentiation of mixtures according to the criteria
of eligibility to fuel standards Euro-4 and Euro-5 by volume
content of aromatics varomatics = 0.35 and total oxygen content
wO/gasoline = 0.027 made up 95.4%.
Additionally, we analyzed 500 samples of motor gasoline on the
excess criterion RI = 1.0522, which corresponds to the content of
aromatics in gasoline varomatics = 0.35. Comparison was carried
out with the data on the total content of aromatic hydrocarbons,
obtained by the method of magnetic birefringence on the installation Mobin (IPL-456). Correctness of gasoline differentiation on
conditioned/inferior to the total content of aromatic hydrocarbons
(varomatics = 0.35) with the use of the value RI = 1.0522 made up
73.3%. When used as a boundary value on aromatics refractive
intercept values RI = 1.0545, corresponding to the case, and when
gasoline has no oxygenates and naphthenes, and olen fraction is

Fig. 4. Refracto-densimetric card of heptane/toluene/iso-butanol mixtures and

their conformity area to the requirements of Euro 4 and 5 on the total content of
aromatics and oxygen.

represented only by diolens, the share of data coincidence of

magnetic birefringence and refracto-densimetry was slightly
increased and reached 86%. However, as follows from Table 4,
there are situations where a high value of refractive intercept,
due to the high content of aromatic hydrocarbons and conjugated
diolens, can be reduced (or masked) by adding oxygenate to
gasoline. Therefore, we believe that as a boundary for good gasoline we should still take the range of RI
1.0522, and as a boundary for bad gasolines the range of RI = 1.0522  1.0545, and for
very bad the area from RI > 1.0545. Reliability of refracto-densimetric discarding of substandard gasolines can be enhanced by
identifying reasonable boundary conditions on sRLL and RI, that
would properly reect the regional peculiarities of raw materials
used in gasoline blending. Results of refracto-densimetric study
of motor gasolines, conducted in 201112 in the Republic of Tatarstan (Russia), are presented in Fig. 4 in the form of identication
card plotted in coordinates refractive intercept RI specic LorentzLorenz refraction sRLL.
Horizontal line in Fig. 5 marks the boundary value on specic
LorentzLorenz refraction sRLL = 0.3373 (Table 2), corresponding
to the content in gasoline 2.7 wt% of oxygen. And two vertical lines
(Table 4) corresponds to the boundary of good gasolines
RI = 1.0522 and the boundary of bad gasolines RI = 1.0545,
beyond which there are very bad gasolines with obviously high
content of aromatic hydrocarbons and conjugated diolens,
probably containing bicyclic aromatics. It is seen from Fig. 4 that

0,351
0,349

Normal-80
0,347
0,345

sRLL

Line 1

1.000

var

1,035

Regular-92

0,343

RI=1,0545

0,341
0,339

Premium-95

0,337
0,335

RI=1,0522

sR LL =0,3373

1,04 1,042 1,044 1,046 1,048 1,05 1,052 1,054 1,056 1,058 1,06

RI
Fig. 5. Refracto-densimetric identication card of motor gasoline in the coordinates
RIsRLL with the boundaries of gasoline, conditional on the total content of
aromatics and total oxygen content.

100

V.F. Nikolaev et al. / Fuel 142 (2015) 94101

probabilistically on this map there can be determined octane

number of an unknown gasoline, if it is produced in the same
region, where these studies were conducted. Since identication
card is built in the coordinates sRLLRI which are proportional to
the weight and volume fractions of components, respectively, by
this card it is possible to judge visually about the proportions of
initial components used in compounding of the particular gasoline
sample, if the starting point components are also plotted on the
identication card. The proximity of the point of gasoline to the
point of a component or a tendency (focus on it) may indicate
that this component is included in the sample of gasoline.
Refracto-densimetric analysis of test results of 500 gasolines indicates that the octane number of the investigated gasoline is provided mainly by introducing arenes and oxygenates into the
gasoline. If the octane number was provided only by alkylates
and oxygenates, then the location of gasoline lines with different
octane number would have changed on this identication card to
the opposite, and the above lying in Fig. 5 would be high-octane
gasoline Super-98 and Premium-95 approaching on refractometric
characteristics to isooctane. Finally, speaking about the refractodensimetric method for detecting counterfeits, we can conclude
that dubious quality gasolines have the maximum value of refractive intercept RI and/or the minimum value of the specic refraction sR. Between refractive intercept RI and specic refraction sR
of various classes of gasoline, there is a denite relationship, so
even if the gasoline meets the boundary values RI and sR, but signicantly drops out of the group, then it must also be classied as
doubtful quality gasolines and tested by standard chromatographic
or spectroscopic methods. Additional attraction of cluster analysis
data to refracto-densimetric ones allows to attribute visually the
gasoline under investigation to one or another group of standard
gasolines introduced into the computer database as reference
points. There is a wide choice of refractometers and densimeters,
but especially suitable for this method of gasoline analysis may
be devices that combine these two functions. To these devices
one can attribute refracto-densimeters: combined meters DR40
and DR45 (Mettler Toledo), the combined system of the analysis
including densitometer DMA M and refractometer RXA (Anton
Paar) as well as general concentration meter WBA-505.
4. Conclusion
When using ow refractometers and densimeters, an approach
to control the quality of gasoline proposed in this paper allows to
visualize the process of gasoline compounding and signicantly
simplify the process of making technological solutions. Availability
of portable refractometers and densimeters allows to control the
quality of the gasoline purchased even the average consumer. Simple mathematical software and tablet computer, to the input of
which the information on two physical properties of gasoline is
supplied, will make the control of gasoline quality available to a
wide range of people interested in the problem of the quality of
fuels. Regional fuel inspections can inform consumers about the
current criteria of gasolines quality in terms of sRLL and RI. At parallel studies of gasoline and arbitrary methods and refracto-densimetry the boundary values of specic refraction and refractive
intercept can be adjusted depending on the regional peculiarities
of raw materials base for hydrocarbon components of fuels and
shifted in one direction or another. Introduction into laboratory
practice the refracto-densimetric gasoline control method will
allow to reduce the time and cost of identifying clearly substandard and counterfeit fuels by tens if not hundreds times. Thus standard methods of gas chromatography, Fourier transform infrared
spectroscopy, etc. could be used as arbitration methods.
According to the algorithm described in this article is designed
the computer Excel-program Euroxtest [38].

Acknowledgements
The authors are grateful to the Russian Foundation for Fundamental Research (RFFR) for nancing the manufacture of a prototype of magneto-optical analyzer of hydrocarbon fuels MOBIN,
which was used in this work, to executive management of the
Republican Inspection on fuel quality control of the Republic Tatarstan (Russia), providing the opportunity for validation of the new
refracto-densimetric method for assessing the quality of motor
gasoline by the total content of aromatic hydrocarbons and the
total content of oxygen in a representative set of samples.
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