Partial Molal Volumes of Hydrocarbons in Water Solution

W. L. Masterton
Citation: J. Chem. Phys. 22, 1830 (1954); doi: 10.1063/1.1739928
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THF:

JOURNAL

OF

CHEMICAL

PHYSICS

VOLUME

22,

NUMBER

11

NOVEMBER,

1954

Partial Molal Volumes of Hydrocarbons in Water Solution

W. L.

MASTERTON*

Department of Chemistry and Chemical Engineering, University of Illinois, Urbana, Illinois

(Received April 12, 1954)
The partial molal volumes of benzene, methane, ethane and propane in water solution have been determined at temperatures ranging from 1D-40C. All the volumes measured were less than those of the same
hydrocarbons in nonpolar solvents. This decrease in volume is explained in terms of the abnormally high
internal pressure of water, which decreases the free volume available to the hydrocarbon molecules. The
temperature dependence of the partial molal volumes of the aliphatic hydrocarbons differs sharply from
. that of benzene. It is suggested that this is caused by a difference in solution structure in the two cases.

INTRODUCTION

HE thermodynamics of aqueous solutions of

hydrocarbons have been investigated in this
laboratory during the past several years. Claussen and
Polglase 1 determined the solubilities, heats of solution,
and entropies of solution of methane, ethane, propane
and butane in water. Bohon and Claussen2 carried out
a similar study for the aromatic hydrocarbons.
It has long been known that the lower aliphatic
hydrocarbons form solid hydrates. Structures of the
clathrate type have been proposed for these hydrates,3
and verified by x-ray diffraction studies/,r; (see urea

IC~--------~II~ 18"
6" ----1"2.!.
8 ~ 6"

-.--- I

r--

-! ! ~I
'T
QI~

oS)

NJ-

clathrates).6 These ice-like structures contain voids

large enough to accommodate hydrocarbon molecules.
Such structures must exist in solution as well as in the
solid phase. One may then picture hydrocarbon molecules in solution as being surrounded by oriented cages
of water molecules. Claussen and Polglase 1 used this
concept to explain the negative enthalpies and entropies
of solution of the aliphatic hydrocarbons.
No hydrates of the aromatic hydrocarbons have ever
been reported, presumably because these molecules are
too large to fit into the voids in the hydrate structures.
It has been found possible to explain the thermodynamics of aqueous solutions of the aromatic hydrocarbons without assuming the presence of structures of
the type described above.
It is of interest to determine whether the partial
molal volumes of hydrocarbons in water solution agree
with this model of their solution structures. The partial
molal volume V in these extremely dilute solutions was
found to be identical with the apparent molal volume 1/-'.
The latter can be determined from the specific gravities
and concentrations of the hydrocarbon solutions by the
following equation:

(1)
-

--

VI

....

LA.....

L--

L..'\..

_ _ _ _ FIG. 1. Copper block (vertical section).

* This paper is based on a thesis presented by the author in

partial fulfillment of the requirements for the Ph.D. degree at
the University of Illinois, June, 1952.
1 W. F. Claussen and M. F. Polglase, J. Am. Chern. Soc. 74
4817 (1952).
'
2 R. L. Bohon and W. F. Claussen,]. Am. Chern. Soc. 73 1571
(1951).
'
3 W. F. Claussen, J. Chern. Phys. 19,259,662, 1425 (1951).
4 R. Cole, Ph.D. thesis, University of Illinois (1951).
5 M. V. Stackelberg, Naturwiss. 36, 327, 359 (1949).

where M 2 =molecular weight of hydrocarbon, y=concentration of hydrocarbon in glcc, and d, do=densities

of solution and pure water, respectively, at the temperature at which y is measured.
Since the solubilities of the hydrocarbons are extremely small (benzene, 1. 70 X 10-3 gl cc; methane,
2.30X 10-5 g/cc), an extremely sensitive method must
be chosen for the determination of the specific gravities.
Such a method should give results accurate to about
seven decimal places.
Several methods are available for the determination
of specific gravities of extremely dilute solutions.
Various modifications of the float method have been
described in the literature. They suffer from the common
problem of temperature control. A procedure in which
the solution and reference liquid were compared simultaneously would obviously reduce this difficulty. Such
6

F. Cramer, Angew. Chern. 64, 437 (1952).

1830

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PAR T I A L

J\I 0 LA L

VOL U M E S 0 F

a method is that of Frivold 7 which utilizes the principle

of communicating tubes.
In this method, solution and reference liquid (airfree conductivity water) are placed in two vertical tubes
connected at the bottom and near the top by valves.
Upon first allowing the upper valves to be opened for
equilibration and then opening the lower valves,. flo.w
will occur if the solution differs from the reference hqmd
in specific gravity. Wirth, Thompson, and Utterback 8
measured indirectly the drop of the liquid level in one
of the tubes as a result of this flow. An alternative
procedure is to measure the volume of liquid which
must be withdrawn from one side of the apparatus to
prevent flow. This volume is simply related to the
specific gravity of the solution by the equation
Vjah=l-djd n,

(2)

where V = volume of water withdrawn to achieve equilibrium, a = cross sectional area of the liquid surfaces in
the tubes, h=distance between the upper a.nd lower
valves, and dj d o= specific gravity of the solutlOn.

H Y D ROC ARB 0 N SIN

87'~--~----,---~

\V ATE R

1831

39r---~----~---.

~ 37

w
~

::J
..J

g 35
40

21

BENZENE

31
TEMP.oC

41

METHANE

54

69

...,.
J

<)

~5

...:li

...
~

::J
.J

::J

>

>

67

..J

050

065

41

41

EXPERIMENTAL

A. The Copper Block Specific Gravity Apparatus

FIG. 3. Change of partial molal volume with temperature.

It was found necessary to construct the apparatus

out of copper so as to allow for the rapid equilibration

1..
FIG.2 . Glass capillary.

1----~-38.1 MM ~
i

4MM.

T'

2~
.46"ii:r-

1 60 MM.

of any temperature difference between the two tubes.

An accuracy of one part in ten million in specific
gravity requires temperature control accurate to
O.OOOloC, which is difficult to achieve in a glass
apparatus. The dimensions of the apparatus are indicated in Fig. 1.
The copper block was enclosed in a wooden insulating
chamber which formed an air ba tho Attached to the
inside of each of the walls of the chamber was a hollow
steel tank one inch thick. By circulating water from a
refrigeration bath through these tanks, experiments
could be made at temperatures as low as Soc. A resistance coil inserted inside the chamber permitted
operating temperatures up to SOC. The temperature of
the air bath could be maintained to within O.O1 c
while the high thermal conductivity of the copper block
itself insured that the temperatures of the two columns
of liquid would be equal within O.OOOOlC. The
copper surfaces of the block were lined with tin to
prevent corrosion.
In order to detect flow of liquid through the lower
valves, a glass capillary was inserted into the lower conO. E. Frivold, Physik. Z. 21, 529 (1920).
8 Wirth, Thompson, and Utterback, J. Am. Chem. Soc. 57,
400 (1935).
7

necting tube and a dye was injected at one edge of the

capillary. The flow of dye through the capillary was
observed through an optical system with the eyepiece
outside the apparatus. The dimensions of the capillary
are quite critical; if it is too large, a significant amount
of flow will occur before it can be detected, leading to
low values of V in Eq. (2). On the other hand, too fine
a capillary would greatly reduce the rate of flow of the
dye and seriously affect the sensitivity of the instrument. The capillary chosen was 1.6 mm in length and
0.4 mm in diameter. Its design is shown in Fig. 2.
The glass tube was sealed into the lower horizontal
tube with sealing wax. It was found that the dye would
move across the capillary by diffusion and mixing in
about ten minutes while a difference of one part in ten
million in specific gravity would cause the dye to flow
across the capillary in three minutes.
The volume of liquid withdrawn to achieve equilibrium was accurately measured in a capillary burette.
This consisted of a piece of calibrated capillary tubing
fastened to a meter stick.
Frequent blank runs were made in the course of the
experimental determinations. These consisted of filling
both sides of the apparatus with conductivity water
and measuring the difference in specific gravities of the
two columns of water. In no case was a difference detected greater than one part in ten million, the limit of
accuracy of the experiments.

B. Preparation and Analysis of Solutions

Special precautions were taken to insure that the only
factor producing a difference in specific gravity between

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1832
TABLE

W.

L.

MASTERSON

I. Apparent molal volumes of benzene in water solution.

T=IO.IOC
I-d/do
cc
X 10'
XlO'

T =2S.2C
I-d/do
cc
XIO'
X1O'

T=30.0C
I-d/do
cc
XIO'
XIO'

1.62
1.96
2.48
3.79
3.99
4.57
6.04

1.24
3.07
3.75
4.00
5.87

1.81
2.13
2.44
3.47
4.72
5.02
5.88
6.52

'"

0.78
0.82
1.09
1.84
1.92
2.26
2.80

81.9
81.4
81.5
81.8
81.8
81.8
81.7

Av.=81.7

'"

0.90
1.95
2.41
2.68
3.53

83.7
83.0
83.1
83.4
82.8

Av.=83.2

T =34.9C
y
I-d/do
XIO'
XIO'

2.50
4.69
6.67

1.85
3.59
4.85

Av. = 84.0

'"

1.29
1.42
1.54
2.26
3.07
3.30
3.78
4.36

83.6
83.2
83.0
83.2
83.2
83.3
83.2
83.4

Av.=83.3

co

'"

XIO'

T=39.9C
I -dido
XIO'

83.9
84.1
83.9

1.76
2.57
4.01
4.58
4.79

1.50
2.16
3.16
3.49
3.89

spectrophotometer. It was found that the absorption

peak at 2537 A obeyed Beer's law within t of 1 percent
at optical densities up to 1.0. Portions of the solution
withdrawn from various sections of the block showed
uniform concentrations within at least 1 percent.
Evaporation of benzene apparently occurred only from
the trays above the vertical tubes provided the solutions
were analyzed within two to three hours after admission
to the block.
From the concentrations of the solutions and their
specific gravities the apparent molal volumes could be
calculated by means of Eq. (1). The data on benzene
solutions is given in Table I.

'"

cc

84.7
84.8
84.4
84.0
84.6

2. Aliphatic Hydrocarbon Solutions

The aliphatic hydrocarbons studied were methane,

ethane, and propane. The hydrocarbons used were all
of research grade (99 mole percent pure). They were

Av. = 84.5
TABLE

solution and standard was the presence of the solute

being investigated. A difference in concentration of dissolved air or of isotopic composition would cause
spurious specific gravity differences. To avoid this a
sample of conductivity water was rendered air-free by
boiling under vacuum. It was then split into two portions, one of which served as the solvent for the hydrocarbon solution and the other as reference liquid.

Methane
T=23.0C
y
I-d/do
cc
X 10'
XIO'

T =16.SC
y
I -did.
cc
XIO'
XIO'

2.30
2.31
2.34
2.35
2.41
2.43

1. Benzene soltttions

2.48
2.58
2.48
2.95
2.54
2.57

'"

33.3
33.8
33.0
36.2"
33.0
33.0

J.

1.35
1.92
2.47
2.38
2.50
2.81
3.42

1.04
1.53
1.95
1.95
1.96
2.25
2.63

36.8
36.2
36.5
35.5
36.5
36.0
36.9

T =29.1 C
I -dido
of
cc
XIO'
XIO'
y

1.63
1.75
1.83

XIO'

T=3S.IOC
I-d/do
XIO'

1.43
1.44
1.49
1.55
1.58

1.95
1.93
2.10
1.92
2.19

2.23
2.44
2.48

38.0
38.4
37.8

Av.=38.0

Av.=36.3

Av.=33.2

The benzene used to prepare the solutions was

purified by the method of Mair et al. 9 The solutions
were prepared by placing one portion of the air-free
conductivity water in contact with benzene vapor
arising from a tube connected to the solution flask. The
solution process was hastened by stirring the water in
the solution flask with a magnetic stirrer. Solution was
carried out under vacuum.
The concentrations of the benzene solutions could be
adjusted by varying the time of exposure of the solution
flask to benzene vapor. Stirring was continued for
several minutes after the solution was shut off from
contact with the benzene vapor. This insured uniform
concentration of the solution. Solution and standard
were then successively admitted to the block. About
fifteen minutes were allowed for the liquids to come to
the temperature of the block. The specific gravity of
the solution was then determined. In each experiment
measurements were taken until three successive determinations agreed within one part in the seventh decimal
place.
Portions of the solution were then withdrawn from
the block and analyzed by means of an ultraviolet
Mair, Termini, Willingham, and Rossini,
Bur. Standards 37, 229 (1946).

II. Apparent molal volumes of aliphatic hydrocarbons

in water solution.

cc

37.9
37.6
38.7
35.9"
38.3

Av.=38.2
T =16.9C

of

I-d/do
XIO'
XIO'
y

3.61

2.17

cc

48.2

T =16.9C

I -dido
X 10' XlO'
y

6.48
6.53
7.79

2.96
2.83
3.45
Av.=63.6

of

cc

64.1
63.2
63.5

Ethane
T=23.0C
y
I-d/do
of
cc
XIO'
X 10'

3.68
4.70
5.14
5.61

2.52
3.20
3.44
3.82

50.7
50.5
50.2
50.5

T =29.1 C
I -dido
of
cc
XIO'
X 10'
y

3.35
4.59

2.49
3.34

52.3
51.9

Av.=50.5

Av.=52.1

Propane
T =23.0C
I-d/d.
Y
cc
XIO'
XIO'

T =29.IC
I-d/d.
of
cc
X 10'
X 10'

4.88
5.30
5.63
6.31

2.52
2.64
2.93
3.13
Av.=66.6

'"

66.8
66.8
67.0
65.9

3.91
4.45
4.66

2.10
2.34
2.45

67.8
67.3
67.3

Av.=67.S

Research Nat!.
a

Value omitted in obtaining average.

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PAR T I A L

MOL A L VOL U M E S 0 F

freed of traces of carbon dioxide by passing over

ascarite. The purified gases were brought into contact
with samples of air-free water stirred by means of a
magnetic stirrer in an apparatus similar to that used
for benzene.
Experiments were run to determine the time necessary for saturation. It was found that four hours were
sufficient to achieve saturation with the technique used.
Samples saturated for periods up to twelve hours gave
partial molal volumes identical with those obtained
after four hours contact.
Before admitting the hydrocarbon gas to the saturation apparatus all the air was removed from the system.
The initial pressure read on the manometer was then
the vapor pressure of water at the temperature of the
solution. Gas was admitted to the solution flask until
the desired pressure, as read on the manometer, was
reached. The final pressure of the gas after saturation
was reached was recorded. The difference between final
and initial pressures gave the partial pressure of the
hydrocarbon gas. From this pressure and the temperature of the solution, it was possible to calculate the
concentration of the solution. Henry'S law was used to
calculate the effect of pressure on the solubility; data
in the literature indicates that it holds within one-half
of one percent for such extremely dilute solutions. The
data of Claussen and Polglase 1 was used to calculate
the solubilities of the gases at one atmosphere pressure
at the temperature of the solution.
The specific gravities of the solutions were measured
in the same manner as those of the benzene solutions.
Once again it was found that the apparent molal
volumes were independent of concentration.
The data on solutions of methane, ethane, and propane is given in Table II. It will be noted that the
precision is considerably less than for the benzene
solutions, probably because the concentration data was
less accurate.
DISCUSSION OF RESULTS

It is instructive to compare the partial molal volumes

of the hydrocarbons in water solution to their volumes
in nonaqueous solvents. The molal volume of pure
benzene at 25C is 89.5 cc; the partial molal volume in
water is 83.1 cc. This is a decrease in water solution
of 6.4 cc.
The simplest explanation of this decrease in volume
involves the large internal pressure of water as compared to that of benzene itself. Gjaldbaek and Hildebrand lO found that the partial molal volume of methane,
ethane, and nitrogen decreased sharply as the internal
pressure of the solvent increased. The fact that the
decrease in volume for benzene is relatively small is
10 J. C. Gjaldbaek and J. H. Hildebrand, J. Am. Chern. Soc. 72,
1077 (1950).

H Y D ROC ARB 0 N SIN

TABLE

W ATE R

1833

III. Partial molal volumes of methane and ethane at 25C.

Solvent

P (int.)

Methane

Ethane

Per-flu oro n-heptane

n-hexane
Carbon tetrachloride
Water

1430 atmos
2190
3050
12000

68.4 cc
60.0
51.7
37.3

82.9 cc
69.3
66.0
51.2

probably due to the rather small compressibility of

benzene at high pressure. l1 The coefficient of expansion
a of benzene in water solution is independent of temperature and slightly smaller than that of pure benzene,
as would be expected in a solvent of high internal
pressure.
The partial molal volumes of the aliphatic hydrocarbons in water solution are considerably less than the
corresponding values in nonaqueous solvents. Table III
gives the partial molal volumes of methane and ethane
at 25C in various solvents. The values for carbon
tetrachloride are taken from Horiuti ;12 those for the
other organic liquids are from Gjaldbaek and Hildebrand. 10 Values of the internal pre?sures are taken from
Hildebrand and ScottY
It will be noted from the curves that the change of
partial molal volume with temperature for the aliphatic
hydrocarbons is of a quite different nature than that
of benzene. The linear increase observed with benzene
does not occur with the aliphatics; instead the rate of
increase of the partial molal volume with temperature
(the coefficient of expansion a) decreases with increasing
temperature. This leads one to believe that there are
two competing processes going on in the case of the
aliphatic hydrocarbons. The normal thermal expansion,
which increases iT, would be expected to give a nearly
linear slope as it does with benzene. The other process
is apparently a breaking down of the cage-like structure
of water molecules around the aliphatic hydrocarbon
molecules. This produces a decrease in the partial molal
volume analogous to that observed when ice melts. The
above curves thus represent the net result of these two
processes.
ACKNOWLEDGMENT

The author is greatly indebted to W. H. Rodebush,

who suggested this problem and under whose advice
and guidance the work was performed. W. F. Claussen
designed the apparatus and supervised its construction,
installation and testing.
The research was aided by funds supplied by the
Office of Naval Research and by a predoctoral fellowship provided by the U. S. Atomic Energy Commission.
II

12

P. W. Bridgman, J. Chern. Phys. 9, 794 (1941).

J. Horiuti, Sci. Papers Inst. Phys. Chern. Research (Tokyo)

17, 125 (1931).

13 J. H. Hildebrand and R. L. Scott, The Solubility oj NonElectrolytes (Reinhold Publishing Corporation, New York, 1950).

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