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Adiabatic Compressibilities of Binary Liquid Mixtures

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BY R. J. FORTAND W. R. MOORE
Polymer Research Laboratories, Dept. of Chemical Technology, Bradford Institute of
Technology, Bradford 7
Received 20th April, 1965
Ultrasonic velocities and densities at 25°C have been determined at different molar concentrations
for fourteen binary liquid systems representing different types and degrees of interaction between the
components. Adiabatic compressibilitiesare calculated. Excess adiabatic compressibilitiestend to
become less positive and then increasinglynegative as the strength of the interaction between the unlike
molecules increases. Excess adiabatic compressibility is approximately proportional to the strength
of the interaction. Excess volumes show a similar variation. The variations of excess adiabatic
compressibility with composition are generally similar to those shown by other excess properties of
binary liquid mixtures.

Adiabatic compressibilities of binary liquid mixtures generally show deviations

from a rectilinear dependence on mole fraction 1-5 and there is evidence 49 5 that the
sign and magnitude of such deviations depend on the strength of the interaction
between unlike molecules. Liquids of not too different molecular size usually mix
with increase in volume and positive excess compressibility if strong interaction
between unlike molecules is absent. If strong interaction leading to complex forma-
tion occurs, excess volumes and compressibilitiesmay be negative. In some mixtures,
interactions leading to positive and negative excess functions may compete, the signs
and magnitudes of such functions depending on the relative strengths of these inter-
actions.
Few systematic studies of the effects of variations in the nature and strength of the
interaction between unlike molecules on the adiabatic compressibilities of binary
liquid mixtures seem to have been made. In the present study we have obtained excess
volumes and adiabatic compressibilitiesfor fourteen binary liquid systems representing
different types and degrees of interaction. Dispersion forces are likely to be dominant
+ +
in the systems benzene cyclohexane and benzene ethylene dichloride, both of
which show positive excess heats and volumes.6-8 Somewhat stronger interaction
believed not to involve hydrogen bonding, occurs in the systems benzene + chloro-
+
form,g benzene carbon tetrachloride,lo chlorbenzene+ carbon tetrachloride 11 and
dimethyl sulphoxide+ acetonitrile.129 13 Hydrogen bonding occurs in the systems
chloroform + dioxan,14 chloroform + acetone,ls s-tetrachlorethane acetone 16 and +
o-chlorphenol+ dioxan.17 It also occurs in the systems acetone+water,lg dimethyl
sulphoxide + water,lg dimethyl sulphoxide + methanol and dimethyl sulphoxide +
acetic acid,20 the second component in each of these systems being associated in the
pure state.

EXPERIMENTAL
The liquids used were all of the best available grades and were further purified and dried
by appropriate methods and fractionally distilled, care being taken to exclude water vapour.
A middle fraction was collected in every case. Boiling points of the organic liquids, corrected
to atmospheric pressure, were : benzene 80-1, cyclohexane 80.8, ethylene dichloride 83-5,
carbon tetrachloride 76-75,chloroform 61'2, chlorbenzene 132.0, acetonitrile 81-6, dimethyl
2102
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R. J . FORT AND W . R. MOORE 2103

sulphoxide 189, dioxan 1015 acetone 56.1, o-chlorphenol 175-7, s-tetrachlorethane 146.2,
methanol 64.65 and acetic acid 118.2"C. These are in good agreement with published
values.21. 22
Mixtures containing 0.20, 0.40, 0.60 and 0-80 mole fraction of a component were pre-
pared by mixing weighed amounts of the pure liquids, precautions being taken to avoid
evaporation of more volatile components and to exclude water vapour. Adiabatic com-
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pressibilities IC, were obtained from densities p and ultrasonic velocities u by use of the
relationship,
IC, = l/v2p.
Densities were determined at 25 &0405"C using pyknometers having capillaries of narrow
bore provided with well-fitting glass caps in order to avoid changes in composition because of
evaporation of more volatile components. Buoyancy corrections were made and densities

TABLE1 .-DENSITIES AND ULTRASONIC VELOCITIES IN PURE LIQUIDS AND BINARY MIXTURES
AT 25°C
component (1) component (2) X1 p(s/ml) o(m/sec)
benzene cyclohexane 0.00 0.7738 1261
0.20 0.7866 1258.5
0.40 0.8033 1251.5
0.60 0.8225 1271
0.80 0.8488 1287
1.00 0.8738 1306.5
benzene ethylene 0.00 1.2457 1203
dichloride 0.20 1.1586 1208
0.40 1.0811 1217
0-60 1.0073 1239
0.80 0.9386 1274
1*oo 0.8738 1306.5
benzene carbon 0.00 1.5848 927
tetrachloride 0-20 1.4514 96 1
0.40 1*3142 1022
0.60 1-1719 1091
0.80 1.0255 1186
1-00 0-8738 1306.5
benzene chloroform 0.00 1-4783 983
0.20 1.3466 1025
0.40 1.2183 1080
0.60 1.0983 1144
0.80 0.9827 1221
1-00 0.8738 1306.5
chlorbenzenr carbon 0.00 1.5848 927
tetrachloride 0-20 1-4847 990
0.40 1-3864 1045
0-60 1.2895 1108
0.80 1.1945 1182
1-00 1.1012 1270
dimethyl acetonitrile 0.00 0.7773 1288
sulphoxide 0.20 0.8599 1319
0.40 0.9311 1379
0.60 0.9929 1415
0.80 1-0474 1448
1-00 1-0957 1497
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2104 ADIABATIC COMPRESSIBILITIES

TABLE1--contd.
component (1) component (2) Xl PWml) u(m/sec)
chloroform dioxan 0.00 1-0279 1359
0.20 1.1145 1242
0.40 1.2033 1175
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0.60 1-2949 1097

0.80 1.3874 1029
1-00 1.4783 983
chloroform acetone 0.00 0.7843 1150
0.20 0.9336 1088
0.40 1-0780 1055
0.60 1.2137 1016
0.80 1.3457 996
1-00 1.4783 983
s-tetrachlorethane acetone 0.00 0.7843 1150
0.20 1-0049 1141
0.40 1.1896 1143.5
0.60 1.3437 1136
0.80 1-4755 1144
1-00 1.5879 1157
o-chlorphenol dioxan 0.00 1-0279 1359
0.20 1,0865 1382.5
0.40 1.1391 1432
0.60 1.1855 1453.5
0.80 1a2228 1446
1-00 1*2491 1420
acetone water 0.00 0.9971 1533
0.20 0.9275 1515
0.40 0.8738 1403
0.60 0.8356 1307
0.80 0.8065 1222
1.00 0.7843 1150
dimethyl water 0.00 0.997 1 1533
sulphoxide 0.20 1-0742 1753
0.25 1,0816 1741
0.40 1-0959 1697
0.60 1-0092 1625
0.80 1a0978 1559
1-00 1,0957 1497
dimethyl methanol 0.00 0.7870 1097
sulphoxide 0.20 0.8911 1238
0.40 0-9653 1335
0.60 1.0193 1424
0.80 1-0617 1480
1moo 1.0957 1497
dimet hy 1 acetic acid 0.00 1-0442 1125
sulphoxide 0.20 1-0722 1279
0.40 1-0854 1369.5
0.60 1~0904 1424
0.80 1.09311 1467
1*oo 1*0957 1497
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R . J . FORT A N D W . R. MOORE 2105

were reproducible to one part in 104. Ultrasonic velocities were measured using a single
crystal interferometer working at 400 kc/sec. The interferometer cell was similar to that of
Hubbard and Loomis23 but incorporated a barium titanate crystal instead of a quartz
crystal thereby avoiding the necessity for high voltages and consequent insulation difficulties.
The cell was almost completely immersed in an oil bath thermostatically controlled at 25 f
0.01"C. The uncertainty in velocity measurements is estimated to be 0.15 %. Densities
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were in good agreement with published values.21.22 The same is true of ultrasonic velocities
where comparison is possible.5~24 The ultrasonic velocity and density for acetone, 1 150
mlsec and 0.7843 glml respectively, are lower than the values of 1165 mlsec and 0.7893 glml
obtained at 27" C by Reddy et aZ.5 Water is a possible contaminant in the latter case and
would lead to higher values of both velocity and density. Our value for the density of ace-
tone is lower than some values cited 21 but is slightly higher than that of Dippy and Hughes 25
who took particular care to remove water.

RESULTS
Densities and ultrasonic velocities are given in table 1. Fig. 1 to 4 show plots of
adiabatic compressibility against X I , the mole fraction of component 1. Fig. 5 to 8
show excess volumes, calculated from densities, as functions of XI.

5 0
0.2 0.4 0.6 0.8
X1

FIG. 1 .-Adiabatic +
compressibility as a function of XI. (0) benzene( 1) cyclohexane (2) (6)
benzene( 1) +ethylene dichloride (2).

DISCUSSION
The excess compressibility rc,E is positive for all compositions in the sys ems
benzene +cyclohexane, benzene + ethylene dichloride, benzene + carbon tetrachloride,
+
benzene +chloroform and chloroform dioxan. Excess compressibilities for the
benzene -tethylene dichloride system agree with the results of other workers 26 and
so do the small positive values of rc; for the benzenefcarbon tetrachloride.26, 27
There is evidence for complex formation in this latter system,lo possibly by electron
transfer.28 A weak bond, of a type between a conventional localized hydrogen bond
 Published on 01 January 1965. Downloaded by Indian Institute of Science on 9/18/2019 7:31:40 AM.

I a

60
70g
C

'\

d
C
5 4

..\O
451 40
l.. .
t I 1 I I I I

0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8

XI X1 X1

FIG. 2.-Adiabatic compressibility as a function
of XI. (a) benzene(1)Scarbon tetrachloride (2) ;
(6) benzene(1) +chloroform (2) ; (c) chlorbenzene
(1) $- carbon tetrachloride (2) ; (d) dimethyl
sulphoxide (1)+ acetonitrile (2).
FIG. 3.-Adiabatic compressibility as a functio FIG.4.-Adiabatic compressibility as a function
of X I . (a) chloroform (l)+dioxan (2) ; (b) chloro- of XI. (a)acetone (I)+water (2); (b) dimethyl
form (1)+acetone (2) ; (c) tetrachlorethane (1) + sulphoxide (1) +methanol (2) ; (c) dimethyl sulph-
acetone (2) ; ( d ) o-chlorphenol (1)Sdioxan (2). oxide (1)+ water (2) ; ( d ) dimethyl sulphoxide
(1)facetic acid (2).
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R. J . F O R T AND W . R. MOORE 2107

and the formation of an electron transfer complex, occurs between the components of
+
the benzene chloroform system,9 which also shows small positive exc.ess compress-
ibilities. Small negative values of # are obtained at lower concentrations of chlor-
+
benzene in the chlorbenzene carbon tetrachloride system but the excess compres-
sibility seems to be zero at higher concentrations. Weak dipole interaction, involving
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015

I I I I

L I I I I

0.2 0.4 0.6 0.8

x1
FIG. 5.-Excess volume as a function of XI. (a) benzene (l)+cyclohexane (2) ; (b) benzene (l)+
ethylene dichloride (2).

O
-o51
*t
0.2 0.4 0.6 0.8
x1
FIG. 6.-Excess volume as a function of XI. (a) benzene (1)fchloroform (2) ; (b) benzene (1)+
carbon tetrachloride (2) ; (c) chlorbenzene (l)+carbon tetrachloride (2) ; ( d )dimethyl sulphoxide (1)
+acetonitrile (2).

polarizable molecules, occurs.11 Apart from chloroform + dioxan, negative excess

compressibilities are shown by the systems involving hydrogen bonding these being
large in those cases where one component is associated in the pure state. The
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2108 A D I A B A T I C COMPRESSIBILITIES
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I I I 1

b
0.5 -

FIG.7.-Excess volume as a function

of XI.
+
(a)chloroform (1) dioxan (2) ;
(6) chloroform (l)+ acetone (2) ;
(c) tetrachlorethane(1)facetone (2) ;
+
( d ) o-chlorphenol (1) dioxan (2).

1 d

;o-:*- 1-0

0.2 0.4 0'6 0.8

I I I 1
b

FIG. 8.-Excess volume as a function

of X I .
(a) dimethyl sulphoxide (I)+ water (2) ;
+
(b) dimethyl sulphoxide (1) methanol
(2) ;
( c ) dimethyl sulphoxide (1) +acetic acid
(2) ;
( d ) acetone (1)-twater (2).
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R . J . FORT A N D W . R . M O O R E 2109
+
dimethyl sulphoxide acetonitrile system shows relatively large negative excess
compressibilities. Acetonitrile does not form hydrogen bonds 12 but its large dipole
moment may lead to large electrostatic forces. There is evidence for solvation of
acetonitrile by dimethyl sulphoxide,l3 possibly involving dipole-dipole interaction.
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UJ
I I I

00 too 120
W
2 -5-
X
rl

8
Y
rd
-10-

-15-

1
-2 0
1 Q)

A b.p., "C
FIG. 9.-Maximum excess compressibility as a function of difference in boiling point. 0,non-
hydrogen bonded systems ; 0 ,hydrogen bonded systems.

I
0

-600 -400 -200

/ 0
I
-I0[

FIG.10.-Maximum excess compressibility as a function of maximum heat of mixing at 25°C.

The excess compressibility is not generally symmetrical with respect to mole fraction.
+
Asymmetry is marked in the o-chlorphenol dioxan, acetone +water and dimethyl
sulphoxide+water systems, K: being greatest at the lower concentrations of dioxan,
acetone and dimethyl sulphoxide respectively.
There seems to be a general tendencyfor positive excess compressibilitiesto decrease
and become increasingly negative as the strength of the interaction between unlike
molecules increases. It is of interest to compare values of rc: with other estimates of
the strength of this interaction. Thacker and Rowlinson 29 and Reddy et aZ.5 have
used the difference in boiling points of the components as a rough measure of the
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21 10 A D I A B A T I C COMPRESSIBILITIES

strength. Fig. 8 shows maximum values of ic,E plotted against difference in boiling
point. Separate lines are drawn for systems which involve hydrogen bonding and
thosethat do not. Although there are only six of the latter the points for them are very
close to the line. Those for the systems involving hydrogen bonding are more
scattered but the maximum values of K,E are related to difference in boiling point and
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hence to the strength of the interaction. This is also suggested by fig. 10 in which
maximum values of K: are plotted against maximum values of the heat of mixing at
25°C for those systems for which the latter are available. In only one case, that of
dimethyl sulphoxide+methanol, is there a marked deviation from a linear relationship.
The variation of excess compressibility with composition may, with the exception
+
of the chlorbenzene carbon tetrachloride system, be represented by
IC:/x1x2 = A + B ( x ,
- x , ) + C ( x , -x2)2,
where A , B and C are constants for a given system. Reddy et aZ.5 report a similar
relationship which also holds for other excess properties of binary mixtures.
Where comparison is possible the signs and magnitudes of the excess volumes are
in general agreement with other results. The negative excess volumes for the
chlorbenzene +carbon tetrachloride system are somewhat less than those obtained by
Anantaraman et al.11 at 40°C. Excess volumes tend to decrease and then become
increasingly negative as the strength of the interaction between the components
increases although they do not completely parallel the excess compressibilities.
+
Excess volumes for the chloroform dioxan system are negative and those for benzene
+ carbon tetrachloride effectivelyzero although the excess compressibilitiesare positive
in each of these systems. Asymmetry of excess volume with respect to mole fraction
is generally similar to that of excess compressibility.
The change from positive to increasingly negative excess values as the strength of
the interaction between the components increases may be qualitatively interpreted in
terms of closer approach of unlike molecules leading to reductions in compressibility
and volume. More than one type of interaction may be concerned in any given system.
Dispersion forces, which are likely to be operative in every case, should make positive
contributions to excess values. Charge transfer, dipole-induced dipole and dipole-
dipole interactions and hydrogen bonding between unlike components should make
negative contributions. The magnitudes of the contributions made by these different
types of interaction will vary with both the components and the composition of the
mixture. Dissociation of a component which is associated in the pure state should
make a positive contribution to excess values.4 Presumably, dissociation of water at
the higher concentrations of acetone and dimethyl sulphoxide is at least partly
responsible for the marked asymmetry of excess values with respect to mole fraction
+ +
in the acetone water and dimethyl sulphoxide water systems.

1 Nomoto, Bull. Kobayasi Inst. Phys. Res., 1952, 2, 137.

2 Danusso, Att. Accad. Nuz. Lincei, 1953,15, 131 ; 1954, 17, 109, 114, 234, 370.
3 Ras and Rao, J. SOC.Ind. Res. B, 1960, 20, 157.
4 Jacobson, Arkiu Kern., 1950,2, 177.
5 Reddy, Subrahmanyan and Bhimasenachar, Trans. Faraahy SOC.,1962,58,2352.
6 Scatchard, Ticknor, Coates and McCartney, J. Amer. Chem. SOC.,1952, 74, 3721.
7 Moore and Styan, Trans. Faraday Soc., 1956, 52, 1556.
SRuiter, Rec. Trw. Chim., 1955,74, 1131, 1467, 1491.
9 Rowlinson, Liquids and Liquid Mixtures (Butterworth, London, 1959), p. 182.
10 Ott, Goates and Budge, J. Physic. Chem., 1%2,66, 1387.
11 Anantaraman, Bhattacharya and Palit, Trans. Faruday SOC.,1961, 57, 40.
12 Rowlinson, Zoc. cit., p. 175.
13 Ritchie and Pratt, Int. Symp. Solvation Phenomena, (Calgary, Canada, August 1963).
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R . J . FORT A N D W . R. MOORE 2111

14 McGlashan and Rastogi, Trans. Farahy Soc., 1958,54,496.
15 Glasstone, Trans. F a r d y SOC.,1937,33,200.
16 Marvel, Copley and Ginsberg, J. Amer. Chem. SOC.,1940, 62, 3109.
17 Naidu, Thesis, (Sri Venkatiswara University, 1964).
18 Rao, Bhatnagar and Pancholy, Indian J. Sci. Ind. Res. B, 1947,6, 35.
19 Cowie and Toporowski, Can. J. Chem., 1961,39,2240.
Published on 01 January 1965. Downloaded by Indian Institute of Science on 9/18/2019 7:31:40 AM.

20 Lindberg and Pietila, Suomen Kem. B, 1962,35, 30.

21 Timmermans, Physicochemical Constants of Pure Organic Compounds (Elsevier, Amsterdam,
1950).
22 Int. Crit. Tables (McGraw-Hill, New York, 1926-1933).
23 Hubbard and Loomis, Phil. Mag., 1938,5, 1177.
24 Parthasarathy, Proc. Indian Acad. Sci., 1935,2,497 ; 1936, 3, 1936.
25 Dippy and Hughes, J. Chem. SOC.,1954,953.
26 Staveley, Tupman and Hart, Trans. Faraday Soc., 1955,51, 323.
27 Tuomikoski and Nurmi, Comm. Phys. Muth. HelsingJ, 1940, 10, 11.
28 Goates, Sullivan and Ott, J. Physic. Chem., 1959, 63, 589.
29 Thacker and Rowlinson, J. Chem. Physics, 1953, 21, 2242.