Partial molal volume behavior of tetraalkylammonium chlorides in

aqueous acetone and aqueous dimethylsulfoxide

DIGBYD. MACDONALD
AND J. B. HYNE
Departmetzt of Chemistry, University of Calgary, Calgary, Alberta
Received February 2, 1970

The partial molal volumes of a series of tetraalkylammonium chlorides in aqueous acetone and aqueous
dimethylsulfoxide at 25.000 "C are reported as a function of solvent composition. It is shown that for
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each solvent composition the partial niolal volume data are better represented by a quadratic in solute
molecular weight than by the linear expression previously employed in similar studies. Extrapolation of
molecular partial molal volumes to zero cation molecular weight has permitted evaluation of the partial
molal volumes of the ions R4N+ and C1-. The variation of molecular and ionic partial molal volume as a
function of solveht composition is discussed.
Canadian Journal o f Chemistry, 48, 2416(1970)

Introduction Fisher spectral grade acetone was used without

In our continuing study of solvolysis reactions
in aqueous organic solvent systems we have
measured partial molal volumes of tetraalkyl-
ammonium chlorides in aqueous acetone and
aqueous dimethylsulfoxide (DMSO) at 25.000 "C
as a function of solvent composition. The purpose
For personal use only.
further purification. Doubly distilled water was used in
preparation of all aqueous organic binary solvent sys-
tems.
Method
The aqueous binary solvent systems were prepared by
volume to + 0.0005 mole fraction. The solvents were
degassed by refluxing beneath a Dry Ice/acetone con-

of this work was to obtain data on the variation
of partial molal volume of stable solute species
with solvent composition which should be of
value as models in interpreting the volumetric
behavior of initial and transition states of
solvolysis reactions in the corresponding solvent
systems.
The tetraalkylammonium chlorides (R,N+-
C1-) were chosen for this study since the surface
charge density of the cation can be conveniently
varied by changing the nature of the alkyl group,
R ; in this case R = Me, Et, n-Pr, and n-Bu. The
two cosolvents, acetone and DMSO, were
selected since, -despite their close structural
similarity, they have markedly different physical
properties which might be expected to be reflected
in the properties of dissolved ions.
Experimental
Materials
Eastman reagent grade tetraalkylammonium chlorides
were purified by multiple recrystallization and dried in
vacuo as described by Conway et al. (1). The purity of all
salts, as determined by the modified Volhard method (2),
was better than 99.8%.
Eastman practical grade DMSO was dried over
freshly cut calcium hydride for a period of not less than
48 h. The decanted product was then distilled a t reduced
pressure (- 10 mm Hg) and the middle 50% cut collected.
The high purity of the distilled liquid was confirmed by
melting point (18.52 "C, lit: 18.55 "C (3)) and refractive
index (nDZ0= 1.3590, lit: nD19.4= 1.35886 (3)).
denser and their compositions checked by density mea-
surements to ensure that the degassing procedure had not
caused any change.
Salt solutions (0.0150 to 0.1500 M ) were prepared to
+ 0.0001 M units in calibrated 100 ml volumetric flasks
and for each salt concentration three replicate density
measurements were made using 25 ml Weld-type pycnom-
eters. The pycnometers were thermostatted to 25.000 +
0.005 "C for a period of not less than 1 h and weighed
after 19 h standing at room temperature. This standardi-
zation of procedure greatly improved reproducibility,
which on average, was found to be + 0.00002 g ml-'.
Some difficulty was experienced in obtaining repro-
ducible densities in aqueous acetone, no doubt due to the
high volatility of the cosolvent acetone. This was particu-
larly troublesome at acetone mole fractions greater than
0.20. It is for this reason that no data are reported for
solutions of salts in solvent systems with greater than 0.20
mole fraction of acetone. No difficulties were experienced
in accurately determining densities of solutions in aqueous
DMSO. This was undoubtedly due to the much higher
boiling point of DMSO (189 "C ( 3 ) )compared to that of
acetone (56.5 "C (4)).
Results
Apparent molal volumes, 4, were calculated
using the equation
where M is the molecular weight of the salt, c is
the concentration in moles I-', and d and do, the
densities of solution and solvent, respectively.
Partial molal volumes at infinite dilution, v O ,
 MACDONALD AND HYNE: PARTIAL MOLAL VOLUME BEHAVIOR 241 7

were then obtained by extrapolating 4 to zero TABLE 1

concentration using the relation Partial molal volumes of tetraalkylammonium chlorides
in aqueous acetone and aqueous DMSO at 25.000 "C
[2I 4 = TO + ~ ~ ' 1 2
where S is the limiting slope. Partial molal volume
Mole (ml mole- ') when salt =
Uncertainties in apparent molal volumes were fraction
calculated using the equation of Redlich and cosolvent Me4NCl Et4NC1 n - p r 4 ~ c 1 ~-BULNCI
Bigeleisen (5). Aqueous acetone
0.000 107.5* 166.8t 232.93 294.33
lOOO6d 1000(d - do)& 106.7 163.3 229.0 288.7
[3] 64=-
+
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0.050
0.100 106.4 166.0 231.2 297.8
doc doc2 0.200 105.6 161.8 228.4 296.7
6d and 6c are uncertainties in density and con- Aqueous DMSO
centration, respectively. 0.100 106.1 162.2 223.0 283.6
0.200 103.3 157.9 220.0 284.7
lllustrative plots of 4 vs. c1I2 for tetramethyl-
ammonium chloride in aqueous acetone at
25.000 O Care shown in Fig. 1. Partial molal
volumes obtained by extrapolation to c1I2 = 0 *Value = 107.4(ref.1).
tValue = 167.0 (ref. 1).
are summarized in Table 1 and corresponding $Reference 1.
numerical values for S (eq. [2]) are listed in TABLE 2
Table 2. Uncertainties in partial molal volume Numerical values for S (eq. [ 2 ] )for tetraalkylammonium
values, determined by inspection of the extra- chlorides in aqueous acetone and aqueous DMSO
polations, are considered not to exceed & 1 ml at 25.000 "C
For personal use only.

-
mole-'. Data contained in Table 1 reveal that
where comparison is possible, the partial molal Mole S* when salt =
fraction
volumes measured in this study are in excellent cosolvent Me4NC1 Et4NCl 11-Pr4NCl 12-Bu4NCI
agreement with those obtained by other workers.
Aqueous acetone
0.000 0.8 -0.6 - -

Aaueous D M S O

Since the solutes under investigation in this

work certainly exist as ions at infinite dilution
the molecular partial molal volume may be
expressed as the sum of the partial molal volumes
of the component ions.
-
[4I Vz4NCI= V z 4 N + Vg1- +
A number of attempts have been+madeto cal-
culate partial molal volumes of individual ions
but the results obtained seem to differ according
0y2 0y3 014 d5 to the method used. For instance, a recent
literature survey published by Lee and Hyne (6)
c1l2 (mole I-?)'/~
reveals that estimates of the partial molal volume
FIG. 1 . Plots of 4 vs. c'IZ for tetramethylammonium ion in water at 25 range from l8
OC
chloride in aqueous acetone (numbers adjacent to each
plot are mole fractions of acetone). to 37 ml mole-'.
 2418 CANADIAN JOURNAL O F CHEMISTRY. VOL. 48, 1970
Conway et al. (1) recently proposed a new
method for obtaining ionic partial molal volumes
in water for tetraalkylammonium salts with a
common anion. This type of analysis has been
recently extended by Lee and Hyne (6) to solutions
of tetraalkylammonium chlorides in aqueous
ethanol binary solvent systems. In the Conway
method anionic partial molal volumes are
obtained by extrapolating Vg,,, to zero cation
weight in a linear plot of Vg4,x VS. molecular
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weight.
-
[5I vg4NX =A +B " ~ 4 ~ ~
When MR4,, = M x - , i.e. at zero cation weight,
the partial molal volume of the anion is given by
es. [61.
and the partial molal volume of the cation can
be calculated using eq. [4].
The use of a linear extrapolation (eq. [5]) in the
present work requires discussion. Since MR4,,, -
For personal use only.
MR4,,,,,where Rand R' are adjacent homologues
(e.g. Me, Et), is constant over the series of salts
employed
- (i.e. AM = 56): eq. [5] demands that
Vg4NC, - Vg4,NC1 also be constant. An examina-
tion of data presented in Table 1 clearly shows
that this condition is not satisfied, necessitating
the conclusion that eq. [5] does not provide a
good functional representation of the dependence
of Vg4NCI on molecular weight. In view of the
demonstrated inadequacy of the linear expression
(eq. [5]) the data presented in Table 1 were fitted
to a quadratic (eq. [7]) by a least squares method
using an IBM 360150 computer.
The same data were fitted to eq. [5] by the
method of least squares so that the validity of
using either the linear or the quadratic function
could be assessed.
As a measure of the reliability of the functions
chosen it is convenient to define a deviation
function as follows
Plots of d vs. molecular weight are shown in Figs.
2 and 3. The dotted lines correspond to experi-
mental error limits in V g 4 N CItI . is clear from
these plots that in both solvent systems the
quadratic (eq. [7]) provides a better representa-
tion of the data than does the linear function
4
2
o
-2
-
': -4
-z
-=
-2
100 100 300
Molecular Weight R4NCI
FIG. 2. Plot of d VS. molecular weight for tetraalkyl-
ammonium chlorides in aqueous acetone: (a) linear
analysis; (b) quadratic analysis (0,0.000; a,0.050; 0,
0.100; A, 0.200 mole fract~onacetone).
(eq. [5]). The lack of random distribution of d
about d = 0 would appear to indicate, however,
that even eq. [7] does not provide a "perfect"
representation of the data. However, since d
obtained usingeq. [7] is comparable - in magnitude
to the experimental error in Vg4NCIfurther
refinement of the polynomial is not justified by
the experimental data available here. Accor-
dingly, eq. [7] was used to extrapolate V:4NCI to
zero cation weight in order to determine V g , - .
Cation partial molal volumes were then calculated
using eq. [4]. The resulting numerical values for
V g , - and Vg,,+ in aqueous acetone and aqueous
DMSO are presented in Table 3.
Discussion
S Values
According to the Debye-Huckel theory for
strong electrolytes (7) the dependence of appar-
ent molal volume, 4, on the square root of con-
centration (eq. [2]) as c + 0 can be expressed as
follows
Cgl Slim =
where Slimis the limiting slope, o is the valence
factor given by eq. [lo]
 MACDONALD AND HYNE: PARTIAL MOLAL VOLUME BEHAVIOR

TABLE 3
Partial molal volumes of various ions in aqueous acetone and
aqueous DMSO at 25.000 "C
--

Mole Partial molal volume* (ml mole-')

fraction
cosolvent C1- Me4NC E4N + n-Pr4N + n-Bu4NC
Aquzous Acetone
0.000 27.3 80.2 139.5 205.6 267.0
0.050 29.7 77.0 133.6 199.3 259.0
0.100 31.8 74.6 134.2 199.4 266.6
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0.200 37.9 67.7 123.9 190.5 258.8

Aa~tenusDMSO

'Calculated using eq. 171.

been confirmed experimentally in studies using

aqueous solutions of alkali halides (7).
Examination of the numerical values for S
listed in Table 2 reveals two interesting features.
First, many values are negative and second, the S
For personal use only.

values for any given solvent depend upon the

nature of the salt. This latter observation is con-
trary to the predictions of the Debye-Huckel
theory (see eq. [9]). Negative dependences of 4
upon c1l2 have been previously reported for
solutions of alkylammonium salts in aqueous
solution (8, 9) and this behavior appears to
persist to much lower salt concentrations than
that used in this work. Similar negative depen-
dences have also been reported for solutions of
other salts in both aqueous (10) and non-aqueous
media (7). Possible origins of these negative
dependences have been discussed in the literature
(9). For solutions in water, wherq (d In Dldp) is
greater than P/3 and the Debye-Huckel limiting
Molecular Weight R4 NCI slope is positive (see eq. [9]), observed negative
FIG.3. Plot of d vs. molecular weight for tetraalkyl- dependences of 4 on c1I2 have been attributed
ammonium chlorides in aqueous DMSO: (a) linear to ion pairing (1 I), hydrophobic bonding (12),
analysis; (b) quadratic analysis (a, 0,100; 0,
0.200; W,
0.300; A, 0.400; A,0.500 mole fractlon DMSO). micelle formation (13), salting-in effects (14), or
solvent structural stabilization due to the effect
of alkyl groups on the nature of hydrogen-
bonding in water (9). Franks and Smith (9),
D is the dielectric constant of the medium, P, the however, show that in sufficiently dilute solutions
isothermal compressibility, and vi is the number (< 0.002 M) of tetraalkylammonium bromides
of ions of species i which have a valence Zi. in water the dependence of 4 on c1I2 does in fact
Clearly S,,, can be positive or negative depending approach the Debye-Huckel limiting value. The
on the relative magnitudes of PI3 and the pressure deviation of the S values obtained in the present
dependence of ln D. Equation [9] predicts a value work from the Debye-Huckel limiting value may
of S,,, = 1.86 ml mole-' M-'I2 for 1 :I elec- result from the fact that the solutions were not
trolytes in water at 25.000 "C. This prediction has sufficiently dilute so that the properties of the ions
 2420 CANADIAN JOURNAL OF CHEMISTRY. VOL. 48, 1970

are determined by electrostatic interactions alone.

It should be noted, however, that in order to
obtain apparent molal volumes to better than
f 0.5 ml mole-' at concentrations less than
0.002 M, densities must be measured to better
than f 1 p.p.m. Few density measurements have
been made with this precision (7,9).
It is difficult to calculate the uncertainty intro-
+
duced into the extrapolation of to cl/' = 0 due
to possible non-conformity of the observed S
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values with the Debye-Huckel theory since the

data required to calculate S,,, are not available
for the mixed solvents used in this study. In water
the deviations of the observed S values from the
theoretical limiting slope are negative. This
probably results in the partial molal volumes 5 1
listed in Table 1 being a little higher than the "OF
c c ~ ~ r r evalues.
~ t " However, where comparison
is possible, the partial molal volumes obtained
in this study are in excellent agreement with those
obtained by other workers, suggesting that the
uncertainty is in fact small and well within the
For personal use only.

precision claimed in this work.

Partial Molal Volumes
Plots of partial molal volume vs. solvent com-
position for tetraalkylammonium chlorides in
aqueous acetone and aqueous DMSO are shown
in Fig. 4. In both solvent systems partial molal
volume exhibits extremum behavior as a function
of solvent composition. Similar behavior has
been recently reported for these same salts in
aqueous ethanol (6). The partial molal volume of
a solute in solution can be divided into two con-
tributions as expressed by eq. [l I ].
where V ; is the contribution due to formation
of a hole in the medium of sufficient size to
accommodate the solute and is the volume
change of the system due to interaction of the
solute with the surrounding solvent. Clearly
V ; can be zero or positive. The magnitude of this
term will increase with the size of the solute,
and decrease with increasing solvent-free volume
available to the solute prior to hole formation.
On the other hand, can be positive or negative
depending upon the nature of the interaction. For
electrostrictive interaction, however, i-ip should
be negative. Numerous attempts have been made
to calculate Vp using the first pressure derivative
of the Born expression for the electrostatic free
Mole Fraction Cosolvent
FIG. 4. Plot of partial molal volume vs. solvent
composition for various salts in aqueous acetone (broken
line) and aqueous DMSO (full line).
energy of solvation of ions in a dielectric con-
tinuum. However, these calculations have proved
unreliable (15) and require knowledge of the
pressure dependence of the solvent dielectric
constant. As previously stated, this information
is not available for the binary solvents used in
this study and therefore the calulations cannot
be attempted here.
In a recent study (16) concerning solvolysis
reactions in mixed solvents, we measured the
partial molal volume of benzyl chloride as a
function of solvent composition in aqueous
acetone and aqueous DMSO at 50.100 "C. In
aqueous acetone the partial molal volume was
found to pass through a large maximum a t
0.1-0.2 mole fraction cosolvent whereas in
aqueous DMSO, only a small maximum at 0.5
mole fraction cosolvent was evident. Since
-
benzyl chloride is non-ionic, the solute-solvent
interactions should be minimal and the partial
 MACDONALD AND HYNE: PART1AL MOLAL VOLUME B E H A V ~ O R 2421

molal volume will reflect predominantly the

behavior of the hole formation term VE. Accor-
dingly, we expect I/; to pass through a maximum
at 0.1-0.2 mole fraction acetone and at
mole fraction DMSO. When interpreting the
- 0.5

behavior of the salts, however, the interaction

term Vp is expected to make a large contribution
to partial molal volume and therefore must be
considered.
In 1ight.of the preceding discussion, an exami-
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nation of the data illustrated in Fig. 4 reveals

several important features. The initial decrease
of Vi,,,, as cosolvent is added to the system can
be attributed to the influence of solute-solvent
interaction (i.e. electrostriction), since the same
behavior is not displayed by non-ionic benzyl
chloride. In the case of Me,NCl, where hole
formation requirements are least but where the
surface charge density is greatest, the partial molal
volume shows no maximum in aqueous acetone
Mole Froctlon Corolvenl
and the least tendency to increase at compositions
greater than 0.2-0.3 mole fraction DMSO. On FIG.5. Plot of partial molal volume vs. solvent
composition for various ions in aqueous acetone (broken
For personal use only.

the other hand, in the case of the larger salts,
where hole formation requirements are greater
but where the surface charge densities are less,
the partial molar volumes exhibit maxima at
0.1-0.2 mole fraction acetone and show pro-
gressively greater tendencies to increase after
passing through minima at 0.1-0.2 mole fraction
DMSO. Clearly, in these latter cases the hole
formation term, 8:, makes an important con-
tribution to the dependence of vi4NC1 on solvent
composition. In the case of Me,NCl, however,
the results are consistent with the hypothesis that
solute-solvent interaction and not hole formation
is the major factor determining the dependence of
V0 on solvent composition.
The interpretation of electrolyte solution
properties is subject to uncertainty as to whether
the observed behavior arises from the cation, the
anion, or both. Plots of ionic partial molal
volume vs. solvent composition for the tetra-
alkylammonium cations and chloride anion in
aqueous acetone and aqueous DMSO are shown
in Fig. 5. In both solvent systems, vg,- initially
increases with solvent composition and in
aqueous DMSO, it passes through a maximum
at 0.2--0.3 mole fraction cosolvent. The fact that
both Vg,NCIand Vg4,+ display similar variations
with solvent composition reveals that the partial
molal volume behavior of the salt is determined
predominantly by the behavior of the cation. The
line) and aqueous DMSO (full line).
"mirror-like" dependences of the partial molal
volumes of the two smallest ions, Me,N+ and
C1-, on solvent composition in both systems
deserves comment. Since these ions are small
(compared to the other ions examined in this
work) and possess high surface charge densities,
it- is reasonable to expect that the behavior of
V i e 4 N +and Vg,- will be greatly influenced by
solute-solvent interaction. Thus the resutts
obtained in this work suggest that the volume loss
due to solute-solvent interaction is not only sen-
sitive to changing solvent composition, as might
be expected from changes in dielectric constant,
but that it is also sensitive to charge type. This
behavior is consistent with the existence of
specific cation-solvent and anion-solvent inter-
actions. Possible types of specific interaction
include chloride anion-water hydrogen bonding
and "hydrophobic hydration" of the hydrocar-
bon groups of the tetraalkylammonium cations.
In summary, the results presented in this paper
have clearly demonstrated the importance of both
solute-solvent interaction and hole formation
factors in determining the properties of salts in
aqueous acetone and aqueous DMSO. The
results also show that the behavior of the cation
determines the variation of Vg4NCIwith solvent
composition in these solvent systems. Finally,
 2422 CANADIAN JOURNAL OF CHEMISTRY. VOL. 48, 1970

the existence of specific cation-solvent and
anion-solvent interaction has been demonstrated
for solutions of tetraalkylammonium chlorides
in aqueous acetone and aqueous DMSO.
General financial assistance by the National Research
Council of Canada as well as a studentship to D. D.
Macdonald is gratefully acknowledged.
1. B. E. CONWAY, R. E. VERRALL, and J. E. DESNOYERS. 12. F. FRANKS
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 110.139.206.3 on 11/02/11
6. I. LEE and J. B. HYNE. Can. J. Chem., 46, 2333
(1968).
7. 0. REDLICH and D. M MEYER. Chem. Rev. 64,221
(1964).
8. R. E. VERRALL and B. E. CONWAY.J. Phys. Chem.
70, 3961 (1966).
9. F. FRANKS and H. T. SMITH. Trans. Faradav Soc.
10. T.' L. BROADWATER and D. F. EVANS. J. Phys.
Chem. 73, 164 (1969).
11. L. G. HEPLER,J. M. STOKES,and R. H. STOKES.
Trans. Faraday Soc. 61, 60 (1965).
and H. T. SMITH. J. Phys. Chem. 68,

Trans. Faraday Soc. 62, 2738 (1966). 3581 (1964).

2. H. H. WILLARD, N. H. FURMAN, and C. E. BRICKER. 13. S. L~NDENBAUM and G . E. BOYD. J. P ~ v s .Chem.
Elements of quantitative analysis. 4th ed. D. Van 68, 911 (1964).
Nostrand Co., Inc., New York. 1956. 14. J. E. DESNOYERS and M. AREL. Can. J. Chem. 45,
3. D. MARTIN,A. WEISE,and H. J. NICLAS. Angew. 359 (1967).
Chem. Int. Ed. Cleveland, Ohio. 6, 318 (1967). 15. D. FEAKINS. Physico-chemical processes in mixed
4. Handbook of chemistry and physics. The Chemical aqueous solvents. Edited by F. Franks, Heinemann
Rubber Co., 46th ed. 1966. Ltd., London. 1967. p. 71.
5. 0. REDLICHand H. BIGELEISEN.J. Amer. Chem. 16. D. D. MACDONALD and J. B. HYNE. TO be
SOC.64, 758 (1942). published.
For personal use only.