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of Chemistry de chimie
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T H F \ A T I O h 4 L R F S t 4 K C H COLNCIL O F C \ Y 4 D 4 L t C O ' d S t I L \ A T I O N A L D t RECHERCHES DU C 4 Y A D A

Volume 57 Number 22 November 15, 1979 Volume 57 numero 22 15 novembre 1979

Effect of solvent (benzene, ethanol, cyclohexane) on the partial rnolah volumes of organic
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compounds

JOHN T. EDLVXRD.
PATRICK
C . FARRLLL,
A N D FEREIDOOU
SHAHIDI'
Dcpcirttnerit q f ' C l z e n ~ i s tMcGIlI
~, Utiil~er.tit.v,801 Sherhrookc S t . W . , Motftreul, P.Q., Conrrikl f f 3 A 2K6
Received May 1 1 . 1979

J O H ~T. EDWARD, PATRICK G . FARRELL, and F E R E I D OSHAHIDI.

C~ Can. J. Chem. 57,
2887 (1979).
The partial molal volumes of n-alkanes and n-alkanols dissolved in benzene, ethanol, or
cyclohexane are given with satisfactory accuracy by the equation previously developed for solu-
tions in carbon tetrachloride, if certain parameters (the covolume, :he volume increment for the
hydroxyl group, and the volume decrement for some gauclre interactions) are changed. Addi-
For personal use only.

tionally, it is necessary to postulate a greater coiling of the alkyl chains when dissolved in cyclo-
hexane.

JOHNT. EDWARD,PATRICK G . FARRELL et FEREIDOON r . J. Chem. 57,2887

S t i ~ t i x ~Can.
(1979).
On obtient avec une precision suffisante les volumes molaires partiels des iz-alcanes et I I -
alcanols dissous dans le benzene, l'ethanol ou le cyclohexane en se servant de I'equation
diveloppee anterieurement pour les solutions dans le tetrachlorure de carbone, si on change
certains paramktres (comme le co-volume, l'increment du volume pour le groupe hydroxyle et
le dCcren1ent du volume pour quelques interactions gauches). De plus il est nicessaire de
concevoir un plus grand encombrement des chaines alkyles en solution dans le cyclohexane.
[Traduit par le journal]

Introduction c11ai11 alkanes (11, haloalkanes (2), ketones ( 3 ) ,

The partial molal volumes V 0 of organic solutes ethers (3), alcohols ( 3 ) , and of cyclic compounds (4)
reflect not only the intrinsic volumes of the solute is given with reasonable accuracy by the equation
molecules, but the extent to which they interact with nz n
solvent. Furthermore, when the solute is made up of [I] ' = Vc + f n n " 1 9 ZgL6'+ C
8 1
flexible chain molecules, T o depends on the extent 1 1
to which the lnolecules are extended or coiled in where V , is a constant covolume of 11.6mL rnol-l,
solution. In the present paper we report V 0 values in k . is the number of, and I"he volume increment
the three solvents, benzene, ethanol, and c ~ c l o - associated with, groups of type k: 2,'is mol fraction
hexane, for several 72-alkanes, which should interact of, and 6' the decrement associated with, gaucl?e
feebly with the solvents, and several n-alkanol~, interactions of type 1, and c is a cyclization param-
which should interact more strongly. Additionally, eter whose magnitude depellds on the number of
we compare the V 0 behaviour of these flexible chain skeletal atoms in the ring or cage. Z , was calculated
molecules with that of the rigid adamantane and the by a method much used by Mann ( 5 ) , which assumed
relatively rigid cycloalkanes. an enthalpy difference AH, of 700 cal m o l l between
In previous work we have shown that in carbon an ar1tiand gauclle(gE/_C,) arrangement in a hydro-
tetrachloride at 2 5 ° C V 0 of straight- and branched- carbon ,-hain. ~h~ / and 6 paralneters were obtained
'Present address: Lash Miller Chemical Laboratories,
by systematic study of a large number of compounds
University of Toronto, 80 St. George Street, Toronto, Ont., chain and 47 ring Or cage in-
Canada M5S 181. cluding many isomers.
0008-40421791222887-05$01.00/0
01979 National Research Council of CanadaIConseil national de recherches du Canada
 2888 C A N J . CHEXI VOL. 57. 1979
I t would be interesting to test [ I ] in a simllar
fashlon for solvents other than carbon tetrachloride,
but for this to be done wlth any pretence to thor-
oughness V 0 values of large numbers of isomeric
compounds must be obtained. Such a project is
beyond our means at the moment, and the present
paper reports only a brief reconno~teringexpedition
into unexplored territory. This shows that V 0 in
other solvents can be accommodated by [I], and in-
dicates the desirability of more extensive studies t o
test [ I ] in a range of solvents.
Can. J. Chem. Downloaded from cdnsciencepub.com by 94.231.192.73 on 01/17/23
Results
Partial inolal volumes in benzene a n d in ethanol
a r e reported in Tables 1 and 5, and in cyclohexane in
Tables 4 and 5. Where comparison with data in the
literature is possible (6, 7), agreement for the most
part is excellent (taking account, where necessary
(6), of small differences in temperature of the mea-
surements). The result for methanol in cyclohexane
(Table 4) is exceptional, but the value reported in the
literature (6) was obtained by extrapolation from
For personal use only.
higher concentrations than those used by us, and
under these conditions the effects of dimerization,
trimerization, etc., can be important (8).
A preliminary analysis of these results was made
using the equation (9):
where N is the Avogadro number, r , the van der
Waals radius (10) of the solute molecule (assumed
spherical), and A a parameter measuring the void
o r empty volume (11) associated with the solute
molecule. We had expected A to diminish in roughly
linear fashion with increase in the internal pressure
Pi(12) o r cohesive energy density (c.e.d.) (13) of the
solvent, but instead A remained approximately con-
stant, 2s shown in Table 2. I t can also be seen in
Table 2 that the a parameter for alkanes, defined by
the equation (1 4) :
where V , is the van der Waals volume of N solute
molecules, likewise remains roughly constant. This
empirical equation holds well for cylindrical inole-
cules such as n-alkanes, the parameter a depending
o n the amount of empty volume associated with the
repeating methylene unit (1 5).
This analysis indicates that about the same empty
volume is associated with methyl, methylene, and
methine groups in the three solvellts under investiga-
tion as in carbon tetrachloride. Accordingly, we
shall assume (as a n approximation) the same values
for the increments 1 for methyl, methylene, and
methine in all four solvents. O n the other hand, the
1. Partial rnolal volumes 7' (in rnL niol-') of n-alkanes
TABLE
and 11-alkanols in benzene and ethanol at 25°C
In benzene In ethanol
----- -
C ~ r n p o ~ l l dVoCalLa
-
V 0,,,,, voCalcd ~OcXpti
n-Pentane
n-Hexane
n-Heptane
//-Octane
n-Nonane
n-Decane
Methanol
Ethanol
n-Propanol
n-Butanol
n-Pentanol
empty volume associated with the hydroxyl group.
which has a substantial dipole moment and hence
can interact with solvents by dipole - induced dipole
effects, would be expected to vary with polarizability
and hence with solvent. F o r this reason I also would
be e x ~ e c t e dto vary with solvent. We have found the
best agreement between experimental and calculated
values of I/' using the values of I listed in Table 3.
We now consider the results for solutions of
tz-alkanes and M-alkanols in benzene. Values of V 0
calculated by [ I ] using the parameters of Table 3,
and Z , values already reported (1, 3) for these solutes
in carbon tetrachloride. are shown in Table 1, Agree- -
ment with exper~mentalvalues is almost within the
limits of experimental error, except for methanol, a
compound aberrant also in carbon tetrachloride.
Values of I/' calculated in the same way for these
solutes in ethanol also agree well with experimental
values. In ethanol (unlike carbon tetrachloride (3))
it was assumed that Z,yiC,, = 0 for n-propanol and
higher alcohols, hydrogen bonding of the hydroxyl
group to solvent tending strongly to inhibit the
ggE, arrangement.
-
The accommodation of [I] to the experimental
V 0 values in cyclohexane (Table 4) offers a more
serious challenge: 8' of n-pentane is larger In cyclo-
hexane than in carbon tetrachloride. but I/' of
n-decane is smaller. These results cannot be accom-
modated if Z,:&, values remain the same in the
two solvents, but require .Z,:i?,, to increase more
rapidly with chain length in cyclohexane. This in turn
requires the enthalpy difference AHg between gauche
and anti to be smaller in cyclohexane. The calculated
 EDWARD ET AL.: I

TABLE2. Solvent parameters

vWa p: c.e.d.' A b
solvent (A3) (cal ~ m - ~ (cal
) cn1r3) (A) cr (rn~
mol-I)

Water 20.6 41 . 0 550.2 0.57 - -

Ethanol 53.0 69.5 161.3 0.745 1.613 23.5
Benzene 80.4 88.4 83.7 0.745 1.654 20.8
Carbon tetrachloride 84.8 80.6 73.6
Cyclohexane 102.0 - 76 66 9
0.740
0.755
1 ,627
1.534
21.2
28.9
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TABLE3. Parameters for calculation of V0 using [ l ]

Hydroxyl
v, I 6 :L$ AH,
Solvent (mL ~ n o l -') (mL mol- ') (mL mol- ') (cal mol- ')
--

Ethanol 12.6 1.1 -2.5 700

Benzene 11.4 5.8 -1.1 700
Carbon tetrachloride 11.6 6.1 -2.5 700
Cyclohexane 13.3 9.7 -2.5 500

values of C / O shown in Table 4 have been obtained been calculated from [ I ] using the parameters of
assuming AH, = 500 cal mol-l. Again, agreement Table 3. Trends in C with ring size run parallel in the
For personal use only.

between calculated and experimental values is rea-
sonable, considering the si~nplicityof the approach;
the data at present are too sparse to warrant a more
elaborate analysis.
The solute molecules so far considered have been
chain molecules existing in solution as mixtures of
conformers. In Table 5 we give partial molal volumes
of adamantane and cyclohexane, which have fixed
or relatively fixed structures, and of several cyclo-
alkanes, most of them existing in one or more mobile
conformations. From these values of VO,Cvalues have
TABLE4. Partial molal volumes (To, in mL mo!-I) of alkanes
and alkanols in cyclohexane at 25'C
different solvents. Possible interpretations of C have
been given earlier (4).
Discussion
It is apparent that with adoption of the parameters
of Table 3, Po in the three solvents under investiga-
tion may be calculated from [I] with reasonable
accuracy. We now consider whether the relative
magnitudes of these parameters accord with the
intuitive picture of partial molal volumes developed
in our previous papers.
The covolume V, is the volume of the solvent
cavity required to accommodate a point kinetic
particle of no intrinsic volume

Compound Z,& o/c

Z,,,-,, v" ,,, voeXptl

n-Pentane 0.79 - 116.3 116.9_+0.5

n-Hexane 1.14 - 132.7 133.6k0.6 It should accordingly be related to the b parameter
n-Heptane 1 .46 - 149.1 150.0&0.5 of Terasawa et al. (14) ( V O= b when V,,, = O), and
n-Octane 1 .80 - 165.4 165.6k0.6 this relationship is shown in Fig. 1 A . We have
it-Nonane 2.13 - 181.7 179.720.6 already given reasons why Vc should be expected to
n-Decane 2.46 - 198.0 196.920.3
Methanol - - 49.8 48.220.3" be less than b (1).
Ethanol - - 67.1 67.8+0.4b There is also an indication (Fig. 1B) that Vc may
n-Propanol - 0.74 83.0 82.020.2" be related to the van der Waals volume v, of the
n-Butanol 0.46 0.72 100.4 99.6+0.3d solvent molecules. Bondi (16) has discussed the effect
n-Pentanol 0.77 0.72 115.3 115.610.5' to be expected from varying particle size on the close-
n-Hexanol 1.10 0.72 131.6 131.Sf
n-Octanol 1 .76 0.72 164.2 164.9jf ness of packing of spheroids, but without firm con-
12-Decanol 2.42 0.72 196.8 198.4* clusions. The present work indicates the desirability
nRefere~~ce
6 reports P at 20°C to be 44.25. of a systematic study of the variation of Vc and b in
b66.5. solvents made up of spherical, aprotic molecules
C81.45.
d99.4.
*I 14.7.
of varying size. The point for the protic solvent,
'Reported by ref. 6 for 20°C. ethanol (not shown), lies far above the straight line
 2890 C A S J . C H E \ I . V O L . 67. 19?9

5. Partial molal volumes Vo and cqclization factors C (both in mL mol-') for cyclic compounds and adamantane in various
TABLE
solvents

CCI," C~HI, C6H6 EtOH

---------A

-
Con~pound V0 C Po C v0 C VO C
-
Cyclopentane 97.5t 0 . 5 -2.2 92.8t0.4 -7.5 - .- -
Cyclohexane 1 1 0 . 9 k0 . 5 -6.0 108.8+0.1 -8.9 111.1~0.3 -4.7 110.6f0.6 -6.4
-
Cycloheptane 124.0k0.6 -9.7 120.0i0.3 -15.1 - - -
Cyclooctane 135.420.4 -13.6 133.2t0.5 -19.3 - .- -
-
-
Cyclodecane 165.320.3 -21.0 163.0i0.3 -24.3 - - -
Adamantane 140.2+0.3 -16.9 137.3+0.5 -21.6 142.7t0.2 -14.3 138.8t0.9 -19.4
Can. J. Chem. Downloaded from cdnsciencepub.com by 94.231.192.73 on 01/17/23

.1Froni ref 4

enthalpy increase of about 900 cal 1x01-I oil going

from nrrti to ga~rchebutane in the gas phase. This
difference is reduced \+hen n-butane is in solution,
perhaps because the internal pressure exerted by the
solvent favours forlnation of the more compact
gauche form (19). However, there is no simple cor-
relation, as might be expected (19), between AH,
(Table 3) and P, o r c.e.d (Table 2). Possibly a more
important parameter is the London dispersion force
between the hvdrocarbon chain and the solvent
For personal use only.

molecules, which would favour a more extended

FIG.1. Relation between Vc and b ( A ) , and between V, and
w
. (B).
of Fig. l B , but the introduction of a partially inert
solute inolecule into a highly structured, hydrogen-
bonded solvent would be expected to break hydrogen
bonds and hence to lead to a n increase in volume
greater than expected from the mere formation of a
cavity in the solveiit.
We now consider the increnlent I for the hydroxyl
chalii and closer solvent-solute contacts: this would
be weakest in cyclohexane s o l u t i o i ~ The
. ~ extent of
coiling of polymer chains has been explained in
similar fashion (20).
Accepting a smaller AH, in cyclohexane, we can
e x ~ e c n-alkane
t chains to 6e more coiled in this sol-
veilt than in carbon tetrachlor~de.Hence each suc-
cessive addition of CH, to the chain causes a smaller
increase in v0
in cyclohexane than in carbon tetra-
chloride. This explains the sinaller a parameter in this
solvent (Table 2).

-
group. If this group interacted with benzene, carbon
tetrachloride, o r cyclohexane as weakly as d o methyl
and methylene, it would have I 16.6 rnL mol-I
(3). The increments in all three solvents are smaller,
and reflect the strength of dipole - induced dipole
interactions in the order: benzene > carbon tetra-
chloride > cyclohexane, the order of decreasing
polarizability (17). In the protic solvent, ethanol,
strong interaction through hydrogen bonding is also
possible, and hence I is smallest in this solvent.
Explanations for the differences of 6E/C, (Table 3)
a n d C (Table 5 ) in the different solvents are less ob-
vious. Variability of 6 (e.g., 6Z':CG, ij:C, (2)) with
so!vent has been noticed before but with molecules
containing polar groups, and for which changes in
conformation should result in changes in dipole
moment.
The reduction of AH, on changing solvent fsom
carbon tetrachloride to cyclohexane is also remark-
able. Latest studies (reviewed in ref. 18) indicate an
In summary, the present work indicates that [I]
will probably prove valid for a variety of organic
solvents made up of spherical molecules. It would
- desirable to test it more stringently by obtaining
be
V 0 values for large nuiilbers of isomeric alkanes in
each single solvent, and thence obtaining ab inifio
the parameters I and 6.as u as done for carbon tetra-
chloride solutions (1).
Experimental
Solvents and solutes were commercial products, and were
purified by methods described earlier (1). The technique for
measuring the densities of solutions has also been described
(I). In all cases linear variation of the apparent molal volume
with concentration was observed over the concentration range
( < 0.5% w/w) employed.
Acknowledgments
We arc grateful to the Natural Sciences and
'This effect would run counter to P, or c.e.d. It is possible
that effects of both types are involved.
 ED\VARD L:T A L . : 1 289 1

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