Journal of Solution Chemistry, Vot. 10, No.

2, 1981

Freezing Points and Enthalpies of Dilute Aqueous

Solutions of Tetrahydropyran, 1,3-Dioxane, 1,4Dioxane, and 1,3,5-Trioxane. Free Energies and
Enthalpies of Solute-Solute Interactions
Byron Y. O k a m o t o , 1 Robert H. W o o d , ~'2
Jacques E. Desnoyers, 3 G~rald Perron, 3 and
Lyne D e l o r m e 3
Received March 16, 1981;
The enthalpies of dilute aqueous solutions of tetrahydropyran, 1,3-dioxane, 1,4dioxane, 1,2,5-trioxane, and an equimolal mixture of tetrahydropyran and 1,3,5trioxane were measured at 25~ and at molalities from about 0.1 to 1.0 tool kg1,
The freezing points of the same aqueous solutions (except for 1,3-dioxane)
were measured over a similar molality range. The results were used to calculate
the enthalpies and Gibbs free energies of the pair-wise interactions of the above
solutes in dilute aqueous solutions at 25~
From these results, the additivity
principle proposed by Savage and Wood was used to get the Gibbs free energy
and enthalpies of interaction for the ether-ether and ether-methylene groups.
Because of the limited number of measurements, the interaction parameters were
not determined with great precision. Nevertheless, the standard errors for the predicted enthalpies and Gibbs free energies are quite reasonable. The signs and
magnitudes are similiar to those determined for other polar groups.

KEY WORDS: Freezing points; enthalpies; aqueous solutions; Gibbs energy;

tetrahydropyran; 1,3-dioxane and 1,4-dioxane; 1,3,5-trioxane; solute-solute
interactions.

1. INTRODUCTION

This paper is part of a continuing study of the thermodynamic

properties of dilute aqueous solutions of non-electrolytes, in order to
determine the influence of various functional groups on solute- solute
interactions. In the first paper of this series, Savage and Wood (1) measured the enthalpies of interaction in dilute aqueous solution of a large
number of compounds containing amide and hydroxyl groups. A

IDepartment of Chemistry, University of Delaware, Newark, Delaware 19711.

:rio whom correspondence should be addressed.

3Department of Chemistry, Universit6 de Sherbrooke, Quebec, CANADA, J 1K 2R1.

139
0095-978218110200-0139503.00/0 ~ 1981 Plenum PublishingCorporation

140

Okamoto, Wood, Oesnoyers, Perron, and Delorme

simple additivity principle was proposed which allowed the sign and
magnitude of the various functional group interactions to be determined from experimental data. In a further study, Okamoto, Wood
and Thompson(2) measured the freezing points of a variety of compounds containing hydroxyl groups and showed the the same additivity
principles works for the free energies of interactions.
Because of the success of the additivity principle, efforts have
been made to extend it to a wider variety of functional groups. Wood
and Hiltzik 3) explored the effect of N-methyl substitution on the
enthalpies of interaction of amides while Lilley and W o o d (4) explored
the effect of N-methyl substitution of the free energies of interaction.
Harris, Thompson and Wood (5) extended the additivity principle to the
interactions of aqueous carboxylic acids. In a recent study, de Visser,
et al.(6) have shown that the additivity principle can be successfully used
to correlate heats of interaction of salts with non-electrolyte and that
the same parameters can be used for CH2 group interactions in
uncharged species and in tetralkylammonium ions. Blackburn, Lilley
and Walmsley(7) showed that the parameters for enthalpies of interaction determined by Savage and Wood were capable of predicting the
measured heats of interactions of N-acetyl glycine amide and several
similar molecules.
The present measurements were undertaken in order to extend
the group additivity principle to the free energies and enthalpies of
interaction of ether groups.
2. EXPERIMENTAL
2.1. Freezing Points

The reagents used for the freezing point determination were

obtained and purified as follows. The 1,4-dioxane (p-D) from Aldrich
was purified by adding 68 ml of 2 M HCI to 600 ml of dioxane and
refluxing for 6 hours. Excess KOH was added, the dioxane layer
poured off, refluxed wth sodium for 4 hours and finally distilled.
Tetrahydropyran (THP) and trioxane (T) were obtained from
Matheson, Coleman and Bell. THP was refluxed with sodium for 4
hours and distilled. T was recrystallized from water, distilled, refluxed
with sodium for 4 hours, and finally redistilled. The water content of
the T was 0.03% by Karl-Fisher titration. Solutions were prepared with
distilled deionized water by weight and buoyancy corrections applied.

Freezing Points and Enthalpies

141

The measurement of the freezing point was done as previously

reported. (2)
2.2. Enthalpies
Reagents used for determination of enthalpies of dilution and of
mixing were obtained and purified as follows: THP (from Aldrich) was
passed through M.N. silica gel G, distilled, and dried with 3 /I, molecular seives; 1,3-dioxane (m-D) (Fluka Purum) was dried over 3 ,g, molecular seives; p-D (Fisher certified reagent) was dried over 3/~ molecular sieves; T (Matheson, Coleman and Bell) was recrystallized from
water and dried over CaCI2.
Enthalpies of mixing and of dilution were measured with a Picker
flow microcalorimeter, a commercial version of one previously
described. (s) Solutions were prepared with distilled deionized water by
weight. The temperature was kept at 25~ throughout the measurements.
3. RESULTS AND DISCUSSION
3.1. Enthalpies of Dilution and of Mixing
The method of extracting interaction parameters hxx, hxy, hxxx,etc.
from the experimental data is the same as previously described. (9) The
molar enthalpy of dilution is expressed by the following equation

-AHIo(mx---*fxmx) = (fx-1)mxhxx + 0Cx2-l)mx2hxxx

(1)

where AHID is the change in apparent molar enthalpy upon dilution

from an initial concentration, mx, to a final concentration, fxmx. This
equation implies that the relative apparent molar enthalpy, (bL, is given
by
(2)
~bL(mx) = -AHID(mx---, 0) = mxhxx + mx2hxxx
As the concentration increases, it is necessary to add higher terms to
Eqs. (1) and (2).
In an enthalpy of mixing experiment, a solution with initial
molality, m~, of component x, is mixed with a solution with initial
molality, my, of component y, to give a final solution in which the concentration of x is f~mx and the concentration of y is fymr In this case,
the experimental enthalpy of mixing per kilogram of solvent can be

142

Okamolo, Wood, Desnoyers, Perron, and Delorme

T a b l e I. E n t h a l p i e s of D i l u t i o n o f Cyclic E t h e r s i n W a t e r at 25~

Solute

THP

m-D

p-D

fm

AHID

moi-kgq

mol-kg]

J-mol q

Solute

0.10331
0.15289
0.19934
0.24614
0.29364
0.31481
0.35067
0.38785
0.48735
0.57713
0.70626
0.76001

0.05166
0.07620
0.09922
0.12189
0.14543
0.16045
0.17311
0.19119
0.23932
0.28255
0.34424
0.36876

- 94.0
-139.8
-188.3
-233.6
-284.5
-300.8
-344.1
-378.3
-484~7
-587.9
-748.7
-800.4

0.18977
0.28066
0.34086
0.50577
0.59950
0.81022
0.89871
0.99338

0.09412
0.13999
0.16926
0.25091
0.29614
0.39521
0.43727
0.48062

-113.4
-170.1
-203.8
-296.7
-351.2
-473.6
-521.6
-574.0

0.09578
0.20192
0.27944
0.35787
0.48474
0.57584
0.71540
0.83863
0.92055
1.08780

0.04771
0.10014
0.13816
0.17639
0.23772
0.28139
0.34768
0.40561
0.44381
0.52106

- 57.2
-118.9
-159.9
-201.4
-267.9
-316.6
-395.9
-465.7
-487.5
-581.2

fm

a/-tiD

mol-kgq

mol-kgq

J.molq

0.18965
0.19990
0.27353
0.29998
0.37478
0.40044
0.49929
0.60140
0.69995
0.79923

0.09408
0.09862
0.14645
0.14743
0A9613
0.19670
0.24376
0.29233
0.33901
0.38459

62.1
-~ 65.7
81.0
- 97.7
-112.4
-127.0
-153,2
-183.0
-209.4
-232,6

0.10126
0.10126
0.20494
0.20494
0.28273
0.38315
0.45901
0.55055
0.73908
0.78508
0.86733
1.06454

0.05045
0.05045
0.10175
0.10175
0.13999
0,18906
0.22590
0.27011
0.36029
0.38212
0.42094
0.51326

- 30.9
35.1
- 66.7
64.8
88.6
-117.3
-139.1
-162.4
-212.8
-227.6
-247.1
-298.0

r e p r e s e n t e d by the e q u a t i o n (9)

A H = f , ffx-1)m~Zh~x + fxff~z-1)mx3hxxx + fyffy-1)my2hyy

Freezing Points and Enthalpies

143

+ fy(fy2-1)my3hyyy+

2fJ'ymxm, hxy + 3f~2fym~2myhxxy

+ 3f,f~2mxmy2hxyy

(3)

Following the previous procedure, (9) we can define the parameter AHM"
such that
A HM" = A H - fxmxaH, D(mx --. fxmx)

- fymyAHiD(my-, frmy)

(4)

where A H is the enthalpy of dilution of the mixture given by Eq. (3).

It then follows that

AHM'/(fxfymxmy) = 2hxy + 3fxmxhxxy + 3fyrnyh,~,

(5)

Results of the enthalpies of dilution of the cyclic ethers in water

at 25~ are given in Table I, while the enthalpies of mixing aqueous
solutions of tetrahydropyran and of trioxane at 25 ~ are given in Table
II. The results of the least-squares fit in Eqs. (1) and (5) are given in
Table III.
The additivity principles of Savage and Wood (1) was used to
determine the enthalpy effects of the pairwise interactions between the
ether group and methylene group. The additivity principle of Savage
and Wood assumes that every functional group on molecule x interacts
with every functional group on molecule y and that each of these interactions has a characteristic effect on the enthalpy and is independent of
the positions of the functional groups in the two molecules. The
enthalpy of interaction is then the sum of all possible interactions. The
resulting equation is
hxy = ~ijnixnjYni,i

(6)

where ni x and n~ are the number of type T groups on molecule x and

type 'j' groups on molecule y respectively, hxr is the coefficient in the
excess enthalpy of the solution reflecting pairwise interactions of solute
x and y (these are the coefficients hxx and hxy in Eqs. (2) and (5)).
Since there are enthalpy data for only four ethers and one
mixture of ethers, it is best to use Eq. (6) to determine only 2 of the 3
interaction parameters. The third parameter, Hca2.cH2 = 40 J-kg-mo1-2,
is taken from Savage and Wood (1) who determined it from a leastsquares fit of the data for a large group of alcohols and amides. Eq. (6)
is a linear equation with 2 unknowns (the ether-methylene and ether-

144

Okamoto, Wood, Desnoyers, Perron, and Delorme

Table II. Enthalpies of Mixing of Aqueous Solutions of Tetrahydropyran and of Trioxane at 25 ~

mT
mol.kg"l

ruTHP
mol.kg"1

mol.kg"1

(fm)rHP
mol.kg1

A/-/a
J.kg"1

(fm)T(fm)THP

0.19990
0.29998
0.40044
0.49929
0.60140
0.69995
0.79923

0.19647
0.30622
0.40228
0.50067
0.60313
0.72844
0.80104

0.09963
0.14949
0.19954
0.24960
0.29799
0.35021
0.40000

0.09855
0.15362
0.20183
0.25038
0.30428
0.36397
0.40013

5.74
7,57
15.1
19.8
24.5
16.6
23.7

3072
2891
2936
2898
2870
2825
2798

(fm) T

AHM"b

"This is the enthalpy of mixing per kg of solvent (Eq. 3), bSee Eqs. (4) and (5); units Jkg.mol"2.

ether interactions) and can be treated by the method of least-squares.

The results are given in Table IV.
Because there are only five data points determining two parameters using an approximate equation, the interaction parameters cannot
be accurately determined.
However, the results show that the
methylene-ether interaction is +71 +- 32 ~bR, which is the expected
size and magnitude for any polar group interacting with a methylene
group. The positive enthalpy effect is due to the breaking of the structured water around the methylene group (~'1~ by the polar group and
this same sign is found for all polar groups as well as for the
methylene-methylene interaction. For instance, the previously determined pairwise enthalpy of interactions for a polar with a methylene

Freezing Points and Enthalpies

145

group are: with urea, 29; ~3) with amide, 41; m with OH, 12; 4 and with
COOH, 107/5)
Table III. Enthalpy of Interaction Parameters of Cyclic Ethers in
Water at 25~ a
Solute

hxx

hxxx

o- c

A) Pure Solutes
THP
m-D
p-D
T

1797
1219
1183
666

B) Mixtures of THP and T b

239.0
-67.
-106.
-87.

4.3
1.3
6.0
2.3

hTHP.T = 1539
hT.T~HP = 0708
hT.THP_THP = -933

aFit of experimental data in Table I to Eq. (1).Units J-kg-mol"2. bFit of experimental data
in Table II to Eq. (5). CStandard deviation of the fit to Eq. (1).

Similarly the ether-ether interaction, Ho,o = -116 --- 102 J-kgmol a, is of the expected sign and of reasonable magnitude. Previous
determinations of polar-polar group enthalpies of interactions are:
urea-urea, -280; ~a) amide-amide, -252; (1) OH-OH, -26; tl)'4 COOHCOOH, -72. (5) This is the first investigation of a polar group which
cannot hydrogen bond to itself. The results indicate that an exothermic enthalpy of interaction does not necessarily depend on hydrogen
bonding between polar groups. Because of the consistency of these

4The linear structure of Eqs. (6) and (12)allows the choice of either CHOH or OH as
the functional group. Both choices produce exactly the same fit to the data. The coefficients are related by the equations
HCH2,CHOH -----(1/2) HCH2,CH2 d- HCH2,OH
and
HCHOH,CHOH = (1/4)HCH2,CH2 -[" HOH,OH -~- HCH2,OH
with identical equations for the free energy parameters. Since for the purposes of these
comparisons, the choice of the OH group seems better than the original choice of the
CHOH group, the parameters for the OH group have been calculated from the original
results for the CHOH group. 0.2)

Okamoto, Wood, Desnoyers, Perron, and Delorme

146

trends, it now appears that most, if not all, of the interactions of a

polar group with a methylene group will be endothermic and that most,
if not all, of the interactions of two polar groups will be exothermic.
Table IV. Ether-Ether and Ether-Methylene Pairwise Enthalpies of
Interaction a
b

-116 (102) c
9

71 (32) c
-2

40

~The enthalples (J-kg-mol) were determined from a least-squares fit of the data in Table
III to Eq. (6). The standard error of the fit was 155 J.-kg-mol"2. The number of methylene and eth.er groups in the molecules are; THP, 5 and 1; D, 4 and 2; T, 3 and 3,
respectively, aDetermined by Savage and Wood. 0) ~rhe figures in parentheses are the
95% confidence limits established from the least-squares fit.

As a further test, the method of least-squares was used to determine all three interaction parameters from the present five data points
and Eq. 6. The results were:
methylene-methylene interaction,
Hcm,c m = 54 --- 46; methylene-ether interaction, Hc.2, o = 49 - 83;
and ether-ether interaction, Ho,o = -83 -+ 166. The accuracy of the
determination of the parameters is even less because there are now
three parameters to be determined with the same five data points.
However, all three parameters are in reasonable agreement with the
previous determinations. This represents another (1'6) determination of
the methylene-methylene enthalpy of interaction using the additivity
principle of Savage and Wood and a completely independent data set.
The consistency of the results is further strong evidence for the utility
of the Savage and Wood equatilan for determining the sign and magnitude of the enthalpies of interaction of the various functional groups.
The standard error of the three-parameter fit was 140 J-kg-mo1-2
whereas the two--parameter fit to the data gave a standard error of 155
J-kg-mol "2. This is about the accuracy expected from the additivity
principle of Savage and Wood since the original fit to the data on
amides and alcohols gave a standard error of 222 J-kg-mol2. (1~ It should
be noted that the predictions of solute-solute interactions are reasonably accurate even though the individual functional group interactions
are not always accurately determined by the present data.

Freezing Poinls and Enthalpies

147

T a b l e V. F r e e z i n g P o i n t D e p r e s s i o n s , 0, M o l a l i t i e s , m, a n d O s m o t i c
C o e f f i c i e n t s (at 25~

m
mol-kg1

0
K

~bR

103Aa

m
mol-kgl

~bR

0
K

A) Tetrahydropyran
0,1436
0.1828
0.2090
0.2606
0.3035
0.3083
0.3465
0.3899

0.2601
0.3282
0.3742
0.4652
0.5393
0.5472
0.6146
0,6891

0.9640
0.9526
0.9480
0.9412
0.9334
0.9319
0.9282
0.9212

0.1744
0.3863
0.5566
0.6215
0.7315
1.0303
1.3235

0.9917
0.9852
0.9814
0.9792
0.9756
0.9639"
0.9536

103A

XAb

B) p-Dioxane
1.2
-1.7
-1.1
1.4
0.4
-0.4
1.1
-0.9

0.1684
0.3058
0.4166
0.5838
0.5964
0.7885
0.9517
1.1880
1.5270

C) Trioxane
0.0943
0.2096
0.3024
0.3381
0.3988
0.5661
0.7321

~R

0.3135
0.5695
0.7764
1.0903
1.1121
1.4740
1.7824
2.2272
2.8680

0.9929
0.9870
0.9827
0.9775
0.9754
0.9698
0.9651
0.9570
0.9470

0.0
-0.5
-0.4
0.6
-1.0
0.1
0.9
0.2
-0.4

D) Tetrahydropyran-Trioxanec
-2.3
-1.6
0.6
0.6
0.8
-0.3
-0.1

0.2769
0.2942
0.3026
0.3987
0.4135
0.4560
0.4749
0.5022
0.6085
0.7759
0,9398

0 . 5 0 7 6 0.9712
0.5364
0.9649
0.5524
0.9656
0.7259
0.9577
0 . 7 5 2 1 0.9559
0 . 8 3 1 7 0.9561
0 . 8 6 2 7 0.9518
0.9136
0.9512
1.t027
0.9415
1.4048 0.9314
1.6971 0.9190

1.2
-3,4
-1.8
-0.8
-1.2
2.6
0.0
1.7
0.3
1.6
-1.5

0.4886
0.4918
0.4964
0.5039
0.5001
0.5143
0.4744
0.5006
0.4981
0.4896
0.4977

aA = gR - $(calc) based on the parameters given in Table VI. bX. is the mole fraction
of THP in the THP-T mixtures. COne point (m = 0.2103 mol-kg"~, 0 = 0.3839 K) was
not used because it was more than 2o- from the preliminary least-squares fit.

3.2. Freezing Points and Osmotic Coefficients

T h e f r e e z i n g p o i n t d e p r e s s i o n s , 0, m o l a l i t i e s , m, a n d o s m o t i c
c o e f f i c i e n t s at t h e r e f e r e n c e t e m p e r a t u r e 25~
~bR, are g i v e n in T a b l e
V. T h e o s m o t i c coefficients at t h e f r e e z i n g p o i n t o f t h e s o l u t i o n , r
were calculated from
1.860 m ~ ' = 0 + 4.9 x 1040 2 - 7.56 x 1060 3

(7)

Okamoto, Wood, Desnoyers,Perron,and Delorme

148

Then the osmotic coefficient at 25~

equation (~)

~bR, was calculated by the

~bR = 4)* - (l/R) (1/T- 1/TR)(h~xm + 2hxxxm2 + ")

+ (1/R)[TR(1/T-1/TR) + ln(T/TR)]
(Cxxm+ 2Cxxxm2 + ')

(8)

where Tis the freezing point of the solution (273.15 - 0), TR is the refe.rence temperature 298.15 K, and R is the gas constant. The coefficients hxx, etc., are found in Table III (evaluated at TR), and the coefficient Cxx is taken from the literature.(14) In the case of a mixture of two
components, (A and B), hxx in Eq. (8) is given by (15)
hxx = hAAXA2 + 2hAaXAXB+ hBaXB2

(9)

where m in Eq. (8) is the total molality (mA + mE), XA is the mole
fraction of A in the mixture ()CA = nA/(nA + riB) and the coefficients
hAA, etc. are found in Table III (evaluated at TR). Similarly, hxxxin Eq.
(8) is given by
hxxx =

hAAAXA3 "1-

3hAABXA2XB"~- 3hABaXAXB2 + hBaaXe3

(10)

with identical equations for Cxx and Cxxxin terms of CAB, CAAB,etc. For
mixtures of tetrahydropyran with trioxane the value of the interaction
term CAB was unknown and assumed zero. For normal values of CAB
(+-- 10 J-K'Lmol'~), this will cause a very small error (less than 0.002 m
in 4~R). The osmotic coefficients at 25~ 4)R, were then fitted by leastsquares to the equation.
RT(~bR- 1) = gxxm + gxxxm2 + gxxxxm3 +

" "

(11)

For mixtures, the values of g~x are given by Eqs. 9 and 10 with gAB,
gAAB, etc., replacing hAB, hAAS, etc. Results of the least-squares fit to Eq.
(11) are given in Table VI.
Again, the additivity principle of Savage and Wood was used to
determine the free energies of pairwise interactions between the ether
group and the methylene group. For free energies, the equation of
Savage and Wood is (2)

gxy = "(M1RT/2) + EijniXniVGij

(12)

where M~ is the molecular mass of the solvent, R is the gas constant, T

Freezing Points and Enthalpies

149

Table VI. Free Energy Interaction Parameters at 25~

Solute

t2

gxx
J-kg-mol"2

gxxx
J-kg2-mol"3

m(max)b
mol-kg!

crc

0.39
1.5
0.73
0.94

0.0013
0.0006
0.0013
0.0014

A) Least-Squares Fits
THP
p-D
T
THP-T

-730(18)d
-106(5)
-157(7)
-294(18)e

603(144)
13(4)
-90(26)e

B) Calculated for the THP-T Mixtures

gTHP-T= -145 (40)f
aCoefficient in Eq. (11) for pure solutes. ~Maximum molality covered by the data.
CStandard deviation of the fit to Eq. (11). aThe numbers in parentheses are the 95% confidence limits, eThis is an approximate value for XA = 0.5 . The actual values of XA
vary from 0.474 to 0.514 (see Table V) . The error caused by this approximation is negligible, fCalculated from the analog of Eq. (9) with gAB replacing hAB,etc., using the coefficient in part A of this table and XA = 0.500.
is the temperature, Gij is the free energy o f an i,j interaction and gxy is
the coefficient in the excess free energy o f the solution reflecting pairwise interactions of solute X and Y (see Eq. (11)). The free energy of
a m e t h y l e n e - m e t h y l e n e interaction (GcH2,CH2 = -34 J-kg-mor 2) has previously been determined by Okamoto, W o o d and T h o m p s o n (2) from a
least-squares fit of data on a series of alcohols and polyols. Using the
previously determined methylene-methylene interaction parameters
together with Eq. (12) in a least-squares procedure, the free energies of
the ether-methylene and ether-ether interactions were determined.
T h e results are given in Table VII.
Because there are only four data points determining two parameters using an approximate equation, the parameters cannot be accurately determined. In fact, the 95% confidence limits of the two parameters are greater than the parameters themselves. At the 80% confidence level, the value of Go,cH2 is 21 +--- 20 J-kg-mo1-2 so that we know
the sign of the e t h e r - m e t h y l e n e interaction with 90% confidence (there
is a 10% chance it is below 21-20 and a 10% chance it is above 2 1 + 2 0 ) .

Okamoto, Wood, Desnoyers,Perron, and Delorme

150

Table VII. Ether-Ether and Ether-Methylene Pairwise Free Energies

of Interaction a

Go,o

-18(141) b

GO,CH2

21(46)

GCH2,CH2

-34 c

aThe values of the free energies (J-kg-mol-x) were determined from a least-squares fit of
the data in Table IV to Eq. (11). The standard error of the fit was 159 J-kg-mol2. Srhe
figures in parentheses are estimates of the 95% confidence limits determined from the
least-squares fit. CDetermined by Okamoto, Wood, and Thompson C2) from results on a
series of alcohols and polyois.

However, for the ether-ether interaction the sign is not known with
even 50% confidence. The need for more data on the free energy of
ether-ether interactions is evident.
However, there are two reasons for believing that the situation
may not be quite as bad as it seems. In the first place, using the present four data points to determine all three interaction parameters
results in ether-methylene and ether-ether interaction which are essentially the same (Go,c.2 = 22 --&-399 and Go,o = -20 +- 784), together
with a value for the methylene-methylene interaction (Gc,~,c.2 = -35
--- 215) which is very close to the value determined by a least-squares
fit of the data on a series of alcohols and polyols.(5) The statistical estimates of the accuracy of the parameters are extremely high; nevertheless the data are quite consistent with the two-parameter fit and with
the previous results on alcohols.
In the second place, these results are consistent in sign and magnitude with previous results. The previously determined pairwise free
energies of interaction of polar groups with a methylene group are:
with OH, +34; 5 with the amide group, -4 and 1; ~2) with COOH, 0. (5~
Thus, the +21 J-kg-mol 2 for the methylene-ether group is consistent
with previous data. It is also reasonable to expect the net repulsion
between methylene and ether groups indicated by these results. The
previously determined pairwise free energies of interactions for polar

5See footnote 4.

Freezing Points and Enthalpies

151

groups with themselves indicate net attractive interactions. The previous results are: OH - OH, -27.5; (5~ amide-amide, -17 - 41 and -73
- 21 (2) (two different determinations); COOH-COOH, -35 --+ 16;(5) and
the present result is: ether-ether, -18 ----- 141. All of these interactions
are negative, indicating attractive forces for the two polar groups and
this is, again, very reasonable.
The standard error of the two-parameter fit was 159 J-tool 2 while
the standard error of the three-parameter fit was 224 J-kg-mol 2. This
is about the accuracy expected from the additivity principle of Savage
and Wood. The original fit to the free energy data on alcohols and
polyols had a standard error of 37 J-kg-mo1-2 while the original fit to the
entlaalpy data on alcohols and amideshad a standard error of 222 J-kgtoOl-2

When this research was started it was hoped that we would be

able to derive more accurate parameters for the functional group interactions with our limited data set. Unfortunately, more data is needed
to determine the sign of Go.o with reasonable confidence. For the
other three interactions (Gcn2,o, Ho,o, and HcH2,o) the signs and magnitude are determined with reasonable confidence. Even though the
individual interaction parameters are not accurately determined, the
standard errors of the fits are reasonable, showing that good predictions
of enthalpies and free energies of solute-solute interactions can be
made.
ACKNOWLEDGMENTS

The support of the National Science Foundation under Grant No.

CHE77-10624 and of the Natural Sciences and Engineering Council of
Canada is gratefully acknowledged.
REFERENCES

1. J. J. Savage and R. H. Wood, J. Solution Chem. 5, 733 (1976).

2. B. Y. Okamoto, R. H. Wood, and P. T. Thompson, J. Chem. Soc. Faraday 1 74,
1990 (1978).
3. R. H. Wood and L. H. Hiltzik, J. Solution Chera. 9, 45 (1980).
4. T. H. Lilley and R. H. Wood, Z Chem. Soc. Faraday 1 76, 901 (1980).
5. A. L. Harris, P. T. Thompson, and R. H. Wood, Z Solution Chem. 9, 305 (1980).
6. C. de Visser, W. J. M. Heuvelsland, and G. Somsen, Z Solution Chem. 1, 193
(1978).
7. G. M. Blackburn, T. H. Lilley, and E. Walmsley, J. Chem. Soc. Faraday 176, 915
(1980).
8. P. Picker, C. Jolicoeur, and J. E. Desnoyers, J. Chem. Thermodynamics 1, 469

Okamoto, Wood, Desnoyers, Perron, and Deiorme

152

(1969).
9. J. E. Desnoyers, G. Perron, L. Avedikian, and J. -P. Morel, J. Solution Chem. 5, 631
(1976).
10. M.J. Mastroianni, M. J. Pikal, and S. Lindenbaum, J. Phys. Chem. 76, 3050
(1972).
11. C. de Visser and G. Somsen, J. Phys. Chem. 78, 1719 (1974); J. Solution Chem. 3,
847 (1974).
12. C. de Visser, W. J. M. Heuvelsland, and G. Somsen, J. Solution Chem. 4, 311
(1975); J. Phys. Chem. 82, 29 (1978).
13. J. E. Desnoyers, C. Ostiguy, and G. Perron, J. Chem. Education 55, 137 (1978),
14. G. Perron and J. E. Desnoyers, Can. s Chem., in press.
15. This is easily derived from the equations for SL of a mixture given by R. B. Cassel
and R. H. Wood, J. Phys. Chem. 78, 2465 (1974). The equations for $ c
are of the same form.