1734 N. R.

ARMSTRONG,
N.E.VANDERBORGH, AND W. D. SPALL

creasing temperature, but not varying linearly with
l / T , in the system of C U ( T F A ) ~ . ~ - > I ~AsP ~eq. 1
implies, the hyperfine coupling constant, A , can be
obtained from the Iinear plot of contact shift us. I / T .
For the C U ( H F A ) ~ . ~ ( ~ - Mand
~ P ~CU(HFA)~.
) elevated temperatures. The fact that CU(HFA)~.
2(4-RIePyO) complexes, the calculated hyperfine cou-
pling constants for y-CHa are, respectively, +3.0 X 105
Hz and +7.7 X 105 Hz.
Kluiber and Horrocks5 have reported a similar
abnormal temperature effect for Cu(TFA)t .4-MePyO
complex. They have proposed that a five-coordinated
complex of low symmetry or a tetrahedral four-co-
ordinated complex (with the opening of one TFA ring)
accounts for the observed temperature variation a t
elevated temperature (above 30") for this complex.
However, this model of Kluiber and Horrocks is not
consistent with our results on the Cu(HFA)z complexes.
C U ( H F A )forms
~ tetragonally distorted octahedral bis
adducts with 4-methylpyridine and 4-methylpyridine
K-oxide in chloroform solution. Since CU(HFA)~is
less stable than C U ( T F A ) ~ ,one
~ ' would expect ring
opening to be easier for CU(HFA)~ than CU(TFA)~ at
2(4-MePy) and C U ( H F A ) ~ . ~ ( ~ - X I ~show
P ~ O ) ap-
preciable spin delocalization and a normal temperature
effect is not consistent, then, with a tetrahedral species
being present for Cu(HFA)* complexes. Thus, since
this tetrahedrally coordinated complex does not occur
for the Cu(HFA)z complexes, we think it even less
likely to occur for the CU(TFA)~ complexes.
Acknowledgment. The authors thank Dr. A. Allen-
doerfer of the State University of New York at Buffalo
for his assistance in obtaining the esr g values.
(27) L.G.Van Uitert, W. C. Fernelius, and B. E. Douglas, J.Amer.
Chem. Soc., 75,457 (1953).

A Cryoscopic Study of the Association of Phenolic

Compounds in Benzene

by Nicholas E. Vanderborgh, NeaI R. Armstrong, and W. DaIe Spa11

Department of Chemistry, University of New Mexico, Albuquerque, New Mexico 87106 (Received June I d , 1969)

The cryoscopic behavior of phenol, positional isomers of chlorophenol and cresol, and 2,5-, 2,6-, 3,4-, and 3,5-
dimethyl phenol were studied in benzene, and equilibrium constants describing this behavior in terms of
association were determined for the concentration range 0-0.8 rn. The results indicate that substitution of
a ring hydrogen of phenol by either chlorine or methyl decreases the amount of association of the parent phenol,
chloro isomers having less association than methyl isomers. The degree of association is qualitatively related
to the effects of the substituents on the T electron cloud of the phenyl ring.

The measurement of colligative properties of liquid
solutions, those properties which depend upon the
number and not the type of dissolved species, has long
been recognized as an important method for the study
of molecular association. Of the several colligative
property techniques, one of the most accurate and
experimentally simple is the depression of the freezing
point, cryoscopy. Early workers studying this tech-
nique discovered that many organic solutes, when used
to depress the freezing points of aprotic solvents,
showed smaller freezing point depressions than would
be predicted on the basis of their formula weights.
The most commonly used explanations for this ob-
served nonideal behavior are the formation of solid
solutions, changes in activity coefficientswith concentra-
tion, and molecular association.
Solid solution formation greatly complicates the
interpretation of cryoscopic data. The existence of
solid solutions may be detected either by chemical
analysis of the frozen solid or by the method of Van
Bijlert. Compounds suspected of forming solid solu-
tions or mixed crystals in benzene solutions include
acetic a ~ i d z -and
~ pheno1.2J However, in these previ-
ous studies, the existence of solid solutions was not
verified by chemical analysis. The usual method for
correcting cryoscopic data for the effects of solid solu-
(1) A. Van Bijlert, 2.Phgs. Chem. (Leipzig), 8, 343 (1891).
(2) C.R. Bury and H. 0. Jenkins, J . Chem. SOC.,688 (1934).
(3) A. G.Milligan, J . Phys. Chem., 33, 1363 (1929).
(4) R.Marc and W.'Wenk, Z. Phys. Chem. (Leipzig), 68, 104 (1910).
(5) F. Garelli, ibid., 21, 122 (1890).
(6) J. A, Davison, J. Amer. Chem. Soc., 67, 222 (1945).

The Journal of Physical Chemistry

 OF PHENOLIC
ASSOCIATION COMPOUNDS
IN BENZENE 1735

Table I: Reagents

Anal. of purityd” >

Method of Re1 wt 5% HzO ’
Reagent Symbol purifioation major wt %

Benzene B a 99.6 0.025

Naphthalene N b 99.9+ Not detectable
Biphenyl BP C 99.9+ Not detectable
Phenol P a 99.7 0.055
o-Cresol oc a 99.3 0.030
m-Cresol MC a 99.3 0.030
p-Cresol PC b 99.4 0.030
o-Chlorophenol OCP a 99.6 0,029
m-Chlorophenol MCP a 99.6 0.033
p-Chlorophenol PCP c and b 99.8 0,019
2,5-Dimethylphenol 25DMP b 99.1 0.041
2,6-Dimethylphenol 26DMP b 99.1 0.048
3,4-Dimethylphenol 34DMP b 99.3 0,043
3,5-Dimethylphenol 35DMP b 99.2 0.047
(1Fractional distillation from Linde 4A molecular sieves; system flushed with dried and purified argon. Fractional crystallization
from benzene, vacuum dried. Sublimation. d Glpc: 2-m Silicone Oil DE-710 on firebrick; T = 190’ for phenols, T = 80”
for benzene. e Error in major component analysis is rrt0.5 wt %.

tion formation is the use of an expression of the form7v8
AT = KtCo(1 - k)
where AT is the observed temperature lowering, Kt
the freezing depression constant, Cothe “observed con-
centration,” and k is the distribution coefficient for the
solute between the solid and liquid phases. Using
an expression this form, Bury and Jenkins2 report a
value of 0.47 for k while Davidson6 reports a value of
0.41 for solutions of phenol in benzene.
Even though the existence of solid solutions is sus-
pected, it is not reasonable to interpret cryoscopic data
solely on this basis for systems which might show other
causes for nonideal behavior. Phenolic solutions in
benzene show infrared spectra characteristic of hydrogen
bonded systems and the nonideal cryoscopic behavior
should be, in part, attributed to association. Devia-
tion from ideal solution behavior for these systems may
also be due to activity effects. Several theories for
the determination of activity coefficients of nonelectro-
lytes in nonaqueous media have been put forth; the one
derived from the normal theory of liquidss is perhaps
the most used. These theories are generally unsatis-
factory in explaining the data since quite large activity
corrections are necessary. For example, phenol has
been reported to have an activity coefficient of less than
0.3 at 0.5 m benzene solution.1°
Another cause for nonideal behavior may be loosely
classified as molecular association. The solute may
associate with itself, the solvent, or with impurities pres-
ent. I n this investigation, equilibrium constants for
the self-association of phenol (P), orthocresol (OC),
metacresol (MC), paracresol (PC), orthochlorophenol
(OCP), metachlorophenol (MCP), parachlorophenol
(PCP), 2,5-dimethylphenol (25DMP), 2,6-dimethyl-
phenol (26DMP) , 3,4-dimethylphenol (34DMP), and
3,5-dimethylphenol (35DMP) are reported in the
solvent benzene. Infrared spectra of these com-
pounds in benzene solution are accepted as showing
hydrogen bonding;lo it is assumed that self-association
of the phenols is the cause of this spectral behavior.
The formation of solid solutions of phenol in benzene
has also been investigated. I n this investigation we
shall assume that the cryoscopic data can be explained
solely on the basis of molecular association after the
effects of possible solid solution formation have been
explored.
Experimental Section
Reagents. The chemicals used for this study as well
as the method of purification and analyzed purity are
shown in Table I.
Apparatus. The apparatus used for these investiga-
tions was designed to measure the freezing points of
solutions at millimolal and higher concentrations using
a procedure to maximize accuracy and to minimize
time spent in data collection. The test solution was
maintained under an atmosphere of dried argon at all
times. Stirring was accomplished by a Teflon disk
stirrer driven at 600 rpm by a synchronous motor.
The apparatus was sealed except when solution concen-
trations were changed. (See Figure 1.)
A Veco 51A1 100,000-ohm thermistor was used as
(7) S. Glasstone, “Textbook of Physical Chemistry,” 2nd ed, Van
Nostrand-Reinhold Co., Inc., Princeton, N. J., 1849,p 649.
(8) See ref 7, p 660.
(9) G. N. Lewis and M. Randal, revised by Pitzer and Brewer,
“Thermodynamics,” 2nd ed, McGraw-Hill Publications, New York,
N. Y., 1961, chapter 20.
(10) G. C. Pirnentel and A . L. McClellan, “The Hydrogen Bond,”
W. H. Freeman and Co., San Francisco, Calif., 1960.

Volume 74, Number 8 April 16, 1OYO

1736
N. E. VANDERBORGH,
60 RPM SYNCHRONOUS
MOTOR.
14:1 GEAR RATIO
I i I,,/ I/
Figure 1. Cryoscopic cell assembly, constructed from Pyrex,
described in text.
-1
R2
Figure 2. Temperature measuring circuit; Ei, = 1.35 V
Mallory mercury battery; R1 = Ra = R3 = 500,000-ohm
cermet trimpot, Rf = 100,000 ohm Veco 5 l A l thermistor;
0-1, Fairchild ADO-44, operational amplifier.
the temperature sensing device with the measuring cir-
cuit shown in Figure 2 . The apparatus shown is cap-
able of an output sensitivity of approximately 150
mV/deg C and can detect 0.001” changes in tempera-
ture under the conditions used in this study. Use of
the full sensitivity of this circuit would allow investiga-
tion of 2.5 X lo-* m solutions. Operating conditions
were such that approximately a 2’ change in the
temperature corresponded to maximum response.
Discussion of the measuring circuit may be found else-
where.”
Experimental Procedure
The apparatus was carefully cleaned and dried in a
vacuum oven (1lOO) before use. A weighed charge of
The Journal of Physical Chernietry
N. R. ARMSTRONG,
AND W. D. SPALL
pure solvent was placed in the cell, a blanket of argon
introduced, and the solvent benzene frozen by raising
a constant temperature bath (0’) into position. The
cooling curve was recorded on a recorder. After melt-
ing the benzene frozen during the initial determination,
a known volume of a solution of known composition
of the solute in benzene was introduced and the freezing
curve for this solution determined. Repeated additions
allowed the measurement of the cryoscopic solution
behavior throughout the desired concentration range.
Solid Solution Studies. Benzene solutions of phenol,
o-chlorophenol, and p-cresol were prepared by weight,
maintained under dry argon, and while vigorously
stirred partially frozen by emersion of the flask contain-
ing the solution into a bath maintained at 2’. The
partially frozen solution was then transferred under an
argon layer into a refrigerated Hirsch funnel and the
liquid fraction separated. The remaining solid was
washed with 5.0 ml of 6” benzene; these washings were
added to the liquid fraction and the total volume noted.
The collection vessel was then changed, the solid al-
lowed to melt, and collected. Analyses of the resulting
solutions were made on a Varian Auto-Prep gas chro-
matograph. The analytical results were compared to
results obtained with standard solutions of the same
compounds. From these measurements, the value for
the distribution coefficient for each solute was deter-
mined. Concentration values for the liquid fraction
were corrected for dilution by the 5.0-ml wash fraction
of benzene.
Experimental Error
An error analysis showed the average error in the
analytical solution concentrations was A 0.5% and
1.0% in the cryoscopically observed concentration.
Maximum error occurred in the lowest analytical con-
centrations studied, below 100 mm, where the error in
CA was from 10.8 to 1.0% and the corresponding
error in CO was from k2.0 to 3.0%. The measuring
circuit was calibrated by comparison with thermometers
traceable to the National Bureau of Standards.
Results
Determination of the Cryoscopic Constant of Ben-
zene. Cryoscopic techniques require a known rela-
tionship between the observed freezing point lowering
and the concentration of a species known to behave
ideally in the solvent under study. If such ideal be-
havior has not been reported, a “reference compound’’
may be selected and all concentrations can be related
to this standard. I n this study, naphthalene and bi-
phenyl were chosen as the nonassociated standards.
Biphenyl is known to be nearly ideal in benzene solu-
(11) “Handbook of Operational Amplifiers,” BurrBrown Research
Corp., Tucson, Ariz., 1960,p 30.
 OF PHENOLIC
ASSOCIATION COMPOUNDS
IN BENZENE 1737

tions;12 positive deviations from Raoult’s law for the

liquid-vapor equilibrium are less than 2% at relatively
0.6
low concentrations. The freezing points of a series of
solutions of naphthalene and biphenyl were determined;
the value of K fdetermined with either compound was
0.5 1
6
5.112”C/m, in good agreement with 5.070 reported by ._
c
0.4 -
Barton and Kraus,13 5.122 by Bury and Jenkins,2 a
C

5.10 by Peterson and Rodebush,145.12 from latent heat C

0.3.
of fusion by Huffman, Parks and Daniels,15 and 5.11 v
>
L

by Auwers,16 but differing with the value of 5.492 re- :

ported by White and Kilpatrick.’7 When using the
8 0.2.
apparatus shown, the output of the temperature mea-
0.1 I
suring circuit was linear with concentration of the stan-
dard species to within 0.0091 Q unit with an intercept V
of 6 X less than experimentally observable. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Analytical concentration, m.
The apparent linearity of data is attributed to a for-
tuitous cancellation of the nonlinear response of the Figure 4. Cryoscopic behavior of cresolb and phenols.
temperature-measuring device with the change of Observed concentration ( m ) us. analytical concentration; line
Kt with temperature. calculated from equilibrium constants shown in Table 11; 0,
OC; 0 MC; A, PC.
Interpretation of Experimental Data
The experimental data determined must be examined
based on the minimization of undetermined thermody-
in terms of association since reliable theories of non-
namic functions and on statistical curve fitting.2e,27
electrolyte activity are nonexistent. As has been
The relationship of CO, the “observed concentration”
pointed out succinctly by Rossotti and Rossotti, l8
determined from the apparent freezing point depression,
association data of this sort result in essentially two
to CA, the “analytical concentration,” for the com-
equations with n unknowns, a problem which may in
pounds used in this investigation is shown in Figures
theory be solved; however, experimental error usually
3-6. Figures 3 and 6 include the data of Davison and
makes the set of equations ill-conditioned. Attempts
those of Bury and Jenkins for purposes of comparison.
to increase the number of equations available for data
Table I1 lists equilibrium constants determined by
analysis results in fixing some arbitrary relationship be-
curve fitting, those determined by Lassettre’s method,
tween successive equilibrium constants for the associa-
as well as those previously reported.
tive reaction. Notable contributions on this line have
been made by L a ~ s e t t r e , l ~Dunken,22t2a
-~~ and Bejer-
rumlZ4modified by Fr0naeus.~5 A second approach is (12) Laszlo and Szabados, Kozp. Fiz. Kut. Intez., Kozlem, 15, 283
(1967).
(13) B. C. Barton and C. A. Kraus, J . Amer. Chem. Hoc., 56, 2017
(1934).
(14) J. M. Peterson and W. H. Rodebush, J. Phys. Chem., 32, 709
(1928).
(15) H. M. Huffman, G. 8. Parks, A. C. Daniels, J . Amer. Chem. SOC.,
52, 1547 (1930).
. 0.5. (16) K. Auwers, Z . Phys. Chem., 42, 513 (1902).
c
0 (17) N. E. White and M. Kilpatrick, J. Phys. Chem., 59, 1044
E (1955).
e 0.4-
.
.
4

c (18) (a) F. J. C. Rossotti and H. Rossotti, “The Determination of

8 Stability Constants,” McGraw-Hill Publications, New York, N. Y.,
0.3-
1961; (b) F. J. C. Rossotti and H. Rossotti, J . Phys. Chem., 65,
‘0 926 (1961).
2 (19) E. N. Lassettre, Chem. Rev., 20, 259 (1937).
2
0
0.2. (20) E. N. Laasettre, J. Amer. Chern. Soc., 59, 1383 (1937).
(21) E. N. Lassettre and R. G. Dickinson, ibid., 61, 54 (1939).
(22) H. Dunken, 2.Phys. Chem., 45B, 201 (1940).
(23) K. L. Wolf, H. Dunken, and K. Merkel, 2.Phys. Chem. (Leip
V
zip), 46B,287 (1940).
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 (24) J. Bjerrum, Kem Maanedsbl. Nord. Handelsblad Kem. Ind., 24,
Analytical concentration, m. 21 (1943).
(25) S. Fronaeus, “Komplexsystem hos Koppar,” Dissertation, Uni-
Figure 3. Cryoscopic behavior of the chlorophenols. versity of Lund, 1948.
Observed concentration ( m )us. analytical concentration; line (26) F. J. Zlesnik and S. Gordon, Ind.Eng. Chem., 60,27 (1968).
calculated from equilibrium constants shown in Table 11; (27) A. Pullman and H. Berthod, Theor. Chim. Acta, 10, 461
0, OCP; 0 , MCP; A, PCP. (1968).

Volume 74, Number 8 April 16, 1970

1738 N. R. ARMSTRONG,
N. E. VANDERBORGH, AND W. D. SPALL

Table I1 : Summary of Cryoscopically Determined Equilibrium Constants for the Association of Phenolic Compounds in Bensene

Equil oonst for amocn 7

This investigation-
V Y
B- - - - - - ourve fitting- -BY method of L a s s e t t r e - --Previously repd-
Compd % assocd“ Kiz Kin Kiz Kis KII Ref
PB 84.75 125 450 0.556 0 190
I 61 32
34DMP 21.81 0.30 2.1 0.653 0.640
35DMP 19.35 0.20 2.0 0.556 0.464
25DMP 31.95 0.47 b 0,309 0,143
26DMP 14.51 0.17 b *.. ...
oc 16.27 0.58 b 0.18 0.14 1.1 3
0.28 19
MC 23.18 0.50 1.80 0.578 0.955
PC 18.96 0.30 1.60 0.675 0.595 1.1 3
0.42 19
OCP 9.09 0.10 b 0.006 0.004
MCP 31 -51 0.46 b 0.168 0.04
PCP 35.49 0.55 b 0.242 0.09
a V = % associated, defined in text. * Kla < 0.01.

The equilibrium constants shown in Table I1 were
determined by a curve-fitting technique. A series of
CA vs. CO curves were generated using incremented
values of monomer concentration and overall equilib-
rium constants. The experimental data were then dis-
played graphically and the resulting curves overlayed
on the various calculated curves to achieve a “best fit.”
Criteria for “best fWJ were that the deviations of the
experimental points from the calculated curves were a
minimum, the same order of magnitude as the experi-
mental error, and that the least number of equilibrium
constants necessary t o describe the data were used.
This leads to the simplest model to adequately explain
the experimental data. To obtain a reasonable value
of the initial dimerization constant, the data obtained
for low analytical concentrations were used since the
contribution of higher order polymers t o CO, the ob-
served concentration, should be small; the initial part
of the CO-CA curve, then, was used to evaluate the
dimerization association equilibrium constant. Once
this was done, this constant was used to evaluate the
trimerixation constant. I n no cases were association
constants higher than the trimerization necessary. This
approach is generally similar to that often used for
the determination of successive formation constants of
complex ions.ls
Also shown in Table I1 is the function V, the per cent
of association, evaluated a t an analytical concentration
of 0.5 m. V = concentration of all associated species X
100 divided by the concentration of all species; V =
(CO - Cmonomer) lOO)/(CO). The monomer concentra-
tion was obtained from solution of the equation relating

1
0.6 ! 0.6 I
c
._
0.5 e 0.5
.-i
i
-
e
2 0.4
c

8
0.4

v
s
0
” 0.3 ’
Bt
0.3

$
6 0.2 2 0.2
0.1 0.1

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 08

. 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Analytical Concentration, m.
Analytical concentration, m.

Figure 5. Cryoscopic behavior of dimethylphenols. Observed Figure 6. Cryoscopic behavior of benzene solutions of
concentration ( m )vs. analytical concentration; line calculated phenol. Observed concentration ( m ) vs. analytical
from equilibrium constants shown in Table 11. 0, 2,6-; concentration; 0, this investigation; 0, Bury and Jenkins;
0, 2,5-; 0, 3,4-; A, 3,6-. A, corrected for solid solution formation.

The Journal of Physical Chemistry

 OF PHENOLIC
ASSOCIATION COMPOUNDS
IN BENZENE 1739

CO to the monomer concentration through the equilib-
rium constants.
If a large concentration range is studied and the re-
sulting data are used to determine equilibrium constants,
corrections for the temperature dependence of these con-
stants may be necessary since the measurements are
not isothermal. In theory, this effect may be used to
predict thermodynamic parameters9 derived from the
van’t Hoff equation. For phenolic systems in benzene,
these deviations of the equilibrium constants with tem-
perature are limited by values of AH for the associative
reaction. lo Calculations based on an average value
of AH for OH. a hydrogen bonds indicate that for ob-
0 the observed partition coefficient for PC, a similar con-
served concentrations of 0.5 m, only 5% change in the
equilibrium constants results from these effects. Since
the highest observed concentrations found in this inves-
tigation were of this magnitude] the temperature depen-
dence effects should introduce error of no greater than
5%.
Table I1 also includes the results obtained by analysis
of our datausing the method described by Lassettre. 19-21
This approach assumes three possible functional forms
for the relationship between CO and CA; two of these
describe a hyperbole and one a quadratic. When the
proper relationship has been selected] the maximum
number of equilibrium constants is determined by the
degree of experimental error. Using the equilibrium
constants obtained from this method, we attempted to
reconstruct our experimental data. It was found that
the reconstruction required a greater number of equilib-
rium constants than the experimental error indicated
were significant. and Rossotti and Rossotti’8
have pointed out that the precision of measurements as
well as computational errors introduced by smoothing
of experimental error seldom justifies more than three
independent parameters. The errors introduced by
forcing the data to conform to a predetermined function
may actually increase the overall error. I n a similar
data analysis, Sil16n28 introduced a graphical curve-
fitting ppocedure which has been expanded in an
attempt to reduce the error. We feel that the curve
for fitting technique which we have described allows
~ ~
more latitude in suggesting B model than does an explicit
solution.
It has been reported previously2J**that phenol forms
solid solutions with benzene. It was therefore rreces-
sary to investigate the extent of this solid solution for-
mation. The results of these studies are shown in
Table 111. I r data indicate that OCP is slightly asso-
ciated,lO in agreement with our cryoscopic studies. It
is therefore reasonable to assume that the partition
coefficient determined for OCP is one which results
from a residual absorption and occlusion with the solid
phase and not from solid solution formation. Due to
clusion results even though the cryoscopic behavior of
PC is indicative of considerably increased association,
OCP and PC mere chosen as reference compounds due
to their structural similarity to phenol. Both show
partition coefficients of 0.19 f 0.08; this value is taken
as representative of absorption and occlusion effects.
No attempt to utilize the Van Biljert method was
made since it was felt that addition of a third component
to the cryoscopic solution could alter the solvent prop-
erties, or, more importantly, alter the extent of solid
solution formation. The average value of the partition
coefficient of OCP and PC was subtracted from the ob-
served value for phenol, 0.36, to yield a partition co-
efficient of 0.17 for phenol corrected for surface absorp-
tion and occlusion inherent in this procedure. Using
this corrected value, the cryoscopic data were then cor-
rected for the effects of solid solutions. These data are
shown in Figure 6 and equilibrium constants are in-
cluded in Table 11.
Discussion
Phenolic compounds are thought to self-associate in
solution because of the favorable difference in energy
between the associated and monomeric forms. This
energy difference is termed the delocalization energy; a
significant fraction of this difference is due to the hydro-
gen bond. Theories of hydrogen bonding piedict that
several factors contribute to the total energy of the
bond. The differences in magnitude of these factors in
different systems have made the complete description of
~~

the hydrogen bond difficult. Hydrogen bonding has

Table 111: Solid Solution Analysis of Benzene Solutions been extensively studied using various spectral tech-
niques. Ultraviolet methods indicate varying degrees
-Concn
Liquid Solid of n cloud interactions while infrared methods indicate
Solute Originalu phase”’ phase* kd varying amounts of hydroxyl interactions in the phen-
o-Chloro- 0.287 2.99 0.57 0.189 olic compounds under study.1° Recent theoretical
phenol s t ~ d i e s ~show
~ , ~T~interactions
-~~ may arise in several
p-Cresol 0,263 2.99 0.54 0.179 ways and may contribute to the stability of the asso-
0.258 2.88 0.58 0.200
Phenol 0.267 2.64 0.92 0.349 (28) L. G. Sill&, Acta Chem. Scand., 10, 186 (1956).
0.481 6.00 2.04 0.340
(29) 9. Brator, Advan. Quantum Chem., 3 , 207 (1967).
0.797 7.59 2.93 0.386
(30) K. Morokumo, H. Kato, T. Yonerawa, and K. Fukui, Bull.
am. Wt %. Corrected for dilution. Apparent dis- Chem. SOC.Jap., 38, 1263 (1965).
tribution coefficient] solid: liquid. (31) A . Ocvirk, H. A. Zuman, and D. Hadji, Theor. Chem. Acta
(Bed), 10, 187 (1968).

Volume Y4, Number 8 April 16, 19YO

 1740 N. E. VANDERBORGH,
N. R. ARMSTRONG,
AND W. D. SPALL

Table IV: Selected CA and CO Values: Cryoscopic Data; CA, Analytical Concentration, m;
CO, Cryoscopically Observed Concentration, m

CO'
oor for
Phenol solid -0-Chlorophenol- -mChloroph enol- ---p-Creaol-- --2,6-Xylenol- --2,5-Xylenol-
CA co soln cA4 co CA co CA co CA co CA co
0.0261 0.0216 0.0260 0.0616 0.0693 0.0552 0.0510 0.0587 0.0570 0.0724 0.0683 0.0941 0.0907
0.0382 0.0305 0.0367 0.1073 0.1021 0.0932 0.0748 0.0993 0.0961 0.1124 0.1088 0.1058 0.1004
0.0498 0.0368 0.0443 0.1207 0.1151 0.1082 0.0973 0.1157 0.1104 0.1407 0.1353 0.1518 0.1395
0,0608 0.0432 0.0520 0.1578 0.1495 0.1390 0.1199 0.1682 0.1519 0.2053 0.1981 0.1710 0.1646
0,0714 0,0495 0 0596 0.1697
I 0.1650 0.1591 0.1424 0.2193 0.1899 0.2137 0.2079 0.2011 0.1842
0.0912 0.0584 0.0704 0.1773 0.1685 0.1822 0.1602 0.2503 0.2101 0.3056 0.2958 0.2439 0.2233
0.1262 0.0800 0.0964 0.2062 0.1994 0.2081 0.1840 0.3152 0.2635 0.3244 0.3210 0.2566 0.2400
0.1562 0,0953 0.1148 0.2317 0,2231 0.2218 0.1958 0,4033 0.3228 0.3891 0.3642 0.3135 0.2889
0.1927 0.1143 0.1377 0.2528 0.2434 0.2552 0.2219 0.4467 0.3442 0.4317 0.4228 0.3179 0.2930
0.2494 0,1329 0.1601 0,2715 0.2587 0.3030 0,2635 0.5230 0.3964 0.5013 0.4843 0.3780 0.3377
0.3091 0.1567 0.1888 0.2839 0.2730 0.3662 0,3264 0.6050 0.4379 0.5289 0.5164
0.3545 0.1828 0.2202 0.2977 0.2908 0,4107 0.3572 0.6763 0.4866 0.6306 0.6015
0.4077 0,2089 0.2517 0.3340 0.3216 0.4535 0.3928 0.7234 0.5020 0.6588 0.6378
0.4508 0,2374 0.2860 0.4614 0,4439 0.4948 0.4273 0,7413 0.6880
0,5326 0.2706 0.3260 0,4937 0,4842 0.5412 0.4652 0,7725 0.7466
0.6091 0.3062 0.3689 0.5538 0.5459 0.5730 0.4902
0.6317 0.3098 0.3733 0.6037 0.5815 0.6111 0.5175
0.6809 0.3264 0.3933 0.6681 0.6527 0.6615 0.5720
0.7672 0.3610 0.4349 0.7022 0.6836 0.6870 0.5934
0.7661 0.3691 0,4447 0.7779 0.6551
-p-Chlorophenol- --o-Cresol- -m-Cresol- ,----3,4-Xylenol---- ------3,6-Xylen01----~
CA co CA co CA co CA co CA co
0.0480 0,0463 0.0635 0.0570 0.0315 0.0368 0.0754 0.0697 0.0438 0.0418
0.0958 0.0950 0.0735 0.0636 0,0711 0.0653 0.1142 0.0963 0.0581 0.0558
0.1485 0.1389 0.1239 0.1128 0,1391 0.1222 0.1470 0.1284 0.0881 0,0809
0.1835 0.1721 0 1437
I 0.1306 0,1796 0.1531 0.2150 0.1842 0.1128 0.0990
0.2247 0.2160 0.2109 0.1899 0.2041 0.1721 0.3100 0,2540 0.1644 0.1437
0.2642 0.2492 0.2776 0.2469 0.2463 0.2018 0.3415 0.2749 0.2283 0.1967
0.3386 0.3086 0.2883 0.2587 0.2800 0.2279 0 3946
I 0.3098 0.2593 0,2233
0.3567 0.3204 0.3381 0.2955 0.3104 0,2492 0.4566 0,3489 0.3171 0.2651
0.4123 0,3537 0.3910 0.3442 0,3428 0.2730 0.5079 0.3768 0.3445 0.2791
0.4400 0.3869 0.4567 0.3988 0.3836 0.3026 0.5617 0,4061 0.3937 0.3182
0.5273 0,4356 0.4853 0.4178 0.4310 0,3323 0.6077 0.4312 0.4215 0.3307
0.6431 0.5222 0.5627 0.4795 0.4932 0.3679 0.6582 0.4605 0.4808 0.3726
0.7100 0,5887 0.6330 0.5329 0.5427 0.4023 0.6963 0.4745 0.5238 0,3935
0.7443 0.6005 0.6591 0.5554 0.6012 0,4320 0.7888 0.5191 0.5711 0.4187
0.7031 0.5839 0.6708 0.4724 0.7998 0.5219 0.6405 0.4605
0 7512
I 0.6231 0.7014 0.4866 0.9410 0,5861 0.7616 0.5164
0.7646 0,5246
0.8120 0.5519

ciated phenolic species much more than was originally
believed.
Initial theories t o explain the hydrogen bond used a
purely electrostatic approach; these have been shown to
be less than completely adequate.1° However, an
electrostatic parameter might be quite successful to
predict trends of associative behavior within a group
of chemically similar compounds, especially if one par-
ticular compound can be selected as an arbitrary refer-
ence. A logical choice for such a reference compound
among the compounds reported in this work might be
the unsubstituted basis compound, phenol. Phenol is
the most associated of all the compounds investigated,
exhibiting a cryoscopic behavior quite similar to that pf
the carboxylic acids. Properties of phenol such as
the dielectric constant, dipole moment, aqueous pK,,
and absorption spectra are not dissimilar to that of the
substituted phenols. This study indicates that addition
of a substituent to phenol lowers the degree of associa-
tion, analogous to the cryoscopic behavior of benzoic
acid and its substituted analogs; benzoic acid is also
the most highly associated. lo For these reasons,
phenol cannot be taken as a reference point.
For the compounds investigated in this study, the
methyl derivatives are more highly associated than the
corresponding chloro compounds. From the extent of
association of the cresols, as well as that of the chloro
substituted compounds, one is led to the conclusion that

The Journal of Physical Chemistry

ASSOCIATION
OF PHENOLIC
COMPOUNDS
IN BENZENE
charge density of the carbon atoms ortho to the hy-
droxyl group is qualitatively related to the extent of
association; increasing this charge density leads to the
increasing association while decreasing the charge
density leads to the opposite effect, on a relative basis.
The order of decreasing association for an ortho-para
directing substituent would then be meta, para, ortho.
For a substituent that directs meta, the order would be
para, ortho, meta. The low extent of association of the
ortho isomers has been attributed to steric effect^;^'-^^
recent work, however, indicates the effect may be pri-
marily a resonance or electrical one.as In either case,
the degree of association for ortho-substituted phenols
is less than would be predicted on the basis of associa-
tion exhibited by meta and para isomers.
Greater complexity is observed with the dimethyl
phenols. If the above assumption is correct and the
effects are additive, a dimeta (3,4-) substitution should
show the highest extent of association followed in order
of decreasing association by meta-para (3,4-) , ortho-meta
(2,5-, then 2,3-), orthopara (2,4-) and the least asso-
ciated should be the ortho-ortho compound (2,6-). Fur-
thermore, one would expect the 3,5-isomer to be slightly
more associated than the meta compound, the 3,4-
isomer slightly more than the para compound, and the
2,3- and 2,5-isomers to both be more associated than
the ortho compound. The 2,6-isomer should show a
1741
small extent of association. On this basis, one would
expect phenol to exhibit an association intermediate to
the chloro and methyl substituted phenols. Clearly,
phenol is more highly associated than either. T h e
effects of solid solution formation upon observed cryo-
scopic data are large and thus a relatively small error
in the determination of the distribution coefficient, k ,
can markedly influence the data. However, a distri-
bution coefficient considerably greater than that re-
ported here would be necessary to yield the expected
behavior.
The general trends predicted above are shown by the
data in Table IV with the sole exception of the reversal
of the expected behavior of the meta and para isomers
of chlorophenol. Calculations are now in progress
to evaluate the net charge densities of the carbon atoms
ortho to the hydroxyl group; these might help to place
the above observations on a more quantitative basis
and, hopefully, help explain the anomaly noted in the
two isomers of chIoropheno1.
Acknowledgment. This work was supported by the
United States Atomic Energy Commission.
(32) M.Davies, Trans. Faraday floc., 36, 333 (1940).
(33) M. Davies, ibid., 34, 410 (1938).
(34) M.Davies, ibid., 34, 1427 (1938).
(35) M.Charton and B. I. Charton, J. Org. Chem., 33, 3872 (1988).
Volume 74,Number 8 April 16, 1070