DECEMBER.

1941 JOURNAL OF CHEM1CAL PHVS1CS VOLUME 9

The Entropy of Acetic Acid

J. O. HALFORDl
Department of Chemistry, University of Michigan, Ann Arbor, Michigan
(Received August 8, 1941)

From third law measurements, vapor pressures and vapor densities, the entropy of the
acetic acid monomer at 25° and one atmosphere is 69.4±1.0 e.u. The value 68.7 is calculated
from the vapor phase ethyl acetate equilibrium. For a model based upon acetone and approxi-
mately representing free rotation the entropy would be 72.7. If there is only a single potential
minimum in the hydroxyl group rotational cycle, the large deficiency below the free rotation
value is explained without assuming an exceptionally high potential barrier. A brief discussion
of the effect of the number of potential minima and their relative depth is appended, and a
possible source of error in third law measurements is suggested.

T HE entropy of the acetic acid monomer as a

hypothetical perfect gas can be calculated
concluded that the entropy of dissociation of the
dimer could not be evaluated from equilibrium
from the third law entropy of the liquid and the data within several entropy units. This uncer-
heat of vaporization with the aid of the constants tainty would of course be carried in some measure
of the reaction into the entropy of each component. The acetic
acid case appears to be more favorable.
Since the publication by MacDougalP of vapor
This procedure or its equivalent is made neces- densities measured at low pressures near room
sary by the wide deviations of acetic acid vapor temperature, it is possible to evaluate the heat of
from perfect gas behavior. The significance and reaction 1 and the composition of the mixture as
accuracy of the result depend upon the complete- a function of temperature with a high probable
ness with which existing vapor density data may accuracy; From MacDougall's results and those
be used to describe the vapor as a mixture of two of Fenton and Garner,4 the heat of dissociation
perfect gases in equilibrium according to Eq. (1). of the dimer becomes
Although it is reasonable to suppose that at iow
~H=18,853-9.76T (2)
pressures this description should be valid, accu-
rate vapor densities at anyone temperature are and, for the dissociation constant,
not available over a wide enough range of pres-
log k = 25.732 -4120jT -4.910 log T. (3)
sures to establish the point by experiment. Conse-
quently the entropy requires support from other Constants calculated by Eq. (3) show an average
sources. The calculation has therefore been made deviation of 2.0 percent from MacDougall's mean
at a series of temperatures from 25 to 100° and an values. If his point at 25° is left out the deviation
average value of the heat capacity between these decreases to 0.8 percent. Similarly average con-
temperatures has been derived and shown to lie stants from the Fenton and Garner data are re-
between the heat capacities of the related sub- produced with a mean deviation of 1.0 percent, or
stances ethyl alcohol and acetone. As a further
TABLE I. Vaporization and association of acetic acid.
and more direct confirmation an independent
value of the entropy is derived from the results of TEMP. flH k (DIS.) P flH
a recent study of the vapor phase ethyl acetate DEG.C DIS. MM MM YAP.

equilibrium. 25 15,944 0.578 15.63 0.0957 10,874

40 15,797 2.080 34.72 .1215 11,011
In a similar study of the nitrogen dioxide- 60 15,602 9.48 88.96 .1611 11,236
nitrogen tetroxide case Giauque and Kemp2 80 15,407 35.8 202.4 .2058 11,497
100 15,212 115.1 417.2 .2540 11,779
1 The author is indebted to Dr. Donald Brundage for
making preliminary calculations.
2 W. F. Giauque and J. D. Kemp, J. Chern. Phys. 6, 41 3 MacDougall, J. Am. Chern. Soc. 58, 2585 (1936).
(1938). 4 Fenton and Garner, J. Chern. Soc. p. 694 (1930).
859
860 JOSEPH O. HALFORD

TABLE II. Entropy of the acetic acid monomer. reliable, however, because they are based upon
low pressures measured over a range of only 20°.
TEMP. S (60 R LN SI
DEG.C G LIQ.) aHI aHI/T PI 760/PI GAS If gas imperfections have been adequately ac-
2.1 38.2" 12,646 42.4' 2.73 1 11.2 3 69.3' counted for in the factor 1 +a, the heats of
40 39.6 7 12,445 39.7" 7.524 9.P 70.24 vaporization derived from Eq. (5) should not be
60 41.5' 12,162 36.5 1 24.6' 6.8 1 71.2'
80 43.45 11,867 33.61 69.0 8 4.77 72.2' in error by more than 100 calories.
100 45.28 11,564 30.9' 169.0 2.9' 73.2' The entropies of vaporization of the monomer
and dimer are most readily obtained with the aid
of individual heats of vaporization calculated
0.3 percent at three of their four temperatures. from the equations
Results obtained by Drucker and Ullmann" at
three temperatures from 80 to 110° are on the MIl (vap.) =t:.H (vap.)/2
average 5 percent above the constants given by +(1-a)t:.H(dis.)/2 (6)
Eq. (3). If the weight at higher temperatures and
were given to the Drucker and Ullmann results it t:.Hz (vap.) =t:.H (vap.) -at:.H (dis.). (7)
would be impossible to bring Eqs. (2) and (3) into
line with the remaining data without an unrea- For 60 grams of liquid the entropy at 25° is 38.2
sonably large t:.Cp term expressed in greater according to Parks, Kelley and Huffman. 8 The
detail. The heat of dissociation according to Eq. added liquid entropy for higher temperatures is
(2) is 15,944 cal. at 25° as compared with calculated from the heat capacity given in the
16,400±800 obtained by MacDougall from his International Critical Tables. 9 After conversion to
own data alone. Since it seems apparent that his calories this becomes Cp = 12.9+0.056T in the
equilibrium constant at 25° is low, and his mean appropriate temperature range. The results of the
heat of reaction therefore high, the correct value entropy calculation are shown in Table II for the
should lie within the lower half of his range of monomer and in Table III for the dimer.
uncertainty. Equation (2) gives heats of dissoci- The mean heat capacity of the monomer and
ation within these limits up to 60°. dimer vapors is now derived from the entropy by
The heat of vaporization is evaluated from the means of the equation dS/dT= Cp/T. For the
vapor pressures in the International Critical monomer, Cp is 17.4 and for the dimer it is 44.1.
Tables,6 which are reproduced with an average Because of structural similarity it is reasonable to
deviation of 0.1 percent from 20 to 100° by the assume that the monomer value should be near
equation the mean of the heat capacities of ethyl alcohol
and acetone. From Table IV these are, respec-
logp=18.8302-2630/T-3.562 log T. (4)
tively, 16.8 and 19.9 at the mean temperature of
For the vaporization of 120 grams of the acid 62°. For reaction 1, t:.Cp is - 9.3 as compared
with -9.76 shown in Eq. (2). This discrepancy
t:.H=(1+a)(12035-7.08T). (5)
is probably due to an oversimplification of Eq.
Table I contains the heat of dissociation, the (5), for which the true heat capacity, there repre-
degree of dissociation a, the dissociation constant, sented as -7.08(I+a), should have the more
the vapor pressure and the heat of vaporization
calculated from the above equations at five TABLE III. Entropy of the acetic acid dimer.
temperatures. The heats of vaporization listed in
TEMP. R LN S,
the International Critical Tables 7 and marked as DEG.C aH, aH2/T p, 760/p, GAS

questionable are as much as 320 cal. lower than 25 9349 31.3" 12.90 8.1 " 99.6 6
those appearing in Table I. MacDougall's values, 40 9092 29.04 27.20 6.6' 101.76
60 8722 26.1' 64.27 4.91 104.4"
11,000 at 25° and 11,270 at 40° are corre- 80 8326 23.5 8 133.3 3.46 107.03
spondingly high. They cannot be taken as more 100 7916 21.2' 248.2 2.2' 109.5"

"Drucker and Ullmann, Zeits. f. physik. Chemie 74,

567 (1910). 8 Parks, Kelley and Huffman. J. Am. Chern. Soc. 51,
6 Vol. 3, p. 218. 1969 (1929).
7 Vol. 5, p. 138. 9 Vol. 5, p. 114.
 THE ENTROPY OF ACETIC ACID 861

detailed form TABLE V. Entropy of ethyl alcohol, ethyl

acetate and acetone at 25°.
~Cp= 2aCp1 +(1- a)Cp2
+~H (dis.) da/dT - 2Cp(1). (8) S t;,H p S
GAS
LIQ. VAP. :\IM

Since the discrepancy involves only a fraction of Ethyl Alcohol 38.4 10,125 58.6 67.3
Ethyl Acetate 62.0 8,596 93.3 86.7
an entropy unit, the second approximation re- Acetone 47.8 7,488 229.2 70.6
quired to produce consistency would not be
justified by the data used.
The above calculation using individual heats of mean temperature dependence of ethyl alcohol
vaporization is different in form from the method and acetone and the constant term is set to give
outlined by Giauque and Kemp.2 Their approach the value 17.4 at 62° consistent with the entropy
leads to two equations, the one expressing the calculation. The experimental entropy of reaction
two unknowns in terms of the entropy of dissoci- 9 is assumed to be correct at the mean tempera-
ation of the dimer, the other relating them to the ture of 135° and the entropy of esterification is
entropy of the mixture and the entropy of mixing. calculated with the aid of the above heat
The t\'iO methods can readily be shown to be capacities to be -4.2 at 25°. There is no good
equivalent, either by algebraic proof or by basis for estimating the probable error of this
numerical substitution. value.
If the entropy calculation is made from The entropy of water vapor at 25° and one
MacDougall's3 data alone the results for SI and atmosphere is taken as 45.10. 11 ,12 For ethyl
S2 at 25° are 70.3 and 100.0, which represent alcohol, ethyl acetate and acetone the required
practical maximum values and show that the quantities are summarized in Table V. In the
entropies are not highly sensitive to the interpre- order given the liquid entropies are those of
tation of the data. Kelley,!3 Parks, Huffman and Barmore,14 and
A further estimate of the monomer entropy can Parks, Kelley and Huffman. 8 Both the vapor
be made from the result of a recent study of the pressure and the heat of vaporization of the
vapor phase ethyl acetate equilibrium by Halford alcohol are values published by Fiock, Ginnings
and Brundage. lo For the reaction and Holton. 15 Other vapor pressures come from
the International Critical Tables, 6 and the heats of
CH 3COOH (g) + C 2H 50H (g)
vaporization are taken from the vapor pressure
= CH 3COOC 2H 5 (g)+H 20(g), (9)
curves and corrected by means of the equation
the minimum mean value of the entropy reason- PV=RT(l-aP), for which a is evaluated from
ably derivable from existing equilibrium data the Mathews l6 heats of vaporization at the
between 40 and 230° is - 3.3 units. To derive the respective boiling points. The similarly derived
value at 25° requires knowledge of the heat value for the alcohol is 10,150 or 10,195 cal.,
capacities of the reactants. Table IV shows esti- according to whether the Fiock, Ginnings and
mated values together with references to the data Holton heat of vaporization or that of Mathews
upon which they are based. In the absence of is taken as correct at the boiling point.
direct data, acetic acid is assumed to have the From the entropy of esterification and the
TABLE IV. Heat capacity of gases, 25 to 150°, Cp=A+BT. results in Table V the entropy of acetic acid at
25° and one atmosphere is estimated to be 68.7.
A B REFERENCES Although this estimate in itself is subject to
H 2O 7.47 0.0017 (a) considerable error, it nevertheless contributes
C 2H.OH 3.4 .040 (b)
CH,COOC 2 H. 8.9 .060 (b), (c) A. R. Gordon, J. Chern. Phys. 2, 65 (1934).
11
CH,COOH 5.1 .037 Estimate Giauque and Stout, J. Am. Chern. Soc. 58,1144 (1936);
12
CH,COCH 3 8.5 .034 (b), (c) Giauque and Archibald, J. Am. Chern. Soc. 59, 561 (1937).
13 Kelley, J. Am. Chern. Soc. 51, 779 (1929).
a A. R. Gordon. J. Chern. Phys. 2, 65 (1934). 14 Parks, Huffman and Barmore, J. Am. Chern. Soc. 55,
b Bennewitz and Rossner, Zeits. f. physik. Chernie B39, 134 (1938). 2733 (1933).
C International Critical Tables. Vol. 5, p. 79. 15 Fiock, Ginnings and Holton, J. Research Nat. Bur.
Stand. 6, 892 (1931).
10 J. O. Halford and D. Brundage, in press. 16 Mathews, J. Am. Chern: Soc. 48,572 (1926).
862 JOSEPH O. HALFORD

TABLE VI. Acetic acid entropy from the entropy of acetone. Table VI is the entropy which acetic acid would
have if the substitution of the hydroxyl group for
ACETONE ACETIC ACID
a methyl group produced the same changes in all
M 58.08 60.05 three molecules, ethane, propane and acetone.
ABC 1.48 1.20, 1.23
IT 18 .) In calculating the external moment product
[eR, 0.0527 0.0527 ABC and the moments of inertia Iof the internal
lOR 0.0131
5(vih.) 2.± 2.4 rotators, all angles between single bonds were
5 298 70.6 72.7 assigned the tetrahedral value, and interatomic
distances were taken as C-C= 1.54A, c-h= 1.09,
c-o= 1.43, c=o = 1.24 and o-h=0.97. For
strongly to the high probability already estab-
acetic acid the two tabulated moment products
lished that the entropy of the acid monomer lies
were calculated for models with the acid hydro-
within the limits 69.4± 1.0.
gen in the cis- and trans-positions relative to the
For comparison, a theoretical value is calcu-
carbonyl oxygen. The hydroxyl group was
lated from the entropy of acetone with the aid of
assumed to rotate as if its center of gravity were
the equation
on the C-O bond.
5 298 =23.730+(3/2)R In M+8.712n It appears from the above results that re-
+(1/2)R In (AaBb . .. Go) -R In 0+5 (vib.) (10) stricted rotation of the acid hydroxyl group
causes an entropy decrease below the free rotation
in which M is the molecular weight in grams, A, value which exceeds the corresponding effect in
B, etc., are moments of inertia, external and in- methyl or ethyl alcohol by nearly three units.
ternal, in c.g.s. units times 1038 , a+b+· .. +g=n This large deficiency can be readily explained in
is the number of rotational degrees of freedom a way that indicates that the experimental
and IT is the symmetry number. Equation (10), entropy of 69.4 is not far from correct. It is
for the entropy with free internal rotation, differs reasonable to assume that in the entire rotational
only negligibly from the theoretically correct
cycle there is only a single potential minimum of
form derived by KasselY It is assumed in its
sufficient depth to trap the hydroxyl group. For
application to acetic acid that the hydroxyl
such a model, with vibration restricted to the
group may be described closely enough as a
ground state, the entropy would be 68.3 plus a
symmetrical internal rotator. The vibrational
small increment entering through the use of the
entropy of acetone is derived from the total
acetone vibrational entropy. The experimental
entropy in Table V by the use of the above
value thus allows 1.1 e.u. to be divided between
equation, and should therefore be low by an
this increment and the actual entropy of the
amount representing the restriction of internal
rotation. For acetone the restricting barrier is torsional motion.
probably small,18 corresponding almost to free Although Pitzer'sl9 method of finding the
restricting potential barrier was developed for n
rotation. Acetic acid is then assumed to have the
same vibrational entropy, and its total entropy, equal sinusoidal potential valleys each covering
shown in Table VI, should therefore be only a one nth of the cycle, his table can be used for the
little lower than the free rotation value. single minimum model postulated for acetic acid.
This approach, rather than the customary one The case is similar to his treatment of the
involving a questionable independent estimate of individual forms of n-butane. 2o It is assumed that
the vibrational contribution, is of special interest the single minimum occupies one-third of the
because it can be used to calculate the entropy of cycle. For an imaginary model with two more
methyl alcohol from that of ethane or of ethyl minima equal in depth to the first the entropy
alcohol from propane within a small fraction of would be 69.4 plus a mixing term R In 3, giving
an entropy unit. Consequently the result of 5 j -5= 1.1 for use in the table. The resulting
potential barrier is about 3000 cal., a value which
17 L. S. Kassel, ]. Chern. Phys. 4, 276 (1936).
18 S. C. Schumann and ]. G. Aston, J. Chern. Phys 6 19 K. S. Pitzer,]. Chern. Phys. 5, 469 (1937).
485 (1938). . ' . , 20 K. S. Pitzer, ]. Chern. Phys. 5, 473 (1937).
 SEC 0 N D VI R IAL C 0 E F F I C lEN T S 0 F POL A R GAS M I X T U RES 863

is subject to an error, probably negligible, because R In 3 should be added to the experimental

the table applies only when the rotational states entropy before the barrier is estimated. If the
are symmetrically disturbed in n regions of the correction is not made the barrier will be high.
cycle, rather than unsymmetrically as they would An interesting possibility occurs for substances
be in the single minimum case. which have stable torsional vibrations resulting
In general, for the hydroxyl group in torsional in optically isomeric configurations. The mole-
motion against an unsymmetrical radical, it will cules might remain asymmetric after crystal-
be necessary to add a mixing term to the experi- lization and might produce crystals of the
mental entropy before a potential barrier can be racemic compound type which would remain
estimated by means of Pitzer's table or the unchanged upon cooling toward the absolute
equivalent functions. This term has a maximum zero. Consequently the entropy at the absolute
value R In n, but may be near zero if the potential zero would not be zero but R In 2, and the third
valleys approach equality in depth. With ethyl law entropy would be in error by this amount.
alcohol, for example, there are probably three How probable this situation is depends upon the
minima of which two are equal but different from relative magnitude of intramolecular and inter-
the third, and a mixing term between zero and molecular forces in the solid state.

DECEMBER, 1941 JOURNAL OF CHEMICAL PHYSICS VOLUME 9

Second Virial Coefficients of Polar Gas Mixturest

W. H. STOCKMAYER*
Research Laboratory of Physical Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts
(Received October 15, 1941)

An empirical equation used by Keyes to represent the second virial coefficients of several
polar gases is compared to a theoretical expression for the same quantity. The constants
appearing in this equation are discussed in terms of intermolecular forces, and their relationship
to analogous constants in the Beattie-Bridgeman equation for non-polar gases is examined.
These considerations permit the construction of simple rules by means of which the second
virial coefficient of any gas mixture may be calculated if the second virial coefficients and
dipole moments of the pure component gases are known. The success of these rules is demon-
strated by comparison with data on H 20-C0 2 , N 2 -NH 3 , and N 2 -H 20 systems. In the case
of N 2 -H 20 mixtures (vapor-liquid equilibrium data) the agreement is not satisfactory at
the higher temperatures. A rough method of including the effect of higher virial coefficients
reduces, but does not remove, this discrepancy.

INTRODUCTION absent from all these calculations is steam, for

the reason that the experimental p - V - T data 3
T HE Beattie-Bridgeman equation of state
for gas mixtures! has been applied success- cannot be adequately represented by an equation
of the Beattie-Bridgeman form. The curvature
fully not only to the calculation of the compres-
sibility of many gas mixtures, but also to the of the isometric lines for steam is so great that
correlation of several types of high pressure the ordinary Beattie-Bridgeman function is
equilibrium data. 2 A substance conspicuously unsatisfactory. Theoretically this great curvature
may be shown to be a direct consequence of the
t Contribution from the Research Laboratory of Physical nature of the forces between highly polar mole-
Chemistry, Massachusetts Institute of Technology, No. 483.
* Present address, Department of Chemistry, Columbia
University, New York. given. See especially Gillespie, J. Am. Chern. Soc. 47.
1 J. A. Beattie, J. Am. Chern. Soc. 51, 19 (1929); J. A. 305 and 3106 (1925); Gillespie and Beattie. Phys. Rev.
Beattie and S. Ikehara, Proc. Am. Acad. 64, 127 (1930). 36, 743, 1008 (1930).
2 L. J. Gillespie, Chern. Rev. 18, 359 (1936), where a 3 F. G. Keyes, L. B. Smith. and H. T. Gerry. Proc. Am.
complete list of references to important earlier work is Acad. 70, 319 (1936).