Spectrochimica Acta, 1960, VoL 16, pp. 1382 to 1392. Pergamon Press Ltd.

Printed in Northern Ireland

The vibrational spectra of phenol and phenol-OD

J. C. EVANS
Chemical Physics Research Laboratory
The Dow Chemical Company, Midland, Michigan

(Received 27 June 1960)

Abstract-Raman spectra (liquid phase) with depolarization measurements and infrared spectra
(vapor, solution, liquid and solid phases) in the 300~3800 cm-I region are reported for phenol
and phenol-OD. A complete vibrational assignment for phenol is presented and a value of
3·37 kcaljmole has been determined for the barrier to internal rotation about the C-O bond.
Thermodynamic functions for phenol as an ideal vapor at 1 atm pressure have been calculated.

Introduction
ALTHOUGH the infrared and Raman spectra of phenol have received considerable
attention a complete vibrational assignment is not available. KOHLRAUSOH and
WITTEK [1] studied the Raman spectrum and assigned most of the observed bands.
In the infrared, published data are confined to the region above 600 cm". DAVIES
[2] has made a study of the spectral changes produced by changes in the degree of
association while more recently DAVIES and JONES [3] and MEOKE and ROSSMY
[4] have reported infrared data for phenol-OD. Earlier studies are referred to in
these papers. In the present study, which was mainly concerned with obtaining a
complete assignment for the purpose of calculating thermodynamic data for the
ideal vapor, the infrared and Raman spectra of phenol and its deuterated analog,
phenol-OD, were examined.
Experimental
Fractionally distilled phenol (Dow) was used. Phenol-OD was prepared by
successive exchanges with DzO.
Infrared spectra of both molecules in the vapor, liquid and solid phases and in
solution in C01 4 , CSz and n-hexane were recorded. In the 3800-450 em>' region an
automatic-recording, double-beam, prism-grating instrument designed and con-
structed in this laboratory was used [5], while between 450-300 cm-I a Perkin-
Elmer double-pass OsBr-prism instrument was used. Vapor spectra were obtained
with heated cells, 10 em long with the first instrument and 5 em long with the
second.
Raman spectra of the liquids were recorded with a Hilger photoelectric
instrument (7Ajmm) using 4358 A excitation. The samples were maintained at
about 50°C. Depolarization measurements were made [6] and the observed values
were corrected [7].
[1] K. W. F. KOHLRAUSCH and H. WITTEK, Monateh, Ohern. 74, 1 (1941).
[2] M. M. DAVIES, J. Ohem. Phys. 16, 274 (1948).
[3] M. M. DAVIES and R. L. JONES, J. Ohern. Soc. 120 (1954).
[4] R. MECKE and G. ROSSMY, Z. Elektrochem. 59, 866 (1955).
[5] L. W. HERSCHER, Spectrochim. Acta 15, 901 (1959).
[6] J. T. EDSALL and E. B. WILSON, JR., J. Ohern. Phys. 6, 124 (1938).
[7] D. H. RANK and R. E. KAGARISE, J. Opt. Soc. Am. 40, 89 (1950).

1382
 The vibrational spectra of phenol and phenol-Of)

Fig. l(a). Infrared absorption spectrum of phenol vapor. Vapor pressures used were not
determined but are estimated to be of the order of 20 mm. Heated cells were used; 10 em
long to 4.50 cm :? and .5 em long between 4.50-300 cm "! •

. . -----, .-----~

01
""'\'1"(
I: 1 \

I
\

',', \ I .. ~\

0.2 :i
i'
II
1'1 ,
I,
I
I"I
0.3 II I, \:
I' "
j
" \1
'I
II
~
300

Fig. 1(b). Infrared absorption spectra of phenol; full line is the spectrum of a thin film of
liquid phenol at approximately .50°0; the dotted lines are solution spectra: (1) 0·0.5 molar
solution in 001 4 in 1·1 mm cell; (2) same as (1); (3) 0·01 molal' solution in CS2 in 1·1 mm
cell; (4) 0·13 molar solution in n-hexane in 2 mm cell.

Fig. 1(c). Infrared absorption spectrum of a solid film of phenol.

Results
The infrared spectra are reproduced in Fig. 1 and 2 while the data are tabulated
in Tables 1 and 2. The Raman data for phenol are in good agreement with the
published data [1] and differ only in some of the very weak bands; no published
data could be found for phenol-Of). The infrared data above 650 cm-1 for solution
and liquid phases did not differ significantly from published data [2,4]. Vapor

1383
 J. C. EVANS

phase infrared data obtained during this study were measured under better
resolution (ca. 1 em-I) than was available to earlier investigators [8].

Discussion
In the absence of published structural data, either electron diffraction or
microwave, the equilibrium configuration of the free phenol molecule is not known.
The indirect evidence available suggests that the configuration is a planar one.
WHELAND [9] discusses the significance of the resonance energy value derived for

"r-r
300

phenol from heat of combustion data, and concludes that the data are consistent
with, but do not prove, the view that quinoid structures contribute to the ground
state of the molecule. Some experimental support for this view may be drawn
from the X-ray structural data obtained for several phenolic compounds-phenol
itself has not been studied [10]. The C-O bond length is about 1·36 A which is
some 0·07 A shorter than the C-O bond in aliphatic alcohols. Part of this differ-
ence is accounted for by the decreased effective radius of the carbon atom due to
its changed hybridization from Sp3 to Sp2, but some degree of electron delocalization
across the C-O bond is indicated. This increase in double bond character is
expected to favor a completely planar equilibrium configuration.
During this study, evidence in support of the planar model was derived from
two sources: from the value of the height of the barrier hindering internal rotation
about the C-O bond and from the shapes of the vapor infrared absorption bands
of the stretching and bending modes of the COR and COD groups. The barrier
height was found to be 3·37 kcaljmole which indicates considerable electron
delocalization across the CO bond.
BADGER and ZUMWALT'S [11] calculations allow us to predict that, for phenol,
vibrational modes which have their dipole moment change in a direction per-
pendicular to the plane of the phenyl ring will yield infrared absorption bands with
a very strong central Q-branch (type-C bands). Reference to Figs. 1 and 2 show

[8] V. WILLIAMS, R. HOFSTADTER and R. C. HERMAN, J. Chern; Phys. 7, 802 (1939).

[9] G. W. WHELAND, Resonance in Organic Chemistry p. 106. John Wiley, New York (1955).
[10] Interatomic Distances. Special Publication No. 11, Chemical Society, London (1958).
[11] R. M. BADGER and L. R. ZUMWALT, J. Chem, Phys. 6, 711 (1938).

1384
 The vibrational spect ra of phen ol and phenol-OD

Table 1. Vibrational data fOI' phenol

I
Infrared Raman (liquid)
Assignmen t a nd
approx. d escr ipti on
Vapor Solution Liquid Solid cm- I
1 n.R
- - - - - - - -- - --
3661)
3653 i 3610 Monomer
3648 3500 3500sh 3500b 5 en d -group
) OR
stretch
3350 3350V8, b 3225 ~33 50 3 polymer
3190 5 1603 + 1598 s,
310 5 3103w 1608 + 1502 Al
3090w 3090 (2 x 1228) + 650
3098 1600 + 1502 B I
3090 3090w 3088 1600 + 1473 Al
3078 3074 3070w 3070sh CH stret ch bl
3061 165 P CH stretch a l
3052 3050sh CH stretch bl
3050 3046 3044m 3043 CH stre t ch bl
3021 3020w 3019 3023 CH stretch al
2925 2955w 2955 1362 + 1597
2835w 2830 1362 + 1473 or 1228 + 1604
2714w 2714 2 x 1362
2590w 2592 1362 + 1228
25 10 25 10 1344 + 1179
2470w 2475 2 x 1228
2432 1259 + 1179
2410 2410w 2410 1600 + 814 Al
2065 2050w 2050 1259 + 814 Al
1931 1944 1952 2 x 972 Al
1918 1923 1930w 1932 958 + 973 B 1
1855 1865 973 + 883 B 1
1830 1835 1843w 1848 958 + 883 B I
1765 1768 1772w 1775 829 + 958 Al
1690 1696 1705w 1710 829 + 883 B1
1608 1604s 1605 1603
28 } n ring stretch a 1
1608) 1600 1597v s 1598 1595 33 ring stretch b1
1602
1555 1555vw 1558 753 + 814 B 2
1531 1528vw 1531 691 + 829 e,
1507}
1501 1502 1500vs 1501 1500 4 r ing stret ch al
1493
11470
478} 1473 1474v s 1473 1471 3 ring stretch bl
1462
1388 1388vw 1388 138 1 1 416 + 972 Al
1362m 1370 Polymer ) ring stretch
1349) 1343w end group with d OB:
1343 1344 monomer character
1335
1332 1332sh 1332 814 + 530 Al
1320 1312 1313vw 1314 416 + 883 B l
1290 1292vvw 1292 CR bend b1

13 85
 J. C. EVANS

Table l-(contd.)

Infrared Raman (liquid)

Assignment and
approx. description
Vapor I Solution Liquid Solid cm~I 1 D.R
---.

1268)
1260 1259 1252 1253 14 0.1 7 X-sensitive a l
1253
1228vs 1230 ~1220b ~4) P Polymer ) <5 OH with
1198sh 1196 ~4 end group ring stretch
monomer character
1182)
1177 1179
1168
1167 1168w 1169 1170 17 D CH bend a I
1158)
1150 1151 1152w 1152 1155 13 D CH bend bl
1142
1107 1108 691 + 416 bI
1072 1070 1072m 1072 1072 4 D CH bend bI
1032)
1026 1026 1025w 1024 1024 47 0.1 5 CH bend a I
1018
1014sh 2 x 509 Al
1000 100 0.1 5 ring breathing a l
988 4 CI3 mol.
972 978vvw (981 CH bend b2
974
958 958vvw 962 CH bend a 2
881(0) 883 888w (888 890 CH bend b2
882
823(0) 829 828w 828 828 10 CH bend a 2
814 814 812s 812 814 50 0.2 0 X-sensitive a l
750(0) 753 752vs 754 755 7 D CH bend i,
686(0) 691 690vs 691 ring def. b 2
620 619 618vw 618 617 16 D ring def. bl
590} 2y(OH)
578
533}
527 530 531w 535 531 17 0·8 X-sensitive a l
518
503(0) 508 508m 507 509 3 D X-sensitive b 2
502
410b 415 415b 1 D ring def. a 2
398 I 404 455 X-sensitive bl
~306 ~300 monomer
I }YOH
!I ~650 --650vb --720b polymer
242 20 D X-sensitive b 2
I
(1) Column headed I gives the relative peak heights uncorrected for variation in spectral sensitivity.
(2) D.R = depolarization ratio, D = depolarized, P = polarized; vs = very strong; s = strong;
m = medium; w = weak; vw = very weak; vvw = very very weak; b = broad; C13 molecule refers
to the breathing mode of the molecule C5 12C ' 3 0 H .
(3) In column (1), (0) means that the band has type-O structure and the wavenumber value quoted is
that of the sharp Q-branch.

1386
 The vibrational spectra of phenol and phenol-OD

Table 2. Vibrational data for pheno1-0D

Infrared Raman (liquid)

Assignment and
I approx. description
Vapor Solution Liquid Solid cm-] I D.R

3650 3610 3350 3225 Phenol

3190 5 1600 + 1596 B]
3105 3105vvw 3105 1602 + 1498 A]
3098 3096vw 3097 1597 + 1498 B]
3085 3083vw 3082 1597 + 1478 A]
3080 3075 3072w 3075 3075 sh CH stretch b]
3062 165 P CH stretch a]
3050sh; 3045m 3049 3046 sh CH stretch b]
3050 3040 3039 CH stretch b]
3019 3020w 3020 3014 4 CH stretch a]
2885 1597 + 1303 A]
2700)
2695 2670 Monomer
2687
2586

2495
2590sh

2490vs 2415
~2590 (obscured by
Hg 4916 A)
2486vb
end group

polymer
f
I
)
v(OD)

2410 1602 -+- 808 A]

2054 2046w 2050 1249 + 808 A]
1985w 1970b 2 J (OD)
1943 1955vw 2 X 972 A]
1925 1936w 1936 958 + 972 B]
1855 1865vw 1870 972 I- 880 B]
1836 1848w 1850 880 + 958 B]
1768 1775w 1775 827 + 958 A]
1698 1706w 1710 827 + 880 B]
1602 1601vs 1602 1600 ring stretch a]
1601 38) 0'8 0
1597 1596 1597 1592sh ring stretch b]
1554vw 1555 752 I- 808 B 2
1525vw 689 + 827 B]
1506}
1501 1498 1498vs 1499 ring stretch a]
1492
1478 1478m 1490b o(OD) + y(OD) assoc.
1463 1463m 1463 ring stretch b]
1389 1391vw 1391 416 + 972 A]
1344 1368 1368 phenol
1333 1337vw 1338 808 + 522 Al
1317 1320vw 1320 416 + 880 B]
1303 1304vw 1305 ring stretch b]
1289 1290vw 1290 CH bend b]
1262)
1258
1252 1249 1241vs 1244 1251 18 0.2 0 X-sensitive a 1
1246
1177 1179 1230sh phenol

1387
 J. C. EVANS

Table 2-(contd.)

Infrared Raman (liquid)

Assignment and
approx. description
Vapor I Solution
---
I
I
Liquid l~solid cm-l I D.R

I '
I I
,
1168) 1168 1169m 1170 1169 19 0.7 0 CR bend a l
1159
1159)
1150 1151 1153w 1154 1156 11 D OR bend bl
1143
1104 1108vw 1108 689 + 416 B l
1085 1076 1078m 1078 5 D OR bend bl
1034)
1026 1026 1026w 1026 1027 48 0.1 5 CR bend a l
1018
1014sh 2 X 508 Al
1000 999 999w 999 1001 100 0.1 5 ring breathing a l
987 4 C13 mol.
970 OR bend b 2
978s 990 Polymer )
932m 935sh end group i5(OD)
monomer
923]
918 918s
915
910
962 OR bend a 2
880(0) 880 888m (889 OR bend b 2
882
827 828w 828 829 11 D? OR bend a 2
815} 0.1 5
808 808 808m 808 807 58 I X-sensitive a l
798
751(0) 752 753vs 754 753 7 D OR bend b 2
686(0) 689 690s 692 690 D ring def. b 2
618 619vw 618 617 25 D ring def. bl
I
523 I 522 528w 528 528 19 0·7 X-sensitive G l
503(0) 504 507m 506 511 5 D X-sensitive b 2
ca. 480 ca. 520b y(OD) assoc.
416 1 ring def. a 2
380 383 423 398 1 X-sensitive bl
241 21 D X-sensitive b 2

See Table 1 for key to the abbreviations used.

that this expectation is fulfilled for bands which are well known to be out-of-plane
CH bending or ring deformation modes. Planar modes should yield type-A (weak
Q-branch) or type-B (no Q-branch) or AIB hybrids. Both the OH and OD stretch-
ing modes yield bands which are best described as type A or AlB. The OD bending
mode at 918 em"! shows a similar band. The OH bending mode in the 1150-1400
cm-l region is not a simple mode; two bands exhibit the behavior, on association
change and isotopic exchange, which is expected for the OH bending mode.

1388
 The vibrational spectra of phenol and phenol-OD

MECKE and ROSSMY [4] have discussed this problem and have concluded that the
OH bending mode is strongly coupled with a ring stretching mode although the
alternatives-coupling with a CH bending mode or with an overtone or com-
bination tone-are not ruled out. If the coupling partner is a fundamental then
this is good evidence for the planar model since only planar modes can occur in
this frequency range. Both bands have structures which indicate planar dipole
moment changes so that, irrespective of the actual assignment, the evidence is
again in favor of the planar model. All five bands discussed above have a P-R
separation of 14 ± 1 em:".
The planar model was accepted as a basis for this study. The phenyl ring was
assumed to have the dimensions of the benzene ring [12], the C-O bond length was
taken to be 1·36 A, the COH angle to be 118 0 and the OH bond length was assumed
to be 0·96 A. The molecular symmetry is C, for which all thirty-three modes are
infrared and Raman active. For convenience in comparing the vibrational
assignment with those of other monosubstituted benzenes of 02V symmetry, the
species designations av bv a 2 , b2 have been appended to the last columns of Tables
1 and 2. Strictly, a l and bi should be replaced by a', and a 2 and b2 by a".
The vibrational assignments were reached on the basis of: (1) comparison
with assignments available for several mono substituted benzenes [13 , 14] ; (2) the
observed depolarization ratios of the Raman bands ; and [3] the vapor band-
envelopes of the infrared bands. Earlier partial assignments already referred to
[1, 2, 4] and the assignment of the five out-of-plane CH bending modes made by
WHIFFEN [15] were also very helpful.
Twenty-four modes may be well described as phenyl ring modes since they are
not particularly sensitive to the nature of the substituent [13]. These require no
discussion beyond a reference to Tables 1 and 2. One of these mode s, the ring
stretching mode derived from the B 2lJ mode of benzene [16] , is said by MECKE and
Rossxv to couple with the OH in-plane bending mode and this assignment, in the
absence of conflicting evidence, is accepted here.
Six modes involve considerable motion of the phenyl ring and CO group and
are described as X-sensitive modes [13] where X is OH or OD. These are at
1260(1253), 814(808), 527(523), 503(503) , 398(380), 242(241) em>' for phenol and
(phenol-O'D), One of these shows a marked change in appearance on changing the
degree of association. In dilute solution of phenol the band appears at 404 cm <
and is sharp while in the liquid a broad absorption centered near 410 cm- 1 is found;
in the solid a band at 455 cm-1 is assigned to this mode. The behavior of the
corresponding mode of the heavy molecule is similar with all bands shifted about
20 cm-I to lower wave number. This behavior is consistent with the approximate
description of the mode-mainly in-plane C-O bending. The other five X-
sensitive modes do not show large shifts on isotope exchange nor are they affected
appreciably by association changes. It should be noted that only the first statement
was checked in the case of the lowest lying mode since it is beyond the infrared
[12 ] B. STOICHEFF, Conad , J. Phys. 32, 339 (1954 ).
[13 ] D. H. WHIFFEK , J. Ohem. Soc. 1350 (1956).
[14] J . C. EVAN S , S pectrochim , A cta 16, 42 8 (1960 ).
[ 15] D. H. WHIFFEN, Spectrochim , Acta 7,253 ( 1955) .
[ 16] R. D. l\IAlli and D. F . HUl' NlG , J. Chem , Phys. 17, 1236 (1949).

8 1389
 J. C. EVANS

range studied and not amenable to study by the Raman effect in dilute solution
because of its intensity and position.
The remaining three modes are OR stretching, OH in-plane bending and the
out-of-plane OH bending or torsional mode. The OR stretching mode, v(OR), is
well known and ha s been the subject of numerous investigations related to hydrogen
bonding [17]. The OH in-plane bending mode was discussed above.
In the associated molecules, DAVIES [2] assigned the broad band in the 600-
700 om ? region to the out-of-plane bending mode, y(OH). The position of this
mode in the free molecule has not been reported. It is undoubtedly near 300 cm " !
where a strong band was observed in the infrared spectra of phenol vapor and of
dilute solutions of phenol in n-hexane. These bands are absent from the corre-
sponding spectra of the heavy molecule and from the spectra of solid and liquid
phenol. The spectra of liquid and solid phenol-OD show broad bands near 500
cm ? which are assigned to the mode y(OD).
Unfortunately the monomeric y(OR) lies at the limit of the range of the infrared
instrument so that the band center could not be determined accurately. However,
the first overtone of y(OR) was found as a well-defined band at 583 cm- 1 in the
infrared spectrum of phenol vapor; the band was absent from the spectrum of
phenol OD vapor but its new location could not be determined. No suitable
alternative assignment could be found for this band .
With this assignment, the molecular geometry described earlier and with the
assumption that the torsional mode is a pure mode not interacting with any other,
we may calculate the height V o of the barrier hindering internal rotation about
the C-O bond. The usually assumed form for such a barrier is (V o/2)(1 - cos nO)
where 0 is the torsional angle and n is the number of equivalent minima in a
complete internal rotation; n = 2 in this case. Using this potential function the
Schrodinger equation reduces to the Mathieu differential equation the eigenvalues
of which have been tabulated [18]. The reduced moment of inertia of the model
assumed is 1·19 X 10- 40 g ern 2 and the height of the barrier to internal rotation
was found to be 3·37 kcaljrnole and the fundamental torsional mode to be 307
em>'. It must be emphasized that the value of V o is rather sensitive to the geo-
metry assumed for the COH group. Thus, with the angle COH of HO°, V O becomes
3·7 kcaljrnole. Over this range V 0 varies linearly with the COR angle.
Theoretical and observed Teller-Redlich products were in good agreement for
the a' species: theoretical product 0·512; observed product 0·521. Of the a"
modes only one was observed to be affected by deuterium substitution, y(OR).
The monomeric values could not be determined but y(OD)/y(OH) using solid
phase frequencies was 0'72 3 , which is to be compared with the theoretical value of
0·726.
Association effects
Considerable work has been done on the association process of phenol [19].
Bands due to the end groups of the polymeric associated complexes have been
assigned previously [2]. Some additional assi gnments of this type were made in
[17] G. PIME:NTEL and A. L. llICCLELLAN, The Hydrog en Bond. Freeman, San Francisco (1960) .
[18] E. B. WILSON, JR., Chern. R evs. 27, 17 (1940).
[19] R. MECKE, Discussions Faraday S oc. 9, 161 (1950) .

1390
 The vibrational spectra of phenol and phenol-OD

Tables 1 and 2. Spectra of solutions with small degrees of association indicate

that the small associated complexes, perhaps dimers, absorb near the frequencies
assigned to the end groups of larger polymeric complexes. A noteworthy observa-
tion was that, while these bands appeared in the liquid-phase infrared spectra as
shoulders on the sides of the main bands, in the liquid-phase Raman spectra the
end group bands were more intense than the bands assigned to the OH bonds
within the polymeric associated complex.
A rather striking feature of the spectrum of the associated phenol molecules,
but not of the monomeric molecules, is the regular progression of bands on the
lower wavenumber side of v(OH). This was not observed for phenol-OD, only one
band being found in the expected range. The component bands of the progression
Table 3. Molal thermodynamic properties of phenol, ideal gas state

T(OK) I C'JJ° So (W - HoO)/T -(FO - HoO)/T

298·15 24·63 75·12 13·93 61·18

300 24·78 75·26 14·00 61·26
400 32·36 83·47 17·67 65·80
500 38·65 91·39 21·27 70·13
600 43·56 98·90 24·59 74·31
700 47·48 105·90 27·58 78·32
800 50·66 112·46 30·28 82·19
900 53·30 118·59 32·69 8;'),89
1000 55·54 124·32 34·87 89·45
1100 57·43 129·71 36·84 92·87
1200 59·06 134·78 38·62 96·16
1300 60·46 139·56 40·24 99·32
1400 61·67 144·08 41·73 102·35
1500 62·73 148·38 43·10 105·28
,
Units are: cal °C-I rnole- I.

are identified by arrows drawn on Fig. l(c). They are separated by 122 ± 5 crn:",
this figure including the separation between the center of v(OH) and the first band
in the series. This first band coincides with the OR stretching bands and gives the
impression that a change of relative intensities of these bands occurs as the degree
of association changes; this does not occur for phenol-OD. On cooling a film of
solid phenol to - 180°0 very little change in intensities and widths of these bands
occurred. Some small changes in position were observed-the center of v(OH)
moved to lower wavenumber by about 20 cm- I while several of the bands in the
progression moved to higher wavenumber by about 10 cm -'. The one explanation
that is compatible with the experimental data is that these bands are combination
and overtones of bands in the 1150-1600 em>' region. All are found to be explic-
able as overtones or combinations of the two o(OH) bands. Some very weak bands
in dilute solution may be explained as the corresponding monomeric bands.
The one band found for phenol-OD is 2 x o(OD).
Thermodynamic functions
These were calculated for the ideal vapor at one atmosphere pressure in the
standard manner using the harmonic-oscillator, rigid-rotator approximation.

1391
 J. C. EVANS

The moment of inertia product was 2·246 x 10-113 g36 em" and the external sym-
metry number, 1, was used. Thirty-two vibrational modes were treated in the
standard manner, while the hindered internal rotation was treated according to
PITZER and GWINN'S methods [20, 21] using the values Vo = 3·37 kcaljmole and
Ireduced = 1·19 X 10-40 g em". Calculated values are collected in Table 3.
PARKS et al. [22] have obtained a value for the entropy of solid phenol at 25°C
from heat capacity measurements in the 90-298°K range with an extrapolation
below 90 0 K . This value, combined with the vapor pressure data and heat of

Table 4. Entropy of phenol at 298·15°K (cal °C-lmole~l)

Solid 34·1 ± 0·8

Vaporization 55·1 ± 0·5
Compression -15,3
Measured for ideal gas 73·9 ± 1·3
Spectroscopic value for ideal gas 75·12

vaporization value measured by BIDDISCOMBE and MARTIN [23], enables us to

obtain a value for the entropy of the vapor at 25°C. Table 4 summarizes the data.
The agreement is not unsatisfactory in view of the uncertainties involved. We may
conclude that there is no evidence for disorder in the phenol crystal at low tem-
perature.
Note added in proof: In a recent paper T. KOJIMA [J. Phys. Soc. Japan 15,284
(1960)] has reported the results of a study of the microwave spectrum of phenol
vapor. The molecule was shown to be planar with moments of inertia almost identi-
cal with those of the model assumed here. From the observed splitting of the rota-
tionallines, a value of 3150 ± 300 caljmole was determined for the height of the
barrier to internal rotation assuming the moment of inertia of the OH group about
the 0-0 bond to be 0·80 a.m.u. A2. Until further structural studies are made it can-
not be decided whether or not this moment of inertia value is to be preferred to
that assumed in this study (0'72 a.m.u. A2). However, the two values of Vo ob-
tained are not sufficiently different to affect the thermodynamic data significantly.

[20] K. S. PITZER and W. D. GWINN, J. Chem. Phys. 10, 428 (1942).

[21] K. S. PITZER, J. Chem, Phys. 14, 239 (1946).
[22] G. S. PARKS, H. M. HUFFMAN and M. BARMORE, J. Am. Chem, Soc. 55, 2733 (1933).
[23] D. P. BIDDISCOMBE and J. F. MARTIN, Trans. Faraday Soc. 54, 1316 (1958).

1392