Thermodynamic Properties of Key Organic Oxygen Compounds in the Carbon

Range C1 to C4 Part 2. Ideal Gas Properties

Jing Chao, Kenneth R.Hall, Kenneth N. Marsh, and Randolph C. Wilhoit
Thermodynamics Research Center, Texas A&M University, College Station, Texas 77843

Received May 1, 1985; revised manuscript received June 6; 1986

The ideal gas thermodynamic properties of forty-four key organic oxygen compounds
in the carbon range C 1 to C4 have been calculated by a statistical mechanical technique.
The properties determined are the heat capacity (C; ), entropy {S' (T) - S' (O)}, enthalpy {Jr (T) - Jr (O)}, and Gibbs energy function {Go (T) - Jr (O)} IT. The calculations have been performed, in most cases, over the temperature range 0 to 1500 K and at 1
bar. The contributions to the thermodynamic properties of compounds having internal- or

pseudo-rotations have been computed by employing a partition function formed by the

summation of the internal rotational or pseudorotational energy level for each rotor in the
given molecule. These energy levels have been calculated by solving the wave equation
using appropriate barrier heights, rotational constants, and potential functions for the
given rotations. The thermodynamic properties have been calculated using a rigid-rotor.
and harmonic-oscillator molecular model for each species. The sources of molecular data
and the selection of the values used in the calculation are described. The calculated C; and

{S' (T) - SO (O)} values are compared with experimental results where appropriate.
Key words: critically evaluated data; enthalpy; entropy; gaseous organic oxygen compounds; Gibbs
energy function; heat capacity; ideal gas thermodynamic properties.

Contents
1.

Introduction .......................... .
1.1. Scope and Objectives .............. .
1.2. Statistical Mechanical Method ...... .
1.3. Internal Rotation .................. .
1.4. Hydrogen Bonding ................ .
1.5. Deuterated Analogs ............... .
1.6. Methylene Increment Method ...... .
1. 7. Presentation of Results ............. .
1.8. Uncertainty Assignment ............ .
1.8.a. Errors in RRHO
Contributions .............. .
1.8.b. Errors in Molecular Models .. .
2. Evaluation of Thermodynamic Properties ..
2.1. . Alkanols ......................... .
2.1.a. Methanol .................. .
2.1. b. Ethanol ................... .
2.1.c. I-Propanol ................ .
2.1.d 2-Propanol ................ .
2.1.c.

1371
1371
1371
1372

1374
1375
1375
1375
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1375
1376

1376
1376
1377
1379
1380

1381

I-Butanol. ................. .

1383

2.1.f. DL-2-Butanol ............. .

2.1.g. 2-Methyl-2-propanol ....... .
2.2. Alkandiols ....................... .
2.3. Ethers .......................... .
2.3.a. Dimethyl Ether ............ .
2.3.b. Dimethyl Ether-d3

1383
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1986 by the U.S. Secretary of Commerce on behalf of the .United

States. This copyright is assigned to the American Institute of Physics
and the American Chemical Society.
Reprints available fron ACS; see Reprint List at back of issue.

0047-2689/86/041369-68/$09.00

2.3.c. Dimethyl Ether-d6

2.3.d. Ethyl Methyl Ether ......... .
2.3.e. Diethyl Ether .............. .
2.4. Alkanones ........................ .
2.4.a. Propanone ................. .
2.4.b. 2-Butanone ................ .
2.5. Alkanals ......................... .
2.5.a. Methanal .................. .
2.5.b. Methanal-d1
2.5.c. Methanal-d2
2.S.d. Ethanal. ................... .
2.5.e. Ethanal-d1
2.5.f. Ethanal-d4
2.5.g. I-Propanal. ................ .
2.S.h. I-Butanal. ................. .
2.6. Alkanoic Acids ................... .
2.6.a. . Methanoic Acid Monomer ... .
2.6.b. Methanoic Acid Dimer ...... .

1369

2.7.

2.6.c.

Mcthanoic Acid Equilibrium

2.6.d.
2.6.e.
2.6.f.
2.6.g.
2.6.h.

Mixture ................... .
Methanoic Acid-d l . . .
Methanoic Acid-d l . . . . . . .
Methanoic Acid-d2
Ethanoic Acid Monomer .... .
Ethanoic Acid Dimer ....... .

2.6.i.

Ethanoic Acid Equilibrium

Mixture ................... .
Alkyl Alkanoates .................. .
2.7.a. Methyl Methanoate ................ ..
2.7.h. Methyl Ethanoate .................. ..

1388
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1370

CHAOETAL.

Epoxyalkanes ......................
2.S.a. Epoxyethane .................
2.8.b. Epoxyethane-d4 .
2.8.c. DL-I,2,-Epoxypropane .......
2.S.d. DL-l,2,-Epoxybutane ........
Miscellaneous Compounds ..........
2.9.a. Furan .......................
2.9.b. 2,5-Dihydrofuran .............
2.9.c. Tetrahydrofuran ..............

1408
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1412
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1412
1413

3. Acknowledgment .............................................

1414

4. References .............................
5. Appendix ..............................

1415
1421

2.8.

2.9.

List of Tables
1. Ideal gas thermodynamic properties of

methanol (CH 30H) at 1 bar ..............

2. Ideal gas thermodynamic properties of
methanol-d1 (CH 30D) at 1 bar ............
3. Ideal gas thermodynamic properties of
methanol-d3 (CD 30H) at 1 bar ............
4. Ideal gas thermodynamic properties of
methanol-d4 (CD 30D) at 1 bar ............

1378
1378
1379
1379

5. Ideal gas thermodynamic l.nopeIties of

ethanol (C 2H sOH) at 1 bar ...............

6. Ideal gas thermodynamic properties of
I-propanol (C3H 70H) at 1 bar ............
7. Ideal gas thermodynamic properties of
2-propanol {(CH3)2CHOH} at 1 bar .......
8. Ideal gas thermodynamic properties of
l~butanol (C4 H 9 0H) at 1 bar .............
9. Ideal gas thermodynamic properties of
DL-2-butanol (C4H 90H) at 1 bar .........
10. Ideal gas thermodynamic properties of
2-methyl-2-propanol (C4H 90H) at 1 bar ...
11. Ideal gas thermodynamic properties of
1,2-ethanediol (CH20HCHzOH) at 1 bar ...

1380
1382
1382
1384
1384
1385
1387

12. Ideal gas thermodynamic: properties of

13.
14.
15.

16.
17.
18.

dimethyl ether (CH 30CH 3) at 1 bar ........

Ideal gas thermodymanic properties of
dimethyl ether-d3 (CH 30CD 3) at 1 bar .....
Ideal gas thermodynamic properties of
dimethyl ether-d6 (CD 30CD 3) at 1 bar .....
Ideal gas thermodynamic properties of
ethyl methyl ether (C2H 50CH 3) at 1 bar ....
Ideal gas thermodynamic properties of
diethyl ether (C2H sOC2H s) at 1 bar ........
Ideal gas thermodynamic properties of
propanone (CH 3COCH3) at 1 bar ..........
Ideal gas thermodynamic properties of
2-butanone (C zH sCOCH 3 ) at 1 bar ...............

19. Idea.l ga.s thermodynamic properties of

methanal (HCHO) at 1 bar ...............
20. Ideal gas thermodynamic properties of
methanal-d t (DCHO) at 1 bar ............
21. Ideal gas thermodynamic properties of
methanal-d2 (DCDO) at 1 bar ............
22. Ideal gas thermodynamic properties of
ethanal (CH 3CHO) at 1 bar ...............

1388
1389
1390
1391
1392
1393

23. Ideal gas thermodynamic properties of

ethanal-d l (CH3CDO) at 1 bar ............
24. Ideal gas thermodynamic properties of
ethanal-d4 (CD 3CDO) at 1 bar ............
25. Ideal gas thermodynamic properties of
I-propanal (CH 3CH 2CHO) at 1 bar ........
26. Ideal gas thermodynamic properties of
I-butanal (CH 3CH2CH 2CHO) at 1 bar .....
27. Ideal gas thermodynamic properties of methanoie acid monomer (HCOOH) at 1 bar .....
28. Ideal gas thermodynamic properties of
methanoic acid dimer {(HCOOH)2} at
1 bar ..................................
29. Ideal gas thermodynamic properties of
methanoic acid monomer-dimer equilibrium
mixture (HCOOH-(HCOOH)2) at 1 bar ....
30. Ideal gas thermodynamic properties of
methanoic acid-d l (HCOOD) at 1 bar .....
31. Ideal gas thermodynamic properties of
methanoic acid-d 1 (DCOOH) at 1 bar .....
32. Ideal gas thermodynamic properties of
methanoic a.cid-d2 (DCOOD) at 1 bar .....
33. Ideal gas thermodynamic properties of
eilul.llui~ a~iu IIlUllUII1t::r (CH 3COOH) at
1 bar ..................................
34. Ideal gas thermodynamic properties of
ethanoic acid dimer {(CH3COOH)2} at
1 bar ....................... ~ ..........
35. Ideal gas thermodynamic properties of
ethanoic acid monomer-dimer equilibrium
mixture (CH3COOH-(CH 3COOH)2) at
1 bar ..................................
36. Ideal gas thermodynamic properties of
methyl methanoate (HCOOCH 3) at 1 bar ...
37. Ideal gas thermodynamic properties of
methyl ethanoate (CH3COOCH3) at 1 bar ..
38. Ideal gas thermodynamic properties of
epoxyethalle (C ZH 40) at 1 bar .............
39. Ideal gas thermodynamic properties of
epoxyethane-d4 (C2D 40) at 1 bar ..........
40. Ideal gas thermodynamic properties of
DL-l,2-epoxypropane (C 3H 6 0) at 1 bar .......
41. Ideal gas thermodynamic properties of
DL-l,2-epoxybutane (C4 H gO) at 1 bar .........
42. Ideal gas thermodynamic properties of
furan(C 4H 40) at 1 bar ....................
43. Ideal gas thermodynamic properties of
2,5-dihydrofuran (C4H 60) at 1 bar .........
44. Ideal gas thermodynamic properties of
tetrahydrofuran (C4H sO) at 1 bar ..........

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List of Tables in Appendix

A-I.

1395
A-2.
1396
1397

1397

A-3.

Equations for calculating ideal gas

thermodynamic properties for poly~
atomic molecules at a pressure of 1 bar ..
Molecular weight, product of moments
of inertia, and vibrational assignments for
C 1-C4 organic oxygen compounds ......
Internal rotational molecular constants ..

J. Phys. Chem. Ref. Data, VoL. 15, No.4, 1986

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1421

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THEHMUDYNAMI\; t"tiUPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

A-4.

Comparison of observed and calculated

heat capacities of methanol(g) ......... .
A-5. Comparison of observed and calculated
entropies of methanol(g) .............. .
A-6. Comparison of observed and calculated
heat capacities of ethanol(g) ........... .
A-7. Comparison of observed and calculated
entropies of ethanol(g) ............... .
A-8. Comparison of observed and calculated
C; and {S" (T) - S" (O)} of I-propanol(s)

A -9.

Comparison of observed and calculated

C; and {S' (T) - S' (O)} of2-propanol (g)
A-10. Comparison of observed and calculated
C; and {S' (T) - S' (O)} of 1-butanol(g) .
A-II. Comparison of observed and calculated
C; and {SO (T) -S' (O)} ofDL-2butanol (g) ................................................. ..

A-12. Comparison of observed and calculated

C; and {S' (T) - S' (O)} of2-methyl2-propanol(g) ............................................. .
A-l3. Comparison of observed and calculated
and {S(T)-SO(O)} of dimethyl ether(g) ..
A-14. Comparison of observed and calculated C;

C;

and {SO(T)-S(O)} of diethyl ether(g) ...

A-I5. Comparison of observed and calculated

heat capacities of propanone(g) ...... '.' .
A-16. Comparison of observed and calculated
entropies of propanone(g) ............. .
A-17. Comparison of observed and calculated C;
and {SO(T)-SO(O)} of 2-butanone(g) .....

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1428
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1429

A-18. Comparison of observed and calculated

heat capacities of ethanal(g) ........... .
A-19. Comparison of observed and calculated
C; and {S' (T) - S' (O)} of 1-propanal (g)
A-20. Comparison of observed and calculated
heat capacities of ethanoic acid (g) . . . . . .
A-21. Comparison of observed and calculated
heat capacities of methyl ethanoate(g) ...
A-22. Comparison of observed and calculated C;

1429

and {SO(T)-SO(O)} of epoxyethane(g) ....

1430

A-23. Comparison of observed and calculated

C; and {S' (T) - S' (O)} offuran(g) ........
A-24. Comparison of observed and calculated
heat capacities of tetrahydrofuran(g) ....
A-25. Calculated ideal gas thermodynamic
properties at 298.15 K and 1 bar ....... .

1430

A 26. Comparison of ideal gas third law entropy

1430

values based on Part I and Part III with

the ideal gas values calculated from the
partition function .....................

1431
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1371

1433
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1434
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1436

List of Figures
1.

The three stable rotational isomers of an

ethanol molecule ........................

2. The potential curve of an asymmetric rotor ....
3. Molecular structures of CH 3COOH and
(CH 3COOH)2 ...........................
4. The rotational conformations of 2-butanol ..

1373
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1432

1. Introduction
1.1. Scope and Objectives
The critical evaluation of the thermodynamic properties of simple chemical substances in the crystal, liquid,
and ideal gas states has been a principal research project

The ideal gas thermal functions calculated include the

heat capacity (C;), entropy {SO(n-SO(O)}, Gibbs energy
function {GO(T)-HO(O)}/T, and enthalpy {HO(T)HO(O)}. The standard state is the ideal gas at a pressure
of 1 bar. Thermochemical properties are being reviewed
in the next part of the series.

at the Thermodynamic Research Center (TRC) for

Calculations were made from 0 up to 1500 K at 1 bar.

many years. The results reported here constitute part of

a research contract entitled "Thermodynamic Properties
of Key Organic Oxygen Compounds in the Carbon
Range C I to C 4 ," between TRC and the Office of Standard Reference Data of the National Bureau of Standards during the period 1970-1984. In Part 1 of this
series, the thermodynamic properties of organic oxygen
compounds (C I-C4) in the condensed phases (including
the glass phase where possible) were critically evaluated
and recommended values were tabulated.
Part 11 (this report) contains the thermodynamic properties of a number of organic oxygen compounds (C I to
C 4) . in the ideal gas phase.. The values were calculated
using a standard statistical mechanical method in which
a rigid-rotor and harmonic-oscillator molecular model
modified where appropriate for internal rotations, was
assumed for each compound. The molecular, spectroscopic, and thermal constants needed for the statistical
mechanical calculations were selected from the literature. In a few cases missing data were estimated by analogy to related compounds.

All calculations were based on the 1973 Fundamental

Physical Constants recommended by the CODATA
Task Group I and on the 1975 Atomic Weights:
C= 12.011, H= 1.0079, and 0= 15.9994.2 Where necessary, previous results were converted to SI units using
the conversion factors: 1 cal=4.184 joules and 1
atm= 1.01325 bar.
Whenever possible the calculated entropies and heat
capacities were compared to those derived from calorimetric measurements. It is intended that these values will
serve as a basis for extrapolation to higher members of
the various homologous series.
1.2. Statistical Mechanical Method
The thermodynamic properties for the ideal gaseous
state were calculated from molecular partition functions,
(1)

where E; is the energy of a molecule in the i-th quantum

state (relative to the energy in the ground. state) and g;
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CHAOETAL.

1372

the corresponding degeneracy. The relationship between

the partition function and the thermodynamic properties

is discussed in several standard textbooks on statistical

mechanics 4-9,21 and various review articles.lO,ll
The energies of molecular quantum states were based
primarily on observed molecular spectra. For molecules
without an internal rotation the

rigiu~rutur harmunic~us

cillator (RRHO) model was used. For this model the

energy of each state was the sum of energies for translational, rotational, vibrational, and electronic states.

Excited electronic states were not significant for the

~olecules . surveyed in this report. Thus the total partition function was the product of independent partition
functions the three types of energy.
(3)

Equations (2) and (3) are suitable for the low energy
states, but not for the higher energy states where corrections are required for anharmonic intramolecular potentials, centrifugal stretching of. chemical bonds and
vibration-rotation interactions. Available informa;ion is
insufficient to permit such corrections for any of the
molecules considered here. At a fixed temperature the
contribution to Q decreases as the quantum state increases. However the higher energy terms become relatively more important as the temperature increases. Thus
the RRHO model has limited accuracy at higher temperatures.
A molecule has 3N degrees of freedom, where N is the
number of atoms in the molecule. These include 3 for
translation and 3 for molecular rotation of a non-linear
molecule. The remaining 3N - 6 can be assigned to the
normal modes of vibration. A linear molecule has 2 degrees of rotational freedom and 3N

1.3. Internal Rotation

If a molecule contains two non-linear groups of atoms
connected by a single chemical bond and if both groups
contain atoms which do not lie on the bond axis, then the
molecule has a mode of internal rotation or torsional oscillation. The groups of concern here are methyl. hydroxyl, carbonyl, carboxyl, and alkoxy and require some
special approximations to evaluate the partition function. 9,12,13,18,20,21,26,27
The approximations depend on the magnitude of the
potential energy associated with the relative rotational
motion. Where the potential was so high that all the corresponding terms, e/kT, are large, the mode was treated
as harmonic torsional oscillation. Where the barriers in
the rotational potential are small the internal rotation can
be approximated as free rotation with the partition function given by equation (13). However this was not assumed for any molecules discussed here.
For intermediate cases the internal rotation energy
levels were obtained by a solution of the Schroedinger

equation with the appropriate Hamiltonian. For a single

symmetric rotor this was
(8)

where p is the angular momentum operator for internal

rotation, Ir is the reduoed moment of inertia, and V(9)

the potential energy as a function of rotational angle, ().

The Schroedinger equation was

~~
87T2 I, d()2
OT,

[e - V(8)]t/I = 0,

(9)

with the energy in units of cm- I,

F

~ + [e'

- V(8)']l/J

= o.

(10)

5 normal vibra-

tions.
The relations between thermodynamic properties and
the partition function are:

The rotational constant, F, is defined by

h
F =---r87TC,
:[ .

(11)

(4)

The potential energy function is usually expressed by

the series
(5)
V(8)

{SeCT) -SOeO)} =R lnk-RT dIn Q

NA
dT
CO = RT2d2lnQ
p
dT2

+ 2RTd InQ

dT .

(6)
(7)

1
= 2"1:
V (1
n

- cos n8).

(12)

Equation (12) reflects the symmetry in the rotor. For

example, a methyl group is a symmetric top with a 3-fold
symmetry. The potential energy function contain5 terms
in which n is a multiple of 3. Usually one term with V3

NA is Avogadro's number. The functions for translation,

vibration, and rotation for the RRHO model expressed
in closed algebraic forms are listed in Table A-I. The
values of the fundamental frequences selected for the

is used for a methyl group. The function should contain

only terms which are multiples of three. The three
equivalent minima in V correspond to positions in which
the C-H bonds in the methyl group are intermediate between two of the bonds on the frame to which it is at-

moleoules and species are listed in Table A-:-2.

tached.

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1373

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

The substitution of one term from equation (12) into
equation (10) gives rise to the Mathieu differential equation. Tables of solutions for this equation have been published. 29- 31
Pitzer and co-workers 15, 18,21 published tables for the
contributions of an internal rotation mode to several
thermodynamic properties. The values are functions of
the partition function for a free rotor,

CH3

CH3

:~H

H~H

gauche

trans

gauche

Fig. 1. The three stable rotational isomers of ethanol.

(13)

and Vn/RT. They are applicable only to a single symmetric top rotor and have been extensively used since
their publication.
The contributions to internal rotations used here were
obtained with the direct sum indicated in equation (1).
Th~ ~U~l'gy

gauche

gauche

levds were obtained from an approximate

solution to equation (10) with the appropriate potential

energy function. 19,28,33 This method is valid for both symmetric and asymmetric rotors. In most cases the parameters, Vn , in equation (12) were taken from the published
literature and were based on spectroscopic observations.
In some cases these values were modified slightly to ob-

Fig 2. The potential curve of an asymmetric rotor.

lain a bettel- fit to measured thermodynamic properties.

In some cases only the 0 ---+ 1 torsional transition for a

methyl group was reported. The value of the parameter
V3 was calculated from the reported torsional frequency,
the rotational constant, F, and a table of Mathieu functions by a procedure given by Fately and Miller. 32
Pitzer and co-workers published methods of calculating the reduced moments of inertia. I4-17 In some cases we
used values of the reduced moments reported in the literature, but usually we calculated them using reported
molecular geometry with a computer program based on
reference (17).
Because complete sets of energy levels were not available for molecules which exhibit internal rotation, approximations were employed to calculate the internal
rotational contribution. Two methods were used. The
frrst was to assume that the internal rotational partition
function could be factored out. Thus,
(14)
where Qir is the partition function for internal l-otatioll,

or the product of such partition functions if there is

more than one mode of internal rotation. The number of
vibrational modes in Qvib was reduced by one for each
mode of internal rotation.
The second method of approximation was to consider
that the system of molecules consisted of an equilibrium
mixture of conformers. 9 Each conformer corresponded
to one of the minima of the potential energy function for
an internal rotation. The different conformers had different ground state energies, as well as different fundamental vibrational frequencies. When the rotating groups
were asymmetric the conformers also had different
molecular moments of inertia and different reduced moments of inertia.

Figure 1 shows the three conformers for the rotation

of the -OH group in ethanol. They correspond to local
minima in the potential energy function curve. The two
gauche forms differ only in their optical activity. Their
thermodynamic properties are identical but they were
considered as two distinct species. Figure 2 is a schematic plot of the potential energy function for this rotation. The gauche forms have a higher energy than the
trans.
The thermodynamic properties of such a mixture were
calculated by the following steps.
1) Calculate the properties of each conformer separately
with equation (14) where all energies are referred to
the same ground state.
2) Calculate the equilibrium constants for isomerization
from the differences in Gibbs energies.
3) Calculate the eqUilibrium mole fraction of each species.

4) Calculate the enthalpy, entropy and Gibbs energy

function of the eqUilibrium mixture, including the entropy of mixing.
5) Calculate the heat capacity of the mixture from the
temperature derivative of enthalpy.
This procedure is mathematically equivalent to calculating the thermodynamic properties from the following
partition function,
s

Q =

1: Qq

(15)

q= 1

where the Qq are the partition functions of the individual

species in the mixture. As in equation (14), the Qq are
J. Phys. Chem. Ref. Data, Vol.1S, No.4, 1986

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1374

CHAOETAL.

products of factors which correspond to separable energy terms. Some of these, such as the translational function, may be the same for all species. Let Qc be the
product of all the common factors. Then the partition
function for the mixture can be written as,
Q

Qc 1: Q'q
q= J

(16)

where Q'q are the product of partition functions that remain for each species after Qc is factored out. Each Q'q
contains at least one factor for internal rotation. Thus
(17)

For equation (16) to be a valid approximation to the partition function of the real molecule, its terms should corn;spuml

appruAiIll~tely to

the terms in equation (1) for

the real molecular quantum states. Thus, the terms for

the quantum states of an internal rotational mode should
be partitioned among the Q' q,i~ for the several conformers.
The wave function for each internal rotational state is
a function of the rotational angle, 8. The probability
function derived from the wave function has a maxima at
angles corresponding to minima in the potential energy.
It is reasonable to assign a particular state to that conformer which corre!itponrl!it to the angle which ha.c;, the
maximum in the probability function. This assignment is
unequivocal for the lower energy states but becomes increasingly less obvious as the energy increases.
This procedure requires reliable and detailed information about the structure and potential energies of the various conformers. Unfortunately in this work this kind of
information was not available for molecules which exhibit relative rotation of unsymmetric tops. In such cases
a complete set of internal rotational levels was used for
each term, Q'q,i" in equations (16) and (17). A constant,
Eo, was added to the levels for the higher energy species
to reflect the difference in energy between the ground
states of the two species. This gave an overabundance of

Molecules which have two rotors with C2v symmetry

exhibit two torsional modes for each kind of rotating
top. Examples are dimethyl and diethyl ether and
propanone. See Fately and Miller l70 and Myers and
Wilson. 37 Although the potential energy function was
the same for any two equivalent tops, the two modes
gave rise to different reduced moments and consequently, different rotational constants. These corresponded to the a2 and b l symmetry species in the spectra.
Each pair of equivalent rotors yields two different contributions to the partition function. However, since the
effect is nearly the same as two identical contributions
based on the geometric mean of the reduced moments
for the two modes and average values for the energy
levels for the two species,wehave used this approximation as well.
The various parameters associated with internal rotations in the molecules considered here are collected in
Table A~3.
1.4. Hydrogen Bonding

Hydrogen bonding is an interaction between a covalently bound H atom and a region of high electron density on an electronegative atom or group of atoms. A
typical example is the acetic acid dimer. The hydrogen
atom of the O-H group of one CH3COOH molecule
forms a strong hydrogen bond with the oxygen atom of
a carbonyl group in another CH3COOH molecule, i.e.
-0 H-O- where the dotted-line is the hydrogen
bond_ The acetic acid dimer ha~ two hydrogen bonds so
the species is very stable. Fig. 3 illustrates the molecular
structure of the CH 3COOH and (CH 3COOH)2
molecules. Formation of a dimeric species results in the
loss of two internal rotational degrees of freedom from
the presence of two linear hydrogen bonds in the dimer
instead of two free OH tops in the two monomers.

terms in the total partition function. To correct for this,

the partition function is divided by s, the number of species assumed for the model. In effect, this procedure assigned an average of terms for the various conformers to
each conformer in equation (16). Mathematically the factor, s, has the same effect as a symmetry number. However s is not a measure of molecular symmetry.

In some cases we approximated the energy levels for

an asymmetric top rotor with two symmetric potentials,

one for a gauche - and one for a trans - species.
In molecules that contain more than one rotor, the
potential energy of internal rotation is a function of all
the angular coordinates which describe the rotational
motions. 38-40,46 However, we assumed that this function
was separable and that the total internal rotational contribution was a sum of the contributions for independent
rotors. The interaction of internal rotation with overall
rotation was considered by Herschbach,36 however we
neglected such effects.

e-c

Fig. 3. Molecular structures of CH3COOH and (CH 3COOHlz,

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1375

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

At room .teJ;llpera!1Ue ~andatmospheric pressure, acetic
acid;vapor.containsmore dimersthanmonomers. As the
temperature" increases, . the conceritration of dimers decreases until at 500 K the vapor is composed predominantly oflIlo~oDl~rs~ To provide a complete analysis,
the thermodynamic properties for the monomers,
dimers,andtheequilibrium mixture .of monomers and
dimers, have~been ,'calculated.for both acetic and formic
acids.

',1.~r'D~ut~rated

Analogs

When pertmenli'molecularand spectroscopic constants were available" the thel1JlodYluUnicproperties'; of

the deuterated,,~jLlg~ofthe selected compounds were
. calculat~d . ,Forjhe d~ut~rated '. species, the bond dis,tancesa.n~"b~lld;~gles'1rhich were used in computing
the moments of'ihertfo:'wete assu~ed' to'be the' same

as

,thos,e' ~rt~e'#d~ut~f~ted C()ml'olilldswhen noexp~ri~

Iiientitl":a1lle~':~~17~~:~~~~kl~~.< :. "..' .....
.' "
',The .})otentiabb~e,rzl1eighto(a. dellterated rotor ,was
ULkento;bet~',~~;~:~~arfor;tll~ und.euterated one ~or
genera.tingtl;t~interpal't()~tional.~n~rgyle\,els. The.data
U~ua1IYrnissil1g'~\VtU'~t~~'~~~pletesets of the: f~lidwnen-

;e7t~0fbt_~'~J.;~:td~:~:tZc:;::
siancesare~m91p~~:;~-~~s:r~po~i.
... ",' ;,::'"".

A comparison of the calculated C; and/or

{S (T) -8 (O)} values with experimental values . was
given for' some selected compounds. Before a compari
son was made, the ideal gas values were calculated fron:
the experimental vapor heat capacity and third lawen
tropy values. In particular, ade~ailed comparison has
been made with the experimental values calculated using
the critically selected properties giveri in Part I and in
Part III (to be published) of this report. The best avail.,
able physical constants and equations of state have beell
used. for these conversions and the results calculatedm
this report were obtained using the most recent molecu~
lar and spectroscopic constants. Hence the values should
be more reliable than those based on earlierspectroscopic and thermodynamic data

;'.11le'ritet~Yl~11~[f~iY,iticrefil~hfffiet~od,has. ;b~en 'use~

~~rofi~1f~~~lig=o~i:.t:f!~
~araffullC;lli~iOqitrl)()~~'(j~itl1()~efor the .. lo\Ver. me~
be1'$ofthe. .s~~~:~;~9,~":retW~d.:In,e~hod. of.increments. lia~

beenemployoo:~y.Sgo#s,q'fof~c2ilculating the thermodynamic prol'erti~oforg~psulfurcompounds. '.

lIlethyl~1l~iJI9r~nl~nt jp.et,!!9~t'*Y~~~()Pted for' calculating ". the.ideat:?~:g~'t~einIddynamic'~~toperties' for some

The.

higher mem1>r~;:~f~1l.1~~:~();rtJ,()lpgous .seriesof 'or~anic

oxygenc()JIl~Q~~~s'~iti,:th.~:Pfesentwoi'k. Values of the
incrementstotlle:'pr()pemes'were taken from reference 49.

1.8.

Un~~rtAint"Assignment

The 'sources of" errors. in the calculated' ,thC!rmodyl1~c.pr()perti~~ .Qf ideal. gases .areconsid~redin ,two
groups. One ,is the errors in caleulating,thcRRHO con- .

tributionsto t~ermodynamicproperjt~~.The other iserrors related to the deviations of real' mQlecules .

thp
RJ,lHOmodel.

from.

..8.a.Errors IIlRR.HO Contributions

<Errors or tDlS typt: rt:ut:CL LIlt: t:ITorsm.the Iilolec~l8t:

parallleters: used. for the 'ca1clllation~ .SpecificaIiy,they
'are'thenioments of inertia of the molectilesandtheval;;
ues.ofthe. vibrational frequencies. As an approximation
we assumed them to beindepengentandapplied'thc
usual statistical formula for calcUlating the standard de
viations'ofa function from those of its arguments. Erron
in 'vibrational' .frequencies affect.allof. the calculated
thennodynamicproperties.
'.
The total uncertainty in '. the vibrational contributioll,
(U)to each . thermodynamic 'property .(X) ata given temperature (T)wascalculated as the sum of the separate
uncertainties in.thevibrational.contributions{Uj ) caused
by tbe error (av) in assigmnent for,each'wavenumbel
(v), which. is represented by the following (foranonliti.
ear .molecule)'

~i11i.;'PtU"'titlbnc)f;Result.

The..va:t~~.~9X;~~:~~~~(t~~~9.0Yl1amicprQPerties

'.

calculatep~y~!ti~/~~~ti,9~ll1rPharriqlQ"tn~~odar~ giv.en,

~1;:;~_2~i~E#1
:. Jhepr(lpeW:'-taP~~~,Q~ut~l"a,t~d~p~ciesare. alw~ys

listeci ~tr:,:Jh9$~5~f1j~~'fijii~~\lieJ;~te9species: of tlle . san:,te

~::=~~_~(~c:ti;~~:~e~::
du~d. direst!Y<JrQ~,tP~~~QRenli~el'ature;'with.a '. suitabl~

=~!a.nt~~5;~~Ws:

~.N.'.l:

. . . )2'(~i)'
. '; ........ 2.]',".*.
. -.ox

- " '.(,

,1

. QXr, ' , ' .

where x ishcvlkT andh isthePlanckconstant,cistlle

speed of light, and k is the BoltzlD.ann:constant.. Based
upon the standard statistical. formulas for calculating the
vibrational' contributions' toe;,.: {SO(T}"':"'S~(O)},
{HO(T)~HO(O)}, .~d{(7(T)'"""H~(O)}IT,thefQllowing
equations were derived:
'~CO
Rx2 -. x
~_e

oX

2 :,. '.1"':'"
[..'~....:

-:-'(1-e-~2:x

'.

.. '2'e'-CoX'
........ ] ".

(l-e-~,

(19)

~yen.

J~ Phys.Cherri. Ref~Data/Vol,;15~No~ 4;1986

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CHAOETAL.

1376

(20)

(M;)2]

_ [3n~- 6(-aSO)2 (llx;) 2 +-~

R2 3
-

a({GO(T) -;. HO(O)}) _ _R_e-_

x
(21)

oX

certainties in both the vibrational and rotational contributions, i. e.

a{SO(T) - SO(O)}
1~;

112

.
(26)

Based upon the estimated ax;, M a , M b , Mn and the

above equations, the uncertainties in the calculated C;,
{SO(T)-SO(O)},
{GO(T)-HO(O)}/T, and {HO(T)
-HO(O)} were determined at the selected temperatures.
These values are given in parentheses after the calculated value in each table.

1 [o{HO(T)-HO(O)}]
oX

3({GO(T)~H\0)} )
(22)

oX

The above quantities were substituted into Eq. (18) to

give the uncertainties in the respective thermodynamic
properties caused by uncertainties in the vibrational assignments for the given compound. There is no general

1.S.b. Errors In Molecular Models

One source of deviation from the RRHO model is

non-linear dependence of intramolecular force constants
on atomic displacements, and on phenomena such as centrifugal stretching of bonds and rotation-vibration interaction. Although there is little direct evidence on the

rule for estimating the uncertainties, ~i' in the vibra-

magnitude of these effects, it is likely that they do not

tional assignments as they are unique for each individual

substance.
The rotational contributions to the Gibbs energy function, {GO(T)-HO(O)}/T, and entropy, {SO(T)-SO(O)},
for a nonlinear polyatomic molecule require the value of
IaIJc. The uncertainties in the {GO(T)-HO(O)}/T value
caused by the uncertainties in the principal moments of
inertia were estimated by the following relations:

affect the calculated heat capacity by more than 1% at

temperature below HXX) K.
The other source of error arises from the approximation made to model internal rotation as described in section 1.3. In fact this is the principal source of error for
those molecules which have internal rotations. In
molecules which contains only symmetric top rotors,
such as the methyl group where potential energy functions are based on reliable spectroscopic evidence, the
errors in calculated heat capacity are expected to be
within 1%. For more complex cases the errors are probably larger, and depend on temperature. Errors from deviations from the RRHO model were not included in the
estimated errors given in the tables of thermodynamic
functions.

!i a(IaI Jc)
2

IaIJc

(23)

or

a( {G O(T) - HO(O)})
T

r r
ROT

=-

~ [( ~a

R[

+ ( ~b

+ ( ~<

(M;)2]~

- -2 ~ I;

2. Evaluation of Thermodynamic

)T

Properties
(24)

The calculated ideal gas properties such as C; and {S

where the values of M a , M b , and Mc were estimated.

The
total
uncertainties
in
the
calculated
{aO(T)-HO(O)}/T, l:aulSt:u by uncertainties in both the
vibrational and rotational contributions, were calculated
as follows:

a( {GO(T) ;
=

HO(O)})

[,nil a(
1

{GO(T) ;W(O)}

))2

aX;

x (ax )2 + ~ i(Mi)2]~.
j

2.1. Alkanols

I;

(25)

Equation (26) was used to calculate the total uncertainties

in the calculated {SO(T)-SO(O)}, which includes the un-

(T)-SO(O)} were compared, where possible, with exper-

imental values to check the reliability of the input data

and the computational method employed. The experimental heat capacities were corrected to their zero pressure value, C;, by correction for gas imperfections.
When P- V-T data for the given compound was available, this correction was done using well-known thermodynamic relationships. However, alkanol vapors contain
polymeric species in addition to the monomeric
molecules, thus a special treatment, described below,
was used to account for the effects of gas imperfection.
DeVries and Collins S2 determined the heat capacity of
methanol vapor and found that the C; values increased
with decreasing temperature near the saturation curve.
Sinke and DeVriess3 and Stromsoe et 01. S4 reached a similar conclusion from C; measurements on the aliphatic
alcohols CH 30H to CSHllOH. Weltner and PitzersS mea-

J. Phys. Chern. Ref. Data, Vol.1S, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

sured the heat capacity of gaseous methanol at a series of

pressures and temperatures. From an analysis of the
preSsure dependence of Cp neat the .saturation curve;
they proposed the existence of a polymerization phenomenon'somewhat similar to that proposed .for hydrogen fluoride., Based upon an assumption that the
enthalpy of .polymerization was constant and floC; of
polymerization was zero, they developed an equation of
state for .methanol vapor:

+ Dpn-1

(27)

b - RT(e-M2IR)(eIili2IR1)

(28)

-(n~ 1) RT (e-MnIR)(elilinIR1). .

(29)

PV = RT + BP
where
B

==

~~=

b::'-

and

'
D =

1377

ers, 510,. using the molecular, spectroscopic, and tbermal

constants available at that time. Tbe sources of input
data' and the method of evaluation' used for each alkanol
are described below. The calculated C; and
{SO(T)-SO(O)} are compared with experimental results
where available.
2.1.a. Methanol

The ideal gas thermodynamic properties of methanol

(methyl alcohol, CH30H) were reevaluated recently by
Chen et al. 65 They employed the molecular structural
parameters lUld rotational constants determined from microwavespectroscopy by Lees and coworkers66-69 for
computiligthe-values oflalile andP.
The fundamental
vibrational assigruilent of
Shimanouchiso was adopted for evaluating the vibra~
tional contributions. Although the vibrational. frequen-

In the .above equations, .b is, the, .covolume, n is the

number of monomer units in the higherpolynier, andK2
andKnarethepressure based equilibrium. constants for
the dissoCiation. of, the, dimer and higher polymers, .resp~tively. '. The .resulting expression . for. t~e ,beai"'al'acity,as proposed by Weltner and PitzerS5 'is
(30)

cies of ,CH3QH vapor have been determined by

numerous'.investigators frominfrared and ,Raman spectra,70-79' some of the repoited'assigntnents'O,71,7S,76
in
conflict.. 'Shimanouchi critically reviewed the reported
specinl1 data, oDlD.ethanol ~d 'its dc;mter~te.clarialogs, in
both the gas and liquid phases, arid made a complete se1

are

of fundamental frequency assignments for these species

at 1 bar andSp is the entropy .of the

.
real gas at pressure P.
., ]fretschirier 'and WiebeS6 measured <P-V-T data for
methanol, thtmol; and2-propanol aIld found that Ec}..
(26) fitted. theit," results. 'They conc1udeci that the above

which' ismternanycollsistent. His results. were adopted.

in tbi~ w~rk~orgeneratinginterna1~otationalenergy
leve~sf()r.CH30H, thepotentia1:futiction.V == '1/2[V3(f
~c()s~8)+ V6(L- cos6tJ)lwas'used'Thevalues orv3
andV6 were obtained from K'Yan and Demiison. 81
Usirlg-the molecular constants given in TablesA-2 :and
A-3; we recalculated the :thermodynamic properties by
. the. standard method of statistical mechanics; The results
are presentedin:Table 1.'
Ivash .et .al. 465 . calcula~ed~thejdeal' gas therm9clynannc
properties .:of methanol.(g) over the . temperature range
from 100 to .1000 .K, and~ these: were adopted by .Stuller
al. in their' book on ."The Chemical'Ther1Ilodynamicsof
Oiganic"CoIIlPound".466 ;Their results' are in 'l::XcetleIl~
agreement with' oUr new values. . ..' '.
.
Kausluk et al4fj7 observed )be microwave spectrum of
CHjOD'(g); and determined the rotational and internal
rotational' constants, i. e~, A,lJ,:C,. F.., and "V3 "fortbis species.)3~e4 upoDthese data, 'we obtained theI~I,Jcand
. 108 'ip.ternal'rotationalellergylevels for calculating the

~~.ti4.J~~lSgavc: :sati~ractoryagl:c:einent -vyith. v~por.heat

capa~ity', IJl~urementsS2.S3;55.57and al~o gavesarlsfactory

_rot:atio.h,~ a~d., m.~ern2!J. r<?tationa:l. cOlltribut~q~. totli~

the~odY'11arnic.properties: 'ofCH30D (g).;The.vibra

where
(31)

(32)

They found that the heat capacity data at 345~6il(

by n =. 4. The followmg,equation'was
used,ss to,cal~ulatethe Ideal gas entropy:'
werefitt~dbest

'{SO(T)-SO(O)}- Sp(T) = RlnP +'dB.p3

. ; . ....
. .. ' . d T 3

(33)

where{So(T)~SC!(O)}isthe staridaJ:'dentropy of the

ide~lgasm.oIlomer

a.greelllent with, the saturated vapor densities. calculated

.tiona.I: wavenuDlbers lor thiscom,pound, ~eJ:l' Jron
:frcuirthe'heatsofvaporization measuredby,Fi6cK.etal,S$
~Shi1'nan~uchi'~'lU'egiveR in.; Table.A~2.The .calcullJ.te<
:."UsingthejlbovemOdelwhiqh~assUli1esa1kanol vapor '.resUlts: are.:l~tedin' Table 2. ... ' '.
.
.th~nnOdYIiamic ~:propert~es .. fQr. CD39H;~ '. aJ;lC,a,
-to contain monomeric; . dinleric, .and,tetrainenc, species;
Barrow57 'aild Gl'eenS?made.the gas imperfectioncorrec'COjOD~'givepin T~1)les 3fUid 4; werecalcu1a~d.us~g<
tions to;the Cp'and_S. vruues for' ethaitoland .compared
thecmetho~sdescribed.; IIFthese .calcuiati()ns;ih~ Iri()lecuthe' resUltingC; .and .{S O(T)~S~(O)lv'aIues with:those .'.;' ~ar':structure of ~achdeuterated' sp~cie~. was_~s~~.t?
calculated i by .. the .$tatistical> :mechanical : method .be the saw-eas' that'oft~~' c;H30Hmol~u1e~The vitii'a" '.
."McKetta and.co~workershave maIle:a.,similarcomparitional way~umbers'~or; these.; speCies-\Vere' taken :froIIl
;son 'of,the:ideat: gas ... thermodynantic . properties, ,of
Shinuinouchiso.anc:i. are lista(in TableA..2;. The'potential
~J-propanol;~2-butanolt 61. and 2~methyl~2~pl'opano16~The'
loocttonemployed for generating. the,int~mal ~()tati()~al
'. ideal.gas- thermodynamic'propeIties-of n~alkanols ~(Ci. to
en~~gy lev~lsfor each .deuterated species'wa..s 'asSufued to
.
-C4) were reported by Chermin63and~Green64 and oth- . be the saIlleas thatf6rCH30iI.

... .i1te'

IOhys. Chem. Ref. Data,Vol.:15;No.4; ;19~6;

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CHAOETAL.

1378
TABLE 1.

Ideal gas thermodynamic properties of methanol (CH 30H) at 1 bar"

M = 32.0420
T

K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000

1100
1200
1300
1400
1500

Co
l!.
J K- 1 mol-I

{SO(T)-SO(O)}
J K- 1 mol-I

-{GO(T)-HO(O)}IT
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

0
196.71 (0.03)
212.04(0.06)
223.28(0.08)
236.12(0.09)
239.81(0.09)
240.08(0.09)
253.77(0.10)
266.16(0.11)
277.71(0.11)
288.58(0.11)
298.84(0.11)
308.54(0.11 )
317.73(0.11)
326.46(0.11)
334.76(0.12)
342.06(0.12)
350.19(0.12)
357.38(0.12)

0
161.62(0.01 )
176.02(0.02)
186.49(0.03)
198.12(0.05)
201.46(0.05)
201.69(0.05)
213.04(0.06)
222.44(0.07)
230.70(0.08)
238.20(0.08)
245.15(0.09)
251.66(0.09)
257.81(0.09)
263.65(0.09)
269.24(0.09)
274.58(0.10)
279.72(0.10)
284.66(0.10)

0
3509(2)
5402(6)
7358(9)
10353(12)
11435(13)
11517(13)
16291(16)
21859(18)
28209(20)
35268(22)
42955(23)
51196(25)
59925(26)
69085(28)
78624(29)
88496(30)
98660(32)
109081(33)

0
36.90(0.07)
38.59(0.07)
39.68(0.06)
42.57(0.04)
44.04(0.03)
44.16(0.03)
51.62(0.03)
59.69(0.03)
67.19(0.03)
73.86(0.02)
79.75(0.02)
84.95(0.02)
89.54(0.02)
93.57(0.02)
97.12(0.02)
100.24(0.02)
102.98(0.02)
105.40(0.02)

aYalues in parenthesis are estimated uncertainties.

TABLE 2.

zK
0
100
150
200
273.15
298.15
300

400
500
600
700
800
900
1000
1100
1200
1300
1400
1"00

Ideal gas thermodynamic properties of methanol-d l (CH 30D) at 1 bar"

M = 33.0482

Cl!.

J K- 1 mol-I

{SO(T)-SO(O)}
J K- 1 mol-I

0
38.24(0.10)
39.82(0.07)
40.88(0.05)
44.04(0.03)
45.61(0.03)
45.73(0.03)
53.40(0.03)
61.52(0.03)
69.07(0.03)
7:5.8:5(0.03)
81.85(0.02)
87.15(0.02)
91. 79(0.02)
95.84(0.02)
99.36(0.02)
102.43(0.02)
105.10(0.02)
1074~(OO?)

0
199.11(0.07)
214.97(0.11)
226.56(0.13)
239.71(0.14)
243.63(0.14)
243.92(0.14)
258.09(0.15)
270.88(0.15)
282.78(0.15)
293.9:5(0.1:5)
304.47(0.16)
314.43(0.16)
323.85(0.16)
332.80(0.16)
341.29(0.16)
349.37(0.16)
357.06(0.16)
':\f\4.19(016)

-{GO(T)-HO(O)}/T
J K- 1 mol-I
0
163.94(0.03)
178.47(0.05)
189.11(0.07)
200.97(0.08)
204.38(0.09)
204.63(0.09)
216.26(0.10)
225.92(0.11)
234.42(0.12)
242.13(0.12)
249.27(0.13)
255.96(0.13)
262.29(0.13)
268.29(0.13)
274.03(0.14)
279.51(0.14)
284.78(0.14)
2~9_R4(O_14)

{HO(T)-HO(O)}
J mol-I

o
3517(5)
5475(9)
7491(12)
10583(15)
11703(16)
11788(lb)
16732(18)
22481(20)
29017(22)
36270(23)

44161(25)
52617(26)
61568(27)
70954('29)
80718(30)
90812(31)
101191(33)
111820(34)

aYalues in parenthesis are estimated uncertainties.

Vapor heat capacities of methanol from 341 to 585.35

K have been measured by DeVries and coworkers, 52,53
Stromsoe et al. ,54 and Weltner and Pitzer. 55 The reported
Cp were converted to the ideal gas heat capacities, C;,
by corrections for the gas imperfection effects. 55 ,56 These

experimental C; values are compared with our calculated values in Table A-4. The differences are within the
experimental uncertainties of 1.3 J K -I mol-I.
Table A-5 gives a comparison of the third-law entropies with our calculated {SO(T)-SO(O)} for methanol
vapor in the temperature range from 313.1 to 383.15 K.
The third-law entropies were calculated based upon the

value S(liq, 298.15 K) = (127.24 0.21) J K- 1 mol- 1,82

the liquid heat capacities83 and the enthalpies of vaporization. 55,58 The entropy of liquid methanol at 298.15 K
was reported as (134.9 8) J K- 1 mol- 1 84 and
(127.19 0.12) J K- 1 mol- 1.&3 Carlson and Westrum 83
reported {SO(298.15 K)-SO(O)} = 239.60 J K- 1 mol-I
for methanol compared with our statistical thermodynamic valueof239;81 J K- 1 mol- l at 1 bar. This value is

in agreement with our selected experimental value given

in Table A-26 of 241.78 J K- 1 mol- 1 based on the evaluations in Part I and III of this report.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEV ORGANIC OXYGEN COMPOUNDS

TABLE

1379

3. Ideal gas thermodynamic properties of methanol-d3 (C0 30H) at 1 bar

M = 35.0606

coe.

{SO(n-SO(O)}
J K- 1 mol-I

-{GO(T)-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

400

0
37.20(0.08)
39.16(0.07)
41.38(0.06)
47.03(0.04)
49.41(0.04)
49.58(0.04)
59.79(0.03)

0
202.24(0.04)
217.72(0.07)
229.27(0.09)
242.91(0.10)
247.13(0.11)
247.43(0.11)
263.12(0.11)

0
3506(3)
5418(7)
7427(10)
10644(13)
11849(14)
11941(14)
17410(17)

500

69.25(0.03)

277.47(0.11)

600

77.32(0.03)
84.14(0.03)
89.8'7(0.03)
94.73(0.02)
98.78(0.02)
102.26(0.02)
105.19(0.02)
107.74(0.02)
109.87(0.02)
111. 75(0.02)

290.86(0.12)
303.28(0.12)
314.91(0.12)
325.79(0.13)
335.96(0.13)
345.54(0.13)
354.58(0.13)
363.11(0.13)
371.15(0.13)
378.80(0.13)

0
167.18(0.02)
181.57(0.03)
192.11(0.04)
203.95(0.06)
207.39(0.06)
207.64(0.06)
219.56(0.07)
229.73(0.08)
238.81(0.09)
247.13(0.09)
254.92(0.10)
262.20{0.1O)
269.06(0.10)
275.58(0.10)
281.78(0.11)
287.72(0.11)
293.41(0.11)
298.85(0.11)

K
0
100
150
200
273.15
298.15
300

700

800
900
1000

1100
1200
1300
1400
1500

J K- 1 mol- 1

23870(19)
31208(21)
39292(23)
48003(25)
57237(27)
66919(28)
76973(30)
87349(31)
97998(33)
108880(34)
119964(35)

Values in parenthesis are estimated uncertainties.

TABLE

4. Ideal gas thermodynamic properties of methanol-d4 (C0 300) at 1 barB

M
{SO(T)-SO(O)}
J K- 1 mol-I

K
0

100
150
200
273.15
298.15

300
400
500
600
700
800
900

1000
1100
1200

1300
14OO[
1500

0
38.66(0.13)
40.46(0.09)
42.63(0.06)
48.49(0.04)
51.00(0.04)
51.63(0.04)
61.59(0.03)
71.09(0.03)
79,24(0.03)
86.19(0.03)
92,01(0.03)
96.94(0.02)
101.04(0.02)
104.52(0.02)
107.45{O.02)
109.91(0.02)
112.05(0.02)
113.80(0.02)

0
204.40(0.12)
220.52(0.16)
232.45(0.18)
246.51 (0.20)
250.90(0.20)
251.19(0.20)
267.34(0.21)
282.15(0.21)
295.84(0.21)
308.60(0.21)
320.48(0.22)
331.61(0.22)
342.09(0.22)
351.86(0.22)
361.06(0.22)
369.77(0.22)
378.01(0.22)
385.79(0.22)

36.0688
-{GO(T)-l((O)}/T
J K- 1 mol-I

{HO(n-HO(O)}

J mol-I
0

169.14(0.04)

3531(8)

183.79(0.08)
194.50(0.10)
206.63(0.12)
210.15(0.13)
210.40(0.13)
222.66(0.15)
233.08(0.16)
242.41(0.17)
250.98(0.18)
258.93(0.18)
266.38(0.18)
273.45(0.19)
280.15(0.19)
286.50(0.19)
292.57(0.19)
298.39(0.20)
303.95(0.20)

5515(13)
7586(17)
10904(20)
12146(21)
12242(21)
17882(24)
24527(26)
32058(28)
40338(29)
49254(31)
587I0(32)
68613(34)
78898(35)
89500(36)
100374(37)
111474(39)
122767(40)

V~lues in parenthesis are estimated uncertainties.

Previous workers, using heat capacity, 55 PVT,S6 and

spectroscopic methods,468.469 concluded that the most
probable major self-association species of methanol vapor were the dimer and the tetramer. However, Tucker
et al 470 and Cheam et al 471 measured the association of
methanol in n -hexadecane and of methanol vapor by
PVT and vapor density methods and suggested that the
predominant associated species are trimers and octamers.

larger associated species (pentamer or hexamer) are

present in the vapor. The results of this treatment have
been combined with the enthalpies of vaporization and
vapor pressure data to give further information on the
deviation of the vapor from ideal-gas behavior.

Counsell and Lee4i2 measured the vapor heat capacity

The ethanol (ethyl alcohol, CH 3CH 20H) molecule has

of methanol in the temperature range 330 to 450 K and at

pressures up to 1 bar. They interpreted the heat capacities on the assumption that dimers, tetramers, and one

two rotating tops: the methyl group (-CH3) and the hydroxyl group (-OH). Modern spectroscopic studies have
identified two conformers corresponding to the trans

2.1.b. Ethanol

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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CHAOETAL.

1380

IIl1d ~imchl' po~;illOll:-' of till'

UII rolo! willi rc!)pcct 10 th(:~
('.,(: hUlld. ThnmodYIHllnic properties have bl~cn clllcu~
luted for un equilibrium mixture of these two forms.

Lovas 473 obtained values for the moments of inertia,

and the rotational constant and barrier for the rotation of
the methyl group from microwave spectra of the trans
confurmer. These were adopted for the statistical calculation and are listed in Tables A-2 and A-3. Takano et
al 85 obtained similar values for the moments of inertia
of this form. The first transition for the calculated energy states is 244 cm -I which is close to the observed
value of 253 cm- I for the methyl torsion. Wavenumbers
for the other vibrational modes were taken from Durig
et 01. ,86 Barnes and Hallam47 and Green. 59
The microwave spectra of the gauche conformer was
investigated by Kakar and Seibt90 and Kakar and

4.97 kJ mol-I. The to estimated by Kakar and Quade was

included for the gauche energy levels.
Comparisons of the calculated C; and {SO(T)-SO(O)}
with the experimental values are presented in Tables A-6
and A-7, respectively. The differences are within the uncertainties of the experimental measurements.
GreenS9 evaluated the thermodynamic properties of
ethanol (g) in the temperature range from 273.16 to 1000
K; this evaluation was adopted by Stull et 01. 466 His calculated results are slightly different from ours, because
we employed a molecular model that assumed the
ethanol vapor to be an equilibrium mixture of trans and
gauche isomers while his calculations were based upon a
molecular model which contains only one isomer. The
calculated value for the entropy at 298.15 K, 280.64 J
K -I mol-I, is in reasonable agreement with our selected

Quade. 474 The overall moments of inertia and the barrier

third law value of 282.5 J Ie-I mol-I, given in table A-26.

to rotation of the methyl group in the gauche form reported by Kakar and Quade were adopted for our calculation. The reduced moments for internal rotation of the
methyl and hydroxyl groups were calculated from the
molecular geometry. The bond lengths and angles were
taken as the same as those of the trans form. 88 A dihedral
angle of 70" for the hydroxyl rotation was assumed.
Kakar and Quade474 also reported a three term potential energy function for the hydroxyl group rotation. The
constants are listed in Table A-3. Energy levels for the
hydroxyl rotation were calculated from this function and
the rotational constants in the trans and gauche forms. The
calculated torsional wavenumber (0---l-1) for OH top in

The propanol (n -propyl alcohol) molecule contains

three internal rotors. The CH3-CH2 rotation is symmetric. The CH3CH2-CH2 and CH2-OH rotations are asymmetric. Conformations about the latter two bonds may
be designated by T, G, and G' for the trans and two
gauche positions. These give rise to nine conformers.
They may be designated by a pair of symbols, the fIrst
for the C-C conformation and the second for the c-o
conformation. These include four pairs of mirror images,
so that only five conformations are energetically distinct.
They are TT, (TG,TG'), (GT,G'T), (GG,G'G') and

the tl'ons isomer, 205.2 em-I, agrees with the observed

(GG',G'G). The mirror image pairs are enolosed in

values of 199 cm- I 89 and 201 cm- 1,47 respectively.

Durig et 01. 86 gave the barrier height for the hydroxyl
rotation in the trans conformer as 2.12 kJ mol-I. The
potential function of Kakar and Quade indicates it to be
TABLE 5.

K
0
100
150
200
273.15
298.15
300
400

500
600
700
800
900
1000
1100
1200
1300
1400
1500

2.1.c. 1Propanol

parentheses. Fukushima and Zwolinski476 carried out a

normal coordinate analysis on the five distinct forms and
reported the bond force constants and fundamental frequencies.

Ideal gas thermodynamic properties of ethanol

M = 46.0688

Cop
J K- 1 mol-I

(C,H~OH)

{S"(1)-SO(O)}
J K- 1 mol-I

-{GO(1)-HO(O)}/T
J K-I mol-I

0
225.44(0.17)
243.37(0.29)
257.56(0.36)
275.10(0.40)
280.64(0.41)
281.04(0.41)
302.04(0.44)
321. 76(0.46)
340.36(0.47)
357.86(0.48)
374.34(0.48)
389.87(0.49)
404.54(0.49)
418.43(0.49)
431.60(0.50)
444.10(0.50)
456.00(0.50)
467.33(0.50)

0
187.03(0.05)
202.96(0.11)
214.89(0.16)
228.73(0.22)
232.85(0.24)
233.14(0.24)
247.77(0.29)
260.62(0.33)
272.37(0.34)
283.35(0.36)
293.70(0.37)
303.53(0.39)
312.91(0.40)
321.88(0.40)
330.47(0.41)
338.74(0.42)
346.69(0.42)
354.36(0.43)

0
41.70(0.31)
46.94(0.26)
52.02(0.20)
61.46(0.15)
65.20(0.14)
65.49(0.14)
81.22(0.14)
95.78(0.13)
108.24(0.12)
118.83(0.11)
127.92(0.10)
135.81(0.09)
142.68(0.08)
148.68(0.08)
153.92(0.07)
158.49(0.07)
162.50(0.06)
166.01(0.06)

at 1 bar-

{HO(1)-HO(O)}
J mo)-I
0
3841(12)
6061(27)
8533(38)
12668(50)
14250(53)
14371(53)
21706(64)
30573(73)
40792(81)
52159(89)
64508(97)
77704(104)
91636(110)
106210(116)
121350(121)
136970(126)
153030(131)
169450(135)

'VcduC;:lj in pan::nthClSis are ClStlmated uncenalntles.

J. Phys. Chem. Ref. Data, Vol.1S, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

Berthelot 103 and Golik et al. 104 reported that the form
in which the central C-C bond was in the trans position
was the one with lowest energy. Mathews and
McKetta60 calculated the ideal gas thermodynamic properties of this trans conformer, including restricted internal rotational contributions for the methyl and hydroxyl
rotors. Based upon the infrared and Raman spectral
data,96-IOO they assigned the fundamental vibrational
wavenumbers. The barriers to rotation were estimated
by analogies with related compounds. 101,102, The potential
function for the central C-C rotation was assumed to be
similar to that of propanethiol. The two parameters, vo,
the height of the trans-gauche barrier, and Eo, the energy
of the gauche conformer relative to the trans were adjusted to fit experimental heat capacity data. This gave
VO = 9.66 kJ mol-I and Eo = 3.56 kJ mol-I. Berthelot
had previously obtained Eo = 3.43 kJ moll, from a
study of the temperature dependence of the Raman spectra of the liquid.
The calculations presented here represent an equilibrium mixture of the trans and gauche conformations
about the central C-C bond. The vibrational wavenumbers of the normal modes were those reported for forms
I and II by Fukushima and Zwolinski. Abdurakhmanov
et al. 480 calculated the relative energies, of several conformers from the microwave spectra. They found that
the energy differences were small but that the GG form
was the lowest. The structure of this form was established by an energy minimization computation. It corresponds to the II' form of Fukushima and Zwolinski. The
relative energies of three other forms were given as 0.25
(TG), 0.31 (GT) and 1.46 (TT) kJmol- l .
In our calculations the energy states of the three rotors
were based on three-fold symmetric potential functions.
The V3 for the methyl rotation was taken from Dreizler
and Scappini47S for the trans conformer and from
Abdurakhamov et al. 480 for the gauche. The V3 value
used by Mathews and McKetta60 for the hydroxyl rotation was used for both forms here. The V3 for the central
C-C bond was taken from Mathews and McKetta for
the trans conformer. For the gauche conformer it was
calculated to match the corresponding torsional frequency given by Fukushima and Zwolinski.
The moments of inertia of the two conformers were
based on the spectroscopic observations of
Abdurakhmanov et al. 479. The values for the trans-isomer
are consistent with those of Abdurahmanov et al. 95 determined hymicrowave spectroscopy. The reduced moments for internal rotation and the correspohding
rotational constants for the three internal rotors were
calculated from structural parameters obtained by Aziz
and Rogowski94 by electron diffraction.
The energy of the trans conformer relative to the
gauche was taken to be'0.837 kJ mor- I. This was obtained by adjustment to give a good agreement between
calculated and observed gas phase heat capacities and
entropies. It is the same order of magnitude as values
obtained by Abdurakhmanov et al. All these parameters
are collected in Tables A-2 and A-3.

1381

The internal rotational energy levels for the trans and

gauche isomers were calculated using the V3 values for
the OH and C 2Hs rotors in the trans isomer and the OH
rotor in the gauche isomer reported by Mathews and
McKetta. 60 The V3 values for the CH 3 group in the trans
and gauche isomers have been reported by Dreizler and
Scappini 475 and Abdurakhmanov et al.,480 respectively.
We selected the value of V3 ( C2H s ) for the gauche isomer
so that the calculated torsional frequency (0 ---+ 1) was
consistent with the reported value 476
Stull et al. 466 adopted the thermodynamic properties of
Mathews and McKetta. 60 These values are slightly different from ours, as their calculations were based upon a
molecular model which assumes that the I-propanol
molecules contain only trans isomers which were assumed to be more stable than the gauche.
A comparison between the calculalt:d and experimental C; and {,so (T) ,so (O)} values is presented in Table
A-8. The average deviations are 0.09% and 0.96%, respectively. which are within the estimated experimental
uncertainties.
Vapor heat capacities of I-propanol have been measured by Sinke and DeVries, S3 and Bennewitz and
Rossner. 106 latkar amI Lakshimal-ayan 107 derived C; from
velocity of sound measurements. Their results agree
with those adopted here. The calculated value for the
entropy at 298.15 k, 322.58 J K- I mol-I, is in good
agreement with our selected third law entopy value of
322.62 J K- I mol-I given in Table A-26.
2.1.d. 2Propanol

The existence of trans and gauche for the -OH rotation

isomers on the 2-propanol (isopropyl alcohol,
(CH3)2CHOH) vapor was reported by Tanaka ll2 from infrared study and by Kondo and Hirota 113 from an anaylsis of the rotational spectrum, respectively. Hirota477
investigated the internal rotation by microwave spectroscopy and found that the energy difference' between
trans and the more stable gauche isomers to be (1.88
0.88) kJ mol-I. Hirota477 and Konda and Hirota ll3 have
also determined the rotational constants for these two
isomers.
Imanov et al. 478 recorded about 1000 lines on a gas
radio spectrometer with electrical molecular modulation
and a number of molecular parameters were determined.
Comparison of calculated results for the three possible
isomeric forms of the molecule with the experimental
results indicates that the molecule exists in the trans
form. Abdurakhmanov et al. 479 calculated the coordinates of the atoms from the experimental structural
parameters of the trans and gauche isomers. The structure obtained was compared with the parameters of
other related molecules.
The ideal gas thermodynamic properties of 2-propanol
were calculated using the statistical mechanical method
by Scluilann and Aston,108 Kobe et al.,I09 and Zhuravlev
and Rabinovich. 11O Green III assigned the fundamental
frequencies and used the molecular structure data to calculate the thermodynamic functions of the compound.
J. Phys. Chem. Ref. Data, Vol. 15, No. 4,1986

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CHAOETAL.

1382
TABLE

Co

J K- 1 mol- 1

0
100

150
200
273.15
298.15
300
400
500

600
100
800
900
1000

6.

Ideal gas thermodynamic properties of I-propanol (C3H 70H) at 1 bar"

M = 60.0956

{S'(T)-SO(O)}
J K- 1 mol- 1

l'.

-{OO(T)-HO(O)}/T
J K- 1 mol- 1
0

2S2.41(O~3S)

210.84(0.14)

4156(22)

58.92(0.23)
66.37(0.17)
80.19(0.14)
85.56(0.14)
85.96(0.14)
108.03(0.15)
128.19(0.15)
145.41(0.15)
160.05(0.15)
172.62(0.15)
183.51(0.15)
192.97(0.15)

274.75(0.46)
292.69(0.51)
315.33(0.54)
322.58(0.55)
323.11(0.55)
350.88(0.57)
377.20(0.58)
402.14(0.59)
425.68(0.60)
447.89(0.61 )
468.87(0.61)
488.70(0.62)

228.59(0.23)
242.43(0.29)
258.99(0.36)
264.02(0.37)
264.38(0.37)
282.51(0.42)
298.88(0.45)
314.03(0.47)
328.32(0.49)
341.89(0.50)
354.84(0.51)
367.25(0.52)

6924(35)
10051(44)
15391(53)
17462(55)
17621(56)
21324(65)
39158(75)
52862(85)
68154(95)
84802(106)
102620(116)
121460(127)
141180(138)
161670(149)
182830(160)
204570(171)
226830(182)

JIoo

ZU1.22(U.l:5)

5U7.49(0.62)

379.15(0.53)

208.40(0.15)
214.67(0.15)
220.14(0.14)
224.93(0.13)

525.32(0.62)
542.25(0.63)
558.36(0.63)
573.72(0.63)

390.59(0.54)
401.61(0.54)
412.24(0.55)
422.50(0.56)

1500

51.53(0.33)

1200
1300

1400

{HO(T)- H'(O)}
J mol- 1

aValues in parenthesis are estimated uncertainties.

TABLE

7.

C'p

J K-l mol- 1

0
100
150
200
273.15
298.15
300
400
500

Ideal gas thermodynamic properties of 2-propanol {(CH 3)2CHOH} at 1 barM = 60.0956

{S'(T)-SO(O)}
J K- 1 mol-I

{HO(n-HO(O)}
Jmol- 1

0
201.15(0.06)
217.37(0.10)
230.33(0.13)
246.33(0.18)
251.29(0.19)
251.64(0.19)
269.82(0.23)
286.34(0.26)
301.75(0.28)

0
3784( 9)
6394(21)
9553(31)
15104(42)
17266(45)
17432(45)
27536(57)
39771(69)
53811(81)

41 :).34(0.41)

316.29(0.30)

69334(93)

437.70(0.42)
458.65(0.43)
478.33(0.44)
496.88(0.44)
514.40(0.45)
530.98(0.45)
546.71(0.46)
561.66(0.46)

330.08(0.31 )
343.22(0.32)
355.75(0.33)
367.75(0.34)
379.25(0.35)
390.29(0.36)
400.90(0.36)
411.13(0.37)

86090(105)
103887(117)
122580(128)
142045(139)
162181(150)
182900( 160)
204130(171)
225800(180)

0
46.04(0.24)
57.98(0.23)
68.28(0.18)
83.72(0.15)
89.32(0.15)
89.74(0.15)
112.15(0.16)
131.96(0.17)
148.30(0.16)

0
238.99(0.14)
259.49(0.23)
278.10(0.28)
301.62(0.33)
309.20(0.34)
309.75(0.34)
338.66(0.37)
365.88(0.39)
391.44(0.40)

700

1(j 1. 7:S(O.1 6)

800
900
1000
1100
1200
1300
1400
1500

173.04(0.15)
182.67(0.15)
190.97(0.15)
198.16(0.14)
204.41(0.14)
209.85(0.13)
214.60(0.13)
218.75(0.12)

600

-{O'(T)-HO(O)}IT
J K-I mol-I

aValues in parenthesis are estimated uncertainties.

The best overall agreement with the experimental values

of entopy and heat capacity was obtained with the selected barrier heights, V3 , of 16.7 kJ mol- 1 and 3.3 kJ
mol-I for the CH3 and OH groups, respectively.
Green III employed estimated molecular parameters
for computing the values of IoIJc and F for the methyl
and hydroxyl groups. Their estimated values are consistent with those determined by electron diffraction by
Aziz and Rogowski94
Inagaki et al. 114 examined the far-infrared spectra of
2-propanol and its deuterated species. From the ob-

served torsional transitions they obtained the poltmiial

function for the OH rotor as V = 1/2l: Vn (l - cos n 8),
where Vl = 30.4 em-I, V2 = -86.2 em-I, and V3 =
401.3 em- t The derived torsional wavenumbers of 210
and 234 em -1 for trans (0 ~ 1) and gauche (0 ~ 1),
respectively, are in good agreement with the observed
values of 209 and 234 cm -1.
For calculating the thermodynamic properties, we
adopted the liP lb and Ie values determined by Kondo
and Hirota 113 to obtain lolt/e. The vibrational frequencies
and V3 and Ffor the CH:; rotor were those assigned by

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1383

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

Green. III The F value and potential function for the OB

rotor were taken from Inagaki et aL 114 The molecular
constants used are listed in Tables A-2 and A-3, and the
results are presented in Table 7. The calculated C; and
{SO(D-S"(O)} of 2-propanol (g) are compared with the
experimental values in Table A-9. The agreement between the calculated values for the third law entropy,
309.20 J K- J mol- 1 and the selected experimental value
of 310.86 J K- 1 mol- 1 at 298.15 K given in Table A-26 is
excellent.

11

2.1.e. i-Butanol

Dyatkina,118 using statistical mechanics, calculated the

thermodynamic properties of I-butanol. Chermin,63
adopting the same molecular constants as Dyatkina, but
using estimated values for the potential barriers for
CH 3, C 2H s, C)H7, and OH rotors, calculated
C;, {H"(T)-HO(O)}/T, {G"(T)-HO(O)}/T, {SO(n
-SO(O)}, L1f Ho and Apo in the temperature range from
298.15 to 1000 K and at 1 atm for l-butanol (g). Green64
obtained values for the above properties by adding the
methylene increment contributions48 to the values for 1propanol. These latter values were adopted by Stull et
al 466 As no new experimental molecular data on this
compound were available, we adopted the molecular
constants reported by Chermin63 to recalculate the thermodynamic properties. The results are presented in
Table 8. The calculated C; at temperatures from 398.15
to 453.15 K and {SO(29S.l5 K)-SO(O)} are in agreement
with the experimental vapor hea.t capa.cities measured by

Counsell et al

)20

and the reported third-law value

{SO(298.15 K)-SO(O)}, respectively, as shown in Table

A-lO. OUf recalculated value at 298.15 K, 361.59 J K-l

mol-', agrees well with the selected experimental third
law entropy value of 361.98 J K- I mol- 1 given in Table
A-26. The molecular constants used in the calculations
are given in Tables A-2 and A-3.
2.1.1 DL-2-Butanol

The2-butanol (sec-butyl alcohol, CH 3CH2C*HOHCH3)

molecule has an asymmetric carbon atom (marked with
the asterisk). It exists in both the D- and L- form. Hindered internal rotation about the central C-C* bond produces three isomers, shown below. which are more
stable than the "eclipsed" forms. These stable configurations correspond to the three minima of the potential
energy curve as a function of the angle of internal rotation.

Bernstein and Pedersen 121 measured the specific optical rotation of 2-butanol in dilute solutions of cyclohexane at temperatures from 20 to 70C and found the
concentrations of rotational isomers I, II, and III to be
42.35%, 42.35%, and 15.3%, respectively, at 20C and
43.0%,43.0% and 14.0% at 70 DC, respectively~ Assuming the configurations I and II have about the same energy, they derived the enthalpy of isomerization All =
(3.36 0.25) kJ mol-I for the reactions: 2-butanol (I) =
2..;butanol (III) and 2-butanol (II) = 2-butanol (III);

Fig. 4. The rotational conformations of 2-butanol.

Berman and McKetta 61 measured the vapor neat capacity, enthalpy of vaporization, and vapor pressure of
2-butanol. A model of an equilibrium mixture containing
monomers, dimers, and tetramers was used to obtain
constants for an equation of state which fitted the Cp data
and the gas imperfections calculated from the Clapeyron
equation.
Based upon the assumed molecular parameters, the
fundamental vibrational frequencies assigned from infrared 96,lOO and Raman97,98 data, and the derived C;,
Berman and McKetta61 selected the internal rotational
b . . .nit'!J- llcightli

fOI"

Ou:: CH), OH, and C2HS rotors in the

D-2-butanol molecule. Using these results, they evaluated the ideal gas thermodynamic properties for D-2-butanol by standard statistical mechanical methods. Their
results were adopted by Stull et aZ. ~1)Cj
We recalculated the ideal gas properties of 2-butanol
using the molecular parameters of Berman and
McKetta61 and a similar procedure. We used the model
of two gauche conformers in equilibrium with one trans
conformer, with the energy difference given by
Bernstein and Pedersen. The other parameters were
taken to be the same for both species. This calculation
applies to a .single enantiomer. The properties of the DL
mixture were obtained by adding Rln 2 to the entropy
and subtracting it from the Gibbs energy function. The
results are given in Table 9. Table A-26 shows that the
calculated entropy at 298.15 K is 4.1 J K -1 mol- 1 higher
than the third-law value. This is greater than the expected experimental uncertainty and undoubtedly reflects the approximations made in the calculated value.
2.1.g. 2-methyl-2-propanol

Beynon and McKetta62 measured the vapor heat capacity of 2-methyl-2-propanol (tert-butyl alcohol,
(CH))OH), over the temperature range 363.15 to 437.15
K and a pressure range from 0.3 to 1.3 bar. The enthalpy
of vaporization from 330.15 to 355.65 K and the vapor
pressure from 330.55 to 363.15 K were also determined.
Using a molecular model of an equilibrium mixture of
monomers, dimers, and tetramers, they correlated the
vapor heat capacity data, and this correlation was used
to extrapolate the Cp data to zero pressure. These
J. Phys. Chern. Ref. Data, Vo 15, No.4, 1986

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CHAOETAL.

1384
TABLE 8.

Co

J K- 1 mol-I

0
100
150
200
~73.15

298.15

300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500

Ideal gas thermodynamic properties of I-butanol (CJI90H) at I bar

M = 74.1224

{SO(T)-SO(O)}
J K-I mol-I

e.

0
58.33(0.47)
70.10(0.35)
81.28(0.26)
100.68(0.24)

-{GO(T)-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

0
276.82(0.46)
302.68(0.61)
324.36(0.69)
352.46(0.74)

0
232.81(0.20)
251.93(0.31)
267.39(0.39)
286.47(0.48)

4392(28)
7613(47)
11393(61)
18025(76)

108.03(0.25)

361.59(0.75)

292.39(0.50)

20633(80)

108.58(0.25)
138.16(0.31)
164.42(0.33)
186.38(0.31)
204.83(0.29)
220.56(0.28)
234.15(0.26)
245.93(0.25)
256.18(0.24)
265.10(0.22)
272.86(0.21)
279.63(0.20)
285.54(0.19)

362.26(0.75)
397.59(0.79)
431.32(0.82)
463.30(0.84)
493.25(0.86)
521.86(0.87)
548.64(0.89)
573.94(0.90)
597.87(0.91)
620.55(0.92)
642.08(0.92)
662.56(0.93)
682.06(0.93)

292.82(0.50)
314.63(0.57)
334.62(0.61)
353.43(0.65)
371.30(0.67)
388.36(0.69)
404.70(0.71)
420.37(0.73)
435.43(0.74)
449.92(0;76)
463.88(0.77)
477.34(0.78)
490.35(0.79)

20834(80)
33184(98)
48350(120)
65923(144)
85509(t68)
106800(191)
129550(213)
153570(234)
178690(253)
204760(272)
231670(289)
259300(306)
287560(321)

Values in parenthesis are estimated uncertainties.

TABLE 9.

Co

J K- 1 mol-I

0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500

Ideal gas thermodynamic properties of DL-2-butanol (C4H 90H) at 1 barM = 74.1224

e.

{SO(T)-SO(O)}
J K- 1 mol- t

-{GO(T)-HO(O)}/T
J K- 1 mo)-I

5.76
270.07(0.39)
296.99(0.47)
320.10(0.51 )
349.97(0.54)
359.53(0.55)
360.23(0.55)
396.60(0.57)
430.75(0.59)
462.87(0.60)
493.06(0.62)
521.45(0.63)
548.18(0.63)
573.42(0.64)
597.28(0.65)
619.9O{0.65)
641.37{0.66)
661. 78(0.66)
681.22(0.67)

5.76
226.35(0.19)
245.54(0.27)
261.35(0.32)
281.16(0.37)
287.33(0.39)
287.78(0.39)
310.49(0.43)
331.16(0.46)
350.47(0.48)
368.70(0.'0)
386.04(0.51)
402.58(0.52)
418.42{0.53)
433.60(0.54)
448.19(0.55)
462.23(0.56)
475.76(0.56)
488.82(0.57)

0
59.06(0.28)
74.17(0.23)
86.94(0.19)
105.90(0.17)
112.74(0.17)
113.25(0.17)
140.74(0.20)
165.63(0.22)
186.83(0.22)
204.82(0.21)
220.27(0.20)
233.65(0.19)
245.30(0.18)
255.45(0.17)
264.30(0.16)
272.03(0.15)
278.77(0.15)
284.66(0.14)

{HO(T)-HO(O)}
J mo)-I
0
4372(21)
7718(32)
11750(40)
18795(51)
21526(54)
21735(54)
34443(66)
49792(81)
67445(97)
87052(113)
108330(130)
131040(145)
155000(160)
t80050(t74)
206040(188)
232870(201)
260420(213)
288600(224)

Values in parenthesis are estimated uncertainties.

derived ideal gas heat capacities. C;, were used. in conjunction with molecular structure and spectroscopic information from the literature, to calculate the barriers to
internal rotation.
The vibrational frequencies of this compound have
been assigned by Pritchard and Nelson 122 and Tanaka. 123
Tanaka's assignment was chosen by Beynon and
McKetta62 for the thermodynamic calculations because it
was based upon a normal coordinate analysis which
yielded better agreement with the frequencies for which
assignments are well established. The numerical values
are given in Table A-2.

Beynon and McKetta62 calculated the values of IaIJc

and Ir for the CH3 and OH tops using an assumed molecular structure. Simple cosine potential barriers of the
type V = 1/2 V3(1 - cos 38) were employed for the
methyl and hydroxyl internal rotations, with the three
methyl tops being considered as equivalent and independent. The barrier heights were selected so that the calculated C; and {SO(T)-SO(O)} were consistent with the
experimental data. These internal rotational constants
are presented in Table A-3.
From the above data, Beynon and McKetta computed
the ideal gas thermodynamic properties in the tempera-

J. Phys. Chern. Ref. Data, Vol.1S, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

ture range from 0 to 1000 K and at 1 atm. Their results

were adopted by Stull et al. 466 Because of the lack of new
values for the molecular constants, we employed the vibrational assignments, reduced moments for the CH3 and
OH rotors and the individual internal rotation barrier
heights reported by Beynon and McKetta62 for recalculating the ideal gas thermodynamic properties. The value
of IJJc was determined by Valenzuela481 from microwave spectroscopy. The results are listed in Table 10.
The calculated C; and {Sft(T)-Sft(O)} values agree with
the experimental values as shown in Table A-12. The
calculated ideal gas entropy value at 298.15K, 326.70 J
K -I mol-I, agrees well with our selected third law entropy value of 327.00 J K- 1 mol- 1 given in Table A-26.
2.2. Alkandiols

Data sufficient for the calculation of ideal gas thermodynamic properties were found only for 1,2-ethanediol
(ethylene glycol). They are summarized below.
. Numerous studies of spectra and molecular stucture of
1,2-ethanediol have been published over the past fifty
years. It is highly associated in condensed phases. It has
long been recognized that an intramolecular hydrogen
bond between the two hydroxyl groups is present in isolated molecules. The interpretation of molecular spectra
of this compound has been a challenge during this period.
Internal rotation takes place about the two C-Obonds
and the C-C bond. Although the intramolecular hydrogen bond is comparatively weak, it does exen a strong
influence on the potential energy governing internal rotation. In fact the three modes are strongly interacting.

TABLE

K
0
100
150
200
273.15
298.15
300

The molecular spectra of solid and liquid phases are

dominated by associated species. The spectra of the gas
phase at room temperature and above is complicated by
rotational-vibrational interactions and by the numerous
energy states associated with internal rotations. In recent
years the availability of spectra of isolated molecules
trapped in inert gas matrices have made possible improved assignments of the fundamental modes.
As a reasonable approximation, 1,2-ethanediol may be
treated as mixture of conformers. Consider labelling the
three staggered rotational conformations corresponding
to potential energy minima about a bond by T (trans,
6 = 180 ), G (gauche l (J = 60), and G' (gauche, 6 = 300).
Any conformation of 1,2-ethanediol may be identified by
a combination of three symbols, such as TGG'. The first
symbol applies to one hydroxyl group, the second to the
c-c rotation, and the third to the other hydroxyl group.
There are 27 combinations, but only 12 are energetically
different. An intramolecular hydrogen bond can exist
only when the C-C rotation is in a gauche position.
From his electron diffraction study Bastiansen414 concluded that the configuration about the C-C bond was
entirely gauche. He could not determine the positions of
the hydrogen atoms in the hydroxyl groups. In 19'0
Allen and Sutton324 published a compilation of molecular
structure of 1,2-ethanediol based on electron diffraction
studies, including some unpublished work of Bastiansen
and Donahue.
Several partial assignments of vibrational modes, such
as those by Kuroda and Kugo41S and White and
Lovell,416 were made before 1960. They were largely
based on spectra of condensed phases. They also assumed that both the trans and gauche configurations of

10. Ideal gas thermodynamic properties of2-methyl-2-propanol (C4 H 90H) at 1 bar"

M = 74.1224

Co
f
J K- mol-I
'

{SO(T)-SO(O)}
J K- ' mol-I

-{GO(T)-HO(O)}IT
J K-I mol-I

{HO(T)- HO(O)}
J mol I

0
52.73(0.35)
70.40(0.31)
85.29(0.25)
106.29(0.21)
113.63(0.21 )
114.18(0.21)

0
240.24(0.21 )
265.07(0.33)
287.40(0.41)
317.07(0.47)
326.70(0.48)
327.40(0.48)

0
201.11(0.11)
218.37(0.15)
232.88(0.20)
251.52(0.26)
257.42(0.28)
257.85(0.28)

400

142.99(0.23)

364.24(0.52)

279.89(0.34)

33742(79)

500

168.39(0.25)
189.64(0.24)
207.48(0.22)
222.71(0.21)
235.85(0.20)
247.26(0.19)
257.10(0.18)
265.84(0.17)
273.37(0.16)
279.92(0.15)
285.62(0.14)

398.96(0.54)
431.60(0.57)
462.21(0.58)
490.93(0.60)
517.94(0.61)
543.40(0.62)
567.44{0.62)
590.20{0.63)
611.78(0.64)
632.29(0.64)
651.80(0.65)

300.27(0.37)
319.46(0.40)
337.69(0.42)
355.07(0.44)
371.68(0.46)
387.59(0.47)
402.86(0.49)
417.53(0.50)
431.65(0.51)
445.26(0.52)
458.38(0.52)

49346(96)
67280(114)
87162(132)
108690(149)
131630(165)
155800(181)
181040(195)
207200(209)
234170(222)
261840(234)
290120(246)

600

700
800
900
1000
1100
1200
1300
1400
1500

1385

0
3912(14)
7004(30)
10904(44)
17907(58)
20656(62)
20867(63)

aValues in parenthesis are estimated uncertainties.

J~

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1386

CHAOETAL.

the C-C rotation were present. Raman spectra were reported by several investigators during this period. 417-419
In 1967 Buckley and Giguere420 published a detailed
IR study of 1,2-ethanediol and several deuterated derivatives in the solid, liquid, and gas phases. They concluded
that the configuration of the C-C rotation is entirely
gauche. They also gave a nearly complete assignment,
including the torsional modes. They made a rough estimate of the barriers to internal rotation but recognized
the

~tTong

At present it appears impractical to calculate directl)

the energy states for the internal rotation modes. W(
therefore assume a RRHO model for an equilibrium mix
ture of the first four low energy conformers, TGG',
GGG', TTT, and TTG'. The energies and geometries
calculated by Van Alsenoy and Van Den Enden were
adopted. The frequencies for the skeletal vibrations assigned by Takeuchi and Tasumi423 and for the O-H and
C-H stretching modes by Buckley and Giguere420 were

interactions among these modes. They com-

used. The symmetrical C-H stretch was taken to be the

pared the statistical entropy of the RRHO model with

the third-law value. The calculated value was about 10 J
K -1 mol- 1 lower than the experimental one. A value
calculated by assuming free rotation was high by about
44.8 J K- 1 mol-I. They concluded that the internal rotations were governed by a complicated three dimensional

same as the asymmetric C-H stretch. The parameters

used in this calculation are included in Tables A-2 and
A-3.
We expect that the harmonic oscillator energy levels
are separated more than those for the real internal rotation modes. The incorporation of the four conformers

function.

roughly approximates the interactions among these

Newer IR studies of 1,2-ethanediol in inert gas matrices have been published. 421 -423 Gunthard and co-workers421 ,422 also concluded that the C-C rotation was in the
gauche position and assigned the fundamental vibrations
accordingly. They calculated an entropy of 293.76 J K- 1
mol- 1 at 298.15 K for the RRHO model. This is 18.1 J

modes. At 298.15 K only the TGG' form makes an appreciable contribution to the thermodynamic functions.
The contribution of the three internal rotors was also
approximated by two free rotors, one for a hydroxyl
group and one for the C-C bond, and one restricted hydroxyl rotor. The restricted rotor was assumed to have

K. -I mol- 1 below the third law value.

a three-fold symmetricnl barrier of 8.12 kJ mol-I and a

Takeuchi and Tasumi 423 identified .the TGG' and

GGG' forms of 1,2-ethanediol when freshly deposited in
an Ar matrix. After suitable infrared irradiation they
found evidence for other forms. They carried out normal
coordinate analysis for the TGG', GGG', TTT and TTG
forms of HOCH2CH20H, DOCH2CH20D and

rotational constant of 22.39 cm -I. The frequencies of the

other vibrational modes were taken for a TGG conformer, and the overall symmetry number was 2. This
gives the heat capacity and entropy of 71.7 and 314.5 J
K- 1 mol-l respectively at 298.15 K and 142.2 and 418.4
J K -1 mol- l at 800 K. The free rotor functions give a

DOCD zCD 20D. They gave partial assignments of fre-

constant contribution to the heat capacity which is too

quencies and listed the bond force constants.

Several microwave studies have been published.
Marstokk and Mollendal 424 could not account for their
observations by assuming a rigid rotor model. They concluded that the two niirror image forms, TGG and GGT,
were present and that tunneling occurred between them.

large at low temperatures and too. small at higher temperatures. The entropies for the two calculations. cross at
700K.
Table A-26 shows that the calculated entropy at
298.15 K is 8.04 J K- 1 mol-I below the accepted third
law value. However, since the third law value is based

They also concluded that extensive coupling between

on heat capacity data only down to 90 K, and the vapor-

vibration and rotation was present. Walder, Bauder and

GunthardSo8 interpreted the microwave spectra of
DOCH2CH20D in terms of a semi-rigid model. The
large amplitudes of motion caused a splitting of all rotational transitions. These would be even greater for
HOCH2CH20H. They could not identify particular conformers and did not assume tunneling between forms.
They found that the two hydroxyl groups rotate in a
concerted manner which could be approximated by a
one dimensional potential function.
Caminati and CorbellilO'J identified only the TGG species from microwave spectra of 1,2-ethanediol and several of its derivatives with deteurium in the hydroxyl
groups. They did assume an intramolecular hydrogen
bond. They did not find evidence of tunneling but could
not rule it out for the mono-deuterated species.
The relative energies of various conformers have been
calculated by ab initio SCF methods. 421 ,422,425,426 The most
complete and probably. most accurate are those of
Van Alsenoy and Van Den Enden. 426 They optiniized
the geometries of ten conformers without constraints.

ization data involve an apprecil;'lble uncertainty, the overall uncertainty is around 4 J K- 1 mol-I. For a single
species it would probably be even larger at higher temperatures. This is compensated to some extent by the
contributions. of the other three species assumed for this
model. Because of the various uncertainties we terminated the table of thermodynamic values at 1000 K.
2.3. Ethers

The ideal gas thermodynamic properties of dimethyl

(CH30CH3), ethyl methyl (C2H sOCH3), and diethyl
(C2H50~H5) ethers have been evaluated by Chao and
Hant 57 using statistical mechanical methods. For calculating the internal rotational contributions, each CH3 rotor was treated as an independent rotor. In other words,
no allowance was made for interactions between the two
CH3 rotors in each of these molecules.
2.3.8. Dimethyl Ether

Numerous researchers have investigated the molecular structure and the torsional frequencies of dimethyl

J. Phys. Chem.Ref. Data, Vol. 15, .No. 4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

11.

Ideal gas thermodynamic properties of 1,2~thanediol (CH20HCH20H) at 1 bar"

M = 68.0682

Co
2JK- 1 mol-I

K
0
100
150
200
273.15
298;15
300
400
500
600
700
800
900
1000

1387

{SO(T) -SO(O)}
J K-I mol-I

0
46.1(0.18)
56.3(0.16)
65.0(0.14)
77.9(0~13)

82.7(0.13)
83.0(0.14)
102.2(0.15)
119.4(0.15)
133.9(0.14)
145.8(0.13)
155.9(0.12)
164.5(0.11 )
171.9(0.10)

0
236.5(0.18)
257.2(0.22)
.274;6(0.25)
296.7(0.26)
303.8(0.26)
304.3(0.29)
330.8(0.30)
355.5(0.32)
378.6(0.33)
400.2(0.34)
420.3(0.34)
439.2(0;35)
456.9(0.36) .

-{GO(T)-HO(O)}/T
J K- 1 mol-I
0
199.2(0.10)
215.2(0.12)
227.9(0.15)
243.5(0.16)
248.2(0.16)
248.6(0.18)
265;9(0.20)
281.3(0.22)
. 295~6(0.23)
309.1(0.25)
321.7(0.26)
333.7(0.26) ,
345.2(0.27)

{HO(T)-HO(O)}
Jmol- I
0
3729(15)
6300(23)
9335(32)
14554(35)
16560(35)
16713(46)
25978(57)
37081(68)
49768(79)
63770(90)
78870(100)
94900(110)
111730(118)

Valuesinparenthesis' are ,estimated uncertainties.

6;524cm---clasreponed b'yU>,vas er al:115 TheV30f the

CH3 tap in the CH30CH3. mOlecule has been p'r(wiously
reported as (lL38 0.58) kJ mol-I, 165(11.32 ::1;0.18) kJ'
mol:: 1y, .and (11 .81 0.50) kJmol-l.178
structure of. this compound byelectTondiffTaction~ From
16s
the- microwave' spectra, KasaiandMyers; Blukis et
Based upon the molecular and~spectroscopicconsiantS
al.;66Durigelal.,45 and Lovas et al.~s determined the
shown in Ta.blesA-2 andA-3~ the therriiodynalnic prop- '
rotational constants and moleculatstructlire of , ~erties of .CH30CH1(~t-~et~evalAAted.:The:rsu1tsare
CH30CH3(g)~ Therota.tional constants ofLovasta/.. 485 , presented in Table -12~ -A comparison ofthe observed and
were selected ,for the calculation of la/Jc and F.
',
calculatedC; and {SO(T)-SO(O)lforthis compound'is
'Theinfrared' ,and--Raman ,spectra ,.'of ' dimethyl-ethr
'givenitl,' TableA-'13~
have", been~ reported ',by, marty" researcheJ,"$~ 1!i7~173 :Funda-,,' ~,', '- ,,'Stull etal; ~'ealqulated' the. thermodynamic, properties
mental" vibrational wavenumbers were assigned fOf,this
of, this compound in the temperature-'range.~298.15 :.10
~mpotmdby Snyder and'Zerbi,l72 'Shimanouchi, BOBloin
1000< K~,emplQying,Jh : vibrational assignments> of
et:'q.l:;I7~anQ::Herzberg.174 Blom, :and ,coworketS~73_re~
I<anazawa-and~Nukada,~7",the moments:, of-inertUi.of
-cently ~xamined<theinfrared, and Raman spectra<of
Kasai,andMyers,165. anc.i-abarrierto ',inte1'llalrQtation;ofCII3C>CH3-(g)-.: A,' complete, "general valence force: field
11.38 kl, mol-.I.'J:'he~C; .valuesare;OA%.and3A%
,calculation:onthis_ compound has been made from db ' bigherthan ours at 298.15 K and I()()()K,i't$pectively~
initio" ;(4--31: G) '"energies.' The observed and '. calculatedTheirentropy:at 298.5-K.,,267~06 J,K- 1 mol~I"coinpares "
wavenumbers for dimethylether,~and six:deuterated
well with our :valu~ 9f 267,.34 JK-llIlol....1.The thermoanalogs were compared. ,Theirassignm~nts. offhefu11dadYmmllc properties of dimethyl / ether have been. r~
mental vibrational ,wavenumbers" ,for,' --C1l30CH3"';(g), ~:p6rted by many. other researchers; 48~2
,given:, in _ Table' A,..2;' were. employed_ for<evaluating ", the
2.3.b~ ,D'methY',Ether-tia
:vibI'ational co~tributions.
'
>The:,CFljOCH3' .J;llolecule ,has ~~"symmetry, with.two
The totational:constants"for' ,4imethy, ether.-d3
ether, It haslwv ...'1 ...............nt' rotor$ of three-fold symmetry attached to ,a central atom. Pauling and:Brockway163
and Kimura - and Kubo l64 determined the :tnolecular

-torsional

mod~~

namely theh z ando z . spedeS:-The

'Wavenumber valuesof,bi were:l'eporte&to be froin 239;1

(CH30GOi)-'have, 'f:,een,~eported: by~R1i11clR~tolI6-and

Durig et,aL ~~-:frotn:ananalysis:pfthe~crQ\Vave spec~ra.

to:270cni-~31.5BasedUpon b2,<==241,cm7'"',1,41:~3:1~~,normal
Th~rotaiional' constants:det~ed: b~r;:Bhikis.et aL 166
:'cool'dinate calculation,s176,177 predicted ai, :::;:- 199 to 202
w~re ~lected 'foJ:' thecalclllati9D 9f,thethr~,'princip~
cm:::: 1 43,l?3Using a t\yo-dimensionalF'ourierSeries in'tormoments: ofinertiti: 10:_==: 2'11~1.TX 'iO~39 'g:cm",tJ,,;=
sional'angles,'Lutz~and Dreizler48,6 determined the coefli'!'
9.711H4'X.JO~39 g cml.,:aI;idlc-=='1.083 17:X lO;-~8,g 9m2.
p:ients'Y3 ,,' and V-ifOf the internal rotational ,potential
Shiman01ich1~ assi~ed.a;complete seto; f~I1(jamental
function Jar' CH30CH3"moieculejn ,excited ,torsiollal
vibration~hfr~quencieS-for: OH3QPD3',. (gtwherethe:tor-'
states. '
sional \Va.venumberSfOJ:'CH3 -and,GD) .'rotors -.were-gjven,"
, .: :F(Jr:generatingthe internal rotational enetgyJevelsfor
-as 227 and,l64 cm""'; r.tively.BI6m.l!iaLxl:},reWrted
~the statistical. calculations;' weusedtheaverage,_ of.tpe
. the'vibr~ti()naLassignments~for-:tpis com,p<>undwhlcp.
two,torsionalwavenumbers, Vtor, = 214.5> ~m:":l,as the '-were slightly: different from ,thevalues.of Shimanouchi.
;;torsional frequency, of each,ofthetwoindependen(CH3 Their two,.torsiona! wav~Wnbers-were"calc\dated',from
'totors. .Thistorsionalfrequency was denved;from..apothe data:_ofl..abarbe~et~LJ7!i_atldil:.ab~be-,andForeIF7:Jo,'
i'Gtentialbarrierheight ,-V3 ,: of 10.807 ,k)-- ;mol ""l~and F.:=:
b~.224~c:l,16~ :'CIll ~1:~These :values'. were -c6nsistent:\Vitb,;

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CHAOETAL.

1388
TABLE 12.

Ideal gas thermodynamic properties of dimethyl ether (CH 30CH3) at 1 bar"

M = 46.0688

Co
I'.
J K- 1 mol-I

T
K
0
100
150
200
273.15
298.15
300

400
500

600
100
800
900

{S'(T)-SO(O)}
J K- 1 mol-I

-{GO(T)-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

0
210.25(0.14)
228.72(0.21)
243.58(0.25)
261. 73(0.27)
267.34(0.28)
267.74(0.28)
288.42(0.29)
307.36(0.30)
325.05(0.31 )
341.68(0.32)
357.38(0.32)
372.21(0.33)

0
174.36(0.04)
189.53(0.09)
201.24(0.12)
215.08(0.16)
219.23(0.17)
219.53(0.17)
234.21(0.20)
246.97(0.22)
258.52(0.23)
269.23(0.24)
279.27(0.25)
288.78(0.26)

0
3589(10)
5879(19)
8467(25)
12742(31)
14344(33)
14465(33)
21683(39)
30193(46)
39915(53)
50720(60)
62480(67)
75080(74)

0
42.27(0.20)
48.99(0.16)
54.47(0.11)
62.56(0.09)
65.57(0.08)
65;80(0.08)
78.68(0.10)
91.36(0.10)
102.86(0.10)
113.03(0.10)
121.99(0.09)
129.84(0.09)

1000

136.70(0.09)

386.25(0.33)

297.84(0.27)

88415(81)

1100
1200
1300
1400
1500
1750
2000
2250
2500
2750
3000

142.69(0.08)
147.89(0.08)
152.41(0.08)
156.35(0.07)
159.77(0.07)
166.57(0.06)
171.50(0.05)
175.15(0.04)
177.91(0.04)
180.03(0.03)
181.70(0.03)

399.57(0.33)
412.21(0.34)
424.23(0.34)
435.67(0.34)
446.58(0.34)
471.75(0.35)
494.33(0.35)
514.75(0.35)
533.35(0.35)
550.41(0.35)
566.15(0.35)

306.48(0.27)
314.77(0.28)
322.73(0.28)
330.39(0.29)
337.78(0.29)
355.15(0.30)
371.16(0.30)
386.00(0.31)
399.82(0.31)
412.75(0.31)
424.88(0.32)

102390(88)
116930(94)
131950(100)
147390(106)
163200(111)
204040(124)
246330(135)
289680(144)
333830(152)
378590(159)
423810(165)

Values in parenthesis are estimated uncertainties.

those observed by Groner and Durig44 from infrared

spectra. Therefore, their vibrational assignments were
adopted in this work.
Based upon the molecular constants listed for
CH 30CD 3 (g) in Tables A-2 and A-3, the thermodynamic properties of this compound were evaluated.
Table 13 contains the calculated results.

The three principal moments of inertia: fa = 3.26586

X 10- 39 g cm2, Ib = 1.12135 X 10- 38 g cm2, and Ie =
1.23448 X 10- 38 g cm2 were derived from the rotational
constants determined by Kasai and Myers l65 from the
microwave spectrum of the CD30CD 3 molecule. Snyder
and Zerbi 172 and Blom et al. 173 reported the fundamental
vibrational assignments for this compound. Those given

timated the a2 torsional wavenumbers to be 145 em-I.

Their assignments were adopted in this work.
The microwave data4S predicted the two torsional fundamental wavenumbers at 190.2 and 141.5 em-I. From
normal coordinate analysis,176,177 these two wavenumbers
were calculated to be 186 and 142-144 em-I. In view of
the above predictions, Groner and Durig44 assigned the
b l torsional wavenumber observed in the infrared spectrum at 188.6 cm- I for the CD 30CD3 (g) molecule.
Durig et al. 42 studied the far infrared spectrum of solid
CD30CD 3, and assigned the b2 and a2 torsional
wavenumbers at 207 and 182 em-I, res9ectively.
Lutz and Dreizler486 have determined the coefficients
V3 and V'I2 of the internal rotation potential function for
this compound in excited torsional states, using a two-dimensional Fourier series in torsional angles. For evaluation of the internal rotational energy levels, an average
torsional wavenumber of 1/2(187.0 + 145.0) = 166.0

by Blom et al. were adopted.

em -I and a calculated internal rotation constant F -

2.3.c. Dimethyl Ether-ds

Dimethyl ether-d6 has two torsional frequencies, i. e.

41
Vb\ and Val' Moller et al.
observed the far-infrared torsional vibrational spectra of one-, two-, and three-(CX 3)
top molecules. They assigned the b l torsional band at
195.5 cm- I as an upper limit and obtained V3 = 1217.2
em-I for CD30CD 3 (g). Based upon b l = 192.0 em-I,

3.637 cm- I were employed for each CD 3 rotor. In the

calculation, each rotor was treated independently, as in
the case of treating the CH 3 rotors in the CH 30CH 3
molecule. From these molecular constants, the internal
rotation barrier height (V3) of each CD 3 rotor was evaluated to be 931.0 em-lor 11.138 kJ mol-I. Based upon a

Tuazon

semirigid rotor model, Durig et al. 4S obtained V30

and

Fateley43

calculated

the

a2

torsional

wavenumbers as 152.8 em-I.

Blom et al. 173 investigated the infrared spectrum of this
compound and observed the torsional wavenumber of hi
.as 187 em -I. From their theoretical calculation, they es-

= 897.0 em-I.

V03

Groner and Durig44 analyzed the torsional far infrared

and Raman spectra of the CD 30CD3 (g) molecule, employing a semirigid two-top model. The analysis allowed

J. Phys. Chem. Ref. Data, Vol. 15, No. 4,19as

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

13. Ideal gas thermodynamic properties of dimethyl ether-d3 (CH)OCD 3) at 1 bara

M = 49.0874

Cop.
J K-I mol- 1

K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1750
2000
2250
2500
2750
3000

1389

{SO(T)-SO(O)}
J K- 1 mol-I

0
43.81(0.15)
50.53(0.11)
56.84(0.09)
67.50(0.09)
71.49(0.10)
71.79(0.10)
87.93(0.12)
102.74(0.12)
115.61(0.11)
126.62(0.11)
136.00(0.10)
143.99(0.09)
150.78(0.08)
156.56(0.08)
161.49(0.07)
165.69(0.07)
169.30(0.06)
172.40(0.06)
178.50(0.05)
182.80(0.04)
185.90(0.03)
188.30(0.03)
190.00{0.02)
191.40(0.02)

{HO(T)-HO(O)}
J mol- 1

-{GO(T)-HO(O)}/T
J K- 1 mo}-I

3673(9)
6037(16)
8719(20)
13256(25)
14993(27)
15125(27}
23115(34)
32664(43)
43597(52)
55723(61)
68867(70)
82877(78)
97625(85)
113000(92)
128910(98)
145270(104)
162030(109)
179120(114)
223000(124)
268200(133)
314300(141)
361100(147)
4084OO(152)
456100(157)

183.49(0.06)
199.05(0.10)
211.09(0.13)
225.40(0.16)
229.73(0.16)
230.04(0.16)
245.54(0.19)
259.25(0.20)
271.81(0.21)
283.54(0.22)
294.60(0.23)
305.09(0.24)
315.08(0.24)
324.63(0.25)
333.77(0.25)
342.54(0.26)
350.97(0.26)
359.08(0.26)
378.11(0.27)
395.61(0.28)
411.71(0.28)
426.71(0.29)
440.61(0.29)
453.71(0.29)

220.21(0.15)
239.30(0.20)
254.69(0.23)
273.93(0.24)
280.01 (0.25)
280.46(0.25)
303.33(0.26)
324.58(0.27)
344.47(0.28)
363. 14(Q.29)
380.68(0.30)
397.17(0.30)
412.71(0.31)
427.36(0.31)
441.20(0.31 )
454.29(0.31)
466.71(0.32)
478.49(0.32)
505.51(0.32)
529.61(0.32)
551.41(0.33)
571.11(0.33)
589.11(0.33)
605.71(0.33)

Values in parentheSis are estimated uncertainties.

the calculation of the torsional wavenumber of the infrared forbidden transition for this compound to be 141.7
cm- I , as compared with 141.5 cm- I from the microwave
data. 45
Using the selected molecular constants given in Tables
A-2 and A-3, we calculated the thermodynamic properties of CD30CD3 (g) given in Table 14.
2.3.d. Ethyl Methyl Ether

Ethyl methyl ether (C2H sOCH3) has two rotational

isomers, trans and gauche, in the vapor phase.179-183 The
infrared spectra observed by Kitagawa and Miyazawa,IISU
and infrared and Raman spectra obtained by Perchard l81
indicate that the more stable isomer is the trans form.

CH 2) = 248 cm -I observed by Kitagawa et 01. 182 and

Hayashi and Kwada,184 and the two rotational constants
F = 7.867 cm- I and 5.306 cm- t were employed for the
evaluation of the internal rotational barrier heights (V3)
of the two methyl rotors in the trans isomer molecule.
From vtor and F for the methyl rotors in the CzHsOCH3
molecule, we obtained the values, V3 = 8.31 kJ mol- 1
. and V3 = 17.01 .kJ mol- 1 which compare with the reported values of (10.46

0.42)

kJ mol- I Ilnd (13.81

0.42) kJ mol- l ;t82 and (10.67 0.42) kJ mol-I and 13.77

kJ mol- 1,184 respectively. The V3 for the CH2-CH 2 rotation was calculated from the torsional wavenumber of
115 cm- 1 reported by Hayashi and Kuwada!1I4
Vibrational assignments for thetrans-C2H sOCH3
molecule were also reported by Snyder and Zerbi;172
A~

They reported the energy difference. "u, as 5.65 lcJ

where the two torsional wavenumber& were g1ven

mol-I.
Hayashi and Kuwada l84 measured the microwave
spectra of trans-ethyl methyl ether and its eleven isotopically substituted species. From the derived moments of
inertia they reported~ 10 = 2.99803 X 10- 39 g cm2, Ib =
2.01758 X 10- 38 g cm2, and Ie = 2.15669 X 10- 38 g cm2
They obtained En=6.28 .kJ mol- 1 for the difference between gauche and trans conformers. These were
adopted.
The fundamental vibrational frequencies assigned by

vtor(CH3-O) =

199 cm- 1 and Vtor(CH3-CH2) = 238

em- t Shimanouchi et 01.185 assigned these two
wavenumbers as 200 cm -I and 252 cm -1. They are consistent with our adopted values. Shild and Hayashi49J
measured the microwave spectra of trans-ethyl methyl
ether and its four deuterated species in the ground and
the four lowest torsionally excited states. The coupling
amongst the two methyl and the skeletal torsions were
analyzed. Ninety-six internal rotational energy levels
were generated, using the selected vtor and F for each

Shimallouchi et al.

rotor.

185

were employed for computing the

vibrational contributions to the thermodynamic properties of trans-C zH sOCH 3 (g). The two torsional
wavenumbers, vtor(CH 3-O) = 202 cm- I and vtor(CH 3-

The molecular structure of gauche -C2HsOCH3(g) was

not available. The molecular parameters of the trans isomer 184 were employed for calculating IolJc and F values
J. Phys. Chern. Ref. Data, Vol.1S, No.4, 1986

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1390

CHAOETAL.
TABLE

K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1750
2000
2250
2500
2750
3000

14.

Ideal gas thermodynamic properties of dimethyl ether-d6 (CD 30CD 3) at 1 bar"

M = 52.1060

Co
I!.
J K- 1 mol-I

{SO(T)-SO(O)}
J K- 1 mol-I

-{OO(T)-HO(O)}/T
J K- 1 mol-I

0
216.55(0.26)
236.37(0.33)
252.38(0.37)
272.80(0.39)
279.37(0.39)
279.85(0.39)
304.84(0.41)
328.14(0.42)
349.89(0.43)
370.17(0.44)
389.10(0.45)
406.79(0.45)
423.34(0.46)
438.85(0.46)
453.43(0.47)
467.16(0.47)
480.11(0.47)
492.36(0.47)
520.31(0.48)
545.11(0.48)
567.31(0.48)
587.31(0.48)
605.61(0.48)
622.41 (0.48)

0
178.91(0.11)
194.91(0.17)
207.33(0.22)
222.18(0.26)
226.70(0.27)
227.93(0.27)
243.39(0.30)
258.04(0.32)
271.56(0.34)
284.21(0.35)
296.15(0.36)
307.47(0.37)
318.24(0.38)
328.51(0.39)
338.32(0.39)
347.71(0.40)
356.71(0.40)
365.34(0.41)
385.51(0.42)
403.91(0.42)
420.91(0.43)
436.51 (0.43)
451.11(0.44)
464.71(0.44)

0
45.67(0.23)
52.37(0.15)
59.50(0.11)
72.61(0.12)
77.45(0.13)
77.81(0.13)
96.48(0.15)
112.56(0.15)
125.98(0.14)
137.11(0.13)
146.31(0.12)
153.90(0.11)
160.16(0.10)
165.35(0.10)
169.65(0.09)
173.25(0.08)
176.28(0.07)
178.84(0.07)
183.70(0.06)
187.10(0.04)
189.50(0.04)
191.30(0.03)
192.60(0.03)
193.50(0.02)

{HO(T)-HO(O)}
J mol-I
0
3764(16)
6220(25)
9010(31)
13827(37)
15703(39)
15846(39)
24578(48)
35053(58)
47001(70)
60173(81)
74359(91)
89381(101)
105094(110)
121377(118)
138134(126)
155285(133)
172766(139)
190526(145)
235900(158)
282300(168)
329400(177)
377000(184)
424900(190)
473200(195)

aValues in parenthesis are estimated uncertainties.

for the three rotors in the gauche isomer molecule. The

dihedral angle of this molecule was estimated to be the
same as that in paraffinic hydrocarbons.
The vibrational wavenumbers for the gauche isomer
were taken from Shimanouchi et al. 185 Based upon the
reported torsional wavenumbers and the calculated F
values, we calculated the barrier heights to be V3(CH 30) = 9.57 kJ mol-I, V3(CH 3-C) = 15.04 kJ mol- 1 and
V3(CH 3CH 2- ) = 14.76 kJ mol-I. From these molecular
constants, 108 internal rotational energy levels were generated for each CH 3 rotor.
Kitagawa et al. 182 measured the far-infrared spectra of
ethyl methyl ether and its deuterated species in the crystalline, liquid, and gaseous states. From an analysis of the
isotope effects on the infrared frequencies, the torsional

wavenumbers of the two CH 3 rotors in the gauche isomer were assigned at 192 cm- I and 239 em-I. Normal
vibrations treated with a local-symmetry force field and
force constants, adjusted by the method of least squares,
gave vtor(CH3-0) = 197 cm- l and vtor(CHrC) = 224
em-I.
Using the molecular constants for the trans and gauche
isomers given in Tables A-2 and A-3, their thermodynamic properties were calculated separately. These values, along with the known eqUilibrium compositions of
the trans-gauche mixture, were used to calculate the
thermodynamic properties of ethyl methyl ether (g) in
the temperature range from 0 to 1500 K and at 1 bar.
They are presented in Table 15.

Neither vapor heat capacity nor third law entropy

measurements of ethyl methyl ether were available for
comparison with our calculated values.
Oyanagi and Kuchitsu 156 investigated the molecular
structure and conformation of this compound by gas
electron diffraction and determined the molar composition of the trans-gauche isomeric equilibrium mixture at
20C. The composition of trans (80 8)% in the equilibrium mixture is in agreement with our calculated molar composition of ethyl methyl ether at 20C which
was 84% of trans isomer.
The thermodynamic propenies reported by Stull el
al 466 were estimated by comparison with those. of the
related hydrocarbons.
2.3.e. Dlethyl Ether

The infrared and Raman spectra of this compound

have been studied by many researchers. 155,172,186,187 At
least two rotational isomers, namely the trans-trans (TT)
and the trans-gauche (TG), exist in the gas and liquid
states. Hayashi and Kuwada l88 determined the molecular
structural parameters of the TT isomer from the microwave spectra of six isotopic species of diethyl ether.
They reported that the TT isomer was more stable than
the TG isomer by from 4.6 to 5.7 kJ mol- 1 186,187 Based
upon their rotational constants and molecular structural
parameters, we obtained the following constants: Ia =
4.67366 X 10- 39 g cm2, Ib = 3.73948 X 10- 38 g cm2, Ie =
3.99288 X 10- 38 g cm2, and F = 6.715 em-I.

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE 15.

J K-! mol"!

0
100
150
200
273.15

298.15
300

Ideal ga, thermodynamic properties of ethyl methyl ether (C,H,OCH,l at 1 bar'

M = 60.0956

l'

1391

{s'(T)

a
51.19(0.19)
6}.4)(0.14)
73. 95(0.111
88.30(0.10)
93.30(0.11)
93.67(0.11)

S'(O)}

J K'" mol-'

{G'(T)

U'(O)}/T

J K-' mol-'

0
233.28(0.25)
256.42(0.31)
276.14(0.33)
301.31(0.36)
309.25(0.36)
309.83(0.36)

{H'(T)

H'(0)2

J mol'

0
193.73(0.12)
210.89(0.17)
224.79(0.21)
241.99(0.25)
247.30(0.25)
247.68(0.25)

0
3955.8(14)
6829.0(21)
10269(26)
16204(32)
J8473(34)
18646(34)

400

(13.""~'().13)

339.33(0.37)

266.99(0.28)

29020(42)

500
600
700
800
900
1000

367.03(0.38)
392.70(0.39)
416.17(0.40)
439.39(0,41)
460.70(0,41 )
480.81(0,42)
499.84(0.42)
517.88(0.42)

284.28(0.30)
300.24(0.31)
315.18(0.32)
329.31(0.33)
342.73(0.34)
355.55(0.35)
367.81(0.35)
379.57(0.36)

41372(51)
55478(61)

lIoo

132.66(0.J4)
149.06(0.14)
163.24(0.13)
175.54(0.12)
186.25(0.11 )
\95.58(0.10)
203.71(0.09)

1200

210.77(0.09)

1300
1400
1500

216.92(0.08)

535.00(0.43)

390.S7(O,36)

187370(1")

222.27(0.07)

551.27(0.43)
566.77(0.43)

401.75(0.37)

209330(130)
231800( 136)

226.94(0.07)

412.24(0.37)

71 tlO(72)

88063(82)
106170(92)
125270(100)
145240(109)
165910(116)

I\Values. in parenthesis are estimated uncertainties.

Vibrational frequencies of the TT-isomer have been

reported by Snyder and Zerbi, J72 Wieser et 01.,186
Perchard,lS1 and Perchard et aL 181 Recently,
Shimanouchi and coworkers'S> critically reviewed the
infrared and Raman spectra of the isomeric diethyl
ethers. Their assigments for the fundamental vibrations
of the TT-isomer were adopted here. See Table A-2 for
numerical values.
We treated the two CH, rotors in the ITCH,CH, OCH2CH, molecule as two identical independent rotors, as before. From l\or = 238 cm-' and F =
6.715 em-I, the potential barrier height (V,) was calculated to be 12.79 kJ mol- l for each rotor. The torsional
wavenumber 238 em'" is the average of two reported
torsional wavenumbers, 231 and 245 cm-,.m One hundred and eight (108) internal rotational energy levels
were generated for each rotor for computing the internal
rotational contributions to the thermodynamic properties of TT-C2HsOC2HS (g). The value of V, for the potential function of the ethyl rotor was calculated from
the
corresponding
torsional
wavenumber
of
Shimanouchi et of. 'S5
The molecular structure of TG-diethyl ether was not
available. Thus the molecular parameters for the TTisomer"s and an estimated dihedral angle of 59.2' from
the trans position were employed for calculating I)",
and F for this isomer.

em -1) for each species, were generated. The V3 for the

ethyl rotor was calculated from the mean value of the
two torsional wavenumbers assigned by Shimanouchi et
oL.
The thermodynamic properties of diethyi ether were
evaluated based upon a molecular model which contained an equilibrium mixture of IT-and TG -isomeric
species. The energy Eo=5.73 kJ mol-' was used for the
TG conformer. All the molecular parameters are listed in
Table A-2 and Table A-3. The calculated results appear
in Table 16.
Using flow calorimetry, Counsell et al 160 and Jennings
and Bixler"" measured the vapor heat capacities of diethyl ether. Jatkar{61 determined C; for this compound
in the temperature range from 310 to 620 K by measuring the speed of sound in the vapor. From equilibrium
studies on tbe gas-pbase dehydration of ethyl alcohol to
ethyl ether, Valentin l62 derived the heat capacities for
diethyl ether from 400 to 500 K. These reported C; values are compared with our calculated values in Table
A14.

Counsell el aL '60 evaluated the third law entropy of

diethyl ether (g) at 298.15 K to be 342.2 J K- 1 mol- J,
based upon their low temperature thermal measurements. Using the same low temperature thermal data, we
calculated the entropy as 342.55 J K-{ mol- 1 while our
selected value in Table A-26 is 342.71 J K- 1 mol-i.

The vibrationol wavenumberG for the TGisomer were

Stull at 01- 466 oaloulated the thermodynamic properties

taken from Shimanouchi et aZ. 185 From lito<

227 cm- J
and F = 5.933 cm- I for the trons-CH, rotor; a potential
barrier height of V:, = 13.01 kJ mol-I was obtained.
With the above molecular constants, two sets of internal
rotational energy levels, with 108 levels (up to 16000

of this compound in the temperature range 298.15 to

1000 K., using a selected value of the ideal gas entropy at
298.15 K of 342.67 J K- 1 mol- 1 and the vapor heat capacities estimated by an empirical structural correlation
method.

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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CHAO ET AL.

1:J!)?
"! ,\

0
100
150
200
213.IS
29B.lS
300
400
500
600
700
800
goo
1000
!I 00
1200
1300
1400
1500

1(1 I

1(,

(((nl

f.\I;"

tknw\dYIIHtnic properties of diethy{ ether (C 1H sOC 1 H 5 ) at

M ~ 74.1224

{S'(T)-S'(O)}.

____ C"
__ :...1'_________

J K- ' mol- i

JK lmol

0
62.50(0.25)
84.80(0.20)
99.70(0.16)
114.30(0.15)
119.46(0.15)
1l9.g6(O.IS)
142.81(0.16)
16S.77(O.17)
\86.35(0.16)
204.35(0.15)
220.04(0.14)
233.74(0.13)
245.6S(0.13)
256.08(0.12)
265.12(0.11)
272.97(0.11)

JK

ImQI

J mol-I

()

242.85(0.62)
272.54(0.67)
299.17(0.69)
332.45(0.71)
342.67(0.72)
343.42(0.72)
380.98(0.73)
415.35(0.74)
447.43(0.75)
477.54(0.76)
505.88(0.76)
532.61(0.77)
557.86(0.77)
581.78(0.17)
604.46(0.78)
626.00(0.78)
646.48(0,78)
665.99(0.78)

279,81(0.10)
285.76(0.09)

{W(T)-H'(O)}

- {G'(T)-H'(O)}/T

t ba.-a

199.29(0.41)
218.84(0.48)
235.66(0.53)
257.26(0.57)
263.99(0.59)
264.48(0.59)
289.00(0.62)
3 \\),81(0.64)
330.99(0.66)
349.80(0.67)
361.55(0.68)
384.42(0.69)
400.52(0.70)
415.92(0.70)
430.69(0.71)
444.89(0.7l)
458.57(0,72)
471. 75(0. 72)

4355.5(23)
8054.8(32)
12701(39)
20539(47)
23459(49)
236B0(50)
36795(60)
52239(7t)

69851(83)
89422(95)
110660( 106)
133360(117)
157350(128)
1S245D(137)
208520(146)
235430(155)
263080(163)
291370(171)

aValues in parenthesis are estimated uncertainties.

Many researchers have observed the infrared 170.2("'209

and Raman,lo.m spectra of propanone (g). The funda-

adopted V, = (3.255 0.084) kJ mol-' and F = 5,727

em -, 49, for calculating the internal rotational energy
levels (0-16780 cm- J). The torsional wavenumber (0 .....
I) was lO4.8 cm-'.
Based upon the two torsional wavenumbers, V" = lOS
em -, and v,. = 109 em. -I and the internal rotational
constants reported by Fateley and Miller,"o the barrier
height was evaluated to be 3.473 kJ mol- l for each CH3
rotor. The value of V3 was reported to be (3.28 0.17)
kJ mol-' by Swalen and Costall1."
The ideal gas thermodynamic properties were calculated u~ing the selected molecular and spectroscopic
constants listed in Tables A-2 and A-3. The results appear in Tahle 17.
Pennington and KobeJB9 measured the vapor heat capacities of this compound as a function of pressure, from
1/3 to Sf'!> atm, and at four temperatures, 338.2, 371.2,
405.2 and 439.2 K. From the CF values measured at 1/3
atm and the second virial coefficients given in the literature,'l' the heat capacities of propanone vapor in the
ideal gaseous state, C;, were calculated at these four
tpmpP-TntllTp., and pr""p.nt"d in Table A-17. The agreement between our calculated C; and the experimental
values is excellent.
Based upon low temperature thermal measurements,

tnent~l

an experimental third.law ~ntf(\I'Y "f(294.6

2.4. Alkanones
Pmp""o"" ("""tUlle, CH,COCH,) Hnd 2-butauune

(ethyl methyl ketone, CH,CH,COCH,) are the two simplest aliphatic alkanones. Their thermodynamic properties in the ideal gaseous state have been reported, m-193
!Jut the <="kulaliuIIS used im;omplete and inac<=urate iuput data for the molecular and spectroscopic parameters.
Due to the availability of a more complete and reliable
set of data on the molecular structure, vibrational a~sign
ments, and torsional frequenCies for these two compounds, Chao and Zwolin~ki '94 reevaluated their
thermodynamic properties. The selection of the input
data and method for calculating the thermodynamic
propenles of these compounds are briefly described.
2.4.a. Propanone

The molecular structure. rotational cnnstants. and pntential barrier to internal rotation of propanone has been
investigated by electron diffraction"""" and microwave
spectroscopy."....."For computing Iahr" the values of
T,n_ h~ And T" cip.tp:l'minp(i by
used.

Npl~nn

J.1nn PiPTC"_I?'_4-9:' We.rp

vibrRtional W:\1venumbers of this compound have

+ 1.0) J K-'

been reported. 219 22 ' Recently Shimanouchi'" critically

reviewed the spectral data in the literature and assigned
a complete set of fundamental vibrational wavenumbers
for the CH,COCH, nrolecule. These valu"., were employed for calculating the vibrational contributions.
In the calculation of the iuternal rotational contributions we treated the two CH, groups in the molecule as

mol- 1 at 298.15 K is given in Table A-26. Our statistical

entropy value is 297.62 J K-' mol-I. The entropies of
propanone (g) calculated by Pennington and Kobe'" and

two independent identical symmetrical

adopted by Stull ,,(

J.

rotors.

We

Sch"umann nnd A~tonlm are e:iv~n in T:lble A .. 1R.

Ideal gas thermodynamic properties of propanone

were calculated by Pennington and Kobe'" in the temperature range from 0 to 1500 K. These results were

at. 466

Phys. Chem. Ref. Data, Vol. 15, No.4, 198&

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

T
K
0
100
150
200
273.15
298.15
300
400
500

600
700
800
900
1000
1100
1200
1300
1400
1500

17.

1393

Ideal gas thermodynamic properties of propanone (CH,COCH l ) at 1 barS

M = 58.0798

Co
l!.
J K- 1 mol- 1

{SO(T)-SO(O)}
J K- 1 mol- 1

-{GO(T)-HO(O)}IT
J K- 1 mol- 1

0
232.11(0.37)
253.95(0.41)
270.76(0.43)
291.22(0.44)
297.62(0.45)
298.08(0.45)
322.03(0.46)
344.33(0.46)
365.31(0.47)
385.09(0.48)
403.75(0.48)
421.37(0.48)
438.03(0.49)
453.81(0.49)
468.77(0.49)
482.98(0.49)
496.49(0.50)
509.37(0.50)

0
190.00(0.20)
207.87(0.26)
221.56(0.30)
237.55(0.34)
242.32(0.35)
242.67(0.35)
259;56(0.37)
274.30(0.39)
287.74(0.40)
300.25(0.41)
312.03(0.42)
323.21 (0.43)
333.87(0.43)
344.06(0.44)
353.83(0.44)
363.23(0.44)
372.27(0.45)
380.98(0.45)

0
51.73(0.14)
56.18(0.10)
61.20(0.10)
71.09(0.10)
75.02(0.11)
75.32(0.11)
92.06(0.12)
108.08(0.13)
122.20(0.12)
134.43(0.11 )
145.00(0.11)
154.15(0.10)
162.09(0.09)
168.96(0.09)
174.92(0.08)
180.09(0.08)
184.58(0.07)
188.49(0.07)

{HO(T)-HO(O)}
J mol- 1
0
4210(18)
6911(23)
9840(27)
14660(31)
16486(33)
16625(33)
24990(40)
35011(48)
46542(57)
59388(66)
73372(75)
88340(83)
104162(91)
120723(99)
137924(105)
155681(112)
173920(118)
192578(124)

aValues in parenthesis are estimated uncertainties.

199.6 cm- I, V32 = 83.27 em-I, and V33 =60.6 cm,-l andthe
three internal rotation constants (see Table A-3),we
evaluated the potential barrier heightsas:V3 (CH 3) =
Infrared spectroscopy, 223 electron diffraction,224 and
2.17 kJ mol-I, V3 (CH3 in ~Hs) = 11.0 kJ mot l, and
microwave spectroscopy,497 indicate that the trans rotaV(C 2H S) = 1/2[VI(1- cos 30)] where-VI = 7.99 kJ mol-l
tional isomer of 2-butanone is far more stable than the . and V3 =4.00 kJ mot-I.
gauche isomer. Therefore, for evaluation of the thermoSinke and Oetting l93 selected two methyL barriers in
dynamic .properties of this compound, thc trans isomer
the propanone molecule as5.02 and 12.34 kJ mol-I and
was selected.
adopted the skeletal rotational potential function for the
Romers and Creutzberg l95 and Abe, et al. 224 have eluethyl rotor simi.ar to that used by Nickerson et al., 193 Le.
cidated . the molecular structure of trans-2~butanone
the potential function shows three minima per .cycle of
byelectrondiffraction. From microwave spectroscopy,
internal rotation with two equal minima' higher than the
Pierce et al. 497 determined the ground-state rotational
third.
constants for trans-2-butanone and V3 and F for the CH3
To calculate the contribution to the thermodynamic
rotor. These molecular constants were adopted to obtain
properties 'of thia compound from the internal rotation of
JaI.,Ic and the internal rotational energy levels for the
the three rotors in the molecule, Nickerson et al. 193 used
CH3 rotor.
V3(CH 3) == 4~18 kJ mol~1 and V3(CH 3 in CzHs) = 10.04
The molecular structural parameters. of Romers and
kJ mol-I. They employed an equilibrium model between
Creutzberg l95 were employed for calculating the internal
rotational' isomers to compute the contribution for the
rotational. constants for the two rotors, .i. e. CH 3 in C 2H s,
internal'rotation of the. ethyl group. The barrier for rotaand CH2H s. They are listed in TableA-3.
tion of the trans form was 4.18 kJ mol-I. The energy
The infrared2OO, 214, 223, 225-227, 230, 231 and Raman2OO, ,214, 228, 229,
difference between trans and gauche isomers was taken
232-:-234 spectra have been observed by many investigators.
as 2.93 kJ mol-I (the value found in butane23S) plus a
Shimanouchi80 critically reviewed the reported infrared
quantity which represented the energy due to the attracand Raman' spectra and the related theoretical calcula~
tive force between oxygen and the extended methyl
group. They adopted a value of 2.51 kJmo}"-:l for-this
tions for 2-butanone (g) and assigned a complete set of
fundamental vibrational frequencies for transinteraction term to obtain.thebest fit between the calcuCH 3CH2COCH3 (g). The assignments were employed in
lated and, experimental heat capacities.
this 'work.
Using the molecular constnats given in Tables A-2 and
The. torsional frequencies and potentional barriers to
AJ, we calculated the thermodynamic properties for 2internal rotation . in 2-butanone were reported by Shibutanone(g) which are presented in Tablel8 .. A.commanouchi,80 Nickerson et al .,193 and Sinke and Oetting. 192
parison of observed and calculatec:J. C; and (s O(n-S (0
Based upon the three torsional wavenumbers, V31 =
values appears in Table A-19.
2.4.b. 2-Butanone

J. Phys. Chem. Ref. Data, Vol~ 15, No.4, 1986

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1394

CHAO ET AL.
TABLE

T
K

0
100
150
200
273.15
298.15
300
400
500
600
700
800
900

18.

Ideal gas thermodynamic properties of 2-butanone (C 2H sCOCH 3) at 1 bara

M = 72.1066

CO

{SO(T)_SO(O)}

J K'" mo)1

J K- 1 mol- 1

. f'... .. __

{HO(T)-HO(O)}

J mol

lOOO

57.03(0.18)
68.98(0.14)
80.20(0.13)
96.12(0.13 )
101.68(0.14)
102.09(0.14)
124.37(0.16)
145.05(0.17)
163.15(0.16)
178.77(0.15)
192.25(0.14)
203.91(0.13)
213.99(0.13)

1100

222.69(0.12)

'48.37(0.71)

403.81 (0.64)

1'9010(130)

1200
1300
1400

230.21(0.12)
236.70(0.11 )
242.31 (0.1 0)

568.07(0.71)
586.76(0.71)
604.51(0.72)

416.69(0.65)
429.06(0.65)
440.96(0.66)

181660(139)
205020(148)
228970(157)

1500

247.17(0.10)

621.40(0.72)

452.43(0.66)

253450(165)

257.11(0.58)
282.50(0.62)
303.90(0.64)
331.25(0.66)
339.90(0.66)
340.54(0.66)
372.97(0.67)
402.99(0.68)
431.07(0.69)
457.43(0.69)
482.20(0.70)
505.53(0.70)
527.55(0.71)

212.04(0.37)
231.44(0.45)
246.94(0.49)
265.94(0.53)
271. 78(0.54)
272.20(0.54)
293.40(0.57)
312.35(0.59)
329.82(0.61)
346.19(0.62)
361.66(0.63)
376.36(0.63)
390.39(0.64)

4507(22)
7659(28)
11392(33)
17839(39)
20312(41)
20500(41)
31828(50)
45319(61)
60751(74)
77866(86)
96433(98)
116260(109)
137160(120)

aValues in parenthesis are estimated uncertainties.

The thermodynamic properties of 2-butanone in the

ideal gas state were calculated by Nickerson et al. 193 and
Sinke and Oetting. l92 The results of !sinke and Uetting 192
were adopted by Stull et al. 466 For the evaluation of the
internal rotational contributions, Nickerson et al. used

constants. Based upon their reported rotational constants, we derived the three principal moments of inertia
as: 1a = 2.97626 X lU-4Q g cmz, 1b = 2.16U96 X lU-:- 39 g
cm 2, and Ie = 2.46807 X 10- 39 g cm2, respectively.
Dangoisse et al. 482 investigated the microwave spectra of

the tahles of Pitzer and Gwinn, 15 whereas Sinke and

methanal and its isotopic species and obtained the rota-

Oetting employed the tables published by Scott and

McCullough.237 Their calculated entropies at 298.15 K
corrected to 1 bar are compared with our calculated
value in Table A-17. The calculated ideal entropy at
298.15 K, 339.90 J K- I mol-I, agrees well with the selected value of 338.91 J K- 1 mol- 1 given in Table A-26.

tional constants of H 2CO, HDCO, and D 2CO in the

ground state. Their results are in excellent agreement
with those reported by Chu et al. 93 The values of IoI"Je
used are given in Table A-2.
The vibrational assignments recommended by
Shimanouchi80 were employed for evaluating the vibrational contributions. The calculated thermodynamic

2.5. Alkanals

Recently Chao et al. 87 evaluated the ideal gas thermodynamic properties of methanal, ethanal, and their
deuterated species. The selection of the molecular constants used in the calculations were discussed in detail.
Their calculated results were adopted in this work. The
numerical values of the input data used appear in Tables
A-2 and A-3.

functions appear in Table 19. Stull et al. 466 adopted the

thermal functions calculated by Pillai and Cleveland. 483
2.5.b. Methanal-d,

The molecular structure of methanal (formaldehyde,

HCHO) is planar with C 2v symmetry. Reported bond dis-

Oka 124 determined the rotational constants for the isotopic methanals from the parameters used in the analysis
of the K-type doubling spectra and the frequencies of 101
<E- 000 transitions. Dangoisse et al., 482 used microwave
spectroscopy to determine the rotational constants of
this compound in the ground state. From the reported
rotational constants for HCDO(g), A = 198112 25
MHz, B = 34910.84 1 MHz, and C
29561.07 1

tances and angles determined do not agree.

MHz, we oaloulated Ia

2.6.a. Methanal

4.23606 X 10- 40 g cm2, It>

Chu et al. 93 observed weak transitions of the type AJ

= 1, liKa = 2, liKe = 3 in HCHO and DCDO
using double resonance method and by direct absorption
using a Stark modulated spectrometer. Adding these
new transitions into the previously known microwave
and millimeterwave data, and employing a least-squares

2.40388 X 10- g cm2, Ie = 2.83892 X 10- 39 g cm 2, and

IaI"Jc = 2.89087 X 10- 117 g3 cm6 The rotational constants, Band C, were later confirmed by analysis of the
millimeter wave spectrum of HCDO (g) by Takagi and
Oka. 125 The fundamental vibrational wavenumbers used,
see Table A-2, were assigned by Shimanouchi. 80 The cal-

analysis, they obtained an improved set of rotational

oulated results are given in Table 20.

39

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

1395

19. Ideal gas thermodynamic properties of methanal (HeHO) at 1 bar"

TABLE

M = 30.0262
T

K
0

{S~(T)-S"(O)}

Ce

J K- 1 mol-I

J K- 1 mol-I
0

-{OO(T)-HO(O)}IT
J K-' mol-I

{HO(T)-HO(O)}
J mol-I
0

3326(0)
4989(0)
6657(0)

100
150
200

33.26(0.00)
33.28(0.00)

182.02(0.04)
195.51 (0.04)

33.50(0.01)

20.5.11(0.04)

148.77(0.04)
162.25(0.04)
171.83(0.04)

273.15

34.70(0.02)

215.69(0.04)

182.22(0.04)

9144(1)

298.15
300
400
500
600
700
800
900

218.76(0.04)
218.98(0.04)
229.67(0.04)
238.90(0.04)
247.27(0.05)
255.01{0.06)
262.24(0.06)
269.02(0.07)
275.40(0.07)

185.16(0.04)
185.36(0.04)

1000

35.39(0.02)
35.44(0.03)
39.24(0.04)
43.74(0.05)
48.18(0.05)
52.28(0.05)
55.94(0.05)
59.16(0.05)
61.95(0.05)

10020(2)
10085(2)
13809(5)
17956(10)
22554(15)
27581(20)
32996(25)
38754(30)
44813(35)

1100
1200
1300

64.37(0.04)

281.42(0.07)

234.94(0.0.5)

51132(39)

66.45(0.04)
68.25(0.04)

287.11(0.08)
292.50(0.08)

239.05(0.05)
242.96(0.05)

57676(43)
64413(46)

1400

69.80(0.04)

297.62(0.08)

246.68(0.05)

71l1&(50)

1500

71.15(0.03)

302.48(0.08)

250.24(0.05)

78367(53)

195.15(0.04)
202.99(0.04)
209.68(0.04)
215.61(0.04)
220.99(0.04)
225.96(0.04)
230.59{0.04)

aValnes in parenthesis are estimated uncertainties.

TABLE

Cp

J K- 1 mol-I

100
150
200
273.15

20.

Ideal gas thermodynamic properties of methanal-d, (DeHO) at 1 bar&

M = 31.0324
{SO(T)-SO(O)}
J K-I mol-I

0
33.26(0.00)
33.33(0.00)
33.78(0.01)
35.62(0.03)

0
190.69(0.07)
204.18(0.07)
213.82(0.07)
224.58(0.07)

-{GO(T)-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
Jmol-'

0
157.43(0.07)
170.92(0.07)
180.49(0.01)
190.92(0.07)

3326(0)
4990(0)
6665(0)
9194(2)

298.15

36.54(0.04)

227.74(0.07)

193.~8(O.O1)

10096(3)

300

36.61(0.04)
41.18(0.05)
46.15(0.06)
50.87(0.06)
55.09(0.06)
58.75(0.06)
61.89(0.05)
64.55(0.05)
66.81(0.05)
68.73(0.04)
70.36(0.04)
71.75(0.04)
72. 94{0.03)

227.97(0.07)
239.10(0.07)
248.83(0.08)

194.09(0.07)
203.99(0.07)
212.00(0.07)

10164(3)
14046(7)
18412(13)

257 Jll1(O.OR)
265.83(0.09)
273.43(0.09)
280.54(0.10)
287.20(0.10)
293.46(0.10)
299.36(0.10)
304.93(0.11)
310.19(0.11)
315.18(0.11)

218.89(007)

23267(19)

225.02(0.07)
230.60(0.07)
235.76(0.07)
24(}.57(0.08)
245.10(0.08)
249.38(0.08)
253.44(0.08)
257.30(0.08)
261.00(0.08)

28570(24)

400
500
600
700
800
900

1000
1100
1200
1300
1400
1500

34267(30)
40303(35)
46629(39)
53200(44)
59980(48)
66936(51)
74043(55)
81279(58)

avrunes in parenthesis are estimated uncertainties.

2.5.c. Methanal-d2

The ground state rotational constants, A = 141653.3

= 32283.37 MHz, and C = 2618:5.34 MHz,
were reported by Dangoisse et al 482 These constants
agreed with those obtained by Tatematsu et al. 132 and
Chu et al. 93 The corresponding moments of inertia were
IQ = 5.9244 X 10-40 g cm 2, 111 = 2.5995 X 10- 39 g cm 2,
and Ie = 3.2049 X 10- 39 g cm2, which were adopted for
computing the value of lolt/c.
MHz, B

ShimanouchiW recommended the six vibrational wavenumbers observed by Cossee and Schachtschneider133 as
the best values for Dena (g). The thermodynamic
properties of this compound given in Table 21 were calculated with the above data.
2.S.d. Ethanal
The molecular structure of ethanal (acetaldehyde,
CH3CHO) has been investigated by electron diffraction 126-128 and microwave spectroscopy.lZ9-131 The two
J .Phys. Chem.Ref. Data, Vol. 15, No.4, 1986

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139(;

CHAOETAL.
TABLE

K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500

21.

Ideal gas thermodynamic properties of methanal-d2 (DCDO) at 1 bar"

M = 32.0386

COp
J K- 1 mol-I

{SO(T)-SO(O)}

-{GO(T)-HO(O)}/T

{HO(T) - HO(O)}

J K- 1 mol-I

J K- 1 mol-I

J mo)-l

0
33.26(0.00)
33.42(0.00)
34.24(0.02)
36.93(0.04)
38.14(0.05)
38.23(0.05)
43.65(0.06)
49.10(0.06)
54.06(0.06)
58.36(0.06)
61.99(0.06)
65.02(0.05)
67.52(0.05)
69.59(0.05)
71.32(0.04)
72.75(0.04)
73.96(0.03)
74.98(0.03)

0
187.55(0.10)
201.06(0.10)
210.76(0.10)
221. 89(0.10)
225.07(0.10)
225.31(0.10)
237.04(0.10)
247.37(0.11)
256.77(0.11 )
265.43(0.12)
273.47(0.12)
280.95(0.12)
287.93(0.13)
294.47(0.13)
300.60(0.13)
306.37(0.13)
311.81(0.13)
316.94(0.14)

0
154.29(0.10)
167.78(0.10)
177.36(0.10)
187.84(0.10)
190.83(0.10)
191.04(0.10)
201.11(0.10)
209.35(0.10)
216.48(0.10)
222.86(0.10)
228.69(0.10)
234.09(0.10)
239.13(0.10)
243.86(0.11)
248.34(0.11)
252.58(0.11)
256.62(0.11)
260.47(0.11)

0
3326(0)
4991(0)
6679(1)
9272(3)
10210(4)
10281(4)
14371(9)
19011(15)
24173(21)
29800(27)
35823(31)
42178(37)
48809(42)
55668(46)
62716(50)
69922(54)
77259(57)
84707(60)

'Values in parenthesis are estimated uncertainties.

carbon atoms and the hydrogen and o~ygen of the carbonyl group are in a single plane. In this work, the structural parameters determined by Nosberger et al. l:ll from
the moments of inertia of isotopically substituted species
were used to calculated the three principal moments of
inertia as fa = 1.4752 X 10- 39 g cm2 Ib
8.2479 X
10- 39 g cm2, and Ie = 9.1889 X 10- 39 g cm 2 The reduced
moment and the internal rotational constant of the CH 3
top were calculated as 3.648 X 10- 40 g cm 2 and 7.673
em - 1, respectively.
The reported torsional frequency and internal rotational barrier height of the methyl rotor in CH 3CHO
were reviewed by Chao et aI.87 The torsional wavenumber of 150 em -I observed by Fateley and Miller32 and the
derived internal rotational constant, 7.673 em-I, were
employed for evaluating the barrier height as V3 = 4.929
kJ mol-I. Based upon a potential function V = 1/2 V3 (1
- cos 38), 96 energy levels (up to 17000 em-I) were
generated. 28 These energy levels were used for computing the internal rotational contribution. The agreement
between our calculated energy levels and those reported
by Fateley and Miller 32 is excellent. 87
Using the selected molecular constants listed in Tables

agreement between C; (exptl.) and C; (calc.) is good.

The average deviations are 0.2 and 0.59 J K- 1 mol-lor
0.2% and 0.9%, respectively. Our calculated C;,
{HO(n-HO(O)}, and {SO(T)-SO(O)} values are consistent with those calculated previously. 136,137,138
2.5.e. EtnanaI-C11

The molecular structural parameters of CH3CDO by

Nosberger et al. I3l were employed for calculating the
three principal moments of inertia: 10 = 1.8621 X 10- 39
g cm2, Ib = 8.2517 X 10- 39 g cm2, and Ie = 9.5797 X
10- 39 g cm2 The reduced moment and rotational constant for the CH 3 rotor in CH3CDO were computed to
be 3.982 X 10- 40 g cm2 and 7.030 cm-l, respectively.
The vibrational assignments were those given by
Shimanouchi. 80 These are consistent with the assignments reported by Cossee and Schachtschneider l33 with
the exception of two wavenumbers, i.e. 3014(2) cm- I
which were reassigned as 3028 and 2917 em - I by
Shimanouchi.
Using the torsional wavenumber V15 = 145 cm- 1 and
the calculated rotational constant, the internal rotation
barrier height (V3) was derived to be 5.067 kJ mol-i.

A-2 and A-3, the thermodynamic propcrtic5 of cthanal

Following the procedure mentioned previous.ly, 96 inter-

were calculated and are presented in Table 22. Stull et

aI. 466 adopted the evaluations of Pitzer and Weltner. 136
A comparison of heat capacities calculated in this
work with some experimental data is given in Table A13. The Cp values listed in column 2 of Table A-13 were
determined by Coleman and DeVries 134 and are the only

nal rotation energy levels (0 - 16000 cm -1) were generated for computing the internal rotational contributions.
The calculated results are presented in Table 23.

experimental measurements available. Two sets of sec-

struotural .parameters of CD 3CDO (g) are the same as

ond vi rial coefficients for this compound were reported 135,136 for converting the measured real gas heat
capacities to ideal gas heat capacities. In general, the

those of CH3CHO (g),131 the three principal moments of

inertia and the reduced moment of the CD 3 top were
calculated to be Ia = 2.4015 X 10- 39 g cm 2, Ib = 9.7752

2.5.1. Ethanal-d4

Based upon an approximation that the molecular

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1397

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

Ideal gas thermodynamic properties of ethanal (CH3CHO) at 1 bar"

22.

M = 44.0530
->

Co

J K- 1 mol-I

0
100
150
200
273.15
298.15
300

{SO(T)-SO(O)}
J K- 1 mol-I

I'.

0
40.27(0.11)
43.26(0.08)
46A7(0.07)
52.80(0.08)
55.32(0.08)
55.51(0.08)
66.28(0.08)
76.68(0.08)
85.94(0.07)
94.04(0.07)
101.07(0.06)
107.19(0.06)
112.49(0.06)

0
214.07(0.15)
230.98(0.19)
243.85(0.20)
259.22(0.22)
263.95(0.22)
264.29(0.22)
281.73(0.23)
297.65(0.24)
312A7(0.24)
326.34(0.25)
339.37(0.25)
351.63(0.25)
363.21(0.26)

llUO

117.U8(U.U5)

- 374;15(U;26)

1200
1300

12 L06(0.05)
124.50(0.05)
127A9(0.05)
130.09(0.04)

384.51(0.26)
394.34(0.26)
403.68(0.26)
412.:17(0.26)

400
-500
600
700
800
900
1000

1400
1;00

aYaliJes 'in' parenthesis

-{OO(T)-HO(O)}/T

{HO(T)-HO(O)}

J K-I mol,-l

Jmo)-l

0
178.12(0.07)
193.07(0.10)
204~22(0.12)

216.95(0.15)
220.69(0.15)
220.96(0.15)
234.01(0.17)
245.17(0.18)
255;17(0.19)
264.35(0.20)
272.92(0.20)
280.99(0.21)
_' 288.64(0,11)
295.92(0.22)
302.82(0.22)
309.54(0,22)
315.93(0.23)
322.08(0.23)

are estimated uncertainties~

TABLE

23.

Ideal

gas thermodynarill~ propertIes of ethanal-d 1 (CH3CDO)at tbat'

M=

45.0592

Co

{SO(T)~S'(O)}

..;.{OO(T)";'HO(O)}/T

J-K-l mol-'-I

J K-Imol-l-

J K-! mol::-!

0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000

1100
1200
1300

1400
1500

0
3595(9)
5686(13)
-7926(16)11545(20)
12896(21)
12999(22)
19085(27)
26241(33)
34382(38)
43390(44)
53154(49) _
63574(54)
74565(58)
86049(63)
97961(67) '110240(71)
122850(74)
. 135730(78)

I'.

0
40.45(0.11)
43.94(0;08)
47.95(0.08)
55.32(0.09)
58.11(0.09)
58.32(0.09)
69.69(0.08)
80.29(0.08)
89.61(0.07)
97.65(0.07)
104.56(0.07)IlOA9(0.06)
115.58(0.06)
119.95(0.06)
123.71(0.05)
126.94(0.05)
129.73(0.05)
132~ 14(0:04)

0
215.62(0:16)
232.69(0.20)
245,86(0.21) ,
261.85(0.23)
266.82(0.23)
267.18(0.23)
285.52(0.24)
302.23(0.25)
- 317.71(0.25)
_332.14(0.26)
345.64(0.26)
358.31(0.26}"
370:22(0;27)
381.45(0.27)
392.06(0.27)
402;08(0.27)
411.60(0.27)
420.63(0.27)

{HO(T)-ir(o)}

Jmol-'l'

0
179:59(0.07)
194.60(0;11)
205.82(0.13) _
218.75(0.15)
222.57(0.16)
222.84(0.16)
236.26(0:18)
Z47.81(0:19)
~58.18(O.20)
'1.67; 73(0.21)
276;63(0.21 )
285.01(0.22)
292;94(0.22)
3(Xt48(0;23)
307.68(0.23)
314.56{O;23)
321.15(0.23)
327.48)~24)

o
3603(9)
5713(14)_
8006(17)
_11775(21)
13192(22)
13300(22)
19702(28)
27211(35)
35717(40)
45090(46)
55208(51)
65968(56)
77279(6i)
89061(65)
101250(69)
113780(73)
126620(77)
139720(80)

es in parenthesis are, estimated uncertainties..

aYalu

X 10,...39 g cm2; Ie = 1.1109 X 10- 38 g cm2, -and Ir=

6.407 -x 10- 40 g cm2,respectively.
Cossee and Schachtschneider 133 measured the infrared
.'and Raman spectra of this compound and performed the
normaI-eoordinate calculations for many of the isotopic
species., of, acetone, acetaldehyde, ,'and formaldehyde.
Their complete set of 14 fundamental vibrational assign;.
~ents were adopted in - 'this work. The. missing
wavenumber, V14, was assigned to he 670 cm- l by
ShiJl1anouchi. s o '
-

The torsional wavenumber (VIS) has been reported to

be J16,cm-l.~.133.139 The barrier height for internal rotation ofCD 3 tQP ,was determined as:V3 ="(4.60 O~29)
and V6 = -0.372kJ mol- l by Lin and Kilb;l40 V3 ::::(4;82
O.13);kJ~mol-l and Y6= 0.243 .kJmol~l by,Kilbet
al. ;129Y3= (4.87 0.03) kJmol-:-~byHerschbach;36~4
V3 = (5.06<O.42) kJmol~lhy Iijima and Tsuchiya: 41
. Based upon the selected Vtor of 116 em-land OUr cal~
cu1atedFof4~370,cm:-l, avalueofV:, =A.85S'kJmol-:-1
. was ,obtaine(f. for'the;Cl)3 top internalrotation;barper
J. Phys. Chem~ Ref. DatajVol. ,15; No. 4~1986

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1398

CHAOETAL.

height in the CD 3CDO molecule. To calculate the internal rotational contributions to the thermodynamic properties, 120 internal rotational energy levels (0 - 16000
cm -I) were employed. Table 24 gives the calculated
thermodynamic properties.
2.5.9. 1-Propanal

Butcher and Wilson l44 studied the microwave spectrum of I-propanal (propionaldehyde, CH 3CH2CHO) vapor in the frequency region 8-38 GHz and confirmed the
existence of two stable rotational isomers, cis and skew.
The cis isomer which has a planar CCCO skeleton is
more stable by (3.77 0.42) kJ mol-I. The skew isomer
is similar but has a dihedral angle of about 131 relative
to the cis. Abraham and Pople,145 using nuclear magnetic
resonance, determined the enthalpy difference between

skew propanal. This information was used for elucidating the internal rotation potential. Their results were
compared with the other recent theoretical calculations. 153,154
From measuring the relative intensities of microwave
spectra, Aleksandrov and Tysovskii484 derived the potential barrier (V3) tor the CH3and CHO tops as (10.8
0.8) kJ mol- 1 and (5.23 0.42) kJ mol-I.
The ideal gas thermodynamic properties of this compound have been reported by Chermin 142 and Vasilev
and Vvedenskii. 143 The values of Chermin were adopted
by Stull et al. 466 In Chermin's calculation the existence
of cis and trans rotamers in I-propanal vapor was not
mentioned, and Vasilev and Vvedenskii only calculated
the thermodynamic properties of the cis isomer.
Frankiss 147 has recalculated the ideal gas thermodynamic

and tl"ans rotamcrs in liquid I-propanal to be 4.18 kJ

properties for I-propanQJ using new molecular data. His

mol-I, while from the temperature dependence of infrared band intensities, Sbrana and Schettino l46 determined this value as (4.31 0.54) kJ mol-I. The value of
Eo in the liquid state is higher than that in the vapor.
The vibrational frequencies of propanal (g) were reported by Chermin,142 Vasilev and V vedenskii, 143
Worden,151 and many others (see reference 143 for details).
The Raman and infrared spectra of this compound in the
liquid (at room temperature) and crystalline state (at
-190 C) were measured between 4000 and 100 cm- 1by
Sbrana and Schettino. l46
Pickett and Scroggin 152 studied the gas-phase microwave spectrum of the skew isomer. They observed

calculated values of {SO(T)-SO(O)} and C; agree with

the experimental results within the experimental uncertainty, as shown in Table A-14. Therefore, his calculated
values were adopted. Frankiss employed the molecular
structural parameters determined by. Butcher and
Wilson l44 from microwave spectroscopy for calculating
IaIJc, I r(-CH 3) and Ir(-CHO) for both the cis and skew
isomers. The fundamental vibrational wavenumbers
were obtained from the infrared arid Raman spectra of
I-propanal. lso Frankiss used a partition function, equivalent in principle to equation (16), to calculate the internal
rotation contribution. He used the classical equation corrected for quantum effects'l to calculate the Q'q.ir terms.

several predicted transitions and \':ollfiulled the theoreti-

The pal-Clmetens he adopted a.re listed in Tables A-2 and

cal treatment for determining the energy level splitting

(471.80 0.07 MHz) of the two lowest levels of the

A-3. His calculated thermodynamic functions for

CH3CH2CHO (g) are listed in Table 25.

cis

TABLE

24. Ideal

Cp

~as

thermodynamic properties of ethanal-d4 (CD 3CDO) at 1 ba~

M = 48.0778

{s O(T) -S O(O)}

J K-I mol- 1

J K-i mol- 1

-{GO(T)-Ha(O)}/T
J K-l mol-I

41.90(0.10)
46.25(0.08)
51. 70(0.09)
61.24(0.10)
64.64(0.10)
64.89(0.10)

220.49(0.24)
239.27(0.27)
252.30(0.28)
269.79(0.29)
275.30(0.30)
275.70(0.30)

400

77 J~6(O_ 10)

2C)tl_18(0.31)

242.91(0.24)

500

89.21(0.09)
98.91(0.08)
107.08(0.08)
113.90{0.08)
119.55(0.07)
124.24(0.07)
128.12(0.06)
131.36(0.06)
134.06(0.05)
136.33(0.05)
138.26(0.04)

314.81(0.31)
331.95(0.32)
347.83(0.32)
362.59(0.33)
376.34(0.33)
389.19(0.33)
401.22(0.34)
412.51(0.34)
423.13(0.34)
433.15(0.34)
442.62(0.34)

255.45(0.26)
266.79(0.26)
277.25(0.27)
287.00(0.28)
296.18(0.28)
304.84(0.29)
313.06(0.29)
320.88(0.30)
328.34(0.30)
335.48(0.30)
342.31 (0.30)

600

1000
1100
1200
1300
1400
1500

100
150
200
273.15
298.15
300

700
800
900

{HO(D-HO(O)}
J mol-I

183.50(0.13)
198.94(0.17)
210.58(0.19)
224.15(0.22)
228.21 (0.22)
228.50(0.22)

3699(12)
5900(16)
8343(19)
12468(23)
14041(25)
14161(25)
21310(32)
29678(39)
39097(46)
49408(52)
60467(58)
72149(64)
84346(69)
96970(74)
109950(79)
123220(83)
136750(87)
150480(91)

aValues in parenthesis are estimated uncertainties.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

:
K

25.

1399

Ideal gas thermodynamic properties of I-propanal (CH 3CH1CHO) at I bar

M = 58.0798

Co
--p-J K- t mo)-I

{SO(n-SO(O)}
J K- t mol- t

-{GO(n-HO(O)}/T

0
240.81(0.22)
245.81 (0.23)
246.21 (0.23)
264.01(0.25)
279.61(0.27)
293.81 (0.28)
307.01(0.29)
319.51(0.30)

J K- 1 mol- 1

{HO(n-HO(O)}
J mol- t
0
15520(29)
17490(31)
17640(31)
26470(38)
36930(46)
49020(54)
62590(63)
77510(71)

0
273.15
298.15
300
400
500
600
700
800

0
77.50(0.10)
80.73(0.10)
80.98(0.10)
96.39(0.12)
112.90(0.12)
128.50(0.11)
142.60(0.11)
155.20(0.10)

0
297.61(0.32)
304.51(0.32)
305.01(0.32)
330.21(0.33)
353.51(0.34)
375.51(0.35)
396.51(0.36)
416.41(0.36)

900

166.40(0.09)

435.41(0.37)

331.41(0.30)

93590(79)

1000
1100
1200

176.30(0.08)
185.10(0.08)
192.90(0.07)

453.51(0.37)
470.81(0.37)
487.31(0.37)

342.71(0.31)
353.71(0.31)
364.11 (0.32)

110700(86)
128800(93)
147800(99)

1300

199.80(0.07)

503.01(0.38)

374.21(0.32)

167400(105)

1400
1500

206.10(0~06)

518.11(0.38)
532.51(0.38)

384.01(0.33)
393.51(0.33)

187700(110)
208600(115)

211.70(0.06)

aValues in parenthesis are estimated uncertainties.

2.5.h. 1-Butanal

The molecular and spectroscopic constants for this

compound were not available so the values of the thermodynamic properties presented in Table 26 w~re estimated. The thermodynamic properties of I-butanal were
computed by addition of the contributions due to the
presence of the CH2 group (see section 1.6) in the
molecule to the corresponding values for I-propanal
which are listed in Table 25. Stull et al. 466 obtained the
thermodynamic properties for this compound from
Chermin. 142
2.6. Alkanoic Acids

mixtures, studied the rapid ethanoic acid dimerization

reaction.
In view of the above experimental evidence, a molecular model of an eqUilibrium mixture of monomers and
dimers was employed for evaluation of the ideal gas
thermodynamic properties of both methanoic and
ethanoic acids.
Employing recent molecular and spectroscopic CODstants, Chao and Zwolinski265 evaluated the ideal gas
thermodynamic properties of methanoic and ethanoic
monomers, dimers, and their monomer-dimer equilibrium mixtures. The sources of input data and methods
of calculation are briefly described below.
2.6.a. Methanolc Acid Monomer

As a result of hydrogen bonding alkanoic (carboxylic)

acid vapor shows significant departure from ideal gas
behavior at low temperatures and/or under high pressures. Vapor density238-247 and heat capacity248,249 measurements suggest the existence of polymeric species in
the vapor, particularly dimers.
Many spectroscopic studies have been made in order
to determine the nature of the hydrogen bonding in the

Methanoic acid (formic acid) monomer (HCOOH) has

two rotational isomers, i. e. cis and trans. In the cis form
the hydrogen on -OB eclipses the oxygen. The molecular structure of the cis isomer has been investigated extensively .by many researchers using microwave, 266-275
electron diffraction,276-280 and infrared281-283 spectroscopy.
The existence of trans isomer in the vapor was men-

dimeric molecules of methanoic and ethanoic acids. The

tioned by Coop et al., 284 Williams,281 and Mariner and

enthalpy of dimerization of methanoic (formic) acid has

been found to range from 46.0 to 61.9 kJ mol- I . 265 The
enthalpy of dimerization of methanoic acid has been determined from the infrared spectra of the dimers as a
function of temperature. 2SO-258 Ramsperger and Porter259
used the ultraviolet absorption spectra to determine the

Bleakney.285 Hocking498 reviewed the studies on the rotational isomerism in methanoic acid.
From spectroscopic studies and additional theoretical
calculations, the cis isomer was found to be more stable
than the trans isomer by from 5.0 to 39.5 kJ mol- I.265
Using microwave relative intensity measurements,

dissociation energy of dimers to monomers. Su 260 ob-

Hocking498 determined the energy difference between

tained the dissociation energy of the dimers from an

electron diffraction study of the effect of temperature on
the molecular structure.
The infrared spectra of ethanoic acid dimers has been
investigated by Weltner,248 Herman and Hofstadter,261
and many others.251-256,263 Cosaro and Atkinson264 using
the ultrasonic absorption in CH 3COOH-CH 3COCH 3

the ground vibrational states of cis and trans-HCOOH

and found the cis rotamers to lie at a higher energy than
the trans rotamers by (1365 30) em-lor (16.33
0.36) kJ mol-I.
Based upon Eo = 8.37 kJ mol- 1 for the reaction: cisHCOOH (g) = trans-HCOOH (g), the concentration of
trans-HCOOH in the equilibrium mixture was calcuJ. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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CHAO ET AL.

I;JOO
I ,\111

r
K
0
273.15
298.15
300
400

500
600
700
800
900
1000
1100
1200
1300
1400
1500

_'I,

Idcnl gas therlllodynamic

coe

J K- 1 mol- 1

properties of I-butanal {CH 3(CH zhCHO} at 1 bar"

M = 72.1066

{SO(T)-SO(O)}
J K- 1 mo}-l

-{GO(T)-HO(O)}/T
J K- 1 mo}-l

0
334.93(0.32)
343.67(0.32)
344.38(0.32)
377.03(0.33)
407.44(0.34)
436.22(0.35)
463.62(0.36)
489.50(0.36)
514.07(0.37)
537.36(0.37)
559.51(0.37)
580.61(0.37)
600.50(0.38)
619.78(0.38)
637.95(0.38)

0
263.45(0.22)
269.78(0.23)
270.27(0.23)
292.84(0.25)
312.75(0.27)
330.96(0.28)
348.01(0.29)
364.15(0.30)
379.53(0.30)
394.13(0.31)
408.10(0.31 )
421.85(0.32)
434.88(0.32)
447.19(0.33)
459.62(0.33)

98.63(0.10)
103.36(0.10)
103.74(0.10)
125.55(0.12)
147.80(0.12)
168.04(0.11 )
185.78(0.11)
201.31(0.10)
214.81(0.09)
226.51 (0.08)
236.98(0.08)
246.04(0.07)
254.19(0.07)
261.33(0.06)
268.18(0.06)

{HO(T)-HO(O)}
J mo}-l
0

19528(29)
22046(31)
22238(31)
33666(38)
47348(46)
63162(54)
80874(63)
100270(71)
121080(79)
143130(86)
166460(93)
190480(99)
215520(105)
241260(110)
268010(115)

aValues in parenthesis are estimated uncertainties.

lated by Fukushima et af. 286 as 2.8% at 298.15 K and

23.7% at 1000 K, respectively. Assuming Eo = 16.74 kJ
mol-I for that reaction, the trans isomer concentrations
in the vapor mixture were evaluated as 0.1 % at 298.15 K
and 9.0% at 1000 K. From microwave spectroscopy,
Lide 287 estimated the minimum possible value of Eo to be
16.74 kJ mol-I. From the foregoing, the thermodynamic
properties of the equilibrium cis -trans mixture are not
significantly different from those of the pure cis form.
Therefore, for the calculation of the ideal gas thermodynamic properties of HCOOH (g), the molecular structure of this compound was taken to be the cis form.
Many experimental determinations on the molecular
structure of methanoic acid have been reported in the
literature. However, only a few results agree. In this
work. the rotational con~tant~ ohtained from microwave
spectroscopy by Willemot et al. 499 were selected to calculate the value of IaI,J" as shown in Table A-2.
Rotational spectra of the methanoic acid monomer
have been studied by numerous investigators261.266-z92 and
reviewed by Willemot et al. ,499 and the fundamental vibrational frequencies for this species have been as~igned. 289-293
Several
normal
coordinate treatments262.286.294-299 have been made. In this work, the vibrational assignments of Millikan and Pitzer293 and
Miyazawa and Pitzer262 were used for evaluation of the
vibrational contributions to the thermodynamic properties.
The internal rotational potential function, (V), for the
OH rotor in the HCOOH (g) molecule ha~ heen ~ug
gested by Radom et al. 300 as V = 1/2[VI (1 - cos 8) +
V2 (l - cos 28) + V3 (l - cos 38)] where 8 = angle of
internal rotation, VI = 24.06, V2 = 37.36, and V3 =
2.3Ul kJ mol-I. Hased upon this potential function and a
calculated value of F = 24.96 cm -1, derived from the
molecular structural parameters of Bellet et aI., 266 we
genera ten sixty internal rotational energy leve18 (0 to

24800 cm -I) for evaluation of the internal rotational contributions to the thermodynamic properties of methanoic
acid vapor. These represent both cis and trans forms.
The reported torsional wavenumber of the OH rotor
in the HCOOH molecule varies from 452 to 695 cm- 1
and the barrier height from 41.84 to 71.13 kJ mol- I.265
Our adopted potential curve indicated that the cis isomer
was more stable than the trans isomer by 26.36 kJ mol- \
and the potential maximum was 51.04 kJ mol-I at 8 =
97 from the cis position. The barrier height of the OH
rotor in HCOOH (g) was estimated to be 45.61 kJ mol- 1
by Miyazawa and Pitzer262 and was recalculated to be
~5.23 kJ mol-I by Bernitt et al. 301 using data of reference
262.
The thermodynamic properties given in Table 27 for
methanoic acid monomer were calculated using the
molecular constants listed in Tables A-2 and A-3. OUf
calculated C; values are higher than those reported by
Green. 302 The C; and {SO(T)-SO(O)} values of Green
are smaller than ours by 1.00/0 and 0.06% at 298.15 K,
and by 6.6% and 0.94% at 1000 K, respectively. Our C;
values are lower than the values of Waring 303 below 550
K and are higher than his values at higher temperatures.
The differences at 298.15 K and 1500 K are -6.6% and
4.8%, respectively. There are no experimental C; data
available for direct comparison. Our calculated
{S(298.1' K)-S"(O)} agrees with the reportt::d lhin.llaw values, (248.70 0.42) J K -I mol-I 303 and (248.11
1.26) J K- 1 mol-,323 respectively. Ideal gas thermodynamic properties of methanoic acid have been calculated
by Green 302 using the available molecular constants. His
results were adopted by Stull et aI. 466
2.6.b. Methanolc Acid Dlrner

Pauling and Brockway,304 using electron diffraction,

suggested the molecular structure of this species,
(HCOOH)l. to be a planar ring with a D 2I symmetry.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1401

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

T
K
0
100
150
200
273.15
298.15
300
400
500
600

700
800
900
1000
1100
1200
1300
1400
1500

27.

Ideal gas thermodynamic properties of methanoic acid monomer (HCOOH) at. 1 bar"
M = 46.0256

Co
f!.

J K- 1 mol-I

{SO(T)-SO(O)}
J K- 1 mol-I

-{GO(T)-HO(O)}/T
J K- 1 mol- 1

0
208.29(0.01)
222.07(0.01)
232.48(0.03)
245.09(0.05)
248.99(0.05)
249.28(0.05)
263.66(0.07)
276.71(0.09)
288.78(0.10)
300.02(0.10)
310.53(0.11)
320.37(0.12)
329.61(0.12)
338.27(0.12)
346.41(0.13)
354.06(0.13)
361.26(0.13)
368.06(0.13)

175.01(0.01)
188.54(0.01)
198.27(0.01)
209.17(0.02)
212.34(0.02)
212.57(0.02)
223.58(0.03)
232.92(0.04)
241.23(0.05)
248.84(0.05)
255.90(0.06)
262.52(0.07)
268.77(0.07)
214.70(0.08)
280.34(0.08)
285.72(0.08)
290.86(0.09)
295.78(0.09)

0
33.44(0.01)
34.91(0.04)
37.83(0.06)
43.54(0.07)
45.68(0.07)
45.84(0.07)
54.52(0.08)
62.63(0.07)
69.81(0.07)
76.04(0.06)
81.34(0.06)
85.77(0.05)
89.40(0.05)
92.33(0.04)
94.65(0.04)
96.48(0.04)
97.91(0.04)
99.02(0.03)

{HO(T)-HO(O)}
J moll

o
3328(0)
5030(1)
6843(4)
9812(9)
10927(10)
11012(10)
16032(18)
21897(24)
28527(31)
35827(36)
43704(42)
52066(46)
60831(51)
69923(55)
79276(58)
88837(61)
98559(64)
108410(67)

aValues in parenthesis are estimated uncertainties.

However, later studies using similar techniques277,280,305

showed its molecular structure to be of C 2h symmetry.
We adopted the molecular parameters reported by
Almenningen et al. 277 for calculating the three principal
moments of inertia for methanoic acid dimer as: fa =
1.3615 X 10- 38 g cm\ Ib
3.7724 X 10- 38 g cm2, and Ie
38
2
= 5.1340 X 10- g cm
The fundamental vibrational. assignments were determined by numerous researchers from a study of its infrared2s0-252,292,306-317 and Raman318.319 spectra. Using a rigid
monomer model. Miyazawa and Pitzer320 made a normal
coordinate treatment of the low frequency vibrations of
the dimer. A normal coordinate treatment of out-ofplane vibrations of this species was performed by them262
using lht: resulLs uf the infrared spectra of four isotopic
species of methanoic acid measured in the vapor phase as
well as in the solid nitrogen matrix in the region 400-800
cm- I . A normal coordinate analysis of the dimeric species has also been made by Kishida and Nakamoto, 321
using the spectral data of Millikan and Pitzer250 and Bonner and Kirby-Smith. 319
Alfllt:llll et ul. m empluyed the best available assignments of fundamental vibrational frequencies and performed a . complete normal coordinate analysis of the
(HCOOH)2 (g) molecule. Their calculated values agreed
well with the experimentally observed ones. 250.251 ,318-320
Therefore, the complete set of fundamental vibrational
assignments reported by Alfeim et af. was adopted.
Tht: thennudynamic pruperties uf methanuic add
dimer (g) were calculated using the molecular constants
as listed in Table A-2 and the results are presented in
Table 28. The statistically calculated entropy at 298.15 K
for methanoic acid dimer (g) was given as 348.74 J K- 1

mol- 1 by Waring303 and 346.81 J K- 1mol- 1 by Green,302

while our recommended value is 332.67 J K- 1 mol- 1 at 1
atm.
2.6.c. Methanoic Acid Equilibrium Mixture

The thermodynamic properties of methanoic acid

were calculated using a molecular mudel uf an t:yuilibrium mixture of monomers and dimers. Using a selected enthalpy of dimerization tlrHO(O) = -61.59 kJ
mol- 1 265 and the calculated {HO(n-HO(O)},
{SO(T)-SO(O)} and C; for HCOOH (g) and (HCOOH)z,
(g), we calculated the ideal gas thermodynamic properties for the methanoic acid eqUilibrium mixture over the
temperature from 50 to 1000 K and at 1 bar as shuwn ill
Table 29. Our calculations showed that at room temperature and atmospheric pressure the methanoic acid. vapor
contained 95% dimers. For evaluation of the thermodynamic properties of methanoic acid vapor, the presence
of dimericspecies in the vapor should not be ignored.
The calculated equilibrium constants for dimerization
are consistent with those reported by Cuulidge ~4'i frum
vapor density measurements.
The .values presented in Table 29 were evaluated
based upon formation of the mixture from one mole of
methanoic acid monomer. From our calculations/6s the
acid vapor contained pure dimers (0.5 mole) attemperatures below 200 K .. As the temperature increases, some
ufthe dimens dt:cumpust: iutu munomt:l-S. This decomposition reaction approaches completion when the temperature . reaches 700 K at 1 bar. If P == 5 bar, this
decomposition temperature is 800 K and when P = 0.1
bar, all dimers decompose into monomers at T = 600 K.
J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1402

CHAOETAL.
TABLE

28.

Ideal gas thermodynamic properties of methanoic acid dimer {(HCOOH)2} at 1 bar"

M = 92.0512

'i
K

0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000

llUU
1200
1300
1400
1500

Co

e.
J K- 1 mol- 1

{SO(T)-SO(O)}

-{GO(T)-HO(O)}IT

{HO(T) - HO(O)}

J K- 1 mol- 1

J K- 1 mol- 1

J mol- 1

0
57.33(0.21)
68.03(0.15)
77.43(0.12)
91.32(0.10)
96.14(0.10)
96.50(0.10)
115.23(0.11)
131.80(0.11)
145.72(0.11)
157.28(0.10)
166.93(0.09)
175.04(0.08)
181.91(0.08)
Hn.76(0.07)
192.76(0.06)
197.05(0.06)
200.74(0.05)
203.94(0.05)

0
208.81(0.30)
227.66(0.37)
242.80(0.41)
261.28(0.45)
266.94(0.46)
267.34(0.46)
287.72(0.49)
305.72(0.51)
322.11(0.52)
337.30(0.53)
351.50(0.54)
364.86(0.55)
377.50(0.55)
389.49(0.56)
400.91(0.56)
411.81(0.56)
422.24(0.57)
432.23(0.'7)

0
252.17(0.48)
277.53(0.53)
298.40(0.55)
324.58(0.57)
332.78(0.57)
333.38(0.57)
363.74(0.58)
391.28(0.59)
416.58(0.59)
439.94(0.60)
461.59(0.60)
481. 73(0.60)
500.54(0.61)
518.16(0.61)
534.71(0.61)
550.32(0.61)
565.06(0.61)
'79.02(0.61)

0
4336(20)
7481(27)
11119(33)
17288(38)
19632(40)
19810(40)
30408(47)
42781(54)
56679(61)
71846(69)
88071(76)
105180(82)
123040(88)
141530(94)
160560(99)
18006O( 104)
199950(108)
220190(112)

"Values in parenthesis are estimated uncertainties.

TABLE

29.

Ideal gas thermodynamic properties of methanoic acid monomer-dimer equilibrium mixture {HCOOH-(HCOOH)2} at 1 bar'
M = 46.0256

K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000

Cop

{SO(T)-SO(O)}

-{GO(T)-HO(O)}IT

{HO(T) - HO(O)}

J K- 1 mol- 1

J K- 1 mol- 1

J K- 1 mol- 1

Jmol- 1

0
28.66(0.21)
34.02(0.15)
38.86(0.12)
58.96(0.10)
84.15(0.10)
86.81 (0.10)
343.17(0.11)
83.72(0.11)
71.47(0.11)
76.80(0.10)
82.19(0.09)
86.83(0.08)
90.68(0.08)

0
126.14(0.48)
138.82(0.53)
149.26(0.55)
163.36(0.57)
169.48(0.57)
170.01(0.57)
232.02(0.58)
275.02(0.59)
288.24(0.59)
299.47(0.60)
309.90(0.60)
319.67(0.60)
328.83(0.61)

0
104.47(0.30)
113.89(0.37)
121.45(0.41)
130.76(0.45)
133.74(0.46)
133.96(0.46)
149.27(0.49)
171.42(0.51)
189.91(0.52)
204.84(0.53)
217.40(0.54)
228.30(0.55)
237.97(0.55)

0
2167(20)
3740(27)
5562(33)
8903(38)
10655(40)
10814(40)
33099(47)
51800(54)
58997(61)
66239(69)
74000(76)
82227(82)
90851(88)

Values in parenthesis are estimated uncertainties.

2.6.d. Methanoic ACld-d1

Willemot et al. 499 determined the rotational constants

for this compound (cis-HCOOD) from microwave .spectroscopy, and these values were adopted for computing
IaIJc.
The infrared spectra of four isotopic species of
methanoic acid, i.e. HCOOH, HCOOD, DCOOH, and
DCOOD, were measured in the vapor phase by Millikan
and Pitzer293 and Miyazawa and Pitzer. 262 They assigned
nine fundamental vibrational frequencies for the four cis
isomers and two trans isomers. Incomplete frequency assignments were reported for the other two trans isomers
(HCOOD and DCOOD).

Fukushima et al. 286 selected the fundamental frequencies of monomeric methanoic acid and its deuteroanalogs by the product rule. On the basis of the selected
frequencies and recent molecular structural parameters,
they performed a normal coordinate treatment for inplane and out-of-plane vibrations.
Because methanoic acid vapor contained predominantly cis isomers, we assumed that this was also true for
its deutero-analogs. Therefore, we only considered the
cis isomer for the evaluation of the thermodynamic properties of methanoic acid-d l .
To calculate the vibrational contributions to the thermodynamic properties of this compound, the vibrational assignments, VI to Vg, reported by Fukushima et al. 286 were used.

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

The internal rotation potential function for the OD

rotor in the cis-HCOOD molecule was adopted from
that for the OH rotor in the HCOOH molecule. The
value of IT was calculated from the molecular structural
parameters given by Bellet et al 266 Sixty internal rotational energy levels were generated for calculating the
internal rotational contributions. The calculated OD torsional wavenumber, 483 cm -I, was in fair agreement
with that reported, 508 cm- I 262 Using the selected
molecular constants listed in Tables A-2 and A-3, the
thermodynamic properties of methanoic acid-dl were
calculated and are presented in Table 30.

methanoic acids. Based upon the selected potential function and a calculated F value, as listed in Table A-3, sixty
internal rotational energy levels (0 to 15000 cm- I ) were
generated for computing the internal rotational contributions to the thermodynamic properties of DCOOD (g)
caused by the presence of a OD rotor. The OD torsional
wavenumber was calculated to be 464 cm -I, compared
with the experimental value of 491 cm- I.262 Using the
selected molecular constants, the thermodynamic properties for methanoic acid-d2 presented in Table 32 were
calculated.
2.6.g. Ethanolc Acid Monomer

2.6.e. Methanoic Acld-d1

For computing the thermodynamic properties of (cisDCOOH), the molecular and spectroscopic constants
were obtained from the same sources as those for the
cis-HCOOD molecule. Their numerical values are listed
in Tables A-2 and A-3. Based upon the same potential
function as that for OH rotor in HCOOH molecule and a
calculated F = 23.76 cm-I, we generated forty-eight internal rotational energy levels (0 to 16000 cm -I). The
calculated OH torsional wavenumber of 595 cm -I is in
fair agreement with the value 629 cm -I reported by
Miyazawa and Pitzer. 262 The evaluated results are presented in Table 31.
2.6.f. Methanolc Acid-d2

The Ia1Jc for cis-DCOOD was calculated from the

rotational constants determined from the rotational spectrum by Bellet et al. 266 The sources of additional molecular and spectroscopic data and the method of calculating
the ideal gas thermodynamic properties of methanoic
acid-d2 were the same as those for the above deuterated

TABLE

30.

The molecular structure of ethanoic (acetic) acid

monomer (CH3COOH) has been studied by electron diffraction 2s0,324,325 and microwave spectroscopy. 326-328,500,501
The cis -ethanoic acid was reported to be more stable
than the trans-ethanoic acid by from 34.7 to 45.6 kJ
mol-I.m
Krisher and Saegebarth328 have determined the rotational constants from microwave spectroscopy. Their results were confirmed by van Eijck et al. SOl and were
adopted in this work for calculating 101Jc, as given in
Table A-2. Using the principal axis method, extended to
include terms through n = 6 in the perturbation series, 329
they identified 30 new E-type transitions.
The internal rotational barrier height V3 of the CH3
rotor was reported by numerous investigators to be from
1.67 to 3.68 kJ mol- I . 26S The values of V3 = (2.02
0.11) kJ mol- i determined by Tabor327 by microwave
spectroscopy, (2.012 O'(X>4) kJ mol-I by Krisher and
Saegebarth,328 and 2.008 kJ mol -1 by Chadwick and Katrih 330 are in good agreement and appeared tn he more
reliable than the others.

Idea.l gas thermodynamic properties of mcthanoic acid-d) (HCOOD) at 1 bar"

M
T

{SO(T)-SO(O)}

J K- 1 mol- t

0
100
150

47.0318
-{GO(T)-HO(O)}/T
J K- 1

JUU]_I

{HO(T)-HO(O)}
J ulul- 1

0
33.82(0.02)
36.28(0.06)
39.92(0.07)
46.07(0.07)
48.25(0.07)
48.41(0.07)

0
209.57(0.02)
223.69(0.03)
234.60(0.04)
247.94(0.06)
252.07(0.07)
252.37(0.07)

19Y.7U(U.UZ)

69HU(6)

210.88(0.03)
214.17(0.03)
214.40(0.03)

10122(11)
11301(13)
11390(13)

"00

57.00(0.07)

267.48(0.09)

225.82(0.04)

16665(19)

500
600
700
800
900
1000

64.94(0.07)
72.04(0.07)
78.29(0.06)

281.07(0.10)
293.55(0.11)
305.13(0.12)
~ 15.9'\(0.12)
326.07(0.13)
335.55(0.13)
344.44(0.13)
352.78(0.14)
360.62(0.14)
367.98(0.14)
374.92(0.14)

235.53(0.05)
244.17(0.06)
252.07(0.07)

22769(26)
29625(32)
37148(37)

259.38(0.07)

45253(42)

266.24(0.08)
272.70(0.08)
278.82(0.09)
284.64(0.09)
290.19(0.10)
295.48(0.10)
300.55(0.10)

53849(47)
62851(51)
72181(55)
81770(59)
91559(62)
101500(65)
111560(68)

200

273.15
298.15
300

lloo

1200
1300
1400
1500

1403

R~.nc;(OOh)

88.13(0.05)
91.78(0.05)
94.70(0.05)
96.97(0.04)
98.73(0.04)
100.07(0.04)
101.08(0.03)

0
176.23(0.02)
189.83(0.02)

0
3333(0)
5078(2)

DValues in parentheSIS are estimated uncertainties.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1404

CHAOETAL.
TABLE 31.

K
0
100
150
200
273.15
298.15
300
400
500
600

700
800
900
1000
1100
1200
1300
1400
1500

Ideal gas thermodynamic properties ofmethanoic acid-d J (DeOOR) at I bar"

M=47.0318

Co
l!.
J K- J mol- 1

{SO(T)-SO(O)}
J K- 1 mol-I

-{GO(T)-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

0
209.97(0.01)
223.80(0.02)
234.36(0.03)
247.38(0.05)
251.46(0.06)
251.76(0.06)
266.90(0.08)
280.66(0.10)
293.33(0.11)
305.10(0.12)
316.05(0.12)
326.28(0.13)
335.83(0.13)
344.77(0.13)
353.14(0.14)
361.00(0.14)
368.37(0.14)
375.32(0.14)

0
176.69(0.01)
190.23(0.01)
199.98(0.01)
210.97(0.02)
214.20(0.02)
214.43(0.02)
225.69(0.03)
235.33(0.04)
243.95(0.05)
251.86(0.06)
259.20(0.07)
266.09(0.07)
272.60(0.08)
278.76(0.08)
284.61(0.09)
290.19(0.09)
295.51(0.09)
300.60(0.10)

0
3328(0)
5036(1)
6875(4)
9944(9)
11110(11)
11199(12)
16484(20)
22665(27)
29630(34)
37268(40)
45478(46)
54164(51)
63236(55)
72617(59)
82241(63)
92053(66)
102010(69)
112070(72)

0
33.47(0.01)
35.17(0.04)
38.66(0.07)
45.42(0.08)
47.87(0.08)
48.05(0.08)
57.51 (0.08)
65.92(0.08)
73.20(0.07)
79.41(0.07)
84.63(0.06)
88.93(0.05)
92.39(0.05)
95.13(0.04)
97.26(0.04)
98.90(0.04)
100.14(0.04)
101.09(0.03)

aValues in parenthesis are estimated uncertainties.

TABLE

K
0
100
150
200
273.15

J K

32.

Ideal gas thermodynamic properties of methanoic acid-d2 (DCOOD) at 1 bara

M = 48.0380

Co
l!.
1 mol-I

{S O(T) -S CeO)}
J K- 1 rpol-I

-{GO(T}-HO(O)}/T
J K- 1 mol- 1

{HO(T)-HO(O)}
Jmol I

0
33.91(0.02)
36.66(0.06)
40.89(0.08)
48.09(0.08)

0
211.13(0.03)
225.33(0.04)
236.43(0.05)
250.23(0.07)

0
177.78(0.03)
191.39(0.03)
201.31(0.03)
212.61(0.04)

0
3335(0)
5091(3)
7026(6)
10277(12)

298.15

50.58(0.08)

254.55(0.08)

215.94(0.04)

11510(14)

300
400
500

50.76(0.08)
60.12(0.08)
68.33(0.08)

254.86(0.08)
270.77(0.10)
285.09(0.11)

216.18(0.04)
227.88(0.05)
237.91(0.06)

11604(14)
17158(21)
23589(29)

600

75.51(0.07)

298.20(0.12)

246.88(0.07)

3n7Rq(15)

700
800
900
1000
1100
1200
1300

81.72(0.06)
86.99(0.06)
91.33(0.06)
94.81(0.05)
97.52(0.05)
99.60(0.04)
101.17(0.04)
102.32(0.04)
103.16(0.03)

310.32(0.13)
321.58(0.14)
332.09(0.14)
341.90(0.15)
351.07(0.15)
359.65(0.15)
367.69(0.15)
375.23(0.15)
382.32(0.16)

255.09(0.08)
262.71 (0.08)
269.84(0.09)
276.56(0.10)
282.92(0.10)
288.96(0.10)
294.71(0.11)
300.20(0.11)
305.44(0.11)

38658(41)
47102(47)
56025(51)
65339(56)
74962(60)
84823(64)
94865(67)
105040(70)
115320(73)

1400
1500

aValues in parenthesis are estimated uncertainties.

We selected the Ir and V3 values determined by

Krisher and Saegebarth328 for calculating the internal ro~
tational contributions of the CH l top in CH)COOH (g).
The torsional wavenumber (0 ~ 1) of the CH 3 top was
calculated to be (75 1) cm- 1 (see Table A-3).
The potential function V = 1/2[VI (1 - cos 8) + V2(1
- cos 28) + V3(1 - cos 38)] with VI = 24.06, V2 =
37.36, and V3 = 2.301 kJ mol-I, suggested for an OH
rotor in HCOOH (g) by Radom et al. ,300 was used. The
molecular structural parameters of Derissen 325 were em~
ployed to calculate the value Ir = 1.317 X 10- 40 g cm2

Based upon the selected V and calculated In sixty internal rotational energy levels (0 to 21500 cm -I) were generated. The OH torsional wavenumber (0 ~ 1) was 565
cm- I
The internal rotational contributions of the CH3 and
OH rotors were evaluated separately. The results of
these two rotor:s were c:uJd~d to yield the total internal

rotational contributions.
The infrared vibrational spectra of ethanoic acid vapor were reported by Sverdlov,318 Weltner,248
Wilmshurst,332 and Haurie and Novak. m Recently,

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

Shimanouchi80 critically reviewed the vibrational spectra

data and assigned a complete set of fundamental vibrational wavenumbers. His assignments were adopted for
evaluating the vibrational contributions to the thermodynamic properties of CH 3COOH (g).
Using the molecular constants listed in Tables A-2
and A-3, we computed the ideal gas thermodynamic
properties of ethanoic acid monomer, which are given in
Table 33. The third law entropy (g, 298.15 K) was reported as 282;84 J K -1 mol- 1 by Weltner. 24s The statistical value was calculated to be (296.2 4.2) J K- I mol- I
by Halford,340 and 282.50 J K- ' mol- I by Weltner,248 respectively. Our value was 283.34 J K -I mol- i at 1 atm. The
thermodynamic properties given in Stull et al. 466 were obtained from W. Weltner (private communication).

2.6.h. Ethanoic Acid Dlmer

Ramsey and Young242.339 measured the vapor pressures

and vapor densities of ethanoic acid and showed that it
was associated in the vapor state. The association of
ethanoic acid vapor by hydrogen bonding was fust suggested by Latimer and Rodebush J ++ and was later verified by Pauling and Brockway304 from electron
diffraction measurements. Because of the importance of
the dimer species in ethanoic acid vapor, its thermodynamic properties. were evaluated.
The molecular structure of ethanoic acid dimer,
(CH 3COOH)i, has been elucidated by Derissen32S and
Karle and Brockwayz80 by the electron diffraction
method. This molecule, similar to the methanoic acid
dimer, has two hydrogen bonds. It has, in addition, two
methyl rotors.

TABLE

T
K

0
100
150
200
273.15
298.15
300

33.

1405

From the molecular structural parameters determined

by Derissen,325 the three principal moments of inertia
were calculated to be 1a = 1.5049 X 10- 38 g cm2, 1b =
9.6817 X 10- 38 g cm 2, and Ie = 1.1078 X 10- 37 g cm2.
The reduced moment of the CH 3 top was 5.221 X 10- 40
g cm2. The potential function was taken to be V = 1V3(1
- cos 38), where V3 = 2.013 kJ mol-I, for each of the
two identical CH 3 tops. Using the selected V3 with a
calculated F of 5.361 cm-I, we generated 108 internal
rotational energy levels (0 to I '(XX) cm 1) for each CH3
rotor.
The vibrational spectra of (CH 3COOH)2 (g) have been
analyzed from infrared,248,2so.311,3Is.332,334,33s,342 far infrared,2s,,252 near infrared,256 and Raman343 spectroscopy
measurements. Incomplete vibrational assignments were
reported. Normal coordinate treatment of this compound has been made by Fukushima and Zwolinski336
and Kishida and Nakamoto. 321 The vibrational assignments of Haurie and Novak333 and Weltner248 were
adopted in this work. Seven missing values were taken
from reference 336. The numerical values of the selected
40 fundamental assignments are listed in TableA-2.
The torsional wavenumber (0 ~ 1) for each CH:; top
was obtained as 74 cm -1 from our internal rotation energy level calculation. Fukushima and Zwolinksi 336 reported the torsional wavenumber V33 = V42 = 100 cm- I.
Table 34 presents the calculated results for ethanoic acid
dimer.
The third law entropy of ethanoic acid dimer at 298.15
K was determined as 410.87 J K-:-l mol- I by Weltner;248
while the .statistical entropy was calculated to be 416. 73
J K- 1 mol- 1 by Halford 340 and 403.50 J K- I mol- I by
Weltner,248 respectively. We obtain 414.28 J K-1mol- 1
at 1 atm.

Ideal gas thermodynamic properties of ethanoic acid monomer (CH,COOH) at 1 bar"

M = 60.0524

Co
e.
J K- 1 mol- 1

{SO(T)-S(O)}

-{GO(T)-HO(O)}/T

J K- 1 mol- 1

JK- 1 mol- 1

0
40.42(0.08)
42.74(0.06)
48.34(0.09)
59.38(0.10)
63.44(0.11 )
63.74(0.11 )

0
231.74(0.41)
248.44(0.43)
261.44(0.44)
278.09(0.45)
283.47(0.45)
283.86(0.45)

{HO(T) - HO(O)}
J mol- 1

0
193.70(0.25)
209.33(0.31)
220.78(0.34)
233.94(0.37)
237.86(0.37)
238.15(0.37)

0
3804(16)
5867(18)
8133(20)
12062(24)
13597(26)
13715(26)

400

79.66(0.11 )

304.41 (0.46)

252.17(0.39)

20i94(33)

500
600
700
800
900
1000
1100
1200
1300
1400
1500

93.93(0.11)
106.18(0.10)
116.63(0.09)
125.50(0.08)
132.99(0.07)
139.26(0.07)
144.46(0.06)
148.76(0.06)
152.30(0.06)
155.22(0.05)
157.63(0.05)

323.75(0.46)
341.99(0.47)
359.16(0.47)
375.33(0.47)
390.56(0.48)

264.57(0.41)
275.97(0.41)
286.64(0.42)
296.73(0.43)
306.32(0.43)
315.46(0.44)
324.22(0.44)
332.60(0.44)
340.66(0.45)
348.39(0.45)
355.84(0.45)

29590(41)
39612(50)
50766(59)
62885(67)
75820(74)
89442(80)
103640(87)
118300(92)
133360(97)
148740(102)
164390(106)

404~91(0.48)

418.43(0.48)
431.19(0.48)
443.24(0.48)
454.64(0.49)
465.43(0.49)

Values in parenthesis are estimated uncertainties.

J. Phys. Chem. Ret Data, Vol. ,15, No. 4,1986 .

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1406

CHAOETAL.
2.6.i. Ethanolc Acid Equilibrium Mixture

The experimental vapor density of ethanoic acid suggests the presence of dimers,240,24I,243,248,253,254,337 trimers,245
and tetramers. 244 In this work, we assumed the vapor
contained monomers and dimers only. The ideal gas en-

scopic method, and 63.0 0.21 kJ mol-I derived from

calculation. 265 Using trial and error, we found that the
value t:,.JI = - 64.02 kJ mol-I at 0 K was optimal. Table
A-20 compares the observed and calculated heat capacities of ethanoic acid (g). The evaluated thermodynamic
properties of ethanoic acid are listed in Table 35.The

thalpy, entropy, and heat capacity data for CH 3COOH

average deviations are 1.0% at P /bar = 0.332, 1.5% at

(g) and (CH 3COOH)2 (g) were obtained from Tables 25

and 26, respectively. The enthalpy of dimerization (I:J.JI)
was adjusted so that the calculated C; values for the
monomer-dimer equilibrium mixture agreed with the experimental values at various temperatures.
The enthalpies of dimerization of ethanoic acid were
determined as (57.7 0.4) to (68.6 3.4) kJ mol-I
(298-483 K; 0.667-153.32 kPa) from vapor density measurements, 47.7 to 71.1 kJ mol-I by infrared spectro-

P /bar = 0.626, and 1.9% at 1 bar.

TABLE

34.

Ideal gas thermodynamic properties of ethanoic acid dimer {(CH 3COOH)2} at 1 bar"
M = 120.l048
{GO(T)

HO(O)}/T
J K- 1 mol- 1

K
0
100
150
200
273.15
298.15

Based upon our calculated values of {SO(400

K)-SO(O)} for ethanoic acid monomers and dimers, the
entropy of dimerization was derived as -149.54 J K- 1
mol- 1 which is consistent with the experimental value of
(-153.9 6.3)J K- ' mol- 1 by Slutsky and Bauer341 and
Taylor. 246 This confirms that our molecular model used
for calculating the ideal gas thermodynamic properties
of ethanoic acid is adequate.

0
86.38(0.28)
96.44(0.18)
108.43(0.17)
129.50(0.17)
137.25(0.17)

0
299.65(1.22)
336.56(1.28)
365.89(1.31)
402.72(1.32)
414.39(1.33)

0
236.09(0.78)
263.73(0.94)
285.71(1.03)
312.22( 1.10)
320.30(1.12)

0
6356(44)
10923(53)
16035(59)
24718(66)
28052(68)

300

137.83(0.17)

415.24(1.33)

320.88(1.12)

28307(69)

400
500

168.63(0.18)
196.49(0.17)
219.96(0.16)

459.16(1.34)
499.87(1.35)
537.83(1.35)

350.04( 1.17)
375.98( 1.21)
399.83(1.23)

43648(78)
61944(88)
82801(99)

700

239.62(0.15)

573.26(1.36)

422.11(1.25)

105810(110)

800

256.19(0.14)
270.27(0.12)
282.29(0.11 )
292.61(0.10)
301.48(0.09)
309.14(0.09)
315.77(0.08)
321.52(0.07)

606.37(1.36)
637.38(1.36)
666.49(1.37)
.693.90(1.37)
719.75(1.37)
744.19(1.37)
767.35(1.37)
789.33(1.37)

443.99(1.26)
462.98(1.27)
481.89(1.28)
499.93(1.29)
517.18(1.29)
533.71(1.30)
549.58(1.30)
564.83(1.31)

130620(120)
156960(130)
184610(139)
213370(147)
243080(155)
273620(162)
304880(168)
336750(174)

600

900
1000

1100
1200
1300
1400
1500

aValues in parenthesis are estimated uncertainties.

TABLE

o
100

150
200

273.15
298.15
300
400
500
600

700
800
900

1000

35.

Ideal gas thennodynamic properties of ethanoic acid monomer-dimer equilibrium mixture

{CH3COOH-(CHjCOOH)2} at 1 bar
M = 33.0482

o
43.19(0.28)
48.22(0.18)
54.30(0.17)
71.81(0.17)
87.52(0.17)
89.09(0.17)
297.22(0.18)
162.30(0.17)
111.33(0.16)
117.30(0.15)
125.64(0.14)
133.03(0.12)
139.27(0.11)

o
149.88(1.22)
168.33(1.28)
183.00(1.31)
201.96(1.32)
208.85(1.33)
209.40(1.33)
258.29{1.34)
318.86(1.35)
341.60( 1.35)
359.11(1.36)
375.32(1.36)
390.56(1.36)
404.91(1.37)

o
118.10(0.78)
131.92(0.94)
142.91(1.03)
156.20(1.10)
160.32(1.12)
160.62(1.12)
177.94(1.17)
200.94(1.21)
222.66(1.23)
240.92(1.25)
256.71(1.26)
270.75(1.27)
283.46(1.28)

o
3178(44)
5462(53)
8018(59)
12498(66)
14470(68)
14634(69)
32138(78)
58959(88)
71363(99)
82728(110)
94881(120)
107820(130)
121450(139)

IV nlues in parcnthcsis are cstimated unccrtainties.

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

2.7. Alkyl Alkanoates

The ideal gas thermodynamic properties of thealkanoates (esters), methyl methanoate and methyl
ethanoate, have been calculated from molecular and
spectroscopic data. Based upon these results, the thermodynamic properties of. the other members of this ho~
mologous series may be estimated by .correlation
methods.
2.7.a. Methyl Methanoate

The molecular structure .of methyl methanoate

(methyl formate, HCOOCH 3) has been studied by electron diffraction346 . and microwave spectroscopy .347,348
O'Gorman et al. 346 reported that the molecular structure
of methylmethanoate has a planarheavy~atom skeleton
with the estermethylgroup cis to the carbonyl oxygen

atom. They also r~ported thatthe average dihedral.angle

of rotation was 25 -from the planar configuration, i.e. a
gauche conformation.
From microwave studies,Cur1347 .and Bauder348 confimiedthat the stable species>of-HCOOCH3(g)was the
cis isomer. They determined the rotational constants,

1407

molecule, respectively. We employed the values V3 ==

4.86 kJ mol-I and F = 5.720 cm- I 348 for generating 108
internal rotational energy levels (0-16800 cm- l) for calculating the internal rotational contributions.
Based upon the molecular and spectroscopic constants, as given in Tables A-2 and A-3, the ideal gas thermodynamicproperties of methyl methanoate were
evaluated. The results appear in Table 36. The thermodynamic properties of this compound reported'by Stull
et al. 466 were estimated based' upon an assumption that
the heat capacity of the gas . was the. same as that of
ethanoic acid gas.
2.7.b. Methyl Ethanoate

The molecular structure of methyl ethanoate. (methyl

acetate, CH3COOCH3) was .determined to. be the cis
form by spectroscopic methods. 351 ,360,36l This is consistent
with.fmdings fQr HCOOCH 3.- Williams et al. 360 studied
the microwave spectrum andfo\1nd the complete ab$ence of any strong non~cis isomer absorPtion Jines .. This
placed a lower litnit on the energy difference _between
the cis and trans conformations ofabout.8.4kJinol~1, ..
Therefore, the cis isomer molecular structure, was used

molecular parameters, and. the internal rotation barrier

for evaluation of the therniodynQ~icproperties .ofthis

height for the CH3 rotor.

Harrisetal. 349 analyzed the Raman spectrao(
aCOOCH 3, DCOOeH3 and HCOOCD 3 iIi the gaseous,
liqpid, a:nd .crystalline states. They collfinnedthe. skeletal
planaritystrllctl.rreproposed from themtcrowave stud-ies.However,theyJound no evidence for a second conformer like trans or gauche presentiri the methyl
methanoate vapor. Consequently, we adopted a cis iso.:.
mer molecular-model for the evaluatioIloflhe ideal gas
thermodynatiric<properties .of this compoiind.
Karpovich359 .investigated. the- rotatiollaLisomers of
methyl methanoate liquid using the ultiisounc1method
and reported the existence of the trans isomer _in the liq;.
uidphase..Thisptoposal was tejected'bythe-later study
of the infrared spectrum of this'compound by
Wibnhurst?Sl
We .. adopted the three principal moments . of inertia
1eriVed from the rotational- constantsdetermined.by
Bauder3~8 from microwave spectroscopy. His results
have been confrrmed by the recent workof Demaisonet

substance.
. Sheridanp~ al. 503 investigated the ,microwave spectrum
of this compound and determined the. three principal
mQmentsof inertia (/a,ib, arid. Ie). and V3andreduced
bamer '. ($) for . each . of the two CH3 ,rotors ':lnth~
CH3COOCHj molecule. Their results were 'selected for
calCUlating the product of the three principal moments
of inertia and for generating internal rotational energy
levels for these two rotors.'
The methyl ethanoate molecule has twomethylro';
tors, namelyO~Ca3and C-CH3.Theeouplingbetween
these two methyl torsional vibrations in the 'methyl
ethanoatemolecule was reported to be small. 360,503 Thus,
we treated the .two rotorsiridependentIy forcal~u1ating
the internal -rotational contributions.
"
. The fundamental .vibrational wavenumbers assigneci
for tlij.s compound by Shitnanouchi80 were adopted, ex;'
ceptfor the two CH3rotor torsional wavenumbers,v26
== 136cm- 1 Cor theC-Ctorsion and v27= UO em-IJoT
the Q~CF!3torsion.Weused133.3 cm- 1 and65!OCril- 1

ci/. S02

for V26 (O..~l) alldvt7 (0-1' 1) respectively, whicll- were

. The vibrational spectra of methyl methanoate349;351-3S8

and the normal coordinate. calculations~Sl-354~~59have been
made by . numerous researchers. Complete.fundamental
vibrational wavenumbershave been assigned by Harris
et al./49 Wilmhurse5l and Suzi and Scherer. 352
Shimanouchi80 critically reviewed the spectral data and
reported a complete 'set of vibrational assignments .for
this compound which we have used ill thiS work;
Pateley'and' Miller32 observed ,the- CH3_torsiollal
~avenUniber; vtor (0 --+ 1) . = 130cm--:\-'aIld determined
rhein!emal:rotation potential bartiet;;;}?) lobe. 4;S7'kJ
mol-I. From mic:rowave spectroscop~,>ellrl347and
Bauder34~ determined 'Y:r as(4.98 0.17) 'Ie] mol ~land
4.86 kJ.mol-lforthe methylrotor:in'the-HCOOCH3
J

derived. .from our selected Vjalld _F valuesfore~cb ro~

tor! 5?3The Nibrational wavenumber of 303 em -1 was adjllstedto 199cm~1 morder to bring the calculated C; to
agree with the experimental values.
Table 37. presents our calculated. idealgastnermoaynamicproperties for methylethanoate. The molecular
data employed for- evaluation are given in TablesA..2
an:dA~3.
.
Vapor heat capacities of methyl ethan()ate for thetempeniturerange from 335 to 450 K and at pressures from
2S:kPato .10L325,kPa,weremeasuredbyvapor-flow
calorimetry by Connett.et al. 362 Extrapolation. of theex~
penmentaLheat:capacities to zero pres8ureiielded"the
values of ideal gas heat capacities; A coniparison"ofour
J~Phys.Chem~

Ref. Data,Vol.15,No~4,1986

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CHAO ET AL.

l.JlHi

I" Iii

---.

"J'
K

0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500

...

-----

\t,

Jd(ld V.,1:. tht:nllodynamic properties of methyl methanoate (RCOOCR 3) at 1 bar"

M = 60.0524

- --

cop

J-K- mol-I
'
0
44.06(0.13)
49.84(0.11)
54.18(0.09)
61.45(0.09)
64.38(0.09)
64.61 (0.09)
77.56(0.11)
90.29(0.11 )
101.57(0.11)
111.26(0.10)
119.53(0.09)
126.61(0.08)
132.68(0.07)
137.89(0.07)
142.38(0.06)
146.24(0.06)
149.58(0.05)
152.48(0.05)

{SO(T)-SO(O)}
J K- ' mol-I
0
227.87(0.20)
246.92(0.24)
261.86(0.26)
279.77(0.27)
285.28(0.28)
285.67(0.28)
306.01(0.29)
324.71 (0.30)
342.19(0.31)
358.59(0.3i)
374.00(0.32)
388.50(0.32)
402.16(0.33)
415.06(0.33)
427.26(0.33)
438.81 (0.33)
449.77(0.33)
460.19(0.34)

-{GO(T)-HO(O)}/T
J K- ' mol-I

{HO(T)-HO(O)}
J mol-I

0
3715(11)
607306)
8675(20)
12892(25)
14465(27)
14584(27)
21684(34)
30086(41)
39693(50)
50347(58)
61897(66)
74214(73)
87186(80)
100721(86)
114740(91)
129176(96)
143971(101)
159077(105)

190.72(0.09)
206.43(0.13)
218.48(0.16)
232.57(0.19)
236.76(0.20)
237.06(0.20)
251.80(0.22)
264.53(0.23)
276.03(0.24)
286.67(0.25)
296.63(0.26)
306.04(0.26)
314.98(0.27)
323.50(0.27)
331.64(0.28)
339.44(0.28)
346.94(0.29)
354.14(0.29)

'Values in parenthesis are estimated uncertainties.

TABLE

K
0
100
150
200

37. Ideal gas thermodynamic Ilrollerties of methy 1 ethanoate (CR 3 COOCH3 ) at 1 bar"
M= 74.0792

Co
e.
J K- 1 mol-I

{SO(T)-SO(O)}
J K:-l mol- 1

0
55.78(0.18)
63.27(0.14)
70.02(0.12)

0
250.35(0.51)
274.46(0.55)
293.57(0.57)

-{GO(T)-HO(O)}/T
J K- 1 mol-I

0
206.13(0.31)
225.07(0.38)
239.89(0.43)

{HO(T)-HO(O)}
J mol-I
0
4422(21)
7407(27)
10738(31)

17i.15

81.56(0_1:2)

317.04(0.58)

257.49(0.47)

16267(37)

298.15
300
400
500

86.03(0.12)
86.37(0.12)
105.31(0.14)
123.40(0.14)
139.25(0.14)
152.84(0.13)
164.47(0.12)
174.46(0.11)
183.06(0.10)
190.47(0.09)
196.87(0.08)
202.39(0.08)

324.38(0.59)
324.91(0.59)
352.34(0.60)

262.79(0.48)
263.17(0.48)
282.09(0.50)
298.71(0.52)
313.91(0.54)
328.08(0.55)
341.44(0.56)
354.12(0.56)
366.20(0.57)
377.75(0.57)
388.82(0.58)
399.44(0.58)

18362(39)
18522(39)
28101(47)
39552(56)
52704(66)
67326(77)
83207(86)
100170(95)
118050(104)
136740(111)
156110(118)
176080(125)

600
100
800
900
1000
1100
1200
1300

377.82(0.61)
401.75(0.61)
424.26(0.62)
445.45(0.62)
465.42(0.63)
484.25(0.63)
502.06(0.63)
518.91(0.63)
534.89(0.63)

1400

2U7.1!S(O.OI)

55U.U7(U.b4)

4UMf/(U.5H)

196!i70(131)

1500

211.34(0.06)

564.51(0.64)

419.51(0.59)

217500(136)

aValues in parenthesis are estimated uncertainties.

calculated C; values with the reported experimental data

appears in Table A-21. The average deviation is 0.3 percent.
Bennewitz and Rossner lO6 determined the heat capacity uf methyl ethanoate vapor at atmospheric pressure,
using flow calorimetry with total condensation. Their
results for C; (g) were 7 J K- 1 mol- 1 higher than those
reported by Connett et aJ. .362

2.8. Epoxyalkanes
The thermodynamic properties of four epoxyalkanes
(alkene oxides), i.e. C2H40, C2D 40, C3H 60, and C4H sO,
were evaluated. A large number uf spel;bolSl;opic investigations have been made in order to determine the
molecular structure and to assign the fundamental vibrational frequencies. but some fundamental freQuency as-

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

signments of ethylene oxide are still subject to controversy. Because of the lack of molecular data, the thermodynamic properties of 1,2-epoxybutane were calculated
from those for 1,2-epoxypropane using the CH 2 increment method.
2.8.a. Epoxyethane

The molecular structure of epoxyethane (ethylene oxide, C 2H 40) has been elucidated by electron diffraction 128,363,364 and microwave spectroscopy. 365-374
Cunningham et al. 368 observed the microwave spectra
of C!2H40, C 12C 13 H 40 and C~2D40. For each isotopic
species; three moments of inertia were derived. From the
nine moments of inertia, they calculated a set of bond
distances and angles. Their results have been reevaluated
by Turner and Howe370 who obtained the three principal
moments of inertia asIa = 3.29413 XlO 39 g cm2 , Ib =
3.79489 X 10- 39 g cm2, and Ie
5.95449 X 10- 39 g cm2.
These values were used for computing the value of IaIJe
given in Tahle A-2_ The values of la. h. and Ie used have
been confirmed by later measurements. 374,392
The infrared and Raman spectra of epoxyethane have
been extensively investigated. The infrared spectra was
measured by Mecke and Vierling,m Bonner/94 and
Linnett. 375 Some overtone and combination bands in the
near infrared were observed by Eyster. 395 The Raman
spectra was measured by Lespiau and Gredy,396 Timmand Mecke,397 Bonner, 394 Ananthakrishnan,398 and
Kohlrausch and Reitz. 399
Later spectroscopic investigations on epoxyethane include those by Thompson and Cave, 376 Lord and
Nolin, 377 Potts, 378 and others.379-386,402-404 A number of
force field calculations387-391 have been reported.
Complete fundamental vibrational assignments for this
substance were reported by Shimanouchi,80 Lord and
Nolin, 377
Potts, 378
Freeman
and
Henshall,389
Venkateswarlu and Joseph,391 Cant and Armstead,400 and
Hirokawa et al. 401 Different authors have proposed considerably different frequencies for V7 (a2, CH2-twisting),
V8 (a2, CH2-rocking), and VI2 (b h ring deformation), for
which no direct spectral evidence has been obtained _374
For evaluation of the vibrational contributions to the
thermodynamic properties of epoxyethane (g), the vibrational assignments VI Vs and V9 VIS reported by Cant
and Armstead,400 and V6 V8 reported by Shimanouchi60
were selected. These values yielded calculated heat capacities and entropies consistent with those determined
. hy Kistiakowski and Rice l58 and Giauqlle and Gordon_ 405
Table A-22 presents a comparison of our calculated C;
and {SO(D-SO(O)} with the experimental values corrected to 1 bar.
Based upon the adopted molecular constants, as given
in Table A-2, the thermodynamic properties of
epoxyethane in the temperature range from 0 to 3000 K
and at 1 bar were evaluated. They appear in Table 38.
Calculated values of the thermodynamic properties of
epoxyethane have been reported by Zeise,504 Gunthard
and Hilbronner,505 Kobe and Pennington,506 and Stull et
al. 466 The calculated statistical entropy at the boiling

1409

point of 283.71 K, 240.66 J K- I mol-I, agrees well with

our selected third law entropy of 240.08 J K -I mol-I.
2.8.b. Epoxyethane-d4

Cunningham et al. 368 studied the microwave spectrum

of epoxyethane-d4 (ethylene oxide-d4,C2D 40) and obtained the three principal moments of inertia. From their
microwave measurements, Turner and Howe 370 redetermined the structural parameters of C 2D 40 (g). The reported moments of inertia: Ia = 4.11521 X 10- 39 g cm2,
Ib = 5.43096 X 10- 39 g cm2, and Ie = 7.27186 X 10- 39 g
cm2370 were employed for computing 101In as listed in
Table A-2.
The infrared and Raman spectra of this species have
been investigated by many researchers 8o,377,383,389,390,391,400
and complete sets of fundamental vibrational wavenumbers .have been assigned. 8o,377,39I,400 In this work, we
adopted the vibrational assignments VI - V5 and V9 - VI5
reported by Cant and Armstead400 and V6 - Vs recommended by Shimanouchi80 for evaluation of the vibrational contributions.
Using the data given in Table A-2, we calculated the
thermodynamic properties of this species in the temperature range from 0 to 3000 K and at 1 bar. The results are
presented in Table 39.
2.8.c. DL-1,2-Epoxypropane

To investigate the effects of hindered internal rotation

of a methyl group for a high barrier, Swalen and Herschbach408 observed the microwave spectrum of 1,2epoxypropane (propylene oxide, C3H60). Rotational
transitions have been assigned up to J = 30 in the
ground torsional state and to J = lOin the frrst excited
torsional state. The structure of the molecule was partially determined by combining the rotational constants
derived from the spectrum with the known structure of
epoxyethane. The reported three principal moments of
inertia: Ia = 4.65756 X 10~39 g cm2, Ib = 1.25628 X
10- 38 g cm2, and Ie = 1.41055 X 10- 38 g cm2 were used
to compute the value of Ia1b1c which is listed in Table
A-2. These three principal moments of inertia408 have
been confirmed by Creswell and Sch\yendeman. 507
The infrared spectra of D L-l ,2-epoxypropane in the
lIquid and vapor phases have been investigated by Tobin:41::l
Based. upon the fundamental vibrational frequencies assigned by Lord and Nollin377 for epoxyethane, he proposed a
complete assignment of fundamental frequencies for nL1,2-epoxypropane (g). These proposed assignments indicated that the substitution of a methyl group for a hydrogen
atom had hardly perturbed the ethylene oxide spectrum.
The major change in the spectrum, aside from the appearance of new bands ascribable to CH3 motions, was the lowering of one wavenumber from about 810 cm- 1 to 745
cm- 1413 The above set of vibrational assignments was the
only set of data available, and it was adopted to compute the
vibrational contributions.
The microwave spectra of the DL-1,2-epoxypropane
molecule were studied by several investigators. 32 ,408--412
J. Phys. Chern. Ref. Data, Vol.1S, No; 4, 1986

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1410

CHAOETAL.
TABLE 38.

K
0
100
150
200
273.15
298.15
300
400
500

600
700
800
900
1000
1100
1200
1300
1400
1500
1750
2000
2250

2500
2750
3000

Ideal gas thermodynamic properties of epoxyethane (C 2H 40) at 1 bar"

M = 44.0530

Cop

J K- 1 mol-I

{SO(T)-SO(O)}
J K- mol-I

-{GO(T)-HO(O)}/T
J K- 1 mol-I

0
202.80(0.04)
216.38(0.04)
226.46(0.04)
238.95(0.04)
242.99(0.05)
243.29(0.05)
259.08(0.06)
274.44(0.08)
289.19(0.09)
303.20(0.10)
316.45(0.11)
328.96(0.12)
340.79(0.12)
351.98(0.13)
362.58(0.13)
372.64(0.13)
382.20(0.14)
391.30(0.14)
412.21(0.14)
431.01(0.15)
447.91(0.15)
463.41(0.15)
477.51(0.15)
490.51 (0.15)

0
169.54(0.04)
183.04(0.04)
192.68(0.04)
203.43(0.04)
206.58(0.04)
206.80(0.04)
217.91(0.04)
227.69(0.04)
236.72(0.05)
245.22(0.05)
253.31(0.06)
261.02(0.06)
268.42(0.07)
275.51(0.07)
282.33(0.08)
288.89(0.08)
295.22(0.09)
301.32(0.09)
315.71(0.10)
328.91(0.10)
341.31(0.11)
352.71 (0.11)
363.51(0.12)
373.51(0.12)

'

0
33.28(0.00)
33.97(0.01)
33.66(0.03)
44.50(0.06)
47.86(0.07)
48.11 (0.07)
62.38(0.09)
75.42(0.09)
86.34(0.09)
95.40(0.08)
103.01(0.07)
109.47(0.07)
11~.01(0.06)

119.77(0.06)
123.87(0.06)
127.43(0.05)
130.51(0.05)
133.19(0.05)
138.50(0.04)
142.40(0.03)
14.5.10(0.03)
147.30(0.02)
149.00(0.02)
150.40(0.02)

{HO(T)-HO(O)}
J mol-I
0
13326(0)
15001(0)
16757(1)
19702(4)
10856(6)
10945(6)
16470(14)
23371(22)
31482(31)
40582(39)
50513(47)
61146(53)
72377('59)
84120(65)
96310(70)
108880(74)
121780(78)
134970(82)
169000(91)
204100(99)
140100(105)
276700(110)
313700(115)
351200(119)

aYalues in parenthesis are estimated uncertainties.

TABLE 39.

Ideal gas thermodynamic properties of epoxyethane-d4 (C 2D 40) at 1 bar"

M = 48.0778

K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200

1300
1400
1500
1750
2000
2250
2500
2750
3000

Cop

{SO(T)-SO(O)}

-{GO(T)-HO(O)}/T

{HO(T)-HO(O)}

J K- ' mol-I

J K- ' mol-I

J K- ' mol-I

J mol-I

0
33.57(0.01)
36.19(0.04)
42.06(0.07)
54.17(0.11)
58.58(0.11)
58.91(0.11)
75.44(0.12)
89.12(0.11)
100.18(0.10)
109.14(0.09)
116.45(0.08)
122.42(0.08)
127.11(0.07)
131.3 8(0.06)
134.73(0.06)
137.54(0.05)
139.89(0.05)
141.88(0.04)
145.70(0.04)
148.30(0.03)
150.20(0.02)
151.60(0.02)
152.60(0.02)
153.40(0.01)

0
207.18(0.04)
221.18(0.04)
232.32(0.05)
247.16(0.06)
252.09(0.07)
252.46(0.07)
271.73(0.10)
290.09(0.12)
307.35(0.14)
323.49(0.15)
338.56(0.16)
352.63(0.17)
1fi" 7Q(0 18)
378.12(0.18)
389.70(0.19)
400.60(0.19)
410.88(0.19)
420.60(0.19)
442.81(0.20)
462.41(0.20)
480.01(0.20)
495.91(0.20)
510.41(0.21)
523.71(0.21)

0
173.89(0.04)
187.44(0.04)
197.30(0.04)
208.69(0.04)
212.12(0.04)
212.37(0.04)
224.81 (0.05)
236.05(0.06)
246.51 (0.07)
256.37(0.08)
265.71(0.09)
274.60(0.10)
'JR10fi(0 11)
291.15(0.11)
298.89(0.12)
306.30(0.12)
313.40(0.13)
320.23(0.13)
336.21(0.14)
350.71(0.15)
364.11(0.15)
376.51(0.16)
388.11 (0.16)
398.81(0.17)

aYalues in parenthesis are estimated uncertainties.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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0
3329(0)
5060(1)
7004(4)
10509(10)
11919(13)
12028(13)
18766(25)
27019(36)
36503(46)
46985(55)
58276(63)
70230(70)
82726(77)
95667(83)
108980(88)
122600(93)
136470(97)
150560(101)
186500(110)
223300(116)
260600(122)
298400(127)
336400(131)
374600(134)

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

Swalen and Herschbach408 determined the internal rotational barrier height for the CH 3 rotor as V3 = 11.34 kJ
mol-I for the ground state and V3 = 10.71 kJ mol-I for
the first excited state.
Herschbach and Swalen409 measured several long progressions of perpendicular transitions in the microwave
spectrum. Rotational transitions have also been assigned
for the first and second excited torsional states. The barrier height V3 for these two excited states was found to
be identical with the ground state result.
Fateley and Miller32 measured the transitions between
excited torsional levels (0 ~ 1, 1 ~ 2, 2 ~ 3) in the far
infrared spectrum. They proposed the potential function:
V (8) = HV3(1 - cos 38) + V6(1 - cos 68)] for the
hindered internal rotation of the CH3 rotor in the
molecule, where (} was the angle of internal rotation.
Based upon the observed torsional wavenumbers: 200
cm- I (0 ~ 1),185.8 cm- I (1 ~ 2),168.8 cm- I (2 ~ 3A),
and 167.5 cm- I (2 ~ 3E), they found V3 = (10.77
0.10) kJ mol-I and V6 = (0.108 0.01) kJ mol-I.
From Raman spectra, Villarreal and Laane 34 confirmed the torsional transitions reported by Fateley and
Miller. 32 They determined the potential function coefficients as V3 = 10.68 kJ mol-I and VtJ = -0.084 kJ
mol-I. The internal rotational barrier height of the
methyl rotor was evaluated to be 10.68 kJ mol-I, and the
torsional wavenumber (0 ~ 1) was calculated as 200
cm -I which was consistent with the observed value.
Employing F = 5.841 cm- I and the above potential

TABLE

function, we generated 108 internal rotational energy

levels for evaluating the internal rotational contributions.
Using the selected molecular constants listed in Tables
A-2 and A-3, we calculated the ideal gas thermodynamic
properties for DL-l,2-epoxypropane as shown in Table 40.
Our calculated value, {S' (298.15 K) -5'" CO)}, was 286.91
J K -I mol-I. The value derived from the low temperature measurements of Oetting407 was (288.4 0.8) J K- I
mol-I.
Thermodynamic functions reported by Green,406
Oetting,407 and Stull et al. ,466 were calculated using statistical mechanical methods and employing slightly different molecular constants. No vapor. heat capacity data
were available for comparison with our calculated C;
values.
2.B.d. DL-1,2-Epoxybutane

The thermodynamic properties of DL-l,2-epoxybutane (butyleneoxide, C4 H sO) were estimated because of the
lack of pertinent molecular and spectroscopic constants required for the statistical mechanical calculation. We evaluated the ideal gas thermodynamic properties of DL-l,2epoxybutane (g) by addition of the thermodynamic properties of a methylene group to the corresponding properties of
DL-l,2-epoxypropane (g) (see section 1.6).
The results are listed in Table 41. The selected third-law
value given in Table A-26 is in reasonable agreement with
the calculated value at 298.15 K.

40. Ideal gas thermodynamic properties ofDL-l,2-epoxypropane (C 3 H 60) at 1 bar"

M= 58.0798

Co

T
K

J K'-I mol-I

{SO(1)-SO(O)}
J K I mol-I

0
100
150
200
273.15

0
39.74(0.05)
46.65(0.08)
54.27(0.09)
67.57(0.11)

5.76
230.12(0.04)
24753(0.05)
261.96(0.07)
280.78(0.10)

298.1:>

1Z.~~(U.12)

21:S6.~HU.lU)

72.92(0.12)
92.99(0.14 )
110.99(0.14)

600

700
800
900
1000
1100
1200
1300
1400
1500
1750
2000
2250
2500
2750
3000

300
400
500

1411

-{GO(T)-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

287.36(0.11 )
311.11 (0.13)
333.85(0.15)

5.76
195.06(0.03 )
209.77(0.04)
221.05 (0.04)
234.57(0.05)
238.70(0.05)
239.00(0.05)
254.08(0.07)
267.78(0.08)

0
3506(1)
5664(5)
8182(9)
12624(15)
14375(17)
14510(18)
22813(29)
33035(41)

126.16(0.13)

355.46(0.17)

280.61 (0.09)

44915(53)

138.89(0.12)
149.68(0.11)
158.91 (0.10)
166.85(0.09)
173.70(0.09)
179.62(0.08)
184.74(0.08)
189.19(0.07)
193.06(0.07)
200.70(0.06)
206.30(0.05)
210.40(0.04)
213.50(0.03)
215.90(0.03)
217.80(0.03 )

375.89(0.19)
395.16(0.20)
413.34(0.21)
340.51 (0.22)
446.74(0.22)
462.11 (0.23)
476.70(0.23)
490.55 (0.24)
503.74(0.24)
534.11 (0.25)
561.29(0.25)
585.84(0.25)
608.17(0.26)
628.64(0.26)
64750(0.26)

292.77(0.10)
304.38(0.12)
315.49(0.12)
326.14(0.13 )
336.37(0.14)
346.21 (0.15)
355.70(0.15 )
364.84(0.16)
373.66(0.16)
394.46(0.18)
413.64(0.18)
431.43(0.19)
448.01 (0.20)
463.51 (0.20)
478.07(0.21 )

58185(65)
72628(76)
88069(85)
104370(94)
1214OO( 102)
139080 (1 09)
1573OO( 116)
176000(122)
195120(128)
244400(141 )
295300(151)
347400 ( 160)
400400( 168)
454100(174)
5083OO( 180)

aValues in parenthesis are estimated uncertainties.

J. Phys. Chern. Ref. Data, Vol.1S, No.4, 1986

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1412

CHAOETAL.
TABLE

41. Ideal gas thermodynamic properties of DL-l,2--epoxybutane (C4 H g O) at 1 bar"

M = 72.1066

Cop
J K- 1 mol-I

K
0
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300

{SO(n-SO(O)}
J K- 1 mol-I

-{GO(n-HO(O)}/T
J K- 1 mol-I

{HO(T)-HO(O)}
J mol-I

0
71.42(0.09)
88.70(0.11 )
95.18(0.12)
95.68(0.12)
122.15(0.14)
145.88(0.14)
165.70(0.13)
182.07(0.12)
195.79(0.11 )
207.32(0.10)
217.06(0.09)
225.60(0.09)
232.80(0.08)
239.10(0.08)

5.76
292.9(0.07)
317.6(0.10)
325.7(0.10)
326.2(0.11 )
357.4(0.13)
387.3(0.15)
415.7(0.17)
442.5(0.19)
467.8(0.20)
491.5(0.21 )
513.8(0.22)
535.0(0.22)
555.0(0.23 )
574.0(0.23)

5.76
238.9(0.04 )
256.7(0.05)
262.2(0.05)
262.6(0.05)
282.4(0.07)
300.4(0.08)
317.3(0.09)
333.3 (0.10)
348.5(0.12)
363.1(0.12)
377.1 (0.13)
390.0(0.14)
403.0(0.15)
416.0(0.15)

0
10800(9)
16630(15)
18930(17)
19110(18)
30010(29)
43450(41)
59060(53)
76470(65)
95390(76)
115600(85)
136800(94)
159100( 102)
181800( 109)
205400 (116)

1400

244.40 (0.07)

:592.0(0.24 )

428.0(0.16)

229600( 122)

1500

249.50(0.07)

609.0(0.24 )

439.0(0.16)

254000 ( 128)

Values in parenthesis are estimated uncertainties.

2.9. Miscellaneous Compounds

In this final section, the selection of the the molecular

and spectroscopic constants are described for furan, 2,5dihydrofuran, and tetrahydrofuran, and the calculated
thermodyanamic properties are discussed.
2.9.a. Furan

Furan (C4H 40) is a five-membered ring compound.

Pauling and Schomaker427 and Beach428 determined its
molecular structure from electron diffraction measurements. The microwave spectrum was observed by
Sirvetz,429 Bak et al. ,430,431 and Sorensen,432 and the rotational and centrifugal distortion constants were reported.
Monostori and Weber433 investigated the pure rotational
Raman spectrum and determined one rotational constant
(a mean value of A and B) and the centrifugal distortion
constant D J With a beam maser spectrometer, Tomasevich et al. 4 .}4 resolved the hyperfine structure in the
rotational spectrum. The rotational constants determined
from the microwave spectrum by Bak et af. 431 were used
for calculating the three principal moments of inertia and

hence IaIJc as given in Table A-2. These constants have

been confirmed recently by Mata et af. 511
The vibrational spectra of furan have been investigated by numerous researchers. The infrared spectra of
this compound were observed by Thompson and
Temple,435 Guthrie et al. ,436Bak et al. ,437 and many others. 439-444 Its Raman spectra were studied by Reitz,438
Guthrie et al. ,436 and Rico et al. 444
Complete fundamental vibrational assignments for the
furan molecule have been reported by many authors. 80,436,437,445-447 Guthrie et al. 436 assigned 18 of the 21
fundamental vibrational frequencies, using the available
spectroscopic data. 435,436.438 They selected the remaining
three frequencies to give agreement between the calcu-

lated and experimentally determined values of vapor

heat capacities and third law entropies.

Bak et al. 437 used a different set of normal vibrational
frequencies obtained from spectral data for calculating
the thermodynamic properties. The agreement between
the calculated and the experimental C; and
{SO(T)-SO(O)} was worse than that reported by Guthrie
et al. ,436 especially at higher temperatures.
Based upon a molecular vibrational analysis, Scott44(i
established a complete set of vibrational assignments,
which was consistent with that given by Shimanouchi. 80
His assignments 446 were adopted in this work.
Using the molecular constants listed in Table A-2, we
calculated the thermodynamic properties of furan (g) by
the standard statistical mechanical method. The results
appear in Table 42. Our calculated C; and
{SO(T)-SO(O)} agree with the experimental data,436 as
indicated in Table A-23. In particular, our calculated
third-law entropy of 267.8 J K- 1 mol- 1 at 298.15 K
agrees well with our statistically calculated value of
267.25 J K- 1 mol-I, as shown in Table A-26. The thermodynamic properties of furan reported by Guthrie et
af. 512 were adopted by Stull et al. 466
2.9.b. 2,5-Dlhydrofuran

The molecular structure of 2,5-dihydrofuran (C4H 60 )

was determined by Beach428 from an analysis of electron
diffraction results. His results suggested that the nonproton skeleton of 2,S-dihydrofuran was probably planar. This proposed molecular structure was later
confirmed by Kowalewski and Kowalewski447 and
Courtieu and Gounelle. 448
From the proton magnetic resonance spectra of 2,5-dihydrofuran dissolved in a nematic phase, Kowalewski
and Kowalewski447 derived the ratios of the interproton
distances in the molecule. Courtieu and Gounelle448 in-

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE

42.

Ideal gas thermodynamic properties of furan (C4H 40) at 1 bar

M = 68.0750

T
K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900

1413

{SO(T)-S"(O)}
J K- 1 mol- 1

-{OO(T)-HO(O)}/T
J K- 1 mol- 1

0
220.60(0.11 )
234.60(0.11)
245.96(0.11)
261.79(0.13)
267.25(0.15)
267.64(0.15)
289.81(0.22)
311. 75(0.31)
332.78(0.37)
352.63(0.43)
371.25(0.47)
388.69(0.50)

0
187.31(0.11)
200.87(0.11)
210.75(0.11)
222.30(0.11)
225.84(0.11)
226.09(0.11)
239.25(0.12)
251.56(0.14)
263.36(0.17)
274.71(0.20)
285.63(0.23)
296.12(0.25)

0
33.53(0.01)
36.39(0.04)
43.60(0.10)
59.43(0.24)
65.40(0.29)
65.85(0.29)
88.80(0.40)
107.82(0.42)
122.77(0.38)
134.59(0.34)
144.13(0.29)
152.00(0.25)

{HO(T)-HO(O)}
J mol- 1
0
3329(0)
5060(1)
7042(4)
10786(16)
12347(22)
12468(23)
20225(58)
30093(99)
41653(138)
54543(174)
68495(205)
83314(232)

1000

158.60(0.22)

405.06(0.52)

306.21(0.28)

98853(255)

1100
1200
1300

164.20(0.19)
168.97(0.16)
173.08(0.15)

420.44(0.54)
434.94(0.55)
448.63(0.56)

315.90(0.30)
325.22(0.32)
334.19(0.34)

115001(275)
131665(292)
148773(307)

1400

176.6'2(0.11)

.461 . ';9(0. ';7)

34'.. 83(0.3';)

166'11'(":\'21)

1500

179.69(0.12)

473.88(0.58)

351.16(0.37)

184081 (332)

Va1ues in parenthesis are estimated uncertainties.

vestigated the nuclear magnetic resonance spectrum of

2,5-dihydrofuran in a liquid crystalline phase. These re-

parameters. However, because later investigators found

the structures to be non-planar, the results reported by

sults support the hypothesis that the ring skeleton is planar.

Beach are only of historical interest.

Uedaand Shimanouchi449 measured the far infrared

absorption spectrum in the 500-50 cm -I region and determined the rotational constants. From their results, we
derived the three principal moments of inertia: Ia =
9.8709 X 10- 39 g cm2, Ib = 1.05002 X 10- 38 g cm2, and
Ie = 1.93007 X 10- 38 g cm2 These values were used to
calculate the product of the three principal moments of
inertia given in Table A-2.
The 2,5:dihydrofuran molecule is considered to have a
pseudo-four-membered-ring structure. The ring-puckering vibrational spectra of this compound were investigated by Ueda and Shimanouchi449 and Carreira and
Lord. 450 The far-infrared spectrum was originally ob-

Engerholm et al. 457 studied the microwave spectrum

of tetrahydrofuran and observed complete rotational
spectra for the ground and eight excited states. The reported three ground state rotational constants were
adopted to calculate the three principal moments of inertia: Ia
1.18251 X 10- 38 g cm2, Ib
1.20300 X 10- 38 g
38
cm2, and Ie = 2.09384 X 10- g cm2, From these the
value of IaIJe given in Table A-2 was calculated.
The infrared spectra of tetrahydrofuran have been observed by many researchers. 452-456 The Raman spectra of
this compound in the liquid phase were reported by
Kohlrausch and Reitz 462 arid Luther et al. 463 These
molecular spectra at room temperature have broad, dif-

served and interpreted by Ueda and Shimanouohi. 449

fuse ba.nds beca.use of unresolved pseudo-rotational fine

Carreira and Lord450 reinvestigated this compound using

higher resolution and found a satellite series appearing
on the high-frequency side of the main series. For evaluating the thermodynamic properties caused by this ringpuckering motion of the molecule, the ring-puckering
vibrational energy levels (0 to 1938.8 em-I), from the

structure. Therefore, it was difficult to assign the fundamental vibrational frequencies for this species.
The far infra-red spectrum of tetrahydrofuran was
first investigated by Lafferty et al. 459 They interpreted
their results in terms of a free pseudorotator. Later,
Greenhouse and Strauss460 proposed the existence of hin-

far- infrared results by Carreira and Lord,45o were em-

dered pseudorotation in the molecule. They analyzed

ployed. The fundamental vibrational frequencies, listed

in Table A-2, were obtained from Laane. 451
U sing the selected molecular constants given in Table
A-2, the thermodynamic properties of 2,5-dihydrofuran
(g) at 1 bar given in Table 43 were calculated.'

their results using a separate Hamiltonian but allowing

for a small barrier to pseudorotation of 0.60 kJ mol-I.
Pseudorotation constants in both the ground and in the
first excited radial states were obtained. The spectra
showed the effects of a considerable number of complex
rotation-vibration interactions.
Engerholm et al. 457 studied the microwave spectrum.
From the strong vibration rotation interaction, they deduced that this molecule contained a small barrier of
about 0.6 kJ mol- 1 hindering free pseudorotation. Based
upon the variation of the dipole moment, they suggested

2.9.c. Tetrahydrofuran

Beach42s elucidated the molecular structure of tetrahydrofuran (C4H sO) by electron diffraction. Using a planar
molecular model, he calculated its molecular structural

J. Phys. Chem. Ref. Data. Vol.1S. No. 4.1986

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1414

CHAOETAL.
TABLE 43.

T
K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900

toOO
1100
1200
1300
1400
1500

Ideal gas thermodynamic properties of 2,5-dihydrofuran (C4H60) at 1 bar"

M = 70.0908

CO
e.
J K-I mol- 1

{SO(T)-SO(O)}

-{GO(T)-HO(O)}IT

J K- 1 mol-I

J K- 1 mol- 1

0
40.54(0.19)
45.04(0.12)
52.82(0.10)
69.24(0.11)
75.60(0.12)
76.08(0.12)
101.45(0.13)
123.50(0.13)
141.44(0.12)
155.99(0.11)
167.99(0.10)
178.02(0.10)
186.49(0.09)
193.70(0.09)
199.87(0.08)
205.17(0.08)
209.73(0.08)
213.69(0.07)

0
228.01(0.58)
24~.20(0.63)

259.14(0.66)
277.92(0.67)
284.25(0.67)
284.72(0.67)
310.13(0.68)
335.21 (0.69)
359.37(0.70)
382.31(0.70)
403.94(0.70)
424.33(0.71)
443.53(0.71)
461.66(0.71)
478.78(0.71)
494.99(0.71)
510.37(0.71)
524.98(0.71)

0
191.17(0.33)
206.46(0.42)
217.93(0.48)
231.49(0.53)
235.65(0.54)
235.95(0.54)
251.32(0.57)
265.60(0.60)
279.13(0.61 )
292.33(0.62)
304.95(0.63)
317.09(0.64)
328.78(0.65)
340.05(0.65)
350.90(0.66)
361.37(0.66)
371.47(0.66)
381.22(0.67)

{HO(T)-HO(O)}
J mol-I
0
3684(26)
:5811(33)
8243(37)
12681(42)
14491(43)
14631(44)
23523(50)
34805(58)
48084(67)
62980(75)
79198(83)
96513(90)
114750(98)
133769(104)
153456(111)
173714(117)
194465(123)
215641(128)

aValues in parenthesis are estimated uncertainties.

that the twisted configuration had a lower energy than

the bent configuration. The results were interpreted in
terms of a model of restricted pseudorotation with a potential function of V = 1/2[0.36(1 - cos 28) + 0.48(1 cos 48)] kJ mol- 1 where 8 is the angle of pseudorotation.
They compared the observed vibrational intervals with

ditional levels needed were estimated to provide a

smooth continuation of those .listed and to approach the
distribution for free pseudorotation with increasing energy. The formula used was: E(cm-l) = 3.25nl + 5.489
+ 9.786/n (n =7) where n is an index that numbers the
pairs of effectively doubly degenerated levels.

their calculated intervals and calculated with both a fac-

We employed the molecular congtants listed in Table

tored Hamiltonian and an unfactored Hamiltonian for

the ring puckering mode. The calculated intervals with
the unfactored Hamiltonian agreed with the observed
ones better than those obtained by using the factored
Hamiltonian. This conclusion was later confirmed by
Davidson and Warsop.461
The ring puckering potential function reported by
Engerholm et al. 457 and a pseudorotation constant F =
3.27 cm- 1 459 were employed for generating 132 pseudorotation energy levels (0 to 14200 em-I) for the calculatiun uf the pseudorotational contributions. The
pseudorotation phenomenon was reviewed by Frankiss
and Green. 9
Hossenlopp and Scott458 assumed a puckered configuration of C 2 point-group symmetry and made a normal
coordinate calculation. Their vibrational assignments
were adopted in this work for calculating the vibrational
contributions. See Table A-2 for the numerical values.
Adopting the value of IaIJc from the work of
Engerholm et al. 457 and using his own vibrational assignments, Scott calculated the ideal thermodynamic properties. 4ss His calculated C; values agreed with the
experimental vapor heat capacities measured by Finke
and Hossenlopp.464 For evaluation of the pseudorotational contributions to the thermodynamic properties of
this compound, he used the first 15 energy levels for
pseudo rotation observed by Engerholm et al. 457 The ad-

A-2, and the 132 pseudorotational energy levels, for the

calculation of the thermodynamic properties of tetrahydrofuran (g). The results are presented in Table 44. Our
calculated C; are compared with the observed vapor
heat capacities in Table A-24. Our calculated results are
in good agreement with those obtained by Hossenlopp
and Scott,458 although the methods used for calculating
the pseudorotational energy levels are different. The calculated ideal gas entropy at 298.15 K, 302.41 J K- 1
mo}- 1, agrees with our selected third law value of 299.1
J K 1 mol I given in Table A-26.

3. Acknowledgment
This work has been financially supported by the Office of Standard Reference Data, National Bureau of
Standards for which the authors are grateful. The help
provided by the Thermodynamics Research Center
(TRC) staff for preparation of this manuscript is acknowledged. We would like to thank Carol Chen for
computer calculation assistance and Leyla Akgermann,
Hermilinda Ryan, and Jean Thomson-Rickoll for technical assistance in the preparation of the manuscript. Our
thanks are due to the editor for his valuable advice and
critical comments on the contents of this manuscript before publication.

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE 44.

T
K
0
100
150
200
273.15
298.15
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500

1415

Ideal gas thermodynamic properties of tetrahydrofuran (C4H sO) at 1 bar

M = 72.1066

coe

J K- I mol-I

{SO(n-SO(O)}
J K- I rnol- I

-{GO(n-HO(O)}IT
J K- I mo)-I

0
246.46(2.87)
263.63(2.88)
277.43(2.89)
296.05(2.89)
302.41(2.89)
302.88(2.89)
329.02(2.89)
355.75(2.90)
382.20(2.90)
407.83(2.90)
432.40(2.90)
455.83(2.91)
478.12(2.91)
499.31(2.91)
519.45(2.91)
538.62(2.91)
556.86(2.91)
574.25(2.91)

0
207.30(2.44)
223.36(2.58)
235.19(2.66)
249.01(2.72)
253.22(2.74)
253.52(2.74)
269.11(2.78)
283.76(2.80)
297.97(2.82)
311.85(2.83)
325.39(2.84)
338.59(2.84)
351.44(2.85)
363.93(2.85)
376.06(2.86)
387.83(2.86)
399.26(2.87)
410.35(2.87)

0
40.61(0.09)
44.77(0.08)
52.15(0.09)
69.23(0.14)
76.25(0.16)
76.78(0.16)
106.36(0.20)
133.58(0.21)
156.62(0.19)
175.86(0.18)
192.02(0.17)
205.68(0.16)
217.31(0.15)
227.23(0.15)
235.72(0.14)
243.02(0.13)
249.30(0.12)
254.74(0.12)

{HO(D-HO(O)}
J rnol- I
0
3916(43)
6041(45)
8448(46)
12849(49)
14667(50)
14808(50)
23965(59)
35994(72)
50538(87)
67191(102)
85608(117)
105511 (130)
126677(143)
148916(155)
172075(166)
196021 (177)
220645(187)
245853(197)

Values in parenthesis are estimated uncertainties.

4. References
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2 Commission on Atomic Weights, IUPAC, Pure Appl. Chern. 47, 77
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4 R. H. Fowler, Statistical Mechanics~ 2nd edition (Cambridge University Press, London, 1936).
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6 J. E. Mayer and M. G. Mayer, Statistical Mechanics (John Wiley and
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171. F. KilpatriCK and K. S. Pit7er, J. Chem. Phys. 17, 1064 (1949).
18 J. C. M. Li and K. S. Pitzer, J. Phys. Chern. 60, 466 (1956).
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2sB. L. Crawford, Jr., J. Chern. Phys. 8, 273 (1940).
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Tables Relating to Mathieu Functions (Columbia University Press,

New York, 1951).
30D. R. Herschbach, Tablesfor the Internal Rotation Problem (Department of Chemistry, Harvard University, Cambridge, Mass., 1957).
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....... -

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

1417

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J. Phys. Chem.,Ref. Data, Vol. 15, No.4; 1986

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1418

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S03J. Sheridan, W. Bossert, and A. Bauder, J. Mol. Spectrosc. 80,
(1980).
504H. Zcise, Z. Elektrocht:lU. 47, :;9:; (1941); 48, 425 (1942).

5osH. Gunthard and E. Heilbronner, Helv. Chim. Acta 31, 2128 (1948).
506K. A. Kobe and R. E. Pennington, Petrol. Ref. 29 (9), 135 (1950).
S07R. A. Creswell and R. H. Schwendeman, J. Mol. Spectrosc. 64, 295
(1977).
s08E. Walder, A. Bauder, and H. H. Giinthard, Chern. Phys. 51, 223
(1980).
S09W. Caminati and G. Corbelli, J. Mol. Spectrosc. 90, 572 (1981).
51OM. E. Dyatkina, Zh. Fiz. Khirn. 29, 377 (1954).
Slip. Mata, M. C. Martin, and G. O. Sorenson, J. Mol. Struct. 48, 157
(1978).
mG. B. Guthrie, Jr., D. W. Scott, W. N. Hubbard, C. Katz, J. P.
McCullough, M. E. Gross, K. D. Williamson, and G. Waddington, J.
Am. Chem. Soc. 74, 4662 (1952).
my. P. Glushko, L. Y. Gurvich, G. A. Bergman, I. Y. Yeyts, Y. A.
Medvedev, G. A. Khachkuruzov, and Y. S. Yungman, Thermodynamic Properties of Individual Substances (Publisher of Academy of
Sciences, SSSR, Moscow, 1978).
514J. C. Hales, R. C. Cogman, and W. J. Frith, J. Chem. Thermodyn.
13, 591 (1981).
5151. A. Hossenlopp, and D. W. Scott, J. Chern. Thermodyn, 13, 405
(1981).
516R. A. McDonald, S. A. Shrader, and D. R. Stull, J. Chem. Eng.
Data 4, 311 (1959).
SI7J. R. Bott and H. N. Sadler, J. Chern. Eng. Data 11,25 (1966).
516A. G. Osborn and U. W. Scott, J. Chem. Thermodyn. 12,429 (1980).
S19R. C. Wilhoit and B. J. Zwolinski, J. Phys. Chem. Ref. Data 2, Supp
1. (1973).
s2D. W. Scott, J. Chem. Thermodyn. 2, 833 (1970).
521W. P. Giauque and J. Gordon, J. Amer. Chem. Soc. 71, 2176 (1949).

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

1421

5. Appendix
TABLE A-I.

Equations for calculating ideal gas thermodynamic properties for polyatomic molecules at a pressure of 1 barab

Contribution

Property

Equation
Linear Molecule

Translation

cop
{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T
{SO(T)-SO(O)}

Rotation

cop
{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T
{SO(T)-SO(O)}

Vibration

C"p

{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T
{SO(T)-SO(O)}

20.786007
20.786007T
28.716930 log M
28.716930 log M

+ 47.861550 log T-30.361772

+ 47.861550 Jog T-9.S75765

8.314403
8.314403T
19.144620 log [(I T X 1039)/0-]-11.583429
19.144620 log [(I T X 103~/0-]-3.269026
8.314403~u~e

uf(l-e-uf
8.314403Tiu;e-ui /(I_e- Ui )
-19.144620 l'.)og (l_e- Ui )
8.3144031'.u;e-u;/(l-e-U' )-19.144620 1'.10g (l_e-Ui )

Nonlinear Molecule
Translation

cop
{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T
{SO(T)-SO(O)}

Rotation

co
p

{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T

{S(T)-SO(O)}

Vibration

cop
{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T
{SO(T)-SO(O)}

Internal rotation

cop
{HO(T)-HO(O)}
-{GO(T)-HO(O)}/T
{SO(T)-SO(O)}

20.786007
20.786007T
28.716930 log M
28.716930 log M

+ 47.861550 log T -30.361772

+ 47.861550 log T -9.575765

12.471604
12.471604T
28.716930 log T --19.144620 log 0" I
9.572310 log (IJtJe X 10117)-12.616271

{H"(T)-HO(O)}/T - {GO(T)-HO(O)}/T

8.3 14403l'.u j2e-Ui /(1_e-Ui)2

8.314403l'.Tuie- ui /(I_e- Ui )
-19.144620 1'.10g (l_e- Ui )
8.3144031'.uie-ui/(l-e-Ui)-19.144620 1'.10g (l-e-U;)

17.211687 ~E?giWi _ (l'.EgiWi)2]

Tz
l'.gjWj
l'.giWj
11.962646(l'.Egiw,)ll'.g,wi
19.144620 log l'.giW;
where Wi

exp(-1.438786E;/T)
{Ir(T)-HO(O)}/T - {GO(T)-HO(O)}/T

Units: J moJ- 1 for {H(T)-HO(O)} and J K- 1 mol- 1 for the remaining properties, g3 cm6 for IJtJe. K for T and cm- 1 for
1.4378786v;/Twhere VI = vibrational wavenumber (in em-I).

Ei.

b UI =

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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1422

CHAOETAL.
TABLE

No.

A-2.

Molecular weight, product of moments of inertia and vibrational assignments for C 1 - C 4 organic oxygen compounds'

Compound name
Methanol

IJiJcx 10 117

Molecular weight

7Cffi6

32.0420

L..21l.2

Methanol-dl

33.0482

10.4152

Methanol-d3

35.0606

21.8237

Methanol-d4

36.0668

26.9037

Ethanol

46.0688

Fundamental vibrational
wave numbers b
cm- 1
3681, 3000,2844, 1477, 14:;:;,

1345, 1060, 1033, 2960,1477,

1165
2718, 3000, 2843, 1473, 1456,
864, 1230, 1040,2960, 1473, 1160

I-Propanol

60.0956

trans

ill.&2

gauche

trans

1660.2

3690, 2260, 2077, 1047, 1134,

1297, 858, 988, 2235, 1075, 877
2724,2260, 2080, 1024, 1135,
1060, 776, 983, 2228, 1080, 892
3659,2985, 2939, 2900, 1460,
1430, 1395, 1320, 1245, 1055,
1026, 883, 422, 2887, 2887,
1460, 1270, 1117, 801
3675, 2985, 2939, 2900, 1460,
1430, 1395, 1320, 1245, 1055,
1026, 887, 596, 2887, 2887,
1460, 1270, 1070, 801
3680, 2940(7), 1478, 1463,
1450(2), 1393, 1381,
890, 860,730, 463, 1341, 1299,
1272, 1220, 1103, 1066, 1052,
Y71, YIC>

gauche

2-Propanol

60.0956

I-Butanol

74.1224

8444.0

DL-2-Butanol

74.1224

7910.0

10

2-Methyl-2-propanol

74.1224

11

1,2-Ethanediol

62.0682

TGG'

1465.3

GGG'

1465.3

TIT'

1465.3

ITG'

1465.3

3705, 2971, 2970, 2941, 2924,

2911, 2903, 2877, 1465, 1462,
1461, 1459, 1394, 1388, 1330,
1255, 1227, 1180, 1075, 1056,
1003, 917, 880, 862, 524, 920,
349
3650, 2940(6), 2875, 1475(2),
1460(2), 1387, 1367, 1340,
1256(2), 1153, 1130, 1072,
955(2), 940, 818, 488, 427, 373
3300, 2950(9), 1470, 1450(4),
1294(7). 1250. 1070. 1050. 955(4),
890(3), 446, 392, 350
3682, 2980(6), 2943(2), 2891,
1450(5), 1394, 1380(2), 1350,
1314, 1290, 1250, 1145, 1110,
1080, 1034, 992, 970, 912, 820,
780, 500, 435, 382, 274
3643, 2980(6), 2910(2), 2880,
1472(5), 1450, 1395, 1374(2),
1330, 1230, 1215, 1106(2), 1140,
1013(3), 919, 748, 462(2), 424,
356, 344
3638, 2941, 2940, 1470, 1414,
1164, 1265, 1046, 1076, 876, 508,
276, 144, 3671, 2878, 2878, 1465,
1381, 1239, 1358, 862, 1098,
372, 309
~fi2~. 294t, 2940. 1471. 1398,
1301, 1179, lOSS, 1096, 874, 508,
181, 139, 3671, 2878, 2878, 1465,
1387, 1232, 1342, 864, 1055, 369,
311
3656, 2941, 1496, 1403, 1244,
1097, 969, 452, 2941, 1301, 1066,
305, 148, 2878, 1252, 871, 292,
3684, 2878, 1440, 1376, 1174,
1042, 516
3656, 3941, 1496, 1396, 1213,
1095, 994, 453, 2941, 1335, 1032,
309, 146,2878, 1287, 864,281,
3684, 2878, 1440, 1349, 1174,
1043, 516

J. Phys. Chern. Ref. Data, Vol.1S, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLEA-2.

No.

1423

Molecular weight, product of moments of inertia and vibrational assignments for C 1-C4 organic oxygen compounds' - Continued

Compound name

Molecular weight

12

Dimethyl ether

46.0688

13

Dimethyl ether-d3

49.0874

14

Dimethyl ether-d6

52.1060

15

Ethyl methyl ether

60.0956

Fundamental vibrational
wave numbersb
cm- I

IJblcx 10 117

7---cmr11.Q.lli

trans

2999(2), 2935, 2920, 2820(2),

1485, 1467, 1463,
1459, 1449, 1432, 1250, 1179,
1178, 1148, 1104,931,424
2994, 2932, 2821,2244, 2189,
2054, 1474, 1457, 1443, 1215,
1165, 1161, 1111, 1075, 1059,
946, 903, 860, 389
2248(2), 2148, 2165, 2054(2),
1162, 1148, 1079, 1063, 1059(2),
1052, 1047, 932, 876, 860, 827,
356
291S9, 2988, 2968, 2962, 29'8,

2881, 2864, 2820, 1485, 1472,

1462, 1456(2), 1445, 1392, 1365,
1269, 1208, 1169, 1150, 1120,
1094, 1015, 853, 815, 468, 298

16

17

Diethyl ether

Propanone

74.1224

gauche

1434.5

trans-trans

221M

trans-gauche

6875.0

58.0798

1390.63

2989, 2988, 2969, 2962, 2959,

2881,2864,2820, 1485, 1472,
1462, 1456(2),1445, 1383, 1365,
1304, 1208, 1164, 1150, 1120,
1068,979, 843, 800,468, 379
2968(2), 2962(2), 2958(2),
2881(2), 2865, 2864,
1490. 1484. 1456(2). 1443(2),
1414, 1383, 1372, 1351, 1350,
1279, 1237, 1168(2), 1153, 1120..
1077, 1043, 935, 822, 794,
440(2), 208
2969, 2963, 2962(2), 2959, 2958,
2881(2), 2865, 2864, 1490, 1484,
1456(2), 1443(2), 1393, 1383,
1372(2), 1350, 1297, 1267,
1168(2), 1153, 1120, 1074, 1023,
916,822, 794,503, 376,318
3019(2), 2972, 2963, 2937(2),
1731, 1454, 1435, 1426, 1410,
1364(2), 1216, 1091, 1066, 891,

18

2-Butanone

72.1066

6268.4

877, 777, 530,484, 385

2983(4), 2941, 2910(2), 2884,
1716, 1460(2), 1422, 1413(2),
1373, 1346, 1263(2), 1182, 1108,

19

Methanal

30.0262

.L.aM

20

Methanal-d,

31.0324

.u2Q2

21

Methanal-d2

32.0386

22

Ethan:d

44.0530

111.80

23

Ethanal-d t

45.0592

147.20

24

Ethanal-d.

48.0778

260.79

1.Propanal

58.0798

cis

1290.0

1089, 997, 952, 939, 768, 760,

590,460,413, 260
2843, 2783, 1746, 1500, 1249,
1167
2844, 2121, 1723, 1400. 1074,
1041
2160, 2056, 1700, 1106, 990,938
3005. 2967, 2917, 2822, 1743,
1441, 1420, 1400, 1352, 1113,
919, 867, 763, 509
3028, 2970, 2917, 2071, 1743,
1442, 1420, 1353, 1109, 1043,
849, 802, 668, 500
2265, 2225, 2130, 2060, 1737,
1151, 1045, 1028(2),938, 747,670,
573,436
25
2993(2), 2927, 2916, 2914, 2759,
1753, 1468(2), 1423, 1398, 1381,
1339, 1093, 1010, 849, 1255,
1129, 896, 672, 658, 271

J. Phys. Chern. Ref. Data, Vol. 15, NO.4, 1986

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CHAOETAL.

1424
TAIIIYA-2.

No.

Molecular weight, product of moments of inertia and vibrational assignments for C 1 -C4 organic oxygen compounds - Continued

Compound name

IJ,JcX 10 117

Molecular weight

7~
skew

1221.0

26

Methanoic acid

46.0256

60.7259

27

Methanoic acid-dl(HCOOD)

47.0318

76.2477

28

Methanoic acid-dl(DCOOH)

47.0318

85.3306

29

Methanoic acid-d1

48.0380

30

Methanoic acid dimer

92.0512

103.740
26369.6

Fundamental vibrational
wave numbers b
cm- I
2993(2), 2927, 2916, 2914, 2759,
1753, 1468(2), 1423, 1398, 1364,
1339, 1243, 1144, 1129, 998,
907, 873, 672, 508, 325
3570, 2943, 1770, 1387, 1229,
1105, 1033, 625
2948, 2632, 1772, 1360, 1178,
1000, 990, 562
3570, 2220, 1756, 1220, 1143,
970, 870, 620
2632, 2232, 1742, 1171, 980,
945, 873, 558
3200, 3110, 2957, 2956, 1754,
1672, 1450, 1395, 1365, 1350,

31

Ethanoic acid

32

33

60.0524

1033.0

Ethanoic acid dimer

120.1048

161410.0

Methyl methanoate

60.0524

806.497

1218, 1204, 1073, 1063,917,697,

677, 675, 519, 248,232, 215, 164,
68
3583. 3051. 2996. 2944. t 788.
1430(2), 1382,
1264, 1182, 1048, 989, 847, 657,
642,581
3193, 3032, 2949, 1675, 1436,
1436, 1370, 1283, 1018, 886, 624,
448, 196, 110, 3140, 3028, 2956,
1715, 1413, 1413, 1359, 1295,
1013, 886,624,480, 188,2990,
1413, 1050, 934, 635, 67, 47,
3000, 1436, 1112, 912, 623, 115
3045, 3012, 2969, 2943, 1754,
1454, 1445, 1443, 1371, 1207,

1168, 1166, 1032, 925, 767, 332,

34

Methyl ethanoate

74.0792

35

Ethylene oxide

44.0530

4495.80

74.4362

318
3035, 3031, 3005, 2994, 2966,
2964, 1771, 1460(2), 1440,
1430(2), 1375, 1248, 1187, 1159,
1060, 1036, 980, 844, 639, 607,
429, 199, 187
3065, 3063, 3018, 3006, 1498,
1472, 1300, 1270, l1S1, 1148,

36

Ethylene oxide-d4

48.0778

162.523

37

Propylene oxide

58.0798

824.586

38

Furan

68.0750

1448.6

39

2,5-Dihydrofuran

7U.U9UH

2000.4

1142, 877, 860, 840, 821

2319, 2250, 2210, 2176, 1309,
1084, 1083, 101.2, 968, 903, 896,
809. 752. 581. 577
3065(2), 3006, 2975, 2929, 2846,
1500, 1456(2), 1406, 1368, 1263,
1166, 1142, 1132, 1102, 1023,
950, 896, 828, 745, 416, 371
3167, 3161, 3140, 3129, 1556,
1491, 1384, 1267, 1180, 1140,
1066, 1040, 995, 873, 871, 863,
838, 745, 728,613, 603
3090(2), 297U(2), 2HbU(2), 15HU,

1480, 1465, 1355, 1345, 1300,

1195, 1165, 1090, 1060, 1030,
1012, 990, 907, 898, 790, 740,
655(2), 384

40

Tetrahydrofuran

72.1066

2970(4),2847(4), 1517(2), 1486,

1452, 1366, 1339, 1289, 1238(2),
1177, 1150(3), 1114, 1076, 1029,
964, 912, 881, 821(2), 654, 596,
278

Underlined values derived from microwave spectra, others calculated from molecular geometry
bNumbers in parenthesis are the degeneracies.

J. Phys. Chem. Ref. Data, Vol.1S, No.4, 1986

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TABLE

No;

1
2
3
4
5

Molecule

.Rotor

CH30H
CH3Ol)
CD30li
CD30D
CH3CH20H
trans

3
1
3
1

U6i
1.329
4.363
1.337

244.1
205.2
261.9
248.2

CH)-CHiCHzOH

6~097

214.2
112.4
226.5
210.5

0.837
0.837
0.S37

.llA2

0.0

.wll.

UOJl

0.0
0.0

13.22

C~Hs-cHiOH

CHi:-CH2CH2OH
C 2H,-CH20H
C3HrOH

CH3CH2CH(0H)CH3
trims

CD

~
....

jh

!)
~

-Q.Q212

till

-Mill

1
1
1
1

:Wl

1
1
3
1

.1.lli
~

.u.m

.llii

1.875
21.34:
5.543
1.791
22.20

233.2

.ll.22
~

.!W.26

.!til
~

o.Q26

l..lfl

3
1

2
1

.I.\Jj6

1.lli

5.559
21.853

25104
209.E

3l:

0.0

0.364

-1.031

.uM
.lJM

0.0
0.0
0.0
0.0

5.043
5.043
30.27
1.320
5.043
5.043
30.27
1.320

5.551
5.551
0.925
21.21
5.551
5.551
0.925
21.21

219.4
251.2
77.0
224.5
219.4
251.2
77.0
224.5

0.0
0.0
0.0
0.0
3.45
3.45
3.45
3.45

.l2..21
.l.6.ll
2.00
l..lfl

C4HrOH

3
3
1
1
3
3
1
1

CH3-C(0Il)(CH3)2
C.JIi-OH

3
3

5.145
1.291

5.441
21.68

242.2
236.4

0.0
0.0

15.90

~*

0.0
0.0
3.68
3.68

C.H9-'OH
CH3-C2H.(OH)CH)

HO":'CH 2CHiOH
H<>cHrCH20H
HO-CH2CH2OH
HOCH1-CH2OH

~*

lliJu*
ill*

-<
Z

i:

n
."

:::D

."

rn

....:::D

-n
m

229.E
ii5.E
12U
152.3

CH3-C~(0H)CH3

~
~

.ll.M
lJl2.6

u.m
~

2.00

lID

(CH3)3COH

GGG'

rn

:::D

iii
(/)

5.772
1.374
':526
22.04

~Hs:"'CH(OH)CH3

HOCH2CHzOH
ITG'

....
::I:

l..lfl

4.85
20.38
IS.35
1.27

~HsCH(0H)-CH3

11

ti22

3
1
1
1

~HsCH(OH)-CH3
~ZH5~(0H)CH3

;:I

V6

-Q,00Q2

CH3CHzCH2CH2OH

gauche

V4

.un

(CH3)2CHOH

::r

V3

CH3ClIzCHzOH
trans

~
"V

0.0
0.0
0.0
0.0

V2

0.0
0.0
0.444
0.494

CJI~H

299.6
215.4
275.
194.

VI

6.414
21.07
6.416
20.94

CzHs-CzH.OH
C]H7-CH10H

10

Eo

CH3-CH2OH
CH3CH:i-OH
CH3-CH2OH
CH3CH2-OH

CDr~OH

CH3-:C~60H

:II

v(~I)

17.44
25.52
15.0S

CH3HT:OH

~
n
::r

p:
2.8.J.2

CH~~CH(CH3)OH

I,.:

1.605
i.097
1.S56

CD3-OD

gauche

Ne

!im

C)HrOH

iT

cori~timts a

3
3
3
3

CH3-OH
CH~-OD

gauche
6

Internal rotation molecular

A-3.

.l1M

"0-<
:::D

"
~

n
0

><
-<

"nrn
Z

3l:

."

c(/)

-.

....
CO

.r:..
~
c.n

.00

en

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..

!-

"

:s'<
f'
(')

:s-

CD

TABLE

No.

Rotor

Molecule

A-3.

Internal rotation molecular constants a

O'

N"

IF

,1(0-1)

Continued
Eo

en
VI

Vz

V3

V4

V6

::a

cDJ

ITT'

<

ITG'

!1

....~

JII

z
P

12
13

CH l OCH3
CH 3OCD 3

cO
C

14
15

CD)OCD 3
CHJ CH2OCH3
trans

gauche

16

CH 3CHzOCH1CH,
IT
TG

17
18

22
23
24
25

CH J COCH3
CH3CH1COCH J

cis

26
27
28
29
31

HCooH
HCooD
DCooH
DCooD
CH3COOH

CH3-CH zOCH 3
CH3CHzO-CH 3
CHJ CH1-OCH3
CH3-CH 2OCH 3
CH3CH1O-CH3
CH 3CH1-OCH3

2
3
3
1
3
3
1
2
2
2
2
2
3
3
1
3
3
3

CH 3-CH1CHO
CzHs-CHO
CH 3-CH2CHO
C 2H s-CHO
HCO-OR
HCO-OD
DCO-OR
DCO-OD
CH3-COOH
CH1CO-OH

3
1

J.QU22* 10.66
ill4
10.66
JQ2lli* 13.35
HQ4
13.35
0.0
214.5

!22.l

6.524

ill2
1M]

6.181
3.862
3.637

5.276
3.558
18.72
4.994
5.046
18.54

5.306
7.867
1.495
5.605
5.548
1.510

4.168
19.46
4.718
22.56
4.888

6.715
1.439
5.933
1.240
5.727

ill.

5.071
5.119

833
199.5
60.5

~.406

5.520
5.468
1.068
7.673
7.030
4.370

4.664
7.135
4.621
10.815
1.122
1.824
1.178
1.978

6.002
3.923
6.058
2.588
24.96
15.35
23.76
14.15

74.
609.5
483.
595.
464.

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

4.955
1.317

5.649
21.26

75.
565.

0.0
0.0

1lli

CH3-CHzOC1H s
CH3CH2-OC1H s
CH 3-CH1OCzH s
CH3CHz-OCzH,
CH 3-COCH 3
C 1H sCO-CH3
CH3-CH2COCH 3
C2H s-COCH)
CH 3-CHO
CH3-CDO
CD 3-CDO

CH3CHO
CH3CDO
CD]CDO
CH1CH1CHO

skew

CH3-OCD3
CH3O-CD 3
CD J-OCD3

~
(1)

HO-CH 2CHzOH
HOCHz-CH2OH
HO-CH2 CH2OH
HOCHz-CHzOH
CH 3-OCH3

2~.21

3.648
3.982

22.ll
ill.!}

liM
~

.ill:.
ll2...

122.
Jli
UQ.
21J..,.
.lQL
104.~

ill:.
133.

.lll8Q1

0.0
0.0
0.0

12.26
10.09
11.14

0.0
0.0
0.0
6.28
6.28
6.28

17.01
8.31
12.48
15.04
9.57
14.76

0.0
0.0
5.73
5.73
0.0

12.79
14.05
13.01
13.05

0.0
0.0
0.0
0.0
0.0
0.0

ill
llOO

(')

J:

0
."
""i
~

r-

L.22.l

!,OO

4.92
5.067
4.858

1.799
1.799

3.965
3.965

9.540
13.94
13.2
13.94

~
~
~

.lU2

.2,MU

UQl

J.U{!

UQl

llil2

1UQ

2.Nl

24.06

37.36

2Jlli
2:JQ1

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0.051
0.051

-I

:x::
m
::0

s:

TABLE

No.

Molecule

Rotor

A-3.

Internal rotation molecular constants a

CT

Nc

I,

v(~l)

o
c
-<
Z

Contimed
Eo

V2

VI

V3

V4

V6

l>

s:

o
32
33

34

37

as

!"'0

(CH 3COOH)2
HCOOCH 3
cis

CH 3-C3H s0 4

HCOO-CH3
HCO-OCH3

5.222

5.361

74.

0.0

2JlU

."
::0

4.894

5.720

130
332'*

0.0

1M

."

::0

-I

CH 3COOCH 3
cis

CH 3-COOCH 3
CH3COO-CH3
CH3CO-OCH 3
CH3-C2H 3O

C 3H 6O

3
3

5.009
4.936

5.589
5.671

4.793

5.841

65
1313
187*
200

0.0
0.0
0.0

.lJ.2.l

in

5.084

.1Ma

en

-0.084

number of identical species of type identified; CT = symmetry number for internal rotation; Nc = number of cor.tributions; 1, = reduced moment of inertia; F = internal rotational constant (eq.
11); v(~I) = wavenumber of 0-1 transition for torsional mode, Eo = energy of lowest state relative to ground state, Vn = coefficient of potential function (eq. 12). Units of E and Vn are kJ
mol-I.

The underlined values of I, atld F have been derived from microwave spectra and reported in the literature. Those not underlined have been calculated from molecular geometry.
The underlined values of VN and have been reported in the literature. Others have been calculated from the relations among Vn , F, and as described in section 1.3 of the introduction.

harmonic oscillator assumed

:r
eI

"m

'"-<

::0

C)

l>
Z

o
><
-<
C)
m

z
o
o
s:

."

::a

c:

z
c
en

J
~
....

$'1

!:
~

....

-.

~
I\)

.....

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CHAOETAL.

14:'H
'I

'j'

1\ III

A-4,

Comparison of observed and calculated heat capacities of methanol(g)

cp

cp

J K- 1 mol-I

J K- ' mol-I

Correlationa

Exptl.
349.65
358.15
358.85
359.85
368.15
382.15
401.15
420.15
442.65
341
363
405
345.6
403.2
464.0
521.2
347.35
356.55
373.35
398.95
401.15
401.35
431.45
442.15
457.35
477.75
485.05
498.95
521.35
555.95
581.35
585.35

72.68
59.79 d
6O.58 d
6O.33 d
56.99 d
54.81 d
54.43 d
54.68d
56.99d
112.97d
58.58d
54.52d
50.960.8e
52.630.2e
57.490.4e
6O.580.8e
86.86h
66.61h
56.19 h
52.97h
54.02h
54.14h
55.77 h
56.02h
56.99 h
57.24h
56.57 h
6O.12h
61.55 h
63.93 h
66.36h
66.82h

46.82
47.57
48.99
51.13
51.34
51.34
53.89
54.77
56.02
57.74
58.37
59.54
61.42
64.31
66.44
66.78

W_pb

K_WC

This work

46.07
46.74
48.20
48.83
50.29
51.30
52.34
53.22
55.90
51.42
49.37
52.59
47.86
52.01 8
57.2OS
60.42
52.72
51.34
51.00
50.75
51.92
52.05
54.52
54.94
56.11
56.52
55.90
59.58
61.09
63.60
66.11
66.57

47.28
45.48
46.86
47.40
48.66
50.04
51.59
52.80
55.73
62.05
47.74
51.92
46.86 f
51.768
57.2OS
60.46
55.61
50.33
49.41
49.96
51.13
51.30
54.22
54.73
55.98
56.48
55.90
59.58
61.13
63.64
55.15
66.61

47.66
48.33
48.28
48.45
49.08
50.17
51.71
53.26
55.10
46.99
48.66
52.01
47.36
51.88
56.82
61.34
47.49
48.16
49.50
51.55
51.71
51.71
54.18
55.06
56.27
57.91
58.49
59.62
61.34
63.97
65.86
66.15

C;/J
mol-I = 10.226(1.73 + 8.20 X 10- 3 1) with the average deviation of 1.34 J K- I mol-I
Virial coefficients Band D of Ref. 55 were used for gas imperfection corrections.
C Virial coefficients Band D of Ref. 56 were used for gas imperfection corrections.
d Observed at 750 mm Hg with the uncertainty of about 1 percent. 5253
e Observed at 260 mm Hgss.
f With the estimated error of 1.3 J K -I mol-I.
1
8 With the estimated error of 0.4 J K- mol-I.
h Observed at 1 atm. 54

TABLE A-5. Comparison of observed and calculated entropies of methanol(g)

T

{S(T)-SO(O)} (EApt:cimenl.al)

J K- I mol-l

Real gas
at saturation

313.1
327.9
337.8
323.15
337.85
363.15
383.15

248.56C
244.79
242.53c
245.95 d
242.91d
237.01d
233.33d

{S"(T)-S"(O)} (Call,;ulatt:~)

J K-I mol-1

Ideal gas at 1 bar

w-p

K_Wb

242.10
244.31
245.95
243.69
245.90
249.13
251.55

241.59
243.94
245.65
243.23
245.61
249.21
251.97

This work

241.99
244.08
245.46
243.41
245.46
248.93
251.57

Weitner-PitzerSS virial coefficients. B and D. were applied to corrections for gas imperfection.
Kretschmer-Wiebe s6 virial coefficients. Band D. were applied to corrections for gas imperfection.
I mol-I
C Derived from enthalpy of vaporization" and CIS) with the estimated error of 1.26 J K8
oJ Derived from enthalpy of vaporization'8 and C1 ' with presumably the same uncertainty as In footnote c.

J. Phys. Chern. Ret. Data, Vol.1S, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

1429

TABLE A-6. Comparison of observed and calculated heat capacities of ethanol (g)

Cpo

T
K

K
Exptl."
350.01
360.00
370.01
380.00
400.08
425.06
450.06
475.10

73.05
74.56
76.02
77.49
80.42
84.06
87.65
91.25

this work
73.35
74.94
76.52
78.10
81.24
85.06
88.76
98.32

200
297
280
367.9
410.16
422
437
476

ExptP

this work

51.38
62.30
62.09
75.52
82.01
83.39
87.99
91.21

52.02
62.32
62.47
76.19
82.79
84.59
86.84
92.48

bRef.91.
bRef.59.

TABLE A-7. Comparison of observed and calculated entropies of ethanol (g)

{SO(n-SO(O)}
J K- I mol-I

K
Exptl.a
298.15
351.5
403.15

282.86
293.66
305.33

Brickweddeb

BarrowC

278.14
290.56
302.53

this work
282.80
294.20
304.20

282.86
294.08
304.91

280.64
292.04
302;68

" Calculated from low temperature thermal measurements. The average uncertainty is
b Ref. 92.
C Ref. 57.
d Ref. 59.

TABLE A-8. Comparison of observed and calculated

T
K

371.2
391.2
411.2
431.2
451.2
8

C; and {SO(n-SO(O)} of I-propanal (g)

T

K
Exptl."
102.26
106.44
110.42
114.35
118.62

Calc.
101.75
106.12
110.42
114.62
118.71

1.67 J K -I mol-I.

298.15
298.15

{SO(n-SO(O)}
J K-I mol-I

Expt1. 8

Calc.

322.49 b
323.20c

322.58

Ref. 60.
Based on low temperature thermal measurements of Parks et ol.;\OS and vapor pressure, enthalpy of
vaporization, and gas imperfection correction of Ref. 60. The uncertainty was 2.93 J K-I mol-I.
Based on S(298.15 K) = 193.59 J K- I mol-I for I-propanol (Hq), a reevaluated value. instead of the
reported value of 192.88 J K -I mol-I.

J_ Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1430

CHAOETAL.
TABLE A-9. Comparison of observed and calculated C; and {S" (T) - S" (O)} of2-propanol (g)

358.72
373.15
398.15
423.15
448.15
473.15

Exptl."

Calc.

103.53
106.28
111.63
117.03
122.09
127.03

103.05
106.27
111.75
117.03
122.13
126.99

{SO(T)-SO(O)}
J K- I mol-I

Exptl."
298.15
324.56
339.25
355.39

31O.14b
31O.65 c
317.42
321.69
326.59

Calc.
309.20
316.94
321.21
325.89

" Ref. 115.

b Based on low temperature thermal data of Andon et al.; liE vapor pressure of Biddiscombe et al.; 117 enthalpy
of vaporization of Hales et al.; IIS and gas imperfection correction of Green. IlIThe uncertainty was 0.8 J
K- 1 mol-I.
c Use the same data as those given in note b, except a value of S(/, 298.15 K) = 181.08 J K- I mol-I is
employed to replace the reported value of 180.58 J K - 1 mol-I for calculation. The uncertainty is 1.26 J
K- I mol-I.

TABLE AIO. Comparison of observed and calculated C; and {S"(T)-S"(O)} of I-butanol (g)

cI!.

J K- 1 mol- 1

Exptl."
398.15
413.15
433.15
453.15

Calc.

137.884
142.064
147.419
152.657

"Ref. 120.
b Ref. 63, interpolated values.
c Ref. 64.
d Recalculated value, based on S(l, 298.15 K)
e Recalculated in this work.

137.65
141.88
147.36
152.67

{S'(T)-S'(O)}

J K- I mol- 1

Exptl."
298.15

Calc.

363.28"
361.83 b
362.444.2b 363.70c
361.61 e
360.19 d

= 225.77 J K- I mol-I instead of 228.03 J K- I mol- I.63

TABLE Al1. Comparison of observed and calculated C; and {S(T)-SO(O)} of DL-2-butanol (2)

T
K

Co
e
J K- I mol-I
Exptl.a

K
Calc.

365.15

131.10

131.30

383.15

136.52

136.21

401.15
419.15
437.15
455.15

141.46
146.23
150.96
155.64

141.04
145.78
150.41
154.92

298.15

{S"(T)-SO(O)}
J K- 1 mol-I

Expt),&

Calc.

359.14'

359.53 b

355.37C

" All data taken from Ref. 61.

b Recalculated in this work.
e Taken from Table A.26.

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

TABLE A-12. Comparison of observed and calculated C; and {S'
T
K

Co
e.
J K- 1 mol-I
ExptP

365.15
383.15
401.15
419.15
437.15

(n -S' (O)} of2-methyl-2-propanol (g)

{SO(n-S(O)}
J K-I mol-I

K
Calc.

Exptl.

Calc.

338.28
342.16
344.62

338.76
342.28
344.50

330.15
339.65
345.65

133.22
138.32
143.30
148.20
152.93

132.63
137.95
142.88
148.07
153.55

1431

All data taken from Ref. 62.

TABLE A-13. Comparison of observed and calculated

CI!.

272.20
300.76
333.25
370.42

C; and {S(n-SO(O)} of dimethyl ether (g)

J K- 1 mol

{SO{I)-SO{O)}
J K-l mol- 1

Ie:

ExptJ.&

Calc.

62.01
65.90
70.33
75.14

62.47
65.90
70.00
74.81

Exptl.&
298.15

267.09 0.84

Calc.
267.34

Ref. 158.
b Evaluated from thelow temperature thermal measurements of Kennedy et aL .m

TABLE A-14. Comparison of observed and calculated

Ce.

309.98
329.98
350.00
375.00
400.01
424.99
450.04
308.15

J K- mol-I
'
Exptl.
121.91"
126.56
131.32
137.35
143.27
149.10
155.11
116.32b

C; and {S(n'-SO(O)} of diethyl ether (g)

Calc.
122.01
126.46
131.05
136.90
142.82
148.70
154.52
121.61

341.1:;

132.63

129.00

370.25
373.15
376.15

144,.77
147.28
143.09

135.78
136.47
137.17

407.15

145.18

144.50

419.15
458.15
473.15
523.15
573.15
623.15
400
450
500

148.95
169.45
171.54
165.27
184.10
186.19
131.38c
144.77
158.58

147.33
156.39
159.80
170.77
181.09
190.74
142.81
154.52
165.77

298.15

{SO(n-SO(O)}
J K- 1 mol- 1
Exptl. &

Calc.

342.31342.55 d
342.71e

342.67

"Ref. 160.
b Ref. 161.
c Ref. 162.
d Evaluated based on low temperature thermal data and other related quantities reported by Counsell et al
e See table A-26.

l60

J. Phys. Chem. Ret. Data, Vol. 15, No.4, 1986

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1432

CHAOETAL.
TABLE A-IS. Comparison of observed and calculated heat capacities of propanone (g)

ce

T
K

J K- I mol- I

Expt1. a
334
348
363
378
393
408
428
438
332.6
347.8
372.3
422.6

80.96
83.38
87.03
89.24
91.84
94.18
99.04
100.50
SO.58
83.35
87.53
96.78

this work
80.92
83.30
85.81
88.37
90.88
93.39
96.70
98.32
80.71
83.26
87.40
95.81

338.2
371.2
405.2
439.2
410.02

Exptl.

this work

81.50b
87.19 b
92.93 b
98.66 b
94.14C

81.63
87.19
92.93
98.53
93.76

Ref. 222; the first 8 data points were measured using reverse-flow calorimeter and the remaining 4 data points
were measured using direct flow calorimeter.
b Ref. 189.
c Ref. 106.

TABLE A-16. Comparison of observed and calculated entropies of propanone(g)

{SO(T)-S"(O)}
J K- 1 mol-I

K
Exptl."
298.15
329.3

294.96 1.05

P.-K.(1957)b

S.-A.(193Sy

this work
297.62
305.33

295.04 1.26
304.292.09

" Calculated from low temperature thermal measurements. 194

b Ref. 189.
c Ref. 108.

TABLE A-17. Comparison of observed and calculated

347.15
372.15
397.15
432.15

C; and {SO(T)-SO(O)} of 2-butanone (g)

K

Exptl!

this work

113.43"
119.03
124.39
131.71

112.97
118.11
123.80
131.21

467.15

138.62

138.41

410.2

124.68 b

126.65

{S O(T)-S (O)}
J K- 1 mol-I
Exptl.

298.15

338.642.51"
338.720.84c
338.300.84d
338.220.84e

this work

339.900.66

Ref. 193; the reported S(298.15 K) value was incorrectl91 due to some mathematical errors involved in calculation, the correct
value should be 338.64 J K- I mol-I.

Ref. 106.
The value was calculated from low temperature thermal measurements,192,236 based on S(l, 298.15 K)
mol- I 194
d Calculated value, based on S(l, 320 K) = 250.29 J K- I mol-I.m
e Ref. 192.
b

(239.07

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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0.63) J K- 1

THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

1433

TABLE A-18. Comparison of observed and calculated heat capacities of ethanal (g)

c'I!.

T
K

J K- 1 mol-I

298.1
322.9

ExptP

ExptJ.b

Exptl.c

Calc.

61.92
61.92

54.81
58.66

54.98
58.03

55.31
57.91

372.7

63.60

62.34

62.43

63.30

422.4

68.20

67.57

67.45

68.70

Ref. 134; the values refer to real gas at 1 atm.

Used second virial coefficient data from Ref. 135 for conversion to C~
c Used second virial coefficient data from Ref. 136 for conversion to C;.

TABLE A-19. Comparison of observed and calculated C; and {S'(T)-S'(O)} ofl-propanal (g)

CI!.
J K- 1 mol-I

325.0
350.1
347.5
8

ExptP

Calc_

84.53
88.39
92.22

84.55
88.33
92.23

{S'(T)-SO(O)}

J K-I mol-I

298.15

Exptl b

C!llC'

304.51

304.51

Ref. 148.
Ref. 149, recalculated value using C; from Table 25.

TABLE A-20. Comparison of observed and calculated heat capacities of ethanoic acid (g)8
p

torr

249

507

760

Cl'.
JK

mol-l

Exptl. b

Calc.

368.4
399.2
419.0
435.8
479.7
509.2
540.0
396.4

300.41
365.26
323.84
261.50
141.00
117.57
107.53
327.61

291.62
357.73
323.42
261.50
141.42
115.06
107.11
317.57

399.1

332.63

323.00

420.1
436.0
470.4
397.5
421.8
443.7
470.9

341.83
307.52
201.25
302.08
332.21
305.01
229.70

335.98
307.52
202.09
291.21
318.82
304.60
229.28

al torr = 133.322 Nm- 2

b Ref. 248.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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1434

CHAOETAL.
TABLE A-21. Comparison of observed and calculated heat capacities

of methyl ethanoate (g)

cop

T
K

J K- 1 mol-I

335
350
375
400
435
450

Exptl. a

Calc.

92.58
95.46
100.39
105.31
109.98
114.63

92.35
95.25
100.09
104.90
109.64
114.27

Ref. 362.

TABLE A-22. Comparison of observed and calculated C; and {SO(T)-SO(O)} of epoxyethane (g)
o

Cp
J K-k mo}-I

Expt1. a
307.18
337.04
371.23

49.37
53.51
58.41

{SO(T)-SO(O)}

J K-l mol- 1

Exptl. a

this work
49.12
53.39
58.28

283.66
298.15

240.77
243.11

this work
240.65
242.99

Ref. 158.
b Evaluated based upon the low temperature thermal data reported by Ref. 405.

TABLE A-23. Comparison of observed and calculated

T
K

T
K

Exptl."
317.25
358.20
402.20
449.20
487.20
a

C; and {SO(T)-SO(O)} of furan (g)

70.29
80.12
90.00
99.58
106.48

ExptJ.8

this work
70.00
79.58
89.29
98.70
105.65

{SO(T)-SO(O)}
J K- 1 mol-I

279.16
293.16
304.52

263.16
266.21
268.64

this work
263.12
266.17
268.64

Ref. 436.

TABLE A-24. Comparison of observed and calculated heat capacities

of tetrahydrofuran (g)

C p

328.2
349.2
399.2
449.2
500.2
a

Exptl.'

Calc.

85.10
91.42
106.15
120.46
133.72

85.06
91.34
106.11
120.25
133.64

Ref. 458.

J. Phys. Chern. Ref. Data, Vol. 15, No.4, 1986

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THERMODYNAMIC PROPERTIES OF KEY ORGANIC OXYGEN COMPOUNDS

14a5

TABLE A-25. Calculated ideal gas thermodynamic properties at 298.15 K and 1 bar

Compound

Methanol
Methanol-d)
Methanol-d3
Methanol-d4
Ethanol
I-propanol
2-Propanol
1-Butanol
DL-2-Butanol
2-Methyl-2-propanol
1,2-Ethanediol
Dimethyl ether
Dimethyl ether-d3
Dimethyl ether-d6
Ethyl methyl ether
Diethylether
Propanone
2-Butanone
Methanal
Methana1;.a')
Methanal-d2
Ethanal
Ethanal;.a')
Ethanal-d4
I':'Propanal
I-Butanal
Methanoic acid monomer
Methanoic acid dimer
Methanoic acid, equil.mixt.
Methanoic acid-d)(HCOOD)
MethllDoic acid-d1{DCOOH)
Methanoic acid-d2
Bthanoic acid monomer
Ethanoic acid dimer
Ethanoic acid, equil. mixt.
Methyl methanoate
Methyl ethanoatp
Epoxyethane
Epoxyethane-d4
DI.r-l,2-Epoxypropane
DL-l,2-Epoxybutane
Furan
2,5-Dihydrofuran
Tetrahydrofuran

{HO(T)-HO(O)}
J mol-)
11435
11703
11849
12146
14250
17462
17266
20633
21526
20656
16560
14344
14993
15703
18473
23459
16486
20312
10020
10096
10210
128%
13192
14041
17490
22046
10927
19632
10655
11301
UllO

11510

13597
28052
14470
14465
18362
10856
11919
14375
18930
12347
14491
14667

-{GO(T)-HO(O)}/T
J K-) mol)
201.46
204.38
207.39
210.15
232.85
264.02
251.29
292.39
287.33
257.42
248.2
219.23
229.73
226.70
247.30
263.99
242.32
271.78
185:16
193.88
190.83
220.69
222.57
228.21
245.81
269.78
212.34
266.94
133.74
214.17
214.20
215.94
237.86
320.30
160.32
236.76
262.79
-206.58
212.12
238.70
262.2
225.84
235.65
253.22

{SO(T)-SO(O)}
J K-) mol-)
239.81
243.63
247.13
250.90
280.64
322.'8
309.20
361.59
359.53
326.70
303.8
267.34
280.01
279.37
309;25
342:67
297.62
339.90
218.76
227.74
225.07
263.95
266;82
-275.30
304.51
343.67
248.99
332.78
169.48
252.07
251.46
254.55
283.47
414.39
208.85
285.28
324.38
242~99

252.09
286.91
325.7
267.25
284.25
302.41

Co

e.
J K-) mol-)
44.04
45.61
49.41
51.00
65.20
8'.:16
89.32
108.03
112.74
113.63
82.7
65.57
71.49
77AS
93.30
119.46
75.02
101.68
35.39
36.54
38.14
55;32
58.11
64;6480.73
103.36
45.68
96.14
84.15
48.25
47.87
50.58
63.44
137.25
87.52
64.38
86.03
47.86
58:58
72.55
95.18
65.40
75.60
76.25

J~ Phys. Chem. Ref. Data, Vol. 15,

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No. 4,1986

1436

CHAOETAL.
TABLE A-26. Comparison of ideal-gas, third-law entropy values based on Part I and Part III
with the ideal gas values calculated from the Partition Function.

Compound

T
K

Methanol
298.15
Ethanol
298.15
I-Propanol
298.15
2-Propanol
298.15
I-Butanol
298.15
DL-2-Butaool
298.15
2-Methyl-2-Propanol 298.15
1,2-Ethanediol
298.15
Diethyl Ether
298.15
Propanone
298.15
2-Butanone
298.15
Methanoic Acid
298.15
Ethanoic Acid
298.15
Epoxyethane
83.71
DL-Epoxypropane 298.15
DL-l,2-Epoxybutane 298.1:>
Furan
298.15
Tetrahydrofuran
298.15

S(I)"

pc

J K- I mol- 1

bar

Rln(~)
p

0.1694
0.0788
0.0255
0.0602
0.0085
0.0244
0.0560
1.189 X 1O- 4e
0.7123
0.3066
0.1263
0.0567
0.0207
1.01325
0.764f

-14.76
-21.13
-30.51
-23.36
-39.56
-30.87
-23.97
-75.14
-2.82
-9.83
-17.20
-23.86
-32.24
+0.11
-2.24

:'!'JUX/U.l

U.:'!'U()!!

177.00.5

0.8015 h
0.2164i

127.270.21
160.1
193.60
181.07
225.78
218.990.3 b
193.10.7
163.22.2
253.760.2
199.81
239.060.4
129.590.5
157.22
149.34O.25
196.50.5

2D4.30.7

llyHd
kJ mol-I

llyS
J K- I mol-I

{S(g)-Sr(g)}
J K- I mol-I

1.92 1
0.80 1
0.211
0.54 1
0.04 1
0.25 1
1.13 I
0.00
0.88 k
0.74k
0.36 k
81.8 0
81.2 0
0.55 m
0.58 m

37.97
42.56
47.50
45.50
52.39
49.79
46.83
66.72 e
27.10
30.99
34.79
20.10
23.36
25.53 j
27.89

127.35
142.75
159.32
152.61
175.72
167.00
157.70
223.78
90.89
103.94
116.69
67.42
78.35
89.99
93.54

-12.87

3U2

105.72

U.31

-1.84
-12.73

27.45
31.99

92.07
107.29

0.52k
0.28 n

{SO(T)-SO(O)}
3rd law this work

241.78
282.52
322.62
310.86
361.98
355.37
327.00
311.84
342.71
294.6
338.91
254.9
284.5
239.99
288.4

239.81
280.64
322.58
309.20
361.59
359.53
326.70
303.8
342.67
297.62
339.90
248.99
283.47
242.99
286.91

324.03

32:;.7

267.8
299.1

267.25
302.41

uI~~llil,; uAy~ell l,;ulIlpuumJs ill the I,;~rbun r~nge CI tu C4, P~rt I.

Value for D-2-Butanol + Rln2
c TRC k-table except as noted.
d Thermodynamic properties of key organic oxygen compounds in the carbon range C 1 to C4 , Part III (in preparation), the values are those selected
by Majer except as noted.
e Ref. 514
f Ref. 516, 517
g Ref. 518
h Ref. 519
i Ref. 520
j Ref. 521
k Calculated from second virial coeff. TRC h-table
1 Ref. 522
m Average as calculated from second virial coeff. for analogous ether, and from the Tsonopoulos correlation.
n Ref. 515
o Calculated from TRC ideal gas tables lltG for monomer and dimer of acids. (This correction and its uncertainty are large. Only dimers are
assumed and there is a large uncertainty in the enthalpy of dimerization.)
a

Thermodynamic 1'Jo1'eJ tics uf key

J. Phys. Chem. Ref. Data, Vol. 15, No.4, 1986

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