Textbook Errors, 62

GUEST AUTHOR
Norman O. Smith
Fordham University The Difference Between Cp and C„
New York City
for Liquids and Solids

In physical chemistry texts* one of the 1

heat capacities represents not only the work done
first exercises in the manipulation of partial derivatives against the environment in isobaric heating, viz.
is the development of an expression for the difference P(bV/bT)P, but also the work done against intcrmolec-
between the heat capacities of a pure substance at con- ular attraction of the substance itself, viz. (bE/bV)T
stant pressure and at constant volume. The most ( bV/bT)P. It is the magnitude of this latter contri-
commonly quoted expression is bution which is easy to overlook.
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Accurate values of (dF/dTV, obtainable from the

coefficient of thermal expansion, a (1/V) (d V/dT)P,
=

are readily available for a large number of substances.

It is then indicated that the expression reduces to
Downloaded via UNIV DE ALICANTE on June 26, 2022 at 16:38:14 (UTC).

Accurate values of (bE/bV)T, the internal pressure,

Cp —

Cv R per mole for ideal gases, and application

=
on the other hand, are more rarely to be found. Apart
of the relation to liquids or solids is usually either ab- from an approach through heats of vaporization which,
sent or dispensed with by a brief statement to the for many substances, is questionable, internal pressures
effect that for liquids and solids the value of Cp Cv —

are evaluated from direct measurement of a and of

is so small as to be negligible for most purposes. Such /?[= (— l/F)(dF/dP)r], the compressibility, or
a conclusion is doubtless the result of a cursory obser- direct measurement of (bP/bT)v. This is because
vation that the factor (dV/'d'T) P, common to both (bE/bV)r (Ta/0)
= P -

T(bP/bT)v = P s -

terms above, is small for condensed phases: it over- T(bP/bT)v. It has been pointed out2 *that many pub-
looks the fact that (d E/b V) r can be, and often is, large lished values of 0 are not values of (1/F) (bV/bP)T,
enough to compensate for the smallness of (bV/bT)P, but of (1/F) (AF/AP)T, where AP is a large increment,
so that Cp Cv is, in fact, appreciable for many liquids
—

and this casts doubt upon the reliability of experimental

and some solids. The difference between the two compressibilities for the purpose of evaluating such
quantities as internal pressure. A direct measurement
Suggestions of material suitable for this column and guest of (bP/bT)v is thus preferable to calculation from
columns suitable for publication directly should be sent with as
many details as possible, and particularly with references to
a/0.
modern textbooks, to William H. Eberhardt, Department of The following table gives the properties of several
Chemistry, Georgia Institute of Technology, Atlanta, Georgia liquids and solids, at 20°C and 1 atmosphere, needed
30332.
1
Since the purpose of this column is to prevent the spread and
continuation of errors and not the evaluation of individual texts,
the source of errors discussed will not be cited. In order to be Hildebrand, Joel H., and Scott, Robert L., “The Solu-
2

presented, an error must occur in at least two independent recent bility of Nonelectrolytes,” 3rd ed., Reinhold Publishing Corp.,
standard books. 1950, p. 428.

Physical Properties of Liquids and Solids at 20°C and 1 Atm

Hg CHsOH CJ-U CC1, CSs Ag NaCl Iodine
V (cc mole-1) 14.81 40.5 88.9 96.5 60.3 10.27 27.0 51.38
a x 104 *(deg-1) 1.80“ 11.9“ 12.2“ 12.2“ 11.9“ 0.583s 1.14“ 2.64s
p X 106(atm-1) 4.00“ 100" 93“ 106“ 84“ 1.03“ 4,2“ 13“
a/p (atm deg-1) 45.0 12 13.1 11.5 14.2 56.6 26 20
(dP/dTjv expt. 12.58' 11.47' 12.67' 27.\2d
(atm deg-1)
(dV/dT)P 1X 10' 26.6 500 1,085 1,177 718 5.99 30.8 135.6
(cc deg mole *)
Tct/p or T(i>P/dT)v 13,190 3,500 3,688 3,363 3,715 16,600 7,952 5,900
(atm)
Cp —
Cv (cal deg-1 0.85 4.2 9.69 9.58 6.46 0.241 0.593 1.9
mole-1)
Cp (cal deg-1 6.68“ 19.22“ 31.71“ 30.61“ 18.27“ 6.045“ 12.01" 13.3“
mole-1)
{Cp -

Cv)/Cv (%) 12.7 22 30.6 31.3 35.4 3.99 4.94 14.3

“
Given or estimated in “International Critical Tables,” McGraw-Hill Book Co., New York, 1929, Vols. Ill and V.
s
“Smithsonian Physical Tables,” 9th rev. ed., The Smithsonian Institution, Washington, D. C., 1954.
‘
Hildebrand, J. II., Phys. Rev., 34, 649 (1929).
d
Interpolated from Hildebrand, J. II., Z. Physik., 67, 127 (1931).

654 / Journal of Chemical Education

for the evaluation of CP —

CV- In addition to (dP/ more than 30% of Cp for three, and more than 10% for
bT)v calculated from a/ft, this quantity as deter- all of these common liquids shows that it is by no means
mined by direct experiment is stated where available. small. For solids the difference is, admittedly, a much
The internal pressure as calculated from this latter smaller percentage of CV, but still nearly 15% for
value is given in such cases. The fact that Cp —

CV is iodine.

Volume 42, Number 12, December 1965 / 655