1956
From the heat of combustion and the heats of formation of carbon dioxide (6)
and water (8), we calculated the standard heat of formation of benzoic acid a t
25" C. (298.15" K.), a t the saturation p r e s s ~ r eWe
. ~ found
(AH?)298.15 = -384,140k290 abs. j. mole-'.
The error involved in this quantity is twice the estimated standard error (9)
calculated from measurements of each compound, applyiilg the root-mean-
square rule.
The heat capacity data of Ginilings and Furultawa are given a t 5" intervals.
The entropy was obtained at different temperatures by integrating C,/T vs. T
using Simpson's one-third rule. From the enthalpy function (HTO-HO0)and
the entropy, the free energy function (FTO--IIoO)was obtained. Dimensionless
values of these quantities are given in Table I. (To is the ice point temperature.)
The accuracy is of the same order as that of the original heat capacity measure-
ments. The precision between 60" and 395" K. is within 0.2y0. Above 395" K.
the results are less reliable (0.3y0), benzoic acid being liquid (m.p. 395.52" K.)
and possibly reacting with the containers. Between 60" and 14" K. the accuracy
decreases to lye because of uncertainties in the temperature measurements.
In Table I, values a t 298.15" K. and 395.52" K. were obtained by a graphical
method. In Table I1 we give the conversion factors for different units.The
molecular weight of benzoic acid has been taken as 122.12.
The standard heat of formation a t 0" K. calculated from that a t 298.15" K.,
'Issued as N.R.C. No. 4065.
2National Research Council of Canada Postdoctorate Fellow 1955-66.
3 A recent determination of the heat of coinbustion of bensoic acid (Coops, J., Adriaanse, N.,
and van Nes, K. Rec. trav. clziin. 7 5 : 257. 1956) agrees very well witlz previozts measzrrenlents.
4The enthalpy difference between saturated pressure and one atnzosphere i s negligible.
GOTON A N D WHALLEY: THERMODYNAMIC PROPERTIES
TABLE I
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 180.214.232.88 on 08/12/17
TABLE I1
To convert
tabulated value Having the dimensions Multiply
of indicated below by
and the enthalpy function for bertzoic acid, graphite (2), oxygen, and hydro-
gen ( l o ) , is
(AIli0)o = -366,761f 310 abs. j. mole-'.
In the last column of Table I we give some values of the free energy of
formation of benzoic acid, calculated from the free energy functions of the
elements (References 2 and 10).
1. ANDREW, D. H., LYNN,G., and JOHNSON,J. J. Am. Chem. Soc. 48: 1274. 1926.
PARKS,G. S., HUFFMAN, H.,and BARMORD, M. J. Am. Chem. Soc. 55: 2733. 1933.
2. DE SORBO,W. and TYLER,W. W. J. Chem. Phys. 21: 1660. 1953.
3. GINNINGS, D. C. and FURUKAWA, G. T. J . Am. Chem. Soc. 75: 522. 1953.
4. JESSUP,R. S. J. Research NBS, 29: 247. 1942.
1508 CANADIAN JOURNAL O F CHEMISTRY. VOL. 34. 1956