CANADIAN JOURNAL O F CHEMISTRY. VOL. 34.

1956

THERMODYNAMIC PROPERTIES OF BENZOIC ACID1

The thermodynamic properties of benzoic acid were required in connection

with its synthesis from benzene and carboil dioxide under high pressure.
Accurate measurements of the heat of combustioil and of the heat capacity
have been made since the last reported thermodyilamic study of Parks and
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Huffman (5), and we have recalculated these properties.

The heat capacity between 14" and 410" K. has been measured with con-
siderable care on exceptionally pure samples by Ginnings and Furukawa (3).
Their measurements appear to be much more accurate than previous ones (I)
and were used exclusively. Likewise the heat of combustion when each of the
gases involved is a t its standard state (benzoic acid being a t one atmosphere
pressure) was determined very accurately by Jessup (4) and his value of
26,428.4k2.6 int. j. gm.-l a t 25" C., confirmed by Prozen and Rossini (7), is
adopted.3 The following conversion factors were used:
1 int. joule = 1.000165 abs. joule
and I abs. joule = 0.239006 defined calorie.
For personal use only.

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
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*Values at these te7nperatztres arc for the liquid.

For personal use only.

TABLE I1

To convert
tabulated value Having the dimensions Multiply
of indicated below by

S0/R, so cal. deg.-' mole-' 1.9871

- (FTo-HO ) / R T - (FTo-Hoo)/T cal. gm.-' deg.-I 0.016272
abs. j. gm.-I deg.-' 0.068083
- (AFr") T/RT - (AF")./T B.t.u. (Ib. mole)-' deg.-' 1.9858
B.t.11. Ib.-' deg.-I 0.016261
(HT' -Ho0)/RTo (HT' -Hoe) cal. mole-'
cal. gnl.-'
j. gm.-'
B.t.u. (Ib. mole)-'
B.t.u. 1b.-1

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

5. PARKS, G. S. and HUFFMAN, H. Free energies of some organic compounds. Monopr.

- Ser.
No. 60. T h e Chemical Catalog Co., Inc., Kew Yorlc. 1932. -
6. PROZEN, E. J., JESSUP, R. S., and ROSSINI,F . D. J. Research NBS, 33(6): 447. 1944.
7. PROZBN. E. I. and ROSSINI,F. D. 1. Research NBS, 33(6): 439. 1914.
8. ROSSINI. F . D . T. ~ e s e a r c hNBS. 22: 407. 1939.
9. ROSSINI,F . D. ahd DEMING,%\'. E. J . \Vash. &ad. Sci. 29(10): 416. 1939. ROSSINI,
F . D. Esperimental ther~nochernistry. Interscience Publishers, Inc., New Yorlc.
1956. p. 308.
10. TABLES OF THERMAL PROPERTIES OF GISES. Li.S. Natl. Bur. Standards, Circ. 564. 1955.
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SEPARATION OF HIGH SPECIFIC ACTIVITY Na22

FROM IRRADIATED ALUMINUM1

Na2?, a positron emitter with a half-life of 2.6 years, is very useful as a

tracer. I t is however difficult to obtain in high specific activity. We have
separated a high specific activity source and are reporting the method because
of the general interest in this radionuclide.
Na22may be produced in a cyclotron by the reaction 13A12?(p,3 ~ 3 n ) ~ ~ N(3).
a??
For personal use only.

Preparation of a solution of high specific activity necessitates the separatioil of

sodium from macro amounts of aluminum without the addition of a "carrier".
This ruled out methods involving precipitation of the sodium. Precipitation
of the aluminum was also ruled o u t because of excessive losses due t o Na22
adsorption. T h e sinter-leach method (1) was not used because of the low
yields suspected (4). T h e two methods remaiiliilg were ( a ) vacuum distillation
and (b) ion exchange separation. T h e ion exchange method was chose11 because
of the relative speed, simplicity, and the quantitative nature of the separation.
In a study of the chemical composition of coal ash by Ellington and
Stanley (2), a ileutral solutioil of sodium and aluminum was adsorbed on a
cation exchange resin. Elution with 0.4 N HC1 caused the sodium to appear
in the effluent while the alumillurn remailled adsorbed on the column. A
variation of this method was adopted.
The irradiated 'spec-pure' aluminum was dissolved in a minimum amount
of a mixture of concentrated hydrochloric acid and hydrogen peroxide which
was gently warmed to hasten solution. The solution was evaporated until
precipitation just commenced. The solutioil was cooled, diluted to 20 ml. with
water triply-distilled from a quartz still, and concentrated ammonia added
dropwise until the aluminum hydroxide precipitate persisted after 30 sec. of
stirring. T h e precipitate was redissolved with a minimum of hydrochloric acid
which had been diluted with the triply-distilled water, and the solution was
adsorbed on an Amberlite IR-120 cation exchange resin. T h e column di-
mensions were 2.5 ~ m . ~ X cm.3 0 and a flow rate of 8 ml./min. was used.
lWitl~financia1assistance from tlze National Research Council and !he Atomic Energy Control
Board.
2Holder of a Russell J . E d d y Award of tlze Clzemical Institute of Canada, 1955.