Oct.

, 1960 THERMODYNAMIC
PROPERTIES FORMATE
OF SODIUM 1553

THE HEAT CAPACITY AND THER&!ODYNA&IICPROPERTIES OF SODIUM

FORMATE FROM 5 TO 350'K.
BY EDGAR
F. WESTRUM,JR.,SHU-SING
CHANG E. LEVITIK
AND NORMAN
Department of Chemistry, University 4 Michigan, Ann Arbor, Michigan
Received M a y 9, 1060

The heat capacity of anhydrous sodium formate has been determined at low temperatures by adiabatic calorimetry, and
found to be normal. Thermodynamic functions were evaluated from these data. The heat capacity a t constant pressure,
entropy, enthalpy increment ( H 0 - Hao), and free energy function [(Po- Hoo)/T]a t 298.15'K. are 19.76 f 0.01 tal./
(deg. mole), 24.80 cal./(deg. mole), 3766.9 cal./mole, and - 12.16 cal./(deg. mole), respectively.

Thermophysicd properties of relatively few salts Below 10"Ii. the temperature scale was obtained by fitting
of organic acids have been reported a t low tempera- the equation R = A + RT* + CTs to the observed resist-
ance of the thermometer a t loOK., at the boiling point of
tures. In t'he present investigation the heat capa- helium, and d R / d T a t 10'K. The temperature scale thus
city of sodium format'e has been investigated and defined is considered to agree with the thermodynamic scale
its thermodynamic properties evaluated. 1T-ithin 0.1" below IOOK., 0.03" from 10 to 90°K. and 0.04"
from 90 to 400°K.
Experimental A Fiberglas insulated constantan wire (150-ohms) wa8
Sodium Formate Sample.-Two crystalline sodium for- bifilarly wound on a double threaded copper sleeve and
mate hydrates exist, in equilibrium with the aqueous solu- served as heater. Measurements of temperature and of
tion1.2; the dihydrzite is the stable form between 15.3 and electrical energy were made with a calibrated White double
27.9', while the trihydrate is stable only a t temperatures potentiometer, calibrated resistors and a calibrated standard
below 15.3" and the anhydrous salt above 27.9'. An aque- cell. Time duration of the energy input was measured by
ous solution of reagent sodium formate (HCOtNa) saturated an electric timer checked against standard time signals.
a t 90" was filtered and allowed to cool very slowly by gradu-
ally decreasing the temperature of the water-bath surround- Results
ing it. However, the temperature was maintained above 30" The experimental heat capacity determinations
t o prevent the formation of hydrate. After two recrystalli- are presented in Table I in chronological sequence
zations from distilled water the crystals of the anhydrous
salt were separated and baked in a a oven at 130' and finally to permit the estimation of the approximate tem-
dried in high vacuum.
hlicrochemical analysis indicated the following percent- TABLE
I
ages by weight: 66.32 & 0.12 format8e,33.86 f 0.05 sodium, OF SODIUMFORMATE
HEAT CAPACITY [IN CAL./(DEG.
17.76 i 0.02 carbon, and 1.51 f 0.3 hydrogen (theoretical:
66.1!3, 33.81, 17.76 and 1.48, respectively). The formate MOLE)]
content was determined by oxidation with alkaline perman- T,OK. Cp T. OK. Cp T,OK. CP
ganate solution, and sodium was determined by the triple Series I 290.46 19.59 13.55 0.146
acetate method. 307.85 20.01 14.77 193
Cryogenic Technique.-The Xark I cryostat employed
for low temperature adiabatic calorimetry was similar to 99.69 11.468 317.34 20.28 16.12 .253
the one used by Westrum, Hatcher and Osborne,a and will 105.55 12.010 326.78 20.56 17.65 .333
be described elsewhere.4 A gold-plated copper calorimeter 113.22 12.661 336.11 20.88 19.27 ,435
(laboratory designation W-10) wus used in these measure- 121.26 13.264 345.33 21.06 20.96 ,556
ments, which is similar to 11'4 previously described5 except
that it, is gold-plated overall, has 110 vanes for thermal con- 129.48 13.808 22.80 ,704
durtion, and the cntirc covcr is rrmovnble for admission of 137.71 14.311 Series I1 24.84 ,903
s:mple. The caiorimc~tvrw:?s loa~lc~cl iri an anhydrous nitro- 146.21 14.765 27.13 1.139
gen :tf mosplicre with 77.0217 g. ( m c i i o ) ol san:plt', wacuatetl 152.68 15.10 294.47 19.65 29.68 1.441
and filled with helium at 8.0 cm. pressure at 300°K. in order
to provide therird c-oi1tac-t hctween ths calorimeter and 161.27 15.50 298.72 19.76 32.42 1.797
sanlple. I3aojzncy cwrrcctions were made on the basis of :L 170.28 15.87 302.09 19.87 35.37 2.216
pywometrir dcnsity of 1.!)67.6 The specific heat of the 179.08 16.25 38.62 2.707
onlorimetcr w:ts determineil sop:mtcl,v with t,he s:tme thor- 189.01 16 57 Series I11 42.41 3.311
rnblj- :iiiCt the s:tnio :~iuountsof' inclium-
r for w:tlin%, of Spiozon-T gre:ise (for 198.36 16.89 46.77 4 042
t 1icmi:tl contnrt ivith t h e r.i:c~rmornetrr.:idhr:ztc.rj m d of 208.09 17.20 4.84 0.006 51.37 4.822
helium gas in the snmplir spicae. The crnl)ty cnlorimeter- 217.17 17.48 5.65 ,011 55.69 5.558
errnometer assc~inblyrcyrcwrited from 25 to 40y0 226.11 17.74 6.39 .014 60.31 6.325
t,al tieat c:ip:icity ohscrvotl.
234.95 18.00 7.03 ,017 6 . 6 9 7,191
243.59 18.23 8.19 ,026 87.93 7.536
252.95 18.49 9.21 .040 74.47 8.487
262.52 lS.76 10 22 ,060 81. 12 9.403
271.95 19.02 11.27 ,083 88.26 10.205
- 281.27 19.26 12.30 .110 95.95 11,106
( 1 ) E. Groschuff. Bw., 86, 1790 ( I D O R ) .
(2) E. Elod and IC. Tremniel, Z. anorg. allgem. Chem., 166. 161 perature increments of the individual runs by dif-
(192i).
(a) E. F. Westrum, Jr., .J. B. Hatcher and D. V. Osborne, J . Chem. ferencing the adjacent meaii temperatures. Cor-
P h y a . , 21, 419 (1953). rections for curvature (amounting to less than
(4) E. F. Westrum, Jr., n n J -2. F. Beale, Jr., t o be published. 0.lyo)occasioned by the finite temperature in-
( 5 ) E. Benjamins and E. F. Westrum, Jr., J . Am. Chem. Soc., 79. crements employed have been made in these values.
287 (1957).
(6) H. Schroder, Bcr., 14, 21 (1881).
The data are presented in terms of the defined ther-
( 7 ) H. J. Hoge a n d F. G. Brickwedde, J . R-search Nall. Bur. Stand- mochemical calorie equal to 4.1840 absolute joules
ards, aa, 381 (1939). and the mole weight of 68.010 g. KO anomalies
1554 F. WESTRUM,
EDGAR JR.,SHU-SING
CHANG E. LEVITIX
AND NORMAN Vol. 64

TABLEI1 computer are provided at selected temperatures i i i

THIERMODYNA4hfICPROPERTIES O F SODIVM FORMATE Table 11. Nuclear spin and isotope mixing con-
(HCOzKa21mole =68.010 g.) tributions have not been included in the ent,ropp or
(:p SO. -(PO - HOC) / in the free energy function. Extrapolatioii below
cal./deg.
1

cal./deg. HO - HaO, T 6°K. was made with the Debye limiting law. The
T, OK. n.ole mole cal./mole cal./deg. mole
5 0.006 0.002 0,007 0.001 estimated probable error in t'he therniodpiianiic
10 ,054 ,016 .124 .004 functions is less than 0.1% above 10O"Ii.
15 . 202 .062 .718 ,014 As a test of the accuracy of thc heat capacity
20 .485 ,156 2.374 ,037 measurements and the ent'halpy integration tech-
25 .914 ,307 5.812 .075 niques, a continuous energy input from 98.31 t.o
148.25"K. was made in 21 minutes. The observed
30 1.481 ,522 11.75 .131
enthalpy increment agreed within 0.04% with that,
35 2'. 161 ,800 20.81 ,206
obt>ainedby numerical quadrature over the same
40 2.925 1,138 33.49 ,300 range of temperahre.
45 3.743 1.529 50.15 ,415
50 4.589 1.967 70.97 ,548 Discussion
60 6.273 2.954 125.33 ,865 The mean specific heat of sodium formate has
70 7.850 4.041 196.07 1.240 been reported as 0.312 cal./(deg. g.) between 21
80 9,255 5.183 281.78 1.661 and 57" by Pagliani8 and 0.2916 cal./(deg. g.) be-
90 10.47 6.345 380.54 2.117 t,ween 10 and 93" by de Heen,g which correspond
100 11.51 7.504 4Y 0.58 2.598 to the mean molal heat capacities of 21.22 and 19.83
110 12.40 8.643 610.2 3.096 cal./(deg. mole), respectively. Over the same
120 13.17 9.756 738.1 3.605 ranges, the data of this investigation indicate mean
l:iO 13.84 10.837 873.3 4.119 molal hea,t capacities of 20.14 and 20.53 cal./(deg.
1-11) 14.44 11.885 1014.7 4.637 mole), respectively.
150 14.97 12.899 1161.8 5.154 By utilizing the enthalpy of solution for sodium
formate,'O the enthalpy of neutralization of aque-
160 15.44 13.881 1313.9 5.669
ous formic acid,10-12the entha,lpy of solution of
170 15.87 14.830 1470.4 6.180
formic acid,13 the enthalpy of vaporization and
180 16.25 15.748 1631.0 6.686
correction for dimerizat,ion,'4 and the heat of com-
190 16.61 16.636 1795.4 7.187
bustion of formic acid," t3heenthalpy of formation
200 16.94 17.497 1963.1 7.681
of sodium format,e equal to - 155.03 k~al./mole'~
210 17.X 18.331 2134.2 8.168 is obtained at 298.15"K. This value, together with
220 17.56 1!1. 141 2308.3 8 . 649 the ent,ropies of the elernent~'~ and the entropy of
230 17.83 l Y ,928 2485.4 9.122 sodium formate from this research. yields a Gibbs'
240 18.14 20,694 2665.4 9.588 free energy of format'ion of sodium form& of
250 18.41 21.440 2848.1 10.048 - 139.12 kcal./mole.
260 18.68 22.167 3033.6 10.500 Acknowledgment.-The authors appreciate the
270 18.96 22.878 3221.8 10.945 assistance of J . C. Trowbridge and Bruce H.
280 19.25 23.572 3412.9 11.384 Justice in the calculation of the data. The partial
290 19.53 24.253 3606.8 11.816 financial support of t,he Division of Research of the
300 19.81 24.920 3803.5 12.241 U. S. Atomic Energy Commission is gratefully ac-
350 21.09 28,078 4828.9 14.281 knowledged.
"3 15 19.05 23.098 3281.7 11.084 (8) S. Pagliani, Aft%Bccad. Scz. T o r i m . 17, 106 (1881): .Inn. I'hva.
298.15 19.76 24.797 3766.9 12.163 Beibl., 1882, 369.
(9) P. de Heen, Bull. Acad. Bela., [3] 5, 760 11883).
were observed at any temperature. It is conaid- (10) 11. Berthelot., Ann. chim. et p h y s . , [ 5 ] 4 , 7 t (1875).
(11) J. Thornsen, "Thermocheniische Untersuchungen," J . A. Barth.
ered that thcA probable error of the heat capacity Leipzig, 1882-1886.
data is less than 0.1% at temperatures above 25OK. (12) AI. Berthelot, A m . chtm. et phys., [4] 30,456 (1873).
Below this temperature the probable error increases (13) W. 4.Kaye and G. 8. Parks, J . Chem. Phljs., 2, 141 (1934);
A. A. Glagoleva, J . Gen. Chem. ( C . S . S. E . ) , 6, 1769 11936).
gradually to about 1% at 10" and to 5% a t 5°K. (14) J. 0. Halford, J . Chem. Phys., 10, 582 (1942).
The therniodynamic properties computed by (15) "Selected Values of Chemical Therniodynaniic Properties,'
quadrature of the heat capacity data on a digital Circular 500, National Bureau of Standards. Washington 25, D. C.