January 1948 INDUSTRIAL A N D ENGINEERING CHEMISTRY
down t o a value of 2.0. However, a bed of such finely divided
material would offer great resistance to flow of liquid; increasing
the particle size would permit better flow rates but decrease the
reaction rate. The Germans evidently encountered a similar
problem, since there are statements (I) that they found the best
catalyst to be large porous particles prepared by sintering finely
ground base-exchange resin, lightly coated with a thermosetting
phenolic.
The authors have no data to support any explanation of the
failure of the bimolecular equation t o hold over the first 4 hours of
the reaction. There appears to be some inhibiting process or
induction period involved when the base-exchange resin is pres-
ent. This is borne out by the fact that the 4-hour acid values
for the runs with coarse catalyst (F and G) are actually higher
than that for the run with no catalyst (A), although the 8- and 12-
hour values are lower. It was thought that this might be due to
adsorbed water on the surface of the catalyst. However, a check
of several runs in which either added water or bone-dry catalyst
was employed (Figure 3) did not bear this out. This matter is of
considerable practical importance for continuous column opera-
tion. If it is due to an integfal part of the reaction mechanism,
the 2 hours' contact time mentioned above would need to be
considerably increased to obtain a product with an acid number of
2 or lower.
The phenol-formaldehyde-ulfonic acid resins are similar to
Zeo-Karb H (6) in maintaining catalytic activity over a series of
Thermochemistry of Sodium
Carbonate and Its Solutions
KENNETH A. KOBE1 AND THOMAS M. SHEEHY2
University of Washington, Seattle, Wash.
T h e solubility and thermochemical data for sodium car-
bonate, its hydrates, and its concentrated solutions have
been reviewed and collated. New data are: Specijic heat
of saturated solution 20-32' C. is 64.0 calories per gram
NaCz03.10H20dissolving during heating; mean specitic
heat from 33' to boiling point is 0.851 calorie per ' per c.
gram of solution? heat of melting for Na2C02.10H~0 is
21,400 calories per gram mole.
I N 1944 the production of sodium carbonate, 4,693,000 tons,
was exceeded only by sulfuric acid as a manufactured chem-
icat utilized for chemical purposes. The physical and chem-
ical properties of such an industrial compound are of the utmost
importance. It is the purpose of this paper to review and collate
the thermochemical properties of sodium carbonate, its hydrates
and its concentrated solutions. New data are given on the
specific heat of the saturated solution and heat of transition.
SOLUBILITY
The solubility data, solid phases, transition temperatures, and
vapor pressures of saturated solutions are of fundamental im-
portance. The solubility data given in the International
Critical Tables (II) were derived mainly from three sources
(8, 84, 40). During the elapsed time several investigators have
given new data from the cryohydric t o the critical temperature.
1 Present address, University of Texas, Austin, Tex.
9 Present address, Standard Oil Company (California). EL Segund6 Calif.
99
runs. The one exception t o this is the sharp drop between m u
118B
and C, the first and second runs with the fine catalyst. This drop
could be due either to the elution of a small amount of adsorbed
strong acid or to the loss of a very finely divided fraction during
the a t r a t i o n of the catalyst from run B.
Data for the uncatalyzed run (A) are a t variance with Suss-
man's findings of no "indication of esterification" for the same
system under similar conditions (6). The close conformity of the
rate found for this run with those for the catalyzed runs (Figure 4)
leads to the belief that tlie authors' results are correct,
ACKNOWLEDGMENT
The samples of base-exchange reain were prepared by B. Coe
and G. Bodamer. The authors are indebted t o R. J. Myers, W.
S. Niederhauser, and L..P. Hammett for advice and criticism.
LITERATURE CITED
(1) Diericks, FIAT Report PB866, O5ce of Technical Services,
Dept. of Commerce, Washington, 1947.
(2) Leyer and Othmer, IND. ENQ.CBEM.,37,968(1945).
(3) Myers, F. J., FIAT Report PB42,802,Office of Technical Serv-
ices, Dept. of Commerce, Washington, 1947.
(4) Myers, Eastes, and Myers, IND. ENQ.CEEM.,38,697-706 (1941).
(5) Sussman, Ibid., 38,1228 (1946).
(6) Sussman, private communication.
(7) Thomas and Davies, Nature, 159,372(1947).
RECBIVED February 11, 1947.
Caspari (4, Hill and Bacon (IO), and Kobe and Leipper (92)
investigated ranges from the cryohydric t o the boiling point.
Seyer and Todd (36)investigated the range 17' t o 173' C., and
Ervin, Giorgi, and McCarthy (9) made determinations a t
100' to 150' C. The high temperature range was investigated
from 50' t o 348' by Waldeck, Lynn, and Hill (B), and from 150'
t o 350' by Schroeder, Beck, and Gabriel (34). These newer
data have been plobted on a large scale and compared with the
data from which the I.C.T. (International Critical Tables) curve
was drawn. The best curve was drawn through the points,
giving due weight t o the reliability the data were believed t o
have. From this curve were taken solubility values a t regular
temperature intervals. These are given in Table I. Below
50' the data of the more recent workers (6,10,@) correspond to
those of the earlier workers (8, 84, 90); the data of Wells and
McAdam (40) from 28' t o 44" are highly accurate. Above 50"
the data of Caspari (6) are definitely high, whereas those of
Kobe and Leipper (82)are lower than I.C.T. values but not so
low as those of Waldeck, Lynn, and Hill (38),whose data are
about 1.5% lower. These latter workers used glass below 100'
and a steel bomb up t o 348", and report their solubility values
accurate t o 0.1% from 50' t o 150', 0.2% from 150" t o 250°,
and 0.3% above 250" C. Schroeder, Beck, and Gabriel (34)
checked the data of Waldeck, Lynn, and Hill a t four tempera-
tures from 150' t o 350' and obtained satisfactory agreement
except at 350°, at whieh temperature the latter workers reported
a zero solubility which is refuted by the former. Waldeck,
Lynn, and Hill also report determinations a t 112.5' 'and 113.0°
100 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 40, No. I
divergence has been reported in the transition temperature of
I. SOLUBILITY
TABLE OF SODIUM
CARBONATE
IN WATER monohydrate to anydrous salt. Waldeck, Lynn, and Hill (38)
Temp.0, Water pf
G. Moles/
1000 G.
G. NazCOa/
100 G. NazCOa,
Vapor reported 112.5' * 1" C. based on the abrupt change in slope of
Pressure,
0 c. Hydration Hz0 HIO % Mm. Ha. the solubility curve a t this temperature. Janecke (14) reported
-2.1 10 0.575 6.10 5.75 .... 107"by a dilatometric method a t approximately 450 atmospheres
0
5
10
10
0.66
0.84
7.00
8.90
6.54
8.2
....
.... pressure. An inspection of his pressure-time curve shows that
10 10 1 . 14
1.55
12.1 10.8 .... 107' represents a minimum value. Keene and Julien (16)
15 10 16.4 14 1 12.3
20 10 2.09 22.2 18.1 16.9 reported approximately 109'. Keene (16) stated that by a
25 10 2.77 29.4 22.7 21.4
90 10 3.70 39.2 28.2 26.8 phase rule method the transition point was determined to he
22.0ou lo+? 4.28 45.4 31.2 29.0 108.8" * 0.2' C. A value of 109" is selected to indicate that
3?.96mU l0+7 4.71 49.9 33.3 29.5
30m 1 4.78 50.7 33.6 .... some uncertainty may exist until further work has been done.
35.37u 4.67 33.1
40
60
7ffl
1
4.60
4.48
4
43
47.5
32.8
32.2
34.0
43.6
74.1
60 1 4.37 46.3 31.6 121.5 HEATS O F FORMATION, SOLUTION, AND DILUTION
70 1 4.30 45.6 31.3 192.7
75 1 4.28 45.4 31.2 239,8 The critical compilation of thermochemical data on heats o f
80 1 4.26 45.2 31.1 296.2
90 1 4.24 44.9 31 .O 442.4 formation, solution, and dilution by Bichomky and Rossini (4)
100 1 4.22 44.7 30.9 631.7 give values sclf-consistent with other thermochemical data in
104.8 1 4.21 44.6 30.8 760.0
(atm. their book. Therefore, their values are taken as the best avail-
109 4.20 44.5 30.8 1.15
able and aregiven in Table 111.
l + p
110 4.20 44.5 30.8 1.19 Kelley and Anderson (20) give Q, for sodium carbonate at
113 0 4.20 44.5 30.8 ..... 25" C. as 271,020 calories per gram mole. Perreu (SO) has
120 0 4.03 42.7 29.9 1.65
130 0 3.86 40.9 29.0 2.25 determined the heat of solution of sodium carbonate decahv-
140 0 3.71 39.3 28.2 3.02
150 0 3.57 37.8 27.4 4.01 drate in solutions of increasing concentration a t 11-12' C. aiid
E60 0 3.44 36.5 26.7 5.27
180 0 3.16 33.5 25.1 8.67 extrapolated the data to give A H = - 13,540 calories per gram
200 0 2.89 30.6 23.4 13.7 mole as the heat of solution in a saturated solution. This valut.
2.20 0 2.56 27.1 21.3 21.0
240 0 2.16 22.9 18.6 30.9 was checked by measuring heats of dilution a t the same teni-
280 0 1 . 95 20.7 17.1 37.0
260 0 1.75 18.6 15.7 44.2 perature. At 20" this value was determined as AH = - 13,960
ZBO 0 1.32 14.0 12.3 61.7 calories per gram mole. Williamson (41) has derived a method
300 0 0.88 9.3 8.5 83.8
850 0 0.19 2.0 2.0 I66 for the calculation of heats of solution from solubility and vapor
Om 1.92 20.4 16.9 .... pressure data, from which he calculates a value of 13,500 ca1oric.s
78
.... per gram mole of decahydrate. Swallow and Alty (36) deter-
10m
P5m
20m
'7Ba
78
2.48
2.79
3.17
26.3
29.6
33.6
20.8
22.8
25.2
,...
.... mined the heats of solution of anhydrous sodium carbonate and
.,..
25m
30n
32.00U
7' !
l O t j 7
3.59
4.08
4.28
38.0
43.2
48.4
27.6
30.2
31.2 ....
. . I .
dilution a t 30' for solutions up to 25% sodium carbonate. Wat-
son and Kowalke (39) have given a method of calculating the
34 78 4.51 47.8 32.3 .... differential heats of solution of sodium carbonate at various cow
35.3713 7-1 4.67 49.5 33.1 ,...
centrations and temperatures. From their dissolution charts
Om 7a 3.01 31.9 24.2 ....
10m 7a 3.57 37.8 27.4 ...* may be obtained the temperature reached in the adiabatir
15m 7a 3.92 41.6 29.4 .... formation of a sodium carbonate solution.
20m
0 U - 7a 4.32 45.8 31.4
transition temperature; m = metastable equilibrium.
....

11. TRANSITIONS
TABLE SODIUM
I N SYSTGV CARBONATE-WATER
Phases Temp., C. References
which give identical results and which represent a point of ab-
ruptly changing slope of the solubility curve. This was inter-
preted by them to be the transition point of the monohydrate to
the anhydrous form; however, other work makes this conclusion
extremely doubtful. This point remains unexplained but is
given full weight because of the check determinations. The
values of Seyer and Todd (36)are definitely low. Solubilities TABLE
111. HEATSOF FORMATION,
SOLUTION, A N D DILCTIOK
OF
of the alpha form of heptahydrate and beta form below 25' were SODIUM CARBONATE
AT 18" C.
determined in 1851 by Loewel (84) and are of doubtful accuracy, Qj = - AMoleb
G. Cal./G. H,
as they have never been checked. The existence of a trihydrate Formula State"
as asserted by Bain ( 8 ) is extremely doubtful. I t is believed NazCOa 269,890
that the solubility data of Table I for decahydrate, heptahydrate
CL - ..._.
27.5 460
6400 275.370
,3200 273,360
from 30" t o 35.5", and monohydrate are accurate within 0.4%. 1600 275,360
The vapor pressure of the saturated solution also is given in 800 275,400
400 2 75,520
Table I. The figures are those of I.C.T. (11 ) up to IOO", which 200 275,770
100 276,lRO
are checked by the data of Rode (33)from 15" to 40" C. Above R0 276.830
the boiling point the data of Waldeck, Lynn, and Hill (38)and of i
5
_. 277.590
20 277,830
Keevil (f7)were used to prepare a log p us. 1 / T plot from which 18 277,940
the vapor pressure was read at the temperatures shown. The 15 278,130
NazCOa, Hz0 C 341,640
sgreement between the two sets of data is excellent. Using NazCOa.7HzO
NazCOa. lOH2O
c
C
764.860
975,380
the vapor pressure curve the heat of vaporization of water a t the HzO 1 68,370
normal boiling point of the solution is calculated as 10,400 cal-
ories per gram mole water evaporated.
a c = crystalline state: 1 = liquid state; 0: -
infinite dilution of t h r
solution numbers refers to the gram moles water in which 1 gram mole sodium
carbonate is dissolved.
The transition temperatures are given in Table 11. The b Heats of dilution are calculated by subtracting the Qf value in the final
temperatures determined by Wells and McAdam (40) with an s t a t e from t h a t in the initial state. Heats of solution are calculated by
subtracting from Q j of the solution the Q j of the crystal minus the Qf of the
accuracy of 0.02" C. remain the most reliable despite various water with the crystal.
determinations by other workers (10, 26,27, 32). Considerable
January 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY 101
SPECfFIC HEATS

The specific heat of anhydrous sodium carbonate has been TABLEIV. HEATCAPACITY
OF SATURATED SODIUM
CARBONATE
FROM 36" TO 95" C.
SOLUTIONS
determined by Anderson ( I ) from 55" to 300" K. The extrap-
Temp.
olated curve gives a value of 26.38 calories per gram mole per Range, Heat Capacity, Cal./Gram/O C.
" C. for the heat capacity at 25' C. The value of Matsui and c. Run 3 Run 4 Run 5 AV.
36-45 0.853 0.855 0.855 0.854
Kitazato (28) a t 25" is too high, as is the value of Regnault (SI), 45-55 0.857 0.854 0.856
while that of Kopp (23) is too low. 55-65 0.851 0:857 0.854 0,857
65-75 0.865 0,862 0.853 0,880
The specific heat of sodium carbonate decahydrate between 75-85 0.851 0.852 0.852
2.6" and 19.2' C. was determined by D'Ans and Tollert ( 7 ) t o be 85-95 ... o:s39 0.843 0.841
127.4 calories per gram mole.
The specific heat of sodium carbonate solutions is given by TABLE:
V. HEATCAPACITYOF SATURATED SODIUM
CARBONATE
I.C.T. ( 1 3 ) a t 20" from the data of Marignag between 21' to FROM 20" TO 32" C.
SOLUTJONS
52' (26) and of Thomsen at 18" (37). Swallow and Alty (36) Heat Capacity
Cal./e.
determined the specific heat of solutions a t various concentra- NazCOd. IOHzO
tions up t o 25% a t 17.6", 30.0°, 76.6', and 98.0" C. with an CSl./O c./g. dissolving
Temp. satd. during
estimated accuracy of 0.5%. For the specific heat curve at Run Range, O C. soln.. av. heating
30" the following equation was derived: 16 20-26 3.93 65.7
18 3.77 61.1
- 0,01123X + 0.000223X2
19 3.87 63.4
830 0.9986 20 3.79 62.3
Av. 3.84 63.4
where Sa0= specific heat at 30"
X = concentration of solutions in per cent sodium 3 26-32 9.72 83.4
4 9.72 64.5
carbonate Av. 9.72 64.0

As no data are available for a solution saturated with sodium

carbonate at all temperatures, such data have been determined
by the authors. The apparatus used was similar to that of Kobe
and Anderson (21) and consists of a 200-cc. wide-mouth Dewar
flask as the calorimeter. Through the rubber stopper in the
mouth of the flask pass a calibrated thermometer graduated in
tenths of a degree, a glass dril) stirring rod driven by a motor
stirrer, and the leads to the heating element. The heating
element consists of 1 meter of No. 28 constantan wire threaded
through a fine glass tube wound into a spiral about 2 inches long
and 1.25 inches wide. A molybdcnum lead wire about 4 inches
long is silver-soldered to each end of the constantan resistance wire
and the glass tubing sealed around the molybdenum lead wire.
The glass coil is then evacuated through a side tube and sealed
off; thus any corrosion or gathering of moisture within the coil is
prevented and a constant resistance is obtained. The ends of
the molybdenum lead wire pass through the stopper and are
connected in the electrical circuit. The Dewar flask is placed
within an iron container and surrounded with a 3-inch layer
of cotton to decrease radiation losses. The water equivalent of
the calorimeter is determined by passing I ampere through the
heating element and raising the temperature of 150 grams of
water from 25" to 95" C. At each 10' interval the current is
shut off and the rate of cooling determined. The room tempera-
ture is maintained constant.
A saturated solution of sodium carbonate is prepared a t 36',
and its density and concentrat,ion are determined. Approxi-
><
080
I saturated solution of sodium carbonate in contact with sodium
$ OB5
$ OB4
IA
2.
t 083
g
0
$ OB2
30 40 50 00 70 80 90 100
I
TEMPERATURE - 'C.
Figure 1. Heat Capacity of Saturated Sodium
Carbonate Solution
mately 150 ml. of solution are weighed into the calorimeter,
and 1 gram of sodium carbonate monohydrate is added. After
stirring for several minutes to bring the solution to equilibrium,
the current is turned on and the temperature brought back t o
approximately 36". The solution then is heated t o approxi-
mately 45", and the cooling rate determined. This procedure is
repeated a t 10" intervals up t o 95'. From the corrected tem-
perature rise and current input, the calories used are computed.
In the calculation of the specific heat of the solution a correction
must be made for the sodium Carbonate monohydrate that
precipitates out during the heating, decreasing both the sodium
carbonate and water in the solution. By a graphical integration
over 10" intervals the average weight of solution in the interval is
determined. The total heat input is corrected for the water
equivalent of the calorimeter and the heat content of the average
amount of suspended sodium carbonate monohydrate present
during each temperature interval. The net heat input thus
found divided by the corrected temperature rise gives the average
hcat capacity over that temperature interval.
The results are given in Table I V and shown in Figure 1.
A graphical integration of the curve of Figure 1 from the
transition temperature (33") to the boiling temperature (104.8')
gives 0.851 calorie per degree per gram of solution graphi-
cally averaged over this same temperature range. Extrapo-
lation of the data of Swallow and Alty (36) at 76.6" to a saturated
solution gives about 0.85 calorie per gram per " C., whereas Figure
I shows 0.855. The heat capacity of the saturated solution in-
cludes the heat of crystallization of the sodium carbonate mono-
hydrate from the solution.
The heat capacity of a saturated sodium carbonate solution
was determined over the range 20" to 32" C. by maintaining a
carbonate decahydrate as the temperature was raised. To a
solution saturatcd a t 19" are added sufficient decahydrate crys-
tals to saturate the solution at 28". The heat input necessary
to raise the temperature of this mixture is measured and corrected
for the graphically determined average weight of decahydrate
crystals undissolved over this range. The average weight of
solution is determined graphically and the heat capacity cal-
culated for this average weight of solution. A similar deter-
mination was made over the range 26" t o 32". The results
are shown in Table V.
The heat capacity of the saturated solution from 20" t o 32'
rises rapidly because of the rapidly increasing solubility over this
 102 I N D U S T R I A L A N D E N G I N E E R IN G C H E M I S.T R Y Vol. 40, No. 1

about 40" and then rises rapidly. By plotting temperature

TABLEVI. HEATOF TRANSITION
OF SODIUM CARBONATE against time the intersection of the two lines gives the end of the
DECAHYDRATETO MONOHYDRATEA T 32.96' C.
transition. Correction is made for the heat necessary to bring
Heat of Transition, the crystals from room temperature and the liquid to the melting
R u n No. Medium Cal./G. Mole
7 Nitrobenzene 20,900 temperature of 32.96", and the liquid, saturated solution, and
9 Nitrobenzene 21,700 monohydrate to the temperature a t the end of the experiment,
11 h-itrobenzene 22,100
12 h7trobenzene 21,400 The results are given in Table VI.
13 Carbon tetrachloride 21,400 The data on heats of fusion and heats of dissociation of sodium
14 Carbon tetrachloride 21,000
Av. 21,400 =k 300 carbonate have been discussed by Kelley (18, 19), who points
out the unreliability of the present data. Sodium carbona€e
melts a t 854" C., and 7000 calories per gram mole may be taken
as an approximate value of the heat of fusion (18). The heat of
range. A more useful value than the heat capacity of the aver- dissociation, calculated to 18" C., is given as 76,900 calories per
age weight of saturated solution is the heat capacity of the solu- gram mole but is a very uncertain value (19).
tion in terms of sodium carbonate decahydrate that must be
dissolved to maintain a saturated solution. This value remains SUMMARY
approximately constant a t 64.0 calories per gram Na2C03.10H20
dissolving during heating, or 18,100 calories per gram mole 1. Data in the literature for the solubility and thermochem-
Na2CO8.lOH2O dissolving. istry of sodium carbonate, its hydrates, and its concentrated
solutions have been reviewed and collated.
HEATS OF DECOMPOSITION 2. The heat capacity of a saturated sodium carbonate solu-
tion in contact with a solid phase has been determined over the
The heats of decomposition of the various hydrates and sodium range 20' to 95" C.
carbonate itself were determined from vapor pressure deter- 3. The heat of transition or melting of sodium carbonate
minations. The pressure of sodium carbonate monohydrate decahydrate to monohydrate has been determined as 21,400 *
was determined by Caven and Sand (6),who obtained the equa- 300 calories per gram mole.
tion
LITERATURE CITED
l o g P = 10.825 - 3000.0
-
T (1) Anderson, J . Am. Chem. SOC., 55. 3621-3 (1933).
(2) Bain, Zbid., 49, 2734-8 (1927),
where P = vapor pressure, mm. Hg (3) Baxter and Cooper, Zbid., 46, '923-33 (1924).
T = OK. (4) Bichowsky and Rossini, "Thermochemistry of Chemical Sub-
stances," pp. 114, 377, New York, Reinhold Pub. Corp., 1936.
From this the heat ofreaction for the equation (5) Caspari, J. Chem. SOC.,125, 2381-7 (1924).
(6) Caven and Sand, Zbid., 99, 1364 (1911).
Na2CO8.€I20(s)-+-Na2C03(s) + H,O(g) (7) D'Ans and Tollert, 2. Elektrochem., 43, 87-91 (1937).
(8) Epple, Dissertation, Heidelburg (1899).
gives 13,800 calories per gram mole as the heat of drying of (9) Ervin, Giorgi, - and McCarthy, J . Am. Chem. Soc., 66, 384-7
sodium carbonate monohydrate. (1944).
Hill and Bacon, Zbid., 49, 2487-95 (1927).
The vapor pressure of sodium carbonate decahydrate was International Critical Tables, 3, 372 (1928).
determined by Baxter and Cooper (5),who obtained the equation I b i d , 4, 237 (1928).
I b i d , 5, 124 (1929).
log P = 11.8071 + 3634.51
+ 46,45
Janecke, 2. physik. Chem., 90, 269 (1915).
Keene, private communication (July 29, 1946).
Keene and Julien, U. S. Patent 2,133,455 (Oct. 18, 1938).
From this the heat of reaction for the equation Keevil. J . Am. Chem. Soc., 64, 849-50 (1942).
Kel1ey:U. S. Bur. Mines, Bull. 371, 68 (1934).
NalCO3.1OH2O(s)--+ Xa2CO3.7HzO(s) + 3H,O(g) Kelley, Zbid., 393, 108 (1936).
Kelley and Anderson, Zbid., 384, 36 (1935).
gives 29,400 calories per gram mole as the heat of drying sodium Kobe and Anderson, J . P h y s . Chem., 40, 429-33 (1936).
carbonate decahydrate t o the heptahydrate. Combining the re- Kobe and Leipper, IND.ENG.CHEM, 3 2 , 198-203 (1940).
Kopp, Trans. Royal SOC.(London), 155,71 (1865).
sult for decahydrate to heptahydrate and monohydrate to Loevel, Ann. chim. phys., 33, 334-90 (1851).
anhydrous, and assuming that the heat required for the six Marignag, Ibid., [5] 8, 410 (1876).
middle molecules is an average of two end values, the heat iMatsui and Kambara, J . Soc. Chem. I n d . (Japan), 35, suppl.
of reaction for the equation binding 308-13 (1932).
Matsui, Kambara, and Yoshino, Zbid., 35, suppl. binding 313-6
h'a~C01.1OH~O(s)
-+- Na2COa(s) + 10HzO(g) (1932).
Matsui and Kitazato, Zbid., 40, suppl. binding, 246-8 (1937).
gives 114,000 caloriesyer gram mole as the heat of drying of Mondain-Monvall, Compt. rend., 174, 1014 (1922); 175, 162
(1922).
sodium Carbonate decahydrate to the anhydrous state. Perreu, Ibid.,189, 167-9, 285-7 (1929).
The heat of transition of sodium carbonate decahydrate to Regnault, Ann. chim. phys., [3] 1, 168 (1841).
monohydrate, or the heat of melting when the decahydrate Richards and Fiske, J . Am. Chem. SOC.,36, 486-90 (1914).
melts incongruently to form monohydrate and saturated solution Rode, Ann. inst. anal. phys-chim. (U.S.S.R.), 6, 97-134 (1933).
has been determined in this work. The equation is: Schroeder, Berk, and Gabriel, J . Am. Chem. Soc., 58, 843-9
(1936).
+
KaiCO3.1OH~O(s)-+ Na2C03.H20(s) 9H20 (satd. soln.) Seyer and Todd, Trans. R a y . Sac. Can.. [3] 23, 67-70 (1929).
Swallow and Alty, J . Chem. SOC.,1931, 3062-79.
The heat of transition or melting was determined by introducing Thomsen, A n n . Phvsik., 142, 337 (1871).
Waldeok, Lynn, and Hill, J . Am. Chem. SOC.,54, 928-36 (1932),
sodium carbonate decahydrate into the calorimeter containing 56, 43-7 (1934).
nitrobenzene (21) or carbon tetrachloride as a heat transfer me- Watson and Kowalke, IND. ENG.CHEM.,22, 370-6 (1930).
dium from the resistance spiral to the crystals of solid. The liquid Wells and McAdam, J . Am. Chem. SOC.,29, 721-7 (1907).
is heated to about 31.6", the decahydratc added, and heatnpplied. \T.'illiarnson, Trans. Faraday Soc., 40, 421-36 (1944).
The temperature rises s l o ~ l yuntil the melting is complete at R E C E I V ESeptember
D 30, 1946.