down t o a value of 2.0. However, a bed of such finely divided runs. The one exception t o this is the sharp drop between m u
118B
material would offer great resistance to flow of liquid; increasing and C, the first and second runs with the fine catalyst. This drop
the particle size would permit better flow rates but decrease the could be due either to the elution of a small amount of adsorbed
reaction rate. The Germans evidently encountered a similar strong acid or to the loss of a very finely divided fraction during
problem, since there are statements (I) that they found the best the a t r a t i o n of the catalyst from run B.
catalyst to be large porous particles prepared by sintering finely Data for the uncatalyzed run (A) are a t variance with Suss-
ground base-exchange resin, lightly coated with a thermosetting man's findings of no "indication of esterification" for the same
phenolic. system under similar conditions (6). The close conformity of the
The authors have no data to support any explanation of the rate found for this run with those for the catalyzed runs (Figure 4)
failure of the bimolecular equation t o hold over the first 4 hours of leads to the belief that tlie authors' results are correct,
the reaction. There appears to be some inhibiting process or
induction period involved when the base-exchange resin is pres- ACKNOWLEDGMENT
ent. This is borne out by the fact that the 4-hour acid values The samples of base-exchange reain were prepared by B. Coe
for the runs with coarse catalyst (F and G) are actually higher and G. Bodamer. The authors are indebted t o R. J. Myers, W.
than that for the run with no catalyst (A), although the 8- and 12- S. Niederhauser, and L..P. Hammett for advice and criticism.
hour values are lower. It was thought that this might be due to
adsorbed water on the surface of the catalyst. However, a check LITERATURE CITED
of several runs in which either added water or bone-dry catalyst (1) Diericks, FIAT Report PB866, O5ce of Technical Services,
was employed (Figure 3) did not bear this out. This matter is of Dept. of Commerce, Washington, 1947.
considerable practical importance for continuous column opera- (2) Leyer and Othmer, IND. ENQ.CBEM.,37,968(1945).
tion. If it is due to an integfal part of the reaction mechanism, (3) Myers, F. J., FIAT Report PB42,802,Office of Technical Serv-
ices, Dept. of Commerce, Washington, 1947.
the 2 hours' contact time mentioned above would need to be (4) Myers, Eastes, and Myers, IND. ENQ.CEEM.,38,697-706 (1941).
considerably increased to obtain a product with an acid number of (5) Sussman, Ibid., 38,1228 (1946).
2 or lower. (6) Sussman, private communication.
The phenol-formaldehyde-ulfonic acid resins are similar to (7) Thomas and Davies, Nature, 159,372(1947).
Zeo-Karb H (6) in maintaining catalytic activity over a series of RECBIVED February 11, 1947.
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- Caspari (4, Hill and Bacon (IO), and Kobe and Leipper (92)
bonate, its hydrates, and its concentrated solutions have investigated ranges from the cryohydric t o the boiling point.
been reviewed and collated. New data are: Specijic heat Seyer and Todd (36)investigated the range 17' t o 173' C., and
of saturated solution 20-32' C. is 64.0 calories per gram Ervin, Giorgi, and McCarthy (9) made determinations a t
NaCz03.10H20dissolving during heating; mean specitic 100' to 150' C. The high temperature range was investigated
heat from 33' to boiling point is 0.851 calorie per ' per c. from 50' t o 348' by Waldeck, Lynn, and Hill (B), and from 150'
gram of solution? heat of melting for Na2C02.10H~0 is t o 350' by Schroeder, Beck, and Gabriel (34). These newer
21,400 calories per gram mole. 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,
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-
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
ical properties of such an industrial compound are of the utmost 50' the data of the more recent workers (6,10,@) correspond to
importance. It is the purpose of this paper to review and collate those of the earlier workers (8, 84, 90); the data of Wells and
the thermochemical properties of sodium carbonate, its hydrates McAdam (40) from 28' t o 44" are highly accurate. Above 50"
and its concentrated solutions. New data are given on the the data of Caspari (6) are definitely high, whereas those of
specific heat of the saturated solution and heat of transition. 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
SOLUBILITY
about 1.5% lower. These latter workers used glass below 100'
The solubility data, solid phases, transition temperatures, and and a steel bomb up t o 348", and report their solubility values
vapor pressures of saturated solutions are of fundamental im- accurate t o 0.1% from 50' t o 150', 0.2% from 150" t o 250°,
portance. The solubility data given in the International and 0.3% above 250" C. Schroeder, Beck, and Gabriel (34)
Critical Tables (II) were derived mainly from three sources checked the data of Waldeck, Lynn, and Hill a t four tempera-
(8, 84, 40). During the elapsed time several investigators have tures from 150' t o 350' and obtained satisfactory agreement
given new data from the cryohydric t o the critical temperature. except at 350°, at whieh temperature the latter workers reported
1 Present address, University of Texas, Austin, Tex. a zero solubility which is refuted by the former. Waldeck,
9 Present address, Standard Oil Company (California). EL Segund6 Calif. 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