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Carbon Dioxide Solubility in Water: Conclusions
Carbon Dioxide Solubility in Water: Conclusions
A11 available data on the solubility of carbon dioxide in ships carrying the names of the originatom such a s Bunsen,
water have been assembled and converted to a uniform Henry, Kuenen, Ostwald, Raoult, and others. Though the
basis. A chart has been prepared which smoothes the data a r e sufficiently identified by the investigator to permit
normal experimental deviations and thus permits a more accurate interpretation, it i s awkward to determine the
accurate determination of solubility and changes in solu- difference between solubilities under any two conditions. In
bility of carbon dioxide in water a s a function of tempera- order to make information on the solubility ot carbon
ture and pressure. dioxide in water more uniform, all the available data have
Solubilities a r e properties that a r e used constantly and been assembled and correlated on a single basis.
therefore solubility data should be available in forms that
a r e both convenient and uniform. Experimental results of HISTORY
any one investigator will not necessarily satisify the needs
of all users, and different investigators will not agree The solubility of carbon dioxide in water has been
exactly in their results. Often data will be reported in determined by many i n v e s t i g a t o r s (1-8, 11-19, 21,
different units o r on different bases -e. g., the solubility of 24-35) and much of their data has been assembled by
gases has been variously defined in coefficients o r relation- others (3,9, 10, 20, 22, 23). The earliest work apparently
Ib 0.33qI) 0.280(1) 0.234(1) 0 218c 0.200(1) ---- 0,172(1] 0.149(1) 0.131d .... 0 105(1) 0.087(1) 0.072(1) _--- ---- ----
0.336C .... 0.213(32) 0.201(21) ---- 0 157e(25) 0 148(18) ---- .... _._- ._._ . . . . . . . . . . . . . . . .
0.353(32) - - _ - 0.2148 ..
0.19M81 ---- 0.15Zf 0,1491161 --.. ._.. .... .... ................
._._ ._._ .... _--- ..-. _._. ..-- _.__-.~. ........
0 353(8)
.... .... .... ....
-.-.
....
0.148(11)
0.149(25) ---- .._. .... ____ _.__..-. ........
5 1.698(32) 1.011(32) 0.901(8) .... .... .... .... _.__ ._._ _.__ __.__._.
1710(8) i.oiid .._. _.._ .___ .... .... .... .-.. .... __. - - -..
10 3.147(32) 1.894(32) 1.647(8) .... ._.. .... ..__ .... .___.... -.- - .-..
3 119(8) 1894% _._. .... .... .... ._.. .... .... .... ........
15 4.283(8) 2.672% 2.326(8) _.._ .... .... .-.- ._._ .... .... ........
20 5.231(32) 3.359(32) ....
2.986(8) .... ..-. ..-- _._. .-.- ._._ ._._ _._. - - -.
- ._
.
5.208(8) 3.3598 ._._ __._ .___ .... ._.. .-.- ._._ .___ .... .._. ........
25 5.997(32) 3.987(32) 3 463(8) 3.830 3.151h .... 2,784 2.542 2.281 1,906 ___. 1.339 1.054(29) 0.982
5 979(8) 3.9938__.. _._. __._.... _.._ .... _.._ .--. .... .... ........
5 989(35) __.. __._ ..__ __._.__. .._. .... .... .... .-.. .... ........
30 6.623(32) 4.564(32) 3 987(8) .-.. 3.516h 1.994h .... .... .... ._._ ........
6.605( 8) 4.564% ._._ .._. .... 2.229h .._. ..-. .... .... .- .- .-..
35 7.210(32) .... 4.421(8) .... _.__ ._.. .__. .... .... .... ._._ . ~ - .
38 7.434(32) .... __.. .-.. 3 826h 3.38ah _._. ..-. 1.724 ._.. .._ . -
.-.
.... .... .... .... .... 2.511h .... .... 1552 .... ........
40 ....
....
.___4.798(8)
__._
._._
.~-.
....
..-.
____
....
__..
.-~.
....
....
....
....
.... ........
-..-
..__ .._. _._.. ........
....
45 5.023(8)
50 .... 6.977l 5.312(8) 6.287 4 981h 5.345(28.30) 4.741 4 360 3.995 3 386 1.939 2.471 1.998(29) 1.8b5
.... .__. ..___-..- .... _._. .... 3.21Zh _.__ .... 2.173 ._.. -..- - -..
.... .___.-.. ._._ .... .... .._. 4.175h .._. .... .... .... ........
125 .... .... .... _._. ._.. .... .... .... 5.636 5 255 5.070 ..-. 3 946(10) 3.946
150 .... 7.5361 ..-- 7.018 _._.
.___ 6.201 5 991 5.769 5.426 .-.. 4.825 1.462[29) 1.338
ZW .... 7.807' -..- 7.296 .... .__. 6 435 6 248 6.034 5 720 .... 5 233 5 043(,29) 5.261
3w .... 8.062l _._. 7,717 ..__ .... .... .... .... 6 152 ..-. 5.793 5.797(24) 5.889
400 .._. __._ .... .... .... 7.581(28,30) 7.220 7.014 6 845 6.535 __.. 6.258 6.358(29) 6 439
5w .... .__. --.. .... .... 7.801(28.30) 7.591 7 457 7.210 .... .... .._. 6.753(19) 6.894
Mx) ..__ __._ -.-. .... .... .... _.._ .... _.__ 7 210 .... .... 7.145(19) 7.361
7w .... .._. .... .._. ..__ ..-- .... .-.. 7.526 .... 7.379 7.557(29) 7.832
a critical temperature of C O ~ .
Pressure of I arm. is CO2 pressure only. Total pressure is %wen a i all other values
Dara at O0 c. and 12.4' c. are actually a t 0.05O C. and 12.5" c. (9).
Data at 31.040 C. are acrually a: 300 C. (I).
;- t = UOC.
I 24O C.
E Data at 12.4' c. are a c r u a ~ i yac 12.43O C. (31).
Exact preasure ar rhe nommal pressures of 25, 30, 38. 50. 52, 75, lw and 125 arm
are respectively 24.2. 29.0, 38.7. 48.4, 53.2. 77.4, 96.8, and I16 atm (21).
' Data a t 12 40 c arc actually ai iz.00 c ,28,30).
Press., Press.,
mm. Hg C02 Solubility mm. Hg C02 Solubility
4
6 5
J i .
-I
0
II
;3.
0 4
n
-I
I
I
ZI
-c-
.-
n
=0 3
v)
0
"
0
0
0 IO 20 30 40 50 60 70 80 90 100 110 120
Temperature- 'C.
was done about 1882 by Wroblewski (31, 32) and about with the original literarure sources cited, are shown in
1899 by Bohr (1). Considerable additional work has been Tables I and 11. Table I shows values a t one atmosphere
done since 1930. Only Wiebe andhis coworkers(28, 29, 30), pressure and above, while Table I1 applies principally to
Prutton and Savage (19), and Sander (21) collected data at pressures below one atmosphere.
pressures above 100 atmospheres. Buch ( 2 ) and Morgan The data of Table I were plotted, and smoothed curves
and Maass (17) determined solubilities at pressures below representing the best interpretation of these data a r e shown
one atmosphere. in Figure 1. Because of the deviationof the various values,
any single curve plotted from the available data would
result in confusion as to where the curve should be. Using
DISCUSSION data directly from such a curve would result in wide
differences in values obtained, depending on whether
All the available data were assembled and in order to interpolation was used o r whether the data were plotted,
minimize confusion about the basis for reporting, they and if so, where the resulting curve was drawn. However,
were converted to weight units. The units used a r e pounds when several curves a r e drawn and when cross plots a r e
of carbon dioxide that would dissolve in 100 pounds of used, the deviations can be minimized, and a family of
water. This is, of course, equivalent to g r a m s of carbon curves can be obtained that will provide more consistent
dioxide soluble in 100 grams of water. The resulting values, information. Figure 1 is such a family of curves.
M e a s u r e m e n t s were made of the solubility relationships by prolonged shaking of solid phases withwater, employing
of various combinations of sodium pentaborate and dibor- those solid phases stable in equilibrium with the final
ate, ammonium pentaborate, tetraborate and diborate, and solution. This has the advantage of ensuring that super-
potassium pentaborate and diborate, in water at 20°, 30°, saturation cannot take place (provided the temperature is
and 40° C. not at any stage allowed to r i s e above the final tempera-
It was demonstrated that the solubility peaks in these ture), and it also enables equilibrium to be established
mixed systems a r e controlled by pH. The narrow composi- relatively quickly. Any desired point on the solubility curve
tion limits governing the solubility peak in the sodium can be obtained by restricting the amount of one o r more
oxide-boric system can be greatly widened by the addition constituents, and thus the steep portions of the curve,
of ammonium ion. where solubility relationships a r e changing rapidly with
Boric acid and sodium borates have been usedas timber minor changes in composition, can be explored fully.
preservatives since 1939 ( 2 ) . Recent developments of the ‘A constant-temperature room was used, controlled to
impregnation process (4) have required the fdrmulation of f0.2’ C. While such a room is notas accurate a s a water
aqueous solutions of maximum boric oxide solubility in the bath, it has considerable ,advantages when samples a r e
pH range 6 to 8. The present work takes the obvious ap- withdrawn for filtration, o r measurement of pH anddensity.
proach of using mixtures of various alkali borates. Eco-
nomic considerations limit interest in such systems to EX P ER IMENTAL
sodium oxide, potassium oxide, ammonium oxide, boric
oxide, and water, and solubility relationships have now In each solubility determination, 20 ml. of water was
been established for the most concentrated boric oxide shaken with weighed amounts of the various desired solid
solutions in this restricted pH range. phases stable in equilibrium with the final solution. Shaking
The system sodium oxide- boric oxide-water has been was continued for approximately4 days. The solutions were
investigated at 30° C. by Dukelski (3), at 00 C. by Rosen- allowed to settle and then filtered rapidly through Whatman
heim and Leyser (7), and over the range Oo to 90° C. by No. 41 paper. If the solutions were not quickly filtered and
Sborgi (8). In addition, the solubilities of boricacid and the covered, the low humidity of the room caused evaporation
various sodium borates in water have been measured by and cooling. With the technique described, no lowering of
Blasdale and Slansky (1). In Dukelski’s paper the system temperature was observed. Immediately after filtration the
potassium oxide-boric oxide-water at 30’ C . is also de- room temperature was raised about 1’ C. to avoid any
scribed, and Sborgi and F e r r i (9) have investigated the possible crystallization. A 10-ml. sample was withdrawn
system ammonium oxide-boric oxide-water from Oo to 90° in a calibrated pipet and weighed in a dry 100-ml. flask,
C. Apart from a few values for the solubility of sodium which was afterwards made up to volume, thus combining
diborate with ammonium diborate given by Sborgi and density measurement with subsequent dilution of a sample
Gallichi (lo), no references have been found to work done for analysis. The pH of the concentrated solution was
on the mixed systems. measured on a glass electrode system at the working tem-
In the present work, solubility measurements were made perature.