Vol. 60
374
NOTES THE SOLUBILITY OF CHLORINE I N TITANIUM TETRACHLORIDE AND OF CARBON DIOXIDE AND OXYGEN I N CHLORINE' BY WALTERF. KRIEVE
AND
DAVID M. MASON^
Jet Propulaion Laboratory California Institute of Technology, Paabdena, CaZif. Received June 67, I966
The solubility of chlorine in liquid titanium tetrachloride was determined at 20 and 30" for mixtures containing from 0 to 100 mole % chlorine. These data were required in a calorimetric determination of the heat of formation of titanium tetrachloride to correct for the heat of solution of chlorine in titanium tetrachloride. The solubility of carbon dioxide in chlorine at 0 and 25" was measured up to about 6.6 mole %
and which was submerged in a constant temperature bath maintained to within 0.1"of a given temperature. The weight of gas admitted to the second bomb was determined by measuring the change in pressure in the first bomb. After equilibrium was established, the pressure in the second bomb was measured and the solubility calculated from the pressure data. All pressure measurements were made to within 0.5%. Gas densities were obtained from existing volumetric data for chlorine,* carbon dioxide4and oxygen.6 The partial pressure of liquid carbon tetrachloride6 was negligible compared with the partial pressure of chlorine.' Corrections were made for the partial pressure of chlorine in the determination of the solubility of carbon dioxide and oxygen by assuming Raoult's law was followed by the chlorine. In Table I are shown results of the measurements
TABLE I EXPERWNTAL VALUESOF THE SOLUBILITY OF CHLORINE IN TITANIUM TETRACHLORIDE AND OF CARBON DIOXIDE AND OXYaEN IN CHLORINE Chlorine (A) in titanium tetrachloride Carbon dioxide (A) in chlorine 200 300 .. 00 25' Partial Partial Partial Partial Mole % pressure A Mole % pressure A Mole % pressure A pressure A Mole % A (atrn.) ~A (atm.) A (atrn.) A (atrn.)
25.13 35.85
43.58 49.64 56.74 64.99 72.29
1.50 2.20 2.71 3.13 3.67 4.24 4.76
42.27 48.44 55.71 64.12 71.07
3.39 3.93 4.63 5.41 6.14
1.06 1.593 2.135 2.983 3.945 4.950 5.640 6.582
carbon dioxide and the solubility of oxygen in chlorine a t 25" up to 1.7 mole % oxygen. The chief impurities in commercially-pure chlorine were found to be carbon dioxide and air, and it thus was of interest to determine the solubility of carbon dioxide and oxygen which would cause errors in the calorimetric determination of the heat of formation of titanium tetrachloride. Such solubility data aided in the purification of liquid chlorine. For the solubility measurements commercial chlorine was purified by fractional distillation to remove air and COz. Titanium tetrachloride of 99.999% purity provided by the National Bureau of Standards and pure samples of carbon dioxide and oxygen manufactured by Matheson Co., Inc., were also used. Stainless steel PVT bombs of 175-cc. capacity and calibrated stainless steel Bourdon gages were employed in the solubility measurements. A known weight of gas was admitted by a system of valves from one PVT bomb to another bomb, which contained a known amount of liquid (1) This paper presents the resulta of one phase of research carried out a t the Jet Propulsion Laboratory, California Institute of Technology, sponsored by the Department of Army, Ordnance Corps, and the Department of Navy, Office of Naval Research, under Contract No. DA-04-495-0rd 18. (2) Department of Chemistry and Chemical Engineering. Stanford University, Stanford, California.
0.772 1.10 I .67 2.29 2.90 3.59 4.10 4.78
0.976 1.42 2.04 2.98 3.80 4.74 5.46 6.43
1.10 1.50 2.21 3.03 3.85 4.80 5.55 6.54
Oxygen (A) in chlorine 25'
Mole % A
Partial pressure A (atrn.)
0.785 0.936 1.31 1.49 1.65
5.22 6.67 9.13 10.53 11.99
of solubility of chlorine in titanium tetrachloride. The data show a slight departure from Raoult's law. Also shown are solubility data for carbon dioxide and oxygen in liquid chlorine, respectively. (3) R. E. Hulme and A. B. Tillman, Chem. Eng., 56 (No. 11, 99 (1949). (4) R. L. Sweigert, P . Weber and R. L. Allen, Ind. Eng. Chem., 38, 185 (1946). (5) R. Millar and J. D. Sullivan, U. S. Bur. Mines Tech. Paper 424 (1928). (6) H. Schafer and F. Zeppernich, 2. anorg. allyem. chem., 272, 274 (1953). (7) M. Pellaton, J . chim. phys., 13, 426 (1915).
W.
EXCHANGE BETWEEN ADSORBED ANT) DISSOLVED SULFATE IONS BY CECILV. KINGAND BORIS LEVY' Chemistry Department, New York University, New York 5, New York Received September 6 , 1966
During the course of a study on the adsorption and exchange of silver salts on silver2 it was found that if a silver coupon were immersed in a radioactive solution of Na2S*04, removed from the solution, and then washed with water, a measurable (1) Chemical & Physical Laboratory, RCA. Lancaster, Penna. (2) C. V. King and B. Levy, THISJOURNAL, 69, 910 (1955).
