COMMUNICATIONS TO THE EDITOR
2112
ON THE MORRIS MECHAKISM O F HYDROLYSIS OF CHLORINE
TARLEI HEATOF DISSOCIATION OF B P
T,"E(. PP,mm.
1473 6.3 9.52
AF/T, cal. mole-' deg.-l -A( F -- H 2 y ~ . I ~ )cal. /T, mole-' deg.-l 40.3 AHzgs,le/T, pal. mole-' deg.-l 49.8 AHII)RJG,kral. mole-' 73.4 Average AHPI~.IB = 73.2 ircnl. mole-'
1523 12.6 8.15
1573 24.2 6 85
39.9 48.0 73.1
39 6 46 4 73 0
heat of phosphorus in a phosphide to be 6 cal. per degree3 and the contribution of phosphorus to the entropy of a phosphide to be 5 cal. deg.-l per gram atom. The value.: of the free energy function for P&) were taken from the tabulation of Stull and Sinke.2 The results of the calculation are presented in Table I. I n view of the findings of h l a t k w ~ i c h the , ~ dissociation reaction is presumed to be
+
(26/11) BP(s) = (2/11) RIIP~(s) Pz(g) STATEUNIVERSITY OF XEWYORE COLLEGE OF CERAMICS AT ALFREDUNIVERSITY ALFRED,N. Y.
Vol. 65
Sir : In a recent paper Lifshitz and Perlmutter-Hayman1 discuss the mechanism of the hydrolysis of chlorine and demonstrate the inadequacy of Morris's scheme2 suggesting hydroxyl ion is the active agent of chlorine hydrolysis even in acid solutions. This demonstration is entirely correct, but we wish to mention that we criticized Morris's reaction scheme already in 1947,3 since it does not fit the kinetic results obtained by us in 1945. Apparently our paper of 1947 was overlooked by Lifshitz and Perlmutter-Hayman. The value of k of the rate of the hydrolysis of chlorine given in the article of Lifshitz and Perlmutter-Hayman is 5.60 see.-' at 9.3". R7e determined k = 1.75 sec.-l a t 0" and 8.97 at 17.6O.' The Arrhenius plot gives the value 1; = 4.3 at 9.5". The comparison of the two results, not made by Lifshitz and Perlmutter-Hayman, means good agreement of the old and new data on the rate of chlorine hydrolysis.
EUGENE SHILOV ACADEMY OF SCIENCIES OF THE UKRAINIAN SSR S. SOLODUSHEKKOV KIEV30, U.S.S.R. CLIFFORD E. MYEES RECEIVED AUGUST 21, 1961
RECEIVED SEPTEMBER 23, 1961 (3) 0.Kubaschewski and J. A. Caterall. "Thermochemical Data of Alloys," F'ergamon Preas, New York, N. Y.,1956, p. 135. (4) V. I. Matkovich, Acta Cryat., 14,93 (1961).
IXSTITUTE OF ORGANIC CHEMISTRY
(1) A. Lifshitz and B. Perlmutter-Hayman, J . Phys. Chem., 64,1663 (1960). (2) J. C. Morris, J . A m . Chem. Soc., 68, 1692 (1946). (3) E. A. Shilov and S. Solodushenkov, J . Phys. Chem. (Russ.). 21, 1159 (1947); Chem. Abstr., 42, 2945 (1948). (4) E . Shilov and S. Solodushenkov, Acta Physicochimico U.R.S.S. 20, 667 (1945).
