𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Base-catalyzed tritium exchange between tritium-containing heavy water and deuterated chloroform–kinetics and equilibrium

✍ Scribed by Jon L. Maienschein; Patrick E. Barry


Publisher
John Wiley and Sons
Year
1986
Tongue
English
Weight
829 KB
Volume
18
Category
Article
ISSN
0538-8066

No coin nor oath required. For personal study only.

✦ Synopsis


We develop a kinetic model for the exchange of tritium and deuterium between tritium-containing heavy water and deuterated chloroform in a two-phase liquid system, catalyzed by hydroxide ion (sodium hydroxide). For the exchange reaction yielding tritiated chloroform and heavy water, the measured equilibrium constant is 0.518 a t 25-45"C, independent of temperature. The rate constant (for the controlling step, deuteron abstraction from chloroform) is 0.22 L/mol s a t 25"C, 0.72 a t 3 5 T , and 2.0 a t 4 5 T , corresponding to an activation energy of 87 kJ/mol. Comparison is made with literature data, and effects of mass transfer on the apparent rate constant are discussed.