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Solubility and hydrolysis of HCFC‐22 (CHF 2 Cl): Upward revision of rate constants for aqueous reactions of CHF 2 Cl with OH − at elevated temperature
Author(s) -
Kutsuna Shuzo,
Hori Hisao,
Naganuma Makoto,
Shimono Akio
Publication year - 2011
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20596
Subject(s) - chemistry , aqueous solution , reaction rate constant , thermodynamics , diffusion , solubility , difluoromethane , analytical chemistry (journal) , hydrolysis , refrigerant , kinetics , organic chemistry , physics , quantum mechanics , gas compressor
Henry's law constants of CHF 2 Cl in water at temperature T in K, K H ( T ) in M atm −1 , were determined to be ln( K H (T))=−(11.1±1.5)+((2290±500)/T) at 313–363 K by means of a phase ratio variation headspace method. The temperature‐dependent rate constants for aqueous reactions of CHF 2 Cl with OH − , k OH −( T ) in M −1 s −1 , were also determined to be 3.7×10 13 exp(−(11, 200/ T )) at 313–353 K, by considering the gas–water equilibrium, the aqueous reaction at room temperature, and liquid‐phase diffusion control. The liquid‐phase diffusion control was approximated with a one‐dimensional diffusion first‐order irreversible chemical reaction model. The k OH −( T ) value we determined is 10 times (at 353 K) or 3 times (at 313 K) as large as the value reported (R. C. Downing, Fluorocarbon Refrigerants Handbook , Prentice Hall: Englewood Cliffs, NJ, 1988). This upward revision of k OH −( T ) indicates that the removal efficiency of CHF 2 Cl directly through the hydrolysis (CHF 2 Cl + OH − ) is higher than previously expected at temperatures, such as 353 K, relevant to wet flue gas cleaning systems for ozone‐destruction substance‐destruction facilities. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 639–647, 2011