Studies of the generation and reactions of gaseous HOCl

Thesis/Dissertation · Tue Jan 01 04:00:00 EST 1985

OSTI ID:5599238

Ennis, C A

A new laboratory source of gaseous hypochlorous acid (HOCl) has been developed and applied to studies of several reactions which have potential importance in the chemistry of the stratosphere. The new source is dynamic, whereby HOCl is formed by reaction of Cl/sub 2/ with aqueous CaCO/sub 3/ and used before it equilibrates to form Cl/sub 2/O and H/sub 2/O. Compared to the conventional static preparation of HOCl by Cl/sub 2/O-H/sub 2/O-HOCl equilibration, the dynamic HOCl source has a substantially lower Cl/sub 2/O impurity level and is useful for studies which are otherwise complicated by large interference from Cl/sub 2/O. In two kinetic studies, the room temperature bimolecular rate constants of the reactions of OH + HOCl and H + HOCl were found to be (2.4 +/- 1.2) x 10/sup -13/ and (5.0 +/- 1.4) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/, respectively. The product distribution in the reaction of Cl + HOCl has been determined in a third investigation; the major reaction channel gives the products Cl/sub 2/ and OH, with a yield of 91% +/- 6% at 298 K. In a fourth investigation, the equilibrium constant (K/sub eq/) of the reaction Cl/sub 2/O + H/sub 2/O = 2 HOCl was determined to be 0.092 +/- 0.011 at 298 K. The results imply that the reactions of OH, H, and Cl with HOCL are not competitive with direct photolysis in the removal of HOCl from the stratosphere.

• Research Organization: Colorado Univ., Boulder (USA)
• OSTI ID: 5599238
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALINE EARTH METAL COMPOUNDS
ATMOSPHERIC CHEMISTRY
CALCIUM CARBONATES
CALCIUM COMPOUNDS
CARBON COMPOUNDS
CARBONATES
CHEMICAL REACTION KINETICS
CHEMISTRY
CHLORINE
EARTH ATMOSPHERE
ELEMENTS
HALOGENS
HYDROGEN COMPOUNDS
HYPOCHLOROUS ACID
INORGANIC ACIDS
KINETICS
NONMETALS
OXYGEN COMPOUNDS
REACTION KINETICS
STRATOSPHERE
SYNTHESIS