Kinetics and mechanisms of the base decomposition of nitrogen trichloride in aqueous solution

Journal Article · Wed Oct 21 04:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00268a005· OSTI ID:7247217

Kumar, K; Shinness, R W; Margerum, D W

The rate expression for the base decomposition of nitrogen trichloride is -d(NCl/sub 3/)dt = 2(k/sub 0/ + k/sub 1/(OH/sup -/) + k/sub HB/(HB)(OH/sup -/) + k/sub 2/(OH/sup -/)/sup 2/)(NCl/sub 3/), based on the stoichiometry 2NCl/sub 3/ + 6OH/sup -/ ..-->.. N/sub 2/ + 3OCl/sup -/ + 3Cl/sup -/ + 3H/sub 2/O. Values of the rate constants (25.0/sup 0/C, ..mu.. = 0.5) are 1.6 x 10/sup -6/ s/sup -1/ for k/sub 0/, 8 M/sup -1/ s/sup -1/ for k/sub 1/, and 890 M/sup -2/ for k/sub 2/. The specific-basegeneral-acid-catalyzed path gives k/sub HB/ values (M/sup -2/ s/sup -1/) of 2.1 x 10/sup 3/ for H/sub 2/PO/sub 4//sup -/, 7.6 x 10/sup 2/ for B(OH)/sub 3/, 65 for HCO/sub 3//sup -/, and 128 for HPO/sub 4//sup 2 -/. In the proposed mechanism Cl/sub 2/NClOH/sup -/ is a common reactive intermediate that can react with acids (H/sub 3/O/sup +/, HB and H/sub 2/O with a Broensted ..cap alpha.. value of 0.48) to form HNCl/sub 2/ and HOCl or it can react with an additional OH/sup -/ to release OCl/sup -/. The HNCl/sub 2/ so formed reacts rapidly with a second NCl/sub 3/ to give products. Kinetics data allow an equilibrium constant of 1.6 x 10/sup 8/ M/sup -1/ (25.0/sup 0/C, ..mu.. = 0.5) to be calculated for the reaction NHCl/sub 2/ + HOCl reversible NCl/sub 3/ + H/sub 2/O.

• Research Organization: Purdue Univ., West Lafayette, IN (USA)
• OSTI ID: 7247217
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:21; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
520100 -- Environment
Aquatic-- Basic Studies-- (-1989)
54 ENVIRONMENTAL SCIENCES
ABSORPTION SPECTROSCOPY
AQUEOUS SOLUTIONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORIDES
CHLORINATION
CHLORINE COMPOUNDS
DATA
DECOMPOSITION
DISPERSIONS
EQUILIBRIUM
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HALOGENATION
INFORMATION
KINETICS
MIXTURES
NITROGEN CHLORIDES
NITROGEN COMPOUNDS
NUMERICAL DATA
QUANTITY RATIO
REACTION INTERMEDIATES
REACTION KINETICS
SOLUTIONS
SPECTROSCOPY