Reactions of PO(x)Cl(y)- Ions with H and H(2) from 298 to 500 K
Abstract
Rate constants and product branching ratios for PO(x)Cl(y)- ions reacting with H and H(2) were measured in a selected ion flow tube from 298 to 500 K. PO(2)Cl-, PO(2)Cl(2)- , POCl(2)-, and POCl(3)- were all unreactive with H(2), having a rate constant with an upper limit of <5 x 10(exp -12) cu cm s(exp -1). PO(2)Cl(2) did not react with H atoms either, having a similar rate constant limit of <5 x 10(exp -12) cu cm s(exp -1). The rate constants for PO(2)Cl-, POCl(2)-, and POCl(3)- reacting with H showed no temperature dependence over the limited range of 298-500 K and were approximately 10-20% of the collision rate constant. Cl abstraction by H to form HCl was the predominant product channel for PO(2)Cl-, POCl(2)- and POCl(3)-, with a small amount of Cl- observed from POCl(2)- + H. Reactions of O(2) and O(3) with the POCl- product ions from the reaction of POCl(2)- + H were observed to yield predominantly PO(3)- and PO(2)-, respectively. POCl- reacted with O(2) and O(3) with rate constants of 8.9 + or - 1.1 x 10(exp -11) and 5.2 + or - 3.3 x 10(exp -10) cu cm s(exp -1), respectively. No associative electron detachment was observed with a PO- secondary product at high H atom concentrations. Results of new G3 theoretical calculations of optimized geometries and energies for the products observed are discussed.
Document Details
- Document Type
- Technical Report
- Publication Date
- Feb 24, 2005
- Accession Number
- ADA442824
Entities
People
- Albert A Viggiano
- Anthony J. Midey
- Robert A. Morris
- Thomas M Miller
Organizations
- Air Force Research Laboratory