Kinetics and product vibrational energy disposal dynamics in the reaction of chlorine atoms with D sub 2 S

• Published in: Journal of physical chemistry (1952) Vol. 94:4
• Main Authors: Hossenlopp, J.M., Hershberger, J.F., Flynn, G.W.
• Format: Journal Article
• Language: English
• Published: United States 22-02-1990
• Subjects: 540110; ABSORPTION SPECTROSCOPY; ATMOSPHERIC CHEMISTRY; CALCULATION METHODS; CHALCOGENIDES; CHEMISTRY; CHLORINE; DATA; DATA ANALYSIS; DEUTERIUM COMPOUNDS; ELEMENTS; ENERGY LEVELS; ENVIRONMENTAL SCIENCES; EXCITED STATES; EXPERIMENTAL DATA; HALOGENS; HYDROGEN COMPOUNDS; HYDROGEN SULFIDES; INFORMATION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; KINETICS; MEASURING INSTRUMENTS; MEASURING METHODS; NONMETALS; NUMERICAL DATA; SPECTROSCOPY; SULFIDES; SULFUR COMPOUNDS 400200 > Inorganic, Organic, & Physical Chemistry; VIBRATIONAL STATES
• ISSN: 0022-3654; 1541-5740
• DOI: 10.1021/j100367a029

The reaction of chlorine atoms with D{sub 2}S, forming DCl and DS, has been investigated by using time-resolved infrared diode laser absorption spectroscopic probing of both the D{sup 35}Cl and D{sup 37}Cl product. The rate constant obtained by using the pseudo-first-order method was found to be 3.2 ({plus minus} 0.3) {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The vibrational energy distribution in the DCl fragment was also determined with 33 ({plus minus} 7)% of the product DCl formed in {nu} = 0, 56 ({plus minus} 7)% in {nu} = 1 and 11 ({plus minus} 3)% in {nu} = 2. These results are consistent with the known vibrational population inversion between the {nu} = O and {nu} = 1 states of DCl previously observed for this reaction. The advantage of using infrared absorption measurements, rather than infrared emission, to determine vibrational distributions is that the {nu} = O population can be directly measured. The relative vibrational populations were modeled by using two different prior functions, both of which led to linear surprisal plots.