14989-32-3Relevant academic research and scientific papers
A selected ion flow tube study of the reactions of gas-phase cations with PSCl3
Critchley, Andrew D.J.,Howle, Chris R.,Mayhew, Chris A.,Tuckett, Richard P.
, p. 235 - 241 (2008/10/09)
A selected ion flow tube was used to investigate the positive ion chemistry of thiophosphoryl chloride, PSCl3. Rate coefficients and ion product branching ratios have been determined at room temperature for reactions with 19 cations; H3O+, CF3+, CF +, NO+, NO2+, SF2 +, SF+, CF2+, O2 +, H2O+, N2O+, O +, CO2+, CO+, N+, N 2+, Ar+, F+ and Ne+ (in order of increasing recombination energy). Complementary data described in the previous paper have been obtained for this molecule via the observation of threshold photoelectron photoion coincidences. For ions whose recombination energies are in the range 10-22 eV, comparisons are made between the product ion branching rations of PSCl3 from photoionisation and from ion-molecule reactions. In most instances, the data from the two experiments are well correlated, suggesting that long-range charge transfer is the dominant mechanism for these ion-molecule reactions; the agreement is particularly good for the atomic ions Ar+, F+ and Ne+. Some reactions (e.g. O2++PSCl3), however, exhibit significant differences; short-range charge transfer must then be occurring following the formation of an ion-molecule complex. For ions whose recombination energies are less than 10 eV (i.e. H3O+, CF 3+, CF+ and NO+), reactions can only occur via a chemical process in which bonds are broken and formed, because the recombination energy of the cation is less than the ionisation energy of PSCl3.
Laser-initiated chemical chain reactions
Nesbitt, David J.,Leone, Stephen R.
, p. 1722 - 1732 (2007/10/02)
A detailed kinetic and experimental analysis is presented for chemical chain reaction processes initiated by well-controlled, low power laser pulses.Realtime evolution of the chain reaction is followed by direct detection of infrared chemiluminescence from vibrationally excited HCl product molecules produced by one of the propagation reactions in the chain.By appropriate choice of conditions, the chain reactions may be analyzed separately for pseudofirst-order, radical-reagent processes as well as for second-order, radical-radical events.The pulsed laser initiation technique is applied to three sample chain systems which exhibit distinctly different chain lengths, rates, and termination behaviors.These systems are Cl2/H2S, Cl2/H2, and Cl2/CH3SH.In the case of Cl2/H2S, detailed rate constant data are obtained for the fundamental chain propagation steps, and appropriate chain termination steps are assigned from the observations.The results demonstrate a new, general technique for the quantitative study of chemical chain reactions and related combustion processes.
SPECTROSCOPIC AND KINETIC STUDIES OF THE SO RADICAL AND THE PHOTOLYSIS OF THIONYL CHLORIDE
DONOVAN RJ,HUSAIN D,JACKSON PT
, p. 2930 - 2940 (2008/10/08)
The primary processes occurring in the photolysis of SOCl//2 have been examined by use of kinetic absorption spectroscopy in the ultraviolet and vacuum ultraviolet. Photodissociation involves the fission of one sulfurchlorine bond, leaving an energized SOCl radical which may then undergo unimolecular decomposition to yield an SO radical and a further chlorine atom, or is stabilized by collision. The kinetics of the SO radical so formed are examined and a mechanism for removal is proposed. Two new electronic states of the SO radical are identified via new absorption systems in the vacuum ultraviolet.
