147-nm photolysis of phosphine and phosphine-d/sub 3/

Journal Article · Thu Jun 25 04:00:00 EDT 1981 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j150613a017· OSTI ID:6341647

Blazejowski, J; Lampe, F W

The 147-nm photodecompositions of PH/sub 3/ and PD/sub 3/ result in the formation of H/sub 2/ (D/sub 2/) and P/sub 2/H/sub 4/ (P/sub 2/D/sub 4/) in the gas phase and a solid deposit which is probably a mixture of phosphorous and polymeric phosphorous hydrides (PH)/sub x/ and (PD)/sub x/. The quantum yields for the gaseous products and for depletion of reactants were measured and were found to increase with increasing pressure of phosphine and to decrease with increasing light intensity. All quantum yields for PD/sub 3/ are lower than those for PH/sub 3/. Isotope distribution analysis of the diphosphines formed in the photolysis of PH/sub 3/-PD/sub 3/ mixtures indicates that diphosphine is formed principally via combination of PH/sub 2/ (PD/sub 2/) radicals. A mechanism involving these primary photodissociations is proposed which is in accord with the experimental facts. The thermal decomposition of P/sub 2/H/sub 4/ at ambient temperature (approx. 300 K) is shown to be second order with a specific reaction rate of (4.25 +- 0.18) x 10/sup -18/ cm/sup 3//(molecule s). 6 figures, 3 tables.

• Research Organization: Pennsylvania State Univ., University Park
• OSTI ID: 6341647
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 85:13; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
400500* -- Photochemistry
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
STABLE ISOTOPES