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Kinetic Study of the Reaction of Diborane with Phosphine

Brumberger, H. and Marcus, R. A. (1956) Kinetic Study of the Reaction of Diborane with Phosphine. Journal of Chemical Physics, 24 (4). pp. 741-746. ISSN 0021-9606. doi:10.1063/1.1742601.

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The homogeneous gas phase reaction between diborane and phosphine at 0°C, yielding a solid product of composition BH_3PH_3, has been observed to give a linear relation between the initial rate of reaction and the pressure of either reactant, provided a certain pressure of each reactant, determined by the equilibrium constant and the pressure of the other gas, is exceeded. The reaction rate is independent of the amount of surface of the solid product or of the wall. When either reagent is in appreciable excess, the rate‐time data obey a pseudo first‐order equation. These facts are consistent with a rate‐controlling reaction of diborane with phosphine to give BH_3PH_3 and BH_3, the borine reacting further with phosphine, and the BH_3PH_3 condensing rapidly to a solid. This mechanism leads to a rate equation which is in good agreement with the experimental evidence. The activation energy of the rate‐controlling step is 11.4±2.0 kcal mole^(-1).

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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1956 American Institute of Physics. Received May 27, 1955. This work was done under Contract No. Nonr 839(09), Project No. NR 051-339 between the Office of Naval Research and the Polytechnic Institute of Brooklyn. From a dissertation presented by Mr. Brumberger in partial fulfillment of the requirements for the Ph.D. degree at the Polytechnic Institute of Brooklyn, 1955.
Funding AgencyGrant Number
Office of Naval Research (ONR)839(09)
Polytechnic Institute of BrooklynNR 051-339
Issue or Number:4
Record Number:CaltechAUTHORS:20131216-133447768
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43024
Deposited By: Tony Diaz
Deposited On:16 Dec 2013 21:43
Last Modified:10 Nov 2021 16:31

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