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. https://resolver.caltech.edu/CaltechAUTHORS:20131216-133447768
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Abstract
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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| 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. | |||||||||
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| Issue or Number: | 4 | |||||||||
| DOI: | 10.1063/1.1742601 | |||||||||
| Record Number: | CaltechAUTHORS:20131216-133447768 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20131216-133447768 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 43024 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 16 Dec 2013 21:43 | |||||||||
| Last Modified: | 10 Nov 2021 16:31 |
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