Deuterium Exchange between Deuteriodiborane and Aluminum Borohydride

Journal Article · Tue Oct 01 04:00:00 EDT 1963 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic50009a001· OSTI ID:4634245

Maybury, P. Calvin.; Larrabee, Joseph C.

The kinetics of the exchange of deuterium between diborane and aluminum borohydride were studied over a temperature range of -7 to 20 deg , and the orders of reaction were found to be dependent on the relative proportions of B/ sub 2/D/sub 6/ and Al(BH/sub 4/)/sub 3/. When the pressure of B/sub 2/D/sub 6/ is less than four times the Al(BH/sub 4/)/sub 3/ pressure, the reaction order was found to be 0.52 with respect to Al(BH/sub 4/)/sub 3/ and 1.2 with respect to B/ sub 2/D/sub 6/. At ratios greater than 4 the order of reaction with respect to Al(BH/sub 4/)/sub 3 /changed to 0.8 and the order with respect to B/sub 2/D/sub 6/ changed to -1.2. The activation energy was found to be 14 plus or minus 1 kcal/mole. A mechanism is proposed involving the thermal dissociation of both Al(BH/sub 4/)/sub 3/ and B/sub 2/D/sub 6/ followed by a rate-determining collision of B/sub 2/D/sub 6 with borane radicals. The changing orders of reaction are consistent with a derived steady-state expression for the exchange. Direct experimental evidence was obtained to prove that the boron atoms are undergoing exchange in the reaction by the use of B/sup 10/ enriched B/sub 2/D/ sub 6/.

• Research Organization: Eastern Nazarene Coll., Quincy, Mass.
• Sponsoring Organization: USDOE
• NSA Number: NSA-17-039042
• OSTI ID: 4634245
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 2; ISSN 0020-1669
• Publisher: American Chemical Society (ACS)
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACTIVATION ENERGY
ALUMINUM COMPOUNDS
ATOMS
BOROHYDRIDES
BORON
BORON 10
BORON COMPOUNDS
BORON HYDRIDES
COLLISIONS
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
ENERGY
EQUATIONS
EXCITATION
FREE RADICALS
HYDROGEN COMPOUNDS
ISOTOPIC EXCHANGE
LABELLED COMPOUNDS
PRESSURE
PYROLYSIS
QUANTITY RATIO
REACTION KINETICS
TEMPERATURE
TESTING
THERMODYNAMICS
TRACER TECHNIQUES