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CARBON AND OXYGEN ISOTOPE EXCHANGE BETWEEN CO AND Ni(CO)$sub 4$

Journal Article · · Journal of Chemical Physics (U.S.)
DOI:https://doi.org/10.1063/1.1733015· OSTI ID:4726173

The single stage factor alpha of the carbon and oxygen isotope exchanges between liquid Ni(CO)/sub 4/ and gaseous CO, according to the reactions Ni(C/sup 12/O)/sub 4/ + C/sup 13/O in equilibrium Ni(C/sup 12/O) /sub 3/C/sup 13/O + C/sup 12/O and Ni(CO/sup 16/)/sub 4/ + CO/sup 18/ in equilibrium Ni(CO/ sup 16/)/sub 3/CO/su p 18/ + CO/sup 18/, respectively, was determined: For the carbon exchange, alpha = 1.020 plus or minus 0.002 at--10 deg and alpha = 1.010 plus or minus 0.002 at + 10 deg , and for the oxygen exchange, alpha = 1.005 plus or minus 0.002 at -10 deg and alpha = 1.000 plus or minus 0.002 at +10 deg . The data are in good agreement with values calculated from spectroscopic data for Ni(CO)/sub 4/ and CO. From the isotope fractionation measured in a packed countercurrent column, the activation energy E for the exchange was estimated. The value of E = 12 kcal/mole agreed with the results obtained from kinetic data for the thermal decomposition of Ni(CO)/sub 4/ and the exchange of Ni(CO)/sub 4/ with labeled CO. The rate of the thermal decomposition of Ni(CO)/sub 4/ was assumed to be the rate determining step in the exchange. (auth)

Research Organization:
Rutgers Univ., Newark, N.J.
Sponsoring Organization:
USDOE
NSA Number:
NSA-17-008052
OSTI ID:
4726173
Journal Information:
Journal of Chemical Physics (U.S.), Journal Name: Journal of Chemical Physics (U.S.) Vol. Vol: 37; ISSN JCPSA
Country of Publication:
Country unknown/Code not available
Language:
English