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( 5 0 p . ) A proposed mechanism for the water - gas shift reaction on ferrochrome catalysts at high T is: H 2

(50p.) A proposed mechanism for the water-gas shift reaction on ferrochrome catalysts at
high T is:
H2O+SharrH2O-S,r1=kl[H2O]S-k-1H2OS
H2O-SharrHO-S-H,r2=k2H2O-S=k-2HO-S-H
HO-S-HharrO-S+H2,r3=k3HO-S-H-k-3[H2]O-S
CO+O-Sharr OCO-Sr4=k4[CO]O-S-k-4Oco-S
OCO-SharrCO2+S,r5=k5oco-5k-5[CO2]
where S is a surface site and H2O-S,HO-S-H,O-S and OCO-S are surface bound species
(each molecule of a surface bound species is chemisorbed onto a single surface site).
(a) What are the units of each one of the ten rate constants? (5p.)
(b) Derive an expression for the rate of the overall reaction (H2O+COH2+CO2)
in terms of the gas phase concentrations, assuming that reaction 3 is the rate
limiting step. (15p.)
(c) Derive an expression for the rate of the overall reaction assuming that CO2
desorption is the rate limiting step. (15p.)
(d) Derive an expression for the rate of the overall reaction assuming that H2O
adsorption is the rate limiting step. (15p.)
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