Product Distribution in Preparative Electrolysis

knowing that (CbA)t=(j = C°, equation (2.30) is obtained. Addition of equations (2.28) and (2.29), followed by time-integration, leads to 

In the case of constant reactant concentration-constant potential electrolysis, equation (2.28) does not apply since 

In constant reactant concentration-constant current electrolysis, the bulk concentration of B also increase proportionally with time, but the proportionality factor is i/FV instead of C°/tc [equation (2.34)]. 

Addition of equations (6.102) and (6.103), followed by integration, taking equations (6.100), (6.101), and (6.104) into account, leads to 

This means that the build up of the sum of the first-order reaction product and twice the second-order reaction product follows exactly the same laws 

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Carbon monoxide at latm has no effect on the voltammetry of cyclohexane in fluorosulfonic acid. In preparative scale electrolysis in fluorosulfonic acid containing 3.0 M water the hydrocarbon cyclohexane affords in 56% current efficiency cyclohexane-carboxylic acid. n-Pentane forms at optimum conditions (latm CO, — 25°C) 74% carboxylic acids in which the alkane skeleton is largely rearranged. The product distribution is 1% 2-methylpentanoic acid, 4% 2-ethylbutanoic acid and 95% 2,2-dimethylbutanoic acid. At higher CO pressure and room temperature only 15% rearranged product is obtained, 54% 2-ethylbutanoic acid and 31% 2-methylpentanoic acid are being formed in a somewhat lower overall yield of 57%. Cyclopentane affords 80% cyclopentanecarboxylic acid. 

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