The reaction of fenitrothion with a series of alpha-nucleophile oximates having pK(a) values in the range of 7.7-11.8 was studied both in the absence and presence of cetyltrimethylammonium (CTA(+)) surfactants. Reaction with CTA-oximates was found to proceed through two pathways: S(N)2(P) and S(N)2(C); an S(N)Ar pathway was not observed. Accordingly, the observed rate constants were dissected into the two corresponding S(N)2(P) and S(N)2(C) pathways. Use of the pseudophase ion exchange (PPIE) model for micellar catalysis in the CTA(+) system allowed evaluation of micellar second-order rate constant (k(2m)) parameters and binding constants, (K(S)). K(S) values for CTA-oximates were found to vary with the counterion, and the rate enhancement depended on a combination of K(S) and k(2m) values. k(2m)/k(2w) values ranged from 0.0025 to 0.64, suggesting that a concentration effect is mainly responsible for the rate enhancement. In the absence of surfactant, an alpha-effect (i.e., k(alpha)/k(normal)) varying from 8 to 450 was observed for the oximate reaction, decreasing with increasing pK(a). It is proposed that differential solvation (transition-state imbalance) is a cause of the alpha-effect in this system.