A new approach in the kinetic analysis of the joint homogeneous-heterogeneous catalysis of the quaternization of silver(I) coordinated triethylamine by ethyl iodide in toluene is presented. This complex competitive process was thoroughly scrutinized and the set of solution and surface rate equations were integrated under a novel perspective thus leading to the calculation of solution rate constants as well as guesstimates of the superficial quaternization rate. Testing the rate equations developed herein also required the performance of kinetic runs over a wider range of experimental conditions, than those previously reported. (C) 2002 Elsevier Science B.V. All rights reserved.