The atomic absorption spectroscopy (AAS) has been successfully utilized for the measurement of the Pd and Ag ion concentrations in the plating baths and to elucidate the effects of temperature, initial metal ion and reducing agent concentrations and agitation on the electroless plating kinetics of Pd and Ag metals. The initial metal ion concentrations for Pd and Ag were varied over a range of 8.2-24.5 mM and 3.1-12.5 mM, respectively. The plating reactions were conducted in a constant temperature electroless plating bath over a temperature range of 20-60 degrees C and an initial hydrazine concentration range of 1.8-5.4 mM. It was found that the electroless plating of both Pd and Ag were strongly affected by the external mass transfer in the absence of bath agitation. The external mass transfer limitations for both Pd and Ag deposition have been minimized at or above an agitation rate of 400 rpm, resulting in a maximum conversion of the plating reaction at 60 degrees C and dramatically shortened plating times with the added advantage of uniform deposition morphology. The derivation of the differential rate laws and the estimation of the reaction orders and the activation energies for the electroless Pd and Ag kinetics were conducted via non-linear regression analysis based on the method of initial rates. For a constant-volume batch reactor, the integrated rate law was solved to calculate the conversion and the reactant concentrations as a function of plating time. The model fits were in good agreement with the experimental data. Furthermore, the bath agitation and the plating conditions used in the kinetics study were adopted for the synthesis of 16-20 mu m thick composite Pd/Ag membranes (10-12 wt% Ag) and a pure-Pd membrane with a hydrogen selective dense Pd layer as thin as 4.7 mu m. While hydrogen permeance of the Pd/Ag membranes A and B at 450 degrees C were 28 and 32 m(3)/m(2)-h-atm(0.5), the H-2 permeance for the 4.7 mu m thick pure-Pd membrane at 400 degrees C was as high as 63 m(3)/m(2)-h-atm(0.5). The long-term permeance testing of all the membranes synthesized from agitated plating baths resulted in a relatively slow leak growth due primarily to the improved morphology obtained via the bath agitation and modified plating conditions. (C) 2009 Elsevier B.V. All rights reserved.