The kinetics of benzonitrile hydrolysis were used to probe the effect of re
actor walls on hydrothermal reaction chemistry. The three key issues of: (1
) reactor use history; (2) material of construction; and (3) surface area t
o volume ratio (S/V) were investigated with respect to reaction rate consta
nt and hydrolysis product yield. A series of identical reactions revealed n
o effect of repeated reactor use on either the rate constant or product sel
ectivity.. Likewise, use of stainless steel and titanium reactors with the
same volume and surface area produced no statistical difference in either r
ate constant or product yield. Finally, the kinetics and product yields wer
e not affected by variation of reactor S/V from 3.68 to 14.84 cm(-1). Analy
sis of possible parallel homogeneous and heterogeneous (wall) reaction at 3
00 degrees C and 200 bar revealed rate constants of 1.02 x 10(-2) min(-1) a
nd 1.22 x 10(-4) cm min(-1), respectively. The maximum heterogeneous contri
bution to the overall rate (5.6 +/- 2.0%) was within the experimental uncer
tainty for the homogeneous rate constant (6.1%). This suggests that the lab
oratory-deduced rate constants will provide a faithful model for the true k
inetics at commercial conditions. (C) 1999 Elsevier Science B.V. All rights
reserved.