• Bulletin of the Korean Chemical Society
• /
• v.26 no.12
• /
• pp.1981-1985
• /
• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• Resources Recycling
• /
• v.12 no.4
• /
• pp.30-37
• /
• 2003

A kinetics study on the dissolution reaction of zinc-ferrite has been made with aqueous sulfuric acid in various temperature and concentration. Fraction reacted(R) and apparent rate constant(K) increased with increasing temperature and concentration of sulfuric acid solution. The rate of dissolution is shown by $1-(1-K)^{1/3}=Kt$ for the initial stage of the reaction in aqueous sulfuric acid, where K is apparent rate constant, R is fraction reacted and t is reaction time, respectively. Activation energy associated with reaction was determined to be 16.3 kcal/mole. The dissolution of zinc-ferrite in sulfuric acid solution is dissolved by sto-ichiometric composition, but Fe and Zn did not dissolved, respectively.