US EPA

1168466 

Journal Article 

Reactivity of alkanols and aryl alcohols towards tetrachloroaurate(III) in sodium acetate-acetic acid buffer medium 

Pal, B; Sen, PK; Sen Gupta, KK 

2001 

Yes 

Journal of Physical Organic Chemistry
ISSN: 0894-3230 

14 

5 

284-294 

English 

10.1002/poc.361 

WOS:000168436600004 

The oxidative behaviour and relative reactivities of three alkanols and 11 aryl alcohols towards gold(III) in sodium acetate-acetic acid buffer were studied. The reactions are first order with respect to [Au(III)] and in each [R1R2CHOH]. Both H+ and Cl- ions retard the rate of reactions. The reactions obey the following rate expression: -d[Au(III)]/dt={k1 + k2 - k1)K2/[Cl-] + (k3 - k1)K2K3/[H+][Cl-]} [R1R2CHOH][Au(III)] AuCl4-, AuCl3(OH2) and AuCl3(OH)- are the reactive species of gold(III) and the reactivity follows the order AuCl3(OH)- > AuCl3(OH2) > AuCl4-. The activation parameters of the reactions were calculated. Alkanols react with gold(III) in the order ethanol > methanol > 2-propanol. The unsubstituted benzyl alcohol reacts with gold(III) at a faster rate than benzhydrol. The pseudo-first-order rate constants in the oxidations of aryl alcohols follow the order NO2 > H > Cl > OMe. The reactions occur via C - H bond cleavage and through the intermediate formation of free radicals. Copyright © 2001 John Wiley & Sons, Ltd. 

tetrachloroaurate(III); oxidation; alkanols; aryl alcohols; kinetics