Health & Environmental Research Online (HERO)


Print Feedback Export to File
8151436 
Journal Article 
The mechanism of aromatic mercuration. II : Reaction kinetics 
Schramm, RM; Klapproth, W; Westheimer, FH 
1951 
1 
Journal of Physical Chemistry
ISSN: 0022-3654 
55 
6 
843-860 
English 
1. The rate of mercuration of benzene in aqueous solution is first order in. mercuric ion and first order in benzene. 2. The second-order rate constant is increased many hundred fold by concentrated solutions of perchloric, sulfuric, or nitric acid; in the concentration range 0-3 M the second-order rate constant is increased as much by the addition of solutions of sodium perchlorate or nitrate as by the corresponding acid. Chlorides strongly inhibit the reaction. 3. In 97 per cent acetic acid as solvent, mercuration is strongly catalyzed by perchloric acid and weakly catalyzed by sodium perchlorate. 4. The reaction thus appears to be catalyzed by anions. 5. These facts are tentatively correlated with a mechanism in which mercuration takes place by way of a mercuric ion complexed with the catalyzing anion.