Mechanism of Substitution Reactions in Complex Ions. VII. Base Hydrolysis of Some Cobalt(III) Complex Ions1,2

1956 ◽  
Vol 78 (4) ◽  
pp. 709-713 ◽  
Author(s):  
Ralph G. Pearson ◽  
Robert E. Meeker ◽  
Fred Basolo
Keyword(s):  
Base Hydrolysis ◽  
Complex Ions ◽  
Substitution Reactions ◽  
Hydrolysis Of

Volumes of Activation for the Base Hydrolysis of [Rh(NH3)5X]2+ Complex Ions

1979 ◽  
Vol 32 (12) ◽  
pp. 2589 ◽  
Author(s):  
DA Palmer
Keyword(s):  
Partial Molar Volumes ◽  
Base Hydrolysis ◽  
Volume Data ◽  
Complex Ions ◽  
Molar Volumes ◽  
Base Mechanism ◽  
Hydrolysis Of ◽  
Conjugate Base

The pressure dependencies of the rates of base hydrolysis of [Rh(NH3)5X]2+ were measured at 313.2 K and μ1M, where X = Cl-, Br-, I- and NO3-, in the range 1-1500 bar. The respective Δν‡exp values are 19.3 � 0.9, 20.2 � 0.5, 20.4 � 0.5 and 22.3 � 0.9cm3 mol-1. The partial molar volumes of these complexes, as well as those of other relevant pentaamminerhodium(III) complexes, were also determined. The volume data are discussed in terms of the conventional dissociative conjugate base mechanism. The Δν‡exp for the aquation of [Rh(NH3)5NO3]2+ was found to be -6.9 � 0.4cm3 mol-1 at 313.2K, [H+] 0.005M and μ0.1 M. An I mechanism is favoured for this process.

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