Kinetics of fast

reactions

INTRODUCTION
What is fast reaction ?
Reaction which go to equilibrium in a few seconds

are known as fast reactions

This reaction even proceed in less time can not be
kinetically studied by conventional methods. Such as
titration,
conductometrically,
colorimetry

Experimental techniques developed by the German

chemist Manfred Eigen in 1950

What is meant by relaxation ?
The reacting system in equilibrium is subjected to a
sudden variation in some parameter on which the
equilibrium constant of reaction depends. The
system changes to new state of chemical
equilibrium. The rate of this change is called
relaxation
Parameters of relaxation methods
Temperature
Pressure
Electric field

TEMPERATURE JUMP
METHOD

Apparatus for the temperature jump method

Capacitor (C)
Photomultiplier tube (PM)
Spark gap (G)

Analyzing a temperaturejump experiment

The equilibrium constant for the autoprotolysis of water,

H20(l) ~ H+(aq) +OH-(aq), is Kw= a(H+)a(OH-) = 1.008 x

10-14 at 298 K. After a temperature-jump, the reaction
returns to equilibrium with a relaxation time of 37 us at 298
K and pH = 7. Given that the forward reaction is first-order
and the reverse is second order overall, calculate the rate
constants for the forward and reverse reactions.

REFERENCES
o Atkins 8th edition ; pg (805)
http://www.britannica.com/EBchecked/topic/10

8758/chemical-kinetics/275833/Measuring-fast
-reaction
s

Thank you