1. Kinetics of reaction in solution

2. Solvent effects
Solvation of reactant
Catalysis
Intermolecular reaction (ions, polar reactant)
Diffusion (solvent viscosity)
Hydrogen bond
Change mechanism

3. 1) Solvent effects on rate constants
CH3I + Cl  CH3Cl + I
solvent
HCONH2
HCONHCH3
HCON(CH3)2
k/ dm3 mol-1 s-1
510-5
1.4 10-4
0.4
The reaction rate depends strongly on the solvent used.

4. Solvent effect on activation energy
Solvent A
standard
Solvent B

5. For evaluation of solvent effect

6. Solvents
102k / dm3mol-1s-1
Hexane
Benzene
0.0058
chlorobenzene
0.023
nitrobenzene
70.1
If the polarity of product is higher than that of reactants, higher polar solvent benefits the reaction.

7. 2) Catalysis of water

8. 3) Effect of ionic strength-primary/kinetics salt effect
For ionic reactions in solution, activity coefficients must be taken into consideration. Therefore, the apparent rate constant depends on the ionic strength of the solution.
For dilute solution

9. 0.0
-0.2
-0.4
0.2
0.4
0.6
0.1
0.3
Effect of ionic strength on the rate of reaction between two ions.
+4: Co(NH3)5Br2+ + Hg2+
+2: S2O82- + I
+1: [NO2NCO2C2H5] + OH
0: CH3COOC2H5 + OH
-1: H2O2 + H+ + Br
-2: Co(NH3)5Br2+ + OH
A substantial amount of inert salt (supporting electrolyte) was added to keep the ionic strength and therefore the activity coefficient of the solution essentially constant.

10. 4) Cage effect
Once reactant molecules meet in one solvent cage through diffusion (an encounter), they will be trapped in the cage for a relatively long time during which they collide repeatedly with each other (collision), providing more chance to react.
Within a solvent cage (for 1~100 ns), two reactant molecules can collide 10 ~105 times.
Does viscosity of solvent affect collision in the solvent cage?
Solvent cage: capture reactant molecules
Diffuse in or out, from or to other solvent cages.
Experimental evidence: photolysis of CH3NNCH3 and CD3NNCD3 in gaseous phase and in solution. Given by Lyon and Levy in 1961.

11. The process can be represented as
A + B → {AB} → products
in which the {AB} term represents the caged reactants including the encounter pair and the activated complex.
10-12 ~ s, collides for 10 ~ 105 times.
Ere > Ediff. Reaction control.
Ediff. > Ere, diffusion control.

12. 5) Diffusion-controlled reactions

13. Discussion:
If reaction is much slow than diffusion, activation control or kinetics control
If diffusion is much slow than reaction, diffusion control

14. For activation control
Resembles gaseous reaction, no effect of solvent.
media
gas
CS2
C6H6
C2H5OH
106 k/ dm3 mol-1 s-1 6 10 20
Solvent effect on reaction between species of low polarity is weak.

15. For diffusion control
Fickian first law
Flux
D diffusion coefficient with unit of m2s-1.
For spherical particle, Einstein-Storks equation
For second-order reaction
Integration yields

16. For second-order reaction
f is electrostatic factor.
Diffusion-Limited Rate Constants, Slow reactions

17. For diffusion, Ea  10 kJmol-1
If rA = rB
For diffusion, Ea  10 kJmol-1

18. 4．Reactions in Solution
4.1 General Properties of Reactions in Solutions
4.2 Diffusion-Limited Rate Constants, Slow reactions
4.3 Effect of Ionic Strength on Reactions between Ions
4.4 Linear Free-Energy Relationships
J.H. Espenson, Chemical Kinetics and Reaction Mechanisms, 2nd Ed (McGraw-Hill, New York, 1995)

19. Stochastic and Dynamic Views of Chemical Reaction Kinetics in Solutions
Author:
A. Kuznetsov
ISBN-10:
ISBN-13:
Published in: January 1999