The Kinetic Salt Effect

not just for diffusion-limited reactions

{AB}
z A + zB
A zA + B zB ⎯⎯
→ products strictly true only for
activated reactions
rate = k [ A ][ B] = kR ⎡⎣{AB}⎤⎦
⎡⎣{AB}⎤⎦ γ AB
For concentrated solutions K{AB} = i
[ ][ ] γ A γ B
A B
⎡{AB}⎤⎦ γ γ γ γ
⇒ k = kR ⎣ = kR K{AB} A B = k0 A B
[ A ][ B] γ AB γ AB
zAzB
According to Debye-Hûckel log10 γ i = −0.509 zi2 I
+2
k
Ionic strength I = 12 ∑ i [X i ]zi2 log10
k0 +1

log10 k = log10 k0 − 0.509 ⎡ zA2 + zB2 − ( zA + zB ) ⎤ I

2
⎣ ⎦ 0

k −1
log10 = 1.02 zA zB I
k0 −2
Used to distinguish transients, such as H, e−aq, Mu I
 The Kinetic Salt Effect − 2
There are small effects even for uncharged reactants.

Suppose A is charged log10 γ A = −CzA2 I + bA I

and B is not log10 γ B = −bB I

⇒ log10 k = log10 k0 + ( bA + bB − bAB ) I

k = k0eb′I → k0 (1 + b′I ) weak linear dependence

 Pressure Dependence of Reaction Rates
From classical ⎛ ∂G ⎞ ⎛ ∂∆G ⎞
dG = VdP − SdT ⎜ ⎟ =V ⎜ ⎟ = ∆V
thermodynamics ⎝ ∂P ⎠T ⎝ ∂P ⎠T

For a reaction ⎛ ∂ ln K ⎞ 1 ⎛ ∂∆G ⎞ ∆V °

⎜ ⎟ = − ⎜ ⎟ = −
at equilibrium ⎝ ∂P ⎠T nRT ⎝ ∂P ⎠T RT

∆V ° = Vprod − Vreact = (V ‡ − Vreact ) − (V ‡ − Vprod ) = ∆ ‡V1° − ∆ ‡V−1°

⎛ ∂ ln k1 ⎞ ⎛ ∂ ln k−1 ⎞ ∆ ‡V1° ∆ ‡V−1°

Since K = k1 / k−1 ⎜ ⎟ −⎜ ⎟ =− +
⎝ ∂P ⎠T ⎝ ∂P ⎠T RT RT

Most books state ⎛ ∂ ln k1 ⎞ ∆ ‡V1° ⎛ ∂ ln k−1 ⎞ ∆ ‡V−1°

⎜ ⎟ =− ⎜ ⎟ =
⎝ ∂P ⎠T RT ⎝ ∂P ⎠T RT

This neglects the difference between K° and Kc only different for ∆ν ≠ 0

Since K c = V °K ° for ∆ν = −1
volume of activation
⎛ ∂ ln k ⎞ ∆ ‡V °
⎜ ⎟ =− − κ0
⎛ ∂ ln V ⎞ 1 ⎛ ∂V ⎞
⎝ ∂ P ⎠T RT compressibility
⎜ ⎟ = ⎜ ⎟
of the solvent ⎝ ∂P ⎠T V ⎝ ∂P ⎠T
 Pressure Dependence − 2
Neglecting κ 0 k
ln ∆V ‡ < VA + VB
k0
∆V ‡
ln k = ln k0 − P
RT 0

If reactants.. expect ∆V ‡ > VA + VB

combine ∆V ‡ < 0
P
dissociate ∆V ‡ > 0

have like charges ∆V ‡ < 0 ⎫⎪ similar effects for polar molecules (dipoles)
⎬
⎪⎭ Solvent effects are often dominant
unlike charges ∆V ‡ > 0

+
+
ordering of the solvent
Electrorestriction molecules reduces
+
+ their effective volume
 Volume of Activation for H Atom Reactions

A + H AH ∆V ‡ = VAH − VA − VH ≈ −VH

A + H A H ∆V ‡ ≈ Vw ( H ) − VH

Comparison of ∆V ( H ) and ∆V ( Mu ) shows that V(Mu) > V(H) in water.

‡ ‡