19/11/2024

CHEM 260:
Physical Chemistry II

Kinetics 8 - The Pre-equilibrium and the

Steady-State Approximations
Dr Matthew Dyer
[email protected]
Office: Surface Science Research Centre (SSRC)
Access to SSRC via telephone in entrance porch

Lecture 7 - reminder
k1 B
A
k2 C
B 𝑡 = ΦB A 1 − 𝑒 −𝑘𝑡
0
x(t) = x0e-kt
C 𝑡 = ΦC A 0 1 − 𝑒 −𝑘𝑡
kf =2, kr = 1
k1 = 2k2

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Lecture 8 - outcomes
By the end of Lecture 8 we aim to:

1. Introduced the pre-equilibrium approximation

2. Seen how apparently negative activation energies can arise
3. Considered reaction kinetics in dilute solution
4. Introduced the steady-state approximation

Additional Resources

1. Physical Chemistry”, Atkins, Oxford University Press, 11th Ed. p748-751, 788-789
2. Elements of Physical Chemistry: p. 284-286, 290-294

Pre-equilibrium
➢Combine sequential reactions (lecture 6) with an equilibrium (lecture 7)
k1 k2
A I P
k−1
➢We will assume all steps to be elementary
➢For pre-equilibrium conditions: k-1 >> k2
➢ A and I in equilibrium at all times
reaction to form products is slow, only a slight “leakage” to form P

[I] 𝑘1
K= = 𝑠𝑒𝑒 𝑙𝑒𝑐𝑡𝑢𝑟𝑒 7 [I] = 𝑘1ൗ𝑘−1 [A]
[A] 𝑘−1

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Pre-equilibrium
k1 k2
A I P
k−1
[I] = 𝑘1ൗ𝑘−1 A

d[P] 𝑘1 𝑘2
= 𝑘2 I = [A]
dt 𝑘−1

kobs = k1k2 / k-1

Overall 1st order

Pre-equilibrium
k1' k2
A+B I P
k−1

➢Assume all steps to be elementary

➢Now k1’ is a second-order rate constant
➢For pre-equilibrium: we still require k-1 >> k2

[I]𝑐 ⊖
K=
A [B]

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Pre-equilibrium
k1' k2
A+B I P
k−1

At equilibrium the forward rate = reverse rate

forward rate = k1’[A][B] reverse rate = k-1[I] • 2nd order rate
equation
So: k1’ [A]eq[B]eq = k-1 [I]eq remember k1’ is 2nd
[I]eq = (k1’ [A]eq[B]eq)/k-1 order

d[P] 𝑘′1 𝑘2 • Introduce kobs

= 𝑘2 I = [A][B]
dt 𝑘−1
kobs

Negative Ea?
k1’ k2
A+B⇌I→P
k-1
𝑘1′ 𝑘2
kobs =
𝑘−1
Ea1′ Ea2
− −
(A1′ e RT )(A2 e RT )
kobs = Ea−1 Observed Ea is positive when:
− RT
A−1 e
Ea1’ + Ea2 > Ea-1
A1′ A2 −Ea1′ +Ea2 −Ea−1
kobs = = e RT
A−1 Observed Ea is negative when:
Ea1’ + Ea2 < Ea-1
Ea(obs) = Ea1’ + Ea2 – Ea-1
Take care when interpreting Ea from complex reactions!

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Reactions in Dilute solution

Diffusion limited
➢ small amount of reactants in an inert solvent
➢ Solvent acts as barrier
➢ Limited by diffusion of A + B together to form
“encounter complex” AB
➢ Reduced collision rate
➢ Leads to expectation of reduced reaction
rate?

Dilute Solution
k1’ k2
A + B ⇌ AB → P
k-1

Reaction scheme
k1’ – Second order rate constant for molecules to diffuse and meet each
other in solution
k-1 – First order rate constant for encounter complex to break apart and
molecules to diffuse away
k2 – First order rate constant for molecules in encounter complex to react
and produce product P

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Dilute Solution
If k-1 >> k2 then pre-equilibrium provides a route to understand
kinetics for this kind of reaction
k1’ k2
A + B ⇌ AB → P
k-1
• 2nd order rate equation
The encounter complex, remember k1’ is 2nd order
AB, is equivalent to our 𝑘1′ 𝑘2
intermediate in the 𝑟𝑎𝑡𝑒 = A B • Simplify = kobs
𝑘−1
previous slides

kobs

Dilute Solution
Solvent cage / Encounter complex
➢ A + B come into close contact
➢ Normally only a fraction react (energetic
requirement)
➢ Gas phase, unreactive collision – molecules
separate
➢ In solution it can be harder for molecules to
separate – they are held together!
➢ Large number of collisions with reactive partner
and solvent (pick up energy!)
➢ Increased reaction probability?

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Dilute Solution
diffusion → reduced collision rate Solvent cage → increased reaction probability

Does pre-equilibrium provides a route to understand kinetics?

k1’ k2
A + B ⇌ AB → P
k-1

Is the assumption that k-1 >> k2 always justified in dilute solution?

No!
Solvent can trap molecules together until they react.
Reverse reaction is not fast compared to making product.

The Steady-State approximation

➢Assume that after induction period the net rate of

concentration change for all intermediates is very
small
k1’ k2
A+B⇌I→P
k-1

d[I]
≈0 Gradient ≈ 0
dt
➢ Can be a better approximation than pre-equilibrium
➢ Greatly simplifies studies of reaction schemes and can explain seeming
complex systems
➢ Best demonstrated with an example

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The Steady-State Approximation

➢Assume that after induction period the net rate of

concentration change for all intermediates is very
small
k1’ k2 d[AB]
A + B ⇌ AB → P ≈0
k-1
dt

d[AB]
➢ = 𝑘1′ A B − 𝑘−1 AB − 𝑘2 AB
dt
d[AB]
➢ = 𝑘1′ A B − 𝑘−1 + 𝑘2 AB
dt
d[AB] 𝑘1′
➢ =0 AB = A B
dt
𝑘−1 + 𝑘2

The Steady-State Approximation

➢Assume that after induction period the net rate of

concentration change for all intermediates is very
small
k1’ k2 d[AB]
A + B ⇌ AB → P ≈0
k-1
dt
𝑑P
= 𝑘2 AB
𝑑𝑡
𝑘1′
𝑑P 𝑘1′ 𝑘2 AB = A B
= A B 𝑘−1 + 𝑘2
𝑑𝑡 𝑘−1 + 𝑘2

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k1’ k2
A + B ⇌ AB → P
Dilute Solution k-1

When k-1 >> k2 activation controlled

𝑑P 𝑘1′ 𝑘2 kk
= A B rate = 2 1' [ A ][B]
k -1
𝑑𝑡 𝑘−1 + 𝑘2
➢ Here the limiting step is the actual reaction (k-1 ~ k1’ >> k2)
➢ Same result as pre-equilibrium
➢ different approximations yield same result under conditions where both are valid!

When k2 >> k-1 diffusion controlled

𝑑 P 𝑘1′ 𝑘2 𝑘2 𝑘1′ A [B]
=𝑘 A B  = k1’[A][B]
𝑑𝑡 −1 + 𝑘2 𝑘2

➢ In this scenario the rate is controlled by how quickly the reagents can diffuse together
the probability for a reaction to occur before the encounter pair leaves the solvent cage
is 1.

Diffusion controlled kinetics

k1’ k2 d[P]
A + B ⇌ AB → P  k1’[A][B]
dt
k-1

• k1’ is the bimolecular diffusion coefficient, often labelled kd

• kd is determined by the speed of diffusion of the molecules, which
depends on the size of the molecules and the viscosity (temperature
dependent) of the solvent.
• (For a derivation, see Atkins’ “Physical Chemistry” p788-9)

8RT
𝑘𝑑 = Where η = viscosity
3𝜂

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Worked Example
Q. Calculate the diffusion limited rate constant for water at 25°C, given that
the viscosity is 9 x10-4 kg m −1 s −1

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Steady State Example: O3

NO2
h k1 NOx induced O3
NO + O
➢ Ozone at ground level is an indirect result of
k2
O + O2 O3 pollution by our industrial society.
k3
➢ industrial and car exhausts → NO and NO2
O3 + NO NO2 + O 2
which is photolysed (UV) to O3
Typical data downwind from an industrial plant
d/km [NO2]/ppb [NO]/ppb [O3]/ppb
0 74.5 20.3 94
13 30.2 5.4 129

Can we rationalise the distance dependence of NO2, NO and O3 ?

Steady State Example: O3

h k1
NO2 NO + O
k2
All steps are elementary:
O + O2 O3 order = number of molecules
k3
O3 + NO NO2 + O 2

➢Intermediates: O, O3
1. d[O3]/dt = k2 [O][O2] - k3 [O3][NO] = 0
2. d[O]/dt = k1 [NO2] - k2 [O][O2] = 0
Summing equations 1 + 2
k1 [NO2 ]
 k3 [O3][NO] = k1 [NO2] [O3] =
k3 [NO]

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Steady State Example: O3

Thus: ozone concentration is proportional to ratio between NO2 concentration
to NO concentration. That is because NO2 is responsible for creating ozone,
whereas NO in fact helps to reduce its concentration by reacting with it.
k1 [NO2 ]
[O3] =
k3 [NO]
d/km [NO2]/ppb [NO]/ppb [O3]/ppb [NO2]/[NO]
0 74.5 20.3 94 3.7
13 30.2 5.4 129 5.6

5.6/3.7 = 1.5 129/94 = 1.4!

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