Physical Chemistry II

Chapter 10: Chemical Kinetics II.

Composite Mechanisms
In this chapter …
10.1 Evidence for a Composite Mechanism
10.2 Types of Composite Reactions
10.3 Rate Equations for Composite Mechanisms
10.4 Rate Constants. Rate Coefficients, and Equilibrium Constants
10.5 Free-Radical Reactions
10.6 Photochemical Reactions
10.9 Catalysis
 Preface
Elementary reactions : occur in a single step: 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 → 𝑎𝑐𝑡𝑖𝑣𝑎𝑡𝑒𝑑 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Composite reactions : involve two or more elementary steps (stepwise or complex reactions).
 Kinetics ➔ gives us information about steps involved in a reaction (𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑚𝑒𝑐ℎ𝑎𝑛𝑖𝑠𝑚)
e.g., 𝑁𝑂2(𝑔) + 𝐶𝑂(𝑔) → 𝑁𝑂(𝑔) + 𝐶𝑂2(𝑔) Experimentally: 𝑅𝑎𝑡𝑒 = 𝑘 𝑁𝑂2 2

Proposed mechanism:
𝑁𝑂2(𝑔) + 𝑁𝑂2(𝑔) → 𝑁𝑂3(𝑔) + 𝑁𝑂(𝑔) (1st elementary step, slow) mechanism is
composed of
𝑁𝑂3(𝑔) + 𝐶𝑂(𝑔) → 𝑁𝑂2(𝑔) + 𝐶𝑂2(𝑔) (2nd elementary step, fast) elementary steps
𝑁𝑂2(𝑔) + 𝐶𝑂(𝑔) → 𝑁𝑂(𝑔) + 𝐶𝑂2(𝑔) (overall reaction)
𝑁𝑂3(𝑔) is an intermediate: a species that is neither a reactant nor a product but is formed and
consumed during the reaction sequence.
Elementary step: a reaction whose rate law can be written from its molecularity (coefficients
in balanced equation).
Slow-step: it is the rate-determining step (RDS).
Preface
Requirements for a proper mechanism:
1. The sum of the elementary steps must give the overall balanced equation for the reaction.
2. The mechanism must agree with the experimentally determined rate law.

Examples of elementary steps

Preface
e.g. Write the rate law for the elementary reactions:
A) 𝑂3(𝑔) + 𝑁𝑂(𝑔) → 𝑂2(𝑔) + 𝑁𝑂2(𝑔) (bimolecular reaction: two reactants)
B) 𝐶𝐻3 𝑁𝐶 → 𝐶𝐻3 𝐶𝑁 (unimolecular reaction: one reactant)
The two reactions are elementary ∴ the rate raw can be written from their molecularity.

A) 𝑂3(𝑔) + 𝑁𝑂(𝑔) → 𝑂2(𝑔) + 𝑁𝑂2(𝑔) 𝑅𝑎𝑡𝑒 = 𝑘 𝑂3 𝑁𝑂

B) 𝐶𝐻3 𝑁𝐶 → 𝐶𝐻3 𝐶𝑁 𝑅𝑎𝑡𝑒 = 𝑘 𝐶𝐻3 𝑁𝐶
Preface
e.g., 2𝑁𝑂2(𝑔) + 𝐹2(𝑔) → 2𝑁𝑂2 𝐹(𝑔) Experimentally: 𝑅𝑎𝑡𝑒 = 𝑘 𝑁𝑂2 𝐹2
Suggested mechanism:
𝑁𝑂2(𝑔) + 𝐹2(𝑔) → 𝑁𝑂2 𝐹(𝑔) + 𝐹(𝑔) (slow)
𝐹(𝑔) + 𝑁𝑂2(𝑔) → 𝑁𝑂2 𝐹(𝑔) (fast)
Is this an acceptable mechanism?
Check the two requirements for a proper mechanism:
1. The sum of elementary steps gives the overall reaction:
2𝑁𝑂2(𝑔) + 𝐹2(𝑔) → 2𝑁𝑂2 𝐹(𝑔) (overall reaction)

2. Rate law from slow step ≡ Experimental rate law

∴ Yes, this is an acceptable mechanism

Preface
e.g., A proposed mechanism for a reaction is:
𝐶4 𝐻9 𝐵𝑟 → 𝐶4 𝐻9+ + 𝐵𝑟 − (slow)
𝐶4 𝐻9+ + 𝐻2 𝑂 → 𝐶4 𝐻9 𝑂𝐻2+ (fast)
𝐶4 𝐻9 𝑂𝐻2+ + 𝐻2 𝑂 → 𝐶4 𝐻9 𝑂𝐻 + 𝐻3 𝑂+ (fast)

A) Write rate law for this mechanism.

B) Write overall reaction.
C) What are the intermediates?

A) Slow step is RDS (1st step) ➔ 𝑅𝑎𝑡𝑒 = 𝑘 𝐶4 𝐻9 𝐵𝑟

B) 𝐶4 𝐻9 𝐵𝑟 + 2𝐻2 𝑂 → 𝐵𝑟 − + 𝐶4 𝐻9 𝑂𝐻 + 𝐻3 𝑂+
C) 𝐶4 𝐻9+ and 𝐶4 𝐻9 𝑂𝐻2+
Preface
e.g., 𝐻2 + 2𝐼𝐶𝑙 → 𝐼2 + 2𝐻𝐶𝑙 Experimentally: 𝑅𝑎𝑡𝑒 = 𝑘 𝐻2 𝐼𝐶𝑙 second order
if this rxn occurred in a single elementary step, it would be third order (∴ it’s a composite rxn)
Suggested mechanism:
𝐻2 + 𝐼𝐶𝑙 → 𝐻𝐼 + 𝐻𝐶𝑙 (slow)
𝐻𝐼 + 𝐼𝐶𝑙 → 𝐻𝐶𝑙 + 𝐼2 (rapid)
𝐻2 + 2𝐼𝐶𝑙 → 𝐼2 + 2𝐻𝐶𝑙 (overall reaction)

➢ The 1st step is the rate-determining step (RDS)

(∴ rxn rate is obtained from 1st step⇒ it is a second-order reaction)
➢ The 2nd step has no effect on the overall rxn rate.
➢ 𝐻𝐼 is a stable intermediate!
Preface
e.g., 2𝐵𝑟 − + 𝐻2 𝑂2 + 2𝐻 + → 𝐵𝑟2 + 2𝐻2 𝑂 Experimentally: 𝑅𝑎𝑡𝑒 = 𝑘 𝐻2 𝑂2 𝐻 + 𝐵𝑟 −
Suggested mechanism:
𝐻 + + 𝐻2 𝑂2 ⇌ 𝐻2 O−OH + (rapid equilibrium)
𝐻2 O−OH + + 𝐵𝑟 − → 𝐻𝑂𝐵𝑟 + 𝐻2 𝑂 (slow)
𝐻𝑂𝐵𝑟 + 𝐻 + + 𝐵𝑟 − → 𝐵𝑟2 + 𝐻2 O (fast)

➢ The 2nd step is the rate-determining step (RDS)

(∴ rxn rate is obtained from 2nd step ⇒ 𝑅𝑎𝑡𝑒 = 𝑘 𝐵𝑟 − 𝐻2 O−OH +
➢ However, from 1st step: 𝐻2 O−OH + ∝ 𝐻 + 𝐻2 𝑂2
𝐻2 𝑂−𝑂𝐻 +
from 𝐾𝑐 = ⇒ 𝐻2 𝑂 − 𝑂𝐻 + = 𝐾𝑐 𝐻 + 𝐻2 𝑂2
𝐻 + 𝐻2 𝑂2

➢ ⇒ 𝑅𝑎𝑡𝑒 = 𝑘 𝐵𝑟 − 𝐻 + 𝐻2 𝑂2 ≡ Experimental rate law

Preface
e.g., 𝐴 + 𝐵 → 𝑌 + 𝑍 Experimentally: rxn is zero order in the reactant 𝐴 and 1st order in 𝐵
Suggest a mechanism that’s consistent with the result.
Suggested mechanism: 𝐵 forms an intermediate 𝑋 in a slow step that reacts rapidly with 𝐴
𝐵→𝑋 (slow)
𝑋+𝐴 →𝑌+𝑍 (fast)
𝐴+𝐵 →𝑌+𝑍 (overall reaction)
Slow step is RDS (1st step) ➔ 𝑅𝑎𝑡𝑒 = 𝑘 𝐵 ≡ Experimental result

Note: in the search for the mechanism of a chemical reaction: kinetic evidence— or
any other kind of evidence— can never prove a reaction mechanism, although the
evidence may disprove a mechanism! as new discoveries might reveal a more accurate
mechanism that contradicts a previously accepted one.
Preface
𝑘 Fe CN 3−
6
2 𝐼− 2
e.g., 2Fe(CN)3− − 4−
6 +2𝐼 → 2Fe(CN)6 +𝐼2 Experimentally: 𝑅𝑎𝑡𝑒 =
Fe CN 4−
6
Proposed mechanism:
𝑘1
Fe CN 4− 𝐼2−
Fe(CN)3−
6 +2𝐼 − ⇆
Fe(CN) 4−
6 +𝐼2
−
𝐾𝑐 =
6
… (1)
𝑘−1 Fe CN 3−
6 𝐼− 2
𝑘 3−
𝐼2− + 3− 2
Fe(CN)6 → Fe(CN)4−
6 +𝐼2 (𝑠𝑙𝑜𝑤) 𝜈𝑅𝐷𝑆 = 𝑘2 𝐼2− Fe CN 6 … . (2)

𝐾𝑐 Fe CN 3−
6 𝐼− 2
From eq. (1): 𝐼2− = … (3) Add eq.(3) to eq.(2):
Fe CN 4−
6

𝑘2 𝐾𝑐 Fe CN 3−
6 𝐼 − 2 Fe CN 3−
6
𝜈𝑅𝐷𝑆 =
Fe CN 4−6
𝑘 Fe CN 3−
6
2 𝐼− 2
𝜈𝑅𝐷𝑆 = 4− ≡ Experimental result ∴ acceptable mechanism
Fe CN 6
 Preface
e.g., 𝐻𝐶𝑙 + 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 → 𝐶𝐻3 𝐶𝐻𝐶𝑙𝐶𝐻3 Experimentally: 𝑅𝑎𝑡𝑒 = 𝑘 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 [𝐻𝐶𝑙]3

Proposed mechanism:
𝑘1 [ 𝐻𝐶𝑙 2 ]
2𝐻𝐶𝑙 ⇌ (𝐻𝐶𝑙)2 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 (𝑓𝑎𝑠𝑡) 𝐾𝐶1 = (1)
[𝐻𝐶𝑙]2
𝑘−1 𝑘 2 [𝐻𝐶𝑙. 𝑃𝑟𝑜𝑝𝑒𝑛𝑒]
𝐻𝐶𝑙 + 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 ⇌ 𝐻𝐶𝑙. 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 (𝑓𝑎𝑠𝑡) 𝐾𝐶2 = (2)
𝑘−2 𝐻𝐶𝑙 [𝑃𝑟𝑜𝑝𝑒𝑛𝑒]
𝑘3
(𝐻𝐶𝑙)2 +𝐻𝐶𝑙. 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 → 𝐶𝐻3 𝐶𝐻𝐶𝑙𝐶𝐻3 + 2𝐻𝐶𝑙 (𝑠𝑙𝑜𝑤) 𝜈𝑅𝐷𝑆 = 𝑘3 (𝐻𝐶𝑙)2 𝐻𝐶𝑙. 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 (3)

𝐻𝐶𝑙 + 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 → 𝐶𝐻3 𝐶𝐻𝐶𝑙𝐶𝐻3 (overall reaction)

From eq. (1): 𝐻𝐶𝑙 2 = 𝐾𝐶1 [𝐻𝐶𝑙]2 (4)
From eq. (2): 𝐻𝐶𝑙. 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 = 𝐾𝐶2 𝐻𝐶𝑙 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 (5) Add eq.(4) and (5) to eq.(3):
𝜈𝑅𝐷𝑆 = 𝑘3 𝐾𝐶1 𝐾𝐶2 [𝐻𝐶𝑙]2 𝐻𝐶𝑙 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 = 𝑘 𝑃𝑟𝑜𝑝𝑒𝑛𝑒 [𝐻𝐶𝑙]3 ≡ Experimental result
10.1 Evidence for a Composite Mechanism
1. When rate law does not correspond to the stoichiometric equation.
e.g., 𝐻2 + 𝐵𝑟2 ⇌ 2𝐻𝐵𝑟
would be first order in hydrogen and first order in bromine if it were an elementary reaction
𝑘 𝐻2 𝐵𝑟2 1Τ2
Experimentally: 𝑅𝑎𝑡𝑒 = 𝑘, 𝑚: constants
1 + 𝑚 𝐻𝐵𝑟 Τ 𝐵𝑟2

2. Detection of reaction intermediates: When this can be done, a kinetic scheme must be
developed that will account for the existence of these intermediates. Sometimes these
intermediates are relatively stable substances; in other cases, they are labile substances such as
atoms and free radicals.
10.2 Types of Composite Reactions
(competition)
1. Parallel rxns (simultaneous rxns): 𝐴→𝑌 𝐴+𝐵 →𝑌
𝐴→𝑍 𝐴+𝐶 →𝑍
𝐵 𝑎𝑛𝑑 𝐶 compete for 𝐴

2. Opposing rxns: 𝐴+𝐵 ⇌𝑍

𝐴→𝑋
𝑋→𝑌
3. Consecutive rxns (in sequence): 𝐴→𝑋→𝑌→𝑍 𝑂𝑅
𝑌→𝑍
• intermediate 𝑌 may catalyze rxn 1 (positive feedback) or inhibit it (negative feedback).
• both the final product and an intermediate can contribute to feedback.
10.3 Rate Equations for Composite Mechanisms
𝑘1 𝑘2
e.g., 𝐴 𝑘−1
𝑋
𝑘−2
𝑍

4 elementary rxn’s:
𝐴→𝑋 𝜈1 𝑋→𝐴 𝜈−1 σ 𝝂𝒙 = 𝜈1 + 𝜈−2 = 𝑘1 𝐴 + 𝑘−2 𝑍
𝜈1 = 𝑘1 𝐴 𝜈−1 = 𝑘−1 𝑋 σ 𝝂−𝒙 = 𝜈−1 + 𝜈2 = 𝑘−1 𝑋 + 𝑘2 𝑋 = 𝑘−1 + 𝑘2 𝑋
𝑋→𝑍 𝜈2 𝑍→𝑋 𝜈−2
Net rate of formation of 𝑋:
𝑑𝑋
𝜈2 = 𝑘2 𝑋 𝜈−2 = 𝑘−2 𝑍 = total rate into 𝑋 − total rate out 𝑋
𝑑𝑡
Total rate into 𝑿: σ 𝝂𝒙
Note: At complete equilibrium:
Sum of rates for rxns that produce 𝑋 total rate into 𝑋 = total rate out 𝑋
Total rate out of 𝑿: σ 𝝂−𝒙
Sum of rates for rxns that remove 𝑋
10.3 Rate Equations for Composite Mechanisms
𝑘1 𝑘2
e.g., Consecutive rxn: 𝐴 𝑋 𝑍 σ 𝝂𝒙 = 𝜈1 = 𝑘1 𝐴
2 elementary rxn’s: σ 𝝂−𝒙 = 𝜈2 = 𝑘2 𝑋

𝐴→𝑋 𝜈1 𝑋→𝑍 𝜈2 Net rate of formation of 𝑋:

𝑑𝑋
= total rate into 𝑋 − total rate out 𝑋
𝜈1 = 𝑘1 𝐴 𝜈2 = 𝑘2 𝑋 𝑑𝑡
𝑑𝑋
1st order = 𝑘1 𝐴 − 𝑘2 𝑋
Integrated rate law 𝑑𝑡
𝑑𝑋
𝐴 = 𝐴 𝑜 𝑒 −𝑘1 𝑡 = 𝑘1 𝐴 𝑜 𝑒 −𝑘1 𝑡 − 𝑘2 𝑋
𝑑𝑡
integration
Equation for 𝑍:
𝐴𝑜= 𝐴 + 𝑋 + 𝑍 𝑘1
𝑍 = 𝐴𝑜− 𝐴 − 𝑋 𝑋 = 𝐴𝑜 𝑒 −𝑘1 𝑡 − 𝑒 −𝑘2 𝑡
𝑘2 − 𝑘1
𝐴𝑜
𝑍 = 𝑘2 1 − 𝑒 −𝑘1 𝑡 − 𝑘1 1 − 𝑒 −𝑘2 𝑡
𝑘2 − 𝑘1
10.3 Rate Equations for Composite Mechanisms
Variations in the concentrations of 𝐴, 𝑋, and 𝑍, for a reaction

Case 1 Case 2

typical (Steady State Approximation)

rxn (SSA)
maximum rate
𝐴 rapidly converted into
intermediate 𝑋. of 𝑍 when 𝑋 𝑋 forms slowly and disappear
is maximum rapidly (𝑋 always present in
𝑋 slowly forms 𝑍, leading
much smaller amounts than
to accumulation of 𝑋 induction period: delay reactants) therefore [𝑋] does
in 𝑍 formation with not build up 𝑑𝑋
little or no rxn initially. ⇒ ≅0
𝑑𝑡
𝐴 falls exponentially
10.3 Rate Equations for Composite Mechanisms
Steady-State Treatment
Back to Case 2: k2 ≫ k1
𝑘1 −𝑘 𝑡
𝑋 = 𝐴𝑜 𝑒 1 − 𝑒 −𝑘2 𝑡
𝑘2
After short time of the reaction, the difference 𝑒 −𝑘1 𝑡 − 𝑒 −𝑘2 𝑡 becomes ≅ 1 ∶
1 1 1 1
𝑖. 𝑒. 𝑒 −𝑘1 𝑡 − 𝑒 −𝑘2 𝑡 = − = 0− ∞ =1−0=1
𝑒 𝑘1 𝑡 𝑒 𝑘2 𝑡 𝑒 𝑒
𝑘1
so 𝑋 = 𝐴𝑜 1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑘2
After this short induction period, 𝑋 remains practically constant, making this a valid approximation:
𝑘1
𝑑𝑋 𝑑𝐴𝑜
𝑘2
= = 0 (Steady State Approximation, SSA)
𝑑𝑡 𝑑𝑡
 10.3 Rate Equations for Composite Mechanisms
𝑘1 𝑘2
e.g., Consider the mechanism 𝐴+𝐵 𝑘−1
𝑋 𝑍
What is the rate law assuming the steady-state (𝑆𝑆) treatment to be applied?
differential rate eq.’s

𝑑𝐴 𝑑𝐵
= = −𝑘1 𝐴 𝐵 + 𝑘−1 𝑋
𝑑𝑡 𝑑𝑡
𝑑𝑋 S.S. approx. 𝑑 𝑋
= 𝑘1 𝐴 𝐵 − 𝑘−1 𝑋 − 𝑘2 𝑋 = 𝑘1 𝐴 𝐵 − 𝑘−1 𝑋 − 𝑘2 𝑋 = 0
𝑑𝑡 𝑑𝑡
𝑑𝑍
= 𝜈𝑍 = 𝑘2 𝑋 … (3)
𝑑𝑡
𝑘1 𝑘2 𝐴 𝐵 add to eq.(3) 𝑘1 𝐴 𝐵
𝜈 = 𝜈𝑍 = 𝑋 =
𝑘−1 + 𝑘2 𝑘−1 + 𝑘2
𝜈 = 𝜈𝑍 = 𝑘 ′ 𝐴 𝐵
The general rate equation (rate law)
10.3 Rate Equations for Composite Mechanisms
Rate-Controlling (Rate-Determining) Steps
A rate-controlling step: a step which has a strong influence on the overall rate of the rxn. A rxn
step is often said to be rate controlling if there are rapid pre-equilibria followed by a slow step.
𝑘1 𝑘2
𝐴+𝐵 𝑘−1
𝑋 𝑍
❑ Suppose 𝑋 → 𝑍 is very rapid compared to 𝑋 → 𝐴 + 𝐵 ⇒ (𝑘2 ≫ 𝑘−1 )
𝑘1 𝑘2 𝐴 𝐵
The 𝑆𝑆 rate equation: 𝜈 = 𝜈𝑍 = becomes 𝜈 = 𝑘1 𝐴 𝐵
𝑘−1 + 𝑘2
∴(𝐴 + 𝐵 → 𝑋 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)
❑ Suppose 𝑋 → 𝑍 is very s𝑙𝑜𝑤 compared to 𝑋 → 𝐴 + 𝐵 ⇒ (𝑘2 ≪ 𝑘−1 )
𝑘1 𝑘2 𝐴 𝐵
The 𝑆𝑆 rate equation: 𝜈 = 𝜈𝑍 = becomes 𝜈 = 𝑘2 𝐾𝑐 𝐴 𝐵
𝑘−1 + 𝑘2
∴(𝑋 → 𝑍 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)
10.3 Rate Equations for Composite Mechanisms
e.g., 𝐴 + 𝐵 → 𝐶 + 𝐷(𝑙) Assume that the intermediate 𝑋 exists in a S.S., derive the general rate
equation. Write the rate equ. for the special cases of low and high 𝐵 and decide which is the
RDS in each case.
The 𝑆𝑆 equ. for 𝑋:
Proposed mechanism: 𝑑𝑋
= 𝜈𝑋 = σ 𝝂𝒙 − σ 𝝂−𝒙 = 0
𝑑𝑡 1 𝑘1 𝐴
𝑘1 𝐴 − 𝑘−1 𝑋 𝐷 𝑙 − 𝑘2 𝑋 𝐵 = 0 𝑋 =
𝑘2 𝑘−1 + 𝑘2 𝐵
𝑋+𝐵 𝐶 The general expression for the rate:
𝑘2 𝐵 𝑘1 𝐴
𝜈𝐶 = 𝑘2 𝐵 𝑋 =
𝑘−1 + 𝑘2 𝐵
1. If 𝐵 is very low: 𝜈𝐶 = 𝐾𝑐 𝑘2 𝐴 𝐵 (2𝑛𝑑 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆: 𝑋 + 𝐵 → 𝐶)

2. If 𝐵 is very high: 𝜈𝐶 = 𝑘1 𝐴 (1𝑠𝑡 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆: 𝐴 → 𝑋 + 𝐷(𝑙) )

 10.3 Rate Equations for Composite Mechanisms
e.g., For the rxn: 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− + 𝐼 − → 𝐶𝑜(𝐶𝑁)5 𝐼 3− + 𝐻2 𝑂
The proposed mechanism of this reaction is believed to go by the mechanism:
𝑘1
1. 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− ⇌ 𝐶𝑜(𝐶𝑁)2−
5 + 𝐻2 𝑂
Assume that the intermediate exists in a 𝑆𝑆 and derive
𝑘−1 the general rate equation. Write the rate equ. for the
𝑘2 special cases of low and high 𝐼 − and decide which is
2. 𝐶𝑜(𝐶𝑁)2− + −
𝐼 → 𝐶𝑜(𝐶𝑁) 5𝐼
3−
5 the RDS in each case.

The 𝑆𝑆 equ. for 𝐶𝑜(𝐶𝑁)2− 𝑑 𝐶𝑜(𝐶𝑁)2−

5 : 5
= 𝜈 𝐶𝑜(𝐶𝑁)2− = σ 𝝂𝒙 − σ 𝝂−𝒙 = 0
𝑑𝑡 5

𝑘1 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− − 𝑘−1 𝐶𝑜(𝐶𝑁)2−

5 𝐻2 𝑂 − 𝑘2 𝐶𝑜(𝐶𝑁) 2−
5 𝐼 −
=0
𝑘1 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22−
𝐶𝑜(𝐶𝑁)2−
5 =
𝑘−1 + 𝑘2 𝐼 −
𝑘1 𝑘2 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− 𝐼 −
The general expression for the rate: 𝜈𝐶𝑜(𝐶𝑁)5 𝐼3− = 𝑘2 𝐼 − 𝐶𝑜(𝐶𝑁)2−
5 =
𝑘−1 + 𝑘2 𝐼 −
10.3 Rate Equations for Composite Mechanisms
e.g., For the rxn: 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− + 𝐼 − → [𝐶𝑜(𝐶𝑁)5 𝐼]3− +𝐻2 𝑂
The proposed mechanism of this reaction is believed to go by the mechanism:
𝑘1
1. 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− ⇌ 𝐶𝑜(𝐶𝑁)2−
5 + 𝐻2 𝑂
Assume that the intermediate exists in a 𝑆𝑆 and derive
𝑘−1 the general rate equation. Write the rate equ. for the
𝑘2 special cases of low and high 𝐼 − and decide which is
2. 𝐶𝑜(𝐶𝑁)2− + −
𝐼 → 𝐶𝑜(𝐶𝑁) 5𝐼
3−
5 the RDS in each case.

𝑘1 𝑘2 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− 𝐼 −
The general expression for the rate: 𝜈𝐶𝑜(𝐶𝑁)5 𝐼3− =
𝑘−1 + 𝑘2 𝐼 −

1. If 𝐼 − is low: 𝜈𝐶𝑜(𝐶𝑁)5 𝐼3− = 𝐾𝑐 𝑘2 𝐶𝑜(𝐶𝑁)5 𝑂𝐻22− 𝐼 − (2𝑛𝑑 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)

2−
2. If 𝐼 − is high: 𝜈𝐶𝑜(𝐶𝑁)5 𝐼3− = 𝑘1 𝐶𝑜(𝐶𝑁)5 𝑂𝐻2 (1𝑠𝑡 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)
 10.3 Rate Equations for Composite Mechanisms
e.g., 𝑁2 𝑂5 + 𝑁𝑂 ⇌ 3𝑁𝑂2 Derive an equation for the rate of consumption of 𝑁2 𝑂5 .
Proposed mechanism: Write the rate equation for the special case of high 𝑁𝑂 and
𝑘1 decide the RDS in this case.
𝑁2 𝑂5 𝑁𝑂2 + 𝑁𝑂3
𝑘−1 𝑆𝑆𝐴: 𝜈𝑁𝑂3 = 𝑘1 𝑁2 𝑂5 − 𝑘−1 𝑁𝑂2 𝑁𝑂3 − 𝑘2 𝑁𝑂 𝑁𝑂3 = 0
𝑘2 𝑘1 𝑁2 𝑂5
𝑁𝑂 + 𝑁𝑂3 2𝑁𝑂2 ⇒ 𝑁𝑂3 =
𝑘−1 𝑁𝑂2 + 𝑘2 𝑁𝑂
𝑑 𝑁2 𝑂5
𝑑𝑡 = 𝜈𝑁2 𝑂5 = −𝑘1 𝑁2 𝑂5 + 𝑘−1 𝑁𝑂2 𝑁𝑂3
𝑘−1 𝑁𝑂2 𝑘1 𝑁2 𝑂5 −𝑘1 𝑘−1 𝑁2 𝑂5 𝑁𝑂2 − 𝑘1 𝑘2 𝑁2 𝑂5 𝑁𝑂 + 𝑘1 𝑘−1 𝑁𝑂2 𝑁2 𝑂5
𝜈𝑁2𝑂5 = −𝑘1 𝑁2 𝑂5 + =
𝑘−1 𝑁𝑂2 + 𝑘2 𝑁𝑂 𝑘−1 𝑁𝑂2 + 𝑘2 𝑁𝑂
−𝑘1 𝑘2 𝑁2 𝑂5 𝑁𝑂 ignore the –ve sign 𝑘1 𝑘2 𝑁2 𝑂5 𝑁𝑂
𝜈𝑁2 𝑂5 = 𝜈
in the final equ ⇒ 𝑁2 𝑂5
=
𝑘−1 𝑁𝑂2 + 𝑘2 𝑁𝑂 𝑘−1 𝑁𝑂2 + 𝑘2 𝑁𝑂
𝒅 𝑁2 𝑂5 −𝒅 𝑁2 𝑂5
≡ 𝒅𝒕
≡ 𝒅𝒕

Special case: If 𝑁𝑂 is very high ⇒ 𝜈𝑁2 𝑂5 = 𝑘1 𝑁2 𝑂5 (1𝑠𝑡 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)

10.3 Rate Equations for Composite Mechanisms
e.g., 2𝑂3 → 3𝑂2 Derive an equation for the rate of formation of 𝑂2 .
Proposed mechanism:
𝑘1
2𝑂3 𝑂3 +𝑂2 + 𝑂
𝑘2
𝑂 + 𝑂3 2𝑂2
𝜈𝑂2 = 𝑘1 𝑂3 2 + 𝑘2 𝑂 𝑂3
2
𝑆𝑆 to 𝑂: 𝜈𝑂 = 𝑘1 𝑂3 − 𝑘2 𝑂 𝑂3 = 0
𝑘1 𝑂3 2 𝑘1 𝑂3
𝑂 = = Plug in 𝜈𝑂2
𝑘2 𝑂3 𝑘2
2
𝑘1 𝑂3
𝜈𝑂2 = 𝑘1 𝑂3 + 𝑘2 𝑂3
𝑘2
𝜈𝑂2 = 2𝑘1 𝑂3 2
(1𝑠𝑡 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)
10.3 Rate Equations for Composite Mechanisms
e.g., 2NO + 𝐻2 → 𝑁2 𝑂 + 𝐻2 𝑂 Derive an equation for the rate of consumption of 𝐻2 .
Proposed mechanism: Write the rate equ. for the special cases of low and
high 𝐻2 and decide which is the RDS in each case.
𝑘1
2𝑁𝑂 𝑁2 𝑂2
𝑘−1
𝑘2
𝑁2 𝑂2 + 𝐻2 𝑁2 𝑂 + 𝐻2 𝑂

𝜈𝐻2 = −𝑘2 𝐻2 𝑁2 𝑂2 Apply 𝑆𝑆 to 𝑁2 𝑂2 ⇒

2
𝑘1 𝑁𝑂 2
𝜈𝑁2 𝑂2 = 𝑘1 𝑁𝑂 − 𝑘−1 𝑁2 𝑂2 − 𝑘2 𝑁2 𝑂2 𝐻2 = 0 𝑁2 𝑂2 = Plug in 𝜈𝐻2
𝑘−1 + 𝑘2 𝐻2
𝒅 𝑯𝟐 −𝑘1 𝑘2 𝐻2 𝑁𝑂 2 ignore the –ve sign 𝑘1 𝑘2 𝐻2 𝑁𝑂 2
≡
𝒅𝒕 𝜈𝐻2 = in the final equ ⇒ 𝜈𝐻2 =
𝑘−1 + 𝑘2 𝐻2 −𝒅 𝑯𝟐
𝑘−1 + 𝑘2 𝐻2
𝒅𝒕
≡
2
1. If 𝐻2 is low: 𝜈𝐻2 = 𝐾𝑐 𝑘2 𝐻2 𝑁𝑂 (2𝑛𝑑 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)
2. If 𝐻2 is high: 𝜈𝐻2 = 𝑘1 𝑁𝑂 2 (1𝑠𝑡 𝑠𝑡𝑒𝑝 𝑖𝑠 𝑡ℎ𝑒 𝑅𝐷𝑆)
10.3 Rate Equations for Composite Mechanisms
e.g., 2𝑁2 𝑂5 → 4𝑁𝑂2 + 𝑂2
𝜈𝑂2 = 𝑘2 𝑁𝑂3 𝑁𝑂2 Apply 𝑆𝑆 to 𝑁𝑂3
Proposed mechanism 1: 𝜈𝑂2 =? ?
𝑘1 𝜈𝑁𝑂3 = 𝑘1 𝑁2 𝑂5 − 𝑘−1 𝑁𝑂2 𝑁𝑂3 − 𝑘2 𝑁𝑂3 𝑁𝑂2 = 0
𝑁2 𝑂5 𝑁𝑂2 +𝑁𝑂3
𝑘−1
𝑘2
𝑘1 𝑁2 𝑂5
𝑁𝑂3 + 𝑁𝑂2 𝑁𝑂 + 𝑁𝑂2 +𝑂2 ⇒ 𝑁𝑂3 =
𝑘−1 + 𝑘2 𝑁𝑂2
𝑘3
𝑁2 𝑂5 + 𝑁𝑂 3𝑁𝑂2 𝑘1 𝑘2 𝑁2 𝑂5 𝑁𝑂2
⇒ 𝜈𝑂2 =
𝑘−1 + 𝑘2 𝑁𝑂2

𝑘1 𝑘2 𝑁2 𝑂5
𝜈𝑂2 = 𝜈𝑂2 = 𝛫 𝑁2 𝑂5
𝑘−1 + 𝑘2

Homework: Derive a rate eq. for 𝑁2 𝑂5 consumption, 𝜈𝑁2 𝑂5 =? ?

2𝑘1 𝑘2
Answer: 𝜈𝑁2 𝑂5 = 𝑁2 𝑂5 (need to apply 𝑆𝑆 to two intermediates 𝑁𝑂3 and 𝑁𝑂)
𝑘−1 +𝑘2
 10.3 Rate Equations for Composite Mechanisms
e.g., 2𝑁2 𝑂5 → 4𝑁𝑂2 + 𝑂2
𝜈𝑂2 = 𝑘2 𝑁𝑂3 𝑁𝑂2 Apply 𝑆𝑆 to 𝑁𝑂3
Proposed mechanism 2: 𝜈𝑂2 =? ?
𝑘1 𝜈𝑁𝑂3 = 𝑘1 𝑁2 𝑂5 − 𝑘−1 𝑁𝑂2 𝑁𝑂3 −
𝑁2 𝑂5 𝑁𝑂2 +𝑁𝑂3
𝑘−1 𝑘2 𝑁𝑂3 𝑁𝑂2 − 𝑘3 𝑁𝑂3 𝑁𝑂 = 0
𝑘2
𝑁𝑂3 + 𝑁𝑂2 𝑁𝑂 + 𝑁𝑂2 +𝑂2 𝑘1 𝑁2 𝑂5
𝑁𝑂3 = Apply 𝑆𝑆 to 𝑁𝑂
𝑘3 𝑘−1 + 𝑘2 𝑁𝑂2 + 𝑘3 𝑁𝑂
𝑁𝑂3 + 𝑁𝑂 2𝑁𝑂2
𝜈𝑁𝑂 = 𝑘2 𝑁𝑂3 𝑁𝑂2 − 𝑘3 𝑁𝑂3 𝑁𝑂 = 0
Note: elementary steps in this mechanism
add up to the overall equation by doubling ⇒ 𝑁𝑂 = 𝑘2 𝑁𝑂2 Τ𝑘3
the 1st step:

𝑘1 𝑘2 𝑁2 𝑂5 𝑁𝑂2 𝑘1 𝑘2 𝑁2 𝑂5 𝑁𝑂2
𝜈𝑂2 = 𝜈𝑂2 =
𝑘−1 + 𝑘2 𝑁𝑂2 + 𝑘3 𝑘2 𝑁𝑂2 Τ𝑘3 𝑘−1 + 𝑘2 𝑁𝑂2 + 𝑘3 𝑁𝑂

𝑘1 𝑘2 𝑁2 𝑂5
𝜈𝑂2 = ⇒ 𝜈𝑂2 = 𝛫 𝑁2 𝑂5
𝑘−1 + 2𝑘2
10.4 Rate Constants, Rate Coefficients and Equilibrium Constants
𝑘1 𝜈1 = 𝑘1 𝐴 𝐵
𝐴+𝐵 𝑘−1
𝑌+𝑍
𝜈−1 = 𝑘−1 𝑌 𝑍
𝑘1 𝑌 𝑍
At equilibrium: 𝜈1 = 𝜈−1 ⇒ 𝑘1 𝐴 𝐵 = 𝑘−1 𝑌 𝑍 ⇒ = = 𝐾𝑐
𝑘−1 𝐴 𝐵
For rxns that occur in two or more stages:
𝐻2 + 2𝐼𝐶𝑙 → 𝐼2 + 2𝐻𝐶𝑙 𝐾𝑐

𝑘1
𝐻2 + 𝐼𝐶𝑙 𝑘−1
𝐻𝐼 + 𝐻𝐶𝑙 𝐾𝑐1
𝑘2 𝐾𝑐 = 𝐾𝑐1 × 𝐾𝑐2
𝐻𝐼 + 𝐼𝐶𝑙 𝐻𝐶𝑙 + 𝐼2 𝐾𝑐2
𝑘−2

𝑘1 𝑘2 𝑘3
In General: 𝐾𝑐 = 𝐾𝑐1 𝐾𝑐2 𝐾𝑐2 … = …
𝑘−1 𝑘−2 𝑘−3
10.5 Free-Radical Reactions
❑ If a bond is homolytically split a free radical will be produced.

❑ In this process, two electrically neutral free radicals are produced.

The hydrogen atom and the hydroxyl radical are both one electron short of the noble gas
structures and, therefore, are very reactive species.

𝑘 𝐻2 𝐵𝑟2 1Τ2
e.g., 𝐵𝑟2 + 𝐻2 → 2𝐻𝐵𝑟 𝑅𝑎𝑡𝑒 = 𝑘, 𝑚: constants
1 + 𝑚 𝐻𝐵𝑟 Τ 𝐵𝑟2

Explanation?
10.5 Free-Radical Reactions
𝑘 𝐻2 𝐵𝑟2 1Τ2
e.g., 𝐵𝑟2 + 𝐻2 → 2𝐻𝐵𝑟 Experimentally: 𝑅𝑎𝑡𝑒 =
1 + 𝑚 𝐻𝐵𝑟 Τ 𝐵𝑟2
Proposed mechanism:
𝑘1
𝜈𝐻𝐵𝑟 = 𝑘2 𝐵𝑟 ∙ 𝐻2 + 𝑘3 𝐻 ∙ 𝐵𝑟2 − 𝑘4 𝐻 ∙ 𝐻𝐵𝑟 … (1)
𝐵𝑟2 2𝐵𝑟 ∙ initiation
Apply 𝑆𝑆 to the two unstable intermediates 𝐻 ∙ and 𝐵𝑟 ∙ ⇒

chain propagation
𝑘2
𝐵𝑟 ∙ + 𝐻2 𝐻𝐵𝑟 + 𝐻 ∙ 𝜈𝐻 ∙ = 𝑘2 𝐵𝑟 ∙ 𝐻2 − 𝑘3 𝐻 ∙ 𝐵𝑟2 − 𝑘4 𝐻 ∙ 𝐻𝐵𝑟 = 0 … (2)
𝑘3
𝐻∙ + 𝐵𝑟2 𝐻𝐵𝑟 + 𝐵𝑟 ∙ 𝜈𝐵𝑟 ∙ = 𝑘1 𝐵𝑟2 − 𝑘2 𝐵𝑟 ∙ 𝐻2 + 𝑘3 𝐻 ∙ 𝐵𝑟2 + 𝑘4 𝐻 ∙ 𝐻𝐵𝑟 − 𝑘−1 𝐵𝑟 ∙ 2 =0
𝑘4
∙
𝐻 + 𝐻𝐵𝑟 𝐻2 + 𝐵𝑟 ∙ we have two equations with two unknowns 𝐻 ∙ and 𝐵𝑟 ∙
𝑘−1
2𝐵𝑟 ∙ 𝐵𝑟2 termination if we add 𝜈𝐻 ∙ and 𝜈𝐵𝑟 ∙ eq.’s ⇒ 𝑘1 𝐵𝑟2 −𝑘−1 𝐵𝑟 ∙ 2 =0
𝐵𝑟 ∙ = 𝑘1 Τ𝑘−1 1Τ2 𝐵𝑟2 1Τ2 plug in eq. (2) ⇒
𝑘 𝑘 Τ 𝑘 1Τ2 𝐵𝑟 1Τ2 𝐻
∙ 2 1 −1 2 2
𝐻 = subtract eq.(2) from (1) ⇒
Experimental ≡
𝑘3 𝐵𝑟2 + 𝑘4 𝐻𝐵𝑟
2𝑘2 𝑘1 Τ𝑘−1 1Τ2
𝐻2 𝐵𝑟2 1Τ2 𝐻𝐵𝑟 inhibits the rxn (by rxn 4)
𝜈𝐻𝐵𝑟 = 2𝑘3 𝐻 ∙ 𝐵𝑟2 𝜈𝐻𝐵𝑟 = 𝐵𝑟2 reduces the amount of inhibition since
1 + 𝑘4 Τ𝑘3 𝐻𝐵𝑟 Τ 𝐵𝑟2 𝑖𝑡 competes with 𝐻𝐵𝑟 for 𝐻 ∙ (rxn 3 &4)
10.6 Photochemical Reaction
❑ Chemical reactions caused by Electromagnetic (EM) and particle radiations are classified as:
- Photochemical reactions (lower energy visible and near-UV EM radiation, no ionization).
- Radiation-chemical reactions (high-energy EM or particle radiation causing ionization).
e.g., (photochemical rxn): 𝐶𝐻3 𝐶𝑂𝐶𝐻3 + 1(ℎ𝜈) → 1𝐶𝐻3 𝐶𝑂𝐶𝐻3 ∗ → 𝐶𝑂 + 2𝐶𝐻3
❑ There is one-to-one relationship between # of absorbed photons (E𝑝ℎ𝑜𝑡𝑜𝑛 = ℎ𝜈) and # of
excited molecules for the reaction (law of photochemical equivalence):
From equation: # 𝐶𝐻3 molecules formed (per 𝑠) = # photons absorbed per 𝑠 × 2
Experimentally: actual # 𝐶𝐻3 molecules formed (per 𝑠) < theoretical (calculated) from equation
# molecules formed per unit time
% Quantum Yield Φ = × 100%
# photons absorbed per unit time
# 𝐦𝐨𝐥𝐞𝐬 molecules formed per unit time
OR % Quantum Yield Φ = × 100% Note: 1 mol photons ≡ 1.0 Einstein
# 𝐦𝐨𝐥𝐞𝐬 photons absorbed per unit time

𝑒𝑛𝑒𝑟𝑔𝑦
10.6 Photochemical Reaction
e.g., Suppose that a 60-watt lamp, operating with 100% efficiency emits radiation only at a
wavelength of 313 𝑛𝑚.
A) How many photons does it emit per second?
B) Suppose that all of radiation emitted is absorbed by heptane-4-one (ketone) and that one
product is ethene, which is formed with a quantum yield of 0.25. How much ethene is
produced in one second?

A) number of photons 𝑛𝑜𝑡𝑒: 1𝑊 = 1 𝐽/𝑠

𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 60 𝑊 60 𝑊 60 × 313 × 10−9 19

# 𝑝ℎ𝑜𝑡𝑜𝑛𝑠 = = = = = 9.45 × 10
𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 1 𝑝ℎ𝑜𝑡𝑜𝑛 ℎ𝜈 ℎ 𝑐 Τ𝜆 6.626 × 10−34 × 3 × 108 𝑝ℎ𝑜𝑡𝑜𝑛𝑠/𝑠

# molecules formed per 𝑠

B) product amount? % Quantum Yield Φ = × 100%
# photons absorbed per 𝑠

# molecules formed per 𝑠 = 𝑄𝑢𝑎𝑛𝑡𝑢𝑚 𝑦𝑖𝑒𝑙𝑑 × # photons absorbed per s

# molecules formed per 𝑠 = 0.25 × 9.45 × 1019 = 2.36 × 1019 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 = 3.92 × 10−5 𝑚𝑜𝑙
10.6 Photochemical Reaction
e.g., Uranyl oxalate is commonly used as a chemical actinometer; to determine the amount of
light emitted by a lamp in a photochemical experiment. It has been established that at a
wavelength of 300 𝑛𝑚 the quantum yield for the decomposition of uranyl oxalate is 0.570. In
a particular experiment it was found that the light of that wavelength, emitted by a lamp in one
hour, brought about the decomposition of 5.78 × 10−5 𝑚𝑜𝑙 of uranyl oxalate. When acetone
was irradiated with the lamp for 10 hours, in such a way that all of the light was absorbed, the
amount of acetone decomposed was found to be 2.32 × 10−4 𝑚𝑜𝑙. What is the quantum yield
for the acetone decomposition under those conditions?
# 𝐦𝐨𝐥𝐞𝐬 formed per ℎ𝑜𝑢𝑟
% Quantum Yield Φ = × 100%
# 𝐦𝐨𝐥𝐞𝐬 photons absorbed per ℎ𝑜𝑢𝑟
5.78×10−5 𝑚𝑜𝑙
0.570 = # moles photons = 1.014 × 10−4 𝑚𝑜𝑙/ℎ𝑟
# 𝐦𝐨𝐥𝐞𝐬 photons absorbed per ℎ𝑟

in 10 hours, 10 × 1.014 × 10−4 = 1.014 × 10−3 einsteins (moles of photons) will be absorbed
−4
since 2.32 × 10−4 𝑚𝑜𝑙 of acetone has been decomposed, the quantum yield is: 2.32 × 10 𝒎𝒐𝒍 = 0.21
1.014 × 10 −3𝒎𝒐𝒍
10.9 Catalysis
Catalyst: a substance that increases the rate of the rxn without
modifying the overall standard Gibbs energy change in the rxn.
Inhibitor: a substance that decreases the rate of reaction.
(formerly called a negative catalyst).
Substrate: The reactant in reactions involving a catalyst.
Complex: it is formed between the substrate and the catalyst.
Sometimes the catalyst changes the reaction mechanisms which
involves more than one transition state and intermediates.
Enzyme Catalyst: a class of catalysts that are responsible for
increasing the rate of many biochemical rxns in plants and animals.
10.9 Catalysis
e.g., Hydrolysis of an ester (substrate, 𝑆).
𝑆→𝑍
𝑅𝑎𝑡𝑒𝑜 vs. 𝑆 is shown in the Figure.
at low 𝑆 : rate varies linearly with 𝑆 (first-order)
at high 𝑆 : rate becomes independent of 𝑆 (zero-order)

This type of behavior was first explained in 1913 by zero-order

Michaelis and Menten:

𝑉[𝑆] 1st order

𝜈= Michaelis-Menten (𝑀𝑀) Equation
𝐾𝑚 + [𝑆]

𝑉 = 𝑘2 𝐸𝑜 𝐾𝑚 = 𝑘−1 + 𝑘2 Τ𝑘1
limiting rate Michaelis constant
(max rate)
10.9 Catalysis
𝑘1
Proposed Mechanism 1. 𝐸 + 𝑆 ⇌ 𝐸𝑆
𝑘−1 The general expression for the rate:
𝑘2
2. 𝐸𝑆 → 𝐸 + 𝑍 ⇒ 𝜈𝑍 = 𝑘2 𝐸𝑆
𝑘1 𝐸 𝑆
𝑆𝑆 𝑡𝑜 𝐸𝑆: 𝜈𝐸𝑆 = 𝑘1 𝐸 𝑆 − 𝑘−1 𝐸𝑆 − 𝑘2 𝐸𝑆 = 0 𝐸𝑆 = Plug in 𝜈𝑍
𝑘−1 + 𝑘2
𝑘1 𝑘2 𝐸 𝑆 𝑘1 𝐸 𝑆
𝜈𝑍 = but 𝐸 𝑜 = [𝐸] + 𝐸𝑆 𝐸 𝑜 = [𝐸] +
𝑘−1 + 𝑘2 𝑘−1 + 𝑘2
𝑘1 𝑆 𝐸𝑜 𝑘1 𝑘2 𝐸 𝑆𝑜
𝐸 𝑜 = 𝐸 1+ 𝐸 = 𝜈𝑍 =
𝑘−1 + 𝑘2 𝑘1 𝑆 𝑘1 𝑆
1+ 𝑘−1 + 𝑘2 1+
𝑘−1 + 𝑘2 𝑘−1 + 𝑘2
𝑘1 𝑘2 𝐸 𝑜 𝑆 𝑘2 𝐸 𝑜 𝑆 𝑉[𝑆]
𝜈𝑍 = 𝜈𝑍 = 𝜈=
𝑘−1 + 𝑘2 + 𝑘1 𝑆 𝑘−1 + 𝑘2 Τ𝑘1 + 𝑆 𝐾𝑚 + [𝑆]

𝑉 = 𝑘2 𝐸 𝑜 𝐾𝑚 = 𝑘−1 + 𝑘2 Τ𝑘1
10.9 Catalysis
𝑉[𝑆] 𝑉 = 𝑘2 𝐸 𝑜
𝜈=
𝐾𝑚 + [𝑆] 𝐾𝑚 = 𝑘−1 + 𝑘2 Τ𝑘1
Limiting cases:
𝑉𝑆
1) 𝐾𝑚 ≫ 𝑆 → 𝜈 = = 𝑘′ 𝑆
𝐾𝑚
the kinetics are first order in 𝑆. (no RDS)

𝑉𝑆
2) 𝐾𝑚 ≪ 𝑆 → 𝜈 = =𝑉
𝑆
the kinetics are zero order in 𝑆. (2nd step is the RDS)
𝑉
3) 𝐾𝑚 = 𝑆 → 𝜈 = 2

∴ 𝐾𝑚 (The Michaelis constant) is the substrate conc.

𝑆 at which the rate is one-half the limiting rate 𝑉
10.9 Catalysis
e.g., The following data apply to an enzyme-catalyzed reaction:
[S]/mol dm-3 Rate, 𝜈/mol dm-3s-1
2.5 × 10 -4 2.3 × 10-4
5.0 × I 0-3 7.8 × 10-4
The concentration of the enzyme is 2 𝑔. 𝑑𝑚−3 and its molecular weight is 50000. Assume the 𝑀𝑀 equation
to apply and calculate the Michaelis constant 𝐾𝑚 , the limiting rate, 𝑉 and the rate coefficient 𝑘2 .
𝑉[𝑆] 𝑉 2.5 × 10−4
𝜈= 2.3 × 10−4 = … … (1)
𝐾𝑚 + [𝑆] 𝐾𝑚 + 2.5 × 10−4
𝑉 5.0 × 10−3
𝑉 = 𝑘2 𝐸 7.8 × 10−4 = … … (2)
𝑜 𝐾𝑚 + 5.0 × 10−3
This is easily solved after cross-multiplication and leads to
𝐾𝑚 = 7.20 × 10-4 mol dm-3 𝑉 = 8.92 ×10-4 mol dm-3 s-1
2 𝑔 𝑑𝑚−3
The molar concentration of the enzyme, 𝐸 𝑜 , is 𝐸𝑜= −1
= 4 × 10−5 𝑚𝑜𝑙 𝑑𝑚−3
50000 𝑔 𝑚𝑜𝑙
𝑉 8.92 × 10−4 −1
𝑘2 = = = 22.3 𝑠
𝐸𝑜 4.0 × 10−5