Mechanisms and the Rate Equation Questions

Rate Equations & Mechanisms

Rate Equations Worksheet

1. Deduce Equations from Mechanisms

Write the overall equation and deduce the rate equation for the following reactions, given their mechanisms.
a)
A + B → C (Slow) C + A → D (Fast)

Overall Equation: 2A + B → D

Rate Equation: Rate = k [A] [B]

b)
A + B → C (Fast) C + A → D (Slow)

Overall Equation: 2A + B → D

Rate Equation: Rate = k [A]2 [B]

c)
X + Z → G (Slow) G + Y → F + Z (Fast)

Overall Equation: X + Y → F
(Note: Z is a catalyst as it is used and regenerated; G is an intermediate).

Rate Equation: Rate = k [X] [Z]

d)
X + Z → G (Fast) G + Y → F + Z (Slow)

Overall Equation: X + Y → F

Rate Equation: Rate = k [X] [Z] [Y]

e)
2X → Y (Slow) Y + Z → H + I (Fast)

Overall Equation: 2X + Z → H + I

Rate Equation: Rate = k [X]2

2. Suggest Mechanisms from Rate Data

Suggest a mechanism for the following reactions, given their equations and their rate equations.
a)
A + 2B → C + D Rate = k [A] [B]
Step 1 (Slow)
A + B
AB
Step 2 (Fast)
AB + B
C + D

Note: Any intermediate letter can be used instead of ‘AB’.

b)
A + 2B → C + D Rate = k [A] [B]2
Step 1 (Fast)
A + B
AB
Step 2 (Slow)
AB + B
C + D
c)
2E + 2F → G + 2H Rate = k [E] [F]
Step 1 (Slow)
E + F
EF
Step 2 (Fast)
EF + F
EFF
Step 3 (Fast)
EFF + E
G + 2H

Note: There are many valid options here, as long as the first slow step involves one E and one F.

d)
2E + 2F → G + 2H Rate = k [E]2 [F]
Step 1 (Fast)
E + F
EF
Step 2 (Slow)
EF + E
E2F
Step 3 (Fast)
E2F + F
G + 2H
e)
2E + 2F → G + 2H Rate = k [E]2
Step 1 (Slow)
2E
E2
Step 2 (Fast)
2F
F2
Step 3 (Fast)
E2 + F2
G + 2H

Other options exist, for example:

Step 1 (Slow)
2E
E2
Step 2 (Fast)
E2 + F
E2F
Step 3 (Fast)
E2F + F
G + 2H
f)
X + Y → F Rate = k [X]
Step 1 (Slow)
X
Intermediate
Step 2 (Fast)
Intermediate + Y
F
g)
X + Y → F Rate = k [X] [Z]
Step 1 (Slow)
X + Z
XZ
Step 2 (Fast)
XZ + Y
F + Z

(Z acts as a catalyst).

h)
X + Y → F Rate = k [X] [Y] [Z]
Step 1 (Fast)
X + Z
XZ
Step 2 (Slow)
XZ + Y
F + Z

3. Real World Mechanisms

Suggest a mechanism for the following real-world reactions, given their equation and their rate equations.
a)
NO2 + CO → NO + CO2 Rate = k [NO2]2
Step 1 (Slow)
2NO2
N2O4 (or NO + NO3)
Step 2 (Fast)
N2O4 + CO
NO + CO2 + NO2
b)
2NO + 2H2 → N2 + 2H2O Rate = k [NO]2 [H2]
Step 1 (Fast)
2NO
N2O2
Step 2 (Slow)
N2O2 + H2
N2O + H2O
Step 3 (Fast)
N2O + H2
N2 + H2O
c)
CCl(CH3)3 + OH → C(OH)(CH3)3 + Cl Rate = k [CCl(CH3)3]
Step 1 (Slow)
CCl(CH3)3
+C(CH3)3 + Cl
Step 2 (Fast)
+C(CH3)3 + OH
C(OH)(CH3)3
d)
CH3CH2Cl + OH → CH3CH2OH + Cl Rate = k [CH3CH2Cl] [OH]

It is a single step mechanism (SN2) so it is the same as the equation above.

CH3CH2Cl + OH
CH3CH2OH + Cl