Chemical Kinetics

Chem 36
Spring 2002

What is it?
ØThermo: Could the reaction happen?
ØKinetics: How does the reaction happen?
Two Goals of Kinetics:
1. Determine the reaction pathway (Mechanism)
üWhat steps are involved in the reaction?

2. Control the Rate of the reaction

ØExample: CO (g) + NO (g) → CO2 (g) + ½N2 (g)
üThermodynamically favored, but is slow
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 Reaction Rates
Ø Let’s look at this reaction:
2N2O5 (g) → 4NO2 (g) + O2 (g)
0.16 Average Decomposition Rate =
-∆[N2O5] = -(0.11 - 0.16) = 8.3 x 10-4
∆t 60 - 0 mol/L-s
[N 2O5], mol/L

0.11

Instantaneous Rate:
Intial rate As ∆t → 0, rate becomes:

0
-d[N2O5] Slope at any
0 60 120 180 240 dt time t
Time, s 3

Rate Laws
Ø Reaction rate varies with [N2 O5]:

Linear relationship:
u
Rate = k[N2O5]
Rate, mol/L-s

u
u
u Rate constant (slope of line)
u
k = rate = 0.056 mol/L-min
[N2O5] 0.160 mol/L
k = 0.35 min-1
[N 2O5], mol/L
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Rate Laws - In General
Ø For any reaction:
aA + bB → products
We can write:
Rate = k[A]m[B]n

üm + n = overall rxn order

m = order of A in rxn
üm and n ≠ a and b
üProducts play no role in
rate of reaction
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The Method of Initial Rates

Ø One way to determine values for m and k
Ø Example: Decomposition of acetaldehyde
CH3CHO (g) → CH4 (g) + CO (g)

Rate Law: Rate = k[CH3CHO]m

Method:
ØMeasure initial rate for reactions having different
[CH3CHO]

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Data and Data Crunching
[CH3CHO] 0.10 0.20 0.30 0.40 mol/L
Initial Rate 0.18 0.72 1.6 2.9 mol/L-s
Find Order (m)
For any two data points:
Rate1 = k[CH3CHO]1m = ([CH3CHO]1)m
Rate2 k[CH3CHO]2m ([CH3CHO]2)m

0.18 = (0.10/0.20)m ] 1/4 = (1/2)m m = 2

0.72
How does one solve for m?
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What about k ?
ØSolve for k:
For any data point:

Rate = k[CH3CHO] 2

k= Rate = 0.18 mol/L-s = 18. L/mol-s

[CH3CHO] 2 (0.10 mol/L)2

ü Knowing m and k, Rate at any concentration can

be predicted
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 How does Reactant
Concentration vary with Time?
Depends on the reaction order:
Integrated Rate Laws
Ø Zero-th Order Reactions
• Rate is independent of concentration:
Rate = k[A]0 = k

[A] [A]t = -kt + [A]0

slope y-intercept
0
Time 9

First-Order Reactions
For the reaction: A → products
Rate = k[A]1
Using a bit of calculus:

Log[A]t = -(k/2.303)t + Log[A]0

NOTE: Reaction rate

Log[A] decreases with time, so that
[A] never reaches zero at any
finite time t.

Time 10

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 1st-Order Reaction Example
Ø Decomposition of hydrogen peroxide:
2H2O2 (l) → 2H2O (l) + O2 (g)
m=1 k=0.0410 min-1

If we start with 0.500 mol/L H2O2, what will

[H2O2] be after 10.0 min?
Plug into 1st-order integrated rate equation:
Log[H2O2]10 min = -(0.0410 min-1/2.303)(10.0 min) + Log(0.500 M)

Log[H2O2]10 min = -0.479

[H2O2]10 min = 0.332 mol/L
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More 1st-Order
How long will it take for [H2O2] to drop to 0.100 M ?

Solve integrated rate law for t :

t = (2.303/k)Log([A]0/[A]t)

Substituting and solving:

t = (2.303/0.0410 min-1) Log (0.500/0.100)
t = 39.3 minutes

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Special Case
How long will it take for half of the H2O2 to react?

t = (2.303/k) Log (2.00) = 16.9 min

For any 1st-order reaction:

t½ = 0.693/k

Half-Life
Time to halve the
concentration is a
constant!
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2nd-Order Reactions
For the reaction: A → products
Rate = k[A]2
Again, with the help of a bit of calculus:

1/[A]t = kt + 1/[A]0

1/[A]

Time 14

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Determining m and k
ØFinding m
Which plot is linear?
[A] vs. t? → m=0
Log[A] vs. t? → m=1
1/[A] vs. t? → m=2
ØFinding k
m = 0 → k = -slope ([A] vs. t plot)
m = 1 → k = -2.303 x slope (Log[A] vs. t plot)
m = 2 → k = slope (1/[A] vs. t plot)
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How do reactions happen?

ØCollision Theory
Reactions take place as a result of
collisions between reactants
Example:
CO (g) + NO2 (g) → CO2 (g) + NO (g)
Rate = k[CO][NO2]
üDoubling [CO] or [NO2] will double reaction rate
üWHY?
Doubling number of reactant species will double
collision frequency 16

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 Not All Collisions
Result in a Reaction
ØMust Be Above a Threshold Energy
üKinetic Energy of reactants must exceed
the Activation Energy (Ea )
• For our example reaction: Ea = 132 kJ/mol

üEa is:
• Independent of temperature
• Independent of concentration
• Always a positive value

üFraction of reactants with K.E. > Ea is

often small
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Sufficient Energy is
Not Enough
Ø Colliding reactants must have proper
orientation in order to react
ü Must be oriented so as to form an
activated complex that will breakup into
products

v Reaction Rate depends on:

1. Collision Frequency
2. Fraction of activated species
3. Geometric Probability 18

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 Activated Complex:
Reaction Pathway unstable, high-
energy transition
state

O≡
≡C . . O. . N=O

Ea = 132 kJ/mol
Energy

CO + NO 2

∆E = -226 kJ/mol

CO 2 + NO

Reaction Coordinate 19

Catalysts
Ø Substances which
increase reaction
rate but are not
changed/consumed
by the reaction
∆E
Ø How? Provide a
reaction pathway
with a lower Ea:

Note: ∆E is unaffected by the catalyst

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 Catalysts: Example
n Catalytic Converters
CO + hydrocarbons → CO2 + H2 O
NO + NO2 → N2 + O2

ü Use Pt and Rh (deposited onto Al2O3 honeycomb)

as catalysts
ü Heterogeneous Catalysis
ü Pb “poisons” catalyst (must use unleaded gasoline)

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Catalysts: Another Example

ØCombustion:
C12H22O11 + 12O 2 → 12CO2 + 11H2O
üVery slow reaction
at body temperature
(37 oC)

üEnzymes act as
catalysts and speed
up reaction:

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 What’s This?
ØJersey
ØGuernsey
ØAngus
ØBrahman
ØTexas Longhorn
ØBrown Swiss
ØHolstein
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Effect of Temperature

Ø Increasing
temperature,
increases
fraction of
reactants with
K.E. > Ea

Rule of Thumb: Rxn rate doubles for every 10 oC increase

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 The Arrhenius Equation
n Allows us to quantify the effect of
temperature on rate constant:

Lnk = -(Ea/R)(1/T) + LnA

Arrhenius Constant
Rate (function of collision
constant frequency and steric
factors)
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Graphical Analysis
Ø Plot Lnk
versus 1/T:

Slope = -Ea/R

Alternately
(for 2 values):
Ln(k2/k1) = (Ea/R)(1/T1 - 1/T2)
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 Reaction Mechanisms
Ø 3-Step Process
1. Propose a Mechanism
Ø Sequence of elementary reactions which sum to
the total reaction
2. Determine Rate Law from Mechanism
Ø Rate Law for any elementary reaction:
aA + bB → products Rate = k[A]a[B] b
3. Compare Rate Law with Experiment
Ø Assess plausibility of the mechanism
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An Example
H2 (g) + I 2 (g) → 2HI (g)
Proposed Mechanism: Single-Step
üReaction proceeds as written: bimolecular

üRate = k[H2][I2]
üRate Law agrees with experiment 28

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Another Mechanism
Ø A 2-Step Mechanism:
1. Iodine Dissociates (unimolecular process)
k1

I2 D 2I rapid, equilibrium
k-1
Reactive Intermediate

2. Iodine atoms combine with H2 (termolecular)

k
2I + H2 →
2
2HI slow

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Rate Law from Mechanism

ØSlow Step determines the rate:
Rate = k2[H2][I]2
From Step 1: Fwd Rate = Rev Rate (equilibrium)

k1[I2] = k-1[I] 2
Solve for [I]2: [I] 2 = (k1/k-1)[I2]

Substitute: Rate = k2k1 [H2][I2]

k-1
Finally: Rate = k[H2][I2] agrees with expt.
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YAM (yet another mechanism)
ØA 3-Step Mechanism:
1. Iodine Dissociates (unimolecular process)
k1
I2 D 2I rapid, equilibrium
k-1

2. Displacement
k2
I + H2 → HI + H slow

3. Combine Remaining Atoms

k3
H + I → HI fast
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On to the Rate Law

Ø From the slow displacement step:
Rate = k 2[I][H2]
From Step 1: Fwd Rate = Rev Rate
(equilibrium)
Does NOT agree with
k1[I2] = k-1 [I] 2 experiment!
MECHANISM 3 is not
plausible.
Solve for [I]: [I] = {(k1/k-1)[I2]}½

Substitute: Rate = k2(k1/k-1 )½[I2]½[H2]

Finally: Rate = k[H2][I2]½

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Which Mechanism is Correct?
ØMechanisms I and II are both plausible
(rate laws are consistent with experiment)

üDo additional experiments:

look for the reactive intermediate
(evidence for the existence of I?)

üResults?
ðEvidence favors Mechanism II
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