Chemical Kinetics

Chemical kinetics is the study of the rate (speed) at

which chemical reactions occur
Rate of reactions
The rate of a chemical reaction is expressed in terms of
the change in amount of reactants or products with time
Rate = Change in concentration
Time taken for change
[A]final - [A]initial Δ [A]
= =
tfinal - tinitial Δ time
where, [A] is the concentration of the substance, t is time
 The relation between concentration and reaction time

 Concentration of reactants are reduced over time

 Concentration of products are increased over time
 The rate is the slope of the tangent at time, t

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 The relation between rate and reaction time

 The rate of forward reaction decreases over time

 The rate of reverse reaction increases over time
 At equilibrium, the rate of reactants = rate of products
Reaction rate and stoichiometry
Consider the generic equation
aA  bB
(Reactant A is used up) (Product B is formed)
 Rate of reduction of reactant A

[A]final - [A]initial [A]t - [A]o d[A]

RA = = = -
t final - t initial t dt
where [A] is the concentration of A
t is time
the (-ve) sign shows decrease in value

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 Rate of increase of product B
RB = [B]final - [B]initial = + d[B]
t final - t initial dt
where, [B] is the concentration of B
the (+ve) sign shows increase in value
 The overall rate of reaction
R = - 1 d[A] = + 1 d[B]
a dt b dt

 For complex reactions

aA + bB  cC + dD
Overall rate, R = - 1 d[A] = - 1 d[B] = + 1 d[C] = + 1 d[D]
a dt b dt c dt d dt

Sample problems
(a) For a generic reaction: 2A + B  C + 3D, the
reduction rate of A is 2.6x10-4 M s-1. Determine
(i) the rate of reaction
(ii) the rate of formation of D
(iii) the time for A to reduce from 0.5 M to 0.49 M

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Solution

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(b) The rate of reaction for A + B  2C is 2.5x10-5 Ms-1.
The initial concentration of A is 0.5 M. Determine
(i) the rate of formation of C
(ii) the concentration of A after 1 minute
Solution

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Rate Law and rate constant
The rate law expression of a generic reaction
A + B  Products
is written as Rate = k[A]x [B]y
where, k is the rate constant
x is the order with respect to reactant A
y is the order with respect to reactant B
(x+y) is the overall order of the reaction
(Rate laws are determined by experiment and are not
related to stoichiometry of a reaction)
Determination of rate law from experimental data
The rate law of a reaction can be determined using initial
concentration of reactants and the rate of reaction
Consider the the following experiment at 600 K
2NO(g) + Br2(g)  2NOBr
where the following data was collected:
Experiment [NO](M) [Br2](M) Rate (M s-1)
1 0.10 0.10 12
2 0.10 0.20 24
3 0.20 0.10 48
4 0.30 0.10 108

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 Determining the rate law and reaction order
Rate law: Rate = k[NO]x[Br2]y
Compare rates for 1 and 2 to solve for y
Rate 2 k(0.1) x (0.2)y 24 (0.2)
y
=  = y
Rate 1 k(0.1) x (0.1)y 12 (0.1)
2 = 2y  ln2 = y ln2  y = 1
Compare rates for 1 and 3 to solve for x
Rate 3 k(0.2) x (0.1)y 48 (0.2) x
  =
Rate 1 k(0.1) x (0.1)y 12 (0.1) x
4 = 2x  ln4 = x ln2  x = 2
The rate Law: R = k [NO]2[Br2]
The order of reaction = (2 + 1) = 3
 Determining the rate constant
Substitute data into rate law expression, solve for k
R = k[NO]2[Br2]
For experiment 1:
12 M s-1 = k(0.1)2(0.1)
 k = 1.2x104 M-2 s-1

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 Determining the rate at a given concentration
What will the rate of reaction be when [NO] = 0.013 M
and [Br2] = 0.075 M ?
Rate = k[NO]2[Br2]
= 1.2x104 M-2 s-1[0.013 M]2 [0.075] = 0.15 M s-1
Order of reactions
(Discussion is limited to 3 types of reactions based on a
single reactant)
 First order reaction

d[A] 1
Rate = k[A]   = [A]  d[A] = -kdt
dt [A]
[A t ]
1 t
  d[A]   k  dt
[A o ] [A] to

 Rate equation: ln[A]t - ln[A]o  - kt ...(1)

 [A]t 
or ln   -kt
 [A]o 
where, [A]t = concentration at time (t)
[A]o = Initial concentration
k = rate constant
t = time of reaction

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 Other ways of stating 1st order rate equations:
ln (a-x) - ln (a) = - kt ...(2)
where, a = [A]o and x = [products]
ln (PA)t - ln (PA)o = - kt ...(3)
where, PA  partial pressure of gases
 ln [A]t versus t plot is linear with slope = -k

 Half-life, t1/2 is the time required for the concentration

of the reactant to be reduced by ½ its original amount
The half-life is the time
- calculated by substituting 1/2[A]o into [A]t in the
 [A]t 
equation: ln   -kt
 [A]o 
- determined at ½[A]o of the [A]t versus time plot

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  [A]t   1/2[A]o 
(i) ln   -kt  ln   k = t1/2
 [A]o   [A]o 
0.693
t1/2 =
k
(ii)

 Second order reaction

Rate = k[A]2
1 1
 Rate Equation:   kt ...(4)
[A]t [A]o
1
 Half-life, t1/2 =
k[A]o
(t1/2 depends on [A]o : when[A]o is high t1/2 is lower)

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 1
 against t plot is linear with slope = +k
[A]t

 Zero order reaction

The reactions for which the change in the reaction is
unaffected by the concentration
Rate = k[A]0
 Rate equation: [A]t - [A]o = –kt ...(5)
[A]o
 t½ =
2k
 [A]t against t plot is linear with slope = -k

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Sample problem
The rate constant for the decomposition of N2O5 is
5.1x10–4 s–1 at 318 K. The reaction is 1st order with
respect to N2O5
2N2O5(g)  4NO2(g) + O2(g)
(a) What is the rate law expression?
(b) If the initial concentration of N2O5 is 1.0x10–2 mol L-1,
what will the concentration be after 10.0 minutes?

Solution

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Determination of order and k using rate equations
 Mathematical method
Consider the experiment where the concentration of
products are given in the following table:
Time (minutes): 0 4 6 10 15 20
(a-x) (M): 8.04 5.30 4.58 3.50 2.74 2.22
(i) Prove that the reaction is second order
(ii) Determine the rate constant
Solution
(i) Assume, (a-x) = [A]t and (a) = [A]o
1 1 1 1
For 2nd order: = + kt  = + kt
[A]t [A]o (a - x) (a)
1 1 1
 k= (  )
(t - t o ) [a - x]t [a]o
Calculate and compare the values of k for each time:
1 1 1
After 4 minutes: k1 = (  )  1.6x10-2
(4 - 0) (5.30) (8.04)
1 1 1
After 6 minutes: k2 = (  )  1.6x10-2
(6 - 0) (4.58) (8.04)
1 1 1
After10 minutes: k3 = (  )  1.6x10-2
(10 - 0) (3.50) (8.04)

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The rate constants are equal (or almost equal) to each
other, a proof that the reaction is 2nd order
(k1  k 2  k 3 )
(ii) k = = 1.6x10-2 M-1 min-1
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 Graphical method
Consider the dimerization reaction: 2C4H6(g)  C8H12(g)
The concentration of C4H6 at time intervals, t was
determined as follows:
[C4H6] (M) Time (s)
0.01000 0
0.00625 1000
0.00476 1800
0.00370 2800
0.00313 3600
0.00270 4400
0.00241 5200
0.00208 6200
(i) Determine the order of the reaction
(ii) What is the value of the rate constant?
(iii) What is the half-life of the reaction?
Solution
(i) Calculate ln[C4H6] and (1/[C4H6]), then plot (ln[C4H6])
versus time and (1/[C4H6]) versus time

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 [C4H6] (M) 1/[C4H6] (M-1) ln [C4H6] Time (s)
0.01000 100 -4.605 0
0.00625 160 -5.075 1000
0.00476 210 -5.348 1800
0.00370 270 -5.599 2800
0.00313 320 -5.767 3600
0.00270 370 -5.915 4400
0.00241 415 -6.028 5200
0.00208 481 -6.175 6200
Plot ln[C4H6] against time

Plot (1/[C4H6]) against time

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Conclusion: The reaction is second order because
(1/[A]o) versus time gives a linear graph with a (-ve)
slope (characteristic of a second order reaction)
(ii) k = slope of the second graph:
Δ y Δ (1/[C 4H6 ])
Slope = = = 6.25x10-2 M-1 s-1
Δx Δt
1
(iii) Half-life, t1/2 =
k[A]o
1
=  2 1 -1
= 1600 s
(6.25x10 M s )(0.01 M)

Factors influencing rates of reactions

The ‘Collision theory’ states that for molecules to react,
they must
 experience effective collision
 have the right amount of energy
 have the right geometry
The following factors influence the rate of reactions:
 Concentration: Increasing the concentration (of
gases and solutions) allows for more collisions and
more correct geometry

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 Temperature: Increasing the temperature increases
the frequency and energy of collision
Activation energy (Ea) is the minimum collision
energy required for a reaction to occur

 Catalyst: A catalyst lowers the activation energy, thus

molecules collide at a lower minimum energy
A catalyst is a substance that increases the rate of
chemical reaction but is not consumed by the reaction

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 Surface area of solids: Increasing the surface area
(of solids) allows for more contact between reacting
materials (gives molecules the right geometry)
The Arrhenius equation
The relation between frequency of collision, activation
energy and rate constant is given by the Arrhenius
equation
E
k = Ae-(Ea/RT) or ln k = ln A - ( a )
RT
where, A = the frequency/collision factor
Ea = Activation Energy
R = 8.314 J mol-1 K-1
T = Temperature (Kelvin)
A more useful form of the Arrhenius equation:
 k 2   Ea  1 1 
ln     
 k1  R  T2 T1 
 k 2  Ea  T2  T1 
 ln    
 k1  R  T1xT2 
where, k2 = rate constant at T2
k1 = rate constant at T1

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The ln k versus (1/T) plot is linear with slope = (-Ea/R)

Sample problems
(a) Consider the following reaction:
2N2O5(g)  4NO2(g) + O2(g)
The rate constant at 318 K is 5.1x10-4 s-1 and the
activation energy for reaction is 100 kJ mol-1. What
is the value of the rate constant at 400 K?
Solution

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(b) The following data was determined for a generic
second order reaction at 30oC and 35oC:
A(g)  B + C
t1/2 is 60 minutes at 30oC and 30 minutes at 35oC
P oA = 0.1 atm
Calculate (i) Ea and (ii) A
Solution

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Reaction mechanism
Chemical reactions proceed by a set of steps called the
reaction mechanism
The slowest step in the mechanism (called the rate
determining step) determines the overall reaction
eg. Step 1: 2NO(g) + H2(g)  N2O(g) + H2O(g) [Slow]
Step 2: N2O(g) + H2(g)  N2(g) + H2O(g) [Fast]
Overall rxn: 2NO(g) + 2H2(g)  N2(g) + 2H2O(g)
N2O is the intermediate (unstable) in the reaction
and it does not appear in the overall reaction
The rate law for an elementary step (that describes an
actual collision which occurs between reacting
molecules) is based on the coefficients of species

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