Reaction order

• The rate law can be written in a generalized form:

v = k [A]a[B]b….
where a is the order of the reaction with respect to the
species A, and b is the order of the reaction with respect to the
reagent B.

• The reaction order is (a + b +… . ).

• The order of a chemical reaction needs not to be an integral. Certain

reactions do not have an overall order !!!

Example 1: v = k [A]1/2[B]1
Example 2: v = k (zero order reaction, such as ……)

• How to determine the unit of k?

 Determination of the rate law
• Isolation method:
v = k [A]a[B]b -----> v = k’[B]b

• Method of initial rates (often used in conjunction with the isolation

method):
v = k [A]a
at the beginning of the reaction
v0 = k [A0]a
taking logarithms gives:
logv0 = log k + a log[A0]
therefore the plot of the logarithms of the initial rates against the
logarithms of the initial concentrations of A should be a straight line
with the slope a (the order of the reaction).
Self-test 22.3: The initial rate of a reaction depended on the
concentration of a substance B as follows:
[B]0/(mmol L-1) 5.0 8.2 17 30
v0/(10-7 mol L-1s-1) 3.6 9.6 41 130
Determine the order of the reaction with respect to B and
calculate the rate constant.
Solution:
Log([B]0) -2.30 -2.086 -1.770 -1.523
Log(v0) -6.444 -6.018 -5.387 -4.886
0
-2.5 -2 -1.5 -1 -0.5 0

-1

-2

-3

Series1

-4

-5

-6

-7
 22.3 Integrated rate law
• First order reaction:
A  Product
d [ A]
  k[ A]
dt
The solution of the above differential equation is:
 [ A] 
ln     kt
 [ A] 0 

or: [A] = [A]0e-kt

• In a first order reaction, the concentration of reactants decreases

exponentially in time.
Self-test 22.4: In a particular experiment, it was found that the concentration
of N2O5 in liquid bromine varied with time as follows:
t/s 0 200 400 600 1000
[N2O5]/(mol L-1) 0.110 0.073 0.048 0.032 0.014
confirm that the reaction is first-order in N2O5 and determine the rate constant.

Solution: To confirm that a reaction is first order, plot ln([A]/[A]0) against

time and expect a straight line:
t/s 0 200 400 600 1000
ln([A]/[A]0) 0 -0.410 -0.829 -1.23 -2.06

0
0 200 400 600 800 1000 1200

-0.5

-1

Series1

-1.5

-2

-2.5
 Half-lives and time constant
• For the first order reaction, the half-live equals:
ln 2
t1 / 2 
k

therefore, is independent of the initial concentration.


• Time constant, , the time required for the
concentration of a reactant to fall to 1/e of its initial value.
1
 
k

for the first order reaction.

 Second order reactions
• Case 1: second-order rate law: d [ A]   k[ A]2 (e.g. A → P)
dt

• Can one use A + A → P to represent the above process?

• The integrated solution for the above function is:

1 1
  kt
[ A] [ A]0
or
[ A]0
[ A] 
1  kt[ A]0

• The plot of 1/[A] against t is a straight line with the slope k.

1
t1 / 2 
k[ A]0
 d [ A]
• Case 2: The rate law   k[ A][ B ] (e.g. A + B → Product)
dt

• The integrated solution (to be derived on chalk board) is :

 [ B] /[ B]0 
ln    ([ B]0  [ A]0 )kt
 [ A] /[ A] 0 
22.4 Reactions approaching equilibrium
Case 1: First order reactions:
A → B v = k [A]
B → A v = k’ [B]
the net rate change for A is therefore
d [ A]
  k[ A]  k '[ B]
dt
if [B]0 = 0, one has [A] + [B] = [A]0 at all time.
d [ A]
dt
  k[ A]  k '([ A]0  [ A])   (k  k ' )[ A]  k '[ A]0
the integrated solution for the above equation is
[A] =  k '  ke ( k  k ') t 
 [ A]0
 k  k' 
As t → ∞, the concentrations reach their equilibrium values:
[A]eq = k '[ A]0 [B]eq = [A]0 – [A]eq = k[ A] 0

k  k' k  k'
 [ B ]eq
• The equilibrium constant can be calculated as K = [ A]eq

k
thus: K
k'

• In a simple way, at the equilibrium point there will be no net change

and thus the forward reaction will be equal to the reverse reaction:
k[A]eq = k’ [B]eq
thus [ B]eq k

[ A]eq k'

the above equation bridges the thermodynamic quantities and

reaction rates through equilibrium constant.

• For a general reaction scheme with multiple reversible steps:

k1 k2
K '
 '  ...
k1 k2
 Determining rate constants with
relaxation method
• After applying a perturbation, the system (A ↔ B) may have a new
equilibrium state. Assuming the distance between the current state and the
new equilibrium state is x, one gets
[A] = [A]eq + x; [B] = [B]eq - x;
d [ A]
  k a ( x  [ A]eq )  kb ([ B]eq  x)  (k a  kb ) x
dt

Because d [ A] dx one gets dx/dt = - (ka + kb)x


dt dt

therefore

x  x0 e t / 1
 ka  kb


 is called the relaxation time

Example 22.4: The H2O(l) ↔ H+(aq) + OH-(aq) equilibrium relaxes in 37 μs at
298 K and pKw = 14.0. Calculate the rate constants for the forward and
backward reactions.

Solution: the net rate of ionization of H2O is

d [ H 2 O]
 k 1 [ H 2 O]  k 2 [ H  ][OH  ]
dt
we write
[H2O] = [H2O]eq + x; [H+] = [H+]eq – x; [OH-] = [OH-]eq – x
and obtain: dx
dt
 

  k1  k 2 ([ H ]eq  [OH  ]eq ) x  k1 [ H 2 O]eq  k 2 [ H  ]eq [OH  ]eq  k 2 x 2

Because x is small, k2x2 can be ignored,

so 1


 
 k1  k 2 ([ H ]eq  [OH ]eq ) 
Because k1[H2O]eq = k2[H+]eq[OH-]eq at equilibrium condition

k1 [ H ]eq [OH ]eq

K w (mol L1 ) 2
 = = Kw
mol L1
k2 [ H 2 O ]eq [ H 2 O ]eq 55.6

1
 k 2 ( K  [ H  ]eq  [OH  ]eq )  k 2 ( K  K w1 / 2  K w1 / 2 )

hence k2 = 1.4 x 1011 L mol-1 s-1
k1 = 2.4 x 10-5 s-1
• Self-test 22.5: Derive an expression for the relaxation time of a
concentration when the reaction A + B ↔ C + D is second-order in
both directions.

To be demonstrated on in class
 22.5 The temperature dependence
of reaction rates
• Arrhenius equation:

k  A e  Ea / RT
A is the pre-exponential factor; Ea is the activation energy. The
two quantities, A and Ea, are called Arrhenius parameters.

• In an alternative expression
Ea
lnk = lnA - RT
one can see that the plot of lnk against 1/T gives a
straight line.
Example: Determining the Arrhenius parameters from the following data:
T/K 300 350 400 450 500
k(L mol-1s-1) 7.9x106 3.0x107 7.9x107 1.7x108 3.2x108

Solution:
1/T (K-1) 0.00333 0.00286 0.0025 0.00222 0.002
lnk (L mol-1s-1) 15.88 17.22 18.19 18.95 19.58

25

20

15

Series1

10

0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035

The slope of the above plotted straight line is –Ea/R, so Ea = 23 kJ mol-1.

The intersection of the straight line with y-axis is lnA, so A = 8x1010 L mol-1s-1
 The interpretation of the Arrhenius
parameters
• Reaction coordinate: the collection of
motions such as changes in
interatomic distance, bond angles, etc.

• Activated complex

• Transition state

• For bimolecular reactions, the

activation energy is the minimum
kinetic energy that reactants must
have in order to form products.
 Applications of the Arrhenius principle
Temperature jump-relaxation method:
consider a simple first order reaction:
A↔B
at equilibrium: ddt[ A]  0
d [ A]
  k a '[ A]  k b' [ B ]
dt

ka '[ A]  k [ B]
'
eq
'
b
'
eq

After the temperature jump the system has a new

equilibrium state. Assuming the distance between the
current state and the new equilibrium state is x, one gets
[A] = [A]eq + x; [B] = [B]eq - x;
 22.6 Elementary reactions
• Elementary reactions: reactions which involves only a small
number of molecules or ions.
A typical example:
H + Br2 → HBr + Br

• Molecularity: the number of molecules coming together to react in

an elementary reaction.

• Molecularity and the reaction order are different !!! Reaction

order is an empirical quantity, and obtained from the experimental
rate law; molecularity refers to an elementary reaction proposed as
an individual step in a mechanism. It must be an integral.
• An elementary bimolecular reaction has a second-order rate law:
A + B → P
d [ A]
  k[ A][ B ]
dt

• If the reaction is an elementary bimolecular process, then it has

second-order kinetics; However, if the kinetics are second-order,
then the reaction might be complex.
 22.7 Consecutive elementary
reactions
• An example:
239U → 239Np →239Pu
• Consecutive unimolecular reaction
A → B → C
The rate of decomposition of A is:
d [ A]
  k1 [ A]
dt
• The intermediate B is formed from A, but also decays to C. The net
rate of formation of B is therefore:
d [ B]
 k1 [ A]  k 2 [ B]
dt

• The reagent C is produced from the unimolecular decay of B:

d [C ]
 k 2 [ B]
dt
• Integrated solution for the first order reaction (A) is:
[ A]  [ A]0 e k1t

• Then one gets a new expression for the reactant B:

d [ B]
 k1 [A]0 e -k1t  k 2 [ B]
dt

the integrated solution for the above equation is:

k1
[ B]  (e k1t  e k2t )[ A]0 when assuming [B]0 = 0.
k 2  k1

• Based on the conservation law [A] + [B] + [C] = [A]0

 k1e  k2t  k 2e  k1t 

[C ]  1  [ A]0
 k 2  k1 
Example. In an industrial batch process a substance A produces the desired
compound B that goes on to decay to a worthless product C, each step of
the reaction being first-order. At what time will B be present in the greatest
concentration?

Solution: At the maximum value of B

d[ B]
0
dt

Using the equation 25.7.6 and taking derivatives with respect to t:

d [ B] k1 [ A]0 (k1e  k1t  k 2 e  k2t )

dt k 2  k1
d[ B]
In order to satisfy 0
dt

k1e  k1t  k2e  k2t =0

tmax = 1 k
ln 1
k1  k 2 k 2

The maximum concentration of B can be calculated by plugging the tmax into

the equation.