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Steady state approximation

Supplementary notes for the course “Chemistry for Physicists”

Course coordinator: Prof. Dr. Mathias Nest

Teaching assistant: Dr. Raghunathan Ramakrishnan

contact: rama@mytum.de, raghu.rama.chem@gmail.com

Department Chemie

Technische Universität München

Summer Term 2013

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1 When is steady state approximation useful?
We apply steady state approximation for reactions where the concentration of the reaction
intermediate can be considered to be constant. Steady state means an chemical equilibrium, i.e.
the rate of formation equals the rate of consumption.

2 Why do we need steady state approximation?


We need steady state approximation to simplify the derivation of rate laws of many step reac-
tions.

3 A general reaction to show the applicability of the steady state


approximation
Consider the following reaction

A→B (1)
Let us say that the reaction occurs in two steps

k
A →1 I (2)
k
I →2 B (3)

The differential rate laws are given by

dct (A)
= −k1 ct (A) (4)
dt
dct (I)
= k1 ct (A) − k2 ct (I) (5)
dt
dct (B)
= k2 ct (I) (6)
dt
The integrated rate laws which are obtained by solving the coupled differential equations are
given by

ct (A) = c0 (A)e−k1 t (7)


c0 (A) k1k−k −k! t − e−k2 t ;
 
1
e k1 6= k2
ct (I) = 2 (8)
c0 (A)k1 te−k1 t ; k1 = k2
ct (B) = c0 (A) − ct (A) − ct (I) (9)

The concentrations of the reactant, intermediate and the product for the cases i) k1  k2 , ii)
k1 = k2 , and iii) k1  k2 are shown below
1.0 1.0 1.0
A A
concentration

concentration

concentration

B B
A B
0.5 0.5 0.5
I k1 >> k2 k1 = k2 k1 << k2
I

I
0.0 0.0 0.0
0.0 2.0 4.0 6.0 8.0 10.0 0.0 2.0 4.0 6.0 8.0 10.0 0.0 10.0 20.0 30.0 40.0 50.0
time time time

2
Clearly the steady state approximation is applicable for the case k1  k2 where the concen-
tration of the intermediate is small and it varies slowly and can be considered to be constant
most of the time during the reaction (i.e. to a good approximation, dcdt t (I)
= 0). The situation
k1  k2 also means that the intermediate is very reactive and this step is very fast. Also note
that the first step is relatively very slow hence the first step determines the rate of the entire
reaction. Now let us apply the steady state approximation for this case to derive the rate law.
In most of the cases, we look for an expression for ct (I) in terms of the rate constants and
the concentration of reactants. Let us apply dcdtt (I)
= 0 which is the steady state approximation
to eq. 5

dct (I) k1
= 0 ⇒ ct (I) = ct (A) (10)
dt k2
Using the above equation we can rewrite the rate laws (differential and integral) as follows

dct (A)
= −k1 ct (A) (11)
dt
dct (I)
= 0 (12)
dt
dct (B)
= k1 ct (A) (13)
dt
and

ct (A) = c0 (A)e−k1 t (14)


ct (I) = constant (15)
k1
ct (B) = c0 (A) − ct (A) − ct (A)
k2
 
−k1 t k1 −k1 t
= c0 (A) 1 − c0 (A)e − c0 (A)e
k2
n o
= c0 (A) 1 − c0 (A)e−k1 t (16)

k1
where in the last equation we have used k2 = 0 because k2 is large.

4 In this course we use steady state approximation only to derive


the differential rate laws of many step reactions
Let us try an example (p. 260 of Chemie by Mortimer, Müller 9. Auflage). PLEASE READ
THIS SECTION IN THE BOOK (p.260) BEFORE READING THE FOLLOWING.
The complete reaction is given by

H3 COH + H+ + Br− → H3 CBr + H2 O (17)

For this reaction the experimentally derived rate law is given by

v = k · c (H3 COH) · c H+ · c Br−


 
(18)

The proposed mechanism has three steps


k
step 1 : H3 COH + H+ →
1
H3 COH+
2 fast (19)

3
k
step 2 : H3 COH+ 2
2 → H3 COH + H
+
fast (20)

k
step 3 : Br− + H3 COH+ 3
2 → H3 CBr + H2 O slow (21)
Since the third step is the rate determining step, we can write the rate of the reaction as
(remember, the slowest step determines the rate of the entire reaction)

v = v3 = k3 · c H3 COH+
 
2 · c Br (22)

This expression involves the concentration of the intermediate. Recall that we usually write
the rate law in terms of the concentration of the reactant
 only. Let us use the stationary state
approximation and see if we can eliminate c H3 COH+ 2 in eq. 22. Let us equate the net rate of
formation of the intermediate to zero
dc H3 COH+

2 −
= k1 c (H3 COH) c H+ − k2 c H3 COH+ +
   
2 − k3 c H3 COH2 c Br = 0 (23)
dt

⇒ k1 c (H3 COH) c H+ − c H3 COH+ k2 + k3 c Br−


  
2 = 0 (24)
k1 c (H3 COH) c (H+ )
⇒ c H3 COH+

2 = (25)
k2 + k3 c (Br− )

Note that the third step is the rate determining step, hence k3  k2 or k2 + k3 c (Br− ) ≈ k2

 k1 c (H3 COH) c (H+ )


c H3 COH+
2 ≈ (26)
k2
By substituting the above equation in eq. 22, we arrive at the experimental rate law
k1 k3
· c (H3 COH) · c H+ · c Br−
 
v = v3 = (27)
k2
= k · c (H3 COH) · c H+ · c Br−
 
(28)

Now let us do a bit of analysis. For the two-step reaction given in page 2 of this document
we saw that steady state approximation is valid if the intermediate is very reactive, right?. But
in this three-step reaction the third step is a slow step, i.e., in the third step the intermediate
reacts slowly. Then why did we use steady state approximation here? The reason is that we
assume that k2 is very large, i.e., the intermediate undergoes a very rapid reverse reaction as in
step 2. In this example if k2  k1  k3 the concentration of the intermediate increases very
rapidly at the beginning of the reaction, for a very short time and then for most of the reaction
it varies very slowly, i.e., dc(I)
dt ≈ 0. This is illustrated in the following figure. Note that in the
bottom figure (short time) the concentration of the intermediate increases very rapidly, but it
stays essentially constant through out the reaction.

4
1.0

CH3Br = H2O

concentration
0.5 k2 >> K1 >> k3
+
CH3OH = H (red)
-
+ Br (green)
CH3OH2
0.0
0.0 5000.0 10000.0
time

1.0
concentration

0.5

0.0
0.0 10.0 20.0
time

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