CHEMICAL KINETICS

CONTENTS :
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RATE LAW
ORDER OF REACTION
RATE CONSTANT
ENERGY OF ACTIVATION
PRE-EXPONENTIAL FACTOR
GIBBS FREE ENERGY OF ACTIVATION
ENTHALPY OF ACTIVATION
ENTROPY OF ACTIVATION
MECHANISM

At 1100 K, the following data were obtained from homogeneous

reaction:
2NO(g) + 2H2(g)
Experiment
No.
1.

[NO]
(mol/dm3)

5.0 10-3

N2(g) + 2H2O (g)

[H2]
(mol/dm3)

Rate , r
(mol dm-3 s1
)

2.5 x 10-3 0.30 x 10-5

2.
3.

10.0 x 10-3 2.5 x 10-3 1.20 x 10-5

10.0 x 10-3 10.0 x
4.80 x 10-5
-3
1. Write rate law expression for10
reaction?
2. Calculate the overall order of reaction?
3. Calculate the rate constant of the reaction?

4. If rate constant of reaction is 72 dm6 mol-2 s-1 at 1500K.

~Calculate activation energy(Ea)and the pre-exponential factor
(A) assuming Arrhenius equation to apply?
~Calculate Gibbs energy of activation at 1100K, the entropy of
activation and enthalpy of activation?

5. Propose the mechanism of the reaction from the given data.

HOW TO DETERMINE ORDER OF REACTION???

Let the rate law be represented as r = k [NO]a[H2]b
Comparing experiment 1 & 2 we get :
0.30 x 10-5

k [5.0 10-3]a [2.5 x 10-3]b

=

(1)

1.20 x 10-5 k [10.0 x 10-3]a [2.5 x10-3]b

so solving equation (1) we get

a=2
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similarly comparing experiment 2 & 3 we get :

1.20 x 10-5 k [10.0 10-3]a [2.5 x 10-3]b
=
4.80 x 10-5

(2)

k [10.0 x 10-3]a [10.0 x10-3]b

solving equation (2) we get

b=1
thus a) rate law of experiment r = k [NO]2[H2]1 Ans.
b) order of reaction is = (a + b)
= (2+1)
= 3 Ans.

HOW TO FIND OUT RATE CONSTANT OF REACTION??

c) using any set of data we can find out rate constant.

Since rate constant is fixed for all set of experiment performed.
k =

r
[NO]2[H2]1

using experiment no. 1 and putting value we get :

k = (0.30 x 10-5) / [(5.0 10-3)2x(2.5 x 10-3)]

k = 48.0 dm6 mol-2 s-1Ans.

HOW TO DETERMINE ENERGY OF ACTIVATION ???

We know at 1100K rate constant is 48.0 dm6 mol-2 s-1 .
It is given that rate constant of reaction is 72.0 dm6 mol-2 s-1 at
1500K.
So by applying Arrhenius Equation :

k = A e- Ea/RT
lnk1 = -Ea/(RT1) + lnA

(1)

lnk2 = -Ea/(RT2) + lnA

(2)

k1 = 48.0 dm6 mol-2 s-1 at temperature T1 = 1100K.

k2 = 72.0 dm6 mol-2 s-1 at temperature T2 = 1500K.
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ln(48) = - Ea /(8.314J K-1 mol-1 X 1100K) + lnA.

lnA = Ea /(8.314J K-1 mol-1 X 1100K) + ln(48)
NOW SUBSTITUTING VALUE OF lnA in equation (2)
ln(72) = - Ea /(8.314J K-1 mol-1 X 1500K) + lnA.
ln(72) = - Ea /(8.314J K-1 mol-1 X 1500K)
+ Ea /(8.314JK-1 mol-1 X 1100K) + ln(48).
ln(72) - ln(48) = - Ea /(8.314J K-1 mol-1 X 1500K)
+ Ea /(8.314JK-1 mol-1 X 1100K).
0.405= - Ea ( 1/(8.314 x 1500K) 1/(8.314 x 1100K))
0.405= Ea x (0.0000292)

Ea = 13,885.80 J/molAns.
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Putting the value of Ea in any of equation (1) & (2)we can get
the value of A:
ln(72) = - (13,885.80)/(8.314 X 1500) + lnA
4.280 = -1.113+ lnA
lnA = 5.393

A = 219.86 dm6 mol-2 s-1.Ans.

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HOW TO DETERMINE GIBBS FREE ENERGY?

Using Eyring equation

k = {(kB T) /h } e - G / (RT)
48 = {(1.38 X 10-23 X 1100)/(6.625X 10-34 )} e - G /( 8.314 X 1100)
48 = (2.29 X 1013) e - G /( 8.314 X 1100)
e - G /( 8.314 X 1100) = 2.095 X 10-12
- G /( 8.314 X 1100) = ln ( 2.095 X 10-12 )
- G = -26.89 X ( 8.314 X 1100)
G = 245,933.83 J/mol
G = 245.93 kJ/mol...........Ans

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HOW TO DETERMINE H

& S

we know that
H = Ea RT as n = -1
H = 13885.80 (8.314 X 1100)
at temp =1100 K
H = 47,40.40 J/ mol
H = 4.74 kJ/mol ...........Ans.
we know that
G = H - T S
putting value of G & H we get
S = (47,40.400 -245933.83)/(1100)
S = -219.26 J K-1 mol-1 .Ans.
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MECHANISM:
A)

2NO(g) + 2H2(g)

so it can undergo
[NO] + [NO]
[N2O2] + [H2]
[N2O] + [H2]

N2(g) + 2H2O (g)

k1

k-1

k2

k3

[N2O2] (fast)

(1)

[N2O] + [H2O] (slow)

[H2O] + [N2] (fast)

(2)
(3)

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d [N2O2] /dt = 2k1[NO]2 - k-1[N2O2] k2[H2][N2O2]

now using S.S.A. , d[N2O2]/dt = 0
2k1[NO]2 - k-1[N2O2] k2[H2][N2O2] = 0
[N2O2] = 2k1[NO]2/ (k-1+ k2[H2])

(4)

now since 2nd step is slow step

r = k2[N2O2][H2]

(5)

r = 2k1k2 [NO]2 [H2] / (k-1+ k2[H2])

By applying fast equilibrium cond.
i.e; [N2O2] is used up in 1st reaction than in 2nd rkn.
so k-1 >>> k2[H2]

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thus
r = 2k1k2 [NO]2 [H2] / (k-1)
here 2k1k2 / (k-1) = k*
r = k*[NO]2 [H2]
(1) Identify the intermediates in the reaction?
(2) From the mechanism represented above, a student correctly
deduces that the rate law for the reaction is rate = k[NO]2[H2].
The student then concludes that (1) the reaction is third-order
and (2) the mechanism involves the simultaneous collision of
two NO molecules and an H2 molecule. Are conclusions (1) and
(2) correct?
(3)What would happen to the rate of the reaction if the
concentration of all the reactants were doubled?
Ans. 1) [N2O2] & [N2O]
2) Yes.
3) solve it.

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MECHANISM
B)
2NO(g) + 2H2(g)
so it can undergo

[NO] + [H2]
[N] + [NO]
[N2O] + [H2]

N2(g) + 2H2O (g)

k1

k-1

k2

k3

[N] + [H2O]
[N2O]
[H2O] + [N2]

(1)
(2)
(3)

But since [N] cant be formed so this mechanism is not possible.

r = k* [NO2]2[H2]/[H20]
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REFERENCES :

1>

https://myportal.bsd405.org/personal/nehrings/APChem12

2> Physical Chemistry byKeith J. Laidler,John H. Meiser

pg no. (374 391)

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THANK YOU

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