Shroff S.

R Rotary institute of chemical technology

Department of Chemical Engineering

Subject:- Chemical reaction Engineering

Semester:- 6

Branch:- Chemical Engineering

ALA Topic:- Third order reaction kinetics by integral method with one
numerical

Presented by:- Jadav Harsh Hitendra Enrollment no:- 160990105013

Guided by :- Shina madam

Academic Year (2018-2019)

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( 2140502
 Integral method

• Steps to find order of reaction

 Guess the particular form of rate equation ( 0,1st,2nd,3rd etc)
 After integration and mathematical manipulation, plot
concentration function versus time graph.
 Graph should be a straight line.
 If good straight line is obtain, rate equation is satisfactory, and
reaction mechanism is valid.
 If not form a straight line then change a rate eqution.

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 Third order reaction
• A reaction is said to be of third order if the rate is determined by the variation
of three concentration terms. In other words, the minimum number of
molecules necessary for the reaction to take place is three.
• There may be three different cases in third order reaction.
• (i) All the three species have equal concentrations.
• A+A+A Product
• (ii) Two species have equal concentrations and one different.

(iii) All three species have unequal concentrations.

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 Example of third order

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For the reaction: 2NO + Cl2 → 2NOCl at 300 K following data are obtained.
Write rate of law for the reaction. What is the order of the reaction? Also
calculate the specific rate constant ?

Expt. No. Initial concentration Initial rates

[NO] [Cl2]

-4
1 0.01 0.01 1.2×10

-4
2 0.01 0.02 2.4×10

-4
3 0.02 0.02 9.6×10
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Solution
Let the rate law for the reaction be
Rate = k[NO]x [Cl2]y
From Expt. (1),
1.2×10-4 = k[0.010]x [0.010]y ... (i)
From Expt. (2),
2.4×10-4 = k[0.010]x[0.020]y ... (ii)
Dividing Eq. (ii) by Eq. (i),
(9.6×10-4)/(2.4×10-4) = ([0.020]x )/[0.010]x
or 2 = (2)y
y=1
From Expt. (2), 2.4×10-4 = k[0.010]x [0.020]y .... (ii)
From Expt. (3), 9.6×10-4 = k[0.020]x [0.020]y .... (ii)

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• Dividing Eq. (ii) by Eq. (ii),
(9.6 × 10-4)/(2.4 × 10-4) = ([0.020]x )/[0.010]x
or 4 = 2x
x=2
Order of reaction = x + y = 2 + 1 = 3
Rate law for the reaction is
Rate = k[NO]2 [Cl2]
Considering Eq. (i) again,
1.2 × 10-4 = k[0.010]2 [0.010]
k = (1.2×10-4)/[0.010]3 = 1.2×102 mol-2 litre2 sec-1
__________

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Advantage
• Easy to be use.
• It is recommended to test
specific condition, or a
simple rate expression.
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Disadvantage
• Use when the data is
scattered and we cannot find
derivative needed.
integral method 12