Introduction to Reaction Kinetics - 1

AB
Homogeneous reactions - Only one phase involved.
Heterogeneous reactions - more than one phase
involved.
[Reactants/ products/ catalysts, etc.]

Batch Reactor
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 Introduction to Reaction Kinetics - 2
Rate of reaction:
Homogeneous reactions
𝟏 𝒅𝑵𝑨 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑨 𝒇𝒐𝒓𝒎𝒆𝒅 𝒎𝒐𝒍 𝑨
𝒓𝑨 = , 𝟑
𝑽 𝒅𝒕 𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒇𝒍𝒖𝒊𝒅 (𝒕𝒊𝒎𝒆) 𝒎 . 𝒔
If A is a reactant, 𝒓𝑨 is –ve, rate of reaction is -𝒓𝑨
If A is a product, 𝒓𝑨 is +ve, rate of reaction is 𝒓𝑨

Heterogeneous fluid-solid catalytic reaction

𝟏 𝒅𝑵𝑨 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝑨 𝒇𝒐𝒓𝒎𝒆𝒅 𝒎𝒐𝒍 𝑨
𝒓𝑨 = = ,
𝒎𝒄 𝒅𝒕 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕 (𝒕𝒊𝒎𝒆) 𝒌𝒈. 𝒔

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 Introduction to Reaction Kinetics - 3
PROBLEM # 1:
A human being (75 kg) consumes 6000 kJ of food per day.
Assume the food is all glucose.
C6H12O6 + 6O2 → 6CO2 + 6H2O; ∆H = -2816 kJ/mol.
Find man’s metabolic rate in terms of O2 used per m3 of
person per second. Density of human body is 1000 kg/m3.

SOLUTION: -ro2 = (1/V). (dNo2/dt) moles of O2/m3 of

person.s
V = 75/1000 = 0.075 m3
Rate of consumption of glucose:
dNC6H12O6/dt = 6000/2816 mol/day
dNO2/dt = 6000/2816*6 = 12.8 mol of O2/day.
-rO2 = (1/0.075)*12.8/(24*3600) = 0.002 mol of O2/m3.s
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 Introduction to Reaction Kinetics - 4
Rate Equation (Equation representing the rate of
reaction):
AB
𝒓𝑨 = f ‘ (T, CA)
At constant T, 𝒓𝑨 = f (CA)
If A is reactant, −𝒓𝑨 = f (CA)

Order of reaction:
A  B: if −𝒓𝑨 ∝ 𝑪𝑨 𝒎 (Powerlaw kinetics).
Order of reaction is m
A + B  C: if −𝒓𝑨 ∝ 𝑪𝑨 𝒎 𝑪𝑩 𝒏 .
Order of reaction is m+n
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 Introduction to Reaction Kinetics - 5
Reaction (kinetic) rate constant. k:
A→B
Rate equation: −𝒓𝑨 = 𝒌𝑪𝒎 𝑨
If m = 1, - 𝒓𝑨 = 𝒌𝑪𝑨
𝒎𝒐𝒍 𝒎𝒐𝒍
= 𝒌 [ 𝟑 ]; [k] = 𝒔−𝟏
𝒎𝟑 𝒔 𝒎
𝒎𝟑 𝒎−𝟏 −𝟏
If m = m, 𝒌 =[ ] .𝒔
𝒎𝒐𝒍
𝒎𝒐𝒍
m = 0, 𝒌 = 𝟑 . 𝒔−𝟏
𝒎
m = 1, [k] = 𝒔−𝟏
𝒎𝟑
m = 2, [k] = [ ]. 𝒔−𝟏
𝒎𝒐𝒍

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 Introduction to Reaction Kinetics - 6
Molecularity
aA + bB → cC + dD
Molecularity is a + b; number of molecules of reactants
involved in the reaction; (from the stoichiometric
equation)
Molecularity – integer constants;
Order of reaction –real constants (determined
empirically/experimentally)
Elementary & Non-elementary reactions:
Rate equation: −𝒓𝑨 = 𝒌𝑪𝒎 𝒏
𝑨 𝑪𝑩
(m & n are order of reactions w.r.t A & B respectively)
Elementary reactions: The rate equation matches with
the stoichiometric equation.
If m = a; n = b  Elementary reaction
If not  Non-elementary reaction
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Examples:
Elementary:
C2H5OH + CH3COOH → CH3COOC2H5 + H2O
-𝒓𝑪𝟐 𝑯𝟓 𝑶𝑯 = 𝒌𝒄𝑪𝟐𝑯𝟓 𝑶𝑯 𝒄𝑪𝑯𝟑 𝑪𝑶𝑶𝑯

Non-elementary:
H2 + Br2 → 2HBr
𝟏
𝒌𝟏 𝒄𝑯𝟐 𝒄𝟐𝑩𝒓
𝟐
−𝒓𝑯𝟐 = 𝒄
𝒌𝟐 + 𝑯𝑩𝒓
𝒄𝑩𝒓
𝟐

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First Order :
C2H6 → C2H4 + H2 ; −𝒓𝑪𝟐 𝑯𝟔 = 𝒌𝒄𝑪𝟐 𝑯𝟔 [Elementary]

Second Order :
C2H5OH + CH3COOH → CH3COOC2H5 + H2O [Non-elementary]

Third Order :
2NO + O2 → 2NO2 [Elementary]
2NO + 2H2 → N2 + 2H2O [Non-elementary]

Zero Order:
Photochemical Reactions

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1. Single Reaction – Single stoichiometric reaction and a
single rate equation are needed to represent the progress
of a reaction. e.g. C2H6 → C2H4 + H2

2. Multiple Reactions – More than one stoichiometric

reaction and more than one rate equation are needed.
(a) Parallel reactions:
(Rate constants k1 and k2)

Example:
(Ethylene oxide)
CH2=CH2 + O2
2CO2 + 2 H20
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(b) Series reaction: A  B  C (Rate constants k1 and
k2)

Example:

 + + NH3  OH-CH2-CH2-NH2 (mono-ethanolamine)

E.O
(Ethylene  (OH-CH2-CH2)2NH (di-ethanolamine)
oxide) E.O
 (OH-CH2-CH2)3N (tri- ethanolamine)

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