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Introduction To Chemical Reaction Kinetics - 1

1. The document introduces reaction kinetics and discusses homogeneous and heterogeneous reactions, rate of reaction equations, and examples of zero, first, second, and third order reactions. 2. Rate equations are presented for homogeneous and heterogeneous reactions, with the rate of reaction defined based on changes in moles of a reactant or product over time and volume or mass of catalyst. 3. An example problem calculates the metabolic rate of a human in terms of oxygen used per cubic meter of person per second by considering the combustion reaction of glucose.

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Parthapratim Gupta
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92 views10 pages

Introduction To Chemical Reaction Kinetics - 1

1. The document introduces reaction kinetics and discusses homogeneous and heterogeneous reactions, rate of reaction equations, and examples of zero, first, second, and third order reactions. 2. Rate equations are presented for homogeneous and heterogeneous reactions, with the rate of reaction defined based on changes in moles of a reactant or product over time and volume or mass of catalyst. 3. An example problem calculates the metabolic rate of a human in terms of oxygen used per cubic meter of person per second by considering the combustion reaction of glucose.

Uploaded by

Parthapratim Gupta
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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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
1
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

2
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

5
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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Introduction to Reaction Kinetics - 7
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

7
Introduction to Reaction Kinetics - 8
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

8
Introduction to Reaction Kinetics - 9
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
9
Introduction to Reaction Kinetics - 10
(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)

10

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