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Chapter #3#
Chapter #3#
Chapter #3#
TECHNOLOGY UNIVERSITY
–rj is the number of moles of j reacting (disappearing) per unit time per unit volume
1 𝑑𝑁𝑗
−𝑟𝑗 = −
𝑉 𝑑𝑡
rj is the number of moles of species j generated per unit volume per unit time
1 𝑑𝑁𝑗
𝑟𝑗 =
𝑉 𝑑𝑡
The rate of reaction has the units of moles per (units of) volume per (unit of) time.
eg. mol L-1 s-1 or Ms-1, mol/dm3⋅s
Reaction rate is independent of the type of reactor(Batch, Plug flow, CSTR etc.)
Cont…
Relative Rates
Relative Rates tell us how fast one species is disappearing or appearing relative to the other
species in the given reaction
The general definition of rate of reaction, r, is given by
1 𝑑𝜑 𝑁𝑗 − 𝑁𝑗0
𝑟= , 𝑤ℎ𝑒𝑟𝑒 𝜑 =
𝑉 𝑑𝑡 ν𝑗
After substituting and differentiating
1 1 𝑑𝑁𝑗
𝑟=
ν𝑗 𝑉 𝑑𝑡
𝑟𝑗 1 𝑑𝑁𝑗
𝑟= where 𝑟𝑗 =
ν𝑗 𝑉 𝑑𝑡
𝑟𝐴 𝑟𝐵 𝑟𝐶 𝑟𝐷
𝑟= = = =
−𝑎 −𝑏 𝑐 𝑑
−𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐷
𝑟= = = =
𝑎 𝑏 𝑐 𝑑
The relative rates of reaction of the various species involved in a reaction can be obtained from the ratio
of the stoichiometric coefficients.
For example:The relationship between the rates of formation of C and D is
𝑐
𝑟𝐶 = 𝑟
𝑑 𝐷
Example2: The rate of change of molar concentration of CH3 radicals in the reaction
2CH3(g)→ CH3CH3(g) was reported as −𝑟𝐶𝐻3 = 1.2 moldm−3s−1 under particular
conditions. What is a) the rate of reaction and b) the rate of formation of CH3CH3.
In homogeneous systems, the volume of fluid(V) in the reactor is often identical to the
volume of reactor(Vr).
In such a case V and Vr are identical and are used interchangeably
Based on unit volume of reacting fluid
Based on unit volume of reactor, if different from the rate based on unit volume of
fluid.
𝑟 = 𝑘𝐶𝐴 𝛼 𝐶𝐵 𝛽 𝐶𝐶 𝛾 𝐶𝐷 𝛿
𝑟 = 𝑘𝑃𝑃𝐴 𝛼 𝑃𝐵 𝛽 𝑃𝐶 𝛾 𝑃𝐷 𝛿
𝑘
where 𝑘𝑃 =
(𝑅𝑇)𝛼+𝛽+𝛾+𝛿
l
Cont...
The overall order of reaction is the sum of all orders with respect to each species
𝑜ver all order = 𝛼 + 𝛽 + 𝛾 + 𝛿
Values of order of reaction must be determined experimentally (can not be
predicted from chemical equation).
Order of reaction can be any real number
Order of reaction can be integer (…-2,-1,0,1,2…) or fraction (1/2)
e.g 2HI H2 + I2 𝑟 = 𝑘𝐶𝐻𝐼 2
3
CH3CHO CH4 + CO 𝑟 = 𝑘𝐶𝐶𝐻3𝐶𝐻𝑂 2
1
CO + O CO2 𝑟 = 𝑘𝐶𝐶𝑂2 −1
2 2
Cont…
Law of Mass Action of kinetics
Law mass action states that rate of reaction is only the dependant of reactant concentrations, not on product
concentrations
Or the rate of reaction increases with increasing concentration of reactants owing the corresponding increase
in the number of molecular collisions.
Consider a reaction 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
𝑟 = 𝑘𝐶𝐴 𝑞1 𝐶𝐵 𝑞2 𝐶𝐶 𝑞3 𝐶𝐷 𝑞4 = 𝑘𝐶𝐴 𝑞1 𝐶𝐵 𝑞2
1
𝑞𝑗 = ( 𝝊𝑗 − 𝝊𝑗 )
2
1 1
𝑟 = 𝑘𝐶𝐴1 𝐶𝐵 2 𝐶𝐶 0 𝑞2 = −2 − −2 = 2+2 =2
2 2
1 1
𝑟 = 𝑘𝐶𝐴 𝐶𝐵 2 𝑞3 = 1 −1 = 1−1 =0
2 2
Cont...
A reaction follows an elementary rate law if the reaction orders just happens to agree
with the stoichiometric coefficients for the reaction as written.
Exapmle: If the reaction below follows an elementary, rate law
2 A B 3C
rA k AC A2CB
rjα f([A],[B],….)
rj = f(T) * f([A],[B],….)
rj = k[A]α[B]β…… or
rj = kCAαCBβ…..
ii. Pressure dependence of the rate of a reaction
For homogenous gas-phase reactions, pressure is often used:
rjα f(PA, PB, ….)
rj = f(T) * f(PA, PB, ….)
rj = k(PA/RT)α(PB/RT)β….= kpPAαPBβ
kp=k/[(RT)α(RT)β]=k/[(RT)α+β]
Cont...
iii.Temperature dependence of the rate of a reaction
Rate(constant)s increase when temperature increases.
𝑟𝑗 = 𝑘. [𝐴]𝑥 [𝐵]𝑦 … .
𝑟𝑗 = 𝑘. 𝐶𝐴 𝑥 𝐶𝐵 𝑦 …
Arrhenius equation:
Example1: The rate constants of a reaction at 500K and 700K are 0.02s-1 and 0.07s-
1respeetively. Calculate the activation energy? Take gas constant R = 8.314J/mol.K
Example2: How much does a reaction rate with an activation energy of 15,000
Cal/mol vary when the temperature is increased from 300 to 310 K? From 300 to 400
K? Take gas constant R = 1.986 cal/mol.K
Solutions
𝑟310 𝑘310 𝑟400 𝑘400
≈ = 2.24 ≈ = 517
𝑟300 𝑘300 𝑟300 𝑘300
This shows that for this activation energy an increase of temperature by 10K
approximately doubles the rate and an increase of 100K increases it by more than a
factor of 500.
This example shows why the temperature is so important in chemical reactions.
Cont…
Collision Theory of chemical reaction
In a chemical reaction, molecules, atoms or ions can only react if they
collide with each other.
During collision, old bonds are broken and new bonds are formed.
Molecular collusion produce kinetic energy
Further collision - kinetic energy can be transferred into vibrational energy
A reaction cannot occur unless the molecules possess sufficient energy to get
over the activation energy barrier.
The minimum energy that must be supplied by collisions for a reaction to
occur is called the activation energy, Ea.
Cont…
Why is there an Activation Energy?
For the reaction to occur, the reactants must overcome an energy barrier or
activation energy EA.
The energy to overcome their barrier comes from the transfer of the kinetic
energy from molecular collisions to internal energy (e.g. Vibrational
Energy).
1. The molecules need energy to disort or stretch their bonds in order to break
them and thus form new bonds
2. As the reacting molecules come close together they must overcome both
stearic and electron repulsion forces in order to react.
Cont…
Activation energy:
Activation energy is the minimum kinetic energy that the
reactants must have in order to react.
Pre-exponential factor
The exponential factor in the equation corresponds to the
fraction of all occurring collisions that have enough kinetic
energy to lead to reaction.
A: rate of successful collisions.
Cont…
CO(g) + NO2(g) CO2(g) + NO(g)
Cont…
Consider a decomposition reaction
2HBr H2 Br2
A B + C
Cont.
3. Reaction Mechanism
A reaction mechanism: is the step by step sequence of elementary reactions involved in a
reaction leading to the overall chemical reaction
Experimental rate
• Non-chain Reactions.
• Chain Reactions.
Example: The irreversible reaction A+B AB has been studied kinetically, and the rate
of formation of product has been found to be well correlated experimentally by the following
rate equation:
• What reaction mechanism is suggested by this rate expression if the chemistry of the
reaction suggests that the intermediate consists of an association of reactant molecules
and that a chain reaction does not occur?
• Because the concentration of A2* is always extremely small we may assume that its rate
is zero
Model 2
• Just interchange A and B in Model 1, put k2= 0 and we will get rAB= k[B]2 = kCA2
Home work!!!
Cont…
Molecularity: the number of free atoms, ions, or molecules that involved in
the elementary reaction.
𝑑𝐴 𝑑𝐶𝐴
AP with − = − = 𝑘 𝐴 = 𝑘𝐶𝐴
𝑑𝑡 𝑑𝑡
Bimolecular:
𝑑𝐴 𝑑𝐶𝐴
2A P with − = − = 𝑘[𝐴]2 = 𝑘𝐶𝐴 2
𝑑𝑡 𝑑𝑡
or
𝑑𝐴 𝑑𝐶𝐴
A+BP with − = − = 𝑘[𝐴][𝐵] = 𝑘𝐶𝐴 𝐶𝐵
𝑑𝑡 𝑑𝑡
Cont…