Chemical Kinetics

Rates of reaction
Rate of reaction

Based upon solid weight for solid-fluid reaction

Based upon surface area for interphase reactions

Rate of reaction
Based upon active site for catalytic reactions

Based upon reactor volume:

Relative rates of reaction aA + bB → cC + dD

rA / -rA
 Rocket engine

A rocket engine burns a stoichiometric mixture of

fuel (H2) in oxidant (O2). The combustion chamber
is cylindrical (figure), and combustion process
produces 108 kg/s of exhaust gases. If combustion
is complete, find the rate of reaction (per volume
of engine) of hydrogen and oxygen.
 Human reactor
Homer (75 kg??) consumes about 6000 kJ per day. Assume
that food is made only of glucose and respiration reaction
can be expressed as:
C6H12O6 + 6O2 → 6CO2 + 6H2O, -∆Hr = 2816 kJ
Find Homer’s metabolic rate in terms of moles of oxygen
used per m3 of person per second. Assume that the body is
mainly water.
Speed of reaction
 Rate of Reaction Form

Concentration and Temperature Dependence

Classification of reactions
If rate controlling mechanism involves collision of
molecules → rate of reaction α [reactants]

With respect to kinetic equation:

Elementary (Rate equation corresponds to a stoichiometric
equation ). A + B → R ---- r=kCACB
Non Elementary (No direct correspondence between
stoichiometry and rate of reaction). A + B → R
a Cb
k1C A
r= B
k2 + f ( C A ,CB )
Regarding number of phases:
Homogeneous (single phase).
Non homogeneous (more than one phase).
Classification of reactions

Non catalytic Catalytic

Most gas-phase Most liquid-phase

Homogeneous
reactions reactions
Coal combustion Ammonia synthesis
Oxidation of ammonia
Roasting of ores
to nitric acid
Heterogeneous Attack of solids by
Cracking of crude oil
acids
Gas-liquid
Oxidation de SO2 a
absorption with
SO3
reaction
Molecularity vs. Order of reaction

Molecularity number of molecules involved in the

reaction. In general is found to be 1, 2 or
occasionally 3. Only applies to elementary
reactions

Order of reaction if rate of reaction can be

expressed in the form: r=kCAaCBbCCc……CXx

Then order of reaction n = a+b+c+d…..+x

Order does not have to be an integer because is

empirically found. Molecularity must be an integer
Classification of reactions
Complexity
Single (one stoichiometric equation, one rate of reaction
represent progress of reaction, A + B → R).
Multiple (more than one stoichiometric equation represents
progress of reaction).
Series (A → R → S).
Parallel (A → R; A → S).
Series-Parallel ( A + B → R; B + R → S).
Independent (A → R; B → S)

Considering chemical equilibria

Irreversible (total conversion).
Reversible (Conversion is limited by thermodynamics of the
system). Not 100% de conversion
 Chemical equilibria from kinetics
A+B↔C+D
r FORWARD=kFCACB r BACKWARD=kBCCCD

in equilibrium r FORWARD= r BACKWARD , then

kFCACB = kBCCCD Elementary reactions

kF/kB=[CCCD/CACB]EQ = KC
Rate equations from proposed mechanisms

A mechanism is a sequence of elementary

steps that determine the overall reaction.

Reaction mechanism: Chain or non-chain

reactions.

1. How is the sequence? Chemists.

2. How is the rate equation from the
mechanism? Chem. Eng.
Rate equations from proposed mechanisms
Always you must assume the presence of
intermediate chemical species.

• Free radicals free atoms or large fragments

of molecules containing one or more
unpaired electrons
• Ions and polar substances Electrically
charged atoms
• Molecules intermediate highly reactive
• Transition complexes Unstable molecules or
unstable association of molecules (total
conversion) that decompose in products or
go back to reactants depending on energy
Rate equations from proposed mechanisms
Chain reaction mechanisms. Usually the intermediates are
free radicals.

Overall reaction: A + B → C

Kinetic mechanism

Initiation: A → A٠

Propagation: B + A٠ → C

Termination: 2A٠ → D

C (the main product) is produced in the propagation step; in

addition there is a little production of D (a byproduct).
Chain reaction - Free radical
General reaction
k1  H 2  Br2 1/2
H2 + Br2 → 2HBr r=
k2 +
 HBr 
 Br2 
Kinetic mechanism

Br2 ↔ 2Br●
H2 + Br● → HBr + H●
H● + Br2 → HBr + 2Br●
Rate equations from proposed mechanisms
Non chain reaction mechanisms.

Overall reaction: A + B → C

A → A*

B + A* → C

C (the main product) is produced by the reaction of

the transition complex A* (the intermediate) with
the reactive B.
Molecular – Non-chain reaction

k  A E0 
General reaction
Enzyme catalysis
r=
A→R  M  +  A
Kinetic mechanism

A + E ↔ (AE)*
(AE)* → R + E
Transition complex – Non-chain
reaction
Azomethane decomposition

(CH3)2N2 → C2H6 + N2 or r = k  A
A→R+S

Kinetic mechanism

A + A → A* + A Formation of activated complex

A* + A → A + A Deactivation of complex
A* → R + S Decomposition in products
Testing kinetic models
Rate controlling step
If one of the elementary steps occurs at much slower
rate than the others, this step will determine the rate
of the overall reaction.

Pseudo Steady-State approximation (PSSA)

An unseen and unmeasured intermediate
component A* usually is present at such small
concentration that its rate of change with time is
negligible. Then:
*]
 A*  is small, and r =
d [ A
0
  A*
dt
Testing kinetic models
Additive rates of reaction
If component i participate in m reactions, its net
rate of reaction is equal to the sum of all
elementary rate of reaction

ri,net =  ri
m
Testing kinetic models
Testing kinetic models
Testing kinetic models
Testing kinetic models
Testing kinetic models
Testing kinetic models
Testing kinetic models
 Rules of thumb to develop a
mechanism
1. Species having the concentration appearing in the
denominator of the rate law probably collide with
the active intermediate
A + A* → [Collision product]
2. If a constant appears in the denominator, one
probable steps is the spontaneous decomposition
of active intermediate
A* → [Decomposition product]
3. Species having the concentration appearing in the
numerator of the rate law probably produce the
active intermediate in one of the reaction steps
[Reactant] → A* + [other product]
 Steps to deduce a rate law
1. Postulate a mechanism using rate law obtained
from experimental data if possible
2. Model each reaction in the mechanism as
elementary reactions
3. Write rate law for desired product and for each of
the active intermediates
4. Use PSSA for active intermediates
5. Eliminate concentrations of active intermediates in
the rate law
6. Check if mechanism is right.
 Azomethane Decomposition
Observations
Experimental evidence that rate of formation of ethane
is first order with respect to AZO at high pressure
However at pressures below 50 mmHg is second order

(CH3)2N2 → C2H6 + N2
A → E +N
Proposed kinetic mechanism

A + A → A* + A Formation of activated complex

A* + A → A + A Deactivation of complex
A* → E + N Decomposition in products
 Azomethane Decomposition
A + A → A* + A r1A* = k1C 2
A
A* + A → A + A r2 A* = −k2 C AC A*
A* → E + N r3 A* = −k3C A*

rE = r3 A* = k3C A*
rA* =  ri A*
i
by PSSA or PSSH
rA* = r1A* + r2 A* + r3 A* = 0
 Azomethane Decomposition
rA* = r1A* + r2 A* + r3 A* = 0
2 −k C C −k C
rA* 1 A 2 A A* 3 A* = 0
= k C

k1C 2
C A* = A
k2 C A + k3
k3 k1C 2
r3 = k3C A* = A
k2 C A + k3
at low concentration k2 C A k3  r3  k1C 2
A
k3 k1C A
at high concentration k2 C A k3  r3  = kC A
k2
Michaelis –Menten model
Michaelis –Menten model
Michaelis –Menten model