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Rate of reaction

Chemical Kinetics
Based upon solid weight for solid-fluid reaction

Rates of reaction
Based upon surface area for interphase reactions

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Rate of reaction
Rocket engine
Based upon active site for catalytic reactions

Based upon reactor volume:

A rocket engine burns a stoichiometric mixture of

Relative rates of reaction
aA + bB → cC + dD fuel (H2) in oxidant (O2). The combustion chamber
is cylindrical (figure), and combustion process
rA / -rA produces 108 kg/s of exhaust gases. If combustion
is complete, find the rate of reaction (per volume
of engine) of hydrogen and oxygen.

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Human reactor Speed of reaction

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.

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Rate of Reaction Form Classification of reactions

If rate controlling mechanism involves collision of
molecules → rate of reaction α [reactants]
Concentration and Temperature Dependence
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
k 2  f  C A ,C B 
Regarding number of phases:
Homogeneous (single phase).
Non homogeneous (more than one phase).

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Classification of reactions Molecularity vs. Order of reaction

Non catalytic Catalytic Molecularity number of molecules involved in the

reaction. In general is found to be 1, 2 or
Most gas-phase Most liquid-phase occasionally 3. Only applies to elementary
Homogeneous reactions
reactions reactions

Coal combustion Ammonia synthesis

Oxidation of ammonia Order of reaction if rate of reaction can be
Roasting of ores
to nitric acid expressed in the form: r=kCAaCBbCCc……CXx
Heterogeneous Attack of solids by
Cracking of crude oil Then order of reaction n = a+b+c+d…..+x
acids
Gas-liquid
Oxidation de SO2 a
absorption with Order does not have to be an integer because is
SO3
reaction
empirically found. Molecularity must be an integer

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Classification of reactions Chemical equilibria from kinetics

Complexity A+B↔C+D
Single (one stoichiometric equation, one rate of reaction
represent progress of reaction, A + B → R). r FORWARD=kFCACB r BACKWARD=kBCCCD
Multiple (more than one stoichiometric equation represents
progress of reaction).
Series (A → R → S). in equilibrium r FORWARD= r BACKWARD , then
Parallel (A → R; A → S).
Series-Parallel ( A + B → R; B + R → S).
Independent (A → R; B → S) kFCACB = kBCCCD Elementary reactions

Considering chemical equilibria

Irreversible (total conversion).
kF/kB=[CCCD/CACB]EQ = KEQ
Reversible (Conversion is limited by thermodynamics of the
system, 100 % de conversion

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Non elementary reactions Free radical – Chain reaction

3/2
 N 2  H 2   NH3  General reaction
N2 + 3H2 → 2NH3 r  k1  k2 k  H  Br2 1/2
 NH 3 2  H 2 3/2 H2 + Br2 → 2HBr r 1 2
Multistep reaction model required with intermediates k2 
 HBr 
Free radicals free atoms or large fragments of molecules
 Br2 
containing one or more unpaired electrons
Kinetic mechanism
Ions and polar substances Electrically charged atoms
Molecules intermediate highly reactive
Transition complexes Unstable molecules or unstable Br2 ↔ 2Br●
association of molecules (total conversion) that decompose in H2 + Br● → HBr + H●
products or go back to reactants depending on energy
H● + Br2 → HBr + 2Br●
Reaction mechanism: Chain or non-chain reaction

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Transition complex – Non-chain

Molecular – Non-chain reaction
reaction

k  A E0 
General reaction Azomethane decomposition

r  k  A
Enzyme catalysis
r
 M    A
A→R (CH3)2N2 → C2H6 + N2 or

A→R+S

Kinetic mechanism Kinetic mechanism

A + enzyme ↔ (A•enzyme)* A + A → A* + A Formation of activated complex

(A•enzyme)* → R + enzyme A* + A → A + A Deactivation of complex
A* → R + S Decomposition in products

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Testing kinetic models Testing kinetic models

Pseudo Steady-State approximation Additive rates of reaction
An unseen and unmeasured intermediate If component i participate in m reactions, its net
component A* usually is present at such small rate of reaction is equal to the sum of all
concentration that its rate of change with time elementary rate of reaction
is negligible. Then:

* ri, net   ri
 A*  is small, and r  d [ A ]  0
  A* dt m

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Rules of thumb to develop a

Testing kinetic models
Catalyst in reaction
Where a homogeneous catalyst of
initial concentration C0 is present
in two forms, either as free catalyst
C or combined in an appreciable
extent to form intermediate X, then
We can assume steady state
1 A* → [Decomposition product]
AC X
2 3.
Or intermediate is in equilibrium
with reactants k X 
K 1
k2  AC 
mechanism
1. Species having the concentration appearing in the
denominator of the rate law probably collide with
the active intermediate
C0   C    X 
A + A* → [Collision product]
2. If a constant appears in the denominator, one
d[ X ] probable steps is the spontaneous decomposition
0 of active intermediate
dt
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]

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Steps to deduce a rate law Azomethane Decomposition

1. Assume an active intermediate Observations
2. Postulate a mechanism using rate law obtained Experimental evidence that rate of formation of ethane
from experimental data if possible is first order with respect to AZO at high pressure
However at pressures below 50 mmHg is second order
3. Model each reaction in the mechanism as
elementary reactions
(CH3)2N2 → C2H6 + N2
4. Write rate law for desired product and for each of A → E +N
the active intermediates Proposed kinetic mechanism
5. Use PSSA for active intermediates
6. Eliminate concentrations of active intermediates in A + A → A* + A Formation of activated complex
the rate law A* + A → A + A Deactivation of complex
A* → E + N Decomposition in products
7. Check if mechanism is right.

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Azomethane Decomposition
Azomethane Decomposition
rA*  r1A*  r2 A*  r3 A*  0
A + A → A* + A r1A*  k1C 2
A 2
rA*  k1C A  k2 C A C A*  k3 C A*  0
A* + A → A + A r2 A*   k2 C A C A*
k1C 2
r3 A*  k3 C A* A
A* → E + N C A* 
k2 C A  k3

rE  r3 A*  k3 C A* k3 k1C 2
r3  k3C A*  A

rA*   ri A*
k 2 C A  k3

i at low concentration k2 C A  k3  r3  k1C 2

A
by PSSA or PSSH k kC
at high concentration k2 C A  k3  r3  3 1 A  kC A
k2
rA*  r1A*  r2 A*  r3 A*  0

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Michaelis –Menten model Michaelis –Menten model

Enzyme substrate reaction
Enzyme
A  R
Observations:
1. Rate is proportional to the
concentration of enzyme
introduced [E0]
2. At low reactant concentration
the rate is proportional to the A E  X
reactant concentration [A]
X RE
3. At high reactant concentration
the rate levels off and becomes
independent of reactant
concentration

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Michaelis –Menten model

A E  X
X RE
[ E0 ]  [ E ]  [ X ]
d[ X ]
 0  k1[ A][ E ]  k2[ X ]  k3[ X ]
dt
d [ R]
 k3[ X ]
dt
d [ R] k k [ A][ E0 ] k3[ A][ E0 ] k [ A][ E0 ]
 13   3
dt ( k1  k3 )  k1[ A] k1  k3 [ M ]  [ A]
( )  [ A]
k1

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