Chemical Kinetics

Rates of reaction
Temperature dependence
Rate of reaction

aA + bB → cC + dD

−rA = f (T , C )
−rA = kC ACB
 Arrhenius equation
It was obtained from experimental data over a large
amount of chemical reactions
Activation Energy

Frecuency factor
Activation energy
Activation energy and temperature
dependence

Arrehnius
Eq.
 Temperature dependence of kinetics

Thermodynamics

Van’t Hoff equation

If Energy of reaction is
independent of
temperature we can
integrate
 Temperature dependence of kinetics
Transition theory
Reactants are combined in an activated complex that
decomposes spontaneously to products

Unsing Van’t Hoff equation

k , Boltzmann's constant
h, Planck's constant
T , Temperature
Activation energy
 Temperature dependence of kinetics

Collision theory
Number of bimolecular collisions of different
molecules (number of collisions per volume per time)
2 2  1
 A +B  N 1 
Z AB = C ACB   8 kT  + 
 2  106  A
M M B
C , concentration (mol/L)
 , Molecule diameter (cm)
N , Avogadro's number (molecules/mol)
R
k = , Boltzmann constant (erg/K)
N
T , Temperature (K)
M , Molecule mass (gr)
Energy distribution during collisions

f(E, T) dE = fraction of molecules with

energies between E and E + dE
Energy distribution for collisions at
different temperatures
 Temperature dependence of kinetics
Collision theory
Not every collision is effective, only the more violent
and energetic will generate products. Fraction of
bimolecular collisions with higher energy than
minimum (Maxwell’s energy distribution function)
 −E  1/2  −E 
f ( E ) = Exp   k  T Exp  
 RT   RT 
E RT
103  −E 
−r = kC ACB = Z AB Exp  
N  RT 
2  1
 A +B  N  −E  1 
−r = C ACB   Exp   8 kT  + 
 2  10 3  RT   A
M M B
 Theory comparison
A + B → AB* → AB
Collision theory
Rate of reaction is determined by number of
collisions energetically enough to produce AB, and
does not take into account what happens with AB*
Transition theory
Rate of reaction is ruled by decomposition rate of
AB*. Rate of formation of activated complex is so high
that its concentration is assumed in equilibrium

m −E
k α T Exp( ) , 0  m  1
RT
 Practice
• Milk is pasteurized after heating at 63 °C for 30 min.
Industrially it is performed in only 15 seconds at 74
°C. Find energy of activation. Assume that the same
amount of microorganisms are degraded with both
treatments (R=8.314 J/mol K). How much time is
required for processing ultra-high temperature (140
°C) pasteurized milk?

• How much does a reaction rate with an activation

energy of 15000 cal/mole vary when temperature is
increased from 300 to 310 K? From 300 to 400K?
 Determination of kinetic model
In general is performed in a two-step procedure
under constant temperature and volume
• Studying variation of rate of reaction with
concentrations at constant T
• Studying variation of kinetic constant with
temperature

Is evaluated experimentally in batch o

continuous reactors using different apparatus
and methods
 Experimental methods for kinetic
model determination
• Chemical A sample is taken and analyzed at specific
times. Reaction is stopped by cooling, removing
catalyst or reactant, adding inhibitor.
• Physical Property changing with time and correlated
to concentration (relative measurement). Rapid, non-
intrusive, preferable. Pressure, dilatometric, optic,
electronic.
• Relaxation For rapid reactions. Reactions is driven to
equilibrium and perturbed to reach another
equilibrium condition. r α relaxation time
Reactors
•Batch Reactor Reactants are loaded at time zero and
reaction evolution is followed. Constant T, Constant V
• Continuous Reactor Reactor is loaded from inlet
point and product is removed continuously. Total
conversion of reaction is evaluated. Inlet conditions
are changed to study effect of variables.

Analysis Methods
• Integral Kinetic expression is selected and integrated
within reactor model.
• Differential Direct evaluation of reaction rate
(1/V)(dN/dt)
Assume that decomposition of benzene diazonium
chloride follows an elementary kinetic model. Find rate
equation taking into account some data
experimentally obtained.

Experimental data
K (1/s) 0.00043 0.00103 0.00180 0.00355 0.00717
T (K) 313 319 323 328 333