1/31/2012

Specific reaction rate

constant
• Specific reaction rate constant, k value is
strongly dependent on temperature
• In gas phase reactions, it depends on
catalyst and may be a function of
Rate Law pressure
• In liquid systems it can be a function of
total pressure and can depend on other
parameters (ionic strength and choice of
solvent)

Specific reaction rate Specific reaction rate

constant constant
• k, specific reaction rate constant determined  Ea
• At temperature T1, k (T1 )  Ae
by Arrhenius equation RT1
 Ea  Ea
k  Ae • At temperature T2, k (T2 )  Ae
RT RT2
where
Ea = activation energy • Taking the ratio to obtain,
R = gas constant
Ea 1 1
T = temperature k (T2 )  k (T1 )e   
A = frequency factor R  T1 T2 
• k and A units depends on overall reaction
order

Specific reaction rate Specific reaction rate

constant constant
• Activation energy, Ea is the minimum energy
that must be possessed by reacting
E1
k (T )  A exp   k molecules before the reaction will occur.
R T 

E1
In k (T )  In A    Slope = -Ea/R
R T  ln k

1/T

1
 1/31/2012

Specific reaction rate Specific reaction rate

constant constant
EXERCISE 1

• The initial stages of the gas phase

Reaction 2: Low Ea
reaction between ammonia and nitrogen
dioxide follow second-order kinetics.
Given that the rate constant at 600 K is
Reaction 1: High Ea 3.85 x 10-4 mol-1m3s-1 and at 716 K is 160
x 10-4 mol-1m3s-1. Calculate the activation
energy and the frequency factor.
1/T
(R = 8.314 J/mol.K)
k with higher Ea is more sensitive to
temperature than those with low Ea

Reaction Order
• The order of reaction is defined as the power
to which its concentration term in the rate
equation is raised.
• EXAMPLE:
A + 2B → C
Reaction Order with a rate equation of –rA = k[A]1[B]2
means the reaction order with respect to A
would be 1 and with respect to B would be 2,
the total reaction order would be 2+1=3
• Reaction orders can be determined only by
experiments

Reaction Order Reaction Order

• Overall reaction order can be determined by
mole mole
the unit of k Reaction rate;  r  but  conc.
vol.time vol

k  time1 concentration 1n The reaction rate become;  r 

conc.
time
Reaction Order Rate Law k unit  
However;  r  k C A CB
Zero -rA=kA mol/dm3.s
One -rA=kACA s-1 C  
Rearrange the equation;  r   k C A CB
Two -rA=kACA2 (dm)3/mol.s t

Three -rA=kACA3 (dm3/mol)2.s-1 Differential equation;  rA   dCA  k CA CB 

dt

2
 1/31/2012

Reaction Order Reaction Order

Zero order Zero order
• A reaction is of zero order when the rate • The zero order rate law for the general
of reaction is independent of the reaction, is written as
concentration of materials. dC A
 k
• The rate of reaction is a constant. When dt
the limiting reactant is completely • Integrate of both sides gives
consumed, the reaction stops abruptly.
CA CA0 kt
 rA  k[A]0
 rA  k
n=0

Reaction Order Reaction Order

Zero order First order
• Plotting CA versus t will give a straight • In a first order reaction the rate is
line with slope -k. proportional to the concentration of
one of the reactants

 rA  k[A] 1
 rA  k[A]
n =1

Reaction Order Reaction Order

First order First order
The first order rate law for the general Plotting ln CA0 / ln CA against t
reaction, is written as creates a straight line with slope k

dC A dC A
  kCA   kdt
dt CA
C A0
ln
Integrating above equation to yield CA
C A0
ln  kt
CA

3
 1/31/2012

Reaction order Reaction order

Second order Second order
• In the second order reaction the rate is
proportional to concentration squared The second order rate law for the general
reaction is given by
dC A dC A
 r  k[A]1[B]1  k[ A][B]   kC A
2
 2
 kdt
A dt CA
 r  k[ A]1[ A]1 k[ A]2
A
Separating the variables and integrating
n = 1+1=2 gives
1 1
  kt
CA CA 0

Reaction order Conversion

Second order
• Conversion XA is the number of moles of
A plot of 1 / CA vs t produces a a that have reacted per moles of a fed to
straight line with slope k and intercept the system:
1 / CA0
moles of A reacted
XA 
moles of A fed
1 • Consider the general equation:
CA aA + bB  cC + dD
The uppercase letters represent chemical
species and the lowercase letters
represent stoichiometric coefficient.

Conversion
• Put every quantity on a “per mole of A”
basis:
b c d
A B  C  D
a a a
• For constant volume reaction system:
Thank you
N AO  N A C AO  C A
XA  
N AO C AO