Chapter 6 Kinetic

23/08/2019
GENERAL CHEMISTRY
Chapter 6
Chemical Kinetics
Kinetics
Kinetics is the study of how fast chemical reactions
occur.
There are 4 important factors which affect the rates of
chemical reactions:
reactant concentration,
temperature,
action of catalysts, and
surface area.
1
23/08/2019
Reaction Rates
• The speed of a reaction is defined as the change that occurs
per unit time.
• It is determined by measuring the change in concentration of a
reactant or product with time.
• The speed the of the reaction is called the reaction rate.
• For a reaction A  B:
change in number of moles of B
Average rate 
change in time
moles of B

t
• Suppose A reacts to form B. Let us begin with 1.00 mol A.
Reaction Rates
– At t = 0 (time zero) there is 1.00 mol A and no B present.

– At t = 10 min, there is 0.54 mol A and 0.26 mol B.
– At t = 20 min, there is 0.30 mol A and 0.70 mol B.
– Calculating,
moles of B 
Average rate 
t
moles of B at t  10   moles of B at t  0 

10 min  0 min
0.26 mol  0 mol
  0.026 mol/min
10 min  0 min
2
23/08/2019
Reaction Rates
For the reaction A  B there are two ways of measuring
rate:
 the speed at which the products appear (i.e. change in moles of
B per unit time), or
 the speed at which the reactants disappear (i.e. the change in
moles of A per unit time).
moles of A 
Average rate with respect to A  
t
• The equation, when calculating rates of reactants, is multiplied
by -1 to compensate for the negative concentration.
Reaction Rates and Stoichiometry
• In general :
aA + bB  cC + dD
1 A 1 B 1 C 1 D

Rate     
a t b t c t d t
• For the reaction:
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)
C4H9Cl C4H9OH
Rate   
t t
3
23/08/2019

The rate-law expression for a reaction in which A, B, . . . are
reactants:
 The constant k: the specific rate constant (or the rate constant)
for the reaction at a particular temperature
 x and y: no necessary relationship to the coefficients in the
balanced chemical equation for the overall reaction and must
be determined experimentally.

 x and y are usually integers or zero but are occasionally
fractional or even negative.
 A power of one means that the rate is directly proportional to
the concentration of that reactant.
 A power of two means that the rate is directly proportional to
the square of that concentration.
 A power of zero means that the rate does not depend on the
concentration of that reactant, so long as some of the reactant
is present.
4
23/08/2019
5
23/08/2019

• For the reaction
NH4+(aq) + NO2-(aq)  N2(g) + 2H2O(l)
we note
– as [NH4+] doubles with [NO2-] constant the rate doubles,
– as [NO2-] doubles with [NH4+] constant, the rate doubles,
– We conclude rate  [NH4+][NO2-].
• Rate law:
Rate  k[ NH4 ][ NO2 ]
• The constant k is the rate constant.

• For a general reaction with rate law
Rate  k[reactant 1]m[reactant 2]n
we say the reaction is mth order in reactant 1 and nth
order in reactant 2.
• The overall order of reaction is m + n + ….
6
23/08/2019
• A reaction is zero order in a reactant if the change in

concentration of that reactant produces no effect.
• A reaction is first order if doubling the concentration
causes the rate to double.
• A reaction is nth order if doubling the concentration
causes an 2n increase in rate.
• Note that the rate constant does not depend on
concentration.

Example:
7
23/08/2019
Concentration Change with Time

First Order Reactions
• Goal: convert rate law into a convenient equation to give
concentrations as a function of time.
[A]
Rate    k[A]
t
lnA t  lnA 0  kt
 A  
ln t   kt
 A 0 
Half-Life Reactions
First Order Reactions
• Half-life is the time taken for the concentration of a
reactant to drop to half its original value.
• For a first order process, half life, t½ is the time taken for
[A]0 to reach ½[A]0.
• Mathematically defined by:
t1  

ln 12 0.693

2 k k
• st
The half-life for a 1 order reactions depends only on k
8
23/08/2019
Compound A decomposes to form B and C in a reaction. At 25°C,

the specific rate constant for the reaction is 0.0450 s-1. What is the
half-life of A at 25°C?
Concentration Change with Time

Second Order Reactions
• Goal: convert rate law into a convenient equation to give
concentrations as a function of time.
1 1
 kt 
At A0
9
23/08/2019
Half-Life Reaction
Second Order
• Mathematically defined by:
1
t 12 
k A 0
• A second order reaction’s half-life depends on the initial
concentration of the reactants
EXAMPLE 16-7
Compounds A and B react to form C and D in a reaction . The rate
constant at 30°C is 0.622 liter per mole per minute. What is the
half-life of A when 4.1010-2MA is mixed with excess B?
10
23/08/2019
The Arrhenius Equation

• Arrhenius discovered most reaction-rate data obeyed the
Arrhenius equation:
 Ea
k  Ae RT
• k is the rate constant, Ea is the activation energy, R is the

gas constant (8.314 J/K-mol) and T is the temperature in
K.
• A is called the frequency factor.
– A is a measure of the probability of a favorable collision.
• Both A and Ea are specific to a given reaction.
Determing Activation Energy
• If we have a lot of data, we can determine Ea and A

graphically by rearranging the Arrhenius equation:
E
ln k   a  ln A
RT
• From the above equation, a plot of ln k versus 1/T will
have slope of –Ea/R and intercept of ln A.
11

Chapter 6 Kinetic

Uploaded by

Copyright:

Available Formats

Chapter 6 Kinetic

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 6 Kinetic

Uploaded by

Copyright:

Available Formats

23/08/2019

– At t = 0 (time zero) there is 1.00 mol A and no B present.

Reaction Rates and Stoichiometry

1 A 1 B 1 C 1 D

Reaction Rates and Stoichiometry

Reaction Rates and Stoichiometry

Reaction Rates and Stoichiometry

Reaction Rates and Stoichiometry

Reaction Rates and Stoichiometry

Reaction Rates and Stoichiometry

Reaction Rates and Stoichiometry

• A reaction is zero order in a reactant if the change in

Reaction Rates and Stoichiometry

Concentration Change with Time

Compound A decomposes to form B and C in a reaction. At 25°C,

Concentration Change with Time

The Arrhenius Equation

• k is the rate constant, Ea is the activation energy, R is the

Determing Activation Energy

• If we have a lot of data, we can determine Ea and A

You might also like