CHEMISTRY

The Central Science

9th Edition

Chapter 14
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.
 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.
Change in Concentration of
Reactions
10 20
 Calculating Reaction Rates
Using Products
– At t = 0 (time zero) there is 1.00 mol A (100 red spheres) 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
 Calculating Reaction Rates
Using Reactants
• 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.
– By convention rates are expressed as positive numbers.
 Reaction Rates
• Most useful units for rates are to look at molarity. Since
volume is constant, molarity and moles are directly
proportional.
• Consider:
• C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

Reactants Products
Reaction Rates for C4H9Cl
 Properties of C4H9Cl
Reaction
• C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)
• We can calculate the average rate in terms of the
disappearance of C4H9Cl.
• The units for average rate are mol/L·s or M/s.
• The average rate decreases with time.
• We plot [C4H9Cl] versus time.
• The rate at any instant in time (instantaneous rate) is the
slope of the tangent to the curve.
• Instantaneous rate is different from average rate.
• We usually call the instantaneous rate the rate.
Instantaneous Reaction Rates
for C4H9Cl
 Reaction Rates and Stoichiometry
• For the reaction
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)
we know  C4H9Cl  C4H9OH 
Rate   
t t
• In general for
aA + bB  cC + dD
1  A  1  B 1  C 1  D
Rate     
a t b t c t d t
 Concentration and Rate
Table
• In general rates increase as concentrations increase.
NH4+(aq) + NO2-(aq)  N2(g) + 2H2O(l)
 Concentration and Rate
Equation
• 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.
 Exponents in the Rate
Law
• 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 + ….
• A reaction can be zeroth order if m, n, … are zero.
• Note the values of the exponents (orders) have to be
determined experimentally. They are not simply related
to stoichiometry.
 Determining Order of Reactions
• 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.
 Concentration Change with Time
First Order Reactions
• Goal: convert rate law into a convenient equation to give
concentrations as a function of time.
• For a first order reaction, the rate doubles as the
concentration of a reactant doubles.
[A]
Rate    k[A]
t
ln A  t  ln A  0   kt
  At 
ln   kt
  A 0 
 Plotting First Order Reactions
• A plot of ln[A]t versus t is a straight line with slope -k
and intercept ln[A]0.
• Put into simple math language : y = mx + b
• Plotting of this equation for given reaction should yield a
straight line if the reaction is first order.
• In the above we use the natural logarithm, ln, which is
log to the base e.
 Example Plots of a 1 Order Reaction st

• Left graph plotted with pressure vs. t, and right graph plotted with
ln(pressure) vs. t.
ln A  t   kt  ln A  0
 Concentration Change with Time
Second Order Reactions
• For a second order reaction with just one reactant
1 1
 kt 
 At  A 0
• A plot of 1/[A]t versus t is a straight line with slope k and
intercept 1/[A]0
• Put into simple math language: y = mx + b
• For a second order reaction, a plot of ln[A]t vs. t is not
linear.
• However, a plot of 1/[A]t versus t is a straight line
 Example plots of a 2nd Order Reaction
• Left is Ln[NO2] vs t, and right is 1/[NO2] vs. t.
1 1
 kt 
 At  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
• The half-life for a 1st order reactions depends only on k
 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
 Temperature and Rate
The Collision Model
• Most reactions speed up as temperature increases. (E.g.
food spoils when not refrigerated.)
• When two light sticks are placed in water: one at room
temperature and one in ice, the one at room temperature is
brighter than the one in ice.
• The chemical reaction responsible for chemiluminescence
is dependent on temperature: the higher the temperature,
the faster the reaction and the brighter the light.
The Collision Model
• As temperature
increases, the rate
increases.
 Collision Model: The Central Idea
• Goal: develop a model that explains why rates of
reactions increase as concentration and temperature
increases.
• The collision model: in order for molecules to react they
must collide.
• The greater the number of collisions the faster the rate.
• The more molecules present, the greater the probability
of collision and the faster the rate.
• Faster moving molecule collide with greater energy and
more frequently, increasing reaction rates.
 The Speed of a Reaction
The Collision Model
• The higher the temperature, the more energy available to
the molecules and the faster the rate.
• Complication: not all collisions lead to products. In fact,
only a small fraction of collisions lead to product.
• Why is this?
The Orientation Factor
• In order for reaction to occur the reactant molecules must
collide in the correct orientation and with enough energy
to form products.
 The Orientation Factor
• Consider:
Cl + NOCl  NO + Cl2
• There are two possible ways that Cl atoms and NOCl
molecules can collide; one is effective and one is not.
 Activation Energy
• Arrhenius: molecules must posses a minimum amount of
energy to react. Why?
• In order to form products, bonds must be broken in the
reactants.
• Bond breakage requires energy.
• Activation energy, Ea, is the minimum energy required to
initiate a chemical reaction.
Energy Profile for Methly Isonitrile
 Fraction of Molecules
Possessing Ea
• How does a methyl isonitrile molecule gain enough
energy to overcome the activation energy barrier?
• From kinetic molecular theory, we know that as
temperature increases, the total kinetic energy increases.
• We can show the fraction of molecules, f, with energy
equal to or greater than Ea is

Ea

f e RT
• where R is the gas constant (8.314 J/mol·K).
Activation Energy, Ea, Plot
 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:

Ea
ln k    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.
 Ln k versus 1/T
• Ea can be determined by finding the slope of the line.
 Reaction Mechanisms
• The balanced chemical equation provides information
about the beginning and end of reaction.
• The reaction mechanism gives the path of the reaction
(i.e., process by which a reaction occurs).
• Mechanisms provide a very detailed picture of which
bonds are broken and formed during the course of a
reaction.
Elementary Steps
• Elementary step: any process that occurs in a single step.
 Properties of the Elementary
Step Process
• Molecularity: the number of molecules present in an
elementary step.
• Unimolecular: one molecule in the elementary step,
• Bimolecular: two molecules in the elementary step, and
• Termolecular: three molecules in the elementary step.
• It is not common to see termolecular processes
(statistically improbable).
 Multistep Mechanisms
• Some reaction proceed through more than one step:
• Consider the reaction of NO2 and CO
NO2(g) + NO2(g)  NO3(g) + NO(g)
NO3(g) + CO(g)  NO2(g) + CO2(g)
• Notice that if we add the above steps, we get the overall
reaction:
NO2(g) + CO(g)  NO(g) + CO2(g)
• The elementary steps must add to give the balanced
chemical equation.
• Intermediate: a species which appears in an elementary
step which is not a reactant or product
 Reaction Mechanisms
Rate Laws for Elementary Steps
• The rate law of an elementary step is determined by its
molecularity:
– Unimolecular processes are first order,
– Bimolecular processes are second order, and
– Termolecular processes are third order.
Rate Laws for Multistep Mechanisms
• Rate-determining step: is the slowest of the elementary
steps.
 Table 14.3, Page 551

• Rate Laws for Elementary Steps

 Initial Fast Step of a Mechanisms
• It is possible for an intermediate to be a reactant.
• Consider
2NO(g) + Br2(g)  2NOBr(g)
• The experimentally determined rate law is
Rate = k[NO]2[Br2]
• Consider the following mechanism
k1
Step 1: NO(g) + Br2(g) NOBr2(g) (fast)
k-1
k2
Step 2: NOBr2(g) + NO(g) 2NOBr(g) (slow)
 Intermediate as a Reactant
• The rate law is (based on Step 2):
Rate = k2[NOBr2][NO]
• The rate law should not depend on the concentration of
an intermediate (intermediates are usually unstable).
• Assume NOBr2 is unstable, so we express the
concentration of NOBr2 in terms of NOBr and Br2
assuming there is an equilibrium in step 1 we have
k1
[ NOBr2 ]  [ NO][Br2 ]
k1
 Intermediate as a Reactant Conts.
• By definition of equilibrium:

k1[ NO][Br2 ]  k1[ NOBr2 ]

• Therefore, the overall rate law becomes

k1 k1
Rate  k2 [ NO][Br2 ][ NO]  k2 [ NO]2[Br2 ]
k1 k1
• Note the final rate law is consistent with the
experimentally observed rate law.
 Catalysis
• A catalyst changes the rate of a chemical reaction.
• Catalyst lower the overall Ea for a chemical reaction.
• There are two types of catalyst:
• Homogeneous and heterogeneous
• Example: Cl atoms are catalysts for the destruction of
ozone.
Homogeneous Catalysis
• The catalyst and reaction is in one phase.
Heterogeneous Catalysis
• The catalyst and reaction exists in a different phase.
The Effects of a Catalyst
 Functions of the Catalysis
• Catalysts can operate by increasing the number of
effective collisions (i.e., from the Arrhenius equation:
catalysts increase k which results in increasing A or
decreasing Ea.
• A catalyst may add intermediates to the reaction.
• Example: In the presence of Br-, Br2(aq) is generated as an
intermediate in the decomposition of H2O2.
End of Chapter 14
Chemical Kinetics