General Chemistry

Course # 111, two credits

Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Textbook: Principles of Modern Chemistry

by David W. Oxtoby, H. Pat Gillis, and Alan Campion (6 edition; 2007)

Dr. Rabih O. Al-Kaysi

Ext: 47247
Email: kaysir@ksau-hs.edu.sa
 Lectures 13 & 14
Chemical Kinetics


Kinetics
• Kinetics is the study of how fast a chemical
reaction occurs.
• There are 4 important factors which affect the rates
of chemical reactions:
• Concentration of the reactants: How close they are to
one another so they could react
• Temperature of the reaction: How much energy the
reactants have before they react
• Suitable catalyst for the reaction
• Surface area of the reacting species: The larger the
total surface area the faster the reaction.

Reaction Rates:
General Formula
• The speed of a reaction is defined as the change that
occurs per unit time. δ change/ δ 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.

Calculating Reaction Rates
Using Product Concentration

– Suppose, 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 ) 10 20
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: an
Example
• Use molarity to measure concentration. Since
volume is constant, molarity and moles are directly
proportional.
• Consider: Hydrolysis of Chlorobutane in water
• C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)

Reactants Products

Experimentally Determined
Reaction Rates for C4H9Cl

Chlorobutane is the reactant


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 (reactant).
• The units for average rate are mol/L·s or Molar/s.
• The average rate decreases with time.
• 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 a reaction
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 concentration of the
reactants 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
m n
Rate = k[reactant 1] [reactant 2]
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
on the rate of the reaction.
• 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 k does not depend on
concentration.

Concentration Change with
Time: [C] vs. t
First Order Reactions
• Goal: convert rate law into a convenient equation to
give concentrations as a function of time. This is
called the Integrated rate equation.
• 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 In this case A is the
reactant
 [ 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 a 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 1st Order

Reaction
• 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: [C] vs. t
Second Order Reactions
• For a second order reaction with just one reactant
• A →B 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
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 of a Reactio: t1/2

First Order Reactions
• Half-life (t1/2 ) is the time taken for the concentration
of a reactant to drop to half its original value.
• For a first order process, t½ is the time taken for [A]0
to reach ½[A]0.
• Equation:
t1 = −
( 2 ) = 0.693
ln 1
2 k k
• The t1/2 for a 1st order reactions depends only on k
and is constant regardless of [A]0


Half-Life of a Reaction: t1/2

Second Order
• Equation:

1
t 12 =
k [ A] 0
• A second order reaction’s half-life depends on the
initial concentration of the reactants. In other words
the reaction is faster the larger the [A]0. The t1/2 is
variable

Effect of Temperature
on Rate
The Collision Model
• Most reactions speed up as temperature increases.
(E.g. Calcium metal reacts very slowly with water at
room temperature, but very fast with boiling water.)

• As temperature
increases, the rate
increases.
• Rule of thumb for
every 10 OC
increase in temp. the
rate doubles

Collision Model: The Central Idea
• Goal: develop a model that explains why rates of
reactions increase as concentration and
temperature increases.
• 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?
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.

Effective collision

Non effective collision


Activation Energy: Ea
• 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.
• Think of Ea as a barrier that the reacting molecules
must jump over in order to react.
• At the peak of the Ea the reacting molecules form a
metastable structure called Activated Complex
 Energy Profile for Methly
Isonitrile Thermal Isomerization

Fraction of Molecules
with Enough Ea
• How does a methyl isonitrile molecule gain enough
energy to overcome the Ea 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: The rate constant k depends on
temperature:
− 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 Kelvin.
• 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.


Determining Ea
• If we have a lot of experimental 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).
• For that we measure the rate of a reaction at
different temperatures.


(Ln k) vs. (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.
Does not mention intermediate pathways.
• 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.
• Mechanistic chemistry is the backbone of chemistry.
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


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.


• 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.