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**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.

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