CHEMICAL KINETICS

Dr Onesmus M Munyati Department of Chemistry, University of Zambia, Zambia

Learning outcomes
Chemical kinetics At the end of this unit you must be o Rates of a Chemical Reactions able to: o Measuring of Reaction Rates Explain and use the terms: rate o Rate of Reaction of a reaction, rate law of a o Integrated Rate Laws reaction, order of a reaction, o Factors Affecting Rates of rate constant, half-life of a Reaction reaction, rate determining step Write the reaction rate expressions of chemical reactions Predict how changes in the conditions affect the rate of a chemical reaction Determine the order of reaction from experimental data
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How fast does a chemical process proceed?

Different chemical processes proceed at

different rates some very fast others very slow Examples: Slow processes: rusting, fermentation, biodegradation of plastics Fast process: fireworks, combustion of most hydrocarbons etc Rates are affected by a number of factors
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How fast does a chemical process proceed?

Temperature is a good example Most milk products sour quickly when stored at room temperature, process is slowed down in the fridge A number of pharmaceutical products require storage in a cool place or fridge to slow down rate of deterioration Warming most reactions results in higher reaction rate Other factors: concentration, surface area and pressure affect the pass of the reaction
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Understanding chemical kinetics?

Allows us

understand the factor that control rates of chemical changes Determine of the feasibility of the process and rates of productions (which are important!) Important in drug stability and degradation (sale by dates can be predicted!) Chemical product throughput can be predicted

How do we monitor the rate of a reaction?

Follow a parameter that changes with time

Typical examples include volume, pressure, absorbance or concentration of the reaction system (common method) Consider the reaction A B We can monitor how fast A molecules are disappearing how fast B molecules are being produce
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 Change in number of moles can also be used

changein number of moles (nB ) nB Average changein time t

nA t

nA and nB are the numbers of species A and B respectively.

Concentration vs time
Rate may also be reflected in terms of

concentrations of the reactants and products

Average rate between 300 and 600 s M t

Conc [A]/M
M

Reactions generally initially

t

100

300

500

600

800

Time/s

start-off rapidly but slow down with time As the concentration of reactants decreases so does the rate of reaction
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Instantaneous reaction rate at 500 s is the slope at that point

Conc [A]/M
M t 100 300 500 600 800

Time/s
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Relationship between reactant concentrations and time

Consider the reaction

2HI (g) H2(g) + I2(g) Rate can be expressed as

Rate 1 2 HI t H2 t I2 t

For the hypothetical reaction aA + bB cC + dD

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Relationship between reactant concentrations and time

Rate 1 a A t 1 b B t 1 c C t 1 d D t

Where [A], [B], [C] and [D] are concentrations of the reactants and products with a, b, c and d as reaction coefficients For a small change
Rate 1dA a dt
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 Rate is found to be proportional to the product of the

molar concentrations of the reactants, each raised to an exponent or power as shown in equation (for many reactions) Rate = k[A]n[B]m
n and m are called orders of reaction with respect to

A and B correspondingly the overall order of reaction is n + m the proportionality constant k is the rate constant for the reaction
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Zero order reactions

n + m = 0 in rate equation

Consider reaction: A
Rate dA dt
dA dt

products
kA
k
0

We can be integrate to obtain an expression that allows the prediction of the concentration at a given time, t.
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At A0

d A
A
0

k dt
0

kt
similar to the equation of a straight line: y = mx + c

At
y m

kt A 0
c

A0 t

At
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The half life of a reaction

An important characteristic of rates of reaction is

the half-life. The half life is defined as the time that is required for one-half of the reactant to be consumed or disappear and is designated . For zero order of reaction the half-life of the equation takes the form

A t1
2

kt1
2

A0
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Solving for

t1
2

1 2

A0 k

Apparent Zero order kinetics

Suspensions are a form of zero order kinetic Example, concentration of drug in solution

depends on the drugs solubility As the drug decomposes in solution, more is released from the suspended particle so that the concentration remains constant The drug concentration remains constant despite its decomposition with time Reservoir of drug is responsible for the constancy
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Apparent zero order kinetics

The equation for an ordinary solution with no

reservoir is first order

d [ A] dt k[ A]

When [A] is rendered constant as in a

suspension then k[A] = k0 so that the first order rate law becomes
d [ A] dt k0
This is an apparent zeroorder equation

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First order reaction

A
Rate
At A0

products
d A dt k A

d A
ln A

k dt
0

integration gives us ln A
ln A

kt

ln A

kt
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First order reaction

In [A]t = (-k) (t) + In [A]o
log A t log A
0

kt 2.303
0 t

A 2.303 k log t A

At

t1
2

At
ln
1 2

1 2

A0
0

ln A

kt1
2
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First order reaction

A 0 ln A 0
1 2

kt 1 2

Solving

t1
2

ln 2 0.693 k k

Important note:
The half-life for a first order reaction is constant Radioactive decay follows 1st order kinetics
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Second order reactions

n + m = 2 , associated with biomolecular reactions A+B products
d A dt dB dt k A B

Let a and b be the initial concentration of A and B respectively Let concentration of reacting species at time t be x.
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Second order reactions

We can write that [A]t = (a x) and [B]t = (b x). The rate equation maybe expressed as
dx k (a dt x)(b x)

If a = b then

dx k (a dt
dx 2 0 (a x)
x

x)
k

t 0

dt

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Second order reactions

giving the solution

1 a x

1 a 0
1 x at a x

kt

We can solve for k

kt

x aa x
A 0 A t A0 A t
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kt

Second order reactions

What is the half-life?

At

1 2

A0
2

Substitution and solving for t 1

t1
2

1 A 0 1 A 0 2 k A 01 A 0 2

t1
2

1 k A

Note that the half-life for a second order reaction is not a constant but depends on the initial concentration and on the rate constant.
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Factors affecting rate of chemical reaction

Concentration rate generally increases with increasing concentration of the reactants. in a few cases increasing the concentration of one the reactants may have little noticeable effect of the rate effect of concentration is explained using the collision theory in order for a reaction to occur the molecules involved must collide
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Factors affecting rate of chemical reaction

What about case involving one reactant?

The number of particles (molecules) with sufficient energy react (decompose) at any one given time Examples: Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)

2H 2 O 2 (aq)

MnO2 (s)

2H 2 O(l) O 2 (g)
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Factors affecting rate of chemical reaction

Pressure

Increasing pressure results in increased rate of reaction Solids and liquids not significantly affected by pressure Increasing pressure, similar to increasing concentration (e.g. squeeze gas into small volume)

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Factors affecting rate of chemical reaction

Mathematical expression
PV nRT n P RT V

Note that n/V is the concentration and RT is constant. The pressure, P, is directly proportional to concentration Explanation collision theory
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Factors affecting rate of chemical reaction

Surface area

Affects reactions
o

o
o

involving a solid and a gas a solid and a liquid cases where the solid is acting as a catalyst

The more finely divided the solid is, the faster the reaction proceeds (single lump slow reaction!) Reason - greater surface area on fine particle than the single lump
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Factors affecting rate of chemical reaction

Example: catalytic converters Catalytic converters use metals like platinum, palladium and rhodium to convert poisonous compounds in vehicle exhausts into less harmful gases
2CO(g) + 2NO(g) 2CO2(g) + N2(g)

exhaust gases are only in contact with the catalyst for a very short time, the reactions have to be very fast

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Effect of temperature
In order for chemical reactions take place molecules

must collide (collision theory) But not all collisions result in successful chemical reaction. Only molecules with sufficient kinetic energy, activation energy (Ea), result in a chemical change Any factor that increases the frequency of collisions results in an increase in the rate of reaction. Increasing temperature increases the average kinetic energy of the molecules, hence a greater fraction of molecules whose kinetic is equal or above the activation energy.
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Orientation of collision
Only molecules with the appropriate orientation lead to

formation of a new product. Other molecules may collide but will simply bounce off. Consider for example the reaction involving an addition reaction

of an alkene (propene) and hydrogen bromide

Bonds broken, new ones formed

Orientation for successful collision

Diagram showing molecular collision resulting in a successful reaction

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Effect of temperature
Transition state theory

This theory proposes that intermediate species form between reactants and products in a chemical reaction The intermediate species in the transition state is known as the activated complex The activated complex can either dissociate back into reactants or into products
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Effect of temperature

Two species reacting

Activated complex

Products

A potential energy diagram is used to

illustrate the reaction profile

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Effect of temperature

Energy
Reactants

Activation energy, Ea Heat evolved, H Products Progress of reaction

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Effect of temperature
Frequency of collisions, temperature and

activation energy are related through the Arrhenius equation

k Ae
-

Ea RT

k is the rate constant A is called the frequency factor or pre-exponential factor Ea is the activation energy
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Effect of temperature

ln k

Ea ln A RT

ln k

Ea 1 ln A R T

lnk versus 1/T yields a straight

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Effect of temperature
Activation energy can also be calculated by

measuring rate constants at two different temperatures through the expression

k2 ln k1 Ea R 1 T2 1 T1

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Radioactive decay
What is radioactivity?

- Elements that are unstable disintegrate and release high-energy streams of electromagnetic radiation. - Such isotopes are radioactive and exhibit a phenomenon known as radioactivity. - Nuclear reactions result in transmutation of one element into a different isotope or indeed different element.
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Radioactive decay
Rate of Radioactive Decay
Every nuclear of radioactive nuclear is

expected for disintegrate (at some point!) but one can not predict when it will disintegrate Statistical method can be used to make predictions for a collection of atoms Radioactive decay law states:
The rate of disintegration of a radioactive material called the activity, A, or decay rate - is directly proportional to the number of atoms present
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Radioactive decay
Radioactivity is a first-order process that

visualizes activity as a rate of reaction where N corresponds to the concentration of reactant and corresponds to the rate constant We can therefore write an integrated rate and half-life expression of the form
ln N N0
t1
2
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t
0.693

Radioactive decay
where No is the number of atoms at initial time (t

= 0), Nt is the number of atoms at later time t, is the half-life Recall that the half-life of a process is - the length of time for half of the substance to disappear - constant for a first order process - the shorter the half-life the larger the value of and the faster the decay process - half-lives for radioactive elements are varied from extremely very short to very long
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Radioactive decay
Radiocarbon dating

In the upper atmosphere is being formed continuously by bombardment with neutrons of Neutrons being produced by cosmic rays
14 7

1 0

14 6

C 1H 1
-

14 6

disintegrates by

emission
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Radioactive decay
Carbon containing compounds in living

organisms maintain an equilibrium with carbon-14 in the atmosphere Organisms replace C-14 atoms that have undergone radioactive decay with fresh C-14 atoms through interaction with the environment Activity associated with C-14 , in equilibrium with its environment is approximately 15 disintegration/minute per gram of carbon
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Radioactive decay
The equilibrium is destroyed when an

organism (e.g. tree is cut) as the organisms no longer interacts with the atmosphere, the disintegration rate therefore falls off Measurement of disintegration rates at a later stage can then give estimates of the age Techniques is commonly used to date archaeological artefacts

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