Reaction Kinetics

Le Chartelier’s Principle
Factors affecting rate of reaction

1. Concentration

2. Temperature

3. Catalyst

4. Pressure
Rate of Reaction

 Methods for determining rate of reaction:

1. Sampling : Taking small samples of reaction mixtures at different times,
quenched and carrying chemical analysis on each sample.
2. Continuous : physical properties is monitored over a period of time. Eg :
Calorimetry – change in colour, conductivity meter – changes in electrical
conductivity (ions are present because different ions have different
electrical conductivity), measuring changes in gas volume or gas
pressure and stopped-flow spectrometry – very fast rate of reaction.
Question pg 327
 Calculating Rate of Reaction Graphically

 Gradient at specific point on the graph tells the exact rate of
reaction at specific time.
 How?
1. Select a point corresponding to a particular time
2. Draw a straight line at this point so that it touches the point.
Angle between the straight line and the curve should look
very similar
3. Extend the tangent to meet the axes of the graph. Calculate
the tangent of the straight line.
 Negative sign in slope indicating the reactant concentration is
decreasing.

 Question pg 329
 Rate Equations
 Rate of reaction = k[cyclopropane]  Rate equation
 k is the rate constant. Can only be determined from experimental data.
 Eg : 2H2 (g) + 2NO (g)  2H2O (g) + N2 (g) rate = k[H2][NO]2
1. Varying the concentration of [H2] while keeping [NO] constant.
2. The results show that the rate is proportional to the [H2] i.e., rate = k1[H2]
3. Varying the concentration of [NO] while keeping [H2] constant.
4. The results show that the rate is proportional to the [NO] i.e., rate = k2[NO]2
5. Combining the two equations, rate = k[H2][NO]2
 Rate equations for some reactions may include compounds that are not present in the
chemical equation
 Question pg 330
 Order of Reaction
 Order of reaction : shows how the concentration of a reagent affects the rate
reaction.
 Rate of reaction with respect to a particular reactant is the power to which the
concentration of that reactant is raised in the rate equation.
 Eg : NO (g) + CO (g) + O2 (g) NO2 (g) + CO2 (g) rate =[NO]2
The rate of reaction is 2 with respect to [NO].
 Eg : 2H2 (g) + 2NO (g)  2H2O (g) + N2 (g) rate = k[H2][NO]2
The rate of reaction is first-order with respect to H2 i.e., [H2] and second-order with
respect to NO i.e., [NO]2 and third-order with respect to overall i.e., 1+2=3.
 Therefore, rate of reaction = k[A]m[B]n for mA + nB  Products.
 A few reactions have fractional orders and it is usually reactions involving free
radicals. Eg : rate = k[CH3CHO]1.5.
 Question pg 331.
Units of k
 Unit of k depends on the rate equation.
 Eg: rate = k[H2][I2], thus, k =
 Question pg 331.

Which Order of Reaction?

 To identify :
1. Plot a graph of reaction rate vs [reactant].
2. Plot a graph of [reactant] vs time.
3. Deduce successive half-lives from graphs of concentration vs. time.
Graphs of reaction rate against concentration
 Zero-order :
Eg : 2NH3 (g)  N2 (g) + 3H2 (g)
rate = k[NH3]0
Plot : Horizontal straight line

 First-order :
Eg : 2N2O (g)  2N2 (g) + O2(g)
rate = k[N2O]1
Plot : Straight line graph
Graphs of reaction rate against concentration
 Second-order :
Eg : NO2 (g) + CO (g)  NO (g) + CO2 (g)
rate = k[NO2]2
Plot : Upward curve line

Question pg 333.
Graphs of reaction Half-Life and Reaction
rate against time Rates
 Half-life, t1/2  time taken for the concentration
of a reactant to fall into half of its original value.
 Zero-order – decrease half-life
 First-order – constant half-life , t1/2 =
 Second-order – increasing half-life
Question pg 334-338
 Kinetics and Reaction Mechanisms
 The rate determining step  slowest step in a chemical reactions.
 A reactant that appears in the chemical equation may have no affect in the
reaction rate.
 Substance that is not a reactant in the chemical reaction can affect the rate of
reaction.
 If the concentration of a reactant appears in the rate equation, the reactant
appears in the rate determining step.
 The kinetic data shows that the proposed reaction mechanism is possible.
 Eg : CH3COCH3 + I2 CH3COCH2I + HI rate = k[CH3COCH3][H+]
 If there is only a single species in the r.d.s, the reaction is unimolecular. Two 
bimolecular. (pg 339)
 Predicting the order of a reaction from
reaction mechanisms
 Given that we know the intermediates present in the RDS, we can predict
the order of reaction.
 CH3COCH3 + Br2 + OH-  CH3COCH2Br + H2O + Br- ; rate = k[CH3COCH3[OH-]
 Catalysis
 Catalyst increase the rate of reaction by providing
an alternative pathway for the reaction with lower
activation energy.
 Homogeneous catalysis
1. Catalyst is in the same phase as the reaction
mixture
2. Involves changes in oxidation number of the ions
involved
3. Eg : Iodine-peroxodisulfate reaction, oxides of
nitrogen and acid rain
4. Has two energy humps due to two-staged
reaction
 Catalysis cont..
 Heterogenous catalysis – catalyst is in different phase to the reaction mixture
 Often involve gaseous molecules reacting at the surface of a solid catalyst
 Mechanism can be explained by theory of adsorption – chemical adsorption
(chemisorption) occurs when molecules become bonded to atoms on the surface of a
solid.
 Eg : Adsorption of hydrogen onto nickel
1. H2 diffuses to the surface of the nickel
2. H2 is physically adsorbed onto the surface – weak VDW forces link the H molecules to
the Ni
3. The H becomes chemically adsorbed onto the surface- causes stronger bonds
between H and Ni
4. This causes weakening of the H-H covalent bond
 Catalysis cont..
 Eg : Fe in Haber process
1. Diffusion : N2 and H2 diffuse to the surface of Fe.
2. Adsorption : the reactant molecules are chemically adsorbed onto the surface of
Fe. The bonds formed between the reactant molecules and Fe are –
• strong enough to weaken the covalent bonds within the N2 and H2 molecules so the
atoms can react with each other
• Weak enough to break and allow the products to leave the surface
3. Reaction : the adsorbed N2 and H2 atoms react on the surface of the Fe to form NH3
4. Desorbtion : the bonds between the NH3 and the surface of Fe weaken and are
eventually broken
5. Diffusion : NH3 diffuses away from the surface of the Fe
Catalysis cont..
Eg : Transition elements in catalytic converters
 Honeycomb structure inside the catalytic converter contains small beads coated with Pt/
Pd/ Rh which acts as heterogeneous catalysts.
 Steps in catalytic process include
1. Adsorption of NO and CO onto the catalyst surface
2. Weakening of the covalent bonds within the NO and CO
3. Formation of new bonds between
• Adjacent N (to form N2)
• CO and O2 to form CO2
4. Desorption of nitrogen molecules and CO2 molecules from the surface of the catalyst.
Question pg 343