Topic 6: Kinetics

6.1 Collision theory and rates of reactions

6.1.1 Species react as a result of collisions of sufficient energy and proper orientation

6.1.2 The rate of reaction is expressed as the change in concentration of a particular reactant/product per unit time

6.1.3 Concentration changes in a reaction can be followed indirectly by monitoring changes in mass, volume and color

6.1.4 Activation energy (Ea) is the minimum energy that colliding molecules need in order to have successful collisions leading to
a reaction
6.1.5 By decreasing Ea a catalyst increases the rate of a chemical reaction, without itself being permanently chemically changed

6.1.6 Descriptions of the kinetic theory in terms of the movement of particles whose average kinetic energy is proportional to
temperature in Kelvin
6.1.7 Analysis of graphical and numerical data from rate experiments

6.1.8 Explanation of the effects of temperature, pressure/concentration and particle size on rate of reaction

6.1.9 Construction of Maxwell-Boltzmann energy distribution curves to account for the probability of successful collisions and
factors affecting these, including the effect of a catalyst
6.1.10 Investigation of rates of reaction experimentally and evaluation of the results

6.1.11 Sketching and explanation of energy profiles with and without catalysts

Collision Theory
 For a reaction between two particles to occur three conditions must be met
o The particles must collide
o They must collide with the appropriate geometry or orientation
o They must collide with sufficient energy to bring about the reaction
 The minimum amount of energy required is known as the activation energy

Factor Effect of increasing factor Explanation

The greater the particle size, the smaller the exposed surface area. Reactions
Surface Area
Decreases rate require collisions for reactions to occur, so if the surface area is smaller, fewer
Particle Size
collisions will occur per unit time

As the temperature increases, the particles will move faster so there will be
more collisions per second. However, the main reason why an increase in
Temperature Increases rate temperature increases the rate is that more of the colliding particles will
possess the necessary activation energy resulting in more successful collisions.
Generally, an increase of 10°C doubles the rate of a chemical reaction

Increasing the concentration increases the frequency of collisions which

Concentration Increases rate
increases the frequency of successful collisions too, thus increasing the rate.

Higher pressure compresses the gas, effectively increasing the concentration, so

Pressure Increases rate
increasing the frequency of collisions and therefore the rate too.

Rate of reaction
 Chemical kinetics is the study of the factors affecting the rate of a chemical reaction
 The rate of a chemical reaction can be defined as the change in concentration of the products/reactants per unit time or
Increase/decrease in concentration of product/reacts per unit time
 Concentration changes in a reaction can be indirectly monitored by monitoring :
o Change in volume of a gas, mass, concentration through titration, gas pressure or electrical conductivity
o Calorimetry and light absorbance
 The results obtained is usually then plotted in a graph of concentration against time
 The rate at any point in time is the gradient of the graph at that time
∆ concentration
 Thus, find the gradient at t by using Rate of Reaction=
∆ time

 The rate of reaction (gradient) will generally be the steepest at the start of the curve
o This is because a high concentration of reactant particles, therefore a high frequency of successful collisions
 The rate of reaction (gradient) decreases over time as time as the concentration of reactant particles decreases, thus the
frequency of successful collisions also decreases
 Hence, the
The Rate of Disappearance of Reactants The Rate of Formation of Products rate of
reaction can
−∆ [R] ∆[ P] also be
Rate= Rate=
∆T ∆T defined as:
Since Rate of Disappearance of Reactants is This is the rate of which the products are formed
decreases over time, the negative sign counteracts
this effect

 Where ∆ [R ] means the change in the concentration of R , and ∆ [P ] means the change in the concentration of P
 The units for rate of reactions are mol dm−3 s−1

Maxwell-Boltzmann distribution curve

 The Maxwell-Boltzmann curve shows the distribution of kinetic energy for a reaction
 Only a small proportion of particles at a given temperature will have sufficient kinetic energy to overcome its E a
 Activation energy (Ea): The minimum amount of energy required for a reaction to occur
 As temperature increases, the area under the curve does not change as the total number of particles remains constant.
 Instead more particles have a very high velocity resulting in an increase in the average kinetic energy which leads to a
broadening of the curve, however still has same activation energy
 Adding a catalyst reduces the activation energy, more particles have enough energy to react
o If a species is both on the reactant and product side of the overall equation, it is probably a catalyst
16.1 Rate expression and reaction mechanism
16.1.1 Reactions may occur by more than one step and the slowest step determines the rate of reaction

16.1.2 The molecularity of an elementary step is the number of reactant particles taking part in that step

16.1.3 The order of a reaction can be either integer or fractional in nature. The order of a reaction can describe, with respect to a
reactant, the number of particles taking part in the rate-determining step
16.1.4 Rate equations can only be determined experimentally

16.1.5 The value of the rate constant (k) is affected by temperature and its units are determined from the overall order of the
reaction
16.1.6 Catalysts alter a reaction mechanism, introducing a step with lower activation energy

16.1.7 Deduction of the rate expression for an equation from experimental data and solving problems involving the rate
expression
16.1.8 Sketching, identifying, and analyzing graphical representations for zero, first and second order reactions

16.1.9 Evaluation of proposed reaction mechanisms to be consistent with kinetic and stoichiometric data

Rate Expression
 The rate of reaction between two reactants, A and B, can be followed experimentally
 The mathematical relationship of reaction rate with reactant concentration can be expressed as a rate expression
For the following hypothetical reaction: aA +bB → cC

The Rate Law can be expressed as: rate=k [ A] x [B] y

 The proportionality constant, k , is known as the rate constant

 The rate constant is different for each reaction and is changed by temperature
 The overall order of a reaction is: order=x + y
2
 For example, take: rate=k [ A ][ B ] .This reaction is third-order overall, first-order in A, and second order in B
 However, the order of a reaction and the rate expression can only be determined experimentally. They cannot be decuded
from the balance equation
 Generally, reaction orders can be classified as zero-order, first-order, second-order and third-order:

Order: Zero order First order Second order Third order

The rate is directly The rate is proportional

The rate does not proportional to to the square of the If the concentration
Description depend on concentration concentration doubles, the rate
concentration If concentration If the concentration increases eight times
doubles, rate doubles doubles, rate quadruples

2
Rate = k[A]3 or
Rate Rate = k[A] or
Rate = k Rate = k[A] Rate = k[A][B]2 or
Expression Rate = k[A][B]
Rate = k[A][B][C]

mol dm−3 s−1 mol dm−3 s−1 mol dm−3 s−1

¿ ¿ 2
¿ 3
Units of Rate ¿ mol dm−3 s−1 mol dm −3 ( mol dm−3 ) ( mol dm−3 )
¿ s−1 ¿ mol−1 dm3 s−1 ¿ mol−2 dm6 s−1
  When graphed, reactions orders will be graphed as:

Reaction Mechanisms
16.2 Activation energy
16.2.1 The Arrhenius equation uses the temperature dependence of the rate constant to determine the activation energy

16.2.2 A graph of 1/T against ln(k) is a linear plot with gradient –E a/R and intercept, lnA

16.2.3 The frequency factor (or pre-exponential factor) (A) takes into account the frequency of collisions with proper orientations
−E a
16.2.4 Analyzing graphical representation of the Arrhenius equation in its linear form RT
lnk= A e + lnA
−E a
16.2.5 Using the Arrhenius equation RT
k=Ae
Describing the relationships between temperature and rate constant; frequency factor and complexity of molecules
16.2.6
colliding
16.2.7 Determining and evaluating values of activation energy and frequency factors from data

 Many reactions do not go in one step. This is particularly true when there are more than two reactant molecules as the
chances of a successful collision between three or more particles is extremely small. Where there is more than one step then
each step will proceed at its own rate. No matter how fast the other steps are the overall rate of reaction will depend only
upon the rate of the slowest step
 The step with the highest activation energy will act as the rate determining step, which acts as a limit on the rate of reaction

Arrhenius equation
 The rate constant for a reaction is only constant if the temperature remains constant. As the temperature increases the
reactants possess more energy and the rate constant increases
 The relationship between rate constant and absolute temperature is given by the Arrhenius equation:
−Ea
RT
k=Ae
k: rate constant/A: Arrhenius constant/Ea: Activation energy/R: Gas constant/T: Temperature

 A graph of the Arrhenius equation allows us to calculate the activation energy of a reaction. We used the integrated version
of the equation to simply the graph into a linear expression ( y=mx+c )

−Ea 1
lnk= +lnA
R T
 The equation can be used to determine both the frequency factor and the activation energy for a reaction