CAPE CHEMISTRY UNIT ONE MODULE 2

RATES OF REACTION

Kinetics is the area of chemistry concerned with reaction rates. The rate of a reaction can be expressed as:
rate = change in concentration of substance/time for change to occur (usually in M/s)

There are several factors that determine the rate of a specific reaction and these are expressed in the "collision
theory" that states that for molecules to react, they must:

1. collide
2. have the right energy
3. have the right geometry

To increase the rate of a reaction, you must make the above factors more likely to occur. This is possible by
changing other factors such as:

 increasing the surface area (of solids)-this allows for more collisions and gives more molecules the right
geometry
 increasing the temperature-this gives more molecules the right energy (also called the activation energy,
Ea)
 using a catalyst which lowers the activation energy

Boltzmann distribution curve

The reaction rate can also be expressed by using a "rate law" and is written as follows:

For the general reaction: mA + nB +  gG + hH

the reaction rate can be calculated by:

Reaction rate = k[A]m[B]n

Where:

[A], [B], are the concentrations of the reactants

k is the rate constant or rate coefficient, a value dependent on temperature.
m,n, are exponents that correspond to stoichiometry in balanced equation. The concentration is raised to the
power of its coefficient in the balanced equation.

Reaction order is a topic that comes with reaction rates. If you have a reaction in that A, B, and C are possible
reactants, then we can describe the order of the reaction following this chart:

The order of the reaction is defined as the sum of the exponents of the coefficients. In general, first order
reactions are most commonly seen, but reactions of other orders are also important. Zero-order reactions --
those for which the change in the reaction is independent of the concentration of the reaction -- are also
possible.
 It is possible to determine the order of a reactant, and eventually the reaction rate, using initial rate
information that includes the concentration of the reactants and the rate at which the product is formed. If you
double the concentration of reactant X and the rate increases by 2a, then the order of reactant X is "a". If you
triple the concentration of reactant Y and the rate increases by 3b, then the order of Y is "b". For example, if you
have a reaction with one reactant, A, and you double [A] and the rate doubles, then the rate=k[A]1.

If, instead, you double [A] and the rate quadruples, the rate=k[A]2.

If you double [A] and the rate stays the same, then the rate=k[A]0.

Solving the rate equation by inspection

If a series of experimental results are obtained for rate at different reactant concentrations the change in rate can
be ascertained for those reactions when the concentration of one of the reactants is kept constant while the other
reactant concentration is changed.

Example

experiment concentration of A concentration of B Rate

1 0.1M 0.1M 6 x 103
2 0.2M 0.1M 1.2 x 104
3 0.4M 0.1M 2.4 x 104
4 0.1M 0.2M 6 x 103
5 0.2M 0.2M 1.2 x 104

For these three experiments. If we inspect the rate of experiments 1,2 and 3 we see that as the concentration of
A is doubled so the rate doubles. In other words the order of reaction must be 1 so that whatever happens to the
concentration must also happen in equal amounts to the rate.

Similar inspection of experiments 1 and 4 (or 2 and 5) show that while A is kept constant there is no effect on
the rate when the concentration of B is changed. The order with respect to B must be 0.

The orders can now be substituted into the rate equation:

Rate = k[A]1[B]0

To obtain a value for the rate constant we simple substitute the values for one of the experiments above using
the newly determined orders. (choose the experiment with the simplest numbers - in this case experiment 1)

Values from experiment 1

6 x 103 = k x [0.1]1 x [0.1]0

k = 6 x 103 / 0.1

k = 6 x 104

The units of k are trickier: units of k = units of rate/(units of concentration)reaction order

Eg: for 2nd order reaction, k=(M/s)/M2=M-1s-1

Example Problem: Find the rate law and rate constant of A + B  C using the following data:
A quantitative way to examine reaction rates is through Arrhenius Equation that states:

k=Ae-Ea/RT

Where:

A is a constant related to the geometry needed

e is a constant, approximately 2.7281
Ea is the activation energy
R is the gas law constant, 8.314 J/mol-K
T is the temperature in kelvins

If it is a simple geometry to attain, A will be large. If a large Ea is needed then the exponent becomes more
negative and therefore decreases k. If the temperature increases then the exponent becomes less negative and
therefore increases k.

The following are two (2) energy profile graphs that help demonstrate energy changes during a reaction.

Graphing results If a graph of reaction concentration against time is plotted a curve is obtained as the reactant
is used up in the course of the reaction. The rate of any reaction is at its greatest at the beginning (time=0). As
the reactants are used up the rate decreases. If a graph of rate against time is plotted then the shape obtained will
depend on the overall order of the reaction.

 0th order graph:- straight flat line

 1st order graph:- straight line
 All other orders: curve

For a zero order reaction, the plot of [A] versus time is a straight line with k = - slope of the line.

For a first order reaction, the plot of the log of [A] versus time is a straight line with k = - slope of the line.
For a second order reaction, the plot of 1/[A] versus time is a straight line with k = slope of the line. Other
graphs are curved for a second order reaction.

Half Life

The half life is the time taken for the concentration of reactants to reach half of its original value. For most
reactions the half life changes as the reaction proceeds but this is not the case for first order reactions where the
half life is constant. (short half life= fast rate)

Using the half life to find the rate constant

The rate constant can be found from a concentration/time graph by taking a point, finding its concentration, then
finding a point on the graph which corresponds to half this concentration. The half life is the time between these
two points. The half life is also equal to ln2/k where k is the rate constant.

Reaction mechanism

The mechanism of a reaction is a series of reactions between the particles of a reaction that eventually lead to
the final products. A reaction may have many steps in the mechanism.

Rate determining step The slowest step in a reaction. It determines the rate of the overall
reaction. (note 1)
Molecularity The number of particles reacting in the rate determining step of a
reaction.
Activated complex As two particles collide (with sufficient energy to react and in the
correct orientation) they form an intermediate called the activated
complex...not literally a chemical substance, but an intermediate in
which the bonds are in the process of being broken and formed.
The order of the This gives information about the particles involved in the rate
reaction determining step (which is one step in the mechanism). For
example, if two of one type of particle are colliding, the order with
respect to that particle will be 2 (and zero to any others).
Reactions only occur when the reacting particles have energy greater than the activation energy and are able to
get over the activation energy barrier.
Not all reactions happen exactly as they are written. Most, in fact, go through an intermediate step. Reaction
mechanism studies look at how a reaction actually occurs. Defined, a reaction mechanism is a series of
elementary reactions that are proposed to account for the rate law (kinetics) of a particular reaction. The
diagram below shows the two steps involved in a particular mechanism, and it shows how we get the reaction
from the mechanism.

It is helpful to remember certain terms and facts when dealing with mechanisms. You cannot derive a
mechanism from the equation and when you combine the steps of a mechanism, you end up with the reaction.
The molecularity of a step tells how many molecules are involved (most involve two (2) molecules so they are
bimolecular). An intermediate product is a molecule formed in one step and then used in another. One of the
most important concepts to keep in mind is that the steps are not equally important. To speed up the reaction,
you must speed up the slowest step (also called the rate-determining step).

rate law of slow step = rate law of reaction

When determining the rate of a step, simply make the exponent of the reactant's concentration in the rate law
the same as the coefficient of the reactant in the step.

Example problem: Find the slow step of the following reaction mechanism

The following is an example of how this can be done.

Practice Problems:

A catalyst is a substance added to a reaction that comes out of the reaction unchanged. As mentioned earlier,
catalysts help lower the activation energy as shown in the following graph. They do this by changing the
reaction mechanism.

Catalysts provide an alternative mechanism with lower activation energy. This means that a greater number of
collisions will be successful and the reaction procedes at a faster rate

Homogeneous catalysts -- catalysts in the same state (phase -- ie solid, liquid or gas) as the reactants.
Heterogeneous catalysts -- catalysts in a different phase (usually a solid) from the reactants.

Homogeneous catalysts operate by reacting with the reactants and eventually producing a reaction pathway of
lower activation energy (and also being regenerated at the end of this process).

Heterogeneous catalysts provide a reactive site on which an activated complex forms, weakening the bonds and
increasing the rate of collisions thus increasing the rate of reaction. Examples of catalysed processes:

Process catalyst used type

Contact (sulphur trioxide) Vanadium pentoxide heterogenous
Haber (ammonia) Iron heterogenous
Hydrogenation of alkenes Nickel heterogenous
Polymerisation Pt (Zeigler Natta) heterogenous
Polymerisation Oxygen homogeneous