THE RATE EXPRESSION

OUTLINE
In this section we cover the concentration and temperature dependence of the reaction rate.

RATE AND CONCENTRATION

If we take a homogeneous reaction:

A+B C
One can imagine that the amount of C formed is related to the amount of molecular collisions between A and B. Statistically one can prove that the likelihood of a collision is directly proportional to the molecular density (concentration) of both A and B. For this ideal situation it can be shown that

Note that the product concentration only influence the rate indirectly due to the decrease in reactant concentration. To incorporate for non-idealities and catalysed reactions, reaction engineers typically generalise the rate-concentration relationship to a generic power law model giving:

RATE AND CONCENTRATION

Sometimes (and only sometimes) it happens that the following reaction:

nA+mB yC
has a rate expression given by:

This is referred to as an elementary reaction. Note that there no need for the rate order to be related to the reaction stoicheometry. The order of the reaction is typically whole numbers, but can be fractions. Power law kinetics do not always represent reaction rates, but for most reactions the power law format is sufficient. It is very important to realise that the rate constant has units that is related to the rate definition (volume or mass) as well as the overall rate order. The units of the constant therefore contains information!

RATE AND TEMPERATURE

Reaction orders do not vary with temperature, only the reaction rate constant. This is due to the increase in molecular motion (more collisions). We use the Arhenius relationship to represent this:

We need the two parameters E and ko (both positive). T is defined as the Kelvin temperature and R is the universal gas constant Plotting this function over the complete temperature range gives:

ko

Typical range for chemical engineering applications

For reactor applications we have an exponential-like behaviour. Note that ko is the rate constant at infinite high temperatures. Make sure you realise that :
This should be a dimensionless group, thus get your units right!

RATE AND TEMPERATURE

Activation Energy (E) has units of J/mol. This parameter quantifies the severity of rate constant increase with increasing temperature. Note that Arhenius implies that HOTTER IS ALWAYS FASTER, and that the activation energy tells us how much faster.

High E

Low E

T
From the graph it should be evident that a high activation energy does not imply a fast reaction for all temperatures!

RATE AND TEMPERATURE

Most people prefer linear graphs to curvy ones, and because of this the Arhenius plot is a linear representation of the Arhenius equation.

Arhenius plot
High E

Low E

ln(k)

Low E

High E

T 1/T
Note that the slope is given by E/R and that ln(ko) is the y-axis intersection. Rate constants measured (or fitted) at different temperatures is normally presented on a Arhenius plot to determine the activation energy and ko.

ln(k)

1/T