Law of Mass Action

The law of mass action is the relation between the rate of a reaction and the molar
concentration of the reacting substances. Two Norwegian chemists Guldberg and Waage gave
this law.

It states that, at a given temperature the rate of are reaction is directly proportional to the product
of the molar concentrations of the reactants. The molar concentration of the reactant is also
called active mass.

Lets us consider a simple reaction

A + B====2AB

According to law of mass action, rate of reaction may be written as:

Rate =K [A] [B]

Where [A] and [B] are the molar concentrations of reactants is constant of proportionality and is
called rate constant. Now, if concentration of each of the reactants involved in the reaction is
unity, i.e. [A] =[B]=1,then substituting these values in the above expression, we get

Rate of reaction=Kx1x1=k
Thus, the rate constant of a reaction at a given temperature may be defined as Rate of the
reaction when the concentration of each of the reactants is unity.

Characteristics of Rate Constant

1) Rate constant is a measure of the rate of the reaction. Larger the value of k, faster is the
reaction and vice versa.
2) Different reactions have different values of k

3) At a fixed temperature, the value of k is constant and is characteristic of the reaction. However
it changes with temperature.

4) For a particular reaction, the reaction constant is independent of concentration.

Difference between Rate of reaction and reaction rate constant.

Elementary Rate Laws

A reaction follows an elementary rate law if and only if the (iff) stoichiometric coefficients are
the same as the individual reaction order of each species. For the reaction in the previous

example ( ), the rate law would be:

if 2NO+O2    2NO2     then -rNO = kNO (CNO)2 CO2  

Molecularity and Order of Reaction

The inolecularity of an elementary reaction is the number of molecules involved in the reaction,
and this has been found to have the values of one, two, or occasionally three. Note that the
molecularity refers only to an elementary re- action.
Rate Constant, k

k is the specific reaction rate (constant) and is given by the Arrhenius Equation:

Where:

       
       
            

Where:

E = activation energy (cal/mol)

R = gas constant (cal/mol*K)
T = temperature (K)
A = frequency factor (units of   

    A, and k, depend on overall

    reaction order)

k=Ae-E/RT
The larger the activation energy, the more temperature sensitive k and thus the reaction rate.

Why is there an Activation Energy?

(1) the molecules need energy to distort or stretch their bonds in order to break them and to thus
form new bonds

(2) as the reacting molecules come close together they must overcome both steric and electron
repulsion forces in order to react

In our development of collision theory we assumed all molecules had the same average energy.
However, all the molecules don�t have the same energy, rather there is distribution of energies
where some molecules have more energy than others. The distraction function f(E,T) describes
this distribution of the energies of the molecules. The distribution function is read in conjunction
with dE

f(E, T) dE = fraction of molecules with energies between E and E + dE

One such distribution of energies is in the following figure.

                

By increasing the temperature we increase the kinetic energy of the reactant molecules which can
in turn be transferred to internal energy to increase the stretching and bending of the bonds
causing them to be in an activated state, vulnerable to bond breaking and reaction.

We see that as the temperature is increased we have greater number of molecules have energies
E A or greater and hence the reaction rate will be greater.

            The activation energy can be thought of as a barrier to the reaction. One way to view the
barrier to a reaction is through the reaction coordinates. These coordinates denote the energy of
the system as a function of progress along the reaction path. For the reaction

the reaction coordinate is

 Progress along reaction path

We see that for the reaction to occur, the reactants must overcome an energy barrier or activation
energy EA.

ou can tell the overall reaction order by the units of k

CA -rA Reaction Order Rate Law k

(mol/dm3) (mol/dm3*s) zero -rA = k (mol/dm3*s)
(mol/dm3) (mol/dm3*s) 1st -rA = kCA s-1
(mol/dm3) (mol/dm3*s) 2nd -rA = kCA2 (dm3/mol*s)

The activation energy is a measure of the minimum energy a that the reacting molecules must
have in order for the reaction to occur.

The reaction of AB + C to form A + BC is shown above along the reaction coordinate. One way
to think of the reaction coordinate is the linear distance between the AB molecule for a fixed
linear distance between the AC molecule. At the start of the reaction the AB distance is small
and the BC distance is large. As the reaction proceeds, the A�C distance remains fixed but B
moves away for A and closer to C and the energy of system increases. At the top of the barrier
molecule B is equal distance from A and C. But as it crosses the barrier it moved close to C to
form the BC molecule and the A molecule alone.

The activation energy is a measure of how temperature sensitive the reactor is. Reactions with
large activations energies are very temperature sensitive.
One can also write the specific reaction rate as:

Consider the following elementary reactions

 
1)   Which reaction has the higher activation energy?

2)   Which reactions have the same activation energy?

3)   Which reaction is virtually temperature insensitive?

4)   Which reaction will dominate (i.e. take place the fastest) at high temperatures if all reactions
were to take place in the same reactor?

5)   Which reaction will dominate (take place the fastest) at moderate temperatures?

6)   Which reaction will take place the fastest at low temperatures?
7)   Which reactions will have the same rate of reaction at a given temperature?

Solutions
Consider the following elementary reactions

1)   Which reaction has the higher activation energy?

Ans. (3)

2) Which reactions have the same activation energy?

Ans. (1) and (2) – Slope (–E/R) is the same.

3)   Which reaction is virtually temperature insensitive?

Ans. (4). k4 does not vary with temperature E4 = 0.

4)   Which reaction will dominate (i.e. take place the fastest) at high temperatures?

At high temperatures (1/T) is small and k3 becomes larger than k1.

Ans. (3)

5)   Which reaction will dominate (take place the fastest) at moderate temperatures?

At moderate temperatures

Ans. (1)

7)   Which reactions will have the same rate of reaction at a given temperature?

      Ans. The rate will be the same when the lines cross.

      a. (1) and (3)

      b. (2) and (3)

      c. (1) and (4)

      d. (2) and (4)

      e. (3) and (4)

The activation energy is a measure of the minimum energy a that the reacting molecules must
have in order for the reaction to occur.