Environmental Chemistry and Microbiology

Dr. Anjali Pal and Dr. Sudha Goel

Lecture -06
Chemical Equilibrium-I

Welcome everyone to our online NPTEL course of Environmental Chemistry and Microbiology.
This course will be taught by Professor Sudha Goel and myself Professor Anjali Pal. We are both
from Civil Engineering Department of IIT Kharagpur. We have divided the course into two
parts. The first part, Environmental Chemistry will be covered by me and the second part
Environmental Microbiology will be taught by Professor Sudha Goel.

In the module 2 which we will start today, I will discuss about the chemical equilibrium. The
chemical equilibrium is a very important topic for Environmental Chemistry and in my next 5
lectures I will throw some light on this topic.
(Refer Slide Time: 01:37)

The first lecture of today will cover the following topics: Reversible reaction, concept on
equilibrium, kinetic approach to equilibrium, laws of mass action, activity and activity
coefficient.
(Refer Slide Time: 01:59)
We all know that when in a chemical reaction, we want to know how much product is formed or
from how much reactants we always use the balanced equation for certain reaction. So, in molar
ratio method when we want to determine the amounts of material produced and the material
consumed in a chemical reaction, we assume that all reactants are converted to the products. That
means 100% conversion. We never consider that the products may react to form the original
reactants also. But in most cases the reaction does not go to completion.

All the reactants are converted to products according to the molar coefficients given in the
balanced chemical reaction. In the complete reaction 100% conversion occurs. But almost all the
chemical reactions do not go to completion. It is so because the products formed, react to
produce the reactant. That means opposite reaction also occurs. The reactants also react and the
products also react to form the reactants. That means reactants form the products and at the same
time products also form the reactants. These types of reactions are called the reversible reaction.
Here both the processes (that means the forward reaction and the reverse reaction (also
sometimes called backward reaction)) occur simultaneously and to indicate that the reaction is
reversible we always use a double arrow in the chemical reaction.
(Refer Slide Time: 03:54)
What is the equilibrium concept? The simplest equilibrium is the equilibrium of water as liquid
and water as gas (shown below as follows:).
H2O(l)⇋H2O(g)..........................................(1)
That means if you take some water that liquid water in a closed vessel and if you keep it for
some time at a certain temperature the phase transfer will occur. Then after some time, the
equilibrium will be reached. At that equilibrium point some amount of water in the liquid form
will be converted to gaseous form. On the other hand, same amount of gas will be converted to
liquid water. This is not the chemical equilibrium, but it is called phase equilibrium. For
chemical equilibrium, we have to consider a chemical reaction:
A+B⇋C+D.................................................(2)
In the reaction (represented by equation (2)) the molar ratio of A and B is taken as 1:1 and that of
C and D is taken as 1:1. The double arrow represents both the forward reaction (i.e. the reaction
of A and B to form C and D) and the reverse reaction (i.e. the reaction of C and D to form A and
B).
Now what is equilibrium? In this case we will call it chemical equilibrium (not phase
equilibrium).

What is chemical equilibrium? When a reaction proceeds to a point where the combination of
reactants to form the products is just balanced by the reverse reaction of products combining to
form the reactants, then we can say that the reaction has attained the equilibrium. That means at
an equilibrium point what will happen? A and B will react to form C and D. At the same time
same amount of A and B will be produced by C and D. That means we can say in a simple way
no more conversion takes place. This is the chemical equilibrium.
(Refer Slide Time: 06:24)

Now there we can have this type of equilibrium by considering the kinetic approach also. The
attainment of state of equilibrium depends on the speed. Say, for example, when we start the
reaction, A and B combines and reacts to form C and D. So, when the reaction just starts then the
reaction process is fast but after some time when it is reaching towards the equilibrium, then we
can say that the rate of the forward reaction and the rate of the backward reaction is the same.
The forward and reverse reaction can be represented as follows:
A+B→C+D (forward reaction) .....................(3)
C+D→A+B (reverse reaction) ......................(4)
That means A + B is going to give C + D (i.e, the forward reaction) and C + D is giving
A + B (i.e., reverse reaction). That means in the forward reaction we know that it depends on the
concentration of A and B (i.e., reactant concentration) and there is a constant which is called the
specific rate constant or rate constant.
The rate of the forward reaction (rf) and reverse reaction (rr) can be mathematically expressed as
follows:
rf=k1[A][B].....................................(5)
rr=k2[C][D].....................................(6)
k1 and k2 are the proportionality constants (rate constants)
So, when these two rates are same then what happens?
(Refer Slide Time: 08:02)

At equilibrium these two rates (rf and rr) are equal. So, equating (5) and (6),
k1[A][B]=k2[C][D]
k1 [C][D]
or, =
k2 [A][B]
k1 [C][D]
or, Kc = = ...........................(7)
k2 [A][B]
Kc is a constant for a given temperature and is called equilibrium constant.
You always remember that the rate constant is always represented as k and equilibrium constant
we always represent by K. In many books also I have seen they that they are confused and
sometimes for the rate constant also they use al K, but this is not okay.
So, this is the simplest case I have expressed. I have told that all the stoichiometric molar ratios
are 1:1. So, considering another type of reaction where stoichiometric molar ratios are not 1:1,
2A+B⇋2C+D.....................................(8)
So, in this case (equation (8)),
k1 [C]2 [D]
Kc = = 2 ...............................(9)
k2 [A] [B]
In general,
aA+bB⇋cC+dD (where a, b, c, d represent the stoichiometric number of particles of A, B, C and
D)................................(10)
So,
k1 [C]c [D]d
Kc = = ...............................(11)
k2 [A]a [B]b

It is also called the law of chemical equilibrium or law of mass action and it can be applied to
many kinds of reactions as ionization reaction, precipitation reaction, dissociation type of
reaction, complex ion formation. This is the basics of the chemical equilibrium. We will see
different many different applications of this type of expression.
(Refer Slide Time: 11:08)

Now in the equilibrium concept, some important points we have to understand when we go for
the equilibrium expression. Say, for example, the concentrations of A, B, C and D in equation
(11) exist only at equilibrium.
When you obtain a very small value of Kc, what does it mean? That means that the equilibrium is
reached after a small fraction of reactants are converted to products. That means the product
obtained is less compared to the reactants that we are taking and on the other hand, for a large
value of Kc it means that the large fraction of reactant molecules is converted to products when
the equilibrium is reached.
On which side the equilibrium will shift, you can understand from the value of Kc. For a system
in equilibrium when you increase the reactant concentration then what will happen? It will go
towards the right. The forward reaction will go on. On the other hand, if you increase the product
concentration then it will go to the reverse direction, this is the actually explained by the Le
Chatelier principle. I will go to this later but for the time being you please remember this thing
that Kc value is constant, but how much it is towards the right-hand side or it is towards the left-
hand side that will be decided by the concentration of the reactants and the products.
(Refer Slide Time: 13:35)

Now, we shall see some examples of reaction where color change is observed.
2NO2(g)⇋N2O4(g).................(12)
The forward reaction is:
2NO2(g)→N2O4(g)...............(13) (upon cooling) (N2O4 is a dimer of NO2)
(The red-brown color fades)
The backward reaction is:
N2O4(g)→2NO2(g)..............(14) (when the temperature is raised)
(The red-brown color is restored)

Now think about these reactions ((12) to (14)). So, depending on the temperature you can see
different colors. If you take a N2O4 in a closed vessel and if you cool it or if you heat it you will
see the two different colors that is prevailing.
You can visualize it because it is two different things at two different colors. That is why you can
see it when you do it in a closed vessel and if you properly maintain the temperature. At high
temperatures the intense red brown color indicates that NO2 predominates. At equilibrium the
rates of forward and the reverse reactions are equal and there is no further net change in the
partial pressures of reactants or products. This is the equilibrium condition and the experimental
value of Kc is 8.8 at 25° C. You will always see that when the Kc value is mentioned we must tell
about the temperature because it varies with temperature. We have also seen when I explain the
acid bases. I have told that either K value or Kb value or Kw value vary with the temperature. So,
temperature is very important.
Now if we express both in terms of partial pressure, then this value of Kc value will be different.
Now partial pressure of N2O4, NO2 are expressed in atmosphere. Then at the at the particular
temperature (say at 250 C) the equilibrium expression will be like this:
PN2O4=K×(PNO2)2 .................(15)
You have to consider this then K is nothing but the here it is partial pressure because it is gas.
This is the expression you always do in case of either gaseous equilibrium or in the aqueous
equilibrium.
(Refer Slide Time: 17:37)
So, concept is the same but you have to use different types of concentrations. In terms of gas if it
is gas then you have to use the partial pressure. If it is in ion form in the aqueous solution then
moles per liter.
Now let us come to activity and activity coefficient. This is also very important for equilibrium
relationship. It is expected that we always use the dilute solution. When it is dilute solution then
concentration the express that we should express the concentration in moles per liter. But as the
concentration is increased then that means not for very dilute solution but the concentration is
higher. Then this activity term should come. why? Because when there are many ions then they
have the influence on each other. In that case, it is noted that as solutions of ionized materials
become more concentrated their quantitative effect in equilibrium relationships become
progressively less than calculated solely from the change in molar concentration. That means in
that case at higher concentration the molar concentration if we use then there may be some
error. Hence the effective concentration we have to use which is also called activity and the
expression the relationship between the activity and the concentration is like this:
{A}=γ[A]..........................(16)
γ is the activity coefficient. So, when we express the activity, we use the second bracket. When
we use the concentration, it is in moles per liter, then this is the third bracket.

So, in case of dilute solution, we can tell that activity is same as the concentration. But in case of
concentrated solution, we have to consider the activity term. Numerical calculations from
equilibrium relationship may be erroneous in actual concentrations, if actual concentrations are
used in place of activities. But the error is not very great for dilute aqueous solution. In that case,
we can consider that activity is same as the concentration and we use mostly the dilute solution.

For practical purpose the rough calculations obtained using molar concentrations are sufficient.
That means we do not have to bother that we have to use the activity term. Besides this the
determination of the activity coefficient is not a very easy task. We cannot determine it with
precision. This is partly because the activity coefficient is increased by the presence of other
ions.
That means for practical purpose we use the concentration term and we ignore the activity
coefficient. One reason is that it is very difficult to determine this thing. Another thing is it is for
practical purpose it is sufficient to use the concentration. We do not have to use always the
activity term.
(Refer Slide Time: 21:11)

Now if we use the activity term for more accuracy in the reaction where a moles of A reacts with
b moles of B and then produces c moles of C and d moles of D. Then in that case K should be
should follow this expression:
{C}c {D}d
K= ....................(17)
{A}a {B}b
That means {C} is the activity. So, in all cases we have to use the activity terms.

And then we all know that activity is nothing but γ  concentration and then for dilute solution
we can think that activity is the same as the concentration. That means we can straight forward
we can use this expression:
k1 [C]c [D]d
Kc = = ...............................(11)
k2 [A]a [B]b
But in case of concentrated solutions in that case we must consider the activity and activity
coefficient. Now some rules to be followed. When you think about the equilibrium expression
then you have to follow the follow some rules.
What are the rules?
1) In case of ions and molecules in dilute solution, concentration is expressed in moles per liter.
So, it is the aqueous solution. So, there we have to use the concentration of ions in terms of
moles per liter.
2) Now in case of solvent in a dilute solution, the concentration is taken as unity.
3) Now when some pure solids or pure liquids is in equilibrium with the solution:
For pure solids or a liquid which is in equilibrium in case of say heterogeneous equilibrium
where all are not in the same case, then it is called heterogeneous equilibrium. In that case pure
solids or liquids in equilibrium with the solutions then the concentration is taken as unity.
4) When there is a mixture of liquids then the concentration should be expressed in mole
fraction.
5) And in case of gases (we have already seen that in case of NO2 and N2O4) we have used the
partial pressure. So, in gas phase when the reaction goes on, the concentration we have to use in
terms of partial pressure in atmosphere. These are the rules that we have to follow when we
develop some equilibrium expression because otherwise everything will be wrong.
(Refer Slide Time: 24:20)

Now for this part we have we can use any text books of physical chemistry, text books of
inorganic chemistry. I have given two references but you can have these explanations in many
books. You can consult these books or other books also. This is from Sawyer McCarty, I have
already given these two references in case of acid, bases and salts in the module 1.

I am giving the same reference here and thank you for hearing this first lecture for this module 2,
(lecture number 6). Thank you.