Environmental Chemistry and Microbiology

Dr. Anjali Pal and Dr. Sudha Goel

Department of Civil Engineering
Indian Institute of Technology, Kharagpur

Lecture -08
Chemical Equilibrium-III

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 the Civil Engineering Department of IIT Kharagpur. We have divided this course into two
parts: Environmental Chemistry and Microbiology. The Environmental Chemistry part will be
covered by me and the second part Environmental Microbiology will be taught by Professor
Sudha Goel.
This is the module 2 (i.e., chemical equilibrium) and this is the lecture number 8.
(Refer Slide Time: 01:16)

In this lecture I will cover many important aspects of chemical equilibrium; i.e., the solubility
product, solubility, common ion effect and the applications.
(Refer Slide Time: 01:29)
We know that solubility product is very important for chemical equilibrium. All solids we know
that even if they are very insoluble still, they are to some extent soluble. For example, silver
chloride (AgCl) and barium sulphate (BaSO4) are very insoluble but in contact with water they
slightly dissolve and they produce the corresponding ions and they establish the following
equilibriums:
AgCl(s)⇋Ag+(aq)+Cl-(aq).............(1)
BaSO4(s)⇋Ba2+(aq)+SO4-2(aq).....(2)
The equilibrium for (1) can be expressed as follows:
[Ag + (aq)][Cl- (aq)]
K= ................(3)
[AgCl(s)]
But [AgCl(s)] is a constant and therefore we define equilibrium constant by a new term Ksp
which is called solubility product or solubility product constant as follows:
Ksp=[Ag + (aq)][Cl- (aq)].................(4)
We have seen that in different ways we can express the equilibrium constant. Say for example in
case of acid dissociation we write Ka, in case of base dissociation we write base Kb, in case of
water dissociation we write Kw. Similarly, here we call equilibrium constant as solubility product
and we express in by Ksp. This is a very important term for chemical equilibrium. It is constant at
a particular temperature. All equilibrium constants are constants at a particular temperature. In
almost all textbooks or handbooks dealing with qualitative and quantitative analysis, the
solubility product values are available.
You can see it. As a list they show at 250C, what is the soluble product values. In a similar way
for a complex salt such as calcium phosphate (Ca3(PO4)2) equilibrium expression and solubility
product can be expressed as follows:
Ca3(PO4)2⇋3Ca2++2PO4-3...........................(5)
Ksp=[Ca 2+ ]3×[PO4-3 ]2 ...................(6)
(Refer Slide Time: 05:25)

Now let us come to an important topic called solubility. Till now we have seen about the
solubility product. Here we will see what is solubility. Let us take the example of barium sulfate
(reaction (2)):
BaSO4(s)⇋Ba2+(aq)+SO4-2(aq).....(2)
Now we know that solubility product of barium sulphate at 25 0C is 10-10.
Let the solubility of barium sulfate be S. Therefore, S=[Ba2+]=[SO4-2]
So, Ksp=SxS=10-10
Therefore, solubility of BaSO4 is S=10-5. This was a very simple example and now we will see
for calcium fluoride (CaF2). Similarly, equilibrium expression and solubility product for calcium
fluoride can be written as follows:
CaF2⇋Ca2++2F-..................(7)
Ksp=[Ca 2+ ]×[F- ]2 ...................(8)
Let the solubility of calcium fluoride be S and from any standard book we will get that the
solubility product of calcium fluoride at 250C is 3x10-11.
So, [Ca2+]=S, [F-]=2S
Ksp=(S)×(2S) 2
or, 4S3 =3×10-11
or,S=19.6×10-5
So, from the above two examples ((2) and (7)) we can see that calcium fluoride is nearly 20
times more soluble than barium sulfate. So, although solubility product of barium sulphate is
higher compared to calcium fluoride but solubility of calcium fluoride is higher compared to
barium sulphate. So, looking at the solubility product immediately without thinking we can tell
that whose solubility product is higher. But it does not always depicts the truth regarding
solubility of the compounds.
(Refer Slide Time: 08:25)

Now we will understand the phenomena of precipitation. We know that what is saturated
solution, what is unsaturated solution and what is super saturated solution. What is unsaturated
solution? Let us take a compound AB,
If [A+][B-]<Ksp then it is an unsaturated solution
If [A+][B-]=Ksp then it is a saturated solution
If [A+][B-]>Ksp then it is a supersaturated solution
Precipitation occurs in case of supersaturated solution. These we can see in crystallization. Say
for example if you want to make some crystals of something say for example sodium chloride or
say sugar. So, you make a very saturated solution (almost super saturated solution). Then you put
a single crystal of that material. Then you will see lot of crystals are coming. That is called
seeding. It means you are disturbing the super saturated solution so that it will try to remove
some crystal from there to get just the saturated solution.
(Refer Slide Time: 10:26)

Now let us see to the common effect on solubility. Say for example we have an electrolyte BA
whose solubility is S moles per liter. Now there is another electrolyte say CA (concentration is c
moles per liter). What is interesting feature here in BA and CA is that both these electrolytes
contain A-. It is the common ion. Now let us add CA to BA. Then what will happen? You see
initially when BA was alone then solubility is S. But now we are adding CA. After adding CA
the solubility will no more be S. It will change. How it will change? Let the new solubility be
denoted by S'. Therefore, we can write:
Ksp=S2 =S'(S'+c)..................(9)
In order to keep Ksp constant, S' should be lower than S. The solubility of an electrolyte is thus
decreased by the presence of a common ion however the solubility product remains the constant.
So, one important question I have given here:
How to get pure sodium chloride precipitate from a a sodium chloride solution?
How will you do it? You take the concentrated sodium chloride solution and then you pass HCl
gas through it. Now you are passing HCl where you are adding a common ion which is nothing
but chloride ion. So, what will happen? Some sodium will go out of the phase. So, it will be
precipitated as sodium chloride. So, you will get pure sodium chloride as a precipitate.
(Refer Slide Time: 13:19)

Now I have already told you, what will happen if you add a common ion to some electrolyte.
Now we will see the quantitative approach. Let us again consider the case of barium sulfate
(BaSO4) (reaction (2)):
BaSO4(s)⇋Ba2+(aq)+SO4-2(aq).....(2)
S=[Ba2+]=[SO4-2]=10-5M
Now say for example I am adding barium chloride from outside source say for example barium
chloride. So, some concentration of barium was already there. Now we are adding some extra
barium iron concentration that is through the application of barium chloride. Barium chloride is
strong electrolyte. So, it will dissociate completely. Then what will happen to the barium
sulphate? That is shown here. Now Ksp is constant.

Now we have added 10x10-5 moles/liter of barium chloride. This will cause in the formation of
an additional y moles of precipitated barium sulphate. When the barium concentration will be
increased then some barium sulphate has to be going out of phase. But how much? This can be
solved as follows:
 Ba2+ + SO4-2 → BaSO4(s)
(1x10-5+10x10-5-y)mol/l (1x10-5-y)mol/l ymol/l
Ksp=(1110-5 -y)(110-5 -y)=110-10
or, y=0.9×10-5 mol/l
So, [Ba2+]=10.1x10-5 mol/l
[SO4-2]=0.1x10-5 mol/l
(Refer Slide Time: 16:05)

After adding barium chloride, solubility is reduced almost 10 times. So, it is observed that
sulphate ion concentration is reduced considerably. This is an application of common ion effect.
So, when the sulphate ion concentration is reduced that means lot of barium sulphate has been
precipitated. So, in this way sulphate determination is done by adding enough excess amount of
barium chloride. This is used extensively in environmental engineering practice and in analytical
chemistry to accomplish complete precipitation of the desired ions. This is also true for hardness
removal. I told you from the outside we are adding some carbonate or hydroxide to get
precipitate the calcium carbonate and magnesium hydroxide to remove the hardness.
(Refer Slide Time: 17:34)
Now come to the common ion effect on ionization. This is general thing but we have seen in
buffer also (ammonium hydroxide ammonium chloride buffer or acetic acid acetate ion buffer).
So, what is happening? In case of ammonium hydroxide ammonium chloride buffer dissociation
of NH4OH is suppressed and in case of the other dissociation of acetic acid is suppressed due to
the presence of common ion. If we increase the concentration of ammonium chloride still it will
be less dissociated. So, degree of dissociation will be less in presence of common ion. Thus, it is
of course a method for controlling the concentration of ions furnished by a weak electrolyte.
(Refer Slide Time: 19:18)
Common ion effect on group separation has enormous applications in many cases, say for
example in group separation. Those who are in chemistry background they will see it in group
separation. what is there? Here solubility product of some sulphide salts is considered:
Salt Solubility product
HgS 4x10-54
CuS 1x10-44
CdS 1.4x10-28
ZnS 1x10-23
MnS 1.4x10-15

You can see here mercury sulphide, copper sulphide and cadmium sulphide have low solubility
product and so they are insoluble compared to this zinc sulphide and manganese sulphide. So,
what is happening on passing H2S gas into a solution of salts of these metals? The metal
sulphides will precipitate when only when product of [M2+] and [S2-] exceeds the solubility
product that is Ksp. This we have seen already that the saturated solution, unsaturated solution
and super saturated solution when this will reach the Ksp value then only they will be
precipitated.
H2S is a weak acid and its dissociation is readily suppressed in presence of H+ ions:
H2S⇋2H++S2-...........................(10)
Now consider a saturated solution of H2S of 0.1M at 250C and the concentration of sulfide ion it
produces is can be written:
1.1×10-23
[S2- ]= ....................(11)
[H+ ]2
Now if we increase the [H+] by means of adding 0.3M HCl, the concentration of S2- will be so
decreased so that solubility product of group II metal (Hg, Cu, Cd) sulfides will be exceeded and
they will be precipitated while that of Fe, Zn, Mn will be in solution. This is an elegant
demonstration of solubility product and common ion effect which has been used in group
separation in analytical chemistry.
(Refer Slide Time: 22:02)
Now let us solve a simple example:
Q. 1. Silver chromate (Ag2CrO4) is a red solid that dissolves in water to the extent of 0.029g/L at
250C. Estimate its Ksp.
(given Mol. wt. of Ag2CrO4 is 331.73)
Solution:
Ag2CrO4⇋2Ag++CrO4-2
Ksp=(2S)2xS=4S3
0.029
So, [CrO4 -2 ]= =8.74×10-5 =S
331.73
[Ag + ]=2S=2  8.74×10-5  1.75 104 M

So, Ksp=[Ag + ]2 [CrO4-2 ]=(1.75 10-4 )2  (8.74 10-5 )=2.7 10-12

(Refer Slide Time: 23:02)
Now as the conclusion we can say that in this lecture it has been explained how electrolytic
dissociation enable us to determine the conditions, under which a substance dissolves or forms
the precipitate. So, solubility product is the key factor that will tell you whether under which
condition it will precipitate but Ksp value is constant while you can vary solubility by adding
either common ion. Without adding common ion, you can change the solubility where we need
to know whether it is in solution phase or it is it has to be precipitated out. So, it is a very
important thing to know in chemical equilibrium in process engineering or in environmental
engineering or in analytical chemistry the concept of solubility product and solubility and what is
the common ion effect. Thank you.