E L

P T
ENVIRONMENTAL CHEMISTRY AND MICROBIOLOGY

N
ANJALI PAL AND SUDHA GOEL
DEPARTMENT OF CIVIL ENGINEERING, IIT KHARAGPUR

Module 02:
Lecture 06 : Chemical Equilibrium – I
 L
Chemical Equilibrium

Topics covered:

TE
P
Ø Reversible reaction
Ø Concept on Equilibrium

N
Ø Kinetic approach to equilibrium
Ø Law of mass action
Ø Activity and activity coefficient
Reversible reaction

L
q When the molar ratio method is used to determine the amounts of material
produced and the material consumed in a chemical reaction, we assume that all

E
reactants are converted to products that means we consider that the reaction is
complete. We do not consider that the products may react to form the original

T
reactants.
q The reaction which goes to completion, all the reactants are converted to
products according to the molar coefficients given in the balanced chemical

P
reaction.
q However many chemical reactions do not go to completion because the products
formed react to produce the reactants.

N
q This type of reaction are called reversible reactions. Here both the processes i.e.
the forward reaction and the reverse reaction occur simultaneously.
q To indicate that the reaction is reversible, a double arrow is used in the chemical
reaction.
Equilibrium concept

L
q Liquid water in a closed vessel at a particular temperature ..... ???
Vapour pressure ???

E
H2O(l) ⇄ H2O(g)
This is one of the simplest and most familiar of all equilibrium processes. It is called
phase equilibrium.

T
q Let us consider the chemical reaction, which is assumed to take place in aqueous
solution:

P
A +B⇌C+D
The double arrow indicates that 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

N
A and B) may occur.
q 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 attained the equilibrium.
This is referred as chemical equilibrium.
Kinetic approach to equilibrium

L
q The attainment of the state of equilibrium depends on the speed of a chemical
reaction.

E
q Every chemical reaction proceeds at a characteristic speed or rate that depends on
(a) the concentration of the reactants, (b) the reaction temperature, (c) the
presence of a catalyst.

T
q If we consider the reaction:
A+B⇌C+D

P
Where
A + B → C + D (forward reaction)
C + D → A + B (reverse reaction)

N
So the rate of the forward reaction (rf) and rate of the reverse reaction (rr) can be
expressed mathematically as
rf = k1 [A] [B]
rr = k2 [C] [D]
k1 and k2 are the proportionality constants (rate constants)
Kinetic approach to equilibrium

L
At equilibrium: rf = rr
or
k1 [A] [B] = k2 [C] [D]

E
Collecting all variable terms in one side and all constant terms on the other side we
get

T
k1 / k2 = [C] [D] / [A] [B]
Kc = k1 / k2 = [C] [D] / [A] [B]
Kc is a constant for a given temperature and is called the equilibrium constant

P
q Similarly for a reaction 2A + B ⇌ 2C + D
Kc = k1 / k2 = [C]2 [D] / [A]2 [B]
And for the general reaction

N
aA + bB ⇌ cC + dD (where a, b, c, d represent the stoichiometric number of
particles of A, B, C, and D)
Kc = k1 / k2 = [C]c [D]d / [A]a [B]b ---------- (a)
It is called law of chemical equilibrium (or law of mass action) and it can be applied
to many kinds of reactions such as ionization, precipitation, dissociation, complex ion
formation etc.
 Equilibrium concept

L
q Some important points to understand
Ø The concentrations of A, B, C, and D in Equation (a) exist only at equilibrium

E
Ø A small value of Kc indicates that equilibrium is reached after a small fraction of
reactants are converted to products. On the other hand a large Kc value reveals
that a large fraction of reactant molecules are converted to products when

T
equilibrium is reached.
Ø Even though Kc is quite large, a reaction may go from right to left if the initial

P
concentration of the product is large and the initial concentration of the
reactants is small.
Ø For a system in equilibrium, an increase in reactant concentration will shift the

N
equilibrium further to the right. On the other hand, an increase in the product
concentration will shift the equilibrium to the left.
Ø If the reactants and products are dissolved in a solvent (e.g. water) then
concentrations are usually expressed in moles per liter.
The shifting of equilibrium by change of concentration is an application of the well-
known Le Chatelier principle
A simple example of chemical equilibrium:

L
2 NO2(g) ⇋ N2O4(g)
The forward reaction

E
2 NO2(g) → N2O4(g) (upon cooling)
(Red-brown colour fades)
The reverse reaction

T
N2O4(g) → 2 NO2(g) (when the temperature is raised)
(The red-brown colour is restored)

P
At high temperatures the intense red-brown colour indicates that NO2 predominates.
At equilibrium the rates of forward and reverse reactions are equal, and there is no
further net change in the partial pressures of reactants or products.

N
The experimental value of K is 8.8 at 25°C, provided the partial pressures of NO2 and
N2O4 are expressed in atm. The NO2-N2O4 reaction mixture is in equilibrium:
2 NO2(g) ⇋ N2O4(g)
At a particular temperature:
PN2O4 = K × (PNO2)2
Activity and Activity coefficient

L
q The equilibrium relationships are frequently applied to equilibrium involving acids,
bases, salts in solution and the molar concentrations are used.

E
q It is noted that as solutions of ionized materials become more concentrated, their
quantitative effect in equilibrium relationships becomes progressively less than
calculated solely from the change in molar concentration. Hence the effective

T
concentration (or activity) of ions is decreased below that of the actual molar
concentration.

P
q The activity (effective concentration) of an ion or molecule can be obtained by
multiplying its concentration by a term called activity coefficient
{A} = γ [A] (here γ is the activity coefficient and {A} is the activity of A)

N
q Although numerical calculations from equilibrium relationships may be erroneous
if actual concentrations are used in place of activities, but the error is not very
great for dilute aqueous solutions. Thus for many practical purposes the rough
calculations obtained using molar concentrations are sufficient.
q Besides this the activity coefficient is not easy to determine with precision. This is
partly because the activity coefficient is influenced by the presence of other ions.
 L
q Activity & Activity coefficient
aA + bB ⇌ cC + dD
K = {C}c {D}d / {A}a {B}b

E
{A} = ϒ [A]
Where {A} = activity (or effective concentration) & ϒ = activity coefficient

T
For dilute solutions
{A} = [A]

P
K = [C]c [D]d / [A]a [B]b
q Some rules to be followed:
1) Ions and molecules in dilute solution. Conc. is expressed in moles/lit

N
2) Solvent in a dilute solution. The conc. is taken as unity (approx.)
3) Pure solids or liquids in equilibrium with the solution. The conc. is taken as
unity.
4) Mixture of liquids. The conc. is expressed as mole fraction.
5) Gases. The conc. is expresses as partial pressure in atm.
References:

E L
T
• Dutt PK, Dutt PK (2000) General & Inorganic Chemistry,
Calcutta

P
• Sawyer CN, McCarty PL, Parkin GF (2000) Chemistry for
Environmental Engineering, Tata McGraw Hill, New Delhi

N
 E L
P T
N
 E L
P T
ENVIRONMENTAL CHEMISTRY AND MICROBIOLOGY

N
ANJALI PAL AND SUDHA GOEL
DEPARTMENT OF CIVIL ENGINEERING, IIT KHARAGPUR

Module 02:
Lecture 07 : Chemical Equilibrium -II
 L
Chemical Equilibrium

T E
P
Ø Le Chatelier principle
Ø Ways of shifting the chemical equilibrium

N
 Chemical Equilibrium

L
q It is a fact that many reactions do not go to completion, but proceed to a certain
point and then apparently stop. Then we say that it has reached the equilibrium.

E
For example:
H2 + I2 ⇄ 2HI

T
3Fe + 4H2O ⇄ Fe3O4 + 4H2
q Effect of insolubility or volatility:

P
Ø A reaction often appears to go to completion instead of going to a state of
equilibrium.
For example:

N
BaCl2 + H2SO4 ⇄ BaSO4 ¯ + 2 HCl (Sulfate determination)
NaCl + H2SO4 ⇄ NaHSO4 + HCl ­ (Lab. method of HCl preparation)
CaCO3 ⇄ CaO + CO2
(closed vessel???) or (current of air???)
Chemical Equilibrium
q Le Chatelier principle:

L
If one of the conditions of a system in equilibrium be altered, the system will adjust
itself in such a direction as partially to neutralise the change in condition.
q For example the well known Haber process of ammonia preparation from N2 and H2

E
N2 + 3H2 ⇄ 2NH3 + 22,000 cal

T
(i) Effect of temperature on equilibrium:
If the temperature is increased what will happen ????

P
(ii) Effect of pressure on equilibrium:
If the pressure is increased what will happen ????

N
(iii) Effect of altering concentration on equilibrium:
NaCl + H2SO4 ⇄ NaHSO4 + HCl

(iv) Effect of adding a substance to a system in equilibrium:

L
q Ways of shifting the chemical equilibrium: Application of Le Chatelier principle
Ø Formation of insoluble substances:

E
1) Copper and Brass waste → Insoluble precipitate (How???)
2) Hard water → Insoluble precipitate (How???) (Lime-soda treatment)

T
ü Solubility product:

P
Mg(OH)2 (9 × 10-12); MgCO3 (4 × 10-5)
CaCO3 (5 × 10-9); Ca(OH)2 (8 × 10-6)

N
1) Metal hydroxide
2) Metal carbonate or metal hydroxide (or metal phosphate)
Q.1. To precipitate Cu2+ as Cu(OH)2 from a copper waste can we use NH4OH ???
Cu(OH)2 or Zn(OH)2 → Cu(NH3)4+2 or Zn(NH3)4+2
Chemical Equilibrium

L
q Ways of shifting the chemical equilibrium: Application of Le Chatelier principle
Ø Formation of a weakly ionized compound:

E
1) H+ (acid waste) + NaOH → H2O + Na+
2) Fe(OH)3 (solid) (or Al(OH)3) (solid) + 3H+ → Fe3+ (or Al3+) + H2O

T
Q.1. How can you determine NH3-N by Kjeldahl’s method in a water sample???
Mechanism???

P
(NH3-N means nitrogen present as NH3 and ammonium ion)
Ø Formation of complex ion:

N
Insoluble salts are dissolved via complex ion formation
1) AgCl (solid) + NH3 → Ag(NH3)2+ + Cl-
2) Cu(OH)2 (solid) or Zn(OH)2 (solid) → Cu(NH3)4+2 or Zn(NH3)4+2
Q.2. How can a cyanide (CN-) containing wastewater be treated??
(a) Fe2+ + CN- → FeII(CN)64- (b) FeII(CN)64- + Fe3+ + K+ → KFe[Fe(CN)6](Prussian blue)
 Chemical Equilibrium

L
q Ways of shifting the chemical equilibrium: Application of Le Chatelier principle

E
Ø Formation of a gaseous product:
FeS + 2H+ → H2S↑ + Fe2+ (Occurs)

T
CuS (or HgS) + 2H+ → H2S↑ + Cu2+ (Does not occur)
In industrial waste treatment cyanides were formerly removed from aqueous

P
solution by treatment with sulfuric acid
2CN- + 2H+ + SO42- → 2HCN ↑ + SO42-

N
The HCN gas was released through tall stack so that it is dispersed and diluted by the
large volume of air.
Ø Oxidation and Reduction:
2CN- + 5Cl2 + 8OH- → 10Cl- + 2CO2 + N2 ↑ + 4H2O
Chemical Equilibrium

q Amphoteric hydroxides:
Ø The hydroxides that are soluble both in acids and bases

E L
T
The stepwise reaction between Al3+ and OH- takes place to form different species

P
such as: Al(OH)2+, Al(OH)2+, Al(OH)3, Al(OH)4- etc. (Coagulation & flocculation)

N
References:

E L
T
• Dutt PK, Dutt PK (2000) General & Inorganic Chemistry,
Calcutta

P
• Sawyer CN, McCarty PL, Parkin GF (2000) Chemistry for
Environmental Engineering, Tata McGraw Hill, New Delhi

N
 E L
P T
N
 E L
P T
ENVIRONMENTAL CHEMISTRY AND MICROBIOLOGY

N
ANJALI PAL AND SUDHA GOEL
DEPARTMENT OF CIVIL ENGINEERING, IIT KHARAGPUR

Module 02:
Lecture 08 : Chemical Equilibrium - III
 L
Chemical Equilibrium

TE
P
Ø Solubility product
Ø Solubility

N
Ø Common ion effect
Ø Application
q Solubility Product:

L
Ø All solids, even if they are insoluble, are soluble to some extent. For example, AgCl
and BaSO4 is considered to be very insoluble. But in contact with water they

E
dissolve slightly, and establish the following equilibria:
AgCl(s) ⇄ Ag+ (aq) + Cl- (aq) -----------(1)

T
BaSO4(s) ⇄ Ba2+ (aq) + SO4-2 (aq) ----------(2)
The equilibrium that exists for reaction (1) can be expressed as:

P
K = [Ag+ (aq)] [Cl- (aq)] / [AgCl (s)]
Ksp= [Ag+ (aq)] [Cl- (aq)]

N
Ksp is called solubility product or solubility product constant
It is a constant at a particular temperature. In almost all text books or hand books
dealing with qualitative and quantitative analysis the solubility product values are
available. In a similar way for a complex salt such as Ca3(PO4)2 we can write
Ca3(PO4)2 ⇄ 3Ca2+ + 2PO4-3
Ksp = [Ca2+]3 × [PO4-3]2
q Solubility

L
BaSO4 (s) ⇄ Ba2+ (aq) + SO4-2 (aq)
If S represents the solubility of BaSO4, then

E
S = [Ba2+] = [SO4-2]
Ksp = S x S = 1x10-10

T
Therefore, S = 1x10-5 = Solubility of BaSO4

P
Similarly for CaF2
CaF2 ⇄ Ca2+ + 2F-
Ksp = [Ca2+] x [F-]2

N
If S is the solubility of CaF2, then So it can be said that calcium
fluoride is 20 times more
[Ca2+] = S; [F-] = 2S soluble than barium sulfate
Ksp = (S) x (2S)2 = 4S3 = 3 x 10-11
S = 1.96 x 10-4 = 19.6 x 10-5
q Understanding of phenomenon of precipitation

L
1. In an unsaturated solution:

E
For a species AB
[A+] [B-] < Ksp

T
Ø If undissolved AB is present, it will dissolve until [A+] [B-] = Ksp
2. In a supersaturated solution:

P
For a species AB
[A+] [B-] > Ksp

N
Ø Nothing will happen until some crystals of AB are introduced in to the solution or
some internal forces allow formation of crystal nuclei
Ø Then precipitation will occur until the situation becomes
[A+] [B-] = Ksp
q Common ion effect on solubility:

L
An electrolyte CA (having concentration c moles per litre) when added to a
saturated solution of another electrolyte BA (of solubility s moles per litre) how

E
will the solubility of BA be affected? Here A- is common to both.
BA ⇄ B+ + A-
CA ⇄ C+ + A-

T
Since the concentration of A- is increased, so the concentration of B+ should
decrease to keep the solubility product of BA constant. This occurs with the

P
precipitation of BA from the solution which resulting in decrease in its solubility.
If the new solubility of BA is s’ then
Ksp = s2 = s’ (s’ + c)

N
Ø The solubility of an electrolyte is thus decreased by the presence of a common
ion. However, the solubility product remains constant.

Q. How to get pure sodium chloride precipitate from a sodium chloride solution???
Common ion effect on solubility: Quantitative approach

L
Let us consider a solution that has been saturated with BaSO4

E
Therefore, S = [Ba2+] = [SO4-2] = 1x10-5 M
Now, if [Ba2+] is increased by addition from an outside source, say BaCl2, then what
will happen???

T
Ksp = [Ba2+] × [SO4-2]

P
BaSO4(s) ⇄ Ba2+ (aq) + SO4-2 (aq)
For example, let us assume that 10 × 10-5 mol/l of BaCl2 is added to the above
solution. This will cause in the formation of an additional y moles of precipitated

N
BaSO4(s). Then the following changes will take place:
Ba2+ + SO4-2 → BaSO4 (s)
(1x10-5 + 10 × 10-5 - y) mol/l (1x10-5 - y) mol/l y mol/l
• So, Ksp = (11 × 10-5 - y) (1x10-5 - y) = 1x10-10
Common ion effect on solubility: Quantitative approach

L
Upon solving we get

E
Y = 0.90 × 10-5 mol/l
So, [Ba2+] = (11 × 10-5 - y) = (11 × 10-5 - 0.90 × 10-5) = 10.1 × 10-5 mol/l

T
[SO4-2] = (1x10-5 - y) = (1x10-5 - 0.90 × 10-5) = 0.1x10-5 mol/l

P
Ø So it is observed that sulfate ion concentration is reduced considerably. This is an
application of common ion effect.

N
This is used extensively in environmental engineering practice and in analytical
chemistry to accomplish complete precipitation of desired ions.

Example: Hardness removal as CaCO3 or Mg(OH)2

L
ü The ionization of a weak electrolyte (a weak acid or base) in solution is

E
suppressed in presence of largely ionised salt having a common ion (present in
the weak electrolyte)
Example:

T
NH4OH / NH4Cl in water
CH3COOH / CH3COONa in water

P
ü The larger the quantity of the added salt, the smaller the ionisation of the weak
electrolyte

N
ü Thus the common ion effect affords a method for controlling the concentration of
ions furnished by a weak electrolyte
q Common ion effect on Precipitation: Group separation

L
If we consider the solubility product of the following metal sulphides
HgS: 4 ´ 10-54
CuS: 1 ´ 10-44

E
CdS: 1.4 ´ 10-28
ZnS: 1 ´ 10-23

T
MnS: 1.4 ´ 10-15
On passing H2S gas into a solution of salts of these metals, the metal sulphides will
precipitate only when [M2+] [S-2] exceeds the solubility product (Ksp).

P
Now H2S is a weak acid and its dissociation H2S ⇄ 2H+ + S-2 is readily suppressed by H+
ions.
A saturated solution of H2S is 0.1 molar at 25°C, and the concentration of S-2 ion it

N
produces is [S-2] = 1.1 ´ 10-23 / [H+]2.
So, when the solution is acidified with 0.3 M HCl the concentration of S-2 is so much
decreased that the solubility product of very insoluble sulfides of group II metals, e.g.
HgS, CuS, CdS, etc. are only exceeded., and they are precipitated, while FeS, ZnS, MnS,
etc. will remain in solution.
(An elegant demonstration of solubility product and common ion effect)
Chemical Equilibrium

E L
Q. 1. Silver chromate (Ag2CrO4) is a red solid that dissolves in water to the extent of
0.029 g/L at 25 °C. Estimate its Ksp.

T
(given Mol. Wt. of Ag2CrO4 is 331.73)
Solution to Q.1.

P
Ag2CrO4 ⇋ 2Ag+ + CrO4-2

Ksp = (2S)2 × S = 4S3

N
[CrO4-2] = 0.029 / 331.73 = 8.74 × 10-5 = S
[Ag+] = 2S = 2 × 8.74 × 10-5 = 1.75 × 10-4 M
Ksp = [Ag+]2 [CrO4-2] = (1.75 × 10-4 )2 × (8.74 × 10-5) = 2.7 × 10-12
 L
Conclusions

T E
ü So in this lecture it has been explained how electrolytic dissociation

P
enable us to determine the conditions under which a substance dissolves
or forms precipitate.

N
ü The concept on solubility product, solubility and common ion effect help
the analytical chemists and the process engineers to solve environmental
problems in a better way.
References:

E L
T
• Dutt PK, Dutt PK (2000) General & Inorganic Chemistry,
Calcutta

P
• Sawyer CN, McCarty PL, Parkin GF (2000) Chemistry for
Environmental Engineering, Tata McGraw Hill, New Delhi

N
 E L
P T
N
 E L
P T
ENVIRONMENTAL CHEMISTRY AND MICROBIOLOGY

N
ANJALI PAL AND SUDHA GOEL
DEPARTMENT OF CIVIL ENGINEERING, IIT KHARAGPUR

Module 02:
Lecture 09 : Chemical Equilibrium -IV
 L
Chemical equilibrium

Ø Dissociation of acids and bases

T E
P
Ø Dissociation of water
Ø Equilibrium concept in complex formation and dissociation

N
Chemical equilibrium

L
q Ionization of Acids and Bases

E
Ø According to Arrhenious theory an acid is a compound which gives H+ in water, and
a base gives OH- in water.

T
Ø Arrhenious theory helps us to explain the strength of acids and bases.
Ø Strong acids dissociate fully (100%) in dilute solution

P
Ø As for example for a monoprotonic acid HA
HA ⇌ H+ + A-
KA ⇌ [H+] [A-] / [HA]

N
For a strong acid KA is very large as because there is almost no undissociated acid (HA)
KA is the dissociation constant of acid
Ø However, for weak acids such as acetic acid (HAc)
HAc ⇌ H+ + Ac- (Ac- is the acetate ion)
KA = [H+] [Ac-] / [HAc] = 1.75 ´ 10-5 (at 25°C)
Chemical equilibrium

L
q Ionization of Acids and Bases

E
Ø For a diprotic acid such as carbonic acid (H2CO3)
H2CO3 ⇌ H+ + HCO3-

T
KA1 = [H+] [HCO3-] / [H2CO3] = 4.45 ´ 10-7 (at 25°C)
Again,

P
HCO3- ⇌ H+ + CO3-2
KA2 = [H+] [CO3-2] / [HCO3-2] = 4.69 ´ 10-11 (at 25°C)

N
Ø Similarly for a typical weak base NH3
NH3 + H2O ⇌ NH4+ + OH-
KB = [NH4+] [OH-] / [NH3] = 1.75 ´ 10-5 (at 25°C)
q Ionization of Water

L
Ø In aqueous solutions one of the most important equilibria is the dissociation of
water into a hydrogen ion (or proton) and hydroxyl ion

E
H2O ⇌ H+ + OH- ---------- (1)
A proton can not exist as such because of its small volume (and extremely large
charge-to-volume ratio).

T
It will attach itself to a water molecule to form H3O+ (hydronium ion).
So the more correct representation of water dissociation is:

P
2H2O ⇌ H3O+ + OH- ----------(2)
However for many practical purposes Eqn. (1) can be considered.
This gives us the ion product of water:

N
[H+] [OH-] / [H2O] = Kw (ion product of water)
However, [H2O] is taken as 1.
Hence, Kw = [H+] [OH-] = 10-14 (at 25°C)
It is important to remember that, the numerical values of [H+] and [OH-] will include
all the H+ and OH- ions present, whether they come from water alone or from other
constituents present in water.
 L
q Complex ion formation and dissociation:
Ø In complex ions we observe the presence of one (or more) metal ion associated

E
with one or more ions or molecules called as ligands.
Ø The common ligands may be some ions or molecules like OH-, CO32-, NH3, F-, Cl-,
CN-, S2O32-, and other organic species like EDTA, humic acid etc.

T
Ø For example Ag+ ions complex with NH3 to form silver-ammonia (silver amine)
complex

P
Ag+ + 2NH3 ⇌ Ag(NH3)2+
So, here the formation (or stability) constant (b2)
= [Ag(NH3)2+] / [Ag+] [NH3]2 = 1.74 ´ 107

N
Ø All such complex ions are destroyed by removing one of the dissociation
products.
Ø For example silver-ammonia complex ion can be destroyed if some source of H+
ions is added.
Ø Because upon addition of H+ ion, NH4+ is produced which is more stable
NH3 + H+ ⇌ NH4+
q Formation of Complex ions

L
Ø As a typical example let us consider the formation of complexes between Hg2+
and Cl- in aqueous medium:

E
• At different proportions Cl- can combine with Hg2+ to form different species like
HgCl+, HgCl2, HgCl3-, HgCl42-
• Equilibrium expressions can be written individually for the formation of the

T
various above mentioned species
• Corresponding formation (or stability) constants at 25°C are obtained from

P
available text books
Hg2+ + Cl- ⇌ HgCl+
HgCl+ + Cl- ⇌ HgCl2

N
HgCl2 + Cl- ⇌ HgCl3-
HgCl3- + Cl- ⇌ HgCl42-
[HgCl+] / [Hg2+] [Cl-] = K1 = 5.6 ´ 106
[HgCl2] / [HgCl+] [Cl-] = K2 = 3 ´ 106
[HgCl3-] / [HgCl2] [Cl-] = K3 = 7.1
[HgCl42-] / [HgCl3-] [Cl-] = K4 = 10
q Formation of Complex ions:

L
• It is also possible to consider the overall reaction by combining the step-wise

E
reaction. For example in case of the previous complexes

Hg2+ + Cl- ⇌ HgCl+ [HgCl+] / [Hg2+] [Cl-] = b1

T
Hg2+ + 2Cl- ⇌ HgCl2 [HgCl2] / [Hg2+] [Cl-]2 = b2 = K1 K2
Hg2+ + 3Cl- ⇌ HgCl3- [HgCl3-] / [Hg2+] [Cl-]3 = b3 = K1 K2 K3

P
Hg2+ + 4Cl- ⇌ HgCl42- [HgCl42-] / [Hg2+] [Cl-]4 = b4 = K1 K2 K3 K4

The reciprocal of b4 is called instability constant

N
So the instability constant (Kinst) = [Hg2+] [Cl-]4 / [HgCl42-]

ü Using these expressions and the equilibrium constants it is possible to determine

E L
T
• Dutt PK, Dutt PK (2000) General & Inorganic Chemistry,
Calcutta

P
• Sawyer CN, McCarty PL, Parkin GF (2000) Chemistry for
Environmental Engineering, Tata McGraw Hill, New Delhi

N
 E L
P T
N
 E L
P T
ENVIRONMENTAL CHEMISTRY AND MICROBIOLOGY
ANJALI PAL AND SUDHA GOEL

N
DEPARTMENT OF CIVIL ENGINEERING, IIT KHARAGPUR

Module 02:
Lecture 10 : Chemical Equilibrium -V
 L
Chemical equilibrium

T
q Implication of Chemical Equilibrium

E
P
Ø Cu2+ detection
Ø Ag+ detection

N
Ø An interesting demonstration
Ø Charge reversal of colloid
Ø Hardness determination
Ø Electroplating
 Complex salt formation: Cu2+ detection

L
Ø Cu + dil. H2SO4 ⇨ CuSO4 (blue solution)

E
Ø CuSO4 (blue solution) + aq. NH3 (little amount) ⇨ CuSO4.Cu(OH)2 (blue-white ppt.)(basic salt)
Ø CuSO4.Cu(OH)2 (blue-white ppt.) + NH3 (higher concentration) ⇨ [ Cu(NH3)4]SO4 (blue solution)

T
q Copper through slow oxidation process in air goes to Cu2+ and that is blue. Copper
produces CuSO4 upon reaction with dil. H2SO4 in air. CuSO4 is known as blue vitriol.

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On the other hand H2SO4 is known as oil of vitriol. CuSO4 is a normal salt and it
forms a complex salt with dilute ammonia. However, concentration of NH3 matters.
Introduction of dilute ammonia to blue CuSO4 solution slowly converts Cu2+ to a

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basic salt i.e. CuSO4. Cu(OH)2 as a blue-white precipitate which finally goes to
complex Cu(NH3)42+ ion and the corresponding salt is [Cu(NH3)4]SO4. This gives a
transparent blue solution. This is a test of Cu2+ ion.
 Complex salt formation: Ag+ detection

AgNO3 + Cl- ⇨ AgCl↓(curdy white ppt.)

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q Aqueous AgNO3 solution is taken in a test tube. It is a colorless solution. To

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this, NaCl solution is added. Curdy white precipitate of AgCl is observed to
form. Now aqueous NH3 is added to the ppt. The precipitate dissolves. This is
because of the formation of silver amine complex. Again HCl is added to the

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solution. The white precipitate reappears due to the formation of AgCl again.
This is a test for Ag+ detection
Application of solubility product concept: An interesting demonstration (Green Chemistry)

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q AgNO3, the most common silver salt, is used for detection of Cl- ion. One can
easily observe a curdy white precipitate formed from AgNO3 and HCl (or water

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soluble chloride salt). This is a test for Cl- in solution (and in turn a test for Ag+ in
solution). AgCl is soluble in conc. HCl.
q Similarly, the test for SO42- ion is performed with water soluble BaCl2. BaCl2

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produces white crystalline BaSO4 ppt with sulfate ion in water. BaSO4 is insoluble
in all acids and alkalis.

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q Now say two test tubes are there with you: one containing BaSO4 ppt. in water,
and the other AgCl in water. Both are white ppt.
q How to know which one is which without using any reagent???

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q If you can do that then you are following some green chemistry protocol.
q Can you do that???
q Yes you can. You can think of classical photography where silver salts are used. If
you hold both the test tubes in Sunlight for a small period of time, then one ppt.
will turn black and the other will remain white. So the one which turns black is
AgCl and the other is BaSO4. A simple experiment indeed!
Charge reversal of colloid

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ü Blank correction in Cl- determination

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ü K2CrO4 as indicator in Cl-
determination

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Hardness determination by EDTA titration

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q Hard waters are those waters that require considerable amounts of soap to
produce lather. Hard water produce scale in hot-water pipes, heaters, boilers

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etc.

q Hardness is caused by Ca2+, Mg2+, Fe2+, Mn2+ (multivalent cations)

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q Complexometric titration is carried out with Na2-EDTA solution in presence of
Eriochrome Black T (EBT) as indicator

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q In M2+-EDTA complex the stoichiometry M2+ : EDTA = 1:1

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q KMetal-EDTA complex : KMetal-Indicator complex is very large (>104)

q Indicator concentration : Metal ion concentration should be low (< 10-2)

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q Sometimes articles of iron or brass are plated with silver, gold, nickel, copper to
protect them from corrosion or just for the decoration purpose.
q In case of metal plating, the electroplating bath consists of a solution of the salt of

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the plating metal, the cathode is the article to be plated and the anode the plating
metal.

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q In silver plating a solution of argentocyanide is electrolysed, the anode is a plate of
pure silver. The cathode is the article to be plated. The electrolytic bath is prepared
by adding excess of KCN to AgNO3 solution.

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q The anion [Ag(CN)2]- is only slightly dissociated (unlike AgNO3) and silver ions are
deposited on the cathode (the article to be plated) to form a thin uniform film of
silver.

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q If AgNO3 alone is used as an electrolyte then a coarse spongey silver deposit is
observed.
q The CN- ions discharge on the silver anode and form AgCN which dissolves in excess
KCN to form potassium argentocyanide
AgNO3 + KCN = K[Ag(CN)2] ; K[Ag(CN)2] ⇌ K+ + [Ag(CN)2]- ; [Ag(CN)2]- ⇌ Ag+ + 2CN-
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ü So we learnt how by applying Chemical Equilibrium concept we
can understand the solubilisation and precipitation phenomenon
in a better way and we can solve many environmental problems.

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ü The concept is also very useful for understanding analytical

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methods for detection and determination of many analytes.

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References:

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• Dutt PK, Dutt PK (2000) General & Inorganic Chemistry,
Calcutta

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• Sawyer CN, McCarty PL, Parkin GF (2000) Chemistry for
Environmental Engineering, Tata McGraw Hill, New Delhi

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