UNIT-4:Equilibrium | RedoxReactions

EQUILIBRIUM

At
equilibrium. two opposing processes (forward
and reverse) take place at equal rates hence it is
LaW OF CHEMICAL EquILIBRIUM
called dynamic equilibrium. Law of chemical equilibrium is a result obtained
Equilibrium can be established for both physical by applying the law of mass action to a reversible
reaction in equilibrium.
processes and chemical reactions.
For example, consider a general reversible reaction,
REVERSIBLEREACTIONS aA +bB C+dd
A reaction which takes place not only in the forward K = C I D

direction but also in the backward direction under ; where, K is equilibrium constant
the same conditions is called a reversible reaction.
Al'IB
Ke is specifñc for a reaction and this equation is
Equilibrium reached Concentration known as law ofchemical equilibriumn.
of products Relations between equilibrium constants for a
general reaction and its multiples:
Concentration
of reactants Chemical equation Equilibrium
Time constant

Forward rate aA +
bB C+dD Ke
Equilibrium reached cC+dD aA + bB K = (1/K)

naA +nbB ncC+ ndD K= (K)"

Backward rate
For agas phase reaction, aA + bB cC+ dD
Time
Ultimately a stage comes in reversible reaction PP» and K= K(RT)";
where concentration of both reactant and product (Pa(Pa
becomes equal which is said to be equilibrium. where, An =

\"gaseous products"gaseous reactants

If An, =0, Kp = Ke 2. Increase in the in backward direction
IfAn,= + ve (i.e, n,> n,), Kp Ke > concentration of one

IfAn,= -ve (i.e., n, < n,), Kp < Ke or more products

in towards endothermic
Increase
Predicting the Direction of the Reaction temperature reaction
aA +bB cC+ dD 4. Decrease in towards exothermic
{G[b" temperature reaction
Reaction Quotient, Q.= favours lesser number
LA1LB 5. Increase in pressure
of gaseous moles
6. Decrease in pressure favours larger
number of gaseous
IfQ> K Q<K moles
Reaction Reaction
proceeds towards
7. Addition ofcatalyst has no effect
proceeds 8. Addition of inert gas
reactants towards products (a) at constant has no effect
(ie, backward) (ie., forward) volume
(b) at constant favours larger
If Q = K pressure number of gaseous
Reaction is in equilibrium moles

lowic EQuILIBRIUM
Effect of Temperatureon Equilibrium Constant
Those substances which conduct electricity in their
dlnK,_AH°
i log A7-]1 aqueous solutions are called electrolytes. Faraday
dT RT2 2.303R 7T, ] further classified electrolytes into two types :
If AH =

0, i.e., no heat is evolved or absorbed in the

reaction,log (K/K,) =0, i.e. K/K; = 1or Kg = K
Strong electrolytes on dissolution in water are
ionized almost completely. They are excellent
i.e., equilibrium constant does not change with conductors of electricity, e.g, HC, HNO,.
temperature. Weak
Ifthen i.e., heat is absorbed in the reaction,
AHlog(K/K,) = + ve, orlog K2 > log Kj or K2> Ki
=+ ve, electrolytes
solution.
are partially ionized in their
conductors of
aqueous They are
poor
i.e., equilibrium constant increases with increase in
electricity, eg, CH,COOH, H,PO, NH,OH.
temperature. Ostwald's Dilution Law
If AH = - ve, i.e., heat is evolved in the reaction, Itis applicable for weak electrolytes only.
log (K2/K)= - ve, ie., log K < log K, or K2 < K, Consider the dissociation of a weak electrolyte
i.e., equilibrium constant decreases with increase in C moles of which has been dissolved in one litre
temperature. and 'a' is its degree of dissociation, then
AB A + B
Le CHATELIER's PRINCIPLE Initial concentration C 0

Concentration at equilibrium C- Cua Ca Ca

If a system in equilibrium is subjected to a change
of concentration, temperature or pressure, the K=A
][B1Cax Coa
equilibrium shifts in a direction so as to undo the AB C(1-a)
effect of the change imposed. In the case of weak electrolytes, 1>> a, sol-a =1
Effect on chemical equilibria:
Change imposed at Equilibrium shift C
equilibrium But Cis concentration in moles/litre i.e., n/V
1. Increase in the in forward direction Ifn
i.e.,
isconstantof(for dilution), of a«

concentration of one degree ionization weak electrolyte

or more reactants
increases with dilution. The above expression is
known as Ostwald's dilution law.
Conjugate Acid-Base Pair or t ase.

A pair ofacid and base, which differs by a proton is The ionic product of water
known as conjugate acid-base pair. K [H'][OH] = 1.0 x 10" at 298 K, where K, is
-H the ionic product of water.
The ionic product of water is constant only at
Acid+ Base Conjugate +Conjugate constant temperature. With increase of temperature,
Base Acid the degree of ionization of water increases. Thus the
+H concentration of H" and OH increases and hence
lonization of Acids and Bases the ionic product also increases
HA H' +A, The pH scale: The pH ofa solution is a measure of
(Acid) the acidity of a solution.
pH - log[H|
K,-And
HA]
a= IfpH<7, acidic solution; if pH = 7, neutral solution
BOH B* +OH, ifpH>7, basic solution.
Base 14
pKpH +pOH =

K - BOH and a= Relation between K, and K,:

BOH For a weak acid, pK, log Kgi
= -

Greater the degree of ionization («) or greater the For a weak base, pK, = - log K,

dissociation constant (Ka or Kg), stronger is the acid pRa+ pK= pK» = 14 at 298 1

Salt Hydrolysis
Salts ofstrong acids and strong bases do not undergo hydrolysis and the resulting solution is neutral.
Salt Hydrolysis Resulting Hydrolysis Degree of pH
solution constant (K)hydrolysis (h)
Weak acid and Anionic Alkaline
K h=VpH lpK + pK, + log C]
Strong base pH>7
KK
Strong acid and Cationic Acidic
Weak base pH 7 h- p- pK-pky-log
Weak acid and Anionic and Neutral,
hK Ipk,+ pK, -pKl
Weak base cationic both pH=7
(If K, =
Kp KKK pH=

Calculation of pH
Types of solution Formula
1. Dilute aqueous solution ofa strong acid or a pH= -log {[Hlacid + [H'|IH,o}
strong base pOH=-logilOH lbase +[OH JH,oB
Highly concentrated solution of a strong acid pH of acidic solution is taken as 0.
or a strong base (concentration> 1 M) pH of basic solution is taken as 14.
3. Solution of a weak acid or a weak base pH -log(C) -logtK.C
=

pOH--log (Ca) =-log(K,C)

4. Mixture of two or more strong monoprotic
acids or strong bases pH--o ) pOH--lo
 5. Mixture of an acid and a base pH=-logNWacid /base (if acid is in excess)
+V
pOH= -log(N,V2)base N/acid (ifbase is in excess)
y+V2
6. Amphiprotic system
pH Pa+pa
2

Buffer Solutions
Solubility product
I t i s defined as the product of molar concentration of The property of resisting change in pH ofa solution
its ions in a saturated solution, each concentration when an acid or an alkali is added to it is known
raised to the power equal to the number of ions as buffer action and such solutions are called buffer

dissociation of one molecule of the solutions.

produced on
Such solution usually consist a mixture of weak
electrolyte
AB, xA* + yB acid and salt of its conjugate base (acidic buffer)
or weak base and salt of its conjugate acid (basic
Applying law of mass action, Kq
LABP buffer) and a salt of a weak acid and a weak base,
[A,B, e.g, ammonium acetate (CH,COONH,)
has a

As conc. of [A B,| undissociated is almost constant. buffer action.

KglAB] = [A"T[E°P Henderson-Hasselbalch equation
Kp [A"[B"" For acidic buffer: pH
(Salt)
pka + lo8Acid
=

Relation between solubility and solubility product

[Salt)
I f solubility of a sparingly soluble salt, A*P is For basic buffer: pOH= pk^ lo88ase
+

S moles/litre, then
Base
Base]
ABy = 2xA" + yB* or. pH= pkKa +
loSalt)
S moles xS moles yS moles On dilution, the ratio of concentrations of salt
Thus, [A"] =xS and [B"]=ys and acid or salt and base will still remain same
K= [A**|EV= (xs)" (yS¥ or x"y'st* thus pH will remain unchanged.

REDOX REACTIONS

Gain of one or more electrons by an atom or an ion

CoNCEPT OF OxDATION AND REDUCTION
or a molecule.

Oxidation Oxidising agent: The species, which gets reduced,

ie., undergoes reduction and oxidises other species.
Addition of oxygen or some other electronegative
atom. Reducing agent: The species, which gets oxidised,
i.e., undergoes oxidation and reduces other species.
Removal of hydrogen or some other electropositive
atom.
Loss of one or more electrons by an atom or an ion
or a molecule.

Reduction
Removal of oxygen or some electronegative atom.
Addition of hydrogen or some other electropositive
atom.
 OxiDATION NUMBER RULES
Applies to Rule
Elements The oxidation number of an atom in an element is zero.

Monoatomic ion Theoxidation number of an atom in a monoatomicionequalsthe charge on theion.

The oxidation number of oxygen is -2 in most of itscompounds (an exception is O in H,O;
Oxygen
and other peroxides, whereoxidation numberis -1)and in oxygen fuoride (OF,). it is +2
The oxidation number of hydrogen is +1 in most of its compounds. (The oxidation number
Hydrogen of hydrogen is -1 in metallic hydrides such as CaHz, NaH,)
The oxidation number of fluorine is -1, in all of its compounds. Each of other halogens
(CI, Br, 1) has an oxidation number of -1 in binary compounds, except when the other
Halogens
elementisanother halogen aboveitinthe periodictable orthe other element is oxygen.
The sum of the oxidation numbers of the atoms in a compound is zero. The sum of the
Compounds and ions
oxidation number of the atoms in a polyatomic ion equals the charge on the ion.

Alkali metals The oxidation number ofalkali metals (Na, K, Li, etc) in compounds is +l.
Alkaline earth metals The oxidation number of alkaline earth metals (Mg, Ca, Ba, Sr, etc.) in compounds is +2.

Sulphides In all sulphides the oxidation number of sulphur is-2.

Variable oxidation number is most commonly shown by transition elements as well as
Transition elements
Fe (+2 and +3), Cu (+1 and +2), Mn (+7, +6, +5, +4, +3, +2),
and p-block elements PDlock elements. eg
As (+3 and +5), Sb (+3 and+5), Sn (+2 and +4) etc
Types of Redox Reactlons

Combination reaction Decomposition reaction|Displacement reaction Disproportionation reaction

A+BAB AB A +B
CH +20 CO^+2H,0| 2KCIO, 2KCI+302
BALANGING OF REDox REaCTIONS
Oxidation Number Method
ldentify atoms which undergo change in oxidation
number in the reaction.
Calculate the increase or decrease in the oxidation
number per atom and multiply it by number
of atoms undergoing that change, if increase or
decrease is not equal then multiply by suitable
number to make them equal.
Add H' (if medium is acidic) or OH (if medium is
basic) on the appropriate side so that the total ionic
charges of reactants and products are equal.
Make the number of hydrogen atoms in the
expression on the two sides equal by adding H,O
to the reactants or products and finally check the
number of oxygen atoms.
AB+CAC+B
+2NaOH- Nal+
2AgNO+Cu-2Ag+Cu[NO,)2|| NaClo+H,O
Half Reaction Method
Separate the equation into half-reactions.
Balance the atoms other than O and H in each half.
reaction individually.
F o r reactions occurring in acidic medium, add H,0
to balance O atoms and H' to balance H atoms and
for basic medium, H atoms are balanced by adding
H,O molecule to the side deficient in H atoms and
equal number of OH ions are added to opposite
side and then duplicacy is removed if any.
Add electrons to one side of the half-reaction
to balance the charges and make the number of
electrons equal in two half-reactions by multiplying
one or both half-reactions by appropriate number.
Add two half-reactions to achieve the overall
reaction and cancel the electrons on both sides.
REDOx REACrioNs AND ELECTRODE PRoCESSES
Redox couple: It is defined as having together the
oxidised and reduced forms of a substance taking
part in an oxidation or reduction half-reaction i.e,a
metal dipped in the solution of its own ions.
Electrode potential: The potential difference set up
between the metal and its own ions in the solution
is called the electrode potential. In general, it is the
tendency of an electrode to gain or lose electrons.
Standard electrode potential (E):
concentration of each species taking part in the
electrode reaction is unity and further the reaction
is carried out at 298 K, then the potential of each
electrode is called standard electrode potential.
Standard electrode potential of hydrogen is
taken as 0.00 volts by convention.
Electrochemical series is a series in which a list
of oxidising agents are arranged in decreasing
order of their strength. It is also called activity
or electromotive series.
A negative E° means that the redox couple is a
stronger reducing agent than the H/H, couple.
If the
A positive E° means that the redox couple is a
weaker reducing agent than the H'/H, couple.

PRACTICE
1. The gasAz in the left flask (a) Ts> T2>Ti (6) T>T Ts
allowed to react with gas (c) T= T2 - Ts
2 mole mole
B present inrightflaskas A2 B2 (d) Nothing could be predicted about temperature
Az) + Bag)2ABg) from given information
4 at 27 °C. What is tre 3 litre
R =

at 27 °C at 27 °C 4. Identify the compounds which are reduced and

the concentration of AB
oxidised in the following reaction
when equilibrium is established?
3NH, +2BrO 3N2 +2Br + 6H,0
(a) 1.33 M (b) 2.66 MM
(a) N,H4 is oxidised and BrO is reduced.
(c) 0.66 M (d) 0.33 M
(b) BrOj is oxidised and NaH4 is reduced.
2. According to Bronsted-Lowry concept of acids and (c) BrO is both reduced and oxidised.
bases, mark the option in which conjugate pair is (d) This is not a redox reaction.
not correctly matched.
5. From the given data, identify the most stable oxide
Species Conjugate acid Conjugate base of nitrogen.
(a) HCO Co H,CO (a) 2NOg)N2(g +202ji K= 6.7x 100 mol L
(b) HPO HPO Po (6) 2N,Osg2N2(t502g
(c) NH3 NH NH K= 1.2x 10 mol' L5
(d) HS HS C) 2NO N 2 ) +O2(gi K= 2.2 x 10
3. The preparation of SOs(g) by (d) 2N,O)2Nat+Oaei K= 3.5 x 10 molL
5ot
reaction, 40T 6. Consider the following reaction,
SO2+ 1/2 Otp SOgg» is 30t 2
COO
an exothermic reaction. 20t CHO +OH >
If the preparation follows 10t CHO CH,OH
the following temperature- I 2 34 Select the incorrect statement.
Pressure (a) It is not a disproportionation reaction.
pressure relationship for its % (atm)
(b) It is intramolecular redox reaction.
yield, then for temperatures T1. T2 and 73, the
correct option is (c) OH is a reducing as well as oxidising agent.
 11. What is the equivalent weight of NH, in the given
CHO is a reducing as well as oxidising agent.
(d) reaction?
CHO 3CuO+ 2NH 3Cu + Na + 3H,0
7. The values of coefficients to balance the following
(a) 17 (b) 17/4 (c) 17/2 (d) 17/3
reaction are
wCr(OH)+xCIO+ aOH>yCrO +2Cl+ bH2Oo 12. Small quantities of aqueous solution of X2, Y2 and

W
Z are put separately in three test tubes. Now, small
3 3 quantities of compounds AX, AY and AZ are added
(a) 2 3
separately to each of the solution of X2. Y2 and Z2.
) 2 3 2
AX does not react with any of the three solutions.
(c) 2 2
AY reacts with both X, and Z2. AZ reacts with X2
(d) 2 3
The decreasing order of ease of oxidation of the
8. Consider the following reaction : anions X, Y and Z is
2X+ Y=2Zig +80 kcal (a) Y,Z,X (b) Z,X, Y
Which combination of pressure and temperature (d) X,Z,Y
(c) Y,X.Z
gives the highest yield of Z at equilibrium? 13. The pK, of a weak acid (HA) is 4.5. The pOH of an
(a) 1000 atm and 500°C (b) 500 atm and 500°C 50% of
aqueous buffered solution of HA in which
(c) 1000 atm and 100°C (d) 500 atm and 100°C the acid is ionized, is
In an experiment, NO; gas is prepared and taken into (a) 4.5 (b) 2.5 (c) 9.5 (d) 7.0
three test tubes X, Y and Z. NO2 gas which is brown
14. Which one of the following ionic species has the
in colour dimerises into N,O, which is colourless. greatest proton affinity to form stable compound?
Test tube X is kept at room temperature, Yis kept in (a) (b) HS (c) NH (d) F
ice and Z is kept in hot water. What colour changes 15. The oxidation numbers of Fe and S in iron pyrites
will you observe in the test tubes and why?
are respectively
2NO2(8) N204(g); AH = -57.2 kJ mol (a) 3,-1 (b) 2,-1 (c) 3, - 1.5 (d) 4,-2
Brown Colourless
16. The solubility of different sparingly soluble salts are
given as follows:

- NO
Hot water S. No. Formula Type Solubility product
1. AB 4.0 x 10-20

2. AB 3.2 x 10l
(a) In test tube X, brown colour intensifies
since backward reaction is favoured at low 3. AB3 2.7 x 103
The correct increasing order of solubility is
temperature.
(b) In test tube Y, brown colour intensifies (a) 1,3,2 (b) 2, 1,3 (c) 1,2,3 (d) 3, 1,2
since backward reaction takes place at room
17. Using the standard electrode potential, find out the
temperature. pair between which redox reaction is not feasible.
(c) In test tube Z, brown colour intensifies since
favours the backward
Evalues: Fe*/Fe* = +0.77 V; 1/T= +0.54 V
high temperature Cu/Cu=+0.34 V; Ag'IAg =+ 0,80
V
reaction. (a) Fe" and I* (b) Ag and Cu
(d) Brown colour of test tubes X, Y and Z remains (d) Ag and Fe**
(c) Fe" and Cu
same since there is no effect of change in
18. pH of water is 7. When a substance X is dissolved
temperature on the reaction.
in water, the pH becomes 13. The substance X is a
10. What is the minimum pH required to prevent the
salt of
precipitation of ZnS in solution that is 0.01 M
a
(a) strong acid and strong base
ZnClh and saturated with 0.10 M H2S? (6) weak acid and weak base
(Given: K= 10, K, x K = 107) (c) strong acid and weak basee

(a) 0 (b) 1 (c) 2 (d)4 (d) weak acid and strong base.
 19. In which of the following processes nitrogen is 2. (b)
oxidised? 3. (b): For exothermic reactions, yield increases as
(a) NHN2 (b) NOj NO temperature decreases ie., T, >T2 > Ts
(c) NO2 NO (d) NO NH; -2 +5

20. Which of the following statements is/are true? 4. (a): 3N,H, +2BrO, 3N,+2Br+6H,0
(a) Weaker the acid, greater will be hydrolysis of its 5. (a): The value of K is the measure of extent of
anion. reaction. For most stable oxide, Keg should be
b) Weaker the base, greater will be hydrolysis of its minimum.

cation. 6. (c): One CHO is oxidised to COO and one CHO

(c) Both (a) and (b). (d) None of these. is reduced to CH,OH.
Thus, reaction.
21. A compound of Xe and F is foundhave
53.4% to it is not a
disproportionation
intramolecular redox reaction. Thus, options (a)
It is
Xe (atomic mass 133). Oxidation number of Xe in
this compound is CHO
and (b) are true and is reducing as well as
(a) (b) +2 (c) +4 (d) +6 CHO
22. Pressure necessary to obtain 50% dissociation of oxidising agent.
7. (d): Cr(OH), + 5OHCro+ 4H,0+ 3e"] x 2
PCls at 500K will
be qual to
(a) Kp (b) 2Kp (¢) 3Kp (d) 4K, Clo+H20+2eCI+20H]x3
23. pOH of H2O is 7.0 at 298 K. If water is heated at 2Cr(OH),+ 40H +3Clo>2CrOf +3Cl+5H,0
350 K, which of the following statement should be 8. (c): The reaction takes place with a reduction in
true? number of moles (volume) and is exothermic. So
(a) pOH will decrease. (b) pOH will increase. and low temperature will favour the
high pressure
(c) pOH will remain 7.0. reaction in forward direction.
(d) Concentration of H ions will increase but that 9. (c)
of OH will decrease. 10. (b): Kp = [Zn2*](s*]
24. 4.8 g of a sample of methanol was placed in an
IS)=0
mpty one litre vessel and heated to 250 °C. Methanol
=1019

first changed into vapour and then decomposed 0.01

into CO and H2. After equilibrium was reached, a HSH+ HS"; K, H [HS]
IHS
hole was made in the vessel. The gas effusing out
showed that it contains 30 times as much H2 as HS=H'+ S2; K, = HIS]
for this
CHOH vapour.
reaction at 250 °C is
The equilibrium constant
Ka,K HHS
HS
(a) 1.1 (b) 2.2 (c) 3.3 (d) 4.4
[HS
25. Buffer capacity ofa buffer solution is x, the volume o-20HFx1o-19
of 1 M NaOH added to 100 mL of this solution if [H']=0.1 or pH =1
0.1
the change of pH by 1 is 11. (d): 2NH3> N2 +6e or, NH,>1/2 N, + 3e
(a) 0.1 xmL (b) 10x mL 17/3
(d) xmL.
Eq. wt.
=M/3 =

(c) 100 x mL
12. (a): Since AX does not react with any of the
SOLUTIONs solutions, it means that X is least easily oxidized.
1. (c) Since AY reacts with both X2 and Z2, i.e.,
Azg)t Bate)2AB) 2Y + X22X + Y2 and 2Y + Z2> 2Z+ Y
Initial moles
Moles at eqm 2-x 4-x therefore, Y is most easily oxidized.

4x
Since AZ reacts with only X2, i.e.,
=4 *= 1.33 mole
2Z +X22X +
Z2 therefore, Z is more easily
(2-x)(4-x) oxidized than X". Combining all the results, the
2x1.33
decreasing order of oxidation of anions follows the
LABg)4 4
= 0.66 M
order Y > Z">X
13. (c): For buffer solution
pH =pK,+log 4.5 +log Salt xP-
PPcI1.5
0.5 P
xP= 0.5pP
PpCl21.5
As HA is 50% ionized, hence [Salt) = [Acid] PpCl3 1.5 3
pH 4.5 pOH =14- 4.5 9.5
PPCI, XPC, -(P/3)(P/3)_
14. (c): Strongest proton affinity will be for the species P/3
which is the strongest base whose PPCls
or conjugate or P=3 Kp
acid is the weakest. The conjugate acid of NH is
NH3 which is the weakest acid out of HI, H2S, NH3 23. (b): [OH]= JK,, in pure water.
and HE As temperature increases K, increases

15. (d) [OH] increases.

16. (a): Solubility of AB = K =2x10-10
24. (a):
Initial moles
CH,OH
4./32 =0.15
CO+2H2g)
Moles at eqm (0.15-x) 2x

Solubility of A,B =i
Ap=2x10 Given, 30 (0.15 -x) = 2x
or 4.5 30x = 2x = 32x =4.5 *=0.14
/4
Solubility of AB, = 10-8 (0.140.28) =1.0976=1.1

17. (d): Forthe reaction, 2Fes* + 21+2Fe* + 12

(0.15-0.14)
25. (c): Moles of NaOH required for 1 L solution = x
Eel Erre Ety - = 0.77 (0.54) = + 0.23 V Moles of NaOH required for 100 mL of
Here, Ecell is +ve so, the reaction is feasible. solution =0.1 x
For the reaction, Now, 0.1x =1x V =V= 0.1 x L = 100 x mL
Cu +2Ag Cu" +2Ag
FcellAglAg-FCu*/Cu= 0.80 (0.34) = +0.46 V

Here, Eel is +ve so, the reaction is

feasible.
Forthe reaction, 2Fe*" + Cu2Fe+ Cu
Pcell EreFe2- FEuyCu 0.77 (0.34) = + 0.433V

Here, Eelt is +ve so, the reaction is feasible.

For the reaction, Ag + Fe"> Ag' + Fe*
Ee EiR-EAg'/Ag 0.77 (0.80) = = -
0.03 V
Here, Eel is negative so, the reaction is not feasible.
18. (d) 19. (a) 20. ()
21. (d): Compound of Xe and F contains 53.4% Xe.
Therefore, amount of Xe and F present are 53.4 g8
and 46.6 g respectively.
Molar ratio of Xe F
53.4 40.0
133
0.401
19
2.45
6
Thus, the empirical formula of the compound is XeF%.
O. N. of Xe in XeF, = + 6.

22. (c):
Initial moles
PCl PCl+ Clh
Moles at eqm. 1-0.5 = 0.5 0.5 0.5
Total = 1.5 moles

If P is the total required pressure, then