SOLUTION (FLOW CHART & IMP FORMOLE)

1 SOLUTION: - Homogeneous mixture of two & more than two components. Example: Gas in solid solution (H2 in
Pd), Liquid in solid (Amalgam-Hg and Na)

2 CONCENTRATION OF SOLUTION:-
𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒘 𝒙 𝟏𝟎𝟎𝟎 𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒘 𝒙 𝟏𝟎𝟎𝟎
(a) Molarity = 𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 (𝒊𝒏 𝑳𝒊𝒕.)
= 𝑴 𝒙 𝑽 (𝒎𝒍) (b) Molality = 𝑾𝒕.𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 (𝒊𝒏 𝑲𝒈.)
= 𝑴 𝒙 𝑾 (𝒈𝒎)

𝑴𝒂𝒔𝒔 𝒐𝒇 𝑺𝒐𝒍𝒖𝒕𝒆 𝑴𝒂𝒔𝒔 𝒐𝒇 𝑺𝒐𝒍𝒖𝒕𝒆

(c) Mass % = 𝑴𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
x 100 (d) ppm = 𝑴𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
x 106

𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝒐𝒏𝒆 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕

(e) Mole Fraction = 𝑻𝒐𝒕𝒂𝒍 𝒎𝒐𝒍𝒆𝒔

3 HENRY’S LAW:- At constant temp, the solubility of a gas in a liquid is directly proportional to the pressure of the
gas.

(i) m = Kh p (ii) p = KhX (KH=Henry’s law constant).

When pressure increases, solubility of gases also increases. (Greater the KH value lower the solubility)

*When temperature increases KH value also increases hence solubility of gases decreases.

Application: 1. To increase the solubility of CO2 in soft drinks, the bottle is sealed under high P.

2.To avoid bends, the tanks used by scuba divers are filled with air diluted with He.

4 VAPOUR PRESSURE:- The pressure which is applied by the vapours above the liquid surface at the equilibrium. It
depends upon nature of liquid (Boiling point) and temperature.

5 VAPOUR PRESSURE OF LIQUID–LIQUID SOLUTIONS:- RAOULT’S LAW:- The partial vapour pressure of each
component in the solution is directly proportional to its mole fraction. [PA = PA0XA and PB = PB0 XB]

6 IDEAL SOLUTIONS:- The soln which obeys Raoult’s law over the entire range of the temp & concentration. Example:
Solution of n-hexane and n-heptane.

(a) PA = PA0 XA & PB = PB0 XB (b) ∆MixH=0 (c) ∆MixV = 0 (d) A-B interaction is same as A-A & B-B interaction

7 NON-IDEAL SOLUTIONS:- The soln which does not obeys Raoult’s law over the entire range of the temp &
concentration.

(a)PA ≠ PA0 XA & PB ≠ PB0 XB (b) ∆MixH ≠ 0 (c)∆V ≠ 0 (d)A-B interaction is different as A-A & B-B interaction

8 DEVIATION FROM IDEAL BEHAVIOR:-

POSITIVE DEVIATIONS NEGATIVE DEVIATIONS

(a) A-B interaction is weaker as A-A & B-B interaction (a) A-B interaction is stronger as A-A & B-B interaction

(b) PA > PA0 XA & PB > PB0 XB (c) ∆MixH >0 (d) ∆MixV > 0 (b) PA < PA0 XA & PB < PB0 XB (c) ∆MixH < 0 (d) ∆V < 0

Ex. (i) Ethanol & Acetone (ii) CS2 and acetone Ex. (i) Acetone & Chloroform (ii) Phenol + aniline
 9 AZEOTROPES AND ITS TYPES:- The composition at which both components of solution boils at the same temp
without changed in concentration is called azeotropic composition or azeotropic mixture or azeotrops. In such
case, it is not possible to separate the components by fractional distillation.
(a) Minimum boiling azeotrope (positive deviation) Ex.-95%aq ethanol
(b) Maximum boiling azeotrope (negative deviation) Ex.-68% aq. nitric acid (by mass).

101. COLLIGATIVE PROPERTIES:- The properties of solution which depend upon the number of solute particles and not
upon the nature of the solute particles.
Elevation in boiling point:- When a non-volatile solute is added to a volatile solvent the vapour pressure of pure
solvent decreases because a part of the surface is occupied by non-volatile solute which can’t volatilise. As a
result, the vapour pressure of solution decreases and hence, the solution requires a comparatively higher
temperature to boil causing an elevation of boiling point.

(A) Relative lowering of Vapour pressure (D) Osmotic Pressure

𝑷𝟎 − 𝑷𝒔 𝒏𝑩
Osmosis:- The flow of solvent through a
= XB (XSOLUTE) XB = Semipermeable membrane to the solution.
𝑷𝟎 𝒏𝑨 + 𝒏𝑩

𝑷𝟎 − 𝑷𝒔 𝑾𝑩 𝑴𝑨 Osmotic pressure:- The extra pressure applied on

= 𝑴𝑩
𝑷𝟎 𝑾𝑨 the soln that just stops the flow of solvent.
[For a very dilute soln nB<< nA]
𝒏
𝑷𝟎 = is vapour pressure of pure component 'A' π = CRT = 𝑽 RT (van't Hoff eqn for dilute soln)
𝑷𝒔 = partial vapour pressure of solution
𝑷𝟎 − 𝑷𝒔 = ΔP= Lowering of vapour pressure π = osmotic pressure, 'V'= volume of the soln,
n'=number of moles of the solute, T= Temp.
R = solution constant (0.0821 L atm mol–)

(B) Elevation in boiling point (C) Depression in F.P. freezing point

2. SOLUTION

ΔTb = Kb m (ΔTb =Tb – T0b). (m = molality) ΔTf = Kf m (ΔTf = T0f – Tf). (m = molality)
Kb = Molal elevation constant or Ebulloscopic Kf = Molal depression constant or cryoscopic
constant constant
Kb is the elevation in the boiling point of one molal Kf is the depression in the freezing point of one
solution. Its unit is K kg mol-1 molal solution. Its unit is K kg mol-1
𝑲𝒃 𝒙 𝒘 𝒙 𝟏𝟎𝟎𝟎 𝑲𝒇 𝒙 𝒘 𝒙 𝟏𝟎𝟎𝟎
𝑴 = 𝑴𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 = 𝜟𝑻𝒃 𝒙 𝑾
𝑴 = 𝑴𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 = 𝜟𝑻𝒇 𝒙 𝑾

112. ADVANTAGE OF USING OSMOTIC PRESSURE AS COMPARED TO OTHER COLLIGATIVE PROPERTIES:-

12 ISOTONIC SOLUTIONS:- Two solutions having same osmotic pressure. 0.91% of sodium chloride is isotonic with
fluid present inside blood cell hence used in injection.

13 HYPERTONIC SOLUTION:- Higher osmotic pressure than a particular solution.

14 HYPOTONIC:- Lower osmotic pressure than a particular solution.

15 REVERSE OSMOSIS (R.O.):- The direction of osmosis can be reversed if a pressure larger than the osmotic pressure
is applied to the solution side. That is now the pure solvent flows out of the solution
Application: Desalination of sea water.

Membrane used in RO = Cellulose nitrate .

163. ABNORMAL VALUES OF COLLIGATIVE PROPERTIES AND VANT – HOFF’S FACTOR (I)
𝐍𝐨 𝐨𝐟 𝐩𝐚𝐫𝐭𝐢𝐜𝐚𝐥𝐞𝐬 𝐚𝐟𝐭𝐞𝐫 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧 𝐨𝐫 𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧 𝐍𝐨 𝐨𝐟 𝐌𝐨𝐥𝐞𝐬 𝐛𝐞𝐟𝐨𝐫𝐞 𝐚𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧 𝐨𝐫 𝐝𝐢𝐬𝐬𝐨𝐜𝐢𝐚𝐭𝐢𝐨𝐧
𝑖 = No.of particales before association or dissociation = No.of Moles after association or dissociation

17 (i−1) (1−i)𝑛
Amount of dissociation, x = (𝑛−1) Amount of association, x = (𝑛−1)
 MOST EXPECTED QUESTIONS
1 Why is molality generally preferred over molarity as unit for expressing concentration of solutions?

2 A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction
of each component in the solution? If the density of solution is 1.2 g mL–1, then what shall be the
molarity of the solution?

3 Aquatic animals are more comfortable in cold water than in warm water. Explain?

4 Deep sea divers are advised not to come to surface immediately from deep waters. Why?

5 A solution is prepared by mixing 50ml of chloroform and 50ml of acetone.

(i) The volume of the resulting solution will be 100 ml or less than 100ml or more than 100 ml?
(ii) What happens to the net vapour pressure of resultant solution- it increases or decreases or
remains same?
Support your answer with suitable explanation
6 State Raoult’s law. Prove that it is a special case of Henry’ law?

7 Vapour pressure of dilute solution of glucose is 750 mm of Hg at 373K. Calculate the mole fraction
of solute.

8 Calculate the vapour pressure of a solution prepared by mixing 349.5 gm of component A (Mol.
Mass 134) and 416.8 gm of component B (Mol. Mass 169) at 298 K. Vapour pressures of pure
components A and B are 421mm Hg and 562mm Hg respectively. Also calculate mole fraction of A
and B in vapour phase.

9 What are colligative properties? Is osmotic pressure a colligative property? Prove it.

10 When a non-volatile solute is added to solvent, there is increase in boiling point of solution. Explain.

11 What is molal elevation boiling point constant or ebullioscopic constant and give its units?

12 What are isotonic, hypo tonic and hyper tonic solutions? Does osmosis take place in all three types
of solutions?

13 Why osmotic pressure is better technique for determination of molar mass of biomolecules?

14 When a non-volatile solute is added to pure water its vapour pressure decreases by 4 mm Hg.
Calculate molality of solution. (Vapour pressure of pure water is 40mm Hg)

15 A decimolar solution of NaCl exerts OP(π) of 4.6 atm at 300K. Find the degree of dissolution.
 ANSWERS
1 Volume changes with temperature whereas mass does not change with temperature. So molality,
which does not have volume term in it is better method for expressing concentration.
1. 10% w/w solution of glucose means 10 g of glucose is present in 100g of solution, i.e., 90g of water.
10 g 90 g
✓ Moles of Glucose = 180 g/mol = 0.0555 mol & Moles of water = 18 g/mol = 5 mol
✓ .

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒 0.0555 mol

✓ Molality = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑖𝑛 𝐾𝑔) = 0.09 𝐾𝑔 = 0.61 mol/Kg

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝐺𝑙𝑢𝑐𝑜𝑠𝑒 0.0555 mol

✓ Mole Fraction of Glucose = = 5.0555 mol = 0.01
𝑇𝑜𝑡𝑎𝑙 𝑀𝑜𝑙𝑒𝑠

✓ Mole Fraction of Water = (1 - Mole Fraction of Glucose) = (1 – 0.01) = 0.99

✓ Volume of 100 g soln of Glucose = Mass/density = 100g/1.2 g/ml = 83.33 ml = 0.08333 L

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒 0.0555 mol

✓ Molarity of the solution = 𝑉𝑜𝑙𝑢𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑖𝑛 𝐿𝑖𝑡𝑟𝑒) = = 0.66 mol/L
0.08333 L

3 This is because “Kh” (Henry constant) values for both N2 and O2 increase with increase in
temperature indicating that the solubility of gases increases with decrease in temperature.
4 Deep sea divers are advised not to come to surface immidiately from deep waters because sudden
change in outside pressure can be fatal for divers because N2 will bubble out of blood vessels
causing severe pain and can be dangerous.
5

(i) When chloroform and acetone are mixed, they form intermolecular hydrogen bonds. The
hydrogen bonds are strong forces of attraction. As a result, volume of the solution will be less than
100ml.
(ii) The net vapour pressure of the solution decreases because newly formed hydrogen bonds are
stronger forces of attraction than the original forces of attraction existing in separate solutions.
6 Raoult’s law states that partial pressure of a volatile component of a solution is directly proportional
to its mole fraction.
It is a special case of Henry’ law because it becomes the same when “Kh” (Henry constant) is equal
to pressure of pure solvent.
7 373K = 100°C
Vapour pressure of pure water (P0) = 760 mm Hg.
Vapour pressure of solution (Ps) = 750 mm Hg (given)
P 0 – Ps
= Xsolute
P0
760−750
= 0.13
760
8 349.5 416.8
No. of moles of A = = 2.608 and No. of moles of B = = 2.466
.
134 169
2.608 2.466
XA = 2.608+2.466 = 0.514 and XB = 2.608+2.466 = 0.486

Since we know that, Ps = P˚AXA+ P˚B.XB = 421 x 0.514 + 526 x 0.486 = 472.03
 216.394
Mole fraction of component A in gaseous phase = = 0.458
472.03
273.132
Mole fraction of component A in gaseous phase = = 0.578
472.03

As shown above component B is more volatile than component A and vapour phase is richer in
component B
9 The properties of solution which depend on the number of solute particles not on the nature.
Yes, osmotic pressure is a colligative property because osmotic pressure of a solution is proportional
to its molarity at a given temperature.
10 When a non-volatile solute is added to a volatile solvent the vapour pressure of pure solvent
decreases because a part of the surface is occupied by non-volatile solute which can’t volatilise. As a
result, the vapour pressure of solution decreases and hence, the solution requires a comparatively
higher temperature to boil causing an elevation of boiling point.
11 The elevation in boiling point which takes place when molality of the solution is unity, is known as
ebullioscopic or molal elevation constant. ∆Tb = Kb m
Its units are K Kg mol-1
12 Two solutions having similar osmotic pressure at a given temperature are called isotonic solutions. If

the given solution has less osmotic pressure it is called hypo tonic and it is hyper tonic if its osmotic

pressure is higher than the the solution on the other side of semi permeable membrane.

Osmosis takes place only in hypo tonic and hypertonic solutions.

13 Osmotic pressure is better technique for the determination of molar mass of biomolecules because
they are generally not stable at higher temperatures and have poor solubility. Therefore, other
techniques like elevation in boiling point and depression in freezing point cannot be used to
determine molecular masses of biomecules.
14 Relative lowering of vapour pressure is equal to the mole fraction of non-volatile solute,

P0 – Ps
= Xsolute = 4/40 = 0.1
0
ThisPmeans solution has 0.1 moles of solute in 0.9 moles of water.
Therefore, the mass of water in the solution = No. of moles of water x M.wt. of water = 0.9 x 18 =
16.2 g
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 0.1
Molality = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 (𝑖𝑛 𝐾𝑔) = 16.2/1000 = 6.17 mol/Kg
15 NaCl → Na+ + Cl -
Initial moles 1 0 0
Moles at Equilibrium 1 – ⍺ ⍺ ⍺
Total moles at equilibrium = 1 – ⍺ + ⍺ + ⍺ = 1 + ⍺
Moles in solution 1+⍺
i = Actual moles = 1 = 1 + ⍺
Since π = i CRT = (1 + ⍺)CRT = 4.6 atm = (1 + ⍺) x 0.1 x 0.0821 x 300
4.6
i = (0.1 x 0.0821 x 300) − 1 = 0.868 = 86.8%
 ELECTROCHEMISTRY (IMPORTANT FORMULAE)

1 CONDUCTANCE (G) 1 l
𝐺= 𝑅=𝜌 ELECTRO-
R a
CHEMICAL SERIES
2 CONDUCTIVITY (K) 𝑘=𝜌 =
1 𝑙 Ra
𝑅𝑎 𝜌= M+n +ne-→ M(s)
(SPECIFIC CONDUCTANCE) 𝑙
Li -3.05
3 Relation b/w Conductivity & l 𝑙
K=G = 𝑐𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
a a
Conductance K -2.93

Ba -290
= k x V ❖ [Unit of K = S/cm &
4 MOLAR CONDUCTIVITY K x 1000
Λ𝑚 = C C = mol/L]
Ca -2.87
5 Debye Huckel Onsager eqn. λm = λm∞- AC½
Na -2.71
6 KOHLRAUSCH’S LAW ∞
λm = ν+λ+∞ + ν-λ- ∞
Mg -2.37
7 Degree of dissociation & Be
Cα2
dissociation constant for weak Ka =
(1-α) Al -1.66
electrolytes
Mn
8 EMF (Electro Motive Force)/Cell ➢ Ecell = Ecathode - Eanode
potential Zn -0.76

9 GIBBS ENERGY ➢ ∆G = ∆G0 + RTlnK ∆G = - nFE & Cr -0.74

∆G0 = nFE0
Fe -0.44
10 Gibbs energy at equilibrium ➢ ∆G0 = - RTlnKeq Cd -0.40

11 NERNST EQUATION:- (Cell➢ E = E0 − 0.0591 logK E0 =

0.0591
logKc Co -0.28
n n
Potential)
Ni -0.25
0.0591 1
12 HYDROGEN ELECTRODE POTENTIAL:- E = 0 − log10[H+] E = −0.0591 PH
n Sn -0.14
H+ + e- → ½ H2
Pb -0.13
13 FARADAY’S 1ST LAWS E H2 0.0
𝑊 = Zit = 𝑖𝑡
96500
Cu +0.34
14 FARADAY’S 2ND LAWS
W1 W2 I2 +0.54
E1
= E2
Ag +0.80
15 LECLANCHE / DRY CELL At anode: Zn → Zn + 2e 2+ -
Br2 +1.08
(Zn, 2NH4+ + MnO2 ZnCl2) At cathode: 2NH4++ MnO2+ 2e- →Mn2O3 + 2NH3 + H2O
Cl2 +1.36
16 MERCURY CELL At anode: Zn + 2OH- → ZnO + H2O + 2e- Au +1.51

Zn, HgO, KOH At cathode: HgO + H2O + 2e- → Hg + 2OH- F2 +2.87

17 LEAD STORAGE CELL At anode: At cathode:

(Pb, PbO2, 2H2SO4) Pb(s) → Pb+2+ 2e- PbO2 + 4H+ + 2e- → Pb+2 + 2H2O
 Pb+2 +SO42-→PbSO4 Pb+2 +SO42-→ PbSO4

18 FUEL CELL ➢ (i) At cathode: O2 + 2H2O + 4e-→4OH-

(ii) At anode : 2H2 + 4OH-→4H2O+4e -
19 CORROSION (i) At anode:- 2Fe → 2Fe+2 + 4e- ……(i)
At cathode:- 4H+ + O2 + 4e- → 2H2O ……(ii)

Overall:- 2Fe + 4H+ + O2 → 2Fe+2 + 2H2O

Atomospheric oxidation Of Fe+2 Ions:

4Fe+2 + O2 + 4H2O → 2Fe2O3 + 8H+

20 Strongest reducing agent (i) In species : N3- & (ii) in Metal : Li

Strongest Oxidising agent (i) In species : OF2 in acidic medium (ii) in Element : F2

ELECTROCHEMISTRY
1 EFFECT OF DILUTION Conductance ↑ (due to increasing of numbers of ions)

Conductivity ↓ (number of ions in per cm3 decreases)

Molar Conductivity ↑

2 Noted:- Conductivity is the conductance of per cm3 solution.

Noted:- Molar conductivity of strong electrolytes ↑ with dilution due to ↓ of inter ionic attraction.
3 KOHLRAUSCH LAW Limiting molar conductivity of an electrolyte can be represented as the sum
of the individual contributions of the anion & cation.

4 ELECTROCHEMICAL Electrochemical Cell

Chemical Energy Electrical Energy
Electrolytic Cell
&

ELECTROLYTIC CELLS

5 DIFFERENCE B/W (i) In Galvanic Cell, electron flow from anode to cathode through external circuit
GALVANIC CELL while in electrolytic cell, electron flow from cathode to anode through internal
circuit. But in both cell oxidations take place at anode & reduction take place at
& cathode.
(ii) In Galvanic Cell ions discharges only at cathode while in electrolytic cell, ions
ELECTROLYTIC CELL discharges at the both electrodes.

6 CELL NOTATION Zn(s) | Zn2+ (aq) || Cu2+(aq)| Cu(s); Trick: LOAN

7 CONCENTRATION CELL A cell in which both the electrodes are of the same type but the solution of
electrolyte in which they dip have different concentration.

SALT BRIDGE & ITS Inverted U-tube containing saturated salt solution such as KCl, KNO3.
8
FUNCTIONS (i) Completes the electrical circuit. (ii) Maintains electrical neutrality.

Noted:- Generally saturated soln of KNO3 is used to make salt bridge b/c
the velocities of both K+ and NO3- are nearly same.
 9 STANDARD ELECTRODE If is the potential difference develop between electrode and electrolyte
POTENTIAL under the standard condition.

10 Reference Electrode It is an electrode of known potential. Eg. Hydrogen/Calomel electrode

11 ELECTROCHEMICAL The arrangement of elements in order of increasing electrode potential

SERIOUS values is called ……….

12 PRIMARY CELL Electrode reactions are irreversible and after use they become dead. Not
chargeable. Example: Dry cell (Leclanche cell), Mercury Cell

13 SECONDARY CELL A. Electrode reaction are reversible i.e., it can be recharged.

Ex. Lead storage cell & Ni-Cd cell etc.
14 FUEL CELL It converts energy of fuels to electrical energy.

15 Role of ZnCl2 in Primary It combine with the produced NH3 & form comp. [Zn(NH3)2Cl2] otherwise the
Ceel pressure developed due to NH3 would crack the seal of the cell.

Dry Cell doesn’t have a Because the acidic NH4Cl corrodes the Zn container even when the cell is
long life not in use.

MERCURY CELL:- Zn, HgO, KOH. potential =1.35V & remains constant
LEAD STORAGE CELL:- During discharging density of H2SO4 decrease from 1.30 to1.20gm/ml.

16 ADVANTAGES OF FUEL Runs continuously. Efficiency of about 70 %. Pollution free. The water
CELL vapours produced during the reaction were condensed and added to the
drinking water supply for the astronauts.

17❖ CORROSION Metals react with air & moisture present in the environment to form
undesirable compounds (usually oxides). Eg. Rusting of iron.

18❖ PREVENTION OF By covering the surface with paint or by some chemicals (bisphenol).
CORROSION Cover the surface by other metals (Sn, Zn, etc.) that are inert or react to
save the object. An electrochemical method (sacrificial electrode like Mg,
Zn, etc.) which corrodes itself but saves the object.

19 FARADAY’S 1ST LAWS Amount of any substance deposited at any electrode is directly
proportional to the quantity of electricity.

20 FARADAY’S 2ND LAWS When same quantity of electricity is passed for same time through different
electrolytes, the weights of the substance deposited at the electrodes are
directly proportional to their chemical equivalent weights.

Note:- liberation of amount does not depend on the molarity of the substance.

21 Store CuSO4 in Zn pot? No. because the following reaction takes place
Zn(s) + CuSO4(aq) → ZnSO4 (aq) + Cu(s)

22❖ ELECTROLYSIS OF SOME ELECTROLYTES:-

(ii) Trick:- Preferred order at Cathode (CPH):- Ag+ > Cu+2 > H+ > Na+
Preferred order at Cathode:- Halogen (Cl-/Br-) > OH- > NO3-/SO4-2
S.N SALT SOLUTION REACTION AT CATHODE REACTION AT ANODE

1 NaCl (Molten), Pt electrodes Na+(l) + e– → Na(s) Cl–→ ½Cl2+e–

2 NaCl (Aq), Pt electrodes 2H+(aq) + 2e- → H2(g) 2Cl– → Cl2 + 2e–

3 Dil. H2SO4, Pt electrodes 4H+(aq) + 4e- → 2H2(g) 4OH-(aq) → 2H2O(l) + O2 (g) + 4e-

4 Conc. H2SO4, Pt electrodes 2H+(aq) + 2e- → H2(g) 2HSO4-1 → H2S2O8 + 2e-

5 Dil. NaOH using Pt electrode 4H+(aq) + 4e- → 2H2(g) 4OH-(aq) → 2H2O(l) + O2 (g) + 4e-

6 Aq. Na2SO4 using Pt electrode 4H+(aq) + 4e- → 2H2(g) 4OH-(aq) → 2H2O(l) + O2 (g) + 4e-

7 Aq. CuSO4 using Pt electrode Cu+2 + 2e- → Cu(s) 4OH-(aq) → 2H2O(l) + O2 (g) + 4e-

Noted:- The colour of copper sulphate would be disappeared and the resulted solution will be acidic due to
presence of Sulphuric acid.
8 aq. CuSO4 using Cu electrode Cu+2 + 2e- → Cu(s) Cu(s) → Cu+2 + 2e-

Since, Cu anode is attacked by SO4-2 ions, Cu of the anode will dissolve to form Cu+2 ions in the solution.
[Cu(s) → Cu+2(aq) + 2e-]

Noted:- In this process number of moles of Cu+2 produced form anode = number of moles of Cu+2 deposited at
cathode. So the concentration of Cu+2 ions remain same in the soln. (IMP)

9 Aq. AgNO3 with Pt electrodes 4Ag+ + 4e- → 4Ag 4OH-(aq) → 2H2O(l) + O2 (g) + 4e-

10 Aq. AgNO3 with Ag electrodes Ag+ + e- → Ag(s) Ag(s) → Ag+(aq) + e-

11 Aq. CuCl2 with Pt electrodes Cu+2 + 2e- → Cu(s) 2Cl-(aq) → Cl2 2e-

12 PbBr2 (Molten), Pt electrode Pb+2 + 2e- → Pb 2Br- → Br2(g) + 2e-

 MOST EXPECTED QUESTIONS
1 How for weak and strong electrolytes, molar conductivity changes with concentration of solute. How is such
change explained?
2 The resistance of 0.01 M NaCl solution at 25° C is 200 Ω. The cell constant of the conductivity cell used is
unity. Calculate the molar conductivity of the solution.
3 Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 Ω. If the resistance of the same
cell when filled with 0.02 mol L–1 KCl solution is 520 Ω, calculate the conductivity and molar conductivity
of 0.02 molL–1 KCl solution. The conductivity of 0.1 mol L–1 KCl solutions is 1.29 S/m.
4 Conductivity of 0.00241 M acetic acid is 7.896 ×10–5 S cm–1. Calculate its molar conductivity. If Λ0m for
acetic acid is 390.5 S cm2 mol–1, what is its dissociation constant?
5 λ0m for NaCl, HCl & NaAc are 126.4, 425.9 & 91.0 S cm2 mol–1respectively. Calculate λ0m for HAc
6 The following chemical reaction is occurring in an electrochemical cell.
Mg(s) +2Ag+ (0.0001 M) → Mg2+(0.10M) + 2 Ag(s) (E0Mg2+/Mg = – 2. 36V, E0Ag+/Ag = 0.81V)
For this cell calculate/write:
(a) Which of the electrode is negatively charged?
(b)The carriers of the current in the cell.
(c) Which of the above two half cells will act as an oxidizing agent and which one will be a reducing
agent?
(d) Individual reaction at each electrode.
(e) Symbolic representation of the above cell.
(g) Standard cell potential Eo cell.
(g) Cell potential E cell
(h) How will the value of Ecell change if the concentration of Ag+ (aq.) is increased?
(i) Will the above cell reaction be spontaneous?
(j) ΔG0 & ΔG
(k)Equilibrium constant.
(l) In above question if Ecell is given as 2.96 V and if concentration of [Ag+] is not given, then calculate
the concentration of Silver ion.
(m) In above galvanic cell, If an opposing potential of 2.96V is applied to this cell, what will happen to the cell
reaction and current flowing through the cell?
7 A Copper – silver is set up. The copper ion concentration in its is 0.10M. The concentration of silver is not known.
The cell potential measured 0.422V. Determine the concentration of silver ion in the cell. (E 0Ag+/Ag= + 0.80V,
E0Cu2+/Cu = +0.34V).
8 Two half cell reactions of an electrochemical cell are given below:
MnO4- + 8 H+ + 5 e- →Mn2+ + 4 H2O Eo =+1.51V
Sn2+ →Sn4++ 2e- Eo = +0.15V.
Construct the redox reaction from the two half cell reaction and predict if the reaction favours
formation of reactants or product shown in the reaction
9 Describe the construction of H2 – O2 fuel cell and the reaction taking place.
10 What type of a battery is lead storage battery? Write the cathode and anode reactions and the overall
cell reactions occurring in a lead storage battery.
11 How much electricity in terms of Coulomb is required to reduce 1 mol of Cr 2O72- to Cr3+.
12 Three electrolytic cells A,B,C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively are
connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of silver
deposited at the cathode of cell B. How long did the current flow? What mass of copper and zinc were
deposited?
13 If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would
flow through the wire?
14 The Gibbs energy change for the reduction of Al2O3 at 500°C is given as:
2/3 Al2O3 ----- > 4/3 Al3+ + O2; ΔG = +960KJ
Calculate the minimum potential difference required to reduce 2/3 mole of Al2O3 at 500°C. ( 1F = 96500C)
15 The molar conductivity vs √c curve for NaCl, HCl, and NH4OH are shown below in random order.

(i) Identify which graph corresponds to HCl, NaCl, and NH4OH.

(ii) Give reasons to justify your answer in (i).
 ANSWERS
1 Molar conductivity of strong electrolytes increases slowly with dilution
because in strong electrolytes the dissociation of the electrolyte into ions is
almost complete however interionic forces are quite strong. Upon dilution
ionic attractions are reduced. This leads to increase in ionic mobility thus
molar conductivity increases with dilution.
Molar conductivity of weak electrolytes increases rapidly with dilution due to
increasing of effective ionization with dilution.
2 1. 𝑘 = 1 𝑙 1
= = (Since, cell constant = 1) = 0.005 S cm-1
𝜌 𝑅𝑎 200
K x 1000 0.005 x 1000
Λ𝑚 = C
= 0.01
= 500 S cm2 mol-1
3 The cell constant is given by the equation:
Cell constant = conductivity × resistance = 1.29 S/m × 100 Ω = 129 m–1 = 1.29 cm–1
Conductivity of 0.02 mol L–1 KCl solution = cell constant / resistance
= 129 m–1/520 Ω = 0.248 S m–1 = 0.248 x 10-2S cm–1
𝐊 𝐱 𝟏𝟎𝟎𝟎 𝟎.𝟐𝟒𝟖 𝐱 𝟏𝟎−𝟐 𝐒 𝐜𝐦–𝟏 𝐱 𝟏𝟎𝟎𝟎 𝐜𝐦𝟑𝐋−𝟏
Molar conductivity: Λ𝑚 = = = 124 S cm2 mol–1
𝐂 𝟎.𝟎𝟐 𝐦𝐨𝐥/𝐋
4 K x 1000 𝟕.𝟖𝟗𝟔 ×𝟏𝟎–𝟓 S cm–1 x 1000 cm3L−1
(i) λcm = = = 32.76 S cm–1mole-1
C 𝟎.𝟎𝟎𝟐𝟒𝟏 𝐌

(ii) λcm = 32.76

= 0.084 & C α2 = 𝟎.𝟎𝟎𝟐𝟒𝟏 𝐱 𝟎.𝟎𝟖𝟒 𝐱 𝟎.𝟎𝟖𝟒
= 1.86 x 10-5
α= 390.5 Ka = (1− 𝟎.𝟎𝟖𝟒)
Λ∞m (1-α)
5 390.5 S cm2 mol–1
6 (a) The negatively charged electrode is the Magnesium electrode. It acts as an anode.
(b) Ions are carriers of current inside the cell. Electrons are the carriers of current outside the cell.
(c)The higher the reduction potential, the higher is the oxidizing power.
Since, E0Ag+/Ag > E0Mg2+/Mg. So Ag+/Ag act as a oxidizing agent while Mg2+/Mg act as a reducing
agent.
(d) Oxidation at anode: Mg(s)→Mg2+(aq)+2e− and Reduction at cathode: Ag+(aq)+e−→Ag(s)
(e) Mg(s)/ Mg 2 +(0.10M) II Ag+ (0.0001)/ Ag(s) ;
(f) E0cell = E0Ag+/Ag – E0Mg+2/Mg = 0.81 – ( – 2.36) = + 3.17 V
0.0591 [𝑀𝑔+2 ] 0.0591 [0.10]
(g) ECell = E0Cel – log10 [𝐴𝑔+1 ]2 = 3.17 – log10[0.0001]2 = 2.96 V
n 2
(h) Value of Ecell increase with increase in concentration of Ag+
(i) Since the value of ECell is positive. So the cell reaction will be spontaneous.
(j) ΔG0 = – nFE0 = – 2 x 96500 x 3.17 = – 611810 J/mol
ΔG = – nFE = – 2 x 96500 x 2.96 = – 571280 J/mol
(k) Since, ∆G = ∆G0 + 2.303RT log10K (At equilibrium, ∆G = 0)
Then, ∆G0 = – 2.303RT log10Keq
– 571280 J/mol = – 2.303 x 8.314 j mol-1K-1 x 300K log10Keq
Then, log10Keq = 99.45 or Keq = 2.85 x 1099
0.0591 [𝑀𝑔+2 ] 0.0591 [0.10]
(l) ECell = E0Cel – log10 [𝐴𝑔+1 ]2 = 2.96 = 3.17 – 2
log10[𝐴𝑔+1 ]2
n

= 2.96 = 3.17 – 0.029 {log[0.1] – log [𝐴𝑔+1 ]2 }

7.10 = {log[0.1] – log [𝐴𝑔+1 ]2}
 8.10 = – 2log [𝐴𝑔+1 ]
Log [𝐴𝑔+1 ] = – 4.05
[𝐴𝑔+1 ] = antilog [– 4.05] = 0.0001M
(m) When an opposing potential of 2.96 V is applied to a galvanic cell having electrical potential of 2.96V then cell
reaction stops completely and no current will flow through the cell.
7 Ecell = 0.422V & E0Ag+/Ag > E0Cu2+/Cu
So, Ag+/Ag is cathode and Cu2+/Cu is anode.
E0cell = E0catohed – E0anode = +0.80 – 0.34 = 0.46V
Cell reaction: Cu + 2Ag+ → Cu+2 + 2Ag
0.0591 [𝐶𝑢+2 ] 0.0591 [0.10]
ECell = E0Cel – log10 [𝐴𝑔+1 ]2 = 0.422 = 0.46 – 2
log10[𝐴𝑔+1 ]2
n

= 0.422 = 0.46 – 0.29 {log[0.1] – log [𝐴𝑔+1 ]2 }

1.310 = {log[0.1] – log [𝐴𝑔+1 ]2 }
2.310 = – 2log [𝐴𝑔+1 ]
Log [𝐴𝑔+1 ] = – 1.155
[𝐴𝑔+1 ] = antilog [– 1.155] = 0.0699M
8 At anode : [Sn2+(aq) → Sn4+(aq)+2e−]×5
At cathode : [MnO4−(aq)+8H+(aq)+5e− → Mn2+(aq)+4H2O(l)]×2
.

Cell reaction : 2MnO4−(aq)+5Sn2+(aq)+16H+(aq)→2Mn2+(aq)+5Sn4+(aq)+8H2O(l)

E∘cell = E∘cathode − E∘anode =1.51V − 0.15V =1.36V
As cell potential is positive therefore the reaction is product favoured.
9 It consist of porous carbon electrodes having KOH or NaOH solution as electrolytes.
➢ In this cell, H2 & O2 are bubbled through porous carbon electrodes into electrolytes soln.
➢ Cell Reaction:
➢ (i) At cathode: O2 + 2H2O + 4e-→4OH- (ii) At anode : 2H2 + 4OH-→4H2O+4e -
Net Cell ren:-2H2O + O2 → 2H2O
10 Lead storage battery is the example of Secondary battery.
Cell reaction of Lead Storage battery (Discharging):-
At anode: Pb(s) → Pb+2+ 2e-
Pb+2 +SO42-→PbSO4
Pb + SO42- →PbSO4+ 2e-E0oxid=0.36V
At cathode: PbO2 + 4H+ + 2e- →Pb+2 + 2H2O
Pb+2 +SO42-→PbSO4
PbO2 + SO42- + 4H+ + 2e- →PbSO4 +2H2O E0o=1.69V
Net ren:-Pb + PbO2 + 2H2SO4 →2PbSO4 + 2H2O ; E0cell=2.05V
11 Cr2O72– + 14H+ + 6e– → 2Cr3+ + 8H2O
Therefore the coulomb of electricity required = 6F, = 6x96500 C= 579000 C
12 E 108
(i) Since, W = 𝟗𝟔𝟓𝟎𝟎it or 1.45g = 𝟗𝟔𝟓𝟎𝟎 x 1.5 x t or t = 863.7 s
E 63.5
(ii) Amount of Cu deposited: W = 𝟗𝟔𝟓𝟎𝟎it = 𝟗𝟔𝟓𝟎𝟎
x 1.5 x 863.7 = 0.426 g
65.3
(iii) Amount of Zn deposited: W = 𝟗𝟔𝟓𝟎𝟎 x 1.5 x 863.7 = 0.438 g
13 Solution: q = it = 0.5 x 2 x 60 x 60 = 3600 C
Flow of 96500 C = 1 mole of electrons i.e. 6.02 x 1023 electrons.
For 3600 C = 6.02 x 1023 x 3600 / 96500 = 2.246 x 1022 electrons.
14 Given is : ΔG = +960 x 103 J ; F = 96500 C
Required formula: ΔG = - nEF
Calculating n for 2/3 moles of Al2O3
Al2O3 > 2Al3+ + 3/2 O2
 (2 Al3+ + 6e > 2Al )
2/3 Al2O3 > 4/3 Al + O2
∵ 1 mole Al2O3 is reduced by 6 mol e-,
∴ 2/3mole Al2O3 is reduced by e- = 6x2/3= 4 mol e-
Substituting the value in formula, 960 x 103J = - 4 x E x 96500 C
E= (- 960x103J/ 4 x 96500 C), E = - 2.487 V
Hence minimum potential difference required= 2.487V OR ≈ 2.5 V
15 (i) 1- HCl , 2- NaCl , 3- NH OH
4

(ii) In any graph of molar conductivity vs √C, a weak electrolyte gives a curved decreasing graph strong
electrolytes give straight-line decreasing graphs, in which the graph of stronger electrolyte will always
be above the graph of the comparatively weaker electrolyte.
Graph III is curved and corresponds to NH4OH which is a weak electrolyte. Graph II & I respectively represent
NaCl and HCl. (∵HCl is a stronger electrolyte among the two).
 CHEMICAL KINETICS

1 Rate of Reaction Change in concentration of a reactant or product in per unit time.

Unit => mol L-1s–1

2 Instantaneous rate It is the rate at a particular instant.

3 Rate law / Rate equation It is the expression of rate in terms of molar concentration of reactants with
/ Rate expression each term have some power, which may or may not be same as the
stoichiometric coefficient of the reacting species in a balanced chemical
equation.

The rate expression for this reaction aA + bB → cC + dD is : Rate = k [A] x [B]y

4 Rate constant 1. It is the rate of chemical reaction when concentration of each reactant is
unity. It is also called specific rate of reaction. It depends only on
temperature.
5 Unit of rate constant For nth order reaction : mol1-n Ln-1 s-1

6 Factors which affects the2. (i) Concentration of Reactants (ii) Surface area (iii) Temperatures (iv)
Rate of Reaction: catalyst (v) Nature of medium (vi) Radiation
7 Order of a Reaction It is the sum of powers of concentration term in the rate law expression.
Eg. Rate = K[A]1[B]2 (Third order reaction)

It is determined experimentally.

8 Elementary rens The reactions taking place in one step are called …….

9 Molecularity of a The number of reacting species taking part in an elementary (one step)
Reaction reaction, which must collide simultaneously. (values are limited from 1 to
3)

It never be zero. It is always whole number.

It is no meaning in complex ren. (Ren involve more than 1 step)

10 Rate Determining Step The overall rate of the reaction is controlled by the slowest step in a
reaction called the rate determining step.

11 Half-life (t1/2) The time in which the concentration of a reactant is reduced to one half
of its initial concentration.

12 Zero Order Reaction [R0]− [R] [R0]

K0 = (Integrated eqn) t½ = (Half life period)
t 2K

13 First Order Reaction 2.303 [R0] .693

K1 = log (Integrated eqn) t½ = k
(Half life period)
t [R]
14 Integrated Rate Equation
for a Gas Phase Reaction: 2.303 (n−1)Pi
Kn = log (n = numbers of gaseous products)
t nPi−Pt

15 Dependence of t1/2 on For zero order : t1/2 α [R]0.

[R]0 For first order reaction t1/2 is independent of [R]0

16 Example of Zero Order Decomposition of gaseous ammonia on a hot platinum surface at high
pressure. Rate = k [NH3]0 = k

17 Ex. of First Order Decomposition of Radioactive compound

18 Pseudo first order ❖ Molecularity is 2 or more than 2 but the order of the ren is one.
Reaction Acidic hydrolysis of ester. CH3COOC2H5 + H2O → CH3CO2H + C2H5OH

19 Threshold energy ❖ The minimum amount of energy which is required to overcome this
energy barrier is called…….
20 Activation energy, Ea:- ❖ The minimum excess energy which must be supplied to the reactants to
undergoing chemical reaction.
Activation energy = Threshold energy – Average kinetic energy of the
reacting molecules

21 ARRHENIUS EQUATION:-❖ A is the Arrhenius factor or the frequency factor or

pre-exponential factor
22 e -Ea /RT ❖ The factor e -Ea /RT corresponds to the fraction of molecules that have
kinetic energy greater than Ea
Ea
(i) log(k) = logA - (ii)
2.303RT

23 Temperature coefficient 𝐑𝐚𝐭𝐞 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 𝐚𝐭 (𝐓+𝟏𝟎) 𝐂

(Rate of ren becomes almost double for
𝐑𝐚𝐭𝐞 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 𝐚𝐭 𝐓 𝐂
every 100C rise in temperature.)

24 COLLISION THEORY For A + B → Products Rate = P.ZAB e−Ea/ RT P is probability or steric factor
ZAB is collision frequency of reactants, A and B
Colloids molecules should have sufficient energy as well as proper
orientation.

25 Collision frequency (Z) The number of collisions per second per unit volume of the reaction
mixture.

26 Action of catalyst A catalyst increases the rate of ren by providing an alternative path of
lower activation energy.
Order of reaction Zero First

27 Graph b/w Rate of

Zero order
Reaction & Conc. of
Rate Rate Rate
Reactant
[R] [R] [R]
28 Graph b/w Conc. of [R0]
reactant & time Slope = -K
[R] [R] [R]

t t t

29 Graph b/w Conc. of

reactant & half-life
t1/2 t1/2

[R] [R]

30 Other graph for Ist order

reaction
 MOST EXPECTED QUESTIONS
1 What do you understand by the rate law and the rate const. of a reaction?
2 Identify the order of reaction if the units of its rate constant are:
(i) mol/L/s (ii) L/mol/s
3 A reaction is of second order with respect to a reactant. How is the rate affected if the
concentration of the reactant is (i) doubled (ii) reduced to half?
4 A reaction is second order in A and first order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of A three times?
(iii) How is the rate affected when the concentration of both A and B are doubled?
5 The rate of reaction depends upon the temperature and is quantitatively expressed as:

(a) What does e -Ea /RT represent?

(Ea)f = 40 J mol-1for forward reaction, (Ea)r = 80 J mol-1 for reverse reaction. Which one will be
faster, forward or reverse reaction and why?
6 The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of
production of N2 and H2 if k = 2.5 × 10–4 mol–1 L s–1?
7 For a first order reaction, show that time required for 99% completion is twice the time required
for the completion of 90% of reaction.
81. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a
constant volume.
SO2Cl2 (g) → SO2 (g) + Cl2 (g)
Experiment Time/s–1 Total pressure/atm
1 0 0.4
2 100 0.7
Calculate the rate constant (Given : log 4 = 0.6021, log 2 = 0.3010)
9 The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact
containing wood had only 80% of the 14C found in a living tree. Estimate the age of the
sample.
1 The following results have been obtained during the kinetic studies of the reaction:
0 2A + B → C + D
Experiment [A]/mol L–1 [B]/mol L–1 Initial rate of formation
of D/mol L–1 min–1
I 0.1 0.1 6.0 × 10–3
II 0.3 0.2 7.2 × 10–2
III 0.3 0.4 2.88 × 10–1
IV 0.4 0.1 2.40 × 10–2
Determine the rate law and the rate constant for the reaction.
1 The rate of a ren quadruples when the temperature changes from 293 K to 313 K.
1 Calculate the energy of activation of the reaction assuming that it does not change with
temperature.
1 Write short notes on the following:
2 (a) Activation energy of a reaction (b) Elementary step in a reaction
(c) Complex reaction
1 (i) A first order reaction has a rate constant 1.15 x10 -3 s -1. How long will 5g of this reactant take to
3 reduce to 3g?
(ii) A reaction is first order in A and second order in B. Write the differential rate equation. How is
the rate affected when the concentrations of both A and B are doubled?
1 For a chemical reaction R → P, the variation in the f concentration (R) vs. time (f) plot is given as
4 (i) Predict the order of the reaction. (ii) What is the slope of the curve?

1 A reaction is first order in A and second order in B.

5 i) Write the differential rate equation.
ii) How is the rate affected on increasing the concentration of B three times?
iii) How is the rate affected when the concentrations of both A and B are doubled?
 ANSWERS
1 Rate Law = It is the expression of rate in terms of molar concentration of reactants with each
term have some power, which may or may not be same as the stoichiometric coefficient of the
reacting species in a balanced chemical equation.
Rate Constant = It is the rate of chemical ren when concentration of each reactant is unity.
2 (i) Zero Order (ii) Second order.
3 (i) Rate of reaction become 4 times.
(ii) Rate of reaction become 1/4 times.
4 (i) Rate = K[A]2[B]1
(ii) Rate of reaction become 9 times.
(iii) Rate of reaction become 8 times.
5 (a) The factor e -Ea /RT corresponds to the fraction of molecules that have kinetic energy greater
than Ea
(b) Forward reaction will be faster because lesser the value of Ea (activation energy), faster will
be the reaction.
6 The decomposition of NH3 on platinum surface is given by following equation:
Pt
2NH3 3H2 + N2
Since reaction is zero order reaction. Therefore,
1 d[NH3] 1 d[H2] d[N2]
–2 =+3 = + = K = 2.5 × 10–4 mol–1 L s–1
dt dt dt

d[N2]
Therefore, the rate of production of N2 is: = 2.5 × 10–4 mol–1 L s–1
dt

d[H2]
And the rate of production of N2 is: = 3 x 2.5 × 10–4 mol–1 L s–1 = 7.5 × 10–4 mol–1 L s–1
dt
7 2.303 R0 2.303 100 2.303
(i) Time taken for 99% completion: t = log = log = x 2 ……. (i)
k R k 1 k

2.303 R0 2.303 100 2.303

(ii) Time taken for 90% completion: t = log = log = x 1……. (ii)
k R k 10 k

Time taken for 99% completion

For equation (i) & (ii) : Time taken for 90% completion = 2
2.303 0.4 2.303
8 K= log 2 x 0.4 −0.7 or K = log4 = 1.38 x 10-2 s-1
100 100
0.693 0.693
9 K= = 5730
t1/2

2.303 R0 2.303 100

t= K
log R = 0.693/5730
log 80 = 1845 years (approx)
10 The rate of reaction is given by: K [A]x[B]y
From Experiment no. 1. ⇒ 6.0 × 10–3 = K [0.1]x[0.1]y …………….(i)
From Experiment no. 2. ⇒ 7.2 × 10–2 = K [0.3]x[0.2]y …………….(ii)
From Experiment no. 3 ⇒ 2.88 × 10–1 = K [0.3]x[0.4]y …………….(iii)
From Experiment no. 3 ⇒ 2.40 × 10–2 = K [0.4]x[0.1]y …………….(iv)
Dividing equation (iv) by (i), we obtain:
⇒ 4 = [4]x
⇒x=1
Similarly, Dividing equation (iii) by (ii), we obtain: y = 2
 Therefore, the rate law is : K [A]1[B]2 6.0 × 10–3
From Experiment no. 1, we obtain, K = [0.1]1[0.1]2 = 6.0 L 2 mol-2 min-1

Similarly, From Experiment no. 2, we obtain, K = 6.0 L2 mol-2 min-1

Similarly, From Experiment no. 3, we obtain, K = 6.0 L2 mol-2 min-1
Similarly, From Experiment no. 4, we obtain, K = 6.0 L2 mol-2 min-1
Therefore, rate constant = 6.0 L2 mol-2 min-1
11
1. (It is given that, K2 = 4K1)
2. .

Ea 313− 293
3. log4 = 2.303 x 8.314 293 x 313

Solve this, then Ea = 52863.33 J/mol or 52.86 kJ/mol

12 (a) The minimum excess energy which must be supplied to the reactants to undergoing
chemical reaction.
(b) The reactions taking place in one step are called elementary reactions.
(c) When a sequence of elementary reactions (called mechanism) gives us the products, the
reactions are called complex reactions.
13 1. From the question, we can write down the following information:
Initial amount = 5 g, Final amount = 3 g, Rate constant = 1.15 x 10-3 s -1
We know that for a first order reaction,

(ii)It is given that a reaction is first order in A and second order in B.

(i) The differential rateequation is as follows: Rate = R =k[A][B]2
When the concentrations of both A and B are doubled, rate becomes 8 times.
R’’ = k[2A][2B]2 = 2x2x2 k[A][B]2 = 8R.
5.A first order reaction takes 30 minutes for 20% completion. Calculate t1/2. [log5= 0.69 , log4 =
0.602
Ans
t = (2.303/k) log100/(100− x)
30 =(2.303/k) log100/(100− 20)
K = 0.0067 min-1
t ½ =0.693/k
t ½ = 0.693/0.0067 = 103 minutes
14 (i) It is zero order reaction. (ii) Slope of the curve = -K
15 (i) Rate = K[A]1 [B]2
(ii) Rate = K[A]1 [3B]2 = 9K[A]1 [B]2 hence, it becomes 9 times.
(iii) Rate = K[2A]1 2[B]2 = 8K[A]1 [B]2 hence, it becomes 8 times.
 D & F- BLOCK ELEMENTS)
Sc [Ar] 3d14s2 +3
Ti [Ar] 3d24s2 +2, +3
V [Ar] 3d34s2 +2, +3, +4
Cr [Ar] 3d54s1 +1,+2,+3,+4,+5,+6
Mn [Ar] 3d54s2 +2,+3,+4,+5, +6, +7
Fe [Ar] 3d64s2 +2, +3, +4, +5, +6
Co [Ar] 3d74s2 +2, +3, +4, +5
Ni [Ar] 3d84s2 +2, +3, +4
Cu [Ar]3d104s1 +1, +2
Zn [Ar]3d104s2 +2
1 ELECTRONIC CONFIGURATION:- (n – 1)d1-10 ns0–2
Noted:- d-block elements are also called Tms. (b/c they have partially filled inner d-orbital. Their
properties are in between those of s & p-block)
Noted:-Electronic conf. of Tms:- (n-1)d1-10 ns1-2 and for non-Tms: ns1-2 or ns2np1-6
Noted: Zn, Cd, and Hg are not considered as Tms. Why?
Noted:- Cu+1 unstable in aq. Solution and it disproportionate to Cu+2 & Cu i.e., 2Cu+1 → Cu+2 + Cu0
(B/c Hydration Enthalpy of Cu+2 is very high as compared to Cu+1 which compensate 2nd I.E.)

21. VARIABLE O.S.:- Tms show variable O.S. b/c they have small energy difference between (n-1)d & ns
orbital as a result both (n-1)d & ns electrons take part in bond formation. (Mn shows highest O.S.
state i.e. +7 in Ist Tms series)
Stable O.S. state: (i) Cr ⇰ +6 & +3 (ii)Mn ⇰ +7, +4 & +2 (iii) Fe ⇰ +2 (Ferrous) & +3 (Ferric)
Noted:- Cr & Cu ⇰ +1 also and Zn ⇰ Only +2 (Noted:- Cu+1 unstable in aq. Solution)
Noted:- Sc : Only +3, b/c it is very little difference between 2nd & 3rd I.E. So it loses all 3 electrons
simultaneously.
Noted:- Stability of +2 O.S. ↑ on going to first half elements (upto Mn) in first Tms serious due to
becoming half-filled orbitals.
Noted:- O.S. of Tms differ each other by unity (Eg. Fe+2, Fe+3) while the O.S. of non-Tms differs normally
by two units (Eg. Sn+2, Sn+4 and Pb+2, Pb+4).
Noted:- Tms show highest O.S. in oxide & fluorides b/c oxygen & fluorine are highly electronegative
elements, small in size (and strongest oxidising agent).
Eg. OsF6, V2O5 (same case in oxometal anion: Eg. MnO4-, Cr2O7-2)
Noted:- Oxide of Tms in lowest O.S. are basic b/c it can donate its valence electrons which are not
involved in bonding while in Highest O.S. it is amphoteric or acidic.
32. ATOMIC RADIUS & ITS EFFECT (ALOY FORMATION):- Same size due to
Nuclear Charge … ↓ & Shielding Effect ….↑ so Size same. lanthanoids contraction
Misch Metal:- 95% Lns + 5% Fe along with trace of S, C, Ca 5d La
& Al. it is used in Mg-based alloy to produce bullets, shells 4d Y (Size of Zr = Hf)Cd, Hg
& 3d Sc Zn
lighter flints.
Fe Co Ni Cu
LANTHANOID CONTRACTION, ITS CAUSES & EFFECT:-

✓ Gradual decrease of atomic radii form La to Lu

✓ Causes:- Shielding effect is very less effective.
✓ Effect:- (i) Density of 5d series become double than 4d series.
✓ (ii) I.E. of 5d series is more than 4d series.
 ✓ Note:- Actinoids contraction is greater from element to element than lanthanoids contraction due to
poorer shielding by 5f electrons.
4 ABCM:- En. OF ATOMIZATION, BOILING & MELTING POINT, COLOURED ION & MAGNETIC PROPERTIES :-
(Due to p/s of large no of unpaired Electrons)

 En. of Atomization:- High W = 34000C

Noted: The enthalpy of atomization of Zn Re
(in 3d serious) is lowest b/c in formation Ta Mo Os
Ru Ir
of metallic bonds; no eletrons from Nb Tc
Pt
3d-orbitals are involved. Cr Rh

MELTING POINT
Pd
𝐗 Fe
 M.P. & B.P. : High due to high enthalpy Hf
𝐗
V II Ni
of atomization) Zr 𝐗 Cu
5d > 4d > 3d
Ti Mn Au
M.P. & B.P. : Zn > Cd > Hg (-380C) Pres Ag

 Coloured:- Due to d-d transition ATOMIC NUMBER Due to stability of

Noted:- KMnO4 is coloured due to L → M Half-filled d-orbital
charge transfer transition

3. Magnetic properties:- Paramagnetic due to having unpaired electrons.

Magnetic movment:-
54. FORMATION OF COMPLEX COMPOUND:- due to (i) Small size (ii) High ionic charge (iii) P/s of vacant d-
orbitals.
5. CATALYTIC PROPERTIES:- Due to (i) Large surface area (ii) p/s of vacant d-orbitals (iii) Variable O.S. (iv)
Complex forming ability
6. FORMATION OF INTERSTITIAL COMPOUND:- Small atoms such as hydrogen, carbon, boron and
nitrogen occupy the empty spaces in their lattices. They are non – stoichiometric, (composition is
not fixed). E.g., steel. They are harder and less malleable and ductile. High melting point.
67. PREPARATION OF K2Cr2O7 and Ren with (i) FeSO4, (ii) KI (iii) H2S (iv) SO2 (v) Na2SO3 (vi) Oxalic acid (vii)
action of Heat (viii) Effect of pH (ix) Chromyl chloride test
Ans: (i) 4FeCr2O4 + 8Na2CO3 + 7O2 ⇾ 8Na2CrO4 + 2Fe2O3 + 8CO2

(ii) 2Na2CrO4 + 2H+ ⇾ Na2Cr2O7 + 2Na+ + H2O (iii) Na2Cr2O7 + KCl⇾K2Cr2O7 +2NaCl
Reaction:- Trick: (Fe →Fe , I → I2, S → S, SO2 → SO4-2, SO3-2 → SO4-2, C2O4-2 → CO2)
+2 +3 - -2

(viii) Effect of pH:- On increasing the pH, i.e. on making the soln alkaline, dichromate ions (orange
coloured) are converted into chromate ions (yellow coloured). And vice versa
(ix) Chromyl chloride test:- K2Cr2O7 + 4KCl + 6H2SO4→ 2CrO2Cl2 + 6KHSO4 + 3H2O
(Reddish brown vapours of chromyl chloride. It is used in detection of chloride ions)

8. PREPARATION OF KMnO4 and Ren with (i) FeSO4, (ii) KI (iii) H2S (iv) SO2 (v) Na2SO3 (vi) Oxalic acid (vii)
action of Heat
 F- BLOCK ELEMENTS
Sym Elements Ele. Confi. O.S. (CEY) 1. ELECTRONIC CONFIGURATION:-
Lanthanoids {[Xe]4f1-14 5d0-16s2} &
La57 Lanthanum 4f05d16s2 +3
Actinoids {[Rn]5f1-14 6d0-1 7s2}
Ce58 Cerium 4f15d16s2 +3, +4
Halogen
LnX3
Pr59 Praseodymium 4f35d06s2 +3, (+4)
C, 2273k Ln3C, Ln2C3 & LnC2
Nd60 Neodymium 4f45d06s2 (+2), +3, (+4) Dil. acid
Liberate H2 gas
Pm61 Promethium 4f55d06s2 +3 O2
Ln Ln2O3
Δ, S
Sm62 Samarium 4f65d06s2 (+2), +3 Ln2S3
Δ, N2
LnN
Eu63 Europium 4f75d06s2 +2, +3 H2O
Ln(OH)3 + H2
Gd64 Gadolinium 4f75d16s2 +3

Tb65 Terbium 4f95d06s2 +3, (+4)

Dy66 Dysprosium 4f105d06s2 +3, (+4)

2 COMPARISON OF LANTHANIDES AND ACTINIDES
Ho67 Holmium 4f115d06s2 +3
❖ SIMILARITIES:- As both Lanthanides and actinides involve filling of f-orbitals, so they show
Er68 similarities
Erbium in many4frespects
125d06s2 +3
as follows:
i. The most common oxidation state is +3 for both lanthanides and actinides.
Tm69ii. Both
Thulium 4f135d06sand
are electropositive
2 (+2),
very+3reactive.
iii. Both exhibit magnetic and spectral properties.
Yb70 Ytterbium 4f145d06s2 +2, +3
iv. Actinides exhibit actinide contraction just like lanthanides.
[

3 Lu71 Lutetium LANTHANOIDS 4f145d16s2 +3 ACTINOIDS

1 1. Besides +3 O.S., they also show +2 and +4 3. Besides +3 O.S., they show higher oxidation
oxidation states. (Exceptional = CEY). states of +4, +5, +6 and + 7 also. (+7 = NpPu)
2. (Due to large energy gap b/w 4f & 5d, they show (They show large number of O.S. b/c of very small
limited number of O.S.) energy gap between 5f, 6d & 7s subshell.)

2 Most of their ions are colourless. Most of their ions are coloured.

3 They have less tendency towards complex They have greater tendency towards complex
formation. formation due to higher charge & smaller sizes.

4 Lanthanide oxides & hydroxides are less basic Actinoids oxides & hydroxides are less basic.

5 Do not form oxocation. Form oxocations such as UO22+, PuO22+, etc

6 Except promethium, they are non-radioactive. All actinides are radioactive

7 Their magnetic properties can be explained Their magnetic properties cannot be explained
easily. easily b/c they are more complex.
 MOST EXPECTED QUESTIONS
1 What is the basic difference between the electronic configuration of the transition and
inner transition metals?

2 Cu, Ag & Au are considered as transition metal though it has 3d10 configuration.

3 Cu2+ (aq) is more stable than Cu+ (aq) despite the d10 configuration of Cu+. Explain.

4 Why is Cr2+ reducing and Mn3+ oxidising while both have d4 configuration.

5 The E0M2+/M for copper is positive (0.34 V). Copper is the only metal in the first series of
transition elements showing this behaviour.

6 What is lanthonoid contraction? What is the reason for lanthonoid contraction? Mention
the consequences of lanthonoid contraction.

7 Most of the transition metals form alloys. Why ?

8 Transition metals form interstitial compounds easily. Why?

9 Transition metals acts as catalyst. Why?

10 Transition elements exhibit higher enthalpies of atomization?

11 Zn, Cd and Hg are volatile and Hg is a liquid metal.

12 Which of the following will be coloured Ti3+,V3+,Cu+,Sc3+,Mn2+, Fe3+ & Co2+, Zn+2

13 Calculate the “spin only” magnetic moment of M2+(aq) ion (Z= 27).

14 How is KMnO4 prepared from pyrolusite ore?

15 How is K2Cr2O7 prepared from chromite ore?

 ANSWERS
1 In transition metals last electron enters the d-orbital of the second last shell but in the inner
transition metals the last electron enters the f-orbital of the third last shell.

2 Cu/Ag has +2 oxidation state having incompletely filled d-orbital

3 Hydration Enthalpy of Cu+2 is very high as compared to Cu+1 which compensate 2nd I.E.
Cu+ in aqueous solution undergoes disproportionation,
2Cu+(aq) → Cu2+(aq) + Cu(s) The E0 is favourable for this

4 Cr2+ is reducing as it changes from d4 to d3, the latter is more stable.

Mn+3 is oxidising as it change from d4 to d5 (Mn+2), the latter is more stable.

5 E0 (M2+ / M) for any metal is the sum of the enthalpy changes taking place in the following
steps:
M(s) + Δa H -------------> M(g), ΔaH = Enthalpy of atomization
M(g) + Δi H -------------> M2+(g), ΔiH = Ionization enthalpy
M2+(g) + aq -------------> M2+(aq) +Δhyd H, ΔhydH = hydration enthalpy
Copper has high enthalpy of atomization and low enthalpy of hydration.

6 Gradual decrease of atomic radii form La to Lu

Reason:- shielding effect is very less effective.
Consequences:- Similar properties of II & III rows transition elements.

7 Because of similar radii

8 Because size of C, N, O, and B is similar to size of interstitial voids of transition metal

9 Transition metals acts as catalyst due to (i) Large surface area (ii) p/s of vacant d-orbitals (iii)
Variable O.S. (iv) Complex forming ability

10 Because of large number of unpaired electrons in their atoms they have stronger interatomic
interaction (Due to strong metallic bonding)

11 b/c they have little tendency of metallic bond formation due to not having unpaired electrons
in d-orbitals.

12 Except Sc3+, Cu+1 and Zn+2, all others will be coloured due to incompletely filled 3d-orbitals,
will give rise to d-d transitions. Sc3+, Cu+1 and Zn+2 are colourless due to not having unpaired
electrons in d-orbitals.
13 Electronic configuration of M atom is 1s22s22p63s23p63d74s2. It has three unpaired electrons in d
orbitals. Magnetic moment = √ n(n+2) BM = √3 (3+2) = √15 = 3.87 BM

(i)14 (i) 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

(ii) 3MnO42- + 4H+→ 2MnO4- + MnO2 + 2H2O

15 (i) 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 (Yellow solution) + 2Fe2O3 + 8CO2

i. (ii) 2Na2CrO4 + 2H+ → Na2Cr2O7 (Orange) + 2Na+ + H2O
(iii) Na2Cr2O7 + KCl → K2Cr2O7 (Orange) + 2NaCl
 COORDINATION COMPOUNDS

1 COORDINATION COMPOUNDS:- Complex compounds in which transition metal atoms or ions are bound
to a number of anions or neutral molecules called ligands.

2 Central metal atom FORMULA ⇌ IUPAC NAME

K4 [Fe(CN)6] 1. [Co(NH3)6]Cl3 →Hexaamminecobalt(III) chloride,

Coordination 2. K3[Cr(C2O4)3] → potassiumtrioxalatochromate(III)
Ligand
Counter ion 3. [Zn(OH)4]-2 → Tetrahydroxozincate(II) ion
Number
4. [Co(NH3)6]Cl3 → Hexaamminecobalt (III) chloride
Coordinate sphere (Entity) 5. [Ni(NH3)6]Cl2 → Hexaamminenickel (II) chloride
6. [Co(en)3]3+ → Tris(ethane-1,2-diamine)cobalt (III)
ion

3 WERNER’S COORDINATION THEORY:- Metal exhibits two types of valencies (linkages) : Primary valencies
and secondary valencies.

PRIMARY VALENCE SECONDARY VALENCE

Ionisable, non-ionisable &
satisfied by negative ions satisfied by negative ions or neutral molecules
It is equal to Oxidation state It is equal to Coordination number of metal.
Written outside the square bracket Written inside the square bracket
4 LIGANDS:- An atom or molecules or ion which donates its lone pair of electrons to the central metal or
ion and forms a coordinate bond with it.
DENTICITY OF LIGANDS:- The number of linking atoms present in ligand is called denticity.

Monodentate Didentate Polydentate Ambidentate ligand

❖ Having one donor atom. ❖ Having two donor ❖ Have more than two Have two donor atom but uses
❖ E.g. Cl–, NH3, H2O atoms. donor atoms. only one at a time.
Eg. C2O42– E.g. EDTA4–
E.g. NO2 , SCN–, CN–

CHELATE LIGAND:- When a di- or polydentate ligand uses its two or more donor atoms to bind a single
metal ion, it is said to be a chelate ligand. E.g. H2NCH2CH2NH2 (ethane-1,2-diamine)

5 ISOMERISM:-

❖ A. STRUCTURAL ISOMERISM:- (i) Ionisation(give different ions in aq. Solution) (ii) Solvent
(iii) Linkage (have different linking atom) (iv) Coordination(interchange of ligands between cationic and
anionic entities)
❖ B. STEREO ISOMERISM:- (i) Geometrical(Cis/Trans or Fac/Mer)(ii) Optical
Noted:-Tetrahedral complex rarely show optical isomerization. They do show only in the presence of
unsymmetrical chelating ligands.
6 VALENCE BOND THEORY(VBT):

C.N. d2sp3,Octahedral, diamagnetic/ Sp3d2 Octahedral, ❖ [Cr(NH3)6]+3 :- Cr+3 = 3d3 4S0 4P0
Paramagnetic, Low spin Paramagnetic, High spin,
complex, inner orbital complex Outer orbital complex.
 ↓ Eg. [Fe(CN)6]4–,[Cr(H2O)6]3+, Eg. [Fe(H2O)6]2+, [CoF6]3–,
[Co(CN)6]3–,[Co(NH3)6]+3 etc [FeF6]3–,[Fe(NH3)6]+2,
6 [Fe(NH3)6]+3, [Cu(NH3)6]+

❖
C.N. dsp2, Square planer, Sp3, Tetrahedral, High spin
diamagnetic. Low spin complex complexes.
↓ . Eg- [NiCl4]2–
Eg- [Ni(CN)4]2–, [PtCl4]2–. (Paramagnetic)
4 [Ni(CO)4] (diamagnetic)

7❖ SPECTROCHEMICAL SERIES:- Arrangement of ligands in a series in the order of increasing field strength.
I–< Br–<SCN–< Cl–< S2–< F –< OH–< C2O42–< H2O < NCS–<edta4–< NH3<en< CN–< CO

8 CFT IN OCTAHEDRAL AND TETRAHEDRAL COMPLEXES:-

 Strong field ligands (high Δ° i.e., Δ° > π) hence pairing of electron & form – low spin complexes.
 Weak field ligands (low Δ° i.e., Δ° < π) hence form – high spin complexes

The crystal field splitting, Δo, depends upon the field produced by the ligand & charge on the metal ion.

9 BONDING IN METAL CARBONYL:– They are

organometallic compounds having both σ and π
bonds. They have M ← CO, σ bond and M → CO π
back bond (synergic bonding)

10 Coordination compounds like [Ni(H2O)6]2+, [Fe(CN)6]4–, [Fe(H2O)6]2+ shows colour due to d-d transitions.

11
❖ FACTORS WHICH EFFECT THE STABILITY OF THE COMPLEXES:-
A. Charge on the Central Metal atom:-
B. Nature of the Metal ion:-
C. Basic Nature of Ligand:-
D. Chelate Effect:-
12
❖ APPLICATION OF COORDINATION COMPOUNDS:-
1. In Metallurgical process (Eg. Ag, Ni)
2. In white photography:- AgBr + 2Na2S2O3 → Na3[Ag(S2O3)2] + NaBr
3. In Analytical chemistry:- For detection of Cu+2, Fe+3 and Sulphide
✓ Cu+2 + 4NH3 → [Cu(NH3)4]+2 (blue coloured complex)
✓ 2Cu+2 + [Fe(CN)6]-4 → Cu2[Fe(CN)6] (Choccolate ppt)
✓ 4Fe+3 + 3[Fe(CN)6]-4 → Fe4[Fe(CN)6]3
Pot ferrocyanide (Ferri-ferrocyanide = Prussian blue)
✓ 2Fe+3 + 6CNS- → Fe[Fe(CN)6] (Ferri-ferric thiocyanate = Red colour)
✓ Na2S + Na2[Fe(CN)5NO] → Na4[Fe(CN)5NOS]
 (Sodium nitropruside) (Violet colour)
4. Biological uses:- (i) [Pt(NH3)2Cl2] known as cisplatin is used as antitumor agent. (ii)
[Ca(EDTA)] complex is used in the treatment of lead poisoning. (iii) Carboxypeptidase A, Hemoglobin,
Chlorophyll, and Vit B12 are the complex of Zn+2, Fe+2, Mg+2 & Co+2.
 MOST EXPECTED QUESTIONS
1 Write IUPAC names of : (i) K3[Fe(C2O4)3] (ii) [Pt(NH3)6]Cl4.

2 Write down the formula

of:
(a) Tris(ethane-1,2-diamine) chromium (III) chloride (b) Potassium tetrahydroxozincate(II)

3 Explain the following terms giving a suitable example in each case :

(i) Ambident ligand (ii) Denticity of a ligand

4 Describe the shape, magnetic behaviour & Hybridisation of following complexes : (i)
[Co(NH3)6]3+ (ii) [Ni(CN)4]2-

5 Explain why [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital complex.

6 When a co-ordination compound CrCl3.6H2O is mixed with AgNO3, 2moles of AgCl are
precipitated per mole of the compound. Write
(i) Structural formula of the complex. (ii) IUPAC name of the complex.

7 Compare the following complexes with respect to their shape, magnetic behaviour and the hybrid
orbitals involved :
(i) [CoF4]2- (ii) [Cr(H2O)2(C2O4)2]– (iii) [Ni(CO)4]

8 State a reason for each of the following situations :

(i) Co2+ is easily oxidized to Co3+ in presence of a strong ligand.
(ii) CO is a stronger complexing reagent than NH3.
(iii) The molecular shape of [Ni(CO)4] is not the same as that of [Ni(CN)4]2-

9 What is meant by crystal field splitting energy? On the basis of crystal field theory, write the electronic
configuration of d4 in terms of t2g and eg in an octahedral field when (i) Δ0 > P (ii) Δ0 < P

10 Explain: Crystal field splitting in an octahedral field

11 Why a solution of [Ni(H2O)6]2+ is green while a solution of [Ni(CN)4]2- is colourless?

12 On the basis of crystal field theory, write the electronic configuration for d4 ion if Δ0 > P.

13 Name the following coordination entities and draw the structures of their stereoisomers :
(i) [Co(en)2Cl2]+ (ii) [Cr(C2O4)3]3- (iii) [Co(NH3)3 Cl3]

14 Explain the following cases giving appropriate reasons :

(i) Nickel does not form low spin octahedral complexes.
(ii) The n-complexes are known for the transition metals only.

15 What is meant by chelate effect?

 ANSWERS
1 (i) Potassium trioxalatoferrate (III) (ii) Hexaammine Platinum (IV) chloride

2 (a) [Cr(en)3] Cl3 (b) K2[Zn(OH)4]

3 (i) Ambidentate ligand : The monodentate ligands with more than one coordinating atoms is known as
ambidentate ligand. Monodentate ligands have only one atom capable of binding to a central metal
atom or ion. For example, the nitrate ion NO2– can bind to the central metal atom/ion at either the
nitrogen atom or one of the oxygen atoms.
Example : — SCN thiocyanate, — NCS isothiocyanate
(ii) Denticity of a ligand: The number of donor atoms in a ligand which forms coordinate bond with the
central metal atom are called denticity of a ligand.
Example : If donor atom is one then it is called Monodentate ligand, if it is two, then it is called
Bidendentate and so on.

4 (i) [Co(NH3)6]3+ :
Orbitals of Co3+ ion :

Hybridization : d2sp3 Shape : Octahedral Magnetic behaviour : Diamagnetic (absence of unpaired

electrons)
(ii) [Ni(CN)4]2-

5 In [Co(NH3)6]3+, the d-electrons of Co3+ ([Ar]3d6 45°) get paired leaving behind two empty d-orbital and
undergo d2sp3 hybridization and hence inner orbital complex, while in [Ni(NH3)6]2+ the d-electrons of
Ni2+ ([Ar]3d8 45°) do not pair up and use outer 4d subshell hence outer orbital complex.

6 (i) The complex formed on mixing a coordination compound CrCl3.6H2O with AgNO3 is as follows
CrCl3.6H2O + AgNO3 → [Cr(H2O5)Cl]Cl2. H2O
(ii) Pentaaquachloridochromium (III) chloride monohydrate
7

8 (i) Because in the presence of strong ligands, the crystal field splitting energy is more than the
energy required to oxidise Co2+.
(ii) This is due to the formation of π – bond by back donation of electrons from metal to carbon of
CO or due to synergic bonding.
(iii) CO is a stronger field ligand than CN. Ni is in zero oxidation state in Ni(CO) 4 and has
tetrahedral geometry. But, Ni is in +2 oxidation state in [Ni(CN)4]2- and has dsp2 hybridization
(different geometry than tetrahedral sp3).

9 Crystal field splitting energy : When ligands approach the central metal ion, the degenerate d-orbitals
split into two sets, one with lower energy (t2g) and the other with higher energy (eg). The difference of
energy between these two sets of orbitals is called crystal field splitting energy. (Δ0 for octahedral
complexes).
The magnitude of Δ0 decides the actual configuration of d-orbitals by the help of mean pairing energy.
• If P > Δ0 then pairing of electrons does not occur and electrons enter in the higher energy e orbitals
and thus form high spin complexes due to weak field ligands.
If P < Δ0 then pairing of electrons occurs within the same set and form low spin complexes due to strong
field ligands.

10 Crystal field splitting: It is the splitting of the degenerate energy levels due to the presence of ligands.
When ligand approaches a transition metal ion, the degenerate d-orbitals split into two sets, one with
lower energy and the other with higher energy. This is known as crystal field splitting and the difference
between the lower energy set and higher energy set is known as crystal field splitting energy (CFSE)

Example : 3d5 of Mn2+

11 [Ni(H2O)6]2+ is an outer orbital complex due to weak field ligand H2O and the presence of unpaired
electrons undergoes d—d transition by absorbing red light and shows green colour while [Ni(CN)4]2- is an
inner orbital complex and has no unpaired electrons hence colourless.

12 Electronic configuration for d4 ion if Δ0 > P is t2g 4eg0

13 (i) [Co(en)2Cl2]+
Name : Dichlorido bis (en = ethan-1, 2-diamine) Cobalt (III)
 The geometrical isomers of [CoCl2(en)2]+ (2 isomers)
(ii) [Cr(C2O4)3]3-
Name : Trioxalatochromate (III) ion

(iii) [Co(NH3)3 Cl3]

Name : Triamminetrichlorido cobalt (III)
Structure : The geometrical isomers of [Co(NH3)3Cl3] (2 isomers) :

14 (i) The electronic configuration of Ni is [Ar] 3d8 4s2 which shows that it can only form two types of
complexes i.e. square planar (dsp2) in presence of strong ligand and tetrahedral (sp3) in presence of weak
ligand. There are four empty orbitals in Ni while octahedral complexes require six empty orbitals.
(ii) Due to presence of empty d-orbitals in transition metals, they can accept electron pairs from ligands
containing π electrons and hence can form ic-bonding complexes.
Example : ligands like C5H5, C6H6 etc.
(iii) Due to greater magnitude of Δ0, CO produces strong fields which cause more splitting of d-orbitals
and moreover it is also able to form π bond due to back bonding.

15 Chelate effect: When a bidentate or a polydentate ligand contains donor atoms positioned in such a way
that when they coordinate with the central metal ion, a five or a six membered ring is formed. This effect
is called Chelate effect. As a result, the stability of the complex increases.
Example: the complex of Ni2+ with ‘+ion’ is more stable than NH3.