M.E.S.

INDIAN SCHOOL,
DOHA – QATAR

SOLUTIONS

MOHMMED.ILIAS
 Solution Homogeneous mixture of two or more components. Eg: sugar solution
Solute + solvent = solution
Solute Lesser amount component which loses its physical state. It will be dissolved in
solvent
Solvent Higher amount component which will not lose its physical state
Physical state of solvent= physical state of solution, It dissolves solutes
Concentration WA = weight of solvent, WB =weight of solute nA = no; of moles of solvent
Expression methods nB =no; of moles of solute V= volume of solution, d= density
Mole fraction in solution: Ratio of number of mole of one component to total number of moles
𝒏𝑨 𝒏𝑩
𝑿𝑨 = 𝒏𝑨#𝒏𝑩 𝑿𝑩 = 𝒏𝑨#𝒏𝑩 Total mole fraction 𝑿𝑨 + 𝑿𝑩 = 𝟏

Molarity: number of moles of solute present in 1L solution

𝑾𝑩 × 𝟏𝟎𝟎𝟎 𝒅 × 𝟏𝟎 × 𝒎𝒂𝒔𝒔%
𝑴𝒐𝒍𝒂𝒓𝒊𝒕𝒚, 𝑴 = 𝑴𝒐𝒍𝒂𝒓𝒊𝒕𝒚, 𝑴 =
𝑴𝑩 × 𝑽 𝑴𝑩

Unit = mol/L or molar or M

Molarity inversely proportional to temperature because volume increases with temperature
Molality: number of moles of solute present in 1kg solvent
Molality is independent on temperature since mass is not depends on temperature.
Unit = mol/kg or molal or m
𝑾𝑩 ×𝟏𝟎𝟎𝟎 𝒎%×𝟏𝟎𝟎𝟎
𝑴𝒐𝒍𝒂𝒍𝒊𝒕𝒚, 𝒎 = 𝑴𝒐𝒍𝒂𝒍𝒊𝒕𝒚, 𝒎 = 𝑴
𝑴𝑩 ×𝑾𝑨 𝑩 ×(𝟏𝟎𝟎-𝒎%)

Relation between molarity, molality and density

𝒅𝒆𝒏𝒔𝒊𝒕𝒚
𝑴𝒐𝒍𝒂𝒓𝒊𝒕𝒚, 𝑴 =
𝟏 𝑴𝑩
(𝒎 + 𝟏𝟎𝟎𝟎 )

Henry‘s law. The partial pressure of the gas in vapour phase (p) is proportional to the
mole fraction of the gas (x) in the solution at a given temperature.
P= KH . x KH = Henry‘s law constant
( Higher the temperature, greater the KH value, lower the solubility.)
Different gases have different KH values at the same temperature
𝑺𝒐𝒍𝒖𝒃𝒊𝒍𝒊𝒕𝒚 , 𝒎 = 𝑿𝒈𝒂𝒔 × 𝟓𝟓. 𝟓

Application of 1.To increase the solubility of CO2 in soft drinks, the bottle is sealed under high
Henry‘s law pressure.
2. To avoid bends, the tanks used by scuba divers are filled with air diluted with
helium.

Temp and Solubility of gas increases with decrease of temperature. Due to this reason that
Solubilty of gas aquatic species are more comfortable in cold waters rather than in warm waters.
Raoult‘s law for For a solution of volatile liquids,
volatile liquids The partial vapour pressure of each component in the solution is directly
or proportional to its mole fraction of the components in a given temperature.
volatile solute in 𝑃/ α 𝑋/ or 𝑃0 α 𝑋0
volatile solvent Raoults law formula
𝑷𝑨 = 𝑷𝟎𝑨 𝑿𝑨 𝒐𝒓 𝑷𝑩 = 𝑷𝟎𝑩 𝑿𝑩
Where 𝑃/1 is the vapour pressure of pure component A , and 𝑃01 is the vapour
pressure of pure component B at the same temperature.
Total vapour pressure Ptot = PA + PB
Mole fraction in YA and YB are the mole fraction in vapour phase
vapour phase 𝑷𝑨 𝑷𝑩
𝒚𝑨 = 𝑷𝑨#𝑷𝑩 𝒚𝑩 = 𝑷𝑨#𝑷𝑩

Ideal solutions are

1.Obey Raoult‘s law over the entire range of concentration.
Ideal Solutions 𝑃/ = 𝑃/1 𝑋/ AND 𝑃0 =𝑃01 𝑋0
2.Force of attractions in pure state = Force of attractions in solution state
𝑭𝑨-𝑨 = 𝑭𝑨-𝑩
3. ∆𝐻 = 0 therefore, solution is neither be cold nor be warmed
4. ∆𝑉 = 0 [final volume =. Initial volume]
Example : Mixture of n-hexane and n-heptane
Mixture of benzene and toluene
Mixture of methanol and ethanol
Mixture of bromo butane and bromo pentane
Mixture of bromo benzene and chloro benzene
Types of non-ideal Positively deviated non-ideal solution
solutions 1. 𝑃/ > 𝑃/1 𝑋/ AND 𝑃0 >𝑃1 𝑋0

2.Force of attractions in pure state > Force of attractions in solution state

𝐹/-/ > 𝐹/-0
3. ∆𝐻 > 0 therefore, solution will be cold
4. ∆𝑉 > 0 [Final volume > initial volume]
Eg: Mixture of Acetone and Carbon disulphide.
Mixture of Acetone and Benzene.
Mixture of Carbon Tetrachloride and Toluene or Chloroform.
Mixture of Methyl Alcohol and Water.
Mixture of Acetone and Ethanol.
Mixture of Ethanol and Water
 Negatively deviated non-ideal solution
1. 𝑃/ < 𝑃/1 𝑋/ AND 𝑃0 < 𝑃1 𝑋0

2.Force of attractions in pure state < Force of attractions in solution state

𝐹/-/ < 𝐹/-0
3. ∆𝐻 < 0 therefore, solution will be warmed
4. ∆𝑉 < 0 [Final volume < initial volume]
Eg: Mixture of Chloroform and acetone
Mixture of Chloroform and Benzene
Mixture of Chloroform and Diether
Mixture of Acetone and Aniline
Mixture of Nitric Acid ( HNO3) and water
Mixture of Acetic Acid and pyridine
Mixture of Hydrochloric Acid ( HCl) and water
Mixtures have same composition in liquid and vapour phase and boil at a constant
temperature.
Types of azeotropes
Azeotropes Minimum boiling azeotrope shows positive deviation from Raoults law and boils
at lower temperature than normal boiling point. Eg- 95% aq ethanol
Maximum boiling azeotrope is negative deviation from Raoults law and boils at
higher temperature than normal boiling point. Eg: 68% HNO3
Properties that depend upon the number of particles of solute and not on the nature
Colligative of solute.
properties 1. Relative lowering in vapour pressure 2. depression of freezing point.
3. Elevation of boiling point, 4. Osmotic pressure
Relative lowering Vapour pressure of solvent gets lowered in a solution containing non-volatile solute.
in vapour pressure 𝑷𝟎𝑨 "𝐏𝐀
𝑷𝟎𝑨
= 𝐗𝐁 where 𝑿𝑩 𝒊𝒔 𝒎𝒐𝒍𝒆𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆

𝑃!" − 𝑃! = 𝑙𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑃!" − 𝑃!
= 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑙𝑜𝑤𝑒𝑟𝑖𝑛𝑔 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑃!"
𝐁𝐧 𝐏𝐀𝟎 "𝐏𝐀 𝐧𝐁
If 𝐗 𝐁 = =𝐧 (amount of solute given in mole)
𝐧𝐀 &𝐧𝐁 𝐏𝐀𝟎 𝐀 &𝐧𝐁

𝐖𝐁 ×𝐌𝐀 𝐏𝐀𝟎 "𝐏𝐀 𝐖 ×𝐌

If 𝐗 𝐁 =
𝐌𝐁 ×𝐖𝐀 𝐏𝐀𝟎
= 𝐌𝐁×𝐖𝐀 (amount of solute given in mass)
𝐁 𝐀

𝐦 𝐏𝐀𝟎 "𝐏𝐀 𝐦
If 𝐗 𝐁 = = 𝐦&𝟓𝟓.𝟓 (amount of solute given in molality)
𝐦&𝟓𝟓.𝟓 𝐏𝐀𝟎
 Boiling point of a liquid is the temperatures at which the vapour pressure of the
liquid becomes equal to the atmospheric pressure.
Boiling point of solvent gets increased in a solution containing non volatile
solute.
∆𝐓𝐛 = 𝐓𝐛 − 𝐓𝐛𝟎
Elevation of
∆𝐓𝐛 = 𝐤 𝐛 × 𝒎
boiling point
𝐊 𝐛 ×𝐖𝐁 ×𝟏𝟎𝟎𝟎
∆𝐓𝐛 =
𝐌𝐁 ×𝐖𝐀

ΔTb = elevation in boiling point, T5 = boiling point in solution.

𝐓𝐛 = 𝐓𝐛𝟎 + ∆𝐓𝐛
T51 = boiling point in pure state, Kb = molal elevation constant or ebullioscopic
constant
Ebullioscopic constant is the elevation in boiling point when one mole of
solute is dissolved in one kilogram of the solvent.
Freezing point is the temperature at which the solid and the liquid forms
of the substance have the same vapour pressure
Freezing point of solvent gets decreased in a solution containing non volatile
solute.
∆𝐓𝐟 = 𝐓𝐟𝟎 − 𝐓𝐟
Depression of
∆𝐓𝐟 = 𝐤 𝐟 × 𝒎
freezing point
𝐊 𝐟 ×𝐖𝐁 ×𝟏𝟎𝟎𝟎
∆𝐓𝐟 =
𝐌𝐁 ×𝐖𝐀

ΔTf = depression of freezing point, T7 = freezing point in solution

𝐓𝐟 = 𝐓𝐟𝟎 − ∆𝐓𝐟 ,
T71 = freezing point in pure state, Kf = molal depression constant or cryoscopic
const
Cryoscopic constant is the depression in freezing point when one mole of
solute is dissolved in one kilogram of the solvent.
Osmosis ; Solvent flows through the semi permeable membrane from pure state
to the solution
Osmotic pressure 𝝅 The excess pressure applied on the solution that just stops
the flow of solvent is called osmotic pressure of the solution
Osmotic pressure 𝛑 = 𝐌𝐑𝐓
 𝐖𝐁 ×𝐑×𝐓×𝟏𝟎𝟎𝟎
𝛑= 𝐌𝐁 ×𝐕

where T is temperature in Kelvin and V is volume in mL

R= 0.0821 L atm mol-1K-1 or 0.083 Lbar mol-1K-1
Advantages of 1. It is measured at room temperature.
osmotic pressure 2. it gives appreciable value at room temperature
3. it is used to calculate the molar mass of protein, biomolecules
(macromolecules)
4. it is calculated by using molarity
The direction of osmosis can be reversed if a pressure larger than the osmotic
Reverse osmosis pressure is applied to the solution side. That is, now the pure solvent flows out of
the solution. Application : Desalination of sea water
Isotonic solutions Two solutions having same osmotic pressure.
Eg: 0.9%NaCl is isotonic with fluids in RBC
𝐖𝐁𝟏 𝐖
For Isotonic solutions, 𝐌𝐁𝟏
= 𝐌𝐁𝟏
𝐁𝟏

Hypertonic Solution has higher osmotic pressure than a particular solutions.

solutions NaCl with concentration more than 0.9% is hypertonic with fluids in RBC
Hypotonic Solutons has lower osmotic pressure than a particular solution
NaCl with concentration less than 0.9% is hypotonic with fluids in RBC
Sometimes while measuring colligative properties abnormal results are obtained
Abnormal due to the following reasons :
Colligative In case of association of two or more solute molecules associate to form a single
Properties. molecule. The number of effective molecules in the solution, therefore decreases.
Consequently, the value of the colligative property is observed become lesser than
that calculated for unassociated molecules.
Eg: Freezing point of mixture of HgI2 and KI is increased due to association
In case of dissociation of the solute in the solution, the number of effective solute
particles increases. Consequently, the value of the collgative property is observed
become greater than that calculated for undissociated molecules.
Eg: Freezing point of mixture of NaCl and water is decreased due to dissociation.
Ratio of normal molar mass to experimentally determined molar mass
van‘t Hoff factor or
(i)
Ratio of observed colligative property to the calculated colligative property.
 For electrolytes (NaCl, KCl, BaCl2 , CaCl2 ) i≠1
For non-electrolyte (glucose, urea ,protein, polymers..) i=1
For completed dissociations
Electrolytes n (number of ions) i (van’t Hoff factor)
NaCl 2 2
MgSO4 2 2
CaCl2 3 3
AlCl3 4 4
Al2(SO4)3 5 5
K4[Fe(CN)6] 5 5
For completed associations
Type of associated n (number of ions) i (van’t Hoff factor)
molecules
Dimer 2 ½
Trimer 3 1/3
Tetramer 4 ¼
Modified 𝐏𝐀𝟎 -𝐏𝐀
= 𝐗𝐁 × 𝐢 Relative lowering in vapour pressure
𝐏𝐀𝟎
colligative
properties formula 𝐊𝐛 ×𝐖𝐁 ×𝟏𝟎𝟎𝟎
∆𝐓𝐛 = × 𝐢 Elevation in boiling points
𝐌𝐁 ×𝐖𝐀

𝐊𝐟 ×𝐖𝐁 ×𝟏𝟎𝟎𝟎
∆𝐓𝐟 = × 𝐢 Depression in freezing point
𝐌𝐁 ×𝐖𝐀

𝐢𝐖𝐁 ×𝐑×𝐓×𝟏𝟎𝟎𝟎
𝛑= × 𝐢 Osmotic pressure
𝐌𝐁 ×𝐕

Freezing point and 𝑻𝒃 ∝ 𝒊 𝒂𝒏𝒅 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆𝒔

Boiling point
𝟏
w.r.to i 𝑻𝒇 ∝
𝒊 𝒂𝒏𝒅 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆𝒔

Colligative properties ∝ 𝒊 𝒂𝒏𝒅 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆𝒔

Dissociation Association
Value of van‘t If ∝ is degree of dissociation, If ∝ is degree of dissociation,
Hoff 𝐢-𝟏 𝟏-𝐢
∝= 𝐧-𝟏 ∝= 𝟏
𝟏-𝐧
factor(i) for
partial dissociation ∝× 100 = 𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 ∝× 100𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

and association
ELECTROCHEMISTRY
Types of Cells Electrochemical Cell Electrolytic cells Cell at equilibrium
Chemical energy converts Electrical energy converts No energy conversion
to Electrical energy. to Chemical energy.
$ $ $
𝐸!"## > 𝐸"%& 𝐸!"## < 𝐸"%& 𝐸!"## = 𝐸"%&
𝐸!"## 𝑖𝑠 + 𝑣𝑒 𝐸!"## 𝑖𝑠 − 𝑣𝑒 𝐸!"## 𝑖𝑠 𝑧𝑒𝑟𝑜
∆𝐺 = −𝑣𝑒 ∆𝐺 = +𝑣𝑒 ∆𝐺 = 0
Reaction is spontaneous. Reaction is non- Rate of spontaneous =
spontaneous. rate of non-spontaneous
Anode is left with -ve Anode is right with +ve No polarities on
charge. charge. electrodes
Cathode is right with +ve Cathode is left with -ve
charge. charge.
Electron flow from left to Electron flow from right No flow of electrons
right. to left.
Current flow from right to Current flow from left to No flow of current
left right
Cathode The electrode at which reduction takes place. [Red Cat]
𝑀'( + 𝑛𝑒 ) → 𝑀 (reduction = gain of electron at cathode) [RIG]
Metals are deposited at cathode.
H2 gas also may produce at cathode.
Electrons are gained at cathode
Anode The electrode at which oxidation takes place. [An OX]
𝑀 → 𝑀'( + 𝑛𝑒 ) (oxidation = lose of electron at anode) [ OIL]
Metal ions are dissolved at anode.
Non-metallic gases such as O2 , Cl2 also produces at anode.
Electrons are lost at anode
Cell Notation of 𝑍𝑛 → 𝑍𝑛*( + 2𝑒 ) (oxidation = lose of electron at anode)
Electrochemical cell 𝐶𝑢*( + 2𝑒 ) → 𝐶𝑢 (reduction = gain of electron at cathode)
𝑍𝑛 + 𝐶𝑢*( → 𝑍𝑛*( + 𝐶𝑢
CELL NOTATION IS 𝑍𝑛/𝑍𝑛*( // 𝐶𝑢*( / 𝐶𝑢
Left anode right cathode
Where 𝑍𝑛*( is product ion 𝐶𝑢*( is reactant ion.
Standard electrode Tendency of an element in 1M electrolyte to being reduced is called at 298K is
potential called standard electrode potential.
𝑬𝒐𝒆𝒍𝒆𝒄𝒕𝒐𝒅𝒆 𝒐𝒓 𝑬𝟎𝑴𝒏" /𝑴 Standard electrode potential of any element is determined by using SHE
SHE or standard It can be defined as hydrogen gas at 1 bar pressure and 298K is passed into 1 M
hydrogen electrode acid in which a foil of Pt coated with Pt black(it simply act as inert electrode
𝟎
𝐇𝟐 → 𝟐𝐇 ( + 𝟐𝐞 𝐄𝐇 " /𝐇 = 𝟎. 𝟎𝟎 𝐯
𝟐

Standard Cell Potential difference between two electrodes in volt which are immersed in their
potential unit molar salt solution at 298 K .
𝑬𝟎𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒃𝒊𝒈𝒈𝒆𝒓 − 𝑬𝟎𝒔𝒎𝒂𝒍𝒍𝒆𝒓
𝑬𝟎𝒄𝒆𝒍𝒍 Example: Daniel Cell Zn + Cu2+ → Zn2+ + Cu
$ $
E>?$" />? = +0.34 v and E@A$" /@A = −0.76 v

$
Then EBCDD = 0.34 − (−0.76) = 1.1v
Electrode potential. Tendency of an element in an electrolyte of any concentration to being reduced at
(𝑬𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 ) 298K is called electrode potential.
𝟎. 𝟎𝟓𝟗
𝑬𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆 = 𝑬𝒐𝒆𝒍𝒆𝒄𝒕𝒐𝒅𝒆 + 𝒍𝒐𝒈 [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒊𝒐𝒏]𝒄𝒐𝒆𝒇𝒇
𝒏
Where n= charge difference between LHS and RHS
Example 1. For the hydrogen electrode, 2H+ + 2eà H2
𝟎 𝟎.𝟎𝟓𝟗
𝑬𝑯" /𝑯𝟐 = 𝐄𝐇 " /𝐇 + 𝒍𝒐𝒈 [𝑯( ]𝟐
𝟐 𝟐

2. For Zinc electrode, Zn2+ + 2eà Zn

𝟎 𝟎. 𝟎𝟓𝟗
𝑬𝒁𝒏𝟐" /𝒁𝒏 = 𝐄𝒁𝒏𝟐" /𝒁𝒏 + 𝒍𝒐𝒈 [𝒁𝒏𝟐( ]𝟏
𝟐
Cell potential Potential differences between two electrodes in electrolytes of any concentrations.
(𝑬𝒄𝒆𝒍𝒍 ) 𝟐. 𝟑𝟎𝟑𝑹𝑻 [𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒊𝒐𝒏]𝒄𝒐𝒆𝒇𝒇
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒆𝒍𝒍 + 𝒍𝒐𝒈
𝒏𝑭 [𝒑𝒓𝒐𝒅𝒖𝒄𝒕 𝒊𝒐𝒏]𝒄𝒐𝒆𝒇𝒇
*.M$MNO *.M$M×R.MST ×*UR $.$WU
At 298 K, = =
AP A×UVW$$ A

Then EBCDD formula becomes

𝐨 𝟎. 𝟎𝟓𝟗 [𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭 𝐢𝐨𝐧]𝐜𝐨𝐞𝐟𝐟

𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 + 𝐥𝐨𝐠
𝐧 [𝐩𝐫𝐨𝐝𝐮𝐜𝐭 𝐢𝐨𝐧]𝐜𝐨𝐞𝐟𝐟
OR

𝐨 𝟎. 𝟎𝟓𝟗 [𝐩𝐫𝐨𝐝𝐮𝐜𝐭 𝐢𝐨𝐧]𝐜𝐨𝐞𝐟𝐟

𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 − 𝐥𝐨𝐠
𝐧 [𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭 𝐢𝐨𝐧]𝐜𝐨𝐞𝐟𝐟
concentration of reactant ion
EBCDD ∝ concentration of product ion

Example: 1. Zn(s) | Zn2+ (aq) || Cu2+(aq)| Cu(s)

Zn(s) à Zn2+ (aq) +2e
Cu2+(aq)+ 2e à Cu(s)

𝐨 𝟎. 𝟎𝟓𝟗 [𝐂𝐮𝟐( ]𝟏
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 + 𝐥𝐨𝐠
𝟐 [𝐙𝐧𝟐( ]𝟏
 Example 2. Zn(s) | Zn2+ (aq) || H+(aq)| H2(g) | Pt(s)
Zn(s). à Zn2+ (aq)
2H+(aq) à H2(s)

𝐨 𝟎. 𝟎𝟓𝟗 [𝐇 ( ]𝟐
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 + 𝐥𝐨𝐠
𝟐 [𝐙𝐧𝟐( ]𝟏
Example:3. 2 AgCl (s)+H2 (g) (1atm) → 2 Ag (s)+2H+ (0. 1 M) +2 Cl− (0. 1 M)
2 AgCl (s)+ 2e → 2 Ag (s)+ 2 Cl− (0. 1 M)
H2 (g) (1atm) → 2H+ (0. 1 M) +2e
𝐨 𝟎. 𝟎𝟓𝟗 𝟏
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 + 𝐥𝐨𝐠 ) 𝟐 ( 𝟐
𝟐 [𝐂𝐥 ] [𝐇 ]
FORMULA FOR ∆G$ = −2.303RTlogKc … … … . (1)
∆𝐺 ] and 𝐾^ [`abc?Bd ebA]%&'((
At Equilibrium EBCDD = 0 and = Kc … … … (2)
[aCgBdgAd ebA]%&'((

b $.$WU [`abc?Bd ebA]%&'((

EBCDD = EBCDD − log [aCgBdgAd ebA]%&'(( ……….(3)
A

b *.M$MNO
(2) in (3) 0 = EBCDD − logKc
AP
b *.M$MNO
EBCDD = logKc…………(4)
AP
b
2.303RTlogKc = E>CDD nF………(5)
𝟎
𝟎 𝐄𝐜𝐞𝐥𝐥 ×𝐧
(5) in (1) ∆𝐆𝟎 = −𝐧𝐅𝐄𝐜𝐞𝐥𝐥 & 𝐥𝐨𝐠𝐊𝐜 =
𝟎.𝟎𝟓𝟗

Product of Product at anode = Non-metal anion or an active metal electrode with lower
Electrolysis E° value oxidizes at anode
Eo value order: Cu electrode <Ag electrode < OH- < Cl- < SO42- < NO3-
But OH- has over potential, therefore Cl- will be oxidized before the OH- ion.
If Ag electrode is given, reaction at anode is. Agà Ag+ + e (Ag+ is dissolved)
If Cu electrode is given, reaction at anode is Cuà Cu2+ + 2e (Cu2+ is dissolved)
If Pt electrode is given and Cl- ion is present in solution,
2Cl-à Cl2 +2e (Cl2 gas liberated)
If Pt electrode is given and Cl- ion is absent in solution,
4OH-à O2 +4e +2H2O (O2 gas liberated)
Product at cathode = Metal or H2 gas with higher E° value reduces at
cathode.
Eo value order: K+くNa+<Mg 2+<Al3+ < Zn2+ <Fe2+ <H +. <Cu2+. <Ag+
If Ag+ ion is present in solution, it is Ag+ + e à Ag ( Ag metal is deposited)
If Cu2+ ion is present in solution, it is Cu2+ + 2e à Cu (Cu metal is deposited)
If Cu2+ ions and Ag+ ions are absent in solution, then it is
2H+ + 2e à H2 ( H2 gas is liberated)
Faraday‘s 1st Law. The amount of product formed at any electrode during electrolysis is proportional to
the quantity of electricity passed through the electrolyte.
𝐀×𝐈×𝐭
𝐦= 𝐧𝐅
m=mass of metal deposited A= atomic mass of metal,

I=current, t=time in sec n = charge difference F=96500 C

Thickness of metal 𝐀×𝐈×𝐭
𝐓𝐡𝐢𝐜𝐤𝐧𝐞𝐬𝐬 =
𝐧 × 𝐅 × 𝐝 × 𝐀𝐫𝐞𝐚
deposited
Charge Q 𝐐 = 𝐧𝐨: 𝐨𝐟 𝐦𝐨𝐥𝐞 × 𝐧 × 𝐅
Q can also be calculated from current and time by Q=It
Number of electrons 𝐐
𝐍𝐮𝐦𝐛𝐞𝐫 𝐨𝐟 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧𝐬 = × 𝟔. 𝟎𝟐𝟐 × 𝟏𝟎𝟐𝟑
𝐅
The amounts of different metals deposited by the same quantity of electricity(Q=It)
Faraday‘s 2nd Law. passing through the electrolytic solution are proportional to their chemical equivalent
weights (Equivalent weights =Atomic Mass of Metal ÷ Number of electrons
required to reduce the cation).
In the primary batteries, the reaction occurs only once, and cannot be reused.

Pri & Sec Batteries Eg: Dry cell, mercury cell

In the secondary batteries, the reaction is reversible and can be re used.
Eg: Lead storage battery, Ni-Cd battery, Lithium-ion battery
Electrolyte (paste of NH4Cl and ZnO)

Dry Cell Anode(Zn) : Zn(s)+ 2Cl- → ZnCl2 + 2e-

Cathode(MnO2 coated on graphite): MnO2 + NH4+ + e- → MnO(OH) + NH3
• MnO2 protect graphite electrode from polarization.
• It cannot be recharged as ZnCl2 react with NH3 form a complex [Zn(NH3)4]Cl2
• It does not have long life as acidic NH4Cl corrode zinc container.
Electrolyte: (aqs KOH)
Anode(Zn) : Zn + 2OH- → ZnO(s) + H2O + 2e-

Mercury Cell Cathode(HgO coated on graphite) : HgO + H2O + 2e- → Hg + 2OH-

Overall: Zn + HgO à ZnO + Hg Voltage= 1.35 V
• Voltage and remains constant during its life as the overall reaction does not
involve any ion in solution those concentration can change Ecell.
Electrolyte : 38% H2SO4

Lead Storage Anode (Pb). : Pb + SO4 2- → PbSO4 + 2e-

Battery Cathode (PbO2 coated on graphite): PbO2 + SO4 2- + 4H+ + 2e- → PbSO4 + 2H2O
Overall: Pb +PbO2 + 2H2SO4 à 2PbSO4 + 2H2O
• It is rechargeable as product PbSO4 can be converted back Pb and PbO2
 Fuel cell is galvanic cell in which chemical energy brings from combustion of fuel
converted to electrical energy.
Electrolyte : Aq NaOH
Anode: 2H2 + 4OH- → 4H2O + 4e-
Fuel Cells
Cathode: O2 + 2H2O + 4e- → 4OH-
Overall : 2H2 +O2 → 2 H2O
The cell runs continuously as long as the reactants are supplied.
Efficiency of about 70 %.
Pollution free as the water vapours produced during the reaction were condensed and
added to the drinking water supply for the astronauts (Apollo space programme)
Corrosion is the process of conversion of a metallic surface into mineral form.

Corrosion of Oxidation: Fe → Fe2+ +2e-

Iron Reduction: O2 + 4H+ +4e- → 2H2O

(Rusting) Atmospheric oxidation : 2Fe2+ + 2H2O + ½O2 → Fe2O3+ 4H+

• By covering the surface with paint or by some chemicals (e.g. bisphenol).

Prevention of • Cover the surface by other metals (Sn, Zn, etc.) that are inert or react to save the

Corrosion object.
• An electrochemical method (sacrificial electrode like Mg, Zn, etc.) which corrodes
itself but saves the object. It is called galvanization
Conductivity Conductivity is the conductance of material of unit length and unit area of cross
section.
𝐆∗
Conductivity, 𝐊 = where 𝐺 ∗ =cell constant in cm-1, R= resistance in ohm
𝐑
𝐥
𝐆∗ = 𝐀 & 𝐀 = 𝛑𝐫 𝟐

𝑈𝑛𝑖𝑡 𝑜𝑓 𝐾 𝑖𝑠 𝑆𝑐𝑚)S 𝑤ℎ𝑒𝑟𝑒 𝑆 = 𝑂ℎ𝑚)S

For a cell with different concentrations 𝐊 𝟏 𝐑 𝟏 = 𝐊 𝟐 𝐑 𝟐
Resistance of Resistance of electrolytic solution cannot be calculated directly by using Wheastone
Electrolytes bridge due to following reasons.
(i) A solution cannot be connected to Wheastone bridge directly
(ii) DC voltage used in Wheastone bridge changing concentration of solution and
electrolyse it.
To overcome these difficulties, the following alternatives are used.
(i) . A conductivity cell containing electrolytic solution will be connected to
Wheastone bridge.
(ii). AC voltage will be used to avoid the electrolysis.
 Molar Molar conductivity is the conductance of electrolytic solution contain unit mole of
conductivity electrolyte
𝝀𝒎 𝐊×𝟏𝟎𝟎𝟎
Molar conductivity, 𝛌𝐦 = (Unit of 𝜆q 𝑖𝑠 𝑆𝑐𝑚* 𝑚𝑜𝑙 )S )
𝐌

where K= conductivity in Scm-1 & M= molarity in mol/L

Differences between Conductivity Molar conductivity
Conductivity and Conductivity is decreases with dilution as Molar conductivity is increases with
Molar conductivity number of ions per unit volume dilution as mobility of ions increased.
decreased.
Molar conductivity of HCl is greater than that of KCl because of smaller size of H+ ion which increases
its mobility.
Limiting molar It can be defined as molar conductivity at infinite dilutions or zero concentration.
conductivity 𝝀𝟎𝒎
Limiting molar Strong electrolyte Weak electrolyte
conductivity for * It dissociates completely in aqs solution * It dissociates partially in aqs solution
different electrolytes * It shows a straight line graph on * It does not show a straight line graph
𝜆q 𝑣𝑠 𝐶 S/* due to its degree of on 𝜆q 𝑣𝑠 𝐶 S/* due to its degree of
dissociation is 1 dissociation increases on dilution.
* Therfore it obeys DeBye-Huckel *Therefore it does not obey DeBye
straight line equation, 𝛌𝐦 = 𝛌𝟎𝐦 − 𝐛√𝐜 Huckel straight line equation
λ"!

λ! NaCl, KCl, HCl λ! CH& COOH

𝐶 #/% 𝐶 #/%

*limiting molar conductivity 𝜆$q can be *limiting molar conductivity 𝜆$q

calculated graphically cannot be calculated graphically

Kohlrausch’s It state that, limiting molar conductivity of an electrolyte is the sum of contribution of
law limiting molar cinductivities cations and anions 𝝀𝟎𝒎 = ¢𝒏( 𝝀𝟎( £ + (𝒏) 𝝀𝟎) )
Eg 𝜆$>sM>tts = ¢1 × 𝜆$s(£ + (1 × 𝜆$>sM>tt )
Applications: 1) it is used to find limiting molar conductivity of weak electrolyte
𝝀
2) It is used to find degree of dissociation of weak electrolyte 𝜶 = 𝝀𝒎
𝟎
𝒎

𝑴×𝜶𝟐
3) it is used to find dissociation constant of weak electrolyte 𝑲𝒂 =
𝟏)𝜶

𝜆$w (>s1 >tts) 𝝀𝟎𝐦 (𝐂𝐇𝟑𝐂𝐎𝐎𝐇) = 𝝀𝟎𝐦 (𝐂𝐇𝟑 𝐂𝐎𝐎𝐍𝐚) + 𝝀𝟎𝐦 (𝐇𝐂𝐥) − 𝝀𝟎𝐦 (𝐍𝐚𝐂𝐥)

𝜆$w (s$ t) 𝝀𝟎𝐦 (𝐇𝟐 𝐎) = 𝝀𝟎𝐦 (𝐍𝐚𝐎𝐇) + 𝝀𝟎𝐦 (𝐇𝐂𝐥) − 𝝀𝟎𝐦 (𝐍𝐚𝐂𝐥)

λ$w (•s2 ts) 𝝀𝟎𝐦 (𝐍𝐇𝟒 𝐎𝐇) = 𝝀𝟎𝐦 (𝐍𝐚𝐎𝐇) + 𝝀𝟎𝐦 (𝐍𝐇𝟒 𝐂𝐥) − 𝝀𝟎𝐦 (𝐍𝐚𝐂𝐥)
 YEAR 2024
1. During electrolysis of aqueous solution of NaCI:
(a) H2 (g) is liberated at cathode (b) Na is formed at cathode.
(c) O2(g) is liberated at anode (d) Cl2 (g) is liberated at cathode
2. The unit of cell constant is :
(a) ohm cm-1 (b) ohm -1 (c) cm-1 (d) ohm-1 cm2 mol-1
3. During electrolysis of aqueous CuCl2
(a) H2 (g) is liberated at cathode (b) Na is formed at cathode.
(c) O2(g) is liberated at anode (d) Cl2 (g) is liberated at anode
4. Calculate emf of the following cell : Zn(s)| Zn2+(0.1 M)||Sn2+(0.001 M)|Sn(s)
Given :E0 Zn2+/Zn= -0.76v. E0 Sn2+/Sn =-0.14 v)
5. (i) The resistance of 0.05 M CH3COOH solution is found to be 100 ohm. If the cell constant is 0.0354
cm-1, calculate the molar conductivity of the acetic acid solution.
(ii) State Faraday's first law of electrolysis. How much charge in Faraday is required for the reduction of 1
mol of MnO4 to Mn2+ ?
6. (i) The conductivity of 0.0025 mol L-1 acetic acid is 5.25 x 10-5 S cm-1 . Calculate its degree of
dissociation if Λ0m for acetic acid is 390 S cm2 mol-1
(ii) Write anode, cathode and overall reaction of lead storage battery.
ANSWERS
1. (a) H2 (g) is liberated at cathode
𝐸€$ " /€$ is greater than 𝐸•‚
$ + +
" /•‚ , therefore H cation is easily reduced than Na cation.

2. (c) cm-1
# !q S
Cell constant 𝐺 ∗ = ƒ = !q$ = !q = 𝑐𝑚)S

3. (d) Cl2 (g) is liberated at anode

$ $ -
O2 has over potential, therefore experimentally 𝐸^# 4 /^# is lower than 𝐸 $4
$ „ /„_* , hence Cl anion is easily

oxidized than O2- anion.

4. Zn(s)| Zn2+(0.1 M)||Sn2+(0.001 M)|Sn(s) Given :E0 Zn2+/Zn= -0.76v. E0 Sn2+/Sn =-0.14 v)
E°cell = E°bigger - E°smaller.
E°cell = -0.14 – (-0.76)= -0.14+0.76= 0.62v

Zn(s) + Sn+ (0.001 M) → Zn2+(0.1 M) + Sn(s)

Product ion = Zn2+(0.1 M). reactant ion = Sn2+(0.001 M).

$ 0.059 [Product ion]BbC†‡eBeCAd

EBCDD = EBCDD − log
n [reactant ion]BbC†‡eBeCAd
n= 2, because of the change in Zn 2+ to Zn is 2 or Sn to Sn 2+ is 2
Coefficients of Sn 2+ is 1 and Zn 2+ is 1
CHEMICAL
KINETICS
Rate of a Chemical Change in concentration of a reactant or product in unit time.Unit=> mol L-1s-1
Reaction
For a reaction: Reactant (R) à Product (P)
! &'[)] ! d[P]
rate of reaction = "#$%% × '+
= "#$%% × dt
!"[$] "[']
Where "&
is rate of disappearance of R and "&
is rate formation of P

Average Rate
It is the overall rate of reaction.
Average &
Instantaneous Rate Instantaneous Rate
it is the rate of reaction at a particular instant.
Rate Law Rate law state that rate of reaction is directly proportional to molar
concentration of reactants in which their coefficients rise to power
For a reaction 𝒂𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫
𝐫𝐚𝐭𝐞 = 𝐤[𝐀]𝐚 [𝐁]𝐛 Where a+b is order of reaction and k is rate constant
Order of a Reaction The sum of powers of the molar concentration of the reactants in the ratelaw
expression is called the order of that chemical reaction.
• It is experimental quantity
• Its value can be 0,1,2,3… or fractional
• It is applicable to both elementary and complex reactions
rate constant (k) • It is rate of reaction when molar concentration of reactants is unit
• Unit of rate constant for 𝑛&* order is 𝐦𝐨𝐥𝟏!𝐧 𝐋𝐧!𝟏 𝐬 !𝟏
Elementary reactions • The reactions taking place in one step are called Elementary reactions.
and complex reaction
• The reactions taking place in several steps are called complex reactions.
• Each step in complex reactions are said to be elementary.
• Slowest elementary step in a complex reaction is called rate determining step.
Molecularity of a The number of reacting species taking part in an elementary reaction,which
Reaction
must collide simultaneously in order to bring about a chemical reaction is
called molecularity of a reaction
• It is theoretical quantity
• Its values must be either 1,2 or 3
• It is applicable to only elementary reaction, not to a complex reaction.
Order of the overall reaction is the same as the molecularity of a slowest elementary step (r.d.s)
Zero Order Reaction not depends upon the concentration called Zero order reaction
Reactions 𝑅𝑎𝑡𝑒 = 𝑘 [𝑅]- ie, rate=k
[𝐑𝟎 ]![𝐑]
Integrated rate constant equation for zero order. 𝐤 =
𝐭
-1 -1
unit of rate constant is mol L s
Eg: Decomposition of ammonia on platinum surface
 Straight line equation for zero order [𝐑𝐭] = −𝐤𝐭 + [𝐑𝟎]
Slope = - k
Intercept = [𝐑𝟎]

First order reactions Reaction in which rate of reaction is increases by x times when the concentration
is increased by x times
Rate = k[R]1
𝟐.𝟑𝟎𝟑 [𝐑 𝟎 ]
Integrated rate constant equation 𝐤= 𝐭
𝐥𝐨𝐠 [𝐑]
𝟐.𝟑𝟎𝟑 𝐏𝟎
In gaseous phase 𝐤= 𝐭
𝐥𝐨𝐠 𝟐𝐏𝟎 −𝐏𝐭

unit of k is s-1
Eg; All the radioactive decomposition reactions
1. Straight line equation for first order= ln [R t] = -kt + ln [Ro]
Slope = -k,
Intercept = ln [Ro]
ln
!𝐤𝐭
2. Straight line equation for first order= log [R t] = 𝟐.𝟑𝟎𝟑 + log [Ro]

!5
slope = ,
6.7-7

intercept = log [Ro]

Half life Time required to consume half of initial concentration of reactant
Half-life in zero order.
ℎ𝑎𝑙𝑓 𝑙𝑖𝑓𝑒 𝑖𝑠 𝑑𝑖𝑟𝑒𝑐𝑡𝑙𝑦 𝑝𝑟𝑜𝑝𝑜𝑟𝑡𝑖𝑜𝑛𝑎𝑙 𝑡𝑜 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛

[𝑹𝟎 ]
𝒕𝟏/𝟐 = 𝒕𝟏/𝟐
𝟐𝒌
[𝑹𝟎 ]
Half-life in first order; ℎ𝑎𝑙𝑓 𝑙𝑖𝑓𝑒 𝑖𝑠 𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑎𝑛𝑡 𝑜𝑛 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
𝟎.𝟔𝟗𝟑
𝒕𝟏/𝟐 = 𝒕𝟏/𝟐
𝒌

[𝑹𝟎 ]
Pseudo first order It can be defined as the second order or bimolecular reaction is made to behave
reaction
like first order.
Eg hydrolysis of ester ; CH3COOC2H5 + H2O à CH3COOH + C2H5OH
Rate law è rate = k [CH3COOC2H5]

It is a second order or bimolecular but behave like 1st order because the
concentration of water does not bring any change on rate of reaction as the
volume of water is large in excess.
So rate is depends only on the concentration of ester.
Condition for concentration of water should not bring any change on rate of reaction bytaking
bimolecular reaction
the volume of water is large in excess. So rate should depends onlyon the
follows first order.
concentration of ester.
Activated complex * According to ACT, reaction takes place through an intermediate formation
theory
*Reactant converts into intermediate by attaining activation energy
* Rate of reaction inversely proportional to Activation energy
Activation energy Activation energy is given by the energy difference betweenintermediate and the
Ea reactant molecules.
Arrhenius equation It explains about the temperature effect on rate of reaction
Every raise in 10 degree temperature, rate constant is increased by double.
𝐤 = 𝐀𝐞$𝐄𝐚/𝐑𝐓 where A= Arrhenius constant, 𝑒 !89/$; = Boltzmann factor
straight line forms of Arrhenius Equation.
𝑬𝒂
1. 𝐥𝐧 𝒌 = 𝐥𝐧 𝑨 −
𝑹𝑻
89
slope = − and intercept is ln A
$

𝑬𝒂
2. 𝐥𝐨𝐠 𝒌 = 𝐥𝐨𝐠 𝑨 −
𝟐.𝟑𝟎𝟑𝑹𝑻
89
slope = − 6.7-7$ and intercept is logA

Boltzmann factor It is the fraction of molecules attains energy equal or greater than activation

𝑒 -.//01 energy

If k1 and k2 are rate 𝒌𝟐 𝑬𝒂 𝑻𝟐 − 𝑻𝟏

constants at T1 and 𝐥𝐨𝐠 = T V
𝒌𝟏 𝟐. 𝟑𝟎𝟑𝑹 𝑻𝟏 𝑻𝟐
T2
Effect of positive Catalyst provides an alternate pathway or reaction mechanism by reducing the
catalyst
activation energy between reactants and products and hence lowering the
potential energy barrier and increasing rate of reaction
Effect of Negative Catalyst provides an alternate pathway or reaction mechanism by increasing the
catalyst
activation energy between reactants and products and hence decreasing rate of
reaction
Catalyst does not change properties such as ∆𝐺 - , ∆𝐻 , ∆𝑈 𝑎𝑛𝑑 𝐾𝑐
Collision frequency The number of collisions per second per unit volume of the reaction mixture.
(Z) For A + B → Products

Rate = P.ZAB e−Ea/ RT

P is probability or steric factor and ZAB is collision frequency of reactants, A & B
For effective collision, ,
(i) Molecules should attains energy equal or greater than Ea
(ii) Proper orientation makes the bonds.
D AND F BLOCK
ELEMENTS
 D -BLOCK ELEMENTS
TRANSITION METALS
1. d- block elements are called transition metals. WHY?
Because they have incompletely filled (n-1) d orbitals in either their ground state or excited state
2. Cu & Ag are transition metals although they have completely filled d-orbitals.
WHY?
Because they have incompletely filled (n-1) d orbitals in their excited state Cu2+& Ag+2
3. Silver atom has completely filled d orbitals (4d10) in its ground state but it is a
transition element. Why?
Silver can exhibit +2 oxidation state wherein it will have incompletely filled d-orbitals (4d9).
4. Zn, Cd and Hg are not regarded as transition metal. Why?
Zn, Cd ,Hg have completely filled(n-1)d-orbital in atomic and ionic state and thus these elements are not
considered as transition elements.

ENTHALPY OF ATOMIZATION AND MELTING POINT

𝟏. 𝑬𝑵𝑻𝑯𝑨𝑳𝑷𝒀 𝑶𝑭 𝑨𝑻𝑶𝑴𝑰𝒁𝑨𝑻𝑰𝑶𝑵, ∆𝒂𝑯. ∝ 𝑵𝑼𝑴𝑩𝑬𝑹 𝑶𝑭 𝑼𝑵𝑷𝑨𝑰𝑹𝑬𝑫 𝑬𝑳𝑬𝑪𝑻𝑹𝑶𝑵𝑺
𝟐. 𝑴𝑬𝑳𝑻𝑰𝑵𝑮 𝑷𝑶𝑰𝑵𝑻 ∝ 𝑵𝑼𝑴𝑩𝑬𝑹 𝑶𝑭 𝑼𝑵𝑷𝑨𝑰𝑹𝑬𝑫 𝑬𝑳𝑬𝑪𝑻𝑹𝑶𝑵𝑺
𝟑. 𝑩𝑶𝑰𝑳𝑰𝑵𝑮 𝑷𝑶𝑰𝑵𝑻 ∝ 𝑵𝑼𝑴𝑩𝑬𝑹 𝑶𝑭 𝑼𝑵𝑷𝑨𝑰𝑹𝑬𝑫 𝑬𝑳𝑬𝑪𝑻𝑹𝑶𝑵𝑺

1.Transition metals have high enthalpy of atomization.

A large number of unpaired electrons take part in bonding, so they have very strong metallic bonds and
hence high enthalpy of atomization.
2.Transition metals have high melting and boiling points
A large number of unpaired electrons take part in bonding, so they have very strong metallic bonds and
hence high melting & boiling point.
3.Which of the 3d series element has highest melting and boiling point? Why?
Chromium, because of large number of unpaired electrons in it take part in bonding so it has very strong
metallic bonds and hence high melting & boiling point.
4. Why Mn and Tc shows anomalous behavior in enthalpy of atomization, melting and boiling
points?
Mn and Tc are of 3d and 4d transition series which have exceptionally low enthalpy of atomization, low
melting and boiling points due to stable d5 configuration where electrons are less delocalized &
interaction is comparatively weaker.
 5. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest.
In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of zinc, while in all
other metals of the 3d series, electrons from the d-orbitals are always involved in the formation of
metallic bonds.
6. Fe has higher melting point than Cu.
This is because Fe (4s23d6 ) has four unpaired electrons in 3d-subshell. While Cu (4s13d10 ) only
one unpaired electron in 4s shell. Hence metallic bonding is stronger in Fe than
7. Zn, Cd & Hg have low boiling points and Hg is liquid.
They have full filled (n-1) d-orbitals and no electrons from d-orbitals are taking part in metallic bonding so
they have weak metallic bonding. Due to larger atomic size Hg is liquid
ATOMIC SIZE

ALONG PERIOD
1. FROM LEFT TO RIGHT, atomic size DECREASES due to increase in effective nuclear charge
2. At RIGHT END, atomic size INCREASES due to increase in inter electronic repulsion
3. At MIDDLE, remains same due to balancing of increasing effective nuclear charge by
increasing inter electronic repulsion.
DOWN A GROUP
4. FROM TOP TO BOTTOM, atomic size INCREASES due to increase in shell numbers
5. At BOTTOM END, atomic size DECREASES due to increase in poor shielding effect.
(Actinoid contraction)
6. At MIDDLE, remains same due to balancing of increasing shell number by increasing poor
shielding effect (Lanthanoid contraction)
1. Atomic size Co and Ni are similar, Why?
It is because of inter electronic repulsion balances increasing the effective nuclear charge
2. Atomic size of Fe is bigger than Co and Ni, why?
It is because of effective nuclear charge of Fe is lesser than that of Co and Ni
3. Atomic size of Cu & Zn is bigger than that of Co and Ni, Why?
It is because of inter electronic repulsion dominates effective nuclear charge in Cu & Zn, therefore its
size becomes bigger than Co and Ni Mn > Fe > Co = Ni < Cu < Zn
4. Ti is smaller than Zr Why?
Because of increasing shell number from Ti to Zr
5. Rf is smaller than Hf Why?
Because of poorer shielding effect of 5f subshell in Rf than that of 4f subshell of 4f in Hf
6. Zr and Hf are similar in size why?
Because increasing the poor shielding effect balances effects by increasing the number of shells
Ti (3d) < Zr(4d) = Hf (5d) > Rf
 IONIZATION ENTHALPY
1.The ionization enthalpies (first and second) in the first series of the transition elements are irregular
Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different
3d- configurations (e.g., d0, d5, d10 are exceptionally stable).
OXIDATION STATES
1. Transition elements have variable oxidation states
Due to very small energy difference between (n-1)d & ns sub-shell electrons from both the sub-shell
take part in bonding
2. What is the common oxidation state of 3d series elements? +2
3. Which of the 3d series element is not showing +2 oxidation state, Why?
Scandium, because by losing one electron 3d and 2 electrons from 4s, they get extra stability (attain
noble gas configuration)
4. Which of the 3d series element is showing +1 oxidation state? Copper
5. d block elements exhibit a large number of oxidation state than f block elements.
The difference in the energy of (n-1)d orbital and ns orbital is very small and thus both sub- shells are
used for bond formation whereas in f block elements (n-2)f orbitals lie underneath and hence are not
available for bond formation
5. Which of the 3d series of the transition metals exhibits the largest number of oxidation states
and why?
Mn show largest number oxidation state. Its electronic configuration is 3d54s2. The energy of 3d and 4s
are close. So, it has maximum number of electrons to lose or share and it shows maximum number of
oxidation states from +2 to +7
6. The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
The oxide of transition metals in lower oxidation states is generally basic because they have partially or
fully filled orbitals which donates electrons, while those in the higher oxidation states are acidic or
amphoteric because most of the orbitals of them are vacant and accept pair of electrons.
.Eg. MnO (basic), Mn3O4 (amphoteric), Mn2O7 (acidic).
7. The lowest oxide of transition metal is ionic while the highest is covalent.
The oxide of transition metals in lower oxidation states is generally ionic due to bigger size of metal ions
while those in the higher oxidation states are covalent due to smaller size of metal ions
.Eg. MnO (ionic), Mn2O7(covalent).
8. Transition metals exhibit higher oxidation states in oxides and fluorides
Because of small size and high electronegativity oxygen or fluorine can oxidize the metal to its highest
oxidation state
9. Transition metals exhibit highest oxidation states in oxides not in fluorides
Because, oxygen is able to form pπ-dπ multiple bond with metal ion whereas fluorine is not able to form
multiple bonds with metal ions,,,,,, Eg: Mn2O7
10. Oxidizing power increases in the series VO2 + < Cr2O72– < MnO4–1
This is due to the decreasing stability of the higher oxidation states which are reduced lower states.
-VE HYDRATION ENTHALPY
1. Transition metals have more -ve enthalpy of hydration.
Transition metal ions are smaller and have higher charge, therefore have high enthalpy of hydration.
DISPROPORTIONATION
1. What is meant by disproportionation? Give two examples.
Those reactions in which same substance undergoes oxidation as well as reduction are called
disproportionation reactions.
e.g. 2Cu+(aq) → Cu2+(aq)+Cu(s)

MnO4 2- + 4H+ → MnO4- + MnO2 + 2H2O

2. Explain why Cu+ ion is not stable in aqueous solutions?
Its because of MORE +ve E0value of Cu+ to Cu and MORE -ve hydration enthalpy of Cu2+ than Cu+.
Thus, Cu+ ion is unstable and disproportionate into Cu and Cu2+
2Cu+(aq) → Cu2+(aq)+Cu(s)
ELECTRODE POTENTIAL OR REDUCTION POTENTIAL

It is observed that, E0(M2+/M) value becoming less negative from left to right as sum of 1st ionization
enthalpy and 2nd ionization enthalpy and enthalpy of atomization increases from left to right.
Only copper shows E0(M2+/M) value is positive(+0.34V), This unique behavior of copper is due
to negative hydration enthalpy is much lower than sum of 1st, 2nd ionization enthalpy and
enthalpy of atomization. This is why, copper does not release H2 gas from diluted acids
However Zinc and manganese show some anomalous results from the general trends due to
their extra stable configurations in M2+ excited state.
The E0(M2+/M) value for Zn is more negative (-0.76V).
It is because of Zn2+ configuration(3d10) is more stable than configuration of Zn (4s2,3d10)
The E0(M2+/M) value for Mn is more negative (-1.18V).
It is because of Mn2+ configuration(3d5) is more stable than configuration of Mn(4s2,3d5)
Oxidizing agents
1. Mn 3+ is strong oxidizing agent because it is spontaneously reduced to stable Mn2+ ion which is half
filled d5 configuration and also its E0Mn3+/Mn2+ value is less negative.
2. Ce4+ is a strong oxidizing agent because it is spontaneously reduced to stable Ce 3+ ion which is
common oxidation state of f- block elements and also its E0Ce3+/Ce2+ value is more negative.
Reducing agents
1. Cr 2+ is strong reducing agent because it is spontaneously oxidized to stable Cr 3+ ion which is half
filled t2g configuration and also its E0Cr3+/Cr2+ value is more negative.
2. Mn is strong reducing agent because it is spontaneously oxidized to stable Mn 2+ ion which is half
filled d5 configuration and also its E0Mn2+/Mn value is more negative.
3. Zn is strong reducing agent because it is spontaneously oxidized to stable Zn 2+ ion which is half
filled d10 configuration and also its E0Zn2+/Mn value is more negative.
4. Fe 2+ is strong reducing agent because it is spontaneously oxidized to stable Fe 3+ ion which is half
filled d5 configuration and also its E0Fe3+/Fe2+ value is more negative.
5. Sc 2+ is strong reducing agent because it is spontaneously oxidized to stable Sc 3+ ion which is noble
gas configuration and also its E0Sc3+/Sc2+ value is more negative.
6. Ni is strong oxidizing agent because it is spontaneously reduced to stable Ni2+ion in aqueous state
because negative hydration enthalpy is much higher than sum of 1st, 2nd ionization enthalpy and
enthalpy ofatomization also its E0Ni2+/Ni value is less negative.
7. Eu2+ is a strong reducing agent because it is spontaneously oxidized to stable Eu 3+ ion which is
common oxidation state of f block elements and also its E0Eu3+/Eu2+ value is more negative.
MAGNETIC PROPERTY
1. Transition metals and many of their compounds show paramagnetic behavior.
Because they have unpaired electrons in (n-1) d orbitals
2. Sc3+ or Cr3+ which of these exhibits paramagnetism?
Sc3+ =[Ar] 4s03d0; it has no unpaired electron so it is diamagnetic
Cr3+ =[Ar] 4s03d3; it has 3 unpaired electron so it is paramagnetic
3. Calculate the “spin only” magnetic moment of M2+(aq) ion (Z= 27).
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
CATALYTIC PROPERTY
1. Transition metals show catalytic properties
Because they have variable oxidation states and provide large surface area with porous structure.
COLOUR OF IONS
1. Transition metals and their salts are generally colored
Because they have unpaired electrons and hence d-d electron transition takes place when they
absorb radiations from visible region and transmit complementary colors.
2. [Ti(H2O)6]+ is colored while [Sc (H2O)6]+3 is colorless.
The oxidation state of Ti in [Ti(H2O)6]+3 is +3 and its configuration is is[Ar]3d1 it has1 unpaired
electron so it undergo d-d transition while the oxidation state of Sc in [Sc (H2O)6]+3 is +3 and its
configuration is is[Ar]3d0 , it has no unpaired electron, therefore it does not undergo d-d transition
COMPLEX FORMATION
1. Transition metals form coordination compounds
Because 1.) they have large number of vacant d orbitals so they can accept electron pairs from ligands
2.) they have high ionic charge 3.) small size.
3. K2[PtCl6]is well known compound where as the corresponding Ni compound is not known.
The oxidation state of Pt in this complex is +4 which is stable for Pt. The+4 oxidation state
for Ni is very difficult to achieve because the sum of first four ionization energies is very high .Hence,
the corresponding Ni(IV) compound is not known( In the case of Ni, Ni(II) is stable)
4. Cobalt(II) is stable in aqueous solution but in presence of complexing agents it gets oxidized.
Oxidation state changes from +2 to +3 because in presence of ligands d-orbitals split up into t2g
and eg having the stable configuration t2g 6 eg0
ALLOY FORMATION
1. Transition metals form alloys
They have comparable atomic size and hence can be mixed uniformly.
2. Name an important alloy, which contains some of the lanthanoid metals. Mention its uses.
An important alloy containing lanthanoid metals is misch metal, which contains 95% to produce bullets,
shells and lighter flint
FORMATION OF INTERSTITIAL COMPOUNDS
1. Transition metals form interstitial compounds ? Why are such compounds well known for
transition metal?
Because small atoms like H, C, N etc can be entrapped in their metallic crystals. These compounds are
well known for transition metals because size of C, N, O, and B is similar to size of interstitial voids of
transition metal
POTASSIUM DICHROMATE:
Preparation: Conversion of chromite ore to sodium chromate.
4FeCr2O4+8Na2CO3+7O2 → 8Na2CrO4+2Fe2O3+8CO2
(YELLOW)
Conversion of sodium chromate to sodium dichromate
2Na2CrO4 +H2SO4→ Na2Cr2O7 + Na2SO4 + H2O
(ORANGE)
Conversion of sodium dichromate to potassium dichromate
Na2Cr2O7 +2KCl → K2Cr2O7 +2NaCl
POTASSIUM PERMANGNATE
Preparation: Conversion of pyrolusite ore to potassium manganate.
2MnO 2 + 4 KOH+O2 → 2 K2MnO4 +2H2O
(GREEN)
Conversion of potassium manganate to potassium permanganate
K2MnO4 + 2H2SO4 → 2KMnO4 + MnO2 + 2H2O + 2 K2SO4
(PURPLE)
1. Complete the reaction : MnO4- + 4H+ +3𝑒 →
MnO4- + 4H+ +3𝑒 → MnO2 + 2H2O
2. What is the effect of pH on dichromate ion solution?
Cr2O72- + H2O → 2CrO42- +2H+ Dichromate ion is orange in acidic solution (pH<7) and turns yellow
in basic solution. It is due to inter conversion of dichromate ion to chromate ion
REDOX REACTION BALANCING
Acidic medium Basic medium
Reduction: Cr2O72- → 2Cr3+. ( difference 6) Reduction:
MnO4- → Mn2+ ( difference 5) MnO4- → MnO2 (difference 3)
Oxidation: Oxidation:
→ I- →. IO3- ( difference 6)
Fe2+. Fe3+ ( difference 1)
Sn2+ → Sn4+ ( difference 2) S2O3-2 →. 2SO42- ( difference 8)
2I- → I2 ( difference 2)
S2- → S ( difference 2)
NO2- → NO3- ( difference 2)
SO3-2 → SO4-2. ( difference 2)
C2O42- → CO2 ( difference 2)
Oxidizing properties of Permanganate ion
(i) MnO4 - à Mn2+ (5) (ii) MnO4 - à Mn2+ (5)
S2- àS (2) Fe2+ à Fe3+ (1)
2MnO4 - + 5 S2- + 16 H+ à 2 Mn2++ 5 S + 8 H2O MnO4 - + 5 Fe2+ + 8H+ à Mn2++ 5 Fe3+ + 4 H2O
(iii) MnO4 - à Mn2+ (5) (iv) MnO4 - à Mn2+ (5)
Sn2+ à Sn4+ (2) 2I-à I2 (2)
- 2+ + 2+ 4+
2MnO4 + 5Sn + 16H à 2 Mn + 5 Sn + 8 H2O
MnO4 - + 10 I- + 16H+ à Mn2++ 5I2+ 8 H2O
(v) MnO4 - à Mn2+ (5) (vi) MnO4 - à Mn2+ (5)
SO32- à SO42- (2) NO2- à NO3- (2)
2MnO4 - +5 SO32-+ 6 H+ à 2 Mn2++ 5SO42-+3H2O 2MnO4 - +5NO2-+ 6 H+ à 2 Mn2++ 5NO3-+3 H2O
(vii) MnO4 - à MnO2 (3) (1) (viii) MnO4 - à MnO2 (3)
I- à IO3- (6) (2) S2O32- à 2SO42- (8)

2MnO4 - + I- + H2O à 2MnO2+ IO3- + 2OH- 8MnO4 - + 3S2O32- +H2O à 8MnO2+6SO42- + 2OH-

Oxidizing properties of Dichromate ion

(i) Cr2O72- à 2Cr3+. (6) (3) (ii) Cr2O72- à 2Cr3+. (6)

C2O42- à 2CO2 (2) (1) Fe2+ à Fe3+ (1)

3+
Cr2O72- +2C2O42- + 14H+ à 2Cr +2CO2 +7 H2O Cr2O72-+ 6 Fe2+ +14H+ à 2Cr3++6 Fe3+ + 7H2O

(iii) Cr2O72- à 2Cr3+. (6) (3) (iv) Cr2O72- à 2Cr3+. (6) (3)

Sn2+ à Sn4+ (2) (1) 2I-à I2 (2). (1)

Cr2O7 +3Sn + 14H à
2- 2+ + 2Cr3+ 4+
+3 Sn + 7 H2O Cr2O72- + 6 I- + 14H+ à 2Cr3++ 3I2+7H2O

(v) Cr2O72- à 2Cr3+. (6) (3) (vi) Cr2O72- à 2Cr3+. (6) (3)

SO32- à SO42- (2) (1) NO2- à NO3- (2) (1)

Cr2O72- +3SO32-+14 H+ à 2Cr3+.+3SO42-+7H2O Cr2O72- +3NO2-+14H+ à 2Cr3++ 3NO3-+7 H2O
F -BLOCK ELEMENTS
1. LANTHANOIDS:
1. The14 elements after Lanthanum having atomic number 58 to 71 are collectively known as
Lanthanoids.
2. The general electronic configuration of these elements is [Xe]4f1-14,5d0-1.6s2
3. Most common oxidation state of these elements is +3, but Ce shows+4, Eu +2, because they
acquire stable configuration.
4. The size of Lanthanoids decreases from expected value due to poor shielding of 4f
electrons. It is known as lanthanoid contraction.
5. It has the following consequences.
a) Zr and Hf have almost same size
b) Separation of lanthanoids in pure state becomes difficult.
c) La(OH)3 is most basic while Lu(OH)3 is the least basic.
d) 2nd and corresponding third row transition elements have similar properties
 6.Oxidation states ....... Common oxidation state is +3
7. Eu2+ is a strong reducing agent. WHY?
It can be converted into the most common oxidation state Eu3+
8. Ce is the only lanthanoids exhibits +4 oxidation state. WHY?
Ce4+ has noble gas configuration [Xe]
2. ACTINOIDS:
1. The14 elements after Actinium having atomic number 90 to 113 are collectively known as Actinoids.
2. The general electronic configuration of these elements is[Rn]5f1-14,6d0-1,7s2.
3. The size of actinoids decreases from expected value due to poor shielding of 5f electrons. It is
known as actinoid contraction.
4. Actinoid contraction is greater than lanthanoid contraction since shielding effect of 5f
electrons is poorer than that of 4f electrons

Comparison of Lanthanoids and Actinoids

Properties Lanthanoids Actinides
Electronic [Xe]4f1-14,5d0-1,6s2 [Rn]5f1-14,6d0-1,7s2.
configuration
Atomic/ionic Size decreases from La to Lu, and size Size decreases from Ac to Lw, and size
sizes is more than actinides. is smaller than lanthanoids due to poorer
shielding of 5f electrons
Oxidation Common oxidation is +3 where other Common oxidation is +3 where other
state oxidation states are +2, +4 . It is due to oxidation states are +2, +4,+5 and+7due
a large energy gap between 4f, 5d and to due to small energy difference between
6s orbitals. 5f, 6d and 7s orbitals
Chemical The earlier member quite reactive but The actinides highly reactive, especially
reactivity with increasing atomic number, they in finely divided state.
behave like Al
Complex Fewer tendencies to form complex due More tendency to form complex
formation less charge density. due to high charge density.

YEAR 2024
1. The product of oxidation of SO32- with MnO4-, in acidic medium is :
(a) SO2 (b) SO42- (c) S2- (d) S2O32-
2. When MnO2 is fused with KOH in air, it gives
(a) KMnO4 (b) K2MnO4 (c) Mn2O7 (d) Mn2O3
3. The correct order for the increasing oxidizing power in 3d series of transition elements is :
(a) MnO4- < Cr2O72- < VO2+ (b) Cr2O72- < VO2+ < MnO4-
(c) VO2+ < Cr2O72- < MnO4- (d) VO2+ < MnO4- < Cr2O72-
4. What is lanthanoid contraction? Actinoid contraction is greater from element to element than
lanthanoid contraction. Why?
5.(i)Why do transition metals have high enthalpy of atomization?
(ii) Which element of 3d-series has lowest enthalpy of atomization?
COORDINATION
COMPOUNDS
 Introduction Compounds made up of simpler compounds are called molecular/ addition
compound. These are of two types –
(i) Double salts (ii) Complex compounds or coordination compounds.
Example CoCl3 and NH3 yields CoCl3 .(NH3)6 which is a complex compounds.
K2SO4 and Al (SO4)3 giveS K2SO4.Al2(SO4)3 (Potash Alum) is a double salt.
Difference i) Double salts dissociate into simple ions completely when dissolved in water.
between a Such compounds will give test for each cations and anions
double salt and K2SO4.Al2 (SO4)3 → 2K+(aq) + 2 Al3+ (aq) + 4 SO4 2-

a complex: ii) Complex compounds such as dissociate into a complex ion and a counter ions.
Such compounds will not give test for ions such as ions present in complex

K4[Fe(CN)6]4 (aq) → 4K+(aq) + [Fe(CN)6]4 4- (aq)

CoCl3· (NH3)6 (aq) → 3 Cl─ + [Co(NH3)6]3+ (aq)

Some important 1. Coordination entity: It constitutes a central metal (atom or ion) linked with a
terms related to fixed number of ions or molecules ligands.
coordination For example, [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4–, [Co(NH3)6]3+are
compounds coordination entity.
2. Ligands The atoms, ions or molecules which donate a pair of electrons to the metal atom to
form a coordinate bond, are called ligands.
For example, NH3, H2O, Cl─, CN─, CO etc.
Depending on the number of donor atoms, a ligand can be of following types:
i) Unidentate or Monodentale ligand
ii) Didentate or Bidentate ligand
iii) Polydentate or Multidentate ligand
iv) Chelate ligand
v) Ambidentate ligand
Unidentate ligand It contains only one donor atom. For example, NH3, H2O, Cl─, CN─, CO

Didentate or It contains two donor atom, For example, Ethylenediamine (H2NCH2CH2NH2) (en),
Bidentate ligand: Oxalte (C2O42-)
Polydentate or It contains more than two donor atom, for example (EDTA4-
Multidentate (Ethylenediaminetetraacetate), is an important hexadentate ligand which can bind
ligand: through two nitrogen and four oxygen donor atoms to a central metal ion
Chelate ligand: A di- or polydentate ligand is said to be a chelate ligand when it uses its two or more
donor atoms to bind a single metal ion.
A complex compound in which the donor atoms are attached to the metal so that the
metal becomes a part of the heterocyclic ring, is called chelate complex.
Ambidentate An unidentate ligand donate electron through different donor atoms.
ligand For example, NO2- , CN- SCN- are ambidentate ligands
In a complex, NO2- ligand is bound to the metal in two different ways.
(i) ligand is bound through oxygen (–ONO), and,
(ii) ligand is bound through nitrogen (–NO2).
In a complex, CN- ligand is bound to the metal in two different ways.
(i) ligand is bound through carbon (-CN), and,
(ii) ligand is bound through nitrogen (–NC).
Out of [Co(en)3]3+ or [Co(F6)]3- , which is more stable complex ?
[Co(en)3]3+ is more stable complex since ethylenedimine form ring structure which increase stability of
the complex
Coordination Total number denticity by ligands directly bonded to the central metal atom/ion is
number (CN): known as the coordination number of that metal ion/atom.

Coordination number = Denticity x number of ligands

[ Ag(NH3)2]2+ Coordination number = 1 x 2= 2

[Zn(CN)4]2─ Coordination number = 1 x4= 4
[Ni(NH3)6]2+ Coordination number = 1 x 6=6
[Fe(C2O4)3]3─ Coordination number = 3 x 2= 6

[Fe(en)3]3+ Coordination number = 3 x 2= 6

[CoCl2)(en)2]+ Coordination number = (1x2) + (2x2) = 6

Homoleptic Complexes in which a metal is bound to only one kind of ligands. e.g[Co(NH3)6]3+
complexes is known as homoleptic.

Heteroleptic Complexes in which a metal is bound to more than one kind of ligands,
complexes e.g., [Co(NH3)4Cl2]+, is known as heteroleptic.
Charge on a The charge carried by a metal ion can be calculated by x,
central metal [Fe(CN)6]3–
ion: Let charge on Fe be x, charge on 6 CN─ = [6 (─1) ]= ─ 6 & sum of the charges are -3
x + (– 6) = − 3 x= 6 – 3 = +3 ie, metal is Fe3+
Werner’s The main postulates of Werner’s theory (proposed by Werner in 1898), are as
theory of follows:
coordination a) In coordination compounds metals show two types of linkages (valancies),
compounds primary and secondary.
b) The primary valancies are normally ionisable and are satisfied by negative ions.
c) The secondary valancies are non-ionisable which are satisfied by negative ions
 or neutral molecules. The secondary valency is equal to the coordination number
and is fixed for a metal.
d) The ions/groups bound by the secondary linkages to the metal have characteristic
spatial arrangements corresponding to different coordination numbers.
Werner further postulated that the most common geometrical shapes of
coordination compounds are octahedral, tetrahedral and square planar.
IUPAC NAMINGS
LIGANDS NAME CHARGE DENTICITY STRENGTH
NH3 Ammine 0 1 SFL
H2 O Aqua 0 1 WFL
CO Carbonyl 0 1 SFL
NO Nitrosyl 0 1 WFL
PPh3 Triphenyl phosphine 0 1 WFL
en Ethylene diamine 0 2 SFL
CN- Cyano -1 1 SFL
NC- Isocyano -1 1 SFL
F- Fluorido -1 1 WFL
Cl- Chlorido -1 1 WFL
Br- Bromido -1 1 WFL
I- Iodido -1 1 WFL
OH- Hydroxido -1 1 WFL
NO2- Nitritio-N -1 1 SFL
ONO- Nitrito-O -1 1 SFL
SCN- Thiocyanato -1 1 SFL
NCS- Isothiocyanato -1 1 WFL
SO42- Sulphato -2 1 WFL
C2O42- oxalato -2 2 WFL
CO32- Carbonato -2 1 WFL
EDTA4- Ethylenediamine tetraacetato -4 6 SFL

LMC NAMING [ L = LIGAND, M= METAL , C= COUNTER ION]

1. [Cr(NH3)3(H2O)3]Cl3 : triamminetriaquachromium(III) chloride
2. [Co(en)3]2(SO4)3 : tris-(ethylene diammine)cobalt(III) sulphate.
3. [CoCl2(en)2]Cl : Dichlorido bis-(ethylene diamine)cobalt(III) chloride

LM NAMING
1. [Ag(NH3)2][Ag(CN)2] : diamminesilver(I) dicyanoargentate(I)
 2. [NiCl2(PPh3)2] : dichlorobis(triphenylphosphine) nickel (II).
3. [Ni(CO)4] : Nickel tetracarbonyl
4. [[Co (en)3]3+ : Tris-(ethylene diamine)cobalt(III)
CLMate NAMING. [C= COUNTER ION, L = LIGAND, Mate= METALLATE.
1. Hg[Co(SCN)4] : Mercury tetrathiocyanatocobaltate(III)
2. K4[Fe(CN)6] :Potassium hexacyano ferrate(II)
3. K2[Ni Cl4] :Potassium tetrachloride nickelate (II)

LMate NAMING
1. [Co(NH3)5Br]2− : Pentaammine bromide cobaltate (III)
2. [Zn(OH)4]2- : Tetrahydroxido zincate(II)
Write the molecular formulas of the following coordination compounds:
(i) Potassium tetrahydroxidoozincate(II) : K2[Zn (OH)4]
(ii) Diamminechloridonitrito-N-platinum(II) : [Pt(NH3)2Cl(NO2)]
(iii) Tetraammineaquachloridocobalt(III) chloride : [Co(NH3)4(H2O)Cl]
(iv) Potassium trioxalatoaluminate(III) : K3[Al(C2O4)3]
Isomerism In Coordination Compounds
Stereoisomerism Stereoisomers have the same chemical formula and chemical bonds but they have
different special arrangements. They are further classified as follows:
1. Geometrical isomerism
2. Optical isomerism
(i) Geometrical It arises in heteroleptic coordination complexes due to different possible geometric
isomerism arrangements of the ligands.
When similar ligands are adjacent to each other, they form cis isomer and when they
are opposite to each other a trans isomer is formed.
Geometrical isomerism is very common in complexes with coordination number 4
and 6.
coordination
number 4
Square Planar
Complexes :-

coordination no:4Tetrahedral complexes do not show geometrical isomerism because the relative
tetrahedral positions of the unidentate ligands attached to the central metal atom are the same with
complex respect to each other.
coordination Cis – Trans : facial (fac) o and meridional (mer)
number 6 isomer
octahedral
Complexes :-

(ii) Optical It arises due to plane of unsymmetry in the complex.

isomerism:
Optical isomers or enantiomers are the mirror images that cannot be superimposed on
one another. The molecules or ions that cannot be superimposed are called chiral.

A chiral molecule is an optically active and has the property of rotating the plane of
polarized light either to its left (called laevo) or to its right (called dextro).

If polarized light remains unrotated, the compound is optically inactive or racemic

(i.e., mixture of 50% laevo and 50% dextro).
Optical isomerism is common in octahedral complexes involving didentate ligands.

In a coordination compound of the type [CoCl2(en)2]2+ only the cis-isomer shows

optical activity due to plane of unsymmetry in the complex.
Structural Same chemical formula but possess different types of bonds , differ in the extent of
isomerism ionization, position of ligands, etc. These are further classified as follows:
Linkage isomerism , Ionisation isomerism , Coordination isomerism and
Solvate isomerism
Linkage It arises in the coordination compounds containing ambidentate ligands.
isomerism NO2- ↔ 𝑂𝑁𝑂- [Co(NH3)(NO2)]Cl2 and [Co(NH3)(ONO)]Cl2
CN- ↔ NC- [Co(NH3)(CN)]Cl2 and [Co(NH3)(NC)]Cl2
SCN- ↔ NCS- [Co(NH3)(SCN)]Cl2 and [Co(NH3)(NCS)]Cl2
Ionisation It arises due to interchanging of counter ion and ligand which results two isomers of
isomerism complexes having different charge
[Co(NH3)5SO4]Br (red complex) &[Co(NH3)5 Br] SO4 (violet complex)
Coordination It arises due to interchange of ligands between cationic and anionic species of
isomerism different metal ions and the ligands present in a complex.
For example, [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
Solvate It is known as hydrate isomerism when water is the solvent or ligand
isomerism It arises due to interchanging of counter ion and ligand H2O which results two isomers
of complexes having different charge. Thus it is also called ionization isomerism
For example, [Cr(H2O)6]Cl3 (violet) and , [Cr(H2O)5Cl]Cl2.H2O (grey green)
Bonding in coordination compounds
Valency Bond Empty Metal orbitals hybridise to form equal number of hybrid orbitals.
Theory The hybrid metal orbitals then overlap with those ligand orbitals and form 𝜎bonds
The resulting complex will be diamagnetic if all the electrons are paired.
If unpaired electrons are present then the complex will be paramagnetic.
Coordination Nature of Type of Distribution of hybrid Type of Complex
number ligands hybridization orbitals in space
4 Weak field sp3 Tetrahedral Outer orbital/ high spin
4 Strong field dsp2 Square planar Inner orbital/ low spin
5 Weak field sp3d Trigonal bipyramidal Outer orbital/ high spin
6 Weak field sp3d2 Octahedral Outer orbital/ high spin
6 Strong field d2sp3 Octahedral Inner orbital/ low spin
NH3 is strong field ligand however it act as weak field ligand in complex with Nickel.
EXAMPLE 1:
[Co(NH3)6]3+. (Given: Atomic number of Co=27). IUPAC name (LM) is Hexaammine Cobalt(III).
Coordination number is 6 ( number vacant orbitals to be hybridized is 6)
NH3 is strong field ligand, therefore pairing electrons.
Co3+ = 27-18-3=6 3d6
↿⇂ ↿⇂ ↿⇂
3d 4s 4p

Hybridization is d2sp3 , Octahedral geometry, low spin complex and diamagnetic

EXAMPLE 2:
[Ni(NH3)6]3+. (Given: Atomic number of Ni=28). IUPAC name (LM) is Hexaammine Nickel(II).
Coordination number is 6 (number vacant orbitals to be hybridized is 6)
NH3 is weak field ligand in complex with Nickel, therefore it does not pair electrons.
Ni2+ = 28-18-2=8 3d8
↿⇂ ↿⇂ ↿⇂ ↿ ↿
3d 4s 4p 4d

Hybridization is sp3d2 , Octahedral geometry, high spin complex and paramagnetic

C2O4 2-is weak field ligand however it act as strong field ligand in complex with Cobalt.
EXAMPLE 3:
[Fe(C2O4 )3]3-. (Given: Atomic number of Fe=26). IUPAC name (LMate) is Trioxalato Ferrate (III).
Coordination number is 6 (number vacant orbitals to be hybridized is 6)
C2O4 2 is weak field ligand, therefore it does not pair electrons.
Fe3+ = 26-18-3=5 3d5
↿ ↿ ↿ ↿ ↿
3d 4s 4p 4d

Hybridization is sp3d2 , Octahedral geometry, high spin complex and paramagnetic

EXAMPLE 4:
[Co((C2O4 )3)3]3-. (Given: Atomic number of Ni=27. IUPAC name (LMate) Trioxalato Cobaltate(III).
Coordination number is 6 (number vacant orbitals to be hybridized is 6)
C2O4 2 is strong field ligand in complex with Cobalt, therefore electrons get paired.
Co3+ = 27-18-3=6 3d6
↿⇂ ↿⇂ ↿⇂
3d 4s 4p

Hybridization is d2sp3 , Octahedral geometry, low spin complex and diamagnetic.

Every ligands are weak field in complex with Chromium.
EXAMPLE 5:
[Cr(C2O4 )3]3-(Given: Atomic number of Cr=24). IUPAC name (LMate) is TrioxalatoChromate (III).
Coordination number is 6 (number vacant orbitals to be hybridized is 6)
C2O4 2 is weak field ligand, therefore it does not pair electrons.
Cr3+ = 24-18-3=3 3d3
↿ ↿ ↿
3d 4s 4p

Hybridization is d2sp3 , Octahedral geometry, high spin complex and paramagnetic

EXAMPLE 6:
[Cr(H2O )6]3+(Given: Atomic number of Cr=24). IUPAC name (LM) is Hexaaqua Chromium(III).
Coordination number is 6 (number vacant orbitals to be hybridized is 6)
H2O is weak field ligand, therefore it does not pair electrons.
Cr3+ = 24-18-3=3 3d3
↿ ↿ ↿
3d 4s 4p

Hybridization is d2sp3 , Octahedral geometry, high spin complex and paramagnetic

Central metal atom does not have charge in metal carbonyl complexes, which consequent to
occupied 4s orbitals.
EXAMPLE 7:
[Ni(CO)4]. (At.no. of Ni = 28) IUPAC name (LM) is Tetracarbonyl Nickel.
Coordination number is 4 ( number vacant orbitals to be hybridized is 4)
CO is strong field ligand, pairing electrons.
Ni does not have charge in carbonyl complexes.
Ni= 28-18=10 3d8 4s2
↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂
3d 4s 4p 4d

In order to make s orbital is vacant, electrons from 4s is shifted to vacant 3d

↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂
3d 4s 4p 4d

Hybridization is sp3, tetrahedral geometry low spin and diamagnetic.

EXAMPLE 8:
[Fe(CO)6]. (At.no. of Ni = 28) IUPAC name (LM) is Pentacarbonyl Iron.
Coordination number is 5 ( number vacant orbitals to be hybridized is 5)
CO is strong field ligand, pairing electrons.
Fe does not have charge in carbonyl complexes.
Fe= 26-18=8 3d6 4s2
↿⇂ ↿⇂ ↿⇂ ↿⇂
3d 4s 4p 4d

In order to make s orbital is vacant, electrons from 4s is shifted to vacant 3d

↿⇂ ↿⇂ ↿⇂ ↿⇂
3d 4s 4p 4d

Hybridization is dsp3, pentagonal bipyramidal geometry low spin and diamagnetic.

EXAMPLE 9:
[Ni(CN)4]2– (Atomic No. of Ni = 28) IUPAC name (LMate) is Tetracyanao Nickelate(II).
Coordination number is 4 ( number vacant orbitals to be hybridized is 4)
CN- is strong field ligand, pairing electrons.
NI2+ = 28-18-2=8 3d8
↿⇂ ↿⇂ ↿⇂ ↿⇂
3d 4s 4p

Hybridization is dsp2 , square planar geometry low spin and diamagnetic.

Crystal Field According to crystal field theory, the bonding between a central metal ion and a

Theory: ligand is purely electrostatic.

 In an octahedral field s-orbital (because of no degeneracy) and p-orbitals (because
of their shape) are not affected, but the degeneracy of d-orbitals is lifted because all
d-orbitals are not spatially equivalent.
The valence d electrons of metal are repelled by the negatively charge ligands,
so that they occupy those d-orbitals which have their lobes away from the
direction of ligands.
The effect of ligands is particularly marked on d-electrons and it depends on the
number of electrons.
Crystal Field The five d-orbitals can be classified into two sets as follows:
Splitting of Three of d-orbitals i.e., dxy, dyz and dzx which are oriented in between the co-
d-orbitals. ordinate axes are called t2g -orbitals.

The other two d-orbitals i.e., dx2-y2 and dz2 oriented along the axes are called eg
orbitals.
In the case of free metal ions, all the five d-orbitals degenerate, i.e., they have equal
energy. But due to presence of negative charge of ligands these five d-orbitals
splitted into eg set and t2g set having different energy.
Energy gap between eg set and t2g is called crystal field splitting energy ∆

The ligands which cause greater crystal field splitting are termed as strong ligands
while those causing lesser crystal field splitting are weak ligands.
What is spectrochemical series ?
Arrangements of ligands in the decreasing order of crystal field splitting energy
Strong The ligands which cause greater crystal field splitting are termed as strong ligands
ligands ∆>𝑷 CO> CN-> en > NH3 >EDTA > NCS-
Weak ligands The ligands which cause lesser crystal field splitting are termed as weak ligands
∆<𝑷 H2O> C2O4-2> OH- > F- > S2- > Cl-> SCN- > Br- > I-

Crystal Field
Splitting in
Octahedral
Complexes

In octahedral complexes, eg set shows higher energy than t2g set. Why?
It is because of six ligands approach the central metal ion along the co-ordinate axes dx2-y2 and dz2
orbitals. Consequently, the eg set of orbitals has higher energy than t2g of orbitals.
Crystal Field
Splitting in
Tetrahedral
Complexes

In tetrahedral complexes, t2g set shows higher energy than eg set. Why?

In tetrahedral complex, four ligands may be imagined to occupy the alternate corners of the cube and the
metal ion at the centre of the cube. In this situation, the t2g set of orbitals (dxy, dyz and dzx) lie relatively
nearer to the approaching ligands and therefore t2g set of d-orbitals have higher energy than , eg set of
orbitals
Splitting energy in tetrahedral complexes are relatively lesser than that of octahedral complexes.
Why?
This is because of tetrahedral complexes contain only 4 ligands and there is no direct interaction between
𝟒
ligand and d-electrons ∆𝒕 = 𝟗 ∆𝒐

Colour of Colour associated with the transition metal complexes is due to d-d transition of
transition metal electrons between t2g and eg. Transition metal complexes having unpaired electron
complexes: absorb some selected wavelengths of visible light and appear coloured.

Why low spin tetrahedral complexes are rarely observed?

Tetrahedral complexes are formed with weak field ligands which are not having sufficient crystal field
splitting energy (∆ < 𝑃)
(i) Metal carbonyls are Homoleptic Complexs of
Bonding in
transition metals with CO.
metal carbonyls
(ii) The metal-carbon bond in metal carbonyls possess
:
𝜎 𝑎𝑛𝑑 𝜋 character
(iii) The M–C 𝜎 bond is formed by the donation of
lone pair of electrons on the carbonyl carbon into a vacant orbital of the metal.
(iv) The M– C 𝜋 bond is formed by the donation of a pair
of electrons from a filled d orbital of metal into the
vacant antibonding 𝜋* orbital of CO.
(v) The metal to ligand bonding creates a synergic effect
which strengthens the bond between CO and the metal
 CO is stronger complexing agent than NH3. Why ?
Because CO form synergic bond with metal ion which increases stability of complex
Application of (i) Complex formation is frequently encountered in analytical chemistry. For
coordination example identification of Cu2+ is based on the formation of a blue complex with NH3
compounds CuCl2 + 4NH3 → [Cu(NH3)4]Cl2
and that of Fe3+on the formation of a red complex with KSCN
FeCl3 + KSCN → K3[Fe(SCN)6]+ 3KCl
Similarly, Ni2+ is estimated as red complex with dimethyl glyoxime (DMG).
(ii) Many biological processes involve complex formation. For example
haemoglobin, chlorophyll, vitaminB12,cisplatinare complexes.
(iii) Hardness of water is estimated by complexometric titration of Ca2+ and Mg2+
with ethylene diamine tetraacetic acid (EDTA
YEAR 2024
1. Ligand EDTA4- is an example of a :
(a) Monodentate ligand (b) Bidentate ligand (c) Tridentate ligand (d) Polydentate ligand
2. The type of isomerism shown by the complex [CoCI2(en)2]+ is :
(a) Linkage isomerism. (b) Geometrical isomerism
(c) Coordination isomerism. (d)Ionization isomerism.
3. The coordination number of Co in [Co(en)3]3+ is :
(a) 4 (b). 3 (c) 6 (d) 5
4. Which of the following ligand forms chelate complex?
(a) C2O42- (b) CI- (c) NO (d) NH3
5. Which one of the following hybrid states is associated only with low spin complex?
(a) sp3d (b) sp3 (c) dsp2 (d) sp3d2
6. Which one of the following complexes is non-ionisable?
(a) [Co(NH3)з CI3] (b) [Co(NH3)4 Cl2] CI (c) [Co(NH3)5 CI]Cl2 (d) [Co(NH3)6]Cl3
7. Answer any five of the following:
(i) How is the crystal field splitting energy for octahedral complex (∆% ) related to that of tetrahedral
complex (∆& )?
(ii) Write the IUPAC name of the following complex: [PtCl2(en)2 ](NO3)2
(iii) Write the geometry and magnetic behaviour of the complex [Ni(CO)4] on the basis of Valency Bond
Theory (VBT).
(iv)What type of isomerism is shown by the complex. [Co(NH3)6][Cr(CN)6]
(v) For the coordination compound on the basis of crystal field theory, write the electronic configuration
for d4 ion if, ∆% < P. Is the coordination compound a high spin or low spin complex ?
(vi) Out of [Co(NH3)6]3+ and [Co(NH3)4Cl2]+, which complex is heteroleptic and why?