2nd Pu Chemistry Important Concept PDF
2nd Pu Chemistry Important Concept PDF
Ph:7411224133 1
2ND PU CHEMISTRY IMPORTANT CONCEPTS
Expected questions:
Solutions:
Difference between ideal and non ideal solution:
Ideal solution Non ideal solution
1. The solution obeys raoult’s law 1. The solution donot obeys raoult’s law
2. For ideal solution ∆Hmix = 0; 2. For ideal solution ∆Hmix ≠ 0;
3. for ideal solution ∆Vmix= 0 3. for ideal solution ∆Vmix ≠ 0
4. They donot form Azeotropes. 4. They form Azeotropes.
5. The interaction between solute and solvent is 5. The interaction between solute and solvent is
always equal to solute – solute and solvent – solvent not equal to solute – solute and solvent – solvent
interactions. interactions.
Ex: n-hexane and n – heptane, bromoethane and Ex: Ethanol and acetone, chloroform and acetone
chloroethane, benzene and toluene.
Difference between non ideal with positive and negative solution: (depending on interaction)
Non ideal solution with positive deviation Non ideal solution with negative deviation
1)for this solution ∆Hmix > 0; 1) for this solution ∆Hmix < 0;
2) for this solution ∆Vmix> 0 2) for this solution ∆Vmix< 0
3) Ptotal > pA + pB 3) Ptotal < pA + pB
4) solvent-solute interactions are weaker than 4) solvent-solute interactions are higher than solvent-
solvent-solvent, solute-solute interactions. solvent, solute-solute interactions.
5) The solutions can form minimum boiling 5) The solutions can form maximum boiling
Azeotropes. Azeotropes.
Ex: Ethanol and acetone, ethanol and water, CS2 and Ex: phenol and aniline, chloroform and acetone and
acetone Nitric acid and water
Due to weaker interactions between Solvent and solute, solution show positive deviation from raoult’s law
Due to stronger interactions between Solvent and solute, solution show negative deviation from raoult’s law
Electro chemistry:
Standard hydrogen electrode(S.H.E):
The standard hydrogen electrode consists of a platinum electrode coated with platinum black. The electrode is
filled with hydrogen gas at one bar pressure. Then hydrogen gas is adsorbed on platinum metal. It is dipped in
one molar HCl solution. Then equilibrium is present in between the adsorbed hydrogen and hydrogen ions in
the solution. H+(aq) + e- ↔ ½ H2(g)
The Standard electrode potential of standard hydrogen electrode (Eo H+/H2) is assume to be 0 V. so it can act
as reference electrode.
Wheatstone bridge:
The electrical resistance can be measured with the help of a wheatstone bridge. It consists of two resistaces R3
and R4, a variable resistance R1 and the conductivity cell having the unknown resistance R2. The wheatstone
bridge is fed by an oscillator O and suitable detector P.
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The bridge is balanced when no current passes though the detector. Under these conditions
Unknown resistance R2 = R1R4/R3
Cell constant of the conductivity cell = R2k
The conductivity cell is now filled with given electrolytic solution. It is connected to wheat stone bridge and
the experiment is repeated. The resistance R2 of the electrolytic solution is determined.
Specific conductance of the electrolytic solution k = cell constant/R2
Fuel cells produce electricity with an efficiency of about 70%. Fuel cells are pollution free and produce drinking
water. So it is used in Apollo space ships.
Corrosion:
Corrosion is a process in which a purified metal converts to its oxide, hydroxide, or sulfide when metal contact
with moisture.
Example: The rusting of iron.
During rusting of iron, iron oxidation changes to +3
Anode reaction: Fe Fe2+ + 2e-
Cathode reaction: O2 + 4H+ + 4e- 2H2O
Overall reaction: 2Fe + O2 + 4H+ 2Fe2+ + 2H2O
Chemical kinetics:
Derivation of Rate constant for Zero order reaction:
Zero order reaction means the rate of the reaction is proportional to zero power of the concentration of
reactants.
Consider the reaction, R → P;
−𝑑[𝑅]
Rate = 𝑑𝑡 = k[R]0
−𝑑[𝑅]
Rate = 𝑑𝑡 = k ………(1)
d[R] = -k dt; integrating on both sides
[R] = -k t + I; where I is the integration constant. …………(2)
At t=0, the concentration of the reactant R =[R]0, where [R]0 is initial concentration of the reactant.
Substituting the values in above equations …..(2)
[R]0 = -k X 0 + I
[R]0 = I; Substituting the value of I in the equation ……..(2)
[R] = -k t + [R]0 …………(3)
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Kt = [R]0 - [R]
[𝑅𝑜]−[𝑅]
rate constant k = 𝑡
Units: Mol. L-1. Sec-1
Potassium permanganate(KMnO4) :
Preparation of potassium permanganate is a two steps process
Step 1: fusion of MnO2 with KOH and an oxidising agent like KNO3 it produces the dark green K2MnO4 solution
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
Step 2: dark K2MnO4 disproportionates in a neutral or acidic solution to give purple colour of permanganate.
3 MnO42- + 4 H+ 2 MnO4 - + MnO2 + 2 H2O
(3K2MnO4 + 2H2SO4 → 2KMnO4 + MnO2 + 2H2O + 2K2SO4)
2) [CoF6]3- complex:
Co( Z= 27) electronic configuration is -[Ar] 3d7 4s2 and
Co3+ electronic configuration is – [Ar] 3d6 4s0
↑↓ ↑ ↑ ↑ ↑
in this coordination complexes fluoride ligand can act as weak ligand. Hence 3d electrons are not paired
3)[Ni(CN)4]2- complex:
Ni( Z= 28) electronic configuration is -[Ar] 3d8 4s2 and
Ni2+ electronic configuration is –[Ar] 3d8 4s0
↑↓ ↑↓ ↑↓ ↑ ↑
-
in this coordination complexes CN ligand can act as strong ligand. It causes the pairing of the unpaired 3d
electrons
Ni2+ electronic configuration is –[Ar] 3d8 4s0 4p0
↑↓ ↑↓ ↑↓ ↑↓
To form complex with CN- ions Ni participate in dsp2 hybridization form four dsp2 hybrid orbital’s.
2+
4)[NiCl4]2- complex:
Ni( Z= 28) electronic configuration is -[Ar] 3d8 4s2 and
Ni2+ electronic configuration is –[Ar] 3d8 4s0
↑↓ ↑↓ ↑↓ ↑ ↑
in this coordination complexes chloride ligand can act as weak ligand. Hence 3d electrons are not paired
Ni2+ electronic configuration is –[Ar] 3d8 4s0 4p0
↑↓ ↑↓ ↑↓ ↑ ↑
To form complex with Cl ions, Ni participate in sp3 hybridization by using 4s and 4p orbitals and form four
- 2+
sp3hybrid orbital’s.
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3 2+
Sp hybrid orbital’s of Ni electronic configuration is –
[Ar] 3d8 sp3 hybrid orbitals
↑↓ ↑↓ ↑↓ ↑ ↑
Four pairs of electrons, one from each Cl- ion, occupy the four hybrid orbitals.
SN1 Mechanism:
The reaction between tert-butyl bromide and sodium hydroxide yields tert-butyl alcohol and follows the first
order kinetics.
It is a two steps process
a) formation of stable 3o- carbo cation
Rate = K [(CH3)3CBr]
so it is first order kinetics.
Reactivity order : 3o > 2o > 1o alkyl halides
SN2 mechanism:
The reaction between CH3Cl and sodium hydroxide yields methanol . It is second order reaction. The rate
depends on the concentration of both chloro methane and sodium hydroxide.
Solutions
Binary solution: The solutions consits of only two components (solute & solvent) are called binary solutions.
Types of Solutions:
Type of Solution Solute Solvent Common Examples
Gaseous Solutions Gas Gas Mixture of oxygen& nitrogen gases
Liquid Gas Chloroform with nitrogen gas
Solid Gas Camphor in nitrogen gas
Liquid Solutions Gas Liquid Oxygen dissolved in water
Liquid Liquid Ethanol dissolved in water
Solid Liquid Glucose dissolved in water
Solid Solutions Gas Solid Solution of hydrogen in palladium
Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold
35% (v/v) Ethylene glycol solution can act as antifreeze. It lowers freezing point of water to 255.4K (-17.6oC)
(2) Molality: Molality (m) is defined as the number of moles of the solute per kilogram (kg) of the solvent
units: mol/kg
Molality not depends on temperature If temperature increases molality of the solution not change.
(3) Molarity: Molarity (M) is defined as number of moles of solute dissolved in one litre of solution
Units:mol/lit
Molarity is a function of temperature and it is inversely proportional to temperature.
If temperature increases molarity of the solution decreases because volume of solution increases.
Solubility of a solid in liquids:
Solubility of solid in liquid depends on nature of solute, nature of solvent and temperature.
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In case of endothermic process, solubility increases with increasing of temperature.
In case of exothermic process, solubility increases with decreases of temperature.
Pressure not show any effect on solubility of solid in liquid because solid and liquids are practically
incompressible.
Henry’s law:
The solubility of a gas in a liquid is directly proportional to the partial pressure of the gas present above the
surface of liquid or solution
p = KH S (Or)
The partial pressure of the gas in vapour phase is proportional to the mole fraction of the gas in the solution
Mathematically p = KH x
Different gases have different KH value. This suggest KH is a function of nature of the gas
Higher the value of KH at a given pressure, the lower is the solubility of the gas in the liquid.
Azeotropes: The solutions which are binary mixtures having the same composition in liquid and vapour phase
and boil at a constant temperature. It is not possible to separate the components by fractional distillation..
Ex: Maximum boiling azeotrope: 95% by volume of aq.ethanol solution ( B.p is 351.3K)
Minimum boiling azeotrope: 68% by volume of aq.nitric acid solution (B.p is 393.5K)
Colligative Properties:
“The properties which depend on the number of solute particles but not nature of solute particles present in
the solution are called colligative properties”. These are
(1) relative lowering of vapour pressure of the solvent
(2) elevation of boiling point of the solvent
(3) depression of freezing point of the solvent
(4) osmotic pressure of the solution.
When non volatile solute is added to pure solvent then vapor pressure of solution decreases, boiling point of
solution increases, freezing point of solution decreases and osmotic pressure increases.
Osmosis:
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The flow of solvent molecules from low concentration solution to high concentration solution through semi
permeable membrane is called osmosis.
Ex: raw mangoes shrivel in brine solution, wilted of flowers in fresh water.
Osmotic pressure:
The pressure that just stops the flow of solvent in osmosis is called osmotic pressure. Or the pressure required
to stop the osmosis is called osmotic pressure.
Osmotic pressure depends on concentration of solution and temperature
Semi permeable membrane is a membrane which allows only solvent particles but not solute particles.
Ex: pig’s bladder, parchment (natural), cellophane (synthetic)
Vanthoff factor (i): It is defined as the ratio of normal molar mass to abnormal moalr mass.
van’t Hoff factor(i) = Normal molar mass
Abnormal molar mass
i < 1 indicates solute participate in association
i >1 indicates solute participate in dissociation.
Isotonic solutions: Two solutions having same osmotic pressure or same concentration
Hypertonic solutions: in two solutions the solution having higher osmotic pressure or higher concentration
Hypotonic solutions: in two solutions the solution having lower osmotic pressure or lower concentration
Electro chemistry
In galvanic cell the gibbs free energy of spontaneous redox reaction is converted to electrical energy.
Daniel cell chemical reaction: Zn + Cu2+ Zn2+ + Cu; Eocell = Eo cathode – Eo anode
= 0.34V – (-0.76)V
= 1.10V
o o
Key points: Higher E indicates cathode and lower E indicates anode
Salt bridge:
it is an inverted U-tube filled with agar-agar jel, NaCl, KCl type of inert electrolytes. It connects the solutions of
two half cells and completes the cell circuit.
Inert electrodes: The electrodes which not participate in chemical reaction but provide their surface for
oxidation or reduction reactions and for the conduction of electrons.
Ex: platinum electrode, gold electrode
Electro chemical cell applications:
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To determine the pH of solutions, solubility product, equilibrium constant, other thermodynamic properties,
and for potentiometric titrations.
Molar conductivity( m): The conductance of all the ions present in one molar solution is called molar
conductivity.
Conductivity(k)
Molar conductivity ( m) = Concentration(C)
Products of Electrolysis:
Product of electrolysis depends on nature of material and types of electrodes.
a) In case of electrolysis of molten NaCl the products are sodium (at cathode) and Chlorine gas (at anode)
b) In case of electrolysis of aqueous NaCl solution, the products are NaOH, Cl2(anode), H2(cathode).
Primary Batteries:
Primary batteries are the galvanic cell in which the reaction occurs only once and cannot be reused again.
Example: Leclanche cell, mercury cell
Secondary Batteries:
A secondary batteries are galvanic cells that can be recharged by passing current through it in the opposite
direction and can be reused. Ex: lead storage battery, Ni-Cd battery
Fuel Cells:
Galvanic cells which convert the energy of combustion of fuels into electrical energy are called fuel cells.
Example: Hydrogen-oxygen fuel cell, Methane-oxygen fuel cell, methanol-oxygen fuel cell.
Prevention techniques:
Covering the surface with paint
Covering the surface with some chemicals like bisphenol
Covering the surface with other metals (Sn, Zn, etc.)
Chemical Kinetics
Rate of a Chemical Reaction:
The rate of a reaction can be defined as the change in concentration of a reactant or product in unit time.
A) For a reaction R P
−Δ[R] +Δ[P] −d[R] +d[P]
Average rate of a reaction = Δt = Δt differential rate of a reaction = dt = dt
Rate expression = K [R]
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B) For a reaction aA + bB cC + dD
−1 Δ[A] −1 Δ[B] +1 Δ[C] +1 Δ[D]
Average rate of a reaction = 𝑎 Δt = = =
𝑏 Δt 𝑐 Δt 𝑑 Δt
−1 d[A] −1 d[B] +1 d[C] +1 d[D]
differential rate of a reaction = 𝑎 dt = 𝑏 dt = 𝑐 dt = 𝑑 dt
Rate expression = K [A]a [B]b
Units of rate of a reaction: mol L-1s–1 or atm.s-1 (for gaseous reactions)
Zero order reaction: The reactions in which rate of reaction depends on zero power of concentration of
reactants.
Ex: some enzyme catalysed reactions, decomposition of ammonia gas on platinum surface, decomposition of
HI on gold surface.
First order reaction: The reactions in which rate of reaction depends on first power of concentration of
reactants.
Ex: All natural and artificial radio active decay of unstable nuclei, hydrogenation of ethane
Pseudo first order reaction: The reactions which are second (higher) order reactions but behave has first
order reactions are called pseudo first order reaction. In pseudo first order reaction the rate is not depends on
concentration of excess reactant but rate constant is depends .
Example: 1) Hydrolysis of ester 2) Hydrolysis of sucrose
Effect of temperature:
For a chemical reaction with rise in temperature by 10°, the rate constant is nearly doubled.
The energy required to form this intermediate (activated complex), is known as activation energy (Ea).
According to Boltzmann and James Clark Maxwell curves When the temperature is increased, which increases
the kinetic energy of the molecules, This will increase the no.of collisions and rate of the reaction is increased.
Arrhenius equation:
−𝐸𝑎
Rate constant(k) = A .𝑒 𝑅𝑇 .
where A is the Arrhenius factor. R is universal gas constant and Ea is activation energy T is temperature.
−𝐸𝑎
𝑒 𝑅𝑇 is the fraction of molecules that have kinetic energy greater than or equal to activation energy.
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Effect of catalyst:
A catalyst is a substance which increases the rate of a reaction without undergoing any chemical change.
𝑀𝑛𝑂2
Ex: 2KClO3 > 2 KCl + 3O2; MnO2 can act as catalyst.
Catalyst can increase the rate of reaction by decrease the activation energy. It can show an alternate path to
the chemical reaction.
Oxidation states:
Transition elements show variable oxidation states due to comparable energies between (n-1)d and ns
orbitals.
They show highest oxidation states in oxides and in fluorides because Fluorine and oxygen’s are small size and
higher electro negative elements.
Manganese show more no.of oxidation states from +2 to +7
Manganese is the 3d series element which show maximum oxidation state (+7) due to presence of max no.of
unpaired electrons.
The transition element which shows only one oxidation state is Sc (+3).
The non transition element which show only one oxidation state is Zn(+2) (no d electrons are involved).
The 3d series element show +1 oxidation state is Copper
The transition element not show +2 oxidation state is Scandium (Sc)
The stability of Cu2+(aq) rather than Cu+(aq) is due to high negative hydration enthalpy of Cu2+.
Cr2+ is stronger reducing agent than Fe2+.
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Magnetic properties:
the ‘spin-only’ formula; magnetic moment μ = √n (n + 2) (BM). where n is the no of unpaired electrons.
Sc3+, Zn2+ magnetic moment is zero due to absence of unpaired electrons.
colour:
transition elements form colored complexes due to presence of unpaired electrons which participate in d-d
transition. Zn2+ and Sc3+ are colorless due to absence of unpaired electrons.
Catalytic Properties:
The transition metals and their compounds show catalytic activity. This activity is due to multiple oxidation
states and to form complexes.
Ex: nickel act as catalyst in hydrogenation of oils
Formation of interstitial compounds:
small atoms like H, C or N are trapped inside the crystal lattices of metals are called interstitial compounds.
Ex: TiC, Mn4N, Fe3H, VH0.56 and TiH1.7
Alloy formation:
Alloys are may be homogeneous solid solutions of one metal randomly distributed in another metal.
Transition metals form alloys due to similar atomic sizes.
Ex: Brass (Cu + Zn) & Bronze (Cu + Sn)
V2O5, Cr2O3 are ampoteric oxides but CrO3, Mn2O7 are acidic oxides.
Potassium dichromate:
𝐻+ 𝑂𝐻−
Chromate > Dichromate Dichromate > Chromate
The reduction half reaction of potassium dichromate is Cr2O72- + 14H+ + 6e- 2Cr3+ +7H2O
Acidified potassium dichromate can convert ferrous to ferric, iodides to iodine, sulphides to sulphur, tin(ii) to
tin(iv). 6Fe2+ 6Fe3+ + 6e-; 6I- 3I2 + 6e-; 3H2S 6H+ + 3S + 6e-; 3Sn2+ 3Sn4+ + 6e-
Potassium permanganate:
Lab preparation: 2Mn2+ + 5S2O82- + 8H2O 2MnO4- + 10 SO42- + 16H+
Potassium permanganate on heating it form potassium manganate. 2KMnO4 K2MnO4 + MnO2 + O2
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f- block elements
The general electronic configuration of f block elements is (n-2)f1-14 (n-1)d0-1ns2
Lanthanoids:
The general electronic configuration of lanthanoids is 4f1-14 5d0-16s2.
Cerium electronic configuration is [Xe] 4f2 6s2
Lanthanoid contraction:
The atomic and ionic radii continuously decrease in lanthanoids (La to Lu) it is called lanthanoid contraction. It
is due to poor shielding effect of 4f electrons.
Consequences:
a) The radii of third transition series are very similar to corresponding members of the second series. The
almost identical radii of Zr (160 pm) and Hf (159 pm)
b) It is difficult to separate one lanthanoid from another lanthanoid.
c) From La3+ to Lu3+ covalent character increases hence basic strength decreases.
Except promethium all lanthanoids are non radio active elements.
lanthanoids general oxidation state is +3. Some times they also show +2 & +4 oxidation states.
Cerium can lose the outermost four electrons in the s and f orbitals to attain the inert gas electronic
configuration. Hence, the oxidation state of Cerium is +4.
Ln + HCl LnCl3 + H2↑; Ln +O2 Ln2O3; Ln + X2 LnX3; ln + H2O Ln(OH)3;
Ln + C LnC2; Ln + N2 LnN; Ln + S Ln2S3
mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al.
Mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.
Mixed oxides of lanthanoids are used as catalyst in petroleum industry, some individual lathanoids are used as
phosphors in TV and similar fluorescing surfaces.
Actinoids
The general electronic configuration of actinoids is 5f1-146d0-17s2.
There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as the
actinoid contraction. It is due to poor shielding by 5f electrons.
The actinoid contraction is greater from one element to another element due to poor shielding effect of 5f
electrons
Actinoids show variable oxidation states due to compable energies between 5f, 6d and 7s orbitals.
The actinoids show in general +3 oxidation state and the maximum oxidation state increases from +4 to +7
The study of chemistry of actinoids is difficult because actinoids are radio active elements with short half life
times and actinoids are available in nanograms only.
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COORDINATION COMPOUNDS
Unidentate ligand: The ligand is bound to a metal ion through a single donor atom. Denticity = 1
Ex: Cl-,H2O, NH3 etc
Bidentate ligand: The ligand is bound to a metal ion through a two donor atoms. Denticity = 2
Ex: oxalate ion(ox2-), ethane-1,2-diamine(en) etc
ambidentate ligand: The ligands which have two different donor atoms and either of the two ligates in the
complex are called ambidentate ligands. Ex: CN-, SCN-, NO2-
Chelate ligand: di or poly dentate ligands which form closed rings with single metal ion are called Chelate
ligands. Ex: oxalate ion(ox2-), ethane-1,2-diamine(en), EDTA4- etc
EDTA4- is hexa dentate ligand (Denticity = 6) , it can bind through two nitrogen and four oxygen atoms to a
central metal ion.
Chelate complexes are more stable than simple complexes.
IUPAC nomenclature:
Anionic complexes: Counter ion + ligands in alphabetical order + metalate (oxidation state)
Cationic complexes: ligands in alphabetical order + metal (oxidation state) + Counter ion
Neutral ligands: ligands in alphabetical order + metal (oxidation state)
Geometrical isomerism:
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Optical isomerism:
Metal carbonyls:
Metal carbonyls are homoleptic complexes of metal and CO as ligands. in metal carbonyls metal oxidation
state is zero.
The bond between metal and CO can possess both sigma and pi character. The sigma bond is formed by the
donation of lone pair of electrons on the carbonyl carbon. The pi bond is formed by the donation of a pair of
electrons from a filled d orbital of metal into the vacant anti bonding π* orbital of CO. such type of bond is
called synergic bod and this effect is called synergic effect.
Finkelstein reaction:
Alkyl chlorides react with sodium iodide in presence of dry acetone form alkyl iodides. NaCl or NaBr form
precipitate in drycetone and forward reaction mainly takes place.
𝐷𝑟𝑦 𝑎𝑐𝑒𝑡𝑜𝑛𝑒
Ex: CH3Cl + NaI > CH3I + NaCl
Swart’s reaction:
Alkyl chlorides react with silver fluoride form alkyl fluorides
Ex: CH3Cl + AgF > CH3F + AgCl
R-X + KCN R-CN + KX, R-X + AgCN R-NC + AgX
R-X + KNO2 R-ONO + KX, R-X + AgNO2 R-NO2 + AgX
Dehydrohalogenation:
Haloalkanes containing beta hydrogen undergo elimination reaction with alcoholic solution of potassium
hydroxide
𝐴𝑙𝑐𝑜ℎ𝑜𝑙𝑖𝑐 𝐾𝑂𝐻
CH3-CH2-CH2-CH(Br)-CH3 > CH3-CH2-CH = CH-CH3 + CH3-CH2-CH2-CH=CH2
2-Bromopentane 2-pentene (major) 1-pentene (minor)
1-chloropropane , 2-chloro propane form propene gas as main poduct.
1-chlororbutane form 1-butene as major product, 2-chorobutane form 2-butene as major product
Grignard reagent: Alkyl magnesium halides are called Grignard reagent. Ex: RMgX (CH3MgBr)
Grignard reagents are used to convert halo alkanes into alkanes
RMgX + H2O RH + Mg(OH)X
Wurtz reaction:
alkyl halides react with sodium in dry ether form higher alkanes is called wurtz reaction
dry ether
Ex: 2CH3Br + 2Na → CH3 – CH3
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Fittig reaction:
Alkyl halides are react with sodium in dry ether form biphenyl is called fittig reacton.
Chloro benzene react with NaOH followed by acid hydrolysis form phenol
Esterification:
Carboxylic acids react with alcohols in presence of dehydrating agent conc. H2SO4 form fruity odour ester is
called esterification.
Ex: CH3COOH + C2H5OH CH3COOC2H5 (ESTER)
Kolbe’s reaction:
Sodium phenoxide react with carbon dioxide followed by acid hydrolysis form 2 – hydroxybenzoic acid
(salicylic acid)
Phenol on oxidation with chromic acid in presence of sulphuric acid form benzoquinone.
Phenols are strong acids than alcohols because phenols form resonancely more stable phenoxide ion.
Phenol is less stable than phenoxide ion due to charge separation.
If electron donating groups ( -CH3) are increases acidic character decreases
If electron drawing groups ( -NO2) are increases acidic character increases
Acidic character of phenols is
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ETHERS
Williamson synthesis of ethers: (SN2 process)
sodium alkoxide react with alkyl halide form either symmetrical or unsymmetrical ethers
R – ONa + R – X R – O – R + NaX
Ex: a) CH3 – CH2 – ONa + CH3 – Cl CH3 – CH2 – O – CH3
(Sodium ethoxide) (Methoxy ethane)
b) CH3 – CH2 – ONa + CH3 – CH2 – Cl CH3 – CH2 – O – CH2 – CH3
(Sodium ethoxide) (Ethoxy ethane)
When tertiary alkyl halide react with sodium methoxide it form an alkene
Lower ethers are soluble in water due to formation of inter molecular hydrogen bonding with water. Ethers
have low boiling points than alcohols due to absence of inter molecular hydrogen bonding between ethers.
CH3 – O – CH3 + HI CH3OH + CH3I CH3CH2 – O –CH3 + HI CH3CH2OH + CH3I
(Sn1 mechanism)
Bromination of anisole:
Anisole react with bromine in ethanoic acid form 2- bromo anisole and 4 - bromoanisole.
Nitration of anisole:
Anisole react with conc. HNO3 and Con. H2SO4 form 2 – nitroanisole and 4 – nitroanisole .
Stephen reduction:
Niriles undergo reduction in presence of stannous chloride and HCl form aldehydes
𝐷𝐼𝐵𝐴𝑙−𝐻 𝐷𝐼𝐵𝐴𝑙−𝐻
RCN 𝐻3𝑂+ > RCHO; RCOOR 𝐻3𝑂+ > RCHO (DIBAl-H; diisobutylaluminiumhydride)
Etard reaction:
Toluene on oxidation with chromyl chloride followed by acid hydrolysis form benzaldehyde
Preparation of ketones:
2RCOCl + R2Cd 2RCOR + CdCl2
𝑅𝑀𝑔𝑋−𝑒𝑡ℎ𝑒𝑟
RCN 𝐻3𝑂+ > RCOR + NH3
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Due to moecular association aldehydes and ketones have high boiling points than ethers. Lower aldehydes and
ketones are solble in water due to formation of inter molecular hydrogen bonding.
Ketones are less reactive towards nucleopillic addition reactions due to steric reasos and electronic reasons.
aldehydes and ketones give orange red crystalline ppt with 2,4-DNP. It is the identification test for aldehydes
and ketones.
Clemmensen reduction:
Aldehydes/ketones react with Zinc amalgam and conc.HCl form corresponding alkanes
Aldehydea and ketones can be differed by tollens reagent and fehiling solution.
Tollens reagent: Ammonical silver nitrate. Aldehydes form silver ppt with tollens reagent but not ketones.
Fehiling solution: it is combination of Fehiling A and Fehiling B solution.
Fehiling A solution: aqueous copper sulphate solution
Fehiling B solution: alkaline sodium potassium tartarate solution. Aldehydes form red brown ppt with fehiling
solution.
Aromatic aldehydes not react with fehiling solution due to absence of α-hydrogen.
Haloform reaction:
Aldehydes and ketones having at least one methyl group linked to the carbonyl carbon atom (methyl
ketones) are oxidised by sodium hypohalite to sodium salts of corresponding carboxylic acids having one
carbon atom less than that of carbonyl compound. The methyl group is converted to haloform.
This oxidation does not affect a carbon-carbon double bond, if present in the molecule.
Aldol condensation:
Aldehydes/ketones containg alpha hydrogens are participate in aldol condensation.
Aldehydes/ketones containing alpha hydrogen undergo self condensation form beta hydroxy
aldehyde/ketone. On dehydration form α,β – unsaturated aldehydes/ketones.
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Cannizaro reaction:
Aldehydes/ketones not containg alpha hydrogens are participate in cannizaro reaction.
Aldehydes with out alpha hydrogen undergoes reduction and oxidation with NaOH form alcohol and
carboxylate
Nitration of benzaldehyde:
Carboxylic acids
In carboxylic acids the Carbon undergo sp2 hybridisation and less electrophilic in nature.
From oxidaton:
𝑎𝑙𝑘.𝐾𝑀𝑛𝑂4/𝐻3𝑂+ 𝑚𝑖𝑙𝑑 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛
RCH2OH 𝑜𝑟 𝐽𝑜𝑛𝑒𝑠 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 > RCOOH; RCHO 𝑠𝑡𝑟𝑜𝑛𝑔 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 > RCOOH
Jones reagent: Cromium trioxide(CrO3) In H2SO4
From hydrolysis:
𝐻+/𝑂𝐻− 𝐻+/𝑂𝐻− 𝐻+/𝑂𝐻−
RCN > RCONH2 ℎ𝑒𝑎𝑡 > RCOOH + NH3 RCOCl > RCOOH + HCl
(Nitriles) (amide) (carboxylic acid) (acid chloride) (carboxylic
acid)
𝐻+/𝑂𝐻− 𝐻+/𝑂𝐻−
RCOOR > RCOOH + ROH RCOOCOR > 2 RCOOH
(Ester) (carboxylic acid) (alcohol) (acid anhydride)
(carboxylic acid)
𝑐𝑜𝑛𝑐 𝐻2𝑆𝑂4
RCOOH + ROH > RCOOR (ester-Alkylalkanoate)
−𝐻2𝑂
𝑃2𝑂5
2 RCOOH > RCOOCOR (acid anhydride)
𝐻+
𝑃𝐶𝑙3 𝑜𝑟 𝑃𝐶𝑙5
RCOOH > RCOCl (acid chloride)
𝑂𝑟 𝑆𝑂𝐶𝑙2
𝐶𝑎𝑂+𝑁𝑎𝑂𝐻(1:3)
RCOONa > RH + Na2CO3
𝐷𝑒𝑐𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑎𝑡𝑖𝑜𝑛
𝐿𝑖𝐴𝑙𝐻4 𝑜𝑟 𝐵2𝐻6
RCOOH > RCH2OH
𝐻3𝑂+
Carboxylate ion is deactivating and form bond with catalyst AlCl3. Due to this reason benzoic acid nor
participate in friedal craft’s reaction.
Carboxylic acids are strong acids in nature due to formation of stable carboxylate ion.
If electron donating groups ( -CH3) are increases acidic character decreases
If electron drawing groups ( -NO2) are increases acidic character increases
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AMINES
R – NH2 R2 – NH R3 – N R4 – N+ X-
1o amine 2o amine 3o amine quaternary ammonium salt
In amines N undergo sp3 hybridisation and shape is Pyramidal with bond angle 107o due to one lone pair.
Preparation:
𝐻2−𝑃𝑑 𝑜𝑟,𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝐻2−𝑃𝑑 𝑜𝑟,𝑒𝑡ℎ𝑎𝑛𝑜𝑙
1. R – NO2 > R – NH2 Ex: CH3 – NO2 𝑆𝑛 𝑜𝑟 𝑭𝒆 𝒊𝒏 𝑯𝑪𝒍 > CH3 – NH2 ( Methanamine)
𝑆𝑛 𝑜𝑟 𝑭𝒆 𝒊𝒏 𝑯𝑪𝒍
𝑁𝑖 𝑁𝑖
2. R – CN 𝐻2 > R – CH2 – NH2 Ex: CH3 – CN 𝐻2 > CH3 – CH2 – NH2 (Ethanamine)
Gabriel’s phthalimide reaction:
Potassium phthalimide react with alkyl halide form N – alkyl phthalimide. It react with KOH form 10 aliphatic
amine.
It is not for 1o aromatic amine because aryl halide do not participate in nucleophilic substitution reaction.
Amines are colourless but on standing they exhibit colour due to oxidation. Lower amines are soluble in water
due to formaton of inter molecular hydrogen bonding with water.
The order of boiling point for isomeric alkanes is 1o amine > 2o amine > 3o amine(H-bonding absent).
Distinguish between amines: Amines can be distinguished and also separated by hinseberg reagent + KOH
Hinsberg reagent = benzene sulphonyl chloride
1o amine react with hinsberg reagent form alkali soluble product
2o amine react with hinsberg reagent form alkali insoluble product
3o amine do not react with hinsberg reagent due to absence of hydrogen attached to Nitrogen
Aniline react with bromine water form a white ppt 2,4,6 – tri bromo aniline.
Aniline undergo nitration form o,m,p-nitro aniline. M-nitroaniline is due to formation of anilinium ion in which
NH3+ act as electron withdrawing group.
Aniline (lewis base) does not undergo friedal crafts reaction due to formation of salt with catalyst AlCl3(lewis
acid). Due to this Nitrogen gain positive charge and act as strong deactivating group.
Basicity of amines:
In gas phase order of basicity is R3 – N > R2 – NH > R – NH2
In overall view the order of basicity is R2 – NH > R3 – N > R – NH2 > NH3 > C6H5 – NH2
Ex: (C2H5)2 – NH > C2H5 – NH2 > NH3 > C6H5 – NH2
If electron donating groups ( -CH3) are increases basic character increases
If electron drawing groups ( -NO2) are increases basic character decreases
b) Alliphatic amines react with NaNO2 in presence of HCl form alkyl diazonium chloride (unstable), they
converted into alcohols.
R – NH2 + NaNO2 + HCl RN2Cl R – OH
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Benzene diazonium chloride is a crystalline solid soluble in cold water but reacts with hot water.
Benzene diazonium fluoro borate is water soluble and more stable at room temperature.
sandmaeyer reaction:
Benzene diazonium chloride react with Cuprous chloride in presence of HCl form chloro benzene.
gatterman reaction:
Benzene diazonium chloride react with copper in presence of HCl form chloro benzene.
Benzene diazonium chloride undergo reduction with H3PO2/H2O or CH3CH3OH form benzene.
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BIOMOLECULES
Carbohydrates: These are optically active poly hydroxy aldehydes or ketones. These are also called
Sachharides
Reducing sugar: The carbohdrtes which reduce tollens reagent and fehiling solutions are called reducing
sugars. Ex: Glucose, fructose (all mono saccharides), lactose, maltose etc
Non Reducing sugar: The carbohdrtes which not reduce tollens reagent and fehiling solutions are called non
reducing sugars. Ex: Sucrose
Mono sachharides: The carbohydrate that can not be hydrolysed to produce simple molecule.
Glucose:
Di sachharides: The carbohydrates on hydrolysis form two mono sachharides are called disachharides.
Sucrose: Sucrose + H2O α-D-glucose + β-D-fructose.
Sucrose is a dextro compound but on hydrolysis mainly form Leavo products. So the products are called invert
sugar. sucrose is non reducing sugar. It has C1 - C2 glycosidic linkage.
Maltose: Maltose + H2O 2 α-D- glucose. It is reducing sugar due to presence of free –CHO group at C1
carbon. It has C1 – C4 glycosidic linkage.
Lactose (Milk sugar): Lactose + H2O β-D-galactose + β-D-glucose. It is reducing sugar due to presence of
free –CHO group at C1 carbon of glucose. It has C1 – C4 glycosidic linkage.
Poly sachharides: The carbohydrates produce more no.of mono sachharides on hydrolysis.
Starch: It is a polymer of α-D- glucose units. Its consists of two components.
Amylose: it is long chain molecule and soluble in water. The percentage of amylose in starch is 15-20%. It has
C1 – C4 glycosidic linkage.
Amylopectin: It is branched chain polymer and it is insoluble in water. The percentage of amylopectin in
starch is 15-20%. It has C1 – C4 glycosidic linkage and C1 – C6 glycosidic linkageat branches.
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Cellulose: The most abundant organic comound in plant kingdom is starch. It is a polymer of β-D- glucose
units.
Glycogen: it is a plymer of α-D- glucose units an it is also called animal starch. It has C1 – C4 glycosidic linkage
The ether linkage between two carbohydrates is called glycosidic linkage.
α – Amino aicds: if both COOH and NH2 grops are present on same carbon they are called α – Amino aicds.
EX: Glycine, Alanine, Valine, Leucine, Isoleucine, Arginine, Lysine, Glutamic acid and Aspartic acid etc
Neutral amino acids: α – Amino aicds with same no.of –COOH & -NH2 groups. EX: Glycine, Alanine, Valine,
Leucine, Isoleucine, Arginine
Basic amino acids: α – Amino aicds with more no.of -NH2 groups Ex: Lysine
Acidic amino acids: α – Amino aicds with more no.of –COOH groups. Ex: Glutamic acid and Aspartic acid
Essential aminoacids:
The amino acids which cannot be synthesised in the body and must be obtained through diet, are known as
essential amino acids.
Ex: Valine leucine, isoleusine, Arginine, Lysine.
The amide linkage between two amino acids is called peptide linkge or peptide bond and the resultant
molecule is called peptide.
Two amino acids are combained form di peptide with one peptide linkage.
Three amino acids are combained form tri peptide with two peptide linkages.
four amino acids are combained form tetrapeptide with three peptide linkages.
Fibrous proteins:
Fibre like proteins are are called fibrous proteins. Ex: Keratin ( Haiir, wool, silk) & Myosin (muscles).
Globular proteins:
spherical shaped proteins are called globular proteins: Ex: Albumin and Insulin.
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0
2 structure of protein refers to the shapes of proteins. It contains reugalr folding and inter moecular
hydrogen bondng.
30 structure of protein gives fibrous proteins or globular proteins.
20 and 30 structures of protein stabilised by hydrogen bonding,disulphide linkages, van der waals forces and
electro static forces of attractions.
Denaturation of proteins:
Due to change in temperature and pH, proteins loss their biological activity is called denaturation of proteins.
Ex: Boiling of egg, curding of milk.
Due to denaturation, proteins structures are changes to 1o structure and it not change. 1o structure is stable.
Enzymes:
Enzymes are complex nitrogeneous organic compounds, they can act as biocatalyst. Almost all enzymes are
globular proteins. The enzyme which can participate In oxidation and reduction is called Oxidoreductase.
𝑀𝑎𝑙𝑡𝑎𝑠𝑒
Ex: C12H22O11 > 2 C6H12O6
Maltose Glucose
Vitamins:
Water soluble vitamins:
vitamins which are soluble in water but insoluble in fat. Ex: Vitamin B and Vitamin C.
Fat soluble Vitamins:
Vitamins which are soluble in fat but insoluble in water. They are stored in liver and adipose tissues.
Ex: Vitamin A, Vitamin D, Vitamin E and Vitamin K.
Vitamins Deficiency disease Vitamins Deficiency disease
A Xero phthamia, C (Ascorbic acid) Scurvy
Night blindness
B1(Thiamine) Beri beri D Rickets
B2 (Riboflavin) Chelosis E Increased fragility of RBCs and
muscular weakness
B6 (Pyridoxine) Convulsions K Increased blood clotting time
B12 Pernicious anemia
Nucleic acids:
Pentose sugar + heterogeneous base Nucleosides
Nucleosides + Phosphate linkage Nucleotides
Poly nucleotides are called nucleic acids.
Nucleic acid Pentose sugar Heterogeneous base
DNA β – D – 2 - deoxyribose Adenine, Guanine, Cytosine, Thymine.
RNA β – D – ribose Adenine, Guanine, Cytosine, Uracil.
The nucleic acid participate In genetic information is D.N.A.
R.N.A molecules are three types. They are messenger RNA(m-RNA), Ribosomal RNA (r-RNA) and transfer RNA
(t-RNA).
Two hydrogen bonds are present between Adenine and Thymine.
Three hydrogen bonds are present between Guanine and Cytosine.
Hormones:
Hormones are inter cellular messengers produced by endocrine glands and poured into blood stream.
Steroidal hormones: Estogens, Androgens
Poly peptide hormones: Insulin, Endophins
Amino acid derivatives: Epinephrine, norephinephrine, Thyroxine
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Thyroxine hormone contains iodine. Low level of Thyroxine causes hypothyroidism and high level of Thyroxine
causes hyperthyroidism and
Insulin and glucagon are two hormones which regulate blood glucose level.
Numerical formulas:
Solutions
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
Mass percentage of a component = X 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
Volume percentage of a component = X 100
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
Mole fraction of solvent (XA) = X 100
𝑡𝑜𝑡𝑎𝑙 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Mole fraction of solute (XB) = 𝑡𝑜𝑡𝑎𝑙 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 X 100
𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Molarity = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒 Units: mol/lit
𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Molality = Units: mol/Kg
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑘𝑔
1000 𝑋 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
Molality = (1000 𝑋 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦)− ( 𝑚𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑋 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠)
Raoult’s law for liquid in liquid type of solution: Ptotal = PA + PB = PA0XA + PB0XB
Relative lowering of vapour pressre = 1 – XA
𝑃𝐴𝑜 −𝑃𝐴 𝑤𝐵 𝑀𝐴
Relative lowering of vapour pressure: = 𝑋
𝑃𝐴𝑜 𝑀𝐵 𝑤𝐴
PA0 is vapour pressure of pure solvent
PA is vapour pressure of solution
wA, wB are weight of solvent and solute.
MA, MB are molar mass of solvent and solute
𝑤𝐵 1000
Elevation of boiling point: ΔTb = Tb - Tbo ; ΔTb = Kb 𝑋
𝑀𝐵 𝑤𝐴
Tbo, Tb are boiling point of pure solvent and solution
Kb is Ebullioscopic constant or molal elevation constant and it is depends on sovent. Units: K.Kg.mol-1
𝑤𝐵 1000
Depression of freezing point: ΔTf = Tfo – Tf ; ΔTf = Kf 𝑋
𝑀𝐵 𝑤𝐴
Tfo, Tf are freezing point of pure solvent and solution
Kf is cryoscopic constant or molal depression constant and it is depends on solvent. Units: K.Kg.mol-1
𝑤𝐵 𝑅𝑇
Osmotic pressure of the solution: π V(lit) = 𝑀𝐵
π is osmotic pressure, V is volume of solution in liter, T is temperature, R is universal gas constant.
Electro chemistry
0 0 0
E cell = E cathode – E anode
0.059
Ecell = E0cell – 𝑛 log Qc
0.059
E0cell = 𝑛 log Kc
ΔG0 = -nFE0cell
ΔG0 = -RT ln K
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Cell constant (l/A) = Resisatnce/Resistivity = Resistane X conductivity = conductivity/conductance
𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑋 1000
Molar conductivity (^m) = 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦
For stong elelctrolyte ^m = ^0m – AC ½
For weak electrolyte Degre of ionisation (α) = ^m/^0m
˄mo = V+𝜆+o + V-𝜆-o
W = ZQ or w = ZIt
Chemical kinetics
−∆[𝑅] [𝑅]2−[𝑅]1
Rate of a reaction = =
∆𝑡 𝑡2−𝑡1
[𝑅𝑜]−[𝑅] [Ro]
For zero order reaction rate constant (k) = and half life time, t1/2 =
𝑡 2𝑘
2.303 [𝑅]0 0.693
For first order reaction rate constant (k) = log and half life time, t1/2 =
𝑡 [𝑅] 𝑘
𝐾2 𝐸𝑎 𝑇2−𝑇1
log (𝐾1) = 2.303𝑅 [ 𝑇1𝑇2 ]
BIOMOLECULES - 9M RU U R R, U R U R, U R U
R – REMEMBER, U – UNDARSTAND, A – APPLY, H - HOT IN VSA - 1M AFTER COMMA QUESTION INDICATES FILL IN THE BLANKS
Part – B: 2M questions are may be comes from the chapters Solutions/chemical kinetics, d&f- block
elements/ coordination compounds, Haloalkanesand haloarenes, Alcohols chapter and Biomolecules.
Part – C: Inorganic chemistry
Physical chemistry
Part – D: Organic chemistry
Part – E: Physical chemistry Numericals