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CH.RAGHAVA RAO, S.D.C PU college, Bangarpet, Kolar.

Ph:7411224133 1
2ND PU CHEMISTRY IMPORTANT CONCEPTS
Potassium dichromate (K2Cr2O7) :
preparation of potassium dichromate is a three step process
Step 1: The chromite ore (FeCr2O4) is fused with sodium carbonate in free access of air to obtain yellow
solution of sodium chromate
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
step 2: The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to obtain orange
sodium dichromate, Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O
Step 3: Sodium dichromate is more soluble than potassium dichromate. Potassium dichromate is prepared by
treating the orange solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Orange crystals of potassium dichromate crystallise out.
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)
Valence bond theory:
1) [Co(NH3)6]3+complex:
Co( Z= 27) electronic configuration is -[Ar] 3d7 4s2 and
Co3+ electronic configuration is –[Ar] 3d6 4s0
↑↓ ↑ ↑ ↑ ↑
in this coordination complexes NH3 ligand can act as strong ligand. It causes the pairing of the unpaired 3d
electrons
Co3+ electronic configuration is –[Ar] 3d6 4s0 4p0
↑↓ ↑↓ ↑↓
To form complex with NH3 molecules Co3+ participate in d2sp3 hybridization form six d2sp3 hybrid orbitals.
d2sp3 hybrid orbitals of Co3+ electronic configuration is –
[Ar] 3d 6 d2sp3 hybrid orbitals
↑↓ ↑↓ ↑↓
Six pairs of electrons, one from each NH3 molecule, occupy the six hybrid orbitals..
[Co(NH3)6]3+ 3d6 d2sp3 hybrid orbitals
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
2 3
Hybridization: d sp
Shape: Octahedral
Magnetic character: diamagnetic

Structure:
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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
Co3+ electronic configuration is – [Ar] 3d6 4s0 4p0 4d0
↑↓ ↑ ↑ ↑ ↑
To form complex with F ion, Co participate in sp3d2 hybridization by using 4s, 4p and 4d orbitals and form
- 3+

six sp3d2hybrid orbital’s.


sp3d2 hybrid orbital’s of Co3+ electronic configuration is –
[Ar] 3d6 sp3d2 hybrid orbitals
↑↓ ↑ ↑ ↑ ↑
Six pairs of electrons, one from each F- ion, occupy the six hybrid orbitals.
[CoF6]3- 3d6 sp3d2 hybrid orbitals
↑↓ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
3 2
Hybridization: sp d
Shape: Octahedral
Structure:

Magnetic character: paramagnetic

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] 3d 8 4s0 4p0
↑↓ ↑↓ ↑↓ ↑↓
To form complex with CN- ions Ni participate in dsp2 hybridization form four dsp2 hybrid orbital’s.
2+

dsp2 hybrid orbital’s of Ni2+ electronic configuration is –


[Ar] 3d8 dsp2 hybrid orbitals
↑↓ ↑↓ ↑↓
Four pairs of electrons, one from each CN- ion, occupy the four hybrid orbitals.
[Ni(CN)4]2- 3d8 dsp2 hybrid orbitals
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
2
Hybridization: dsp Shape: square planar

Structure:
Magnetic character: diamagnetic).
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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.
Sp3 hybrid orbital’s of Ni2+ electronic configuration is –
[Ar] 3d 8 sp3 hybrid orbitals
↑↓ ↑↓ ↑↓ ↑ ↑
Four pairs of electrons, one from each Cl- ion, occupy the four hybrid orbitals.

[Ni(Cl)4]2- 3d8 sp3 hybrid orbitals


↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓
Hybridization: sp3
Shape: Tetrahedral
Magnetic character: paramagnetic.

Structure:

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)
Kt = [R]0 - [R]
[𝑅𝑜]−[𝑅]
rate constant k = 𝑡
Units: Mol. L-1. Sec-1
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Graph: slope = –k and intercept equal to [R]0.

Derivation of Rate constant for First Order Reactions:


First order reaction means the rate of the reaction is proportional to the first power of the concentration of
the reactant
Consider the reaction, R → P;
−𝑑[𝑅]
Rate = = k[R]1
𝑑𝑡
−𝑑[𝑅]
Rate = = k[R] ……..(1) or
𝑑𝑡
−𝑑[𝑅]
= -k dt; integrating on both sides
[𝑅]
ln [R] = -k t + I; where I is the constant of integration. …………(2)
At t=0, the concentration of the reactant R =[R0], where [R]0 is initial concentration of the reactant.
Substituting the values in above equations …..(2)
ln [R]0 = -k X 0 + I
ln [R]0 = I; Substituting the value of I in the equation ……..(2)
ln [R] = -k t + ln [R0] …………(3)
Kt = ln [R]o – ln [R]
1 [𝑅]0
Rate constant k = 𝑡 lne [𝑅]
2.303 [𝑅]0
Rate constant (k) = log
𝑡 [𝑅]

Units: Sec-1
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.

Chloro methane Transition state Methanol


(Invertion configuration)
Rate = K [CH3Cl] [OH-];
so it is second order kinetics.
Reactivity order : 1o > 2o > 3o alkyl halides
SN1 Mechanism:
The reaction between tert-butyl bromide and sodium hydroxide yields tert-butyl alcohol and follows the first
order kinetics.
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It is a two steps process
a) formation of stable 3o- carbo cation

3o- butyl bromide 3o- butyl carbocation


( 2-bromo-2-methyl propane)
b) 3 -carbocation is attacked by OH- nucleophile
o

Rate = K [(CH3)3CBr]
so it is first order kinetics.
Reactivity order : 3o > 2o > 1o alkyl halides

Acid dehydration ethanol into ethene:


Etanol undergoes dehydrtion with concentrated H2SO4 and form Ethene
𝐶𝑜𝑛𝑐.𝐻2𝑆𝑂4
CH3 – CH2 – OH 443𝐾 > CH2 = CH2 + H2O
Mechanism:
Step 1: Formation of protonated alcohol

Step 2 : formation of carbocation

Step 3: elimination of a proton to foem ethene

Nuclophilic addition of HCN to carbonyl compounds:


Carbonyl compounds react with HCN in presence of base form cyanohydrin.

Ald / ketone cyanohydrin


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Mechanism:
Step 1: formation of nucleophile
HCN + OH- → H2O + CN-
Step 2: addtion of nucleophile to carbonyl compounds

Step 3: addition of proton to form cyanohydrin

Solutions Q.No; 1 (mcq) + 16 (fib) + 21 (2m) +33 (3m) + 44,45 (NP-3m) = 13M
Binary solution: The solution consisting of two components only (solute & solvent).
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 the freezing point of water to 255.4K
(-17.6oC)
(1) Mole fraction(X):
Mole fraction of a component is defined as the ratio of number of moles of one component to the total
number of moles of the solution.
Molefraction not depends on temperature If temperature increases molefraction of the solution not change.
(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 gas in liquids:
The solubility of a gas in liquid depends on low temperature and high pressure
If temperature increases solubility of a gas in liquid decreases. Because it is an exothermic process.
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
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Different gases have different KH value. This suggest K H 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.
Henry’s law applications :
1) To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure.
2) Scuba divers are suffers from bends disease so scuba divers carry diluted air with composition
11.7% helium, 56.2% nitrogen and 32.1% oxygen.
3) At high altitudes peoples are suffers from anoxia disease.
4) Aquatic species are more comfortable in cold waters rather than in warm waters due to high solubility of
Oxygen gas in cold water.
Raoult’s law: (SOLUTION = Solvent (A) + solute (B))
The partial vapour pressure of each component of the solution is directly proportional to its mole fraction in
the solution. Mathematically
PA ∝ xA or PA = pA0 xA and pB ∝ xB or pB = pB0 xB
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 nd toluene.
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
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, solute-solute interactions. solvent-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
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.
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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:
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,
Reverse Osmosis and Water Purification:
At high pressure than osmotic pressure the flow of solvent molecules from high concentration solution to low
concentration solution through semi permeable membrane is called reverse osmosis.
Ex: Desalination of sea 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)
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
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.
Compound Van’t hoff factor I for complete dissociation/association
NaCl, KCl, MgSO4 2
BaCl2, MgCl2, ZnCl2, K2SO4 3
CH3COOH in benzene 1/2
C6H12O6, Urea, Sucrose 1
van’t Hoff factor(i) is required when the solute is participate in association or dissociation.

Electrochemistry Q.No; 2,3 (mcq) +34,35 (3m) + 46,47 (NP-3m) = 14M


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
Key points: Higher Eo indicates cathode and lower Eo 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.
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 present between the adsorbed hydrogen and hydrogen ions in the
solution.
H+(aq) + e- ↔ ½ H2(g)
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The Standard electrode potential of hydrogen electrode is assume to be 0 V. so it can act as reference
electrode.
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:
To determine the pH of solutions, solubility product, equilibrium constant, other thermodynamic properties,
and for potentiometric titrations.
Difference between Electronic & Electrolytic conductors:
Electronic (metallic) conductors Electrolytic (ionic) conductors
1)Electrical current flows by movement of electrons 1)Electrical current flows by movement of ions
2) no chemical change occurs 2) chemical change occurs
3) it does not involve the transfer of any matter 3) it involves the transfer of matter in the form of
4) Resistance increases with increase of temperature ions
5) Faraday’s law is not followed 4) Resistance decreases with increase of
Ex: Metal(Cu,Ag,Al…), non metal(graphite), alloys temperature
5) Faraday’s law is followed
Ex: Acids, bases and salt solutions (electrolytes)
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. 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

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)

Units: m(S m2 mol-1)


On dilution conductivity of solution decreases due to decease of no.of ions per unit volume
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On dilution molar conductivity increases to maximum due to decreasing of concentration of solution. At
infinite dilution the molar conductivity is increase to maximum it is called limiting molar conductivity (˄mo)
For strong electrolyte: ˄m = ˄mo – A √C
Foe weak electrolyte: Degree of ionization (α) = ˄m/˄mo

Kohlrausch law of independent migration of ions:


Limiting molar conductivity of an electrolyte is the sum of the individual contributions of the anion and cation
of the electrolyte.
˄mo = V+𝜆+o + V-𝜆-o.
Ex: ˄mo(NaCl) = 𝜆Na+o + 𝜆Cl-o, ˄mo(BaCl2) = 𝜆Ba2+o +2 𝜆Cl-o ˄mo(CH3COOH) = 𝜆CH3COO-o +2 𝜆H+o
Kohlrausch law applications:
To calculate limiting molar conductivity for any electrolyte
To calculate degree of dissociation and dissociation constant
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, Cl 2(anode), H2(cathode).
Faraday’s Laws of Electrolysis:
First Law: The amount of chemical reaction which occurs at any electrode is proportional to the quantity of
electricity passed through the electrolyte.
W = Zit
Second Law: The amounts of different substances liberated by the same quantity of electricity passing through
the electrolytic solution are proportional to their chemical equivalent weights
One mole of substance deposited No.of farady required
+ -
Ag + 1e → Ag 1F = 96500C
Mg2+ + 2e- → Mg 2F = 193000C
3+ -
Al + 3e → Al 3F = 289000C
MnO4 → MnO2
- 3F
MnO4- → Mn2+ 5F
Cr2O7 → 2Cr
2- 3+ 6F
F = 96487C/mol or approximate 1F ≅ 96500 C/mol.
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.
Hydrogen – oxygen fuel cell:
In this cell hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated aqueous
sodium hydroxide solution. Catalysts like finely divided platinum or palladium metal are added to electrode for
increasing the rate of electrode reactions. The electrode reactions are
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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
Prevention techniques:
Covering the surface with paint
Covering the surface with some chemicals like bisphenol
Covering the surface with other metals (Sn, Zn, etc.)

Leclanche Anode: zinc Anode reaction: Zn → Zn2+ + 2e-


cell Cathode: Carbon +MnO2 Cathode reaction: MnO2 + NH4+ + e- → MnO(OH) +
Electrolyte: NH4Cl + ZnCl2 NH3
Mn oxidation state is changes from +4 to +3
Mercury Anode: zinc mecury amalgam Anode reaction: Zn(Hg)+ 2OH- → ZnO + 2H2O
cell Cathode: Carbon + HgO Cathode reaction: HgO + H2O + 2e- → Hg + 2OH-
Electrolyte: KOH + ZnO
Lead storage Anode: lead Anode reaction: Pb + SO42- → PbSO4 +2e-
battery Cathode: grid of lead with PbO2 Cathode reaction: PbO2 + SO42- + 4H+ → PbSO4 + 2H2O
Electrolyte: 38% aq. H2SO4 solution
Rusting of Anode: zinc Anode reaction: Fe → Fe2+ + 2e-
iron Cathode: Carbon +MnO2 Cathode reaction: O2 + 4H+ + 4e- → 2H2O
Electrolyte: NH4Cl + ZnCl2

Chemical Kinetics Q.No; 4 (mcq) +17 (fib) +22 (2M) + 36 (3m) + 46,47 (NP-3m) = 13M
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]
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)
Units of rate constant:
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Zero order reaction: mol. L-1.Sec-1;
First order reaction: Sec-1;
Second order reaction: mol-1.L.Sec-1
Units of rate of a chemical reaction are similar to zero order reaction.
First order reaction units are not depends on concentration it depends on only time
Difference between order and molecularity:
Order Moleculairy
1) It is defined as the sum of powers of the 1)It is defined as The number of reacting species
concentration of the reactants in the rate law (atoms, ions or molecules) taking part in an
2)It is applicable to elementary as well as complex elementary reaction
reactions 2) It is applicable to elementary reactions
3) order can be zero 3) molecularity never not be zero
4) order values are positive, negative and fraction also 4) molecularity values are 1,2,3.
Example for molecularity of a reaction:
NH4NO2 → N2 + 2H2O molecularity = 1 (unimolecular reaction)
2HI → H2 + I2 molecularity = 2 (bi molecular reaction)
2NO + O2 → 2NO2 molecularity = 3 (tri molecular reaction)
Factors effect on rate of a reaction:
concentration of reactants (pressure in case of gases), temperature and catalyst
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

For first order reaction [R]0 = [R]e-kt


1 [𝑅]0 2.303 [𝑅]0 1 [𝑅]1
Rate constant (K) = 𝑡 ln (or) (K) = log (or) (K) = 𝑡2−𝑡1 ln[𝑅]2
[𝑅] 𝑡 [𝑅]
Derivation of Rate constant for first Order gas phase reaction:
Let us consider a first order gas phase reaction A(g) → B(g) + C(g)
At time t=0 Pi atm 0 atm 0 atm (Pi is initial pressure)
At time t Pi-x atm x atm x atm
Total pressure Pt = Pi-x + x + x = Pi + x and x = Pt – Pi
Pressure of gas A, PA = Pi – x = Pi – Pt + Pi = 2Pi – Pt
2.303 𝑃𝑖
Rate constant (K) = log 𝑃𝐴
𝑡
2.303 𝑃𝑖
K= log 2𝑃𝑖−𝑃𝑡
𝑡
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Half-Life of a Reaction:
The time required to convert initial concentration of reactants into half of initial concentration is called half
life of a reaction.
[𝑅𝑜]−[𝑅]
a) For a zero order reaction K = 𝑡
at t = t1/2 then [R] = [R]o/2, then the rate constant becomes
[𝑅𝑜]
[𝑅𝑜]−
2
k= 𝑡1/2
[Ro]
t1/2 = 2𝑘
The t1/2 for a zero order reaction is directly proportional to the initial concentration of the reactants.
2.303 [𝑅𝑜]
b) For a first order reaction, k = log
𝑡 [𝑅]
At t1/2 R = [Ro]/2 so, the above equation becomes
2.303 [𝑅𝑜]
k= log [𝑅𝑜]/2
𝑡1/2
2.303
k= log 2
𝑡1/2
2.303
k= X 0.3010
𝑡
0.693
k= or
𝑡1/2
0.693
t1/2 = 𝑘
For a first order reaction, half-life period is constant, it is independent of initial concentration of the reactants
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
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.

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.

Collision theory of chemical reactions:


The no.of collisions per second per unit volume of the reaction mixture is known as collision frequency (Z).
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The factors effects on effective collisions are activation energy and proper orientation of the molecules
−𝐸𝑎
Rate = P Z 𝑒 𝑅𝑇 where p is called probability or steric factor
The d & f block Elements Q.No; 5 (mcq) + 18 (fib) + 27,28,29 (3m) = 11M
d-block elements : The general electronic configuration of d block elements is (n-1)d1-10ns1-2
Scandium (Sc-21) [Ar] 3d1 4s2 Iron (Fe-26) [Ar] 3d6 4s2
Titanium (Ti-22) [Ar] 3d2 4s2 Cobalt ( Co-27) [Ar] 3d7 4s2
3 2
Vanadium (V-23) [Ar] 3d 4s Nickel (Ni- 28) [Ar] 3d8 4s2
Chromium (Cr = 24) [Ar] 3d5 4s1 Copper (Cu = 29) [Ar] 3d10 4s1
Manganese ( Mn-25) [Ar] 3d5 4s2 Zinc ( Zn-30) [Ar] 3d10 4s2
Chromium and copper show anomalous electronic configuration.
Zinc has completely filled d orbital’s in ground state and in oxidation state. So it is not considered as transition
elements.
In ground state Chromium contains more no.of unpaired electrons (6 electrons)
Transition elements have high melting points due to involvement of (n-1)d and ns electrons in inter atomic
metallic bonding.
Due to large no.of unpaired electrons in transition elements, theyhave stronger interactions, stronger boding
between atoms and higher enthalpies of atomization.
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
adhigher 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 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+.
Magnetic properties:
the ‘spin-only’ formula magnetic moment μ = √n (n + 2) (BM). where n is the number 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.
Formation of complex compounds:
The transition metals form a large number of complex compounds. This is due to smaller sizes of the metal
ions, high ionic charges and the availability of d orbital’s for bond formation.
Ex: [Fe(CN)6]4–, [Cu(NH3)4]2+ and [PtCl4]2–.
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.
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Ex: TiC, Mn4N, Fe3H, VH0.56 and TiH1.7

Properties of interstitial compounds:


a) They have high melting points, higher than those of pure metals.
b) They are very hard, some borides approach diamond in hardness.
c) They retain metallic conductivity.
d) They are chemically inert.
Alloy formation:
Alloys are may be homogeneous solid solutions of one metal randomly distributed in another metal.
Ex: Brass ( Cu + Zn) & Bronze (Cu + Sn)
Potassium dichromate:
𝐻+ 𝑂𝐻−
Chromate > Dichromate Dichromate > Chromate

The reduction half reaction of potassium dichromate is Cr 2O72- + 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

In acid medium MnO4- converted to Mn2+ (oxi.State changes from +7 to +2).


In alkali and neutral medium MnO4- converted to MnO2 (oxi.State changes from +7 to +4).
2MnO4- + 10I- + 16H+ → 2Mn2+ + 5I2 + 8H2O; 2MnO 4- + H2O + I- → 2MnO2 + 2OH- + IO3-
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 4f 1-14 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.
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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.
Lanthanoids Actinoids
1. They show +2, +3 and +4 oxidation states 1. They show +3 to +7 oxidation states
2. Except promethium all are non radio active elements 2. All actinoids are radio active elements
3. Lanthanoid compounds are less basic 3. actinoid compounds are more basics

COORDINATION COMPOUNDS Q.No; 6 (mcq) +23 (2m) + 30,31,32 (3m) = 12M


Werner’s theory of coordination compounds:
1. In coordination compounds metals show two types of linkages (valences)-primary and secondary.
2. The primary valences are normally ionisable and are satisfied by negative ions.
3. The secondary valences are non ionisable. These are satisfied by neutral molecules or negative ions. The
secondary valence is equal to the coordination number and is fixed for a metal.
4. The ions/groups bound by the secondary linkages to the metal have characteristic spatial arrangements
corresponding to different coordination numbers. In modern formulations, such spatial arrangements are
called coordination polyhedra.
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.
Coordination number: C.N = Ʃ (no.of ligands X denticity). (C.N may be 4 or 5 or 6 generally)
Homoleptic and heteroleptic complexes :
The Complexes in which a metal is bound to only one type of ligands are known as homoleptic complexes.
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Ex:[Co(NH3)6]3+
The Complexes in which a metal is bound to more than one type of ligands are known as heteroleptic
complexes. Ex: [Co(NH3)4Cl2 ]+
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:

Optical isomerism:

(i) Linkage isomerism:


Linkage isomerism arises in a coordination compound containing ambidentate ligand due to different linkages.
Ex: [Co(NH3)5(NO2)]Cl2 & [Co(NH3)5(ONO)]Cl2
[Co(NH3)5(SCN)]Cl2 & [Co(NH3)5(NCS)]Cl2
(ii) Coordination isomerism:
This type of isomerism arises from the interchange of ligands between cationic and anionic entities of different
metal ions present in a complex.
Ex: [Co(NH3)6][Cr(CN)6] & [Cr(NH3)6][Co(CN)6].
(iii) Ionisation isomerism:
These type of isomerism arises from the interchange of solvent ligands and counter ion in a complex
Ex: [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4
(iv) solvate isomerism:
These type of isomerism arises from the interchange of ligands and counter ion in a complex
Ex: [Co(H2O)6]Cl3 & [Co(H2O)5Cl]Cl2.H2O
Crystal field theory in octahedral complexes:
Metal ions are combained with ligands form a crystal filed. Up to crystal field degeneracy orbitals not change.
When ligands are arranged in octahedral shape d – orbitals of metal splitted into two sets t2g and eg set.
t2g set has dxy, dyz and dzx and they have less energy than atomic orbitals.
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eg set has dx2-y2 and dz2 orbitals they have higher energy than atomic orbitals. eg set orbitals have more
repulsions.
Some amount of energy required to break the orbitals is called crystal field splitting energy in octahedral
complexes (Δo).

Crystal field theory in tetrahedral complexes:


Metal ions are combained with ligands form a crystal filed. Up to crystal field degeneracy orbitals not change.
When ligands are arranged in tetrahedral shape d – orbitals of metal splitted into two sets t2g and eg set.
t2g set has dxy, dyz and dzx and they have higher energy than atomic orbitals.
eg set has dx2-y2 and dz2 orbitals they have less energy than atomic orbitals.
Some amount of energy required to break the orbitals is called crystal field splitting energy in tetrahedral
complexes(Δt).

C.F.S.E in tetrahedral complex (Δt) = 4/9 C.F.S.E in octahedral complex (Δo)


a) If Δo < P (pairing energy) the ligand can act as weak field ligand and form high spin complexes and d4
configuration is like t2g3eg1
b) If Δo > P (pairing energy) the ligand can act as strong field ligand and form low spin complexes and d4
configuration is like t2g4eg0
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.
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Halo alkanes and Haloarenes 7 (mcq) +19 (fib) +24 (2m) +37 (5m) = 9M
In allyl halide and benzyl halide the halogen attached to sp3 hybrisised carbon.
In vinyl halide the halogen attached to sp2 hybrisised carbon.
CH3-CHCl2 Ethylidine chloride(geminal) ClCH2-CH2Cl Ethylene dichloride(vicinal)
Alkyl chloride have high dipole moments
Alkyl halides are slightly soluble in water.
Due to symmetry para isomers fits in crystal lattice and have high melting points than ortho and meta isomers.
𝑅𝑒𝑑 𝑃
1. CH3OH + Cl2 > CH3Cl
𝑆𝑂𝐶𝑙2
2. CH3OH > CH3Cl(pure) + SO2 + HCl
SOCl2 is best reagent to prepare pure alkyl chloride because the bi products are escapable gases.
48% HBr and KI in 95% H3PO4 required for preparation of alkyl bromides and iodides from alcohols.
Halo arenes are not prepared from phenol, because in phenol the bond between C-OH group is partial double
bond.
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,

Chiral carbon or asymmetric carbon or stereo center:


carbon attached to four different atoms or groups are called chiral carbon.
Chirality: the objects which are on super imposable on their mirror image are said to be chiral and the
property is called chirality.
Enaniomers: the optically active non super imposable mirror images are called enantiomers.
Racemic mixture: The mixtue of equal amount of dextro and leavo compounds is called racemic mixture. It is
optically inactive.
Racemisation: The process of convertion of enantiomers into racemic mixture is called racemisation.
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 (CH 3MgBr)
Grignard reagents are used to convert halo alkanes into alkanes
RMgX + H2O → RH + Mg(OH)X
Halo arenes are less reactive towards nucleophilic substitution reactions :
it is due to halogen attached to sp2 hybridised carbon
in stability of phenyl carbocation
due to resonance effect
repulsions between electron rich to nuclophile and electron rich arenes.
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Wurtz reaction:
alkyl halides react with sodium in dry ether form higher alkanes is called wurtz reaction
dry ether
Ex: 2CH3Br + 2Na → CH3 – CH3
Fittig reaction:
Alkyl halides are react with sodium in dry ether form biphenyl is called fittig reacton.

Wurtz – Fittig reaction:


Alkyl halide and aryl halide react with sodium in dry ether form alkyl arene

Chlorination of chloro benzene:

Nitration of chloro benzene

Sulphonation of chloro benzene:

Friedal craft’s acylation of chloro benzene:

Friedal craft’s alkylation of chloro benzene:

chloro fluoro carbons of methane and ethane are called freons


Chloroform on oxidation form a posinous gas phosgene (carbonyl chloride).
Iodoform can act as antiseptic due to liberation of iodine.
DDT is p,pl – dichloro diphenyl trichloro ethane.
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Alcohols, Phenols and Ethers Q.No: 8,9 (mcq) + 38,39 (5m) = 12M
H3O+
CH3 – CH = CH2 → CH3 – CH2 – CH2– OH + CH3-CH(OH)-CH3
(2-Propanol-major)
B2H6, H2O2/OH−
CH3 – CH = CH2 → CH3 – CH2 – CH2– OH + CH3-CH(OH)-CH3
(1-Propanol-major)
𝑅𝑀𝑔𝑋−𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 𝑅𝑀𝑔𝑋−𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 𝑅𝑀𝑔𝑋−𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
HCHO RCH2OH RCHO R2CHOH RCOR R3COH
𝐻3𝑂+ 𝐻3𝑂+ 𝐻3𝑂+
(10-alcohol ) (20-alcohol ) (30-alcohol )
Due to inter molecular hydrogen bonding alcohols and phenols have high boiling points than ethers,
haloalkanes etc
Due to formation of inter molecular hydrogen bonding lower alcohols and phenols are soluble in water.
Benzene sulphonic acid react with NaOH followed by acid hydrolysis form phenol

Chloro benzene react with NaOH followed by acid hydrolysis form phenol

Benzene diazonium chloride react with warm water form phenol

Preparation of phenol from cumene:


Cumene (isopropyl benzene-C9H12) is oxidized in air form cumene hydroperoxide. It is treated with dilute acid
form phenol and acetone.

Esterification:
Carboxylic acids react with alcohols in presence of dehydrating agent conc. H 2SO4 form fruity odour ester is
called esterification.
Ex: CH3COOH + C2H5OH → CH3COOC2H5 (ESTER)
Distinguish between 1o, 2o & 3o alcohols:
Conc. HCl and an hydrous ZnCl2 is called Lucas reagent
1o alcohol donot form turbidity but it form turbidity on heating
2o alcohol form turbidity ofter some time
3o alcohol form turbidity immediately
𝐶𝑢 𝐶𝑢 𝐶𝑢
CH3 – CH2 – OH 573𝐾 > CH3 – CHO; CH3–CHOH–CH3 573𝐾 > CH3 – CO – CH3; (CH3)3COH 573𝐾 > (CH3)2C=CH2

Phenol on nitration with dilute nitric acid for o-nitrophenol (intra molecular hydrogen bonding-low boliling
point, steam volatile) and p-nitrophenol (inter molecular hydrogen bonding- high boliling point, steam non
volatile) which are separated by steam distillation
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Phenol on nitration with concentrated HNO3 it form an yellow ppt is called 2,4,6 – trinitrophenol (picric acid).

Phenol react with bromine in CS2 o-bromophenol and p-bromophenol (major)


Phenol react with bromine water form a white ppt is called 2,4,6 – tribromophenol

Kolbe’s reaction:
Sodium phenoxide react with carbon dioxide followed by acid hydrolysis form 2 – hydroxybenzoic acid
(salicylic acid)

Reimer – Tiemann reaction:


Sodium phenoxide react with chloroform followed by acid hydrolysis form 2 – hydroxybenzaldehyde
(salicylaldehyde).

Phenol react with zinc form benzene.

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
𝐻2𝑆𝑂4
2 C2H5OH 413𝐾 > CH3CH2OCH2CH3 (SN2 process)
Ethanol Ethoxyetane
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 .

Friedal – crafts alkylation of anisole:


Anisole react with methyl chlore in presence of an hydrous AlCl 3 form 2 – methoxytoluene and 4 – methoxy
toluene
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s
Friedal - crafts acylation:
Anisole react with acetyul chloride in presence of an hydrous AlCl3 form 2 – methoxyacetophenone and 4 –
methoxyacetophenone.

Water gas undergo reduction form methanol (wood spirit-CH3OH)


Invertase enzyme can convert sucrose into glucose and fructose.
Zymase enzyme can convert glucose and fructose into ethyl alcohol.
Denauration of alcohols contains CuSO4 and pyridine.

Aldehydes, ketones & carboxylic acids Q.No: 10,11 (mcq) + 25 (2M) + 40,41 (5m) = 14M
In aldehydes ketones and carboxylic acids carbon undergo SP 2 hybridisation
Rosenmund reduction:
Acyl chloride undergo reduction inpresence of Pd and BaSO4 form aldehydes

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

Gatterman – Koch reaction:


Benzene react with CO2 and HCl in the presence of anhydrous AlCl3 form benzaldehyde
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Preparation of ketones:
2RCOCl + R2Cd → 2RCOR + CdCl2
𝑅𝑀𝑔𝑋−𝑒𝑡ℎ𝑒𝑟
RCN 𝐻3𝑂+ > RCOR + NH3

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

Wolff – Kishner reduction:


Aldehydes/ketones react with hydrazine and KOH form corresponding alkanes

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.

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)
From grignards reagent:
Grignard reagent react with CO2 followed by acid hydrolysis form carboxylic acid
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 𝐻3𝑂+
RMgBr + CO2 > RCOOMgBr > RCOOH
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 𝐻3𝑂+
CH3MgBr + CO2 > CH3COOMgBr > CH3COOH
Due to molecular association through intermolecular hydrogen bonding Carboxylic acids exist as dimers even
in vapour state and have very high boiling points.
Due to formation of intermolecular hydrogen bonding with water lower Carboxylic acids are soluble in water.
Carboxylic acid react with ammonia form ammonium carboxylate. It on heating form amide
RCOOH + NH3 → RCOONH4 → RCONH2 + H2O
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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+
Hell volhard zelinsky reaction: (H.V.Z reaction)
carboxylic acids containg alpha hydrogen react with chlorine in presence of Red P form

Benzoic acid undergo electrophilic substitution reactions form meta derivatives.

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

AMINES Q.No; 12,13 (mcq) +20 (fib) + 42 (5m) = 8M


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.
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1o
It is not for aromatic amine because aryl halide do not participate in nucleophilic substitution reaction.
Hofmann bromamide degradation reaction:
Amide react with bromine in presence of NaOH form primary amine with less no.of carbon atoms.
RCONH2 + Br2 + 4NaOH → R – NH2 + Na2CO3 + 2 NaBr + 2H2O
Ex: 1) CH3CONH2 + Br2 + 4NaOH → CH3NH2 + Na2CO3 + 2 NaBr + 2H2O
Methanamide Methanamine
2) C6H5CONH2 + Br2 + 4NaOH → C6H5 NH2 + Na2CO3 + 2 NaBr + 2H2O
Benzamide Benzanamine (aniline)
RX RX RX RX
NH3 NaOH> RNH2 NaOH> R2NH NaOH> R3N > R4NX
Ammonia 1o amine 2o amine 3o amine quaternary ammonium salt
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:
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
Carbyl amine reaction:
1o amines react with chloroform in presence of KOH form foul smell isocyanide.

allipatic amines undergo diazotisation and hydrolysis form corresponding alcohol


𝑁𝑎𝑁𝑂2 H2O NaNO2 H2O
R – NH2 > R – N2+ Cl- > R – OH Ex: CH3 – NH2 > CH3 – N2+ Cl- > CH3 – OH
𝐻𝐶𝑙 HCl
P-bromoaniline is prepared by using following methods

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 undergo sulphonation formsulphanic acid is the major product.


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Aniline (lewis base) does not undergo friedal crafts reaction due to formation of salt with catalyst AlCl 3(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

Bezene diazonium chloride:


Diazotisation:
Aniline react with NaNO2 in presence of HCl form benzene diazonium chloride

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.

Benzene diazonium chloride Resonace structures of Benzene diazonium chloride


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 Q.No; 14,15 (mcq) + 26 (2m) + 43 (5m) = 9M


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.
Non Reducing sugar: The carbohdrtes which not reduce tollens reagent and fehiling solutions are called non
reducing sugars.
Mono sachharides: The carbohydrate that can not be hydrolysed to produce simple molecule.

Open chain structure of glucose:


Glucose is a monosachharide, Aldohexose and dextro rotatary compound molecular formula is C 6H12O6.
1) Glucose react with HI form n-hexane. This reaction indicates glucose contains six carbon atom chain.
𝐻𝐼,𝐻𝑒𝑎𝑡
C6H12O6 > CH3-CH2-CH2-CH2-CH2-CH3
2) Glucose react with hydroxyl amine to form oxime and with HCN form cyanohydrin. This reacton indicates
glucose has carbonyl roup.
3) Glucose react with bromine water form gluconic acid. This reacton indicates glucose has aldehyde.
𝐵𝑟2 𝑤𝑎𝑡𝑒𝑟
C6H12O6 > Gluconic acid (carboxylic acid)
4) Glucose react with acetic anhydride form glucose penta acetate. This reacton indicates glucose contains
five –OH groups.
𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑛ℎ𝑦𝑑𝑟𝑖𝑑𝑒
C6H12O6 > glucose penta acetate
5) Glucose (and gluconic acid) react with nitric acid form saccharic acid. This reacton indicates glucose has
primary alcohol.
𝑁𝑖𝑡𝑟𝑖𝑐 𝑎𝑐𝑖𝑑
C6H12O6 > Saccharic acid (dicarboxylic acid)
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Cyclic structure of glucose:
1) Glucose not react with schiff’s reagent and NaHSO3.
2) glucose penta acetatedoes not react with hydroxyl amine.
This reactions indicates glucose not contains free –CHO group. Glucose is available in two forms α-D-glucose
and β -D-glucose
Glucose:

α-D- (+)- Glucopyranose β-D- (+)- Glucopyranose


Fructose:
it is a monosachharide, Ketohexose and laevo rotatary compound molecular formula is C 6H12O6.

α – D - (-) - Fructofuranose β - D - (-) - Fructofuranose


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.
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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.
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

General structure Zwitter ion structure


Glycine is optically inactive. And all are laevo rotatory compounds.
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
Non Essential amino acids:
The amino acids, which can be synthesised in the body are known as non essential amino acids.
Ex: Glycine, Alanine, Glutamic acid, 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.
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Proteins are polypeptides are polymer of α – Amino aicds
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.
20 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 r 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
A Xero phthamia, night blindness
B1(Thiamine) Beri beri
B2 (Riboflavin) Chelosis
B6 (Pyridoxine) Convulsions
B12 Pernicious anemia
C (Ascorbic acid) Scurvy
D Rickets
E Increased fragility of RBCs and muscular weakness
K Increased blood clotting time

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.
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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:
Hormoes 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
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.
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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) = 𝑡𝑜𝑡𝑎𝑙 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 X 100
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)
Henrys law for gas in liquid type of solution: P = kH.X or p = kH.S
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
0
PA 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
𝑤 1000
depression of freezing point: ΔTf = Tfo – Tf ; ΔTf = Kf 𝐵 𝑋
𝑀𝐵 𝑤𝐴
o
Tf , 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) = 𝑀
𝐵
π is osmotic pressure, V is volume of solution in liter, T is temperature, R is universal gas constant.
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Electro chemistry:
E0cell = E0cathode – E0anode
0.059
Ecell = E0cell – 𝑛 log Qc
0.059
E0cell = 𝑛 log Kc
ΔG0 = -nFE0cell
ΔG0 = -RT ln K
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 ]

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