IMPORTANT

FACTS
AND
FORMULAE

FOR JEE
Sr.No. Subjects Page No.

1. Physics 1 - 39

2. Chemistry 40 - 90

3. Mathematics 91 - 158
40 CHEMISTRY

IMPORTANT FACTS AND FORMULAE FOR JEE

IIT CHEMISTRY

SOME BASIC CONCEPTS

1. 1 mole = NAvg u number of species = 6.023 u 1023 species
i.e., atoms, molecules, ions, etc.
2. Atomic mass = Mass of one atom
Gram-atomic mass = Mass of one mole of atoms
= Mass of 6.023 u 1023 atoms in gms.
e.g. Atomic mass of O is 16 amu.
gm-atomic mass of O is 16 gm.
? 16 gm O-contains 6.023 u 1023 oxygen atoms.
Average mass of an atom
Atomic mass =
1/12 u Mass of an atom of C12
R.A.(1) u M.No + R.A.(2) u M.No
Average atomic mass =
R.A.(1)+ R.A.(2)
Here R.A = Relative Abundance, Mass No. = Mass number.

1
3. 1 amu (atomic mass unit) = = 1 Avogram
NAvg

1
= gm = 1.66 u 10-24 gm = 1 Dalton
6.023 u 1023

4. Molecular weight = Weight of one molecule

Molar mass or gm-molecular weight = weight of one mole of molecule

= wt. of 6.023 u 1023 molecules

Weight(gm) volume of gas at STP(L)

5. Moles = =
Molar mass (gm / mole) 22.4 lit.

= Molarity u Volume (in L)

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Millimoles = Molarity u Volume (mL)

Weight(gm)
6. No. of equivalent =
gm.equivalent weight

= Normality u Volume (L)

Milliequivalent = Normality u Volume (ml)
Molar mass
7. Equivalent Weight =
n - factor
8. For acid-base, n-factor : No. of replaceable H+ or OH- ions per mole of the
species.
For compounds undergoing redox reaction, n-factor, no. of moles of
electrons gained or lost per mole of the species.
Example,
Mol. wt
For H3PO4, Eqv. weight = n-factor = 3(3 replaceable H+ ions)
3
Mol. wt.
For NH3, Eqv. weight = n-factor = 1(can replace one mole H+
1
per mole)
Mol. wt
For Ag3PO4, Eqv. wt. = n-factor = 3
3
Mol. wt.
For Ba3(PO4)2, Eqv. wt. = n-factor = 6
6
Mol. wt.
For I2 o I- , Eqv. wt. I2 =
2
Eq. mass of KMnO4 in acidic medium
Formula wt.
MnO-4 + 8H+ + 5e- o Mn2+ + 4H2O Eq. Mass of KMnO4 =
5
Eq. Mass of KMnO4 in neutral medium
Formula wt.
MnO-4 + 4H+ + 3e- o MnO2 + 4H2O Eq. Mass if KMnO4 =
3
Eq. Mass of KMnO4 in basic medium
Formula wt.
MnO-4 + e- o MnO2- 4 Eq. Mass if KMnO4 =
1
Molar mass
9. Vapour density =
2

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10. Molar volume = volume of 1 mole of gas at NTP/STP = 22.4 L or 22400
mL
11. Dulong and Petits law :
6.4
Atomic mass (approx.) = (for metals only) (cal/g)
specific heat
The law is applicable only to solid elements except Be, B, C and Si.
Approx. Atomic mass
Valency =
Eqv. mass
The exact valency is a whole number nearest to the approximate valency
calculated. The exact valency is multiplied by the Eqv. mass to get
Atomic mass.
Exact atomic mass = Exact valency u Eq. mass.
12. Relation between molecular and empirical formulae :
Molecular formula = n u Empirical formula
Molecular formula weight
?n =
Empirical formula weight
Moles of solute
13. Molarity =
volume of solution (L)
mole of solute
14. Molality =
mass of solvent(kg)
nA
15. Mole fraction = mole fraction of A in mixture of A and B = X A =
nA + nB
nB
mole fraction of B in mixture of A and B = XB =
n A + nB
number of gm equivalent of solute
16. Normality =
volume of solution(L)
Cp
17. Atomicity (J ) = (1.66 for mono-atomic, 1.4 for di-atomic, 1.33 for tri-
Cv
atomic gas)
mol. mass
At mass of gaseous element =
Atomicity
(Atomicity = number of atoms present in a molecule of the element).
Cp Cv = R = 1.98 cal mol-1 K-1
Molar heat = specific heat u mol. mass

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STATES OF MATTER
Boyles law
PV = constant [at constant n, T] ? P1V1 = P2V2

Charles
V V1 V2
= constant [at constant n, P] ? = ;
T T1 T2
t
Vt = V0 1+ [T (kelvin) = 273 + t (0C)]
273
Gay-Lussacs law
P P P
= constant [at constant n, V] ? 1 = 2
T T1 T2
Ideal gas equation
PV
= R = 0.0821 l. atm.K-1 mol-1
nT
= 1.987 Cal K-1 mol-1 = 8.314 J K-1 mol-1
1 atm = 760 mm of Hg = 76 cm of Hg = 101325 pascal ; 1 bar = 0.9862
Atm
Standard Temperature and pressure (STP) or Normal Temperature and
Pressure (NTP)
P = 1 atm, T = 00 C or 273 K

Density and molar mass relation

PM
Density (d) =
RT
Daltons law of Partial Pressure
PTotal = P1 + P2 + P3 + ..
Where P1, P2,..etc. are partial pressures of individual gases.
Partial pressure = Total pressure u mole function
Partial pressure of water in air
Relative Humidity =
Vapour pressure of water
Vap. Pressure of dry gas = Vap. Pressure of wet gas Vap. pressure of
water vapour (aqu. tension)

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Grahams law (Diffusion and Effusion)
( rA )Rate of effusion of gas A UB MB
= = [at constant pressure]
( rB )Rate of effusion of gas B UA MA

rA PA MB PA UB
= = [at different pressure]
rB PB MA PB UA
Velocity of Molecules
3RT 3P
Root mean square velocity (CRMS) = =
M d
8RT
Average velocity (CAVG) =
SM
2RT
Most probability velocity (CMP) =
M
CMP  C Avg  CRMS
CMP : C Avg : CRMS : :1 :1.128 :1.224

Real Gases, Compressibility factor

PV
Z=
n RT
Z measures the extent of non-idealness of an ideal gas.
Z < 1 , implies that gas is more compressible
Z > 1 , implies that gas is less compressible
Z = 1, implies that gas is ideal.

Gas Equation (van der Waals)

n 2a
P + 2 (V - nb) = nRT
V
2.303 RT1T2 P
'Hvap = log 2
(T2 - T1 ) P1
P1,P2 vapour pressure at T1, T2
n 2a
P + 2 (V - nb) = nRT
V

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a
i) At low pressure : p + 2 V = RT
v
ii) At high pressure : P (V - b) = RT
Units of a are atm L2 mol-2 and b are L mol-1
Greater is the value of a means gas can be easily liquefied
4 3
Co-volume or excluded volume = 4N0Vm Vm = 3 Sr

SC Avg V2 (N / V)2
i) Collision frequency, Z =
2
V
ii) Mean free path (O ) = , where V =molecular diameter
2SV2N
N/V = number of molecules per unit volume

Nature of Gas Constant R

P u V Pressure u Volume (Force / Area) u (Volume) Force u Length
R= = = =
nT Moles u Degree(K) Moles u Degree(K) Moles u Degree(K)
= Work done per degree per mole

Units of gas constant (R)

R = 0.0821 atm L K-1 mol-1 = 0.0821 atm dm3 K-1 mol-1
(Here P = 1 atm, V = 22.4 L, T = 273 K, 1 L = 1 dm3)
If P is expressed in dynes per square centimeter
(P = 76 u 981 u 13.6 dyne /cm2 )
V = 22400 dm3 and T = 273 K
then R = 8.314 u107 ergs K-1 mol-1 = 8.314 J K-1 mol-1 and R = 1.987cal K-
1 mol-1

1 atm. Pressure = 0.76 m u 13.6 u 103 kg m-3 u 9.81ms -2 = 101.325 u 103

Nm-2 = 101.325 u 103 Pa ['1 Nm-2 = 1 Pa]
(101.325 u 103 Nm-2 ) u (22400 u 10-6 m3 )
Thus, the gas constant R =
(273K) u (1mol)
= 8.314 Nm K-1 mol-1
= 5.189 u 1019 eVK-1 mol-1
[' 1 eV = 1.602 u 10-19 volts coulomb (Joule)]

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i) Avogadros Law
V v n or V v N (at constant T, P)
ii) Calculation of Kinetic Energy
1
According to gas equation, PV = Mu2 for 1 mole of gas
3
2 1
or PV = u Mu2
3 2
1 3 3
or Mu2 = PV = RT = K.E.
2 2 2
For 1 molecule, the K.E.
3 RT 3 R
= = KT = K (Boltzmann constant)
2 N0 2 N0
iii) Average molecular weight of a gaseous mixture
ni Mi
Mmix = where ni is the number of moles and Mi is the
ni
molecular weight of the component.
a
iv) Critical Pressure (PC) : PC =
27b 2
8a
v) Critical Temperature (TC) : TC =
27Rb
vi) Critical Volume (VC) : VC = 3b
PC TC 3
vii) Relationship between PC, VC and TC : =
RTC 8
a
viii) Boyles Temperature : TB =
bR

ATOMIC STRUCTURE

Plancks Quantum theory

hc
E = hv =
O
Where, h = Plancks constant (6.023 u 10-34 Js), v = Frequency of
radiation, c = Velocity of light, O = wavelength of radiation
1
c = vO and wave number (v) =
O

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Moseleys Equation, Q = a (z - b)
Heisenbergs uncertainty equation,
h h
'p. 'x t and 'E. 't t
4S 4S
1 Zke 2
Kinetic energy of electron in nth quantum state =
2 rn
Zke2
Potential energy of electron in nth quantum state = -
rn
Zke2 (13.6)Z 2
Total energy (E) = - =- eV per atom
2rn n2
313.6 1312
=- 2
kcal/mol = - kJ/mol
n n2
Z2
= -21.8 u10-19 J/atom.
n2
n2 h2 n2 a 0 0
Radius of nth quantum state = = (a0 = 0.529 A )
4S 2 mkZe 2 Z
Velocity of electron,
2SZke2 Z
vn = = u 2.188 u 106 m/s
nh n
v Zv n
No. of revolution per second in r.p.s = n =
2Srn 2Sn2a 0
Wave number of spectral line,
1 1 1
v= = R H Z2 2 - 2 (RH = 109743 cm-1
O
n1 n2
2S2 me 4 k 2
= R H = 109743cm-1 =
h3c

de Broglie equation
h h
O= =
p mv
Azimuthal (or angular) Quantum number (l); 0 d l d n -1
h
Orbital angular momentum, L = l (l +1)
2S
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Magnetic quantum number (m); -l d m d l , total (2l + 1) values.
eh
Magnetic moment, P L = l (l +1)
4Smc
eh
Spin angular momentum P s = s(s +1)
2Smc

Aufbau Principle : subshell with lowest (n + l), value us filled first, if two
subshells have same (n + l ) value, lower value of n is filled up first.

Photoelectric effect
Maximum kinetic energy of ejected electron
1 2 1 1
mv max = hQ - hQ 0 = hc -
2 O O0
Stopping potential, eV0 = h (Q - Q 0 )
Binding energy = Mass defect u 931 MeV
i) Radius of Nucleus (rn) = r0 u A1/3
where A is the mass number and r0 is proportionality constant
whose value is 1.4 u 10-13cm.
ii) The radius of the nucleus is approximately 10-5 times the radius of
the atoms. Volume of the nucleus of an atom is about 10 -5 times
the volume of the atom.
iii) Energy of an electron in nth shell of hydrogen atom En v 1/ n2
iv) Although the energy of electron increases with increase in the
value of n(orbit), yet the difference of energy between successive
orbits decreases.
Thus, E2 E1 > E3 E2 > E4 E3 > E5 E4, etc.
v) No. of spectral lines when electron comes from nth level to ground
n(n -1)
level =
2
vi) Number of sub-shells in a main energy level = n
vii) Number of orbitals in a main energy level = n2
viii) Number of orbitals in a sub-shell = (2l + 1)
ix) Number of electrons in each orbital = 2
x) Maximum number of electrons in a subshell = 2(2l + 1)
xi) Maximum number of electrons in main shell = 2n 2

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SOLUTIONS

Solubility
'Hsolution = 'Hlattice - 'Hhydration
If hydration energy > lattice energy, the solute goes into solution and
'Hsolution comes out to be negative value i.e., the process is exothermic.

Henrys law
Mass of the gas dissolved per unit volume (n) v pressure (P)

Parts per million

Mass of A
ppm(A) = u 106
Total mass of the solution
Weight % = wt. of solute per 100g of solution.
Volume % : (a) wt. of solute per 100 ml of solution.
(b) Volume of solute per 100 ml of solution.
Moles of solute
Mole % = u 100
Moles of solute + Moles of solvent
Relationship between Molality (m) of a solution and mole fraction of the
solute (X2)
mM1
X2 = where M1 is the molecular mass of the solvent.
1+ mM1
Relationship between Molality (m), Molarity (M) and density of the solution
(d)
M
Molality, m = u 1000
1000d - MM2
where M2 is the molecular mass of the solute.
Relationship between mole fraction of the solute (x 2) and Molarity (M) of
the solution
MM1
X2 =
M(M1 - M2 )+ d
where M1 and M2 are the molecular masses of solvent and solute
respectively. Density of solution is d. For isotonic or iso-osmotic
solutions

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n1 m2
= [' S1 = S2 ]
V1 V2
Raoults law (Vapour-Pressure lowering of solution)
ps = p0 . Xsolvent
p0 - p s n
=
ps N
p0 = pressure of pure solvent; ps = pressure of solvent

D during dissociation.
i -1
D= , n = no. of ions after dissociation
n -1
D during association.
1- i
D=
1- (1/ n)
Variation of vapour pressure with temperature
P2 'H 1 1
log10 = -
P1 2.303 R T1 T2
Variation of vapour pressure with external pressure
P V0
log10 2 = (P2 - P1 )
P1 2.303 RT

Osmotic Pressure
n
S = i 1 RT = hdg (due to association or dissociation)
V
Van Hoff Factor
P ('p)observed (' Tb )observed (' Tf )observed
i = observed = = =
Pnormal ('p)normal ('Tb )normal ('Tf )normal
Normal molecular mass
=
Observed molecular mass
For solution showing dissociation, the Vant Hoff factor i ! 1
For solution showing association, the Vant Hoff factor i  1
For solution showing no dissociation or association, the Vant Hoff factor
i=1

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Raoults Law
P = PA + PB = PA0 X A + PB0 X B = (1- X B )PA0 + PB0 X B

Ideal Solutions
They obey Raoults law for all range of concentration and temperature.
' Hmix = 0 and ' Vmix = 0
e.g., Hexane + Heptane. Ethyl bromide + Ethyl chloride, Chlorobenzene +
Bromobenzene, etc.

Non-Ideal Solutions
The non-ideal solution do not obey Raoults law for all concentrations.
' Hmix z 0 and ' Vmix z 0
If Vmix ! 0 and ' Hmix z 0, then non-ideal solutions show positive
deviations.
If Vmix  0 and ' Hmix  0, then non-ideal solutions show negative
deviations.
e.g. Acetone + ethyl alcohol, water + ethyl alcohol. CCl4 + CHCl3 ethanol
+ CHCl3.
Acetone + carbon disulphide, Acetone + Benzene, etc.

Types of Azeotropic Mixtures

(i) Minimum Boiling Azeotropes :
e.g., Ethanol (95.5 % ) + water (4.5 % ) mixture boiling.
(ii) Maximum Boiling Azcotropes :
e.g., HNO3 (68 % ) + water (32 % ) mixture boiling at 393.5 K.

Elevation in boiling point

' Tb = Tb - T0 = Kb m
K u WB u 1000
= b where WA = mass of solvent (g) and WB = mass of
MB u WA
solute (g)
Molal elevation constant (Kb)
RTb2
Kb = [Lv = latent heat of vapourisation]
1000L v

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Depression in freezing point
k F u WB u 1000
' Hr = T0 - Tp = k f u m =
MB u WA
Molal depression constant (Kf)
RTf2
Kf = [Lf = latent heat of fusion]
1000L f
It is interesting to note that all the above relations hold good. Only when
Kf and Kb are expressed in Kelvin m-1.

CHEMICAL ENERGETICS AND THERMODYNAMICS

Mechanical work
W = - Pext ('V) [during expansion]
First law of Thermodynamics
'V = 0
W = P 'V = 0
'E = q + W
' E = q P 'V
Cyclic change (reversible)
'E = 0
q = - W = P 'V
q = - Wmax = P dV
Isothermal reversible expansion
'H = 'E = 0 ('internal energy is function of temperature)
V P
q = - Wmax = 2.303 nRT log 2 = 2.303 nRT log 1
V1 P2
Joule Thomson coefficient
wT wH
P JT = = / Cp
w P H w P T
(i) For cooling, u ! 0 (-ve sign)
(ii) For heating, u  0 (+ve sign)

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Second Law of Thermodynamics
q 2 - q1 T2 - T1 T
Efficiency of the Carnot engine = K = = = 1- 1
q2 T2 T2
q2 = heat absorbed by engine
q1 = heat lost to sink

Entropy Change

' Stotal = ' Ssystem + ' Ssurrounding

'Hfus 'Hvap
' Sfusion = ; ' Svap =
Tfus Tvap
Gibbs free energy (G)
' G = G2 - G1
' G = ' H T ' S (Gibbs Helmholtz equation)
' G  0 (means spontaneous process),
' G ! 0 (means non-spontaneous process)
' G = 0 (means system is at equilibrium)

Kirchoffs equation
'H2 - 'H1 'E2 - 'E1
= 'Cp and = 'C v
T2 - T1 T2 - T1
Where, 'Cp = Cp (products) - Cp (reactants) and
'C v = C v (products) - C v (reactants)

Degree of dissociation (x)

D - d M1 - M0
x= =
d M0
where D = theoretical vapour density and d = observed vapour density.

pH of a solution
pH = - log [H3O+]
pOH = - log [OH-]
pH + pOH = pKW = 14
For neutral solution ; pH = pOH = 7 at 298 K
For acidic solution; pH  7. But pOH ! 7 at 298 K

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For basic solution; pH ! 7, But pOH  7 at 298 K

Isothermal (reversible)
V2
' S = 2.303 nR log
V1
T2
At constant pressure, ' S = 2.303 Cp log10
T1
'Hvap
For vaporization, 'S =
Tbp

'G0 = -nFE0cell
Sign Convention
If work is done on the system, W is positive.
If work is done by the system, W is negative.
If heat is absorbed by the system, q or 'H is positive.
If heat is given out by the system, q or 'H is negative.
If energy is absorbed by the system, i.e. internal energy increases. 'E is
positive.
If energy is released i.e., internal energy of the system decreases. 'E is
negative.

Heat capacity
wE
(i) Heat capacity at constant volume, C v =
wT v
wH
(ii) Heat capacity at constant pressure, Cp =
wT p
For an ideal gas, Cp - Cv = R
Heat of Reaction
'H = H(p) - H(R)
For exothermic reactions : Hp  HR ?' H is - ve

For endothermic reaction : Hp ! HR ?' H is + ve

Heat change at constant pressure = q p = 'H

Heat change at constant volume = q v = 'E

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' H = ' U + P' V
'H = 'U + 'n(g) RT

If 'n(g) = 0, 'H = ' U

'n(g) ! 0 , 'H ! 'U

'n(g)  0 , 'H  'U

Clausis Clapeyron equation :

p2 'H v T1 - T2
2.303 log = where, 'Hv = molar heat of vapourisation.
p1 R T1T2

i) Calorific value is the amount of heat evolved when one gram of fuel as food is
burnt in the presence of air or excess of oxygen.
ii) Joules relationship between work done (w) and heat produced (H) W v H or W = JH
Where, J is called mechanical equivalent of heat. Its value is J = 4.184 u 107
erg Cal-1 4.184 J Cal-1.

S1 'H 1 1
Log = -
S2 2.303R T1 T2

Where S1 and S2 are solubility at temperature T1 and T2 respectively.

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56 CHEMISTRY
CHEMICAL AND IONIC EQUILIBRIUM

dx dx
Equilibrium in water = =
dt forward dt backward

aA + bB U cC + dD
dx a b
dt v K forward A B
forward
dx c d
dt v K backward C D
backward
c d
C D K forward
Equilibrium constant, K = a b
= = Kc
A B K backward
In terms of partial pressure
pcC pdD
Equilibrium constant, K p =
paA pbB
'n g

K p = Kc RT ' n g = n p - nr
Vant Hoff equation
k2 'Ho 1 1
log10 = -
k1 2.303R T1 T2
Gibbs Free energy
'G = 'H - T'S
'Go = -2.303RT log10 K
Buffer:
conjugate base
pH = pK a + log
acid
conjugate acid
pOH = pK b + log
base
Mixture of weak acids = k1c1 + k 2c 2
 conjugation
D=
100
A x B y U x A y+ +y Bx -

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x y
? K sp = A y+ Bx - , when A x By

K sp = Solubility product.

Arrhenius concept : Substances which give H+ ions when dissolved in water,

while which gives OH- ion are called bases.

Bronsted Lowry concept : Acid donates proton, base accepts proton.

K
Ostwalds dilution law, D = ,
C
K = dissociation constant of weak electrolyte
C = Concentration
D = degree of dissociation
K w = H+ OH- [ionic product of water]

Hydrolysis constant
h2C
kh =
1- h
Amount of salt hydrolysed
h=
Total salt taken
Kh Kw
h= =
C Kb u C

Kw
Strong acid + weak base, Degree of hydrolysis (h) =
CK b
1
pH = pK w - K b - logC
2
Kw
Strong base + weak base, Degree of hydrolysis (h) =
CK a
1
pH = pK w + pK a + logC
2

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Kw
Weak acid + weak base, Degree of hydrolysis (h) =
Ka u Kb
1
pH = pK a + pK w - pK b
2

REDOX REACTIONS AND ELECTROCHEMISTRY

0.059 Product
Ecell = Eo cell - log
n Practant

-'G = nFEcell ;-'Go = nFEocell

2.303RT 0.591
Eocell = log K eq = log K eq [At = 25o C ]
nF n
'Go = -2.303 RT log K

Gibbs Helmholtz equation

d'G
'G = 'H + T
dt p
dE
'H = nF T - E
dT p
Faradays second law
w = Zit, 1 Faraday is the quantity of charge carried by 1 mol of electrons.
equivalent mass
Z= ; Z = weight deposited when 1A passed for 1 sec.
96500
Faradays second law
m1 E1
=
m2 E2
m1, m2 are masses deposited and E1 and E2 are their equivalent weights; for
same amount of passed charge.
Actual current
 current efficiency = u 100
Ammeter current
Ohms law = I = E R
Ions are always discharged / produced in equivalent amounts whatever their
speeds of deposition are,

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59 CHEMISTRY
1
Specific conductance = k = , U = specific resistance
U
l l 1
k= uC = cell constant, C = conductance =
a a R
Conductivity = cell constant u observed conductance
k k u 1000cm3L-1
S eq = =
Ceq Normality

Equivalent conductance, /
/ =kuV
V = volume in mL containing 1g equivalent of the electrolyte.
Molar conductance P = [Equivalent conductance]
P = n/
Molecular mass
n=
Equivalent mass
P =kuV V(mL) containing 1g mole of an electrolyte
At infinite dilution, / 0 = O a + O c
O c = kuc
O a = kua
O a , O c ionic conductance of anion and cation
k = 96500 C
ua = mobility of anions and uc = mobility of cations
/
degree of dissociation, D =
/f
Relation between equivalent and molar conductance at infinite dilution
1 1
/ f = + O f+ + - O f-
z z
Units of molar conductance are O -1cm2mol-1
Units of equivalent conductance are O -1cm2 (g. eq.)-1
For weak electrolytes,
K OC OC
D= = ef = m OC C
e , O m = equivalent and molar conductance
C Oe O Pf

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Ostwalds equation
2
C OC
m
K=
f f C
Om Om - Om
Oxidation state of Cr in Cr2O3 and CrO5 is +3 .
The oxidation number of Ni(CO)4 and Fe(CO)5 is zero.
The strength of oxy-acids of chlorine decreases in the order.
HClO4 ! HClO3 ! HCLO2 ! HClO
The maximum oxidation number of an element = no. of valence electron
present.
The minimum oxidation number of an element = 8  n , where n is the
no. of valence electrons.

Cell notation

Transport number
Current carrired by ion
Transport number =
Total current carried
Transport number of cation + Transport number of anion =1
nc + na = 1

RATES OF CHEMICAL REACTIONS AND CHEMICAL KINETICS

aA + bB + cC + dD
dx
Rate of reaction =
dt
1d A 1d B 1d C 1d B
=- =- = =
a dt b dt c dt d dt
d A n
- D A 1 . n1 order of reaction with to A
dt
d B n
- D B 2 n2 order of reaction with to B ..etc
dt
dx n n
= k A 1 B 2 n 1 + n 2 - overall order of reaction.
dt

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Rate Laws
Zero-Order reaction
dx 0
= k0 A ? x = k 0 ,t
dt
First-Order reaction
dx 1 2.303 a
= k1 A k1 = log10 A = A 0
e-kt
dt t a-x
nth Order reaction
dx n 1 1 1
= kn A kn = n-1
- n-1
; nt2
dt n -1 t a - x
a
Half Life Period
0.693
T1 2 = , for n = 1
k1
2n-1 -1
T1 2 = ; for n t 2
n -1 k na n-1
t1 2 v a n-1 ; t3 4 = 2 u t1 2 ; t87.5% = 3 u t1 2

Arrhenius equation
k = Ae-Ea RT
Ea
log k = logA -
2.303RT
k2 Ea T2 - T1
log10 = k1 & k2 at T1 and T2 temperature
k1 2.303R T2 T1
d ln k E
= a2
dT RT
Rates of chemical reactions and chemical kinetics
Units of rate and rate constant
(i) Rate of reaction: mol L-1 S-1
(ii) Rate constant (K)

Order of reaction Units

Zero order mol litre-1 time-1
1st order time-1
2nd order mol-1 L time -1
nth order (mol L-1)1-n time-1

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Quantum yield or quantum efficiency of a photochemical reaction

number of reactant molecule reacting in a given time

I=
number of photons quanta of light absorbed in the same time

SURFACE CHEMISTY

The isothermal variation of extent of adsorption with pressure is

x x 1
= Kp1 n or log = logK + log P
m m n
where x = mass of gas adsorbed by the mass m of adsorbent at the pressure P.
K and n are constant for a given pair of adsorbent and adsorbate.

Colloidal state

x True solution (size <1nm)

x Colloidal solution (size 1 nm 100 nm) and
x Suspensions (size > 100 nm)
1
Flocculation value v
coagulating power
Hardy Schulze Rule
(i) The ion having opposite charge to sol particles cause coagulation
and
(ii) Coagulating power of an electrolyte depends on the valency of ion
i. e., greater the valency more is the coagulating power.

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To coagulate negative sol of As2S3, the coagulating power of
different cations has been found the decrease in the order
as:
Al3+ ! Mg 2+ ! Na +
Similarly, to coagulate a positive sol such as Fe(OH)3, the
coagulating power of different anions has been found to decrease
in the order:
4-
3- 2- -
Fe CN 6 ! PO4 ! SO4 ! Cl
Thus, larger the charge on the coagulation ion, larger the
coagulation.

Gold Number

The no. of milligrams of the protective collide required to just present the
coagulation of 10 mL of red gold sol when 1 mL of 10% solution of
sodium chloride is added to it.

Lower is the value of gold number greater is the protective power.

CHEMICAL FAMILIES PERIODIC PROPERTIES

Modern Periodic law: The properties of elements are periodic functions of

their atomic numbers.
Ionisaton Energy: Ionisation energy (IE) of an element is defined as the
amount of energy required to remove an electron from an isolated gaseous
atom of that element resulting in the formation of postitive ion.
IE
M g o M+ g + e-
Electron Affinity: Electron Affinity (EA) of an element is defined as the
amount of energy associated with the gain of electrons by the gaseous
atom.
EA
F g + e-  o F- g
Electronegativity: It is a measure of the tendency of an element to
attract electrons to itself.
G+ G-
x
A u
B o A - B
B is said to be more electronegative than A as it pulls bonding pair
towards itself.
Shielding or Screening Effect : A valence electron in a multi electron
atom is attracted by the nucleus, and repelled by the electrons of inner
shells. The combined effect of this attractive and repulsive force acting on
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the valence electron is that the valence electron experiences less
attraction from the nucleus. This is called Shielding or Screening Effect.

Lanthanides
General Electronic Configuration : 4F 2-14 5d0.1 6s2

Actinides
General Electronic Configuration : 5f 2-14 5d 0,1 7s2

CHEMICAL BONDING AND MOLECULAR STRUCTURES

Table gives an idea regarding the effect if bonding and loan pairs on
geometry and bond angles of molecules.

Number
of Distorted
Number Of
orbitals Theoretical VSEPR Bond geometry
Example
on geometry Notation angle due to
central Bond Lone repulsion
atom pairs pairs
BeF2 2 Linear 2 0 AX2 180o Linear
Plane
BF3 3 Triangular 3 0 AX3 120o
triangle
Plane
SO2 3 2 1 AX2E 119o Angular
triangle
109o
CH4 4 Tetrahedral 4 0 AX4 Tetrahedral
28
107o Trigonal
NH3 4 Tetrahedral 3 1 AX3E
48 pyramidal
102o
NF3 4 Tetrahedral 3 1 AX3E Pyramidal
35
104o
H 2O 4 Tetrahedral 2 2 AX2E2 Angular
27
F 2O 4 Tetrahedral 2 2 AX2E2 102o Angular
Tetrahedral Angular
H 2S 4 2 2 AX2E2 90o
Trigonal
120o Bipyramidal
Triogonal
PCl5 5 5 0 AX5 and Irregular
pyramidal
90o tetrahedral
Triogonal 101o
SF4 5 4 1 AX4E (See-saw)
pyramidal 36

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Triogonal
CIF3 5 3 2 AX3E2 87o40 T-shaped
pyramidal
Triogonal
I3- 5 2 3 AX2E3 180o Linear
pyramidal
SF6 6 Octahedral 6 0 AX6 90o Octahedral
Square
BrF5 6 Octahedral 5 1 AX5E 84o30
pyramidal
Square
XeF4 6 Octahedral 4 2 AX4E2 90o
planar

CHEMISTRY OF NON- METALS I

x Heavy hydrogen is also called deuterium.

x Occlusion of Hydrogen : Metals like Pd, Pt, etc. have the property of
absorbing large quantity of hydrogen at normal or higher temperature.
This phenomenon is known as Occlusion of Hydrogen.
x Oxidation and reduction by H2 O2 in acidic medium is generally slow
while it its rapid in alkaline medium.
x Polyoxides
(i) Peroxides : In Perioxides, the two oxygen atoms are linked to each other
by a single covalent bond and each oxygen has oxidation state of 1,
e.g., BaO2, H2O2.
-
(ii) Superoxides : These oxides contain O O unit pertaining to oxidation
state of each O atom as +1 2 , e.g., KO2, RbO2.
(iii) Suboxides : These oxides contain low content of oxygen than expected,
e.g., Na2O and C3O2.
(iv) Mixed Oxides: These oxides are made up of two simpler oxides,
e.g., Pb3 PbO2 .2PbO .
x Liquid oxygen mixed with finely divided carbon is used in place of
dynamite in Coal mining.
x Nitric acid is also called aqua fortis (meaning Strong water)
x Oxides of Nitrogen

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CHEMISTRY OF NON METALS- II

x Boron trihalides are Lewis acids and acid strength decreases as

BBr3 ! BCl3 ! BF3 .
x Hydrides of borons are known as boranes having general formula
Bn Hn+7 and Bn Hn+6
x Diborone is the simplest borne and borazene is known as the inorganic
benzene.

x Boron Carbide (B4C3) is the hardest artificial substance and is called

Norbide.
x Acidic nature of hydrides of halides follows the order
HI ! HBr ! HCI ! HF .
x Acidic nature increase with increase in oxidation number of halogen.
HCIO  HCLO2  HCIO3  HCIO4
x In any given series of acids, the acidic character decreases with decrease
in the electronegativity of central halogen atom.
HCIO4 ! HBrO4 ! HIO4
x Species which behave in the chemical behavior are called Pseudo
halogens, e.g. (CN)2 Cyanogen; thiocyanate (SCN)2; Selenocyanogen
(ScCN)2, etc.
x Compounds contaming C, Cl, Br, F elements are called Halons, e.g.,
Halon 1211 (CF2ClBr), Halon 1301 (CF3Br) and Halon 2402 (C2F4Br).
x B(OH)3 is known as Boric Acid.
x CO combines with Cl2 in the presence of sunlight to form another
poisonous gas phosgene
Sunligth
CO + Cl2 
o COCl2
Phosgene

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x CO + H2 is known as water gas.
x Acetyl ides: The Carbides which on hydrolysis give acetylene are called
acetylides.
e.g., MgC2 + H2O o Mg OH 2 + HC { CH
acetylene
x Allylides: The carbides which on hydrolysis give allylene or propyne are
called allylides. e.g., Mg 2C3 + 4H2O o 2Mg OH 2 + CH3C { CH
Allylen or Propynes
CHEMISTRY OF LIGHTER METALS

x Sodium teraborate decarbohydrate (Na2B4O7. 10H2O) is commonly

known as Borax.
x A mixture of Al(C2H5)3 and TiCl4 is known as Ziegler Natta catalyst
which is used for polymerization of ethylene.
x Extent of hydration of alkali metal ions is of the order
Li+ ! Na + ! K + ! Rb+ + Cs+ .
x A mixture of Na2Cl3 and K2CO3 is known as fusion mixture.
x K2CO3 is known as Pearl ash.
x Aqueous solution of sodium chloride is known as Brine.
x CaH2 is known as Hydrolith.
x Sorel cement is a mixture of MgO and MgCl2. 6H2O.
x Aluminiun chloride exists as diamers (Al 2Cl6).

dimeric structure of aluminium chloride.

CHEMISTRY OF HEAVY METALS

x The two elements with the highest densities are osmium (22.57 g cm-3)
and Iridium (22.61 g cm-3)
x Alums are double sulphates having general formula
X2SO4.M2(SO4)8.24 H2O
+
where, X = Monovalent cations such as NA+ ,K + ,NH4 ,etc.
M = Trivalent cations such as Al3+ ,Cr 3+ ,Fe3+ , etc.
x KMnO4, K2Cr2O7 and CrO3 are coloured due to charge transfer and not
due to dd transition.

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x Titanium has been called The wonder metal because of useful
properties.
x Among transition metals, mercury has the lowest melting point and is
liquid at room temperature and Tungsten has the highest melting point
among all the metals.

CHEMISTRY OF REPRESENT ATIVE ELEMENTS

x Oxides: The binary compounds of oxygen with various elements are

called oxides. They can be classified into different categories depending
upon their acid-base characteristics.
x Acidic Oxides: Theses are formed by combination of non metals and
oxygen.
Examples: P4O10, SO3, CO2, N2O5 etc.
x Basic Oxides: These are formed by combination of oxygen with highly
electropositive elements.
Examples: MgO, K2O, CaO, BaO, Na2O etc.
x Amphoteric Oxides: These are formed by combination of oxygen with
borderline elements between metals and non metals.
Examples: Al2O3, SiO2, Zn, PbO etc.
x Neutral Oxides: they are neutral to litmus and do not react with acid or
base.
Examples: CO, NO, N2O etc.
x Air contains about 1% of noble gases.
x Argon is the most abundant noble gas.
x Radon is produced by radioactive decay of (Ra-226). 226 222 4
88 Ra o 86 Rn +2 He
x Silicones: These are polymeric organsilicon compounds containing
Si O Si bonds and having general formula (R2SiO)n; R have may be
CH3 or C6H5 group.
x Solvay Process: Sodium carbonate is generally prepared by this process.
It can not be employed for the manufacture of potassium carbonate
because potassium bicarbonate is fairly soluble in water and hence does
not precipitate easily (in carbonation tower).

TRANSITION METALS INCLUDING LANTHANIDES & ACTINIDES

x The magnetic moment P eff is given by the expression P eff = n n + 2 ,

B.M. where n is the number of unpaired electrons.
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x Colour: The colour of the compounds of the transition metals is related
to the existence of the incomplete s shell and the easy excitation of an
electron from one energy level to another.
x Catalytic Properties: The catalytic behavior of transition elements is
due to their variable oxidation states.
x Ability to form complexes: Transition elements because of their smaller
sizes of the ions and high ionic charges are well suited to attracted
ligands which are usually negative or neutral molecules.

CO- ORDINATION CHEMISTRY AND ORGANO METALLICS

x Ligands containing S bonds and capable of accepting appreciable

electron density form metal atom into empty S antibonding orbital of
their own are called S - acid ligands. e.g., CO, CH2 = CH2 , etc.
x The compounds containing complex cation are cationic complexes.
x The compounds containing complex anion are anionic complexes.
x The compounds which do not ionize in aqueous solutions are neutral or
molecular complexes.
- +
K + Ag CN Cl-
2 Ag NH3 2 CoCl3 NH3 3
Anionic complex Cationic complex Neutral complex
x Compounds containing very stable complex part i.e., the part which does
not dissociate in solution are also called perfect complexes or penetration
complexes.
x Compounds containing the complex part which has tendency to ionize
reversibly in aqueous solution are called imperfect or normal complexes.
4-
K 4 Fe CN 6 o 4K + + Fe CN 6
Perfect complex
4-
Fe CN has least tendency to dissociate in solution
6
3+
Co NH3 Cl o 3Cl- + Co NH3
6 3 6
Imperfect complex
x Monodentate ligands capable of coordinating with metal atom by two
different sites are called ambidentate ligands. Examples are: nitro
m NO2 and nitrite m ONO .
x Ligands containing S bonds are capable of accepting appreciable
electron density from metal atom into empty antibonding orbital S of
their own are called S acid ligands.
Examples are: CO,CH2 CH2 ,C2H5 (cyclopentadienly ion), etc.

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x The number of coordinate bonds formed by the ligands surrounding the
metal atom is called coordination number (CN) of the metal.
C.N. of metal = 1 u No. of monodentate ligands or
= 2 u No. of bidentate ligands or
= 3 u No. of tridentate ligands
x Charge on the complex = O.N. of metal atom + O.N. of various ligands

NUCLEAR CHEMISTRY

Rate of disintegration
dN
- = O.N O = disintegration constant
dt
n
1
Amount left after n half life N = N0
2
2.303 N
= log10 0 and N = N0 e-Ot
O N

Half Life Period

0.693
t1 2 =
O
1 Average Life
1
= 1.44 t1 2
O
For radioactive equilibrium, A o B o C .
If no. of atoms A, B, C etc, at equilibrium are NA, NB, NC etc, then
dNA dNB dNC
- =- =- or O A NA = O B NB = O C NC
dt dt dt
N O t1 2
Or A = B = A
NB O A t1 2
B
Mass defect = M'- M , where M = actual isotopic mass and
M' = Z u mp + Z u me + A - Z mn
= ZmH + A - Z mn ' mp + m c = mH
Binding energy per nucleon
Binding energy calculated from mass defect
=
mass number

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Isotopic mass -Mass number
Packing function = u 104
Mass number
Energy released by loss of 1 amu mass = 931.5 MeV

1 amu = 1.66 u 10-24 g,1MeV = 106 eV,1eV = 1.6 u 10-19 J, 1J= 10 7 ergs,1cal = 4.184J

PURIFICATION & CHARACTERIZATION OF ORGANIC COMPOUNDS

12 mco2
x Percentage of carbon in organic substance = u u 100
44 mcompound

2 mH2O
x Percentage of hydrogen in organic substance = u u 100
18 mcompound
mN2
x Percentage of nitrogen in the compound = u 100
mcompound
[Dumas Method]
Volume of N2 STP
u 28
= u 100
22.4 u mcompound
1.4 u N u vol.of acid used
x Percentage of nitrogen =
Mass of the subs tan ce taken
[Kjeldhals Method]
1.4 u Molarity of the acid u vol. u Basicity
=
Mass of the subs tan ce taken
wt.of silver halide ppt. 35.5 u 100
% of X = u
mol.mass of silver halide wt. of org. chloro comp.
[Carius Method]
35.5 mAgCl
x Percentage of Chlorine = u u 100
143.5 mcompound
80 mAgBr
x Percentage of Bromine = u u 100
188 mcompound
127 mAgI
x Percentage of Iodine = u u 100
235 mcompound

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x Percentage of sulphur =
wt. of BaSO4 precipitate 32 u 100
u
Molecular mass of BaSO4 weight of organic compound containing sulphur

32 mBaSO4
x Percentage of Sulphur = u u 100
233 mcompound
62 mMg2P2O7
x Percentage of phosphorus = u u 100
222 mcompound

Determination of Molecular mass

x Victor Meyers method:

Mass of liqiud or solid w u 22400
Molecular mass =
Volume of air displaced at STP
x Volumetric method:
1000 u W
Molecular mass of the acid = un
Vux
x By silver salt method:
Mass of silver salt chemcial equivalent of silver salt E +108
= =
Mass of silver residue chemical equivalent of silver 108

x From the platinichloride method for organic bases:

1 equivalent of salt { 1 equivalent of H2PtCl6
1
{ 1 equivalent of base { (molar mass of Pt)
2
195
{ g eq-1
2
Equivalent mass of platinum salt
mass of platinumsalt 195
Msalt eq = u g eq -1
mass of platinum 2
Equivalent mass of base
410
Mbase eq = Msalt eq - MH2PtCl6 = Msalt eq - g eq -1
eq 2
Mbase = acidity Mbase eq

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A few more expressions to compute molar mass of a compound are as follows.
x From relative lowering of vapour pressure
m2
M2 =
'P
m1 M1 - o1
P1
x From elevation of boiling point
K m
M2 = b . 2
'Tb m1
x From depression of freezing point
Kf m
M2 = . 2 [m1 = wt. of solvent]
-'Tf m1
x From osmotic pressure
m RT
M2 = 2 [where, m2 = wt of solute, M2 = mol. Wt of solute]
V S

ORGANIC CHEMISTRY

x Aldol Condensation
Aldehydes having D - hydrogen (s) undergo self- condensation on
warming with dilute or mild base to give E - hydroxyl aldehydes, called
aldols.
OH 4
ZZZZX CH3 C H OH CH2CHO
e.g., CH3CHO + CH3CHO YZZZZ

x Beckmann Rearrangement

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x Benzilic acid rearrangement
Benzil on treatment with a strong base froms benzillic acid (salt), whence
the name benzilic acid rearrangement.

x Mechanism

x Crossed aldol condensation

When condensation is between two different carbonyl compound, it is
called Crossed aldol condensation.
OH
(a) R 3C CHO + Ch3CHO 
o R 3C CH OH CH2 CHO
Crossed product

OH
ZZZZZX
(b) CH3CHO + CH3COCH3 YZZZZZ CH3 CH OH CH2 COCH3
Crossed product

x Birch Reduction
When aromatic rings are reduced with sodium, potassium or lithium in
liquid ammonia or amine in the presence of alcohol, addition of hydrogen
takes place at position 1 and 4 to give an unconjugated diene.
e.g.

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x Cannizzaro Reaction
In the presence of a strong base, aldehydes without D hydrogens, i.e.
nonaldolizable aldehydes undergo self oxidation reduction, i.e.,
disproportions reaction.
'
e.g. 2C6 H5CHO + NaOH o C6H5CH2OH + C6H5COONa
' '
2HCHO + NaOH o CH3OH + HCOONa
x Claisen Rearreangement
Claisen rearrangement involves the shift of a group from oxygen to
carbon. Thus, when aryl allyl ethers are heated (200oC) they rearrange to
o-allylphenols.
e.g.

x Clemmenson Reduction
The reduction of carbonyl group of aldehydes and ketones to methylene
groups with amalgamated zinc and concentrated hydrochloric acid.
Zn-Hg.HCl
e.g. C6H5COCH3 
Reflux
o C6H5CH2CH3

x Diels Alder Reduction

Diels alder reaction involves the 1, 4- addition of an alkene to a
conjugated diene to form an adduct of six-membered ring.

Electron withdrawing substituents in the dienophile, such as

! C = O, CHO, COOR, CN, NO2 , etc. promote the reaction.

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The reaction rate is also accelerated by the presence by the presence of

electron-releasing groups in the dienes.

x Fridel Crafts Reaction

Alkylation and acylation of the aromatic compounds with alkyl halides
and acid halides or anhydrides in the presence of a metal halide (Lewis
acid) is known as Fridel Crafts reaction.
Catalyst, usually aluminium chloride is used.
Anhydrous,AlCl
e.g. C6 H6 + CH3CH2 Cl 
o
3 o C H CH CH + HCl
6 5 2 3
80 C
Anhy.AlCl3
C6 H6 + CH3COCl 
C6 H5NO2
o C6H5COCH3 + HCl
Anhy.AlCl
C6H5 + CH3CO 2
O 
3 o C H COCH + CH COOH
6 5 3 3
The order of reactivity of some of the catalysts is
AlBr3 ! AlCl3 ! FeCl3 ! SbCl5 ! SnCl4 ! BCl3 ! BF3
x Fries Rearrangement
Phenolic esters on heating with aluminium trichloride (lewis acid) give o
and p aryl phenol.

In general, low temperature favours the Paraproduct and high

temperature favours the orthoproduct.

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x Gabriel Synthesis
The reaction involves the preparation of primary amines free from
secondary or tertiary amines by reacting alkyl halides with alkali
phthalimide and subsequent hydrolysis.

x Hell Volhard Zelinsky Reaction

Aliphatic carboxylic react with bromine or chlorine (but not iodine and
fluorine) in the presence of small amount of red phosphorus to give
exclusively mono D halogenated acids. [Only by aliphatic acids having
D hydrogen].
Red P
e.g. CH3CH2COOH + Br2 o CH3CHBrCOOH + HBr

x Hoffmann Rearrangement or Hofmann Bromamide reaction

The reaction involves the conversion of an amide into a primary amine
with one carbon loss, by the action of alkaline hypohalite (NAOH
solution + Br2 or Cl2).
e.g. RCONH2 + Br2 + 4NaOH o RNH2 + 2NaBr + Na 2CO3 + 2H2O

x Houben Hoesch reaction

Polyhydroxy phenols, phenolic ethers and some reactive heterocyclic
compounds (e.g. pyrrole) undergo acylation with nitrile in the presence of
a lewis acid.
e.g.

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x Knoevenagel reaction
Condensation of aldehydes and Ketones with compounds having active
methylene group in the presence of basic catalyst to form
D, E unsaturated compounds.

x Michael Reaction
The base-catalysed addition of compounds having active methylene
group (or relatively acidic hydrogens) to an activated olefinic bond of the
type C C Z (Z = electron withdrawing) is classified as Michael
| |
reaction.

4
H2C COOC2H5 + C2H5ONa U HC COOC2H5 2
+ C2H5OH

x Oppenauer Oxidation
The oxidation of a secondary alcohol with a ketone and a base to the
corresponding ketone of the alcohol.
Al OCMe3 2
e.g., R 2CHOH + CH3 ZZZZZZZZZX
CO YZZZZZZZZZ R 2CO + CH2CHOHCH3
2

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x Perkin Reaction
In Perkin reaction, condensation has been effected between aromatic
aldehydes and aliphatic acid anhydrides in the presence of sodium or
potassium salt of the acid corresponding to the anhydride, to yield
D, E unsaturated aromatic acids. The acid reaction should have at least
two D hydrogens.
e.g.
AcONa
C6 H5CHO + CH3CO 2
O 
o o C6H5 CH CH COOH + CH3COOH
170 180 ,5Hr

x Pinacol - Pinacolone Rearrangenent

The acid catalyzed rearrangement of diols (1, 2diols) to ketones or
aldehydes with elimination of water is known as pinacal or pinacol
pinacalone rearrangement.
e.g,

x Reformasky Reaction
Reaction of an D halo ester, usually an D bromoester with an aldehyde
or ketone in the presence of zinc metal to produce a E hydroxyester.
e.g.,

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x Reimer Tiemann Reaction
Formylation of phenols with chloroform in alkaline solution.
e.g.,

x Schmidt Reaction
Carboxylic acids and hydrazoic acid react in the presence of sulphuric
H SO
acid to give amines RCOOH + N3H  2 4 o RNH + CO + N
2 2 2
x Ullmann reaction
The synthesis of diphenyl amines, diphenyl amines, diphenyl ethers and
diphenyls is known as Ullmann reaction.
e.g.,
Cu
C6 H5NHCOCH3 + C6H5BR + K 2CO3  reflux
o C6H5 2 NH + CO2 + CH3COOK + KBr
Cu
C6 H5OH + C6H5BR + KOH 
Reflux
o C6 H5 2
O + KBr + H2O
C H NO
2C6H5I + Cu 
6 5
'
2 o C H C H + CuI
6 5 6 5 2

x Witting reaction
Synthesis of alkenes by the treatment of aldehydes or ketones with
alkylidenetriphenylphosphorane Ph3P = CR 2 or simply known as
phophorane.

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x Wolff Kishner reduction

Involves the conversion of carbonyl groups of aldehydes and ketons to
methylene groups by heating their hydrozones, semicarbazones or azines
in the presence of strong base such as C2H5ONa or NaOH.
e.g.,

Addition Reactions
(i) Electrophilic addition reaction:
CCL
4 o CH Br CH BR
CH2 = CH2 + Br2  2 2
Mechanism:

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Relative rates of addition

Markovnikov Rule

Peroxide effect

. .
R+ H : Br o RH + B r

Addition to conjugate dienes

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Addition to alkynes

(ii) Nucleophilic addition reaction

Electron withdrawing groups are

Reactivity of the carbonyl groups decreases in the order

H2C O ! RCHO ! R 2CO ! ArCHO ! AR 2CO

(iii) Bisulphite addition

NaHSO3 U N a +H+SO324

(iv) Carbanion addition

SN 1 mechanism
Rate v R 3CX
First order Reaction
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The rate of hydrolysis of alkyl halides by SN 1 path is Allyl, Benzyl
! 3o ! 2o ! 1o ! CH3 X

SN 2 mechanism
Rate v Rx Nu
Second under Reaction
The rate of hydrolysis of alkyl halides by SN 2 path is CH3 X ! 1o ! 2o ! 3o

Elimination reactions
(a) E1 mechanism
Kinetically of the first order.

E1 reaction is facilitated by

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(i) branching at the D and E carbons of the substrate for stability of the
olefin,
(ii) strong polar solvent to aid ionization,
(iii) low concentration of base the greater stability of the alkene over the
carbocation makes the extraction of proton easy.

E2 mechanism
Rate D [substrate] [reagent]

E2 reaction is facilitated by
(i) branching at D and E carbons since more stable olefin is formed,
(ii) strong base of high concentration since a strong C H bond has to
break,
(iii) solvent of low polarity polar solvents form a strong solvent wall around
the base restricting the attack. Hence DMF or DMSO are usually used as
solvents.
E1cB mechanism

Difference between SN1 and SN2 reaction.

SN1 reaction SN2 reaction

1. It is two step reaction. It is one step reaction.
2. Rate depend only on concentration Rate depend on concentration of
of substrate. substrate and nucleophile.
3. It is unimolecular reaction. It is bimolecular reaction.
4. The nucleophile can attack on the The nucleophile can attack on the
carbon of substrate from front side carbon of substrate from backside
and backside. only.
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5. Reactivity order alkyl halides are Reactivity order of alkyl halides are
o o o
3 ! 2 ! 1 ! methyl halide. methyl halide ! 1o ! 2o ! 3o .
6. Rearrangement product is Rearrangement product is not
possible. possible.
7. Favoured by mild and low Favoured by strong and high
concentractionof nucleophile. concentration of nucleophile.
8. Favoured by solvents of high Favoured by solvents of low polarity.
polarity.

Difference between SN2 and E2:

Points S N2 E2
1. Step One step One step

2. Reagent Strong Nucleophile strong base.

3. Solvent Non- hydroxylic solvents of Non-hydroxylic solvents & high
high polarity increase the rate. polarity increase the rate.
4. Structure
and
reactivity
nature of 1o ! 2o ! 3o 3o ! 2o ! 1o
alkyl
group
5. Trasition
State

6. Kinetics The rate = K [substrate] [Nu] The rate = K[substrate] [Base]

7. Stereo Stereospecific, inversion of Stereospecific, usually trans-
specificity configuration occurs. elimination takes place.

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Difference between SN1 and E1

Points E1 SN 1
1. Step 2 steps 2steps

2. Reagent Solvent plays the Solvents and weakly

role of the reagent basic reagents of low
concentration
3. Solvent Polar solvents Polar solvents
4. Structure and reactivity 30 ! 20 ! 10 30 ! 20 ! 10
nature of alkyl group
5. Kinetics The second step is The first step is rate
rate determining determining step. It
step. It follows the follows first order
first order kinetics. kinetics.
6. Transition State

7. Stereochemistry Non-stercospecific Racemisation and partial

inversion occur.

Prediction of number of Optical Isomers

i) When the molecule is unsymmetrical
Number of d and A isomers (A) = 2n
Number of meso forms (m) = 0
? Total number of optical isomers = (a + m) = 2n
Where n is the number of chiral carbon atom (s).
Common example is CH3 . CHBr . CHBr . COOH
ii) When the molecule is symmetrical and has even number of chiral
carbon atoms
Number of d and A isomers (A) = 2(n-1)
Number of meso forms (m) = 2(n/2-1)
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? Total number of optical isomers = (a + m)
Common example is tartaric acid, HOOC . CHoH . CHOH . COOH
iii) When the molecule is symmetrical and has an odd number of chiral
carbon atoms
n 1
-
Number of d and A forms (A) = 2(n-1) - 2 2 2

n 1
-
Number of meso forms (m) = 2 2 2
? Total number of optical isomers = (a + m) = 2(n-1) .

Halogenation
The order of case of substitution is
Tertiary hydrogen ! Secondary hydrogen ! Primary hydrogen
UV light
RH + X2 
or A
o RX + HX
Reactivity of X2 ; F2 ! Cl2 ! Br2 ! I2

SYNTHETIC AND NATURAL POLUMERS

HOMOPOLYMERS
Common name of the Monomer Uses
homopolymer
Polyethylene CH2 = CH2 In the manufacture of pipes,
Ethylene toys, bags, wire insulators,
bottles etc.
Polyvinyl Chloride CH2 = CHCl In the manufacture of sheets,
(PVC) Vinyl chloride water pipes, hoses, hand
bags etc.
Polystyrene C6H5CH = CH2 In the manufacture of combs,
Styrene toys and radio and television
cabinets etc.

Polyacrylonitrile (PAN) CH2 = CH CN In the manufacture of orlon

Acrylonitrile (fiber) and acrilon films.
Teflon (Polytetrafluoro CF2 = CF2 In the manufacture of
ethane) Tetrafluoro insulars, gaskets etc.
ethylene

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Buna rubber CH2 = CH In the manufacture of tyres
CH=CH2 etc.
1, 3- Butadiene

COPOLYMERS
Common name of the Monomer Uses
copolymer
Dacron or Terylene (i) HOCH2CH2OH In the manufacture of
Ethylene glycol fabrics and magnetic
(ii) H3COOC(C6H4) recording
COOCH3
Nylon-66 (i) H2N(CH2)6NH2 In the manufacture of
Hexamethylene fabrics, tyre cords,
diamine ropes, carpets etc.
(ii) HOOC(CH2)4COOH
Adipic acid
Bakelite (i) HCHO In the manufacture of
Formaldehyde electrical goods,
(ii) C6H5OH phonograph records,
Phenol fountain pen etc.

Classification of Polymers

Classification based upon origin :

(i) Natural Polymer : Examples silk, wool, starch, cellulose, enzymes,
natural rubber, heamoglobin etc. `
(ii) Semi-synthetic polymer : Examples-Nitrocellulose, cellulose acetate,
cellulose xanthate etc.
(iii) Synthetic Polymer : These are man made polymers.
Examples : Polyethylene, Polystyrene, Teflon

Classification based upon synthesis :-

i) Addition polymers: Examples-Ethene, vinyl chloride and vinyl cynide
ii) Condensation polymers : Examples-Proteins, starch, cellulose etc.

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Classification based upon molecular forces :
i) Elastomers : These are the polymers having very weak intermolecular
forces of attraction between the polymer chains. Examples-Vulcanised
rubber.
ii) Fibers : These polymers can be used for making fibers as their molecules
are long and thread like. Example-Nylon-66.
iii) Thermoplastics : These can be easily moulded by heating.
Example-Polyethylene, Polypropylene.
iv) Thermosetting polymers : A thermosetting polymer becomes hard on
heating. Example-Bakelite.

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