JEE Chemistry Formulas

JEE Chemistry Important Formulas

Atomic Structure
 Energy of electron in species with one electron.
22me 4 Z 2
En 
n 2h 2
For energy in SI system,
22me 4 Z 2
En 
n2h2 (40 )2
1312Z2
En  kJ mol1
n2
where 0 is permitivity constant and its value is 8.8542 × 10–12 coulomb2 newton–1
metre–2.

n2h2  n2 
 r 2 2
 0.529   Å
4 mZe Z
 Total energy of electron in the nth shell
e2  kZe2  kZe2
 K.E.  P.E.  kZ     
2rn  rn  2rn

1 1 1
   RZ2  2  2  , R  1.0968  107 m1 
  n1 n2 
 No. of spectral lines produced when an electron drops from nth level to ground level =
n(n  1)
2
 Heisenberg Uncertainty Principle (x) (p)  h/4
 Nodes (n – 1) = total nodes,  = angular nodes, (n –  – 1) = Radial nodes
h
 Orbital angular momentum : (   1)  (   1)h
2
 Radial probability density curves:
n=1
n=2
R .4r .dr

R .4r .dr
2

1s 2s
2

r r
n=2
n=3
R2 .4r2 .dr

R2 .4r2 .dr

3s 2p

r r

n=3
R .4r .dr

R .4r .dr

n=3
2

3p 3d
2

r r

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 JEE Chemistry Formulas

Chemical Bonding
 (a) % ionic character =
Actual dipole moment
 100
Calculated dipole moment
1
   X A  XB  
4
(b) Pauling equation % ionic character = 100 1  exp 
 
 Fajan’s Factors : Following factors are helpful in bringing covalent character in Ionic
compounds
(a) Small cation (b) Big anion
(c) High charge on cation/anion
(d) Cation having pseudo inert gas configuration (ns2p6d10)
e.g. Cu+, Ag+, Zn+2, Cd+2
 M.O. theory :
(a) Bond order = ½(Nb–Na)
(b) Higher the bond order, higher is the bond dissociation energy, greater is the
stability, shorter is the bond length.
(c) Species Bond order Magnetic properties
H2 1 Diamagnetic
+
H2
0.5 Paramagnetic
Li2 1 Diamagnetic
3 2 2 3 2
 Relative bond strength : sp d > dsp > sp > sp > sp > p-p (Co-axial) > s-p > s-s >
p-p (Co-lateral)
 VSEPR theory
(a) (LP-LP) repulsion > (LP-BP) > (BP-BP)
(b) NH3  Bond Angle 106° 45’ because (LP-BP) repulsion > (BP-BP) H2O  104°
27’because (LP-LP) repulsion > (LP-LB) > (BP-BP)
 Bond angle :
(a) NH3 > PH3 > AsH3 (b) H2O > H2S > H2Se
(c) NH3 > NF3 (d) Cl2O > OF2
Chemical Equilibrium
n g
 Kp = Kc (RT) where ng’ nP – nR
 Free Energy change (G)
(a) If G = 0 then reversible reaction would be in equilibrium, KC = 0
(b) If G = (+) ve then equilibrium will be displace in backward direction; Kc < 1
(c) If G = (–) ve then equilibrium will displace in forward direction; Kc > 1
 (a) Kc unit  (moles/lit)n,
(b) Kp unit  (atm)n
 Reaction Quotient and Equilibrium Constant
Consider the following reversible reaction
A + B  C + D
[C][D]
 Qc =
[A][B]
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 JEE Chemistry Formulas

Case I : If Qc < Kc then : [Reactants] > [Products] then the system is not at equilibrium
Case II : If Qc = Kc then : The system is at equilibrium and the concentration of the
species C, D, B, A are at equilibrium.
Case III : If Qc > Kc then : [Products] > [Reactants]
The system is not at equilibrium.
 A relationship between the equilibrium constant KC, reaction quotient and Gibbs energy.
G = G° + RT In Q
At equilibrium G = 0 and Q = K then
G° = –RT In Kc
 G° = –RT In Kp
 Le chatelier’s principal
(i) Increase of reactant conc. (Shift forward)
(ii) Decrease of reactant conc. (Shift backward)
(iii) Increase of pressure (from more moles to less moles)
(iv) Decrease of pressure (from less moles to more moles)
(v) For exothermic reaction decrease in temp. (Shift forward)
(vi) For endothermic increase in temp. (Shift backward)
Acids and Bases
 (a) Lewis Acid (e– pair acceptor)  CO2, BF3, AlCl3, ZnCl2, normal cation
(b) Lewis Base (e– pair donor) NH3, ROH, ROR, H2O, RNH2, normal anion
 Dissociation of weak Acid & Weak Base 
(a) Weak Acid  Ka = Cx2/(1 – x) or Ka = Cx2; x << 1
(b) Weak Base  Kb = Cx2/(1 – x) or Kb = Cx2; x << 1
 Buffer solution {Henderson equation} :
(a) Acidic  pH = pKa + log {Salt/Acid}.
For Maximum buffer action pH = pKa
Range of Buffer pH = pKa ± 1
(b) Alkaline  pOH = pKb + log {Salt/Base} for max. buffer
action pH = 14 – pKb
Range pH = 14 – pKb ± 1

Moles / lit of Acid or Base Mixed

(c) Buffer Capacity =
change in pH

 Necessary condition for showing neutral colour of Indicator

pH = pKln or[HIn] = [In–] or [InOH] = [In+]
Ionic Equilibrium
 Relation between ionisation constant (Ki) & degree of ionisation() :-

2  2C
Ki =  (Ostwald’s dilution law)
(1   )V (1   )

It is applicable to weak electrolytes for which  << 1 then

Ki
  Ki V  or V  C   
C

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 JEE Chemistry Formulas

 Common ion effect : By addition of X mole/L of a common ion, to a weak acid (or weak
base) a becomes equal to

Ka  Kb 
X  or X  [where  = degree of dissociation]
 
 (A) If solubility product > ionic product then the solution is unsaturated and more of
the substance can be dissolved in it.
(B) If ionic product > solubility product the solution is super saturated (principle of
precipitation).
 Salt of weak acid and strong base :

Kh K
pH = 0.5 (pKw + pKa + log c); h = ; K h  w (h = degree of hydrolysis)
c Ka

Salt of weak base and strong acid :

Kw
pH = 0.5 (pKw – pKb – log c); h =
Kb  c

Salt of weak acid and weak base :

Kw
pH = 0.5 (pKw + pKa – pKb); h =
K a  Kb

Chemical Kinetics
 Differences between order and molecularity of reaction:

Order of reaction Molecularity

1. It is experimentally determined It is a theoretical concept.
quantity
2. It can have integral, fractional Always integral values only,
or negative values never zero or negative
3. It cannot be obtained from It can be obtained.
balanced or stoichiometric
equation.
4. It tells about the slowest step It does not tell anything
in the mechanism about mechanism
5. It is sum of the powers of the It is the number of reacting
concentration terms in the species undergoing
rate law equation. simultaneous collision in the reaction.
 Unit of Rate Constant :
k = mol1–n litn–1 sec–1
 Order of Reaction It can be fraction, zero or any whole number.
 Molecularity of Reaction is always a whole number. It is never more than three. It
cannot be zero.
 First Order Reaction :
2.303 a 0.693
k log10 & t1/12 
t (a  x) k
[A]t = [A]0e –kt

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 JEE Chemistry Formulas

 Second Order Reaction :

When concentration of A and B taking same.

1 x 
k2   
t  a(a  x) 

When concentration of A and B are taking different -

2.303 b(a  x)
k2  log
t(a  b) a(b  x)

 Zero Order Reaction :

a
x = kt & t1/2 =
2k
The rate of reaction is independent of the concentration of the reacting substance.
 Time of nth fraction of first order process,
 
2.303  1 
t1/ n  log  
k  1  1 
 n
 Arrhenius Equation :

Ea k  Ea  T2  T1 
k = Ae Ea / RT & slope = & Temperature Coefficient log  2    
2.303R  k1  2.303  T1T2 
 It has been found that for a chemical reaction with rise in temperature by 10 °C, the rate
constant gets nearly doubled.
Oxidation-Reduction
 Oxidant itself is reduced (gives O2) Or Oxidant  e– (s) Acceptor
Reductant itself is oxidised (gives H2) Or reductant  e– (s) Donor
 (i) Strongness of acid  O.N
(ii) Strongness of base  1/O.N
 (a) Electro Chemical Series:- Li, K, Ba, Sr, Ca, Na, Mg, Al, Mn, Zn, Cr, Fe, Cd, Co,
Ni, Sn, Pb, H2, Cu, Ag, Pt, Au.
(b) As we move from top to bottom in this series
(1) Standard Reduction Potential 
(2) Standard Oxidation Potential 
(3) Reducing Capacity 
(4) IP 
(5) Reactivity 
Volumetric Analysis

Atomic wt of the element

 Equivalent weight of element =
Valency of element

 The law of Dulong and Petit Atomic wt.×specific heat  6.4

number of equivalents
 Normality (N) =
volume of the solution in litres
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 JEE Chemistry Formulas

number of moles
 Molarity (M) = volume of the solution in litres

 Common acid-base indicators

Indicator Acid colour A lkaline colour pH range of change

Methyl orange Red Yellow 3.2–4.4
Methyl red Red Yellow 4.2–6.2
Litmus Red Blue 4.5–8.3
Phenolphthalein Colourless red 8.3–10
Thermo-Dynamics
 First Law : E = Q + W
Expression for pressure volume work W = –PV
Maximum work in a reversible expansion :

V2 P
W = –2.303n RT log = –2.303 nRT log 1 W rev  W irr
V1 P2

 qv = cvDT = DU, qp = cpT = H

Enthapy changes during phase transformation
(i) Enthalpy of Fusion
(ii) Heat of Vapourisation
(iii) Heat of Sublimation
 Enthalpy : H = E + PV = E + ngRT
 Kirchoff’s equation :
ET2  ET1 + CV (T2 – T
T1) [constant V]

HT2  HT1 + CP (T2 – T

T1) [constant P]
 Entropy(s) : Measure of disorder or randomness
S = Sp – SR

qrev V P
S   2.303 nR log 2  2.303 n R log 1
T V1 P2

 Free energy change : G = H – TS – G = W(maximum) – PV

 H S G Reaction characteristics
– + Always negative Reaction is spontaneous at all temperature.
+ – Always positive Reaction is nonspontaneous at all temperature
– – Negative at low Spontaneous at low temp. & non spontaneous at
temperature but high temperature
positive at high
temperature
+ + Positive at low Non spontaneous at low temp. & spontaneous at
temp. but high temp.
negative at high
temperature

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 JEE Chemistry Formulas

Electrochemistry
 m = Z.I.t
 eq Equivalent conduc tance at given concentration
 Degree of dissociation :  = 0 =
 eq equivalent conduc tan ce at inf inite dilution
 Specific conductance
1 1  1000
 sp    ; m    sp .
S RA /  RA C
 Kohlrausch’s law : m0  x 0A  yB0

0.0591 [Pr oduct]

 Nernst Equation : E = E° – log10
n [Re ac tan ts]

 nE 
& E°Cell = E°right + E°left & Keq. = antilog   G = –nFEcell & G° = –nFE° cell
 0.0591

 G 
& W max = +nFE° & G = H + T  
  T P
Ecell  0.2415
 Calculation of pH of an electrolyte by using a calomel electrode : pH =
0.0591
 Thermodynamic efficiency of fuel cells :
G nFEocell
 
H H
For H2–O2 fuel cells it is 95%.
Solution and Colligative Properties
 Raoult’s law
P = pA + pB = p°AXA + p°BXB
 Characteristics of an ideal solution:
(i) solV = 0
(ii) solH = 0
 Relative lowering of vapour pressure
PAo  PA

PAo

PAo  PA nB
 XB 
PAo nA  nB

 Colligative  Number of particles

properties  Number of ions (in case of electrolytes)
 Number of moles of solute
 Depression of freezing point, Tf = Kfm
 Elevation in boiling point with relative lowering of vapour pressure

1000K b  po  p 
Tb =   (M1 = mol. wt. of solvent)
M1  po 

 Osmotic pressure (P) with depression in freezing point Tf

dRT
P  Tf 
1000K f
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 JEE Chemistry Formulas

 Relation between Osmotic pressure and other colligative properties:

 po  p  dRT
(i)  =  A o A  Relative lowering of vapour pressure
 p A  MB

dRT
(ii)  = Tb × Elevation in boiling point
1000K b
dRT
(iii)  = Tf × Depression in freezing point
1000K f

Normal molar mass Observed colligative property

 i = 
Observed molar mass Normal colligative property
Observed osmotic pressure
i = –
Normal osmotic pressure

n
 Degree of association a = (1 – i)
n 1
i 1
& degree of dissociation () =
n 1
Gaseous State
 Ideal gas equation : PV = nRT
(i) R = 0.0821 liter atm. deg–1 mole–1
(ii) R = 2 cals. deg.–1 mole–
(iii) R = 8.314 JK–1 mole–1
 Velocities related to gaseous state

3PV 3RT 3P
RMS velocity C =  
M M d

8RT 2RT
Average speed = & Most probable speed =
M M
Average speed = 0.9213 × RMS speed
RMS speed = 1.085 × Average speed
MPS = .816 × RMS; RMS = 1.224 MPS
MPS : A.V. speed : RMS = 1 : 1.128 : 1.224

1
 Rate of diffusion 
density of gas

 van der Waal’s equation

 n2 a 
 P  2  (V – nb) = nRT for n moles
 V 

PV
 Z(compressibility factor) = ; Z = 1 for ideal gas
nRT

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 JEE Chemistry Formulas

Solid and Liquid State

 Available space filled up by hard spheres (packing fraction):


Simple cubic = = 0.52
6
 3
bcc   0.68
8

 2
fcc   0.74
6

 2  3
hcp   0.74 di amond   0.34
6 6
 Radius ratio and co-ordination number (CN)

Limiting radius ratio CN Geometry

[0.155  0.225] 3 [plane triangle]
[0.255  0.414] 4 [tetrahedral]
[0.414  0.732] 6 [octahedral]
[0.732  1] 8 [bcc]
 Atomic radius r and the edge of the unit cell:
Pure elements :

a 3a 2a
Simple cubic = r = ; bcc r  ; fcc 
2 r 4
 Relationship between radius of void (r) and the radius of the sphere (R) : r (tetrahedral)
= 0.225 R ; r (octahedral) = 0.414 R
 Paramagnetic : Presence of unpaired electrons [attracted by magnetic field]
 Ferromagnetic : Permanent magnetism [   ]
 Antiferromagnetic : net magnetic moment is zero [   ]
 Ferrimagnetic : net magnetic moment is three [    ]
Surface Chemistry & Colloidal State
 Emulsion : Colloidal soln. of two immiscible liquids [O/W emulsion, W/O emulsion]
 Emulsifier : Long chain hydrocarbons are added to stabilize emulsion.
 Lyophilic colloid : Starchy gum, gelatin have greater affinity for solvent.
 Lyophobic colloid : No affinity for solvent, special methods are used to prepare sol. [e.g.
As2S3, Fe(OH)3 sol]
 Preparation of colloidal solution :
(i) Dispersion methods (ii) Condensation method.
 Properties of colloidal solution :
(i) Tyndall effect (ii) Brownian movement
(iii) Coagulation (iv) Filtrability.

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 JEE Chemistry Formulas

Inorganic Chemistry
Periodic Table
 General electronic configuration (of outer orbits)
s-block
p-block ns2np1–6
d-block (n–1)d1–10 ns1–2
f-block (n–2) f1–14 s2p6d10 (n–1)s2p6d0 or 1 ns2
 Property Pr (L To R) Gr(T to B)
(a) atomic radius  
(b) ionisation potential  
(c) electron affinity  
(d) electro negativity  
(e) metallic character or  
electropositive character
(f) alkaline character 
of hydroxides
(g) acidic character  
(i) reducing property  
(j) oxidising property  
(k) non metallic character  

1 1
 IP  Metallic character  Re ducing character

1
 EA   nuclear charge.
size
Second electron affinity is always negative.
Electron affinity of chlorine is greater than fluorine (small atomic size).
 The first element of a group has similar properties with the second element of the next
group. This is called diagonal relationship. The diagonal relationship disappears after IV
group.
s-Block Elements
 Atomic radii : Li < Na < K < Rb < Cs
 Electronegativity : Li > Na > K > Rb > Cs
 First ionization potential : Li > Na > K > Rb > Cs
 Melting point Li > Na > K > Rb > Cs
 Colour of the flame Li - Red, Na - Golden, K - Violet, Rb - Red, Cs - Blue, Ca - Brick
red, Sr - Blood red, Ba-Apple green
 Rb and Cs show photoelectric effect.
 Stability of hydrides : LiH > NaH > KH > RbH > CsH
 Basic nature of hydroxides : LiOH < NaOH < KOH < RbOH < CsOH
 Hydration energy : Li > Na > K > Rb > Cs
 Reducing character : Li > Cs > Rb > K > Na

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 JEE Chemistry Formulas

Boron Family
 Stability of +3 oxidation state : B > Al > Ga > In > Tl
 Stability of +1 oxidation state : Ga < In < Tl
 Basic nature of the oxides and hydroxides :
B < Al < Ga < In < Tl
 Relative strength of Lewis acid : BF3 < BCl3 < BBr3 < BI3
 Ionisation Energy : B > Al < Ga > In < Tl
 Electronegativity : Electronegativity first decreases from B to Al and then increases
marginally.
Carbon Family
 Reactivity : C < Si < Ge < Sn < Pb
 Metallic character : C < Si < Ge < Sn < Pb
 Acidic character of the oxides :
CO2 > SiO2 > GeO2 > SnO2 > PbO2 Weaker acidic (amphoteric)
 Reducing nature of hydrides
CH4 < SiH4 < GeH4 < SnH4 < PbH4
 Thermal stability of tetrahalides
CCl4 > SiCl4 > GeCl4 > SnCl4 > PbCl4
 Oxidising character of M+4 species
GeCl4 < SnCl4 < PbCl4
 Ease of hydrolysis of tetrahalides
SiCl4 < GeCl4 < SnCl4 < PbCl4
Nitrogen Family
 Acidic strength of trioxides : N2O3 > P2O3 > As2O3
 Acidic strength of pentoxides
N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5
 Acidic strength of oxides of nitrogen
N2O < NO < N2O3 < N2O4 < N2O5
 Basic nature, bond angle, thermal stability and dipole moment of hydrides
NH3 > PH3 > AsH3 > SbH3 > BiH3
 Stability of trihalides of nitrogen : NF3 > NCl3 > NBr3
 Lewis base strength : NF3 < NCl3 > NBr3 < NI3
 Ease of hydrolysis of trichlorides
NCl3 > PCl3 > AsCl3 > SbCl3 > BiCl3
 Lewis acid strength of trihalides of P, As and Sb
PCl3 > AsCl3 > SbCl3
 Lewis acid strength among phosphorus trihalides
PF3 > PCl3 > PBr3 > PI3
 Nitrogen displays a great tendency to form p – p multiple bonds with itself as well as
with carbon and oxygen.
 The basic strength of the hydrides
NH3 > PH3 > AsH3 > SbH3
 The thermal stability of the hydrides decreases as the atomic size increases.

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 JEE Chemistry Formulas

Oxygen Family
 Melting and boiling point of hydrides
H2O > H2Te > H2Se > H2S
 Volatility of hydrides
H2O < H2Te < H2Se < H2S
 Reducing nature of hydrides
H2S < H2Se < H2Te
 Covalent character of hydrides
H2O < H2S < H2Se < H2Te
 The acidic character of oxides (elements in the same oxidation state)
SO2 > SeO2 > TeO2 > PoO2 ; SO3 > SeO3 > TeO3
 Acidic character of oxide of a particular element (e.g. S)
SO < SO2 < SO3 ; SO2 > TeO2 > SeO2 > PoO2
Halogen Family
 Bond energy of halogens : Cl2 > Br2 > F2 > I2
 Solubility of halogen in water : F2 > Cl2 > Br2 > I2
 Oxidising power : F2 > Cl2 > Br2 > I2
 Enthalpy of hydration of X– ion :
F– > Cl– > Br– > I–
 Reactivity of halogens : F > Cl > Br > I
 Ionic character of M - X bond in halides
M – F > M – Cl > M – Br > M – I
 Reducing character of X– ion : I– > Br– > Cl– > F–
 Acidic strength of halogen acids : HI > HBr > HCl > HF
 Conjugate base strength of halogen acids
I– < Br– < Cl– < F–
 Reducing property of hydrogen halides
HF < HCl < HBr < HI
 Oxidising power of oxides of chlorine
Cl2O > ClO2 > Cl2O6 > Cl2O7
 Acidic character of oxyacids of chlorine
HClO < HClO2 < HClO3 < HClO4
 Oxidising power of oxyacids of chlorine
HClO > HClO2 > HClO3 > HClO4
Transition Elements (d-and f-Block Elements)
 The element with exceptional configuration are
Cr24[Ar] 3d54s1, Cu29[Ar] 3d104s1 Mo42[Kr] 4d55s1, Pd46[Kr] 4d105s0
Ag47[Kr] 4d105s1, Pt78[Xe] 4f145d106s0
 Ferromagnetic substances are those in which there are large number of electrons with
unpaired spins and whose magnetic moments are aligned in the same direction.
 Inner Transition Elements
(i) Electronic Configuration : The general electronic configuration of these elements
is
[Xe]4f0–14 5d0–1 6s2
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(ii) Magnetic properties : Magnetic properties have spin and orbit contributions
(Contrast “spin only” of transition metals). Hence magnetic momentums are given
by the formula.

  4S(S  1)  L(L  1)

where L = Orbital quantum number, S = Spin quantum number

Coordination Compounds
 Coordination number is the number of the nearest atoms or groups in the coordination
sphere.
 Ligand is a Lewis base donor of electrons that bonds to a central metal atom in a
coordination compound.
 Paramagnetic substance is one that is attracted to the magnetic field, this results on
account of unpaired electrons present in the atom/molecule/ion.
 Effective atomic number EAN = (Z – Oxidation number) + (2 × Coordination number)
 Factors affecting stability of complex
(i) Greater the charge on the central metal ion, greater is the stability.
(ii) Greater the ability of the ligand to donate electron pair (basic strength) greater is
the stability.
(iii) Formation of chelate rings increases the stability.
 Isomerism in coordination compounds :
(i) Structural Isomers
(ii) Ionization Isomers
(iii) Hydration Isomers
(iv) Linkage Isomers
(v) Coordination Isomerism
(vi) Ligand isomerism
(vii) Polymerisation Isomerism
(viii) Valence Isomerism
(ix) Coordination position isomerism
(x) Stereo isomerism
(a) Geometrical
(I) Square planar complexes of the type
MA2X2 ; MABX2 ; MABXY
(II) Octahedral of the type : MA4XY, MA4X2 MA3X3
MA2X2Y2. M(AA)2X2 and M(ABCDEF).
(b) Optical isomerism
GOC
 The order of decreasing electronegativity of hybrid orbitals is sp > sp2 > sp3.
 Conformational isomers are those isomers which arise due to rotation around a single
bond.
 A meso compound is optically inactive, even though it has asymmetric centres (due to
internal compensation of rotation of plane polarised light)
 An equimolar mixture of enantiomers is called racemic mixture, which is optically inactive.

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 Reaction intermediates and reagents :

Homolytic fission  Free radicals
Heterolytic fission  ions (Carbonium, ion carbonium, etc.)
 Nucleophiles – electron rich
Two types : 1. Anions 2. Neutral molecules with lone pair of electrons (Lewis bases)
Electrophiles : electron deficient.
Two types : 1. Cations 2. Neutral molecules with vacant orbitals (Lewis acids).
 Inductive effect is due to  electron displacement along a chain and is permanent effect.
+I (inductive effect) increases basicity, – I effect increases acidity of compounds.
 Resonance is a phenomenon in which two or more structures can be written for the same
compound but none of them actually exists.

Organic Chemistry
Alkanes
 Pyrolytic cracking is a process in which alkane decomposes to a mixture of smaller
hydrocarbons, when it is heated strongly, in the absence of oxygen.
 Ethane can exist in an infinite number of conformations. They are

 Conformations of Cyclohexane : It exists in two nonplanar, strainless forms, the boat

and the chair form

Alkenes
 In dehydration and dehydrohalogenation the preferential order for removal of hydrogen
is 3° > 2° > 1° (Saytzeff’s rule).
 The lower the Hh (heat of hydrogenation) the more stable the alkene is.
 Alkenes undergo anti-Markonikov addition only with HBr in the presence of peroxides.
Alkynes
 Alkynes add water molecule in presence of mercuric sulphate and dil. H2SO4 and form
carbonyl compounds.
 Terminal alkynes have acidic H-atoms, so they form metal alkynides with Na, ammonical
cuprous chloride solution and ammoniacal silver nitrate solution.
 Alkynes are acidic because of H-atoms which are attached to sp ‘C’ atom which (a) has
more electronegativity (b) has more ‘s’ character than sp2 and sp3 ‘C’ atoms.

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Arenes
 All o and p-directing groups are ring activating groups
(except – X)
They are : – OH, – NH2, – X, – R, – OR, etc.
 All m-directing groups are ring deactivating groups.

They are : – CHO, – COOH, – NO2, – CN, – NR3 , etc.
Halogen Compounds
 The order of reactivity is
(a) RI > RBr > RCl > RF
(b) Allyl halide > Alkyl halide > Vinyl halide
(c) Alkyl halide > Aryl halide
 SN1 reaction : Mainly 3° alkyl halides undergo this reaction and form racemic mixture. SN1
is favoured by polar solvent and low concentration of nucleophile.
 SN2 reaction : Mainly 1° alkyl halides undergo this substitution. Walden inversion takes
place. SN2 reaction is preferred by non-polar solvents and high concentration of nucleophile.
 Reaction with metals:
Dry ether
(i) R  X  Mg   R  Mg  X
Alkyl halides Grignard reagent

(ii) Wurtz reaction :

Dry ether
R  X  2 Na  X  R   R  R  2Na  X
Alkane

Alcohols
 Alkenes are converted to alcohol in different ways as follows
Reagent Types of addition
dil H2SO4
–Markovnikov
B2H6 and H2O2, OH– – Anti-Markovnikov Oxymercuration demercuration – Markovnikov
 Oxidation of
1° alcohol  aldehyde  carboxylic acid
(with same no. (with same no. of
of C atom) C atom)
2° alcohol  ketone  carboxylic acid
(with same no. (with less no. of
of C atom) C atom)
3° alcohol  ketone  carboxylic acid
(with less no. (with less no. of
of C atom) C atom)
Phenols

CHCl3 / OH
 Phenol aldehyde   Phenolic (Reimer-Tieman reaction)
CO2
 Phenol 

 Phenolic carboxylic acid (Kolbe reaction)

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 Acidity of phenols
(a) Increase by electron withdrawing substituents like

NO2  CN, CHO, COOH  X,  NR3
(b) decrease by electron releasing substituents like
–R, –OH, –NH2, –NR2, –OR
Ethers
Al2 O3
 2ROH 
250 C
R – O – R + H2O
 RONa + X – R’  ROR’ + NaX (Williamson’s synthesis)
dil. H2 SO4
 ROR + H2O  
 2ROH
Carbonyl Compounds
 Formation of alcohols using RMgX
Hydrolysis
(a) Formaldehyde + RMgX  1° alcohol
Hydrolysis
(b) Aldehyde + RMgX  2° alcohol
(other than HCHO)
Hydrolysis
(c) Ketone + RMgX  3° alcohol
 Cannizzaro reaction (Disproportionation)
Hot conc.
Aldehyde 
alkali
 Alcohol + Salt of acid (no  H-atom)
 Aldol condensation :
Carbonyl compound + dil. alkali  -hydroxy carbonyl
(with  H-atom) compound
 Benzoin condensation
ethanolic
Benzaldehyde 
NaCN
 Benzoin
 The relative reactivities of different acid derivatives towards nucleophilic acyl substitution
reactions follow the order:

Carboxylic Acids
 The rate of esterfication decreases when alcohol, acid or both have branched substituents.
 Ortho effect : All ortho substituted benzoic acids (irrespective of type of substituent) are
stronger than benzoic acid.
Nitrogen Compounds
 Order of basicity : (R = – CH3 or – C2H5)
2° > 1° > 3° > NH3
Br2 / KOH
 Hofmann degradation Amides   1° amine
 The basicity of amines is
(a) decreased by electron withdrawing groups
(b) increased by electron releasing groups

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 Reduction of nitrobenzene in different media gives different products

Medium Product
Acidic Aniline
Basic Azoxy, Azo and finally hydrazobenzene
Neutral Phenyl hydroxylamine
Carbohydrates, Amino Acids and Polymers
 Carbohydrates are polyhydroxy aldehydes or ketones.
 Monosaccharides are simple sugars, containing three to nine carbon atoms.
 Characteristic reactions : Homologous series
Type of reactions
(a) Alkanes Substitution (Mostly free radical)
(b) Alkenes and alkynes Electrophillic addition
(c) Arenes Electrophillic substitution
(d) Alkyl halides Nucleophillic substitution
(e) Aldehyde and ketones Nucleophillic addition
 Tests to differentiate :
1°, 2° and 3° alcohols (1) Lucas test
(2) Victormeyer’s test
1°, 2° and 3° amines Hinsberg test
1°, 2° and 3° nitro compounds Test with HNO2 and KOH
Aryl halides and alkyl halides Test with AgNO3 solution
Aldehydes and ketones Tollen’s test/Fehling’s test
Aromatic aldehydes and Fehling’s test
Aliphatic aldehydes
Important Reagent
 Dil H2SO4 [or Conc. H2SO4 + H2O]
Use  Hydrating agent (+HOH)
 Alc. KOH or NaNH2(Use  -HX)
alc. KOH
CH3 CH2Cl   CH2  CH2
 Lucas reagent ZnCl2 + Conc. HCl
Use  for distinction between 1º, 2º & 3º alc.
 Tilden Reagent NOCl (Nitrosyl chloride)
NOCl
C2H5NH2   C2H5 Cl
 Alkaline KMnO4(Strong oxidant)
Toluene  Benzoic acid
 Bayer’s Regent : 1% alkaline KMnO4(Weak oxidant)
Use:  For test of > C = C < or –C = C –
BR
CH2  CH2  H2O  [O]   CH2OH  CH2OH
[O]
 Acidic K2Cr2O7 (Strong oxidant) : RCH2OH   RCHO
 SnCl2/HCl or Sn/HCl use  for redn of nitrobenzene in acidic medium.
SnCl2 / HCl
C6H5NO2 6H
 C6H5NH2

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 Lindlar’s Catalyst = Pd/CaCO3 + in small quantity (CH3COO)2Pb

2 – butye + H2  Cis-2-butene (main product)
 Ziegler –Natta Catalyst (C2H5)3Al + TiCl4
Use  In Addition polymerisation
Identification Tests :
(a) Unsaturated compound (Bayer’s reagent)
Decolourising the reagent
(b) Alcohols (Ceric ammonium nitrate solution)
Red colouration
(c) Phenols (Neutral FeCl3 solution)
Violet/deep blue colouration
(d) Aldehydes and ketones (2, 4-D.N.P.)
Orange precipitate
(e) Acids (NaHCO3 solution)
Brisk effervescence (CO2 is evolved)
(f) 1° amine (CHCl3 + KOH)
Foul smell (isocyanide)
(g) 2° amine (NaNO2 + HCl)
Yellow oily liquid (Nitrosoamine)

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