FORMULA SHEET CHEMISTRY

CHEMISTRY

Some Basic Concepts of Chemistry

Average relative mass of one molecule

 Molecular mass = 1
×mass of C−12 atom
12
 Molecular mass = 2 × VD
wt. of metal
 Eq. wt. of metal = wt. of H2 displaced
× 1.008
wt. of metal
 Eq. wt. of metal = wt. of Oxygen combined × 8
wt. of metal
= × 35.5
wt. of chlorine combined
 Molecular formula = (Empirical formula)n

Atomic Structure

 Energy of electron in species with one electron.

−2π2 me4 Z2
En = n2 h2
For energy in SI system,
−2π2 me4 Z2
En = n2 h2 (4πε0 )2
−1312 Z2
En = n2 kJ mol−1
nh
mvr = 2π
n2 h2 n2
 r= = 0.529 ( ) Ȧ
4π2 mZe2 Z
e2 kZe2 kZe2
 Total energy of electron in the nth shell = K.E. + P.E. = kZ 2r + (− rn
) =− 2rn
n
1 1 1
 𝑣̅ = λ
= RZ 2
[n2 − n22
], [R = 1.0968 × 107 m-1]
1
hc
E = hv = λ
h
λ=
√2m×K.E.
 No. of spectral lines produced when an electron drops from n th level to ground
n(n−1)
level = 2
 Heisenberg's Uncertainty Principle (∆x) (∆p) ≥ h/4π
 Nodes (n − 1) = total nodes, ℓ = angular nodes,

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(n − ℓ − 1) = Radial nodes
ℎ
 Orbital angular momentum: √ℓ(ℓ + 1) 2𝜋 = √ℓ(ℓ + 1)ℎ

Chemical Bonding

Actual dipole moment

 (i) % ionic character = Calculated dipole moment
× 100
(ii) Dipole moment is helpful in predicting geometry and polarity of molecule.
 Fajan's Rule: Following factors are helpful in increasing covalent character in
ionic compounds
(i) Small cation
(ii) Big anion
(iii) High charge on cation/anion
(iv) Cation having pseudo inert gas configuration (ns2p6d10)
 M.O. Theory:
(i) Bond order = 1/2(Nb−Na)
(ii) Higher the bond order, higher is the bond dissociation energy, greater is the
stability, shorter is the bond length.
 Formal charge (F.C.) on an atom in a Lewis structure
= [total number of valence electrons in the free atoms]
−[total number of non-binding (lone pair) electrons]
1
− [total number of bonding (shared) electrons]
2
 Relative bond strength: sp3d2 > dsp2 > sp3 > sp2 > sp > p-p
(Coaxial) > s-p > s-s > p-p (Co-lateral)
 VSEPR theory
(i) (Lp – LP) repulsion > (LP – BP) > (BP – BP)
(ii) NH3 → Bond Angle 106° 27' because (LP – LP) repulsion > (LP – LB) > (BP –
BP)
 Hybridisation:
number of valence electrons of central atom
1
= 2 (+number of monovalent atoms attached to it )
+negative charge if any − positive charge if any

Chemical Equilibrium

 KP = KC (RT)∆ng where ∆𝑛𝑔 = 𝑛𝑃 − 𝑛𝑅

 Free Energy Change (∆G)
(i) If ∆G = 0 then reversible reaction would be in equilibrium, KC = 0
(ii) If ∆G =(+)ve then equilibrium, will be displaced in backward direction; KC < 1
(iii) If ∆G = (-)ve then equilibrium will shift in forward direction; KC > 1
 (i) KC unit → (moles/lit)∆n, (ii) KP unit → (atm)∆n
 Reaction Quotient and Equilibrium Constant
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Consider the following reversible reaction

A+B⇌C+D
[C][D]
∴ QC = [A][B]
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.
Case III: If QC > KC then: [Products] > [Reactants], the system is not at equilibrium.
 A relationship between the equilibrium constant KC, reaction quotient and Gibb's
energy.
∆G = ∆G° + RT ln Q
At equilibrium ∆G = 0 and Q = K then
∆G° = −RT ln KC
∴ ∆G° = −RT ln KP
 Le-Chatelier's principle
(i) Increase of reactant conc. (Shift reaction forward)
(ii) Decrease of reactant conc. (Shift reaction 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)

Ionic Equilibrium

 (i) Lewis Acid (e- pair acceptor) → CO2, BF3, AlCl3 ZnCl2, normal cation
(ii) Lewis Base (e- pair donor) → NH3, ROH, ROR, H2O, RNH2, normal anions
 Dissociation of Weak Acid and Weak Base
(i) Weak Acid, Ka = Cx2/(1 − x) or Ka = Cx2; x ≪ 1
(ii) Weak Base, Kb = Cx2/(1 – x) or Kb = Cx2; x ≪ 1
 Buffer solution (Henderson equation):
(i) Acidic, pH = pKa + log (Salt/Acid).
For maximum buffer action pH = pKa
Range of buffer pH = pKa ± 1
(ii) 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
(iii) Buffer Capacity = Change in pH
 Relation between ionisation constant (Ki) and degree of ionisation (𝛼):
α2 α2 C
Ki = (1−α)V
= (1−α) (Ostwald's dilution law)
It is applicable to weak electrolytes for which 𝛼 ≪ 1 then
K
𝛼 = √k i V = √ Ci or V ↑ C ↓ α ↑
 Common ion effect: By addition of X mole/L of a common ion, to a weak acid (or
Ka K
weak base) 𝛼 becomes equal to X
or ( Xb ) [where 𝛼 = degree of dissociation]

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 (i) If solubility product > ionic product then the solution is unsaturated and more
of the substance can be dissolved in it.
(ii) If ionic product > solubility product the solution is super saturated (principle
of precipitation).
 Salt of weak acid and strong base:
K KW
pH = 0.5 (pKW + pKa + log c); h = √ h; K h = (h = degree of hydrolysis)
C Ka
Salt of weak base and strong acid:
KW
pH = 0.5 (pKW – pKb – log c); h = √K
b ×c

Salt of weak acid and weak base:

KW
pH = 0.5 (pKW + pKa – pKb); h = √
K a ×Kb

Chemical Kinetics

 Unit of rate constant: k = mol1−n lit n−1 sec −1

 Order of reaction: It can be fraction, zero or any whole number.
 Molecularity of reaction: It is always a whole number. It is never more than three.
It cannot be zero.
 First Order Reactions:
2.303 a 0.693
k= log10 (a−x) and t1/2 =
t k
[A]t = [A]0 e−kt
 Second Order Reactions:
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 = t(a−b)
log a(b−x)
 Zero Order Reactions:
a
x = kt and 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 = k
log ( 1 )
1−
n
[A]0
 Amount of substance left after 'n' half-lives = 2n
−Ea
 Arrhenius equation: k = Ae −Ea /RT
, slope = 2.303R
and Temperature Coefficient
k Ea T −T
log ( 2 ) = ( 2 1)
k1 2.303 T 1 T2
 It has been found that for a chemical reaction with rise in temperature by 10°C,
the rate constant gets nearly doubled.
k = pZAB e−Ea/RT

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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) Strength of acid ∝ O.N (ii) Strength of base ∝ 1/O.N
 (i) Electrochemical Series: Li, K, Ba, Sr, Ca, Na, Mg, Al, Mn, Zn, Cr, Fe, Cd, Co,
Ni, Sn, Pb, H2, Cu, Ag, Pt, Au.
(ii) As we move from top to bottom in this series
(a) Standard Reduction Potential ↑
(b) Standard Oxidation Potential ↓
(c) Reducing Capacity ↓
(d) IP ↑
(e) Reactivity ↓

Thermodynamics

 First Law of Thermodynamics:

∆E = Q + W
Expression for pressure volume work
W = −P∆V
Maximum work in a reversible expansion:
V2
W = −2.303 nRT log V1
P1
= −2.303 nRT log P2
Wrev ≥ Wirr
 qv = cv∆T = ∆U, 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 – T1) [constant V]
∆HT2 = ∆HT1 + ∆CP (T2 – T1) [constant P]
 Entropy(s): Measure of disorder or randomness
∆S = ∑ SP − ∑ SR
qrev V2 P1
∆S = = 2.303 nR log = 2.303 nR log
T V1 P2
 Free energy change: ∆G = ∆H – T∆S, ∆G° = −nFE°cell
−∆G = W(maximum) −P∆V, ∆Gsystem = −T∆Stotal
 ∆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. & nonspontaneous
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temperature but at high temperature.

positive at high
temperature
+ + Positive at low Nonspontaneous at low temp. & spontaneous
temperature but at high temperature.
negative at high
temperature

Electrochemistry
 m = Z.I.t
λeq
 Degree of dissociation: 𝛼 = λ0eq
 Specific conductance
1 ℓ ℓ
k= p𝑅.𝑎
== G × a = G × cell constant (G*);
k×1000 k×1000
∆m = , ∆eq =
M N
 Kohlrausch's law: ∆0m = xλ0A + yλ0B
 Nernst Equation
0.0591 [Products]
E = E0 − n
log10 [Reactants]
0 0 0 nE0
& Ecell = Eright + Eleft and K eq. = antilog [0.0591]
∆G = −nEFcell & ∆G0 = −nFE0cell = −2.303 RT log KC
∂∆G
& Wmax = +nFE0 & ∆G = ∆H + T ( )
∂T P
Ecell −0.2415
 Calculation of pH of an electrolyte by using a calomel electrode: pH = 0.0591
−∆G −nFE0cell
 Thermodynamic efficiency of fuel cells: η = =
∆H ∆H
For H2–O2 fuel cells it is 95%.
 P = KH∙x
number of equivalents
 Normality (N) = volume of the solution in litres
number of moles
 Molarity (M) = volume of the solution in litres

Solution & Colligative Properties

 Raoult's law
P = pA + pB = p°A XA + p°B XB
 Characteristics of an ideal solution:
(i) ∆solV = 0 (ii) ∆solH = 0
 Relative lowering of vapour pressure
P°A −PA
= P°A

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P°A −PA nB
P°A
= XB = nA +nB
 Colligative ∝ Number of particles/ions/moles of solute properties
 Depression of freezing point, ∆Tf = Kfm
 Elevation in boiling point with relative lowering vapour pressure
1000Kb P°−P
∆Tb = M1
( P° ) (M1 = mol, wt. of solvent)
 Osmotic pressure (P) with depression in freezing point ∆Tf
dRT
P = ∆Tf × 1000Kf
 Relation between Osmotic pressure and other colligative properties:
P°A −PA dRT
(i) 𝜋 = ( P°A
) × M Relative lowering of vapour pressure
B
dRT
(ii) 𝜋 = ∆Tb × 1000K Elevation in boiling point
b
dRT
(iii) 𝜋 = ∆Tf × 1000K Depression in freezing point
f
Normal molar mass Observed colligative property
 i = Observed molar mass = Normal colligative property
n
 Degree of association a = (1 – i) n−1
i−1
& Degree of dissociation (𝛼) = n−1

Gaseous State

 Ideal gas equation: PV = nRT

(i) R = 0.821 litre atm. deg.-1 mole-1
(ii) R = 2 cals. deg.-1 mole-1
(iii) R = 8.314 jK-1 mole-1
 Velocities related to gaseous state
3PV 3RT 3P
RMS velocity = √ M
=√ M
= √d
8RT 2RT
Average speed = √ M
& Most probable speed = √ 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 Waals' equation
n2 a
(P + V2
) (V − nb) = nRT for n moles
PV
 Z (compressibility factor) = ; Z = 1 for ideal gas
nRT
8a a a
TC = 27Rb
, PC = 27b2
, VC = 3b, Tb = bR

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Solid and Liquid State

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

π
Simple cubic = 6 = 0.52
π√3 π√2 π√2 π√3
bcc = 8
= 0.68 fcc = 6
= 0.74 hcp = 6
= 0.74 diamond = 6
= 0.34
 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 = 2
; bcc r = 4
; fcc = 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 [↑↓↑↓]

Surface Chemistry & Colloidal State

 Ferrimagnetic: Net magnetic moment is three [↑↓↓↑↑]
 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
1
 Coagulating power ∝ Flecculating value
 Properties of colloidal solution:
(i) Tyndall effect; (ii) Brownian movement; (iii) Coagulation; (iv) Filterability

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Periodic Table

 General electronic configuration (of outer orbits)

s-block ns1-2
p-block ns2np1-6
d-block (n-1)d1-10ns1-2
f-block (n-2)f1-14s2p6d10
(n-1)s2p6d0 or 1ns2

1 1
 IP ∝ ∝
Metallic character Reducing character
1
 EA ∝ size ∝ nuclear charge.
Second electron affinity is always negative.
Electron affinity of chlorine is greater than fluorine (small atomic size).
 The first element of a graph 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 hybrides: LiH > NaH > KH > RbH > CsH
 Basic nature of hydroxides: LiOH < NaOH < KOH < RbOH < CsOH
 Hydration energy: Li > Na > K > Rb > Cs

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 Reducing character: Li > Cs > Rb > K > Na

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 hybrides: 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 𝑝𝜋 − 𝑝𝜋 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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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 powder: F2 > Cl2 > Br2 > I2
 Enthalpy of hydration of X − ion: F − > Cl− > Br − > I −
 Reactivity of halogen: F > Cl > Br > I
 Ionic character of M-X bond in halides: M-F > M-Cl > M-Br > MI
 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

Noble Gases
 XeF2 + PF5 ⟶ [XeF]+ [PF6]
XeF4 + SbF5 ⟶ [XeF3]+ [SbF6]
XeF6 + H2O ⟶ XeOF4 + 2HF
XeF6 + 2H2O ⟶ XeO2F2 + 4HF
2XeF4 + 3H2O ⟶ Xe + XeO3 + 4HF + F2
XeF6 + 3H2O ⟶ XeO3 + 6HF
2XeF6 + SiO2 ⟶ 2XeOF4 + SiF4
2XeOF4 + SiO2 ⟶ 2XeO2F2 + SiF4
2XeO2F4 + SiO2 ⟶ 2XeO3 + SiF4

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Transition Elements (d-andf-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
 Inner Transition Elements
(i) Electronic configuration- [Xe]4f0-145d0-16s2
(ii) Magnetic properties- Magnetic moment is given by the formula
𝜇 = √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 of groups in the

coordination sphere.
 Ligands 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 fields, this
results on account of unpaired electrons present in the atom/molecule/ion.
 Effective atomic number EAN = (Z – Oxidation) + (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 increase the stability.
 Isomerism in coordination compounds:
(i) Structural Isomerism (ii) Ionization Isomerism
(iii) Hydration Isomerism (iv) Linkage Isomerism
(v) Polymerisation Isomerism (vi) Valence Isomerism
(vii) Coordination Position Isomerism
(Viii) Stereo Isomerism
(a) Geometrical
(1) Square planar complexes of the type: MA2X2; MABX2; MABXY
(2) Octahedral of the type: MA4XY, MA4X2, MA3X3, MA2X2Y2∙M(AA)2X2 and
M(ABCDEF).
(b) Optical isomerism

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General Organic Chemistry

 The order of decreasing electronegativity of hybrid orbitals is sp > sp 2 > 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.
 Reaction intermediates and reagents:
Homolytic fission ⟶ Free radicals
Heterolytic fission ⟶ Ions (Carbonium ions, carbanions etc.)
 Nucleophiles: Electron rich
Two types: (i) Anions; (ii) Neutral molecules with lone pair of electrons (Lewis
bases)
Electrophiles: Electron deficient.
Two types: (i) Cations; (ii) Neutral molecules with vacant orbitals (Lewis acids).
 Inductive effect is due to 𝜎 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.

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

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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
has more electronegativity and 's' character than sp2 and sp3 'C' atoms.

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.

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Halogen Compounds

 The order of reactivity is

(i) RI > RBr > RCl > RF
(ii) Allyl halide > Alkyl halide > Vinyl halide
(iii) 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 places. 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
Dry ether
(ii) Wurtz reaction: R – X + 2Na + 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 (with same no. of ⟶ carboxylic acid (with
C atom) same no. of C atom)
2° alcohol ⟶ ketone (with same no. of C ⟶ carboxylic acid (with
atom) less no. of C atom)
3° alcohol ⟶ ketone (with less no. of C ⟶ carboxylic acid (with
atom) less no. of C atom)

Phenols
CHCl3 /OH⊝
 Phenol → Phenolic aldehyde (Reimer-Tieman reaction)
CO2
 Phenol → Phenolic carboxylic acid (Kolbe's reraction)
∆
 Acidity of phenols
(i) Increases by electron withdrawing substituents like
+
−NO2, −CN, −CHO, −COOH, −X, −NR3
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(ii) Decreases by electron releasing substituents like

−R, −OH, −NH2, −NR2, −OR

Ethers
Al2 O3
 2ROH → R – O – R + H2 O
250°C
 RONa + X – R' ⟶ ROR' + NaX
(Williamson's synthesis)
dil.H2 SO4
 ROR + H2O → 2ROH
∆

Carbonyl Compounds
 Formation of alcohols using RMgX
Hydrolysis
(i) Formaldehyde + RMgX → 1° alcohol
Hydrolysis
(ii) Aldehyde + RMgX → 2° alcohol (other than HCHO)
Hydrolysis
(iii) Ketone + RMgX → 3° alcohol
 Cannizzaro reaction (Disproportionation)
Hot conc.
Aldehyde → Alcohol + Salt of acid (no 𝛼 H-atom)
alkali
 Aldol condensation:
Carbonyl compound + dil. alkali ⟶ β-hydroxy carbonyl compound (with 𝛼 H-
atom)
 Benzoin condensation:
ethanolic
Benzaldehyde → Benzoin
NaCN
 The relative reactivities of different acid derivatives towards nucleophilic acyl
substitution reaction follow the order:

Carboxylic Acids

 The rate of esterfication decreases when alcohol, acid or both have branched
substituents.

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 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
(i) decreased by electron withdrawing groups
(ii) increased by electron releasing groups
 Reduction of nitrobenzene in different media gives different
Medium Product
Acidic Aniline
Basic Azoxy, Azo and finally hydrazobenzene
Neutral Phenyl hydroxylamine

Carbohydrates, Amino Acids & Polymers

 Carbohydrates are polyhydroxy aldehydes or ketones.
 Monosaccharides are simple sugars, containing three to nine carbon atoms.
 Characteristic reactions:
Homologous series Type of reactions
(i) Alkanes Substitution Mostly free radical
(ii) Alkenes & alkynes Electrophillic addition
(iii) Arenes Electrophillic substitution
(iv) Alkyl halides Nucleophillic substitution
(v) Aldehyde & ketones Nucleophillic addition
 Tests to differentiate:
1°, 2° and 3° alcohols (i) Lucas test
(ii) Victor meyer's test
1°, 2° and 3° amines Hinsberg test
1°, 2° and 3° nitro compounds Test with HNO2 & KOH
Aryl halides & alkyl halides Test with AgNO3 solution
Aldehydes & ketones Tollen's test/Fehling's test
Aromatic aldehydes and Fehling's test
Aliphatic aldehydes

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Important Reagent

 Dil. H2SO4 [or Conc. H2SO4 + H2O]

Use → Hydrating agent (+HOH)
 Alc. KOH or NaNH2
Use → −HX
alc. KOH
CH3CH2Cl → CH2=CH2
 Lucas Reagent ZnCl2 + Conc. HCl
Use → For distinction between 1°, 2° and 3° alc.
 Tilden Reagent NOCl (Nitrosyl chloride)
NOCl
C2H5NH2 → C2H5Cl
 Alkaline KMnO4(Strong oxidant)
Toluene → Benzoic acid
 Bayer's Reagent: 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 used for reduction of nitrobenzene in acidic medium.
SnCl2 /HCl
C6H5NO2 → C6H5NH2
6H
 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

IDENTIFICATIONS TESTS:
(i) Unsaturated compound (Bayer's reagent) {Decolourising the reagent}
(ii) Alcohols (Ceric ammonium nitrate solution) {Red colouration}
(iii) Phenols (Neutral FeCl3 solution) {Violed/deep blue colouration}
(iv) Aldehydes and ketones (2, 4-D.N.P.) {Orange precipitate}
(v) Acids (NaHCO3 solution) {Brisk effervescence (CO2 is evolved)}
(vi) 1° amine (CHCl3 + KOH) {Foul smell (isocyanide)}
(vii) 2° amine (NaNO2 + HCl) {Yellow oily liquid (Nitrosoamine)}

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