PHYSICAL CHEMISTRY

SOME BASIC CONCEPTS OF u=

1 é1 1 ù
= RZ2 ê 2 - 2 ú , [R = 1.0968 × 107 m–1]
CHEMISTRY l êë n1 n 2 úû
Multiplie ed by hc h
Amount of a
d by Multipli Number
E = hv = ,l=
NA 23 l 2m ´ K.E.
substance Molar mass Mol (6.023 × 10 ) of
(in gram) entities
No. of spectral lines produced when an electron drops from
b y by D Divided by
Divi d ed
d iv n(n - 1)
plie id nth level to ground level =
ti 22.4 L ed 2
ul by
M Heisenberg's Uncertainty Principle (Dx) (Dp) ³ h/4p
Volume of gas (in L) at STP Nodes (n – 1) = total nodes, l = angular nodes,
(n – l – 1) = Radial nodes
Molecular mass
Average relative mass of one molecule h
= Orbital angular momentum : l (l + 1) = l(l + 1)h
1 2p
´ mass of C-12 atom
12
Molecular mass = 2 × VD CHEMICAL BONDING
Eq. wt. of metal Actual dipole moment
(i) % ionic character = ´ 100
wt. of metal Calculated dipole moment
= ´ 1.008
wt. of H 2 displaced (ii) Dipole moment is helpful in predicting geometry and
wt. of metal polarity of molecule.
Eq. wt. of metal = ´8 Fajan’s Rule : Following factors are helpful in increasing
wt. of oxygen combined covalent character in ionic compounds
wt. of metal (i) Small cation
= ´ 35.5 (ii) Big anion
wt. of chlorine combined
(iii) High charge on cation/anion
Molecular formula = (Empirical formula)n (iv) Cation having pseudo inert gas configuration
(ns2p6d10) e.g. Cu+, Ag+, Zn2+, Cd2+
ATOMIC STRUCTURE M.O. theory :
(i) Bond order = ½(Nb–Na)
Energy of electron in species with one electron. (ii) Higher the bond order, higher is the bond dissociation
energy, greater is the stability, shorter is the bond length.
-2 p 2 me 4 Z 2
En = Formal charge (F.C.) on an atom in a Lewis structure
n 2h 2 = [total number of valence electrons in the free atoms]
-2 p 2 me4 Z2 – [total number of non-binding (lone pair) electrons]
For energy in SI system, En = 2 2
n h (4 pe 0 ) 2 1
– [total number of bonding (shared) electrons]
-1312Z2 2
En = kJ mol-1 Relative bond strength : sp3d2 >dsp2 >sp3 >sp2 >sp >p-p
n2 (Co-axial) > s - p > s - s > p - p (Co-lateral)
nh VSEPR theory
mvr =
2p (i) (LP-LP) repulsion > (LP-BP) > (BP-BP)
(ii) NH3 ® Bond Angle 107° 45’ because (LP-BP) repulsion
n 2h 2 æ n2 ö > (BP-BP) H2O ® 104° 27’because (LP-LP) repulsion >
r= = 0.529 çç ÷÷ Å (LP-LB) > (BP-BP)
4 p 2 mZe 2 è Z ø Hybridisation :
Total energy of electron in the n th shell
æ number of valence electrons of central atom ö
e 2 æ kZe 2 ö kZe 2 1ç ÷
= K.E. + P.E. = kZ + ç- = - = ç + number of monovalent atoms attached to it ÷
2rn è rn ÷ø 2rn 2ç ÷
è + negative charge if any - positive charge if any ø
10 CHEMISTRY

Mol / lit of Acid or Base Mixed

CHEMICAL EQUILIBRIUM (iii) Buffer Capacity =
Change in pH
Δn g Relation between ionisation constant (Ki) and degree of
K p = K c (RT) where Dng = nP – n R
a2 a2C
Free Energy Change (DG) ionisation(a) : – K i = = = (Ostwald’ss
(1 - a )V (1 - a )
(a) If DG = 0 then reversible reaction would be in
dilution law)
equilibrium, Kc = 0 It is applicable to weak electrolytes for which a <<1 then
(b) If DG = (+) ve then equilibrium will be displaced in
backward direction; Kc < 1 Ki
a= Ki V = or V ­ C ¯ a ­
(c) If DG = (–) ve then equilibrium will shift in forward C
direction; Kc > 1 Common ion effect : By addition of X mole/L of a common
(a) Kc unit ® (mol/lit)Dn, ion, to a weak acid (or weak base) a becomes equal to
(b) Kp unit ® (atm)Dn Ka æ Kb ö
Reaction Quotient and Equilibrium Constant X çè or X ÷ø [where a = degree of dissociation]
Consider the following reversible reaction A + B ƒ C + D (i) If solubility product > ionic product then the solution is
[C][D] unsaturated and more of the substance can be dissolved
\ Qc = [A][B] in it.
(ii) If ionic product > solubility product the solution is
Case I : If Q c < Kc then : [Reactants] > [Products] super saturated (principle of precipitation).
then the system is not at equilibrium Salt of weak acid and strong base :
Case II : If Q c = Kc then : The system is at equilibrium. Kh Kw
pH = 0.5 (pKw + pKa + log c); h = ; Kh = K
Case III : If Q c > Kc then : [Products] > [Reactants] c a
The system is not at equilibrium. (h = degree of hydrolysis)
A relationship between the equilibrium constant KC, reaction Salt of weak base and strong acid :
quotient and Gibb's energy. Kw
DG = DG° + RT ln Q pH = 0.5 (pKw – pKb – log c); h = Kb ´ c
At equilibrium DG = 0 and Q = K then DG° = –RT ln Kc
Salt of weak acid and weak base :
\ DG° = –RT ln Kp
Le-Chatelier’s principle Kw
pH = 0.5 (pKw + pKa – pKb ); h =
(i) Increase of reactant conc. (Shift reaction forward) Ka ´ Kb
(ii) Decrease of reactant conc. (Shift reaction backward)
(iii) Increase of pressure (from more moles to less moles) CHEMICAL KINETICS
(iv) Decrease of pressure (from less moles to more moles)
(v) For exothermic reaction decrease in temp. (Shift Unit of rate constant : k = mol1–n litn–1 sec–1
forward) Order of reaction It can be fraction, zero or any whole number.
(vi) For endothermic increase in temp. (Shift backward) Molecularity of reaction is always a whole number. It is never
more than three. It cannot be zero.
IONIC EQUILIBRIUM First Order Reactions :
(i) Lewis Acid (e– pair acceptor) ® CO2, BF3, AlCl3, ZnCl2,
2.303 a 0.693
normal cation k= log10 & t1/12 = [A]t = [A]0e–kt
(ii) Lewis Base (e– pair donor) ® NH3, ROH, ROR, H2O, t (a - x) k
RNH2, normal anions Second Order Reactions : When concentration of A and B
Dissociation of Weak Acid and Weak Base
(i) Weak Acid, Ka = Cx2/(1 – x) or Ka = Cx2 ; x << 1 1 æ x ö
taking same. k2 = ç ÷
(ii) Weak Base, Kb = Cx2/(1 – x) or Kb = Cx2 ; x << 1 t è a(a - x) ø
Buffer solution {Henderson equation} : When concentration of A and B are taking different -
(i) Acidic, pH = pKa + log {Salt/Acid}.
2.303 b(a - x)
For maximum buffer action pH = pKa k2 = log
Range of buffer pH = pKa ± 1 t(a - b) a(b - x)
(ii) Alkaline ® pOH = pKb + log {Salt/Base} for max. buffer a
action pH = 14 – pKb Zero Order Reaction : x = kt and t1/2 =
Range pH = 14 – pKb ± 1 2k
The rate of reaction is independent of the concentration of
the reacting substance.
FORMULAE BOOK 11

Time of nth fraction of first order process, DH DS DG Reaction characteristics

æ 1 ö – + Always negative Reaction is spontaneous at
2×303
t1/n = log ç 1÷ all temperature.
k çè 1 - ÷ø + – Always positive Reaction is nonspontaneous
n
at all temperature
[ A]o – – Negative at low Spontaneous at low temp. &
Amount of substance left after 'n' half lives =
2n temperature but non spontaneous at high
-E a positive at high temperature
Arrhenius equation : k = Ae–Ea/RT, slope = temperature
2.303R
+ + Positive at low Non spontaneous at low
æ k2 ö E a æ T2 - T1 ö temp. but temp. & spontaneous at high
and Temperature Coefficient log ç k ÷ = ç ÷ negative at high temp.
è 1 ø 2.303 è T1T2 ø
It has been found that for a chemical reaction with rise in temperature
temperature by 10 °C, the rate constant gets nearly doubled.
k = PZ AB e - Ea /RT ELECTROCHEMISTRY

REDOX REACTIONS m = Z.I.t

l eq
Oxidant itself is reduced (gives O2) Degree of dissociation : a = l 0
Or Oxidant ¾¾ ® e– (s) Acceptor eq
Reductant itself is oxidised (gives H2) Specific conductance
Or reductant ¾¾ ® e– (s) Donor 1 l l
(i) Strength of acid µ O.N k= = = G ´ = G ´ cell constant (G*) ;
r R.a a
(ii) Strength of base µ 1/ O.N
(i) Electrochemical Series:- Li, K, Ba, Sr, Ca, Na, Mg, Al, k ´ 1000 k ´ 1000
Lm = , L eq =
Mn, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, H2, Cu, Ag, Pt, Au. M N
(ii) As we move from top to bottom in this series
(a) Standard Reduction Potential ­ Kohlrausch’s law : L 0m = xl 0A + yl 0B
(b) Standard Oxidation Potential [Products]
(c) Reducing Capacity ¯ 0.0591
Nernst Equation E = Eº – log10
(d) IP ­ n [Reactants]
(e) Reactivity ¯ é nEº ù
& EºCell = Eºright + Eºleft & Keq. = antilog ê ú
THERMODYNAMICS ë 0.0591 û
DG = – nFEcell & DGº = –nFEº cell = –2.303 RT logKc
First Law of Thermodynamics : DE = Q + W
Expression for pressure volume work W = –PDV æ ¶DG ö
& Wmax= +nFEº & DG = DH + T ç ÷
Maximum work in a reversible expansion : è ¶T ø P
V2 P1 Calculation of pH of an electrolyte by using a calomel
W = –2.303n RT log = –2.303 nRT log E cell - 0.2415
V1 P2
electrode : pH =
Wrev ³ Wirr 0.0591
qv = cvDT = DU, qp = cpDT = DH -DG -nFEocell
Enthapy changes during phase transformation Thermodynamic efficiency of fuel cells : h= =
(i) Enthalpy of Fusion DH DH
(ii) Heat of Vapourisation For H2–O2 fuel cells it is 95%.
(iii) Heat of Sublimation P = KH . x
Enthalpy : DH = DE + PDV = DE + DngRT number of equivalents
Normality (N) =
Kirchoff’s equation : volume of the solution in litres
DE T2 = DE T1 + D C V (T2 – T1) [constant V] number of moles
Molarity (M) =
DH T2 = DH T1 + DCP (T2 – T1) [constant P] volume of the solution in litres
Entropy(s) : Measure of disorder or randomness
DS = SSp–SSR
SOLUTIONS
q rev V2 P1 Raoult’s law
DS = = 2.303 nR log V = 2.303 n R log P P = pA + pB = p°AXA + p°BXB
T 1 2
Characteristics of an ideal solution:
Free energy change : DG = DH – TDS, DGº = –nFEºcell
–DG = W(maximum) – PDV, DGsystem = –TDStotal (i) DsolV = 0 (ii) DsolH = 0
12 CHEMISTRY

PAo – PA PV
Relative lowering of vapour pressure = Z (compressibility factor) = ; Z = 1 for ideal gas
PAo nRT
PAo – PA nB 8a a a
= XB = TC = , PC = 2
, VC = 3b, Tb =
PAo n A + nB 27Rb 27b bR
Colligative µ Number of particles/ ions/ moles of solute
properties SOLID STATE
Depression of freezing point, DTf = Kfm Available space filled up by hard spheres (packing fraction):
Elevation in boiling point with relative lowering of vapour p
Simple cubic = = 0.52
1000K b æ po - p ö 6
pressure DTb = çç o ÷÷ (M 1 = mol. wt. of
M1 p 3 p 2 p 2
è p ø bcc = = 0.68; fcc = = 0.74; hcp = = 0.74
solvent) 8 6 6
Osmotic pressure (P) with depression in freezing point DTf p 3
dRT diamond = = 0.34
P = DTf ´ 6
1000K f Radius ratio and co-ordination number (CN)
Relation between Osmotic pressure and other colligative Limiting radius ratio CN Geometry
properties: [0.155– 0.225] 3 [Plane triangle]
æ p o - p ö dRT [0.255–0.414] 4 [Tetrahedral]
(i) p = ç A o A ÷´ [0.414–0.732] 6 [Octahedral]
ç p ÷ M Relative lowering of vapour pressure
è A ø B
[0.732–1] 8 [bcc]
dRT Atomic radius r and the edge of the unit cell:
(ii) p = DTb ´ Elevation in boiling point
1000K b Pure elements :
dRT a 3a 2a
(iii) p = DTf ´ Depression in freezing point Simple cubic = r = ; bcc r = ; fcc r =
1000K f 2 4 4
Relationship between radius of void (r) and the radius
Normal molar mass Observed colligative property
i= = of the sphere (R) : r (tetrahedral) = 0.225 R ; r (octahedral)
Observed molar mass Normal colligative property = 0.414 R
n Paramagnetic : Presence of unpaired electrons [attracted by
Degree of association a = (1 – i) magnetic field]
n -1
Ferromagnetic : Permanent magnetism [­ ­ ­ ­]
i -1
& degree of dissociation (a) = Antiferromagnetic : Net magnetic moment is zero [­ ¯ ­ ¯]
n -1

GASEOUS STATE SURFACE CHEMISTRY

Ideal gas equation : PV = nRT Ferrimagnetic : Net magnetic moment is three [­ ¯ ¯ ­ ­
(i) R = 0.0821 liter atm. deg–1 mole–1 Emulsion : Colloidal soln. of two immiscible liquids [O/W
(ii) R = 2 cals. deg.–1 mole– emulsion, W/O emulsion]
(iii) R = 8.314 JK–1 mole–1
Velocities related to gaseous state Emulsifier : Long chain hydrocarbons are added to stabilize
emulsion.
3PV 3RT 3P
RMS velocity = = = Lyophilic colloid : Starchy gum, gelatin have greater affinity
M M d
for solvent.
8RT 2RT Lyophobic colloid : No affinity for solvent, special methods
Average speed = & Most probable speed =
M M are used to prepare sol. [e.g. As2S3, Fe(OH)3 sol]
Average speed = 0.9213 × RMS speed
Preparation of colloidal solution :
RMS speed = 1.085 × Average speed
MPS = .816 × RMS; RMS = 1.224 MPS (i) Dispersion methods (ii) Condensation method.
MPS : A.V. speed : RMS = 1 : 1.128 : 1.224 1
Coagulating power µ
1 Flecculating value
Rate of diffusion µ
density of gas
Properties of colloidal solution :
van der Waal’s equation
(i) Tyndall effect (ii) Brownian movement
æ n 2a ö
ç P + 2 ÷ (V - nb) = nRT for n moles (iii) Coagulation (iv) Filtrability.
è V ø
FORMULAE BOOK 13

INORGANIC CHEMISTRY
Basic nature of the oxides and hydroxides : B < Al < Ga < In < Tl
PERIODIC TABLE Relative strength of Lewis acid : BF3 < BCl3 < BBr3 < BI3
Ionisation energy : B > Al < Ga > In < Tl
General electronic configuration (of outer orbits) Electronegativity : Electronegativity first decreases from B
s-block ns 1–2 to Al and then increases marginally.
p-block ns 2 np 1–6
d-block (n–1)d1–10 ns1–2 CARBON FAMILY
f-block (n–2)f1–14 s2 p6 d10
(n–1)s2p6d0 or 1 ns2 Reactivity : C < Si < Ge < Sn < Pb
Property Pr (L To R) Gr (T toB) Metallic character : C < Si < Ge < Sn < Pb
(i) Atomic radius ¯ ­ Acidic character of the oxides :
(ii) Ionisation potential ­ ¯ CO2 > SiO2 > GeO2 > SnO2 > PbO2
(iii) Electron affinity ­ ¯ Weaker acidic (amphoteric)
(iv) Electronegativity ­ ¯ Reducing nature of hydrides
(v) Metallic character or ¯ ­ CH4 < SiH4 < GeH4 < SnH4 < PbH4
electropositive character Thermal stability of tetrahalides
(vi) Alkaline character ¯ CCl4 > SiCl4 > GeCl4 > SnCl4 > PbCl4
of hydroxides Oxidising character of M+4 species
(vii) Acidic character ­ ¯ GeCl4 < SnCl4 < PbCl4
(viii) Reducing property ¯ ­ Ease of hydrolysis of tetrahalides
SiCl4 < GeCl4 < SnCl4 < PbCl4
(ix) Oxidising property ­ ¯
(x) Non metallic character ­ ¯
NITROGEN FAMILY
1 1
IP µ Metallic character µ Re ducing character Acidic strength of trioxides : N2O3 > P2O3 > As2O3
Acidic strength of pentoxides
1 N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5
EA µ µ nuclear charge. Acidic strength of oxides of nitrogen
size
Second electron affinity is always negative. N2O < NO < N2O3 < N2O4 < N2O5
Basic nature, bond angle, thermal stability and dipole moment
Electron affinity of chlorine is greater than fluorine (small
of hydrides NH3 > PH3 > AsH3 > SbH3 > BiH3
atomic size). Stability of trihalides of nitrogen : NF3 > NCl3 > NBr 3
The first element of a group has similar properties with the Lewis base strength : NF3 < NCl3> NBr3 < NI3
second element of the next group. This is called diagonal Ease of hydrolysis of trichlorides
relationship. The diagonal relationship disappears after IV NCl3 > PCl3 > AsCl3 > SbCl3 > BiCl3
group. Lewis acid strength of trihalides of P, As and Sb
PCl3 > AsCl3 > SbCl3
s-BLOCK ELEMENTS Lewis acid strength among phosphorus trihalides
PF3 > PCl3 > PBr3 > PI3
Atomic radii : Li < Na < K < Rb < Cs Nitrogen displays a great tendency to form pp – pp multiple
Electronegativity : Li > Na > K > Rb > Cs bonds with itself as well as with carbon and oxygen.
First ionization potential : Li > Na > K > Rb > Cs The basic strength of the hydrides
NH3 > PH3 > AsH3 > SbH3
Melting point Li > Na > K > Rb > Cs
The thermal stability of the hydrides decreases as the atomic
Colour of the flame Li - Red, Na - Golden, K - Violet, Rb - size increases.
Red, Cs - Blue, Ca - Brick red, Sr - Blood red, Ba-Apple green
Rb and Cs show photoelectric effect. OXYGEN FAMILY
Stability of hydrides : LiH > NaH > KH > RbH > CsH
Basic nature of hydroxides : Melting and boiling point of hydrides :
LiOH < NaOH < KOH < RbOH < CsOH H2O > H2Te > H2Se > H2S
Hydration energy : Li > Na > K > Rb > Cs Volatility of hydrides:H2O < H2Te < H2Se < H2S
Reducing character : Li > Cs > Rb > K > Na Reducing nature of hydrides : H2S < H2Se < H2Te
Covalent character of hydrides : H2O < H2S < H2Se < H2Te
BORON FAMILY The acidic character of oxides (elements in the same oxidation
state) SO2 > SeO2 > TeO2 > PoO2 ; SO3 > SeO3 > TeO3
Stability of +3 oxidation state : B > Al > Ga > In > Tl Acidic character of oxide of a particular element (e.g. S)
Stability of +1 oxidation state : Ga < In < Tl SO < SO2 < SO3 ; SO2 > TeO2 > SeO2 > PoO2
14 CHEMISTRY
HALOGEN FAMILY TRANSITION ELEMENTS (d- and f-
Bond energy of halogens : Cl2 > Br 2 > F2 > I2
BLOCK ELEMENTS
Solubility of halogen in water : F2 > Cl2 > Br2 > I2 The element with exceptional configuration are
Oxidising power : F2 > Cl2 > Br2 > I2 Cr24[Ar] 3d54s1, Cu29[Ar] 3d104s1
Enthalpy of hydration of X– ion : F– > Cl– > Br– > I– Mo42 [Kr] 4d5 5s1, Pd46 [Kr] 4d10 5s0 Ag47 [Kr] 4d105s1 ,
Pt78[Xe] 4f145d106s0
Reactivity of halogens : F > Cl > Br > I
Inner Transition Elements
Ionic character of M - X bond in halides 0 -1
(i) Electronic Configuration - [ Xe ] 4f 0 -14 5d 6s 2
M – F > M – Cl > M – Br > M – I
Reducing character of X– ion : I– > Br– > Cl– > F– (ii) Magnetic properties - Magnetic moment is given by the
formula m = 4 S (S + 1) + L(L + 1) where L = Orbital quantum
Acidic strength of halogen acids : HI > HBr > HCl > HF
Conjugate base strength of halogen acids: I– < Br– < Cl– < F– number, S = Spin quantum number
Reducing property of hydrogen halides : HF < HCl < HBr < HI COORDINATION COMPOUNDS
Oxidising power of oxides of chlorine
Cl2O > ClO2 > Cl2O6 > Cl2O7 Coordination number is the number of the nearest atoms or
groups in the coordination sphere.
acidic character of oxyacids of chlorine Ligand is a Lewis base donor of electrons that bonds to a
HClO < HClO2 < HClO3 < HClO4 central metal atom in a coordination compound.
Oxidising power of oxyacids of chlorine Paramagnetic substance is one that is attracted to the
magnetic field, this results on account of unpaired electrons
present in the atom/molecule/ion.
NOBLE GASES Effective atomic number EAN
= (Z – Oxidation number) + (2 × Coordination number)
HClO > HClO2 > HClO3 > HClO4
Factors affecting stability of complex
® [XeF]+ [PF6 ]
XeF2 + PF5 ¾¾ (i) Greater the charge on the central metal ion, greater is
the stability.
® [XeF3 ]+ [Sb F6 ]
XeF4 + SbF5 ¾¾ (ii) Greater the ability of the ligand to donate electron pair
(basic strength) greater is the stability.
XeF6 + H 2 O ¾¾
® XeOF4 + 2HF (iii) Formation of chelate rings increases the stability.
Isomerism in coordination compounds :
XeF6 + 2H2O ¾¾
® XeO2 F2 + 4HF (i) Structural Isomerism (ii) Ionization Isomerism
(iii) Hydration Isomerism (iv) Linkage Isomerism
2XeF4 + 3H 2 O ¾¾
® Xe + XeO3 + 4HF + F2 (v) Polymerisation Isomerism (vi) Valence Isomerism
(vii) Coordination Position Isomerism
XeF6 + 3H 2 O ¾¾
® XeO 3 + 6HF (viii) Stereo Isomerism
2XeF6 + SiO 2 ¾¾
® 2XeOF4 + SiF4 (a) Geometrical Isomerism
(1) Square planar complexes of the type
2XeOF4 + SiO 2 ¾¾
® 2XeO 2 F2 + SiF4 MA2X2 ; MABX2 ; MABXY
(2) Octahedral of the type : MA4XY, MA4X2 MA3X3
2XeO 2 F4 + SiO2 ¾¾
® 2XeO3 + SiF4
MA2X2Y2. M(AA)2X2 and M(ABCDEF).
(b) Optical isomerism

ORGANIC CHEMISTRY
GENERAL ORGANIC CHEMISTRY Heterolytic fission ® Ions (Carbonium ions, carbanions etc.)
Nucleophiles – Electron rich
Two types : (i) Anions (ii) Neutral molecules
The order of decreasing electronegativity of hybrid orbitals with lone pair of electrons (Lewis bases)
is sp > sp2 > sp3. Electrophiles : Electron deficient.
Conformational isomers are those isomers which arise due Two types : (i) Cations (ii) Neutral molecules with vacant
to rotation around a single bond. orbitals (Lewis acids).
A meso compound is optically inactive, even though it has Inductive effect is due to s electron displacement along a
asymmetric centres (due to internal compensation of rotation chain and is permanent effect.
of plane polarised light) +I (inductive effect) increases basicity, – I effect increases
An equimolar mixture of enantiomers is called racemic acidity of compounds.
mixture, which is optically inactive. Resonance is a phenomenon in which two or more structures
Reaction intermediates and reagents : can be written for the same compound but none of them
Homolytic fission ® Free radicals actually exists.
FORMULAE BOOK 15

ALKANES SN1 reaction : Mainly 3° alkyl halides undergo this reaction

and form racemic mixture. SN1 is favoured by polar solvent
Pyrolytic cracking is a process in which alkane decomposes and low concentration of nucleophile.
to a mixture of smaller hydrocarbons, when it is heated SN2 reaction : Mainly 1° alkyl halides undergo this
strongly, in the absence of oxygen. substitution. Walden inversion takes place. SN2 reaction is
Ethane can exist in an infinite number of conformations. They preferred by non-polar solvents and high concentration of
HH H H H nucleophile.
H H Reaction with metals:
H Dry ether
are HH
(i) R – X + Mg ¾¾¾¾® R – Mg – X
HH H H
H
H H H Alkyl
halides
Grignard reagent

Eclipsed q = 60° Staggered q < 60° > 0 Skew (ii) Wurtz reaction:
Conformations of Cyclohexane : It exists in two nonplanar,
Dry ether
strainless forms, the boat and the chair form R – X + 2 Na + X – R ¾¾ ¾ ¾® R - R + 2Na + X –
Alkane

ALCOHOLS
Chair form Half Chair
Most Stable
Alkenes are converted to alcohol in different ways as follows
Reagent Types of addition
dil H2SO4 Markovnikov
Twist Boat Boat form B2H6 and H2O2, OH– Anti-Markovnikov
(Least Stable) Oxymercuration demercuration – Markovnikov
Oxidation of
ALKENES 1° alcohol ¾¾ ® aldehyde ¾¾ ® carboxylic acid
(with same no. (with same no. of
In dehydration and dehydrohalogenation the preferential of C atom) C atom)
order for removal of hydrogen is 3° > 2° > 1° (Saytzeff’s rule). 2° alcohol ¾¾ ® ketone ¾¾ ® carboxylic acid
The lower the DHh (heat of hydrogenation) the more stable (with same no. (with less no. of
the alkene is. of C atom) C atom)
Alkenes undergo anti-Markonikov addition only with HBr 3° alcohol ¾¾ ® ketone ¾¾ ® carboxylic acid
in the presence of peroxides. (with less no. (with less no. of
of C atom) C atom)
ALKYNES
Alkynes add water molecule in presence of mercuric sulphate PHENOLS
and dil. H2SO4 and form carbonyl compounds.
3 CHCl /OH Q
Terminal alkynes have acidic H-atoms, so they form metal Phenol ¾¾¾¾¾¾
® Phenolic aldehyde
alkynides with Na, ammonical cuprous chloride solution and (Reimer-Tieman reaction)
ammoniacal silver nitrate solution. 2®
Phenol ¾¾¾
CO
Phenolic carboxylic acid (Kolbe's reaction)
Alkynes are acidic because of H-atoms which are attached D
to sp ‘C’ atom which has more electronegativity and ‘s’ Acidity of phenols
character than sp2 and sp3 ‘C’ atoms. (i) Increases by electron withdrawing substituents like
+
– NO2, – CN, – CHO, – COOH, –X, - N R 3
ARENES (ii) decreases by electron releasing substituents like
– R, – OH, – NH2, – NR2, – OR
All o and p-directing groups are ring activating groups
(except – X)
They are : – OH, – NH2, – X, – R, – OR, etc.
ETHERS
All m-directing groups are ring deactivating groups. 2ROH ¾¾¾¾
Al O
2 3® R - O - R + H O
250ºC 2
+
They are : – CHO, – COOH, – NO2, – CN,– NR 3 , etc. RONa + X - R ' ¾¾
® ROR '+ NaX
(Williamson's synthesis)
dil. H 2SO4
HALOGEN COMPOUNDS ROR + H 2O ¾¾¾¾¾
D
® 2ROH

The order of reactivity is

CARBONYL COMPOUNDS
(i) RI > RBr > RCl > RF
(ii) Allyl halide > Alkyl halide > Vinyl halide Formation of alcohols using RMgX
(iii) Alkyl halide > Aryl halide Hydrolysis
(a) Formaldehyde + RMgX ¾¾¾¾¾ ® 1° alcohol
16 CHEMISTRY

Hydrolysis
(b) Aldehyde + RMgX ¾¾¾¾¾ Tests to differentiate :
® 2° alcohol
1°, 2° and 3° alcohols (i) Lucas test
(other than HCHO)
(ii) Victor meyer’s test
Hydrolysis
(c) Ketone + RMgX ¾¾¾¾¾ ® 3° alcohol 1°, 2° and 3° amines Hinsberg test
Cannizzaro reaction (Disproportionation) 1°, 2° and 3° nitro compounds Test with HNO2 and KOH
Hot conc. Aryl halides and alkyl halides Test with AgNO3 solution
Aldehyde ¾¾¾¾® Alcohol + Salt of acid Aldehydes and ketones Tollen’s test/Fehling’s test
alkali
(no a H-atom) Aromatic aldehydes and Fehling’s test
Aldol condensation : Aliphatic aldehydes
Carbonyl compound + dil. alkali ––® b-hydroxy carbonyl
(with a H-atom) compound IMPORTANT REAGENTS
ethanolic
Benzoin condensation Benzaldehyde ¾¾¾¾ Dil. H2SO4 [or Conc. H2SO4 + H2O]
® Benzoin
NaCN Use ® Hydrating agent (+HOH)
The relative reactivities of different acid derivatives towards Alc. KOH or NaNH2(Use ® -HX)
nucleophilic acyl substitution reaction follow the order: alc.KOH
CH3CH2Cl ¾¾¾¾ ® CH2=CH2
O O O O O
|| || || || || Lucas Reagent ZnCl2 + Conc. HCl
R – C – Cl > R – C – O – C – R ' > R – C – OR ' > R – C – NH 2 Use ® For distinction between 1º, 2º
Acid chloride Anhydride Ester Amide
& 3º alc.
Tilden Reagent NOCl (Nitrosyl chloride)
CARBOXYLIC ACIDS
C2H5NH2 ¾¾¾ NOCl
The rate of esterfication decreases when alcohol, acid or
® C2H5Cl
both have branched substituents. Alkaline KMnO4(Strong oxidant)
Or tho effect : All orth o substituted benzoic acids Toluene ® Benzoic acid
(irrespective of type of substituent) are stronger than benzoic Bayer’s Reagent : 1% alkaline KMnO4(Weak oxidant)
acid. Use: ® For test of > C = C < or –C = C –
NITROGEN COMPOUNDS BR
CH2=CH2+H2O+[O] ¾¾® CH2OH–CH2OH
Order of basicity : Acidic K2Cr2O7 (Strong oxidant) : RCH2OH ¾¾®[O] RCHO
(R = – CH3 or – C2H5) 2° > 1° > 3° > NH3
Hofmann degradation SnCl2/HCl or Sn/HCl used for reduction of nitrobenzene in
SnCl / HCl
Br2 /KOH
Amides ¾¾¾¾® 1° amine acidic medium. C6H5NO2 ¾¾¾¾¾
2 ® C6H5NH2
6H
The basicity of amines is (i) decreased by electron with Lindlar’s Catalyst = Pd/CaCO 3 + in small quantity
drawing groups (ii) increased by electron releasing groups
Reduction of nitrobenzene in different media gives different (CH3COO)2Pb 2 – butye + H2 ¾¾ "
® Cis-2-butene
products (main product)
Medium Product Ziegler –Natta Catalyst (C2H5)3Al + TiCl4
Acidic Aniline
Use ®In Addition polymerisation
Basic Azoxy, Azo and finally hydrazobenzene
Neutral Phenyl hydroxylamine
IDENTIFICATION TESTS
BIOMOLECULES Unsaturated compound (Bayer’s reagent)
Decolourising the reagent
Carbohydrates are polyhydroxy aldehydes or ketones. Alcohols (Ceric ammonium nitrate solution)
Monosaccharides are simple sugars, containing three to nine Red colouration
carbon atoms. Phenols (Neutral FeCl3 solution)
Characteristic reactions : Violet/deep blue colouration
Homologous series Type of reactions Aldehydes and ketones (2, 4-D.N.P.)
(i) Alkanes Substitution Orange precipitate
Mostly free radical Acids (NaHCO3 solution)
Brisk effervescence (CO2 is evolved)
(ii) Alkenes and alkynes Electrophillic addition
1° amine (CHCl3 + KOH)
(iii) Arenes Electrophillic substitution Foul smell (isocyanide)
(iv) Alkyl halides Nucleophillic substitution 2° amine (NaNO2 + HCl)
(v) Aldehyde and ketones Nucleophillic addition Yellow oily liquid (Nitrosoamine)