PHYSICAL CHEMISTRY

Total energy of electron in the n th shell

SOME BASIC CONCEPTS OF
CHEMISTRY e2 kZe 2 kZe 2
= K.E. + P.E. kZ
2rn rn 2rn
Multiplie ed by
Amount of a
d by Multipli
NA 23 Number 1 1 1
substance Molar mass Mol (6.023 × 10 ) of = RZ2 , [R = 1.0968 × 107 m–1]
(in gram)
b y by entities n12 n 22
Divid ed
d D Divided by
iv
plie id hc h
ti 22.4 L ed E hv
ul by ,
M 2m K.E.
Volume of gas (in L) at STP No. of spectral lines produced when an electron drops from
n(n 1)
Molecular mass nth level to ground level =
2
Average relative mass of one molecule Heisenberg's Uncertainty Principle ( x) ( p) h/4
1 Nodes (n – 1) = total nodes, = angular nodes,
mass of C-12 atom (n – – 1) = Radial nodes
12
Molecular mass = 2 × VD Orbital angular momentum : h
( 1) ( 1)h
2
Eq. wt. of metal
wt. of metal
1.008
CHEMICAL BONDING
wt. of H 2 displaced
Actual dipole moment
(i) % ionic character = 100
wt. of metal Calculated dipole moment
Eq. wt. of metal 8 (ii) Dipole moment is helpful in predicting geometry and
wt. of oxygen combined
polarity of molecule.
wt. of metal Fajan’s Rule : Following factors are helpful in increasing
35.5 covalent character in ionic compounds
wt. of chlorine combined (i) Small cation
Molecular formula = (Empirical formula)n (ii) Big anion
(iii) High charge on cation/anion
(iv) Cation having pseudo inert gas configuration
ATOMIC STRUCTURE (ns2p6d10) e.g. Cu+, Ag+, Zn+2, Cd+2
M.O. theory :
Energy of electron in species with one electron. (i) Bond order = ½(Nb–Na)
2 2 me 4 Z2 (ii) Higher the bond order, higher is the bond dissociation
En = energy, greater is the stability, shorter is the bond length.
n 2h 2
2 Formal charge (F.C.) on an atom in a Lewis structure
2 me4 Z2 = [total number of valence electrons in the free atoms]
For energy in SI system, En =
n 2 h 2 (4 0)
2
– [total number of non-binding (lone pair) electrons]
1312Z2 1 –
1
[total number of bonding (shared) electrons]
En = kJ mol 2
n2
Relative bond strength : sp3d2 >dsp2 >sp3 >sp2 >sp >p-p
nh (Co-axial) > s - p > s - s > p - p (Co-lateral)
mvr
2 VSEPR theory
(i) (LP-LP) repulsion > (LP-BP) > (BP-BP)
n 2h 2 n2 (ii) NH3 Bond Angle 106° 45’ because (LP-BP) repulsion
r= 2 2 = 0.529 Å
4 mZe Z > (BP-BP) H2O 104° 27’because (LP-LP) repulsion >
(LP-LB) > (BP-BP)
 10

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

Time of nth fraction of first order process, H S G Reaction characteristics

1 – + Always negative Reaction is spontaneous at
2 303
t 1/n = log 1 all temperature.
k 1 + – Always positive Reaction is nonspontaneous
n
at all temperature
Ao
Amount of substance left after 'n' half lives = – – Negative at low Spontaneous at low temp. &
2n temperature but non spontaneous at high
Ea positive at high temperature
Arrhenius equation : k = Ae–Ea/RT, slope = temperature
2.303R
+ + Positive at low Non spontaneous at low
k2 Ea T2 T1 temp. but temp. & spontaneous at high
and Temperature Coefficient log k = T1T2 negative at high temp.
1 2.303
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

eq
Oxidant itself is reduced (gives O2) Degree of dissociation : = 0
Or Oxidant e– (s) Acceptor eq
Reductant itself is oxidised (gives H2) Specific conductance
Or reductant e– (s) Donor 1
(i) Strength of acid O.N G G cell constant (G*) ;
R.a a
(ii) Strength of base O.N
(i) Electrochemical Series:- Li, K, Ba, Sr, Ca, Na, Mg, Al, 1000 1000
m
, 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 0 0 0
(a) Standard Reduction Potential Kohlrausch’s law : m x A y B
(b) Standard Oxidation Potential [Products]
(c) Reducing Capacity 0.0591
Nernst Equation E = Eº – log10
(d) IP n [Reactants]
(e) Reactivity nEº
& EºCell = Eºright + Eºleft & Keq. = antilog
THERMODYNAMICS 0.0591
G = – nFEcell & Gº = –nFEº cell = –2.303 RT logKc
First Law of Thermodynamics : E = Q + W
G
Expression for pressure volume work W = –P V & Wmax= +nFEº & G = H + T
Maximum work in a reversible expansion : T 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 Wirr 0.0591
qv = cv T = U, qp = cp T = H G nFEocell
Enthapy changes during phase transformation Thermodynamic efficiency of fuel cells :
H
(i) Enthalpy of Fusion For H2–O2 fuel cells it is 95%.
(ii) Heat of Vapourisation P = KH . x
(iii) Heat of Sublimation
Enthalpy : H = E + P V = E + ngRT number of equivalents
Normality (N) =
Kirchoff’s equation : volume of the solution in litres
ET2 ET1 CV (T2 – T1) [constant V] number of moles
Molarity (M) =
volume of the solution in litres
H T2 H T1 CP (T2 – T1) [constant P]
Entropy(s) : Measure of disorder or randomness SOLUTIONS
S = Sp– SR
Raoult’s law
q V2 P1
S = rev = 2.303 nR log = 2.303 n R log P P = pA + pB = p°AXA + p°BXB
T V1 2 Characteristics of an ideal solution:
Free energy change : G = H – T S, Gº = –nFEºcell (i) solV = 0 (ii) solH = 0
– G = W(maximum) – P V, Gsystem = –T Stotal
 12

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 Number of particles/ ions/ moles of solute
properties SOLID STATE
Depression of freezing point, Tf = Kfm Available space filled up by hard spheres (packing fraction):
Elevation in boiling point with relative lowering of vapour
Simple cubic = = 0.52
1000K b po p 6
pressure Tb (M 1 = mol. wt. of
M1 po 3 2 2
bcc = = 0.68 fcc = = 0.74 hcp = = 0.74
solvent) 8 6 6
Osmotic pressure (P) with depression in freezing point Tf 3
dRT diamond = = 0.34
P Tf 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]
p oA p A dRT [0.255–0.414] 4 [Tetrahedral]
(i) M B Relative lowering of vapour pressure [0.414–0.732] 6 [Octahedral]
p oA
[0.732–1] 8 [bcc]
dRT Atomic radius r and the edge of the unit cell:
(ii) Tb Elevation in boiling point
1000K b Pure elements :
dRT a 3a 2a
(iii) Tf Depression in freezing point Simple cubic = r = ; bcc r = ; fcc =
1000K f 2 4 4
Relationship between radius of void (r) and the radius
Normal molar mass Observed colligative property of the sphere (R) : r (tetrahedral) = 0.225 R ; r (octahedral)
i= =
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 Antiferromagnetic : Net magnetic moment is zero [ ]
& degree of dissociation ( ) =
n 1
SURFACE CHEMISTRY
GASEOUS STATE
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
1 Coagulating power
Rate of diffusion Flecculating value
density of gas
van der Waal’s equation Properties of colloidal solution :

n 2a (i) Tyndall effect (ii) Brownian movement

P (V nb) nRT for n moles
V2 (iii) Coagulation (iv) Filtrability.
 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 Reducing character Acidic strength of trioxides : N2O3 > P2O3 > As2O3
Metallic character
Acidic strength of pentoxides
1 N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5
EA 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 p – p 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

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 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
XeF2 PF5 [XeF] [PF6 ] (i) Greater the charge on the central metal ion, greater is
the stability.
XeF4 SbF5 [XeF3 ] [Sb F6 ] (ii) Greater the ability of the ligand to donate electron pair
(basic strength) greater is the stability.
XeF6 H 2O XeOF4 2HF (iii) Formation of chelate rings increases the stability.
Isomerism in coordination compounds :
XeF6 2H2O XeO2 F2 4HF (i) Structural Isomerism (ii) Ionization Isomerism
(iii) Hydration Isomerism (iv) Linkage Isomerism
2XeF4 3H 2 O Xe XeO3 4HF F2 (v) Polymerisation Isomerism (vi) Valence Isomerism
(vii) Coordination Position Isomerism
XeF6 3H 2 O XeO 3 6HF (viii) Stereo Isomerism
2XeF6 SiO 2 2XeOF4 SiF4 (a) Geometrical Isomerism
(1) Square planar complexes of the type
2XeOF4 SiO 2 2XeO2 F2 SiF4 MA2X2 ; MABX2 ; MABXY
(2) Octahedral of the type : MA4XY, MA4X2 MA3X3
2XeO 2 F4 SiO2 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 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.
 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 R – Mg – X
HH H H
H
H H H Alkyl Grignard reagent
halides
Eclipsed = 60° Staggered < 60° > 0 Skew
(ii) Wurtz reaction:
Conformations of Cyclohexane : It exists in two nonplanar,
strainless forms, the boat and the chair form Dry ether
R – X + 2 Na + X – R 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
B2H6 and H2O2, OH– Anti-Markovnikov
Twist Boat Boat form
(Least Stable) Oxymercuration demercuration – Markovnikov
Oxidation of
ALKENES 1° alcohol aldehyde 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 ketone carboxylic acid
The lower the Hh (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 ketone 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. CHCl3 /OH
Terminal alkynes have acidic H-atoms, so they form metal Phenol Phenolic aldehyde
alkynides with Na, ammonical cuprous chloride solution and (Reimer-Tieman reaction)
ammoniacal silver nitrate solution. Phenol
CO2
Phenolic carboxylic acid (Kolbe's reaction)
Alkynes are acidic because of H-atoms which are attached
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
Al2O3
R O R H 2O
250ºC
They are : – CHO, – COOH, – NO2, – CN,– NR 3 , etc. RONa X R ' ROR ' NaX
(Williamson's synthesis)

HALOGEN COMPOUNDS ROR H 2 O

dil. H 2SO 4
2ROH
The order of reactivity is
(i) RI > RBr > RCl > RF CARBONYL COMPOUNDS
(ii) Allyl halide > Alkyl halide > Vinyl halide Formation of alcohols using RMgX
(iii) Alkyl halide > Aryl halide (a) Formaldehyde + RMgX Hydrolysis
1° alcohol
 16

(b) Aldehyde + RMgX Hydrolysis

2° alcohol Tests to differentiate :
1°, 2° and 3° alcohols (i) Lucas test
(other than HCHO)
(ii) Victor meyer’s test
(c) Ketone + RMgX Hydrolysis 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 Alcohol + Salt of acid Aldehydes and ketones Tollen’s test/Fehling’s test
alkali
(no H-atom) Aromatic aldehydes and Fehling’s test
Aldol condensation : Aliphatic aldehydes
Carbonyl compound + dil. alkali –– -hydroxy carbonyl
(with H-atom) compound IMPORTANT REAGENTS

Benzoin condensation Benzaldehyde ethanolic 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 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 NOCl C2H5Cl
The rate of esterfication decreases when alcohol, acid or
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 CH2=CH2+H2O+[O] BR CH2OH–CH2OH
Order of basicity : Acidic K2Cr2O7 (Strong oxidant) : RCH2OH [O] RCHO
(R = – CH3 or – C2H5) 2° > 1° > 3° > NH3
Hofmann degradation SnCl2/HCl or Sn/HCl used for reduction of nitrobenzene in
SnCl 2 / HCl
Amides Br2 /KOH 1° amine acidic medium. C6H5NO2 C6H5NH2
6H
The basicity of amines is (i) decreased by electron with
drawing groups (ii) increased by electron releasing groups Lindlar’s Catalyst = Pd/CaCO 3 + in small quantity
Reduction of nitrobenzene in different media gives different (CH3COO)2Pb 2 – butye + H2 "
Cis-2-butene
products
Medium Product (main product)
Acidic Aniline Ziegler –Natta Catalyst (C2H5)3Al + TiCl4
Basic Azoxy, Azo and finally hydrazobenzene Use In Addition polymerisation
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)
(ii) Alkenes and alkynes Electrophillic addition Brisk effervescence (CO2 is evolved)
(iii) Arenes Electrophillic substitution 1° amine (CHCl3 + KOH)
(iv) Alkyl halides Nucleophillic substitution Foul smell (isocyanide)
(v) Aldehyde and ketones Nucleophillic addition 2° amine (NaNO2 + HCl)
Yellow oily liquid (Nitrosoamine)