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CHEMISTRY

Energy of electron in species with one (a) % ionic character =


electron.
ATOMIC -2 p 2 me 4 Z 2 Actual dipole moment
En = CHEMICAL ´ 100
STRUCTURE n 2h 2 BONDING Calculated dipole moment
For energy in SI system, (b) Pauling equation % ionic
-2 p 2 me4 Z2 character
En = 2 2
n h (4 pe 0 ) 2 é - (XA - X B ) ù
1
-1312Z2 = 100 êë1 - exp 4 úû
En = kJ mol-1
n2 Fajan’s Factors : Following factors are helpful in bringing
where e0 is permitivity constant and its value is 8.8542 × covalent character in Ionic compounds
10–12 coulomb2 newton–1 metre–2 (a) Small cation (b) Big anion
n 2h 2 æ n2 ö (c) High charge on cation/anion
r= = 0.529 çç ÷÷ Å (d) Cation having pseudo inert gas configuration (ns2p6d10)
4 p 2 mZe 2 è Z ø e.g. Cu+, Ag+, Zn+2, Cd+2
Total energy of electron in the nth shell M.O. theory :
e 2 æ kZe 2 ö kZe 2 (a) Bond order = ½(Nb–Na)
= K.E. + P.E. = kZ + ç- ÷ =-
(b) Higher the bond order, higher is the bond dissociation
2rn è rn ø 2rn
energy, greater is the stability, shorter is the bond length.
1 é1 1 ù (c) Species Bond order Magnetic properties
u= = RZ2 ê 2 - 2 ú , [R = 1.0968 × 107 m–1]
l ëê n1 n 2 úû H2 1 Diamagnetic
H2 + 0.5 Paramagnetic
No. of spectral lines produced when an electron drops from
Li2 1 Diamagnetic
n(n - 1)
nth level to ground level = Relative bond strength : sp3d2 >dsp2 >sp3 >sp2 >sp >p-p
2
(Co-axial) > s - p > s - s > p - p (Co-lateral)
Heisenberg Uncertainty Principle (Dx) (Dp) ³ h/4p
Nodes (n – 1) = total nodes, l = angular nodes, VSEPR theory
(n – l – 1) = Radial nodes (a) (LP-LP) repulsion > (LP-BP) > (BP-BP)
(b) NH3 ® Bond Angle 106° 45’ because (LP-BP) repulsion
Orbital angular momentum : l (l + 1) h = l(l + 1)h > (BP-BP) H2O ® 104° 27’because (LP-LP) repulsion > (LP-
2p LB) > (BP-BP)
Radial probability density curves:
Bond angle :
n=1 (a) NH3 > PH3 > AsH3 (b) H2O > H2S > H2Se
n=2
R .4pr .dr

R .4pr .dr

(c) NH3 > NF3


2

1s 2s (d) Cl2O > OF2


Δn
2

K p = K c (RT) g where Dng' nP – n R


2

®r ®r Free Energy change (DG)


CHEMICAL
(a) If DG = 0 then reversible reaction
n =2 EQUILIBRIUM
n=3 would be in equilibrium, Kc = 0
R .4pr .dr

R .4pr .dr

3s (b) If DG = (+) ve then equilibrium will


2p
2

be displace in backward direction;


2

Kc < 1
®r ®r
(c) If DG = (–) ve then equilibrium will displace in forward
direction; Kc > 1
n=3 (a) Kc unit ® (moles/lit)Dn,
R .4pr .dr

R .4pr .dr

n=3
(b) Kp unit ® (atm)Dn
2

3p 3d
2

®r ®r

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Reaction Quotient and Equilibrium Constant
Ki
Consider the following reversible reaction a= Ki V = or V ­ C ¯ a ­
C
A+BƒC+D
Common ion effect : By addition of X mole/L of a common
[C][D] ion, to a weak acid (or weak base) a becomes equal to
\ Qc = [A][B]
Ka æ K b ö
or [where a = degree of dissociation]
Case I : If Q c < Kc then : [Reactants] > [Products] X çè X ÷ø
then the system is not at equilibrium (A) If solubility product > ionic product then the solution is
Case II : If Q c = Kc then : The system is at equilibrium and unsaturated and more of the substance can be dissolved in it.
the concentration of the species C, D, B,A are at equilibrium. (B) If ionic product > solubility product the solution is super
Case III : If Q c > Kc then : [Products] > [Reactants] saturated (principle of precipitation).
The system is not at equilibrium. Salt of weak acid and strong base :
A relationship between the equilibrium constant KC, reaction Kh Kw
quotient and Gibbs energy. pH = 0.5 (pKw + pKa + log c); h = ; Kh = K
c a
DG = DG° + RT ln Q (h = degree of hydrolysis)
At equilibrium DG = 0 and Q = K then Salt of weak base and strong acid :
DG° = –RT ln Kc Kw
\ DG° = –RT ln Kp pH = 0.5 (pKw – pKb – log c); h = Kb ´ c
Le chatelier’s principal Salt of weak acid and weak base :
(i) Increase of reactant conc. (Shift forward)
Kw
(ii) Decrease of reactant conc. (Shift backward) pH = 0.5 (pKw + pKa – pKb ); h =
Ka ´ Kb
(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 Differ ences between order and
forward) molecularity of reaction:
CHEMICAL
(vi) For endothermic increase in temp. (Shift backward)
(a) Lewis Acid (e– pair acceptor) ® KINETICS
CO2, BF3, AlCl3, ZnCl2, normal
cation
ACIDS AND (b) Lewis Base (e– pair donor) NH3,
BASES ROH, ROR, H2O, RNH2, normal Order of reaction Molecularity
anion 1. It is experimentally It is a theoretical concept.
Dissociation of weak Acid & Weak determined quantity
Base ® 2. It can have integral, Always integral values only,
(a) Weak Acid ® Ka = Cx2/(1 – x) or fractional or negative never zero or negative
Ka = Cx2 ; x << 1 values
(b) Weak Base ® Kb = Cx2/(1 – x) or Kb = Cx2 ; x << 1 3. It cannot be obtained It can be obtained.
Buffer solution {Henderson equation} : from balanced or
(a) Acidic ® pH = pKa + log {Salt/Acid}. stoichiometric equation.
For Maximum buffer action pH = pKa 4. It tells about the slowest It does not tell anything
Range of Buffer pH = pKa ± 1 step in the mechanism about mechanism
(b) Alkaline ® pOH = pKb + log {Salt/Base} for max. buffer 5. It is sum of the powers It is the number of reacting
action pH = 14 – pKb of the concentration species undergoing
Range pH = 14 – pKb ± 1 terms in the rate law simultaneous collision in the
Moles / lit of Acid or Base Mixed equation. reaction.
(c) Buffer Capacity =
change in pH
Unit of Rate constant :
Necessary condition for showing neutral colour of Indicator k = mol1–n litn–1 sec–1
pH = pKln or[HIn] = [In–] or [InOH] = [In+] Order of reaction It can be fraction, zero or any whole number.
Molecularity of reaction is always a whole number. It is never
Relation between ionisation constant more than three. It cannot be zero.
(Ki) & degree of ionisation(a):- First Order reaction :
IONIC a2 a2 C 2.303 a 0.693
Ki = = (Ostwald’ss
EQUILIBRIUM (1 - a)V (1 - a) k= log10 & t1/12 =
t (a - x) k
dilution law) [A]t = [A]0e–kt
It is applicable to weak electrolytes Second Order Reaction :
for which a <<1 then When concentration of A and B taking same.

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1 æ x ö First Law : DE = Q + W
k2 = ç ÷ Expression for pressure volume work
t è a(a - x) ø W = –PDV
When concentration of A and B are taking different - THERMO- Maximum work in a reversible
2.303 b(a - x) DYNAMICS expansion :
k2 = t(a - b) log a(b - x)
V2
Zero Order Reaction : W = –2.303n RT log = –2.303 nRT
T
V1
a
x = kt & t1/2 = P1
2k log P
The rate of reaction is independent of the concentration of 2
the reacting substance. Wrev ³ Wirr
Time of nth fraction of first order process, qv = cvDT = DU, qp = cpDT = DH
æ 1 ö Enthapy changes during phase transformation
2×303
t 1/n = log ç 1÷ (i) Enthalpy of Fusion
k çè 1 - ÷ø
n (ii) Heat of Vapourisation
Arrhenius equation : (iii) Heat of Sublimation
-E a Enthalpy : DH = DE + PDV = DE + DngRT
k = Ae–Ea/RT & slope = & Temperature Coefficient
2.303R Kirchoff’s equation :
æ k2 ö E a æ T2 - T1 ö DET2 = DET1 + DCV (T2 – T1) [constant V]
log ç k ÷ = ç ÷
è 1 ø 2.303 è T1T2 ø DH T2 = DH T1 + DCP (T2 – T1) [constant P]
It has been found that for a chemical reaction with rise in
Entropy(s) : Measure of disorder or randomness
temperature by 10 °C, the rate constant gets nearly doubled.
DS = SSp–SSR
Oxidant itself is reduced (gives O2) q rev V2 P1
Or Oxidant ¾¾ ® e– (s) Acceptor DS = = 2.303 nR log V = 2.303 n R log P
T 1 2
Reductant itself is oxidised (gives H2)
OXIDATION - Free energy change : DG = DH – TDS
Or reductant ¾¾ ® e– (s) Donor –DG = W(maximum) – PDV
REDUCTION
(i) Strongness of acid µ O.N
DH DS DG Reaction characteristics
(ii) Strongness of base µ 1/ O.N
(a) Electro Chemical Series:- Li, K, Ba, – + Always negative Reaction is spontaneous at
Sr, Ca, Na, Mg, Al, Mn, Zn, Cr, Fe, Cd, Co, all temperature.
Ni, Sn, Pb, H2, Cu, Ag, Pt, Au. + – Always positive Reaction is nonspontaneous
(b) As we move from top to bottom in this series at all temperature
(1) Standard Reduction Potential ­ – – Negative at low Spontaneous at low temp. &
(2) Standard Oxidation Potential ¯ temperature but non spontaneous at high
(3) Reducing Capacity ¯ positive at high temperature
(4) IP ­ temperature
(5) Reactivity ¯ + + Positive at low Non spontaneous at low
Equivalent weight of element temp. but temp. & spontaneous at high
negative at high temp.
Atomic wt of the element temperature
=
Valency of element
VOLUMETRIC
ANALYSIS The law of Dulong and Petit
Atomic wt.×specific heat » 6.4 m = Z.I.t
Normality (N) l eq
number of equivalents ELECTRO- Degree of dissociation : a = l 0 =
= CHEMISTRY eq
volume of the solution in litres Equivalent conductance at given concentration
number of moles equivalent conductance at infinite dilution
Molarity (M) =
volume of the solution in litres Specific conductance
Common acid-base indicators 1 1 l 1000
L sp = = = ; Lm = ´ Lsp .
Indicator Acid colour Alkaline colour pH range of S RA / l RA C
change
Methyl orange Red Yellow 3.2–4.4
Kohlrausch’s law : L 0m = xl 0A + yl 0B
Methyl red Red Yellow 4.2–6.2 Nernst Equation
Litmus Red Blue 4.5–8.3 0.0591 [Products]
Phenolphthalein Colourless red 8.3–10 E = Eº – log10
n [Reactants]

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Ideal gas equation : PV = nRT
é nEº ù
& EºCell = Eºright + Eºleft & Keq. = antilog ê ú (i) R = 0.0821 liter atm. deg–1 mole–1
ë 0.0591 û (ii) R = 2 cals. deg.–1 mole–
DG = – nFEcell & DGº = –nFEº cell GASEOUS (iii) R = 8.314 JK–1 mole–1
STATE Velocities related to gaseous state
æ ¶DG ö
& Wmax= +nFEº & DG = DH + T ç ÷
è ¶T ø P 3PV 3RT
RMS velocity C = = =
Calculation of pH of an electrolyte by using a calomel M M
E cell - 0.2415 3P
electrode : pH =
0.0591 d
Thermodynamic efficiency of fuel cells :
8RT 2RT
-DG -nFEocell Average speed = & Most probable speed =
h= = M M
DH DH Average speed = 0.9213 × RMS speed
For H2–O2 fuel cells it is 95%. RMS speed = 1.085 × Average speed
MPS = .816 × RMS; RMS = 1.224 MPS
Raoult’s law MPS : A.V. speed : RMS = 1 : 1.128 : 1.224
P = pA + pB = p°AXA + p°BXB
Characteristics of an ideal solution: 1
Rate of diffusion µ
SOLUTION AND (i) DsolV = 0 density of gas
COLLIGATIVE (ii) DsolH = 0
van der Waal’s equation
PROPERTIES Relative lowering of vapour pressure
PAo – PA æ n 2a ö
= ç P + ÷ (V - nb) = nRT for n moles
PAo è V2 ø
PAo – PA nB PV
= XB = Z (compressibility factor) = ; Z = 1 for ideal gas
PAo n A + nB nRT
Colligative µ Number of particles Available space filled up by hard
properties µ Number of ions (in case of electrolytes) spheres (packing fraction):
µ Number of moles of solute p
Depression of freezing point, DTf = Kfm SOLID AND Simple cubic = = 0.52
Elevation in boiling point with relative lowering of vapour 6
LIQUID STATE
pressure p 3
1000K b æ po - p ö bcc = = 0.68
DTb = 8
ç ÷
M1 çè po ÷ø (M1 = mol. wt. of solvent)
p 2
Osmotic pressure (P) with depression in freezing point DTf fcc = = 0.74
6
dRT
P = DTf ´ p 2 p 3
1000K f hcp = = 0.74 diamond = = 0.34
Relation between Osmotic pressure and other colligative 6 6
properties: Radius ratio and co-ordination number (CN)
Limiting radius ratio CN Geometry
æ p oA - p A ö dRT
(i) p = çç o
÷´
÷ Relative lowering of vapour pressure [0.155– 0.225] 3 [plane triangle]
è pA ø M B [0.255–0.414] 4 [tetrahedral]
dRT [0.414–0.732] 6 [octahedral]
(ii) p = DTb ´ Elevation in boiling point [0.732–1] 8 [bcc]
1000K b
Atomic radius r and the edge of the unit cell:
dRT Pure elements :
(iii) p = DTf ´ Depression in freezing point
1000K f a 3a 2a
Normal molar mass Observed colligative property Simple cubic = r = ; bcc r = ; fcc =
i= = 2 4 4
Observed molar mass Normal colligative property
Relationship between radius of void (r) and the radius of the
Observed osmotic pressure sphere (R) : r (tetrahedral) = 0.225 R ; r (octahedral) = 0.414 R
i =
Normal osmotic pressure Paramagnetic : Presence of unpaired electrons [attracted by
n magnetic field]
Degree of association a = (1 – i)
n -1 Ferromagnetic : Permanent magnetism [­ ­ ­ ­]
i -1 Antiferromagnetic : net magnetic moment is zero [­ ¯ ­ ¯]
& degree of dissociation (a) = Ferrimagnetic : net magnetic moment is three [­ ¯ ¯ ­ ­]
n -1
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Emulsion : Colloidal soln. of two Lyophobic colloid : No affinity for solvent, special methods
immiscible liquids [O/W emulsion, are used to prepare sol. [e.g. As2S3, Fe(OH)3 sol]
SURFACE W/O emulsion] Preparation of colloidal solution :
CHEMISTRY & Emulsifier : Long chain (i) Dispersion methods (ii) Condensation method.
COLLOIDAL hydrocarbons are added to Properties of colloidal solution :
STATE stabilize emulsion. (i) Tyndall effect (ii) Brownian movement (iii) Coagulation
Lyophilic colloid : Starchygum, gelatin (iv) Filtrability.
have greater affinity for solvent.

INORGANIC CHEMISTRY
General electronic configuration Stability of +3 oxidation state : B >
(of outer orbits) Al > Ga > In > Tl
s-block ns1–2 Stability of +1 oxidation state : Ga
PERIODIC p-block ns 2 np 1–6 BORON < In < Tl
TABLE FAMILY Basic nature of the oxides and
d-block (n–1)d1–10 ns1–2 hydroxides :
f-block (n–2) f1–14 s 2 p 6 d 10 (n– B < Al < Ga < In < Tl
1)s2 p6d0 or 1 ns2 Relative strength of Lewis acid :
Property Pr (L To R) Gr (T to B) BF3 < BCl3 < BBr3 < BI3
(a) atomic radius ¯ ­ Ionisation energy : B > Al < Ga > In < Tl
(b) ionisation potential ­ ¯ Electronegativity : Electronegativity first decreases from B to
(c) electron affinity ­ ¯ Al and then increases marginally.
(d) electro negativity ­ ¯ Reactivity : C < Si < Ge < Sn < Pb
(e) metallic character or ¯ ­ Metallic character : C < Si < Ge <
electropositive character Sn < Pb
(f) alkaline character ¯ Acidic character of the oxides :
CARBON
of hydroxides CO2 > SiO2 > GeO2 > SnO2 > PbO2
(g) acidic character ­ ¯ FAMILY
Weaker acidic (amphoteric)
(i) reducing property ¯ ­ Reducing nature of hydrides
(j) oxidising property ­ ¯ CH4 < SiH4 < GeH4 < SnH4 < PbH4
(k) non metallic character ­ ¯ Thermal stability of tetrahalides
1 1 CCl4 > SiCl4 > GeCl4 > SnCl4 > PbCl4
IP µ µ Reducing character Oxidising character of M+4 species
Metallic character
GeCl4 < SnCl4 < PbCl4
1 Ease of hydrolysis of tetrahalides
EA µ µ nuclear charge. SiCl4 < GeCl4 < SnCl4 < PbCl4
size
Second electron affinity is always negative. Acidic strength of trioxides : N2O3
Electron affinity of chlorine is greater than fluorine (small > P2O3 > As2O3
atomic size). Acidic strength of pentoxides
The first element of a group has similar properties with the N2O5 > P2O5 > As2O5 > Sb2O5 >
second element of the next group. This is called diagonal NITROGEN Bi2O5
relationship. The diagonal relationship disappears after IV FAMILY Acidic stren gth of oxides of
group. nitrogen
Atomic radii : Li < Na < K < Rb < Cs N2O < NO < N2O3 < N2O4 < N2O5
Electronegativity : Li > Na > K > Basic nature, bond angle, thermal
Rb > Cs stability and dipole
First ionization potential : Li > Na moment of hydrides
s-BLOCK > K > Rb > Cs NH3 > PH3 > AsH3 > SbH3 > BiH3
Melting point Li > Na > K > Rb > Stability of trihalides of nitrogen : NF3 > NCl3 > NBr 3
ELEMENTS Lewis base strength : NF3 < NCl3> NBr3 < NI3
Cs
Colour of the flame Li - Red, Na - Ease of hydrolysis of trichlorides
Golden, K - Violet, Rb - Red, Cs - NCl3 > PCl3 > AsCl3 > SbCl3 > BiCl3
Blue, Ca - Brick red, Sr - Blood red, Lewis acid strength of trihalides of P, As and Sb
Ba-Apple green PCl3 > AsCl3 > SbCl3
Rb and Cs show photoelectric effect. Lewis acid strength among phosphorus trihalides
Stability of hydrides : LiH > NaH > KH > RbH > CsH PF3 > PCl3 > PBr3 > PI3
Basic nature of hydroxides : LiOH < NaOH < KOH < RbOH < Nitrogen displays a great tendency to form pp – pp multiple
CsOH bonds with itself as well as with carbon and oxygen.
Hydration energy : Li > Na > K > Rb > Cs The basic strength of the hydrides
Reducing character : Li > Cs > Rb > K > Na NH3 > PH3 > AsH3 > SbH3

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14
The thermal stability of the hydrides decreases as the atomic Coordination number is the number of
size increases. the nearest atoms or groups in the
Melting and boiling point of hydrides coordination sphere.
H2O > H2Te > H2Se > H2S COORDINATION Ligand is a Lewis base donor of
Volatility of hydrides electrons that bonds to a central metal
COMPOUNDS
H2O < H2Te < H2Se < H2S atom in a coordination compound.
OXYGEN Reducing nature of hydrides Paramagnetic substance is one that is
FAMILY H2S < H2Se < H2Te attracted to the magnetic field, this results
Covalent character of hydrides on account of unpaired electrons present
H2O < H2S < H2Se < H2Te in the atom/molecule/ion.
The acidic character of oxides Effective atomic number EAN
(elements in the same oxidation state) = (Z – Oxidation number) + (2 × Coordination number)
SO2 > SeO2 > TeO2 > PoO2 ; SO3 > SeO3 > TeO3 Factors affecting stability of complex
Acidic character of oxide of a particular element (e.g. S) (i) Greater the charge on the central metal ion, greater is the
SO < SO2 < SO3 ; SO2 > TeO2 > SeO2 > PoO2 stability.
Bond energy of halogens : Cl2 > (ii) Greater the ability of the ligand to donate electron pair
Br2 > F2 > I2 (basic strength) greater is the stability.
(iii) Formation of chelate rings increases the stability.
Solubility of halogen in water : F2 Isomerism in coordination compounds :
HALOGEN > Cl2 > Br2 > I2
FAMILY Oxidising power : F2 > Cl2 > Br2 > (i) Structural Isomers (ii) Ionization Isomers
I2 (iii) Hydration Isomers (iv) Linkage Isomers
Enthalpy of hydration of X– ion : (v) Coordination Isomerism (vi) Ligand isomerism
F– > Cl– > Br– > I– (vii) Polymerisation Isomerism (viii) Valence Isomerism
Reactivity of halogens : F > Cl > Br > I (ix) Coordination position isomerism
Ionic character of M - X bond in halides (x) Stereo isomerism
M – F > M – Cl > M – Br > M – I (a) Geometrical
Reducing character of X– ion : I– > Br– > Cl– > F– (I) Square planar complexes of the type
Acidic strength of halogen acids : HI > HBr > HCl > HF
Conjugate base strength of halogen acids MA2X2 ; MABX2 ; MABXY
I– < Br– < Cl– < F– (II) Octahedral of the type : MA4XY, MA4X2 MA3X3
Reducing property of hydrogen halides MA2X2Y2. M(AA)2X2 and M(ABCDEF).
HF < HCl < HBr < HI (b) Optical isomerism
Oxidising power of oxides of chlorine
Cl2O > ClO2 > Cl2O6 > Cl2O7 The order of decreasing
Acidic character of oxyacids of chlorine electronegativity of hybrid orbitals is sp
HClO < HClO2 < HClO3 < HClO4 > sp2 > sp3.
Oxidising power of oxyacids of chlorine Conformational isomers are those
HClO > HClO2 > HClO3 > HClO4 isomers which arise due to rotation
The element with exceptional GOC around a single bond.
configuration are A meso compound is optically
Cr24[Ar] 3d54s1, Cu29[Ar] 3d104s1 inactive, even though it has asymmetric
Mo 42 [Kr] 4d 5 5s 1 , Pd 46 [Kr] centres (due to internal compensation of
4d10 5s0 rotation of plane polarised light)
TRANSITION Ag 47 [Kr] 4d 10 5s 1 , Pt 78 [Xe] An equimolar mixture of enantiomers
ELEMENTS 4f145d106s0 is called racemic mixture, which is optically inactive.
(d- and f-BLOCK Ferromagnetic substances are Reaction intermediates and reagents :
ELEMENTS those in which there are large Homolytic fission ® Free radicals
number of electrons with unpaired Heterolytic fission ® ions (Carbonium, ion carbonium, etc.)
spins and whose magnetic Nucleophiles – electron rich
moments are aligned in the same Two types : 1. Anions 2. Neutral molecules
direction. with lone pair of electrons (Lewis bases)
Inner Transition Elements Electrophiles : electron deficient.
Two types : 1. Cations 2. Neutral molecules with vacant
(i) Electronic Configuration - The general electronic orbitals (Lewis acids).
configuration of these elements is Inductive effect is due to s electron displacement along a
0 -1
[ Xe ] 4f 0 -14 5d 6s 2 chain and is permanent effect.
+I (inductive effect) increases basicity, – I effect increases
(iii) Magnetic properties - Magnetic properties have spin and acidity of compounds.
orbit contributions (Contrast “spin only”of transition Resonance is a phenomenon in which two or more structures
metals). Hence magnetic momentums are given by the can be written for the same compound but none of them
formula. actually exists.
m = 4 S (S + 1) + L(L + 1)
where L = Orbital quantum number, S = Spin quantum number
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15

ORGANIC CHEMISTRY
Pyrolytic cracking is a process in The order of reactivity is
which alkane decomposes to a mixture (a) RI > RBr > RCl > RF
of smaller hydrocarbons, when it is HALOGEN (b) Allyl halide > Alkyl halide > Vinyl
ALKANES heated strongly, in the absence of halide
oxygen. COMPOUNDS
(c) Alkyl halide > Aryl halide
Ethane can exist in an infinite number SN1 reaction : Mainly 3° alkyl halides
of conformations. They are undergo this reaction and form racemic
HH H H H mixture. SN1 is favoured by polar solvent
H H and low concentration of nucleophile.
SN2 reaction : Mainly 1° alkyl halides undergo this
H
H substitution. Walden inversion takes place. SN2 reaction is
HH H H
H
H
H H H preferred by non-polar solvents and high concentration of
Eclipsed q = 60° Staggered q < 60° > 0 Skew nucleophile.
Conformations of Cyclohexane : It exists in two nonplanar, Reaction with metals:
strainless forms, the boat and the chair form (i) Dry ether
R – X + Mg ¾¾¾¾ ® R – Mg – X
Alkyl Grignard reagent
halides
(ii) Wurtz reaction:
Dry ether
Chair form Half Chair
R – X + 2 Na + X – R ¾¾ ¾ ¾® R - R + 2Na + X –
Alkane
Most Stable
Alkenes are converted to alcohol in
different ways as follows
Reagent Types of addition
ALCOHOLS dil H2SO4
Twist Boat Boat form – Markovnikov
(Least Stable) B2H6 and H2O2, OH– –
In dehydration and Anti-Markovnikov
dehydrohalogenation the preferential Oxymercuration demercuration –
order for removal of hydrogen is 3° > 2° > Markovnikov
1° (Saytzeff’s rule).
ALKENES Oxidation of
The lower the DHh (heat of
hydrogenation) the more stable the 1° alcohol ¾¾® aldehyde ¾¾ ® carboxylic acid
alkene is. (with same no. (with same no. of
Alkenes undergo anti-Markonikov of C atom) C atom)
addition only with HBr in the presence 2° alcohol ¾¾® ketone ¾¾ ® carboxylic acid
of peroxides. (with same no. (with less no. of
Alkynes add water molecule in
of C atom) C atom)
presence of mercuric sulphate and dil.
H2SO4 and form carbonyl compounds. 3° alcohol ¾¾® ketone ¾¾ ® carboxylic acid
Terminal alkynes have acidic H-atoms, (with less no. (with less no. of
ALKYNES of C atom) C atom)
so they form metal alkynides with Na,
ammonical cuprous chloride solution and CHCl /OH Q
3
Phenol ¾¾¾¾¾¾
® Phenolic
ammoniacal silver nitrate solution.
Alkynes are acidic because of H-atoms aldehyde
which are attached to sp ‘C’ atom which (a) has more PHENOLS
electronegativity (b) has more ‘s’ character than sp2 and (Reimer-Tieman reaction)
sp3 ‘C’ atoms. CO
2 ® Phenolic carboxylic
Phenol ¾¾¾
All o and p-directing groups are ring D
activating groups acid (Kolbe reaction)
(except – X) Acidity of phenols
They are : – OH, – NH2, – X, – R, – (a) Increase by electron withdrawing substituents like
ARENES OR, etc. +
– NO2, – CN, – CHO, – COOH, –X, - N R 3
All m-directing groups are ring
deactivating groups. (b) decrease by electron releasing substituents like
They are : – CHO, – COOH, – NO2, – – R, – OH, – NH2, – NR2, – OR
+
CN, – NR 3 , etc.
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16
Al O Carbohydrates are polyhydroxy
2ROH ¾¾¾¾
2 3® R - O - R + H O
2 aldehydes or ketones.
250ºC
RONa + X - R ' ¾¾
® ROR '+ NaX Monosaccharides are simple sugars,
CARBOHYDRATES,
containing three to nine carbon atoms.
ETHERS (Williamson's synthesis) AMINO ACIDS AND Characteristic reactions :
dil. H SO POLYMERS Homologous series
ROR + H 2 O ¾¾¾¾¾
2 4 ® 2ROH
Type of reactions
D
(a) Alkanes
Substitution
(Mostly free radical
Formation of alcohols using RMgX (b) Alkenes and alkynes Electrophillic addition
(a) Formaldehyde + RMgX (c) Arenes Electrophillic substitution
CARBONYL (d) Alkyl halides Nucleophillic substitution
Hydrolysis
¾¾¾¾¾ ® 1° alcohol (e) Aldehyde and ketones Nucleophillic addition
COMPOUNDS Tests to differentiate :
Hydrolysis 1°, 2° and 3° alcohols (1) Lucas test
(b) Aldehyde + RMgX ¾¾¾¾¾ ®
2° alcohol (2) Victormeyer’s test
1°, 2° and 3° amines Hinsberg test
(other than HCHO) 1°, 2° and 3° nitro compounds Test with HNO2 and KOH
Hydrolysis Aryl halides and alkyl halides Test with AgNO3
(c) Ketone + RMgX ¾¾¾¾¾ ® solution
3° alcohol Aldehydes and ketones Tollen’s test/Fehling’s
Cannizzaro reaction (Disproportionation) test
Aromatic aldehydes and Fehling’s test
Hot conc. Aliphatic aldehydes
Aldehyde ¾¾¾¾® Alcohol + Salt of acid
alkali Dil H2SO4 [or Conc. H2SO4 + H2O]
(no a H-atom) Use ® Hydrating agent (+HOH)
Aldol condensation : Alc. KOH or NaNH2(Use ® -HX)
alc.KOH
Carbonyl compound + dil. alkali ––® b-hydroxy carbonyl IMPORTANT CH3CH2Cl ¾¾¾¾ ® CH2=CH2
(with a H-atom) compound REAGENT Lucas reagent ZnCl2 + Conc. HCl
Benzoin condensation Use ® for distinction between 1º, 2º
& 3º alc.
ethanolic Tilden Reagent NOCl (Nitrosyl
Benzaldehyde ¾¾¾¾ ® Benzoin
NaCN chloride)
The relative reactivities of different acid derivatives towards C2H5NH2 ¾¾¾ NOCl
® C2H5Cl
nucleophilic acyl substitution reactions follow the order: Alkaline KMnO4(Strong oxidant)
O O O O O Toluene ® Benzoic acid
|| || || || || Bayer’s Regent : 1% alkaline KMnO4(Weak oxidant)
R – C – Cl > R – C – O – C – R ' > R – C – OR ' > R – C – NH 2 Use: ® For test of > C = C < or –C = C –
Acid chloride Anhydride Ester Amide BR
CH2=CH2+H2O+[O] ¾¾® CH2OH–CH2OH
Acidic K2Cr2O7 (Strong oxidant) : RCH2OH ¾¾® [O] RCHO
The rate of esterfication decreases
when alcohol, acid or both have SnCl2/HCl or Sn/HCl use ® for red of nitrobenzene in acidic
n
branched substituents. medium.
SnCl / HCl
CARBOXYLIC Or tho effect : All ortho C6H5NO2 ¾¾¾¾¾
2 ® C6H5NH2
substituted benzoic acids (irrespective 6H
ACIDS of type of substituent) are stronger than Lindlar’s Catalyst = Pd/CaCO3
benzoic acid. + in small quantity (CH3COO)2Pb
"
Order of basicity : (R = – CH3 or 2 – butye + H2 ¾¾ ® Cis-2-butene
– C2H5) (main product)
2° > 1° > 3° > NH3 Ziegler –Natta Catalyst (C2H5)3Al + TiCl4
Use ®In Addition polymerisation
NITROGEN Hofmann degradation IDENTIFICATION TESTS :
Br2 /KOH (a) Unsaturated compound (Bayer’s reagent)
COMPOUNDS Amides ¾¾¾¾® 1° amine Decolourising the reagent
The basicity of amines is (b) Alcohols (Ceric ammonium nitrate solution)
(a) decreased by electron withdrawing Red colouration
groups (c) Phenols (Neutral FeCl3 solution)
Violet/deep blue colouration
(b) increased by electron releasing groups (d) Aldehydes and ketones (2, 4-D.N.P.)
Reduction of nitrobenzene in different media gives different Orange precipitate
products (e) Acids (NaHCO3 solution)
Medium Product Brisk effervescence (CO2 is evolved)
Acidic Aniline (f) 1° amine (CHCl3 + KOH)
Basic Azoxy, Azo and finally hydrazobenzene Foul smell (isocyanide)
(g) 2° amine (NaNO2 + HCl)
Neutral Phenyl hydroxylamine Yellow oily liquid (Nitrosoamine)
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