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@iitandneetwale On Telegram: Iit - Chemistry
IIT – CHEMISTRY
1
3. 1 amu (atomic mass unit) = = 1 Avogram
NAvg
1
= gm = 1.66 u 10-24 gm = 1 Dalton
6.023 u 1023
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Millimoles = Molarity u Volume (mL)
Weight(gm)
6. No. of equivalent =
gm.equivalent weight
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10. Molar volume = volume of 1 mole of gas at NTP/STP = 22.4 L or 22400
mL
11. Dulong and Petit’s law :
6.4
Atomic mass (approx.) = (for metals only) (cal/g)
specific heat
The law is applicable only to solid elements except Be, B, C and Si.
Approx. Atomic mass
Valency =
Eqv. mass
The exact valency is a whole number nearest to the approximate valency
calculated. The exact valency is multiplied by the Eqv. mass to get
Atomic mass.
Exact atomic mass = Exact valency u Eq. mass.
12. Relation between molecular and empirical formulae :
Molecular formula = n u Empirical formula
Molecular formula weight
?n =
Empirical formula weight
Moles of solute
13. Molarity =
volume of solution (L)
mole of solute
14. Molality =
mass of solvent(kg)
nA
15. Mole fraction = mole fraction of A in mixture of A and B = XA =
nA + nB
nB
mole fraction of B in mixture of A and B = XB =
n A + nB
number of gm equivalent of solute
16. Normality =
volume of solution(L)
Cp
17. Atomicity (J ) = (1.66 for mono-atomic, 1.4 for di-atomic, 1.33 for tri-
Cv
atomic gas)
mol. mass
At mass of gaseous element =
Atomicity
(Atomicity = number of atoms present in a molecule of the element).
Cp – Cv = R = 1.98 cal mol-1 K-1
Molar heat = specific heat u mol. mass
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STATES OF MATTER
Boyle’s law
PV = constant [at constant n, T] ? P1V1 = P2V2
Charle’s
V V1 V2
= constant [at constant n, P] ? = ;
T T1 T2
§ t ·
Vt = V0 ¨1+ [T (kelvin) = 273 + t (0C)]
© 273 ¸¹
Gay-Lussac’s law
P P P
= constant [at constant n, V] ? 1 = 2
T T1 T2
Ideal gas equation
PV
= R = 0.0821 l. atm.K-1 mol-1
nT
= 1.987 Cal K-1 mol-1 = 8.314 J K-1 mol-1
1 atm = 760 mm of Hg = 76 cm of Hg = 101325 pascal ; 1 bar = 0.9862
Atm
Standard Temperature and pressure (STP) or Normal Temperature and
Pressure (NTP)
P = 1 atm, T = 00 C or 273 K
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Graham’s law (Diffusion and Effusion)
( rA )Rate of effusion of gas A UB MB
= = [at constant pressure]
( rB )Rate of effusion of gas B UA MA
rA PA MB PA UB
= = [at different pressure]
rB PB MA PB UA
Velocity of Molecules
3RT 3P
Root mean square velocity (CRMS) = =
M d
8RT
Average velocity (CAVG) =
SM
2RT
Most probability velocity (CMP) =
M
CMP C Avg CRMS
CMP : C Avg : CRMS : :1 :1.128 :1.224
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§ a ·
i) At low pressure : ¨ p + 2 ¸ V = RT
© v ¹
ii) At high pressure : P (V - b) = RT
Units of a are atm L2 mol-2 and b are L mol-1
Greater is the value of a means gas can be easily liquefied
ª 4 3º
Co-volume or excluded volume = 4N0Vm « Vm = 3 Sr »
¬ ¼
SC Avg V2 (N / V)2
i) Collision frequency, Z =
2
V
ii) Mean free path (O ) = , where V =molecular diameter
2SV2N
N/V = number of molecules per unit volume
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i) Avogadro’s Law
V v n or V v N (at constant T, P)
ii) Calculation of Kinetic Energy
1
According to gas equation, PV = Mu2 for 1 mole of gas
3
2 1
or PV = u Mu2
3 2
1 3 3
or Mu2 = PV = RT = K.E.
2 2 2
For 1 molecule, the K.E.
3 RT 3 R ½
= = KT ® = K (Boltzmann constant)¾
2 N0 2 ¯ N0 ¿
iii) Average molecular weight of a gaseous mixture
¦ ni Mi
Mmix = where ni is the number of moles and Mi is the
¦ ni
molecular weight of the component.
a
iv) Critical Pressure (PC) : PC =
27b 2
8a
v) Critical Temperature (TC) : TC =
27Rb
vi) Critical Volume (VC) : VC = 3b
PC TC 3
vii) Relationship between PC, VC and TC : =
RTC 8
a
viii) Boyle’s Temperature : TB =
bR
ATOMIC STRUCTURE
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Moseley’s Equation, Q = a (z - b)
Heisenberg’s uncertainty equation,
h h
'p. 'x t and 'E. 't t
4S 4S
1 Zke 2
Kinetic energy of electron in nth quantum state =
2 rn
Zke2
Potential energy of electron in nth quantum state = -
rn
Zke2 (13.6)Z 2
Total energy (E) = - =- eV per atom
2rn n2
313.6 1312
=- 2
kcal/mol = - kJ/mol
n n2
Z2
= -21.8 u10-19 J/atom.
n2
n2 h2 n2 a 0 0
Radius of nth quantum state = = (a0 = 0.529 A )
4S 2 mkZe 2 Z
Velocity of electron,
2SZke2 Z
vn = = u 2.188 u 106 m/s
nh n
v Zv n
No. of revolution per second in r.p.s = n =
2Srn 2Sn2a 0
Wave number of spectral line,
1 § 1 1 ·
v= = R H Z2 ¨ 2 - 2 ¸ (RH = 109743 cm-1
O ¨n n ¸
© 1 2 ¹
§ 2S2 me 4 k 2 ·
= ¨¨ R H = 109743cm-1 = ¸¸
© h3c ¹
de Broglie equation
h h
O= =
p mv
Azimuthal (or angular) Quantum number (l); 0 d l d n -1
h
Orbital angular momentum, L = l (l +1)
2S
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Magnetic quantum number (m); -l d m d l , total (2l + 1) values.
eh
Magnetic moment, PL = l (l +1)
4Smc
eh
Spin angular momentum P s = s(s +1)
2Smc
Aufbau Principle : subshell with lowest (n + l), value us filled first, if two
subshells have same (n + l ) value, lower value of ‘n’ is filled up first.
Photoelectric effect
Maximum kinetic energy of ejected electron
1 2 ª1 1 º
mv max = hQ - hQ 0 = hc « - »
2 ¬ O O0 ¼
Stopping potential, eV0 = h (Q - Q 0 )
Binding energy = Mass defect u 931 MeV
i) Radius of Nucleus (rn) = r0 u A1/3
where A is the mass number and r0 is proportionality constant
whose value is 1.4 u 10-13cm.
ii) The radius of the nucleus is approximately 10-5 times the radius of
the atoms. Volume of the nucleus of an atom is about 10-5 times
the volume of the atom.
iii) Energy of an electron in nth shell of hydrogen atom En v 1/ n2
iv) Although the energy of electron increases with increase in the
value of n(orbit), yet the difference of energy between successive
orbits decreases.
Thus, E2 – E1 > E3 – E2 > E4 – E3 > E5 – E4, etc.
v) No. of spectral lines when electron comes from nth level to ground
n(n -1)
level =
2
vi) Number of sub-shells in a main energy level = n
vii) Number of orbitals in a main energy level = n2
viii) Number of orbitals in a sub-shell = (2l + 1)
ix) Number of electrons in each orbital = 2
x) Maximum number of electrons in a subshell = 2(2l + 1)
xi) Maximum number of electrons in main shell = 2n2
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SOLUTIONS
Solubility
'Hsolution = 'Hlattice - 'Hhydration
If hydration energy > lattice energy, the solute goes into solution and
'Hsolution comes out to be negative value i.e., the process is exothermic.
Henry’s law
Mass of the gas dissolved per unit volume (n) v pressure (P)
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n1 m2
= [' S1 = S2 ]
V1 V2
Raoult’s law (Vapour-Pressure lowering of solution)
ps = p0 . Xsolvent
p0 - p s n
=
ps N
p0 = pressure of pure solvent; ps = pressure of solvent
D during dissociation.
i -1
D= , n = no. of ions after dissociation
n -1
D during association.
1- i
D=
1- (1/ n)
Variation of vapour pressure with temperature
P2 'H ª 1 1 º
log10 = « - »
P1 2.303 R ¬ T1 T2 ¼
Variation of vapour pressure with external pressure
§P · V0
log10 ¨ 2 ¸ = (P2 - P1 )
© P1 ¹ 2.303 RT
Osmotic Pressure
n
S = i 1 RT = hdg (due to association or dissociation)
V
Van Hoff Factor
P ('p)observed (' Tb )observed (' Tf )observed
i = observed = = =
Pnormal ('p)normal ('Tb )normal ('Tf )normal
Normal molecular mass
=
Observed molecular mass
For solution showing dissociation, the Van’t Hoff factor i ! 1
For solution showing association, the Van’t Hoff factor i 1
For solution showing no dissociation or association, the Van’t Hoff factor
i=1
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Raoult’s Law
P = PA + PB = PA0 X A + PB0 X B = (1- X B )PA0 + PB0 X B
Ideal Solutions
They obey Raoult’s law for all range of concentration and temperature.
' Hmix = 0 and ' Vmix = 0
e.g., Hexane + Heptane. Ethyl bromide + Ethyl chloride, Chlorobenzene +
Bromobenzene, etc.
Non-Ideal Solutions
The non-ideal solution do not obey Raoult’s law for all concentrations.
' Hmix z 0 and ' Vmix z 0
If Vmix ! 0 and ' Hmix z 0, then non-ideal solutions show positive
deviations.
If Vmix 0 and ' Hmix 0, then non-ideal solutions show negative
deviations.
e.g. Acetone + ethyl alcohol, water + ethyl alcohol. CCl4 + CHCl3 ethanol
+ CHCl3.
Acetone + carbon disulphide, Acetone + Benzene, etc.
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Depression in freezing point
k F u WB u 1000
' Hr = T0 - Tp = k f u m =
MB u WA
Molal depression constant (Kf)
RTf2
Kf = [Lf = latent heat of fusion]
1000L f
It is interesting to note that all the above relations hold good. Only when
Kf and Kb are expressed in Kelvin m-1.
Mechanical work
W = - Pext ('V) [during expansion]
First law of Thermodynamics
'V = 0
W = P 'V = 0
'E = q + W
' E = q – P 'V
Cyclic change (reversible)
'E = 0
q = - W = P 'V
q = - Wmax = P dV³
Isothermal reversible expansion
'H = 'E = 0 ('internal energy is function of temperature)
V P
q = - Wmax = 2.303 nRT log 2 = 2.303 nRT log 1
V1 P2
Joule – Thomson coefficient
§wT· § wH·
P JT = ¨ ¸ =¨ ¸ / Cp
© w P ¹H © w P ¹ T
(i) For cooling, u ! 0 (-ve sign)
(ii) For heating, u 0 (+ve sign)
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Second Law of Thermodynamics
q 2 - q1 T2 - T1 T
Efficiency of the Carnot engine = K = = = 1- 1
q2 T2 T2
q2 = heat absorbed by engine
q1 = heat lost to sink
Entropy Change
Kirchoff’s equation
'H2 - 'H1 'E2 - 'E1
= 'Cp and = 'C v
T2 - T1 T2 - T1
Where, 'Cp = ¦ Cp (products) - ¦ Cp (reactants) and
'C v = ¦ C v (products) - ¦ C v (reactants)
pH of a solution
pH = - log [H3O+]
pOH = - log [OH-]
pH + pOH = pKW = 14
For neutral solution ; pH = pOH = 7 at 298 K
For acidic solution; pH 7. But pOH ! 7 at 298 K
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For basic solution; pH ! 7, But pOH 7 at 298 K
Isothermal (reversible)
V2
' S = 2.303 nR log
V1
T2
At constant pressure, ' S = 2.303 Cp log10
T1
'Hvap
For vaporization, 'S =
Tbp
'G0 = -nFE0cell
Sign Convention
If work is done on the system, W is positive.
If work is done by the system, W is negative.
If heat is absorbed by the system, q or 'H is positive.
If heat is given out by the system, q or 'H is negative.
If energy is absorbed by the system, i.e. internal energy increases. 'E is
positive.
If energy is released i.e., internal energy of the system decreases. 'E is
negative.
Heat capacity
ª wE º
(i) Heat capacity at constant volume, C v = « »
¬ wT ¼ v
ª wH º
(ii) Heat capacity at constant pressure, Cp = « »
¬ wT ¼ p
For an ideal gas, Cp - Cv = R
Heat of Reaction
'H = ¦ H(p) - ¦ H(R)
For exothermic reactions : ¦ Hp ¦ HR ? ' H is - ve
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' H = 'U + P'V
'H = 'U + 'n(g) RT
p2 'H v § T1 - T2 ·
2.303 log = ¨ ¸ where, 'Hv = molar heat of vapourisation.
p1 R © T1T2 ¹
i) Calorific value is the amount of heat evolved when one gram of fuel as food is
burnt in the presence of air or excess of oxygen.
v H or W = JH
ii) Joule’s relationship between work done (w) and heat produced (H) Wv
Where, J is called mechanical equivalent of heat. Its value is J = 4.184 u 107
erg Cal-1 4.184 J Cal-1.
S1 'H § 1 1 ·
Log = ¨ - ¸
S2 2.303R © T1 T2 ¹
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CHEMICAL AND IONIC EQUILIBRIUM
§ dx · § dx ·
Equilibrium in water = ¨ ¸ =¨ ¸
© dt ¹forward © dt ¹ backward
aA + bB U cC + dD
§ dx · a b
¨ ¸ v K forward A B
© dt ¹forward
§ dx · c d
¨ ¸ v K backward C D
© dt ¹ backward
c d
C D K forward
Equilibrium constant, K = a b
= = Kc
A B K backward
In terms of partial pressure
pcC pdD
Equilibrium constant, K p =
paA pbB
'n g
K p = Kc RT ª ' n g = n p - nr º
¬ ¼
Van’t Hoff equation
k2 'Ho ª 1 1 º
log10 = « - »
k1 2.303R ¬ T1 T2 ¼
Gibb’s Free energy
'G = 'H - T'S
'Go = -2.303RT log10 K
Buffer:
conjugate base
pH = pK a + log
acid
conjugate acid
pOH = pK b + log
base
Mixture of weak acids = k1c1 + k 2c 2
conjugation
D=
100
A x B y U x A y+ +y Bx -
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x y
? K sp = ª¬ A y+ º¼ ª¬Bx - º¼ , when A x By
K sp = Solubility product.
K
Ostwald’s dilution law, D = ,
C
K = dissociation constant of weak electrolyte
C = Concentration
D = degree of dissociation
K w = ª¬H+ º¼ ª¬OH- º¼ [ionic product of water]
Hydrolysis constant
h2C
kh =
1- h
Amount of salt hydrolysed
h=
Total salt taken
Kh Kw
h= =
C Kb u C
Kw
Strong acid + weak base, Degree of hydrolysis (h) =
CK b
1
pH = ªpK w - K b - logC º¼
2¬
Kw
Strong base + weak base, Degree of hydrolysis (h) =
CK a
1
pH = ªpK w + pK a + logC ¼º
2¬
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Kw
Weak acid + weak base, Degree of hydrolysis (h) =
Ka u Kb
1
pH = ªpK a + pK w - pK b ¼º
2¬
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1
Specific conductance = k = , U = specific resistance
U
l l 1
k= uC = cell constant, C = conductance =
a a R
Conductivity = cell constant u observed conductance
k k u 1000cm3L-1
S eq = =
Ceq Normality
Equivalent conductance, /
/ =kuV
V = volume in mL containing 1g equivalent of the electrolyte.
Molar conductance P = [Equivalent conductance]
P = n/
Molecular mass
n=
Equivalent mass
P =kuV V(mL) containing 1g mole of an electrolyte
At infinite dilution, / 0 = O a + O c
O c = kuc
O a = kua
O a , O c ionic conductance of anion and cation
k = 96500 C
ua = mobility of anions and uc = mobility of cations
/
degree of dissociation, D =
/f
Relation between equivalent and molar conductance at infinite dilution
1 1
/ f = + O f+ + - O f-
z z
Units of molar conductance are O -1cm2mol-1
Units of equivalent conductance are O -1cm2 (g. eq.)-1
For weak electrolytes,
K OC OC
D= = ef = m OC C
e , O m = equivalent and molar conductance
C Oe O Pf
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Ostwald’s equation
2
C OC
m
K=
f f
Om Om - OC
m
Cell notation
Transport number
Current carrired by ion
Transport number =
Total current carried
Transport number of cation + Transport number of anion =1
n c + na = 1
aA + bB + cC + dD
dx
Rate of reaction =
dt
1d A 1d B 1d C 1d B
=- =- = =
a dt b dt c dt d dt
d A n
- D A 1 . n1 order of reaction with to A
dt
d B n
- D B 2 n2 order of reaction with to B …..etc
dt
dx n n
= k A 1 B 2 n 1 + n 2 - overall order of reaction.
dt
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Rate Laws
Zero-Order reaction
dx 0
= k0 A ? x = k 0 ,t
dt
First-Order reaction
dx 1 2.303 § a ·
= k1 A k1 = log10 ¨ ¸ A = A 0
e-kt
dt t ©a-x¹
nth Order reaction
dx n 1 ª 1 1 º
= kn A kn = « n-1
- n-1
»; nt2
dt n -1 t « a - x a »¼
¬
Half Life Period
0.693
T1 2 = , for n = 1
k1
2n-1 -1
T1 2 = ; for n t 2
n -1 k na n-1
t1 2 v a n-1 ; t3 4 = 2 u t1 2 ; t87.5% = 3 u t1 2
Arrhenius equation
k = Ae-Ea RT
Ea
log k = logA -
2.303RT
k2 Ea ª T2 - T1 º
log10 = « » k1 & k2 at T1 and T2 temperature
k1 2.303R ¬ T2 T1 ¼
d ln k E
= a2
dT RT
Rates of chemical reactions and chemical kinetics
Units of rate and rate constant
(i) Rate of reaction: mol L-1 S-1
(ii) Rate constant (K)
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Quantum yield or quantum efficiency of a photochemical reaction
SURFACE CHEMISTY
Colloidal state
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To coagulate negative sol of As2S3, the coagulating power of
different cations has been found the decrease in the order
as:
Al3+ ! Mg 2+ ! Na +
Similarly, to coagulate a positive sol such as Fe(OH)3, the
coagulating power of different anions has been found to decrease
in the order:
4-
ªFe CN º ! PO3- 2-
4 ! SO4 ! Cl
-
¬ 6¼
Thus, larger the charge on the coagulation ion, larger the
coagulation.
Gold Number
The no. of milligrams of the protective collide required to just present the
coagulation of 10 mL of red gold sol when 1 mL of 10% solution of
sodium chloride is added to it.
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the valence electron is that the valence electron experiences less
attraction from the nucleus. This is called Shielding or Screening Effect.
Lanthanides
General Electronic Configuration : 4F 2-14 5d0.1 6s2
Actinides
General Electronic Configuration : 5f 2-14 5d 0,1 7s2
Table gives an idea regarding the effect if bonding and loan pairs on
geometry and bond angles of molecules.
Number
of Distorted
Number Of
orbitals Theoretical VSEPR Bond geometry
Example
on geometry Notation angle due to
central Bond Lone repulsion
atom pairs pairs
BeF2 2 Linear 2 0 AX2 180o Linear
Plane
BF3 3 Triangular 3 0 AX3 120o
triangle
Plane
SO2 3 2 1 AX2E 119o Angular
triangle
109o
CH4 4 Tetrahedral 4 0 AX4 Tetrahedral
28’
107o Trigonal
NH3 4 Tetrahedral 3 1 AX3E
48’ pyramidal
102o
NF3 4 Tetrahedral 3 1 AX3E Pyramidal
35’
104o
H 2O 4 Tetrahedral 2 2 AX2E2 Angular
27’
F 2O 4 Tetrahedral 2 2 AX2E2 102o Angular
Tetrahedral Angular
H 2S 4 2 2 AX2E2 90o
Trigonal
120o Bipyramidal
Triogonal
PCl5 5 5 0 AX5 and Irregular
pyramidal
90o tetrahedral
Triogonal 101o
SF4 5 4 1 AX4E (See-saw)
pyramidal 36’
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Triogonal
CIF3 5 3 2 AX3E2 87o40’ T-shaped
pyramidal
Triogonal
I3- 5 2 3 AX2E3 180o Linear
pyramidal
SF6 6 Octahedral 6 0 AX6 90o Octahedral
Square
BrF5 6 Octahedral 5 1 AX5E 84o30’
pyramidal
Square
XeF4 6 Octahedral 4 2 AX4E2 90o
planar
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CHEMISTRY OF NON – METALS- II
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x CO + H2 is known as water gas.
x Acetyl ides: The Carbides which on hydrolysis give acetylene are called
acetylides.
e.g., MgC2 + H2O o Mg OH 2 + HC { CH
acetylene
x Allylides: The carbides which on hydrolysis give allylene or propyne are
called allylides. e.g., Mg 2C3 + 4H2O o 2Mg OH 2 + CH3C { CH
Allylen or Propynes
CHEMISTRY OF LIGHTER METALS
x The two elements with the highest densities are osmium (22.57 g cm-3)
and Iridium (22.61 g cm-3)
x Alums are double sulphates having general formula
X2SO4.M2(SO4)8.24 H2O
+
where, X = Monovalent cations such as NA+ ,K + ,NH4 ,etc.
M = Trivalent cations such as Al3+ ,Cr3+ ,Fe3+ , etc.
x KMnO4, K2Cr2O7 and CrO3 are coloured due to charge transfer and not
due to d–d transition.
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x Titanium has been called ‘The wonder metal’ because of useful
properties.
x Among transition metals, mercury has the lowest melting point and is
liquid at room temperature and Tungsten has the highest melting point
among all the metals.
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x Colour: The colour of the compounds of the transition metals is related
to the existence of the incomplete s shell and the easy excitation of an
electron from one energy level to another.
x Catalytic Properties: The catalytic behavior of transition elements is
due to their variable oxidation states.
x Ability to form complexes: Transition elements because of their smaller
sizes of the ions and high ionic charges are well suited to attracted
ligands which are usually negative or neutral molecules.
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x The number of coordinate bonds formed by the ligands surrounding the
metal atom is called coordination number (CN) of the metal.
C.N. of metal = 1 u No. of monodentate ligands or
= 2 u No. of bidentate ligands or
= 3 u No. of tridentate ligands
x Charge on the complex = O.N. of metal atom + O.N. of various ligands
NUCLEAR CHEMISTRY
Rate of disintegration
dN
- = O.N O = disintegration constant
dt
n
§1·
Amount left after n half life N = ¨ ¸ N0
© 2¹
2.303 §N ·
= log10 ¨ 0 ¸ and N = N0 e-Ot
O © N ¹
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Isotopic mass -Mass number
Packing function = u 104
Mass number
Energy released by loss of 1 amu mass = 931.5 MeV
1 amu = 1.66 u 10-24 g,1MeV = 106 eV,1eV = 1.6 u 10-19 J, 1J= 10 7 ergs,1cal = 4.184J
§ 12 · § mco2 ·
x Percentage of carbon in organic substance = ¨ ¸ u ¨¨ ¸ u 100
© 44 ¹ © mcompound ¸
¹
§ 2 · § mH2O ·
x Percentage of hydrogen in organic substance = ¨ ¸u¨ ¸ u 100
© 18 ¹ ¨© mcompound ¸¹
mN2
x Percentage of nitrogen in the compound = u 100
mcompound
[Duma’s Method]
Volume of N2 STP
u 28
= u 100
22.4 u mcompound
1.4 u N u vol.of acid used
x Percentage of nitrogen =
Mass of the subs tan ce taken
[Kjeldhal’s Method]
1.4 u Molarity of the acid u vol. u Basicity
=
Mass of the subs tan ce taken
wt.of silver halide ppt. 35.5 u 100
% of X = u
mol.mass of silver halide wt. of org. chloro comp.
[Carius Method]
35.5 mAgCl
x Percentage of Chlorine = u u 100
143.5 mcompound
80 mAgBr
x Percentage of Bromine = u u 100
188 mcompound
127 mAgI
x Percentage of Iodine = u u 100
235 mcompound
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x Percentage of sulphur =
wt. of BaSO4 precipitate 32 u 100
u
Molecular mass of BaSO4 weight of organic compound containing sulphur
32 mBaSO4
x Percentage of Sulphur = u u 100
233 mcompound
62 mMg2P2O7
x Percentage of phosphorus = u u 100
222 mcompound
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A few more expressions to compute molar mass of a compound are as follows.
x From relative lowering of vapour pressure
m2
M2 =
§ 'P ·
m1 M1 ¨¨ - o1 ¸¸
© P1 ¹
x From elevation of boiling point
K m
M2 = b . 2
'Tb m1
x From depression of freezing point
Kf m
M2 = . 2 [m1 = wt. of solvent]
-'Tf m1
x From osmotic pressure
§ m · RT
M2 = ¨ 2 ¸ [where, m2 = wt of solute, M2 = mol. Wt of solute]
© V ¹ S
ORGANIC CHEMISTRY
x Aldol Condensation
Aldehydes having D - hydrogen (s) undergo self- condensation on
warming with dilute or mild base to give E - hydroxyl aldehydes, called
aldols.
OH 4
ZZZZX CH3 C H OH CH2CHO
e.g., CH3CHO + CH3CHO YZZZZ
x Beckmann Rearrangement
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x Benzilic acid rearrangement
Benzil on treatment with a strong base froms benzillic acid (salt), whence
the name benzilic acid rearrangement.
x Mechanism
OHΘ
ZZZZZX
(b) CH3CHO + CH3COCH3 YZZZZZ CH3 – CH OH – CH2 COCH3
Crossed product
x Birch Reduction
When aromatic rings are reduced with sodium, potassium or lithium in
liquid ammonia or amine in the presence of alcohol, addition of hydrogen
takes place at position 1 and 4 to give an unconjugated diene.
e.g.
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x Cannizzaro Reaction
In the presence of a strong base, aldehydes without D – hydrogens, i.e.
nonaldolizable aldehydes undergo self oxidation reduction, i.e.,
disproportions reaction.
'
e.g. 2C6 H5CHO + NaOH o C6H5CH2OH + C6H5COONa
'
2HCHO + NaOH o CH3OH + HCOONa
x Claisen Rearreangement
Claisen rearrangement involves the shift of a group from oxygen to
carbon. Thus, when aryl allyl ethers are heated (200 oC) they rearrange to
o-allylphenols.
e.g.
x Clemmenson Reduction
The reduction of carbonyl group of aldehydes and ketones to methylene
groups with amalgamated zinc and concentrated hydrochloric acid.
Zn-Hg.HCl
e.g. C6H5COCH3 Reflux
o C6H5CH2CH3
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The reaction rate is also accelerated by the presence by the presence of
electron-releasing groups in the dienes.
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x Gabriel Synthesis
The reaction involves the preparation of primary amines free from
secondary or tertiary amines by reacting alkyl halides with alkali
phthalimide and subsequent hydrolysis.
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x Knoevenagel reaction
Condensation of aldehydes and Ketones with compounds having active
methylene group in the presence of basic catalyst to form
D, E – unsaturated compounds.
x Michael Reaction
The base-catalysed addition of compounds having active methylene
group (or relatively acidic hydrogens) to an activated olefinic bond of the
type – C C– Z (Z = electron – withdrawing) is classified as Michael
| |
reaction.
4
H2C COOC2H5 + C2H5ONa U HC COOC2H5 2
+ C2H5OH
x Oppenauer Oxidation
The oxidation of a secondary alcohol with a ketone and a base to the
corresponding ketone of the alcohol.
Al OCMe3 2
e.g., 2CHOH + CH3 ZZZZZZZZZX
CO YZZZZZZZZZ 2CO + CH2CHOHCH3
2
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x Perkin Reaction
In Perkin reaction, condensation has been effected between aromatic
aldehydes and aliphatic acid anhydrides in the presence of sodium or
potassium salt of the acid corresponding to the anhydride, to yield
D, E – unsaturated aromatic acids. The acid reaction should have at least
two D – hydrogens.
e.g.
AcONa
C6 H5CHO + CH3CO 2
O
o o C6H5 – CH CH – COOH + CH3COOH
170 –180 ,5Hr
x Reformasky Reaction
Reaction of an D – halo ester, usually an D – bromoester with an aldehyde
or ketone in the presence of zinc metal to produce a E – hydroxyester.
e.g.,
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x Reimer Tiemann Reaction
Formylation of phenols with chloroform in alkaline solution.
e.g.,
x Schmidt Reaction
Carboxylic acids and hydrazoic acid react in the presence of sulphuric
H SO
acid to give amines RCOOH + N3H 2 4
o RNH2 + CO2 + N2
x Ullmann reaction
The synthesis of diphenyl amines, diphenyl amines, diphenyl ethers and
diphenyls is known as Ullmann reaction.
e.g.,
Cu
C6 H5NHCOCH3 + C6H5BR + K 2CO3 o C6H5 2 NH + CO2 + CH3COOK + KBr
reflux
Cu
C6 H5OH + C6H5BR + KOH o C6 H5
Reflux 2
O + KBr + H2O
C H NO
2C6H5I + Cu 65'
2o C6H5 – C6 H5 + CuI2
x Witting reaction
Synthesis of alkenes by the treatment of aldehydes or ketones with
alkylidenetriphenylphosphorane Ph3P = CR 2 or simply known as
phophorane.
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x Wolff Kishner reduction
Involves the conversion of carbonyl groups of aldehydes and ketons to
methylene groups by heating their hydrozones, semicarbazones or azines
in the presence of strong base such as C2H5ONa or NaOH.
e.g.,
Addition Reactions
(i) Electrophilic addition reaction:
CCL
CH2 = CH2 + Br2 4
o CH2Br – CH2 BR
Mechanism:
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Relative rates of addition
Markovnikov Rule
Peroxide effect
. .
R+ H : Br o RH + B r
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Addition to alkynes
SN 1 mechanism
Rate v ª¬ 3CX º¼
First – order Reaction
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The rate of hydrolysis of alkyl halides by SN 1 path is Allyl, Benzyl
! 3o ! 2o ! 1o ! CH3 X
SN 2 mechanism
Rate v Rx Nu
Second under Reaction
The rate of hydrolysis of alkyl halides by SN 2 path is CH3 X ! 1o ! 2o ! 3o
Elimination reactions
(a) E1 mechanism
Kinetically of the first order.
E1 reaction is facilitated by
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(i) branching at the D – and E – carbons of the substrate for stability of the
olefin,
(ii) strong polar solvent to aid ionization,
(iii) low concentration of base – the greater stability of the alkene over the
carbocation makes the extraction of proton easy.
E2 mechanism
Rate D [substrate] [reagent]
E2 reaction is facilitated by
(i) branching at D – and E – carbons – since more stable olefin is formed,
(ii) strong base of high concentration – since a strong C – H bond has to
break,
(iii) solvent of low polarity – polar solvents form a strong solvent wall around
the base restricting the attack. Hence DMF or DMSO are usually used as
solvents.
E1cB mechanism
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5. Reactivity order alkyl halides are Reactivity order of alkyl halides are
o o o
3 ! 2 ! 1 ! methyl halide. methyl halide ! 1o ! 2o ! 3o .
6. Rearrangement product is Rearrangement product is not
possible. possible.
7. Favoured by mild and low Favoured by strong and high
concentractionof nucleophile. concentration of nucleophile.
8. Favoured by solvents of high Favoured by solvents of low polarity.
polarity.
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Difference between SN1 and E1
Points E1 SN 1
1. Step 2 steps 2steps
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? Total number of optical isomers = (a + m)
Common example is tartaric acid, HOOC . CHoH . CHOH . COOH
iii) When the molecule is symmetrical and has an odd number of chiral
carbon atoms
§n 1·
¨ - ¸
Number of d and A forms (A) = 2(n-1) - 2© 2 2¹
§n 1·
¨ - ¸
Number of meso forms (m) = 2© 2 2 ¹
? Total number of optical isomers = (a + m) = 2(n-1) .
Halogenation
The order of case of substitution is
Tertiary hydrogen ! Secondary hydrogen ! Primary hydrogen
UV light
RH + X2 or
A
o RX + HX
Reactivity of X2 ; F2 ! Cl2 ! Br2 ! I2
HOMOPOLYMERS
Common name of the Monomer Uses
homopolymer
Polyethylene CH2 = CH2 In the manufacture of pipes,
Ethylene toys, bags, wire insulators,
bottles etc.
Polyvinyl Chloride CH2 = CHCl In the manufacture of sheets,
(PVC) Vinyl chloride water pipes, hoses, hand
bags etc.
Polystyrene C6H5CH = CH2 In the manufacture of combs,
Styrene toys and radio and television
cabinets etc.
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Buna rubber CH2 = CH– In the manufacture of tyres
CH=CH2 etc.
1, 3- Butadiene
COPOLYMERS
Common name of the Monomer Uses
copolymer
Dacron or Terylene (i) HOCH2–CH2OH In the manufacture of
Ethylene glycol fabrics and magnetic
(ii) H3COOC(C6H4) recording
COOCH3
Nylon-66 (i) H2N(CH2)6NH2 In the manufacture of
Hexamethylene fabrics, tyre cords,
diamine ropes, carpets etc.
(ii) HOOC(CH2)4COOH
Adipic acid
Bakelite (i) HCHO In the manufacture of
Formaldehyde electrical goods,
(ii) C6H5OH phonograph records,
Phenol fountain pen etc.
Classification of Polymers
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Classification based upon molecular forces :
i) Elastomers : These are the polymers having very weak intermolecular
forces of attraction between the polymer chains. Examples-Vulcanised
rubber.
ii) Fibers : These polymers can be used for making fibers as their molecules
are long and thread like. Example-Nylon-66.
iii) Thermoplastics : These can be easily moulded by heating.
Example-Polyethylene, Polypropylene.
iv) Thermosetting polymers : A thermosetting polymer becomes hard on
heating. Example-Bakelite.
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