No.

of photons emitted by a sample of H atom :

PHYSICAL CHEMISTRY
n ( n  1)
ATOMIC STRUCTURE 2
Heisenberg’s uncertainty principle :
Planck's Quantum Theory : h h h
x.p > or m x.v  or x.v 
hc 4 4 4m
Energy of one photon = h =
 Quantum Numbers :
* Principal quantum number (n) = 1, 2, 3, 4 .... to .
Photoelectric Effect :
nh
1 * Orbital angular momentum of electron in any orbit = .
h = h0 + m 2 2
2 e
* Azimuthal quantum number () = 0, 1, ..... to (n – 1).
Bohr’s Model for Hydrogen like atoms : * Number of orbitals in a subshell = 2 + 1
* Maximum number of electrons in particular subshell = 2 × (2 + 1)
h
1. mvr = n (Quantization of angular momentum) h
2 * Orbital angular momentum L = ( 1) =   (  1)
2
E1 z2 z2  h 
2. En = – z2 = –2.178 × 10–18 J/atom = –13.6 eV
n2 n2 n2   2  
 
 2 2 me 4
E1 =
n2
STOICHIOMETRY

h 2 Mass of one atom of an element

n2 0 . 529  n2  Relative atomic mass (R.A.M) =
3. rn = × 2 2 = Å 1
Z 4 e m Z  mass of one carbon atom
12
2 ze 2 2 .18  10 6  z = Total Number of nucleons
4. v= = m/s  Y-map
nh n
De–Broglie wavelength : Number lt Volume at STP
2.4
×N
h h  A
×2 lt
=  (for photon) N
A 2 2.4
mc p 
Mole
Wavelength of emitted photon :

1 
 1

1   mol. wt. × mol. wt.
=  = RZ2  2  2   At. wt. × At. wt.
 n
 1 n2 


Mass

Page # 1 Page # 2
Density : % Calculation :
density of the subs tance mass of solute in gm
Specific gravity = density of water at 4C (i) % w/w = mass of solution in gm  100

For gases : mass of solute in gm

(ii) % w/v =  100
Volume of solution in ml
Molar mass of the gas
Absolute density (mass/volume) = Molar volume of the gas Volume of solute in ml
(iii) % v/v =  100
Volume of solution
PM
 = Derive the following conversion :
RT
x 2   1000
dgas PMgas RT Mgas M gas 1. Mole fraction of solute into molarity of solution M = x M  M x
1 1 2 2
Vapour density V.D.= d = PM = M =
H2 H2 RT H2 2
MM1  1000
Mgas = 2 V.D. 2. Molarity into mole fraction x2 =   1000  MM
2
Mole-mole analysis :
x 2  1000
Mole-mole
3. Mole fraction into molality m = x1M1
At. wt. / Mol. Wt.
Mass Mole relationship Mole
of equation t.
t. w mM1
wt./A × 22.4 lt 4. Molality into mole fraction x2 = 1000  mM
ol.
1
×m

Mass Volume at STP

m   1000
5. Molality into molarity M = 1000  mM
2
Concentration terms :
M  1000
Molarity (M) : 6. Molarity into Molality m = 1000   MM
2
w  1000 M1 and M2 are molar masses of solvent and solute.  is density of solution
 Molarity (M) = (Mol. wt of solute )  V
inml (gm/mL)
Molality (m) : M = Molarity (mole/lit.), m = Molality (mole/kg), x1 = Mole fraction of
solvent, x2 = Mole fraction of solute
number of moles of solute
Molality =  1000 = 1000 w / M w Average/Mean atomic mass :
mass of solvent in gram 1 1 2

Mole fraction (x) : a1x 1  a 2 x 2  .....  an x n

Ax =
100
n
 Mole fraction of solution (x1) = Mean molar mass or molecular mass :
nN jn

 Mole fraction of solvent (x2) =

N
n1M1  n 2M2  ......nnMn
n M
j1
j j

nN Mavg. = or Mavg. =

n1  n 2  ....nn jn
x1 + x 2 = 1
n
j1
j

Page # 3 Page # 4
Calculation of individual oxidation number : Volume strength of H2O2 :
Formula : Oxidation Number = number of electrons in the valence shell 20V H2O2 means one litre of this sample of H2O2 on decomposition
– number of electrons left after bonding gives 20 lt. of O2 gas at S.T.P.

Concept of Equivalent weight/Mass : Volume,strengthof H2O2

Normality of H2O2 (N) =
5.6
Atomic weight
For elements, equivalent weight (E) = Valency - factor Volume strength of H2 O 2
Molarity of H2O2 (M) =
11.2
M Measurement of Hardness :
For acid/base, E
Basicity / Acidity
mass of CaCO3
Where M = Molar mass Hardness in ppm = 10 6
Total mass of water
M Calculation of available chlorine from a sample of bleaching powder :
For O.A/R.A, E
no. of moles of e – gained / lost 3.55  x  V (mL )
% of Cl2 = W (g) where x = molarity of hypo solution
Atomic or moleculear weight and v = mL. of hypo solution used in titration.
Equivalent weight (E) =
v.f.
(v.f. = valency factor) GASEOUS STATE
Concept of number of equivalents : Temperature Scale :
Wt W W R  R(O)
No. of equivalents of solute = Eq. wt.  E  M/n CO K  273 F  32
 
100  0 373  273 212  32
= R(100)  R(O)
No. of equivalents of solute = No. of moles of solute × v.f. where R = Temp. on unknown scale.

Normality (N) : Boyle’s law and measurement of pressure :

1
Number of equivalents of solute At constant temperature, V 
Normality (N) = Volume of solution (in litres) P
P1V1 = P2V2
Normality = Molarity × v.f. Charles law :
Calculation of valency Factor : V1 V2
At constant pressure, VT or 
n-factor of acid = basicity = no. of H+ ion(s) furnished per molecule of the T1 T2
acid. Gay-lussac’s law :
n-factor of base = acidity = no. of OH– ion(s) furnised by the base per
P1 P2
molecule. At constant volume, PT   temp on absolute scale
T1 T2
At equivalence point : Ideal gas Equation :
N1V1 = N2V2 PV = nRT
n1M1V1 = n2M2V2 w d
PV = RT or P = RT or Pm = dRT
m m
Page # 5 Page # 6
Daltons law of partial pressure : Van der Waal’s equation :
n1 RT n RT n RT 2
P1  , P2  2 , P3  3 and so on.  P  an
 
 (v – nb) = nRT
v v v
Total pressure = P1 + P2 + P3 + ...........

 v2 

Partial pressure = mole fraction X Total pressure.
 Critical constants :
Amagat’s law of partial volume : 8a
a
V = V1 + V2 + V3 + ....... Vc = 3b, PC = 2 , TC = 27 Rb
27b
Average molecular mass of gaseous mixture :
Total mass of mixture n1 M1  n 2 M2  n3 M3 THERMODYNAMICS
Mmix = Total no. of moles in mixture = n1  n 2  n3 Thermodynamic processes :
1. Isothermal process : T = constant
Graham’s Law :
dT = 0
1 T = 0
Rate of diffusion r  ; d = density of gas 2. Isochoric process : V = constant
d
dV = 0
r1 d2 M2 V . D2 V = 0
r2 = = = 3. Isobaric process : P = constant
d1 M1 V . D1
dP = 0
Kinetic Theory of Gases : P = 0
4. Adiabatic process : q=0
1
PV = mN U2 Kinetic equation of gases or heat exchange with the surrounding = 0(zero)
3
IUPAC Sign convention about Heat and Work :
1 2 3 3 Work done on the system = Positive
Average K.E. for one mole = NA  m U  = K NA T = RT
 2  2 2 Work done by the system = Negative
 Root mean suqare speed 1st Law of Thermodynamics
U = (U2 – U1) = q + w
3R T
Urms = molar mass must be in kg/mole. Law of equipartion of energy :
M
f
 Average speed U= nRT (only for ideal gas)
Uav = U1 + U2 + U3 + ............ UN 2

8RT 8KT f
E = nR (T)
Uavg. = = K is Boltzmman constant 2
M m
where f = degrees of freedom for that gas. (Translational + Rotational)
 Most probable speed f=3 for monoatomic
=5 for diatomic or linear polyatmic
2 RT 2 KT =6 for non - linear polyatmic
UMPS = =
M m

Page # 7 Page # 8
Calculation of heat (q) : Application of Ist Law :
Total heat capacity : U = Q + W  W = –P V
q dq  U = Q –PV
CT =  = J/ºC
T dT Constant volume process
Molar heat capacity : Heat given at constant volume = change in internal energy
 du = (dq)v
q dq
C=  = J mole–1 K–1 du = nCvdT
nT ndT
1 du f
R R Cv = . = R
CP =  – 1 CV =  – 1 n dT 2
Specific heat capacity (s) : Constant pressure process :
H  Enthalpy (state function and extensive property)
q dq
S=  = J gm–1 K–1 H = U + PV
m T mdT
 Cp – Cv = R (only for ideal gas)
WORK DONE (w) :
Second Law Of Thermodynamics :
Isothermal Reversible expansion/compression of an ideal gas :
W = – nRT ln (Vf/Vi) S universe = S system + S surrounding > 0 for a spontaneous process.

Reversible and irreversible isochoric processes. Entropy (S) :

Since dV = 0 B
dqrev
So dW = – Pext . dV = 0.
Ssystem =  T
Reversible isobaric process : A
W = P (Vf – Vi)
Entropy calculation for an ideal gas undergoing a process :
Adiabatic reversible expansion : irr
State A  State B
 T2 V2  1 = T1V1 1 Sirr

Reversible Work : P1, V1, T1 P2, V2, T2

P2 V2  P1V1 nR (T2  T1 ) T2 V2
W= = Ssystem = ncv ln T + nR ln V (only for an ideal gas)
 1  1 1 1
Irreversible Work : Third Law Of Thermodynamics :
P2 V2  P1V1 nR (T2  T1 ) The entropy of perfect crystals of all pure elements & compounds is zero
W= = = nCv (T2 – T1) = – Pext (V2 – V1)
 1  1 at the absolute zero of temperature.
P1V1 P2 V2 Gibb’s free energy G) : (State function and an extensive property)
and use  Gsystem = H system – TS system
T1 T2
Criteria of spontaneity :
Free expansion–Always going to be irrerversible and since Pext = 0
(i) If G system is (–ve) < 0  process is spontaneous
so dW = – Pext . dV = 0
(ii) If G system is > 0  process is non spontaneous
If no. heat is supplied q = 0
(iii) If G system = 0  system is at equilibrium.
then E = 0 so T = 0.

Page # 9 Page # 10
Physical interpretation of G : Enthalpy of Reaction from Enthalpies of Formation :
The maximum amount of non-expansional (compression) work which The enthalpy of reaction can be calculated by
can be performed. Hr° =  B Hf°,products –  B Hf°,reactants
G = dwnon-exp = dH – TdS. B is the stoichiometric coefficient.

Standard Free Energy Change (Gº) : Estimation of Enthalpy of a reaction from bond Enthalpies :
1. Gº = –2.303 RT log10 K
 Enthalpy required to   Enthalpy released to 
2. At equilibrium G = 0.    
H =  break reactants into    form products from the 
3. The decrease in free energy (–G) is given as :  gasesous atoms
   gasesous atoms 
V2 Resonance Energy :
–G = W net = 2.303 nRT log10
V1 H°resonance = H°f, experimental – H°f, calclulated
= H°c, calclulated– H°c, experimental
4.  G ºf for elemental state = 0

5. º
 G ºf = Gproducts º
– GRe ac tan ts CHEMICAL EQUILIBRIUM
Thermochemistry : At equilibrium :
0 0 (i) Rate of forward reaction = rate of backward reaction
Change in standard enthalpy H° = Hm ,2 – Hm ,1
(ii) Concentration (mole/litre) of reactant and product becomes constant.
= heat added at constant pressure. (iii) G = 0.
= CPT. (iv) Q = Keq.
If Hproducts > Hreactants Equilibrium constant (K) :
 Reaction should be endothermic as we have to give extra heat to reactants rate constant of forward reaction Kf
to get these converted into products K = rate constan t of backward reaction = K .
b
and if Hproducts < Hreactants
Equilibrium constant in terms of concentration (KC) :
 Reaction will be exothermic as extra heat content of reactants will be
released during the reaction. Kf [ C ] c [D ] d
Kb = K =
[ A ] a [B ] b
C
Enthalpy change of a reaction :
Hreaction = Hproducts – Hreactants
H°reactions = H°products – H°reactants Equilibrium constant in terms of partial pressure (KP ) :
= positive – endothermic [PC ] c [PD ] d
= negative – exothermic KP =
[PA ]a [PB ]b
Temperature Dependence Of H : (Kirchoff's equation) :
For a constant pressure reaction Equilibrium constant in terms of mole fraction (Kx) :
H2° = H1° + CP (T2 – T1) x cC x Dd
where CP = CP (products)  CP (reactants). Kx =
x aA x Bb
For a constant volume reaction
Relation between Kp & KC :
E 02  E10  C V .dT
 Kp = Kc.(RT)n.

Page # 11 Page # 12
 Demerits in Mendeleev’s Periodic Table :
INORGANIC CHEMISTRY  Position of hydrogen is uncertain .It has been placed in lA and VIIA groups
 No separate positions were given to isotopes.
PERIODIC TABLE & PERIODICITY  Anomalous positions of lanthanides and actinides in periodic table.
 Order of increasing atomic weights is not strictly followed in the arrangement
Development of Modern Periodic Table : of elements in the periodic table.
 Similar elements were placed in different groups.
(a) Dobereiner’s Triads : He arranged similar elements in the groups of
 It didn’t explained the cause of periodicity.
three elements called as triads
(b) Newland’s Law of Octave : He was the first to correlate the chemical (e) Long form of the Periodic Table or Moseley’s Periodic Table :
properties of the elements with their atomic masses.
(c) Lother Meyer’s Classification : He plotted a graph between atomic MODERN PERIODIC LAW (MOSELEY’S PERIODIC LAW) :
masses against their respective atomic volumes for a number of elements. If the elements are arranged in order of their increasing atomic number,
He found the observations ; (i) elements with similar properties occupied after a regular interval, elements with similar properties are repeated.
similar positions on the curve, (ii) alkali metals having larger atomic volumes PERIODICITY :
occupied the crests, (iii) transitions elements occupied the troughs, (iv) The repetition of the properties of elements after regular intervals when the
the halogens occupied the ascending portions of the curve before the elements are arranged in the order of increasing atomic number is called
inert gases and periodicity.
(v) alkaline earth metals occupied the positions at about the mid points of CAUSE OF PERIODICITY :
the descending portions of the curve. On the basis of these observations
The periodic repetition of the properties of the elements is due to the
he concluded that the atomic volumes (a physical property) of the elements
recurrence of similar valence shell electronic configurations after certain
are the periodic functions of their atomic masses.
regular intervals.
(d) Mendeleev’s Periodic Table : The modern periodic table consists of horizontal rows (periods) and vertical
Mendeleev’s Periodic’s Law column (groups).
the physical and chemical properties of the elements are the periodic Periods :
functions of their atomic masses. There are seven periods numbered as 1, 2, 3, 4, 5, 6 and 7.
 Each period consists of a series of elements having same valence shell.
Periods Number of Elements Called as  Each period corresponds to a particular principal quantum number of the
(1)st n = 1 2 Very short period valence shell present in it.
(2)nd n = 2 8 Short period  Each period starts with an alkali metal having outermost electronic
(3)rd n = 3 8 Short period configuration as ns1.
(4)th n = 4 18 Long period  Each period ends with a noble gas with outermost electronic configuration
(5)th n = 5 18 Long period ns2np6 except helium having outermost electronic configuration as 1s2.
(6)th n = 6 32 Very long period
 Each period starts with the filling of new energy level.
(7)th n = 7 19 Incomplete period
 The number of elements in each period is twice the number of atomic
orbitals available in energy level that is being filled.
Merits of Mendeleev’s Periodic table:
 It has simplified and systematised the study of elements and Groups :
their compounds. There are eighteen groups numbered as 1, 2, 3, 4, 5, ........... 13, 14, 15,
 It has helped in predicting the discovery of new elements on the 16, 17, 18.
basis of the blank spaces given in its periodic table. Group consists of a series of elements having similar valence shell
electronic configuration.

Page # 34 Page # 35
CLASSIFICATION OF THE ELEMENTS :  Nonmetals do not lose electrons but take up electrons to form corresponding
(a) s-Block Elements anions. Nonmetals are located at the top right hand side of the periodic
Group 1 & 2 elements constitute the s-block. General electronic table. Nonmetals are usually solids, liquids or gases at room temperature
configuration is [inert gas] ns1-2 with low melting and boiling points. They are poor conductors of heat and
s-block elements lie on the extreme left of the periodic table. electricity. Oxides of nonmetals are generally acidic in nature.

(b) p-Block Elements Metalloids (Semi metals) :

Group 13 to 18 elements constitute the p-block. General electronic The metalloids comprise of the elements B, Si, Ge, As, Sb and Te.
configuration is [inert gas] ns2 np1-6
Diagonal relationship :
(c) d-Block Elements 2nd period Li Be B C
Group 3 to 12 elements constitute the d-block. General electronic
configuration is [inert gas] (n – 1) d1-10 ns1-2
(d) f-Block Elements 3rd period Na Mg Al Si
General electronic configuration is (n – 2) f1-14 (n – 1) d0-1 ns2. All f-block Diagonal relationship arises because of ;
elements belong to 3rd group. (i) on descending a group, the atoms and ions increase in size. On
Elements of f-blocks have been classified into two series. (1) st inner moving from left to right in the periodic table, the size decreases.
transition or 4 f-series, contains 14 elements 58Ce to 71Lu. (2). IInd inner Thus on moving diagonally, the size remains nearly the same.
transition or 5 f-series, contains 14 elements 90Th to 103Lr. (Li = 1.23 Å & Mg = 1.36 Å ; Li+ = 0.76 Å & Mg2+ = 0.72 Å)
(ii) it is sometimes suggested that the diagonal relationship arises because
Prediction of period, group and block : of diagonal similarity in electronegativity values.
 Period of an element corresponds to the principal quantum number of the (Li = 1.0 & Mg = 1.2 ; Be = 1.5 & Al = 1.5 ; B = 2.0 & Si = 1.8)
valence shell. The periodicity of atomic properties :
 The block of an element corresponds to the type of subshell which receives
(i) Effective nuclear charge :
the last electron.
The effective nuclear charge (Zeff) = Z – , (where Z is the actual nuclear
 The group is predicted from the number of electrons in the valence shell
charge (atomic number of the element) and  is the shielding (screening)
or/and penultimate shell as follows. constant). The value of  i.e. shielding effect can be determined using the
(a) For s-block elements ; Group no. = the no. of valence electrons Slater’s rules.
(b) For p-block elements ; Group no. = 10 + no. of valence electrons
(ii) Atomic radius :
(c) For d-block elements ; Group no. = no. of electrons in (n – 1) d sub shell
+ no. of electrons in valence shell. (A) Covalent radius : It is one-half of the distance between the centres of
two nuclei (of like atoms) bonded by a single covalent bond. Covalent
Metals and nonmetals : radius is generally used for nonmetals.
 The metals are characterised by their nature of readily giving up the (B) Vander Waal’s radius (Collision radius) : It is one-half of the internuclear
electron(s) and from shinning lustre. Metals comprises more than 78% of distance between two adjacent atoms in two nearest neighbouring
all known elements and appear on the left hand side of the periodic table. molecules of the substance in solid state.
Metals are usually solids at room temperature (except mercury, gallium). (C) Metallic radius (Crystal radius) :
They have high melting and boiling points and are good conductors of heat It is one-half of the distance between the nuclei of two adjacent metal atoms in
and electricity. Oxides of metals are generally basic in nature (some metals the metallic crystal lattice.
in their higher oxidation state form acid oxides e.g. CrO3).  Thus, the covalent, vander Wall’s and metallic radius magnitude wise follows
the order,
rcovalent < rcrystal < rvander Walls
Page # 37 Page # 38
 (C) Shielding or screening effect : The larger the number of electrons in
Variation in a Period Variation in a Group the inner shells, greater is the screening effect and smaller the force of
In a period left to right : In a group top to bottom : attraction and thus ionization energy (IE) decreases.
Nuclear charge (Z) increases by one unit Nuclear charge (Z) increases by more than one unit
(D) Penetration effect of the electron : Penetration effect of the electrons
follows the order s > p > d > f for, the same energy level. Higher the
Effective nuclear charge (Zef f ) almost remains
Effective nuclear charge (Zef f ) also increases
penetration of electron higher will be the ionisation energy.
constant because of increased screening effect of
inner shells electrons. (E) Electronic Configuration : If an atom has exactly half-filled or completely
But number of orbitals (n) remains constant But number of orbitals (n) increases. filled orbitals, then such an arrangement has extra stability.
(V) Electron Gain Enthalphy : (CHANGED TOPIC NAME)
As a result, the electrons are pulled closer to the The effect of increased number of atomic shells The electron gain enthalpy egH, is the change in standard molar enthalpy
overweighs the effect of increased nuclear charge. As
nucleus by the increased Zef f .
a result of this the size of atom increases from top to
when a neutral gaseous atom gains an electron to form an anion.
1 bottom in a given group. X (g) + e– (g)  X– (g)
rn 
Z* The second electron gain enthalpy, the enthalpy change for the addition of
Hence atomic radii decrease with increase in
atomic number in a period from left to right.
a second electron to an initially neutral atom, invariably positive because
the electron repulsion out weighs the nuclear attraction.
(iii) Ionic radius :
The effective distance from the centre of nucleus of the ion up to which it  Group 17 elements (halogens) have very high negative electron gain
has an influence in the ionic bond is called ionic radius. enthalpies (i.e. high electron affinity) because they can attain stable noble
gas electronic configuration by picking up an electron.
Cation Anion
It is formed by the lose of one or more electrons from It is formed by the gain of one or more electrons in the  Across a period, with increase in atomic number, electron gain enthalpy
the valence shell of an atom of an element. valence shell of an atom of an element. becomes more negative
Cations are smaller than the parent atoms because, Anions are larger than the parent atoms because
(i) the whole of the outer shell of electrons is usually (i) anion is formed by gain of one or more electrons in the  As we move in a group from top to bottom, electron gain enthalpy becomes
removed. neutral atom and thus number of electrons increases but less negative
(ii) in a cation, the number of positive charges on the magnitude of nuclear charge remains the same.
nucleus is greater than number of orbital electrons (ii) nuclear charge per electrons is thus reduced and the  Noble gases have large positive electron gain enthalpies
leading to incresed inward pull of remaining electrons electrons cloud is held less tightly by the nucleus leading to
causing contraction in size of the ion. the expansion of the outer shell. Thus size of anion is
 Negative electron gain enthalpy of O or F is less than S or Cl.
increased.  Electron gain enthalpies of alkaline earth metals are very less or positive
 Nitrogen has very low electron affinity
(iv) Ionisation Energy :
1
Ionisation energy (IE) is defined as the amount of energy required to remove  (i) Electron affinity  (ii) Electron affinity  Effective nuclear
Atomic size
the most loosely bound electron from an isolated gaseous atom to form a charge (zeff)
cation. 1
(IE1 ) (iii) Electron affinity  Screening effect . (iv) Stability of half filled and
M(g)   M+(g) + e– ; M+ (g) + IE2  M2+ (g) + e–
completely filled orbitals of a subshell is comparatively more and the
M2+ (g) + IE3  M+3 (g) + e–
addition of an extra electron to such an system is difficult and hence the
IE1, IE2 & IE3 are the Ist, IInd & IIIrd ionization energies to remove electron
electron affinity value decreases.
from a neutral atom, monovalent and divalent cations respectively. In
general, (IE)1 < (IE)2 < (IE)3 < .............. (VI) Electronegativity :
 Factors Influencing Ionisation energy Electronegativity is a measure of the tendency of an element to attract
(A) Size of the Atom : Ionisation energy decreases with increase in atomic shared electrons towards itself in a covalently bonded molecules.
size. (a) Pauling’s scale :
(B) Nuclear Charge : The ionisation energy increases with increase in the  = XA – XB = O.208 E.A B  E A  A  EB B
nuclear charge.
Page # 39 Page # 40
 EA-B = Bond enthalpy/ Bond energy of A – B bond.
EA - A = Bond energy of A – A bond CHEMICAL BONDING
EB –B = Bond energy of B – B bond
(All bond energies are in kcal / mol) Chemical Bond :
In the process each atom attains a stable outer electronic configuration
 = XA – XB = O.1017 E.A B  E A  A  EB B
of inert gases.
All bond energies are in kJ / mol. Ionic or Electrovalent Bond :
(b) Mulliken’s scale : The formation of an ionic compound would primarily depends upon :
IE  EA * The ease of formation of the positive and negative ions from the respective
M = neutral atoms.
2
Paulings’s electronegativity P isrelated to Mulliken’s electronegativity M * The arrangement of the positive and negative ions in the solid, that is the
as given below. lattice of the crystalline compound.
Conditions for the formation of ionic compounds :
P = 1.35 (M)1/2 – 1.37 (i) Electronegativity difference between two combining elements must be
Mulliken’s values were about 2.8 times larger than the Pauling’s values. larger.
(ii) Ionization enthalpy (M(g)  M+(g) + e–) of electropositive element must be
(VII) Periodicity of Valence or Oxidation States :
low.
There are many elements which exhibit variable valence. This is particularly
(iii) Negative value of electron gain enthalpy (X (g) + e–  X –(g)) of
characteristic of transition elements and actinoids.
electronegative element should be high.
(VIII) Periodic Trends and Chemical Reactivity : (iv) Lattice enthalpy (M+(g) + X– (g)  MX (s)) of an ionic solid must be high.
 In a group, basic nature of oxides increases or acidic nature decreases.
Lattice Enthalpy :
Oxides of the metals are generally basic and oxides of the nonmetals are
The lattice enthalpy of an ionic solid is defined as the energy required to
acidic. The oxides of the metalloids are generally amphoteric in nature.
The oxides of Be, Al, Zn, Sn, As, Pb and Sb are amphoteric. completely separate one mole of a
solid ionic compound into gaseous constituent ions.
 In a period the nature of the oxides varies from basic to acidic.
Na2O MgO Al2O3 SiO2 P4O10 Factors affecting lattice energy of an ionic compound :
SO3 Cl2O7 1
Strongly basic Basic amphoteric Weakly acidic Acidic (i) Lattice energy  where (r+ + r– ) = Inter-ionic Distance.
r  r
Acidic Strongly acidic
(ii) Lattice energy  Z+, Z–
Electron Gain Enthalpy Z+  charge on cation in terms electronic charge.
Z–  charge on anion in terms electronic charge.
Electron Gain Enthalpy

Ionization Enthalpy
Ionization Enthalpy

Determination of lattice energy :

Electronegativity

Atomic Radius

Born-Haber Cycle :
lic chara
cter It inter relates the various energy terms involved during formation of an
nonmeta
characte
r ionic compound.
metalic
It a thermochemical cycle based on the Hess’s law of constant heat
summation.
Atomic Radius

Electronegativity

Page # 41 Page # 42
Hydration : Fajan’s gives some rules which govern the covalent character in the ionic
All the simple salts dissolve in water, producing ions, and consequently compounds, which are as follows:
the solution conduct electricity. Since Li+ is very small, it is heavily (i) Size of cation : Size of cation  1 / polarisation.
hydrated. This makes radius of hydrated Li+ ion large and hence it
(ii) Size of anion : Size of anion  polarisation
moves only slowly. In contrast, Cs+ is the least hydrated because of its
bigger size and thus the radius of the Cs+ ion is smaller than the radius of (iii) Charge on cation : Charge on cation  polarisation.
hydrated Li+, and hence hydrated Cs+ moves faster, and conducts
(iv) Charge on anion : Charge on anion  polarisation.
electricity more readily.
(v) Pseudo inert gas configuration of cation :
Hydrolysis :
Hydrolysis means reaction with water molecules ultimately leading to Covalent Bond :
breaking of O-H bond into H+ and OH– ions. It forms by sharing of valence electrons between atoms to form molecules
Hydrolysis in covalent compounds takes place generally by two e.g., formation of Cl2 molecule :
mechanisms
(a) By Coordinate bond formation : Generally in halides of atoms having Cl Cl
vacant d-orbitals or of halides of atoms having vacant orbitals.
Cl + Cl

(b) By H-bond formation : For example in Nitrogen trihalides

8e
–
8e
–

General properties of ionic compounds : or Cl – Cl

(a) Physical state : At room temperature ionic compounds exist either in Covalent bond between two Cl atoms
solid state or in solution phase but not in gaseous state. The important conditions being that :
(b) Simple ionic compounds do not show isomerism but isomorphism is their (i) Each bond Is formed as a result of sharing of an electron pair between the
important characteristic. atoms.
e.g. , FeSO4 .7H2O | MgSO4 . 7H2O (ii) Each combining atom contributes at least one electron to the shared pair.
(iii) The combining atoms attain the outer- shell noble gas configurations as a
(c) Electrical conductivity : result of the sharing of electrons.
All ionic solids are good conductors in molten state as well as in their
aqueous solutions because their ions are free to move. Coordinate Bond (Dative Bond):
The bond formed between two atom in which contribution of an electron
(d) Solubility of ionic compounds : pair is made by one of them while the sharing is done by both.
Soluble in polar solvents like water which have high dielectric constant
+
H H
Covalent character in ionic compounds (Fajan’s rule) : •x
x +
|
(i) NH4 (ammonium ion) H •x Nx H H–N–H
Fajan’s pointed out that greater is the polarization of anion in a molecule, •x |
more is covalent character in it. H H

Donor Acceptor
O
(ii) O3 (ozone) or
O O
More distortion of anion, more will be polarisation then covalent
Other examples : H2 SO4 , HNO3 , H3O+ , N2O, [Cu(NH3)4]2+
character increases.

Page # 43 Page # 44
Formal Charge : Valence bond theory (VBT) :
H2(g) + 435.8 kJ mol –  H(g) + H(g)

Orbital Overlap Concept

Formal charges help in the selection of the lowest energy structure from a according to orbital overlap concept, the formation of a covalent bond
between two atoms results by pairing of electrons present, in the valence
number of possible Lewis structures for a given species.
shell having opposite spins.
Limitations of the Octet Rule : Types of Overlapping and Nature of Covalent Bonds
1. The incomplete octet of the central atom The covalent bond may be classified into two types depending upon the
LiCl, BeH2 and BCl3, AlCl3 and BF3. types of overlapping :
2. Odd-electron molecules (i) sigma() bond, and (ii) pi () bond
nitric oxide, NO and nitrogen dioxide. NO2 (i) Sigma () bond : This type of covalent bond is formed by the end to end
(head-on) overlap of bonding orbitals along the internuclear axis.
 s-s overlapping
3. The expanded octet

 s-p overlapping:
PF5 SF6 H2SO4
10 electrons around 12 electrons around 12 electrons around
the P atom the S atom the S atom

4. Other drawbacks of the octet theory

(i) some noble gases (for example xenon and krypton) also combine with  p-p overlapping : This type of overlap takes place between half filled
oxygen and fluorine to form a number of compounds like XeF2 , KrF2 , p-orbitals of the two approaching atoms.
XeOF2 etc.,
(ii) This theory does not account for the shape of molecules.
(iii) It does not explain the relative stability of the molecules being totally
silent about the energy of a molecule.

Page # 45 Page # 46
(ii) pi() bond : In the formation of  bond the atomic orbitals overlap in such Important conditions for hybridisation :
a way that their axes remain parallel to each other and perpendicular to (i) The orbitals present in the valence shell of the atom are hybridised.
the internuclear axis. (ii) The orbitals undergoing hybridisation should have almost equal energy.
(iii) Promotion of electron is not essential condition prior to hybridisation.
(iv) It is the orbital that undergo hybridization and not the electrons.
Determination of hybridisation of an atom in a molecule or ion:
Steric number rule (given by Gillespie) :
Steric No. of an atom = number of atom bonded with that atom + number
of lone pair(s) left on that atom.
Table-3
Strength of Sigma and pi Bonds : Steric Types of Geometry
In case of sigma bond, the overlapping of orbitals takes place to a larger Number Hybridisation
extent. Hence, it is stronger as compared to the pi bond where the extent 2 sp Linear
of overlapping occurs to a smaller extent. 3 sp2 Trigonal planar
Valence shell electron pair repulsion (VSEPR) theory : 4 sp3 Tetrahedral
The main postulates of VSEPR theory are as follows: 5 sp3 d Trigonal bipyramidal
(i) The shape of a molecule depends upon the number of valence shell electron 6 sp3 d2 Octahedral
pairs [bonded or nonbonded) around the central atom. 7 sp3 d3 Pentagonal bipyramidal
(ii) Pairs of electrons in the valence shell repel one another since their electron Hybridization Involving d-orbital :
clouds are negatively charged. Type of ‘d’ orbital involved
(iii) These pairs of electrons tend to occupy such positions in space that dZ2
sp3 d
minimise repulsion and thus maximise distance between them.
(iv) The valence shell is taken as a sphere with the electron pairs localising on 3 2
sp d dx2 – y2 & d 2
Z
the spherical surface at maximum distance from one another. dx2 – y2 , d 2 & d
sp3 d3 Z
(v) A multiple bond is treated as if it is a single electron pair and the two or xy

three electron pairs of a multiple bond are treated as a single super pair. dsp 2 dx2  y 2
(vi) Where two or more resonance structures can represent a molecule, the
VSEPR model is applicable to any such structure. Molecular Orbital Theory (MOT) :
developed by F. Hund and R.S. Mulliken in 1932.
The repulsive interaction of electron pairs decreases in the order : (i) Molecular orbitals are formed by the combination of atomic orbitals of
lone pair (p) - lone pair (p) > lone pair (p) - bond pair (bp) > bond pair comparable energies and proper symmetry.
(bp) -bond pair (bp) (ii) An electron in an atomic orbital is influenced by one nucleus, while in a
Hybridisation : molecular orbital it is influenced by two or more nuclei depending upon the
number of the atoms in the molecule. Thus an atomic orbital is
Salient features of hybridisation : monocentric while a molecular orbital is polycentric.
1. The number of hybrid orbitals is equal to the number of the atomic orbitals (iii) The number of molecular orbitals formed is equal to the number of combining
that get hybridised. atomic orbitals. When two atomic orbitals combine, two molecular orbitals
2. The hybridised orbitals are always equivalent in energy and shape. called bonding molecular orbital and anti-bonding molecular orbital
3. The hybrid orbitals are more effective in forming stable bonds than the are formed.
pure atomic orbitals. (iv) The molecular orbitals like the atomic orbitals are filled in accordance with
4. These hybrid orbitals are directed in space in some preferred direction to the Aufbau principle obeying the Pauli Exclusion principle and the
have minimum repulsion between electron pairs and thus a stable Hund’s Rule of Maximum Multiplicity. But the filling order of these
arrangement is obtained. Therefore, the type of hybridisation indicates the molecular orbitals is always experimentally decided, there is no rule
geometry of the molecules. like (n + l) rule in case of atomic orbitals.
Page # 47 Page # 48
Conditions for the combination of atomic orbitals : The shift in electron density is represented by crossed arrow ( )
1. The combining atomic orbitals must have the same or nearly the same above the Lewis structure to indicate the direction of the shift.
energy. a molecule will have a dipole moment if the summation of all of the individual
2. The combining atomic orbitals must have the same symmetry about the moment vector is non-zero.
molecular axis.
3. The combining atomic orbitals must overlap to the maximum extent.
Energy level diagram for molecular orbitals :
The increasing order of energies of various molecular orbitals for O2 and F2
is given below :
1s < * 1s < 2s < *2s < 2pz < (2px = 2py) < (*2px = *2py) < *2pz R= P 2  Q 2  2PQ cos  ,
The important characteristic feature of this order is that the energy of where R is resultant dipole moment.
2pz molecular orbital is higher than that of 2px and 2py molecular
orbitals. Resonance :
Definition : Resonance may be defined as the phenomenon in which
Bond Order
two or more structures involving in identical position of atom, can be
Bond order (b.o.) = ½ (Nb – Na)
A positive bond order (i.e., Nb > Na) means a stable molecule while a written for a particular compound.
negative (i.e., Nb < Na) or zero (i.e., Nb = Na) bond order means an unstable For example, the ozone, O3 molecule can be equally represented by the
molecule. structures I and II shown below :
Nature of the Bond :
Integral bond order values of 1, 2 or 3 correspond to single, double or triple
bonds respectively.
Bond-Length :
The bond order between two atoms in a molecule may be taken as an
approximate measure of the bond length. The bond length decreases as Resonance in the O3 molecule
bond order increases. Resonance Hybrid : It is the actual structure of all different possible
Magnetic Nature : structures that can be written for the molecule without violating the rules
If all the molecular orbitals in a molecule are doubly occupied, the substance of maximum covalance for the atoms.
is diamagnetic (repelled by magnetic field) e.g., N2 molecule.

Dipole moment : 
Dipole moment (µ) = Magnitude of charge (q) × distance of separation (d) Resonance hybrid
Dipole moment is usually expressed in Debye units (D). The conversion
factors are Hydrogen Bond :
 1 D = 3.33564 × 10 –30
Cm, where C is coulomb and m is meter. – – – H+ – F – – – – H+ – F– – – – H+ – F–

 1 Debye = 1 × 10–18 e.s.u. cm. Conditions required for H-bond :

(i) Molecule should have more electronegative atom (F, O, N) linked to
For example the dipole moment of HF may be represented as
H-atom.
(ii) Size of electronegative atom should be smaller.
(iii) A lone pair should be present on electronegative atom.

Page # 49 Page # 50
 Order of H-bond strength Intermolecular forces (Vander Waal’s Forces) :
Intermolecular attractions hold two or more molecules together. These are
> O H - - - - - - :O weakest chemical forces and can be of following types.
(a) Ion-dipole attraction (b) Dipole-dipole attraction
(c) Ion-induced dipole attraction (d) Dipole-induced dipole attraction
> N H - - - - - - :N > N H - - - - - - :O (e) Instantaneous dipole- Instantaneous induced dipole attraction :
(Dispersion force or London forces)
TYPES OF H-BONDS :  Strength of vander waal force  molecular mass.
(A) Intramolecular H-Bonding :  van der Waal’s force  boiling point.
it is formed when hydrogen atom is present in between the two highly
electronegative (F, O, N) atoms within the same molecule. Metallic bond :
Two models are considered to explain metallic bonding:
(A) Electron-sea model (B) Band model
Some special bonding situations :
(a) Electron deficient bonding: There are many compounds in which
some electron deficient bonds are present apart from normal covalent
bonds or coordinate bonds. These electron deficient bonds have less
It has lower boiling point (i.e. more volatile) than its para-derivative
number of electrons than the expected such as three centre-two electron
Necessary conditions for the formation of intramolecular hydrogen-bonding: bonds (3c-2e) present in diborane B2H6, Al2(CH3)6, BeH2(s) and bridging
(a) the ring formed as a result of hydrogen bonding should be planar. metal carbonyls.
(b) a 5- or 6- membered ring should be formed.
(b) Back Bonding : Back bonding generally takes place when out of two
(c) interacting atoms should be placed in such a way that there is minimum bonded atoms one of the atom has vacant orbitals (generally this atom is
strain during the ring closure. from second or third period) and the other bonded atom is having some
(B) Intermolecular H-Bonding : non-bonded electron pair(generally this atom is from the second period).
it is formed between two different molecules of the same or different Back bonding increases the bond strength and decreases the bond length.
compounds. For example, in BF3
(a) In water molecules

(b) The hydrogen bonds in HF link the F atom of one molecule with
the H-atom of another molecule, thus forming a zig-zag chain
(HF)n in both the solid and also in the liquid.

the extent of back bonding in boron trihalides.

BF3 > BCl3 > BBr3

Page # 51 Page # 52
s-BLOCK ELEMENTS & THEIR COMPOUNDS ANOMALOUS PROPERTIES OF LITHIUM
(i) exceptionally small size of its atom and ion, and (ii) high polarising
Group 1 of the periodic table consists of the elements : lithium, sodium,
power (i.e., charge/ radius ratio ).
potassium, rubidium, caesium and francium .
The similarity between lithium and magnesium is particularly striking and
The elements of Group 2 include beryllium, magnesium, calcium, strontium,
arises because of their similar size: atomic radii, Li = 152 pm, Mg = 160
barium and radium.
pm; ionic radii : Li+ = 76 pm, Mg2+ = 72 pm.
Hydration Enthalpy :
GROUP 2 ELEMENTS : ALKALINE EARTH METALS
The hydration enthalpies of alkali metal ions decrease with increase in
The first element beryllium differs from the rest of the member and shows
ionic [Link]+ has maximum degree of hydration and for this reasons
diagonal relationship to aluminium.
lithium salts are mostly hydrated e.g., LiCl . 2H2O
Hydration Enthalpies
Physical properties :
Hydration enthalpies of alkaline earth metal ions. Be2+ > Mg2+ > Ca2+ >
All the alkali metal are silvery white, soft and light metals. Because of the
Sr2+ > Ba2+. The hydration enthalpies of alkaline earth metal ions are larger
larger size, these element have low density. The melting and boiling point
than those of alkali metal ions. Thus, compounds of alkaline earth metals
of the alkali metals are low indicating weak metallic bonding alkali metals
are more extensively hydrated than those of alkali metals , e.g., MgCl2
and their salts impart characteristic colour to an oxidizing flame.
and CaCl2 exist as MgCl2 .6H2O and CaCl2. 6H2O while NaCl and KCl do
Metal Li Na K Rb Cs not form such hydrates.
Violet/
Physical Properties
Colour Crimson Yellow Lilac Red Blue
The alkaline earth metals, in general, are silvery white, lustrous and relatively
red violet
soft but harder than the alkali metals. The melting and boiling point of
Chemical Properties: these metals are higher due to smaller sizes. Because of the low ionisation
enthalpies they are strongly electropositive in nature. The electrons in
The alkali metal are highly reactive due to their larger size and low ionization
beryllium and magnesium are too strongly bound to get excited by flame.
enthalpy.
Hence these elements do not impart any colour to the flame.
 Reactivity towards air : They burn vigorously in oxygen forming
Calcium, strontium and barium impart characteristic colour to the flame.
oxides. Lithium forms monoxide, sodium forms peroxide, the other metals
form superoxide. M e ta l Be Mg Ca Sr Ba
 Reducing nature: The alkali metals, are strong reducing agents, Colour No No Brick Crim son Apple
lithium being the most and sodium the least powerful. colour colour red green
 Solution in liquid ammonia: The alkali metals dissolve in liquid
ammonia giving deep blue solution which are conducting in nature. Chemical Properties
+
M+ (x + y) NH3  [M(NH3 )x ] + [e(NH3)y] –  Reactivity towards air and water : Beryllium and magnesium are
The blue colour of the solution is due to the ammoniated electron and the inert to oxygen and water. Magnesium is more electropositive and burns
solutions is paramagnetic. with dazzling brilliance in air to give MgO and Mg3N2 .Calcium, strontium
and barium are readily attacked by air to form the oxide and nitride.
on s tan ding
M+(am) + e– + NH3 ()    
 MNH2(am) + 1/2 H2(g) ,

 Reducing nature : The alkaline earth metals are strong reducing

In concentrated solution, the blue colour changes to bronze colour and agent. This is indicated by large negative value of their reduction potentials.
becomes, diamagnetic. ,

Page # 73 Page # 74
  Solution in liquid ammonia: The alkaline earth metals dissolve in 3. Sodium Hydroxide (NaOH) :
liquid ammonia to give deep blue black solution forming ammoniated ions.
M + (x + y) NH3  [ M(NH3)x]2+ + 2 [e(NH3)Y ]–
From these solutions, the ammoniates, [M(NH3)6]2+ can be recovered.
ANOMALOUS BEHAVIOUR OF BERYLLIUM
Beryllium the first member of the Group 2 metals, shows
anomalous behaviour as compared to magnesium and rest of the members.
Further, it shows diagonal relationship to aluminium.

Diagonal Relationship between Beryllium and Aluminium

The ionic radius of Be2+ is estimated to be 31 pm; the charge/
radius ratio is nearly the same as that of the Al3+ ion. Hence beryllium
resembles aluminium in some ways.
Compounds of s-block elements :
1. Sodium Oxide (Na2O) :

4. Sodium Carbonate (Na2CO3) :

2. Sodium peroxide (Na2O2) :

5. Quick Lime, Slaked Lime and Lime Water :

Page # 75 Page # 76
 3Ca(OH)2 + 2Cl2  Ca(OCl)[Link](OH)2.CaCl2.2H2O (bleaching powder).

p-BLOCK ELEMENTS & THEIR COMPOUNDS

TRENDS IN PROPERTIES OF p-BLOCK ELEMENTS.
Electronegativity,
ionization enthalpy,
oxidizing power.

B C N O F Ne
Al Si P S Cl Ar Electronegativity,
Covalent radius, enthalpy of atomization
van der Waals' Ga Ge As Se Br Kr (except for N2, O2, F2),
radius,
metallic character In Sn Sb Te I Xe ionization enthalpy,
oxidizing power.
Tl Pb Bi Po At Rn

Covalent radius, van der Waals'

radius, enthalpy of atomization
(upto group 14), metallic character

(A) GROUP 13 ELEMENTS : THE BORON FAMILY

Oxidation state and trends in chemical reactivity :
General Oxidation State = + 3.
Reactivity towards acids and alkalies
2 Al(s) + 6 HCl(aq)  2 Al3+ (aq) + 6 Cl–(aq) + 3 H2(g)
2Al(s) + 2NaOH (aq) + 6H2O (1)  2Na+ [Al(OH)4]– (aq) + 3H2(g)
Sodium tetrahydroxoaluminate (III)
Reactivity towards halogens
2E(s) + 3X2 (g)  2EX3 (s) (X = F, Cl Br, I)

Page # 77