a p SELF CHECK

fcc 4
2 2 3 2 5. Sodium metal crystallizes in a body centred cubic
lattice with a unit cell edge of 4.29 Å. The radius of
a 3 h p
hcp 6 sodium atom is approximately
, × 3 2
2 2 4 (a) 5.72 Å (b) 0.93 Å
(c) 1.86 Å (d) 3.22 Å
‰ Limiting radius ratio: It is the ratio of the radii of
(JEE Main 2015)
positive and negative ions in a crystal.
6. The arrangement of X– ions
Radius of cation r+
Radius ratio = = around A+ ion in solid X–
Radius of anion r− AX is given in the figure
‰ Limiting radius ratio, coordination number and (not drawn to scale). If the A+
geometry radius of X– is 250 pm, the
r+/r– C. No. Geometry radius of A+ is
< 0.155 2 linear (a) 104 pm (b) 125 pm
(c) 183 pm (d) 57 pm
0.155 - 0.225 3 plane triangular (JEE Advanced 2013)
0.225 - 0.414 4 tetrahedral 7. CsCl crystallises in body-centred cubic lattice. If
0.414 - 0.732 6 octahedral ‘a’ is its edge length then which of the following
0.732 - 1.000 8 cubic (body centred) expressions is correct?
‰ For a tetrahedral void, r = 0.225 R (a) rCs + + rCl − = 3a (b) rCs+ + rCl– = 3a
For an octahedral void, r = 0.414 R 3a 3
where r is the radius of the void and R is the radius (c) rCs + + rCl− = (d) rCs + + rCl − = a
2 2
of the spheres in the close packed arrangement. (JEE Main 2014)
‰ Imperfections in solids : Any deviation from the perfectly ordered arrangement of constituent particles in a
crystal is called imperfection or defect.
Imperfections/Defects in Solids

Point defects Line defects

Deviations from ideal arrangement Deviations from ideal arrangement in
around a point or an atom. entire rows of lattice points.

Stoichiometric/Intrinsic/Thermodynamic defects Impurity defects Non-stoichiometric defects

Do not disturb stoichiometry of solid. Arise when foreign atoms are present at Disturb stoichiometry of solids.
lattice site e.g., SrCl2, CdCl2, AgCl etc.

Vacancy defect : Arises
when lattice sites are
vacant. Decreases density,
shown by non-ionic
solids.
Interstitial defect : Arises
when constituent particles
occupy interstitial site.
Increases density, shown
by non-ionic solids.
Frenkel defect : Smaller ion
(usually cation) dislocates
from its normal site to an
interstitial site. Does not
change density, shown by
ionic solids, e.g., ZnS, AgCl,
AgBr, AgI, etc.
Schottky defect : Arises
when equal number of
cations and anions are
missing. Decreases
density, shown by ionic
solids, e.g. , NaCl, KCl,
CsCl, AgBr, etc.

Metal excess defect Metal deficiency defect

Due to anionic vacancies
A negative ion is missing from its lattice site,
leaving a ‘hole’ which is occupied by an electron
to maintain electrical neutrality, e.g., LiCl, NaCl
Arises when metal shows
Due to the presence of extra cations variable valency e.g., Fe2+, Fe3+
Usually arises when metal oxides are
heated, e.g., ZnO.

40 chemistry tODAy | JULY ‘15

Electrical Properties
‰ Piezoelectricity : The electricity produced when
mechanical stress is applied on polar crystals
e.g., PbZrO3, NH4H2PO4 and quartz.
‰ Pyroelectricity : The electricity produced when
some polar crystals are heated.
‰ Ferroelectricity : In some piezoelectric crystals,
the dipoles are permanently polarized even in the
absence of electric field. However, on applying
electric field, the direction of polarization changes.
This phenomenon is called ferroelectricity due to
analogy with ferromagnetism e.g., BaTiO3, Rochelle
salt and KH2PO4.
‰ Anti-ferroelectricity : In some crystals, the dipoles
in alternate polyhedra point up and down so that
the crystal does not possess any net dipole moment.
Such crystals are said to be anti-ferroelectric e.g.,
PbZrO3.
 Conductors : Electrical conductivity, 104 to
107 ohm–1 m–1.
 Insulators : Electrical conductivity, 10–20 to
10–10 ohm–1 m–1.
 Semiconductors : Electrical conductivity, 10–6
to 104 ohm–1 m–1.
— n-type semiconductors : Group 14 elements
doped with group 15 elements, free electrons
increase conductivity.
— p-type semiconductors : Group 14 elements
doped with group 13 elements, holes
increase conductivity.
Magnetic Properties
‰ Paramagnetic substances : They are weakly
attracted by a magnetic field. They have one or more
unpaired electrons and lose their magnetism in the
absence of magnetic field, e.g., O2, Cu2+, Fe3+, Cr3+.
‰ Diamagnetic substances : They are weakly repelled
by a magnetic field. They have no unpaired electrons
and hence have zero magnetic moment, e.g., H2O,
NaCl and C6H6.
‰ At present, about 35 different subatomic particles are known but electrons, protons and neutrons are called
fundamental particles.
Quantity Unit Electron (e)
Mass amu 0.000549
gram 9.108 × 10–28
Relative 1/1837
‰ Ferromagnetic substances : They show permanent
magnetism even in the absence of magnetic field
as when placed in magnetic field, their unpaired
electrons (or magnetic domains) get permanently
oriented in one direction, e.g., Fe, Ni, Co, Gd, CrO2
etc.
‰ Anti-ferromagnetic substances : They are expected
to possess paramagnetism or ferromagnetism but
actually have zero net magnetic moment due to
equal number of domains in opposite direction,
e.g., MnO.
‰ Ferrimagnetic substances : They are expected
to have large magnetism but actually have small
net magnetic moment due to unequal number
of domains in opposite direction, e.g., magnetite
(Fe3O4), ferrites like MgFe2O4 and ZnFe2O4. These
substances lose ferrimagnetism on heating and
become paramagnetic.
KEY POINT
• Polonium is the only metal that crystallizes in
simple cubic lattice.
• On pressurising a crystal its coordination number
increases while on heating coordination number
decreases.
• AgBr shows both Schottky as well as Frenkel
defect.
atomic Structure
l Introduction
l Nature of Electromagnetic Radiations
l Atomic Spectra
l Bohr’s Atomic Model
l Dual Nature of Matter and Quantum Mechanics
l Quantum Numbers
tipS to rememBer
‰ Atom is not the smallest indivisible particle but have
a complex structure of its own.
Proton (p) Neutron (n)
1.00728 1.00867
1.673 × 10–24 1.675 × 10–24
1 1
chemistry tODAy | JULY ‘15 41
 Charge coulomb –1.602 × 10–19 +1.602 × 10–19 zero
esu –4.803 ×10–10 +4.803 × 10–10 zero
Relative –1 +1 zero
Discovered by J.J. Thomson Goldstein Chadwick

Atomic Models order of their wavelengths is called electromagnetic

‰ According to Thomson’s plum pudding model of spectrum.
atom, positive charge is spread over a sphere of Cosmic rays, -rays, X-rays, UV rays, visible, IR, microwaves,
radiowaves
radius ≈ 10–8 cm and electrons are embedded in it.
Decreasing frequency
 Thomson’s model could explain the electrical
‰ Atomic spectra represent the radiation or energy
neutrality of atom but not the other observations
like spectra and a-scattering experiment. absorbed or emitted by an atom.
‰ Rutherford’s model was based upon the results of
‰ Different types of spectra :
scattering experiments. Atomic spectra Molecular spectra
 According to Rutherford’s model, the nucleus of
atom is hard dense core and consists of protons
while electrons revolve around the nucleus. Line spectra Absorption
‰ Some important terms : Each line in spectra spectra
Term Description Examples represents one Spectra
electronic transition
Isotopes Different atoms of same 1H, 21H, 31H;
1
Emission
element having same atomic 35Cl, 37Cl Band spectra spectra
17 17
number but different mass
numbers.
40 Continuous spectra Discontinuous spectra
Isobars Atoms of different elements 18 Ar, 4019K,
having same mass number 20 40
Ca Atomic Spectra of Hydrogen
but different atomic
‰ Radiations emitted by hydrogen in discharge tube
numbers.
experiments when passed through prism gives five
Isotones Atoms of different elements 146 C, 157 N, series of lines named after the researchers.
containing same number of 168 O
neutrons. Name of Wavelength n1 n2 Region
series
Isodiaphers Atoms having same isotopic 235 92U,
number (i.e., no. of neutrons 231 1 1 1 
90Th 1. Lyman = RH  −  1 n > 1 UV
– no. of protons = same) l 12 n2 
Isosters Molecules having same CO2, N2O
number of atoms and 1 1 1
2. Balmer = RH  −  2 n > 2 Visible
electrons. l  2 n2 
2

Nature of Electromagnetic Radiations 1 1 1

‰ Electromagnetic wave theory : Energy is emitted
3. Paschen = RH  −  3 n > 3 IR
l  3 n2 
2
continuously from any source in the form of
radiations travelling in the form of waves and 1 1 1
associated with electric and magnetic fields, 4. Brackett = RH  −  4 n > 4 IR
2
l 4 n2 
oscillating perpendicular to each other and to the
direction of radiations. 1 1 1
‰ All electromagnetic radiations have wave 5. Pfund = RH  −  5 n > 5 far IR
characteristics and do not require any medium for
l  5 n2 
2

their propagation. 6. Humphrey 1 6 n > 6 far-far

1 1
‰ The arrangement of various radiations in the = RH  −  IR
decreasing order of their frequencies or increasing
l  6 n2 
2

42 chemistry tODAy | JULY ‘15

 1  1 1  2 ‰ Limitations of Bohr’s Model
‰ Rydberg formula : v = = RH − Z
l  2 2  Mathematically, Bohr’s model explains only
 n1 n2 
monoelectronic atoms and fails to explain
where, RH is Rydberg constant and has a value equal
electronic repulsions in multielectronic atoms.
to 109,677 cm–1.
 It does not explain the distribution of electrons
KEY POINT in orbits.
• The number of spectral lines possible for hydrogen  It does not provide mathematical support to
or hydrogen like species when the electrons from nh
assumption, mvr = .
nth energy level return to ground state in different 2p
1
atoms = n(n − 1)  It is against de-Broglie and Heisenberg’s
2 uncertainty principles.
• Absorption and emission spectra are
complementary to each other. A line missing in  It does not explain the splitting of spectral lines
absorption spectrum will appear in emission under the influence of electric field (Stark effect)
spectrum. and magnetic field (Zeeman effect).
Bohr’s Atomic Model ‰ According to Planck’s quantum theory, a body
can emit or absorb energy not continuously but
‰ The main postulates are :
discontinuously in the form of small packets called
 Atom consists of a small, heavy and positively
quanta (called photon in case of light).
charged nucleus in centre, and electrons revolve hc
around the nucleus in fixed paths called orbits. Energy of photon, E = hv = (h is Planck’s
l
 Energy of an electron in the orbit does not
constant having value 6.62 × 10–34 J s)
change with time.
 The electron can revolve only in those orbits ‰ Ejection of electrons from the surface of a metal
whose angular momentum is an integral by irradiating it with light of suitable frequency is
multiple of h/2p i.e., known as photoelectric effect.
nh  The kinetic energy of emitted photoelectrons is
mvr = , n = 1, 2, 3, ....
2p mathematically given as
 When electron jumps from one level to another, K.E. = hv – hv0 = h(v – v0)
energy is either emitted or absorbed. hc hc 1 1 
K.E. = − = hc  − 
— The energy difference between two states is l l0  l l0 
given by  Maximum kinetic energy of photoelectrons
DE = E2 – E1 is directly proportional to frequency but
— As the distance of the orbits increases
is independent of intensity of the incident
from the nucleus, the energy gap goes on radiation.
decreasing, i.e.,
E2 – E1 > E3 – E2 > E4 – E3 > ......  Number of photoelectrons ejected per unit area
th per unit time is directly proportional to the
‰ Derivations from Bohr’s Theory (for n orbit)
intensity of the incident radiation.
For hydrogen For H– like
 Each photon can eject only one electron
particles
(provided frequency of the incident radiation is
Energy (En)
−1312 −1312 Z 2 greater than the threshold frequency).
kJ/mol kJ/mol
n2 n2 ‰ The radiation emitted by a black body which is a
perfect absorber and perfect radiator of energy is
2 0.529 n2 called black body radiation.
Radius (rn) 0.529 × n Å Å
Z
‰ Properties like diffraction, interference, refraction
Speed (vn) 2.18 × 10 8
2.18 × 10 8 etc. explain the wave like nature of radiations while
×Z properties like photoelectric effect, black body
n n
cm sec–1
cm sec–1 radiation explain the particle like properties.

chemistry tODAy | JULY ‘15 43

Dual Nature of Matter and de Broglie Relationship Quantum or Wave Mechanical Model of Atom
‰ Every material particle in motion has dual nature ‰ Quantum mechanics developed by Erwin
i.e., particle nature and wave nature and the relation Schrodinger is based on the wave motion associated
between them is called de Broglie relation. with the particles.
 The wavelength of wave associated with such an Schrodinger wave equation :
object is given by
h (Significant only for microscopic ∂2 y ∂2 y ∂2 y 8 p2 m
l= + + + (E − V )y = 0
mv particles) ∂x 2 ∂y 2 ∂z 2 h2
‰ According to Heisenberg’s uncertainty principle, ‰ The wave function y for an electron in an atom
it is impossible to measure simultaneously the has no physical significance as such but y2 gives
position and momentum of a fast moving particle
the intensity of electron wave at that point or the
like electron with absolute accuracy. The product of
probability of finding the electron at that point.
uncertainty in the position (Dx) and uncertainty in
the momentum (Dp) is always constant. ‰ An atomic orbital may be defined as three
h dimensional space around the nucleus where the
Dx × Dp ≥
4p probability of finding an electron is maximum
SELF CHECK (upto 90-95%).

8. Which of the following is the energy of a possible ‰ Variation of y and y2 with r :

1s 2s
excited state of hydrogen?
(a) –3.4 eV (b) +6.8 eV
(c) +13.6 eV (d) –6.8 eV
(JEE Main 2015)
9. The kinetic energy of an electron in the second
Height of graph
Bohr orbit of a hydrogen atom [a0 is Bohr radius] indicates density
2
1s 2
2s
h2 h2 of dots as we Node
(a) (b) move towards
2
4p ma02 16p 2
ma02 the origin
2 2
h h r r
(c) (d)
32p 2
ma02 64p2ma02 Plots of 2 vs. r
(IIT-JEE 2012)
10. Energy of an electron is given by
 Z2  1s 2s
(r) (r)
E = −2.178 × 10−18 J   .
 n2 
Wavelength of light required to excite an electron in + +
an hydrogen atom from level n = 1 to n = 2 will be r – r
Plots of  vs. r
(h = 6.62 × 10–34 J s and c = 3.0 × 108 m s–1)
(a) 8.500 × 10–7 m (b) 1.214 × 10–7 m Quantum Numbers
–7
(c) 2.816 × 10 m (d) 6.500 × 10–7 m ‰ A set of four numbers which gives complete
(JEE Main 2013) information about an electron in an atom.
Quantum number Values Information conveyed
Principal quantum Any integer value i.e. 1, 2, — Main shell of the electron.
number (n) 3, 4 etc. — Approximate distance from the nucleus.
— Energy of shell.
— Maximum number of electrons present in the shell
(2n2).
— Explains the main lines of spectrum.

44 chemistry tODAy | JULY ‘15

 Azimuthal quantum For a particular value of n, — No. of subshells present in the main shell.
number (l) l = 0 to n – 1 — Relative energies of the subshells.
l = 0, s-subshell — Shapes of orbitals.
l = 1, p-subshell — Explains the fine structure of the line spectrum.
l = 2, d-subshell
l = 3, f-subshell
Magnetic quantum For a particular value of l, — No. of orbitals present in any subshell.
number (ml) m = –l to +l including zero. — Explains the splitting of lines in a magnetic field.
Spin quantum number 1 1 — Direction of electron spin (clockwise or anticlockwise).
+ , −
(ms) 2 2 — Explains the magnetic properties of substances.

‰ Aufbau principle : Orbitals are filled in the order chemical Bonding and molecular
of increasing energy. Lower the (n + l) value, lower Structure
is the energy and if two orbitals have same l Introduction l Types of Bonds

(n + l) value, orbital with lower value of n has lower l VSEPR Theory l Valence Bond Theory

energy. l Hybridisation l Resonance

l Molecular Orbital Theory

‰ Pauli’s exclusion principle : An orbital can
accommodate maximum of two electrons and the tipS to rememBer
electrons must have opposite spins. ‰ The phenomenon of union of two or more atoms
‰ Hund’s rule of maximum multiplicity : Pairing involving redistribution of electrons, so that
of electrons does not occur in orbitals of the same each atom involved in bonding acquires stable
energy until each of them is singly filled. configuration in order to gain stability is known as
‰ Exactly half-filled or completely filled electronic chemical bonding.
configurations are extra stable due to symmetrical ‰ The main reason for bonding between atoms is the
distribution and greater exchange energy. tendency to acquire nearest noble gas configuration
and the tendency to acquire minimum energy or
SELF CHECK
maximum stability.
11. The electrons identified by quantum numbers n ‰ Kossel and Lewis proposed that atoms combine so
and l : as to complete their octets or duplet.
(1) n = 4, l = 1 (2) n = 4, l = 0
Types of Bonds
(3) n = 3, l = 2 (4) n = 3, l = 1
can be placed in order of increasing energy as Bond
(a) (4) < (2) < (3) < (1) (b) (2) < (4) < (1) < (3)
(c) (1) < (3) < (2) < (4) (d) (3) < (4) < (2) < (1) Between atoms of Between atoms of
same molecule different molecules
(AIEEE 2012)
KEY POINT
Ionic Covalent Coordinate Metallic
• Lowest limit of Dp⋅Dx i.e., h/4p is rarely attained bond bond bond bond
and usually it is h/2p or even h.
• Number of radial nodes increases with increasing Hydrogen bond van der Waals attractions
value of principal quantum number (n).
‰ Ionic or electrovalent bond : It is the bond formed
• Radial nodes = n – l – 1
by transference of electrons from one atom to
• Angular nodes = l
another so as to complete their octets or duplet.
• Total nodes = n – 1
 Factors affecting the formation of ionic bond :
• For monoelectronic atoms, all the subshells and
— Low ionization enthalpy of metal.
orbitals belonging to same shell, have same energy
— High electron gain enthalpy of non-metal.
and depends on the value of n only.
— High lattice enthalpy of ionic compounds,
• For multielectronic atoms, the energy depends on
for which charge on the ions should be high
both n and l. and size of ions should be small.

chemistry tODAy | JULY ‘15 45