ATOMIC STRUCTURE 2. What are quantum numbers?

Explain each
1. What are the postulates of Bohr’s model of quantum number along with its significance?
hydrogen atom? Discuss the importance of this To describe the electron completely in a multi
model to explain various series of line spectra in electron atom four quantum numbers are required.
hydrogen atom? They are
Postulates of Bohr’s theory: 1. Principal quantum number (n)
1. Electrons revolve around the nucleus in a fixed 2. Azimuthal quantum number (l)
path called orbit. 3. Magnetic quantum number (m)
2. Each orbit contain definite amount of energy. So 4. Spin quantum number (s)
these orbits are known as energy levels. Principal quantum number:
3. As long as the electron revolves in a given orbit, 1. It was proposed by Neils Bohr.
it does not emit or absorb energy. 2. It is denoted by symbol ‘n’.
4. The orbits are designated as 1,2,3,4 .. or K,L,M,N 3. It has the values 1, 2, 3, 4, 5…
5. As the orbit number increases, the size and energy 4. The total no .of electrons are given by 2n2.
of the orbit increases. 5. Significance: It tells about size and energy of the
6. When electrons absorb energy they jump to orbit
higher energy level. When electrons emit energy 2. Azimuthal quantum number:
they jump to lower energy level. 1. It was proposed by Sommerfeld
nh 2. It is denoted by symbol ‘l’
7. Angular momentum of electron is mvr =
2π 3. It has values 0,1, 2, 3, 4, 5…… (n-1)
Hydrogen spectrum: 4. Significance: It tells about shape of the orbital.
1. Hydrogen contains one electron and one proton. S-orbital – Spherical
2. When hydrogne gas absorb 13.56 ev energy the p – orbital – dumb bell
electrons absorb energy and jumps to higher energy d – orbital – double dumb bell
levels. f – orbital – four fold dumb bell
3. But in the exited state, electrons are unstable and 3. Magnetic quantum number:
electrons jumps back to lower energy levels in one 1. It was proposed by Lande.
step or several steps. 2. It is denoted by ‘m’
4. Due to this different spectral lines are formed. 3. It has values –l …..0…….+l
They are (i) Lyman series. (UV region) 4. Significance: It tells about orientation of orbital in
(ii) Balmer series. (Visible region) space.
(iii) Paschen series, Bracket series and Pfund 4. Spin quantum number
series. (IR region) 1. It was proposed by Uhlenbeck & Goudsmith
n=7 2. It is denoted by symbol ‘S’.
n=6 3. It has values +1/2 and –1/2
4. +1/2 indicates clockwise direction and -1/2
n=5 indicates anti clockwise direction.
Pfund (Far IR) 5. Significance: It tells about spin of the electron
n=4
Bracket (IR) 3. Explain the difference between emission and
absorption spectrum.
n=3 Emission spectrum Absorption spectrum
Paschen (Near IR) It is formed when an It is formed when an
electron jumps from electron jumps from
n=2
higher orbit to lower lower orbit to higher
Balmer (visible region)
orbit. orbit.
It is formed due to It is formed due to
n=1 Lyman (UV region) emission of energy. absorption of energy.
It consists of bright lines It consists of dark lines
on a dark background. on a bright background.
It is classified into It is not classified.
continuous and Ex: 1. Nitrogen 1s2 2s2 2p3
discontinuous spectrum. PERIODIC TABLE
1. What is a periodic property? How the
4. Show that the circumference of the Bohr orbit following properties vary in a period and group?
for the hydrogen atom is an integral multiple of Explain a) Atomic radius (b) Ionization energy
the de Broglie wave length associated with the c) Electron affinity d) Electro negativity e)
electron revolving around the orbit? Electro positivity
According to Bohr’s model of atom, the angular Periodic properties: The repetation of properties of
elements gradually with a change in the electronic
configuration. This trend repeats itself at regular
momentum of an electron in an orbit is intervals. This property is called periodicity and the
properties are called periodic properties.
On rearranging the equation …….. (1) Property In groups In periods
Atomic Increases, due Decreases, due to
But according to de Broglie theory …. (2) radius to no. of shells increase of
Substituting (2) in equation (1) increase. nuclear attraction.
2πr = nλ
Electronegati Decreases, due Increases, due to
Therefore the circumference of the orbit is equal to
integral multiple of wave length of electron wave. vity to increase in decrease in
atomic size. atomic size.
5. Write limitations of Bohr’s atomic theory? Electron gain ” “ “ “
Merits: enthalpy or
1. It explains the stability of atom. EA
2. It explains the spectra of hydrogen and hydrogen Ionisation “ “ “ “
like species (He+, Li+2 etc)
3. It explains values of Rydberg’s constant and energy
frequencies of spectral lines. Nature of Basic nature Acidic nature
Demerits: oxides increases due to increases due to
1. It cannot explain spectra of multi electron atoms. increase of increase of non
2. It cannot explain fine spectrum of hydrogen atom. metallic nature. metallic nature.
3. It cannot explain Zeeman and stark effects. Electopositiv Increases, due Decreases, due to
ity (or) to increase in increase of
6. Explain (i) Pauli’s (ii) Auf bau principle
(iii) Hunds’s principles Metallic atomic size. nuclear attraction.
Pauli’s exclusion principle: nature
“No two electrons in an atom can have the same set
of all the four quantum numbers”. 2. Define first and second IE? Why second
Ex: He n l m s ionization energy is greater than first IE? Discuss
1st ele 1 0 0 +1/2 the factors affecting the ionization energy.
He (1s )
2 First IE: The minimum amount of energy required
2nd ele 1 0 0 -1/2 to remove an electron form the outermost shell of
Auf-bau principle: gaseous atom is called first ionization energy.
“In the building up of atoms, the electrons enter the X(g) X+(g) + e–
various orbitals in the increasing order of energies”. Second IE: The minimum amount of energy
Ex: 2s and 2p orbitals. required to remove an electron from the unipositive
The (n+l) rule for 2s is 2+0=2 gaseous ion is called second IE.
The (n+l) rule for 2p is 2+1=3 X+(g) X2+(g) + e–
2s orbital has lower energy than 2p. Units: KJ / mole or Kcal / mole.
Hund’s rule: IE2>IE1: Second ionization energy is greater than
Paring of electrons takes place after all the first ionization energy because the effective nuclear
degenarate orbitals are half-filled with one electron charge is more in unipositive ion than neutral atom.
each. Factors effecting on IE:
Atomic radius: As atomic radius increases, IE The General electronic configuration is (n-2)f1-14 (n-
decreases. This is due to decrease of nuclues 1) d0-1 ns2
attraction. Properties:
1 1. All are metals.
Atomic radius α
IE 2. They show variable oxidation state.
Shielding effect: As shielding effect increases, IE 3. Common oxidation state is +3.
decreases. This is due to decrease of nuclear charge. 4. Give any four characteristic properties of
1 transitions elements.
Shielding effect α Def: The elements in which the last two shells n, n-1
IE
Nuclear charge: As nuclear charge increases IE are incompletely filled are called transition
increases. Due to increase of nucleus attraction. elements.
Nuclear charge α IE General electronic configuration is (n-1) d1-10 ns1-2
Half filled and completely filled orbitals: Properties:
Half filled and completely filled orbitals are more 1. They exhibit variable oxidation states
stable. IE also high for half filled and completely 2. They form coloured ions.
filled orbitals. 3. They form complex compounds.
Ex: IE of N > IE of O 4. They act as good catalysts.
5. They are paramagnetic in nature.
3. Write an essay on s, p, d and f – block 6. They form alloys.
elements.
S-block elements: In these elements last electron 5. What is lanthanide contraction? What are its
enters into s-sublevel is called s-block elements. consequences?
(i) IA, IIA elements are s-block elements. Cerium to Lutetium the 14 elements are called
(ii) The General electronic configuration is ns1-2 lanthanides.
Properties: In lanthanides atomic and ionic radii gradually
1. They are active metals decrease with increase in atomic number. This is
2. They form ionic compounds. lanthanide contraction.
3. They act as good reducing agents. Explanation:
P-block elements: In these elements last electron In lanthanides, the last electron enters the 4f sub
enters into p-sublevel is known as p-block elements. level. Due to poor shielding effect and dispersed
IIIA to VIIIA group elements are p-block elements. shape of 4f orbitals atomic and ionic sizes decreases.
The General electronic configuration is ns2 np1-6 Consequences:
Properties: 1. Hardness, Bp and Mp values increase in
1. They form ionic and covalent compounds. lanthanides.
2. They show variable oxidation states. 2. The atomic and ionic radii of 5d series elements
d-block elements: are very close to 4d series elements.
In these elements last electron enters into d-sublevel Ex: Zr – Hf , Nb – Ta, Mo – W.
is known as d-block elements.
(i) IIIB to VIIB, VIII, IB & IIB group elements are
d-block elements.
(ii) The General electronic configuration is (n-1)d1-10
ns1-2
Properties:
1. They form coloured compounds
2. They form complex ions
3. They act as catalysts.
4. The common oxidation state is +2
5. They show variable oxidation states.
f-block elements:
In these elements last electron enters into f-sublevel
is known as f-block elements.
Lanthanides & Actinides are f-block elements.
 CHEMICAL BONDING 2. What are the main features of VSEPR theory?
1. Define hybridistion? Explain Sp, Sp2, Sp3 VSEPR theory was proposed by Sidgwick and
hybridisation with examples. Powell. Later it was extended by Gillespie and
Hybridisation: Intermixing of orbitals of nearly Nyholm.
equal energies of an atom to give the same number 1. The shape of the molecule is depends on the no.
of identical hybrid orbitals is called hybridisation. of electron pairs around the central atom.
Sp-hybridisation: Intermixing of one S-orbital and 2. Lone pair electrons occupy more space than bond
one P-orbital to form 2 Sp-hybrid orbitals is called pair electrons.
Sp-hybridisation. 3. Lone pair electrons cause more repulsions than
Ex: BeCl2, C2H2, CO2. bond pair repulsions.
Formation of Beryllium Dichloride (BeCl2): 4. The order of repulsions
1. In BeCl2 the central atom is Beryllium. Lone pair-lone pair > lone pair- bond pair > bond
2. The excited electronic configuration of Be is 1s2 pair – bond pair.
2s1 2px1 2py0 2pz0 5. If there are both Bond pairs and lone pairs the
3. The 2s, 2px orbitals of Beryllium undergoes shape of molecule is distorted shape and deviation in
hybridization to form 2SP hybrid orbitals. bond angle.
4. These hybrid orbitals overlap with two Chlorine 6. Triple bonds cause more repulsions than double
atoms to form BeCl2 molecule. bonds. Double bonds cause more repulsions than
5. Shape of the molecule is single bond
Linear. Bond angle is 1800.
Bond pairs Shape of the Example
Sp2-hybridisation: Intermixing of one S-orbital and molecule
two P-orbital to form 3 Sp2-hybrid orbitals is called
Sp2-hybridisation. Two Linear BeCl2
Ex: BCl3, BF3, SO2 etc. Three Trigonal planar BCl3, BF3
Formation of Boron trichloride (BCl3): Four Tetrahedral CH4
1. In BCl3 the central atom is Boron. Five Trigonal bipyramidal PCl5
2. The excited electronic configuration of boron is Six Octahedral SF6
1s2 2s1 2px1 2py1 2pz0
3. Now boron undergoes hybridization to form 3 SP2 3. Explain the hybridization involved in PCl5
hybrid orbitals. molecule.
4. These hybrid orbitals overlap 1. In PCl5 molecule Phosphorus is central atom.
with Chlorine atoms to form BCl3 2. The excited electronic configuration of P is [Ne]
molecule.
3s13 p1x 3 p 1y 3 p1z 3 d1z 2
5. Shape of the molecule is
trigonal planar. The bond angle is 1200. 3. Now phosphorus undergoes hybridisation and
forms 5 sp3d hybrid orbitals.
Sp3-Hybridisation: Intermixing of one S-orbital 4. These hybrid orbitals react with
and three P-orbitals to form 4 Sp3-hybrid orbitals is Chlorine atoms to form PCl5
called Sp3-hybridisation. molecule.
Ex: CH4, C2H6, NH3, H2O etc. 5. Shape of molecule is Trigonal
Formation of methane (CH4) molecule: bipyramidal. Bond angle is 900 and
1. In CH4 Central atom is Carbon. 1200.
2. The excited electronic configuration of carbon is
1s2 2s1 2px1 2py1 2pz1. 4. Even though nitrogen in Ammonia is in sp3
3. Carbon undergoes hybridisation to form 4SP3- hybridization, the bond angle is not 109028’
hybrid orbitals. explain.
4. These hybrid orbitals overlap  In ammonia (NH3), nitrogen undergoes sp3
with H-atoms to form 4 sigma hybridisation. The expected shape is tetrahedral
bonds. and bond angle is 109028’.
5. Shape of the molecule is  But observed shape is pyramidal and bond angle is
Tetrahedral. Bond angle is 109028l. 107.50. This is due to repulsions between lp-bp
repulsions.
5. Explain the hybridisation involved in SF6 Hydrogen bond formed between the same or
molecule. different molecules is called inter molecular
1. In SF6 molecule sulphur is central atom. hydrogen bond.
2. The 2nd excited electronic configuration of sulphur Ex: H2O, NH3, HF, etc.
is [Ne]3s13 p1x 3 p 1y 3 p1z 3 d1z 2 3 1x 2− y 2
3. Now sulphur undergoes hybridisation to
forms 6 sp3d2 hybrid orbitals. 2) Intra molecular hydrogen bond:
4. These hybrid orbitals react with fluorine A hydrogen bond formed between atoms of same
atom to form SF6 molecule. molecule is called intra molecular hydrogen bond.
5. Shape of molecule is Octahedron. Bond Ex: Salicylaldehyde, Salicilic acid etc.
angle is 900 and 1800.
9. Explain the formation of coordinate covalent
6. Explain Fajan’s rules and give suitable bond with examples.
examples. Def: It is a special type of covalent bond in which
1. Covalent character increases with increasing in the bond pair of electrons is contributed by one of
size of anion. the two bonded atoms.
Ex: KI is more covalent than KF It is represented by
2. Covalent character increases with decrease in size Formation of Ammonium ion (NH4+): In NH3,
of cation. nitrogen has one lone pair electron. It donates the
Ex: LiF is more covalent than KF. lone pair to H+ ion form a co-ordinate covalent
3. Covalent character increases with increasing bond.
charge on anion or cation. NH3 + H+ [H3N H]+ = NH4+
Ex: SnCl4 is more covalent than SnCl2. Formation of Hydronium ion (H3O+):
4. Covalent character increases with cation having In H2O, oxygen has lone pair electrons. It donates
pseudo inert gas configuration. the lone pair to H+ ion form a co-ordinate covalent
bond.
7. Define Dipole moment. Write its applications. H2O + H+ [H2O H]+ = H3O+
Def: The product of charge on one of the two
bonded atoms and the distance between two poles is
called dipole moment.
It is represented with
μ=exd STATES OF MATTER
e = Charge on the bonded atom 1. Give the important postulates of kinetic
d = distance b/w two charges molecular theory of gases.
Dipole moment is expressed in Debye (D) units. 1. Gases contain large number of tiny particles
1 Debye = 10–18 esu – cm called molecules.
Applications: 2. The molecules move randomly in all directions
1. Shape of the molecule can be predicted. with high speed.
2. Cis and trans isomers can be separated. 3. There is no attractive or repulsive forces between
3. Percentage of ionic character can be determined. gas molecules.
μ obs 4. All collisions are perfectly elastic.
% ionic = x 100 5. Molecular motions are unaffected by gravity.
μ cal
6. The average kinetic energy of a gas is directly
proportional to the absolute temp.
8. What is hydrogen bond? Explain the types of
Average K.E ∞ T
hydrogen bonds with examples
Def: The weak electrostatic force of attraction
2. State and explain Graham’s law of diffusion.
present between hydrogen and high electronegative
Write its applications.
element of the same molecule or different molecules
Statement: At constant temp and pressure the rate
is called hydrogen bond.
of diffusion of a gas is inversely proportional to the
It is represented by dotted lines (………).
square root of its density or molecular weight or
Hydrogen bond is two types
vapour density.
1) Inter molecular hydrogen bond:
 1 2
rα PV = x KT (KE = KT)
√d 3
Consider r1 and r2 are rates of diffusion of two gases 2 KT
and d1 and d2 are its densities. V= x
3 P
constant
V=
P
1
Vα
P
This is boyles law.
Charles’s law:
1
Applications: Kinetic gas equation is PV = mnc2
3
1. It is used to compare the rates of diffusion of two 2 1
gases. PV = x mnc2
3 2
2. Marsh gas alarm used in coalmines works on this 2 1
principle. PV = x KE (KE = mnc2)
3 2
3. It is used to separate the isotopes.
2
PV = x KT (KE = KT)
3. State and explain Dalton’s law of partial 3
pressure. 2 KT
V= x
Statement: At constant T and V, the total pressure 3 P
exerted by a mixture of non reacting gases is equal V = constant x T
to the sum of partial pressures of the all component VαT
gases. This is Charles law.
P = P1 + P2 + P3 + ------- Kinetic energy:
Let P1, P2, P3 are the pressures of three gases and n1, 1
Kinetic gas equation is PV = mnc2
n2, n3 are the no. of moles of the gases respectively. 3
PV = nRT 2 1
nRT PV = x mnc2
P= 3 2
V 2 1
n1 RT n2 RT n3 RT PV = x KE (KE = mnc2)
P1 = P2 = P3 = 3 2
V V V 3
According to Dalton’s law KE = x PV
2
n RT n RT n RT
P= 1 + 2 + 3 3
V V V KE = x RT
2
P= ( )RT
V
(n1 + n2 + n3) For ‘n’ moles
3
nRT KE = x nRT
P= 2
V Graham’s law:
Partial pressure = molefraction x total pressure 1
Kinetic gas equation is PV = mnc2
3
4. Deduce (a) Boyle’s law (b) Charle’s law (c)
If a gas contains Avogadro no. of molecules mn = M
Graham’s law (d) Kinetic energy from kinetic 1
gas equation. PV = Mc2
3
Boyle’s law:
3 PV
1 C2 =
Kinetic gas equation is PV = mnc2 M
3
2 1
PV = x mnc2
3 2
C=
√ 3 PV
M
2
PV = x KE
3
1
(KE = mnc2)
2
C=
√ 3P
d
 constant From Charles law V α T ------- (2)
C=
√d From Avogadro’ law V α n -------- (3)
1 1
Cα (c = r = velocity) From equations 1, 2 and 3, V α Tn
P
√d RTn
1 V=
rα P
√d PV = nRT
This is Graham’s law R = Universal gas constant
R = 0.0821 lit atm K–1 mole–1
Dalton’s law: R = 8.314 J K–1 mole–1
1
Kinetic gas equation is PV = mnc2
3 7. Write Vanderwaal’s equation.
2
1 m1 n1 C 1 The Vanderwaal’s equation is
Consider two gases, for 1st gas P1 =

For 2nd gas P2 =

1 m2 n2 C22
3 V
( )
a n2
P+ 2 (V – nb) = nRT
V
3 V  ‘a’ and ‘b’ are Vanderwaal’s parameters
Suppose that the two gases are taken in same vessel,  ‘a’ indicates attractive forces between the
the total pressure of the mixture will be sum of molecules. A gas with higher value of ‘a’ can be
easily liquefied.
partial pressures.
 ‘b’ indicates the size of the gas molecule. Greater
1 m1 n1 C21 1 m 2 n2 C22 the value of ‘b’ larger the size and smaller is
PT = +
3 V 3 V compressible.
PT = P1 + P2
This is Dalton’s law.

5. Define (a) RMS velocity (b) average velocity (c)

most probable velocity of a gas molecules. Give
their interrelation ship.
a) RMS velocity: The square root of mean of
squares of velocities of all molecules present in the
gas is called RMS velocity
Urms =
√3 RT
M
b) Average velocity: The ratio of sum of the
velocities of gas molecules to the total number of
molecules is called average velocity.
Uav =
√
8 RT
πM

c) Most probable velocity: The velocity possessed

by the maximum number of molecules in the gas is
called most probable velocity.
Ump =
√
2 RT
M

Inter relationship:
Ump : Uav : Urms = 1 : 1.128 : 1.224

6. Derive ideal gas equation.

From Boyle’s law V α 1/p ------(1)