Easy study material for 10+2 AP chemistry students. Specially prepared for Intermediate Public Examination, Andhra Pradesh.

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Easy study material for 10+2 AP chemistry students. Specially prepared for Intermediate Public Examination, Andhra Pradesh.

Attribution Non-Commercial (BY-NC)

- Analytical Chemistry Questions
- Electrochemistry
- IUPAC Nomenclature Exercises in Organic Chemistry
- Solutions & Colligative Properties IPE
- ATOMIC STRUCTURE STUDY MATERIAL & ASSIGNMENT
- Exercise in Organic Chem
- Electrochemistry IPE
- Solved Problems in Advanced Organic Synthesis CSIR NET
- Atomic Structure Exercises by Resonance
- Metallurgy IIT
- Chemical Bonding IPE
- Periodic Table IPE
- Solid State Chemistry IPE
- Chemical Thermodynamics IIT Part 2
- Transition Elements IPE
- Atomic Structure IIT
- IIT Class XI Chem Structure of Atoms
- Detailed Solution Csir Net Dec 2015 Final
- Solid State Chemistry IIT
- jee p-block elements

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Aditya vardhan

Atomic structure 1 adichemadi @ gmail.com

ATOMIC STRUCTURE

INTRODUCTION

Atom:- The smallest particle which can take part in a chemical reaction with out losing its identity is known

as atom.

Subatomic particles: Electrons, protons and neutrons are known as subatomic particles.

Electron:- The negatively charged fundamental particle present in an atom with negligible mass is called

electron.

The mass of an electron is 1/1836 of mass of proton or hydrogen atom. In atomic mass units it is equal

to 0.000548 amu or 9.1095 X 10-31kg. Its charge is 1.6022 X 10-19coulomb.

Discovery of Electron : -

Sir William Crookes designed a cathode ray discharge tube in which cathode rays are observed only

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at very low pressures and very high voltages. These rays consist of negatively charged particles called

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electrons.

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To vacuum pump

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by

Cathode - LL + Anode

ed

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Pr

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High voltage

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1) Cathode rays are not visible but their behavior can be observed with the help of a fluorescent or a

phosphorescent.

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V.

3) These rays travel in straight lines in the absence of electric and magnetic fields.

4) But these rays deflect like negatively charged particles in electric and magnetic fields. Hence the rays

constitute negatively charged particles and are known as electrons.

5) These rays are independent of the nature of the cathode material and nature of the gas present in the

cathode ray tube.

These facts conclude that electrons are the negatively charged fundamental particles present in all the

substances.

Charge to mass ratio of Electron (e/me) : - Charge to mass ratio of electron is calculated by J.J.

Thomson as follows.

e

1.75882 x 1011 C kg 1

me

Charge on the Electron :- The charge on the electron was calculated by Millikan in oil drop experiment

as 1.60 x 10-19 coulombs.

The mass of the electron can be derived as follows.

e

me 9.1094 x 10-31 kg

e / me

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Proton:- The positively charged fundamental particle present in the atom is called proton.

The mass of a proton is 1.007277 amu or 1.67252 X 10-27 kg. Its charge is same as that of electron.

Discovery of proton : -

Protons are discovered in canal ray experiment. These rays are produced in modified cathode ray

tube.

1) Canal rays constitute positively charged particles. The characteristics of these rays depend on the nature

of gas present in the cathode ray tube

2. The e/m ratio of the particles depend on the nature of gas taken.

3. Some of the positively charged particles carry a multiple of the fundamental unit of electrical charge.

4. The behavior of these particles in the magnetic or electric field is opposite to that observed for electron.

5. When hydrogen gas is used in the discharge tube, the positively charged particles emitted are found to

possess mass of 1 amu and these are called protons.

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Neutron:- The neutral fundamental particle present in the atom is called neutron.

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The mass of a neutron is 1.00898 amu or 1.67495 X 10-27kg. It has no charge.

Discovery of neutrons: Chadwick discovered neutrons by bombarding a thin layer of Be with par-

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ticles.

RD

EG

by

Relative LL

ed

charge

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Pr

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Atomic number (Z):-The number of protons or the number of electrons in an atom is called atomic

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Moseley discovered a simple relation between the frequencies of the characteristic X-rays of an

element and its atomic number.

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v = a(Z-b)

V.

= frequency of X-rays

Z = atomic number

a,b are constants which are characteristic of elements

Mass number(A):- The total number of protons and neutrons in an atom is called mass number. It is

denoted by 'A'.

A = no. of protons + no. of neutrons

A = Z + no. of neutrons

no. of neutrons = A - Z

Isotope:- Isotopes are the atoms of an element with same atomic number but differ in their mass numbers

i.e., The isotopes of an element have same number of protons but differ in the number of neutrons.

eg., Hydrogen has three isotopes - Hydrogen(1H1), Deuterium (1H2) and Tritium (1H3). They have same

number of protons (one) but the numbers of neutrons are 1,2 and 3 respectively.

Isobars :- The atoms of different elements with same mass number but different atomic numbers are called

“Isobars”.

Eg., 6C14, 7N14

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Atomic weight:- The atomic weight of an element is the average weight of all the isotopes of that element.

Note:- Atomic number is a whole number but Atomic weight may be a fractional number.

ATOMIC MODELS

J.J.Thomson’s model:

According to this model, an atom has a spherical shape in which the positive charge is uniformly

distributed. The electrons are embedded into it in such a manner as to give the most stable electrostatic

arrangement.

Experiment:

A narrow beam of - particles is passed through a thin gold foil which is surrounded by circular

screen made up of fluorescent zinc sulphide. Whenever - particles strike the screen, a tiny flash of

light was produced at that point.

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Gold foil

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EG

by

LL

ed

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AN IOR

Pr

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Photographic plate

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J

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Observations:

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2) A small fraction of the - particles were deflected by small angles.

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V.

Conclusions:

1. Most of the space in the atom is empty.

2. The positive charge in the atom is concentrated in the small dense portion called the nucleus.

3. Electrons revolve around the nucleus in circular paths called orbits. It resembles the solar

system.

4. Electrons and the nucleus are held together by electrostatic forces of attraction.

Drawbacks:

1) Rutherford’s model could not explain the stability of atom. According to electromagnetic theory,

the charged particle under acceleration should continuously emit radiation. Hence the electron moving in

the orbits must lose energy and fall into the nucleus. But this is not happening.

2) This model could not explain the electronic structure and energy of electrons.

3) It could not explain the atomic spectra.

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NATURE OF LIGHT

Light is considered as an electromagnetic radiation. An electromagnetic radiation consists of two

components i.e., Electric component and Magnetic component which are perpendicular to each other as

well as to the direction of path of radiation. The electromagnetic radiations are produced by the vibrations

of a charged particle.

wavelength

E amplitude of electric field

M amplitude of magnetic field

The properties of light can be explained by considering it as either wave or particle as follows.

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HA

WAVE NATURE OF LIGHT

By considering light as wave, following properties can be defined for it.

Wavelength: The distance between two successive similar points on a wave is called as wavelength. It is

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by

denoted by .

Units: cm, Angstroms(Ao), nano meters(nm), milli microns(mµ) etc.,

LL

ed

1 Ao = 10-8 cm.

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Frequency: The number of vibrations done by a particle in unit time is called frequency. It is denoted by

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' '.

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Velocity: Velocity is defined as the distance covered by the wave in unit time. It is denoted by 'c'.

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Note: For all types of electromagnetic radiations, velocity is a constant value.

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The relation between velocity, wavelength and frequency can be given by following equation.

V.

c

Wave number: The number of waves spread in a length of one centimeter is called wave number. It is

denoted by

1

units: cm , m-1

-1

Amplitude: The distance from the midline to the peak or the trough is called amplitude of the wave. It is

usually denoted by 'A' (a variable).

Amplitude is a measure of the intensity or brightness of light radiation.

Problems

1) The wave length of a radiation emitted by a sodium lamp is 300 nm. Find its frequency.

2) The frequency of an electromagnetic radiation is 300 Hz. Calculate its wave length.

3) The wave number of a radiation is 9000 cm-1. Calculate its frequency.

4) Calculate the wave number of the yellow light of wave length 600 m emitted from sodium lamp.

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Though most of the properties of light can be understood by considering it as a wave, some of the

properties of light can only be explained by using particle (corpuscular) nature of it. Newton considered

light to possess particle nature. In the year 1900, in order to explain black body radiations, Max Planck

proposed Quantum theory by considering light to possess particle nature.

Black body:- The object which absorbs and emits the radiation of energy completely is called a black

body.

Practically it is not possible to construct a perfect black body. But a hollow metallic sphere coated

inside with platinum black with a small aperture in its wall can act as a near black body.

When the black body is heated to high temperatures, it emits radiations of different wavelengths.

Following curves are obtained when the intensity of radiations are plotted against the wavelengths, at

different temperatures.

N

HA

E

RD classical theory

EG

by

7000 K

LL

ed

VA

intensity

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G C

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AN IOR

Pr

YA

5000 K

AR N

W U J

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wavelength

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VA

V.

1. At a given temperature, the intensity of radiation increases with wavelength and reaches a maximum

value and then starts decreasing.

2. With increase in temperature, the wavelength of maximum intensity ( max ) shifts towards lower wave-

lengths.

According to classical physics, energy should be emitted continuously and the intensity should in-

crease with increase in temperature. The curves should be as shown by dotted line.

In order to explain above experimental observations Max Planck proposed following theory.

1. Energy is emitted due to vibrations of charged particles in the black body.

2. The radiation of energy is emitted or absorbed discontinuously in the form of small discrete energy

packets called quanta.

3. Each quantum is associated with definite amount of energy which is given by the equation E=h

Where

h = planck's constant

= 6.625 x 10-34 J.sec

= 6.625 x10-27 erg.sec

= frequency of radiation

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4. The total energy of radiation is quantized i.e., the total energy is an integral multiple of h . It can only

have the values of 1 h or 2 h or 3 h . It cannot be the fractional multiple of h .

5. Energy is emitted and absorbed in the form of quanta but propagated in the form of waves.

Einstein generalized the quantum theory by applying it to all types of electromagnetic radiations. He

explained photoelectric effect using this theory.

Photoelectric Effect:- The ejection of electrons from the surface of a metal, when the metal is exposed to

light of certain minimum frequency, is called photoelectric effect.

The frequency of light should be equal or greater than a certain minimum value characteristic of the

metal. This is called threshold frequency.

Photoelectric effect cannot be explained by considering the light as wave.

Einstein explained photoelectric effect by applying quantum theory as follows,

1. All electromagnetic radiations consists of small discrete energy packets called photons. These photons

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are associated with definite amount of energy given by the equation E=h .

2. Energy is emitted, absorbed as well as propagated in the form of photons only.

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3. The electron is ejected from the metal, when a photon of sufficient energy strikes the electron.

When a photon strikes the electron, some part of the energy of photon is used to free the electron

E

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from the attractive forces in the metal and the remaining part is converted into kinetic energy.

EG

by

h = W + K.E

LL

ed

where

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AL O

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G C

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AN IOR

Pr

YA

Problems

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1) Calculate the energy of one photon of radiation whose frequency is 3x1012 Hz.

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2) The energy of a electro magnetic radiation is 6.625x10-19 J Calculate The Wavelength of radiation.

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SPECTRA

When electromagnetic radiation is passed through a prism or grating it is splitted and forms a collec-

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V.

Spectra can be divided into two types viz., emission and absorption spectra as given below.

1) These are obtained due to emission of radiation These are obtained when substance absorb the

from the substances. radiation.

2) White lines are formed on the black back ground. Black lines are formed on the white back ground.

3)These are formed when atoms or molecules are de-These are formed when atoms or molecules are

excited from higher energy level to lower energy excited from lower energy level to higher energy

level. levels.

Spectra can also be divided into line and band spectra as given below.

1) It consists of sharp and well defined It consists of closely spaced lines

lines. called bands.

2) Characteristic of atoms Characteristic of molecules.

3) Formed due to the excitation and de- Formed due to the vibrations and

excitation of electrons in the atoms. rotations of atoms in molecules.

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HYDROGEN ATOMIC SPECTRUM

A bright light is emitted when a high potential is applied to hydrogen gas at low pressure in a discharge

tube. This bright light is dispersed and forms a spectrum upon passing through a prism or grating. The

spectrum consists of separate lines corresponding to different wavelengths. This is called Hydrogen atomic

spectrum.

The spectral lines are formed due to electronic transitions from one energy level to another. These

lines are divided into five series according to the range of wavelengths as follows.

1. Lyman series Ultra-violet 1 2,3,4,5,6,7,_ _ _ _

2. Balmer series Visible 2 3,4,5,6,7,_ _ _ _

3. Paschen series near infra-red 3 4,5,6,7,_ _ _ _

4. Brackett series infra-red 4 5,6,7,_ _ _ _

5. Pfund series far infra-red 5 6,7,_ _ _ _

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n1and n2 are the principal quantum numbers of the energy levels.

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The wave numbers of spectral lines in each series can be calculated using Rydberg's equation as follows.

RD

EG

by

1 1

LL

ed

RH Z 2 2 - 2

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n1 n2

AL O

ar

G C

ep

where

AN IOR

Pr

n1and n2 are the principal quantum numbers of orbits corresponding to electronic transition.

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AR N

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Z = atomic number

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n=7

n=6

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n=5

Pfund

V.

n=4

Brackette

n=3

Paschen

n=2

Balmer

n=1

Lyman

Note: Every element has its own characteristic line spectrum. There is regularity in the line spectrum of each

element. Hydrogen has the simplest line spectrum among all the elements. The line spectra become com-

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Atomic structure 8 adichemadi @ gmail.com

plex with increase in atomic number of the element.

Problems

1) An electronic transition from n=3 to n=1 shell takes place in a hydrogen atom. Find the wave number

and the wave length of radiation emitted. [Given R=1,09,677 cm-1]

In order to explain the Hydrogen atomic spectrum, Bohr proposed following atomic model based on

quantum theory.

1. The electrons in an atom revolve around the nucleus in definite closed circular paths called orbits (energy

levels or states or shells).

2. The orbits are represented by principal quantum number 'n'. These are numbered 1,2,3,4 _ _ _ (or

K,L,M,N,_ _ _) from the nucleus.

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3. The energy of an electron in a particular orbit is constant and the electron neither emits nor absorbs

energy as long as it revolves in the orbits. Hence these orbits are called stationary orbits.

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n=3

E

n=2

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n=1

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Nucleus

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AN IOR

Pr

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nh

angular momentum = mvr =

VA

2

V.

Where

m = mass of an electron

v = velocity of an electron

r = radius of orbit

h = Planck's constant

= 6.625 X 10-34 J.sec

= 6.625 X 10-27 erg.sec

n = principal quantum number which can have only positive integer values(1,2,3,4 _ _ _).

The electron revolves only in those orbitals where the angular momentum of it is the integral multiple

h h h h

of i.e, 1 or 2 or 3 ___

2 2 2 2

5. Each orbit is associated with definite amount of energy and radius. The energy of the orbit (and of

electron in it) increases with increase in the radius of the orbit. Thus farther the orbit from nucleus greater is

the energy.

6. The energy of an electron changes when it moves from one energy level to another.

Energy is absorbed when the electron jumps from lower orbit to higher orbit. Whereas energy is

emitted when the electron jumps from higher orbit to lower orbit.

The energy absorbed or emitted during electronic transitions between two orbits is equal to the

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energy difference between these orbits. It is given by

E = E2 - E1

The energy released in the form of radiation will appear as a spectral line in the atomic spectrum.

Radius of Orbit

In hydrogen atom, there is one proton in the nucleus, and an electron revolving around the nucleus in

a circular orbit of radius 'r'. Let

the charge on proton = +e

the charge on electron = -e.

Centrifugal force

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-e

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r

+e

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by

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The attraction between the nucleus and electron acts centripetally towards the nucleus. As per

G C

ep

Coulomb's law,

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Pr

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e 2

AR N

force of attraction =

r2

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There is also centrifugal force acting away from the nucleus due to the revolving of electron in the

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orbit.

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mv 2

centrifugal force =

r

VA

where

V.

m = mass of electron,

v = velocity of electron

During the orbiting of electron in a stationary orbit, these two forces must be equal.

e 2 mv 2

i.e., 2 =

r r

e2

or mv 2 --------- 1

r

According to Bohr's theory, Angular momentum of electron in an orbit is given by

nh

mvr

2

nh

or v

2 mr

n2h2

or v2

4 2 m 2 r 2

By substituting the value of v2 in equation-1

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e2 mn 2 h 2

2 2 2

r 4 m r

n2h2

or r ------------- 2

4 2 me 2

By substituting the values of

planck's constant = h = 6.625 x 10-27erg.sec

mass of electron = m = 9.1 x 10-28 g

charge on electron = e = 4.802 x 10-10 e.s.u

radius of nth orbit = r = 0.529 x 10-8 x n2 cm

Energy of Electron

The total energy of electron is equal to the sum of Kinetic and Potential energies.

i.e., Total Energy (T.E) = Kinetic Energy (K.E) + Potential Energy (P.E)

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1 1 e2 e2

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where K.E = mv 2 (since mv 2 from equation 1)

2 2 r r

e2

E

and P.E =

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by

r

LL

ed

e2 e2

VA

AL O

Hence T .E

ar

2r r

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AN IOR

Pr

e2

YA

T .E

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2r

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2 2 me 4

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T .E 2 2

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nh

By substituting the values of constants, the energy of electron (En) in the nth orbit can be written as

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V.

21.7 x10-12

En erg per atom

n2

21.7 x10-19

Joule per atom

n2

21.7 x10-22

kJ per atom

n2

Bohr could successfully explain the hydrogen atomic spectrum using his postulates as given below.

The energy of an electron in hydrogen atom is given by

2 2 me 4 1

En . 2 (1)

h2 n

2 2 me 4 1

Therefore E1 . 2

h2 n1

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2 2 me 4 1

E2 . 2

h2 n2

2 2 me 4 1 2 2 me 4 1

And E2 E1 . 2 . 2

h2 n2 h2 n1

2 2 me 4 1 1

Therefore E2 E1 2 2 (2)

h2 n1 n2

According to Bohr’s postulates,

E2 E1 h

But c

Therefore E2 E1 hc

2 2 me4 1

N

1

Hence 2 2 2 hc

h n1 n2

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1 2 2 me 4 1 1

2 2 (3)

E

or ch3 n1 n2

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EG

by

ed

VA

AL O

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1 1 1

G C

RH 2 2

ep

n1 n2

AN IOR

Pr

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AR N

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2π 2 me 4

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Where RH is equal to and its value can be determined by substituting the following values.

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ch 3

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= 3.14, c = 3 x 1010 cm, h = 6.626 x 10-27 erg. sec

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V.

2π 2me4

RH = 3

1,09,681cm 1

ch

Above value is almost equal to Rydberg’s constant (RH = 1,09,677 cm-1). The frequencies of spectral

lines in hydrogen atomic spectrum can also be determined by using Bohr’s theory.

Merits

1. This theory successfully explained the spectra of mono-electronic species like Hydrogen, He+, Li2+, Be3+

etc., .

2. Bohr successfully calculated the frequencies of spectral lines, radii and energies of orbits which are in

excellent agreement with experimental results.

Demerits (defects)

1. Bohr's atomic model is a flat model. But atoms are spherical.

2. This theory could not explain the spectra of atoms containing multi-electrons.

3. It was shown later on that the each spectral line in hydrogen atomic spectrum was actually closely

spaced group of fine lines. These fine lines were revealed when the spectrum was taken on high resolution

spectrometer in later years. Bohr could not explain this fine spectrum.

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4. Splitting of spectral lines when the atoms are placed in strong magnetic field is called Zeeman effect.

Splitting of spectral lines when the atoms are placed in strong electric field is called Stark effect.

Bohr could not account for these effects.

5. According to Heisenberg's uncertainty principle, it is not possible to calculate the velocity and position of

an electron accurately and simultaneously. But Bohr calculated them. This is a contradiction.

6. According to De Broglie's wave concept, electron has wave nature. But Bohr's theory considered

electron as a particle.

QUANTUM NUMBERS

Quantum numbers are the numbers used to describe the position and energy of an electron in an

atom. There are four types of quantum numbers.

ii) Azimuthal quantum number

iii) Magnetic quantum number

N

iv) Spin quantum number

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Principal quantum number (n)

1. Principal quantum number was proposed by Bohr to explain the hydrogen atomic spectrum

E

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EG

by

3. It is denoted by 'n'. It can have positive integral values from 1,2,3,4,_ _ _ (or K,L,M,N_ _ _ ).

LL

ed

4. It also describes the energy and size of the orbit. The energy and the size of orbit increases with increase

VA

AL O

ar

in 'n' value.

G C

ep

5. The maximum number of electrons that can be accommodated in a given shell is equal to 2n2 .

AN IOR

Pr

YA

AR N

W U J

1. Azimuthal quantum number was proposed by Sommerfield in order to explain the fine hydrogen atomic

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spectrum.

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3. The number of sub-levels in a given main energy level is equal to the principal quantum number 'n'. These

sub-levels are indicated by azimuthal quantum number 'l' which can have values from 0 to n-1.

VA

V.

For ex: In an orbit of principal quantum number n=3, there are three sublevels denoted by l =0,1 and 2.

4. Azimuthal quantum number also describes the angular momentum of electron and shape of orbitals

present in that sublevel.

For ex:

l = 0 (s)--- spherical

l = 1 (p)--- dumbbell

l = 2 (d)--- double dumbbell

1. Magnetic quantum number was proposed by Lande in order to explain the Zeeman and Stark effects.

The splitting of spectral lines in strong magnetic field is called Zeeman effect and splitting in strong

electric field is called Stark effect.

3. The number of orientations possible for orbitals in a given sublevel 'l' is equal to the (2l+1) and can have

values from -l_ _ _ 0 _ _ _+l.

For ex: The number of orientations (m values) possible for a sublevel l=2 is (2X2)+1 = 5 and the values of

m = -2,-1,0,+1 and +2.

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(n) (l) (m)

n=1 l=0 m=0

n=2 l = 0,1 m = -1,0,+1

n=3 l = 0,1,2 m = -2,-1,0,+1,+2

1. It was proposed by Goudsmit and Uhlenbeck to explain the double line structure of alkali metal spectra.

2. Spin quantum number denotes the spin of the electron on its own axis. It is denoted by 's'. It can have

only two values(+½ and -½).

3. The clockwise spin is indicated by +½ or upwards arrow( ) and anti-clockwise spin by -½ or down-

wards arrow( ).

N

1. Prinicipal quantum number (n) 1,2,3,4_ _ _ _ _ Denotes the size and energy

HA

of orbit.

2. Azimuthal quantum number (l) 0 to n-1 Denotes the sub-level and

E

RD shapes of orbitals in that sub-

EG

by

LL momentum of electron.

ed

VA

AL O

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orientation of orbital.

G C

ep

AN IOR

4. Spin quantum bumber (s) +1/2 or -1/2 Denotes the spin of electron.

Pr

YA

AR N

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Problems

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1) What is the shape of orbital if the quantum numbers for the electron in it are n = 3, l = 2, m = -1, and

I

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s = +1/2

AD

a) n = 3, l = 2, m = -2, s = +1/2

VA

b) n = 2, l = 2, m = -1, s = +1/2

V.

c) n = 4, l = 3, m = 0, s = +1/2

d) n = 3, l = 1, m = -2, s = +1/2

3) How many electrons in an atom may have the quantum numbers, n = 3 and ms= -1/2 ?

4) How many sub-shells, orbitals and electrons are present in n = 3 main shell?

According to de Broglie, every particle in motion is associated with wave nature. The wavelength

( ) of every particle wave can be expressed by the following equation.

h h

(or)

p mv

where

h = Planck's constant

m = mass of the particle

v = velocity of the particle

p = mv = momentum of the particle

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Derivation

According to Einstein, mass and energy equivalence can be expressed as

E = mc2

According to Planck's quantum theory,

E h

Hence

mc 2 h ------------ 1

But

c

or

c

By substituting the value in the 1st equation

N

hc

mc 2

HA

or

E

h h

RD

EG

by

(or)

mc p

LL

ed

where

VA

AL O

ar

p = momentum of a photon

G C

ep

de Broglie proposed that above equation is applicable to every particle in motion and above equation

AN IOR

Pr

can be written as

YA

AR N

h h

W U

J

mv p

AG T

VI

I

The wavelengths of macro bodies like cricket ball or stones are very small as their masses are large

DE

AD

and hence can be ignored. But for micro particles like electrons, the wavelengths are considerable.

VA

V.

revolve around the nucleus in a circular orbit. In order to behave as a stationary and non-energy radiating

wave, the electron wave must be in phase i.e., the two ends of the wave must meet at one place and there

should be constructive interference of crests and troughs.

inter ference destructive inter ference

To satisfy this condition, the circumference(2 r) of the orbit must be equal to the integral multiple of

the wavelength( ) of the electron wave.

i.e., n 2 r

Prepared by V. Aditya vardhan

Atomic structure 15 adichemadi @ gmail.com

2 r

or where 'n' is an integer

n

But according to de Broglie's theory

h

mv

Hence

2 r h

n mv

nh

or mvr

2

This is Bohr's equation. According to Bohr's theory, the angular momentum (mvr) of electron revolv-

h

ing in a stationary orbit is an integral multiple of i.e., angular momentum is quantized.

2

N

But when the 'n' is not an integer, there is destructive interference and the wave will go out of phase.

HA

This results in loss of energy by the electron wave.

E

Problems RD

EG

by

LL

8) What will be the wavelength of a ball of mass 0.1 Kg moving with a velocity of 10 m/sec.

ed

VA

9) The mass of an electron is 9x10-31 kg and its velocity is 930 m/sec.Calculate its wave length.

AL O

ar

G C

ep

AN IOR

Pr

YA

AR N

According to Heisenberg, it is impossible to calculate the position and momentum of micro particles

W U J

AG T

VI

I

DE

AD

h

or greater than

n

VA

h

V.

x.p

n

where

Δx = uncertainty in position

Δp = mΔv = uncertainty in momentum

m = mass of the particle

Δv = uncertainty in velocity

h = planck's constant

n = 1,2,3,4,......

For an electron n 4

Hence we can write

h

x.p for an electron

4

h

or Δx.Δv ( Δp = mΔv )

4 m

Prepared by V. Aditya vardhan

Atomic structure 16 adichemadi @ gmail.com

Explanation

Case-1

When the position is calculated accurately, Δx = 0

then Δp becomes infinity

i.e., it is not possible to calculate the momentum accurately

Case-2

When the momentum is calculated accurately, Δp = 0

then Δx becomes infinity

i.e., it is not possible to calculate the position accurately.

Problems

11) Calculate the uncertainty in the position if the uncertainty in its velocity is 5x105 m/sec for an electron.

12) Calculate the uncertainty in the velocity if the uncertainties in its position is 1A0 for an electron.

N

13) The uncertainties in the position and velocity of a particle are respectively 1x10-12m and 3x10-24 m/sec.

HA

Calculate the mass of the particle.

E

RD

EG

by

LL

ed

VA

AL O

ar

G C

the exact position of an electron in an atom. But it is possible to predict the probability of finding an electron

ep

AN IOR

in space around the nucleus. To determine the probability of finding an electron, Erwin Schrodinger pro-

Pr

YA

posed wave mechanical model for the motion of electron. He considered electron as a three dimensional

AR N

wave moving in the electric field of a positively charged nucleus. He derived an equation which describes

W U J

the motion of an electron wave along the three axes x, y and z as follows

AG T

VI

2 2 2 8 2 m

I

DE

2 E V 0

AD

x 2 y 2 z 2 h

In the above equation,

VA

m = mass of electron

V.

V = potential energy of electron

= wave function

:- It is called wave function. It denotes the amplitude or intensity of the electron wave.

2:- It is called probability function. It denotes the probability of finding an electron in space at a given

point.

When Schrodinger’s wave equation is solved for hydrogen atom, the solutions give possible energy

levels and corresponding values for the electrons. But the accepted solutions to wave functions, which

are called eigen wave functions, are obtained by applying following boundary conditions.

Boundary conditions

1) must be continuous.

2) must be finite.

3) must be single valued at any point.

4) The probability of finding the electron over the space from + to - must be equal to one.

Prepared by V. Aditya vardhan

Atomic structure 17 adichemadi @ gmail.com

Important features of quantum mechanical model of atom

1) The energy of an electrons in an atom is quantized.

2) The quantized energy levels of electrons are derived from the accepted solutions of Schrodinger’s wave

equation by considering electron as a wave.

3. All the information about electron in an atom is contained in its orbital wave function .

4. The path of the electron can never be determined accurately. Therefore we find only the probability of

the electron at different points in space around an atom.

5. The probability of finding an electron at a point within an atom is proportional to the square of the orbital

wave function ( 2 ) at that point. 2 is known as probability density and is always positive.

It is possible to predict the region around the nucleus in this region 2 has maximum values. Which is

called atomic orbital, from the 2 values.

Atomic orbital:-The space around the nucleus where the probability of finding electron is maximum

N

( 2 > 95%) is known as atomic orbital.

HA

The shapes of atomic orbitals can be known by solving the Shrodinger's wave equation for 2 values

at different points in the space around the nucleus.

E

RD

EG

by

Radial Probability Function (D-function):- The function which denotes the probability of finding an

electron in small volume at a radial distance from the nucleus, without any reference to its direction, is

LL

ed

VA

AL O

ar

G C

D 4 r 2 dr. 2

ep

AN IOR

Pr

YA

Nodal Plane:- The plane where the probability of finding the electron is zero ( 2 = 0) is known as nodal

AR N

W U

plane.

J

AG T

The nodal plane passes through the nucleus and hence is also known as angular node.

VI

The number of nodal planes for a given orbital = l (azimuthal quantum number)

I

DE

AD

VA

V.

s 0 0

p 1 1

d 2 2

f 3 3

Nodal region:- The region around the nucleus where the probability of finding the electron is zero

( 2 = 0) is known as nodal region.

The nodal region does not pass through the nucleus and hence known as radial node.

The number of nodal regions for a given orbital = n - l - 1

For example, the number of nodal regions

for 1s orbital = 1-0-1 = 0

for 2s orbital = 2-0-1 = 1

for 2p orbital = 2-1-1 = 0

Note:-The total of no. of nodal planes and regions for a given orbital = n - l

Radial Probability Distribution curves:- The graphs plotted between the D-function and the radial

Prepared by V. Aditya vardhan

Atomic structure 18 adichemadi @ gmail.com

distance from the nucleus are known as radial probability distribution curves. These curves give an idea

about the variation of electron density with radial distance around the nucleus for a given orbital.

s-orbital

s-orbitals are spherical in shape with spherical symmetry.

There are no nodal planes for s-orbitals.

The nodal regions for s-orbitals are given as follows

orbital no. of nodal regions

1s 0

2s 1

3s 2

The radial probability curves and shapes of 1s and 2s orbitals are given as follows.

N

HA

E

radial distance

RD

EG

by

LL

ed

VA

AL O

ar

G C

ep

AN IOR

Pr

YA

radial node

AR N

W U J

AG T

VI

I

DE

AD

VA

radial distance

V.

p-orbitals

The p-orbitals are double dumbbell in shape.

Each p-orbital contains a nodal plane.

The shapes and orientations of p-orbitals in a given sub level along with the nodal planes are shown as

follows.

radial distance

px py pz

Prepared by V. Aditya vardhan

Atomic structure 19 adichemadi @ gmail.com

d-orbitals

The d-orbitals are double dumbbell in shape.

There are two nodal planes for every d-orbital

In a given sub level, there are five degenerate d-orbitals. These are divided into two groups based on

their orientation i.e., t2g group and eg group.

The lobes of d-orbitals in t2g group are oriented in between the axes by making 450 of angle with

them. There are three t2g orbitals i.e., dxy, dxzand dyz.

Where as the lobes of d-orbitals in eg group are oriented along the axes. There are two such eg

orbitals i.e., d x 2 y2 and d z 2 .

In case of d z 2 orbital, there are only two lobes oriented along the z axis and there is a concentric ring

called torus along the xy axes.

N

HA

x-axis x-axis

E

RD

EG

by

LL

ed

VA

AL O

ar

z-axis

y-axis y-axis

G C

ep

AN IOR

Pr

dxy d x2 y2 d z2

YA

AR N

W U J

AG T

VI

I

DE

AD

The electronic configurations of atoms are represented by two methods i.e., nlx method and box

VA

method

V.

nlx method

'n' is principal quantum number

'l' is azimuthal quantum number, indicated by letters s,p,d,f....

'x' is the number of electrons in the orbital

For example, the electronic configuration of 'He' atom can be represented as 1s2.

Here, 'l' is principal quantum number, 's' represents azimuthal quantum number, l = 0 and the super-

script 2 represents the number of electrons present.

Box method

In this method, the orbitals are represented by boxes and the electrons are denoted by upward and

downward arrows in the boxes.

For example, the electronic configuration of 'He' can be represented as follows.

1s2

Principles and rules: The following principles and rules are used in writing the electronic configurations.

Prepared by V. Aditya vardhan

Atomic structure 20 adichemadi @ gmail.com

Pauli's Exclusion Principle: No two electrons in an atom can have same set of quantum numbers.

For example, the electronic configuration of 'He' is 1s2

The set of quantum numbers of two electrons in 'He' atom are

For first electron, n = 1, l = 0, m = 0, s = +1/2

For second electron, n = 1, l = 0, m = 0, s = -1/2

Aufbau Rules

The electrons in an atom are arranged according to aufbau rules. According to these rules, the differ-

entiating electron in an atom enters into the orbital with lowest energy. The relative energy of an orbital can

be decided from following rules.

1. The orbital with least (n + l) value possesses lowest energy.

For example, the (n + l) values of 1s and 2s orbitals are

for 1s, n + l = 1 + 0 = 1

for 2s, n + l = 2 + 0 = 2

Hence 1s orbital has lower energy than 2s, as it has low n + l value, and the electron will first enter into

N

1s orbital.

2. If two are more orbitals possess same (n + l) value, the orbital with lower 'n' value has low energy.

HA

For example, the (n + l) values of 2p and 3s orbitals are same

for 2p, n + l = 2 + 1 = 3

E

for 3s, n + l = 3 + 0 = 3

RD

EG

by

But 2p orbital with lower 'n' value (=2) possesses lower energy and hence the electron enters first into

LL

ed

this orbital.

VA

AL O

ar

G C

ep

Hund's Rule of Maximum Multiplicity: No pairing of electrons occur until all the degenerate orbitals in

AN IOR

Pr

YA

For example, the electronic configuration of carbon is 1s2 2s2 2px1 2py1

AR N

W U J

AG T

VI

I

DE

AD

In above case, the differentiating electron is entering into the 2py orbital instead of 2px because both 2px and

2py orbitals are degenerate orbitals. Hence no pairing occured.

VA

V.

Chromium and copper exhibit anomalous electronic configurations as the atoms with half filled or full-

filled d-orbitals are more stable.

Cr (Z =24) has [Ar] 3d5 4s1 configuration instead of [Ar] 3d4 4s2 as the half filled d-sub level is more

stable.

Cu (Z =29) has [Ar] 3d10 4s1 configuration instead of [Ar] 3d9 4s2 as the full filled d-sub level is more

stable.

Problems

1) Arrange the electrons, for which the quantum numbers are given below, in their increasing order of

energy.

a) n = 3, l = 1, m = -1, s = +1/2

b) n = 4, l = 0, m = 0, s = -1/2

c) n = 3, l = 2, m = -2, s = -1/2

d) n = 5, l = 3, m = +2, s = +1/2

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