0 Voturi pozitive0 Voturi negative

17 (de) vizualizări53 paginiChem lecture notes

Jul 15, 2018

© © All Rights Reserved

PDF, TXT sau citiți online pe Scribd

Chem lecture notes

© All Rights Reserved

17 (de) vizualizări

Chem lecture notes

© All Rights Reserved

- N1 Industrial Electronics
- Chem Topic 2 Questions + Answers
- Electron Cloud Lab
- lesson plan chemistry form 4
- Chapter 04 - Atomic Structure
- 1 Introduction
- Atom
- F4T2 06
- BIO 156 Chapter 2 Powerpoint
- eoc - chemistry blog
- AIDS
- subatomic particles.pptx
- SIM for 3rd year by Beatriz R. Rubico
- Islamic Correspondece Course - Advanced - 1 of 4
- 1.1 Notes
- Atom Facts
- Basic Atomic Structure Worksheet ANSWERS.docx
- 1st nine weeks exam review
- 0-Introducción
- Benhar - Short-range Correlation

Sunteți pe pagina 1din 53

CHEMISTRY

ATOMIC STRUCTURE

LECTURE # 1 TO 10

Lecture : 1

Atomic structure

1. Introduction :

STRUCTURE OF ATOM

Rutherford's Model Bohr's Model Wave mechanical model

Dalton’s concept of the indivisibility of the atom was completely discredited by a series of experimental

evidences obtained by scientists. A number of new phenomena were brought to light and man’s idea about

the natural world underwent a revolutionary change. the discovery of electricity and spectral phenomena

opened the door for radical changes in approaches to experimentation. It was concluded that atoms are

made of three particles : electrons, protons and neutrons. These particles are called the fundamental particles

of matter.

CATHODE RAYS - DISCOVERY OF ELECTRON

In 1859 Julius Plucker started the study of conduction of electricity through gases at low pressure

(10–4atm) in a discharge tube When a high voltage of the order of 10,000 volts or more was impressed across

the electrodes, some sort of invisible rays moved from the negative electrode to the positive electrode these

rays are called as cathode rays.

(i) Path of travelling is straight from the cathode with a very high velocity as it produces shadow of an

object placed in its path.

(ii) Cathode rays produce mechanical effects. If small paddle wheel is placed between the electrodes,

it rotates. This indicates that the cathode rays consist of material part.

(iii) When electric and magnetic fields are applied to the cathode rays in the discharge tube. The rays

are deflected thus establishing that they consist of charged particles. The direction of deflection

showed that cathode rays consist of negatively charged particles called electrons.

(iv) They produce a green glow when strike the glass wall beyond the anode. Light is emitted when they

strike the zinc sulphide screen.

(v) Cathode rays penetrate through thin sheets of aluminium and metals.

(vi) They affect the photographic plates

(vii) The ratio of charge(e) to mass(m) i.e. charge/mass is same for all cathode rays irrespective of the

gas used in the tube. e/m = 1.76 × 1011 Ckg–1

Thus, it can be concluded that electrons are basic constituent of all the atoms.

RESONANCE Page # 2

POSITIVE RAYS –DISCOVERY OF PROTON :

The existence of positively charged particles in an atom was shown by E. Glodstein in 1886.He repeated the

same discharge tube experiments by using a perfoated cathode. It was observed that when a high potential

difference was applied between the electrodes, not only cathode rays were produced but also a new type of

rays were produced simultaneously from anode moving towards cathode and passed through the holes or

canal of the cathode. These rays are termed as canal ray or anode ray

(i) The e/m ratio of for these rays is smaller than that of electrons.

(ii) Unlike cathode rays, their e/m value is dependent upon the nature of the gas taken in the tube. For

different gases used in the discharge tube, the charge to mass ratio (e/m) of the positive particles

constituting the positive rays is different. When hydrogen gas is taken in the discharge tube, the

e/m value obtained for the positive rays is found to be maximum. Since the value of charge (e) on the

positive particle obtained from different gases is the same, the value of m must be minimum for the

positive particles obtained from hydrogen gas. Thus, the positive particle obtained from hydrogen

gas is the lightest among all the positive particles obtained from different gases. This particle is

called the proton.

(iii) They are capable to produce ionisation in gases.

(iv) They can produce physical and chemical changes.

Discovery of Neutron :

Later, a need was felt for the presence of electrically neutral particles as one of the constituent of

atom. These particles were discovered by Chadwick in 1932 by bombarding a thin sheet of Beryllium

with -particles, when electrically neutral particles having a mass slightly greater than that of the

protons were emitted. He named these particles as neutrons.

9

4 Be 24He 12 1

6 C 0n

The NUCLEUS :

Electrons, protons & neutrons are the fundamental particles present in all atoms,(except hydrogen)

Electron 0 9.1096 x 10-31 kg

–1e or – 1.602 x l0–19 J.J. Thompson

Coulombs Stoney Lorentz 1887

0.000548 amu – 4.803 × 10–10 esu

Proton 1

1H 1.6726 x 10–27 kg + 1.602 x 10–19 Goldstein

Coulombs Rutherford1907

1.00757 amu + 4.803 x 10–10 esu

Neutron 1

0n 1.6749 x 10–27 kg neutral James Chadwick

1.00893 amu 0 1932

1 amu 1.66 × 10–27 kg

RESONANCE Page # 3

Lecture : 2

ATOMIC MODELS :

(A) Thomson’s Model of the Atom :

An atom is electrically neutral. It contains positive charges (due to the presence of protons ) as well

as negative charges (due to the presence of electrons). Hence, J J Thomson assumed that an atom is a

uniform sphere of positive charges with electrons embedded in it.

1. Most of the -particles passed straight through the gold foil without suffering any deflection from

their original path.

2. A few of them were deflected through small angles, while a very few were deflected to a large extent.

3. A very small percentage (1 in 100000) was deflected through angles ranging from 90° to 180°.

(i) The atom of an element consists of a small positively charged ‘nucleus’ which is situated at the

centre of the atom and which carries almost the entire mass of the atom.

(ii) The electrons are distributed in the empty space of the atom around the nucleus in different concentric

circular paths, called orbits.

(iii) The number of electrons in orbits is equal to the number of positive charges (protons) in the nucleus.

Hence, the atom is electrically neutral.

(iv) The volume of the nucleus is negligibly small as compared to the volume of the atom.

(v) Most of the space in the atom is empty.

1. This was not according to the classical theory of electromagnetism proposed by maxwell. According

to this theory, every accelerated charged particle must emit radiations in the form of electromagnetic

waves and loses it total energy.

Since energy of electrons keep on decreasing, so radius of the circular orbits should also decrease

and ultimately the electron should fall in nucleus.

2. It could not explain the line spectrum of H-atom.

RESONANCE Page # 4

PROPERTIES OF CHARGE :

1. Q = ne ( charge is quantized)

2. Charge are of two types :

(i) positive charge (ii) Negative Charge

e = –1.6 x 10–19

p = + 1.6 x 10–19C

This does not mean that a proton has a greater charge but it implies that the charge is equal and opposite.

Same charge repel each other and opposite charges attract each other.

3. Charge is a SCALAR Qty. and the force between the charges always acts along the line joining the

charges.

The magnitude of the force between the two charge placed at a distance ‘r’ is given by

1 q1q2

FE = 4 0 r2

(electrical force)

4. If two charge q1 and q2 are sepreated by distance r then the potential energy of the two charge system is

given by.

The magnitude of the force between the two charge placed at a distance ‘r’ is given by

1

q1q2

P.E. = 4 0

r

5. If a charged particle q is placed on a surface of potential V then the potential energy of the charge is

q x V.

Ex. An -particle is projected from infinity with the velocity V0 towards the nucleus of an atom having atomic

number equal to Z then find out (i) closest distance of approach (R) (ii) what is the velocity of the -particle at

the distance R1 (R1 > R) from the nucleus.

1 3 2

V

Sol. +

m

R

R1

1 K( Ze)(2e)

0+ m V2= +0

2 R

4KZe 2

R= 2 (closest distance of approch)

m V

Let velocity at R1 is V1.

From energy conservation P.E1 + KE1 = P.E3 + KE3

1 K( Ze)(2e) 1

0+ m V2= R1 + m V2

2 2 1

RESONANCE Page # 5

Size of the nucleus :

The volume of the nucleus is very small and is only a minute fraction of the total volume of the atom. Nucleus

has a diameter of the order of 10–12 to 10–13 cm and the atom has a diameter of the order of 10–8 cm.

Thus, diameter (size) of the atom is 100,000 times the diameter of the nucleus.

The radius of a nucleus is proportional to the cube root of the number of nucleons within it.

R = R0 (A)1/3 cm

where R0 can be 1.1 × 10–13 to 1.44 × 10–13 cm ; A = mass number ; R = Radius of the nucleus.

Nucleus contains protons & neutrons except hydrogen atoms which does not contain neutron in the nucleus.

Atomic number and Mass number :

Atomic number of an element

= Total number of protons present in the nucleus

= Total number of electrons present in the atom

Atomic number is also known as proton number because the charge on the nucleus depends upon

the number of protons.

Since the electrons have negligible mass, the entire mass of the atom is mainly due to protons and

neutrons only. Since these particles are present in the nucleus, therefore they are collectively called

nucleons.

As each of these particles has one unit mass on the atomic mass scale, therefore the sum of the

number of protons and neutrons will be nearly equal to the mass of the atom.

The mass number of an element is nearly equal to the atomic mass of that element. However, the

main difference between the two is that mass number is always a whole number whereas atomic

mass is usually not a whole number.

The atomic number (Z) and mass number (A) of an element ‘X’ are usually represented alongwith the

symbol of the element as

23 35

e.g. 11 Na, 17 Cl and so on.

1. sotopes : Such atoms of the same element having same atomic number but different mass numbers

are called isotopes.

1 2

1H, 1 H and 13H and named as protium, deuterium (D) and tritium (T) respectively. Ordinary hydrogen

is protium.

2. Isobars : Such atoms of different elements which have same mass numbers (and of course different

atomic numbers) are called isobars

40 40 40

e.g. 18 Ar, 19 K, 20 Ca.

3. Isotones : Such atoms of different elements which contain the same number of neutrons are called

isotones

14 15 16

e.g. 6 C, 7 N, 8 O.

4. Isoelectronic : The species (atoms or ions) containing the same number of electrons are called

isoelectronic.

For example, O2–, F–, Na+, Mg2+, Al3+, Ne all contain 10 electrons each and hence they are

isoelectronic.

Example. Complete the following table :

Nitrogen atom – – – 7 7

Calcium ion – 20 – 20 –

Oxygen atom 16 8 – – –

Bromide ion – – – 45 36

RESONANCE Page # 6

Sol. For nitrogen atom.

No. of electron = 7 (given)

No. of neutrons = 7 (given)

No. of protons = Z = 7

( atom is electrically neutral)

Atomic number = Z = 7

Mass No. (A) = No. of protons + No. of neutrons

= 7 + 7 = 14

For calcium ion.

No. of neutrons = 20 (Given)

Atomic No. (Z) = 20 (Given)

No. of protons = Z = 20 ;

No. of electrons in calcium atom

= Z = 20

But in the formation of calcium ion, two electrons are lost from the extranuclear part according to the

equation Ca Ca2+ + 2e– but the composition of the nucleus remains unchanged.

No. of electrons in calcium ion

= 20 – 2 = 18

Mass number (A) = No. of protons + No. of neutrons

= 20 + 20 = 40.

For oxygen atom.

Mass number (A) = No. of protons + No. of neutrons

= 16 (Given

Atomic No. (Z) = 8 (Given)

No. of protons = Z = 8,

No. of electrons = Z = 8

No. of neutrons = A – Z = 16 – 8 = 8

For bromide ion.

No. of neutrons = 45 (given)

No. of electrons = 36 (given)

But in the formation of bromide ion, one electron is gained by extra nuclear part according to equation

Br + e– Br – , But the composition of nucleus remains unchanged.

No. of protons in bromide ion = No. of electrons in bromine atom = 36 – 1 = 35

Atomic number (Z) = No. of protons = 35

Mass number (A) = No. of neutrons + No. of protons = 45 + 35 = 80.

80

Ex. (NCERT) Calculate the number of protons, neutrons and electrons in 35 Br .

80

Sol. In this case, 35 Br , Z = 35, A = 80, species is neutral

Number of protons = number of electrons = Z = 35

Number of neutrons = 80 – 35 = 45.

Ex. (NCERT) The number of electrons, protons and neutrons in a species are equal to 18, 16 and 16 respectively.

Assign the proper symbol to the species.

Sol. The atomic number is equal to number of protons = 16. The element is Sulphur (S).

Mass number = number of protons + number of neutrons = 16 + 16 = 32

Species is not neutral as the number of protons is not equal to electrons. It is anion (negatively

32 2 –

charged) with charge equal to excess electrons = 18 – 16 = 2. Symbol is 16 S .

RESONANCE Page # 7

LECTURE : 3

Electromagnetic wave radiation :

The oscillating electrical/magnetic field are electromagnetic radiations. Experimentally, the direction of oscillations

of electrical and magnetic field are prependicular to each other.

E = Electric field, B = Magnetic field

Wavelength of a wave is defined as the distance between any two consecutive crests or troughs. It is

represented by (lambda) and is expressed in Å or m or cm or nm (nanometer) or pm (picometer).

1 Å = 10– 8 cm = 10–10 m

1 nm = 10– 9 m, 1 pm = 10–12 m

Frequency of a wave is defined as the number of waves passing through a point in one second. It is

represented by (nu) and is expressed in Hertz (Hz) or cycles/sec or simply sec–1 or s–1.

1 Hz = 1 cycle/sec

Velocity of a wave is defined as the linear distance travelled by the wave in one second. It is represented by

v and is expressed in cm/sec or m/sec (ms–1).

Amplitude of a wave is the height of the crest or the depth of the trough. It is represented by ‘a’ and is

expressed in the units of length.

Wave number is defined as the number of waves present in 1 cm length. Evidently, it will be equal to the

reciprocal of the wavelength. It is represented by (read as nu bar).

1

RESONANCE Page # 8

If is expressed in cm, will have the units cm–1.

Relationship between velocity, wavelength and frequency of a wave. As frequency is the number of

waves passing through a point per second and is the length of each wave, hence their product will give the

velocity of the wave. Thus

v=×

Cosmic rays < – rays < X-rays < Ultraviolet rays < Visible < Infrared < Micro waves < Radio waves.

Ex. (NCERT)

The Vividh Bharati station of All India Ratio, Delhi, broadcasts on a frequency of 1,368 kHz (kilo hertz).

Calculate the wavelength of the electromagnetic radiation emitted by transmitter. Which part of the

electromagnetic spectrum does it belong to ?

Sol. The wevelength, , is equal to c/, where c is the speed of electromagnetic radiation in vacuum and is the

c 3.00 10 8 ms 1

frequency. Substituting the given values, we have = = 219.3 m

1368 10 3 s 1

Ex. (NCERT)

The wavelength range of the visible spectrum extends from violet (400 nm) to red (750 nm). Express these

wavelengths in frequencies (Hz). (1 nm = 10–9 m)

c 3.00 10 8 ms 1

Sol. Frequency of violet light = 7.50 × 1014 Hz

400 10 9 m

c 3.00 10 8 ms 1

Frequency of red light = 4.00 × 1014 Hz

750 10 9 m

The range of visible spectrum is from 4.0 × 1014 to 7.5 × 1014 Hz in terms of frequency units.

Ex. (NCERT)

Calculate (a) wavenumber and (b) frequency of yellow radiation having wavelength 5800 Å.

Sol. (a) Calculation of wavenumber ( ) = 5800 Å = 5800 × 10–8 cm = 5800 × 10–10 m

1 1

= 1.724 × 106 m–1 = 1.724 × 104 cm–1

5800 10 10 m

c 3 10 8 m s 1

(b) Calculation of the frequency () = 5.172 × 1014 s–1

5800 10 10 m

Some of the experimental phenomenon such as diffraction and interference can be explained by the wave

nature of the electromagnetic radiation. However, following are some of the observations which could not be

explained

(i) the nature of emission of radiation from hot bodies (black - body radiation)

(ii) ejection of electrons from metal surface when radiation strikes it (photoelectric effect)

When solids are heated they emit radiation over a wide range of wavelengths.

The ideal body, which emits and absorbs all frequencies, is called a black body and the radiation emitted by

such a body is called black body radiation. The exact frequency distribution of the emitted radiation (i.e.,

intensity versus frequency curve of the radiation) from a black body depends only on its temperature.

RESONANCE Page # 9

The above experimental results cannot be explained satisfactorily on the basis of the wave theory of light.

Planck suggested that atoms and molecules could emit (or absorb) energy only in discrete quantities and

not in a continuous manner.

The smallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation is called

as quantum of light.

According to Planck, the light energy coming out from any source is always an integral multiple of a smallest energy

value called quantum of light.

Let quantum of light be = E0(J), then total energy coming out is = nE0 (n = Integer)

Quantum of light = Photon ( Packet or bundle of energy)

Energy of one photon is given by

E0 = h (- Frequency of light)

h = 6.625 x 10–34 J-Sec (h - Planck const.)

hc

E0 = (c - speed of light)

( - wavelength)

10 34 10 8

Order of magnitude of Eo = = 10–16 J

10 10

One electron volt (e.v.) : Energy gained by an electron when it is accelerated from rest through a potential difference

of 1 volt.

Note : Positive charge always moves from high potential to low potential and –ve charge always. moves from low

potential to high potential if set free.

P.E.i + K.E.i = P.E.f + K.E.f

1

(– e) 0 + 0 = (– e)(1V) + mVf2

2

1

K.E. = mVf2 = e(1 volt)

2

RESONANCE Page # 10

If a charge ‘q’ is accelerated through a potential dirrerence of ‘V’ volt then its kinetic energy will be increased by q.V.

1eV = 1.6 x 10–19J

Ex. (NCERT)

Calculate energy of one mole of photons of radiation whose frequency is 5 × 1014 Hz.

Sol. Energy (E) of one photon is given by the expression E = h

h = 6.626 × 10– 34 J s

= 5 × 1014 s–1 (given)

E = (6.626 × 10–34 J s) × (5 × 1014 s–1) = 3.313 × 10–19 J

energy of one mole of photons = (3.313 × 10–19 J) × (6.022 × 1023 mol–1) = 199.51 KJ mol–1

Ex. (NCERT)

A 100 watt bulb emits monochromatic light of wavelength 400 nm. Calculate the number of photons emitted per

second by the bulb

Sol. Power of the bulb = 100 watt = 100 J s–1

6.626 10 –34 J s 3 10 8 m s –1

Energy of one photon E = h = hc/= = 4.969 × 10–19 J

400 10 – 9 m

100 J s –1

Number of photons emitted = 2.012 × 1020 s–1

4.969 10 –19 J

Ex. If a charged particle having charge of 2e on being accelerated by 1 volt, its K.E. will be increased by ?

Sol. K.E. = (2e) . (1V)

= 2 x 1eV

= 2 x 1.6 x 10–19 J

= 3.2 x 10–19 J

Ex. A charged particle having a charge +3e is projected towards +ve plate, from –ve plate with K.E.i = 12eV What

is the minimum potential that should be applied between the plates so that the charged particle cannot strike

the +ve plate ?

Sol. K.E.i + P.E.i = P.E.f + K.E.f

(+3e) 0 + 12eV = 3e(V) + 0

12eV

V= = 4Volts

s

3e

Ex. Number of photons emitted by a bulb of 40 watt in 1 minute with 50% efficiency will be approximately

( = 6200 Å, hc = 12400 eV Å)

(A) 7.5 × 1020 (B) 3.75 × 1020 (C) 3.75 × 1019 (D*) 3.75 × 1021

12400

Sol. E = = 2eV..

6200

2 × 1.6 × 10–19 × n = 40 × 60 × 0.5

n = 3.75 × 1021

Ex. Bond energy of Br2 is 194 kJ mole–1. The minimum wave number of photons required to break this bond is (h

= 6.62 x 10–34 Js, c = 3 x 108 m/s)

(A) 1.458 × 1023 m–1 (B*) 1.620 × 106 m–1 (C) 4.86 × 1014 m–1 (D) 1.45 × 107 m–1

hc

Sol. x NA = 194 x 103

1 194 x 10 3

= = 6.63 x 10 34 x 10 8 x 6 x 10 23

~ 1.62 x 106 m–1

RESONANCE Page # 11

Dual nature of electron (de-Broglie Hypothesis):

(a) Einstein had suggested that light can behave as a wave as well as like a particle i.e. it has dual character.

(b) In 1924, de-Broglie proposed that an electron behaves both as a material particle and as a wave.

(c) This proposed a new theory wave mechanical theory of matter. According to this theory, the electrons

protons and even atom when in motion possess wave properties.

(d) According to de-Broglie, the wavelength associated with a particle of mass m, moving with velocity v is

given by the relation,

h

=

mv

where h is Planck’s constant

(e) This can be derived as follows according to Planck’s equation.

h.c

E = h =

Energy of photon on the basis of Einstein’s mass energy relationship

h

E = mc2 or =

mc

Equating both we get

h.c

= mc2

h

or =

mc

Which is same as de - Broglie relation.

This was experimentally verified by Davisson and Germer by observing diffraction effects with an electron

beam.

Let the electron is accelerated with a potential of V then the K.E. is

1

mv2 =eV

2

m2v2 = 2emV

mv = 2emV = p (momentum)

h

=

2emV

If we associate Bohr’s theory with de - Broglie equation then

2r

2r = n or =

n

From de-Broglie equation

h h 2r

= therefore =

mv mv n

nh

so, mvr =

2

m0

m = dynamic mass =

2

v

1

c

depended on velocity

c = velocity of light

If velocity of particle is zero then :

dynamic mass = rest mass

RESONANCE Page # 12

Rest mass of photon is zero that means photon is never at rest

1

* K.E. = mv2

2

1 2 2

m (K.E.) = m v multiplied by mass on both side

2

m.v. = 2m(K.E.)

h

=

2m(K.E.)

If a charge q is accelerated through a potential difference of ‘V’ volt from rest then K.E. of the charge is equal

to : “ q.V”

h

= 2m(q.V )

* If an electron is accelerated through a potential difference of ‘V’ volt from rest then :

h

=

2m e (eV )

1

150 2

= Å (on putting values of h, me and e)

V

12.3

= Å (V in volt)

V

h

* mvr = n ×

2

h

=

mv

h nh

mv = putting this in mvr =

2

h nh 2r

r= n de Broglie wavelength

2

Ex. (NCERT)

What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s–1 ?

Sol. According to de Broglie equation

= =

mv (0.1 kg) (10 m s –1 )

= 6.626 × 10–34 m (J = kg m2 s–2)

Ex. (NCERT)

RESONANCE Page # 13

The mass of an electron is 9.1 × 10–31 kg. If its K.E. is 3.0 × 10–25 J, calculate its wavelength.

1

Sol. Since K.E. = mv2

2

1

1

2 K.E. 2 2 3.0 10 – 25 kg m 2 s – 2 2

v= = = 812 m s–1

m 9.1 10 – 31 kg

h 6.626 10 –34 Js

= =

mv (9.1 10 – 31kg) (812 m s –1 )

= 8967 × 10–10 m = 896.7 nm

Ex. Find the wavelength associated with a dust particle of mass 5 mg. moving with velocity 200 m/s.

= = = = 6.62 ×10–31 m

mv 5 10 6 200 1000 10 6

Note : Since order of the wavelength is extremely small, therefore de-Broglie wavelength calculation for daily life

particle has no physical significance

Ex. Find the wavelength associated with the electron moving with the velocity 106 m/s.

= = = 0.7 × 10–9 m = 7× 10–10m = 7 Aº

mv 9.1 10 31 10 6 9.1

Note Since wavelength associated with the electron has considerable value therefore we can conclude that

electron has more of wave nature and less of particle nature.

Ex. Calculate ratio of wavelength for an particle & proton accelerated through same potential difference.

h h

p

Sol. , 2 qpm p V , m = 4mp , q = 2qp

2 q m V

qpmp 1 1 1 1

. Ans.

p q .m 2 4 8 2 2

Ex. (a) Hydrogen sample is in st excited state A photon of energy 8eV is used to excite the hydrogen sample.

Find the de-Broglie wavelength of the electron.

(a) n=2

K.E. of electron = 8 – 3.4 = 4.6 eV

150

= Aº = 5.71 Å

4 .6

OR

1

mv2 = 4.6 × 1.6 × 10–19 (m = 9.1 × 10– 31 kg)

2

v = 1.27 × 106 m/sec

h

Putting the value of v in = , we get :

mv

6.626 10 –34

= 5.7 Å

9.1 10 – 31 1.27 10 6

RESONANCE Page # 14

Ex. An electron having Initial K.E. of 6eV is accelerated through a potential difference of 4V find the wavelength

of associated with electron

Ans. Total K.E. = 6eV + 4eV = 10eV

1

150 2 150

= = = 15 = 3.87 Å

10 10

Ex. De-Broglie wavelength of electron in second orbit of Li2+ ion will be equal to de-Broglie of wavelength of

electron in

(A) n = 3 of H-atom (B*) n = 4 of C5+ ion (C) n = 6 of Be3+ ion (D) n = 3 of He+ ion

h z

Sol. = Now v

mv n

n

so

z

2

for second orbit of Li2+

3

4 2

for n = 4 of C5+ ion, = Hence the result.

6 3

Ex. An electron, practically at rest, is initially accelerated through a potential difference of 100 volts. It then has

a de Broglie wavelength = 1 Å. It then get retarded through 19 volts and then has a wavelength 2 Å.

3 2

Its further retardation through 32 volts changes the wavelength to 3, What is 1 ?

20 10 20 10

(A) (B) (C*) (D)

41 63 63 41

h k h k h k

Sol. 1 = = , = = = =

2mq (100) 10 2 2mq(81) 9 3 2mq( 49) 7

k k 2k

–

3 – 2 7 9 63 20

= = =

1 k k 63

10 10

so the required answer.

RESONANCE Page # 15

LECTURE : 4

Photoelectric Effect :

When certain metals (for example Potassium, Rubidium, Caesium etc.) were exposed to a beam of light

electrons were ejected as shown in Fig.

The phenomenon is called Photoelectric effect. The results observed in this experiment were :

(i) The electrons are ejected from the metal surface as soon as the beam of light strikes the surface, i.e., there

is no time lag between the striking of light beam and the ejection of electrons from the metal surface.

(ii) The number of electrons ejected is proportional to the intensity or brightness of light.

(iii) For each metal, there is a characteristic minimum frequency, 0 (also known as threshold frequency)

below which photoelectric effect is not observed. At a frequency > 0, the ejected electrons come out with

certain kinetic energy. The kinetic energies of these electrons increase with the increase of frequency of the

light used.

When a photon of sufficient energy strikes an electron in the atom of the metal, it transfers its energy

instantaneously to the electron during the collision and the electron is ejected without any time lag or delay.

Greater the energy possessed by the photon, greater will be transfer of energy to the electron and greater the

kinetic energy of the ejected electron. In other words, kinetic energy of the ejected electron is proportional to

the frequency of the electromagnetic radiation. Since the striking photon has energy equal to h and the

minimum energy required to eject the electron is h0 (is also called work function, W 0) then the difference in

energy (h – h0) is transferred as the kinetic energy of the photoelectron. Following the conservation of

energy principle, the kinetic energy of the ejected electron is given by the equation

1

h = h0 + m 2

2 e

where me is the mass of the electron and v is the velocity associated with the ejected electron.

Example 1.

The threshold frequency 0 for a metal is 6 × 1014 s–1. Calculate the kinetic energy of an electron emitted when

radiation of frequency = 1.1 × 1015 s–1 hits the metal.

1

Sol. K.E. = m V2 = h ( – 0)

2 e

K.E. = (6.626 × 10–34) (1.1 × 1015 – 6 × 1014)

K.E. = (6.626 × 10–34) (5 × 1014)

= 3.313 × 10–19 J

RESONANCE Page # 16

Example 2.

When electromagnetic radiation of wavelength 310 nm fall on the surface of Sodium, electrons are emitted

with K.E. = 1.5 eV. Determine the work function (W 0) of Sodium.

12400

Sol. h = = 4 eV

3100

1

m V2 = 1.5 eV

2 e

1

h0 = W 0 = h – m V2 = 4 – 1.5 = 2.5 eV

2 e

Ex. (NCERT)

When electromagnetic radiation of wavelength 300 nm falls on the suface of sodium, electrons are emitted

with a kinetic energy of 1.68 × 105 J mol–1. What is the minimum energy needed to remove an electron from

sodium ? What is the maximum wavelength that will cause a photoelectron to be emitted ?

Sol. The energy (E) of a 300 nm photon is given by h = hc / =

300 10 9 m

= 6.626 × 10–19 J

The energy of one mole of photons

= 6.626 × 10–19 × 6.022 × 1023

= 3.99 × 105 J mol–1

The minimum energy needed to remove a mole of electrons from sodium = (3.99 – 1.68) 105 J mol–1

2.31 10 5 J mol 1

= 2.31 × 105 J mol–1 The minimum energy for one electron =

6.022 10 23 electrons mol 1

= 3.84 × 10–19 J

This corresponds to the wavelength = = 517 nm.

E 3.84 10 19 m

Ex. (NCERT)

The threshold frequency 0 for a metal for a metal is 7.0 × 1014 s–1. Calculate the kinetic energy of an electron

emitted when radiation of frequency = 1.0 × 1015 s–1 hits the metal.

Sol. According to Einstein’s equation Kinetic energy - 1/2 mev2 = h( – 0) = (6.626 × 10–34 J s) (1.0 × 1015 s–1 – 7.0

× 10–14 s–1) = (6.626 × 10–34 J s) × (3.0 × 1014 s–1) = 1.988 × 10–19 J

RESONANCE Page # 17

Lecture : 5

BOHR’S ATOMIC MODEL

Bohr’s model is applied only on one electron species like H, He+, Li++, Be+++ etc.

The important postulates of Bohr model of an atom are

(a) Electron revolves around the nucleus in a fixed circular orbit of definite energy. As long as the electron

occupy a definite energy level, it does not radiate out energy i.e. it does not lose or gain energy. These orbits

are called stationary orbits.

(b) Electron revolves only in those orbits whose angular momentum (mvr) is an integral multiple of the factor

h/2(where ‘h’ is Plank’s constant)

h

mvr = n

2

where :

m = mass of the electron v = velocity of the electron

n = number of orbit in which electron revolves i.e. n = 1, 2, 3 ........

r = radius of the orbit.

(c) The energy is emitted or absorbed only when the electron jumps from one energy level to another. It may

jump from higher energy level to a lower level by the emission of energy and jump from lower to higher energy

level by absorption of energy.

This amount of energy emitted or absorbed is given by the difference of the energies of the two energy levels

concerned.

Calculation of the radius of the Bohr’s orbit : Suppose that an electron having mass ‘m’ and charge ‘e’

revolving around the nucleus of charge ‘Ze’ (Z is atomic number & e = charge) with a tangential/linear velocity

of ‘v’. Further consider that ‘r’ is the radius of the orbit in which electron is revolving.

According to Coulomb’s law, the electrostatic force of attraction (F) between the moving electron and nucleus

is –

KZe 2 1

F= 2 where : K = constant = 4 = 9 x 109 Nm2/C2

r 0

mv 2

and the centrifugal force F =

r

For the stable orbit of an electron both the forces are balanced.

mv 2 KZe 2

i.e =

r r2

KZe 2

then v2 = ......... (i)

mr

RESONANCE Page # 18

From the postulate of Bohr, V

nh nh

mvr = v=

2 2mr

n 2h 2 +

On squaring v2 = ........ (ii)

4 2m 2r 2

From equation (i) and (ii)

KZe 2 n 2h 2

=

mr 4 2m 2r 2

On solving, we will get

n 2h 2

r=

4 2mKZe 2

On putting the value of e , h , m, the radius of nth Bohr orbit is given by :

n2

rn = 0.529 x Å

Z

Ex. Calculate radius ratio for 2nd orbit of He+ ion & 3rd orbit of Be+++ ion.

22

nd + Å

Sol. r1 (radius of 2 orbit of He ion) = 0.529 2

32

Å

r2 (radius of 3rd orbit of Be+++ ion) = 0.529 4

r1 0.529 2 2 / 2 8

Therefore r = 2 =

2 0.529 3 / 4 9

Ex. If the radius of second orbit of Li2+ ion is x then find the radius of Ist orbit of He+ in terms of x.

22

Sol. r1 (radius of 2nd orbit of Li2+) = 0.529 × Å = x (given) ... (i)

3

12 3x 1 3x

r2 (radius of 1st orbit of He+) = .0529 × = =

2 4 2 8

Angular momentum of the revolving electron in nth orbit is given by

nh

mvr =

2

nh

v= ......... (iii)

2mr

put the value of ‘r’ in the equation (iii)

nh 4 2mZe 2K

then, v=

2mn 2h2

Ze 2K

v=

nh

on putting the values of , e-, h and K

Z 1

velocity of electron in nth orbit vn = 2.18 x 106 x m/sec vZ ; v

n n

RESONANCE Page # 19

2r

T, Time period of revolution of an electron in its orbit =

v

v

f, Frequency of revolution of an electron in its orbit =

2 r

Calculation of energy of an electron :

The total energy of an electron revolving in a particular orbit is

T.E. = K.E. + P.E.

where :

P.E. = Potential energy , K.E. = Kinetic energy , T.E. = Total energy

1

The K.E. of an electron = mv2

2

KZe 2

and the P.E. of an electron = –

r

1 KZe 2

Hence, T.E. = mv2 –

2 r

mv 2 KZe 2 2 =

KZe 2

we know that, = or mv

r r2 r

substituting the value of mv2 in the above equation :

KZe 2 KZe 2 KZe 2

T.E. = – =–

2r r 2r

KZe 2

So, T.E. = –

2r

substituting the value of ‘r’ in the equation of T.E.

KZe 2 4 2 Ze 2m 2 2 Z 2 e 4 m K 2

Then T.E. = – x 2 2 =–

2 n h n 2h 2

Thus, the total energy of an electron in nth orbit is given by

2

2 2 me 4 k 2 z

T.E. = En = – n2 ... (iv)

h2

Putting the value of m,e,h and we get the expression of total energy

Z2

En = – 13.6 eV / atom n T.E. ; Z T.E.

n2

1

T.E. = P.E.

2

T.E. = – K.E.

The K.E. at the infinite = 0

(a) The negative sign of energy indicates that there is attraction between the negatively charged electron and

positively charged nucleus.

(b) All the quantities on R.H.S. in the energy equation [Eq. iv] are constant for an element having atomic

number Z except ‘n’ which is an integer such as 1,2,3, etc . i.e. the energy of an electron is constant as long

as the value of ‘n’ is kept constant.

(c) The energy of an electron is inversely proportional to the square of ‘n’ with negative sign.

RESONANCE Page # 20

Failures / limitations of Bohr’s theory:

(a) He could not explain the line spectra of atoms containing more than one electron.

(b) He also could not explain the presence of multiple spectral lines.

(c) He was unable to explain the splitting of spectral lines in magnetic field (Zeeman effect) and in electric

field (Stark effect)

(d) No conclusion was given for the principle of quantisation of angular momentum.

(e) He was unable to explain the de-Broglie’s concept of dual nature of matter.

(f) He could not explain Heisenberg’s uncertainty principle.

Ex. (NCERT)

What are the frequency and wavelength of a photon emitted during a transition from n = 5 state to the n = 2

state in the hydrogen atom ?

Sol. Since ni = 5 and nf = 2, this transition gives rise to a spectral line in the visible region of the Balmer series.

1 1

E = 2.18 × 10–18 J 2 – 2 = – 4.58 × 10–19 J

5 2

It is an emission energy

The frequency of the photon (taking energy in terms of magnitude) is given by

E 4.58 10 –19 J

= =

h 6.626 10 – 34 Js

= 6.91 × 1014 Hz

c 3.0 108 ms –1

= = = 434 nm

6.91 1014 Hz

Ex. (NCERT)

Calculate the energy associated with the first orbit of He+. What is the radius of this orbit?

(2.18 10 –18 J) Z 2

Sol. En = atom–1

n2

For He+, n = 1, Z = 2

(2.18 10 –18 J)

E1 = – = – 8.72 × 10–18 J

12

The radius of the orbit is given by equation

52 .9 (n 2 ) (0.0529 nm) n2

rn = pm =

Z Z

Since n = 1, and Z = 2

(0.0529 nm )12

rn = = 0.02645 nm

2

Ex. Calculate energy ratio for 3rd orbit of Li++ ion & 2nd orbit of Be+++ ion.

Sol. E1 for 3rd orbit of Li++ ion

32

= – 13.6 × ev/atm

32

E2 for 2nd orbit of Be+++ ion

42

= – 13.6 × ev/atm

22

E1 1

E 2 4 Ans.

RESONANCE Page # 21

Ex. Radius of two different orbits in a H like sample is 4R and 16R respactively then find out the ratio of the

frequency of revolution of electron in these two orbits.

r1 0.529 n12 4R

Sol. r2 = 0.529 n22 = 16 R

n12 1

=

n 22 4

n1 1

or n2 = 2

2

f1 v1 / 2r1 n32 n2 2

3

Now, =

= 3 = = =8:1

f2 v 2 / 2r2 n1 n1 1

Lecture : 6

Energy Level Diagram :

(i) Orbit of lowest energy is placed at the bottom, and all other orbits are placed above this.

(ii) The gap between two orbits is proportional to the energy difference of the orbits.

0 eV n=

-0.85 eV n=4

-1.51eV n=3

-3.4eV n=2

12.1eV

10.2eV

-13.6eV n=1

Energy level diagram of H-atom

(i) Ground state :

Lowest energy state of any atom or ion is called ground state of the atom It is n = 1.

Ground state energy of H–atom = – 13.6 ev

Ground state energy of He+ on = – 54.4 ev

(ii) Excited State :

States of atom other than the ground state are called excited states :

n=2 first excited state

n=3 second excited state

n=4 third excited state

n=n+1 nth excited state

(iii) Ionisation energy (E) :

Minimum energy required to move an electron from ground state to

n = is called ionisation energy of the atom or ion.

onisation energy of H–atom = 13.6 ev

onisation energy of He+ ion = 54.4 ev

onisation energy of Li+2 ion = 122.4 ev

(iv) Ionisation Potential (.P.) :

Potential difference through which a free electron must be accelerated from rest, such that its kinetic energy

becomes equal to ionisation energy of the atom is called ionisation potential of the atom.

.P. of H atom = 13.6 V, .P. of He+ on= 54.4 V

(v) Excitation Energy :

Energy required to move an electron from ground state of the atom to any other state of the atom is called

excitation energy of that state.

Excitation energy of 2nd state = excitation energy of 1st excited state = 1st excitation energy = 10.2 ev.

RESONANCE Page # 22

(vi) Excitation Potential :

Potential difference through which an electron must be accelerated from rest to so that its kinetic energy

become equal to excitation energy of any state is called excitation potential of that state.

Excitation potential of third state = excitation potential of second exicited state = second excitation potential =

12.09 V.

(vii) Binding Energy ‘or’ Seperation Energy :

Energy required to move an electron from any state to n = is called binding energy of that state.

Binding energy of ground state = .E. of atom or on.

Sol. I.E.H = E – E1

= 0 – (– 13.6) = + 13.6 ev/atom

E Z2

I.E for Li++ = (ZLi++)2 × IEH = 9 × 13.6 = 122.4 ev Ans.

Sol. n1 = 1 n2 = 3 Z=2

22

E1 = – 13.6 × 22 = – 54.4 ev E3 = – 13.6 × ev = – 6.04 ev

32

Ex. Binding Energy of H like system corresponding to second excited state is given by 13.5 eV. then

(a) Identify the sample

(b) Ionisation energy of sample

(c) Energy of photon required to cause the transition from 2nd state to 3rd excited state.

(d) Wavelength of the emitted photon when electron fall from 1st excited state to ground state.

Ans. (A)

1.5 Z2 = 13.5

13.5

Z2 = =9

1 .5

Z=3

Ans. Li++

(C) n = 2 to n = 4

4

3

2

1

Energy of photon needed = (E)2 4

(3.4 – 0.85) 32

2.55 × 9

––––––––––––

22.95 eV

(d) (E)2 1 = 10.2 Z2

10.2 × 32 = 10.2 × 9 = 91.8 eV

12400

= = 135.1 Å

91.8

RESONANCE Page # 23

Ex. If st excitation potential of H like sample is 15V, find : The .E. and nd excitation potential of sample.

Sol. st excitation energy 15 eV (E)

13.6 Z 2

E=–

n2

13.6 Z 2

E1 = – (E0 = 13.6 Z2 = IE)

1

13.6 Z 2

E2 = –

22

E1 = – E0

E0

E2 = –

4

E0

E = E2 – E1 = E0 – = 15eV

4

3E o

= 15

4

15 4

Eo = = 20eV

3

IE = 20eV

13.6Z 2

E1 = –

1

13.6Z 2

E3 = –

32

Eo 8

(E)1 – 3 = Eo – = E

9 9 o

8

= × 20 = 17.75 eV..

9

2nd excitation potential = 17.75 V.

HYDROGEN SPECTRUM :

Study of Emission and Absorption Spectra :

An instrument used to separate the radiation of different wavelengths (or frequencies) is called spectroscope

or a spectrograph. Photograph (or the pattern) of the emergent radiation recorded on the film is called a

spectrogram or simply a spectrum of the given radiation The branch or science dealing with the study of

spectra is called spectroscopy.

Spectrum

Based on Based on

Nature origin

spectrum spectrum

Band Line

Spectrum Spectrum

RESONANCE Page # 24

Emission spectra :

When the radiation emitted from some source e.g. from the sun or by passing electric discharge through a

gas at low pressure or by heating some substance to high temperature etc, is passed directly through the

prism and then received on the photographic plate, the spectrum obtained is called ‘Emission spectrum’.

Depending upon the source of radiation, the emission spectra are mainly of two type :

When white light from any source such as sun, a bulb or any hot glowing body is analysed by passing

through a prism it is observed that it splits up into seven different wide band of colours from violet to red.

These colours are so continuous that each of them merges into the next. Hence the spectrum is called

continuous spectrum.

(i) Band spectrum

Dark space

Band

Band spectrum contains colourful continuous bands sepearted by some dark space.

Generally molecular spectrum are band spectrum

This is the ordered arrangement of lines of particular wavelength seperated by dark space eg. hydrogen

spectrum.

Line spectrum can be obtained from atoms.

2. Absorption spectra :

When white light from any source is first passed through the solution or vapours of a chemical substance and

then analysed by the spectroscope, it is observed that some dark lines are obtained in the continuous

spectrum. These dark lines are supposed to result from the fact that when white light (containing radiations

of many wavelengths) is passed through the chemical substance, radiations of certain wavelengths are

absorbed, depending upon the nature of the element.

RESONANCE Page # 25

EMISSION SPECTRUM OF HYDROGEN :

When hydrogen gas at low pressure is taken in the discharge tube and the light emitted on passing electric

discharge is examined with a spectroscope, the spectrum obtained is called the emission spectrum of

hydrogen.

Line spectrum of hydrogen is observed due to excitation or de-excitation of electron from one stationary orbit

to another stationary orbit

Let electron make transition from n2 to n1 (n2 > n1) in a H-like sample

2

– 13.6 Z

2 eV n2

n 2

– 13.6 Z2 n1

2

eV

n1

photon

Energy of emitted photon = (E)n2 n1

13.6Z 2 13.6Z 2

= –

n 22 n12

1 1

= 13.6Z2 2 2

n1 n2

Wavelength of emitted photon

hc

= ( E)

n 2 n1

hc

=

1 1

13.6Z 2 2 2

n n

1 2

1 (13.6)z 2 1

1

=

hc n 2 n 2

1 2

RESONANCE Page # 26

1 1 1

Wave number, = = RZ 2 2 2

n

1 n2

13.6eV

R = Rydberg constant = 1.09678 × 107m–1 ; R ~ 1.1 × 107 m–1 ; R = ; R ch = 13.6 eV

hc

Ex.1 Calculate the wavelength of a photon emitted when an electron in H- atom maker a transition from n = 2 to n = 1

1 1 1

Sol. = RZ2 2 2

n1 n 2

1 1 1

= R(1)2 2 2

1 2

1 3R 4

= or

4 3R

Lecture : 7

SPECTRA LINES OF HYDROGEN ATOM :

LYMAN SERIES

* It is first spectral series of H.

* It was found out in ultraviolet region in 1898 by Lyman.

* It’s value of n1 = 1 and n2 = 2,3,4 where ‘n1’ is ground state and ‘n2’ is called excited state of electron present

in a H - atom.

1 1 1

* = RH 2 2 where n2 > 1 always.

1 n 2

n12 1

* The wavelength of marginal line = for all series. So for lyman series = R .

RH H

nd line of lyman series = 3 1

Last line of lyman series = 1

[10.2 eV (E) lyman 13.6 eV]

RESONANCE Page # 27

12400 12400

Aº

13.6 lyman 10.2

12400

* Longest line : longest wavelength line longest or max. = ( E)

min

12400

* Shortest line : shortest wavelength line shortest or min = ( E)

max

* First line of any spectral series is the longest ( max) line.

* Last line of any spectral series is the shortest ( min) line.

Series limit :

t is the last line of any spectral series.

Wave no of st line of Lyman series

1 1 1

= = = R × 12 2 2

1 2

4 1

2

= R × 1 4

R3 3R

= 4

=

4

4

3R

1 1

= R × 12 2 2

1

=R

For Lyman series,

12400 12400

longest = , shortest =

( E)2 1 E 1

BALMER SERIES :

* It is the second series of H-spectrum.

* It was found out in 1892 in visible region by Balmer.

* It’s value of n1 = 2 and n2 = 3,4,5,.............

n12 22 4

* The wavelength of marginal line of Balmer series = = = R

RH RH H

1 1 1

* = RH 2 2 where n2 > 2 always.

2 n2

All the lines of balmer series in H spectrum are not in the visible range. nfact only st 4

lines belongs to visible range.

12400 12400

Aº Å

3 .4 balmer 1. 9

3648 Å balmer 6536 Å

Ist line of balmer series = 3 2

last line of balmer series = 2

RESONANCE Page # 28

1 1 5R

( ) 1st line = R ×1 2 2 =

2 3 36

1 1 R

( ) last line = R 2 2 =

2 4

PASCHEN SERIES :

(a) It is the third series of H - spectrum.

(b) It was found out in infrared region by Paschen.

(c) It’s value of n1 = 3 and n2 = 4,5,6 ........

n12 32 9

(d) The wavelength of marginal line of Paschen series = = = R .

RH RH H

1 1 1

(e) = RH 2 2 where n2 > 3 always.

3 n2

BRACKETT SERIES :

(a) It is fourth series of H - spectrum.

(b) It was found out in infrared region by Brackett.

(c) It’s value of n1 = 4 and n2 = 5,6,7 ..............

n12 42 16

(d) The wavelength of marginal line of brackett series = = = R

RH RH H

1 1 1

(e) = RH 2 2 where n2 > 4 always.

4 n2

PFUND SERIES :

(a) It is fifth series of H- spectrum.

(b) It was found out in infrared region by Pfund.

(c) It’s value of n1 = 5 and n2 = 6,7,8 ............... where n1 is ground state and n2 is excited state.

n12 52 25

(d) The wavelength of marginal line of Pfund series = = = R

RH RH H

1 1 1

(e) = RH 2 2 where n2 > 5 always.

5 n2

HUMPHRY SERIES :

(a) It is the sixth series of H - spectrum.

(b) It was found out in infrared region by Humphry.

(c) It’s value of n1 = 6 and n2 = 7 , 8 , 9 ...................

n12 62 36

(d) The wavelength of marginal line of Humphry series = = = R

RH RH H

1 1 1

(e) = RH 2 2 where n2 > 6.

6 n2

Ex. Calculate wavelength for 2nd line of Balmer series of He+ ion

1 1 1

Sol. R(2)2 2 2

n1 n2

n1 = 2 n2 = 4

1 1 1

R( 2 2 ) 2 2

2 4

RESONANCE Page # 29

1 3R 4R

= Ans.

4 3

If an electron is in any higher state n = n and makes a transition to ground state, then total no. of different

n (n 1)

photons emitted is equal to .

2

If an electron is in any higher state n = n2 and makes a transition to another excited state n = n1, then total

n ( n 1)

no. of different photons emitted is equal to , where n = n2 – n1

2

Note In case of single isolated atom if electron make transition from n th state to the ground state then max.

number of spectral lines observed = (n-1)

Ex. If electron make transition from 7th excited state to 2nd state in H atom sample find the max. number of

spectral lines observed.

n = 8 – 2 = 6

6 1 7

spectral lines = 6 = 6× = 21

2 2

Ex. An electron in isolated hydrogen atom is in 4th excited state, then, upon de excitation:

(A) the maximum number of possible photons will be 10

(B) the maximum number of possible photons will be 6

(C) it can emit two photons in ultraviolet region

(D*) if an infrared photon is generated, then a visible photon may follow this infrared photon.

Ex. In a hydrogen like sample, ions are in a particular excited state, if electrons make transition upto 1st

excited state, then it produces maximum 15 different types of spectral lines then electrons were in

(A) 5th state (B) 6th state (C*) 7th state (D) 8th state

n n 1

Sol. = 15

2

n = 5

n–2=5

n=7

Ex. In a Hydrogen like sample, all the ions are in a particular excited state. When electron make transition up to

ground state, then 6 diff. types of photons are observed. If second excitation potential of the sample is 193.64

V, then :

(a) dentify the sample

(b) Find the excited state of sample

(c) Find ionisation energy

(d) Find binding energy of 3rd state

(e) Shortest and longest wavelength belonging to above transition

(f) Series limit of Brackett series (wavelength) (in terms of R)

(g) Find the diff between the wave number of 2nd line of Lyman series and st line of Balmer series

(h) If 2nd line of Balmer series of this sample is used to excite the He+ ion already in ground state, then find

the final excited state of He+

(i) Find the no of lines not in visible range.

(j) If single isolated atom is considered in the above sample then find the max. number of spectral lines

observed in the above transition

Sol. (a) Second excitation energy = 193.6 eV.

12.1 Z2 = 193.6 eV

RESONANCE Page # 30

193 .6

Z2 = = 16

12.1

Z2 = 16

Z = 16 = 4

Hence sample is Be3+

n(n 1) 6

(b) =

2 1

n=4

Hence sample is in 3rd excited state or 4th state

13.6 16

(c) .E. = 13.6 Z2 = eV

218 .6

(d) B.E. of 3rd state = 1.5 × 42 = 1.5 × 16 = 24.0 eV

12400 12400

(e) longest = ( E) =

43 (1.5 0.85 ) 4 2

12400

shortest = ( E)

4 1

1 1 1

2 2

(f) = R × 4 4 2

1 1

= R, = R

1 1 8R 128R

(g) Lyman series 1 = R × 42 2 2 = ×16 =

1 3 9 9

1 1 R 80 20R

( 2 ) balmer = R × 42 2 2 = =

2 3 36 9

1 2 = – = =

9 9 9 9

3

-3.4 eV 2

(h)

-13.6 eV n=1

H

-3.4 eV 6

5

4

-13.6 eV 3

2

n=1

++

Li

RESONANCE Page # 31

Note : Let electron make transition from n2 to n1 in a Hydrogen like sample having atomic number Z1 and n3 n4

transition in a sample having atomic no z2 then,

(E) n n = (E) n n

2 1 4 3

1 1 1 1

13.6 Z12 2 2 = 13.6 Z2

2

n 2 n 2

n1 n2 3 4

=

n12 n2 2 n3 2 n4 2

On comparing,

Z12 Z22 Z1 Z 2 n1 Z

1

n12 n3 2

n1 n3 n3 Z 2

Z12 Z22 n2 Z1

& 2

2 n Z

n2 n4 4 2

n1 n2 Z1

n3 = n4 = Z2

H4 2

use for He+ sample n2 = 4, n1 = 2, Z1 = 1

2 4 1

n3 = n 4 = Z 2

n3 = 2Z2, n4 = 4Z2

n1 = 2 , n2 = 4,

Z1 = 4, Z2 = 2.

2 4 4

n3 = n 4 = 2

n3 1

n 2

4

(i)

RESONANCE Page # 32

0.65 16

10.40eV

visible range 4000 visible 8000 Aº

12400 12400

8000 E 400

1.55 eV E 3.1 eV

There are no lines in visible range all the lines are lie in the ultraviolet region.

4

3

(j)

2

1

3+

Be

The exact position and momentum of a fast moving particle cannot be calculated precisely at the same

moment of time. If x is the error in the measurement of position of the particle and if p is the error in the

measurement of momentum of the particle, then:

h h

x . p or x . (mv)

4 4

where, x = uncertainty in position

p = uncertainty in momentum

h = Plank’s constant

m = mass of the particle

v = uncertainty in velocity

If the position of a particle is measured precisely, i.e. x 0 then p .

If the momentum of the particle is measured precisely. i.e. p 0 then x .

This is because of a principle of optics that if a light of wavelength ‘’ is used to locate the position of a

particle then maximum error in the position measurement will be

i.e. x =

If x 0 ; 0

h

But, p= p

So, to make x 0 , 0 a photon of very high energy is used to locate it.

When this photon will collide with the electron then momentum of electron will get changed by a

large amount.

h

* p.x (multiplied & divided by t)

4

P h P

t . x ( = rate of change in momentum = F)

t 4 t

h

F.x.t

4

h

E . t

4

t uncertainty in time

RESONANCE Page # 33

In terms of uncertainty in energy E, and uncertainty in time t, this principle is written as,

h

.

E.t

4

Heisenberg replaced the concept of definite orbits by the concept of probability.

Ex. (NCERT)

A golf ball has a mass of 40 g, and a speed of 45 m/s. If the speed can be measured within accuracy of 2%,

calculate the uncertainty in the position.

2

Sol. The uncertainty in the speed is 2%, i.e., 45 × = 0.9 m s–1.

100

Using the equation

h 6.626 10 –34

x = = = 1.46 × 10–33 m

4m v 4 3.14 40 10 – 3 (0.9 m s –1 )

This is nearly ~ 1018 times smaller than the diameter of a typical atomic nucleus. As mentioned earlier for

large particles, the uncertainty principle sets no meaningful limit to the precision of measurements.

Ex. A microscope using suitable photons is employed to locate an electron in an atom within a distance of 0.1Å:

What is the uncertainty involved in the measurement of its velocity?

[Mass of electron = 9.1 x 1031 kg and Planck’s constant (h) = 6.626 x 1034Js)

h h

Sol. x × p = or x × mv =

4 4

h 6.626 10 34 J s

v = = = 0.579 × 107 ms–1 (1J = 1 kgm2s–2)

4 x m 4 3.14 0.1 10 10 m 9.1 10 31kg

= 5.79 × 106 ms–1

Ex. Uncertainty in position is twice the Uncertainty in momentum Uncertainty in velocity is -

1 h 1 h 1 h h

(A) (B) (C*) (D) 4 m

m 2m 2m 2

Sol. x = 2p

h

Now x. p

4

h h 1 h

2p2 ; 2(mv)2 ; v

4 4 2m 2

Lecture : 8

THE SCHRODINGER EQUATION :

The de Broglie wave relation is the basis for predicting the behavior of freely moving particles. Shortly after it

was proposed, Erwin Schrodinger demonstrated that the de Broglie expression could be generalized so as

to apply to bound particles such as electrons in atoms. The heart of Schrodinger's theory is that the allowed

energies of physical systems can be found by solving an equation which so resembles the equations of

classical wave theory that it is called the wave equation. For the motion of one particle in one (the x)

direction, the Schrodinger wave equation is

h2 d2

– + V = E .

82m dx 2

RESONANCE Page # 34

The "knowns" in this equation are m, the mass of the particle, and V, its potential energy expressed as a

function of x. The "unknowns" to be found by solving the equation are E, the quantized or allowed energies of

the particle, and , which is called the wave function. The quantity d2/dx2 represents the rate of change of

d/dx, the rate of change of . When this equation is applied to real systems such as the hydrogen atom, it

is found that it cannot be solved unless E takes on certain values which are related by integers. Thus

quantized energy and quantum numbers are an automatic consequence of the Schrodinger theory, and do

not have to be tacked on to Newtonian mechanics as was done by Bohr.

What is ? By itself, it has no physical meaning. However, the square of the absolute value of , 2, does

have an important physical interpretation. It is a mathematical expression of how the probability of finding a

particle varies from place to place. Thus the exact trajectories of Newtonian mechanics and the Bohr theory

do not appear in the results of the Schrodinger quantum mechanics; this, according to the Uncertainty

Principle, is as it should be.

A similar analysis is possible for the other 2p-functions. The px function has the yz-plane as an angular node,

since the function is proportional sin cos and cos = 0 everywhere in the yz-plane. The maximum values

of 1 for sin and cos occur along the positive x-axis. The py function, proportional to the sin sin ,

vanishes in the xz-plane, where sin = 0, and has a maximum along the positive y-axis, where both sin

and sin are unity.

(a) Wave function () provides several useful informations about an electron. These are :

(i) enegy of electron in an orbital.

(ii) position of electron in space in a particular allowed energy state.

(b) On the basis of values of ||2, i.e., probability of finding electron, electron clouds may be drawn and the

region where they are dense shows region of high probability.

(c) The plane and point where ||2 is zero (i.e., no probability) is called nodal plane or nodal point respectively.

(d) Orbital wave function is the product of two functions, radial function and angular function i.e.,

= (r). ( – )

(r) is the function of distance (r) from the nucleus while (, ) is the function of two sphereical

co-ordinates and as shown in figure.

(e) (r) i.e. radial part of wave function depends upon quantum number n and l and decides the size of an

orbital.

(f) Angular part of wave function (– ), depends upon quantum numbers l and m and describes the

shape of orbital. For the sake of convenience the (r) vs. r and ( – ) vs. angle are plotted seperately.

RESONANCE Page # 35

(A) The s-orbitals :

(a) All the s-orbitals are spherical and show spherical symmetry. Being symmetrical, they do not have

directional dependance.

(b) The size (or radii) of s-orbital depends upon the value of n and increases in proportionality of n2.

(c) The area covered under orbital correspond to high probability (> 90%) of finding an electron.

(d) There are different ways to correlate radial variation of ns-orbital (n = 1, 2, 3...) with distance r. Their

brief discussion is given below. :

(1) Contour diagrams : In this method, orbital is represented as 3-D sphere and probability of finding

electron (i.e., 2 value) are shown by dotted areas. The area in which shading is dense, shows area of

high probability while lighter region represents the area of low probability.

(2) By plotting 2 vs. r (i) In this method, wave functions of different orbtials like 2ls, 22s etc. are plotted

against as a function of r.

Note : The figure and reveal that the boundary surfaces of 2 and are similar, however, the main

difference lies in the fact that values may have negative sign whereas 2 is always positive.

(ii) The distance (i.e., value of r), where value of 2 is high shows the area of high probability of finding

electron.

(iii) On the other hand, the distance at which 2 is zero, shows node (i.e., area of zero probability of

finding an electron).

(iv) In 1s orbital, there is not node while in 2s and 3s, there are one and two radial nodes repsectively.

The distance of node is at r where 2 is zero.

(v) Graphs plotted 2 vs r, represents the variation of 2 with distance from nucleus and are knwon as

probability distribution curves. (figure)

RESONANCE Page # 36

(vi) The function 2 is a measure of probability of finding an electron in unit volume around a particullar

point, so it is also referred as probable density.

(3) By plotting (r) vs r :

(i) Plots (r) vs. r are shown in figure. The distance at which (r) is zero or negative show the distance of zero

electron probability.

Variation of (a) (r)1s with r nucleus; (b) (r) 2s vs. r from the nucleus; (c) (r)3s vs. r

(ii) These plots differs from plots of 2 in that value of may be negative but 2 is always positive.

(B) The p-orbitals :

(i) p-orbitals are not spherically symmetrical and have dumb-bell shape.

(Ii) p-subshell is constituted by three p-orbitals px, py and pz named with respect to axis, along which its

electron density lies.

(iii) Each p-orbital consists of two lobes joined together by a node (nucleus).

(iv) For a p-orbital to exist, minimum values of n = 2, because for p-subshell l= 1, and the minimum value of

n which gives l = 1 is 2. Thus 1p-orbital does not exist and they start from 2p.

(v) For l = 1, value of m = – 1, 0, + 1 and each other of m indicates one p-orbital. e.g.

2p-subshell contains 2px, 2py, and 2pz orbitals.

All the three have same shape and energy (i.e., degenerate) and differ in orientation only.

(vi) The wave function for pz has maximum amplitude along z-axis. It is zero along xy plane. Similarly px and

py has maximum probability of finding electron along x and y-axis.

(vii) Contour diagram for 2p-orbitals are shown in the figure given below :

RESONANCE Page # 37

(C) The d-orbitals :

(i) For d-subshell, value of l = 2 and minimum value of n, which gives l = 2, is 3. Thus, 1d or 2d-orbitals have

no existence and they starts from 3d.

(ii) For l = 2, the values of m = – 2, 0 + 1, + 2, (five values), thus each d-subshell is made up of five d-orbitals

which are dxy, dyz, dxz, dx2–y2, dz2.

(iii) Except dz2, they have four lobes seperated by a dnode (nucleus) while dz2 has only two lobes. Their

shapes have been show below :

(iv) Lobes of dxy, dyz, and dxz lie between the axes, while dx2–y2 and dz2 lie on the axes.

(v) dz2 has two lobes on z-axis and doughnut in xy-plane. It looks like baby soother.

(vi) All the d-orbitals belonging to a subshell have same energy and so are degenerate (five fold degeneracy).

Although dz2 appers different in shape, it also has same energy as that of other d-orbitals.

(D) The f-orbitals :

(i) For f-subshell l - 3 and thus m will have seven values m = – 3, – 2, – 1, 0, + 1, + 2, + 3. For l = 3, minimum

value of n must be four thus if, 2f of 3f have no existence and f-orbitals starts from n = 4 (i.e., 4f).

(ii) In a f-subshell, there are seven f-orbitals. Their contour diagram which are 3-D, are difficult to draw on

paper.

(iii) The seven f-orbitals are :

fx(x2 – y2), fy(x2 – y2), fz(x2 – y2), fxyz, fz3, fyz2 and fxz2.

Note :

1. Sometimes an orbital is represented in terms of n, l, m also. Usually for m = 0, z – axis is chosen.

e.g., 420 reveals that n = 4, l = 2, and m = 0, thus it is 4dz2 y310 reveals that n = 3, l = 1, m = 0 thus it 3pz.

2. For an orbital (or subshell) as the value of n increases, the size of orbital increases i.e., 1s < 2s < 3s etc.

3. As r approaches to 0, also approaches zero except s-orbital. It concludes that only s-electron can

penetrate through nucleus and has probability to be found at nucleus.

4. For one electron system (e.g., H, He+, Li2+, Be3+ etc.), energy of orbital depends only on value of n and

not on l, thus all hte subshells belonging to same shell will have same energy.

5. There is no unique way of representing the angular dependence functions of all seven f-orbitals. An

alternative way may be as fz3, fxz2, fyx2, fzy2, fx(x2 – 3y2)fy(y2 – 3z2) and fz(z2 – 3x2).

RESONANCE Page # 38

Radial probability density for some orbitais of the hydrogen atom. Ordinate is proportional to

4 r2 R2, and all distributions are to the same scale.

Orbital :

An orbital may be defined as the region of space around the nucleus where the probability of finding an

electron is maximum (90% to 95%)

Orbitals do not define a definite path for the electron, rather they define only the probability of the electron

being in various regions of space around the nucles.

Orbit Orbitals

1. It is well defined circular path followed 1. It is the region of space around the nucleus

by revolving electrons around the nucleus where electron is most likely to be found

2. It represents planar motion of electron 2. It represents 3 dimensional motion of

an electron around the nucleus.

3. The maximum no. of electron in an 3. Orbitals can not accomodate more than

orbits is 2n2 where n stands for no. 2 electrons.

of orbit.

4. Orbits are circular in shape. 4. Orbitals have different shape e.g. s-orbital is

spherical, p - orbital is dumb- bell shaped.

5. Orbit are non directional in character. 5. Orbitals (except s-orbital) have directional character.

Hence, they cannot explain shape of Hence, they can account for the shape of molecules.

molecules

6. Concept of well defined orbit is against 6. Concept of orbitals is in accordance with Heisenberg’s

Heisenberg’s uncentainty principle. principle

RESONANCE Page # 39

Shape of the orbitals :

Shape of the orbitals are related to the solutions of Schrodinger wave equation, and gives the space in which

the probability of finding an electron is maximum.

s- orbital is non directional and it is closest to the nucleus, having lowest energy.

s-orbital can accomodate maximum no. of two electrons.

Dumb bell shape consists of two loops which are separated by a region of zero probability called node.

RESONANCE Page # 40

d - orbital can accomodate maximum no. of 10 electrons.

(i) Node represents the region where probability of finding an electron is zero (i.e., and 2 = 0). Similarly

nodal plane represents the plane having zero probability of finding electron.

(ii) Nodes are of two types :

(a) Radial node (b) Angular node

A radial node is the spherical region around nucleus havingt and 2 equal to zero. An orbital having higher

number of nodes has more energy.

(iii) Calculation of number of nodes :

Radial nodes = n – – 1

Angular nodes =

Total nodes = n – 1

n and l are principal and zimuthal quantum numbers. e.g., in 3p-orbital.

Radial nodes = 3 – 1 – 1 = 1 (= n – – 1)

Angular nodes = 1 (= )

Total nodes = 2 (one radial, one angular) for 4d orbital

Total nodes = 3 (one radial and two angular)

(iv) For one electron system, the energy depends only upon the number of nodes (n – 1) and not upon types

of nodes.

Note :

It is thus evident that number of radial nodes increases with increasing value of principal quantum

numebr n. It is thus evident that asn ns-orbital has (n – 1) radial nodes (a radial node for an ns-orbital is

a spherical shell about the nucleus on which and 2 approache to zero). The larger the number of

nodes, the higher the energy of the orbital. The second feature is qualitatively the size of an orbital which

increases with increasing quantum number n. It implies that the electron is most likely to be found

farther from the nculeus for larger n. Thus, a 3s-orbital is larger than a 2s-orbital, which in turn in larger

than 1s-orbital. This is the quantum mechanical analogue of the increase in radius of the Bohr orbit with

n.

RESONANCE Page # 41

Degenerate and Non-degenerate Orbitals

Orbitals belonging to same subshell have same energy are known as degenerate orbitals. Degeneracy

is maintained in absence of magnetic field but destroyed if degenerate orbitals are kept in magnetic field.

Thus,

Lecture : 9

QUANTUM NUMBERS :

The set of four numbers required to define an electron completely in an atom are called quantum numbers.

The first three have been derived from Schrodinger wave equation.

(i) Principal quantum number (n) : (Proposed by Bohr)

It describes the size of the electron wave and the total energy of the electron. It has integral values

1, 2, 3, 4 ...., etc., and is denoted by K, L, M, N. ..., etc.

* Number of subshell present in nth shell = n

n subshell

1 s

2 s, p

3 s, p, d

4 s, p, d, f

* The maximum number of electrons which can be present in a principal energy shell is equal to 2n2.

No energy shell in the atoms of known elements possesses more than 32 electrons.

nh

* Angular momentum of any orbit =

2

(ii) Azimuthal quantum number () : (Proposed by Sommerfield)

It describes the shape of electron cloud and the number of subshells in a shell.

* It can have values from 0 to (n – 1)

* value of subshell

0 s

1 p

2 d

3 f

* Maximum number of electrons in particular subshell = 2 × (2 + 1)

h h

* Orbital angular momentum L = ( 1) = ( 1) 2

2

h

i.e. Orbital angular momentum of s orbital = 0, Orbital angular momentum of p orbital = 2 ,

2

h

Orbital angular momentum of d orbital = 3

2

(iii) Magnetic quantum number (m) : (Proposed by Linde)

It describes the orientations of the subshells. It can have values from – to + including zero, i.e.,

total (2 + 1) values. Each value corresponds to an orbital. s-subshell has one orbital, p-subshell three

RESONANCE Page # 42

orbitals (px, py and pz), d-subshell five orbitals (d xy , d yz , d zx , d x 2 y 2 , dz 2 ) and f-subshell has seven orbitals.

The total number of orbitals present in a main energy level is ‘n2’.

(iv) Spin quantum number (s) : (Proposed by Goldschmidt & Uhlenbeck)

It describes the spin of the electron. It has values +1/2 and –1/2. (+) signifies clockwise spinning and

(–) signifies anticlockwise spinning.

eh

* Spin magnetic moment s = 2 mc s( s 1) or = n (n 2) B.M. (n = no. of unpaired electrons)

h

* It represents the value of spin angular momentum which is equal to s( s 1)

2

1

* Maximum spin of atom = x No. of unpaired electron.

2

Ex. (NCERT)

What is the total number of orbitals associated with the principal quantum number n = 3 ?

Sol. For n = 3, the possible values of are 0, 1 and 2. Tthere is one 3s orbital (n = 3, = 0 and m = 0) ; there are

three 3p orbitals (n = 3, = 1 and m= – 1, 0, + 1) ; there are five 3d orbitals

(n = 3, = 2 and m= – 2, – 1, 0, + 1+, + 2).

Therefore, the total number of orbitals is 1 + 3 + 5 = 9

The same value can also be obtained byusing the relation; number of orbitals = n2, i.e. 32 = 9.

Ex. (NCERT)

Using s, p, d, f notations, describe the orbital with the following quantum numbers

(a) n = 2, = 1, (b) n = 4, = 0, (c) n = 5, = 3, (d) n = 3, = 2

Sol. n orbital

(a) 2 1 2p

(b) 4 0 4s

(c) 5 3 5f

(d) 3 2 3d

Ex. Find orbital angular momentum of an electron in (a) 4s subshell and (b) 3p subshell

Ans. (a) 0

h

(b) 2

2

h

Ex. Orbital angular momentum of an electron in a particular subshell is 5 then find the maximum number

of electrons which may be present in this subshell.

h

Sol. Orbital angular momentum = ( 1)

2

h h

( 1) = 5

2

( 1) = 2 5 = 20 = 4.

hence maximum number of electrons in this subshell = 2(2 + 1) = 18.

Ans. 18

1 1

(A) n = 3, l = 2, m = 2, s = + (B) n = 2, l = 0, m = 0, s = –

2 2

1 1

(C) n = 4, l = 2, m = –1, s = + (D*) n = 4, l = 3, m = 4, s = – ( m > is not possible)

2 2

RESONANCE Page # 43

Electronic configuration :

Pauli’s exclusion principle :

No two electrons in an atom can have the same set of all the four quantum numbers, i.e., an orbital cannot

have more than 2 electrons because three quantum numbers (principal, azimuthal and magnetic) at the most

may be same but the fourth must be different, i.e., spins must be in opposite directions.

Aufbau principle :

Aufbau is a German word meaning building up. The electrons are filled in various orbitals in order of their

increasing energies. An orbital of lowest energy is filled first. The sequence of orbitals in order of their

increasing energy is :

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ....

The energy of the orbitals is governed by (n + ) rule.

‘n + Rule :

The relative order of energies of various sub-shell in a multi electron atom can be predicated with the help

of ‘n + ’ rule

The sub-shell with lower value of (n + ) has lower energy and it should be filled first.

eg. 3d 4 s

(n +) = 3 + 2 (n +) = 4 + 0

=5 =4

Since, (n + ) value of 3d is more than 4s therefore, 4s will be filled before 3d.

If two sub-shell has same value of (n + ) then the sub-shell with lower value of n has lower energy and

it hs ould be filled first.

eg. 3d 4p

(n +) = 3 + 2 =4+1

=5 =5

3d is filled before 4p.

MEMORY MAP :

1s

2s 2p

3s 3p 3d 1– s

2 – s,p

3 – s,p

4s 4p 4d 4f 4 – s,d,p

5 – s,d,p

5s 5p 5d 5f 6 – s,f,d,p

6 – s,f,d,p

7 – s,f,d,p

6s 6p

Hund’s rule :

No electron pairing takes place in the orbitals in a sub - shell until each orbital is occupied by

one electron with parallel spin. Exactly half filled and fully filled orbitals make the atoms more stable, i.e., p3,

p6, d5, d10, f7 and f14 configuration are most stable.

Ex. Write the electronic configuration and find the no. of unpaired electrons as well as total spin for the following

atoms :

(1) 6

C

(2) 8

O

(3) 15

P

(4) 21

Sc

RESONANCE Page # 44

(5) 26

Fe

(6) 10

Ne

(i) 6

C 1s2, 2s2, 2p2

2 2

Total spin = or

2 2

(ii) 8

O 1s2, 2s2, 2p4

1s 2s 2p

No. of unpaired electrons = 2

2 2

Total spin = or

2 2

(iii) 15

P 1s2, 2s2, 2p6, 3s2, 3p3

3s 3p

No. of unpaired electrons = 3

3 3

Total spin = or

2 2

(iv) 21

Sc 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d1

3d 4s

[Ar] 3d1 4s2

No. of unpaired electrons = 1

1 1

Total spin = or

2 2

26

or [Ar] 4s2, 3d6

4s 3d

No. of unpaired electrons = 4

4 4

Total spin = or

2 2

(vi) 10

Ne 1s2, 2s2 2p6

Total spin = 0

RESONANCE Page # 45

EXCEPTIONS :

(1) 24

Cr = [Ar] 4s2, 3d4 (Not correct)

[Ar] 4s1, 3d5 (correct : as d5 structure is more stable than d4 structure)

(2) 29

Cu = [Ar] 4s1, 3d10 (correct : as d10 structure is more stable than d9 structure)

Ex. Find the electronic configuration of Fe2+ and Cr3+ and their magnetic moments.

Ans.

(i) Fe [Ar] 3d6, 4s2

Fe2+ [Ar] 3d6

3d

No. of unpaired electrons = 4

B.M. = 2 6 B.M.

Cr3+ [Ar] 3d3

No of unpaired electrons = 3

Ex. Write all four quantum numbers for the last electrons of Na

1s2, 2s2,2p6, 3s1

n=3

=0

m=0

1

s=±

2

RESONANCE Page # 46

Lecture : 10

Stability of Nucleus

Nucleus of an atom contains all the protons and neutrons in it while all the electrons are in the outer sphere.

Nuclides can be grouped on the basis of nuclear stability, i.e., stable and unstable nucleus. The question

naturally arises why some nuclides are stable while others are unstable. The stability of atom has been

explained in terms of Coulombic forces of attraction and forces of motion. The stability of nucleus cannot be

explained in terms of these forces because of similar charged particles present in nucleus. No single rule

allows us to predict whether a particular nucleus is radioactive and how it might decay.

Note : (1) A common term nucleons is referred for the proton and the neutron.

(2) Generally nuclei are spherical but nuclei of Hf and Ta are reported to be oval shaped.

(3) Recall that nuclear density is of the order of 1017 kg/m3 and is approximately same for all nuclei.

The stability of nucleus has been explained in terms of strong interaction forces known as nuclear forces

which operate between sub-atomic particles when they approach each other with in the range of 10–12 cm.

In nucleus, the particles are closer than 10–13 cm (or 1 fermi) and thus, nuclear forces operate. The nuclear

force between two nucleons decreases rapidly as the separation between them increases and becomes

negligible at separation more than 10 fermi. Nuclear forces are about 50-60 times more stronger than

electromagnetic forces. Nuclear forces are basically attractive forces and are responsible for keeping nucleons

bound in the nucleus.

Note : (1) As the distance of separation increases (> 10–13 cm) nuclear forces becomes insignificant. The range

up to which the nuclear force is effective is called nuclear range. At the distance of separation of 10–12 cm,

interaction among nucleons becomes electromagnetic. Nuclear forces are about 50-60 times more stronger

(in nuclear range) than electromagnetic forces.

These forces are charge independent and operate between p-p, n-n and p-n. As a result of these foces, the

potential energy barrier of nucleus is lowered due to evolution of energy involving mass decay according to

Einstein mass-energy relationship, E = mc2. The resultant nucleus thus, acquired lower energy level and

attains stability. The mass difference between a nucleus and its constituent nucleons respoinsible for

binding energy, is called the mass defect.

The total energy given out during binding up of nucleons in nucleus is known as binding energy. Greater is

binding energy, lesser is energy level of nucleus and thus, more is its stability.

Therefore, B.E. = m × c2 erg (m in g) (c in cm/sec)

= 1.6605 × 10–24 × m × c2 erg (m in amu)

= 1.6605 × 10–24 × m × (2.9979 × 1010) erg

= 14.923 × 10–4 × m erg

= 14.923 × 10–11 × m J (107 erg = 1 J)

= eV (1.602 × 10–19 J = 1 eV)

1.602 10 19

= MeV (106 eV = 1 MeV)

1.602 10 19 10 6

~ 931.478 m MeV (Mega or Million electron volt)

if m = 1 amu then, B.E. = 931.478 MeV, i.e., decay of 1 amu produces 931.478 MeV energy.

Also, 1 amu = 931.478 MeV

Total B.E.

B.E. per nucleon, B =

No. of nucleons

B.E./nucleon has been found to increase with increase in atomic number and becomes maximum for 26Fe

at 8.78 MeV. After Fe, it continuously decreases and becomes almost constant at 7.6 MeV for 82Pb and

onwards.

RESONANCE Page # 47

Plot of nuclear binding energy per nucleon against the mass number for naturally occuring

nuclides.

56

Note : (1) The greater the binding energy per nucleon, the more stable is nucleus and thus 26 Fe is most stable

nucleus.

(2) Elements with mass number 4, 12 and 16 have high values of and B therefore, 24 He , 12

6

C and 16

8 O are

stable nuclei.

19

16

8 O 8 O + 1.06 × 108 kcal/mol

( excited state ) ( ground state )

Sol. E = m × c2 × 10–3 J.

c m/sec

10 3

E = m × c × cal.

4.18

10 3

1.06 × 1011 = m × 3 × 108 × 3 × 108 ×

4.18

m = 0.49 × 10–2 gm

m ~ 5 × 10–3 gm.

Neutrons apparently help to hold protons together within the nucleus. The number of neutrons necessary to

create a stable nucleus increases rapidly as the number of protons increases ; the number of neutron to

proton ratio of stable nuclei increases with increasing atomic number. The area within which all stable

nuclei are found is known as the belt of stability. The majority of radioactive nuclei occur outside this belt.

RESONANCE Page # 48

Note : (1) For elements mass number A < 40, Nature prefers the number of protons and neutrons in the nucleus

to be about the same to attain stability.

(2) For elements having A > 40, Nature prefers n > p to attain stability. As the number of protons increases,

the coulombic repulsive force increases and so the excess of neutrons which produce only attractive force

(nuclear force) is required for stability. It is therefore neutron vs. proton curves departs from n = Z line.

(3) Even in light nuclei n may exceed Z but except (in 1H and 32 He ) is never smaller e.g., 11

5 B is stable but

11 is not.

6 C

The type of radioactive decay that a particular radio isotope will undergo depends to a large extent on its

neutron to proton ratio compared to those of near by nuclei that are with in belt of stability.

n n

(a) A nucleus whose high ratio places it above the belt of stability emits a -particle in order to lower

p p

ratio and move towards the belt of stability.

1

0n 11p + 0

1e + ( is Anti neutrino)

e.g, 82 82 + 2 01e

34 Se 36 Kr

n

(b) A nucleus whose low ratio places it below the belt of stability either emits positrons or undergo

p

electron capture. Both modes of decay decrease the number of protons and increase the number of neutrons

n

in the nucleus and thus, positron emission or electron capture results in an increase in ratio. Positron

p

emission is more common than electron capture among the higher nuclei, however, electron capture becomes

increasingly common as nuclear charge increases. In such nuclides, the nucleus captures an electron from

the K-shell and thus also known as K-electron capture. The vacancy created in K-shell is filled by electrons

from higher energy levels giving rise to characteristic X-rays.

1 1 + 0

1p 0n 1e

RESONANCE Page # 49

e.g., 11 11 + 0 (Positron emission)

6 p 5 B 1e

1p 1e 0n

56 Ba 1e 55 Cs + X-ray

(K-electron)

Note : A positron has same mass as electron but carries opposite charge. The positron has a very short life

because it is annihilated when it collides with an electron, producing gamma rays. This phenomenon is

known as pair annihilation.

0 + 0 2 00

1e 1e

Similarly pair production occurs when a photon passes through the matter

h = 0 + 0

1e 1e

(c) The nuclei lying beyond the upper right edge (i.e., nuclei with atomic number > 83), outside the belt of

stability, undergo -emission. Emission of an -particle decreasing both the number of protons and neutrons

n

and thereby increasing ratio.

p

92 U 90 Th 2 He

n n

Thus, > 1.0, unstable nuclei ; < 1.0, stable unclei

Z Z

Note : (1) Some elements say 234 should undergo -decay on the basis of above guide line (c), whereas, it

90 Th

undergoes -decay.

233 233 + 0

90 U 91 Pa 1e

(2) A few radioactive nuclei lie within the belt of stability, e.g., 146 and 148 are stable and lie in the

60 Nd 60 Nd

60 Nd

The nuclear shell model of nuclear structure is analogous to the electron shell model of atomic structure.

Just as certain number of electrons (2, 8, 18, 36, 54 and 86) correspond to stable closed shell electron

configuration, certain number of nucleons leads to closed shell in nuclei. The protons and neutrons can

achieve a closed shell. Nuclei with 2, 8, 20, 28, 50 or 82 protons or 2, 8, 20, 28, 50, 82 or 126 neutrons

correspond to closed nuclear shell. Closed shell nuclei are more stable than those that do not have closed

shells. These number of nucleons that corresponds to closed nuclear shells are called magic numbers.

Note : (1) There are theoretical predictions that a nucleus with 114 protons or 184 neutrons will aos be a closed

shell. These predictions are being used in the search for new elements beyond hte currently known.

(2) All nuclei with Z > 83 and A > 239 spontaneously transform into lighter ones showing radioactive

changes.

Rutherford identified two types of these penetraining rays and named them alpha () and beta () particles.

Later on P. Villard identified and named, the third category as gamma () rays.

Table1 :

Properties of , -particles and -rays, Becquerel radiations.

RESONANCE Page # 50

S.No. Properties Alpha Beta Gamma

Fast moving He High energy

1 Nature First moving electrons

nuclei radiations

4 0

2 Notation 2He or –1e or or 00

Same as light

5 Velocity 1/10 of light 33% to 90% of light

waves

6 Nature of path Straight line Crooked Waves

Relative 10,000 or

1 or 100 or

7 penetrating (8 m lead or 25

(0.01 mm of Al foil) (0.1 cm of Al foil)

power cm steel)

Travel distance

8 2-4 cm 200-300 cm 500 m

in air

9 Tissue depth 0.05 mm 4-5 mm 50 cm or more

Heavy clothing, lab Lead,

10 Shielding Paper, clothing

coats, gloves thick concrete

11 Mass g/particle 6.65 × 10-24 9.11 × 10-28 0

Relative ionising

12 10,000 100 1

power

Electrical

Deflected towards Deflected towards

13 or magnetic Not deflected

– ve pole + ve pole

field's influence

Rutherford and Soddy

The ejection of , and -rays from a radioactive material has been satisfactorily explained by Rutherford

and Soddy.

Step I : An excited nucleus (a nucleus of low B.E. or higher energy level) tries to attain lower energy level

in order to attain stability. Therefore, -particles come out of nucleus as energy carrier.

n

Step II : During -decay no doubt that energy level comes down but ratio increases and therefore to

p

n

decrease ratio and attain stability, nucleus undergoes neutron decay or neutron transformation to show

p

emission of -particles.

1 1 1

0n 1p + –1e +

Step III : The resultant nucleus after , -emission still possesses higher energy level than required for its

stability, the difference of energy comes out in form of -rays. Thus gamma radiations are given off by nuclei

in an excited state.

Therefore, , -emission are primary emissions and -emissions are secondary emissions.

Note : (1) -particles originates in the nucleus; they are not orbital electrons.

(2) -radiations always accompany or -emissions and thus, are emitted after and -decay.

(3) In gamma decay neither the atomic number nor the mass number changes. Only the quantum state of

the nucleons change.

(4) , and -decay are collectively called radioactive decay ; the material showing radioactive decay is

RESONANCE Page # 51

called radioactive material and the emission of , - and - are collectively called nuclear radiations.

(i) A radiactive atom on losing an -particle shows a loss in mass number by 4 units and a loss in atomic

number by 2 units.

Thus, newly formed element occupies two position left to the parent element in periodic table.

226 222 218

88 Ra

86 Rn

84 Po

II gp 0 gp VI gp

(ii) A radioactive atom on decay of a -particles shows a gain in its atomic number by 1 unit whereas, mass

number remains same.

Thus, newly formed element occupied one position right to the parent element in periodic table.

214

Pb 214 214

83 Bi 84 Po

82

VI gp V gp VI gp

Ex. 23

Na is the most stable isotope of Na. Find out the process by which 24 can undergo radioactive decay..

11 Na

24

Sol. n/p ratio of Na is 13/11 and thus greater than one. It will therefore decay following -emission.

24 24 0

11 Na 11 Mg + 1e

dY

(A) (B) d + 2 + c (C*) d + 2 – a (D) d + 2 – c

4

Sol. c b

a X d Y + m 24 He + n 01e

c = b + 4m ......(i)

and a = d + 2m – n ......(ii)

by (i) & (ii)

c b

n = d + 2 – a.

7 N

(A) 13 + 0 (B*) 13 + 0

8 O 1e 6 C 1e

6 C

13

n

Sol. 7 N

is positron emitter ; p ratio is low..

Ex. An element of group III with atomic number 90 and mass number 238 undergoes decay of one -particle.

The newly formed element belongs to :

(A) 1st group (B) 13th group (C) IInd group (D) 14th group

Sol. The finally formed stable element for all three natural radioactive series is Pb belonging to group 14.

Ex. A radioactive element X has an atomic numbers of 100. It decays directly into an element Y which decays

directly into an element Z. In both processes a charged particle is emitted. Which of the following statement

would be true?

(A) Y has an atomic number of 102. (B) Z has an atomic number of 101.

(C) Z has an atomic number of 97. (D*) Z has an atomic number of 99.

Sol. X and Y can decay one each or one each or X-decays, 1 , Y-decays 1 or X-decays 1 . In either case

(a), (b) and (c) cannot be true.

Radioactive Series

RESONANCE Page # 52

A series of nuclear reactions that begins with an unstable nucleus and terminates with a stable one is

known as radioactive series or a nuclear disintegration series.

About 42 radioactive nuclides with Z > 82 occur in nature. Systematic studies established that these

nuclides are the daughter products of the three natural decay series. The parent members of the series are

232

Th, 238U and 235U. An atom of these three elements undergoes a series of successive , -decay forming

intermediates eventually leading to the formation of a stable isotope of lead.

232

90 Th

208 + 6 24 He + 4 01e (4n series)

82 Pb

238 206 + 8 24 He + 6 01e (4n + 2 series)

92 U 82 Pb

235 207 4 0

92 U 82 Pb + 7 2 He + 4 1e (4n + 3 series)

The parent elements, intermediates and final stable element of 232Th series have masses which are integral

multiple of 4. That is why this series is known as 4n series. Similarly, 238U and 235U series are known as (4n

+ 2) and (4n + 3) series.

Nuclear Reactions

The phenomenon of interaction of nucleons giving rise to the formation of a new nucleus or a process in

which one nuclide in converted to another by interaction with another nuclide. The first ever nuclear

reaction in laboratory was carried out by Rutherford when the bombarded N atoms with -particles.

14 4 17

7 N 2 He 8 O 11H Q

14

Another, method of representing this nuclear reaction is 7 N (: p).

Nuclear Fission :

(a) The phenomenon of splitting up of a heavy nucleus, on bombardment with slow speed neutrons, into two

fragments of comparable mass, with the release of two or more fast moving neutrons and a large amount of

energy, is known as nuclear fission.

236

(b) 235 1

92 U 0n 92 U

A loss in mass occurs releasing a vast quantity of energy ~ 2.041 × 1010 kJ per mol of 235U

20.41 10 9

(c) Fission of 1 mole g235 U releases energy = kJ = 8.68 × 107 kJ

235

Fission of 1 mole 235U releases energy = 20.41×109 kJ

Fission of an atom of 235U 5500 pound coal 33

Nuclear Fusion :

(a) The phenomenon of joining up of two light nuclei into a heavier nucleus is called fusion, e.g.,

2 3 4

1 H 1 H 2 He 10 n ; (H = –17.6 MeV)

(b) Huge amount of energy of required to overpower the Coulombic forces of repulsion in between two nuclie

which is obtained by triggering on nuclear fission.

RESONANCE Page # 53

- N1 Industrial ElectronicsÎncărcat deFuture Managers Pty Ltd
- Chem Topic 2 Questions + AnswersÎncărcat deOscarHigson-Spence
- Electron Cloud LabÎncărcat despecops47
- lesson plan chemistry form 4Încărcat deanon_482140092
- Chapter 04 - Atomic StructureÎncărcat deAsullivan424
- 1 IntroductionÎncărcat dePatricia Lim
- AtomÎncărcat deThess Tecla Cuarez Mendoza
- F4T2 06Încărcat deFidree Aziz
- BIO 156 Chapter 2 PowerpointÎncărcat deDrPearcy
- eoc - chemistry blogÎncărcat deapi-312162583
- AIDSÎncărcat deMohit Pathak
- subatomic particles.pptxÎncărcat deRamon Gasgas
- SIM for 3rd year by Beatriz R. RubicoÎncărcat deLorena Dizon
- Islamic Correspondece Course - Advanced - 1 of 4Încărcat deQanber
- 1.1 NotesÎncărcat deZiddi Bachi
- Atom FactsÎncărcat deaaditya panwar
- Basic Atomic Structure Worksheet ANSWERS.docxÎncărcat delex marantal
- 1st nine weeks exam reviewÎncărcat deapi-233187566
- 0-IntroducciónÎncărcat deBruno Luis Villarroel Dávalos
- Benhar - Short-range CorrelationÎncărcat dezcapg17
- Models of the AtomÎncărcat deakash
- Chapter 3 Atomic Structure and the Periodic TableÎncărcat deGrace Ann Samson
- Umass Physics 131 Unit 4 1.1Încărcat dekim kim
- BIO 156 Chapter 2 PowerpointÎncărcat deDrPearcy
- Assignment 02 A1Încărcat desundus
- Science and Technology (Std-9)Încărcat devk singh
- Kinetic EnergyÎncărcat deCherubin Queil Saguil
- Chapter 2 Outline NotesÎncărcat deFernando Mora
- reviewer.pptxÎncărcat dehayi013
- 1.Al KhaliliÎncărcat dePrasad Ravichandran

- ASSIGNMENT.docÎncărcat deRamJiPandey
- Chapter01 - Logarithm.pdfÎncărcat deRamJiPandey
- AITS-2014-CRT-III-JEEM+JEEA-Advanced-PAPER-1-Questions-PAPERÎncărcat delonglostloner889
- Stoichiometry.pdfÎncărcat deRamJiPandey
- 12 Chemistry Impq CH01 the Solid State 01Încărcat deSanjay Gupta
- 12_chemistry_impq_CH03_electro_chemistry_02.pdfÎncărcat deaman
- 12345.docxÎncărcat deRamJiPandey
- manmad chem.pdfÎncărcat deRamJiPandey
- 9780521270731_Excerpt_001.pdfÎncărcat deRamJiPandey
- Electrostatics (JEE).pdfÎncărcat deRamJiPandey
- 2_Current Electricity.docÎncărcat deRamJiPandey
- Sheet Mole Concept TheoryÎncărcat deRamJiPandey
- Sheet_goc_1_theory_english.pdfÎncărcat deRamJiPandey
- bitsatpaper.pdfÎncărcat deRam Ji
- Chapter19 - Area Under CurvesÎncărcat deRamJiPandey
- WORK AND ENERGY.docÎncărcat deRamJiPandey
- Sterling_JEE_Physics_(Elasticity Thermal Exp, Calorimetry & Heat Transfer)_EngÎncărcat deRamJiPandey
- acÎncărcat deJhon Harrison
- ContentÎncărcat deRamJiPandey
- (2097)Lecture Notes Solutions and Colligative Proerties eÎncărcat deRamJiPandey
- (2095)Lecture Notes Mole Concept eÎncărcat deRamJiPandey
- (2099)Lecture Notes p Block 15 16 e.pdf.TmpÎncărcat deRamJiPandey
- (2091)Lecture Notes Electrochemistry e.pdf.TmpÎncărcat deRamJiPandey
- (2090)Lecture Notes Chemical Kinetics Radioactivity eÎncărcat deRamJiPandey
- Allen Test PaperÎncărcat deshambhavi26
- Rotational Mechanics (NEET).pdfÎncărcat deRamJiPandey
- Scibd Test DocÎncărcat deRamJiPandey

- Breast Feeding Techniques and Positions PEDIATRIC NURSING PptÎncărcat deGovindaraju Subramani
- Optimal Management of an Energy Storage Unit in a PV-Based Microgrid Integrating Uncertainty and RiskÎncărcat deKaiba Seto
- ch08Încărcat deShreshtha Verma
- Ashtakavarga Par 1Încărcat demagicalseas
- Admissibility of Scientific EviÎncărcat deVilakshan Saxena
- C Language NotesÎncărcat deapi-3820001
- Prosperidad_1_Daily Drilling Report No_02_ Feb_11th_2019.pdfÎncărcat deAlexandra Molina
- fry list 400 check boxesÎncărcat deapi-291490402
- Hydraulic MachinesÎncărcat deZohaib Alam Warraich
- Vasyl Stefanyk - NEWSÎncărcat deandreusDADA
- RAPID SELF-HYPNOSIS: A SUGGESTION METHOD FOR SELF-CONTROLÎncărcat dejemf
- A Guide to Salivary Gland Disorders.pdfÎncărcat dedanny17ph
- Numerical Approaches to Combustion ModellingÎncărcat deRefik Alper Tuncer
- 2009 New FLP Products!Încărcat deLeo Tesoro
- Presentation 1Încărcat deManish Bhattacharjee
- Newport Células SolaresÎncărcat deluciano_gularte
- SAES-S-070Installation of Utility Piping SystemsÎncărcat deWaqar Ahmed
- General PM Detail - WeeklyÎncărcat denunkp
- ICAO an Report en Final 30042014Încărcat demirela-2811
- Zefiq - 260 Godina Doseljenja Klimenti u SrijemÎncărcat deninodjukic
- HCC Case Book.pdfÎncărcat deRahul Bajaj
- Op-Amp Internal CircuitÎncărcat deNazeer Hussain
- Autocad Raster Design 2012 Getting StartedÎncărcat deZubic Vila
- MSSPs Targeting SMBs-WPÎncărcat demoxdy
- Tank Protection May 05Încărcat dejm.mankavil6230
- A Critical Account of Some of Joseph Albers' Concepts of ColorÎncărcat desandipkluis
- HULL FORM AND GEOMETRYÎncărcat deMahmoud Elsayed
- Dressing ChoicesÎncărcat degrinninggreen
- mandiri 2012-2016.pdfÎncărcat deLionel Mus
- Finance Director in Boston MA Resume James ReynoldsÎncărcat deJamesReynolds2

## Mult mai mult decât documente.

Descoperiți tot ce are Scribd de oferit, inclusiv cărți și cărți audio de la editori majori.

Anulați oricând.