Chapter

STRUCTURE OF ATOM

INTRODUCTION
* The earliest concept of atom ( smallest indivisible part of matter ) was given by ancient (600-400 BC) Indian and Greek philosophers.
John Dalton revived the concept of atom in the beginning of nineteenth century in terms of his atomic theory which successfully
explained the laws of chemical combination.
* Atom is the smallest indivisible particle of the matter. Atom is made of electron, proton and neutrons.

2.1 SUB ATOMIC PARTICLES

Electron Proton Neutron

Discovery Sir. J. J. Thomson (1869) Goldstein (1886) Chadwick (1932)
Nature of charge Negative Positive Neutral
Amount of charge 1.6 × 10–19 Coloumb 1.6 × 10–19 Coloumb –
Mass 9.11 10–31 kg 1.672614 10–27 kg 1.67492 10–27 kg

2.1.1 Discovery of Electron To vacuum pump

* Cathode ray discharge tube experiment : A cathode ray discharge
tube made of glass is taken with two electrodes. At very low – + anode
Cathode
pressure and high voltage, current starts flowing through a stream
of particles moving in the tube from cathode to anode.
These rays were called cathode rays. When a perforated anode
was taken, the cathode rays struck the other end of the glass tube
at the fluorescent coating and a bright spot on the coating was
developed . High voltage
Results: Figure : A cathode ray discharge tube
(a) Cathode rays consist of negatively charged electrons.
(b) Cathode rays themselves are not visible but their behavior can be observed with help of fluorescent materials.
(c) In absence of electrical or magnetic field cathode rays travel in straight lines. In presence of electrical or magnetic field,
behaviour of cathode rays is similar to that shown by electrons.
(d) The characteristics of the cathode rays do not depend upon the material of the electrodes and the nature of the gas
present in the cathode ray tube.
* Charge to mass ratio of an electron was determined by Thomson. Charge to mass ratio of an e– as 1.758820 × 1011 C kg–1
* Charge on an e– was determined by R A Millikan by using an oil drop experiment. The charge on an electron is -1.6 × 10–19C.
* The mass on an electron was determined by combining the results of Thomson's experiment and Millikan's oil drop experiment.
The mass of an electron was determined to be 9.1094 × 10–31 kg.

2.1.2 Discovery of protons

* Modified cathode ray tube experiment was carried out which led to the discovery of protons.
* Characteristics of positively charged particles:
(a) Charge to mass ratio of particles depends on gas from which these originate.
(b) The positively charged particles depend upon the nature of gas present in the cathode ray discharge tube.
(c) Some of the positively charged particles carry a multiple of fundamental of electrical charge.
(d) Behaviour of positively charged particles in electrical or magnetic field is opposite to that observed for cathode rays.
2.1.3 Discovery of Neutrons :
* Neutrons were discovered by James Chadwick by bombarding a thin sheet of beryllium by -particles.
* They are electrically neutral particles having a mass slightly greater than that of the protons.

STUDYMATERIAL: XI CHEMISTRY 1 STRUCTURE OF ATOM

2.2 ATOMIC MODELS
2.2.1 Thomson Atomic Model : Thomson atomic model :
* J.J. Thomson proposed an atomic model which is called apple pie pudding model Positively
of atom. (Plum Pudding Model). According to this model, an atom is made up of charged Electron
positively charged substance which is spread very thinly in the form of a sphere. sphere
Into this sphere are embedded negatively charged electrons, much the same way
as pieces of apple are embedded in the apple pie.
* Furthermore, it was assumed that total positive charge is equal to total negative
charge, therefore, the atom remains electrically neutral. J.J. Thomson's model of
atom was not accepted by fellow physicists, as it was unable to explain how Fig. : Thomson Atomic Model
positively charged particles are shielded from the negatively charged particles,
without getting neutralised.

2.2.2 Rutherford’s Model :

* -particle emitted by radioactive substance were shown to be dipositive Helium ions (He++) having a mass of 4 units and 2
units of positive charge. Rutherford allowed a narrow beam of -particles to fall on a very thin gold foil of thickness of the
order of 4 × 10–4cm and determined the subsequent path of these particles with the help of a zinc sulphide fluorescent
screen.
* The zinc sulphide screen gives off a visible flash of light when struck by an -particle, as ZnS has the remarkable property of
converting kinetic energy of particle into visible light. [For this experiment, Rutherford specifically used -particles because
they are relatively heavy resulting in high momentum].

Gold foil

Source of Lead
alpha particles Photographic plate
plate

(a) (b)
Figure (a) : Rutherford’s scattering experiment (b) Schematic molecular view of the gold foil
Observation :
(a) Majority of the -particles pass straight through the gold strip with little or no deflection.
(b) Some -particles are deflected from their path and diverge.
(c) Very few -particles are deflected backwards through angles greater than 90°.
(d) Some were even scattered in the opposite direction at an angle of 180°.
On the basis of the above observation, and having realized that the rebounding -particles had met something even more
massive than themselves inside the gold atom, Rutherford proposed an atomic model as follows.
(i) All the protons (+ve charge) and the neutrons (neutral charge) i.e. nearly the total mass of an atom is present in a very
small region at the centre of the atom. The atom’s central core is called nucleus.
(ii) The size of the nucleus is very small in comparison to the size of the atom. Radius of the atom is about 10–10 m while
that of nucleus is 10–15 m.
(iii) Most of the space outside the nucleus is empty.
(iv) The electrons, equal in number to the net nuclear positive charge, revolve around the nucleus with high speed in
various circular orbits.

Defects in Rutherford’s model of atom :

(i) When electron (Negatively charged particle) revolve continuously around the positively charged nucleus then energy
would be lost and due to the attraction of nucleus electron will merge with the nucleus. Rutherford has no explanation for
this problem.
(ii) If electron will continuously radiate energy then its spectra should be continuous but this is not the case. Atoms give line
spectra.
In order to overcome the defects of Rutherford Neil Bohr proposed the atomic model.

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2.2.3 Atomic number and mass number
* Atomic number (Z) : The number of protons present in the nucleus (Moseley 1913).
* Mass Number (A) : Sum of the number of protons and neutrons present in the nucleus.
Mass number
(A) = Protons + Neutrons
6 C   Element
12
symbol

Atomic number
(Z) = protons only
2.2.4 Isobars and Isotopes
Isotopes: These are the atoms of the same element having the same atomic number but different mass number. eg, 1H1, 1H2, 1H3
Isobars: The atoms of different elements having the same mass number but different atomic number. eg, 18Ar40 , 20Ca40.
Isoelectronic species: These are those species which have the same number of electrons.

2.3 DEVELOPMENTS LEADING TO BOHRS MODEL

2.3.1 Electromagnetic radiations: The radiations which are associated with electrical and magnetic fields are called electromagnetic
radiations. When an electrically charged particle moves under acceleration, alternating electrical and magnetic fields are produced
and transmitted. These fields are transmitted in the form of waves. These waves are called electromagnetic waves or electromagnetic
radiations.
Properties of electromagnetic radiations:
(a) Oscillating electric and magnetic field are produced by oscillating charged particles. These fields are perpendicular to each
other and both are perpendicular to the direction of propagation of the wave.
(b) They do not need a medium to travel. That means they can even travel in vacuum.

Characteristics of electromagnetic radiations:

(a) Wavelength: It may be defined as the distance between two neighbouring crests or troughs of wave. It is denoted by .
(b) Frequency () : It may be defined as the number of waves which pass through a particular point in one second.
(c) Velocity (v) : It is defined as the distance travelled by a wave in one second. In vacuum all types of electromagnetic radiations
travel with the same velocity. Its value is 3 × 108 m sec–1. It is denoted by v.
(d) Wave number : Wave number is defined as the number of wavelengths per unit length.
Velocity = frequency × wavelength ; c = 
1
Wave number ( ) is the reciprocal of wavelength  

Wavelength (in m)

10–10 10–9 10 –8 10–7 10–6 10–5 10–4 10 –3 10–2 10 –1

FAR
Radio waves
Gamma rays

X-rays Far IR
Visible

UV UV Near IR Microwave

10 19 10 18 1017 1016 1015 10 14 1013 1012 1011 1010 109

Frequency (in Hz)

Visible spectrum

Violet Indigo Blue Green Yellow Orange Red

400 450 500

550 600 650 700 750
Wavelength (in nm)
Figure : The electromagnetic spectrum
* Radiowave light has the lowest energy.
* Gamma ray light has the highest energy.
STUDYMATERIAL: XI CHEMISTRY 3 STRUCTURE OF ATOM
Example 1 :
The yellow light given off by a sodium vapour lamp used for public lighting has a wavelength of 589 nm. What is the frequency
of this radiation ?
Sol. The relationship between wavelength and frequency is given by Equation
 = c .......... (1)
We can solve for frequency, , because we know both  and c.
c = 3.00 × 108 m/s
Solving equation (1) for frequency gives: = c/
When we insert the values for c and , we note that the units of length in these two quantities are different. We can convert the
wavelength from nanometers to meters, so the units cancel:

c  3.00  108 m / s   1 nm 
    9   5.09  10 s
14 1
  589nm  10 m
The high frequency is reasonable because of the short wavelength. The units are proper because frequency has units
of “per second” or s–l.

2.3.2 Planck's Quantum Theory :

* The radiant energy is emitted or absorbed not continuously but discontinuously in the form of small discrete packets of
energy called quantum. In case of light , the quantum of energy is called a photon.
* The energy of each quantum is directly proportional to the frequency of the radiation, i.e. E  or E = h
where h = Planck's constant = 6.626 × 10–34 Js.
Black body: An ideal body, which emits and absorbs all frequencies, is called a black body. The radiation emitted by such a body
is called black body radiation.
At a given temperature, intensity of radiation emitted increases with decrease of wavelength, reaches a maximum value at a given
wavelength and then starts decreasing with further decrease of wavelength, as shown in figure.

T2 > T1

T2
Intensity

T1

1000 2000 3000

Wavelength  (nm)
Figure Wavelength-intensity relationship

2.3.3 Photoelectric effect :

* When radiation with certain minimum frequency (0), called threshold frequency, strike the surface of a metal, electrons
(called photoelectrons) are ejected from the surface. With this frequency, the kinetic energy of the photoelectrons ejected is
zero. However, if the incident radiation having frequency  > 0, the difference of energy (h – h0) is converted into kinetic
1
energy of the photoelectrons i.e mv 2  h  h0 .
2
* The minimum energy h0 required for emission of photoelectrons is called threshold energy or work function. No photoelectric
effect is shown if incident frequency is less than 0 even if intensity of a radiation is increased. However, number of
photoelectrons ejected is proportional to the intensity of incident radiation.

STUDYMATERIAL: XI CHEMISTRY 4 STRUCTURE OF ATOM

 Light Evacuated
chamber
e–

Metal surface
Positive
terminal Current
Voltage meter
Light Emitted source
electrons

Metal surface
(a) (b)
Figure : The Photoelectric effect

Example 2 :
In a photoelectric experiment, the collector plate is at 2.0 V with respect to emitter plate made of copper (work function 4.5 eV). The
emitter is illuminated by a source of mono-chromatic light of wavelength 200 nm. Find the minimum and maximum kinetic energy
of photoelectrons reaching the collector.
Sol. Since plate potentials 2 V, minimum K.E. will be 2 eV. For max. K.E. use the following relation:
Absorbed energy = Threshold energy + K.E.

c 6.626  10 –34  3  108

h  4.5  1.6  10 –19  K.E. ;  4.5  1.6  10 –19  K.E.
 200  10 –9
K.E. = 2.739 × 10–19 J = 1.7 eV ; Max K.E. = 2eV + 1.7 eV = 3.7 eV.

2.3.4 Dual nature of electromagnetic radiation

* According to de Broglie concept, all material particles (microscopic as well as macroscopic) possess wave character as well
as particle character. The wave associated with a material particle is called de Broglie wave or matter wave.
* The relationship between the wavelength () of the wave and the mass (m) of the material particle moving with a velocity v
h h
is called de Broglie equation. It is given by    , where h is Planck's constant and p is momentum of the particle.
mv p
* The wave nature of electron has been confirmed by Davisson and Germer's experiment whereas the particle nature is
confirmed by the photoelectric effect.

Example 3 :
Compare the wavelengths of an electron traveling at 1.00 × 105 m/s and a PingPong ball of mass 11 g traveling at 2.5 m/s.
Sol. This problem deals with particle-waves that have mass.
The de Broglie equation, relates the mass and speed of an object to its wavelength.
For the electron: me = 9.109 × 10–31 kg, u = 1.00 × 105 m/s

h (6.626  1034 Js) (1 kg m 2 s 2 / J)

 electron   = 7.27 × 10–9 m
mu (9.109  1031 kg) (1.00  105 m / s)
For the Ping-Pong ball : mball = 11g, u = 2.5 m/s

h (6.626  1034 Js) (1 kg m 2s 2 / J)

 ball   = 2.4 × 10–32 m
mu (11g) (103 kg / g) (2.5 m / s)
The wavelength of the electron is about the same size as the radius of an atom, but the wavelength of the ball is shorter than the
radius of an atomic nucleus. Thus the wavelength of a Ping-Pong ball is inconsequential compared to its size. For an electron,
however, the wavelength is large enough to play a significant role in electron-atom interactions.

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2.3.5 SPECTRUM
* When a white light is passed through a prism, it splits into a series of coloured bands known as spectrum.
* Spectrum is of two types: Continuous and line spectrum.
(a) The spectrum which consists of all the wavelengths is called continuous spectrum.
(b) A spectrum in which only specific wavelengths are present is known as a line spectrum. It has bright lines with dark
spaces between them.
* Electromagnetic spectrum is a continuous spectrum. It consists of a range of electromagnetic radiations arranged in the order
of increasing wavelengths or decreasing frequencies. It extends from radio waves to gamma rays.
Spectrum is also classified as emission and line spectrum.
(a) Emission spectrum: The spectrum of radiation emitted by a substance that has absorbed energy is called an emission
spectrum.
(b) Absorption spectrum is the spectrum obtained when radiation is passed through a sample of material. The sample
absorbs radiation of certain wavelengths. The wavelengths which are absorbed are missing and come as dark lines.
The study of emission or absorption spectra is referred as spectroscopy.

2.4 BOHRS MODEL

Bohr proposed the following postulates for revising the Rutherford model.
* Electrons moves around the nucleus in stationary circular orbits of fixed energy. They are termed as energy levels or shells.
h
* Electrons move around only in those circular orbit in which its angular momentum is integral multiple of ,
2
nh
where h = Planck’s constant. mvr  ; n = 1, 2, 3, ........
2
* The electron can change its orbit by absorbing or releasing energy. An electron at a lower (initial) state of energy, Ei can go
to a (final) higher state of energy, Ef by absorbing a single photon of energy given by E = h = Ef – Ei
Similarly, when electron changes its orbit from a higher initial state of energy Ei to a lower final state of energy Ef , a single
photon of energy h is released
* Energy is absorbed or emitted in the form of quanta or bundles, so various energy levels of atom are quantised.

2.4.1 Applications of Bohr's theory :

* Line spectrum of one electron system can be explained like H, He+, Li2+, Be+3.
n2
* Radius of the Bohr's orbit : r = 0.529 × Å
z
Radius of first orbit of hydrogen atom = 0.529 Å = 0.529 × 10–10 m

2 2 Z2 e2 m  R H Z2
* Energy of an electron : E = =
n2h2 n2
where RH is called Rydberg constant, RH = 2.18 × 10–18 J

* Relation between P.E., K.E. & T.E. :

P.E.
T.E. = – K.E. or T.E. = – K.E. =
2
Z2 Z2
(a) T.E. = – 13.6 × eV/atom (b) T.E. = – 21.8 × 10–19 J/atom (c) T.E. = – 21.8 × 10–12 × erg/atom
n 2
n2
Z2 1
(d) T.E.= – 313.6 × kcal/mole. or T.E.  – Z2 and T.E.  –
n 2
n2
* Calculation of wavelength :
The energy gap between two orbits
 R    R 
E  E f  Ei   2H    2H  where, n = initial orbit, n = final orbit
 nf   ni  i f

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  1 1
 2.18  1018 J  2  2 
 ni nf 

E 2.18  1018  1 1 
15 1 1
     = 3.29  10   2
Hz
h 6.626  1034  n i2 n f2   ni nf 
2

1  3.29  1015  1 1  1 1
       1.0967  10 7
  2
 c 3  108  n i2 n f2   ni nf 
2

If nf > ni = absorption spectrum, If ni > nf = emission spectrum

2.4.2 Principal Energy Levels in Hydrogen

–19
n=4 E4 = – 1.36 × 10 J
–19
n=3 E3 = – 2.42 × 10 J
Energy

–19
n=2 E2 = – 5.45 × 10 J

–18
n=1 E2 = – 2.18 × 10 J

2.4.3 Quantization of energy of electron :

(i) In ground state : No energy emission. In ground state minimum energy state of atom for 1st orbit of H-atom, n = 1.
 E1 = – 13.6 eV
(ii) In Excited state : Energy levels greater than n1 are excited state.
i.e. for H-atom n2, n3, n4 are excited state. For H-atom first excitation state = n2
(iii) Excitation potential : Energy required to excite electron from ground state to any excited state.
Ground state  excited state
Ist excitation potential for H atom = E2 – E1 = – 3.4 + 13.6 = 10.2 eV
IInd excitation potential = E3 – E1 = – 1.5 + 13.6 = 12.1 eV
(iv) Ionization Potential or Ionization energy :
The amount of energy required to remove an electron from an isolated gaseous atom in its ground state to the infinite excited
state is called ionization potential. The result is ion formation.
Ground state  infinite
I.P. = E  – E1 = 0 – E1
So I.P. = – E1
 I.P. = – (– 13.6)
For H-atom I.P. = + 13.6 eV
(v) Separation energy : Energy required to excite an electron from excited state to infinity.
S.E. = E – Eexcited

2.4.4 Hydrogen Energy Transitions

* The light absorbed or emitted as a result of an electron changing orbits produces characteristic absorption or emission
spectra which can be recorded on the photographic plate as a series of lines, the optical spectrum of hydrogen consists of
several series of lines called Lyman, Balmar, Paschen, Brackett and Pfund series.
* The Lyman series lies in the ultra-violet region (wavelength lesser than violet). Balmer series in the visible region and
Paschen, Brackett and Pfund series lie in the infra-red region. (wavelength more than red)
 1 1 
* Wave number (  ) = 1/ = R  2  2 
 nI n II 

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 * Further, when the electron jumps from an orbit of higher energy to that of lower energy in a hydrogen atom, it emits energy
and produces spectrum. Different series of lines produced, when we substitute the value of R, nI and nII in equations above
are assigned the following names ;
Lyman from n = 2, 3, 4.....to n = 1 ; Balmer from n = 3, 4, 5.....to n = 2
Paschen from n = 4, 5, 6.....to n = 3 ; Brackett from n = 5, 6, 7.....to n = 4
Pfund from n = 6, 7, 8.....to n = 5 (where n is the quantum number).

n=
n=5
n=4
n=3
Paschen series (infrared)
n=3

Balmer series (visible)

n=2
Blue
Violet
Green
Red

434 nm 486 nm 657 nm

violet Blue-green Red

n=5

Lyman series (ultraviolet)

Energy

e– n=4
e–

n=3
e–
n=2
n=1

n=1 Figure : The Bohr model and emission spectra

Figure : Transitions of the electron in the
hydrogen atom (The diagram shows
the Lyman, Balmer and Paschen series
of transitions)

2.4.5 Failure of Bohr Model :

(i) Bohr theory was very successful in predicting and accounting the energies of line spectra of hydrogen i.e. one e– system.
It could not explain the line spectra of atoms containing more than one e– .
(ii) This theory could not explain the presence of multiple spectral lines.
(iii) This theory could not explain the splitting of spectral lines in magnetic field (Zeeman effect). The intensity of these lines
was also not explained by the Bohr model.
(iv) This theory was unable to explain de -broglie’s concept of dual nature of matter.
(v) This theory could not explain uncertainty principle.
(vi) No conclusion was given for the principle of quantization.

Example 4 :
What is the wavelength (in nanometers) of a photon emitted during a transition from the ni = 5 state to the nf = 2 state in the
hydrogen atom ?
Sol. Because nf < ni, this is an emission process and the fact that nf = 2 means that the transition will give rise to a spectral line in the
Balmer series. We can calculate the energy change and hence the energy of the emitted photon.
 1 1   1 1
E  R H  2  2  = 2.18 × 10–18 J   2  = – 4.58 × 10–19 J
 ni n f  5 2
2 

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 The negative sign indicates that this is energy associated with an emission process. To calculate the wavelength we will omit the
minus sign for E because the wavelength of the photon must be positive. Because E = hor  = E/h, we can calculate the
wavelength of the photon by writing

c ch (3.00  108 m / s) (6.63  1034 Js)

  = = 4.34 × 10–7 m
 E 4.58  1019 J

 1  109 nm 
= 4.34 × 10–7 m ×   = 434 nm, which is in the visible region of the electromagnetic region.
 1m 

Example 5 :
The energy of electron in first Bohr’s orbit of H-atom is –13.6 eV. What will be its potential energy in n = 4.
13.6 1
Sol. Energy of fourth Bohr’s orbit of H-atom =  eV = –13.6 × eV = – 0.85 eV
2
4 16
P.E. of electron in nth orbit = 2 × En
So P.E. of electron in 4th orbit = 2 × (– 0.85) = – 1.70 eV

Example 6 :
Calculate the ionization energy of the Be3+ ion with the electron in its ground state.
Sol. The Be3+ ion has one electron in the 1s orbital (n = 1) in its ground state. Since beryllium has four protons in its nucleus (Z = 4),
the energy of the electron in the 1s orbital of Be3+ can be calculated.
 Z2   42 
E    2  (1310) kJ / mole    2  (1310) kJ / mole = 2.10 × 104 kJ/mol
n  1 
Recall that this energy (E) is negative since the electron is bound to the nucleus. An equal amount of energy must be applied to
remove the electron. Thus, the ionization energy is positive and is 2.10 × 104 kJ/mol.

2.5 HEISENBERG'S UNCERTAINTY PRINCIPLE

* It is impossible to measure simultaneously the position and momentum of a microscopic particle with absolute accuracy. If one
of them is measured with greater accuracy, the other becomes less accurate.
h
The product of their uncertainties is always equal to or greater than .
4
h
Mathematically , x  p 
4
where x = uncertainty in position, p = uncertainty in momentum.
* It rules out existence of definite paths or trajectories of electrons and other similar particles.
* The effect of Heisenberg Uncertainty Principle is significant only for motion of microscopic objects and is negligible for that of
macroscopic objects.

Example 7 :
It is impossible to specify the radius of an atom precisely, the hydrogen atom has a radius on the order of 0.05nm. Assuming that
we know the position of an electron to an accuracy of 1% of the hydrogen radius, calculate the uncertainty in the velocity of the
electron using the Heisenberg uncertainty principle. Then compare this value to the uncertainty in the velocity of a ball of mass
0.2 kg and radius 0.05m whose position is known to an accuracy of 1% of its radius.
Sol. From Heisenberg’s uncertainty principle the smallest possible uncertainty in the product x . (mv) is h/4, that is,
h
x . (mv) =
4
We will assume that the masses of the electron and the ball are constant, which means that the uncertainty in mv is due only to
an uncertainty in velocity, that is  (mv) = m (v)
With this assumption the uncertainty principle becomes
h h
x. (mv)  x.m.v  or x.v 
4 m.4
STUDYMATERIAL: XI CHEMISTRY 9 STRUCTURE OF ATOM
 We will use the equation in this form to solve for the uncertainty in velocity (v) for the electron and the ball.
For the electron the uncertainty in position (x) is 1% of 0.05nm, or x = (0.01) (0.05nm) = 5 × 10–4 nm

109 m
Converting to meters gives, 5 × 10–4 nm × = 5 × 10–13 m
1nm
The values of the constants are m = mass of the electron = 9.11 × 10–31 kg

kg m 2 s
h = 6.626 × 10–34 Js = 6.626 × 10–34 ,  = 3.14
s2

kgm2 s
6.626  1034
h s2
We solve for v : v   = 1 × 108 m/s
x m 4 (5  10 m) (9.11  10 kg) (4) (3.14)
13  31

Thus if we know the electron’s position with a minimum uncertainty of 5 × 10–13 m, the uncertainty in the electron’s velocity is
at least 1 × 108 m/s. This is a very large number; in fact, it is the same magnitude as the speed of light (c = 3 × 108 m/s).
At this level of uncertainty we have virtually no idea of the velocity of the electron.
For the ball the uncertainty in position (x) is 1% of 0.05m, or 5 × 10–4 m.

kgm 2 s
6.626  1034
h s2
Thus the minimum uncertainty in velocity is v   = 5 × 10–31 m/s
x.m.4 (5  10 m) (0.2 kg) (4) (3.14)
 4

This means there is a very small (undetectable) uncertainty in our measurements of the speed of a ball.
Note that this uncertainty is not due to the limitations of measuring instruments ; v is an inherent uncertainty.

2.6 QUANTUM MECHANICALMODELOFATOM

* Classical mechanics is based on Newton's laws of motion. It successfully describes the motion of macroscopic particles but fails
in the case of microscopic particles.
Reason : Classical mechanics ignores the concept of dual behaviour of matter especially for sub-atomic particles and the
Heisenberg's uncertainty principle.
* Quantum mechanics is a theoretical science that deals with the study of the motions of the microscopic objects that have both
observable wave like and particle like properties.
* Quantum mechanics is based on a fundamental equation which is called Schrodinger equation.
* Schrodinger's equation: For a system (such as an atom or a molecule whose energy does not change with time) the Schrödinger
d2 d2 d2 8 2 m
equation is written as:    (E – V)   0
dx 2 dy 2 dz 2 h2
where x, y, z are certain coordinates of the electron, m = mass of the electron, E = total energy of the electron.
V = potential energy of the electron; h = Planck’s constant and (psi)= wave function of the electron.
* When Schrödinger equation is solved for hydrogen atom, the solution gives the possible energy levels the electron can occupy
and the corresponding wave function(s) of the electron associated with each energy level. Out of the possible values, only
certain solutions are permitted. Each permitted solution is highly significant as it corresponds to a definite energy state. Thus, we
can say that energy is quantized.
* Significance of : gives us the amplitude of wave. The value of  has no physical significance.
* Significance of 2:2 is a probability factor. It describes the probability of finding an electron within a small space. The space
in which there is maximum probability of finding an electron is termed as orbital. The important point of the solution of the wave
equation is that it provides a set of numbers called quantum numbers which describe energies of the electron in atoms, information
about the shapes and orientations of the most probable distribution of electrons around nucleus.
* Quantum numbers : The result of schrodinger wave equation gives three variable parameters and these 3 parameters are called
quantum numbers n, , m. These tell the position and energy of electron.
But 4th quantum number was discovered by spectroscopy. Exact information of an electron can be determined by 4 set of
quantum numbers.
n, , m  position & energy (By schrodinger wave equation), s  spin (By spectroscopic study).
These are principal, azimuthal, magnetic and spin quantum numbers. Each orbital in an atom is specified by a set of three quantum
number and each electron is designated by four quantum numbers.

STUDYMATERIAL: XI CHEMISTRY 10 STRUCTURE OF ATOM

2.7 QUANTUM NUMBERS
The four quantum numbers provide the following informations :
(i) Principal quantum number (n) : n = 1, 2, 3, 4, .........
It identifies shell, determines sizes and energy of orbitals and number of orbitals in the nth shell which is equal to n2.

N 1 2 3 4
Shell no. K L M N
Total number of orbitals
2 1 4 9 16
in a shell = n
Maximum number of
2 2 8 18 32
electrons = 2n

(ii) Azimuthal quantum number () : For a given value of n, it can have n values ranging from 0 to n – 1. It identifies subshell,
determines the shape of orbitals, energy of orbitals in multi-electron atoms along with principal quantum number and orbital
h
angular momentum, i.e.,  (  1) . The number of orbitals in a subshell = 2 + 1.
2
Subshell notation s p d f g
Value of ‘l’ 0 1 2 3 4
Number of orbitals 1 3 5 7 9
(iii) Magnetic orbital quantum number (m) : For a given value of '', m has a total of (2 + 1) values ranging from – to +
including '0'. It determines the orientation of orbital.
(iv) Magnetic spin quantum number (ms) : It can take the values of +½ or ½ and determines the orientation of spin.
Allowed Quantum Numbers

Quantum number Values Number of values Significance

Principal, n 1, 2, 3, ....... – Distance from nucleus
Azimuthal,  0, 1, 2, ..., n – 1 n Shape of orbital

Magnetic, m –, ...., 0, ..... +  2 + 1 Orientation of orbital

Spin, ms –½, + ½ 2 Direction of electron spin

Example 8 :
State whether each of the following sets of quantum numbers is permissible for an electron in an atom. If a set is not permissible,
explain why ?
(a) n = 1,  = 1, m = 0, s = + 1/2 (b) n = 3,  = 1, m = –2, s = – 1/2
(c) n = 2,  = 1, m = 0, s = + 1/2 (d) n = 2,  = 0, m = 0, s = 1
Sol. (a) Not permitted. The  quantum number must be less than n.
(b) Not permitted. The magnitude of the m quantum number (that is , the m value, ignoring its sign) must not be greater than .
(c) Permitted.
(d) Not permitted. The s quantum number can only have values +1/2 or –1/2.

Example 9 :
Calculate total spin, magnetic moment for the atoms having at no. 7, 24, 34 and 36.
Sol. The electronic configuration are
7N : 1s2, 2s2 2p3 Unpaired electron = 3
24Cr : 1s2, 2s2 2p6, 3s2 3p5 3d5, 4s1 Unpaired electron = 6
34 Se : 1s2, 2s2 2p6, 3s23p63d10, 4s24p4 Unpaired electron = 2
36Kr : 1s2, 2s2 2p6, 3s2 3p63d10, 4s24p6
Unpaired electron = 0
 Total spin for an atom = ± 1/2 × no. of unpaired electron
For 7N, it is = ± 3/2 ; For 24Cr, it is = ± 3 ; For 34Se, it is = ± 1; For 36Kr, it is = 0
Also magnetic moment = [n (n  2)] Bohr magneton

For 7N, it is = (15) ; For 24Cr, it is = (48) ; For 34Se, it is = (8) ; For 36Kr, it is = 0

STUDYMATERIAL: XI CHEMISTRY 11 STRUCTURE OF ATOM

2.7.1 Atomic Orbitals on the basis of quantum number :
An atomic orbital is defined as "the region in space around the nucleus in which the probability of finding an electron is
maximum".
(i) s-orbital: An electron in considered to be immersed out in the form of a cloud. y

The shape of the cloud is the shape of the orbital. The cloud is not uniform but
denser in the region where the probability of finding the electron in maximum.
The orbital with the lowest energy is the 1s orbital. It is a sphere with its center 1s 2s
of the nucleus of the atom. The s-orbital is said to spherically symmetrical about nucleus x

the nucleus, so that the electronic charge is not concentrated in any particular
direction. 2s orbital is also spherically symmetrical about the nucleus, but it is Z radial node
larger than (i.e., away from) the 1s orbit.

(ii) p-orbitals: There are three p-orbitals: px, py and pz They are dumb-bell shaped, the two levels being separated by; a nodal
plane, i.e., a plane where there is no likely hood of finding the electron. The p-orbitals have a marked direction character,
depending as whether px, py and pz orbital is being considered. The p-orbitals consist of two lobes with the atomic nucleus
lying between them. The axis of each p-orbital is perpendicular to the other two. The px, py and pz orbitals are equivalent
except for their directional property. They have same energy; orbitals having the same energy are said to be degenerated.
z z
z

y y y

x x x

px py pz

(iii) d-orbitals: There are five d-orbitals. The shapes of four d-orbitals resemble four leaf cloves. The fifth d-orbital loops
different. the shapes of these orbitals are :
y z z

x y x

dxy dyz dzx

z
y

d 2 2 dz2
x y
2.7.2 Node and nodal plane :
Node is defined as a region where the probability of finding an electron is zero.
The planes passing through the angular nodal points are called nodal planes.
Nodes : No. of radial or spherical nodes = n –  – 1.
No. of angular nodes = , Total no. of nodes = n – 1

STUDYMATERIAL: XI CHEMISTRY 12 STRUCTURE OF ATOM

2.8 SHIELDING EFFECT OR SCREENING EFFECT
Due to the presence of electrons in the inner shells, the electron in the outer shell will not experience the full positive charge on
the nucleus. So, due to the screening effect, the net positive charge experienced by the electron from the nucleus is lowered and
is known as effective nuclear charge. Effective nuclear charge experienced by the orbital decreases with increase of azimuthal
quantum number ().
In a given shell, the decreasing order of screening effect is : s > p > d > f.

Penetration & Shielding :

* the radial distribution function shows that the 2s orbital penetrates more deeply into the 1s orbital than does the 2p,
* the weaker penetration of the 2p sublevel means that electrons in the 2p sublevel experience more repulsive force, they are
more shielded from the attractive force of the nucleus.
* the deeper penetration of the 2s electrons means electrons in the 2s sublevel experience a greater attractive force to the
nucleus and are not shielded as effectively.
* the result is that the electrons in the 2s sublevel are lower in energy than the electrons in the 2p,

1s
2p
2s Shielding Penetration
Total radial probability

Experiences
e– e– full 3+ charge
Penetration 3+ e–
of 2s Nucleus Experiences Nucleus
net charge
e– of about 1+ e–

0 200 400 600 800 (a) (b)

r (pm)

NOTE :
* Because of penetration, sublevels within an energy level are not degenerate
* Penetration of the 4th and higher energy levels is so strong that their s sublevel is lower in energy than the d sublevel of the
previous energy level
* The energy difference between levels becomes smaller for higher energy levels.

2.9 ELECTRONIC CONFIGURATION OF ELEMENTS

The distribution of electrons in various shells and sub-shells is called electronic configuration of elements. This arrangement of
electrons in an atom decides the properties of an element.
There are two common ways of representing the electronic configurations. These are
(i) Orbital notation method : In this method the filled orbitals are written in the order of increasing energies . The respective
electrons in them are indicated as superscripts as shown in the example given below. For example, the electronic configuration
of nitrogen atom (atomic number 7) is written as 1s2 2s2 2px1 2py1 2pz1.

(ii) Orbital diagram method: In this method the filled orbitals are represented by circles or boxes and are written in the order of
increasing energies. The respective electrons are indicated as arrows whose direction represents their spin. For example, the
electronic configuration of nitrogen in the orbital diagram notation can be written as
1s 2s 2p

The following rules are used for writing the electronic configuration.

STUDYMATERIAL: XI CHEMISTRY 13 STRUCTURE OF ATOM

 (I) Aufbau principle :
Aufbau is a German word meaning ‘building up’. This gives us a
sequence in which various sub-shells are filled up depending on 1s
the relative order of the energy of the subs-hells. The sub-shell
with minimum energy is filled up first and when this obtains maxi- 2s 2p
mum quota of electrons, then the next sub-shell of higher energy
starts filling. 3s 3p 3d
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p.
4s 4p 4d 4f
Exceptions to Aufbau Principle: In some cases it is seen that
actual electronic arrangement is slightly different from arrangement 5s 5p 5d
given by Aufbau principle. A simple reason behind this is that half-filled
and full-filled sub-shell have got extra stability. 6s 6p
Cr(24) 
 1s 2 , 2s 2 2p6 , 3s 2 3p6 3d 4 , 4s 2 (wrong)
7s

 1s23 , 2s 2 2p 6 ,3s 2 3p6 3d 5 , 4s1 (right)

Cu(29) 
 1s 2 , 2s 2 2p6 , 3s 2 3p 6 3d9 , 4s 2 (wrong)

  1s 2 , 2s 2 2p6 , 3s2 3p6 3d10 , 4s1 (right)

Similarly the following elements have slightly different configurations than expected.
Nb 
 [Kr] 4d 4 5s1 ; Mo 
 [Kr] 4d 4 5s1 ; Ru 
 [Kr] 4d 7 5s1 ; Rh 
 [Kr] 4d8 5s1

Pd 
 [Kr] 4d10 5s 0 ; Ag 
 [Kr] 4d10 5s1 ; Pt 
 [Xe] 4f 14 5d9 6s1 ; Au 
 [Xe] 4f 14 5d10 6s1

(II) Hund's rule of maximum multiplicity :

(a) According to this rule, "pairing of electrons in sub-shell starts after all the available atomic orbitals of that sub shell are
singly filled (half-filled) with electrons having parallel spins" or pairing of electrons in a sub-shell is impossible in the
presence of vacant atomic orbitals in that sub shell.
(b) In p-sub shell, the fourth electron starts pairing, and the sixth electron starts pairing in d-sub-shell. In f-sub-shell,
pairing starts with eighth electron.
(c) This rule gives the number of unpaired electrons in an atom, ion or molecule.
(d) Exactly half-filled sub-shells have lesser energy and thus assume more stability than any other arrangement. Thus, p3
is more stable arrangement than p2, p4 or p5.
(e) When the electronic configuration ns2np6 is attained in the outermost shell of an atom, the next incoming electron
enters the (n + ) s-subshell. The nd-and nf-sub-shells will be vacant.

(III) Pauli's exclusion principle :

(a) According to this principle, "No two electrons in an atom can have all the four quantum number n, , m and s identical.
(b) In an atom, any two electrons may have three quantum number identical but fourth quantum number must be different.
(c) Since this principle excludes certain possible combinations of quantum number for any two electrons in an atom, it was
given the name exclusion principle,
Its results are as follows :
* The maximum capacity of a main energy shell is equal to 2n2 electron.
* The maximum capacity of a subshell is equal to 2(2 + 1) electrons.
* Number of sub-shells in a main energy shell is equal to the value of n.
* Number of orbitals in a main energy shell is equal to n2.
* One orbital cannot have more than two electrons.

NOTE
* Electronic configurations can also be written in a short hand form. In this method the last completed orbital shell is represented
in terms of a noble gas. For example, the electronic configuration of lithium and sodium can be written as
Li : [He] 2s1
Na : [Ne] 3s1
* The electrons in the noble gas configuration are termed as core electrons while the ones in the outer shell are called valence
electrons.

STUDYMATERIAL: XI CHEMISTRY 14 STRUCTURE OF ATOM

Example 10 :
Complete the following table:

Element Valence electron configuration Valence orbital notation Set of quantum numbers
0
[Ar]
4s

[Ar] 3d 6

–1 0 +1

1s 2s 2p
5, 1, 0, +1/2
4p5
6, 0, 0, –1/2

Sol. Element Valence electron Valence orbital notation Set of quantum

configuration numbers (n, , m,
ms )
K 0 4, 0, 0, +1/2
[Ar] 4s1 [Ar]
4s

Fe 0 –2 –1 0 +1 +2 3, 2, –2, –1/2
[Ar] 4s23d6 [Ar] 
4s 3d
N –1 0 +1 2, 1, 1, +1/2
1s22s22p3
1s 2s 2p
Sn –1 0 +1 5, 1, 0, +1/2
[Kr] 5s 4d 5p
2 10 2
Kr
5s 4d 5p

Br –1 0 +1 4, 1, 0, –1/2
[Ar] 4s23d104p5 [Ar]
4s 3d 4p

Ba 0 6, 0, 0, –1/2
[Xe] 6s2 [Xe]
6s

ADDITIONAL EXAMPLES
Example 1 :
(a) Predict the number of subshells in the fourth shell. that is, for n = 4.
(b) Give the label for each of these subshells. (c) How many orbitals are in each of these subshells?
Sol. (a) There are four subshells in the fourth shell, corresponding to the four possible values of  (0, 1,2, and 3).
(b) These subshells are labeled 4s, 4p, 4d, and 4f. The number given in the designation of a subshell is the principal quantum
number, n; the following letter designates the value of the azimuthal quantum number, .
(c) There is one 4s orbital (when  = 0, there is only one possible value of m : 0).
There are three 4p orbitals (when  = 1, there are three possible values of m: 1, 0, and –1).
There are five 4d orbitals (when  = 2, there are five allowed values of m : 2, 1,0, –1, –2).
There are seven 4f orbitals (when  = 3, there are seven permitted values of m : 3, 2, 1, 0, –1, –2, –3).

STUDYMATERIAL: XI CHEMISTRY 15 STRUCTURE OF ATOM

Example 2 :
What is the characteristic outer-shell electron configuration of the group 7 A elements, the halogens?
Sol. We first locate the halogens in the periodic table, write the electron configurations for the first two elements, and then determine
the general similarity between them.
The first member of the halogen group is fluorine, atomic number 9. The abbreviated form of the electron configuration for
fluorine is F: [He]2s22p5
Similarly, the abbreviated form of the electron configuration for chlorine, the second halogen, is Cl : [Ne] 3s23p5
From these two examples, we see that the characteristic outer-shell electron configuration of a halogen is ns2np5, where n range
from 2 in the case of fluorine to 6 in the case of astatine.

Example 3 :
(i) Write the electronic configurations of the following ions : (a) H– (b) Na+ (c) O2– (d) F–
(ii) What are the atomic numbers of the elements whose outermost electrons are represented by (a) 3s1 (b) 2p3 and (c) 3d6.
(iii) What atoms are indicated by the following configurations : (a) [He] 2s1 (b) [Ne] 3s2 3p3 (c) [Ar] 4s2 3d1
Sol. (i) The electronic configurations of the given species are,
(a) H– 1s2 (b) Na+ 1s2 2s2 2p6 3s1
(c) O 1s 2s 2p
2– 2 2 6 (d) F– 1s2 2s2 2p6

(ii) Outer Complete Total Atomic

Species Electronic configuration Electronic configuration no. of electrons number
(a) 3s 1 1s2 2s2 2p6 3s1 11 11
(b) 2p3 1s2 2s2 2p3 7 7
(c) 3d6 1s2 2s2 2p6 3s2 3p6 4s2 3d6 26 26

(iii) Condensed Complete electronic Total no. of Atomic Element

Electronic configuration configuration electrons number
(a) [He] 2s1 1s2 2s1 3 3 Li
(b) [Ne] 3s2 3p3 1s2 2s2 2p6 3s2 3p3 15 15 P
(c) [Ar] 4s2 3d1 1s2 2s2 2p6 3s2 3p6 4s2 3d1 21 21 Sc

Information for Example 4-6

The figure shows an energy level diagram for the hydrogen atom.
Several transitions are marked as I, II, III.........
Principal quantum no.

The diagram is only indicative and not scale. III

Example 4 : II IV V VI
In which transition is a Balmer series photon absorbed
Sol. For Balmer series, n1 = 2, n2 = 3, 4
I
Example 5 :
Find the wavelength of the radiation involved in transition II.
Sol. In transition II, E2 = – 3.4 eV, E4 = – 0.85 eV, E = 2.55 eV
hc hc
E   = 487 nm.
 E

Example 6 :
Which transition will occur when a hydrogen atom is radiated with radiation of wavelength 103 nm.
1240 Å
Sol. = 103 nm = 1030 Å ; E  1030 Å  12.0 eV .

So difference of energy should be 12 eV.

Hence n1 = 1, 13.6 eV ; n2 = 3, –1.51 eV

STUDYMATERIAL: XI CHEMISTRY 16 STRUCTURE OF ATOM