STRUCTURE OF ATOM

CLASS XI





Introduction

The evidence of the electrical nature of matter preceded the first theories
about the structure of matter. In 1832, Michael Faraday discovered
electrolysis. He gave the first important clue relating electricity to matter and
about the electric nature of atoms.

However, the first definite modern theory on the structure of matter was
John Dalton's Atomic theory in 1890. It surmised that all matter was
composed of indivisible and extremely small structureless, hard, spherical
particles called atoms. However, later discoveries at the turn of the
20
th
century showed that atoms had still a further complex structure and
consisted of smaller sub-atomic particles called electrons, protons and
neutrons. These were considered to be the fundamental particles of all
atoms.

Discovery of Atomic Particles

Electron - Discharge Tube experiments

J.J. Thomson studied the passage of electricity through gases at extremely
low pressure in a cylindrical glass tube in detail. He was discovered that at
extremely low pressure, gases become conductors of electricity and emit
streaks of light, which flows in the form of cathode rays.

Experiment and observations

In its simplest form, the electron-discharge tube consists of a cylindrical
glass tube about 50 cm long, closed at both ends. It is also called the
discharge tube or Crookes tube. The tube is fitted with two metallic
electrodes, which are connected to a source of high voltage. It is filled with
gas and is connected to a side tube, through which the gas can be evacuated
to any desired pressure with the help of a vacuum pump.



Discharge Tube Experiment

The following observations were discovered:

At normal temperatures, all gases were non-conducting, in spite of high
voltage (5000-10,000 volts) being applied between the electrodes in the
discharge tube.

The residual gas in the tube became 'conducting'. When the pressure of the
gas was reduced to 10
-2
atm. the gas emitted a flow of light evacuating some
of the gas with the help of vacuum pump, through the side tube.

When the pressure in the discharge tube was further reduced, the residual
gas continued to conduct electricity but its light emission glow became
weaker and finally stopped glowing at about 10
-4
atm pressure. At this
pressure, the glass tube only showed a greenish fluorescence at the anode
end.

The glow in the tube at low gas pressures of 10
-2
to 10
-4
atm was due to the
bombardment at the glass by certain rays, which were emitted from the
cathode as streaks of light and moved towards the anode end. The colour of
the light depended on the nature of the gas used.

These rays were named as cathode rays because their point of origin was the
cathode.

Nature of cathode rays

Further experiments established the following properties of cathode rays.

The rays travel in straight lines from the cathode to the anode. This is proved
because when an object is placed in the path of a cathode ray in the
discharge tube, the light gets blocked in the area of the object and
fluorescence is seen only in regions outside the shadow. Further it casts a
shadow away from the cathode, on the opposite side).

The rays consist of material particles and can produce a mechanical effect.
For example, when a small paddle wheel is placed between the electrodes of
the discharge tube, it rotated.

These material particles are charged with a negative charge. This is proved
on exposing cathode rays to electrical or magnetic fields. They deflect
towards the positively charged plate.


They have a heating effect i.e., when they strike a thin metal foil it gets
heated up.

They produce fluorescence or glow on striking glass or certain other
materials.

They produce X-rays on striking hard metals like copper, tungsten etc.

They penetrate through thin sheets of aluminium or other metal.

Cathode rays affect photographic plates.

The ratio of charge to mass (charge/mass) is the same for all the cathode
rays irrespective of the type of gas used in the tube.

The above observations confirmed the existence of negatively charged
particles called electrons as particles that made up the cathode rays.


Charge and mass of electron

Ratio of the charge of electrons to its mass (e/m):

The charge to mass ratio is found by measuring the deflection of a ray under
the simultaneous influence of electrical and magnetic fields, applied
perpendicularly to each other as well as to the direction of the flow of light.
This is illustrated in the figure below:



Determining e/m ratio


A high voltage charge accelerates cathode ray electrons between cathode
and anode. After the anode, a circular disc selects a straight beam and
directs it past the electric and magnetic fields, which are perpendicular to
each other as well as to the direction of the motion of the light beam. The
beam is deflected according to the relative strengths of the electric and
magnetic fields and the ratio of e/m controls the deflection. By measuring the
deflection and the field strengths of the two fields the e/m ratio can be
calculated.


Determination of the charge of electrons

The charge of electrons is determined by Millikan's experiment in 1909. Small
drops of oil formed by a sprayer are allowed to fall in between a positively
charged upper metal plate and a negatively charged lower metal plate. The
space between the two plates is irradiated with X-rays. This displaces some
electrons of the air molecules, which consequently get attached to the oil
droplet. The fall of the oil drop is observed through a microscope. The
charged plates create an electrical field in the upper direction, which
counteracts the gravity influence on the drop of oil. By adjusting the electric
field strength to a level equal to the downward gravitational force, the drop
remains stationary in mid-air. The charge on the droplet is then determined
by the amount of charge on the plates and the mass of the droplet. The mass
of the droplet is determined earlier, from the rate of fall of droplet through
the air when the metal plates were uncharged.


From the experiments of Millikan, the charge on the electron is found to be
1.602 x 10
-19
coulombs.



Millikan's oil drop experiment

Calculation of the mass of the electron

The mass of an electron (m) is determined by dividing the value of 'e' by
e/m.

Charge/mass (e/m) = 1.76 x 10
8
coulomb/g

Charge (e) = 1.602 x 10
-19
coulombs.



= 9.1 x 10
-28
g

Electron

An electron is defined as a subatomic particle which carries one unit of
electrical charge (1.602 x 10
-19
C) and has a mass of 9.1 x10
-28
g.

The mass of an electron is almost negligible, being 1/1837th the mass of an
atom of hydrogen. The charge of an electron is the smallest known electrical
charge and is referred to as unit negative charge.

The discharge tube experiments showed that irrespective of the gas used or
the nature of the material of the cathode, all electrons were found to have
the same mass and same charge and therefore the same e/m ratios. Thus
electrons of all cathode rays are the same and only electrons (no gaseous
atoms) make up the fundamental common particles of the rays.

Later on it was found that all electrons emitted from all sources and by all
methods have the same mass and same charge. Thus, the electron in the
atom is the universal constituent of all matter.

Anode rays and the discovery of protons

Since atoms on the whole are neutral, the presence of negatively charged
electrons suggested the presence of positively charged particles.

Experiment and characteristics

E.Goldstien modified the discharge tube experiments by using a perforated
cathode. After evacuating the tube he applied high voltage across the
electrodes. Apart from the usual cathode rays emerging from the
perforations, he found a new set of rays emerging and travelling in the
opposite direction. In similar experiments to those of Thomson's involving
electric and magnetic fields he observed, that like the cathode rays, these
rays also deflect but in the opposite direction. They were attracted towards
negative plates establishing their positive nature. He called these rays as
anode rays.



Anode rays Goldstein's experiment

Characteristics of anode rays

These travel in straight lines and cast shadow of the object placed in their
path.

They are deflected by magnetic and electric fields in the opposite direction to
that of cathode rays.

The anode rays produce mechanical and heating effects also.

The charge to mass ratio is smaller than that of the electrons, showing that
these particles are heavier than the cathode ray particles.

The charge to mass ratio depends upon the nature of the gas.


The charge and mass of the positive particles

The e/m ratio of the anode rays obtained from hydrogen gas was found to be
highest and equivalent to 9.58 x 10
4
C g
-1
. These particles also carried a
charge of 1.602 x 10
-19
C. Thus, the mass of the positive particle from
hydrogen gas is,



As the mass of the electron is 9.1 x 10
28
g, the ratio of the mass of positive
particle obtained from hydrogen to the mass of an electron is,



The positive particle from hydrogen is 1837 times heavier than the electron.
This positively charged particle was called proton. The proton is produced by
the loss of an electron from a neutral hydrogen atom and is thus a hydrogen
ion H
+
. The mass of H is found to be 1837 times that of an electron and so
the mass of the proton is nearly the same as that of a hydrogen atom.

Proton

The proton has a mass equal to that of hydrogen atom, which is equal to
1.67 x 10
-24
g or 1.0073 amu while it has an unit positive charge of +1.602 x
10
-19
C.

Discovery of Neutrons

The whole mass of an atom has found to be in the nucleus, which means that
the nucleus must contain protons equal to the mass of the atom. As the
number of protons is equal to the atomic number, the atomic mass should be
equal to the atomic number. But for all atoms except hydrogen the atomic
mass was found to be more than the atomic number. To account for the
remaining mass Rutherford predicted the presence of neutral particles having
mass equal to that of protons.

In 1932, James Chadwick bombarded a thin sheet of beryllium element with
particles and observed the generation of highly penetrating rays consisting of
neutral particles. These particles had a mass nearly the same as that of
hydrogen atom and did not have a charge. Since these particles were
electrically neutral, they were named as neutrons.

Neutron

A neutron is a particle having a mass equal to 1.67 x 10
-24
g same as that of
a hydrogen atom and no electrical charge.

Some Important Terms Relating to Atomic Structure

Atomic number

This is the number of protons present in the nucleus or the number of
electrons present outside the nucleus. It is denoted by the letter 'Z'.

Atomic number (Z) = Nuclear charge or number of protons (p)

= Number of electrons (e)

Mass number

The sum of the number of protons and neutrons in the nucleus of an atom is
called the mass number. It is represented by the letter A.

Mass number (A)= Number of protons (p) + number of neutrons (n)

From the knowledge of atomic number and mass number the number of
electrons, protons and neutrons in an atom can be easily predicted.

For example, Lithium has an atomic number = 3 and mass number = 7

Number of electrons = Atomic number = 3

Number of protons = Atomic number = 3

Number of neutrons = A - Z = 7 - 3 = 4

An atom is represented by its symbol for the element (X) with the atomic
number written on the lower side of the symbol and the mass number
written on the upper side.

Problem

1. How many protons and neutrons are there in the following nucleus?




Solution



Atomic number Z = 8, Mass number A = 17

Number of protons = Z = 8

Number of neutrons + number of protons = A

Number of neutrons + 8 = 17

Number of neutrons = 17- 8 = 9



Atomic number Z = 12, Mass number A = 25

Number of protons = Z = 12

Number of neutrons = A - number of protons

= 25 - 12 = 13


2. Find (i) the total number of neutrons and (ii) total mass of neutrons in 7
mg of
14
C. Assume: mass of neutron = mass of hydrogen atom.


Solution

Mass number of
14
C is 14.

So, 14 g of
14
C contain 6.023 x 10
23
atoms of
14
C

0.007g of
14
e contains

= 3.012 x 10
20
atoms

Number of neutrons in 1 atom of
14
C = 14 - 6 = 8

Number of neutrons in 7 mg of
14
C = (8 x 3.012 x 10
20
)

= 24.1 x10
20


Mass of the neutron = mass of hydrogen atom

= 1.675 x 10
-27
kg

Hence, mass of the neutron in 7 mg of
14
C

= 1.675 x 10
-27
kg x 24.1 x10
20


= 40.36 x 10
-7
kg

Isotopes

Sometimes, atoms of the same element have the same atomic number but
different mass numbers. These are called isotopes.

The nuclei of these atoms have same number of protons but different
number of neutrons.

The properties of isotopes differ depending upon their mass

Different isotopes of an element exhibit similar chemical properties.

Hydrogen has three isotopes namely, hydrogen-H (protium), deuterium-D
and tritium-T with mass numbers 1, 2 and 3 respectively.



Three isotopes of hydrogen

Isotopes of some common elements



Isobars

The atoms of different elements, which have the same mass number but
different atomic number are called isobars. These have different number of
protons but equal sum of the number of protons and neutrons.

Some typical isobars




Isotones

The atoms of different elements, having the same number of neutrons but
different atomic number are called isotones.

Some typical isotones





Thomson's Model and its Limitation

J.J.Thomson proposed the first simple and most primitive model of the
structure of an atom in 1898, when the neutron was not yet discovered. He
tried to explain the arrangement of electrons and protons within an atom by
considering an atom to consist of a diffused sphere of uniform positive
charge, of radius 10
-8
cm, into which the negatively charged electrons were
embedded just like raisins dotted evenly in a plum pudding. The model was
thus called as 'raisin pudding' model of the atom.

Limitations of Thomson's model

There was no distinct place of existence for the electrons or the protons i.e.,
they were not concentrated in any particular part of the atom.

It would be difficult to separate the positive and negative charges by this
model as evidenced by the discharge tube experiments.

The mass of the atom was spread evenly throughout it. Since the model
could not satisfy experimental facts, scientists later discarded it.

The subsequent detection of radioactive rays by Henry Becquerel and
discovery of radioactivity by Marie and Pierre Curie led to more discoveries
on the structure of the atom. Rutherford found out the nature of the
radioactive , and rays and devised an alternate theory of atomic structure.


Properties of , and rays





Rutherford's model

The discovery of radioactive particles let Rutherford to perform an
experiment where he bombarded a thin sheet of gold with '' particles
obtained from a radioactive substance. On striking the gold foil some of the
particles scattered and produced flashes on a zinc sulphide (ZnS) screen
placed at the back of the gold foil. These tiny flashes were observed by a
movable microscope. The observations made in this scattering experiment
were as follows:

Most of the '' particles pass through the metal and are undeflected.

Some of the '' particles are deflected through small angles.

Only a very few of them are deflected through as much as 90
o
or even larger
angles.

As Thomson's atomic model was not in conformity with the results of the
scattering experiment.

Rutherford concluded that:

Most of the space inside the atom was empty or hollow since most of the ''
particles passed undeflected.

Some of the particles that deflect with large angles indicated that some
heavy positively charged body was present inside the body of the atom,
which repelled the like charge of the '' particle. This heavy, positively
charged body was named as nucleus.

As the number of heavy positively charged particles that undergo deflection
was very small, the volume occupied by the nucleus must also be very small
compared to the volume of the atom.

As heavy particles like the '' particles deflected, the nucleus of the atom
must also have an appreciable mass.


Rutherford's nuclear model

On the basis of the scattering experiment, Rutherford described the structure
of the atom as:

An atom consists of a positively charged nucleus surrounded by electrons
that move around it. The positive charge of the nucleus is due to the protons.

Electrons and protons are held together by coulombic force of attraction.

The effective volume of the nucleus is extremely small as compared to the
effective volume of the atom. The volume occupied by the nucleus is smaller
by about 10
-12
times the volume of the atom.

The entire mass of the atom is concentrated at the nucleus.

Since each atom is electrically neutral, the number of positive charges in the
nucleus of an atom is equal to the number of electrons in it.



Rutherford's model of an atom

Limitations of Rutherford's model

Rutherford's model suffered some drawback. It could not explain the stability
of the atom in-spite of the electrons revolving around the nucleus. Moving
electrons should in principle emit radiations and lose energy. This should
cause them to slow down, gradually get pulled towards the nucleus by
following a spiral path and then ultimately fall into the nucleus. This should
make the atom collapse and hence unstable. But this is not so in reality.

Planck's quantum theory

At around the same time of the discovery of radio activity, Max Planck, in
1900, presented the results of his famous black body radiation experiments,
which showed that light has a dual character, behaving like a particle as well
as a wave. He gave the Quantum Theory of Radiation explaining
electromagnetic radiation and energy.

Its main features were:

Radiant energy is emitted or absorbed discontinuously in the form of small
packets of energy called 'quanta' (and not continuously as thought earlier).
Each such quantum is associated with a definite amount of energy. In the
case of light, the quantum of energy is called 'photon'.

The amount of energy (e) associated with a quantum of radiation is




where 'h' is proportionality constant, universally referred to as Planck's
constant. It has a fixed value of:

h = 6.63 x 10
34
joule/sec or h = 3.99 x 10
-13
kJ sec mol
-1


The total amount of energy emitted or absorbed by a body will be some
whole number multiple of the quantum, i.e. E = nh , where n = 1, 2, 3, 4, ....

In other words, a body can emit or absorb energy equal to 1h , 2h , 3h etc.,
and not as 1.6h , 2.4h , 3.2h etc.


From electromagnetic wave nature of light

this can be written as

where '' is the frequency, '' is the wavelength and 'c' is the velocity of the
light wave.


We know that


Thus, the energy associated with a quantum of radiation depends inversely
on its wavelength (or conversely with its frequency) i.e., higher the
wavelength of radiation, lesser the energy associated with its quantum. For
example, a photon of violet light will have more energy than that of a red
light because the former has a lower wavelength. The concept of energy
packets of light supports the corpuscular character.

Quantum theory of radiation

Albert Einstein used the Planck's quantum theory in 1905 to explain the
photoelectric effect. According to Einstein when a photon struck a metal
surface, a part of the total energy of the incident, called binding energy (the
energy that binds the electron to the nucleus), was utilized in ejecting
electrons from the metal atom. The remaining part of the total energy is
given to the ejected electron in the form of kinetic energy.

As light is propagated in the form of energy packets called photons, it can be
treated as particles of light. On the other hand as light also exhibits the
phenomena of interference and diffraction, which indicates that light, also
has wave like character. These facts suggest that light has dual character
i.e., particle as well as wave character.

Problem

5. Calculate the energy of a photon of light having frequency of 3.0 x 10
15
s
-1

(Planck's constant h = 6.63 x 10
-34
Js)

Solution

The energy of a photon is given by E = h

where the frequency of light = 3.0 x 10
15
s
-1


Planck's constant, h = 6.63 x 10
-34
J s

E = (6.63 x 10
-34
J s) x (3.0 x 10
1
s
-1
)

= 6.63 x 3 x 10
19
J





Bohr's Atomic Model

In 1913, Neils Bohr proposed a model of an atom based on the Planck's
quantum theory of radiation. The basic postulates of Bohr's theory are:

An atom consists of a small, positively charged nucleus heavily around which
electrons revolve in definite circular paths called orbits.

These orbits are associated with definite energies called energy shells/energy
levels. They are designated as K, L, M, N, .... etc. shells or numbered as 1, 2, 3,
4, ......etc. from the nucleus.

As long as the electron remains in a particular orbit /energy shell its energy
remains constant. This accounts for the stability of an atom.

Only those orbits are permitted in which the angular momentum of the electron
is a whole number multiple of h/ 2 where h is Planck's constant.

Any moving body taking a circular orbit has an angular momentum equal to the
product of its mass (m), velocity of movement (v) and radius of orbit (r). In
other words the angular momentum of an electron (m x v x r) is a whole
number multiple of h/ 2 .

Thus,

mvr = n * h/ 2 ; where n = 1,2,3,.
i.e. for (n=1), h/ 2 is the electrons angular momentum

for (n=2), h/ is the electrons angular momentum
for (n=3), 3h/ 2 is the electrons angular momentum and so on.

This postulate introduces the concept of quantisation of angular momentum.

Electrons can jump from one energy level to another and when they do so, they
either lose or absorb energy abruptly. For instance when an electron moves from
the 'normal or ground state - E
2
' of an atom i.e., the state of lowest energy as
required by its 'n' and 'l' values, to a higher level, it causes the atom to be in
what is called 'excited state-E
2
'. This is where electrons in an atom occupy
energy levels higher than those permitted by its 'n' and 'l' values. The reverse is
also true and the change in energy is E,

E = E
2
- E
1
= h



Energy changes in an electron jump

Bohr's atomic model explained successfully:

The stability of an atom. Bohr postulated that as long an electron remains in a
particular orbit it does not emit radiation i.e. lose energy. Hence it does not
become unstable.

Atomic spectra

A spectrum is an assembly of energy levels in the form of radiations emitted by
an atom in its excited state. Every atom gives discontinuous line spectra. Each
line in the spectra corresponds to a specific wavelength and it is unique to a
given element. The atoms of two elements give same pattern of lines in their
spectra.

Atomic emission spectra

When a substance is heated to a high temperature, the atoms in the vapours get
energized. These energized atoms then return to the ground state by emitting
electromagnetic light radiations of certain definite wavelength. These radiations
appear as a series of bright lines separated from each other by dark spaces
when made strike a photographic plate. This representation of emitted radiation
is called atomic emission spectra.



Mechanism of emission spectra

Atomic absorption spectra

When the atomic vapours from a sample are placed in the path of white light
from an arc lamp, it absorbs the light of certain characteristic wavelengths and
the light of other wavelengths get transmitted. In such conditions a series of
dark lines on a white background are formed on the photographic plate. This is
called an absorption spectrum.


The dark lines in the absorption spectrum and the bright lines in the emission
spectrum of a given element appear at the same wavelength.



Comparison of Absorption and emission spectra of sodium vapour

Since each element gives a definite pattern of lines at certain definite
frequencies or wavelengths, the atomic spectra is used in chemical analysis to
identify and estimate the elements present in any sample.

Atomic spectra of hydrogen atom

Hydrogen is the simplest element with its atom having only one electron. Hence,
the atomic spectrum of hydrogen has played a significant role in the
development of atomic structure. In the emission spectrum of hydrogen, when
an electric discharge is passed through hydrogen gas, the molecules of hydrogen
break into atoms. The hydrogen atoms get energized and go into an excited
state. The excited atoms then return to the ground state by emitting light.
Hydrogen atoms emit a bluish light. On passing this light through a prism, a
discontinuous line spectrum consisting of several sharp lines is obtained. This is
the line spectrum of hydrogen.

Four sharp coloured lines were observed in the visible region of this spectrum by
Balmer, in the ultra violet region by Lyman, and in the infrared region by
Paschen, Brackett and Pfund. These series of lines are named after these
scientists who discovered them. Balmer expressed these lines in terms of
inverse of their wavelength ( ) by a mathematical relation, which was later
modified by Rydberg.




where 'RH' is the Rydberg's constant and 'n
1
', 'n
2
' are integers with values equal
to or greater than 3 and ' ' is the wavelength.



Line spectrum of hydrogen atom

The atomic spectrum of hydrogen: This was explained due to the concept of
definite energy levels. The one electron of hydrogen being closest to the nucleus
is in its lowest energy shell (n =1) or normal ground state can absorb a definite
amount of energy and jump to a higher energy state. This excited state being
unstable, the electron comes back to a lower energy level. When the emitted
energy during transition, strikes a photographic plate, it gives its impression in
the form of a line. This difference is also the energy of photon expressed as E
2
-
E
1
= h .

The frequency of the emitted radiation is:



Since E
2
and E
1
have only definite values and are characteristic of energy levels
of atoms, the values of '' will also be definite and characteristic of the atoms.
Thus each transition will produce a light of definite wavelength, which is
observed as a line in the spectrum.

For example, if the electron jumps down from the third to the first energy level
having energies E
3
and E
1
respectively, then the wavelength of the spectral line
would be



Similarly, when the electron jumps down from the fourth to the first energy level
having energies E
4
and E
1
respectively or from the fifth to the second i.e., E
5
and
E
2
, then we have

These will give different lines in the spectrum of the atom corresponding to
different transitions having definite wavelengths.

Different spectral lines: Any sample of hydrogen gas contains a large number of
atoms and when energy is supplied, the electrons in different hydrogen atoms
absorb different amounts of energies. These are raised to different energy
states. For example, the electrons in some atoms may jump to second energy
level (L), while in others it may be to the third (M), fourth (N) or fifth (O) and so
on. These electrons come back from the higher energy levels to the ground state
in one or more jumps emitting different amount of energies.



Different routes to the ground state from n = 4

The different spectral lines depending upon the difference in energies of the
levels concerned can be summarized in the form of series named after the
scientists who have discovered them.

Lyman series from n = 2, 3, 4, 5....to n = 1

Balmer series from n = 3, 4, 5, 6.....to n = 2

Paschen series from n = 4, 5, 6, 7.....to n = 3

Brackett series from n = 5, 6, 7, 8.....to n = 4

Pfund series from n = 6, 7, 8, 9.....to n = 5.

The energy of the electron in a particular orbit of hydrogen atom. This could be
calculated by Bohr's theory. The energy of the electron in the 'nth' orbit has
been found to be



where 'm' is the mass and 'e' is the charge of the electron. The energy
expression for hydrogen like ions such as He, Li can be written as:



where 'Z' is the nuclear charge, which is equal to atomic number.

Note :

The electronic energy is negative because when unlike charges are brought
together energy is released by the system due to the force of attraction. Thus
when electron moves closer to the nucleus its energy decreases and it becomes
less than zero i.e., negative.

Although Bohr's model successfully explained the stability and the line spectrum
of hydrogen, it still had its limitations. These were:


Limitations and problems

It could not explain the line spectrum of multi electron atoms.

This model failed to explain the effect of magnetic field on the spectra of atoms
(Zeeman effect).

The effect of an electric field on the spectra could also not be explained by
Bohr's model (Stark effect).

The shapes of molecules arising out of directional bonding could not be
explained.

The dual nature of electrons (both as wave and particle) was not explained,
further the path of motion of electrons in well defined orbits were not correct.

Problems

7. If the energy difference between the electronic states of hydrogen atom is
214.68 kJ mol
-1
, what will be the frequency of light emitted when the electron
jumps from the higher to the lower energy state? (Planck's constant = 39.79 x
10
-14
kJ mol
-1
)

Solution

The frequency () of emitted light is related to the energy difference of two
levels ( E) as



E = 214.68 kJ mol
-1
, h = 39.79 x 10
-14
kJ mol
-1






= 5.39 x 10
14
s
-1


8. The wavelength of first spectral line in the Balmer series is 6561 units.
Calculate the wavelength of the second spectral line in Balmer series.

Solution

According to Rydberg equation:



For the first line in Balmer series, n
1
= 2, n
2
= 3



For the second line in Balmer series, n
1
= 2, n
2
= 4



Dividing equations (i) by (ii)





Quantum Mechanical Model of the Atom

Two new concepts came to substantially modify Bohr's Atomic model. These are:

1. Wave nature of materials objects

2. Heisenberg's uncertainty principle


Wave nature of material objects

In 1924, de Broglie's suggested that all material objects including an electron
have a dual character; they behave as particles as well as waves. The
wavelength associated with a particle of mass 'm', moving with velocity 'v' is
given by de Broglie's relation as:



Note :

This discovery of the wave like character of the electron helped in the making of
the modern electron microscope.

Heisenberg's uncertainity principle

Heisenberg, in 1927 pointed out that it is not possible to measure
simultaneously the momentum (or velocity) as well as the position of a
microscopic particle with absolute accuracy. Mathematically, this may be
expressed as:



where, x = uncertainity in position

p = uncertainity in momentum

The constant on the right side of the equation (the product of the two
uncertainties) tells us that the two uncertainties are inversely related. If the
momentum of the particle is measured with more accuracy there is a larger
uncertainity in its position and vice versa.

Uncertainity is not due to the lack of refined techniques available for
measurement but observes on microscopic bodies cannot be made without
disturbing them. Observations made as result of the impact of light suffer a
change in the position or velocity of these microscopic objects. This does not
hold good for large objects of daily life, as the changes that occur are negligible.

Probability picture of an electron

According to Heisenberg's uncertainty principle, it is impossible to describe the
exact position of an electron at a given moment in terms of position. We can
speak of most probable regions where the probability of finding an electron in
the space around the nucleus of an atom is high. The electron does not always
remain at a fixed distance from the nucleus. It keeps moving in the whole space
around the nucleus but tends to remain most of the time within a small volume
around the nucleus, where the probability of locating the electron is maximum.
Hence a new atomic model, was needed to explain the

Wave nature (dual character) of atoms

The idea of uncertainity in the position of electrons in an atom

The concept of fixed energy states

In view of these facts, Schrodinger put forward the wave model or quantum
mechanical model of atomic structure. In this model, the behavior of an electron
is defined by the mathematical equation:



where, = (psi) is a wave function of space coordinates 'x', 'y', 'z' and represents
the amplitude of the electron wave.

m = mass of the electron

E = the total permissible energy level, which the electron can have.

V = potential energy of the electron given by ze
2
/r.

h = Planck's constant having the value 6.626 x 10
-34
J s. = (delta) stands for
infinitesimal change.

The wave length function (psi) describes a number of possible states of an
electron in an atom. Since a large number of solutions are possible, only
meaningful permissible values of energy and location of the electron with
respect to the nucleus are considered. Four important solutions in the name of
"quantum numbers describe the position of the electron accurately.



Atomic orbitals

Electrons cannot exist at a particular point or in a well-defined orbit (path),
according to the above new approach of wave mechanics. This led to the
concept of 'most probable regions' in space around the nucleus. These
regions are called atomic orbitals, where the probability (chances) of finding
the electron is maximum (90%-95%)'.

An atomic orbital differs from an orbit (Bohr's orbit) in the following ways.














Quantum Numbers

Orbitals of electrons in atoms differ in size, shape and orientation. Definite
energies and angular movements characterize atomic orbitals. The state of
an electron in any atom is defined by certain permissible values of energy
and angular momentum, which describe its location with respect to its
nucleus and its energy level. These permissible states are called orbitals and
are expressed by a set of four numbers 'n', 'l', 'm' and 's' called quantum
numbers. These numbers serve as the signature of the electrons, uniquely
describing its position in the atom. The 'n', 'l' and 'm' indicate the spatial
distribution while 's' indicates the spin orientation of the electrons.

Principal quantum number

The principal quantum number gives the average distance of the electron
from the nucleus and the energy associated with it, i.e., it determines the
main energy shell or energy level in which the electron is present.

It is denoted by the letter 'n' that can take whole number values starting
from 1, 2, 3, 4,..... The shell with n = 1 is called first shell or 'K' shell. The
shell with n = 2 is the 'L' shell and so on. The first shell is closest to the
nucleus. As the value of 'n' increases, the distance from the nucleus as well
as the energy of the electrons increases.


Azimuthal quantum number or angular quantum number

The Azimuthal quantum number determines the angular momentum of the
electron, denoted by the letter 'l'. The value of 'l' gives the sub level or sub
shell in a given principal energy shell to which the electron belongs. It can
have only positive integral values from zero to (n-1) where 'n' is the principal
quantum number. The various sub shell values of 'l' are also designated by
the letters s, p, d, f,... For any main energy level, the energies of the sub-
shell follow the order s > p > d > f.

The different sub-shells are represented by, first writing the value of 'n' and
then the letter designated for the value of 'l'.

To illustrate,

n = 1 l = 0 one sub shell 1s

n = 2 l = 0,1 two sub shells 2s, 2p

n = 3 l = 0,1,2 three sub shells 3s, 3p, 3d

n = 4 l = 0,1,2,3 four sub shells 4s, 4p, 4d, 4f


Thus for each value of 'n' there are 'n' values of 'l'.

The value of azimuthal quantum number gives the shape of the sub shell or
orbital. So it is also called as orbital quantum number.

Magnetic quantum number

The magnetic quantum number denoted by the letter 'm' describes the
behaviour of electron in a magnetic field. In the absence of an external
magnetic field, electrons orbitals having same values of 'n' and 'l' but
different values of 'm' have the same energies. They are called degenerate
orbitals. However, in the presence of an external magnetic field the orbitals
vary in their energies slightly. This happens because the preferred orientation
of the orbital in space is a result of interaction of its own magnetic field with
that of the external magnetic field.

The magnetic quantum number 'm', depend on 'l' for its values. This
quantum number can have all integral values from '-l' to '+l' including 0.
Thus for a given 'l' value there are (2l + 1) values of 'm'. Two orbitals in the
same shell can have identical 'n' and 'l' values but they must have different
fixed values of 'm'.

The number of orbitals in each sub shell are given below:

s sub shell l = 0 m = 0 only one orientation one orbital

p sub shell l = 1 m = +1,0, -1 three orientations three orbitals

d sub shell l = 2 m = +2,+1,0,-1,-2 five orientations five orbitals

Spin quantum numbers

The orientation of spin of an electron is designated by its spin quantum
number 's'. The spin orientation is an intrinsic characteristic of the electron
connected more with its magnetic behaviour rather than rotation of an
electron about its own axis. This number can have only two values
corresponding to clockwise and anticlockwise spins i.e., + and -. The
clockwise spin is represented by an arrow pointing upwards (h). The anti
clockwise spin is represented by an arrow pointing downwards (i). Each
orbital can accommodate a maximum of two electrons provided they have
opposite spins.



Number of sub shells and orbitals in the K, L and M shells

Problem

9.(a) What are the permissible values for 'l' and 'm' when 'n' = 3?

(b) Which orbital is specified by 'l' = 2 and 'n' = 3?

Solution

(a) For n = 3, the permissible values for 'l' and 'm' are: 'l' = 0, 1, 2

For 'l' = 0 m = 0 (s-orbital)

For 'l' = 1 m = +1, 0, -1 (p-orbital)

For 'l' = 2 m = +2, +1, 0, -1, -2 (d-orbital)


(b) For 'n' = 3 and 'l' = 2:

'l' = 2 means 'd' orbitals

The given orbital is '3d'.



Shapes of Atomic Orbitals

An atomic orbital is the space around the nucleus in which the probability of
finding the electron is maximum. These most probable regions can be
diagrammatically represented by cloud density or dot diagrams. The density
of dots (or lack of them) in any region of the cloud diagram, indicates the
degree of probability of finding the electron in that region. It is not always
convenient to draw dot diagrams of orbitals, since the probability of finding
an electron decreases with distance (but does not become zero), thus not
giving it any definite shape. Drawing boundary surfaces, which enclose 95-
99% of the probability of locating an electron, is the method generally used
to show the shape of an orbital.

As definite energies and angular momentums characterize atomic orbitals,
the permissible values of these parameters are expressed in terms of
quantum numbers. The azimuthul quantum 'l', is related to orbital angular
momentum of the electron in terms of the quantity given below:



Thus different values of 'l' correspond to different orbital angular
momentums. As a result the azimuthul quantum 'l' determines the shape of
orbitals.

Shape of 's' orbitals

The orbital angular momentum of a 's' orbital is zero, as 'l' = 0. This means
that the probability of finding an electron at a particular distance from the
nucleus is the same in all directions or at all angles. Since the distribution of
electron density is symmetrical, the shape representing the 's' orbital is a
sphere.

It is to be noted that firstly the total number of concentric spheres at any
given main energy level in an 's' orbital equals the principle quantum number
of that level. Thus for example '1s' orbital consists of only one sphere while a
'3s' orbital consists of three concentric spheres. Secondly, as the value of the
principal quantum number 'n' increases, the 's' orbital becomes larger and
the energy of the 's' orbital increases, while retaining the spherical
symmetry. The energies of the various 's' orbitals follow the order 1s < 2s <
3s < 4s.


Shape of 'p' orbitals

The 'l' value for 'p' orbitals is equal to one. So,




Thus the distribution around the nucleus is not spherical. The 'p' orbital
probability diagram is dumb-bell shaped i.e., it consists of distorted spheres
of high probability, one on each side of the nucleus, concentrated along a
particular direction. The probability of finding the electron in a particular 'p'
orbital is equal in both the lobes.


Since 'l' = 1, irrespective of the value of n, three values of magnetic quantum
number 'm' exists i.e., +1, 0 and 1. Thus, three 'p' orbitals exist in each 'p'
sub-shell. These are oriented symmetrically around the three axes 'x', 'y'and
'z'.



Shapes of 2px, 2py and 2pz orbitals

Shape of 'd' orbitals

For 'd' orbitals 'l' = 2. Therefore the angular momentum of an electron does
not show a spherical symmetry. For 'l' = 2, five values of 'm'-the magnetic
quantum number exists i.e., -2, -1, 0, +1, and +2. Accordingly, there are
five space orientations for 'd' orbitals, which are not identical in shape. These
are designated as:

m = -2 m = -1 m = 0 m = +1 m = +2



Shapes of five 'd' orbitals

Relative Energies of Atomic Orbitals

Single electron atoms:

The relative energies of various orbitals of single electron atom depend on
the value of the principal quantum number 'n' and is independent of the
value of 'l'. This can be shown by an arrangement known as the energy level
diagram. The diagram given below, illustrates the relative energy of various
energy levels for hydrogen and hydrogen like atoms.



Relative energy levels of hydrogen and hydrogen like atoms


Multi-electron atoms

In atoms with a number of electrons the energy of orbitals have the same
values of 'n' but different values of 'l'. Thus both values of 'n' and 'l'
determine the energy of an orbital. The following facts hold good for multi-
electron atoms.

Different orbitals that have the same principle quantum number 'n' (sub-
shell) may have different energies.

For a particular main energy level, the orbital having higher value of the
azimuthal quantum number 'l' has higher energy. In general, energies of
orbitals belonging to the same main energy level follow the order, 's' < 'p'<
'd'< 'f' .

When 'n' 3 some orbitals belonging to a lower main energy level may have
higher energy than some orbitals belonging to the higher main energy levels.
For example, the energy of '3d' orbitals is greater than '4s' orbitals.

The orbital having lower (n + l) value has lower energy. However for orbitals,
whose (n+l) values are equal, the orbital having the lower value of 'n' has
lower energy. For example,

4s orbital, n + l = 4 + 0 = 4

3p orbital, n + l = 3 + 1 = 4.

So, '3p' orbital has lower energy than '4s'.


Rules for filling the orbitals

Aufbau principle

The principle states that the electron in an atom are so arranged that they
occupy orbitals in the order of their increasing energy. Since the energy of a
'n' orbital in the absence of any magnetic field depends on the 'n' and 'l'
quantum number values, the order of filling orbitals may be obtained from
the (n + l) rule of Bohr Bury's rule.


According to this principle, the orbital with the lowest energy is filled first.
The orbital having lower (n + l) value has lower energy. However for orbitals
whose (n + l) values are equal, the orbital having lower value of 'n' has lower
energy. It is important to remember that because of this rule, the sequence
of energy levels pertains to an increasing order of energy level up to an
increasing order of '3p'. Thereafter, '4s' orbitals comes earlier to the '3d'
energy level. Thus, the orbitals are filled in the following order:

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




A simple way to determine the relative energies of different orbitals


Pauli's exclusion principle

The Paulis exclusion principle states, that no two electrons in an atom can
have the same values of all the four quantum numbers. If one electron in the
atom has the quantum numbers n = 1, l = 0, m = 0 and s = +1/2, no other
electron can have the same four quantum numbers. In other words, we
cannot place two electrons with the same value of 's' in a '1s' orbital.

Secondly, each orbital can accommodate a maximum of two electrons only if
their spins are of opposite directions. Each sub-shell holds a maximum of two
electrons in an orbital.




It can be inferred that the maximum number of orbital in each shell is n
2
and
the maximum number of electrons is 2n
2
.

Hund's rule of maximum multiplicity

This rule states that when more than one orbital of equal energies are
available then the electrons first occupy these orbitals separately with
parallel spins. The pairing of electrons starts only after all the orbitals of a
given sub level are singly occupied. This is because electrons with parallel
spins tend to be as far apart as possible to minimize the electrostatic
repulsion.

For example, the three electrons that are filled into the three 'p' orbitals can
be represented in two different ways:




Electronic Configuration

The distribution of electrons in different orbitals is known as its electronic
configuration. This characterizes each electron in an atom. The electronic
configuration is expressed by indicating the principal quantum number and
its respective orbital along with the number of electrons present in it. For
example the notation 3p
x
1
indicates that in the third principal shell there is
one electron in the 'p
x
' orbital.

Sometimes the electronic configuration is also described in the box notation
form, by putting an arrow for single electron in a box or a pair of arrows for
two electrons in a box. The direction of the arrows gives the orientation of its
spin.

Further the box is labelled on top by writing the symbol of the orbital as
shown below:



Based on the various rules of filling the orbitals the electronic configuration of
some of the important elements can be written as follows:







In the electronic configuration of elements Na to Argon the filled sub shells
can be represented by the inert gas notation of Ne as shown:




Similarly, after argon the first orbital to be filled is '4s' followed by '3d' as
shown for Ca.




Stability of half filled and completely filled orbitals:

In some cases the actual configuration differs slightly from the expected ones
e.g., Cu (atomic number 29) and Cr (atomic number 24) because of the
condition of achieving extra stability by half-filled and completely filled sub
shell configuration.

The extra stability of half-filled and completely filled sub shell configuration is
due to the following two reasons:

a) Symmetry of orbitals

The configurations in which all the orbitals of the same subshell are half-filled
or completely filled is due to the symmetrical distribution of electrons.
Symmetry of electronic distribution leads to extra stability. Example:



or




b) Exchange energy

In an atom, the electrons present in various orbitals of the same subshell
tend to exchange their positions by a very small amount of energy change.
Half-filled and completely filled sub-shell configurations allow maximum
exchange of electrons to take place in this manner. Therefore, such
configurations have maximum stability e.g., molybdenum (half-filled '4d'
orbitals) and silver (completely filled '4d' orbitals).

Electronic configuration of ions

The electronic configuration of cations is written by determining the number
of electrons in this state. It is determined by subtracting the number of
positive charges on the cation from the atomic number.

For example,

Na
+
, atomic number = 11, number of positive charges = 1

Number of electrons in Na
+
= (11 - 1) = 10

Electronic configuration is 1s
2
2s
2
2px
2
2py
2
2pz
2
.

Similarly the electronic configuration of anions is written by determining the
number of electrons in the anion. This is done by adding the number of
negative charges on the anion to the atomic number.

For example,

Cl
-
, atomic number = 17, number of negative charges = 1

Number of electrons in Cl
-
= (17 + 1) = 18

Electronic configuration is 1s
2
2s
2
2p
x
2
2p
y
2
2pz
2
3s
2
3p
x
2
3py
2
3p
z
2



The ions and atoms that have the same number of electrons are termed as
isoelectronic e.g., O
2-
, Na
+
, Al
3+
, Mg
2+
and Ne (each containing ten
electrons).

Problem

10. How many sublevels are possible in each energy level?

Solution

The total number of sublevels or sub-shells possible in each energy level is
equal to the numerical value of 'n'. Thus 'n' = 1 energy level can have only
one sublevel which is 'l' = 0 or the 's' orbital, 'n' = 2 energy level can have
two sublevels corresponding to 'l' = 0 (s) and 'l' = 1(p).

Similarly 'n' = 3 energy level can have 3 sublevels 's', 'p' and 'd'.