Atomic Structure

Defining of Atom
Drawbacks of Rutherford Atomic Model

➢ As before, the Rutherford atomic model was also challenged and

questioned by many. Rutherford atomic model failed to explain
about the stability of electrons in a circular path.

➢ As per Rutherford’s model, electrons revolve around the nucleus

in a circular path. But particles that are in motion on a circular
path would undergo acceleration, and acceleration causes
radiation of energy by charged particles. Eventually, electrons
should lose energy and fall into the nucleus. And this points to the
instability of the atom. But this is not possible because atoms are
stable. Hence, Rutherford failed to give an explanation on account
of this.
Bohr atom model:
The work of Planck and Einstein showed that
the energy of electromagnetic radiation is
quantized in units of hν (where ν is the
frequency of radiation and h is Planck's
constant 6.626 × 10-34 Js). Extending
Planck’s quantum hypothesis to the energies
of atoms, Niels Bohr proposed a new atomic
model for the hydrogen atom.
This model is based on the following
assumptions:
1. The energies of electrons are quantized
2. The electron is revolving around the
nucleus in a certain fixed circular path called
stationary orbit.
3. Electron can revolve only in those orbits in
which the angular momentum (mvr) of the
electron must be equal to an integral multiple
of h/2π. i.e. mvr = nh/2π

where n = 1,2,3,...etc.,
4. As long as an electron revolves in the fixed
stationary orbit, it doesn’t lose its energy.
However, when an electron jumps from higher
energy state (E2) to a lower energy state (E1), the
excess energy is emitted as radiation. The
frequency of the emitted radiation is
E2 – E1 = hν
and ν = (E2 – E1)/h
Applying Bohr’s postulates to a hydrogen
like atom (one electron species such as H,
He+ and Li2+ etc..) the radius of the nth
orbit and the energy of the electron
revolving in the nth orbit were derived. The
results are as follows:
Limitation of Bohr's atom model:

The Bohr's atom model is applicable only to species

having one electron such as hydrogen, Li2+ etc... and not
applicable to multi electron atoms.

It was unable to explain the splitting of spectral lines in the

presence of magnetic field (Zeeman effect) or an electric
field (Stark effect).

Bohr’s theory was unable to explain why the electron is

restricted to revolve around the nucleus in a fixed orbit in
which the angular momentum of the electron is equal to
nh/2π and a logical answer for this, was provided by Louis
de Broglie.
Sommerfeld atomic model

This model explains the fine spectrum of Hydrogen atom. The important postulates of
Sommerfeld atomic model are
1- The orbits may be both circular and elliptical.
Wave particle duality of matter

• Albert Einstein proposed that light has dual nature. i.e. light photons behave both like a
particle and as a wave.
• Louis de Broglie extended this concept and proposed that all forms of matter showed dual
character.
• To quantify this relation, he derived an equation for the wavelength of a matter wave. He
combined the following two equations of energy of which one represents wave character (hυ)
and the other represents the particle nature (mc2).
 λ = h / mc ------------(2.8)

The equation 2.8 represents the wavelength of photons whose momentum is given by mc
(Photons have zero rest mass).

For a particle of matter with mass m and moving with a velocity v, the equation 2.8 can be
written as .

λ = h / mv ------------ (2.9)

This is valid only when the particle travels at speeds much less than the speed of Light.

This equation implies that a moving particle can be considered as a wave and a wave can
exhibit the properties (i.e momentum) of a particle. For a particle with high linear momentum
(mv) the wavelength will be so small and cannot be observed. For a microscopic particle such
as an electron, the mass is of the order of 10-31 kg, hence the wavelength is much larger than
the size of atom and it becomes significant.
 Quantisation of angular
momentum and de Broglie concept:
According to the de Broglie concept, the electron that revolves around the nucleus
exhibits both particle and wave character.

In order for the electron wave to exist in phase, the circumference of the orbit should be
an integral multiple of the wavelength of the electron wave. Otherwise, the electron wave
is out of phase.
Planck’s Quantum Theory
According to Planck’s quantum theory,

[Link] atoms and molecules can emit or absorb energy in discrete quantities only. The
smallest amount of energy that can be emitted or absorbed in the form of electromagnetic
radiation is known as quantum.

[Link] energy of the radiation absorbed or emitted is directly proportional to the frequency of
the radiation.
 Black body radiation
- A black body is a theoretical object that absorbs 100% of the radiation
that hits it. Therefore it reflects no radiation and appears perfectly
black.
- Roughly we can say that the stars radiate like blackbody radiators.
This is important because it means that we can use the theory for
blackbody radiators to infer things about stars.
- At a particular temperature the black body would emit the maximum
amount of energy possible for that temperature.
- Blackbody radiation does not depend on the type of object emitting it.
Entire spectrum of blackbody radiation depends on only one parameter,
the temperature, T.
• As the temperature increases,
the peak wavelength emitted by
the black body decreases.
• As temperature increases, the
total energy emitted increases,
because the total area under the
curve increases.
• The curve gets infinitely close
to the x-axis but never touches
it.
Photoelectric effect
 De Broglie

MATTER WAVES
We have seen that light comes in discrete units (photons) with
particle properties (energy and momentum) that are related to the
wave-like properties of frequency and wavelength.

In 1923 Prince Louis de Broglie postulated that ordinary matter can have
wave-like properties, with the wavelength λ related to momentum
p in the same way as for light

de Broglie relation h Planck’s constant

= h = 6.63 10−34 Js
de Broglie wavelength
p
wavelength depends on momentum, not on the physical size of the particle
Prediction: We should see diffraction and interference
of matter waves
 ELECTRON DIFFRACTION
The Davisson-Germer experiment (1927)
G.P.
The Davisson-Germer Davisson Thomson
θi experiment: scattering a beam of
electrons from a Ni crystal.
Davisson got the 1937 Nobel
prize.
θi

At fixed angle, find sharp peaks in

intensity as a function of electron energy

Davisson, C. J.,
At fixed accelerating voltage (fixed "Are Electrons
electron energy) find a pattern of Waves?," Franklin
sharp reflected beams from the Institute Journal
crystal 205, 597 (1928)

G.P. Thomson performed similar

interference experiments with thin-film
samples
The wave nature of electron was experimentally confirmed by Davisson
and Germer.

They allowed the accelerated beam of electrons to fall on a nickel crystal

and recorded the diffraction pattern.

The resultant diffraction pattern is similar to the x-ray diffraction pattern.

The finding of wave nature of electron leads to the development of

various experimental techniques such as electron microscope, low energy
electron diffraction etc...
Heisenberg’s uncertainty principle

The dual nature of matter imposes a limitation on the simultaneous

determination of position and velocity of a microscopic particle.

Based on this, Heisenberg arrived at his uncertainty principle, which

states that ‘It is impossible to accurately determine both the position as
well as the momentum of a microscopic particle simultaneously’.

Δx.Δp ≥ h/4π

where, Δx and Δp are uncertainties

in determining the position and
momentum, respectively

Classical optics shows that the electron

position can be resolved only up to an
uncertainty Δx that depends on θ and the
wavelength λ of the incoming light.
[Link]
istry-1-and-2-mot-unit-cell-
pptppt/267281344
Hybridization, in Chemistry, is defined as the concept of mixing two atomic orbitals to give rise
to a new type of hybridized orbitals. This intermixing usually results in the formation of hybrid
orbitals having entirely different energy, shapes, etc.

The atomic orbitals of the same energy level mainly take part in hybridization. However, both
fully-filled and half-filled orbitals can also take part in this process, provided they have equal
energy.
Key Features of Hybridization

•Atomic orbitals with equal energies undergo hybridization.

•The number of hybrid orbitals formed is equal to the number of atomic orbitals mixed.

•It is not necessary that all the half-filled orbitals must participate in hybridization. Even
completely filled orbitals with slightly different energies can also participate.

•Hybridization happens only during the bond formation and not in an isolated gaseous atom.

•The shape of the molecule can be predicted if the hybridization of the molecule is known.

•The bigger lobe of the hybrid orbital always has a positive sign, while the smaller lobe on the
opposite side has a negative sign.
Linear combinations: Molecular Orbitals

• Both atomic orbitals and hybrids

centred on different atoms combine
to form covalent bonds.
• σ-bonds (sigma-bonds) are made
up from overlapping orbitals
directed along the bond direction.
• π-bonds (pi-bonds) are made up
from overlapping orbitals at an
angle to the inter-nuclear direction:
• πp bonds are combinations of p-
orbitals perpendicular to the bond
direction
• πp-d bonds are combinations of p-
and d-orbitals but not precisely
perpendicular to the bond-
direction
Types of Hybridization
Based on the types of orbitals involved in mixing, the hybridization can be classified as sp3, sp2,
sp, sp3d, sp3d2 and sp3d3.

sp Hybridization
sp hybridization is observed when one s and one p orbital in the same main shell of an atom mix
to form two new equivalent orbitals. The new orbitals formed are called sp hybridized
orbitals. It forms linear molecules with an angle of 180°.
•This type of hybridization involves the mixing of one ‘s’ orbital and one ‘p’ orbital of equal
energy to give a new hybrid orbital known as an sp hybridized orbital.
•The sp hybridization is also called diagonal hybridization.
•Each sp hybridized orbital has an equal amount of s and p characters – 50% s and 50% p
characters.

Examples of sp Hybridization:
•All compounds of beryllium, like BeF2, BeH2, BeCl2
•All compounds of a carbon-containing triple bond, like C2H2.
sp2 Hybridization
sp2 hybridization is observed when one s and two p orbitals of the same shell of an atom mix to
form 3 equivalent orbitals. The new orbitals formed are called sp2 hybrid orbitals.
•sp2 hybridization is also called trigonal hybridization.
•It involves the mixing of one ‘s’ orbital and two ‘p’ orbitals of equal energy to give a new
hybrid orbital known as sp2.
•A mixture of s and p orbital formed in trigonal symmetry and is maintained at 1200.
•All three hybrid orbitals remain in one plane and make an angle of 120° with one another. Each
of the hybrid orbitals formed has a 33.33% ‘s’ character and 66.66% ‘p’ character.
•The molecules in which the central atom is linked to 3 atoms and is sp2 hybridized have a
triangular planar shape.
Examples of sp2 Hybridization
•All the compounds of Boron, i.e., BF3 and BH3
•All the compounds of carbon, containing a carbon-carbon double bond, Ethylene (C2H4)
sp3d Hybridization
sp3d hybridization involves the mixing of 1s orbital, 3p orbitals and 1d orbital to form 5 sp3d
hybridized orbitals of equal energy. They have trigonal bipyramidal geometry.
•The mixture of s, p and d orbital forms trigonal bipyramidal symmetry.
•Three hybrid orbitals lie in the horizontal plane inclined at an angle of 120° to each other, known
as the equatorial orbitals.
•The remaining two orbitals lie in the vertical plane at 90 degrees plane of the equatorial orbitals,
known as axial orbitals.
•Example: Hybridization in phosphorus pentachloride (PCl5)
sp3d2 Hybridization
•sp3d2 hybridization has 1s, 3p and 2d orbitals, that undergo intermixing to form 6
identical sp3d2 hybrid orbitals.
•These 6 orbitals are directed towards the corners of an octahedron.
•They are inclined at an angle of 90 degrees to one another.
What is the Aufbau Principle?
It states that electrons are filled into atomic orbitals in the increasing order of orbital energy
level. According to the Aufbau principle, the available atomic orbitals with the lowest energy
levels are occupied before those with higher energy levels.
Hunds Rule of Maximum Multiplicity
According to this rule electron pairing in p, d and f orbitals cannot occur until each orbital of a given subshell
contains one electron each or is singly occupied.
State Hund’s Rule
It states that:
1. In a sublevel, each orbital is singly occupied before it is doubly occupied.
2. The electrons present in singly occupied orbitals possess identical spin.
Explanation of Hund’s Rule
The electrons enter an empty orbital before pairing up. The electrons repel each other as they are negatively
charged. The electrons do not share orbitals to reduce repulsion.
When we consider the second rule, the spins of unpaired electrons in singly occupied orbitals are the same.
The initial electrons spin in the sub-level decides what the spin of the other electrons would be. For instance,
a carbon atom’s electron configuration would be 1s22s22p2. The same orbital will be occupied by the two 2s
electrons although different orbitals will be occupied by the two 2p electrons in reference to Hund’s rule.
UNIT-II Periodic properties
Periodic properties – classification of elements as s, p, d and f-block elements – variation of
atomic volume – atomic and ionic radii – ionization potential – electron affinity and
electronegativity along period and groups – variation of metallic characters - Factors affecting the
periodic properties. Periodic table anomalies and variations in atomic radius, ionic radius,
electronic configuration, electron affinity and electronegativity, ionization energy and metallic
character of elements along the group and periods and their influences on stability, colour,
coordination number, geometry, physical and chemical properties.
Atomic volume

The volume occupied by a mole of atoms at room temperature is called atomic volume.
The formula to calculate atomic volume is, Atomic volume =atomic weight/density
Its units are m3 or cm3

Periodic trends of atomic volume across a period firstly decrease from left to right and then increase.
The main role in this trend is played by nuclear charge. Nuclear charge is a positive charge exerted by a
nucleus on electrons of the atom. From left to right in a period, the number of shells remains the same. But,
the number of electrons, protons and neutrons increases with increase in atomic number.

Due to the increase in the number of protons in the shell, more nuclear charge is exerted on the electrons of
that atom. It results in increased nuclear charge per electron and thus it attracts the electrons and holds them
tightly. Due to this phenomenon, the volume of an atom goes on decreasing from left to right of the period.

In the extreme right end noble gases are the inert gaseous atoms that have complete atomic orbitals. The
volume of noble gases is relatively large because they have large van der waals radii, due to complete.
Valence shell and paired electrons. These electrons cause repulsion and lead to increase in volume of the
noble gas.
• One way to think about atomic size is to look at the
units that form when atoms of the same element are
joined to one another.
• These units are called molecules.
• Because the atoms in each molecule shown below are
identical, the distance between the nuclei of these
atoms can be used to estimate the size of the atoms.
• This size is expressed as an atomic radius.
• The atomic radius is one-half of the distance
between the nuclei of two atoms of the same
element when the atoms are joined.
 • The distances between atoms in a molecule are
extremely small.

• The atomic radius is often measured in picometers

(pm).
– Recall that there are one trillion, or 1012,
picometers in a meter.
The distance between the nuclei in an iodine molecule is 280 pm.
Distance between the nuclei
280 pm
• Because the atomic radius is one-half the
distance between the nuclei, a value of
140 pm (280/2) is assigned to the radius
of the iodine atom.

140 pm
Atomic radius
In general, atomic size increases from top to
bottom within a group,and decreases from left
to right across a period.
 Group Trends in Atomic Size
• The atomic radius within these groups increases
as the atomic number increases.
• This increase is
an example of a
Atomic radius (pm)

trend.

Atomic number
Group Trends in Atomic Size
• As the atomic number increases within a group, the
charge on the nucleus increases and the number of
occupied energy levels increases.

• These variables affect atomic size in opposite

ways.
• The increase in positive charge draws electrons
closer to the nucleus.
• The increase in the number of occupied orbitals shields
electrons in the highest occupied energy level from the
attraction of protons in the nucleus.
• The shielding effect is greater than the effect of the
increase in nuclear charge, so the atomic size
increases.
 Periodic Trends in Atomic Size
• Across a period, the electrons are added to the
same principal energy level.
• The shielding effect
is constant for all
elements in a period.
Atomic radius (pm)

• The increasing
nuclear charge pulls
the electrons in the
highest occupied
energy level closer to
the nucleus, and the
atomic size
Atomic number decreases.
• Electrons can move to higher energy levels when
atoms absorb energy. Sometimes the electron has
enough energy to overcome the attraction of the
protons in the nucleus.
• The energy required to remove an electron from an atom
is called ionization energy.
– This energy is measured when an element is in its gaseous state.
• The energy required to remove the first electron from an
atom is called the first ionization energy.
• First ionization energy tends to decrease from top to
bottom within a group and increase from left to right
across a period.
 Ionization Energies of Some Common Elements
Symbol First Second Third
H 1312
He (noble gas) 2372 5247
Li 520 7297 11,810
Be 899 1757 14,840
C 1086 2352 4619
O 1314 3391 5301
F 1681 3375 6045
Ne (noble gas) 2080 3963 6276
Na 496 4565 6912
Mg 738 1450 7732
S 999 2260 3380
Ar (noble gas 1520 2665 3947
K 419 3096 4600
Ca 590 1146 4941
• Ionization energies can help you predict what
ions an element will form.
• It is relatively easy to remove one electron from a
Group 1A metal atom, but it is difficult to remove a
second electron.

• This difference indicates that Group 1A metals tend

to form ions with a 1+ charge.
Energy generally
increases
Energy generally
decreases
 Look at the data for noble gases and alkali metals.

• In general, first
First ionization energy (kJ/mol)

ionization energy
generally
decreases from
top to bottom
within a group.

Atomic number
Electron Affinity

• The amount of energy released when an electron is added to a neutral atom to form an
anion.
• The electron affinity is the potential energy change of the atom when an electron is
added to a neutral gaseous atom to form a negative ion. So the more negative the
electron affinity the more favourable the electron addition process is. Not all elements
form stable negative ions in which case the electron affinity is zero or even positive.
• During reactions between metals and nonmetals, metal
atoms tend to lose electrons and nonmetal atoms tend
to gain electrons.
• This transfer of electrons has a predictable effect on the size
of the ions that form.
• Cations are always smaller than the atoms from which they
form.
• Anions are always larger than the atoms from which they
form.
Group Trends in Ionic Size
• For each of these elements, the ion is much
smaller than the atom.
• The radius of a sodium ion (95
pm) is about half the radius of a
sodium atom (191 pm).
• When a sodium atom loses an
electron, the attraction between
the remaining electrons and the
nucleus is increased. As a
result, the electrons are drawn
closer to the nucleus.
 Group Trends in Ionic Size
• The trend is the opposite for nonmetals, like the
halogens in Group 7A.

• For each of these elements, the

ion is much larger than the atom.
– For example, the radius of a fluoride
ion (133 pm) is more than twice the
radius of a fluorine atom (62 pm).
– As the number of electrons
increases, the attraction of the
nucleus for any one electron
decreases.
• From left to right across a period, two trends are
visible—a gradual
• decrease in the
• size of the positive
• ions (cations),
• followed by a
• gradual decrease
• in the size of the
• negative ions
• (anions).
• The figure below summarizes the group and
period trends in ionic size.
Size of cations decreases Size of anions decreases
Size generally increases
Trends in Electronegativity
• There is a property that can be used to predict the
type of bond that will form during a reaction.
• This property is called electronegativity.
• Electronegativity is the ability of an atom of an
element to attract electrons when the atom is in a
compound.

– Scientists use factors such as ionization energy to

calculate values for electronegativity.
 Interpret Data

This table lists electronegativity values for representative elements in Groups 1A

through 7A.

Electronegativity Values for Selected Elements • The data

H in this
2.1 table is
Li Be B C N O F expressed
1.0 1.5 2.0 2.5 3.0 3.5 4.0
in Pauling
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
units.
K Ca Ga Ge As Se Br
0.8 1.0 1.6 1.8 2.0 2.4 2.8
Rb Sr In Sn Sb Te I
0.8 1.0 1.7 1.8 1.9 2.1 2.5
Cs Ba Tl Pb Bi
0.7 0.9 1.8 1.9 1.9
Trends in Electronegativity
In general, electronegativity values
decrease from top to bottom within a
group. For representative elements, the
values tend to increase from left to right
across a period.
• Metals at the far left of the periodic table have low values.
• By contrast, nonmetals at the far right (excluding noble gases)
have high values.
• Values among transition metals are not as regular.
Trends in Electronegativity
The least electronegative element in the
table is cesium, with an electronegativity
of 0.7.
• It has the least tendency to attract electrons.
• When it reacts, it tends to lose electrons and form cations.
Trends in Electronegativity

The most electronegative element is

fluorine, with a value of 4.0.
• Because fluorine has such a strong tendency to attract
electrons, when it is bonded to any other element it either
attracts the shared electrons or forms an anion.
Trends in Electronegativity
• This figure summarizes several trends that exist
among the elements.
Glossary Terms
• atomic radius: one-half the distance
between the nuclei of two atoms of the same
element when the atoms are joined
• ion: an atom or group of atoms that has a
positive or negative charge
• cation: any atom or group of atoms with a
positive charge
• anion: any atom or group of atoms with a
negative charge
Glossary Terms
• ionization energy: the energy required to
remove an electron from an atom in its
gaseous state
• electronegativity: the ability of an atom to
attract electrons when the atom is in a
compound
Metallic and Nonmetallic Character
Metallic character refers to the level of reactivity of a metal. Metals tend to lose electrons in
chemical reactions, as indicated by their low ionization energies. Within a compound, metal
atoms have relatively low attraction for electrons, as indicated by their low electronegativities.
By following the trend summary in the figure below, you can see that the most reactive metals
would reside in the lower left portion of the periodic table. The most reactive metal is cesium,
which is not found in nature as a free element. It reacts explosively with water and will ignite
spontaneously in air. Francium is below cesium in the alkali metal group, but is so rare that most
of its properties have never been observed.

Why metallic character decreases across a period and increases down a group?

As the effective nuclear charge acting on the valence shell electrons increases across a period,
the tendency to lose electrons will decrease. Down the group, the effective nuclear charge
experienced by valence electrons decreases because the outermost electrons move farther away
from the nucleus. Therefore, these can be lost easily. Hence metallic character decreases across
a period and increases down a group.
Thermodynamics