1-Atomic Structure & Periodic Properties of Elements-fl-S24

Atomic Structure & Periodic
Properties of Elements
12/18/2023 Atomic Structure & Periodic Properties of Elements 1

• This is the image that quickly
strikes our mind when speaking
of an atom
• Neutrons are neutral, but protons
and electrons are electrically
charged. Protons have a relative
charge of +1, while electrons
have a relative charge of -1.

• Dalton stated that the atoms are indivisible and it was found later that it comprises
of subatomic particles.
• Thomson discovered electrons (called it as corpuscles). It stated that atoms are
composed electrons scattered throughout the spherical cloud of positive charge.
This model did not speak about the nucleus.
• Neil Bohr model was similar to a planetary model where nucleus is at the center,
whereas electrons orbit around it as planet revolve around the Sun.
• Arnold Sommerfeld modification to Bohr’s model was an electron revolving around
a central positively charged nucleus is influenced by the nuclear charge and that it is
set into motion in elliptical orbits with the nucleus situated at one of the foci
• Rutherford fired positively charged α-particles on gold foil; some got deflected and
hence realized that positive charge is localized in the nucleus of the atom and
electrons move in an orbit around the nucleus.
• Schrödinger solved a series of mathematical equations to come up with a model for
distributions of electrons in an atom. His model shows the nucleus surrounding by
clouds of electron density
• James Chadwick (a student of Ernest Rutherford) discovered the
existence of neutron, completing our picture of the subatomic particles
that make up an atom.
• The story doesn’t end there either; physicists have since discovered that
the protons and neutrons that make up the nucleus are themselves
divisible into particles called quarks

Bohr’s Model of atom
• Niels Bohr proposed the Bohr Model of the Atom in
1915. Because the Bohr Model is a modification of the
earlier Rutherford Model, some people call Bohr's
Model the Rutherford-Bohr Model.
• The Bohr Model is a planetary model in which the

negatively-charged electrons orbit a small, positively-
charged nucleus similar to the planets orbiting the Sun.

• The gravitational force of the solar system is
mathematically similar to the electrostatic
attraction between the positively-charged
nucleus and the negatively-charged electrons.

• Following are the Bohr’s postulates:
1. Electrons in the atom orbit the nucleus
2. The electrons can only orbit stably (i.e. without

radiating), in certain orbits (called by Bohr as the
‘stationary orbits’)
3. A specific number of electrons can be held in each

orbit
4. The orbits are at certain discreet set of distances

from the nucleus and are associated with definite
energies. Therefore the orbits are also called as
energy shells or energy levels
5. The energy of the orbit is related to its size. The

lowest energy is found in the smallest orbit.
6. Electromagnetic radiation is absorbed or emitted

when an electron moves from one orbit to another.
7. The frequency of the electromagnetic radiation

absorbed or emitted is determined by the energy
difference of the two levels between which the
electron moves
Bohr’s Planetary Model
• There is a small, positively charged nucleus
surrounded by electrons that travel in circular
orbits around the nucleus
• Presence of electrostatic forces between electrons
and nucleus
• Electrons move in circular orbits of fixed sizes
called stationary orbits (or energy levels) K, L, M,
N He gave a quantum number ‘n’ , which
determines the energy level of electron

• Electrons absorb and emit radiation: electrons absorb energy and jump
from one orbit (allowed) to another one and emit electromagnetic
radiation with a frequency 𝑣 as per Planck’s relation.
∆𝐸 = 𝐸2 − 𝐸1 = ℎ𝑣, where h is Planck's constant.
The energy thus released in the form of a radiation of a certain
frequency appears in the form a line in the atomic spectrum.
• Based on the Bohr theory, Bohr calculated the radii of the various orbits
and the energies associated with the electrons present in those shells.
Success of Bohr's Model:
1. Bohr's theory was successful in explaining absorption spectrum
when an electron jumps from lower energy level to higher energy
level.
2. Similarly the theory explained emission spectrum when an electron
falls to lower energy level.
3. Using Bohr's theory, radius of nth orbit, velocity and energy of
electron can be calculated.
4. This theory could also explain successfully the positions of various
series of spectral lines in the hydrogen spectrum.
Limitations of Bohr model
• Assumption of structured ‘stationary fixed orbit’ cannot be
considered. i.e the path of electrons are not well-defined
• It can only explain spectral lines of hydrogen atom and could not
explain fine lines in the spectrum
• After first 20 elements, Bohr model makes it difficult to predict
their spectra
• Could not explain chemical bonding of atoms
• No explanation of the distribution of electrons within an atom

Wave-Particle Duality
• In Bohr model, electron was treated as a particle and the electrons revolve around
the nucleus in definite orbits
• However, it is not possible to determine precisely both the position and the
momentum of a small moving particle (electron)
• Sommerfeld theory could not explain with mathematical exactness the spectra of
atoms containing multielecron system.
The limitations of Bohr’s model was cracked by quantum mechanical model

emerging as dual nature of matter.
• Davisson-Germer gave an experimental evidence of wave-particle nature.
• L. de Broglie (1924) suggested the wave particle dualism for matter such as,
electrons

Series of lines in the rear screen proves deflection of Simulation of electron diffraction through a single slit
electrons (wave-like nature)
Classically, we would predict that electrons passing through slits in a screen should continue in straight
lines, forming an exact image of the slits on the rear screen. In practice, however, a series of lines is
formed on the rear screen, suggesting that the electrons have been somehow deflected by the slits.
Schrödinger Wave Equation
The wave like nature of an electron is confirmed, but What does a wave associated to a
particle look like mathematically?
A partial differential equation given as
Electron is described as a three dimensional wave in the electric field of a positively

charged nucleus.
• A particle of mass (m) moving with velocity (v) has total energy (E)
and potential energy (U), then the particle has an associated wave
A whose amplitude
wave function (displacement
(Ψ) is the of particle
location of an electron from
at a given pointmean
in spaceposition)
(identified is
bywave
12/18/2023 function
x, y, and Ψ. to the amplitude of its wave, which corresponds to its energy.
z coordinates) Atomic Structure & Periodic Properties of Elements 16
The Schrödinger wave equation is to describe the total energy of an
electron as it moves through the 3-D space surrounding the atom’s
nucleus.
As for any object or particle, total energy includes both kinetic and
potential energy contributions. But the potential energy is the most
important in describing the structure of atoms.
The potential energy of electrons in atoms is associated with the

coulombic attraction between the positively charged nucleus and
negatively charged electrons as well as the repulsion between like-
charged electrons.

δ2 Ψ δ2 Ψ δ2 Ψ 8π2 m
2
+ 2
+ 2
+ 2
E − U Ψ = 0 … time independent
δx δy δz h
where ∇ = laplacian operator
• The functions Ψ are satisfactory solutions of wave equation only for

certain values of energy E and such values are called eigen values.
• The eigenvalues of the wave equation are equal to the energy levels of
the electron

ELECTRONIC THEORY OF VALENCY :
The combining tendency of atoms was explained by Kossel and Lewis

(1916) through their theory called electronic theory of valency. The
main postulates of this theory are,
(i) The tendency of an atom to take part in chemical combination is

determined by the number of valence electrons. The valence
electrons are the electrons in the outermost shell of the atom.
(ii) The atoms combine by mutual sharing or by transfer of one or

more electrons. In doing so, each combining atom acquires stable
noble gas electronic configuration having 8 electrons in its
12/18/2023 outermost shell. ThisAtomic
is called
Structure & octet rule.of Elements
Periodic Properties 19
ELECTRONIC THEORY OF VALENCY :
(iii) The number of electrons which an atom loses, gains or mutually

shares to attain the nearest noble gas configuration is called its
valency. For example, Li, Be, B and C having respectively 1, 2, 3 and
4 electrons, have valence of 1, 2, 3 and 4. The elements N, O, F and
Ne having 5, 6, 7 and 8 electrons in their outermost shell show
common valency of 3, 2, 1 and 0.
• Thus, "the common valency of an element is either equal to the

number of valence electrons, or it is equal to 8 minus the number
of valence electrons."

Electronic Configurations
• What is meant by “electron configuration?”
• The electron configuration is the specific way in
which the atomic orbitals are filled.
• Think of it as being similar to your address. The
electron configuration tells us where all the
electrons “live” around the nucleus.

Rules for Electronic Configurations
The diagonal rule • In order to write an electron

configuration, we need to know the
RULES.
• 3 rules govern electron

configurations.
– Aufbau Principle
– Pauli Exclusion Principle
– Hund’s Rule
The diagonal rule • Using the orbital filling diagram at

the left helps to figure out HOW to
write them
– Start with the 1s orbital. Fill

each orbital completely and
then go to the next one, until all
of the elements have been
accounted for.
Fill Lower Energy Orbitals FIRST
Each line
represents an
orbital. Ex.
1 (s), 3 (p), 5 (d)
High Energy
Refer to the diagonal rule
12/18/2023 Low Energy Atomic Structure & Periodic Properties of Elements 24

Fill Lower Energy Orbitals FIRST
• The Aufbau Principle states

that electrons enter the lowest
High Energy
energy orbitals first.
• Within an energy level, s

orbitals are of lowest energy,
followed by p, d and then f, for
that energy level.
12/18/2023 Low Energy Atomic Structure & Periodic Properties of Elements 25

No more than 2 Electrons in Any Orbital…ever.
• The next rule is the Pauli Exclusion Principle.
• The Pauli Exclusion Principle states that an
atomic orbital may have up to 2 electrons
and then it is full. And, the spins of the

Wolfgang Pauli, Nobel
Prize in Physics (1945)
electrons have to be paired.
Electrons must have opposite spins from each other in order to

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“share” the sameAtomic
orbital.
Structure & Periodic Properties of Elements 26
No more than 2 Electrons in Any Orbital…ever.
• We usually represent spin pairing with an up arrow
and a down arrow.
• Thus, one ‘s’ orbital will have a maximum of 2

electrons.
• Similarly, there are three ‘p’ orbitals which can hold a

maximum of 6 electrons (i.e. 2 electrons in each of
the px, py and pz orbitals)
Wolfgang Pauli, Nobel
Prize in Physics (1945) • Similarly, there are five ‘d’ orbitals which can hold a
These numbers indicate the maximum
number of electrons in those orbitals
maximum of 10 electrons
• And, there are seven ‘f’ orbitals that can hold a

s 2 p6 10
d f 14
12/18/2023 maximum of 14 electrons.
Atomic Structure & Periodic Properties of Elements 27
Hund’s Rule
• Hunds Rule states that when we get to degenerate orbitals,
we fill them all half way first, and then we start pairing up the
electrons.
• What are degenerate orbitals?
• Degenerate means they have the same energy.

Orbital diagram for carbon
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Don’t pair up the 2p electrons until all three orbitals are half full with the same spin.
Use the Hund’s Rule
• Similarly, the three p orbitals on each level (i.e. 2nd, 3rd, 4th, etc.)
are degenerate, because they all have the same energy.
• Similarly, the ‘d’ and ‘f’ orbitals are degenerate too.
Orbital diagram for nitrogen
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Use the Hund’s Rule
Orbital diagram for oxygen
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The diagonal rule

The diagonal rule

Atomic Orbitals
‘s’ block elements

1s ‘p’ block elements
2s 2p
3s ‘d’ block elements 3p
4s 3d 4p
5s 4d 5p
6s 5d 6p
7s 6d 7p
4f ‘f’ block elements

5f

s, p, d, f-block elements
• A block of the periodic table is a set of elements unified by the

atomic orbitals where the last or the valence electron enter.
• s-block elements: valence electrons enter the s-orbital
• p-block elements: valence electrons enter the p-orbital
• d-block elements: valence electrons enter the d-orbital
• f-block elements: valence electrons enter the f-orbital

Sheilding effect
• In a multi electron atom the valence shell electrons are attracted by the nucleus
and also at the same time repelled by the electrons present between the nucleus
and valence shell electrons i.e. the inner shell electrons.
• The combined effect of this attraction and repulsion is that the actual force
exerted by the nucleus on the valence shell electrons is partially decreased.
• Thus the inner shell electrons screen or shield the valence shell electrons from
the nucleus.
• This decrease in the attractive force exerted by the nucleus because of the inner
shell electrons is called shielding or screening effect.

Effective nuclear charge:
• The effective nuclear charge is the net positive

charge experienced by an electron in a
polyelectronic atom.
• The decrease in the attractive force exerted by the nucleus
because of the inner shell electrons is called shielding or
screening effect.
• Effective nuclear charge can be defined as, the actual nuclear
charge Z minus the screening effect caused by the electrons
intervening between the nucleus and the outer electrons.
• Greater the number of electrons intervening between the

nucleus and the outer electrons more will be the magnitude of
σ and hence the magnitude of effective nuclear charge Z* will
decrease.
• This shielding effect reduces the nuclear charge. This decreased nuclear
charge is called effective nuclear charge and represented as Z*.
Z* = Z – σ
Z = atomic number and σ = screening constant (roughly number of core
electrons)
• Screening constant is a measure of the extent to which the other electrons in
an atom are able to screen the nucleus from the chosen electron.

Steps involved
• Write the electronic configuration as per the Aufbau’s Principle
• Any electrons to the right of the electron of interest do not
contribute to shielding constant because they are in the higher
shells.
• The shielding constant for each group is formed as the sum of the following
contributions:
1. Each other electron in the same group (ex. s or p) as the electron of interest
shield to an extent of 0.35 nuclear charge units except 1s group, in which the
other electron contributes only 0.30.
2. If the group is of [s, p] type, an amount of 0.85 from each electron in (n-1)th shell
and an amount of 1.00 for each electron from (n-2)th shell onward
3. If the group is of [d] or [f] type, an amount of 0.35 from each electron in nd or nf
shell, and an amount of 1.00 for each electron from in (n-1)th shell onward
Write the electron configuration of the atom in the
following form:
Slater's Rules (1s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p) . . .

Effective nuclear charge (Example):
(a)Calculate effective nuclear charge in Nitrogen for 2p electron.
• Electronic configuration- (1s2) (2s2, 2p3).
• Screening constant, σ = (0.35 × 4) + (0.85 × 2) = 3.10
• Effective nuclear charge, Z* = Z – σ = 7 – 3.10 = 3.90

(b)Calculate effective nuclear charge and screening constant seen
in 3p electron in Silicon.
• Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p2).
• σ = (0.35 × 3) + (0.85 × 8) + (1 × 2) = 9.85
• Z* = Z – σ = 14 – 9.85 = 4.15
(c)Calculate effective nuclear charge in Zinc for 4s electron & for 3d electron.
Electronic configuration- (1s2) (2s2, 2p6)(3s2, 3p6)(3d10)(4s2).
• For 4s electron,
• σ = (0.35 × 1) + (0.85 × 18) + (1 × 10) = 25.65
• Z* = Z – σ = 30 – 25.65 = 4.35
• For 3d electron,
• σ = (0.35 × 9) + (1 × 18) = 21.15
• Z* = Z – σ = 30 – 21.15 = Atomic
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8.85Structure & Periodic Properties of Elements 45
Explaining periodicity: Effective nuclear charge and
shielding
• Inner shell (core) electrons screen the outer (valence) electrons

from the nuclear attraction
– Shielding is more effective/ strong for electrons with higher angular
momentum (higher l value: 3d > 3p > 3s)
– Decreases as the valence shell fills
• Increased shielding means lower effective nuclear charge

Atomic Radii - Concept and periodicity
• The absolute size of an atom is difficult to define as the electronic
probability distribution is never zero even at far away distances
from the nucleus.
• Generally, the radius of atom or an ion is defined as the distance

from the centre of the nucleus to the outermost shell of atom or an
ion.
• As it is impossible to isolate an individual atom, it is assumed that

atoms behave as perfect hard spheres.
• In a homonuclear diatomic molecules two such spheres are just in
contact with each other. The distance between the centres of two
atoms i.e. internuclear distance (bond length) in a molecules can be
measured by X-Ray and spectral studies. So the radius of an atom is
one half of the distance between the centres of the two atoms.

• The size of an atom decreases from left to right across the periodic
table. For eg as we move from Li {Z =3 } to F (Z=S), electrons are
added to the same valence shell, as a consequence atom will
contract in size.
• The size of atom increases

Elements Li Be fromB top toC bottom
N in aO groupF this
Atomic radius (pm) 152 111 88 77 70 66 64
is due to addition of(+3)new(+4)
Nuclear charge (Z) (+5) (+6) (+7) (+8) (+9)
Effective Nuclear charge (Z*) 1.3 1.95 2.60 3.25 3.90 4.55 5.20
Electronic configuration 1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5

Periodicity in atomic radii:
• As we move from left to right say Li (Z =3) to F (Z=9), electrons are added to the same
valence shell. Also, the screening constant is same for all electrons in the same valence
shell. So the value of Effective Nuclear charge will increase from left to right (as Z value
increases but sigma is constant) i.e the positive attraction experienced by the nucleus will
increase from left to right in the period and as a consequence atom will contract in size.
Elements Li Be B C N O F
Atomic radius (pm) 152 111 88 77 70 66 64

Nuclear charge (Z) (+3) (+4) (+5) (+6) (+7) (+8) (+9)
Effective Nuclear charge (Z*) 1.3 1.95 2.60 3.25 3.90 4.55 5.20
Electronic configuration 1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5

The size of atom increases from top to bottom in a group this is due to addition of new
electrons in newer shells. Eg. Li (Z =3) to Cs (Z=55)
Elements of Atomic radius Nuclear charge (Z) Effective Nuclear Electronic configuration
group I (pm) charge (Z*)
Li 152 3 1.3 1s22s1

Na 186 11 2.2 1s22s22p63s1
K 231 19 2.2 1s22s22p63s23p64s1
Rb 244 37 2.2 1s22s22p63s23p64s23d10 4p65s1
Cs 267 55 2.2 1s22s22p63s23p64s23d104p65s24d10 5p66s1
Therefore the Factors affecting Atomic Size are

• No. of Shells- atomic size directly proportional to the number of shells i.e as
number of shells increase, atomic size increases.
• Nuclear charge- atomic size inversely proportional to the Nuclear charge
Correlating atomic radius and effective nuclear charge
(Zeff) across a period

Iso electronic species
The iso electronic species are those which have the same number of electrons
Size of isoelectronic cationic species decreases with increase in atomic number
As atomic number increases the nuclear charge increases and the nuclear charge acts on same number of electrons in
species and therefore size decreases
Ions Na+ Mg 2+ Al3+ Si4+

No of electrons 10 10 10 10
At no( nuclear 11 12 13 14
charge)
Ionic size (pm) 95 72 53.5 40
Anions with greater negative charge will have larger ionic radius , in this case net repulsion of electrons will out weigh
nuclear charge and ion size will increase.
O2-> F-
Among isoelectronic cation and anion , Anions with High charges will have higher radius
O2-> F-> Na+ >Mg2+
Isoelectronic species
• Species with the same no. of electrons, but different no. of
protons
• Ex. F- & Na+
10 electrons 10 electrons
9 protons 11 protons
Ex. O2- & F-1
10 electrons 10 electrons
8 protons 9 protons
Ionization energy
• It is possible to remove one or more electrons from an atom, ion or
molecule provided sufficient energy is given to the system. The
ionization energy of an element is defined as the amount of energy
required to remove the most loosely bound electron from an atom of
the element in the gas phase.
M(g) = M(g)+ + e
• As I increases, atoms are harder to ionize
• Successive ionizations for electrons are represented by Ii (i = 1,2,3,…)
I1 < I2 < I3 <…

Periodicity in ionization energy
• Within each period for example, Li (Z = 3) to Ne (Z = 10) as atomic size

decreases, nuclear charge increases, the ionization energy rises steeply
from Li to Ne.
• Exception:
Element the irregularity
Li Bei.e.higher
B IE Cvalue can
N be Oexplained
F on Ne
the
basis of empty,half- filled and completely filled configuration having
Radius (pm) 123 89 80 77 74 74 72 -
extra stability as seen for Be which has
Nuclear charge +3 +4 +5 +6 +7 +8 +9 +10
• filled 2s2 orbital and N has half-filled 2p5 orbital
Ionization energy (kJ
520 900 800 1090 1400 1310 1680 2080
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mol-1) Atomic Structure & Periodic Properties of Elements 56
Periodicity in ionization energy (IE)
• Exception: the irregularity i.e. higher IE value can be explained on
the basis of empty, half- filled and completely filled configuration
having extra stability as seen for Be which has filled 2s2 orbital and
N hasElement
half-filled 2pLi orbitals.
Be B C N O F Ne
Radius (pm) 123 89 80 77 74 74 72 -
Nuclear charge +3 +4 +5 +6 +7 +8 +9 +10
Ionization energy (kJ

520 900 800 1090 1400 1310 1680 2080
12/18/2023
mol-1) Atomic Structure & Periodic Properties of Elements 57
Periodicity in ionization energy (IE)
• As we move from top to bottom in a group the IE value decreases. Due to
addition of new electrons in newer shells, distance between nucleus and the
valence electrons increases, therefore less energy is required to expel the
valence electron as the attractive force of the nucleus is less.

Electron Affinity (EA)
• The electron affinity of an atom is defined as, change in energy (energy
released or spent) when an electron is added to neutral gaseous atom to form
a negative ion.
X(g) + e- → X(g)-
• The electron affinity is a measure of the attraction between the incoming
electron and the nucleus - the stronger the attraction, the more energy is
released.
• When an electron is added to a neutral atom with ease (i.e., first
electron affinity) energy is released; thus, the first electron affinity
is negative.
• First Electron Affinity (negative energy because energy
released):
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X(g)+e−→X−(g)
• However, more energy is required to add an electron to a negative ion
(i.e., second electron affinity) which overwhelms the release of energy from the
electron attachment process and hence, second electron affinities are positive.
• Second Electron Affinity (positive energy because energy is gained):
X−(g)+e−→X2−(g)

Periodicity in Electron Affinity (EA)
• Within each period for example, Li (Z = 3) to F (Z = 9) the size
of atom decreases and their nuclear charge increases, both
these factors favour increase in electron affinity.
• As we move from top to bottom in a group the EA value
decreases.
_
Exception: In halogens group 17,the low value of EA of F (-328Kj/mole)

relative to that of Cl (- 349KJ/mole) is due to the strong inter electronic
repulsion in the relatively small and compact 2p orbital of F on the
addition
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of another electron.
Electronegativity
• Electronegativity is defined as a measure of the ability of an atom in a molecule to attract
the shared electron pair towards itself.
• In a homonuclear diatomic molecule such as H2 and Cl2 the shared electron pair is
attracted equally by both the bonding atoms and there is no net polarity in the molecule.
H He
2.2 -
Li Be B C N O F Ne
1.6 1.5 2.0 2.5 3.1 3.5 4.1 -
Na Mg Al Si P S Cl Ar
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
K Ca Ga Ge As Se Br Kr
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
Rb Sr In Sn Sb Te I Xe
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
Cs Ba Tl Pb Bi Po At Rn
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Atomic Structure 1.7of Elements 1.8 2.0 - 64
Electronegativity
• This is because the electronegativity of both the atoms is same.
• However, in a heteronuclear molecule such as HCl the shared electron pair is
not equally attracted by the bonding atoms.
H He
2.2 -
Li Be B C N O F Ne
1.6 1.5 2.0 2.5 3.1 3.5 4.1 -
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
0.7 0.9 1.8 1.8 1.7 1.8 2.0 -
Electronegativity
• The electron pair is shifted more towards Cl than H and the molecule acquires polarity H
δ+…….Cl δ− . These charges are of equal magnitude but are of opposite sign and the overall
charge is zero.
• This implies that the Cl is more electronegative than H because it has more electron
affinity to complete its octet.
H He
2.2 -
Li Be B C N O F Ne
1.6 1.5 2.0 2.5 3.1 3.5 4.1 -
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
0.7 0.9 1.8 1.8 1.7 1.8 2.0 -
Periodicity in Electronegativity
• Within each period for example, Li (Z = 3) to F (Z = 9),

Electronegativity increases.
H He
2.2 -
Li Be B C N O F Ne
1.6 1.5 2.0 2.5 3.1 3.5 4.1 -
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
0.7
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Atomic Structure 1.7 of Elements 1.8 2.0 - 67
• As we move from top to bottom in a group for example, Li (Z =3) to
Cs (Z=55) Electronegativity decreases. This is due to addition of new
electrons in newer shells.
H He
2.2 -
Li Be B C N O F Ne
1.6 1.5 2.0 2.5 3.1 3.5 4.1 -
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
0.7
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Atomic Structure 1.7 of Elements 1.8 2.0 - 68
Electronegativities of the main group elements on Pauling scale

H He
2.2 -
Li Be B C N O F Ne
1.6 1.5 2.0 2.5 3.1 3.5 4.1 -
1.0 1.2 1.3 1.7 2.1 2.4 2.8 -
0.9 1.0 1.8 2.0 2.2 2.5 2.7 3.1
0.9 1.0 1.5 1.7 1.8 2.0 2.2 2.4
0.7 0.9 1.8 1.8 1.7 1.8 2.0 -
Semiconductors
• Semiconductors are a class of crystalline solids intermediate in electrical

conductivity between a conductor and an insulator.
• Semiconductors are employed in the manufacture of various kinds of

electronic devices, including diodes, transistors, and integrated circuits.
• Such devices have found wide application because of their

compactness, reliability, power efficiency, and low cost.

Semiconductors
• As discrete components, semiconductors have found use in power

devices, optical sensors, and light emitters, including solid-state lasers.
• They have a wide range of current- and voltage-handling capabilities

and, more important, lend themselves to integration into complex but
readily manufacturable microelectronic circuits.

Semiconductors
• Insulators, such as fused quartz and glass, have very low conductivities,
on the order of 10−18 to 10−10 S/cm; and conductors, such as aluminum,
have high conductivities, typically from 104 to 106 S/cm.
• The conductivities of semiconductors are between these extremes and

are generally sensitive to temperature, illumination, magnetic fields,
and minute amounts of impurity atoms. For example, the addition of
about 10 atoms of boron (known as a dopant) per million atoms of
silicon can increase its electrical conductivity a thousand fold.
Metalloids
• Metalloids are the smallest class of elements (the other two classes of
elements are metals and nonmetals).
• The term is normally applied to a group of between six and nine

elements (boron, silicon, germanium, arsenic, antimony, tellurium, and
possibly bismuth, polonium, astatine) found near the center of the p-
block
12/18/2023 or main block of the periodic
Atomic Structure &table.
Periodic Properties of Elements 73
Metalloids
• In terms of their position and properties, metalloids fall between metals

and nonmetals in the periodic table.
• Chemically, metalloids correspond to atoms having intermediate

electronegativities and an ability to display a range of both positive and
negative oxidation states in their compounds.
Metalloids
• Metalloids have from three to six electrons in their outer energy level. Boron
(B), is the only metalloid with just three electrons in its outer energy level.
• B tends to act like a metal by giving up its electrons in chemical reactions.

Metalloids with more than four electrons in their outer energy level (arsenic,
antimony, and tellurium) tend to act like nonmetals by gaining electrons in
chemical reactions.
• Those with exactly four electrons in their outer energy level (silicon and
germanium) may act like either metals or nonmetals, depending on the other
elements in the reaction.
Metalloids
• Silicon is a typical metalloid.
• It has luster like a metal, but is brittle like a nonmetal. Silicon is used
extensively in computer chips and other electronics because its
electrical conductivity is in between that of a metal and a nonmetal.

Arrhenius Acids
• Swedish chemist Svante Arrhenius (who first

proposed the theory of ionization) identified
acids as substances that ionize in water to
produce hydronium ion.
• For example:
HCl + H2O → H3O+ + Cl-
hydronium ion
Any substance that ionizes in water to produce

12/18/2023
hydronium ionAtomic
canStructure
be classified as an acid.
& Periodic Properties of Elements 77
H3O+ (i.e. H+)
• The hydronium ion is also known as a hydrogen ion.
• This allows us to shorten the ionization reactions for acids.

The following equations represent the same chemical
change:
HCl + H2O → H3O+ + Cl-
and
HCl → H+ + Cl-
However, it should be understood that H+ is an abbreviation
for the hydronium ion. H+ ions DO NOT exist in aqueous
solutions but are snatched up by water molecules to form
hydronium ions.
Hydronium Ion
Unknown to Arrhenius free H+ ions do not exist in water. They covalently react
with water to produce hydronium ions, H3O+.
or:
H+ (aq) + H2O (l)  H3O+ (aq)
This new bond is called a coordinate covalent bond since both new bonding
electrons come from the same atom (i.e. oxygen in this case)
What is H+?
e-
+ +
Hydrogen (H atom) Proton (H+) (no electron)

Arrhenius Base
• Svante Arrhenius also identified bases as substances that ionize
in water to produce hydroxide ion.
• For example:
NaOH → Na+ + OH-
Any substance that ionizes in water to produce

hydroxide ion can be classified as a base.
Disadvantage of the Arrhenius concept
• The key to the Arrhenius description is that we need water to

act as a solvent to promote the dissociation of the acid or
base.
• Many substances (like NH3) that do not contain OH- act like
bases in water!

Disadvantage of the Arrhenius concept
• A major problem with the Arrhenius definition of

acids and bases is that it limits acids and bases to
water (aqueous) solutions.
• Since an acid requires water to ionize and form

hydronium ions, there can be no Arrhenius acids
unless water is involved as the solvent.

Bronsted-Lowry Definitions
• Bronsted and Lowry felt that Arrhenius concept was too
limiting, since there are many non-aqueous systems (ie. no
water is present in such systems).
• They came up with the following definitions for acids and

bases.
An acid is a proton (H+ ion) donor
A base is a proton acceptor

An example
In the reaction below there are no Arrhenius acids or bases
present (because no hydronium ions or hydroxide ions are
formed).
However, the HCl is acting as a Bronsted-Lowry acid (proton donor)

because it is giving a H + ion to the NH3 (which is acting as a H + ion
acceptor i.e. a Bronsted-Lowry base)
Acid & Bases are Roles
• In the Bronsted-Lowry definition, substances are classified as

acids or bases depending on how they behave in a given
situation.
• This means that the same substance can act as a acid in one
reaction (by donating a proton) and act as a base in another
reaction (by accepting a proton)

HCl as a proton donor (i.e. acid)
• Consider the following reaction:
• Since the HCl gives up a H+ ion to the water it is acting as a Bronsted-Lowry acid. In
the process of donating the proton it also forms a hydronium ion, and that makes it
an Arrhenius acid as well.

Water as a proton acceptor (i.e. base)
• But what does that make the water molecule?
• Since the water molecule is accepting the H+ ion, it is acting as a Bronsted-Lowry

base. Since there is no hydroxide ion (OH-) formed, the water is not acting as an
Arrhenius base in this reaction.

Ammonia as a proton acceptor (i.e. base)
• Let’s look at another example:
• Here the ammonia molecule is accepting a H+ ion and therefore is acting as an

Bronsted-Lowry base. However, in the process of reacting with the water it is also
forming a hydroxide ion. That makes the ammonia an Arrhenius base as well.

But what about the water?
Water as a proton donor (i.e. an acid)
Since the water is giving up a H+ ion, it is acting as a Bronsted-Lowry

acid. Since it does not form hydronium ions, it is NOT acting an
Arrhenius acid.

So is water an acid or a base?
• In one example, we said that water was acting as a base, and in another
example we said that it was acting as an acid.
• Thus, a given substance can either act as an acid or a base depending

upon whether it is donating or accepting protons respectively, in the
given reaction

Amphiprotic
• Sometimes a molecule can donate a proton (act as an acid) and
sometimes it can accept a proton (act as a base).
• Molecules that have this ability to act as both an acid and a base are
called amphoteric or amphiprotic.
• Water is the most common example of an amphoteric substance.

Amphoteric species
• Another example, HCO3- acts as a proton donor (an acid)
in the presence of OH- (which acts as a base)
− − 2−
HCO3 (aq) + OH (aq) → CO3 (aq) + H 2O(l )
–H+

Amphoteric species
• Alternatively, HCO3 can act as a proton acceptor
(a base) in the presence of HF.
− −
HCO 3 (aq ) + HF(aq ) → H 2CO 3 (aq ) + F (aq )
H+

Examples
• For each of the following reactions identify any Bronsted-
Lowry acids and bases.
• HNO3 + H2O → H3O+ + NO3-

acid base
• HNO3 + NH3 → NH4+ + NO3-

acid base
• S2- + H2O → HS- + OH-

base acid
• HS- + OH- → S2- + H-OH

acid base
• HS- + HCl → H2S + Cl-

base acid
Lewis Concept of Acids and Bases
• The Lewis concept defines an acid as an
electron pair acceptor and a base as an
electron pair donor.
– This concept broadened the scope of acid-

base theory to include reactions that did not
involve H+.
– The Lewis concept embraces many reactions
that we might not think of as acid-base
reactions.
Lewis Concept of Acids and Bases
• The reaction of boron trifluoride with ammonia is an example.
:
:
:F : H :F : H
: :
: :
:F B + :N H :F B N H
:F : H :F : H
:
:
• Boron trifluoride accepts the electron pair, so it is a
Lewis acid. Ammonia donates the electron pair, so it is
12/18/2023 the Lewis base.

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Atomic Structure & Periodic

12/18/2023 Atomic Structure & Periodic Properties of Elements 1

12/18/2023 Atomic Structure & Periodic Properties of Elements 2

12/18/2023 Atomic Structure & Periodic Properties of Elements 4

• The Bohr Model is a planetary model in which the

12/18/2023 Atomic Structure & Periodic Properties of Elements 5

12/18/2023 Atomic Structure & Periodic Properties of Elements 6

1. Electrons in the atom orbit the nucleus

2. The electrons can only orbit stably (i.e. without

3. A specific number of electrons can be held in each

4. The orbits are at certain discreet set of distances

5. The energy of the orbit is related to its size. The

6. Electromagnetic radiation is absorbed or emitted

7. The frequency of the electromagnetic radiation

12/18/2023 Atomic Structure & Periodic Properties of Elements 10

12/18/2023 Atomic Structure & Periodic Properties of Elements 13

The limitations of Bohr’s model was cracked by quantum mechanical model

12/18/2023 Atomic Structure & Periodic Properties of Elements 14

Electron is described as a three dimensional wave in the electric field of a positively

The potential energy of electrons in atoms is associated with the

12/18/2023 Atomic Structure & Periodic Properties of Elements 17

where ∇ = laplacian operator

• The functions Ψ are satisfactory solutions of wave equation only for

12/18/2023 Atomic Structure & Periodic Properties of Elements 18

The combining tendency of atoms was explained by Kossel and Lewis

(i) The tendency of an atom to take part in chemical combination is

(ii) The atoms combine by mutual sharing or by transfer of one or

(iii) The number of electrons which an atom loses, gains or mutually

• Thus, "the common valency of an element is either equal to the

12/18/2023 Atomic Structure & Periodic Properties of Elements 20

12/18/2023 Atomic Structure & Periodic Properties of Elements 21

The diagonal rule • In order to write an electron

• 3 rules govern electron

– Pauli Exclusion Principle

The diagonal rule • Using the orbital filling diagram at

– Start with the 1s orbital. Fill

Refer to the diagonal rule

12/18/2023 Low Energy Atomic Structure & Periodic Properties of Elements 24

• The Aufbau Principle states

• Within an energy level, s

12/18/2023 Low Energy Atomic Structure & Periodic Properties of Elements 25

• The next rule is the Pauli Exclusion Principle.

• The Pauli Exclusion Principle states that an

atomic orbital may have up to 2 electrons

and then it is full. And, the spins of the

Electrons must have opposite spins from each other in order to

• Thus, one ‘s’ orbital will have a maximum of 2

• Similarly, there are three ‘p’ orbitals which can hold a

• And, there are seven ‘f’ orbitals that can hold a

• What are degenerate orbitals?

• Degenerate means they have the same energy.

are degenerate, because they all have the same energy.

• Similarly, the ‘d’ and ‘f’ orbitals are degenerate too.

Orbital diagram for nitrogen

Orbital diagram for oxygen

12/18/2023 Atomic Structure & Periodic Properties of Elements 31

12/18/2023 Atomic Structure & Periodic Properties of Elements 32

‘s’ block elements

4f ‘f’ block elements

12/18/2023 Atomic Structure & Periodic Properties of Elements 33

• A block of the periodic table is a set of elements unified by the

• s-block elements: valence electrons enter the s-orbital

• p-block elements: valence electrons enter the p-orbital

• d-block elements: valence electrons enter the d-orbital

1-Atomic Structure & Periodic Properties of Elements-fl-S24

1-Atomic Structure & Periodic Properties of Elements-fl-S24