Chapter one

Atomic Structure and Periodicity

At the end of this chapter, you should be able to:

 understand the historical development of atomic structure;

 explain the experimental observations and some famous scientists to characterize

the atom;

 list and describe the subatomic particles;

 explain the terms “atomic mass” and “isotope”;

 understand electromagnetic radiation, atomic spectra and Bohr’s models of the

atom;

 do calculations involving atomic structure;

 Atomic Structure and Periodicity

Atom
– The smallest particle of an element that retains its
identity in a chemical reaction.
 Atom contains a very small nucleus composed of positively
charged protons and uncharged neutrons, surrounded by
negatively charged electrons.
 Early Models of the Atom
• Greek Philosopher Democritus (460 BC – 370 BC)
– Among the first to suggest the existence of atoms
• He believed that atoms were indivisible and
indestructible
• Although his ideas agree with later scientific theory,
they did not explain chemical behavior and lacked
experimental support – not based on the scientific
method – just philosophy
  Aristotle
• He Believes that;
 matter was continuous (composed of 4 elements ; fire, air,

earth & water); i.e. impossible to het individual particles .

 he says atoms are infinitely divisible

 But both ideas were not supported by experiment though

Aristotle theory was predominant up to John Dalton’s atomic
theory.
 Who was next?
John Dalton (1766 – 1844)

• Experiment based – transformed Democritus’

ideas into scientific theory .
• Results of his experimentation and observations
are summarized in Dalton’s Atomic Theory
• Dalton studied the ratios in which elements
combine in chemical reactions
 Postulates of Dalton’s atomic theory are:
 The matter is made up of tiny indivisible particles called atoms.

 Atoms can neither be created nor destroyed.

 Atoms of a given element are identical in size, mass, and other

properties.
 Atoms of different elements differ in size, mass, and other properties.
 Atoms combine in simple whole-number ratios to form compounds. In
chemical reactions, atoms are combined, separated, or rearranged.
 Two or more atoms of different elements combine in a fixed whole
number ratio to form compounds.
 Atoms are combined, separated or rearranged in chemical reaction
 Drawbacks of Dalton's atomic theory of matter
• he indivisibility of an atom was proved wrong: an atom can be

further subdivided into protons, neutrons and electrons.

• atoms of different elements are different in all respects. This has

been proven wrong in certain cases: argon and calcium atoms each
have an atomic mass of 40 amu. These atoms are known as isobars.
• atoms of different elements combine in simple whole number ratios
to form compounds. This is not observed in complex organic
compounds like sugar (C12H22O11).
• he theory fails to explain the existence of allotropes ; it does not
account for differences in properties of charcoal, graphite, diamond.
This theory made use of the three natural laws;
o conservation mass law
o law of definite proportion
o law of multiple proportion
 Conservation mass law
 States that the mass can neither be created nor destroyed but
is transformed from one form to another.
 The total mass of a substance does not changed during a
chemical reaction.

Example :CH4 (16g) + 2O2(64g) ͢ CO2(44g) + 2H2O(36g)

 The Combustion reaction of methane. Where 4 atoms of

hydrogen, 4 atoms of oxygen, and 1 of carbon are present
before and after the reaction.
 The total mass after the reaction is the same as before the
reaction.
 Multiple proportions
• The law of multiple proportions states that if elements A and B
react to form two compounds, the different masses of B that
combine with a fixed mass of A can be expressed as a ratio of
small whole numbers .
Example - Consider two compounds that are formed from carbon
and oxygen. Let call them carbon oxides I and II. They have very
different properties.
 Analysis shows that their compositions by mass are:

• Carbon oxide I: 57.1 mass % oxygen and 42.9 mass % carbon

• Carbon oxide II: 72.7 mass % oxygen and 27.3 mass % carbon
 The ratio of the mass of carbon to the mass of oxygen in carbon
⟹The mass of oxygen (O) per gram of carbon (C) is:
57.1 g O / 42.9 g C = 1.33 g O per g C
 In the 100 grams of the second compound, there are 72.7 grams of
oxygen (O) and 27.3 grams of carbon (C). The mass of oxygen per
gram of carbon is:
72.7 g O / 27.3 g C = 2.66 g O per g C
 Dividing the mass O per g C of the second (larger value)
compound: 2.6 / 1.3 = 2
This means that the masses of oxygen that combine with carbon are in
a 2:1 ratio.
The whole-number ratio is consistent with the law of multiple
proportions.
For e.g. consider CO and CO2. Both are compounds of carbon and
oxygen.

• In the carbon monoxide (CO) ,12 parts by mass of the carbon

combine to the 16 parts by mass of the oxygen.

• On the other hand in the carbon dioxide (CO2) ,12 parts by mass of
carbon combine to the 32 parts by mass of the oxygen.

• Thus the masses of the oxygen which combines with the carbon is in
the proportion of 16 : 32 , that is in the ratio 1 : 2 , which is a simple
whole number ratio
 The law of definite proportion constant composition
• The law of definite proportions states that a pure compound is
always composed of the same elements combined in a definite ratio
by mass.
For example, water (H2O) is composed of two hydrogen and one
oxygen only.
The ratios by mass of the elements in that compound are fixed
independent of the origins or preparation of that compound.
A compound is unique because of the specific arrangement and
weights of the elements which make up that compound.
E.g. When 0.0976 g of magnesium was heated in air, 0.1618 g of
magnesium oxide (MgO) was produced.
(a) What is the percent of Mg in MgO?
 The Modern Atomic Theory
 Atoms are not indivisible; they are composed
of subatomic particles.
 There can be atoms of the same element which
are not identical. These are called isotopes.
 Atoms are not always combined in small
numbers. In polymers, a large number of atoms
are combined to create the molecule.
 Atoms can be destroyed by fission (ex: atom
bomb).
 Sometimes, subatomic particles take place in
certain reactions. (ex: radioactive decay)
 Subatomic Particles
• One important change to Dalton’s Atomic Theory…
– Atoms are known to be divisible
– Atoms can be broken down into even smaller,
more fundamental particles called subatomic
particles
• Three kinds of subatomic particles are electrons,
protons and neutrons
 Discovery of the Electron

 J.J. Thomson found that the beam was deflected by both

electrical and magnetic fields.
 In an electric field, they bend toward the positive plate.
 From this he concluded that the cathode rays are made up
of very small negatively charged particles, which he
named electrons
His experiment led to the precise determination of the
charge-to-mass ratio (e–/m) of an electron, and this ‘e–/m’
value was found to be 1.76 × 108 coulomb/g. Coulomb is a
unit of electric charge.
 Cathode rays possess the following properties:
1. An object placed between the cathode and the opposite end of the
tube, casts a shadow on the glass. This shows that the cathode rays
travel in a straight line.
2. A paddle wheel placed in the path of cathode rays rotates. This
indicates that cathode rays are of particle nature-the particles strike
the paddle and therefore move the wheel.
3. When an electric or magnetic field is applied in the path of
cathode rays, they are deflected towards the positive plate. This
shows that cathode rays are negatively charged.

Fig (a) Electric discharge in an fig (b) The cathode ray is bent in
the presence of a magnet evacuated tube..
 Discovery of charge of electron
• In 1909, Robert Millikan determined the charge of an electron
(e–), using the oil drop experiment.
• He found the charge of an electron to be 1.60 × 10–19 coulombs.
• Combination of e–/m and e– values are used to determine the mass
of an electron, which is found to be 9.11 × 10–31 kg.
 Discovery of the Atomic Nucleus
 In 1909, Rutherford discovered proton in his famous gold foil experiment.
 in his gold foil experiment, Rutherford bombarded a beam of alpha particles on an
ultrathin gold foil and then detected the scattered alpha particles in zinc sulfide
(ZnS) screen.
Rutherford’s Conclusion
 Since most of the α-particles passed through the gold foil un deflected, most of the
space in an atom is empty.
 Some of the α-particles were deflected by small angles. This indicated the presence
of a heavy positive center in the atom, which Rutherford named the nucleus.
 Only a few particles (1 in about a million) were either deflected by a very large
angle or deflected back. This confirmed that the space occupied by the heavy
positive center must be very small.

Fig. Rutherford’s a – particles experiment.

 Discovery of Neutrons
 In 1932, an English scientist, James Chadwick, identified
the existence of neutrons.
 He bombarded a thin foil of beryllium with α-particles of a
radioactive substance.
 He then observed that highly penetrating rays, consisting
of electrically neutral particles of a mass approximately
equal to that of the proton, were produced.
 These neutral particles are called neutrons.
 Discoveries of subatomic particles

Its value determines the

identity of the atom
e.g. Determine the atomic number, mass number, and number of
neutrons in 39
19 K.
 Atoms are electrically neutral if they contain the same number of
positively charged protons and negatively charged electrons.
 When the numbers of these subatomic particles are not equal, the
atom is electrically charged and is called an ion.
 The charge of an atom is defined as follows:

Atomic charge = number of proton – number of electron

 Due to the atoms can gain or loss electrons, they can become
anion or cations
EXAMPLE: Based on the table, answer the following
questions:
i. Which of the species are neutral?
ii. Which of them are negatively charged and positively
charged ?
Atom or ion A B C
of elements

No of electron 5 12 9
No of proton 5 10 10
No of neutron 5 10 10
 Exercise
A. What is the mass number of an isotope of tin that has 66
neutrons and 50 protons?
B. Element X is toxic to humans in high concentration but essential
to life at low concentrations. Identify element X whose atoms
contain 24 protons and write the symbol for the isotope with 28
neutrons.
 Average Atomic Mass
• This is equal to the sum of each individual isotope’s mass
multiplied by its fractional abundance.

For example, the element boron is composed of two isotopes: About 19.9% of all
boron atoms are 10B with a mass of 10.0129 amu, and the remaining 80.1% are 11B
with a mass of 11.0093 amu.

The average atomic mass for boron is calculated to be:

Exercise
1. What is the relative atomic mass of an element
whose isotopic composition is 90% of 20X and
10% of 22X?
2. Copper (Cu: atomic mass 63.546 mu) contains the isotopes
63Cu (mass =62.9298 mu) and 65Cu (mass = 64.9278 mu).
What percent of a Cu atom is 65Cu?
 Electromagnetic Radiation

 Electromagnetic Radiation (light)

It is a form of energy:
 which has both electrical and magnetic properties, hence
called electromagnetic radiation.
 It is a type of energy that is transmitted through space at
enormous velocity.
 It takes numerous form e.g. -rays, X-rays, Ultraviolet, Visible
light, Microwave, Radio wave radiations.
 Whose behavior is described by the properties of both waves
and Particles (Dual nature of light).
 Cont
 Wave Properties of EMR
 EMR as a wave is composed of two component:
A. The electric field and
B. The magnetic field
 Each of the above components oscillates in plane perpendicular to
both the direction of propagation and the other component.

Figure 1: Plane-polarized EMR showing Electric field, the magnetic field and the
direction of propagation 30
 Parameters that used to characterize wave Properties of EMR
are:
I. Wavelength () :
is the distance between two successive
peaks which is measured in the unit
Angestron (Å) or nanometers (nm).
1 Å = 10-8 cm, 1 nm = 10-9 m

Different colors of light have different values of their wavelengths.

• We perceive different wave lengths (or frequencies) of visible light as
different colours, from red (λ = 750 nm) to violet (λ = 400 nm).
 Light of only one wavelength is called monochromatic light. Light that consists of more than
one wavelength is called polychromatic light. White light is an example of polychromatic light.
 N.B. Unlike frequency, wavelength depends on the electromagnetic wave’s velocity, where:

Wave nature of light can explain phenomena such as reflection, refraction and
31
diffraction.
 Example

1. What is the wavelength of an electromagnetic wave that has a

frequency of 3.0 × 108 hertz?

32
Exercise
1. Some diamonds appear yellow because they contain nitrogenous
compounds that absorb purple light of frequency 7.23×1014 s–1.
Calculate the wavelength (in nm) of the absorbed light.

33
 Cont
II. Wave number ( ):
 Is defined as the total number of waves which can distribute in a space of
one centimeter.
 It is frequently used in IR-spectroscopy.
 Wave number is just the inverse of wavelength .
 The units for wave number is cm-1

III. Frequency:
 It is the number of complete cycles or wavelength passing through per
unit time (second).
 The common unit of frequency is the Hertz (Hz) or inverse second (s-
1
); an older term for frequency is the cycle per second (cps). One hertz
equals one cycle per second (cps).
 Greater the wavelength, smaller the frequency, therefore un
inverse relation between frequency and wavelength is:

34
Amplitude (A)
It is the distance from the propagation line to the maximum
Speed (v)
 It is the rate at which the wave front is propagated
Speed of light in vacuum is 2.99792 x 108 m/s: v' = where, v'
speed of light in medium, c speed of light in vacuum and n refractive
index of a medium. (c > v‘)
 If the difference between v and c is small enough (< 0.1%) that the
speed of light rounding to three significant figures, 3.00 * 108 m/s,
is sufficiently accurate for most purposes.
 λ decreases from vacuum to a medium and increases from vacuum
to a medium. 35
 Particle Nature of Electromagnetic Radiation

 When a particle interacts with electromagnetic radiation, it

undergoes a change in its energy state.
 Electromagnetic radiation consists of a beam of discrete energetic
particles called photons.
 Photons are particles of light, which is characterized by their
energy,EE.= hυ
 all
The characteristics
Each of light
photon carries the energy, E (Joule).
can be related as follows:

c
E = hυ = h = hc υ Where; h: is planks constant (6.63 x 10-34 Js )
λ
c: is speed of
The greater the energy, the higher the frequency and wavenumber light
and the (3 x 10the
shorter 8
)
wavelength 36
v: is frequency
Example

37
 EXAMPLE

Sodium atoms have a characteristic yellow color when excited in flame.

The color comes from the emission of light of 589.0 nm
1. What is the frequency of this radiation?

2. What is the change in energy associated with this photon? Per mole
of photons?
1 mol photons = 6.023x1023 photon
Energy of one photon (E)= (6.626x10−34J.s x 3x108ms−1)/(486x10−9m)

• Energy of one mole photon (E)

=(6.023x1023 x6.626x10−34J.s x 3x108ms−1)/(486x10−9m)
• Energy of one mole photon (E) =2.46x105J
Figure 5.1: One-dimensional sinusoidal waves show the relationship among wavelength, frequency,
and speed. The wave with the shortest wavelength has the highest frequency.
Figure 5.2: Portions of the electromagnetic spectrum are shown in order of decreasing frequency and
increasing wavelength
 Atomic spectra
• Atomic or line spectra are produced from the emission of
photons of electromagnetic radiation (light).
• The excess energy is released by emitting light of various
wavelengths to produce the emission spectrum of hydrogen
atom.
 Continuous spectrum: Contains all the wavelengths of light.
 Line (discrete) spectrum: Contains only some of the
wavelengths of light. Only certain energies are allowed, i.e., the
energy of the electron in the hydrogen atom is quantized.
• It is a source emit only a few discrete wavelengths of light, and
the intensity is a strong function of the wavelength
 Bohr Model of the hydrogen Atom

• In 1913, Niels Bohr suggested a new model of the atom

that explained why hydrogen had a discrete line spectrum

rather than a continuous spectrum.

• Bohr's basic theory was electrons in atoms can only be at

certain energy levels, and they can give off or absorb

radiation only when they jump from one level to another.

• In his model, an atom consists of an extremely dense

nucleus that is surrounded by electrons that travel in set

of orbits around the nucleus.

 Bohr proposed the following three postulates for his
model.

1. The hydrogen atom has only certain allowable energy levels, called
stationary states. Each of these states is associated with a fixed circular
orbit of the electron around the nucleus.

2. The atom does not radiate energy while in one of its stationary states.
That is, even though it violates the ideas of classical physics, the atom
does not change energy while the electron moves within an orbit.
3. The electron moves to another stationary state (orbit) only by absorbing or
emitting a photon whose energy equals the difference in the energy between
the two states.
 The sizes of the circular orbits for hydrogen-like atoms
are given in terms of their radii by the following
expression

 where α0 a constant is called the Bohr radius, with a

value of 5.292 ×10−11 m
 When a sample of atomic hydrogen absorbs energy, different
hydrogen atoms absorb different amounts

Fig Electronic Transitions in the Bohr Model for the Hydrogen Atom
 larger orbit radius means a higher atomic energy level, the
farther the electron drops, the greater is the energy (higher v,
shorter λ) of the emitted photon
 A very useful result from Bohr’s work is an equation for
calculating the energy levels of an atom,
 Since Bohr’s model involved only a single electron, hydrogen-
like atoms (He+, Li2+, Be3+, and so forth) the energy expression for
hydrogen-like atoms is
, where Z is the nuclear charge (+1 for hydrogen, +2 for He,
+3 for Li, and so on) and k has a value of 2.179 × 10–18 J.

 This equation is easily adapted to find the energy difference

between any two levels:
 Exercise
1. Calculate the energies of the states of the hydrogen atom with ni
= 2 and nf = 3, and calculate the wavelength of the photon
emitted by the atom when an electron makes a transition
between these two states.
2. What is the wavelength of a photon emitted during a transition
from the ni = 5 state to the nf = 2 state in the hydrogen atom?
3. Calculate the energy required for the ionization of an electron
from the ground state of the hydrogen atom.
 • Bohr Model of the Atom
• Contribution
• It suggested a reasonable explanation for the discrete line
spectrum of the elements, and
• It introduced the idea of quantized electron energy levels
(orbits).
• Limitation
 It only works for hydrogen atoms and if there are more
than one electron, the calculations for the electron
energy and the orbit radii breakdown.
 Therefore, a new theory is needed to be developed for
multi-electron elements.
 de Broglie Equation
• In the 1920s, de Broglie proposed that all moving particles have
wave properties.
• This can be described using: h
 
mv
– Where, λ=wavelength of the particle, h = Planck's constant, m = mass
of the particle, v = velocity of the particle.
• Particles massive enough to be visible have very short
wavelengths, too small to be measured.
• On the other hand, electrons have wave properties because of
their very small mass.
• Electrons moving in circles around the nucleus can be thought of
as forming standing waves that can be described by the de Broglie
equation.
 Example
1. Calculate the de Broglie wavelength of an electron that has a
velocity of 1.00 × 106 m/s. (electron mass, me = 9.11 × 10–31 kg;
h = 6.626 × 10–34 J s)
Exercise
1. What is the characteristic wavelength of an electron (in
nm) that has a velocity of 5.97 × 10 6 m s–1 (me = 9.11 × 10–
31
kg)?
 Quantum Mechanical Model
• The current understanding of the atom is based on Quantum
Mechanics.
• this model sees the electrons not as individual particles, but
as behaving like a cloud - the electron can be “anywhere” in
a certain energy level
 Based on the wave properties of the atom Schrodinger’s
equation is (too complicated to be detailed here),
Wave function () – a wave representing the spatial
distribution of a “particle”.

H = E 
 = wave function
H= mathematical operator
E = total energy of the atom
A specific wave function is often called an orbital.
This equation is based on operators – not simple algebra.
This is a mathematical concept you will not have dealt with
yet.
 Heisenberg Uncertainty principle

• which states that it is impossible to know simultaneously both the

momentum p (p = mν) and the position of a particle with certainty
 He stated that it is impossible to describe the motion of an electron in an atom
as it moves around the nucleus so precisely.
 The more accurately we know a particle’s position, the less accurately we can
know its momentum.
 Both the position and momentum of a particle can not be determined
precisely at a given time.
 This states that there is a relationship between the inherent uncertainties in
the location and h
momentum where,
of an Δx= uncertainty
electron moving in the xposition
in the of the
direction:
x p 
4 electron, Δp= uncertainty in the momentum of the
x
electron.

 The energy of spectral lines can be measured with great precisions which
allows precise determination of the energy of electrons in atoms.
It implies electron cannot be treated as simple particles
with their motion described precisely,

 But we must instead consider the wave properties of

electrons by a degree of uncertainty in their location.

 So we can only describe orbitals rather than describing

precise orbits of electrons.
 Orbitals- are regions that describe the probable location
of electrons.
or the region of space where the electrons of an atom or
molecule are found.
 Quantum Numbers
• Are parameters that describe the distribution of electrons in the
atom, its fundamental nature such as :
• the size, energy, shape and position of the orbitals.

• There are four types of quantum numbers: principal, angular

momentum, magnetic and spin.

Principal Quantum Number (n)

• Represents the main energy level, or shell, occupied by an

electron.

• It is always a positive integer that is n= 1, 2, 3...

 Relative size of the orbital or the relative distance of the electron
from the nucleus. Size of orbital increases with the increase of
principal quantum number n.

 Energy of the orbital. Higher the n value, greater is the energy.

Maximum number of electrons present in any shell (given by the

formula 2n2).
 Angular Momentum Quantum Number

Angular Momentum Quantum Number (l) - represents the energy

sublevel, shape and type of orbital occupied by the electron.
 The value of l depends on the value of n such that l= 0, 1,... n-1.

Example1: For principal quantum level n = 5, determine the

number of allowed subshells (different values of l), and give the
designation of each
l=0 l=1 l=2 l=3 l=4
5s 5p 5d 5f 5g
Exercise: Give the sublevel notation for each of the following sets of
quantum numbers.
A. n = 3, l = 2 C. n = 4, l = 1
B. n = 2, l = 0 D. n = 4, l = 3
Magnetic Quantum Number (ml )- represents the number of
possible orientations in 3-D space for each type of orbital. Since the
type of orbital is determined by l, the value of ml ranges between –l

and +l such that ml= -l, ...0, ...+l.

• The number of possible ml values or orbitals for a given l

value is (2l + 1).

• It prescribes the orientation of the orbital in the three-

dimensional space about the nucleus.

It specifies the relative spatial orientation of a particular orbital.

Example :What values of the angular momentum quantum number (l) and magnetic
quantum number (ml ) are allowed for a principal quantum number (n) of 3? How
many orbitals are allowed for n = 3?
Solution:
1. Determining l values:
For n = 3, l = 0, 1, 2
Determining ml for each l value:
For l = 0, ml = 0
For l = 1, ml = –1, 0, +1
For l = 2, ml = –2, –1, 0, +1, +2
Number of orbitals = n2, n is 3 and n2 = 32 = 9 orbitals
3s : 1 orbital
3p : 3 orbitals
3d : 5 ortbitlas
Total = 9 orbitals
 Exercise
1. What are the n, l and ml quantum numbers corresponding
to the 3sorbital?
• Spin Quantum Number (mS)- represents the two possible
orientations that an electron can have in the presence of a magnetic
field.
has only two possible values, +½ (represented by the arrow, ↑) and – ½
(represented by the arrow ↓).
• Only two electrons can occupy the same orbital, and they must
have opposite spins.
• When this happens, the electrons are said to be paired.
Exercise: Which of the quantum numbers relates to the electron only?
Which relate (s) to the orbital?
Table of Allowed Quantum Numbers

n l ml Number of Orbital Number of

orbitals Name electrons

1 0 0 1 1s 2
2 0 0 1 2s 2
1 -1, 0, +1 3 2p 6
3 0 0 1 3s 2
1 -1, 0, +1 3 3p 6
2 -2, -1, 0, +1, +2 5 3d 10
4 0 0 1 4s 2
1 -1, 0, +1 3 4p 6
2 -2, -1, 0, +1, +2 5 4d 10
3 -3, -2, -1, 0, +1, 7 4f 14
+2, +3

64
 (Electronic configuration)
• Electron configuration: the arrangement of electrons in the orbitals
of an atom is called of the atom.
• We describe an electron configuration with a symbol that
contains three pieces of information:
1. The number of the principal quantum shell, n,
2. The letter that designates the orbital type (the subshell, l), and
3. A superscript number that designates the number of electrons
in that particular subshell.
2
He 1s2

• In writing electronic configurations or electron filling of orbitals, we

follow the Aufbau principle, Hund’s rule, and the Pauli Exclusion
Principle.
• The Aufbau Principle (building up principle) -explains the order
in which the electrons fill the various orbitals in an atom. Filling
begins with the orbitals in the lowest energy to higher energy:
1s,2s,2p,3s…

Figure: Increasing order of filling orbitals.

Hund's rule-states that each degenerate orbital, (e.g.2px, 2py, and
2pz) must first receive one electron before any of the orbitals can
receive a second electron.
Degeneracy: energies of all the orbitals with the same n are the
same (such as He+, Li2+,…).
Degenerate orbitals: the energy levels for the same principal
quantum number, n.
Orbitals within the same subshell are still degenerate and have the
same energy.
Pauli Exclusion Principle- states that no two electrons can have the
same four quantum numbers.
Example: 2s2
• The electron configuration and the orbital diagram for single hydrogen atom
(atomic number 1): For (n = 1, l = 0, ml = 0, m s = +1/2)

• For Helium: (n = 1, l = 0, ml = 0, m s = 1/2)

• The electrons occupying the outermost shell orbital(s) (highest value of n) are
called valence electrons, and those occupying the inner shell orbitals are
called core electrons.
Na 1s22s22p63s1 , abbreviation [Ne]3s1
Core electrons: 1s22s22p6 valence electrons: 3s1

Exercise :Write the electron configuration of an element with (Z = 20

and A = 40 mu).

05/08/2024 68
• In the case of Cr and Cu, we find that half-filled and
completely filled subshells apparently represent conditions of
preferred stability.
24
Cr: Predicted= [Ar]4s23d4 experimental= [Ar]4s13d5
29
Cu: Predicted= [Ar]64s23d9 experimental=
[Ar]4s13d10

• Other exceptions for example, niobium (Nb, atomic number 41)

predicted electron configuration [Kr]5s24d3, experimentally
[Kr]5s14d4.

• Because the electron–electron repulsions experienced by pairing

the electrons in the 5s orbital are larger than the gap in energy
between the 5s and 4d orbitals.

• There is no simple method to predict the exceptions for atoms

where the magnitude of the repulsions between electrons is
greater than the small differences in energy between subshells.
 Orbital Shapes and Energies
The s subshell electron density distribution is spherical and the p
subshell has a dumbbell shape

The d and f orbitals are more complex

These shapes represent the three-dimensional regions within

which the electron is likely to be found
 These shapes represent the three-dimensional regions within which the electron
is likely to be found.

Figure 5.8: Shapes of s, p, d, and f orbitals.

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 Electron Configurations and the Periodic Table
• The periodic table arranges atoms based on increasing atomic number so that
elements with the same chemical properties recur periodically.

• Valence electrons play the most important role in chemical reactions and also
the determining factor in some physical properties of the elements. Many
chemical properties depend on the valence electrons.

• The outer electrons have the highest energy of the electrons in an atom and
are more easily lost or shared than the core electrons.

• Elements in any one group (or column) have the same number of valence
electrons.

• The similarity in chemical properties among elements of the same group occurs
because they have the same number of valence electrons.

• The periodic table was developed on the basis of the chemical behavior of
the elements.
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• Elements in the periodic table can be
1. Main group elements (representative elements): are those in which the
last
electron added enters an s or a p orbital in the outermost shell.
• This category includes all the nonmetals, metals and metalloids
• The valence electrons are with the highest n level.
2. Transition elements or transition metals.
• These are metallic elements in which the last electron added enters a d
orbital.
• The valence electrons in these elements include the ns and (n – 1) d
electrons.
• The official IUPAC definition of transition elements specifies those with
partially filled d orbitals.
3. Inner transition elements are metallic elements in which the last electron
added occupies an f orbital.
• The valence shells of the inner transition elements consist of the (n – 2)f,
the (n – 1)d, and the ns subshells.
• There are two inner transition series:
a. The lanthanide series: lanthanide (La) through lutetium (Lu)
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b. The actinide series: actinide (Ac) through lawrencium (Lr)
• Rules to calculate Screening effect-
• The most accepted method for the calculation or determination of the value of the screening
factor is given by Slater. There are some rules to find screening factor. According to Slater,
• 1) Each electron of the orbit higher than the electron under consideration contributes zero.
• 2) Each electron of the same orbit contributes 0.35 except the ‘1s ‘ electron which contributes
0.30.
• 3) Electron of (n-1) orbit contributes 0.85.
• 4) All the electrons in the (n-2 ) shell contribute 1.0.
• For Example:
• 30 Zn – 1s2 , 2s2 , 2p6 , 3s2 , 3p6 , 4s2 , 3d10
• Screening factor ‘σ ‘ = 1 x 0.35 + 18 x 0.85 + 10 x 1 ‘
• σ = 0.35 + 15.30 + 10 = 25.65 Ans.
• Zeff = Z – σ
• Z = 30
• Z eff = 30.0 – 25.65 = 4.35
Figure . Classification of elements according to the type of subshells being filled
 Electron Configurations of Ions
 Ions are formed when atoms gain or lose electrons.

 A cation (positively charged ion) forms when one or more electrons are
removed from a parent atom.

 For main group elements, the electrons that were added last are the first
electrons removed.

 For transition metals and inner transition metals electrons from the highest
ns are lost, and then the (n – 1)d or (n – 2)f electrons are removed.

 An anion (negatively charged ion) forms when one or more electrons are
added to a parent atom.

 The added electrons fill in the order predicted by the Aufbau principle.

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 Exercise
Write The Electron Configuration Cr2+ and O2-
 Periodic Variation in Element Properties
1. Atomic Size (Atomic Radii)

• period: decrease as you move across

because increase in nuclear charge(+),
because it implies that atoms with more
electrons have a smaller atomic radius
and due to increasing Zeff..

•group: increase as we go down

because increasing number of
energy levels in an atom or
increasingly distant from the nucleus or
due to increasing value of n

Figure 5.17: (a) The radius (covalent) of an atom is defined as one-

half the distance between the nuclei in a molecule consisting of
two identical atoms joined by a covalent bond. The atomic radius for
the halogens increases down the group as n increases. (b) Covalent
radii of the elements are shown to scale. The general trend is that
radii increase down a group and decrease across a period.
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 Effective Nuclear Charge (Zeff)

 In a many-electron atom, electrons are both

attracted to the nucleus and repelled by other
electrons.
 The nuclear charge that an electron “feels”
depends on both factors. It’s called Effective
nuclear charge.
 electrons in lower energy levels “shield” outer
electrons from positive charge of nucleus.

Shielding is determined by the probability of another

electron being between the electron of interest and
the nucleus, as well as by the electron–electron
repulsions the electron of interest encounters.

Factors Affecting Atomic Orbital Energies

 The energies of atomic orbitals are affected by
• nuclear charge (Z) and shielding by other electrons.
 A higher nuclear charge increases nucleus-electron interactions and lowers sublevel
energy.
 Shielding by other electrons reduces the full nuclear charge to an effective nuclear
charge (Zeff).
• Zeff is the nuclear charge an electron actually experiences.
 Orbital shape also affects sublevel energy.
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 5.5.2. Variation in Ionic Radii
Atomic vs. Ionic Size  used to describe the size of an ion
Metals Nonmetals
 lose electrons and become positive ion (cations)  Gain electrons
 A cation always has fewer electrons  become negative ions (anion)
 Ion is smaller than parent atom  Formed by the addition of one or
 Cations with larger charges are smaller than cations more electrons to the valence shell
of an atom
with smaller charges (e.g., V2+ has an ionic radius of 79
 Ion is larger than atom
pm, while that of V3+ is 64 pm).  Results in a greater repulsion
 As electrons are removed from the outer valence shell, among the electrons and a
the remaining core electrons occupying smaller shells decrease in Zeff per electron
experience a greater effective nuclear charge Z eff and  For consecutive elements
are drawn even closer to the nucleus. proceeding down any group, anions
 Proceeding down the groups of the periodic table, have larger principal quantum
numbers and, thus, larger radii.
cations of successive elements with the same charge
generally have larger radii, corresponding to an
increase in n.
Na Na+ + 1e Cl + 1e Cl-

due to the lost electrons due to the gained electrons

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Exercise: Arrange the following atoms in order of
increasing atomic radius: F, P, S, As.
2. Calculate the Zeff of Fe and Na
 Variation in Ionization Energies

• The amount of energy required to remove the most loosely bound electron
from a gaseous atom in its ground state is called its first ionization energy
(IE1).

• The first ionization energy for an element, X, is the energy required to form
a cation with +1 charge: X(g) ⟶ X+(g) + e- IE1

• The energy required to remove the second most loosely bound electron is
called the second ionization energy (IE2). X +(g) ⟶ X2+(g) + e- IE2

• Ionization processes are endothermic and IE values are always positive.

• Thus, as size (atomic radius) increases, the ionization energy should decrease.

• Generally, IE increases across the period and decreases down the group
(since Z increases).
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• There are some systematic deviations from this trend
• Note that IE of boron ([He]2s22p1) ) is less than beryllium ([He]2s2).

• Within any one shell, the s electrons are lower in energy than the p electrons.
• Another deviation occurs as orbitals become more than one-half filled.

• The first ionization energy for oxygen is slightly less than that for nitrogen,
despite the trend in increasing IE1 values across a period.
O 1s22s22p4 N 1s22s22p3

• Removing an electron from a cation is more difficult than removing an

electron from a neutral atom because of the greater electrostatic
attraction to the cation.

• Likewise, removing an electron from a cation with a higher positive charge is

more difficult than removing an electron from an ion with a lower charge.

• Thus, successive ionization energies for one element always increase.

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Example Ranking Ionization Energies
• Predict the order of increasing energy for the following
processes: IE1 for Al, IE1 for Tl, IE2 for Na, IE3 for Al.
Solution
• Removing the 6p1 electron from Tl is easier than removing
the 3p1 electron from Al because the higher n orbital is farther
from the nucleus, so IE1(Tl) < IE1(Al).
• Ionizing the third electron from Al(Al2+⟶Al3++e−) requires
more energy because the cation Al2+ exerts a stronger pull on
the electron than the neutral Al atom, so IE1(Al) < IE3(Al).
• The second ionization energy for sodium removes a core
electron, which is a much higher energy process than
removing valence electrons.
• Putting this all together, we obtain: IE1(Tl) < IE1(Al) <
IE3(Al) < IE2(Na).

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 Electronegativity
measure of the tendency of an element to attract
electrons to itself
On moving down the group,
• Z increases but Z* almost remains constant
• number of shells (n) increases
• atomic radius increases
• force of attraction between added electron and nucleus
decreases
Therefore EN decreases moving down the group
On moving across a period left to right

• Z and Z* increases

• number of shells remains constant

• atomic radius decreases

• force of attraction between added electron and nucleus

decreases

Hence EN increases along a period

 IE increases
IE decreases
EN decreases EN increases
Radius increase Radius decrease

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 Electron Affinities
• The electron affinity (EA): is the energy change for the process of
adding an electron to a gaseous atom to form an anion (negative ion).
X(g) + e- ⟶ X-(g) EA1
• This process can be either endothermic or exothermic, depending on
the element.

• The second EA is the energy associated with adding an electron to an

anion to form a 2– ion, and so on.

• It becomes easier to add an electron across a series of atoms as the

effective nuclear charge of the atoms increases.

• As we move from left to right across a period, EA tend to become

more negative.
• The exceptions found among the elements of group 2 (2A), group 15
(5A), and group 18 (8A) can be understood based on the electronic
structure
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of these groups. 88
• The noble gases, group 18 (8A), have a completely filled shell and the incoming
electron must be added to a higher n level, which is more difficult to do.

• Group 2 (2A) has a filled ns subshell, and so the next electron added goes into
the higher energy np, so, again, the observed EA value is not as the trend
would predict.

• Finally, group 15 (5A) has a half-filled np subshell and the next electron must
be paired with an existing np electron.

• The atom at the top of each group to have the most negative EA; their first
ionization potentials suggest that these atoms have the largest effective
nuclear charges.

• However, as we move down a group the second element in the group most often
has the most negative EA.

• This can be attributed to the small size of the n = 2 shell and the resulting
large electron – electron repulsions.
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 Metallic Character
• Metallic character refers to the chemical properties associated with
elements classified as metals.

• As one moves across a period from left to right in the periodic table,
the metallic character

• decreases, as atoms are more likely to gain electrons to fill their

valance shell rather

• than to lose them to remove the shell. Down a group, the metallic
character increases,

• due to the lesser attraction from the nucleus to the valence electrons.
Thank you