Electronic Structure of Atoms

Quantum Theory
Quantum Theory:
Enables us to predict and understand the critical
role that electrons play in chemistry.
Questions:
1. How many electrons are present in a
particular atom?
2. What energies do individual electrons
possess?
3. Where is the atom of an electrons be found?
• The answers to these questions have a direct
relationship to the behavior of all substances in
chemical reactions.
Planck’s Quantum Theory:
When solids are heated, they emit electromagnetic
radiation over a wide range or wavelengths. The dull red
glow of an electric heater and the bright white light of a
light bulb/light globe are examples of radiation from
heated solids.
• Planck said that atoms and molecules could emit (or
absorb) any arbitrary amount of “radiant energy” in
discrete quantities (small packages and boundaries).
Quantum – the name given by Planck to the smallest
quantity of energy that can be emitted (or absorb) in the
form of electromagnetic radiation.
The energy E of a single quantum is given by;

E = hv

h = is Planck’s constant: 6.63X10⁻³⁴ J.s

v = frequency of radiation
• According to Q theory, energy is always emitted in
multiples of hv (eg. hv2., hv3…….) never in 1.67hv or
4.98 hv.
The Dual Nature of the Electron
1924 Louis de Broglie
* If light waves can behave like a stream of
particles (photons), then perhaps particles such as
electrons can possess wave properties.
• Electrons and other particles may exhibit wave-
like properties in the same way as light can
exhibit particle-like properties.
• The de Broglie Relation states that the particle
and wave properties can be related by the
equation;
𝜆 = _h_
mu
𝜆: wavelength in m
u: velocity in m/s
m: mass in kg
h: Planck’s constant in J.s or Hz
Example: Calculate the wavelength of the “particle” in
two cases;
a. The fastest serve in tennis is about 63 m/s. calculate
the wavelength associated with a 6.0x10⁻²kg tennis
ball travelling at this speed.
Given: h: 6.63x10⁻³⁴J.s, m: 6.0x10⁻² kg, u: 63 m/s
Formula:
𝜆= _h_
mu
= ____6.63x10⁻³⁴ J.s____
(6.0x10⁻² kg)(63 m/s)
= 1.8x10⁻³⁴ m
Quantum Number
- Numbers that describe the distribution of electron
in hydrogen and other atoms.
• These numbers are derived from the mathematical
solution of the Schrodinger equation for the hydrogen
atom.
• They are called the principal quantum number, the
angular momentum quantum number and the magnetic
quantum number. These numbers will be used to describe
atomic orbitals and to label electrons that reside in them.
• The spin quantum number describes the behavior of a
specific electron and completes the description of
electrons in atoms.
Types of Quantum Numbers:
Quantum Numbers of an Atomic Orbital:
Principal quantum number (n)
- Is a positive integer (1, 2, 3, …..)
- Indicates the “relative size” of the orbital.
- Specifies the energy level of the H atom: the higher
the n value, the higher the energy level.
- The number of electrons that can occupy a given shell is
determined by the value of n. (the further a shell is
from the nucleus, the larger its volume becomes, and
the more electrons it can hold).
- when the electron occupies an orbital with n=1, the H
atom is in “ground state” has its lowest energy.
Angular momentum quantum number (l)
- Is a integer from 0 to n-1.
- It is related to the “shape” of the orbital.
- n limits l
- For an orbital with n=1, l can have only one value 0.
- For an orbital with n=2, l can have two values, 0 or 1.
- For an orbital with n=3, l can have 3 values, 0, 1, or 2.
- The number of possible l values equals the value of n.
Magnetic quantum number (ml)
- Is an integer from – 1 through 0 to +1
- It prescribes the three-dimensional “orientation” of
the orbital in the space around the nucleus.
- l limits ml
- an orbital with l=0, can have only mℓ =0.
- An orbital with l=1, can have one of three values -1,0,+1
The Hierarchy of Quantum Numbers for Atomic Orbitals:
Name, Symbol
(Property)____Allowed Values__Quantum Numbers____
Principal n Positive integer 1 2 3
(size, energy) (1, 2, 3,………..)

Angular Integers from 0 0 1 0 1 2

Momentum ℓ 0 to n -1
(shape)

Magnetic mℓ Integers from 0 0 -1,0,+1 0 -1,0,+1 -2,-1,0,+1,+2

(orientation) -1 to 0 to +1
Distribution of Electrons in the first 4 shells.
Shell Number of Electrons in a shell
4- 32
3- 18
2- 8

1- Increasing energy level 2 Increasing number

Lowest energy level of electrons

Shells are divided into subshells, identified by the letters s,

p, d and f. the subshells consist of orbitals.
The Angular Momentum Quantum Number (ℓ)
* ℓ tells us the shape of the orbitals.
Value of ℓ depends on the value of the principal
quantum number n.
___ℓ______
The Magnetic Quantum Number (mℓ)
• Describes the orientation of the orbital in
space.
• Within the subshell, the value of mℓ depends
on the value of the angular momentum
quantum number ℓ.
The Spin Quantum Number (ms)
• A spinning charge can generate a magnetic field.
• The direction of an electron’s spin can be
determined by its response to the magnetic
field.
Quantum Numbers and Energy Levels:
The energy states that orbitals of the atom are
described with specific terms and are associated
with one or more quantum numbers.

Level
- The atoms energy level, or shells are given by
the n value; the smaller the n value, the lower
the energy level and the greater the probability
that the electron is closer to the nucleus.
Sublevel
- The atom’s level are divided into sublevels, or subshells
that are given by the l value. Each designates the orbital
shape with a letter.
• l = 0 is an s sublevel
• l = 1 is a p sublevel
• l = 2 is a d sublevel
• l = 3 is an f sublevel
The letters derived from the names; spectroscopic lines;
sharp, principal, diffuse, and fundamental.
Sublevels with l values greater than 3 are designated by
consecutive letters f: g sublevel, h sublevels and so on.
.

- Is a region of space where the probability of finding an

electron is high.
- Each orbital can hold 2 electrons.
- Is the wave function of an electron in an atom.
• The two electrons in an orbital must have opposite spins, if
one electron has a clockwise spin, the second electron in
the orbital must have a counterclockwise spin.
Relationship between Quantum Numbers and Atomic
Orbitals:
n ℓ mℓ Numbe Atomic Orbital
r of Designations
Orbitals
1 0 0 1 1s
2 0 0 1 2s
1 - 1, 0, 1 3 2px, 2py, 2pz
3 0 0 1 3s
1 -1, 0, 1 3 3px, 3py, 3pz
2 -2,-1, 0,1,2 5 3dxy, 3dyz, 3dxz
4dx², 4dy², 4dz²
• A particular type of subshell contains a specific
number of orbitals.
An s subshell contains only 1s orbital.
A p subshell has 3p orbitals.
A d subshell has 5d orbitals.
An f subshell has 7f orbitals.
• The number of subshells in a given shell equals the
value of n.
s orbitals p orbitals d orbital f orbital
lowest energy highest energy
The first shell of electrons around a nucleus (n =
1) has only s orbital.
• this orbital is called the 1s orbital since it is the s
orbital in the first shell.
• It can hold two electrons
Shell number 1s - the s orbital in the 1st shell
(principal energy level)
• The second shell of electron (n=2) has two
types of orbitals, 1s and 3p orbitals. This details
are called the 2s and 2p orbitals since they are
located in the second shell. Since each orbital
can hold 2 electrons and there are 4 orbitals.
• The 2nd shell can hold 8 electrons.
one 2s orbital three 2p orbitals = 4 orbitals in the 2nd shell
2s 2p 2p 2p 4 orbitals x 2electrons = 8
1 orbital

Each orbital can hold 2 electrons 8 electrons in the 2nd shell

• The third shell of electrons (n = 3) has 3 types of
orbitals; 1s,3p, and 3d orbitals. These orbitals are
called 3s, 3p, and 3d orbitals since they are
located in the 3rd shell. Since each orbital can hold
2 electrons and the 3rd shell has a total of 9
orbitals; the 3rd shell can hold 18 electrons.
One 1s orbital three 3p orbitals five 3d orbitals
1s 3p 3p 3p 3d 3d 3d 3d 3d = 5 orbitals in the 3 rd shell
9 orbitals x 2 electrons =
Each orbital holds two electrons
18 electrons in the 3rd
shell
• The fourth shell of electrons (n = 4) has four
types of orbitals; 1s, 3p, 5d, 7f orbitals. These
orbitals are called 4s, 4p, 4d orbitals since they
are located in the 4th shell. Since each orbital can
hold 2 electrons and the 4th shell has a total of 16
orbitals, the 4th shell can hold 32 electrons.

One 4s orbital three 4p orbitals five 4d orbitals seven 4f orbitals

4s 4p 4p 4p 4d 4d 4d 4d 4d 4f 4f 4f 4f 4f 4f 4f
= 16 orbitals in the 4th shell

16 orbitals x 2 electrons = 32 electrons in the 4th shell

1 electron
Orbitals and Electrons contained in the Principal Energy
levels (n = 1 - 4).
Shell Orbitals Electron in each Maximum No. of
Subshell electrons
1 1s 2 2
2 2s 2 8
2p 2p 2p 3 X 2 =6
3 3s 2 18
3p 3p 3p 3 X 2 = 6
3d 3d 3d 3d 3d 5 X 2 = 10
4 4s 2 32
4p 4p 4p 3 X 2 = 6
4d 4d 4d 4d 4d 5 X 2 = 10
4f 4f 4f 4f 4f 4f 4f 7 X 2 = 14
Electron Configuration
- Is the arrangement of electrons in any given atom.
- Is how the electrons are distributed among the
various atomic orbitals in order to understand
electrons behavior.
Aufbau Build-up Principle
- States that electrons of an atom will occupy orbitals from
orbitals with lowest energy to orbitals of the highest energy.
- German word meaning “build –up”
- Also called the “ The Concert Hall “ principle.
Build Up Period 1
Period 1 whose ground-state elements have only the n=1
level thus, only 1s sublevel which consists of only the 1s
orbital.
Hydrogen has a set of quantum numbers n=1, l=0, ml=0
and mi = +1/2
Hydrogen Electron Configuration & Orbital diagram
H (Z = 1) 1sˡ ↑
Helium has the same quantum numbers as the
electron in H, but the second electron has
opposing spin (exclusion principle) n=1, l=0,
ml=0, mi= -1/2 . EC and OD is;
He (Z =2) 1s² ⇅
Building Up Period 2:
Period 2 begins with the 2s sublevel which is the next
lowest in energy. And consists of only 2s orbital.
When the 2s orbital is filled we proceed to fill the 2p.
Lithium the first two electrons in Li fill the 1s sublevel,
and the last added Li electron has quantum numbers n=2,
l=0, ml=0, mi=+1/2. EC and OD is;

Li (Z = 3) 1s², 2sˡ ⇅ ↑

Be (Z = 4) 1s², 2s² ⇅ ⇅

B (Z = 5)1s²,2s²,2pˡ ⇅ ⇅ ↑
 ⇅ ⇅
C (Z = 6) 1s²,2s², 2p² ↑ ↑

⇅ ↑
N (Z = 7) 1s²,2s², 2p³ ⇅ ⇅ ↑ ↑ ↑

O (Z = 8) 1s², 2s², 2p⁴ ⇅ ⇅ ⇅ ↑ ↑

F (Z = 9) 1s², 2s², 2p⁵ ⇅ ⇅ ⇅ ⇅ ↑

Ne (Z = 10) 1s² ,2s² ,2p⁶ ⇅ ⇅ ⇅ ⇅ ⇅

Build Up Period 3
The Period 3 elements Na through Ar, lie directly under
the period 2 elements Li through Ne. Even though the n=3
level splits into 3s, 3p, and 3d sublevels, period 3 fills only
3s and 3p; 3d is filled in period 4.

Partial orbital diagram shows only the sublevels being

filled. (3s and 3p).
Condensed electron configuration have the element
symbol of the previous noble gas in brackets, to stand for
its configuration, followed by the electron configuration of
filled inner sublevels and the energy level being filled.
Example: S (Ne) 3s², 3p⁴ (Ne) stands for 1s², 2s², 2p⁶
Partial Orbital Diagrams and Electron Configurations P – 3
Atomic # Element Partial Orbital Full EC Condensed EC
3s 3p
11 Na ↑ ↑ 1s²,2s²,2p⁶,3sˡ, (Ne)3sˡ
12 ⇅ Mg ⇅ 1s²,2s²,2p⁶,3s² (Ne)3s²
13 Al ⇅ ↑ 1s²,2s²,2p⁶,3s²,3pˡ (Ne)3s²,3pˡ
14 Si ⇅ ↑ ↑ 1s²,2s²,2p⁶,3s²,3p² (Ne)3s²,3p²

15 P ⇅ ↑ ↑ 1s²,2s²,2p⁶,3s²,3p³
↑ (Ne)3s²,3p³
16 S ⇅ ⇅ ↑ 1s²,2s²,2p⁶,3s²,3p⁴
↑ (Ne)3s²,3p⁴
17 Cl ⇅ ⇅ ⇅ 1s²,2s²,2p⁶,3s²,3p⁵
↑ (Ne)3s²,3p⁵
18 Ar ⇅ ⇅ ⇅ 1s²,2s²,2p⁶,3s²,3p⁶
⇅ (Ne)3s²,3p⁶
Building Up Period 4: The First Transition Series
Period 4 contains the first series of “transition elements”,
those in which d orbitals are being filled.
Exemption:
The last electron of the next element Cr, does not enter a
4th empty d orbital to give (Ar) 4s²,3d⁴; instead Cr has 1
electron in the 4s sublevel and 5 in the 3d sublevel making
both sublevel half-filled. Cr: (Ar) 4sˡ, 3d⁵.
Cu would be expected to have the configuration (Ar) 4s²,
3d⁹. Instead, the 4s sublevel of Cu is half-filled with 1
electron, and the 3d sublevel is filled with 10. Cu: (Ar) 4sˡ,
3dˡ⁰.
Cr and Cu conclusion: half-filled and filled sublevels are
unexpectedly stable (low in energy)
Partial Orbital Diagrams & Electron Configuration Period 4 Elements.
Atomic# E Partial Orbital Diagram Full EC Condensed EC
4s 3d 4p
↑
19 K 1s²,2s²,2p⁶,3s²,3p⁶,4sˡ (Ar)4sˡ
20 Ca ⇅ 1s²,2s²,2p⁶,3s,²3p,⁶4s² (Ar)4s²
⇅ ⇅↑ 21 Sc
1s²,2s²,2p⁶,3s²,3p⁶,4s²,3dˡ (Ar)4s²,3dˡ
↑ 22 Ti
23 V
↑ ↑ ↑ ↑ ↑ ↑
24 Cr 1s²,2s²,2p⁶,3s²,3p⁶,4s²,3d⁵ (Ar)4s²,3d⁵
25 Mn
26 Fe
27 Co
28 Ni
↑
29 Cu ⇅ ⇅ ⇅ ⇅ ⇅ 1s²,2s²,2p⁶,3s²,3p⁶,4s²,3dˡ⁰(Ar)4s²,3dˡ⁰
General Principles of Electron Configuration:
a. Similar outer electron configuration within a
group.
Among the main-group elements (A groups 1A – 8A) –
the s block and p block elements - outer electron
configuration within a group are “identical”. Some
variations in the transition elements (B group,3B – 2B d
blocks) and inner transition elements (f blocks) occur.
b. Orbital filling order
When the electrons are “built – up” by filling levels and
sublevels in order of increasing energy, we obtain the
sequence in the periodic table.
1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p

7s 5f 6d 7p
Hydrogen denotes the number of
electrons in the orbital or
subshell

1sˡ
denotes the Principal denotes the angular
number n momentum quantum
number

Example: Beryllium (₄Be) has 4 electrons.

Note: Atomic number = number of electrons
1s², 2s²
Can also be presented in
⇅ ⇵
diagram form 1s² 2s²
• The symbol He is called the helium core and represents
1s². (H, He)
• The symbol Ne is called the neon core and represents
1s², 2s², 2p⁶. (Li – Ne)
• The symbol Ar is called the argon core and represents
(Ne) 3s², 3p⁶. (Na- Ar)
• The symbol Kr is called the krypton core and
represents (Ar) 4s², 3dˡ⁰, 4p⁶ (K – Kr)
• The symbol Xe is called the xenon core and represents
(Kr) 5s², 4dˡ⁰, 5p⁶ (Rb – Xe)
• The symbol Rn is called the radon core and represents
(Xe) 6s², 4fˡ⁴, 5dˡ⁰, 6p⁶ (Cs – W)
Points to Remember:
• The Periodic Table gives the ground-state of electron
configuration form H (Z=1) through Mt (Z=109).
• The electron configuration of “all elements” except H
and He are represented by a noble gas core.
• Li (Z=3) through Ne (Z=10) down to Cs (Z=55) through
Rn (Z=86) follow a similar pattern.
• 4s subshell is filled before 3d subshell in many electron
atom. The EC of K (potassium) (Z=19) is
1s²,2s²,2p⁶,3s²,3p⁶,4sˡ. Since this is also the EC of Ar
(Argon), Aufbau simplify it by writing (Ar)4sˡ. Ar
denotes the Argon core.
Example: Ca (Calcium) (Z=20) as (Ar)4s²
• The elements from Sc (Scandium) (Z=21) to Cu (Copper)
(Z=29) are transition metals.
• There are some irregularities in the EC of elements. The
reason for this is that a slightly greater stability is
associated with the half-filled (3d⁵) and completely
filled (3dˡ⁰) subshell). Electrons in te same subshell (in
this case the d orbitals) have equal energy but different
spatial distributions. (relating to occupying in space).
Example:
Chromium Cr (Z=24) Cr (Ar) 3d⁵, 4sˡ
↑ ↑ ↑ ↑ ↑ ↑
- has a total of 6 unpaired electrons.
Copper Cu (Z=29) Cu (Ar) 3dˡ⁰ 4sˡ
↑ ⇅ ⇅ ⇅ ⇅ ⇅
Pauli Exclusion Principle: Wolfgang Pauli Swiss Physicist
- States that no two electrons in an atom can have the same 4 quantum
numbers.
Example: If 2 electrons in an atom should have the same n, ℓ, mℓ values
(that is, these two electrons are in the same atomic orbital), then they
must have different value of ms. Only 2 electrons may occupy the same
atomic orbital, and these electrons must have opposite spins.
Helium (²He) C is physically acceptable 1 electron
has the quantum numbers (1, 0
⇅ ⇈ ⇊ ⇅
a b c 0, + ½).
1s² 1s² 1s² 1s²
A both electrons have the same upward spin and would have the quantum
numbers (1,0,0, + ½).
B Both electrons have downward spin and would have the quantum numbers
(1, 0,0, - ½)
• When all electrons of a given element are
paired up, “no net magnetic field” is observed,
this element is considered diamagnetic.
1s²
Example: Helium (²He) ⇅
• When an element contains an unpaired or
multiple unpaired electrons, a magnetic
moment is observed and is considered
paramagnetic. 1s² 2sˡ
Example: Lithium (³Li) ⇅ ↑
Hund’s Rule of Maximum Multiplicity
Frederick Hund (German Physicists)
- States that most stable arrangement of
electrons in subshell is the one with the greatest
number of parallel spin.
Example: Carbon (⁶C ) Oxygen (⁸O)
1s² 2s² 2p² 1s² 2s² 2p⁴
⇅ ⇅ ↑ ↑ ⇅ ⇅ ⇅ ↑ ↑

• The filling of orbitals require placing individual

electrons of the same spin on all orbitals first before
pairing up with the opposite spin.
The orbital diagram:
O ⇅ ⇅ ⇅ ↑ ↑ Paramagnetic
1s² 2s² 2p⁴

Kr ⇅ ⇅ ⇅ ⇅ ⇅ ⇅ ⇅ ⇅ ⇅ Diamagnetic
4s² 3dˡ⁰ 4p⁶
Gilbert N. Lewis (1875-19460)
- Suggested that electrons in atoms might be arranged in
shells, starting close to the nucleus and building outward.
Valence electrons
- means the electrons in the outermost parts of the
atom that determine chemical behavior.
• For main group elements (those in groups designated
by a number and letter A), the only valence electrons
are those with the highest principal quantum number.
• For main-group elements, the number of valence
electrons is given by the “A group” number.
Lewis Dot Symbol:
- An element symbol is surrounded by a number of dots
equal to the number of valence electrons.
Rules:
• The dots are placed to the right of the symbol, to the
left, above and below.
• Dots are added one at time until all valence electrons
are represented.
• If there are more than 4 valence electrons, dots are
paired with ones already there
Core electrons
- Are electrons in filled inner shells and subshells
of an atom
- Includes all those electrons with lower values
of n
Practice Exercises:
Write the electron configuration, condensed
electron configuration, valence electron, and
Lewis dot structure of the following elements:
1. Bromine
2. Xenon
3. Barium
• Trends in Three Atomic Properties.

Atomic properties reflect the central importance of

electron configuration and effective nuclear charge;
atomic size, ionization energy, and electron affinity.
These properties are “periodic”, which means they
generally exhibit consistent change, or trends within a
group or period.
• Trends in Atomic Size
Atomic size
- Often represented by “spherical contours in which the
electrons spend 90% of their time.
- is the extent of the contour in terms of how, closely
one atom lies next to another.
- We measure the distance between atomic nuclei in a
sample of an element and divide that distance in half.
- An elements atomic size varies slightly from substance
to substance.
- SI unit: pm (picometer) = 10⁻ˡ²m
Common Definitions of Atomic Size:
1. Atomic radii (mostly metals)
- Is the radius of a sphere that represents an atom.
198 pm Half the distance
between the atomic
nuclei

• •
Cl Cl
If atoms in a chemical
bond are assumed to be
spheres that just
96 pm touched, then the radius
of an atom ….

• it is one-half the shortest distance between nuclei of

adjacent, individual atoms in a crystal
Trend Analysis:
• Atomic radii increases (main-group elements) going
down in a group in the periodic table and decreases
going across a period.
3 Important Effects:
1. Atomic radii increases from the top to bottom of a group in the
PT, because electrons occupy atomic orbitals that are
successively larger as the value of (n), the principal quantum
number increases.
2. There is a large increase in AR going from any noble-gas atom to
the following group 1A atom, where the outmost electron is
assigned to the next larger shell (higher n value). Example;
compare the AR of Ne (68pm) and Na (191pm).
3. AR decreases from left to right across a period.
• Atomic radii (transition metals) change very little across
a period especially group 5B (Nb and Ta).
• The nearly identical radii of the 5th and 6th –period
transition elements lead to difficult problems in
separating them from one another. (Rn, Os, Rh, Ir, Pd,
and Pt) are called “platinum-group metals” because
they occur together in nature.
2. Covalent radii (used for elements occurring as
molecules , mostly nonmetals).
- one-half the shortest distance between nuclei of
bonded atoms. 177pm
Distance between nuclei C – Cl bond
Cl – Cl bond
• •
199 pm

• •
77pm 100pm
Covalent radius Covalent radius

Cl – Cl bond 100 pm Covalent radius

Radii measured for some elements are used to determine the
radii of the other elements from distances between atoms in
compounds.
Example: Carbon – Chlorine compound
The distance between nuclei in a C – Cl bond is 177 pm. Using the
known covalent radius of Cl (100pm), we find the covalent radius
of C (177pm – 100pm = 77pm).
3. Ionic radii
- Is the radius of a sphere representing a positive or negative
sign.
- A consistent set of ionic radii can be determined from the
distances between adjacent positive (+) and negative (-) ions in
a crystalline ionic solids.
Trend Analysis:
• In the same periodic group, cations increase in size
down the group.
• The radius of the cation is always smaller than the radius
of the neutral atom from which the cation is formed.
• When an atom form more than one cation, the larger
the charge is, the smaller the ion is.
Note:
• The radius of a “cation” is always “smaller than the
radius of the neutral atom from which the cation is
formed
• The radius of “anion” is always “larger” than the radius
of the neutral atom from which the anion is formed.
Comparison of Sizes of Atoms and Positive and Negative
Ions.
Li atom Li⁺ cation F atom F⁻ anion
(r=157pm) (r=90pm) • (r=72pm) (r=119pm)

Li Li⁺ F
• F⁻
• •
•
72pm

157pm 90pm 199pm

1s²,2sˡ 1s² 1s²,2s²,2p⁵ 1s²,2s,2p⁶

Protons 3⁺ Protons 3⁺ Proton 9⁺ Protons 9⁺

Electron 3⁻ Electrons 2⁻ Electrons 9⁻ Electrons 10⁻

net charge 0 net charge 1⁺ net charge 0 net charge 1⁻

Main Group Elements:
Among the main-group elements, atomic size varies
within both groups and periods as a result of opposing
influences.
1. Changes in n
As the principal quantum number (n) increases, the
probability that outer electrons spend most of their time
farther from the nucleus increases as well. Thus, atomic
size increases.
2. Changes in Zeff (is the positive charge on the nucleus)
As the effective nuclear charge (Zeff) increases, outer
electrons are pulled closer to the nucleus. Thus atomic
size decreases.
The net effect of these influences depends on how
effectively the inner electrons shield the increasing
nuclear charge.

Down a group n dominates

• Atomic radius generally increases down a group.
Across a period Zeff dominates
• Atomic radius generally decreases across a
period.
Transition Elements:
Atomic size trend are not as consistent for the transition
elements.
1. Down a transition group n increases
But shielding by an individual level of inner electrons result
in only a small size increase from Period 4 to 5 and none
from 5 to 6.
2. Across a transition series
Atomic size shrinks through the first two or three elements
because of the increasing nuclear change. But from then
on, size remains relatively constant because shielding by
the inner d electrons counteracts the increase in Zeff.
Example: In Period 4, the 3rd transition element Vanadium
(V: Z = 23) , has the same radius as te last, Zinc (Zn: Z = 30).
This pattern also appears in Periods 5 and 6 in the
transition and both inner transition series.
3. Transition series affects atomic size in neighboring
main group.
Shielding by d electrons causes a major size “decrease”
from Group 2A(2) to 3A(13) in Period 4 through 6.
The greatest decrease occurs in Period 4 Calcium (Ca: Z =
30) in Group 2A(2) is nearly 50% larger than Gallium (Ga: Z
= 31) in 3A(13). In fact, d orbital shielding causes gaalliu to
be slightly smaller than Aluminum (Al: Z = 13), the element
above it.
Atomic Radii of the Main group and Transition elements.
1A 2A 3A 4A 5A 6A 7A 8A
1 H 37 He 31

2 Li 152 Be 112 B 88 C 77 N 75 O 73 F 72 Ne 71
3 Na 186 Mg 160 Al 143 Si 118 P 110 S 103 Cl 100 Ar 98
4 K 227 Ca 197 Ga 135 Ge 122 As 120 Se 119 Br 114 Kr 112
5 Rb 248 Sr 215
In 167 Sn 140 Sb 140 Te 142 I 133 Xe 131
6 Cs 265 Ba 222
Ti 170 Pb 146 Bi 150 Po 168 At 168 Rn 140
7 Fr 270 Ra 220

3B 4B 5B 6B 7B 8B 1B 2B
8 9 10
Sc 162 Ti 147 V 134 Cr 128 Mn 127 Fe 126 Co 125 Ni 124 Cu 128 Zn 134

4
Y 180 Zr 160 Nb146 Mo Tc 136 Ru 134 Rh 134 Pd 137 Ag 144 Cd 151
5 139

6 La 187 Hf 159 Ta 146 W 139 Re 137 Os 136 Ir 136 Pt 138 Au 144 Hg 151
Practice Exercise:
Rank the following Elements in Order of by its decreasing
Atomic size.
1. Ca, Mg, Sr
2. K, Ga, Ca
3. Br, Rb, Kr
4. Sr, Ca, Rb
• Trends in Ionization Energy
IE (ionization energy)
- Is the energy required for the “complete removal of 1
mol of electrons from 1 mol of gaseous atoms or ions.
- Pulling an electron away from the nucleus requires
energy to overcome their electrostatic attraction.
- Because energy flows into the system, the IE is “always
positive”.
- Is the key factor in an element’s reactivity.
• Atoms with low IE tend to form cations during reaction
• Atoms with high IE (except noble gases) tend to form
anions during reaction.
• The first IE (IE1) removes an outermost electron (highest
energy sublevel) from a gaseous atom.
Atom ion⁺(g) + e⁻ 𝛥E = IE1 ˃ 0
• The second IE (IE2) removes a second electron. Since
this electron is pulled away from a positive ion, IE2 is
always lager than IE1.
Ion⁺(g) ion²⁺(g) + e⁻ 𝛥E = IE2 (always ˃ IE1)
Group Trends and their Exemptions:
1. Down a group
As we move down a main group, the n value increases, so
atomic size does as well. As the distance from the nucleus
to outer electron increases, their attraction lessens, so
electron is easier to remove.
• IE generally “decreases” down a group.
• Exemption: Groups 3A (13) IE decreases from Boron (B)
to Aluminum (Al) bu not for the rest of the group.
2. Across a period
As we move left to right across a period Zeff increases and
atomic size decreases. The attraction between nucleus and
outer electrons increases, so the electron is harder to
remove.
• IE generally “increases” across a period.
• Exemptions: Periods 2 and 3, there are dips at the Group
3A ((13) elements B and Al.
Periods 2 and 3, there are dips at Group 6A (16)
elements. Oxygen (O) and sulfur (s)
Practice Exercises:
Rank the following elements in each set in order
of decreasing IE.
1. Kr, He, Ar
2. Sb, Te, Sn
3. K, Ca, Rb
4. I, Xe, Cs
• Trends in Electron Affinity
EA (Electron Affinity)
- Is the energy charge when an electron is added to a
gaseous atom to form 1 – ion
- Is a measure of the attraction an atom has for an
additional electron.
F(g) + e⁻ F⁻(g) 𝛥E = EA = -328 kJ/mol
(He)2s²,2p⁵ (He)2s²,2p⁶

• The first electron is “attracted” by the nucleus, in most

cases EA is negative (energy is released).
• The second EA (EA2) is always positive because energy
must be absorbed.
 Ne + e⁻ Ne⁻ 𝛥E = +120 kJ/mol
(He)2s²,2p⁶ (He)2s².2p⁶,3sˡ
Down a group
We might expect a smooth decrease (smaller negative
number)down a group because size increases, and the
nucleus is farther away from an electron being added .
Only in group 1A (1) exhibits this behavior.
Across a period
We might expect a regular increase (larger negative
number) across a period because size decreases and
higher Zeff should attract the electron being added more
strongly. There is an over-all left to right increase, but it
is not all regular.
EA by Periodic Table Group (kJ/mol)

1A 2A 3A 4A 5A 6A 7A 8A
H He
-73 +50
Li Be B C N O F Ne
-60 +50 -27 -122 +70 -141 -328 +120
Na Mg Al Si P S Cl Ar
-53 +40 -43 -134 -72 -200 -349 +96
K Ca Ga Ge As Se Br Kr
-48 +96 -30 -120 -78 -195 -325 +96
Rb Sr In Sn Sb Te I Xe
- 47 -5 -30 -120 -103 -190 -295 +80
Three General Patterns of IE and EA:
1. Reactive nonmetals
Members of group 6A(16) and especially group 7A (17)
The halogens have high IEs and highly negative
(exothermic)EAs: these elements lose electrons with
difficulty but attract them strongly. Therefore in their ionic
compounds, they form negative ions.
2. Reactive metals
Members of group 1A (1) and 2A (2) have low IEs and
slightly negative (exothermic) EAs: they lose electrons
easily but attract them weakly. Therefore in their ionic
compounds, they form negative ions.
3. Noble gas
Members of group 8A(18) have very high IES and slightly
positive (endothermic) EAs: they tend not to lose or gain
electrons . In fact, only the larger members of the group
( Kr, Xe, and Rn) form compounds at all.
Summary: AS, IE, EA