CHY 40

ATOMIC STRUCTURE

The Atomic Theory of Matter

Democritus (460–370 BC) - All matter can be divided into indivisible atomos.

John Dalton - proposed atomic theory with the following postulates:

1. Elements are composed of atoms.
2. All atoms of an element are identical.
3. In chemical reactions atoms are not changed into different types of atoms. Atoms are neither created nor destroyed.
4. Compounds are formed when atoms of elements combine.

Atoms are the building blocks of matter.

Laws of Chemical Combination

1. Law of Constant Composition
The relative kinds and numbers of atoms are constant for a given compound. A compound always has the same formula.

2. Law of Conservation of Mass

During a chemical reaction, the total mass before reaction is equal to the total mass after reaction. Conservation means
something can neither be created nor destroyed. Here, it applies to matter.

3. Law of Multiple Proportions

If two elements A and B combine to form more than one compound, then the mass of B which combines with the mass of A
is a ratio of small whole numbers.

The Discovery of Atomic Structure

By 1850 scientists knew that atoms consisted of charged particles.
Subatomic particles (protons, electrons, and neutrons) - particles that make up the atom.

Cathode Rays and Electrons

Figure 1. The cathode ray tube

Cathode rays first discovered in mid-1800s from studies of electrical discharge through partially evacuated tubes (cathode ray
tubes or CRTs). Cathode rays are radiations produced when high voltage is applied across the tube. The voltage causes
negative particles to move from the negative electrode (cathode) to the positive electrode (anode). The path of the electrons
can be altered by the presence of a magnetic field. Consider cathode rays leaving the positive electrode through a small hole. If
they interact with a magnetic field perpendicular to an applied electric field, then the cathode rays can be deflected by different
amounts. The amount of deflection of the cathode rays depends on the applied magnetic and electric fields.

J. J. Thomson (1897) - demonstrated that cathode rays are composed of tiny, negatively charged subatomic particles called
electrons.

Millikan oil-drop experiment - performed to determine the charge on the electron to subsequently determine it’s mass.

Figure 2. Millikan oil-drop experiment setup

Oil drops are sprayed above a positively charged plate containing a small hole. As the oil drops fall through the hole they
acquire a negative charge. Gravity forces the drops downward. The applied electric field forces the drops upward. When a drop
is perfectly balanced, then the weight of the drop is equal to the electrostatic force of attraction between the drop and the
positive plate. Millikan carried out the above experiment and determined the charges on the oil drops to be multiples of 1.60 x
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10–19 C. He concluded the charge on the electron must be 1.60 x 10–19 C. Knowing the charge to mass ratio of the electron, we
can calculate the mass of the electron:

1.60x10 −9 C
Mass = = 9.10x10 − 28 g
1.76x108 C / g

Radioactivity - the spontaneous emission of radiation.

Consider the following experiment:
A radioactive substance is placed in a lead shield containing a small hole so that a beam of radiation is emitted from the shield.
The radiation is passed between two electrically charged plates and detected.

Figure 3 Particles produced by a radioactive substance

Three spots are observed on the detector:

1. A spot deflected in the direction of the positive plate.
2. A spot that is not affected by the electric field.
3. A spot deflected in the direction of the negative plate.

• A large deflection towards the positive plate corresponds to radiation that is negatively charged and of low mass. This is
called -radiation which consists of electrons.
• No deflection corresponds to neutral radiation. This is called -radiation that is similar to X-rays.
• A small deflection toward the negatively charged plate corresponds to high mass, positively charged radiation. This is called
-radiation, positively charged core of a helium atom.
• X-rays and  radiation are true electromagnetic radiation, whereas - and -radiations are actually streams of particles -
helium nuclei and electrons, respectively.

Eugene Goldstein (late 1880) - canal rays are composed of positively charged subatomic particle which was found to be
protons (p+).

James Chadwick (1935) - discovered the neutron (n0), the neutral subatomic particle.

The Nuclear Atom

1. J. J. Thomson’s Model of the Atom (1900) - Plum Pudding Model
The Thomson model pictures the atom as a sphere with small electrons embedded in a positively charged mass called
protons.

Figure 4. The plum pudding model of the atom

2. Rutherford’s Model of the Atom (1910)

Rutherford carried out the gold foil experiment (Figure 5) wherein a source of -particles was placed at the mouth of a
circular detector. The -particles were shot through a piece of gold foil. Both the gold nucleus and the -particles are
positively charged, so they repel each other.

Observations:
• Most of the -particles went straight through the foil without deflection.
• Some -particles deflected or bounce back.
• If the Thomson model of the atom was correct, then Rutherford’s result was impossible.

Rutherford modified Thomson’s model as follows:

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1. Assume the atom is spherical, but the positive charge must be located at the center with a diffuse negative charge
surrounding it.
2. In order for the majority of -particles that pass through a piece of foil to be undeflected, the majority of the atom must
consist of low mass, diffuse negative charge - the electron.
3. To account for the small number of large deflections of the -particles, the center or nucleus of the atom must consist of a
dense positive charge – the proton.

Figure 5. Rutherford’s gold foil experiment setup

Figure 6. Modern view of the structure of the atom

The atom consists of positive, negative and neutral entities (protons, electrons and neutrons). Protons and neutrons are located
in the nucleus of the atom which is small. Most of the mass of the atom is due to the nucleus. Electrons are located outside of
the nucleus. Most of the volume of the atom is due to electrons.

The quantity 1.602 x 10–19 C is the electronic charge. The charge on an electron is -1.602 x 10–19 C, the charge on a proton is
+1.602 x 10–19 C and the neutrons are uncharged. Atoms have an equal number of protons and electrons thus they have no net
electrical charge.

Masses are so small that we define the atomic mass unit, amu where 1 amu = 1.66054 x 10–24 g. Hence, the mass of a
proton is 1.0073 amu, a neutron is 1.0087 amu, and an electron is 5.486 x 10–4 amu.

The angstrom is a convenient non-SI unit of length used to denote atomic dimensions. Since most atoms have radii around 1 x
10–10 m, we define 1 Å = 1 x 10–10 m.

Table 1. Properties of Protons, Neutrons, and Electrons

Subatomic
Charge Location Mass (amu)
Particle
proton +1 inside nucleus 1.00728
neutron 0 inside nucleus 1.00866
electron -1 outside nucleus 0.00055

Isotopes, Atomic Numbers, and Mass Numbers

All atoms of a specific element have the same number of protons.
Isotopes of a specific element differ in the number of neutrons.
Atomic number (Z) = number of protons in the nucleus.
Mass number (A) = total number of nucleons in the nucleus (protons + neutrons).
A
By convention, for element X, we write, z X .
Thus isotopes have the same Z but different A. There can be a variable number of neutrons for the same number of protons.
Isotopes have the same number of protons but different numbers of neutrons. An atom of a specific isotope is called a
1 2 3
nuclide. Examples of nuclides include that of hydrogen namely 1 H = hydrogen (protium); 1 H = deuterium, and 1 H =
tritium.
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The nucleus of an atom (containing protons and neutrons) remains unchanged after ordinary chemical reactions but atoms
can readily gain or lose electrons. Ions are the species formed when an atom either losses or gains electrons.

EXERCISE 1
Complete the following table:
No. of No. of No. of Net
Symbol Atomic no. Mass no.
electrons protons neutrons charge
23
11 Na
11 10 12
80 35 -1
47 46 60
33 42 -3
40
20 Ca
19 18 20
127 53 -1

The Wave Nature of Light

Light travels through space as a wave - a disturbance that transmits energy through a medium.

Electromagnetic radiation - a form of energy transmission through vacuum or a medium in which electric and magnetic
fields are propagated as a wave. It carries energy through space and is therefore also known as radiant energy.

Figure 7. The electromagnetic spectrum

Visible region - portion of the electromagnetic spectrum within the wavelength range of 400 - 750 nm that we can perceive as
color.

Waves have the following characteristics:

1. Wavelength,  - distance between two identical points of the wave
2. Frequency, ν - the number of troughs or crest that passes through a given point per unit of time.
3. Amplitude, A - relates to the intensity of radiation.

Figure 8. Characteristics of a wave

Relationship between Wavelength and Frequency

 = c where: c (speed of light) = 3.0 x 108 m/s

When light is passed through a transparent medium such as a prism, the “white” light is refracted or dispersed into an unbroken
or continuous band or spectrum of colors as a rainbow - ROYGBIV.

Classical Descriptions of Matter

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John Dalton (1803) - atoms are hard, indivisible particles. Atoms have distinct masses that distinguish one type of atom from
another. All atoms of same element are the same.

J.J. Thomson (1890s) - discovered charge-to-mass ratios of electrons; atoms are divisible because the electrons are one part
of atom.

Ernest Rutherford (1910) - shot positive alpha particles at a thin foil of gold from which he discovered the atomic nucleus.

James Maxwell (1873) - visible light consists of electromagnetic waves.

Transition between Classical and Quantum Theory

Max Planck (1900) - noted matter did not emit energy in continuous bursts but in whole-number multiples of certain well-
defined quantities.

Quantum theory - Matter absorbs or emits energy in bundles or “quanta.” Radiant energy is quantized, it is limited to
a discrete set of specific values. The smallest amount of energy that can be emitted or absorbed as electromagnetic radiation is
called quantum.

Photoelectric effect (Albert Einstein, 1905) - a beam of electrons is produced when light strikes a clean metal surface.

Figure 9. The photoelectric effect

Observations:
• When a light strikes the metal, its energy is transferred to an electron in a metal. A certain minimum amount of energy,
threshold energy, is required for an electron to overcome the attractive forces that hold it within the metal.
• If the light has a less energy than the threshold energy, the electron cannot escape from the surface of the metal even if
the light beam is intense.
• If the light has more energy than the minimum requirement to free an electron, the excess appears as the kinetic energy of
the emitted electron.

To explain the photoelectric effect, Einstein assumed that the radiant energy striking the metal surface is a stream of tiny
energy packets. Each energy packet behaves like a tiny particle of light which is called a photon having a characteristic energy
E = hν. Light exists as a stream of “particles” called photons.

Energy is proportional to the frequency, ν, and wavelength, λ, of radiation, and the proportionality constant h which is called
Planck's constant.
c
E = h = h where: h = 6.63 x 10-34 Js

Radiant energy may be considered to consist of fluctuating electric and magnetic fields which travel through space in a wavelike
motion. It may be described in two ways:
1. Waves of photons - possessing wave-like properties.
2. Stream of photons - possessing particle-like properties.

Dual nature of matter (Louis de Broglie) - The electron can be imagined as both particle (it has mass) and a wave (it
moves rapidly) and either of these two natures can become predominant at a given time.

If light can behave like a wave and a particle, matter also (electron) can behave like waves. If electron behaves like a standing
wave, it can only have specific wavelengths and specific frequencies and thus, energies:

For wave: E = mc 2
For matter: E = h
Combining the two equations, we can solve for the wavelength for any matter.
h
De Broglie relation: = where: m = mass in kg
m
ν = velocity m/s

This relation is true for all matter whether microscopic or macroscopic.

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Illustration:
1. A baseball with a mass of 0.143 kg is thrown towards a batter at a velocity of 42.5 m/s.
a. Calculate the wavelength in m associated with the baseball’s motion.
6.63x10 −34 Js
= = 1.89x10 −34 m
(0.143kg)(42.5m / s)

b. How does the wavelength compare in size to the baseball (diameter = 0.08 m)?
The baseball’s wavelength is very much less than its diameter.

2. Calculate the wavelength in m associated with an electron traveling at the same velocity. (The mass of the electron is
9.1095 x 10-31 kg.)
6.63x10 −34 Js
= = 1.71x10 −5 m
(9.1095x10 −31 kg)(42.5m / s)

The wavelength of the electron is much larger than its diameter.

Thus, although all matter can have wave properties, such properties are only significant for microscopic
particles.

Bohr model of a hydrogen atom (Neils Bohr, 1913) - The electron of the atom can exist only in certain circular orbits
around the nucleus in certain specific radii.

“Tennis ball and stairs” analogy for electrons and energy levels, respectively - a ball can bounce up to or drop from one stair to
another but it can never be halfway between two levels.

According to the Bohr’s model:

1. The electron has a definite energy characteristic of the orbit in which it is moving (like the planetary model of the solar
system).
2. When the electron of an atom is as close to the nucleus as possible, it is in a state of lowest possible energy called the
ground state. The ground state is the lowest energy state for atom when the electron is in most stable orbit.
3. When the atom absorbs energy, an electron can jump from a lower energy level to a higher energy level. The electron is
said to be in the excited state when the electron is in a higher energy orbit (n = 2, 3, 4, etc.).
4. When an electron falls back to the lower level, it emits a definite amount of energy in the form of a quantum of light.

Limitations of the Bohr Model - Quantum Mechanical Model

Unfortunately, the Bohr Model failed for all other elements that had more than one proton and one electron. (The multiple
electron-nuclear attractions, electron-electron repulsions, and nuclear repulsions make other atoms much more complicated
than hydrogen.)

In 1920s, a new discipline, quantum mechanics, was developed to describe the motion of submicroscopic particles confined
to tiny regions of space. Quantum mechanics makes no attempt to specify the position of a small particle at a given instant or
how the electron got there. It only gives the probability of finding small particles - just like taking snapshot of a location and
estimating where greatest number of people is likely to be, it takes a snapshot of the atom at different times and “see” where
the electrons are usually found.
Heisenberg’s uncertainty principle - It is impossible to determine accurately both the exact position and momentum of a
particle simultaneously.

Erwin Schrödinger (1926) - developed a differential equation that allows us to find the electron's wave function, ψ which
ultimately allows us to determine the probability of finding the electron in a given place.

Probability density for an electron - called the “electron cloud” which dictates the shape of the area where the electron
resides. Regions where there is a high probability of finding the electron are said to be regions of high electron density.

Schrodinger equation - describes an electron in an atom by a mathematical expression called a wave function, .
It determines the following:
1. The shape of the orbital the electron occupies
2. The energy of the electron in the orbital
3. The probability of finding the electron in some region

The complete solution to Schroedinger’s equation yields a set of wave functions called orbitals and their corresponding
energies. Each orbital describes a specific distribution of electron density in space.

Quantum numbers - dimensionless numbers which completely describe the state of an electron. Four quantum numbers
describe distribution and behavior of electrons in atoms. Each wave function, ψ, corresponds to a set of three quantum numbers
and is referred to as an atomic orbital.

The four quantum numbers:

1. Principal quantum number, n - describes the distance between the nucleus and the shell. A shell is the level to
which the electrons belong - as n increases, on the average, the electron is found farther out of the nucleus. It also
describes the energy level of the shell - as n increases, the energy of the electron increases and is therefore less tightly
bound to the nucleus.
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The principal quantum number, n can have integral values 1, 2, 3, etc.

The number of electrons that can be accommodated in a given shell is equal to 2n2.

2. Azimuthal quantum number, l - defines the shape of the orbital. It describes the energy level of the subshells. The
number of subshells in a shell is equal to n.
It has any integral value starting from 0 → (n - 1).

Table 2. Azimuthal quantum number values

l values Symbol No. of orbitals Shape
0 s 1 spherical
1 p 3 dumbbell
2 d 5 four-lobe
3 f 7 eight-lobe

s orbital

p orbitals

d orbitals

f orbitals

Figure 10. Shapes of the s, p, d, and f orbitals, respectively

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Each subshell consists of a set of orbitals. All the orbitals in the same subshell have the same energy. So within a given
shell, the energies of electrons in the orbitals increase in the following order: ns < np < nd < nf.

c. Magnetic quantum number, ml - determines the spatial orientation of an orbital (the axes/planes to which the orbital is
oriented). It has an integral value of +l, … 0, … ,-l.

d. Spin quantum number, ms - describes the direction of spin of an electron about its own axis: counterclockwise, ms = -
½; and clockwise, ms = +½.
Electrons with the same spin quantum numbers are said to have parallel spins while those with different ms values
are said to have opposite spins.

Table 3. Relationship among n, l, ml values through n = 4

No. of Total no. of
l Subshell
n ml values orbitals in orbitals in
values designation
subshell subshell
1 0 1s 0 1 1
2 0 2s 0 1
1 2p 1, 0, -1 3 4
3 0 3s 0 1
1 3p 1, 0, -1 3
2 3d 2, 1, 0, -1, -2 5 9
4 0 4s 0 1
1 4p 1, 0, -1 3
2 4d 2, 1, 0, -1, -2 5
3 4f 3, 2, 1, 0, -1, -2, -3 7 16

EXERCISE 2
1. a. What is the designation for the subshell with n = 5 and l = 1?
b. How many orbital are in this subshell?
c. Indicate the ml values for each of these orbitals.
2. What is the maximum number of electrons that can occupy each of the following subshells:
a. 3d c. 2p
b. 4s d. 5f
3. Give the subshell designation for:
a. n = 3, l = 1 c. n = 2, l = 0
b. n = 6, l = 2 d. n = 4, l = 3
4. Give the complete set of quantum numbers for the following:
a. 2p2 d. 4s1
b. 3d 4
e. 5f3
c. 4p 6
f. 5d9

Electronic Configuration of an Atom

Electronic configuration - the arrangement of electrons in the orbital of an atom.
It is described by:
a. a number that designates the number of principal shell
b. a letter that designates the subshell (orbital)
c. a superscript that designates the number of electrons in that particular subshell (orbital)
e.g. 2p4 indicates 4 electrons in the p subshell of the 2nd shell
3d8 indicates 8 electrons in the d subshell of the 3rd shell

Guidelines:
1. Aufbau (building-up) principle
Electrons are distributed in orbitals of increasing energy levels where the lowest energy orbitals are filled first. Once an
orbital has the maximum number of electrons it can hold, it is considered “filled.” Remaining electrons must then be placed
into the next highest energy orbital, and so on.
The orbitals in order of increasing energy:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p

Figure 11. The Aufbau principle

2. Pauli’s exclusion principle - No two electrons in the same atom can have the same set of four quantum numbers. That
is, the maximum number of electron in an orbital is limited to two and the two electrons in the same orbital must have
opposite spins.
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For 1s orbital: one electron: n = 1, l = 0, ml = 0, ms = +½

another electron: n = 1, l = 0, ml = 0, ms = -½

For example, with the helium atom, there are three ways to represent two electrons in 1s orbital (where spin is represented

with the electron pointing up or down):

But the Pauli exclusion principle rules out (a) and (b) since these show two electrons in the same orbital with the same spin.

An orbital can hold a maximum of two electrons:

• An s orbital can hold up to 2 electrons.
• A set of p orbitals can hold up to 6 electrons.
• A set of d orbitals can hold up to 10 electrons.
• A set of f orbitals can hold up to 14 electrons.

3. Hund’s rule - Every orbital in a subshell (degenerate orbitals - same energy) is occupied with one electron first before
any one orbital is doubly-filled and all electrons in singly-occupied orbitals have the same spin.
The most stable arrangement of electrons in subshells has the greatest number of parallel spins.
To do this, distribute electrons with same spin (up or down) and do not pair electrons until all subshells have an electron.

For example, the electron configuration of carbon is: 1s2 2s2 2p2.
The orbital diagram can be shown in the following ways:

But from Hund's rule, we know (c) would be the most stable.

Orbital diagrams of some elements

Total Orbital diagram Valence
Element Electronic configuration
electrons 1s 2s 2p 3s electrons
H 1  1s1 1
He 2  1s2 2
Li 3   1s2 2s1 1
Be 4   1s2 2s2 2
B 5    1s2 2s2 2p1 3
C 6     1s2 2s2 2p2 4
N 7      1s2 2s2 2p3 5
Ne 10      1s2 2s2 2p6 8
Na 11       1s2 2s2 2p6 3s1 1

Valence electrons - outer shell electrons.

Isoelectronic - atoms or ions of different elements that have the same electronic configuration.
For example, O2-, F-, Ne, Na+, and Mg2+ have a total number of electrons which is equal to 10. If this is so, hence, they have the
same electronic configuration 1s2 2s2 2p6 and are therefore isoelectronic.

Magnetic behavior - the effect of magnetic field on an atom.

1. Diamagnetism - atoms with completely paired electrons which are slightly affected by magnetic field.
2. Paramagnetism - atoms with unpaired electrons which are greatly affected by magnetic field.

EXERCISE 3.
1. Give the electronic configuration of the following elements:
a. Ca d. Mo
b. Al e. As
c. Sr
2. Determine whether the following elements are diamagnetic or paramagnetic by drawing the orbital diagram of the valence
shell. Determine also the number of valence electrons.
a. O d. Zn
b. Br e. Mg
c. Ti
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Exceptions to the Building-Up Principle

Atoms gain extra stability when their d subshells are half-filled or completely filled.
If we can fill or half-fill a d subshell by promoting an electron from an s orbital to a d orbital, we do so to gain the extra stability.

For example, chromium has a total number of electrons equal to 24. Its electron configuration is 1s2 2s2 2p6 3s2 3p6 4s2 3d4
and an orbital diagram as follows:

However, chromium assumes a more stable configuration by promoting one 4s electron to the 3d subshell to attain half-filled
stability. Its actual configuration becomes 1s2 2s2 2p6 3s2 3p6 4s1 3d5 with an orbital diagram as shown.

Similarly, silver assumes a more stable configuration by promoting one 4s electron to the 3d orbital via completely filled stability.
From 1s2 2s2 2p6 3s2 3p6 4s2 3d9, its actual configuration becomes 1s2 2s2 2p6 3s2 3p6 4s1 3d10.

Writing Electron Configurations Using the Periodic Table

The periodic table's shape actually corresponds to the filling of energy sublevels. The numbers on atop the columns in the
following figure gives the ml values of the corresponding subshell. In the first half of the set of ml values, the electrons have
+½ spin quantum number while the on other half, they will assume -½ spins.

Figure 12. The periodic table showing the different sublevels

Abbreviated Electron Configurations

Since noble gases are at the end of each row in the periodic table, all of their electrons are in filled orbitals. Such electrons are
called core electrons since they are more stable (less reactive) when they belong to completely filled orbitals.

Noble gas core notation - noble gas electron configurations can be used to abbreviate the core electrons of all elements.

[He] = 1s2
[Ne] = 1s2 2s2 2p6
[Ar] = 1s2 2s2 2p6 3s2 3p6
[Kr] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
[Xe] = 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6

EXERCISE 4
1. Give the noble gas core notation of the following elements:
a. Fe d. Au
b. Cd e. Y
c. Ni
2. Write the electronic configuration for each of the following atoms or ions. Determine the quantum number describing the
last electron. Identify the number of unpaired electrons and indicate whether paramagnetic or diamagnetic. State the
number of valence electrons.
a. O d. Fe3+
b. Cd e. Cu+
c. Ge 2-
f. Sr
3. Give the set of quantum numbers that describe the 4th electron in the 3p subshell.
4. How many electrons can be placed in
a. shell where n = 3
b. shell with n = 4 before the first electron enters the shell with n = 5
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Development of the Periodic Table

Periodic table - the most significant tool chemists use for organizing and remembering chemical facts. The periodic table
arises from the periodic patterns in the electronic configurations of the elements. Elements in the same column contain the
same number of valence electrons. The trends within a row or column form patterns that help us make predictions about
chemical properties and reactivity.

Dmitri Mendeleev and Lothar Meyer - arranged the elements in order of increasing atomic weight.

Periodic law - When the elements are arranged in order of increasing atomic masses, certain sets of properties recur
periodically.

Henry Moseley - developed the concept of atomic numbers. He identified the atomic number with the number of protons in
the nucleus of the atom and the number of electrons in the neutral atom.

Modern periodic table - an arrangement of the atoms in increasing order of their atomic numbers that collects atoms with
similar properties in vertical columns.

Period/series - elements in a row.

Family/group - elements in a column.

Note that it is the loss, gain, or sharing of valence electrons that determines the reactivity of elements. Hence, the valence
electrons of an atom determine its chemical property.

Periodic Classification of Elements

A. Based on Properties
1. Metals - elements in the left side and in the center of the periodic table. They have lustrous, silvery, appearance, good
conductors of heat and electricity, malleable and ductile, high melting point, lose electrons
In terms of reactivity, metals form basic oxides:
Metal oxide + water → metal hydroxide Na 2 O + H 2 O → 2 NaOH
CaO + H 2 O → Ca (OH ) 2

Metal oxide + acid → salt + water CaO + 2 HCl → CaCl 2 + H 2 O

MgO + 2 HBr → MgBr2 + H 2 O

2. Nonmetals - elements on the right side of the periodic table. They are nonconductors, nonmalleable, nonductile and have
no metallic luster.
On the other hand, nonmetals form acidic oxides:
Nonmetal oxide + water → acid CO2 + H 2 O → H 2 CO3
P4 O10 + 6 H 2 O → 4 H 3 PO4

Nonmetal oxide + base → salt + water CO2 + 2 NaOH → Na 2 CO3 + H 2 O

SO3 + 2 KOH → K 2 SO4 + H 2 O

Nonmetal + metal → salt 2 Al + 3Br2 → 2 AlBr3

2 Na + Cl 2 → 2 NaCl
B. Based on their Electronic Configuration
1. Representative/main group elements - elements in which the last electron added enters an s or p orbital in the
outermost shell but in which this shell is incomplete. They are found in Groups 1A - 7A.

2. Transition elements - elements that have filled or partially-filled inner d subshell. They are found in Groups 1B - 8B.

3. Inner transition elements - elements that have filled or partially-filled inner f subshell. They are otherwise known as the
lanthanoids and actinoids.

4. Noble/inert gases - have filled valence subshell and are thus very stable since they have closed shells (ns2 np6). They
are the elements in Group 8A.

Properties of some groups of elements

1. Group 1A - Alkali Metals
• with typical valence of 1 corresponding to their ns1 electronic structure
• light metals, soft and lustrous but so reactive that they have to be kept from air or moisture (the most reactive metals)
• their hydroxides have an intensive basic or alkaline action, hence members of this family are referred to as alkali
metals

2. Group 2A - Alkaline Earth Metals

• also active metals but generally less reactive than the alkali metals
• has 2 valence electrons (ns2)
• all form chlorides that are water-soluble and carbonates that are water-insoluble
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3. Hydrogen
• a colorless, diatomic gas and the first element in the periodic table
• it does not belong to any family
• has a 1s1 electronic configuration

4. Group 6A - Chalcogens - chalk formers

5. Group 7A - Halogens
• listed in the order of increasing atomic weight, melting and boiling points
• fluorine and chlorine are pale yellow and greenish yellow gases, respectively, bromine is a volatile reddish brown liquid
and iodine is a volatile deep violet solid
• order of increasing activity: iodine < bromine < chlorine < fluorine
• their H compounds are all acids

Periodic variation of properties

Periodicity - trends in the behavior of the elements which arise from the periodic patterns in the electronic configuration of the
elements.

Effective nuclear charge (Zeff) - the net positive charge experienced by an electron on a many-electron atom. It is not the
same as the charge on the nucleus because of the effect of the inner electrons.

The electron is attracted to the nucleus but is repelled by the inner-shell electrons that shield or screen it from the full nuclear
charge. This shielding is called the screening effect. The nuclear charge experienced by an electron depends on its distance
from the nucleus (n) and the number of electrons in the spherical volume out to the electron in question.

For example, for lithium (1s2 2s1) the nuclear charge felt by the lone electron in the 2nd shell is screened by the two electrons
residing in the 1st shell.

Relationships:
1
S As the average number of screening electrons (S) increases, the effective nuclear charge decreases.
Z eff

nS As the distance from the nucleus increases, S increases.

1
n As the distance from the nucleus increases, Zeff decreases.
Z eff

Periodic Trends
1. Atomic size/atomic radius - derived from the distance between atoms when bonded together.
• Within each group - atomic radius increases from top to bottom due to increasing n or number of shells
• Within each period - atomic radius decreases from left to right - with increasing atomic number, the number of protons
increases but the screening electrons remain constant, hence, the effective nuclear charge, Zeff increases and the size
decreases.

Figure 13. Periodic trends in atomic radius

Ionic size - depends on its nuclear charge, the number of electrons it possesses, and the orbitals in which the outer-shell
electrons reside.
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• Cations - generally smaller than the metals from which they were formed. The removal of one or more electrons from the
outermost region of the atom not only vacates the outermost orbitals but also decreases the total electron-electron
repulsions. The atom losses electron(s) but the number of protons remains the same. The effective nuclear charge is
distributed to a lesser number of electrons and each would experience greater attraction to the nucleus. This would
correspondingly decrease the size.
• Anions - generally larger than the nonmetal from which they were formed. The gained electron(s) would reside in the
valence shell causing an increase in electron-electron repulsion. As a result, the electrons spread out more in space.

Figure 14 Comparison between ionic size and atomic radius of parent atom

Isoelectronic series of ions - manifests the effect of varying nuclear charge on ionic radii.

All ions herein are isoelectronic - they have 10 electrons arranged in 1s2 2s2 2p6 electronic configuration like Ne but have
increasing number of protons. Because the number of electrons remains constant, the radius of the ion decreases with
increasing nuclear charge, as the electrons are more strongly attached to the nucleus.

2. Ionization energy (IE) - minimum energy required to remove an electron from the ground state of the isolated gaseous
atom.

First ionization energy (I1) - energy needed to remove the first (outermost) electron.
For the successive removal of 1 electron from magnesium, the following ionization energies are required:
Mg ( g ) ⎯⎯→
I1
Mg + ( g ) + 1e − I1 = 738 kJ/mol
Mg + ( g ) ⎯⎯→ Mg 2+ ( g ) + 1e −
I2
I2 = 1450 kJ/mol
2+ 3+ −
Mg ( g ) ⎯⎯→ Mg ( g ) + 1e
I3
I3 = 7730 kJ/mol
An electron residing in the inner shell is harder to remove than those found in the valence shell. Generally, I1 < I2 < I3.

Table 5. Successive values of ionization energies

Small atoms are expected to have high IE because their valence electrons are nearer and more strongly attracted to the
nucleus.
• Within each group - IE decreases with increasing atomic number due to the increase in size.
• Within each period - IE increases with increasing atomic number due to increase in Zeff.
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Figure 14. Periodic trends in ionization energy

3. Electron affinity (EA) - energy change associated to the addition of an electron to a gaseous atom/ion. An exothermic
process hence, most values are negative.
E
F ( g ) + 1e − ⎯⎯→ F − (g) E = -328 kJ/mol

Large atoms are expected to have low EA because their valence electrons are farther from the nucleus.
Small atoms have high EA because added electron will be closest to the nucleus.

• Within a group - EA decreases from top to bottom.

• Within a period - EA increases from left to right.

Figure 15. Electron affinity values for representative element

4. Electronegativity (EN) - the ability of a bonded atom to attract electrons to itself.

• Within a group - EN decreases from top to bottom.
• Within a period - EN increases across a period.
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Figure16. Periodic trends in electronegativity

5. Metallicity/metallic character
• Within a group - metallicity increases from top to bottom.
• Within a period - metallicity decreases from left to right.

Nonmetallicity/nonmetallic character
• Within a group - nometallic character decreases from top to bottom.
• Within a period - nonmetallic character increases from left to right.

Figure 17. Periodic trends in metallicity

In general, metals have low ionization energy and low electron affinity while nonmetals have high ionization energy and
high electron affinity.

EXERCISE 5
Arrange the following in increasing order of the indicated property:
1. Co+, Co2+, Co3+ Atomic radius 6. Br, Se, Cl Electron affinity
2. S2-, Ar, K+ Atomic radius 7. Al, Cl, P Ionization energy
3. Zn, Br, Ge Metallic property 8. F, Cl, Br Electron affinity
4. Fe, Fe2+, Fe3+ Ionization energy 9. O, As, P Electronegativity
5. Fe3+, Na, Zn2+ Paramagnetism 10. Be, B, Mg Nonmetallic property