CHM 101.

Modern electronic theory of atoms.

Electronic configuration, periodicity, and building up of the periodic table

The modern electronic theory of atoms is a fundamental concept in chemistry and physics that
explains the structure and properties of atoms and essential for grasping various chemical and
physical phenomena, including chemical bonding, periodic trends, and the behavior of electrons
in atoms.

The following Key Components of the Modern Electronic Theory

1. Atomic Structure

The modern electronic theory describes an atom as consisting of three main components:
protons, neutrons, and electrons. Protons and neutrons reside in the nucleus, which is the central
part of the atom. The protons have a positive charge, while the neutrons are neutral. The
electrons, on the other hand, are negatively charged and occupy specific energy levels or shells
around the nucleus. The table below summarizes the properties of these three subatomic
particles.
Name of Particles Symbol Mass (approx.. in Charge
Kg)
Proton P⁺ 1.6 × 10-27 1+
-27
Neutron n, n⁰ 1.6 × 10 none
Electron e⁻ 9.1 × 10-31 1-

The modern theory went further to explain that atoms of one element are the same, while atoms
of different elements are different. The fundamental characteristic that all atoms of the same
element share is the number of protons. All atoms of hydrogen have one and only one proton in
the nucleus; all atoms of iron have 26 protons in the nucleus. This number of protons is so
important to the identity of an atom that it is called the atomic number of the element. Thus,
hydrogen has an atomic number of 1, while iron has an atomic number of 26. Each element has
its own characteristic atomic number.

Atoms of the same element can have different numbers of neutrons, however. Atoms of the same
element (i.e., atoms with the same number of protons) with different numbers of neutrons are
called isotopes. Most naturally occurring elements exist as isotopes. For example, most
hydrogen atoms have a single proton in their nucleus. However, a small number (about one in a
million) of hydrogen atoms have a proton and a neutron in their nuclei. This particular isotope of
hydrogen is called deuterium. A very rare form of hydrogen has one proton and two neutrons in
the nucleus; this isotope of hydrogen is called tritium. The sum of the number of protons and
neutrons in the nucleus is called the mass number of the isotope.

2. Electron Shells and Subshells

Electron shells are the energy levels that electrons occupy around the nucleus. These shells are
further divided into subshells, which are designated by the letters s, p, d, and f. Each subshell has
a specific capacity for electrons, and the arrangement of electrons in these subshells determines
the chemical properties of an element.

Characteristic of Shells

The principal quantum number is denoted by ‘n’. It represents the name, size and energy of
the shell to which the electron belongs. The value of n lies between 1 to ∞.

Shells

The maximum number of electrons present in the shell on the 2n2 rule.

Name of Shell The value of Maximum electrons present (2n2)

‘n’
K 1 2
L 2 8
M 3 18
N 4 32

Subshell

All the electrons having the same shall do not have the same energy. Based on the energy of the
electrons, the shells are divided into sublevels or subshells. Each shell is composed of one or
more subshells, which are themselves composed of atomic orbitals

The subshells are described with the help of Azimuthal quantum numbers (l).
The value of ‘l’ depends upon the value of the shell (n) with which it is associated.
These subshells have been designated as s (l = 0), p (l =1), d (l = 2) and f (l =3) .
The energies of the various subshells in the same shell are in the order s < p < d <f.
The subshell having equal ‘l’ value but with different n values have similar shape but their size
increases as the value of n increases. 2s- subshell is greater in size than 1s- subshell.

The maximum electrons present in a subshell = 2(2l +1).

Number of electrons present in the shell and subshell

Name of Shell The value of ‘n’ Maximum electrons Electrons in the

present (2n2) subshell
K 1 2 1s2
L 2 8 2s2 2p2
M 3 18 3s2 3p6 3d10
N 4 32 4s2 4p6, 4d10, 4f14

3. Orbitals

Orbitals are mathematical descriptions of the probability of finding an electron within a

particular region around the nucleus. The shape and orientation of orbitals depend on the energy
level and subshell that the electron occupies. There are four main types of orbitals: s-orbitals
(spherical), p-orbitals (dumbbell-shaped), d-orbitals (four-leaf clover-shaped), and f-orbitals
(complex shapes).

4. Electron Configuration

Electron configuration refers to the arrangement of electrons in an atom's orbitals. This

arrangement is determined by the Aufbau principle, the Pauli Exclusion Principle, and
Hund's rule. The electron configuration of an atom determines its chemical properties, such as
its reactivity and the types of bonds it can form.

Pauli Exclusion Principle

Pauli's exclusion principle states that no two electrons in an atom can have the same set of
quantum numbers. Quantum numbers describe the energy, shape, and orientation of an orbital, as
well as the spin of an electron. This principle explains why electrons occupy specific orbitals and
why atoms have a limited capacity for electron. The Pauli Exclusion Principle, which
summarizes experimental observations, states that no two electrons in an atom can have the same
four quantum numbers. If one electron in an atom has the quantum numbers n = 1, l = 0, ml = 0,
and ms +1/2, no other electron can have these same quantum numbers. In other words, you
cannot place two electrons with the same value of ms in a 1s orbital. The orbital diagram

Hund’s Rule
This is an empirical rule determining the lowest-energy arrangement of electrons in a subshell.
Hund’s rule states that the lowest-energy arrangement of electrons in a subshell is obtained by
putting electrons into separate orbitals of the subshell with the same spin before pairing
electrons. E.g, the Oxyen atom, whose ground-state configuration is 1s 22s22p4. The first seven
electrons are first placed. The last electron is paired with one of the 2p electrons to give a doubly
occupied orbital. The orbital diagram for the ground state of the oxygen atom is below.
The Building-Up Principle (Aufbau principle) states that electrons occupy the lowest available
energy levels in an atom. This means that electrons will fill the lowest-energy orbitals before
moving to higher-energy orbitals. The Aufbau principle helps explain why atoms tend to gain or
lose electrons to achieve a more stable electron configuration.
The scheme used to reproduce the electron configurations of the ground states of atoms
by successively filling subshells with electrons in a specific order (the building-up order).
Following this principle, you obtain the electron configuration of an atom by successively
filling subshells in the following order: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p,
7s, 5f. etc.

Writing Electron Configurations Using the Periodic Table

There is a definite pattern to the order of filling of the subshells as you go through the elements
in the periodic table, and from this you can write the building-up order. E.g

The 1s orbital, which is the smallest and has the lowest energy, eventually comes first in the
filling order. As a result, the first electron enters the 1s orbital, giving the hydrogen atom its 1s 1
electronic configuration.

The second electron then follows, and since the s orbital can accommodate two electrons, it also
enters the 1s orbital. The electronic configuration is now 1s2 which is thus the inert gas helium.

The atomic number rises by one for every electron that is added because a proton is also added.
The third electron enters the second orbital after the first one is filled, giving the lithium atom,
which is located directly beneath hydrogen in the periodic table, its electronic configuration of
1s2 2s1. Therefore, the same is true for beryllium, 1s2 2s2.

Applications

1. Chemical Bonding

The modern electronic theory of atoms provides a fundamental understanding of chemical

bonding. By understanding how electrons are arranged in atoms, we can explain how
atoms share or exchange electrons to form chemical bonds. This knowledge is essential for
understanding the properties and behavior of molecules.

2. Periodic Trends

The modern electronic theory also explains periodic trends in the periodic table, such as
atomic radius and electronegativity. By understanding how electrons are arranged in
atoms, we can explain why certain elements exhibit specific properties and why these
properties vary across the periodic table.

3. Quantum Mechanics
The modern electronic theory is grounded in quantum mechanics, which provides a
mathematical framework for understanding the behavior of electrons in atoms. Quantum
mechanics explains the probabilistic nature of electron behavior and provides a basis for
understanding the strange and counterintuitive phenomena that occur at the atomic and
subatomic level.

Periodicity

Periodicity is a regular periodic variation of properties of elements with atomic number

and position in the periodic table. This simply means that some elements in the periodic
table have the same properties as other elements in the same column of the periodic table.

The elements are in a certain group and period. Elements in a group (group 1) have similar
properties. Elements in a period have periodicity.

The modern periodic table has evolved through a long history of attempts by chemists to arrange
the elements according to their properties as an aid in predicting chemical behavior.

The first to suggest such an arrangement was the German chemist Johannes Dobereiner
(1780–1849). He noticed that many of the known elements could be grouped in triads, i.e, sets
of three elements that have similar properties. E.g. chlorine, bromine, and iodine. But
subsequent attempts to expand his concept were unsuccessful, because it could only be
applicable to elements that are available a the time. It was however, known that portions of the
periodic table—the d block in particular—contain triads of elements with substantial similarities.
The middle three members of most of the other columns, such as sulfur, selenium, and tellurium
in group 16 or aluminum, gallium, and indium in group 13, also have remarkably similar
chemistry.

By the mid-19th century, the atomic masses of many of the elements had been determined. The
English chemist John Newlands (1838–1898), hypothesizing that the chemistry of the elements
might be related to their masses, arranged known elements in order of increasing atomic mass
and discovered that every seventh element had similar properties. Newlands therefore suggested
that the elements could be classified into octaves Unfortunately, Newlands’s “law of octaves”
did not seem to work for elements heavier than calcium, he also assumed that here are only 56
elements in nature, and when other elements were discovered they did not fit into the law of
octave. His idea was publicly ridiculed. He was later able to do the arrangement elements in
alphabetical order, and found out that, Atomic mass does increase with Atomic number, and
similar properties occur every time a set of ns 2np6 subshell is filled. This also come with few
exception, there no logical place for d-orbital elements.

Newlands noticed that elemental properties repeated every seventh (or multiple of seven)
element, as musical notes repeat every eighth note according to the law of octave.

The periodic table achieved its modern form through the work of the German chemist Julius
Lothar Meyer (1830–1895) and the Russian chemist Dimitri Mendeleev (1834–1907), both of
whom focused on the relationships between atomic mass and various physical and chemical
properties. In 1869, they independently proposed essentially identical arrangements of the
elements. However, Mendeleev’s periodic table came into being in the same year by not
assuming that all the elements had been discovered, he deliberately left blanks in his table at
some atomic masses that could be discovered. By so doing he was able to gain a key difference
in the arrangement of the elements and that of Meyer and other past scientist. More elements
were able to subsequently fit in as they are been discovered using the atomic mass, and
correction were made on previous elements too.
Despite its usefulness, Mendeleev’s periodic table was based entirely on empirical observation
supported by very little understanding. It was not until 1913, when a young British physicist, H.
G. J. Moseley (1887–1915), while analyzing the frequencies of x-rays emitted by the elements,
discovered that the underlying foundation of the order of the elements was by the atomic
number, not the atomic mass. During the analysis, he noticed that the atomic number of argon is
18, whereas that of potassium is 19, which indicated that they were indeed placed correctly.
Moseley also noticed three gaps in his table of x-ray frequencies, so he predicted the existence of
three unknown elements: technetium (Z = 43), discovered in 1937; promethium (Z = 61),
discovered in 1945; and rhenium (Z = 75), discovered in 1925.

The table is split into blocks; in each block the elements are filling, or have just filled,
particular types of orbital.

S block 1 and 2 end in s 1 or s 2

P block 13, 14, 15, 16, 17 and 18 end in p 1 to p 6
D block Transition elements (3-12) end in d 1 to d 10
F block Actinides and Lanthanides end in f

The merits of the modern periodic table:

1. Anomalies in the Mendeleev’s periodic table was corrected.

Mendeleev’s table was based on atomic mass while the modern table is based on atomic number.
This is based on the modern periodic Law, which state that properties of elements are a
periodic function of their atomic number. The Isotopes could be used to explain further.
According to the definition of Isotope, element with same atomic number but different mass
number, they identical chemical properties. Isotopes could not fit into Mendeleev’s table but in
the modern table they fit in because they have the same atomic number.

2. Mendeleev’s table made exception for some certain elements. These are corrected in the
modern periodic table. For example, the position of cobalt and Nickel, Cobalt should
come first because it has a low atomic number as compared to Nickel, because the
modern periodic table is based on atomic number not atomic mass

Some Periodic Properties.

The electron configurations of the atoms display a periodic variation with increasing atomic
number (nuclear charge). As a result, the elements show periodic variations of physical and
chemical behavior. The periodic law states that when the elements are arranged by atomic
number, their physical and chemical properties vary periodically, as such the following
properties are noticeable properties across a period:

Atomic radius, Ionic radius, melting and electrical conductivity, Ionizations energy,
Electronegativity, Electron affinity and boiling point.

Atomic radius

The general trends in atomic radius are that it decreases left to right in a period and that it
increases from top to bottom of a group. Compare any two elements in the same period, or in
the same group, to decide which of the two is smaller. E.g Note that C is above Si in Group 4A.
Therefore, the radius of C is smaller than that of Si (the atomic radius increases going down a
group of elements). Note that Al and Si are in the same period. Therefore, the radius of Si is
smaller than that of Al (radius decreases with Z in a period). Hence the order of elements by
increasing radius is C, Si, Al.

Ionic radius

While the atomic radius measures the size of a neutral atom, the ionic radius gauges the size of
an electrically charged atom. The ionic radius is the radius of a monatomic ion of an element
within an ionic crystal or half the distance between two bonded gas atoms. Ionic radius values
range from 31 pm to over 200 pm. Ionic radius increases as you move from top to bottom on the
periodic table. Ionic radius decreases as you move across the periodic table, from left to right

Summary:

 Atomic and ionic radius increase moving down a group or column of the periodic table.
This is because atoms gain an electron shell.
 Atomic and ionic radius generally decrease moving across a period or row of the periodic
table. This is because the increasing number of protons exerts a stronger attraction to the
electrons, drawing them in more tightly. Noble gases are the exception to this trend. The
size the noble gas atom is larger than the halogen atom that precedes it.
Atomic radius and ionic radius

Atomic radius and ionic radius follow the same trend on the periodic table. But, the ionic radius
may be either larger or smaller than the atomic radius of an element, depending on the electrical
charge. Ionic radius increases with negative charge and decreases with positive charge.

Ionization Energy

The first ionization energy (or first ionization potential) of an atom is the minimum energy
needed to remove the highest-energy (that is, the outermost) electron from the neutral atom
in the gaseous state. (When the unqualified term ionization energy is used, it generally
means first ionization energy.) For the lithium atom, the first ionization energy is the
energy needed for the following process (electron configurations are in parentheses):

Li⁺ (s1s2 2s1) → Li⁺ (1s2) + e⁻

Values of this energy are often quoted for one mole of atoms (6.02 × 10 23 atoms). Thus, the
ionization energy of the lithium atom is 520 kJ/mol. Ionization energies display a periodic
variation when plotted against atomic number, as Figure 8.18 shows. Within any period,
values tend to increase with atomic number. Thus, the lowest values in a period are found
for the Group 1A elements (alkali metals). It is characteristic of reactive metals such as
these to lose electrons easily. The largest ionization energies in any period occur for the
noble-gas elements. In other words, a noble-gas atom loses electrons with difficulty. The
ionization energy is proportional to the square of the effective nuclear charge and increases
going across a period. Ionization energies tend to decrease going down any column of main-
group elements. This is because atomic size increases going down the column.

Electron affinity

The electron affinity of an atom is defined as the energy required to remove an electron from the
atom’s negative ion (in its ground state). Or, if you wish, the electron affinity is the negative of
the energy change obtained when the neutral atom picks up an electron. The quantity is positive
if a stable negative ion forms. A large positive value means that the neutral atom has a strong
affinity for an electron (picks up an electron easily)

When a neutral atom in the gaseous state picks up an electron to form a stable negative
ion, energy is released. For example, a chlorine atom can pick up an electron to give a chloride
ion, Cl ,and 349 kJ/mol of energy is released. We can write this process, including the electron
configurations, as follows:

Cl([Ne]3s23p5) + e– → Cl–([Ne]3s23p6); ∆E = –349 kJ/mol

What is often measured is the energy of the electron detachment from the negative ion, which is
essentially the ionization energy of the negative ion.

Cl–([Ne] 3s23p6) → Cl([Ne]3s23p5) + e–; ∆E = 349 kJ/mol

Electronegativity

Electronegativity is defined as an atom’s ability to attract electrons towards it in a chemical

bond. There are several different ways of measuring it, the most common being the Pauling
scale. Different elements have different electronegativities based on a number of factors such as
size and number of protons, neutrons, and electrons. It is often viewed on an electronegativity
chart of the elements, where trends and values can easily be seen. The higher the
electronegativity, the stronger an atom attracts electrons.

Electronegativity was developed by Linus Pauling, who won the Noble prize twice. Pauling set
the definition of electronegativity as “the power of an atom in a molecule to attract electrons to
itself”. He did not come up with the concept, which was introduced by Jöns Jacob Berzelius in
1811, but he did develop a measurable scale, circa 1935.

On the periodic table, electronegativity generally increases as you move from left to right
across a period and decreases as you move down a group, because of the increasing size of
the atoms. As a result, the most electronegative elements are found on the top right of the
periodic table (e.g fluorine), while the least electronegative elements are found on the bottom left
(Cesium). Halogens are considered to have a high electronegativity, while it is low for the alkali
metals and alkaline earth metals.

Electronegativity is closely related to electron affinity in general, if an element has a high

electronegativity, they it will have a high electron affinity, i.e, the ability to want to hold electron
to itself

Periodicity in the Main-Group Elements

The chemical and physical properties of the main-group elements clearly display periodic
character. For instance, as you move left to right in any row of the periodic table, the metallic
character of the elements decreases. As you progress down a column, however, the elements tend
to increase in metallic character.. These variations of metallic–nonmetallic character can be
attributed in part to variations in the ionization energies of the corresponding atoms.

Elements with low ionization energy tend to be metallic, whereas those with high
ionization energy tend to be nonmetallic. As you saw in the previous section, ionization energy is
a periodic property, so it is not surprising that the metallic–nonmetallic character of an element is
similarly periodic.
The basic–acidic behavior of the oxides of the elements is a good indicator of the
metallic–nonmetallic character of the elements. Oxides are classified as basic or acidic
depending on their reactions with acids and bases.
A basic oxide is an oxide that reacts with acids. Most metal oxides are basic.
An acidic oxide is an oxide that reacts with bases. Most nonmetal oxides are acidic
oxides.
An amphoteric oxide is an oxide that has both basic and acidic properties. In the
following brief descriptions of the main-group elements, we will note the metallic–nonmetallic
behavior of the elements, as well as the basic–acidic character of the oxides. Although elements
in a given group are expected to be similar, the degree of similarity does vary among the groups.
The alkali metals (Group 1A) show marked similarities, as do the halogens (Group 7A). On the
other hand, the Group 4A elements range from a nonmetal (carbon) at the top of the column to a
metal (lead) at the bottom. In either case, however, the changes from one element in a column to
the next lower one are systematic, and the periodic table helps us to correlate these systematic
changes.