Unit III: Classification of Elements and Periodicity in Properties (Periods 8)

Significance of classification, brief history of the development of periodic table, modern periodic law and
the present form of periodic table, periodic trends in properties of elements –atomic radii, ionic radii, inert
gas radii, ionization enthalpy, electron gain enthalpy, electronegativity, valence. Nomenclature of elements
with atomic number greater than 100.

What is an Atom?
Atom, the smallest unit in which matter can be separated without the release of electrically charged
particles. This is also the smallest unit of matter with the characteristic properties of a chemical element.
As such, the atom is the fundamental building block for chemistry.
Example: Ne, O, P, S
Elements: A substance that is made entirely from one type of atom.
What is a Molecule?
A molecule can be defined as the combinations of two or more atoms which are held together by chemical
bonds.
A molecule is the smallest portion of a substance which showcases all the properties of the substance. On
breaking down a molecule further, we see properties of the constituent elements.
Example: O2
Compound: A compound is a substance made from two or more different elements that have been
chemically joined. Some examples of compounds are water (H 2O), table salt (NaCl), table sugar
(C12H22O11) and chalk (CaCO3).

The Nucleus of an atom consists of a tightly packed arrangement of protons and neutrons. These are the
two heavy particles in an atom and hence 99.9% of the mass is concentrated in the nucleus.

The total number of protons in a nucleus is equal to the number of electrons revolving around the nucleus
and hence the atom, on the whole, is electrically neutral.
Effective Nuclear Charge
In a multielctronic atom electrons of the inner shells put a screen of negative charge on the nucleus.
Therefore, outer electrons experience lesser attractive effect of nucleus. The actual nuclear charge an outer
electron experiences is called ‘Effective Nuclear Charge’ (Z*).
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It is given as, Z* = Z – σ, where Z = atomic number, σ = screening (or shielding) constant.
Thus, if σ is known, Z* can be calculated. It is calculated using Stater’s rule.

 The nuclear charge experienced by an electron is reduced by shielding by other electrons. Trends in
effective nuclear charge can be used to rationalize the trends in many properties. As a result of the
combined effects of penetration and shielding, the order of energy levels in a shell of a manyelectron
atom is s < p < d < f.

SHIELDING
The electrons residing in the shells between the nucleus and the valence-shell are called intervening
electrons. These electrons reduce the force of attraction between the nucleus and the outer-most shell
electrons. The reduction produced in the force of attraction due to the presence of intervenining electrons is
called shielding (or screening) effect. With the decrease in the force of attraction caused by the shielding
effect of intervening electrons, the actual nuclear charge (which is equal to the atomic number, Z of the
element) is decreased by the quantity, σ (sigma) which is called screening (or shielding) constant. The
decreased nuclear charge which is obviously equal to (Z- σ) is called effective nuclear charge.
The rules for determining σ = screening (or shielding) constant for a specific electron are as follows:
1. The electronic structure of the atom is written in groupings as follows:
(1s) (2s,2p) (3s,3p) (3d) (4s,4p) (4d) (4f) (5s,5p ~1e,tc .
2. Electrons in higher groups (to the right in the list above) do not shield those in lower groups.
3. For ns or np valence electrons:
a. Electrons in the same ns, np group contribute 0.35, except the 1s, where 0.30 works better.
b. Electrons in the n - 1 group contribute 0.85.
c. Electrons in the n - 2 or lower groups contribute 1.00.
4. For nd and nf valence electrons:
a. Electrons in the same nd or nf group contribute 0.35.
b. Electrons in groups to the left contribute 1.00.
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1. What is the shielding constant experienced by a 2p electron in the nitrogen atom?
Given: Nitrogen (N)
Strategy:
A. Determine the electron configuration of nitrogen, then write it in the appropriate form.
B. Use the appropriate Slater Rule to calculate the shielding constant for the electron.

Solution A N: 1s2 2s2 2p3

N: (1s2) (2s2,2p3)
Solution B
S[2p]=0.85(2) +0.35(4) =3.10

the 1s electrons the 2s and 2p electrons

Z* = Z – σ
=7-3.10=3.9

2. What is the shielding constant experienced by a 4s electron in the iron atom?

Solution A Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2

Fe: (1s2) (2s22p6) ( 3s23p63d6) (4s2)

Solution B
S[2p]= 1.0(10) + 0.85(14) + 0.35(1) =22.25
Z* = Z – σ = 26-22.25=3.75

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Atomic Radius
Finding the size of an atom is a lot more complicated than measuring the radius of a ball. Firstly, because
the size of an atom (~ 1.2 Å i.e., 1.2 × 10–10 m in radius) is very small. Secondly, since the electron cloud
surrounding the atom does not have a sharp boundary, the determination of the atomic size cannot be
precise. In other words, there is practical way by which the size of an individual atom can be measured.
The practical approach to estimate the size of an atom of a non-metallic element is to measure the distance
between two atoms when they are bound together by a single bond in a covalent molecule and from this
value, the “Covalent Radius” of the element can be calculated.
For example, the bond distance in the chlorine molecule (Cl2) is 198 pm and half this distance (99 pm), is
taken as the atomic radius of chlorine.

For metals, we define the term “Metallic Radius” which is taken as half the internuclear distance separating
the metal cores in the metallic crystal.

For example, the distance between two adjacent copper atoms in solid copper is 256 pm; hence the metallic
radius of copper is assigned a value of 128 pm.
Atomic radii can be measured by X-ray or other spectroscopic methods.
Variation of Atomic Radii in the Periodic Table
The atomic size generally decreases across a period as illustrated in Fig. 1 for the elements of the second
period. It is because within the period the outer electrons are in the same valence shell and the effective
nuclear charge increases as the atomic number increases resulting in the increased attraction of electrons to
the nucleus.
Within a family or vertical column of the periodic table, the atomic radius increases regularly with atomic
number as illustrated in Fig. 2. For alkali metals and halogens, as we descend the
groups, the principal quantum number (n) increases and the valence electrons are farther from the nucleus.
This happens because the inner energy levels are filled with electrons, which serve to shield the outer

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electrons from the pull of the nucleus. Consequently the size of the atom increases as reflected in the atomic
radii.

Ionic Radius
The removal of an electron from an atom results in the formation of a cation, whereas gain of
an electron leads to an anion.
The ionic radii can be estimated by measuring the distances between cations and anions in ionic crystals. In
general, the ionic radii of elements exhibit the same trend as the atomic radii.

A cation is smaller than its parent atom because it has fewer electrons while its nuclear charge remains the
same. The size of an anion will be larger than that of the parent atom because the addition of one or more
electrons would result in increased repulsion among the electrons and a decrease in effective nuclear charge.
For example, the ionic radius of fluoride ion (F–) is 136 pm whereas the atomic radius of fluorine is only 64
pm. On the other hand, the atomic radius of sodium is 186 pm compared to the ionic radius of 95 pm for
Na+.
When we find some atoms and ions which contain the same number of electrons, we call them isoelectronic
species.
For example,
O2–, F–, Na+ and Mg2+ have the same number of electrons (10). Their radii would be different because of
their different nuclear charges. The cation with the greater positive charge will have a smaller radius because
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of the greater attraction of the electrons to the nucleus. Anion with the greater negative charge will have the
larger radius. In this case, the net repulsion of the electrons will outweigh the nuclear charge and the ion will
expand in size.
Cations are produced when atoms lose electrons

Anions
When electrons are added to an atom, anion is produced.

In an anion number of electrons is larger than protons. In addition to this Z* of an anion is smaller than its
neutral atom. Therefore, nucleus exerts lesser attractive force on outer electrons and size of an anion is
larger than the neutral atom.

Trends in ionic radii

Irrespective of which set of ionic radii are used, the following trends are observed:
1 . In the main groups, radii increase on descending the group, e.g.
Li+ = 0.76 Å, Na+ = l.02 Å, K+-= l.38 Å, because extra shells of electrons are added.
2. The ionic radii decrease moving from left to right across any period in the periodic table, e.g. Na + = 1.02
Å, Mg2+ = 0.720 Å and Al3+ = 0.535 Å. This is partly due to the increased number of charges on the nucleus,
and also to the increasing charge on the ions.
3. The ionic radius decreases as more electrons are ionized off, that is as the valency increases, e.g. Cr 2+ =
0.80 Å (high spin), Cr3+ = 0.615 Å, Cr4+ = 0.55 Å, Cr5+ = 0.49 Å and Cr6+ = 0.44 Å.

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4. The d and f orbitals do not shield the nuclear charge very effectively.
Thus there is a significant reduction in the size of ions just after 10d or 14f electrons have been filled in. The
latter is called the lanthanide contraction, and results in the sizes of the second and third row transition
elements being almost the same.
Important Conclusions
(i) Among isoelectronic cations, the cation which has highest charge is smallest in size,
Na+, Mg2+, Al+3 (10 es)
rNa+ > rMg2+ > rAl+3

(ii) Among isoelectronic anions, the anion which has highest charge is largest in size.

(iii) Among isoelectronic cation and anion both, radii decreases with increase in nuclear charge.

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Ionization Enthalpy
The ionization energy is defined as the amount of energy required to remove an electron from an isolated
gaseous atom (X) in its ground state.
The first ionization enthalpy for an reaction depicted in equation 1.
X(g) → X+(g) + e– (1)
The ionization enthalpy is expressed in units of kJmol–1.
The second ionization enthalpy as the energy required to remove the second most loosely bound electron; it
is the energy required to carry out the reaction shown in equation 2.
X+(g) → X2+(g) + e– (2)
Energy is always required to remove electrons from an atom and hence ionization enthalpies are always
positive. It is, thus, an endothermic process.
The second ionization enthalpy will be higher than the first ionization enthalpy because it is more
difficult to remove an electron from a positively charged ion than from a neutral atom. In the same
way the third ionization enthalpy will be higher than the second and so on.
For all elements, successive values of IE increases i.e.,
IE1 < IE2 < IE3 < IE4 ………… etc.
It is due to the fact that the removal of each electron decreases number of electrons consequently effective
nuclear charge (Z*) increases, therefore, nuclear attraction on remaining electrons increases successively
resulting into increase in IE.

Ionization energy depends on many factors, viz

(a) Atomic size i.e., distance between the electron and the nucleus,
These factors are usually interrelated. In a small atom the electrons are tightly held, whilst in a larger atom
the electrons are less strongly held. Thus the ionization energy decreases as the size of the atoms increases.
(b) Nuclear charge
The higher the nuclear charge (protons in nucleus), the higher is ionisation potential. Because of the higher
nuclear charge, the electrons are bound with more force and hence higher shall be the energy required for its
removal. Magnesium has higher nuclear charge (12 protons) as compared to sodium (11 proton). Hence
ionisation energy in case of magnesium is higher as compared to sodium.
(c) Nature of orbital from which electron is removed,
The ionization energy also depends on the type of electron which is removed. s, p, d and f electrons have
orbitals with different shapes. An s electron penetrates nearer to the nucleus, and is therefore more tightly
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held than a p electron. For similar reasons a p electron is more tightly held than a d electron, and a d electron
is more tightly held than an f electron. Other factors being equal, the ionization energies are in the order s >
p > d > f. Thus the increase in ionization energy is not quite smooth on moving from left to right in the
periodic table.
(d) Stability of electron configuration.
The atoms whose orbitals are half-filled (p3 ,d5 ,f7) or fully filled (s2, p6, d10, f14) have greater stability than
the other. Therefore, they require greater energy to remove an electron. However, stability of fully filled
orbitals is greater than that of the half-filled orbitals.

Variation of ionization energy in the Periodic Table

(1) IE and Period elements
When we move from lithium to fluorine across the second period, successive electrons are added to orbitals
in the same principal quantum level and the shielding of the nuclear charge by the inner core of electrons
does not increase very much to compensate for the increased attraction of the electron to the nucleus. Thus,
across a period, increasing nuclear charge outweighs the shielding. Consequently, the outermost electrons
are held more and more tightly and the ionization enthalpy increases across a period.

(2) Ionization Energy and Group Elements

In a group, with increase in atomic number, the outermost electron being increasingly farther from the
nucleus, there is an increased shielding of the nuclear charge by the electrons in the inner levels. In this case,

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increase in shielding outweighs the increasing nuclear charge and the removal of the outermost electron
requires less energy down a group.

Important Facts
(a) First IE of Be is greater than the first IE of B
The first ionization enthalpy of boron (Z = 5) is slightly less than that of beryllium (Z = 4) even though the
former has a greater nuclear charge. When we consider the same principal quantum level, an s-electron is
attracted to the nucleus more than a p-electron. In beryllium, the electron removed during the ionization is
an s-electron whereas the electron removed during ionization of boron is a p-electron. The penetration of a
2s-electron to the nucleus is more than that of a 2p-electron; hence the 2p lectron of boron is more shielded
from the nucleus by the inner core of electrons than the 2s electrons of beryllium. Therefore, it is easier to
remove the 2p-electron from boron compared to the removal of a 2s- electron from beryllium. Thus, boron
has a smaller first ionization enthalpy than beryllium.
(b) The first IE of N is greater than Oxygen
The first ionization enthalpy of oxygen is smaller compared to nitrogen. This arises because in the nitrogen
atom, three 2p-electrons reside in different atomic orbitals (Hund’s rule) whereas in the oxygen atom, two of
the four 2p-electrons must occupy the same 2p-orbital resulting in an increased electron-electron repulsion.
Consequently, it is easier to remove the fourth 2p-electron from oxygen than it is, to remove one of the three
2p-electrons from nitrogen.
(c) The first IE of Al and Ga are almost equal (reason, equal radii).
(d) Variation of 1st IE along each transition series is small (reason, small difference in radii).
(e) The first IE of third transition series elements is larger than second transition series elements (reason –
lanthanide contraction).
(f) The change in first IE for lanthanide elements is small (reasons, small change in the radii of lanthanide
elements from Ce to Lu).

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Electron Gain Enthalpy
When an electron is added to a neutral gaseous atom (X) to convert it into a negative ion, the enthalpy
change accompanying the process is defined as the Electron Gain Enthalpy (∆egH).
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to form anion as
represented by equation 1.
X(g) + e– → X–(g)
Depending on the element, the process of adding an electron to the atom can be either endothermic or
exothermic. For many elements energy is released when an electron is added to the atom and the electron
gain enthalpy is negative.
For example, group 17 elements (the halogens) have very high negative electron gain enthalpies because
they can attain stable noble gas electronic configurations by picking up an electron.
On the other hand, noble gases have large positive electron gain enthalpies because the electron has to enter
the next higher principal quantum level leading to a very unstable electronic configuration. It may be noted
that electron gain enthalpies have large negative values toward the upper right of the periodic table
preceding the noble gases.
Exothermic → releases energy → negative energy change.
Endothermic → absorbed energy → positive energy change.

Factors Affecting Electron Affinity

Atomic size or atomic radius: When the atomic size/radius increases, the electrons entering the outermost
orbit is more weakly attracted by the nucleus and the value of electron affinity is lower.
Effective Nuclear charge: When effective nuclear charge is more, then, the atomic size is less. Then, the
atom can easily gain an electron and possess a higher value of electron affinity.
Stability of Fully-Filled and Half-Filled orbitals: The stability of the configuration having fully-filled
orbitals (p6, d10, f14) and half—filled orbitals (p3 ,d5 ,f7) is relatively higher than that of other configurations.
Hence, such type of atoms have a lesser tendency to gain an electron, therefore, their electron affinity values
will be very low or zero.

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Variation of Ea in the Periodic Table
The variation in electron gain enthalpies of elements is less systematic than for ionization enthalpies. As a
general rule, electron gain enthalpy becomes more negative with increase in the atomic number across
a period. The effective nuclear charge increases from left to right across a period and consequently it will be
easier to add an electron to a smaller atom since the added electron on an average would be closer to the
positively charged nucleus.
We should also expect electron gain enthalpy to become less negative as we go down a group because the
size of the atom increases and the added electron would be farther from the nucleus.
Exceptions
(i) The Ea of F is lower than Cl (although Cl is below F in 17th group).
Explanation
The electron gain enthalpy of O or F is less negative than that of the succeeding element. This is because
when an electron is added to O or F, the added electron goes to the smaller n = 2 quantum level and suffers
significant repulsion from the other electrons present in this level. For the n = 3 quantum level (S or Cl), the
added electron occupies a larger region of space and the electron-electron repulsion is much less.

What is the significance of the terms – ‘isolated gaseous atom’ and ‘ground state’ while defining the
ionization enthalpy and electron gain enthalpy?
Ionization enthalpy is the energy required to remove an electron from an isolated gaseous atom in its ground
state. Although the atoms are widely separated in the gaseous state, there are some amounts of attractive
forces among the atoms. To determine the ionization enthalpy, it is impossible to isolate a single atom. But,
the force of attraction can be further reduced by lowering the pressure. For this reason, the term ‘isolated
gaseous atom’ is used in the definition of ionization enthalpy.
Ground state of an atom refers to the most stable state of an atom. If an isolated gaseous atom is in its
ground state, then less amount energy would be required to remove an electron from it. Therefore, for
comparison purposes, ionization enthalpy and electron gain enthalpy must be determined for an ‘isolated
gaseous atom’ and its ‘ground state’.

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Electronegativity (χ, Chi)
The tendency of an atom in a molecule to attract bond pair electrons towards itself is called
electronegativity.
When a covalent bond is formed, the electrons used for bonding need not be shared equally by both atoms.

If the bonding electrons spend more time round one atom, that atom will have a δ- charge, and consequently

the other atom will have at δ+ charge. In the extreme case where the bonding electrons are round one atom

all of the time, the bond is ionic.

The electronegativity of any given element is not constant; it varies depending on the element to which it is
bound. Though it is not a measurable quantity, it does provide a means of predicting the nature of force that
holds a pair of atoms together.
Unlike ionization enthalpy and electron gain enthalpy, it is not a measureable quantity. However, a
number of numerical scales of electronegativity of elements viz., Pauling scale, Mulliken-Jaffe scale,
Allred-Rochow scale have been developed.
Variation of Electronegativity in the Periodic Table
Electronegativity generally increases across a period from left to right (say from lithium to fluorine) and
decrease down a group (say from fluorine to astatine) in the periodic table. The attraction between the outer
(or valence) electrons and the nucleus increases as the atomic radius decreases in a period. The
electronegativity also increases.
On the same account electronegativity values decrease with the increase in atomic radii down a group. The
trend is similar to that of ionization enthalpy.
Generally, small atoms attract electrons more strongly than large ones, and hence small atoms are more
electronegative. Atoms with nearly filled shells of electrons tend to have higher electronegatives than those
with sparsely occupied ones.
Important Points
(a) F is most electronegative (χF = 4.0) and Cs is least electronegative (0.7) elements.

Periodicity of Valence or Oxidation States

The valence is the most characteristic property of the elements and can be understood in terms of their
electronic configurations. The valence of representative elements is usually (though not necessarily) equal to
the number of electrons in the outermost orbitals and / or equal to eight minus the number of outermost
electrons as shown below.

Nowadays the term oxidation state is frequently used for valence.

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Consider the two oxygen containing compounds: OF2 and Na2O.
The order of electronegativity of the three elements involved in these compounds is F > O > Na.
Each of the atoms of fluorine, with outer electronic configuration 2s22p5, shares one electron with oxygen in
the OF2 molecule. Being highest electronegative element, fluorine is given oxidation state –1. Since there
are two fluorine atoms in this molecule, oxygen with outer electronic configuration 2s22p4 shares two
electrons with fluorine atoms and thereby exhibits oxidation state +2.
In Na2O, oxygen being more electronegative accepts two electrons, one from each of the two sodium atoms
and, thus, shows oxidation state –2. On the other hand sodium with electronic configuration 3s1 loses one
electron to oxygen and is given oxidation state +1. Thus, the oxidation state of an element in a particular
compound can be defined as the charge acquired by its atom on the basis of electronegative consideration
from other atoms in the molecule.

Variation of valence in a period: On moving along the period, the number of valence electrons increases
from 1 to 8. Consequently, the valence of the elements with respect to hydrogen increases from 1 to 4 up to
group IV and then decreases to 1. However, valence with respect to oxygen increases from one to seven
along the period.
Variation of valence in group: On moving down the group, the number of valence electrons remains the
same. Therefore, all the elements in a group have the same valence. For example, elements of group I have
valency 1 and elements of group II have valency 2.
Variation of valence in transition elements: Transition metals show variable valence of 1, 2 or 3 as they
can use electrons from their outermost as well as penultimate shell, during chemical reactions as energy
difference between them is small.

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Oxidation Number
The charge which an atom appears to have in a molecule (or ion) is known as its “Oxidation Number”. It is
calculated using accepted rules of valency, viz.,
(i) Bond pair electrons are equally divided between two like atoms.

Neither of the H atoms loses or gains electron. Therefore, oxidation number (ON) of H in H 2 is zero.
(ii) Bond pair electrons between unlike atoms is counted with more electronegative atom.

Here H appears to lose one electron and Cl appears to gain one electon. Therefore, ON of H in HCl is +1 and
that of Cl is –1.
Rules to calculate Oxidation Number (ON)
(a) The ON of an element in uncombined state is zero. Example, Na, Fe, H, Cl etc., have oxidation number
zero.
(b) In mononuclear ions, the charge on it is its oxidation number

(c) Common ON of H is +1, except in the metal hydrides (Gr1 and Gr2), when it is –1.

(d) Common On of oxygen is –2, except in peroxides when it is –1, superoxides –½,
Fluorine is more electronegative than oxygen, so oxygen has positive ON in fluorine oxides.

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(e) The sum of the oxidation numbers of all the atoms in a compound is zero.

(f) The sum of the oxidation numbers of all the atoms in a complex ion (polynuclear) is equal to the charge
on the ion.

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NOMENCLATURE OF ELEMENTS WITH ATOMIC NUMBERS > 100
(a) The name is derived directly from the atomic number of the elements using the following numerical
roots:

(b) The roots are put together in the order of the digits which make up the atomic number and are terminated
by ‘ium’ to spell out the name. The final ‘n’ of ‘enn’ is removed when it occurs before ‘nil’ and the final ‘i’
of ‘bi’ and of ‘tri’ when it occurs before ‘ium’

(c) The symbol of the element is composed of the initial letters of the numerical roots which make up the
name.

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