Modern Periodic Law:
Properties of elements are the periodic function to their atomic
numbers.
The periodicity in properties is due to repetition of similar outer
shell electronic configuration at a certain regular intervals.
In modern periodic table is based on modern periodic law in which
elements are arranged in increasing order of their atomic
numbers.
In the modern periodic table, the elements are arranged in rows
and columns. These rows and columns are known as periods and
groups respectively.
The table consists of 7 periods and 18 groups
Period indicates the value of ‘n’ (principal quantum number) for
the outermost or valence shell.
Same number of electrons is present in the outer orbitals (that is,
similar valence shell electronic configuration
GENERAL ELECTRONIC CONFIGURATION:
Periodicity in Atomic Properties:
1. Atomic Radius:
It is of 4 kinds : Covalent radius, Crystal Radius (Metallic radius), Ionic
radius and Vanderwaal Radius.
Vanderwaal radius > Crystal radius > Covalent radius
Within Ionic radius
Cationic radii are smaller than the parent atom radius because
of increased Zeff and lowered no. of electrons so Nucleus tightly
binds to Lowered no. of outer shell electrons .
Anionic Radii are larger the parent atom Due to increased
no..of electrons that are loosely bound to nucleus ,the net
repulsion of the electrons will outweigh the nuclear charge
and the ion will expand in size.
R- > R >R+
Within a given period atomic radius decreases from left to right.
This is due to the effect of increase in nuclear charge while the
electrons are being added to the same shell.
Within a given group atomic radius increases down the group. This
is due to the increase in number of shells.
In the first transition series the atomic size slightly decreases from Sc to
Mn because effect of effective nuclear charge is stronger than the
shielding effect. The atomic size from Fe to Ni remains almost the same
because both the effects balance each other.
The atomic size from Cu to Zn slightly increases because shielding effect
is more than effective nuclear charge due to d 10 structure of Cu and Zn.
Inner transition elements – As we move along the lanthanide series,
there is a decrease in atomic as well as ionic radius. The decrease in size
is regular in ions but not so regular in atoms. This is called lanthanide
contraction.
2) Ionisation potential or Ionisation Energy:
IONIZATION ENERGY: It is defined as energy required to
remove an electron from a gaseous isolated atom in their
ground state.
X(g) → X+(g) + e–
Ionization energy increases along the period while decreases down the
group.
Factors which influence I.E.
Atomic size: the larger the size of the atom, the smaller the I.E. i.e., I.E.
µ
Effective nuclear charge: The greater the effective charge on the
nucleus of an atom, the more difficult it would be to remove an electron
from the atom because electrostatic force of attraction between the
nucleus and the outermost electron increases. So greater energy will be
required to remove the electron.
Penetration effect of orbitals: The order of energy required to remove
electron from s,p,d-and¦-orbitals of a shell is s>p>d>¦.
Shielding or screening effect : Screening effect results in decrease of force
of attraction between the nucleus and the outermost electron and lesser
energy is required to separate the electron. Thus the value of I.P. decreases.
Stability of half-filled and fully-filled orbitals : According to Hund's rule
the stability of half filled or completely filled degenerate orbitals is
comparatively high. So comparatively more energy is required to separate the
electron from such atoms.
QUESTION FOR PRACTICE.
The first ionization enthalpy (∆i H ) values of the third period elements, Na, Mg and
Si are respectively 496, 737 and 786 kJ mol–1. Predict whether the first ∆i H value
for Al will be more close to 575 or 760 kJ mol–1 ? Justify your answer
Electron Affinity:
ELECTRON AFFINITY/ELECTRON GAIN ENTHALPY : It is defined as
the energy required to add an electron to neutral gaseous atom (OR)
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)
*** the negative of the enthalpy change for the process depicted in equation 3.3 is defined as the
ELECTRON AFFINITY (Ae ) of the atom under consideration.
Electron affinity increases along the period while decreases down the
group.
Factors affecting the magnitude of electron affinity
Atomic size – In general electron affinity value decreases with the
increasing atomic radius because electrostatic force of attraction decreases
between the electron being added and the atomic nucleus due to increase
of distance between them.
Effective nuclear charge – Electron affinity value of the element
increase as the effective nuclear charge on the atomic nucleus increases
because electrostatic force of attraction between the electron being added
and the nucleus increases. As the electrostatic force of attraction increases,
amount of energy released is more.
Screening or Shielding effect – Electron affinity value of the elements
decreases with the increasing shielding or screening effect. The shielding
effect between the outer electrons and the nucleus increases as the
number of electrons increases in the inner shells.
Stability of half filled and completely filled orbitals – The
stability of half filled and completely filled degenerate orbitals of a sub
shell is comparatively more, so it is difficult to add electron in such orbitals
and lesser energy is released on addition of electron hence the electron
affinity value will decrease.
QUESTION FOR PRACTICE: Which of the following will have the most negative
electron gain enthalpy and which the least negative?
P, S, Cl, F.
Explain your answer.
Electronegativity:
A qualitative measure of the ability of an atom in a chemical
compound to attract shared electrons to itself is called
electronegativity.
Electronegativity of elements increases along the period while decreases down the
group.
Electronegativity scales
Some arbitrary scales for the quantitative measurement of electronegativities are as
und
Like Pauling scale, Milliken scale, Alfred Rochow scale
Factors affecting the magnitude of electronegativity
Atomic radius: As the atomic radius of the element increases the
electronegativity value decreases.
Effective nuclear charge : The electronegativity value increases as
the effective nuclear charge on the atomic nucleus increases.
Oxidation state of the atom : The electronegativity value increases
as the oxidation state (i.e. the number of positive charge) of the
atom increases.
Hybridisation state of an atom in a molecule: If the s- character in
the hybridisation state of the atom increases, electronegativity
also increases.
F>O>N Electronegativity order
VALENCY:
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 .
Valency is given by the number of electrons in outermost shell.
If the number of valence electrons ≤4: valency = number of valence
electrons
If the number of valence electrons >4: valency = (8 - number of valence
electrons)
Many elements exhibit variable valence (particularly transition elements
and actinoids).
Variation in a period − Increases from 1 to 4 and then decreases from 4 to
zero on moving from left to right.
Variation in a group − No change in the valency of elements on moving
down a group. All elements belonging to a particular group exhibit same
valency.