Periodic properties-GoIITians
Periodic properties-GoIITians
Periodic properties-GoIITians
DIAGONAL RELATIONSHIP:
Some elements of certain groups of 2nd period resemble much in properties with the elements of third period of
next group i.e. elements of second and third period are diagonally related in properties. This phenomenon is known
as diagonal relationship.
2nd period Li Be B C
3rd period Na Mg Al Si
Diagonal relationship arises because of
(i) similar size of atom and ions
(Li = 1.23 Å & Mg = 1.36 Å ; Li+ = 0.76 Å & Mg2+ = 0.72 Å)
(ii) similar polarising powers (charge to radius ratio)
(iii) similarity in electronegativity values
(Li = 1.0 & Mg = 1.2 ; Be = 1.5 & Al = 1.5)
Sum the shielding constants from steps 1–4 for s or p orbital or from steps 1–3 for d or f orbital and subtract them
from the actual nuclear charge (Z) of the atom in question to obtain the Zeff felt by the electron in question.
The relative extent to which the various orbital penetrates the electron clouds of of other orbitals is s > p > d > f.
Thus, for any given principal quantum number n, an electron will experience the greatest effective nuclear charge
when in s-orbital than p-orbital and so on.
Ques: What is the effective nuclear charge at the periphery of nitrogen atom when a extra electron is added during the
formation of an anion. Compare the value of Zeff when the atom is ionized.
Sol. Ground state electron configuration of N (Z = 7) = 1s2 2s2 2p3
Electron configuration of N– = (1s2) (2s2 2p4)
Shielding constant for the last 2p electron,
= [(5 × 0.35) + (2 × 0.85)] = 3.45
Zeff = Z –
Zeff for last p electron on N– = 7 – 3.45 = 3.55
Electron configuration of N+ = (1s2) (2s2 2p2)
Shielding constant for the last 2p electron,
= [(3 × 0.35) + (2 × 0.85)] = 2.75
Zeff for last electron on N+ = 7 – 2.75 = 4.25
2. ATOMIC RADIUS:
(A) Covalent radius:
It is one-half of the distance between the centres of two nuclei (of like atoms)
bonded by a single covalent bond. Covalent radius is generally used for non-
metals.
For heteronuclear diatomic molecule, A–B, where difference between the electronegativity values of atom A and
atom B is relatively larger,
dA – B = rA + rB – 9.0
Electronegativity values are given in Pauling units and radius in picometers.
= XA – XB where XA and XB are electronegativity values of high electronegative element A and less
electronegative element B. This formula is given by Stevenson & Schomaker.
Elements H O F S Br
Variation in a period: On moving left to right due to increased nuclear charge the size decreases.
Variation in a group: On moving top to bottom due extra addition of a shell the size increases.
Some Irregularities
(a) The atomic radius of inert gas (zero group) is given largest in a period because it is represented as van der Waals’s
radius which is generally larger than the covalent radius. The van der Waal’s radius of inert gases also increases
from top to bottom in a group.
(b) In the transition series (e.g. in first transition series), the covalent radii of the elements decrease from left to right
across a row until near the end when the size increases slightly. On moving from left to right, extra protons are
placed in the nucleus and the extra electron are added. The orbital electrons shield the nuclear charge
incompletely. Thus the nuclear charge attracts all the electrons more strongly, hence a contraction in size occurs.
The radii of the elements from Cr to Cu, are very close to one another because the extra electron being added
increases the repulsion between the electrons and counter balances the increased nuclear charge on the outer
electrons (4s). As a result of this, the size of the atom does not change much in moving from Cr to Cu and for
zinc this repulsion even dominates the nuclear charge so size slightly increases.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (Å) 1.44 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17 1.25
IONIC RADIUS :
The sizes of ions increases as we go down a group (considering the ions of same charge). For example:
Li+ < Na+ < K+ < Rb+
Be2+ < Mg2+ < Ca2+ < Sr2+
F– < Cl– < Br – < –
Cation is smaller than parent atom but anion is bigger than parent atom.
The species containing the same number of electrons but differ in the magnitude of their nuclear charges are
called as isoelectronic species. For example, N3– , O2–, F–, Ne, Na+ , Mg2+ and Al3+ are all isoelectronic species with
same number of electrons (i.e. 10) but different nuclear charges of +7, +8, +9, +10, +11, +12 and +13 respectively.
Within a series of isoelectronic species as the nuclear charge increases, the force of attraction by the nucleus on
the electrons also increases. As a result, the ionic radii of isoelectronic species decrease with increases in the
magnitude of nuclear charges. For example,
Al3+ Mg2+ Na+ F– O2– N3–
(I.E.)3 > (I.E)2 > (I.E.)1 – Difficult to remove an electron from a positively charged ion than from a neutral atom
(b) Zeff Z
eff I.E. but (i.e. Zeff ) E
(c) Electronic configuration – For a stable electronic configuration i.e. half-filled or fully filled configurations (stable
because of symmetry) I.E. will be larger
(d) The relative extent to which the various orbital penetrates the electron clouds of other orbitals is s > p > d > f. Thus,
for any given principal quantum number n, an electron will experience the greatest effective nuclear charge when in
s-orbital than p-orbital and so on. Hence the order of I.E. is as follows: s > p > d > f
Periodicity
Irregularities
(a) In period (also in period )
Periodicity
E.A. (high) Al Si P S Cl
(added electron goes to the bigger n = 3 i.e. occupies larger region of space and the electron-electron repulsion is
much less.)
(c) 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.
e.g.H in kJ / mol of groups 16th and 17th
S Se Te Po O
–200 –195 –190 –174 –141
Cl F Br I At
–349 –328 –325 –295 –270
Electronegativity.
A qualitative measure of the ability of an atom in a chemical compound to attract shared electrons to itself iscalled
electronegativity not a measurable quantity. A number of numerical scales of electronegativity have been
proposed.
Differences in E.A. & E.N.
(a) E.A. is defined in isolated gaseous state while E.N. is defined in bonded state
(b) E.A. is a absolute term, it has proper units while E.N. is a relative concept has no units
(b) Mullikan’s scale : Electronegativity (chi) can be regarded as the average of the ionisation energy (IE) and the
electron affinity (EA) of an atom (both expressed in electron volts).
M =
IE EA
2
Elements H Li Be B C N O F Na P S Cl Br I
Electronegativity 2.1 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0.9 2.1 2.5 3.0 2.8 2.5
Periodicity
L – R Zeff E.N T – P Size E.N
Applications
Acc. to Pauling, if
XA – XB = 1.7 50% ionic
< 1.7 more covalent less ionic > 1.7 more ionic less covalent
Henny smith formula % ionic character = 16 + 3.5 2 = | XA – XB|
Bond to be 50% ionic = 2.1
Ques: Calculate % ionic character of bond formed between the most electropositive element Cs (x = .7) and most
electronegative element F (x = 4.0).
Ans:
According to Henny Smith formula % ionic character
= 16(3.3) + 3.5 (3.3)2 = 52.8 + 38 .115 = 91.915 %
The outer shell ‘s’ electrons (ns2) penetrate to (n – 1) d electrons and thus become closer to nucleus and are more
effectively pulled towards the nucleus. This results in less availability of ns2 electron pair for bonding of ns2 electron
pair becomes inert. The inert pair effect begins after n 4 and increases with increases value of n.
(i) Dominance of lower oxidation state on moving down the group in boron, carbon & nitrogen family may also be
explained by the inert pair effect.
(ii) The inert pair effect is not the explanation of monovalency, bivalency and trivalency in group 13, 14 & 15. It
merely describes what happens, i.e. two electrons do not participate in bonding. The reason that they do not take
part in bonding in energy.
Tl Tl 3
Pb 2
Pb 4 Ga In Tl Sn2 Pb2 Sb3 Bi3
Bi 3 Bi 5
Ga 3 In 3 Tl 3 Sn4 Pb4 Sb5 Bi5
Types of Oxides and acidic / basic nature of oxyacid and hydra acid:
BeO BeO + 2HCl BeCl2 + H2O, BeO + 2NaOHNaAlO2 (Sodiuni meta aluminate)
ZnO ZnO + HCl ZnCl2 , ZnO + NaOH Na2ZnO2 (sodium zincate)
SnO (stannous oxide)
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