Periodic Properties
PERIODIC PROPERTIES
Hints for Subjective Problems
LEVEL – I
2. Larger particles size and nearly perfect lattice.
- pπ-pπ back bonding between F and Al.
- (BeCl2)n formation.
- Inert pair effect.
- Successive ionization potentials have to be considered.
- Half filled and fulfilled shells have high stability.
- Metal in higher oxidation state in oxide compounds show acidic nature.
LEVEL – II
1. K is an alkali metal which can lose its electron quite easily and has got a low I.E. so that K+ formation occurs readily.
- I.E. of Mg is greater than Na and Al because in either case removal of an electron from valence orbital will render the ion formed, to be full-filled which has got extra stability.
- Atomic size, type of hybridisation, oxidation state, partial charge of an ion.
- s-character of sp, sp2 and sp3hybridised orbitals are to be considered.
- % ionic character has to be considered.
LEVEL – III
- This is because of increasing nuclear charge which outweighs the shielding effect of diffuse d-shell.
- This arises mainly from the coupling of spins of the added electron and an electron in an orbital originally only singly occupied.
- s > p > d > f
- For half filled stability of N
- Be+< C+3 < O+5 < F+
- The increased effective nuclear charge due to poor screening by inner 4f and 5 d orbitals enhances the attracting ability and hence it has got high electron affinity.
- In solution Cu+ disproportionate to Cu2+ and Cu.
2Cu+ → Cu + Cu2+ ΔG = –0.35 F for the reaction.
So it occurs readily.
Solution to Subjective Problems
LEVEL – I
1. |
- This is probably because of larger particle size and more nearly perfect lattice.
- This is because of pπ-pπ back bonding between F & Al, thereby Al becomes electronically saturated hence no further attack by H2O to vacant 3pz orbital of Al
- This is because of (BeCl2)n formation in the solid phase. It is a chain polymer.
- This is due to the decrease in the size of the ions on the atomic no. increases among the isoelectronic ions.
- Due to inert pair effect, it is difficult to unpair s-electrons the hence the higher oxidation state is less prominent.
- By giving the I.P., Na is converted to Na+. Now Na+ has an additional amount of energy equal to its I.P and in order to go back to its original state – it will liberate energy and this we call as electron affinity.
- The alkali metals have one electron in excess of their octet while alkaline earth metals have 2 e’s excess of their octet. So after 1st I.P. the alkali metal attain the inert gas configuration while alkaline earth metals attain it after 2nd I.P. Now removal from a noble gas core needs high I.P., so there is a jump in the 2nd I.P. for alkali and 3rd I.P. for alkaline earth metals.
- In Be the extra electron is to be added in 2p orbital because 2s orbital is completely filled and in N, it is to be added to a half filled 2p orbital. Since half-filled and full-filled orbitals are more stable, reluctancy in accepting electron is found.
- In Mn2O7, Mn is in +7 state i.e., highly electron deficient. So its tendency to accept electron increases and therefore it is an acidic oxide.
LEVEL – II
- K is an alkali metal which can lose its electron quite easily and has got a low I.E. so that K+ formation occurs readily. But in case of Ag, d-orbitals can’t screen the nuclear charge effectively and thus valence electrons is not readily lost so that it has got high I.E. That’s why Ag is relatively inert.
- While F– is formed from F then electron is added to an electronegative, neutral atom and energy (E.A.) is released by this process but even though O– formation from O is energy releasing process, formation of O2- from O– is highly energy consuming. So combined effect is O2- formation from O is endothermic.
- Hint: Decreases down the group. This is because SO42- is very large in size, so it has got low hydration energy and down the group the hydration energy of cations also decreases.
- I.E. of Mg is greater than Na and Al because in either case removal of an electron from valence orbital will render the ion formed, to be full-filled which has got extra stability. (Na : 2s22p63s1 ; Al : 2s22p63s23p1 ).That’s why their I.E. is smaller than Mg whose electron has to be removed from a 3s 2 (filled) orbital. Also s-orbital lies closer to the nucleus than the p- orbital.
- This is due to a pair of electrons remaining paired in –ous form and becoming unpaired in –ic form (e.g. Sn, P, Te etc.]. But in transition metals different no. of d-electrons may take part in bonding [e.g. Fe2+, Fe3+ & Cu+, Cu2+ etc.]
- Atomic size, hybridisation mode, oxidation state, partial charge of an ion.
- Hybrid orbitals sp3 sp2 sp
s-character 25% 33% 50%
Electronegativity 3.68 3.92 4.67
- I > II > III
- NF2 (3.78) > Cl3 (2.96) > NH2 (2.78) > CH3(2.3)
- % ionic character =
As electronegativity difference is higher in HF than HI hence the order.
LEVEL – III
- For 100% ionic bond the dipole moment = 4.8 × 92 D
∴ % ionic character = = 44%
- This is because of increasing nuclear charge which outweighs the shielding effect of diffuse d-shell.
3 i) s, p electrons are taken to equally affected by the nucleus
- ii) s, p, d f electrons equally shield the electron in n, (n-1)th shell.
- This arises mainly from the coupling of spins of the added electron and an electron in an orbital originally only singly occupied.
- s > p > d > f
- For half filled stability of N
- Be+< C+3 < O+5 < F+
- i) Size of the nuclear charge
- ii) The atomic radius
iii) The screening effect of inner electron shells
- iv) Ellipticity of electron’s orbit
- II < I (1.14Å) = III (1.95Å)
- X ⎯→ X+ + e; ΔH = IE1 = a eV
X + e ⎯→ X–; ΔH = –EA1 = b eV
If N/2 atoms of X lose electrons which are taken up by remaining N/2 of X to give X–, then
or a – b =
∴ a – b = 8.477
Now N/2 of X– lose two electrons to give X+
X– ⎯→ X + e; ΔH = EA1 = + b
X ⎯→ X+ + e; ΔH = + IE1 = +a
or a + b =
a + b = 15.194
∴ a = 11.835 eV and b = 3.358 eV
- AlCl3 + aq. ⎯→ AlCl3(aq); ΔH = ?
ΔH = Energy released during hydration – Energy used during ionisation
= –4665 – 3 × 381 + 5137 = –671 kJ/mole
Thus formation of ions will take place.
- The increased effective nuclear charge due to poor screening by inner 4f and 5 d orbitals enhances the attracting ability and hence it has got high electron affinity.
- As we go down the period the electronegativity decreases. But after Al, due to the presence of d electrons which have minimum shielding effect, the nuclear charge increases and hence electronegativity also increases.
- Packing in crystal latice is not compact due to small size of Li+ and bigger size of . But O2– being smaller in size can stabilise Li2O.
- In solution Cu+ disproportionate to Cu2+ and Cu.
2Cu+ → Cu + Cu2+ ΔG = –0.35 F for the reaction.
So it occurs readily.
Solution to Objective Problems
LEVEL – I
1. Alred – Rochow Scale.
- Hybridised orbital accommodates σ bond pairs.
- Electronegativity of silicon <carbon.
- Mulliken’s scale.
- Periodic variation.
- Solvation energy > lattice energy.
- Octet or fulfilled shells.
- Overlapping.
- Low lattice energy.
- Maximum covalency less melting point.
- Cations have less diameter compared to atoms.
- More negative charge larger species.
- High salvation energy of Ba+2 and SO4–2.
- Less than 1.7.
- More the bond order more will be the bond energy.
LEVEL – II
1. High effective nuclear charge makes high ionization potential.
- Slater’s rule.
- Electrostatic repulsion is greater than the coupling energy.
- High φ value.
- Ionic potential = .
- I– is highly polarisable.
- Radius values.
- No. of valency electrons will reduced.
- I.P. = IP1 + IP2
- Characteristic of silicon.
- F2 is highly oxidizing.
- Half filled shells.
- Half filled or fulfilled shells have high stability
- I.P. nearly equal to EA.
- Noble gases.
6