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Question Bank.....

PERIODIC PROPERTIES
(SUMMARY)

1.

shielding effect in multi electrons systems


calculated by slaters rules for ns & npe/(n1)des
For ns/npe
0.35 (no. of remaining es in nth shell) + 0.85 (no. es in/n1) th shell) +
1.0 (no. of es in (n2) th or lower shells)
For (n1)des
0.35 (no. of remaining es in (n1) d subshell) + 1.0 (no. es in(n1)s/(n1)p and other lower
shell)

Periodicity in :
From (L R) as no. of es
From (T B) as no. of es
2.
Z* Effective Nuclear charge
Z* = Z
Z at. no. of the given the specy.
Periodicity
From (L R) (Z* ) and therefore becomes dominating factor across the period.
From (T B) (Z* ) almost remains same & therefore size factor dominates down the group.
Ionisation energy :
It is the min. energy required to remove an e from an isolated gaseous specy from its. Ground
state.
A A+ + e
H = 1 of A
+
2+

A A + e
H = 2 of A and 1 of A+
2+
3+

A A + e H = 3 of A and 2 of A+ and 1 of A2+


*

For a particular element 3 2 1


Factors affecting E. 1. as size E.
3. as Z* E.
4. half filled & full config. have greater E. This factor is dominant only upto adjacent element.
Periodicity L R)
Z* dominates

Z* E.
also approx. E. 13.6

Z 2 eff
n2

for multi e system.

TB
(size) dominates
(size) E.
Irreg. In E.
Be B but C Be

N O but F N

Stable config.

Ga > Al d-orbital contrac.


5d < 3d > 4d Lanthanide contrac. also continuous in last two elements of Pblock.
Application of .E.
* With in the same block as .E.

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* Down the group in Sblock


as E. Ionic nature (Basic structure of hydroxides)
(as M(OH) easily conyerts into M+ & OH ions giving basic solutions)
* A group elements are almost all more electropositive then A group.

E. values (kJ/mol)
Li
Na
K
Rb
Cs
4.

520
496
419
403
376

Be
Mg
Ca
Sr
Ba

899
737
590
549
503

At. radius
* e is a wave so directly its distance from the nucleus cant be predicted.
Therefore at. radii is categorised into three types
(a) Covalent radius
r

for homonuclear species

d A A
2

r covalent radius of A

dAA covalent bond length of A2

1.

d A A
2

r average covalent radius of A/B


dAB covalent bond length of AB

* d A 2 r A + rA
*dAB < rA + rB dAB 0.09 (XA ~ XB) stevenson equation.
XA & XB are electronegativities on Paulings Scale.
2.

Crystal/Metallic Radii
CD = rcrystal
Metallic crystal of element X

3.

Vabderwaals radius In Liq./solid phase for noble gases.

AB
Vanderwaals radius of H
2

CD
Vanderwaals radius of X
2

AB and CD are distances between nearest molecules.

Periodicity
(L R)
(T B)

Z* r
size r

Also rcovalent rcrustal < randerwaals

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4.

Ionic radius
dist. of outermost e from the nucleus in the given ion.
* rA, < rA
* rB < rB

For isoelectronic species


n
for multi e system.
Z*
n = same
same (as no. of es are same)
& Z* = Z

rn = 0.529

1
Z
* Vanderlwalls raidus normally for noble gases
* for other neutral species normally covalent radius
* for ions ionic radius
Irregularity in Radius
Noble gases > halogen family
Al Ga (due to d-orbital contraction)
4d 5d (due to lanthanoid contraction) also continuous in last two elements of P block.
* Largest atom Fr, Smallest atom H, Largest cation Cs+
smallest cation H+, Largest anion , smallest anion H
* also in 3d rCr to rCu remains almost const.

rn

Electron affinity
Erel. when an e is added to an isolated gaseous specy in its G.S.

A + e A
H = 1st E.A. of A
A + e A2
H = 1st E.A. of A & 2nd E.A. of A
* 2nd E.A. of A is Eabsorb
Factors affecting E.A. (assuming E.A. To be exel)
1. as size E.A.
2. as Z* E.A.
3. as E.A.
4. stable config. have Eabsorb while addition of e.
* While comparison of E.A., all Erel are kept an greater side than those of Eabsorb
* E.A. of Noble gases are said to zero or highly + ve.
In Pblock elements
3rd period has greater E.A. then 2nd period due to exceptionally small size and thus high e
density on the surface of 2nd period elements. (Valid only for Pblock density not for Sblock
element) Li > Na
Irreg. in E.A.
B > Be O > N
F > Ne
Li > Be
C>N
Li > Na
Also
N > Be (E.A.)
66kJ/mol
Reason Be being metallic has lesser tendency to gas es. This were H +ve 31 kJ/mol
ornegativity
Relative tendency to attract shared pair of e towards itself.
Difference between EN & EA
1. EA solated Gaseous atom whereas EN atoms in combined state.
2. EA Absolute value of whereas EN Relative value.
Three different scales of EN
1. Pauling Scale
XA ~ XB = 0.208/0.182

AB

where AB = E AB (E A 2 EB 2 )1/ 2

EAB, E A 2 and EB 2 are Bond energies of AB, A2 and B2 in Kcal/mol.


If B.E. are in kJ/mol replace 0.208 by 0.1017.

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Common Pauling EN values


H
2.1
Li
Be
B
C
1.0
1.5
2.0
2.5
Na
Si
0.9
1.8

N
3.0
P
2.1

O
3.5

He
zero
F
4.0
Cl
3.0

Br. 2.8

Pairs have same EN values are :


(a) N & Cl (3.0)
(b) H & P (2.1)
(c) C, S, (2.5)
*
highest EN F,
Lowest EN Cs (0.7)
2.

Mulliken Scale :
EN =

I.E E.A
(Put magnitude of E.A. only & formulae not valid for stable config.)
2

X mulliken
also X
= 2.8
Pauling

All red Roschow scale


0.359 Z *

XAR =

rA2

+ 0.744

rA covalent radii in

Zeff.e 2
( force of attraction
Factors affecting EN EN
2

1. as Z* EN
2. as n EN
3. as EN
4. as cationic charge EN (Mn2+ < Mn+4 < Mn+7) for the same element
5. as Anionic charge EN (A1 > A2 > A3) for the same element
6. as % s charac. EN
sp3 < sp2 < sp
Periodicity in EN
Across the period from (L R) Z* (EN)
down the group (T B) size (EN)
Irreg. in EN
* EN of Noble gases in zero.
Applications of EN
1.
Nature of Bond
(a) When XA ~ XB = 0, Pure covalent Bond.
(b) XA ~ XB < 1.7/2.1 Polar covalent Bond
Pure covalent Bond.
Given by Pauling
(c) XA ~ XB = 1.7/2.1 50% ionic and 50% covalent
(d) XA ~ XB > 1.7/2.1 more ionic lesser covalent.
* % ionic character = [16 | XA ~ XB | + 3.5 (XA ~ XB)2]
for 50 = 16 EN + 3.5 (EN)2 EN = 2.1
2.

Nature of Oxides
(cosidency

excess

X O
H2O

one bond only)

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3.

B.Str. among Polar covalent Bonds.


as EN polarity % ionic character B. Str. Thermal Stability
Eg. of B. Str.
(efficiency of overlapping) as ions come closer
HF> HCl > HBr > H

1
* Vice versa is the order of the B. lnegth. B.h. B. Str.

4.

More is EN, More is the Non Metallic character


Tendency to gain e s

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