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Coordination Chemistry
 Coordination Chemistry Exceptions

1. If Co+3 is bonded with O donor atom (e.g. H2O and oxalato) then
ligand acts as strong field ligand.
2. If Cu+2 is bonded with H2O then ligand acts as strong field ligand.
3. If Ni+4 is bonded with fluoride ion then ligand acts as strong field
ligand.
4. If Fe+2 and Mn+2 are bonded with NH3 then ligand acts as weak
field ligand.
5. 3d series elements in +2 oxidation state form outer orbital
complexes up to NH3 in spectrochemical series.
1. Match the column:
Column–I Column–II
(Number of unpaired µ(B.M.)
electron)
(a) [Fe(NH)3)6]2+ (p) 0 0
(b) [MnO4]– (q) 5 5.9
(c) [Mn(NH3)6]2+ (r) 1 1.73
(s) 4 4.90
(a) a-s; b-p; c-q; (b) a-r; b-s; c-s;
(c) a-r; b-s; c-p; (d) a-qs; b-qs; c-pq; d-q
P Block Elements
Trends/Exceptions of Boron Family
 Exceptions of Boron Family
1. Atomic radius :
(a) Al > Ga (b) In ≈ Tl
 IonizationofEnthalpy
Exceptions Boron Family
2. The observed discontinuity In the ionisation enthalpy values
between Al and Ga and between In and Tl are due to inability of d–
and f–electrons, which have low screening effect, to compensate
the increase in nuclear charge.

Ionisation Enthalpy :
B > Tl > Ga > Al > In
 Exceptions of Boron Family
Electronegativity
3. Electronegativity first decreases from B to Al and then Increases
marginally.

B > Tl > In > Ga > Al

 Exceptions of Boron Family

4. M.P.:
B > Al > Tl > In > Ga
Exp. High Exp. Low
Physical Properties:
5. Gallium with unusually low melting point (303 K), could exist in
liquid state during summer. Its high boiling point (2676 K) makes it
a useful material for measuring high temperatures.
6. Chemical Properties:
Due to small size of boron, the sum of its first three ionization
enthalpies is very high. This prevents it to form +3 ions and forces
it to form only covalent compounds.
1. Given below are two statements:
STATEMENT–1 : Boron always forms covalent bond and
STATEMENT–2 : The small size of B3+ favours formation of
covalent bond
[IIT–JEE–2007]
(1) Statement I is incorrect but statement II is correct.
(2) Both the statements I and II arc correct
(3) Statement I is correct but statement II is incorrect
(4) Both the statements I and II are incorrect
2. Given below are two statements:
Statement I : The decrease in first ionization enthalpy from B to Al
is much larger than that from Al to Ga.
Statement II : The d orbitals in Ga are completely filled.
In the light of the above statements, choose the most appropriate
answer from the options given below
(1) Statement I is incorrect but statement II is correct.
(2) Both the statements I and II arc correct
(3) Statement I is correct but statement II is incorrect
(4) Both the statements I and II are incorrect
Carbon Family Exceptions/Trends
 Carbon Family Exceptions
Covalent Radius
7. There is a considerable increase in covalent radius from C to Si
thereafter from Si to Pb a small increase in radius is observed.
This is due to the presence of completely filled d and f orbitals in
heavier members.

Covalent radius
Order : C < Si < Ge < Sn < Pb
But Si ≈ Ge Sn ≈ Pb
(poor shielding of d) (due to poor shielding of f)
 Ionization
Carbon FamilyEnthalpy
Exceptions
8. The ionisation enthalpy decreases down the group. Small decrease
in ΔfH from Si to Ge to Sn and slight increase in ΔfH from Sn to Pb
is the consequence of poor shielding effect of intervening d and f
orbitals and increase in size of the atom.

Ionisation Enthalpy :
Order : C > Si > Ge > Pb > Sn
 Carbon Family Exceptions
Electronegativity

9. The electronegativity values for elements from Si to Pb are almost

the same.

Electronegativity :
C > Si = Ge = Sn < Pb
 Carbon Family Exceptions
Density
10. Density :
C > Si < Ge < Sn < Pb
 Carbon Family Exceptions
Melting Point

11. Melting point :

C > Si > Ge > Sn < Pb
Exp. High
 Carbon Family Exceptions
Catenation

12. Catenation :
C > Si > Ge ≈ Sn
Pb has no catenation tendency.
 Chemical Properties

13. Since the sum of the first four ionization enthalpies is very high,
compounds in +4 oxidation state are generally covalent in nature.
 Reactivity towards Halogen

14. The central metal atom in these halides undergoes sp3

hybridisation and the molecule is tetrahedral in shape. Exceptions
are SnF4 and PbF4, which are ionic in nature.
15. PbI4 does not exist because Pb—I bond Initially formed during the
reaction does not release enough energy to impair 6s2 electrons
and excite one of them to higher orbital to have four unpaired
electrons around lead atom.
Trends/Exceptions of Nitrogen Family
 Exception
Atomic of
andNitrogen
Ionic Radii
Family

16. As to Bi only a small increase in covalent radius is observed.

This is due to the presence of completely filled d and/or f orbitals
in heavier members.
 Exception of Nitrogen
Ionization Family
Enthalpy
17. Ionisation enthalpy :
– Much greater than GP–14 due to extra stable half filled
p–orb e– configuration.
 Exception of Nitrogen Family
Electronegativity
18. Electronegativity :
N > P > As > Sb = Bi
 Exception of Nitrogen Family
Melting Point

19. Melting point :

The M.P. first increase from nitrogen to arsenic and than
decreases from antimony to bismuth order : As > Sb > Bi > P > N
 Physical Properties:
20. The boiling points, in general, increase from top to bottom in
the group but the melting point increases upto arsenic and then
decreases upto bismuth,

21. Except nitrogen, all the elements show allotropy.

Chemical Properties:
22. In the case of nitrogen, all oxidation states from +1 to +4 tend to
disproportionate in acid solution. For example,
3HNO2 -> HNO3 + H2O + 2NO
Chemical Properties:
23. In case of phosphorus nearly all intermediate oxidation states
disproportionate into +5 and –3 both in alkali and acid. However
+3 oxidation state in case of arsenic, antimony and bismuth
becomes increasingly stable with respect to disproportionate.
 Anomalous Properties of Nitrogen

24. N—N bond is weaker than the single P–P bond because of high
interelectronic repulsion of the non–bonding electrons, owing to
the small bond length.
 Reactivity towards Hydrogen
25. Basicity decreases in the order NH3 > PH3 > AsH3 > SbH3 ≥ BiH3.

26. Due to high electronegativity and small size of nitrogen, NH3

exhibits hydrogen bonding in solid as well as liquid state. Because
of this, it has higher melting and boiling points than that of PH3.
 Reactivity towards Halogens

28. All the trihalides of these elements except those of nitrogen

are stable. In case of nitrogen, only NF3 is known to be stable.
Q3. PCl5 is well known, but NCl5 is not. Because.
(A) nitrogen is less reactive than phosphorus.
(B) nitrogen doesn't have d–orbitals in its valence shell.
(C) catenation tendency is weaker in nitrogen than phosphorus.
(D) size of phosphorous is larger than nitrogen.
Q4. Based on the compounds of group 15 elements, the correct
statement(s) is (are)
(JEE(Advanced) 2018
(1) Bi2O5 is more basic than N2O5
(2) NF3 is more covalent than BiF3
(3) PH3 boils at lower temperature than NH3
(4) The N–N single bond is stronger than the P–P single bond
Q5. Among the following, the correct statement is
(1) Between NH3 and PH3, NH3 is a better electron donor because
the lone pair of electrons occupies spherical s orbital and is
less directional
(2) Between NH3 and PH3, PH3 is a better electron donor because
the tone pair of electrons occupies sp3 orbital and is more
directional
(3) Between NH3 and PH3, NH3 is a better electron donor because
the lone pair of electrons occupies sp3 orbital and is more
directional
(4) Between NH3 and PH3, PH3 is a better electron donor because
the lone pair of electrons occupies spherical s orbital and is
less directional
Trends/Exceptions OXYGEN FAMILY
 Exception of Oxygen Family

29. Electron Gain Enthalpy

Because of the compact nature of oxygen atom, it has less
negative electron gain enthalpy than sulphur. However, from
sulphur onwards the value again becomes less negative upto
polonium.

Electron gain enthalpy

S > Se > Te > Po > O
–200 –195 –190 –174 –141
30. Ionisation enthalpy
The elements of this group have lower ionisation enthalpy values
compared to those of Group 15 In the corresponding periods. This
is due to the fact that Group 15 elements have extra stable half–
filled p–orbitals electronic configurations.
Q6. Given below are two statements. One is labelled as
Assertion A and the other is labelled as Reason R.
PYQ JEE 2022
Assertion A : The first ionization enthalpy for oxygen is lower than
that of nitrogen.
Reason R : The four electrons in 2p orbitals of oxygen experience
more electron–electron repulsion.
In the light of the above statements, choose the correct answer
from the options given below,
(A) Both A and R are correct and R is the correct explanation of A.
(B) Both A and R are correct but R is NOT the correct explanation
of A.
(C) A is correct but R is not correct.
(D) A is not correct but R is correct
Q7. The correct order of melting points of hydrides of group 16
elements is :
(A) H2S < H2Se < H2Te < H2O (B) H2O < H2S < H2Se < H2Te
(C) H2S < H2Te < H2Se < H2O (D) H2Se < H2S < H2Te < H2O
 Reactivity towards the halogens (HALIDES)

33. Reactivity towards the halogens:

Amongst hexahalides, hexafluorides are the only stable halides.
Sulphur hexafluoride, SF6 is exceptionally stable for steric reasons.
34. All elements except oxygen form dichlorides and dibromides.

35. These dihalides are formed by sp3 hybridisation and thus, have
tetrahedral structure. The well known monohalides are dimeric in
nature. Examples are S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These
dimeric halides undergo disproportionation as given below:
2Se2Cl2 🡪 SeCl4 + 3Se
Trends/Exceptions HALOGEN FAMILY
 Exception of Halogen Family

36. Electron gain enthalpy :

Cl > F > Br > I >
–349 –333 –325 –296

37. Bond dissociation enthalpy :

Cl2 > Br2 > F2 > I2
242.6 kJ/mol 192.8 158.8 151.1
 General Trends in Physical Properties

38. Non metallic Characters:

– The non–metallic character, decreases down the group,
– Iodine shows some distinct metallic properties
– e.g., it possesses metallic lustre and forms positive ions like I+, I3+
etc.
 Electron Gain Enthalpy

The negative electron gain enthalpy of fluorine Is less than that of

chlorine. It Is due to small size of fluorine atom, As a result, there
are strong interelectronic repulsions in the relatively small 2p
orbitals of fluorine and thus, the incoming electron does not
experience much attraction.
Physical Properties:
One curious anomaly we notice from is the smaller enthalpy of
dissociation of F2 compared to that of Cl2 whereas X–X bond
dissociation enthalpies from chlorine onwards show the expected
trend: Cl – Cl > Br – Br > I – I. A reason for this anomaly is the
relatively large electron–electron repulsion among the lone pairs
in F2 molecule where they are much closer to each other than in
case of Cl2.
39. Fluorine oxidises water to oxygen whereas chlorine and
bromine react with water to form corresponding hydrohalic and
hypohalous acids. The reaction of iodine with water is non–
spontaneous. In fact, I– can be oxidised by oxygen In acidic
medium; Just the reverse of the reaction observed with fluorine.
2F2 (g) + 2H2O (I)  4H+ (aq) + 4F– (aq) + O2 (g)
X2 (g) + H2O (I) HX (aq) + HOX (aq)
(where X = Cl or Br)
4I– (q) + 4H+ (aq) + O2(g) 2I2 (s) + 2H2O(I)
Most of the reactions of fluorine are exothermic [due to the small
and strong bond formed by it with other elements). It forms only
one oxoacid while other halogens form a number of oxoacids.
Reactivity towards hydrogen:
They all react with hydrogen to give hydrogen halides but affinity
for hydrogen decreases from fluorine to iodine. Hydrogen halides
dissolve in water to form hydrohalic acids. Some of the properties
of hydrogen halides are given in Table 7.9, The acidic strength of
these adds varies In the order: HF < HCI < HBr < HI. The stability of
these halides decreases down the group due to decrease In bond
(H–X) dissociation enthalpy in the order: H–F > H – Cl > H – Br > H
–L
42. In this family, higher oxides of halogen are more stable.
43. Some O.S.
I > Cl > Br  lacks both
Greater Multiple
polarisability bond
formation
Q8. Which is incorrectly given according to order indicated?
(1) F2 > CI2 > Br2 > I2 ; Oxidising power
(2) HI > HBr > HCI > HF ; Acidic strength
(3) F2 > CI2 > Br2 > l2 ; Bond dissociation enthalpy
(4) HF > HI > HBr > HCI ; Boiling point
Trends/Exceptions NOBLE GASES
44. Exception of Noble Gases:
Electron gain enthalpy
Ne > Ar = Kr > Xe > Rn > He
 JEE 2023 (Jan)

Q9. Inert gases have positive electron gain enthalpy. Its correct order
is
(1) Xe < Kr < Ne < He (2) He < Ne < Kr < Xe
(3) He < Xe < Kr < Ne (4) He < Kr < Xe < Ne
45. Physical Properties:
Helium has the lowest boiling point (4.2 K) of any known
substance.
46. It has an unusual property of diffusing through most commonly
used laboratory materials such as rubber, glass or plastics.
 PERIOD-WISE TRENDS ATOMIC RADII

47. Li > Be > B > C > N > O > F < Ne

48.
H < He (120 pm)
(152 pm) Li < Ne (160 pm)
(186 pm) Na < Ar (190 pm)
(227 pm) K > Kr (200 pm) due to poor
(248 pm) Pb > Xe (220 pm) shielding of e’s
 PERIOD-WISE TRENDS IONIZATION ENTHALPY

49. Ionisation Energy (2nd period)

Li < Be > B < C < N > O < F < Ne

50. Ionisation energy (3d series)

Sc < Ti > V < Cr < Mn < Fe > Co > Ni < Cu < Zn
Veena ko nahi dena paisa
 PERIOD-WISE TRENDS ELECTRON AFFINITY

51. Electron affinity

(a) Li > Be < B
(b) Na > Mg < Al
(c) Ne < N < Be < Li < C < O < F
D & F Block Elements
● Reason - Increase in atomic radii towards the end may be attributed to the
electron-electron repulsions. In fact, the pairing of electrons in d-orbitals occurs
after d5 configuration. The repulsive interactions between the paired electrons in
d-orbitals become very dominant towards the end of the period and cause the
expansion of electron cloud and thus, resulting in increased atomic size. The ionic
radii also follow the similar trend.
THE INNER TRANSITION ELEMENTS OR f-BLOCK ELEMENTS :
OXIDATION STATES :
— Oxidation number (II) and (IV) do occur, perticularly when they lead to
1. A noble gas configuration, e.g. Ce+4 (f º)
2. A half filled f shell e.g. Eu+2 & Tb+4 (f 7)
3. A completely filled f level, e.g. Yb+2 (f 14)
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