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 ASSIGNMENT SOLUTIONS GUIDE (2016-2017)
C.H.E.-2
Inorganic Chemistry
Disclaimer/Special Note: These are just the sample of the Answers/Solutions to some of the Questions given in the

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Assignments. These Sample Answers/Solutions are prepared by Private Teachers/Tutors/Authors for the help and guidance
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information, data and solution. Student should must read and refer the official study material provided by the university.

Q. 1. (a) Give the electronic configuration of elements discovered by Lars Fredrick Nilson and Winkler.
Ans. Element discovered by Lars Fredrick nilson Scandium with atomic no. 21 and by klinkler germanium with
at no. 32 electronic configuration of
Sc (21) – 1S2, 2S2 2p6, 3S2 3p6 3d1, 4s2
Ge (32) – 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4d2
(b) What are the IUPAC nomenclature rules for naming elements ? Give IUPAC names of the elements
having atomic numbers 112 and 115.
Ans. NOMENCLATURE OF ELEMENTS HAVING Z > 100
The IUPAC has made an official recommen-dation that until a new element’s discovery has been proved, a
systematic nomenclature be applied according to the following IUPAC nomenclature rules:
(1) The name be derived directly from the atomic member of element using the following numerical roots:
0 1 2 3 4 5 6 7 8 9
nil un bi tri quad pent hex sept oct enn
(2) The roots be put together in the order of the digits when make the atomic number and be terminated by
‘ium’, and ending occuring in the names of all the metallic elements, as these are. The final ‘n’ of emn be dropped
when it occurs before ‘nil’ and the final ‘i’ of ‘bi’ and ‘tri’ be dropped, when it occurs before ‘ium’.
(3) The symbol of the element be composed of the initial letters of the numerical roots, which make up the
name.
In given table systematic names and symbols of elements having z = 101 to 106 derived by IUPAC names are
listed.
Atomic Number Systematic Name Symbol Trivial Name
101 unnilunium unu Mond elevium
102 unnilbium unb Nobelium
103 unniltrium unt Low rencium
104 unnilauadium unq —
105 unnilpentium unp —
106 unnilhexium unh —
Nomenclature of elements having Z >100 IUPAC name of the element having atomic number
112 Ununbium Uub
115 Ununpentium Uup

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 (c) Which out of Ca and Zn atoms has higher ionization energy and why?
Ans. Out of Ca and Zn antoms Zn has higher ionization energy as completely filled orbitals are comparatively
more stable and hence more energy is needed to remove an electron from such atoms. The ionization potential of
such atoms is, therefore, relatively higher than expected normally from their position in the periodic table.
(d) Discuss briefly the factors affecting electron affinity.
Ans. Factors Affecting Electron Affinity: Factors affecting electron affinities are generally the same which
affect ionisation energies. These factors are:
Atomic radius: When an electron adds on to any atom, the nucleus of the atom holds it by an electrostatic

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force of attraction, which depends upon the effective nucleur charge and size of the atom. The smaller is the size of
the atom, the greater will be the force of attraction of the nucleus for the extra electron and, therefore, higher will be
the electron affinity of the atom, that is more energy will be released in picking up an electron.
Effective nuclear charge: The higher the effective nuclear charge, greater the force of attraction exerted by
the nucleus on the added electron and hence, higher will be the electron affinity of the atom.
Electronic Configuration: Electronic configuration of the atom plays an important role in determining the
magnitude and sign of electron affinity. Halogens can achieve a stable noble gas configuration by accepting just one
electron. Therefore, they have large negative (exothermic) electron affinities. On the other hand, the noble gases
with closed shell ns2 np6 configuration, beryllium and magnesium will ns2 (stable due to filled subshell) and nitrogen
having ns2np3 (stable due to half-filled p sub-shell) configuration strongly resist the addition of any electron. Therefore,
the electron affinities of these elements are either zero or have small positive values.
Periodic Variations. It will be observed from the table that:
(i) the electron affinities increase as we move from left to right in a period (exceptions : Mg, Be, N, P, inert
gases).
(ii) Elements with stable electronic configuration find it difficult to accept an electron.
The exceptions mentioned above in (i) can be readily explained. Beryllium and magnesium have filled s-
orbitals (1s2, 2s2) and the new electron will have to go to the p orbital which has considerable high energy and as such
the electron affinity is zero. Similarly for the inert gases, the s and p orbitals are completely filled and the incoming
electron has to go to a shell with larger value of principal quantum number n. Nitrogen and phosphorus have half
filled 2p sub-shells and because of this relatively stable condition, their electron affinity is less than what would
otherwise be expected.
(iii) In general electron affinities decrease in moving down a group as is evident from these values for Cl, Br
and I and for oxygen and sulphur (for two electrons). The decrease is due to a steady increase in the atomic size from
Cl to I and from oxygen to sulphur.
Q. 2. Explain the following:
(a) Boiling points of NH3 and HF are abnormally high as compared to those of hydrides of other elements
in their respective groups.
Ans. Boiling Point and Melting Point: If you look at the melting and boiling points of the hydrides of
Group 14 elements, i.e. CH4, SiH4, GeH4 and SnH4 in the figure. You will observe that melting and boiling points
of the hydrides generally increases with the increase in molecular weight of the hydrides. But NH3 in group 15, H2O
in group 16 and HF in group 17 have abnormally high melting and boiling points as compared to other hydrides
in their respective groups in the periodic table. This is anomaly is explained on the basis of hydrogen bond
formation.

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 400
Melting Point H2O Boiling Point

350

H2Te
HF
300
SbH3
H2O
H2Te H2Se HI
250 HI NH3
Temperature (K)
H2Se
AsH3 SnH4
NH3
200 SbH3 HBr
HF H2S H2S GeH4
HBr HCI

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150 HCI SnH4 PH3
AsH3
SiH4
GeH4
PH3
CH4
100 CH4
SiH4

50

0
2 3 4 5 2 3 4 5
Period of combining element

(a) Melting point curves and (b) Boiling point curves of the molecular hydrides
Because of strong Intermolecular Hydrogen Bonding H2O, HF and NH3 exist as associated molecules. Therefore,
their melting and boiling points are much higher than those of the corresponding hydrides in their respective groups.
(b) Intramolecular hydrogen bonding takes place in ortho-nitrophenol but not in para- nitrophenol.
Ans.(i) Intermolecular Hydrogen Bonding
In this case, two or more molecules of the same compound or of different compounds are involved in hydrogen
bonding. Some common examples of the intermolecular hydrogen bonding occurring between the molecules of
same compound are HF, H2O, alcohols, etc.
F F

H H H H H
F F F
Hydrogen fluoride, (HF)n

O H O H O H O H

H H H H
Cluster of water molecules, (H2O)n

Examples of the intermolecular hydrogen bonding occurring between two different kinds of molecules are as
following:
CH3
F H O C
CH3
Hydrogen fluoride Acetone

Cl
CH3
Cl C H O C
CH3
Cl
Chloroform Acetone

H
CH3 O H N H
H
Methanol Ammonia

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 H
CH3CH2 O H O
H
Ethanol Water

Intramolecular Hydrogen Bonding

Intramolecular hydrogen bond is formed between two atoms of the same molecule. As a consequence of this,
generally a five or six membered ring called chelate ring is formed, e.g.

O H

N
N C
O O
H H
O O
o-Nitrophenol Salicylaldehyde

you have seen above, that intramolecular hydrogen bonding takes place in molecules like o-nitrophenol
and salicylaldehyde. Now, you may ask why inter-molecular hydrogen bonding does not take place in p-nitrophenol?
This is due to the large distance between the two groups (NO2 and OH) in p-nitrophenol.
O

N O

O H
This type of hydrogen bonding is not possible.
However, it does show the usual intermolecular hydrogen bonding.
H O N O H O N O

O O
P-Nitrophenol
(c) Alkali metals are good conductors of electricity.
Ans. The outermost electron in alkali metals is very loosely bound and can go from one metal ion to other easily.
Therefore, these metals are good conductors of electricity.
(d) Alkali metals are poor complexing agent.
Ans. Because of the large size and low charge on the alkali ions, they have poor complexing power.
Q. 3. (a) How is the trend in the solubilities of fluorides and hydroxides different from that of sulphates of
the alkaline earth metals?
Ans. The solubility of hydroxides in water increases from Be (OH)2 to Ba (OH)2 as increasing values of their
solubility products while solubility of halides in water decreases from Be to Ba and the fluorides are almost
insoluble calcium sulphate is sufficiently soluble in water while strontium and barium sulphates are almost in-
soluble.
(b) How is borazine prepared? Why is it called inorganic benzene ? How does borazine differ from ben-
zene ?
Ans. It combines with two molecules of ammonia at 120°C to give diammoniate of diborane, B2H6.2NH3
which is a white solid and gives a conducting solution in liquid ammonia. It has been assigned an ionic structure viz.
[H2B(NH3)2]+ [BH4]–. When this substance is heated at 200°C, a stable cyclic compound B3N3H6 (called borazole
or borazine) is obtained which is an electronic isomer of benzene and is, therefore, known as inorganic benzene

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 NH

HB BH
200°C
3(B2H6.2NH3) 2 +12 H 2
HN NH

BH
Borazole
(B3N2H6)
Borazole has a flat hexagonal ring containing —BH— and —NH— groups alternately. Its nucleus is fairly
reactive on account of its polarities. It thus adds three molecules of HCl, H2O, CH3OH etc. The more negative group

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generally attaches to boron atoms.
NH2
NH H H
B B
HB BH Cl Cl
+ 3HCl
H2N NH2
HN NH
B
BH
H Cl
At high temperature borazole undergoes hydrolysis
B3N3H6 + 3H2O → 3B(OH)3 + 3NH3
(ii) Properties of Diborine: Borazine differ from benzene as benzene is C6 H6 while borazine is in organic
benzene with chemical for made B3 N3H6 and borazine is more rective than benzene.
Q. 4. (a) How is lithium aluminium hydride prepared ? Discuss its properties and uses.
Ans. Lithium Aluminium Hydride: Lithium aluminium hydride is much more useful than aluminium hydride.
It is prepared in the laboratory by the action of LiH on AlCl3 in diethyl ether:
4LiH + AlCl3 ether
→ LiAlH4 + 3LiCl↓
Lithium aluminium hydride is a greyish white solid which decomposes into its elements above 400k. It is stable
in dry air but reacts violently with water.
LiAlH4 + 4H2O → LiOH + Al(OH)3 + 4H2↑
LiAlH4 is readily soluble in ethers. It is a very important reducing agent for both inorganic and organic compounds.
It reduces inorganic halides to hydrides, e.g.
4BCl3 + 3LiAlH4 → 2B2H6 + 3LiCl + 3AlCl3
MCl4 + LiAlH4 → MH4 + LiCl + AlCl3
(M = Si, Ge, Sn)
LiAlH4 is one of the most important reducing agents in organic chemistry because it reduces as many as 60
functional groups including ethylenic > C = C< double bonds.
(b) Graphite and diamond both are allotropes of carbon, still graphite acts as a lubricant and is a good
conductor of electricity, but diamond is hard and does not conduct electricity.
Ans. Graphite has a sheet structure where the carbon atoms are arranged in layers. The two layers are bonded by
weak van der Waals forces, and can slide over each other. This gives graphite softness and makes it useful as a
lubricant, while the tetrahedral geometry of diamond makes it very hard.
Q. 5. Why are lead pipes not used for domestic water supply? Explain.
Ans. Hydrides of lead are easily dissolve in water and lead is toxic to humans and builds up in the body over time
exposure to small amounts of lead in drinking water over a multi year period can produce high lead levels in the
body, leading to permanent or crippling damage to the brain, kidneys nervous system and bone marrow. That is why
lead pipes are not used for domestic water supply.
(b) Why do the first and the second ionization energies of Group 14 elements decrease from carbon to tin
whereas, the third and the fourth ionization energies vary irregularly.
Ans. The first and second ionization energy of group-14 elements is higher due to comparatively smaller size
and high nuclear charge the lonization energy decreases as the descend down a group due to increasing size and

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screening effect of core but third and fourth ionization energies vary irregularly Ionization energy of lead is higher
than tin due to filled inner orbitals of f. block elements. Therefore, valence electrons in lead are strongly attracted
towards nucleus and higher value of ionization energy is obtained.
(c) Describe in brief the hydrides of nitrogen.
Ans. HYDRIDES: All elements of Group 15 form trihydrides of the type EH3. In addition to these, nitrogen
also forms N2H4 and N3H and phosphorus gives P2H4. Bond energy of the M—H bond decreases from NH3 to BiH3
because of increase in the size of the element on descending the group.
Properties of Group 15 Hydrides, EH3
Property Ammonia Phosphine Arsine Stibine Bismuthine

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NH3 PH3 AS6H3 Sb6H3 BiH3
Melting point (K) 195 139 157 185 —
Boiling point (K) 240 186 211 256 295
Solubility in water (V/V at 293 K) 739 0.26 0.20 0.20 —
Odour pungent decaying-fish garlic-like — —
Bond energy, E—H (kJ mol–1) 389 322 297 255 —
Bond angle 106°47' 93°30' 92° 91°30' —
Dipole moment (D) 1.44 0.55 0.15
Decomposition to elements (K) 775 on gentle heating 295 295 very unstable
Ammonia
Ammonia is obtained on a small scale from ammonium salts which decompose when treated with caustic soda
or lime.
2NH4Cl + Ca(OH)2 → 2NH3 + 2H2O + CaCl2
(NH4)2SO4 + 2NaOH → 2NH3 + 2H2O + H2SO4
Ammonia is manufactured industrially by Haber process. Nitrogen from air and hydrogen from synthesis gas,
are released together at a high pressure of about 250 atmosphere and at a temperature of 800K in the presence of a
finely divided catalyst.
N2 + 3H2 2NH3 4H° = –92.0 kj mole–
Liquid Ammonia as a Non-aqueous Solvent
Liquid ammonia functions as a good solvent for many substances and many type of reactions.
Degree of ionisation of ammonia:
2NH3 NH 4+ + NH 2−
2H2O H3O+ + OH–
Acid base neutralisation reaction in liquid ammonia:
NH4Cl NH 4+ + Cl −
NaNH2 Na+ + NH 2−
 → Nacl + 2NH3
NH 3
NH4Cl + NaNH2
HCl + NaOH H

2O
→ Nacl + H2O
Similarly
→ PbCl2 + 3NH3
NH 3
2NH4Cl + PbNH
lead imide
NH
3NH4Cl + AlN 
3 → AlCl3 + 4NH3
Aluminiumnitride

Acid-base reaction of ammonia:

CH3COOH + H2O CH3COO– + H3O+
CH3COOH + NH3 CH3COO– + NH 4+
Reactions arrociated with complex formation are also comparable in water and liquid ammonia:
excess
ZnCl2 + 2NaOHwater
→ Zn(OH)2→ [Zn(OH)4]2–
NaOH

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 precipitate soluble complex

liquid NH3 excess

ZnCl2+2NaNH2  →Zn(NH2)2  → [Zn(NH2)4]2–
NaNH2
precipitate soluble
complex
Hydrazine, N2H2
It is obtained easily by the action of sodium hypochloride, NaoCl, on concentrated ammonia in presence of
glue.
NH3 + NaoCl → NH2 . Cl + NaOH
NH3 + NH2Cl → NH2 . NH2 + HCl

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or 2NH3 + Naocl → NH2 . NH2 + NaCl + H2O
Properties. (a) Physical. Free hydrazine is colourless liquid, very hygroscopic and soluble in alcohol and
water (b.pt. 113.5°; m.pt. 1.4°). It is not very stable. On exposure to air, it readily absorbs carbon dioxide and
moisture. It dissolves sulphur, arsenic, selenium and phosphorus.
(b) Chemical. (i) Decomposition. Hydrazine decomposes on heating into ammonia and nitrogen :
3NH2 . NH2 → N2 + 4NH3
(ii) Oxidation. When heated in air, it gives nitrogen :
NH2 . NH2 + O2 → N2 + 2H2O
Ozone and hydrogen peroxide oxidise it to hydrazoic acid, N3H,
3N2H4 + 5O3 → 2N3H + 5H2O + 5O2
3N2H4 + 5H2O2 → 2N3H + 10H2O
(iii) Reaction with sodium. In the absence of oxygen, it reacts with sodium to form sodium hydrazide:
2NH2NH2 + 2Na → 2NH2 . NH . Na + H2
(iv) Basic nature. With sulphur trioxide, a sulphonic acid is produced :
NH2NH2 + SO3  → NH2 . NH. SO3 . H
It is a weak base and forms two series of salts NH2NH2 . HCl and HClNH2 . NH2 HCl.
(v) Reducing action. Hydrazine is a powerful reducing agent :
(a) It reduces halogens to the corresponding halogen acids
NH2NH2 + 2Cl2 → N2 + 4HCl
NH2NH2 + 2Br2 → N2 + 4HBr
NH2NH2 + 2I2 → N2 + 4HI
(b) It reduces gold chloride solution to gold :
4AuCl3 + 3NH2NH2 → 4Au + 3N2 + 12HCl
Hydrazoic Acid, HN3 and Azides
Hydrazoic acid is also known as hydrogen azide. It is a colourless, highly explosive liquid. When sodamide is
reacted with N2O at 450K, sodium azide is formed which on treatment with sulphuric acid gives hydrazoic acid :
2NaNH2 + N2O → NaN3 + NaOH + NH3
2NaN3 + H2SO4 → 3HN3 + Na2SO4
It is a weak acid and dissociates only slightly in water. With electropositive metals it forms azides. Pb(N3)2 is
covalent and explosive in nature and it is used as a detonator. NaN3 is ionic and non-explosive. For the azide ion.
N 3− , three resonance structures can be drawn :
.. .. ..
: N..- = N+ = N:
.. ←→:N
-
.. —N ≡N: ←→
2- +
≡+ —N..2-:
:N N
For covalent azides and hydrazoic acid, which is largely covalent, three resonance structures may also be
drawn. But, according to Pauling's Adjacent Charge rule, one structure is excluded, since in it, two adjacent atoms
have the same charge.

HN=N=N -  - — N+ ≡N: HN ≡N+ — N
: ←→HN  2-:
  Not possible 
Thus the increased stability of the ionic azides may be due to a larger number of resonance form.

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Phosphine, PH3
Phosphine, PH3 is the most stable hydride of phosphores. It is intermediate in thermal stability between ammonia
and arsine. Phosphine can be easily prepared by any of the following methods :
(i) hydrolysis of metal phosphides such as Alp or Ca3P2 :
Ca3P2 + 6H2O → 2PH3 + 3Ca(OH)2
(ii) Pyrolysis of phosphorus acid at 480-485 K :
4H3PO3 → PH3 + 3H3PO4
(iii) Alkaline hydrolysis of phosphonium iodide:
PH4I + KOH → PH3 + KF + H2O

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(iv) Alkaline hydrolysis of white phosphorus (industrial process)
P4 + 3KOH + 3H2O → PH3 + 3KH2PO2
Q. 6. (a) Why does oxygen exist as a diatomic molecule while the other elements in the Group 16 exist as
polyatomic molecules ? Calculate the number of unpaired electrons in O2+ and O22 –. ions by drawing molecu-
lar orbital diagrams.
Ans. Oxygen-oxygen double bond is O2 molecule has bond energy three times that of oxygen-oxygen single
bond. The molecule, therefore, prefers to be in the diatomic form. While the bond energy of sulphur-sulphur double
bond is less than twice the sulphur sulphur single bond energy. The S—S bond stable makes the element exist in poly
atomic form.
Species No. of unpaired electron
(i) O 2+ 1
(ii) O 2− 1
(iii) O 2−
2
0
(b) How is sulphuric acid manufactured by contact process? Why is contact process preferred over the
lead chamber process for manufacture of sulphuric acid?
Ans. Modern Process–Contact Process: The following steps are used:
(i) Production of SO2:
∆
S + O2 → SO2
∆
4FeS2 + 11O2  → 2Fe2O3 + 8SO2
(ii) Purification of SO2:
Gases are first cooled and dust particles are removed by steam. Water vapour is removed by conc. H2SO4 and
Arsenic by ferric hydroxide. Then the gases are filtered through coke filters. Purity is tested in the Tyndall box, pure
gases are taken to contact or catalyst chamber after being preheated to 450° C.
(iii) Reactions in the contact or catalyst chamber:
2SO2 + O2 2SO3 + x cal
Conditions:
(a) Temperature 450° C–500° C.
(b) Pressure 1.6 to 1.7 atm.
(c) Concentration of gases = constant volume of SO2 + Excess of pure O2
Catalyst: Formerly platinised asbestos were used. But it is costly and is easily poisoned by impurities. Modern
catalyst is vanadium pentoxide (V2O5), which is cheap, efficient and is not easily poisoned by impurities. The
mechanism of the formation of SO3 in the presence of this catalyst is as follows:
V2O5 + SO2 → V2O4 + SO3
V2O4 + 2SO2 + O2  → 2VOSO4
2VOSO4  → V2O5 + SO2 + SO3
Net reaction:
2SO2 + O2 → 2SO3

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 SO3, if absorbed by water liberates a large amount of heat, producing an acid tog. Hence, it is absorbed by conc.
H2SO4 and then water is added to produce acid of desired concentration.
H2SO4 + SO3 → H2S2O7
(Oleum or pyrosulphuric acid)
H2S2O7 + H2O → 2H2SO4
The acid is pure and concentrated. It has specific gravity 1.8 and is 98 per cent by weight. Its normality is 36.
Modern Process-Contac Process Contact process is preferred over the lead chamber proces for manufacture of
sulphuric acid as it gives 98% pure H2S4
Q. 7. (a) Fluorine acts as the strongest oxidizing agent among the halogens, explain.

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Ans. Oxidising Power
Oxidation may be regarded as the removal of electrons. So that the oxidising agent gains electrons. Since halo-
gens have a greater tendency to pick up electrons, they act as strong oxidising agents. Their oxidising power, how-
ever, decreases on moving down the group. The strength of an oxidising agent or its ability to accept electrons
depends on several energy terms. The reactio:
1
X2 (standard) + e →X– (aq) ...(i)
2
representing the oxidising action of a halogen, is actually a complicated process. It involves the following steps:
1 1
X2 (standard) ∆H
 V
→ X2 (g) ...(ii)
2 2
1 ∆H
X2 (g) 
d
→ X (g) ...(iii)
2

 → X–(g)
EA
X(g) + e ...(iv)
∆H
X–(g) + aq  
hyd
→ X–(aq) ...(v)

The above changes are represented in the form of Born-Haber cycle, as shown below :
∆H ∆Hd
1
2
X2 (standard)  v 12→X2 (g) 
III
 X→
(g)
| II |
I || IV || E
↓ ∆Η Ηyd ↓
A

X – (aq) ←       
X –
(g)
V

Evidently, since energy is invariably absorbed in steps (II) and (III), enthalpy of vaporisation. ∆HV and enthalpy
of dissociation, ∆Hd, always have positive values. However, energy is released in steps (IV) and (V), hence, electron
affinity, EA, and enthalpy of hydration, ∆HHyd are negative. Consequently, from Hess's law, the net enthalpy change,
∆E for the reduction reaction (I) is given by the expression:
∆E = ∆HV + ∆Hd + EA + ∆Hhyd
For fluorine and chlorine which are gases at room temperature, the enthalpy of evaporation is omitted. Enthalpy
changes associated with each of the above steps and the net enthalpy change, ∆E are given in table:
Molecule Enthalpy of Enthalpy Electron Enthalpy of E
vapourisation, of dissociation, affinity, hydration, kJ mol–1
HV kJ mol–1 Hd kJ mol–1 EA kJ mol–1 Hhyd kJ mol–1
F2 — +79.2 – 333 – 460 – 714
Cl2 — 122.0 –348 – 385 –611
Br2 15 96.0 –340 –351 –580
I2 30 76.0 –297 –305 –496

Another important factor which makes fluorine the strongest oxidising agent in the high element - fluorine
covalent bond energy as shown in following table:

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 Halogen element bond energy, kJ mol–1
Element B C N O F Si P S Cl H

F 644 489 286 213 158 598 498 285 251 565
Cl 433 326 192 205 251 402 331 272 244 431
Br 368 272 201 251 331 268 213 209 364
I 272 238 243 234 184 209 299

(b) Why does hydrofluoric acid among the hydrohalic acids behave as the weakest acid?
Ans.

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Hydrohalic Acids
Aqueous solutions of hydrogen halides are called hydrohalic acids, viz., hydrofluoric, hydrochloric, hydrobromine
and hydriodic acid. Hydrohalic acids form constant boiling point mixtures with water. The aqueous solutions of
acids ionise as follows :
HX (aq) + H2O → H3O+ (aq) + X– (aq)
Their acid strength follows the order HI > HBr > HCl > HF. Acid strength is in general the tendency of HX (aq)
to give H3O+ (aq) and X–(aq). The enthalpy changes associated with the dissociation of hydrohalic acids can be
represented with the help of Born-Haber cycle in its simplest form as given below:
∆Hd
Hx(g) H(g) + x(g)

i EA

∆Hdehyd + –
H (g) x (g)

+ –
Hx(aq) H (aq) +x (aq)

The acid strength depends upon the sum of all enthalpy terms for various stages indicated in the Born Haber
cycle. Of these the most marked change is in the enthalpy of dissociation of H—X bond, which decreases from F – >
Cl– > Br– > I–. The total enthalpy change becomes more negative i.e., the reaction.
HX (aq) → H+ (aq) + X– (aq)
becomes more exothermic from HF to HI. As expected, acid strength varies in the reverse order, HI being the
strongest acid and HF the weakest acid.
(c) How do halogens react with water?
Ans. Chemical Properties: Halogens react with hydrogen to form hydrides which are called hydrogen halides.
Fluorine and chlorine react with hydrogen with expensive violence, fluorine-hydrogen mixture explodes even in the
dark chlorine-hydrogen mixture does so only in presence of light. This is called a photochemical reaction. It has
been shown that this reaction starts with the formation of halogen free radicals. It is not surprising in view of the
lower X—X bond energy as compared to H—H bond energy. Reaction of bromine and iodine with hydrogen are
slow. The latter being reversible.
Cl—Cl  → Cl ⋅ + Cl ⋅ initiation
hv
.........Step I
Cl ⋅ + H—H 
→ HCl + H ⋅ propagation .......Step
II
H ⋅ + Cl—Cl 
→ HCl + Cl propagation ......Step
III
Cl ⋅ + H ⋅ 
→ HCl termination .........Step

12
IV
Such reactions are called Chain Reaction since after the initiation of the reaction, the propagation steps II and
III are repeated in sequence till the reactants are consumed. The reaction gets terminated when free radicals start
combining with each other as in Step IV.
Fluorine reacts vigorously with water to form hydrofluoric acid and oxygen:
2F2 + 2H2O → 4HF + O2
The other halogens are sparingly soluble in water (Br2 > Cl2 > F2) and react partly to give a mixture of
hydrohalic and hypohalous acids:
X2 + H2O HX + HOX
Some Reactions of Halogens

N
General Reaction Remarks
nX2 + 2M     2MX → n F2, Cl2 with practically all metals; Br2, I2 with all except noble metals.
X2 + H2     2HX → Reaction with iodine reversible.
3X2 + 2P     2PX → 3 Similar reactions with As, Sb, Bi.
5X2 + 2P     2PX → 5 With excess X2, but not with I2; SbF5, SbCl5, AsF5. AsCl5 and BiF5 may
be prepared similarly.
X2 + 2S     S→ 2X2 With Cl2, Br2
X2 + H2O     H→ + + X– + HOX Not with F2
2X2 + 2H2O     4H →+ + 4X– + O2 F2 rapidly, Cl2 and Br2 slowly in sunlight.
X2 + H2S     2HX → +S
X2 + CO     COX → 2 X2 = Cl2, Br2
X2 + SO2     SO →2X2 X2 = F2, Cl2
X2 + Y2     2XY → Formation of interhalogen compounds (all except IF).
[X and Y are two different halogens]
Halogens react with aqueous alkali, the reactivity decreasing from fluorine to iodine. Fluorine behaves differently
from other halogens. It reacts with alkalies violently forming fluorides and fluorine oxides or oxygen as shown
below:
2F2 + 2NaOH incold
→ 2NaF + OF2 + H2O

2F2 + 4NoH inhot

→ 4NaF + O2 + H2O
Other halogens react with alkalies in cold to give hypohalides (XO–) and in hot to form halates ( XO 3– ):

2NaOH + X2 incold
→ NaOX + NaX + H2O

6NaOH + 3X2 inhot

→ NaXO3 + 5NaX + 5H2O (where X = Cl, Br or
I)
Q. 8. (a) Why were the noble gases and their compounds discovered late?
Ans. Chemical inertness of lighter noble gases, i.e. He, Ne and Ar, and rare abundance of comparatively reactive
noble gases, i.e. Kr, Xe and Rn were the reasons for the late discovery of noble gases.
(b) How was the first noble gas compound prepared?
Ans. Compounds of Noble Gases: The atoms of inert gases have stable energy states and consequently posses
high ionisation potential and negligible electron affinity. This is very little likelihood, therefore, of their forming
compounds of the usual type. The formation of compounds, however, has been reported under unusual conditions
but it is still doubtful whether argon or helium enter into chemical combination or not.
(i) Compounds formed through co-ordination. In 1935 Booth and Wilson carried out a thermal analysis of
the system argon, boron trifluoride and from the existence of a series of maxima in the freezing point-composition
diagrams, they concluded that the following compounds exist at low temperature:
Ar. BF3 ; Ar 2BF3 ; Ar (8 – 16) BF3

13
 These compounds bear an analogy to the compounds which boron trifluoride forms with dimethyl ether.
(CH3)2O → BF3 ; Ar → BF3 or F3B → Ar  → BF3
Similar compounds with krypton and xenon were also postulated but Wiberg and Karbe were not able to
confirm any of the compounds of this type and are doubtful whether such compounds could exist.
(ii) Compounds formed through dipole-induced dipole attraction. A strong dipole like water when brought
in contact with an inert gas under pressure at low temperature is likely to cause the polarisation of the gas atom so
that it could act as a dipole itself and attract the original dipole i.e. water. Hydrates of the following type have been
reported
Ar . 6H2O decomposing at – 24.8° C

N
Kr. 6H2O decomposing at – 39.2° C
Xe. 6H2O decomposing at 0° C
Recent work of Wiberg and Karbe has, however, cast a doubt upon the existence of these compounds.
(iii) Compounds formed under excited conditions. Boomer (1925) reported the information of compounds
of the type WHe2 by subjecting helium to electron bombardment. Manley (1927) reported that in presence of electric
flow discharge mercury and helium can be made to combine to form halides of the type HgHe 10 or HgHe2. Recent
work has shown that helium is probably absorbed on the surface of the metal and the reported compounds are not
true chemical compounds.
(c) Why are the highest oxidation states of the transition metals stabilised in the oxide and fluoride com-
pounds ?
Ans. The oxidation state of an element is related to the number of electrons that an atom loses, gains or appears
to use when joining with toher atom in compounds. If also determines the ability of an atom to oxidies (to lose
electrons) or to reduce (to gain electrons) other atoms or species oxidation results in an increase in the oxidation
state while reduction results in a decrease in the oxidation state if an atom is reuced, it has a higher number of
valence shell electrons, and therefore a higher oxidation state and is a strong oxidant. Oxygen and fluorine are very
strong oxidants and both oxide and fluoride ions are highly electronegative and have a very small size. Due to these
properties, they are able to oxidise the metal to its highest oxidation state.
(d) Explain why Cu+ ion is not coloured?
Ans. It may be seen from the table that the ions which have completely filled d-orbitals are colourless, since in
these there are no vacant d-orbitals to permit the promotion of electrons. Thus Cu+ (3d10) and Zn2+ (3d10) ions are
colourless. The cations having empty d-orbitals are also colourless e.g. Sc3+ (3d0) and Ti4+ (3d0) are colourless. It is
only cations having partially filled d-orbitals which are coloured.
Q. 9. (a) Why are zinc and cadmium not counted as transition metals even though they belong to the d-
block ?
Ans. A transition element is defined as the one which has incompletely filled d-aorbitals in its ground states or
in any one of its oxidation states. Zn and Cd of group 12 have full d10 configuration in their ground state as well as in
their common oxidation states and hence do not show the properties of typical transition metals. That is why zinc
and cadmium are not counted as transition metals.
(b) The electronic configuration of the free manganese and copper atoms are [Ar]3d54s2 and [Ar]3d104s1,
respectively. What are the configurations of the free ions Mn4+ and Cu3+ions?
Ans. Electronic configuration of Mn4+ – [A2] 3d3
Cu3+ i – [Ar] 3d8
(c) From crystal field theory, find out the number of unpaired electrons in the low-spin complex
[Co(CN)6]3–.

Ans. [Co (CN)6]3–

Unpaired electrons are 4 in number.
Crystal Field Splitting of d-orbitals: This theory consider the effect of the ligands on the energy of the outer
d-electrons in the central metal cation. Let us apply this theory to an octahedral complex. In such a complex the
central metal ion is at the centre and the six ligands occupy the six corners of the octahedron.
In the free metal ion all the five d-orbitals are degenerate as shown in Fig. (a). Now when the six ligands
approach the central metal cation along the axes, they exert an electrostatic force of repulsion on the outer d-

14
electrons i.e. d-electrons are repelled by the lone pairs the energy of the degenerate d-orbitals shown in Fig. (a) to
give five excited degenerate orbitals shown in Fig. (b). (A hypothetical State) since the lobes of d x 2 and d x 2 − y 2
orbitals (called e.g. set of orbitals) lie directly in the path of the approaching ligands, the electrons in these orbitals
experience greater repulsion exerted by the electron clouds of the ligands then do the electrons in the dxy . dyz and
dzx orbitals (called t2y set of orbitals) which are directed in space between x, y and z - axes. Hence under the
influence of the approaching ligands the obital viz d x 2 − y 2 and d z 2 are raised in energy while the orbitals viz. dxy, dyz
and dzx, are lowered in energy relative to the excited levels. (see figure (c))

2 2 2
dz dx –y
eg

N
+0.6∆ 0
∆ 0 or 10 Dq

Engery Increasing
+0.4∆ 0

t2g
dxydyzdzx
2 2 2
dz dx –y

dxy dyzdzx

(a) (b) (c)

Crystal Field Splitting in an octahedral complex

(a) The five degenerate d-orbitals in the isolated central metal ion
(b) Hypothetical degenerate d-orbitals at a higher energy level if all the ligands approach the metal ion at an equal distance from each of the d-
orbitals
(c) Crystal field splitting of d-orbitals into t2g and eg sets by the electrostatic field of the six approaching ligands.
The separation of five d-orbitals into t2g and eg sets of different energies is known as crystal field splitting. The
eg - set which is of higher energy is doubly degenerate while d2g-set which is lower in energy is triply degenerate.
The energy difference between eg and t2g sets is denoted by ∆e or 10 Dg where 0 in ∆0 indicates on octahedral
arrangent of ligands round the metal ion. ∆0 is called crystal field stabilisation energy (CFSE). It can be shown that
on the formation of an octahedral complex, the energy of t2g set is decreased by 0.4 ∆0 while that of eg set is increased
by 0.6 ∆0 as shown in above figure.
(d) Why is the contribution of orbital motion to paramagnetism not quenched in lanthanide ions?
Explain.
Ans. Magnetic Properties: The electronic configuration of the lanthanides is 2, 8, 18, 4s24p64d104f0–14,
5s 5p65d0–1, 6s2. These elements generally form trivalent cations (Ln3+) by losing two electrons from 6s-orbital and
2

one electron from 5d or 4f-orbital. Thus Ln3+ cations have partly filled 4f-orbital which is the source of their mag-
netic properties. Since in these cations 4f-orbtial is quite deeply seated, it is well shielded from the ligands surround-
ing the Ln3+ ion by the overlying 5s and 5p-sub-shells. The surrounding ligands are, therefore, not able to interact
with the 4f-electrons to quenet (i.e. nuillify) the orbital magnetic moment. Consequently for determining the effec-
tive magnetic moment, µeff for Ln+3 ion bolt spin moment and orbital moment of the electron are considered. The
orbital magnetic moment which is ignored in case of d-block elements, cannot be ignored here. Thus the spin-only
formula, viz.

µeff = n (n + 2) BM
where n = number of unpaired electrons which is used to calculate µeff for d-block elements cannot be used in case
of Ln3+ ions. The formula used for Ln3+ ions is

µeff = g J (J + 1) BM ...(1)
where g = Lande splitting factor, J = total angular momentum which is a vector sum of L (orbital angular momentum)
and S (spin angular momentum), i.e.,
J = (L + S). Only Sm3+ ions do not obey the relationship represented by equation (1).

15
 The calculated [from equation (1)] and experimental values of µeff (in BM) for the sulphates of Ln3+ ions show
that La3+ and Lu3+ ions, which are 4f 0 and 4f 14 type respectively are diamagnetic while the remaining Ln3+ ions are
paramagnetic.
Q. 10. (a) Give the possible electronic configurations of both octahedral and tetrahedral complexes of
2+
CO ion.
Ans. The electronic configuration of octahedral complex of Co2+ ion is–

[Co(NH3)6]2+

N
d s p2 hybridisation

The electronic confignuration of tetrahedral complex of Co2+ ion is [co(NH3)5Cl]2+

sp3 hybridisation

sp3

(b) Explain the role of depressor in Froth Floatation process. What information do Ellingham diagrams
provide?
Ans.

Foam + Sulphide Ore Air

Oil +
Air Pipe Water

Powdered Ore

Froth flotation process

n n

16