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Halogen and Noble Gases
Halogen and Noble Gases
Contents
Topic Page No.
Theory 01 - 16
Exercise - 1 17 - 23
Exercise - 2 24 - 26
Exercise - 3 27 - 29
Exercise - 4 30 - 30
Answer Key 31 - 32
Syllabus
Halogen & Noble Gases
Halogens: hydrohalic acids, oxides and oxyacids of chlorine,
bleaching powder.
Noble gas : Isolation, Xenon fluorides, Xenon oxygen compounds.
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HALOGEN & NOBEL GAS
GROUP 17 ELEMENTS : THE HALOGEN FAMILY
Fluorine, chlorine, bromine, iodine and astatine are members of Group 17. These are collectively known as
the halogens (Greek halo means salt and genes born i.e., salt producers). The halogens are highly reactive
non-metallic elements.
Electronic Configuration
All these elements have seven electrons in their outermost shell (ns2 np5) which is one electron short of the
next noble gas.
Atomic and Ionic Radii
The halogens have the smallest atomic radii in their respective periods due to maximum effective nuclear
charge . Atomic and ionic radii increase from fluorine to iodine due to increasing number of quantum shells.
Ionisation Enthalpy
They have little tendency to lose electron. Thus they have very high ionisation enthalpy. Due to increase in
atomic size, ionisation enthalpy decreases down the group.
Electron Gain Enthalpy
Halogen have maximum negative electron gain enthalpy in the corresponding period. This is due to the fact
that the atoms of these elements have only one electron less than stable noble gas configurations. Electron
gain enthalpy of the elements of the group becomes less negative down the group. However, 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
extra electron (incoming) does not experience much attraction.
Electronegativity
They have very high electronegativity. The electronegativity decreases down the group. Fluorine is the most
electronegative element in the periodic table
Bond Energy :
F F bond dissociation energy is less than that of Cl Cl and Br Br. It is due to larger inter
electronic (electron - electron) repulsion between the non bonding electrons in the 2P orbitals of fluorine
atom. then these in the 3p orbitals of chlorine atoms.
F F Cl Cl Br Br I I
38 kcal/mol 57 kcal/mol 45.5 kcal/mol 35.6 kcal/mol
Cl2 > Br2 > F2 > l2
Physical Properties
Fluorine and chlorine are gases, bromine is a liquid whereas iodine is a solid. Their melting and boiling
points steadily increase with atomic number. All halogens are coloured. This is due to absorption of radiations
in visible region which results in the excitation of outer electrons to higher energy level. By absorbing different
quanta of radiation, they display different colours. For example, F2, has yellow, Cl2, greenish yellow, Br2, red
and I2, violet colour. Fluorine and chlorine react with water. Bromine and iodine are only sparingly soluble in
water. But are soluble in organic solvents such as chloroform, carbon tetrachloride, carbon disulphide and
hydrocarbons to give coloured solutions. Except the smaller enthalpy of dissociation of F2 compared to that
of Cl2. The X-X bond disassociation enthalpies from chlorine onwards show the expected trend : Cl Cl > Br
Br > F F > I I. The reason for the smaller enthalpy of dissociation of F2 is the relatively larger electrons-
electrons repulsion among the lone pairs in F2 molecule where they are much closer to each other than in
case of Cl2.
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Atomic and physical properties
Element F Cl Br I
Atomic Number 9 17 35 53
Atomic Mass 19 35.45 79.90 126.90
Electronic configuration 2
[He] 2s 2p
5
[Ne] 3s 3p
2 5 10
[Ar] 3d 4s 4p
2 5 10
[Kr] 4d 5s 5p
2 5
More the value of the SRP, more powerful is the oxidising agent. Hence the order of oxidising power is
F2 > Cl2 > Br2 > 2
Hydration energy of X :
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Anomalous behaviour of fluorine
Fluorine differs considerably from other halogens due to -
(i) Small size
(ii) High electronegativity.
(iii) Non availability of d - orbitals in its valency shell.
(iv) Low bond dissociation energy of F F bond.
(a) Boiling point of HF is the highest and for other increases down the group.
(b) Due to hydrogen bonding HF is a liquid while HCl, HBr and HI are gases.
(c) Fluorine, being the most electronegative gives SF6 while other member do not form hexahalides with
sulphur.
(d) It exhibits oxidation state of only 1.
(e) It is the strongest oxidising agent.
(f) It liberates oxygen as well as ozone with water.
(g) HF does not ionize while HCl, HBr and HF ionize in aqueous solution.
(h) Solubility of salts :
(i) AgF is soluble in water while AgCl, AgBr and AgI are insoluble.
(i) It combines with hydrogen with explosion at a low temperature and even in the dark. No other halogens
combines so readily.
H2 + F2 2HF
(j) It liberates oxygen as well as ozone with water.
2H2O + 2F2 4HF + O2
3H2O + 3F2 6HF + O3
Comparison of [Cl2, Br2 and I2]
Explosive in Light
7. Combination with H2 Only on Heating Heating + Catalyst
Slow in Dark
CHLORINE (Cl2) :
Preparation :
(i) By heating chloride with concentrated H2SO4 in presence of MnO2.
4H+ + MnO2 + 2X X2 + Mn+2 + 2H2O
Bromides and iodides also liberate Br2 and I2 respectively with concentrated H2SO4 and MnO2.
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Properties :
(i) It is a greenishyellow gas with pungent and suffocating odour. It is about 25 times heavier than air. It can
be liquefied into greenishyellow liquid which boils at 239 K. It is soluble in water.
(ii) At low temperature it forms a hydrate with water having formula Cl2 . 8H2O which is infact a clathrate compound.
(iii) Oxidising & bleaching properties : Chlorine dissolves in water giving HCl and HOCl. Hypochlorous acid
(HOCl) so formed, gives nascent oxygen which is responsible for oxidising and bleaching properties of
chlorine.
(a) It oxidises ferrous to ferric, sulphite to sulphate, sulphur dioxide to sulphuric acid and iodine to iodic
acid.
2 FeSO4 + H2SO4 + Cl2 Fe2(SO4)3 + 2 HCl
Na2SO3 + Cl2 + H2O Na2SO4 + 2 HCl
SO2 + 2 H2O + Cl2 H2SO4 + 2 HCl
I2 + 6 H2O + 5 Cl2 2 HIO3 + 10 HCl
(b) Chlorine oxidises both Br and l to Br2 and I2 respectively.
X + Cl2 X2 + 2Cl
(c) It is a powerful bleaching agent ; bleaching action is due to oxidation.
Cl2 + H2O 2 HCl + O
Coloured substance + O Colourless substance
It bleaches vegetable or organic matter in the presence of moisture. Bleaching effect of chlorine is permanent.
Note : The bleaching action of SO2 is temporary because it takes place through reduction.
SO2 + 2 H2O H2 SO4 + 2 H
O2 of air
Reduced Colourless material Coloured material.
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(v) Reaction with dry slaked lime, Ca(OH)2 : To give bleaching powder.
2 Ca(OH)2 + 2 Cl2 Ca(OCl)2 + CaCl2 + 2 H2O
Uses : Cl2 is used
1. for bleaching wood pulp (required for the manufacture of paper and rayon), bleaching cotton and
textiles,
2. in the manufacture of dyes, drugs and organic compounds such as CCl4 , CHCl3 , DDT, refrigerants,
etc.
3. in the extraction of gold and platinum.
BROMINE (Br2) :
Preparation :
Properties :
(i) Reddish brown liquid, fairly soluble in water. It also forms hydrate like Cl2
(Br2 . 8H2O) Clathrate compound
IODINE (I2) :
Preparation :
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Properties :
(i) It is a dark violet solid, undergoes sublimation, least soluble (among halogens) in water but much more
soluble in K(aq.) due to formation of K3 . It is soluble in organic solvents like CHCl3, CCl4 etc. to get violet
solutions.
(ii) Reaction with hypo :
S2 O32 (thiosulphate ions) + 2 S4O62 (tetrathionate ions) + 2
This reaction is the basis of iodometric titration, which is carried out for the estimation of iodine using starch
indicator.
(iii) Reaction with NH3 :
NH3 (g) + 2 No Reaction
Preparation :
(i) By direct combination of elements :
H2 + Cl2 2HCl ; Pt
2HBr ;
H2 + Br2
Pt , 450 C
H2 + 2 2H
(ii) By heating a halide with concentrated acid :
150 C
(a) NaCl + H2SO4 NaHSO4 + HCl
550 C
NaHSO4 + NaCl Na2SO4 + HCl
This method is called as salt cake method as it involves the formation of NaHSO4 (salt cake).
HCl cannot be dried over P2O5 (P4O10) or quick lime since they react with gas chemically.
CaO + 2HCl CaCl2 + H2O
P4O10 + 3HCl POCl3 + 3HPO3
HCl is, hence dried by passing through concentrated H2SO4 .
(b) HBr (or H) cannot be prepared by heating bromide (iodide) with concentrated H2SO4 because HBr
and H are strong reducing agents and reduce H2SO4 to SO2 and get themselves oxidised
to bromine and iodine respectively.
KX + H2SO4 KHSO4 + HX
H2SO4 + 2HX SO2 + X2 + 2H2O (X = Br or )
Hence, HBr and H are prepared by heating bromides and iodides respectively with concentrated H3PO4.
3KBr(K) + H3PO4 K3PO4 + 3HBr (H)
(iii) By reaction of P4 (Laboratory Method) :
P4 + 6Br2 (62) 4PBr3 (4P3) (product in situ)
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Properties :
(i) It is colourless, corrosive liquid with pungent smell with high boiling point due to hydrogen bonding.
(ii) Dry HF does not attack metals under ordinary conditions (except K), but in presence of water it
dissolves metals with liberation of hydrogen gas.
(iii) It is a weak dibasic acid (due to strong HF bond) and forms two series of salt.
NaOH + H2F2 NaHF2 + H2O ; NaHF2 + NaOH 2NaF + H2O
Preparation :
(i) 2 NaClO3 + SO2 + H2SO4 traces of NaCl
2ClO2 + 2NaHSO4
(ii) 90 C
2KClO3 + 2 H2C2O4 2ClO2 (g) + 2CO2 (g) + K2C2O4 + 2H2O
(iii) 90 C
2AgClO3 + Cl2 2AgCl (white) + 2ClO2 + O2
Properties :
(i) Yellow gas at room temperature dissolves in water evolving heat and giving a dark green solution.
light
ClO2 ClO + [O]
It kill bacteria better than Cl2.
e + ClO2 ClO2 ] 2
H2 O2 + 2ClO2 2ClO2 + 2H+ + O2
or H2O2 + 2ClO2 + 2OH 2ClO2 + 2H2O + O2
(iv) Reaction with H :
In this reaction H behaves as a reducing agent where it reduces ClO2 into Cl and itself is oxidised to 2 .
Properties :
Cl2O is yellow-brown gas very soluble in water.
3Cl2O + 10NH3 6NH4Cl + 2N2 + 3H2O
OXY-ACIDS OF HALOGENS :
Oxidation state Chlorine Bromine Iodine Name of acid Name of salt
of halogens
Acidity increases
(i) The acid is known only in solution, It is obtained by shaking precipitate of HgO with chlorine water.
2HgO + 2Cl2 + H2O Hg2 OCl2 (Oxychloride of mercury) + 2HClO
(ii) Commercially, it is obtained by passing CO2 through suspension of bleaching powder and then distilling.
2CaOCl2 + H2O + CO2 CaCl2 + CaCO3 + 2HClO
Maximum concentration obtained is 25% as in the process of distillation, the acid decomposes into its anhydrides,
Cl2O.
2HOCl H2O + Cl2O
Properties :
(i) It is a weak acid. Its concentrated solution is yellow in colour while dilute solution is colourless. It is unstable
and decomposes.
2HClO 2HCl + O2
(ii) It dissolves magnesium with evolution of hydrogen.
Mg + 3HClO Mg(ClO)2 + H2
(iii) With alkalies, it forms salts called hypochlorites.
(iv) It acts as a powerful oxidising and bleaching agent. This is due to release of nascent oxygen easily.
HClO HCl + O
HXO2 SERIES :
Preparation :
It is obtained in aqueous solution when barium chlorite suspension in water is treated with H2SO4. The
insoluble barium sulphate is filtered off.
Ba(ClO2)2 + H2SO4 BaSO4 + 2HClO2
Properties:
(i) The freshly prepared solution is colourless but it soon decomposes to ClO2 which makes the solution yellow.
5 HClO2 4 ClO2 + HCl + 2H2O
(ii) Salts of HClO2 are called chlorite and prepared by one of the following methods.
2ClO2 + 2NaOH NaClO2 + NaClO3 + H2O
2ClO2 + Na2O2 2NaClO2 + O2
Chlorites are used as bleaches. They are stable in alkaline solution even when boiled, but in acid solution
they disproportionate, particularly when heated.
5HClO2 4ClO2 + HCl + 2H2O and 4HClO2 2ClO2 + HClO3 + HCl + H2O
HXO3 SERIES
CHLORIC ACID [HClO3] :
Preparation :
This acid is only known in solution. The acid is prepared by the action of the dilute H2SO4 on barium chlorate.
Ba (ClO3)2 + H2SO4 BaSO4 + 2HClO3.
After reaction, BaSO4 is removed by filtration, and the filtrate is evaporated in vacuum till 40 percent solution
is obtained. However, further concentration by evaporation leads to decomposition.
3HClO3 HClO4 + Cl2 + 2O2 + H2O
HBrO3 can be prepared by similar method using Ba(BrO3)2 .
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Properties:
(i) Anhydrous HClO4 is a colourless liquid which turns dark on keeping. It fumes in moist air.
(ii) It is one of the strongest acid and ionises as follows :
HClO4 H+ + ClO4
(iii) It dissolves most of the metals.
Zn + 2HClO4 Zn(ClO4)2 + H2
(iv) Hot concentrated acid (73%) behaves as a remarkable oxidising agent :
4HClO4 2Cl2 + 7O2 + 2H2O
(v) 2HClO4 + P2O5 2HPO3 + Cl2O7
Mg (ClO4)2 is used in dry batteries and is also an effective desiccant called anhydrone. KClO4 is used in fire
works and flares.
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Cyanide ions (CN) : Isocyanide ion (NC)
Cyanate ion (OCN) : Fulminate ion (ONC)
Thiocyanate ions (SCN) : Isothiocyanate ion (NCS)
Selenocyanate ion (SeCN) :Tellurocyanate ion (TeCN)
Azide ion (N3) : Azido carbon disulphide ion (SCSN3)
As the dimers of halide ions are called halogens, the covalent dimers of the pseudohalide ions are
called halogens or halogenoids.The pseudohalogens known are :
Cyanogen (CN)2 : Oxycyanogen (OCN)2
Thiocyanogen (SCN)2 : Selenocyanogen
(SeCN)2
Tellurocyanogen (TeCN)2 : Azido carbon
disulphide (SCSN3)2
INTERHALOGEN COMPOUNDS :
We know that halogen atoms have different electronegativity. Due to this difference in electronegativity the
halogen atoms combine with each other and give rise to the formation of binary covalent compounds, which
are called interhalogen compounds. These are of four types.
AB AB3 AB5 AB7
ClF ClF3 ClF5 lF7
BrF BrF3 BrF5
ICl ICl3 IF5
IF IF3
Properties :
Group 18 consists of six elements: helium, neon, argon, krypton , xenon and radon . All these are gases and
chemically unreactive. They form very few compounds . Because of this they are termed noble gases.
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Occurrence
All the noble gases except radon occur in the atmosphere. Their atmospheric abundance in dry air is ~ 1%
by volume of which argon is the major constituent. Helium and sometimes neon are found in minerals of
radioactive origin e.g., pitchblende, monazite, cleveite. The main commercial source of helium is natural gas.
226
Xenon and radon are the rarest elements of the group. Radon is obtained as a decay product of Ra.
226 222
88 Ra
86 Rn + 24He
Most abundant element in air is Ar. Order of abundance in the air is Ar > Ne > Kr > He > Xe.
ISOLATION
Except He, non-radioactive noble gases are commercially isolated from air by two method.
(a) Done on coconut. Gas particles are adsorbed in surface of coconut charcoal
(b) Larger the size, more will be the adsorption so maximum adsorption of Xe at highest temp.
Physical properties
All the noble gases are mono-atomic. They are colourless, and tasteless. They are sparingly soluble in
water. They have very low melting and boiling points because the only type of interatomic interaction in
these elements is weak dispersion forces,. Helium has the lowest boiling point (4.2K) of any known sub-
stance. It has a unusual property of diffusing through most commonly used laboratory materials such as
rubber, glass or plastics.
Atomic and physical properties
Element He Ne Ar Kr Xe
Atomic Number 2 10 18 36 54
Atomic Mass 4 20.18 39.10 83.80 131.30
Electronic configuration 1s
2 2
[He] 2s 2p
6 2
[Ne] 3s 3p
6 10 2
[Ar] 3d 4s 4p
6 10 2
[Kr] 4d 5s 5p
6
Chemical Properties : In general, noble gases are least reactive. Their inertness to chemical reactivity is
attributed to the following reasons:
(iii) Hg ( arc )
Xe + F2 XeF2
(iv) Recently discovered method :
K+ [AgF4] [potassium tetrafluoroargentate ()] is first prepared and this is reacted with BF3 .
K+ [AgF4] BF3
AgF3 (red solid) + KBF4
2 AgF3 + Xe 2 AgF2 (Brown solid) + XeF2
Properties :
(i) Colorless crystalline solid and sublimes at 298 K.
(ii) Dissolves in water to give a solution with a pungent odour. Much soluble in HF liquid.
(iii) This is stored in a vessel made up of monel metal which is a alloy of nickel.
(iv) Reaction with H2 : It reacts with hydrogen gas at 4000C
XeF2 + H2 Xe + 2HF
(v) Hydrolysis :
(a) 2XeF2 + 2H2O 2Xe + 4HF + O2 (slow)
The above is neither a cationic hydrolysis nor an anionic hydrolysis as seen in ionic equilibrium. It is
a covalent compound and hydrolysis is like that of PCl5 .
(b) Hydrolysis is more rapid with alkali.
XeF2 + 2 NaOH Xe + O2 + 2NaF + H2O (fast)
The reaction (a) is slower probably due to dissolution of XeF2 in HF.
(vi) Oxidising properties :
Higher the value of SRP better is the oxidising property of the species.
The standard reduction potential for XeF2 is measured to be + 2.64 V. Therefore, it acts as a strong oxidising
agent.
2e + 2H+ + XeF2 Xe + 2HF; SRP = + 2.64 V
873 K,
Xe + 2F2
XeF4
7 bar ,
1 : 5 Nitube
Properties :
(i) It is a colorless crystalline solid and sublimes at 298 K.
(ii) It undergoes sublimation, soluble in CF3 COOH. It undergoes hydrolysis violently hence no moisture
must be present during its preparation.
(iii) Reaction with H2O : 6 XeF4 + 12 H2O 4 Xe + 2XeO3 + 24 HF + 3O2
XeO3 is white solid and explosive compound (dry), soluble in water (well behaved in water)
XeO3 reacts with NaOH forming sodium xenate
XeO3 + NaOH Na+ [HXeO4] (sodium xenate)
It disproportionates into perxenate ion in basic medium.
4
2 [HXeO4] + 2OH [XeO6] + Xe + O2 + 2H2O
Xenic acid (H2XeO4) is a very weak acid.
(iv) Oxidising properties of XeF4 :
XeF4 + 2 H2 Xe + 4 HF ; XeF4 + 2 Hg Xe + 2HgF2
(v) Addition reactions : XeF4 reacts with fluoride ion acceptors to form cationic species and fluoride ion donors
to form fluoroanions.
XeF4 + SbF5 [XeF3]+ [SbF6]
XENON HEXAFLUORIDE (XeF6) :
Preparation:
573 K , 60 70 bar
(i) Xe 3F2 XeF6 (ii) XeF4 + O2 F2 XeF6 + O2
1 : 20 Ni tube
XENONOXYGEN COMPOUNDS :
Hydrolysis of XeF4 and XeF6 with water gives XeO3.
6 XeF4 + 12 H2O 4 Xe + 2 XeO3 + 24 HF + 3 O2
XeF6 + 3 H2O XeO3 + 6 HF
Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4 and XeO2F2 .
XeF6 + H2O XeOF4 + 2 HF
XeF6 + 2 H2O XeO2F2 + 4 HF
XeO3 is a colourless explosive solid and has a pyramidal molecular structure. XeOF4 is a colourless volatile
liquid and has a square pyramidal molecular structure.
Uses :
Helium is a noninflammable and light gas. Hence, it is used in filling balloons for meteorological observations.
It is also used in gascooled nuclear reactors. Liquid helium (b.p.4.2 K) finds use as cryogenic agent for
carrying out various experiments at low temperatures. It is used to produce and sustain powerful
superconducting magnets which form an essential part of modern NMR spectrometers and Magnetic
Resonance Imaging (MRI) systems for clinical diagnosis. It is used as a diluent for oxygen in modern diving
apparatus because of its very low solubility in blood.
Neon is used in discharge tubes and fluorescent bulbs for advertisement display purposes. Neon bulbs are
used in botanical gardens and in green houses.
Argon is used mainly to provide an inert atmosphere in high temperature metallurgical process (arc welding
of metals or alloys) and for filling electric bulbs. It is also used in the laboratory for handing substances that
are airsensitive.
Xenon and Krypton are used in light bulbs designed for special purposes.
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PART - I : OBJECTIVE QUESTIONS
Group 17th
1. The halogens are :
(A) transition elements (B) inner-transition elements
(C) noble elements (D) representative elements
2. Astatine is the element below iodine in the group VIIA of the periodic table. Which of the following statements
is not true for astatine ?
(A) It is less electronegative than iodine.
(B) It will exhibit only 1 oxidation state.
(C) Intermolecular forces between the astatine molecules will be larger than that between iodine molecules.
(D) None of these.
3. H2O is oxidised to O2 by :
(A) ClO2 (B) H2O2 (C) H2O (D) F2
13. Elements of which one of the following groups will form anions most readily ?
(A) oxygen group (B) nitrogen group (C) halogens (D) alkali metals
16. Which one of the hydracid does not form any precipitate with AgNO3 ?
(A) HF (B) HCl (C) HBr (D) HI
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33. Concentrated H2SO4 cannot be used to prepare HBr from NaBr, because it ;
(A) reduces HBr (B) oxidises HBr
(C) disproportionates HBr (D) reacts slowly with NaBr
34. The following acids have been arranged in order of decreasing acid strength. Identify the correct order.
ClOH (), BrOH (), IOH ()
(A) > > (B) > > (C) > > (D) > >
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44. The solubility of iodine in H2O may be increased by the addition of -
(A) Na2S2O3 (B) CHCl3 (C) KI (D) CS2
45. When thiosulphate ion is oxidised by iodine, the new product formed is :
(A) SO32 (B) SO42 (C) S4O62 (D) S2O62
49. Which amongst the following reactions cannot be used for the respective preparation ?
(A) 2KBr + H2SO4 (conc.) K2SO4 + 2HBr (B) NaCl + H2SO4 (conc.) NaHSO4 + HCl
(C) NaHSO4 + NaCl Na2SO4 + HCl (D) CaF2 + H2SO4 CaSO4 + 2HF
50. In the preparation of HBr or HI , NaX (X = Br, I) is treated with H3PO4 and not by concentrated H2SO4 since,
(A) H2SO4 makes the reaction reversible
(B) H2SO4 oxidises HX to X2 (Br2 , I2)
(C) Na2SO4 is water soluble and Na3PO4 is water insoluble
(D) Na3PO4 is water insoluble and Na2SO4 is water soluble
51. HBr and HI can reduce H2SO4, HCl can reduce KMnO4 and HF can reduce :
(A) K2Cr2O7 (B) KMnO4 (C) H2SO4 (D) none of these
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60. HCl cannot form H2Cl2, while HF can form hydrogen bonds -
(A) Fluorine is more reactive
(B) HF is more reactive
(C) Fluorine atom is small and can form hydrogen bonds
(D) None
65.* Which of the following salts will evolve halogen on treatment with conc. H2SO4 ?
(A) NaCl (B) KI (C) NaBr (D) none of these
68.* Which of the following product(s) is/are obtained when Cl2O6 reacts with KOH ?
(A) KCl (B) KClO2 (C) KClO3 (D) KClO4
69.* Which of the following product(s) is/are obtained when Cl2O reacts with NH3 ?
(A) NO2 (B) N2 (C) NCl3 (D) NH4Cl
Group 18th
1. The formation of O2+ [PtF6] is the basis for the formation of xenon fluorides. This is because :
(A) O2 and Xe have comparable sizes.
(B) both O2 and Xe are gases.
(C) O2 and Xe have comparable ionisation energies.
(D) O2 and Xe have comparable electronegativities.
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5. The inert gases can be isolated and separated by -
(A) Electrolysis of their compounds (B) Fractional distillation of liquid air
(C) Adsorption on charcoal (D) Both (B) and (C)
7. Which of the following noble gas was reacted with PtF6 by Bartlett to prepare the first noble gas compounds-
(A) He (B) Xe (C) Ar (D) Kr
8. Molecular shapes of SF4, CF4 and XeF4 are -
(A) The same, with 2, 0 and 1 lone pairs of electrons respectively
(B) The same, with 1, 1 and 1 lone pairs of electrons respectively
(C) Different, with 0, 1 and 2 lone pairs of electrons respectively
(D) Different, with 1, 0 and 2 lone pairs of electrons respectively
13. Helium oxygen mixture is used by deep sea divers in preference to nitrogen oxygen mix ture because-
(A) Helium is much less soluble in blood than nitrogen
(B) Nitrogen is much less soluble in blood than helium
(C) Due to high pressure deep under sea nitrogen and oxygen react to give poisonous nitric oxide
(D) Nitrogen is highly soluble in water
16. Number of lone pairs of electrons on Xe atoms in XeF2, XeF4 and XeF6 molecules are respectively -
(A) 3, 2 and 1 (B) 4, 3 and 2 (C) 2, 3 and 1 (D) 3, 2 and 0
21. Which one fo the following is a correct pair with respect to molecular formula of xenon compound and
hydridization state of xenon in it -
(A) XeF4, sp3 (B) XeF2, sp (C) XeF2, sp3d (D) XeF4, sp2
25. Among the following molecules, (i) XeO3 (ii) XeOF4 (iii) XeF6
those having same number of lone pairs on Xe are :
(A) (i) and (ii) only (B) (i) and (iii) only (C) (ii) and (iii) only (D) (i) , (ii) and (iii)
27. The product of the reaction between one mole of XeO3 and two mole of XeF6 is :
(A) XeO2F2 (B) XeOF4 (C) XeO3F2 (D) XeO4
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PART - I : MIXED OBJECTIVE
9. I4O9 is an
(A) covalent bond (B) coordinate compound
(C) ionic compound (D) double salt
11. When chlorine water is added to an aqueous solution of sodium iodide in the presence of chloroform,
a violet colouration is obtained. On adding more of chlorine water and vigorous shaking, the violet
colour disappears. This shows the conversion of.......into.....
(A) I2, HIO3 (B) I2, HI (C) HI, HIO3 (D) I2, HIO
12. A greenish yellow gas reacts with an alkali hydroxide to form a halate which can be used in fireworks
and safety matches. The gas and the halate are
(A) Br2, KBrO3 (B) Cl2, KClO3 (C) I2, NaIO3 (D) I2, KIO3
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More than one choice type
cgqfod Yih izd kj
13. Which of the following product(s) is/are obtained in the following reaction
KBrO3 + F2 + KOH product(s)
(A) KBrO4 (B) KF (C) HOF (D) Br2
15. Which of the following will not displace the halogen from the solution of the halide ?
(A) Br2 added to NaI (B) Br2 added to NaCl (C) Cl2 added to KCl (D) Cl2 added to NaF
20. Na2S2O3 may react with the compounds given in column (I). Na2S2O3 exhibits the properties of the type given
in the column (II)
Column - I Column - II
(reactant) (type of property shown)
(A) Chlorine (CI2) (p) Complexing reagent
(B) Silver bromide (q) Disproportionation
(C) Hydrochloric acid (r) Only as reductant
(D) Iodine (I2) (s) An-antichlor
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PART - II : SUBJECTIVE QUESTIONS
2. (a) When HCl reacts with finely powdered iron, it forms ferrous chloride and not ferric chloride. Why ?
(b) Chlorine water turns blue litmus red but solution becomes colourless after sometime.
3. CaOCl2 in aqueous solution changes to Cl2 . What is the type of this change ?
9. Identify [A] [B] and [C] and gives the complete chemical reactions involved.
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PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)
3. The reaction, 3ClO (aq) ClO3 (aq) + 2Cl (aq) is an example of : [JEE 2001 (S) , 3/35]
(A) oxidation reaction (B) reduction reaction
(C) disproportionation reaction (D) decomposition reaction
4. A gas X is passed through water to form a saturated solution. The aqueous solution on treatment with silver
nitrate gives a white precipitate. The saturated aqueous solution also dissolves magnesium ribbon with
evolution of a colourless gas Y. Identify X and Y. [JEE 2002 (S), 3/90]
(A) X = CO2 , Y = Cl2 (B) X = Cl2, Y = CO2 (C) X = Cl2 , Y = H2 (D) X = H2 , Y = Cl2
5. Reaction of Br2 with Na2CO3 in aqueous solution gives sodium bromide and sodium bromate with evolution
of CO2 gas. The number of sodium bromide molecules involved in the balanced chemical equation is
[JEE 2011, 4/80]
6.* Which fo the following hydrogen halides react(s) with AgNO3 (aq) to give a precipitate that dissolves in
Na2S2O3 (aq) ? [JEE 2012, 4/210]
(A) HCl (B) HF (C) HBr (D) HI
Paragraph
Bleaching poweder and bleach solution are produced on a large scale and used in several house hold
products. The effectiveness of bleach solution is often measured by iodometry.
7. Bleaching powder contains a salt of an oxoacid as one of its components. The anhydride of that oxoacid is
[JEE 2012, 3/198]
(A) Cl2O (B) Cl2O7 (C) ClO2 (D) Cl2O6
Group 18th
Paragraph for Question Nos. 1 & 2
The noble gases have closed-shell electronic configuration and are monoatomic gases under normal conditions.
The low boiling points of the lighter noble gases are due to weak dispersion forces between the atoms and
the absence of other interatomic interactions.
The direct reaction of xenon with fluorine leads to a series of compounds with oxidation numbers +2, +4 and
+6. XeF4 reacts violently with water to give XeO3. The compounds of xenon exhibit rich stereochemistry and
their geometries can be deduced considering the total number of electron pairs in the valence shell.
1. Argon is used in arc welding because of its : [JEE 2007 (P-I), 4 /81]
(A) low reactivity with metal (B) ability to lower the melting point of metal
(C) flammability (D) high calorific value
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3. XeF4 and XeF6 are expected to be : [JEE 2007 (P-I), 4 /81]
4. All the compounds listed in Column I react with water. Match the result of the respective reactions with the
appropriate options listed in Column II. [JEE 2010, (P-II) 8/79]
Column I Column II
(t) O2 formation
The reactions of Cl2 gas with cold-dilute and hot-concentrated NaOH in water give sodium salts of two
(different) oxoacids of chlorine, P and Q, respectively. The Cl2 gas reacts with SO2 gas, in presence of
charcoal, to give a product R. R reacts with white phosphorus to give a compound S. On hydrolysis, S gives
an oxoacid of phosphorus, T.
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PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. Concentrated hydrochloric acid when kept in open air sometimes produces a cloud of white fumes. This is
due to : [AIEEE 2003]
(1) strong affinity of HCl gas for moisture in air results in forming of droplets of liquid solution which appears
like a cloudy smoke.
(2) strong affinity for water, conc. HCl pulls moisture of air towards self. The moisture forms droplets of water
and hence the cloud.
(3) conc. HCl emits strongly smelling HCl gas all the time.
(4) oxygen in air reacts with emitted HCl gas to form a cloud of chlorine gas.
2. Which one of the following statements regarding helium is incorrect ? [AIEEE 2004]
(1) It is used to produce and sustain powerful superconducting magnets
(2) It is used as a cryogenic agent for carrying out experiments at low temperatures
(3) It is used to fill gas balloons instead of hydrogen because it is lighter and non-inflammable
(4) It is used in gas-cooled nuclear reactors
3. Which among the following factors is the most important in making fluorine the strongest oxidizing halogen?
[AIEEE-2004]
(1) Hydration enthalpy (2) Ionization enthalpy (3) Electron affinity (4) Bond dissociation energy
4. The correct order of the thermal stability of hydrogen halides (H X) is : [AIEEE 2005]
(1) HI > HBr > HCl > HF (2) HF > HCl > HBr > HI
(3) HCl < HF < HBr < HI (4) HI > HCl < HF < HBr
5. Which of the following chemical reactions depicts the oxidizing behaviour of H2SO4? [AIEEE 2006]
(1) 2HI + H2SO4 I2 + SO2 + 2H2O (2) Ca(OH)2 + H2SO4 CaSO4 + 2H2O
(3) NaCl + H2SO4 NaHSO4 + HCl (4) 2PCl5 + H2SO4 2POCl3 + 2HCl + SO2Cl2
6. What products are expected from the disproportionation reaction of hypochlorous acid? [AIEEE 2006]
(1) HClO3 and Cl2O (2) HClO2 and HClO4 (3) HCl and Cl2O (4) HCl and HClO3
7. The stability of dihalides of Si, Ge, Sn and Pb increases steadily in the sequence : [AIEEE 2007, 3/120]
(1) GeX2 < SiX2 < SnX2 < PbX2 (2) SiX2 < GeX2 < PbX2 < SnX2
(3) SiX2 < GeX2 < SnX2 < PbX2 (4) PbX2 < SnX2 < GeX2 < SiX2
8. Identify the incorrect statement among the following. [AIEEE 2007, 3/120]
(1) Cl2 reacts with excess of NH3 to give N2 and HCl.
(2) Br2 reacts with hot and strong NaOH solution to give NaBr, NaBrO4 and H2O.
(3) Ozone reacts with SO2 to given SO3.
(4) Silicon reacts with NaOH(aq) in the presence of air to give Na2SiO3 and H2O.
9 Which one of the following reactions of Xenon compounds is not feasible ? [AIEEE 2009, 4/144]
(1) 3XeF4 + 6H2O 2Xe + XeO3 + 12HF + 1.5O2 (2) 2XeF2 + 2H2O 2Xe + 4HF + O2
(3) XeF6 + RbF Rb[XeF7] (4) XeO3 + 6HF XeF6 + 3H2O
10. Which of the following exists as covalent crystals in the solid state ? [JEE Mains_2013]
(1) Iodine (2) Silicon (3) sulphur (4) Phosphorus
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NCERT QUESTIONS
3. Explain why inspite of nearly the same electronegativity, nitrogen forms hydrogen bonding while chlorine
does not.
7. How can you prepare Cl2 from HCl and HCl from Cl2? Write reactions only.
8. What inspired N. Bartlett for carrying out reaction between Xe and PtF6?
11. How are xenon fluorides XeF2, XeF4 and XeF6 obtained?
12. With what neutral molecule is ClO isoelectronic? Is that molecule a Lewis base?
14. Arrange the following in the order of property indicated for each set :
(i) F2, Cl2, Br2, I2 - increasing bond dissociation enthalpy.
(ii) HF, HCl, HBr, HI - increasing acid strength.
(iii) NH3, PH3, AsH3, SbH3, BiH3 - increasing base strength.
16. Give the formula and describe the structure of a noble gas species which is isostructural with :
(i) ICl4 (ii) IBr2 (iii) BrO3
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EXERCISE # 1
PART - I
Group 17th
1. (D) 2. (B) 3. (D) 4. (D) 5. (A) 6. (B) 7. (D)
8. (C) 9. (A) 10. (D) 11. (D) 12. (B) 13. (C) 14. (D)
15. (A) 16. (A) 17. (A) 18. (C) 19. (B) 20. (D) 21. (A)
22. (A) 23. (C) 24. (C) 25. (A) 26. (C) 27. (D) 28. (D)
29. (B) 30. (C) 31. (D) 32. (B) 33. (B) 34. (A) 35. (B)
36. (D) 37. (A) 38. (A) 39. (A) 40. (B) 41. (D) 42. (A)
43. (A) 44. (C) 45. (C) 46. (B) 47. (C) 48. (D) 49. (A)
50. (B) 51. (D) 52. (A) 53. (D) 54. (D) 55. (C) 56. (B)
57. (D) 58. (C) 59. (B) 60. (C) 61. (A) 62. (D) 63.* (BC)
64.* (ABC) 65.* (BC) 66.* (AC) 67.* (ABD) 68.* (CD) 69.* (BD)
Group 18th
1. (C) 2. (B) 3. (A) 4. (A) 5. (D) 6. (C) 7. (B)
8. (D) 9. (B) 10. (B) 11. (B) 12. (A) 13. (A) 14. (A)
15. (C) 16. (A) 17. (B) 18. (A) 19. (B) 20. (A) 21. (C)
22. (A) 23. (B) 24. (C) 25. (D) 26. (C) 27. (B) 28. (A)
29.* (ABCD) 30.* (ABCD)
EXERCISE # 2
PART - I
1. (C) 2. (D) 3. (B) 4. (D) 5. (C) 6. (D) 7. (A)
8. (C) 9. (C) 10. (D) 11. (A) 12. (B) 13. (AB) 14. (AB)
15. (BCD) 16. (AB) 17. (BCD) 18. (ABCD)
19. (A q) ; (B s) ; (C p) ; (D p,r) 20. (A - r, s) ; (B - p) ; (C - q) ; (D - r)
PART - II
1. Br2 + OH (hot) Br + BrO3
distillation
Br + BrO3 + H+ Br2
2. (a) It forms H2 gas.
Fe + 2 HCl FeCl2 + H2. Liberation of hydrogen prevents the formation of ferric chloride.
(b) Blue litmus change into red due to acidic nature (Cl2 + H2O HOCl + HCl) but it is bleaching agent
also (oxidising agent),therefore, it decolourises the red litmus.
3. CaOCl2 + H2O Ca(OH)2 + Cl2 Redox reaction.
4.
5. (a) Cl2 being a stronger oxidising agent than I2, first oxidises KI to I2 which imparts brown colour to the
solution. But when Cl2 is passed in excess, the I2 so formed gets further oxidised to HIO3 (colourless)
2KI (aq) + Cl2(g) 2KCl (aq) + I2(s) ; 5Cl2 + I2 + 6H2O 10HCl + 2HIO3
(b) Oxidation state of Cl in HClO4 is + 7 and that of S in H2SO4 is + 6. (Cl is more electronegative than S). As
a result, ClO3 part of HClO4 can break the OH bond more easily to liberate a proton than SO2 part in H2SO4.
Thus HClO4 is a stronger acid then H2SO4.
(c) HI is a stronger reducing agent. It, therefore, reduces H2SO4 to SO2 and itself gets oxidised to I2.
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NaI + H2SO4 NaHSO4 + HI] 2
H2SO4 + 2HI SO2 + I2 + 2H2O
2NaI + 3H2SO4 2NaHSO4 + I2 + 2H2O + SO2
6. (A) Argon.
(B) Helium ; Exists as mono-atomic molecules and are held together by weak van der Waals forces.
These van der Waals forces increase with the increase in atomic size of the atom, and therefore, the
boiling points increases from He to Rn. Hence He has least boiling point.
7. It can be used to separate mixture of inert gases containing say He and Xe. Process is much cheaper than
say distillation as a means of separation.
8. 80 C
XeF4 + H2O XeOF2 + 2HF..
The oxidation states of all the elements in the products remain the same as it was in the reacting state.
hence, it is a not redox reaction.
9. [A] = Br ; [B] = BrO3 ; [C] = concentrated H2SO4
10. Anhydrous HF is only slightly ionized and is, therefore a poor conductor of electricity Thus a mixture of KF
and HF is electrolysed to increase the conductivity.
EXERCISE # 3
PART - I
Group 17th
1. 2K(aq.) + Cl2 2KCl(aq.) + 2
In the reaction Cl2 oxidises iodide ion (1 oxidation state) to 2 (0 oxidation state). Cl2 has higher oxidation
potential than 2 and thus oxidises iodide to iodine getting itself reduced to chloride ion. Similarly,
2I (aq.) I2 (s) + 2e .
Cl2 (g) + 2e 2Cl (aq).
Group 18th
1. (A) 2. (C) 3. (A) 4. (A p, s) ; (B p, q, r, t); (Cp, q) ; (Dp)
5. (A) 6. (A)
PART - II
1. (4) 2. (3) 3. (4) 4. (2) 5. (1) 6. (4) 7. (3)
8. (2) 9 (4) 10. (2)
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