p-Block

Group 13
(a) Concentrated deposits of crystalline borax [Na2B4O5(OH)4.8H2O] are found in ancient lake beds, such as the Mojave
Desert and Death Valley in the western United States. (b) Borax is used in various cleaning products, including 20 Mule
Team Borax, a laundry detergent named for the teams of 20 mules that hauled wagons full of borax from desert deposits to
railroad terminals in the 1880s.
 Occurence
• Boron = Orthoboric acid (H3BO3), Borax (Na2B4O7.10H2O), Kernite (Na2B4O7.4H2O). In India, Borax occurs in Puga Valley
(Ladakh) and Sambhar Lake (Rajasthan). The Abundance of Boron in earth crust is less than 0.00001% by mass. Isotopic
10 11
abundance of B (19%) and B (81%)
• Aluminium = earth crust (8.3% by mass), Bauxite (Al2O3.2H2O), Cryolite (Na3 AlF6). In India, it is found as mica in Madhya
Pradesh, Karnataka, Orissa and Jammu
• Gallium, Indium, Thallium = less abundant in nature.
• Nihonium = Synthetically prepared radioactive element
 Properties of Group 13:
1. Electronic Configuration:

Valence Electron
Atomic Symbol Atomic No Atomic mass (u)
Configuration

Boron B 5 10.81 2s2 2p1

Aluminium Al 13 26.98 3s2 3p1

Gallium Ga 31 69.72 3d10 4s2 4p1

Indium In 49 114.82 4d10 5s2 5p1

Thallium Tl 81 204.38 4f14 5d10 6s2 6p1

2. Melting Point :

Order : B > Al > Tl > In > Ga

Element B Al Ga In Tl

[Link] (K) 2348 933 302.7 429.6 577

3. Boiling Point :

Order : B > Al > Ga > In > Tl

Element B Al Ga In Tl

[Link] (K) 4273 2792 2477 2345 1746

4. Atomic Size:

Element B Al Ga In Tl

Covalent radius
87 143 135 167 170
(pm)

Size increases due to increase in no. of shells

5. Electronegativity

Order : B > Tl > In > Ga > Al

Element B Al Ga In Tl

Electronegativity 2.0 1.5 1.6 1.7 1.8

6. Density:
Element B Al Ga In Tl

Density (g/cc) 2.35 2.70 5.90 7.31 11.85

Density increases due to increase in mass is more dominant over increase in size.

7. Ionisation Enthalpy: Generally IE decreases as size increases.( D-block contraction 3p → 4p , Lanthanoid contraction
5p → 6p , Actinide contraction 6p → 7p)

Element B Al Ga In Tl

1st IE (KJ/mol) 801 577 579 558 589

Element B Al Ga In Tl

2nd IE (KJ/mol) 2427 1816 1979 1820 1971

Element B Al Ga In Tl

3rd IE (KJ/mol) 3659 2744 2962 2704 2877

 ∘
8. Standard Electrode Reduction Potential E :

Element B Al Ga In Tl

E ∘ /V ( M+3/M) - -1.66 -0.56 -0.34 1.26

∘
E /V ( -0.79(Acid)
M+1/M) - 0.55 -0.18 -0.34
-1.39 (Alkali)

9. Oxides :

Oxides B2O3 Al2O3 Ga2O3 In2O3 Tl2O3

Natures Acidic Amphoteric Amphoteric Basic Basic

10. Halides:
Halides BF3 BCl3 BBr3 BI3

Back Bonding Max Min

Lewis Acidic Strength Min Max

 Physical & Chemical Properties
• Boron =Non metallic in nature, Extremely hard and black coloured solid, exist in many allotropic form, unusual high melting
point due to strong crystalline lattices & used as refractory material.
• Al, Ga, In, Tl = soft metals with low melting points and high electrical conductivity
• During summer, Ga exist in liquid state([Link].=303K). Its high [Link] (2676K) makes it a useful material for high temperature.
•
Property B Al Ga In Tl

unreactive in crystal
Product of reaction with amorphous form
form but amorphous Ga2O3 In2O3 Tl2O3
O2 reactive
form reactive

Type of oxide Acidic Amphoteric Amphoteric Basic Basic

Product of reaction with

BN AlN GaN InN TlN
N2 (high T only)

Product of reaction with

BX3 AlX3 GaX3 InX3 TlX3 except TlI3
X2

Product of reaction with Dissolve in Mineral

Unreactive Alkali - - -
Acid and Alkaline Acid / Alkali
 Structure of Group 13 Compounds
• Structure of AlCl3(s) : Structure of B2H6 :

• Structure of Boric Acid : Structure of Borax:

 Group 14
(a) The 78.86-carat Ahmadabad diamond, a historic Indian gem purchased in Gujarat in the 17th century by the French
explorer Jean-Baptiste Tavernier and sold in 1995 for $4.3 million, is a rare example of a large single crystal of diamond, the
less-stable allotrope of carbon. (b) Large single crystals of highly purified silicon are the basis of the modern electronics
industry. They are sliced into very thin wafers that are highly polished and then cut into smaller pieces for use as chips.
 Occurence
• Carbon = Elemental state available as coal, graphite and diamond. In combined state, Matal carbonates, Hydrocarbon, CO2non
12 13 14
air. Natural Isotopes : C and C, Radioactive isotope : C (half-life = 5770 years) and used for radioactive dating.
• Silicon = 2nd most abundant element on earth crust, In nature found as silica, silicates. Ceramic, Glass and cement are component
of silicon.
• Germanium = only traces
• Tin = mainly in Cassiterite (SnO2)
• Lead = Galena (PbS)
• Flerovium = Synthetically prepared Radioactive Element
 Properties
Property Carbon Silicon Germanium Tin Lead

Atomic No. 6 14 32 50 82

Atomic mass(u) 12.01 28.09 72.64 118.71 207.2

Electronic Configuration [He] 2s2 2p2 [Ne] 3s2 3p2 [Ar] 3d10 4s2 4p2 [Kr] 4d10 5s2 5p2 [Xe] 4f14 5d10 6s2 6p2

Melting Point (K) 4373 1693 1218 505 600

Boiling point (K) - 3550 3123 2896 2024

Density (g/mL) 3.51(diamonds) 2.34 5.32 7.26 11.34

IE1 (KJ/mol) 1086 786 761 708 715

IE2 (KJ/mol) 2352 1577 1537 1411 1450

IE3 (KJ/mol) 4620 3228 3300 2942 3081

IE4 (KJ/mol) 6220 4354 4409 3929 4082

Covalent Radius /pm 77 118 122 140 146

Electrical resistivity /
1014- 1016 50 50 10-5 2*10-5
ohm-cm
 Properties of Carbon Family
Property Carbon Silicon Germanium Tin Lead

Product of reaction with O2 CO2, CO SiO2 GeO2, GeO SnO2, SnO PbO2, PbO

Acidic (CO2),
Type of oxide Acidic Acidic, distinctly acidic Amphoteric, Amphoteric Amphoteric, Amphoteric
Neutral (CO)

Product of reaction with N2 - Si3N4 - Sn3N4 -

PbX4, PbX2,
Product of reaction with X2 CX4 SiX4 GeX4 SnX4
Except PbI4

Product of reaction with H2 CH4 - - - -

1
• Thermal Stability ∝ Polarity ∝
size
• Order of Thermal Stability : CX4 > SiX4 > GeX4 > SnX4 > PbX4

• Order of Thermal Stability : CF4 > CCl4 > CBr4 > CI4

• Most of MX4 are covalent but SnF4 and PbF4 are ionic in nature

• SiCl4 undergo hydrolysis but CCl4 does not because of availability of d-e −.
• SiCl4 + 4H2O → Si(OH)4 + 4HCl
Silicic Acid
 Properties of Carbon Family
• Catenation : C >> Si > Ge ≈ Sn and Pb does not show catenation. Due to C-C bonds are very strong. Down the group the size increases and
electronegativity decreases, and, thereby, tendency to show catenation decreases.
• Carbon also has unique ability to form pπ – pπ multiple bonds with itself and with other atoms of small size and high electronegativity. Heavier
elements do not form pπ – pπ bonds because their atomic orbitals are too large and diffuse to have effective overlapping.
• Due to property of catenation and pπ – pπ bond formation, carbon is able to show allotropic forms.
• Carbon exhibits many allotropic forms; both crystalline as well as amorphous. Diamond and graphite are two well-known crystalline forms of carbon.
While third form of carbon known as fullerenes.
Graphite :
• Hexagonal Layered structure and bond length in the layer is 141.5pm while bond length in between the layer is 340pm. Hybridisation is sp 2 (3σ + 1π).
Fourth electron is free electron which conducts electricity. Graphite cleaves easily between the layers and, therefore, it is very soft and slippery. For
this reason graphite is used as a dry lubricant in machines running at high temperature, where oil cannot be used as a lubricant.
 Properties of Carbon Family
Diamond :
• Three dimensional network of Carbon atoms having bond length of C-C bond is 154pm. Hybridisation is sp 3 (4σ).
• It is very difficult to break extended covalent bonding and, therefore, diamond is a hardest substance on the earth.
• Used as an abrasive for sharpening hard tools, in making dyes and in the manufacture of tungsten filaments for electric light bulbs.

Fullerene :
• Fullerenes are made by the heating of graphite in an electric arc in the presence of inert gases such as helium or argon. The sooty
material formed by condensation of vaporised C n small molecules consists of mainly C60 with smaller quantity of C70 and traces of
fullerenes consisting of even number of carbon atoms up to 350 or above. Fullerenes are the only pure form of carbon because they
have smooth structure without having ‘dangling’ bonds. Fullerenes are cage like molecules. C60 molecule has a shape like soccer
ball and called Buckminsterfullerene .
• It contains twenty six- membered rings and twelve five-membered rings. A six membered ring is fused with six or five membered
rings but a five membered ring can only fuse with six membered rings. All the carbon atoms are equal and they undergo sp 2
hybridisation.
• Each carbon atom forms three sigma bonds with other three carbon atoms. The remaining electron at each carbon is delocalised in
molecular orbitals, which in turn give aromatic character to molecule. This ball shaped molecule has 60 vertices and each one is
occupied by one carbon atom and it also contains both single and double bonds with C–C distances of 143.5 pm and 138.3 pm
respectively. Spherical fullerenes are also called bucky balls in short.

• It is very important to know that graphite is thermodynamically most stable allotrope of carbon and, therefore, Δf H ∘ of graphite is
taken as zero. Δf H ∘ values of diamond and fullerene, C60 are 1.90 and 38.1 kJ/mol, respectively.
 Properties of Carbon Family
Amorphous Carbon:
• Other forms of elemental carbon like carbon black, coke, and charcoal are all impure forms of graphite or fullerenes. Carbon black is obtained by
burning hydrocarbons in a limited supply of air. Charcoal and coke are obtained by heating wood or coal respectively at high temperatures in the
absence of air.
Uses of Carbon :
• Graphite fibres embedded in plastic material form high strength, lightweight composites. The composites are used in products such as tennis rackets,
fishing rods, aircrafts and canoes. Being good conductor, graphite is used for electrodes in batteries and industrial electrolysis. Crucibles made from
graphite are inert to dilute acids and alkalies. Being highly porous, activated charcoal is used in adsorbing poisonous gases; also used in water filters to
remove organic contaminators and in airconditioning system to control odour. Carbon black is used as black pigment in black ink and as filler in
automobile tyres. Coke is used as a fuel and largely as a reducing agent in metallurgy. Diamond is a precious stone and used in jewellery. It is
measured in carats (1 carat = 200 mg).
 Properties of Silicones
Silicones:

• The starting materials for the manufacture of silicones are alkyl or aryl substituted silicon chlorides,RnSiC(4−n), where R is alkyl or aryl group.

• Hydrolysis of R3SiCl = dimer (R3Si − O − SiR3)

• Hydrolysis of R2SiCl2 = Linear Chain Polymer (−O − (R2)Si − O− )

• Hydrolysis of RSiCl3 = Cross-Linked Polymer

• Hydrolysis of SiCl4 = 3D-silicates

• Hydrolysis of R4Si = not possible

Silicates:

Silicates No. of shared O-atom per tetrahedral unit General Formula

Orthosilicate 0 SiO44-
Pyrosilicate 1 Si2O76-
Linear Chain Silicate 2 SiO32-
Ring Silicate 2 SiO32-
Double stranded chain Silicate 3 Si4O116-
Sheet Silicates 3 Si2O52-
3D- Silicate 4 SiO2
 Group 15 (Pnicogen family)
Antimony was Probably the first pnicogen to be obtained in elemental form and recognised as an element. It is found in
stibnite (Sb2S3), a black mineral that has been used as a cosmetic (an early form of mascara) since biblical times, and it is
easily reduced to the metal in a charcoal fire. The Egyptians used antimony to coat copper objects as early as the third
millennium BC, and antimony is still used in alloys to improve the tonal quality of bells.
 Occurence
• Nitrogen = NaNO3(Chile Salt Petre or sodanitre), KNO3(Indian Salt Petre), atmospheric air
• Phosphorus = apatite family (Ca3(PO)4 . CaX2, where X = F(fluoroapatite), X = Cl(Chloroapatite), X = OH (hydroxyapatite))
• Arsenic = mispickel ( Arsenopyrite, FeAsS), Realgar (As4S4), orpiment (As2S3)
• Antimony = Stibnite ( Sb2S3 )
• Bismuth = Bismuthinite( Bi2S3 ), bismite (Bi2O3)

• Note : Indian Saltpetre a mineral substance gathered from sandy areas of Bengal and Bihar was an important item of export from
Bengal up to mid-nineteenth century. Also used in drinks as a cooling agent, it is an important ingredient for manufacturing
gunpowder, glassware, dye and some [Link] European explorers discovered the sea routes to India at the very end of the 15th
century they found a culture and civilisation as old as their own and one which was as advanced, in many areas even more advanced.
By the closing decades of the 16th century ships were regularly trading with the Indian sub-continent as well as with much of South
East Asia – mostly in high value goods, such as spices, which brought the best returns on their investments. But spices were not the
only commodity that they found and in India the European merchants discovered that saltpetre was being made – and made in large
quantities. From the beginning of the 17th century, many European nations, mainly the Portuguese, Dutch and the English but also the
Danes, French and Swedes organised their trade to the East and set up monopoly trading companies for the purpose. And from then on
saltpetre was increasingly traded and exported to Europe.
 Properties of Group 15:
1. Electronic Configuration:

Valence Electron
Atomic Symbol Atomic No Atomic mass (u)
Configuration

Nitrogen N 7 14.01 2s2 2p3

Phosphorus P 15 30.97 3s2 3p3

Arsenic As 33 74.92 4s2 4p3

Antimony Sb 51 121.76 5s2 5p3

Bismuth Bi 83 209.98 6s2 6p3

2. Melting Point :

Order : As > Sb > Bi > P > N

Element N P As Sb Bi

[Link] (K) 63 317 1089 904 544

3. Boiling Point :

Order : Sb > Bi > As > P > N

Element N P As Sb Bi

[Link] (K) 77.2 554 888 1860 1837

4. Atomic Size:

Element N P As Sb Bi

Covalent radius
70 110 121 141 148
(pm)

Size increases due to increase in no. of shells

5. Electronegativity

Order : N > P > As > Sb ≈ Bi

Element N P As Sb Bi

Electronegativity 3.0 2.1 2.0 1.9 1.9

6. Density:
Element N P As Sb Bi

Density (g/cc) 0.879 1.823 5.778 6.697 9.808

Density increases due to increase in mass is more dominant over increase in size.

7. Ionisation Enthalpy: Generally IE decreases as size increases.( D-block contraction 3p → 4p , Lanthanoid contraction
5p → 6p , Actinide contraction 6p → 7p)

Element N P As Sb Bi

1st IE (KJ/mol) 1402 1012 947 834 703

Element N P As Sb Bi

2nd IE (KJ/mol) 2856 1903 1798 1595 1810

Element N P As Sb Bi

3rd IE (KJ/mol) 4577 2910 2736 2443 2466

 Chemical Properties of Group 15:
Oxidation states :
3HNO2 → HNO3 + H2O + 2NO Element N P As Sb Bi
Common
O.S.
-3 to +5 -3, +3, +5 +3, +5 +3, +5 +3
Inert Pair Dispropotionation Reaction
OS = +3 OS = +5
Effect

N (only P (acidic
As, Sb
N O.S. in acidic as well
& Bi
medium) as
alkaline
Valency Covalency
P +1
Nitrogen = 3 Nitrogen = 4

As +2 e.g: NH3 e.g: NH +

4

Become
Phosphorus = 5 Phosphorus = 6
increasingly
Sb +3 stable with
e.g: PCl5 e.g: PCl6−
respect to
disproportion
ation

Bi Increases Decreases +4
2. Reactivity with Hydrogen:

Property NH3 PH3 AsH3 SbH3 BiH3

Thermal Decreases due to N-H bond is more stronger than Bi-H so BiH3 will dissociates
Stability easily

BDE Decreases due to increases in size

Bond Angle Decreases due to Drago compound

Basicity Decreases due to lone pair on nitrogen atom accept proton more easily than bismuth.

Reducing
Increases due to larger size and small BDE
Character
Melting point : NH3 > SbH3 > AsH3 > PH3

Boiling Point : BiH3 > SbH3 > NH3 > AsH3 > PH3

Formation enthalpy (in KJ/mol): BiH3 > SbH3 > AsH3 > PH3 > NH3 (formation of ammonia is exothermic process)
3. Reactivity towards oxygen:

Group 15 elements + Oxygen E2O3 & E2O5.

Acidic strength : E2O5 > E2O3 (due to higher OS)

Acidic strength : N2O3 > P2O3 > As2O3 > Sb2O3 > Bi2O3 (due to increase of metallic character)

Acidic strength : N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5 (due to increase of metallic character)

Acidic strength : N2O < NO < N2O3 < NO2 < N2O5 (due to increases in OS)

Nature of oxide of E2O3 : N & P are purely acidic , As & Sb are amphoteric, Bi is basic.

Stability of E2O5 : N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5 (due to inert pair effect)

Oxides N2O NO N2O3 NO2 N2O5 P4O6 P4O10 As4O6 Sb2O5 Bi2O3

Nature Neutral Neutral Acidic Acidic Acidic Acidic Acidic Acidic Amphoteric Basic
4. Reactivity towards Halogen:

Group 15 elements + Halogen EX3 & EX5.

All trihalide except nitrogen are stable. In case of nitrogen only NF3 is known to be stable.

Except BiF3, other trihalides are predominantly covalent.

Pentahalides (EX5) are more covalent than trihalides (EX3).

Nitrogen do not form EX5 due to absence of d - orbital.

5. Reactivity towards metal:

Group 15 elements + Metal binary compound (-3 OS)

Ca3N2 , Ca3P2, Na3 As, Zn3Sb2, Mg3Bi2

Element N P As Sb Bi

Product of Rxn with O2 NO, NO2 P4O6, P4O10 As4O6 Sb2O5 Bi2O3

Product of Rxn with N2 - None None None None

Product of Rxn with X2 None PX3, PX5 AsF5, AsX3 SbF5, SbCl5, SbBr3, SbI3 BiF5, BiX3

Product of Rxn with H2 None None None None None

 Dinitrogen
Preparation:
1. Because the atmosphere contains several trillion tons of elemental nitrogen with a purity of about 80%, it is a huge source of nitrogen gas. Distillation of liquefied
air yields nitrogen gas that is more than 99.99% pure (commercially), but small amounts of very pure nitrogen gas can be obtained from the thermal decomposition
of sodium azide or barium azide.

2NaN3(s) → 2Na(l) + 3N2(g)

2. In Laboratory, NH4Cl(aq) + NaNO2(aq) → N2(g) + 2H2O(l) + NaCl(aq),

Small amount of NO & HNO3 are also formed in this reaction as impurities can be be removed by passing the gas through H2SO4 containing K2Cr2O7.
heat
3. By thermal decomposition of (NH4)2Cr2O7 N2 + 4H2O + Cr2O3

4. NH4 NO2(aq) → N2 + 2H2O

>570K
5. 2NH4 NO3(s) 2N2 + O2 + 4H2O

In contrast, Earth’s crust is relatively poor in nitrogen. The only important nitrogen ores are large deposits of KNO3 and NaNO3 in the deserts of Chile and Russia,
which were apparently formed when ancient alkaline lakes evaporated. Consequently, virtually all nitrogen compounds produced on an industrial scale use
atmospheric nitrogen as the starting material. Phosphorus, which constitutes only about 0.1% of Earth’s crust, is much more abundant in ores than nitrogen. Like
aluminium and silicon, phosphorus is always found in combination with oxygen, and large inputs of energy are required to isolate it.
 Dinitrogen
Physical Properties:

Two stable isotopes Colourless

14
N & 15N Odourless

N2 Tasteless
Very low solubility in water

Non toxic gas

Low freezing and boiling point High BDE

Chemical Properties:
Δ
1. Reaction with metal: 6Li + N2 2Li3N
Dinitrogen is generally unreactive. It combines slowly with Li at ambient temperatures , and, when
heated, with the group 2 metals, Al, Si, Ge and many d-block metals. The reaction between CaC2 and N2
2. Haber’s process is used industrially for manufacturing the nitrogenous fertiliser calcium cyanamide. Many elements (e.g.
Na, Hg, S) which are inert towards N2 do react with atomic nitrogen, produced by passing N2 through
3. At high T (≈2000K). N2(g) + O2(g) ↔ 2NO(g) an electric discharge. At ambient temperatures, N2 is reduced to hydrazine (N2H4) by vanadium(II) and
magnesium hydroxides
 Ammonia
Preparation:

1. From nitrogenous organic compound:

Urea + water → Ammonia + water + CO2

2. On small scale: Ammonium salt decomposes when treated with caustic soda or lime.

2NH4Cl + Ca(OH)2 → 2NH3 + H2O + CaCl2

3. On large scale, Haber’s Process:

The Haber process is a classic application of physicochemical principles to a system in equilibrium. The decrease in number of moles of gas means
that Δr S ∘(298 K) is negative. For industrial viability, NH3 must be formed in optimum yield and at a reasonable rate. Increasing the temperature
increases the rate of reaction, but decreases the yield since the forward reaction is exothermic. At a given temperature, both the equilibrium yield and
the reaction rate are increased by working at high pressures. The presence of a suitable catalyst also increases the rate. The rate-determining step is
the dissociation of N2 into N atoms chemisorbed onto the catalyst. The optimum reaction conditions are T = 723 K, P = 20 260 kPa, and Fe3O4 mixed
with K2O, SiO2 and Al2O3 as the heterogeneous catalyst. The Fe3O4 is reduced to give the catalytically active α − Fe. The NH3 formed is either liquefied
or dissolved in H2O to form a saturated solution of specific gravity 0.880.

4. Ammonia is obtained by hydrolysis of nitride of Li or Mg.

 Ammonia
Physical Properties:

Colourless

Very High solubility in water Pungent

NH3

freezing point = 198.4K

toxic gas
boiling point = 239.7K

Barrier of inversion is very low (24KJ/mol)

Chemical Properties:

1. Ammonia is a Lewis base and helps in detection of metal ions such as Cu 2+, Ag +.

Cu 2+(aq) + 4NH3(aq) → [Cu(NH3)4]2+(aq) AgCl(s) + 2NH3(aq) → [Ag(NH3)2]Cl(aq)

(Blue)
(Deep Blue) (White ppt) (colourless)
 Ammonia
Chemical Properties:

2. Ammonia is weak Lewis base, so it precipitates hydroxide of many metals from their salt solutions.

FeCl3(aq) + 3NH4OH(aq) → Fe2O3 . xH2O + 3NH4Cl

Brown ppt

ZnSO4(aq) + 2NH4OH(aq) → Zn(OH)2(s) + (NH4)2SO4(aq)

White ppt
3. Ammonium salts are easily prepared by neutralization reactions. Industrial syntheses are carried out using the Solvay [Link] ammonium sulfate and
ammonium nitrate are important fertilizers, and NH4 NO3 is a component of some explosives.
 Nitric Acid
Preparation:

1. Laboratory, prepared by heating KNO3 or NaNO3and conc H2SO4 in glass retort.

NaNO3 + H2SO4 → NaHSO4 + HNO3 (pure nitric acid)

2. Nitric acid is an important industrial chemical and is manufactured on a large scale in the Ostwald process, which is closely tied to NH3 production in
the Haber–Bosch process. The first step is the oxidation of NH3 to NO . After cooling, NO is mixed with air and absorbed in a countercurrent of water. The
reactions involved are summarized in scheme given below. This produces HNO3 in a concentration of 60% by weight and it can be concentrated to 68% by
distillation.

Summarized
 Nitric acid
Physical Properties:

Colourless Liquid

freezing point = 231.4K In aqueous solution,

HNO3
boiling point = 355.6K strongly acidic

Sp. gravity = 1.504

Chemical Properties:

1. must be stored below 273K to prevent slight decomposition which gives the acid a yellow colour

4HNO3 → 4NO2 + 2H2O + O2

Ordinary concentrated HNO3 is the azeotrope containing 68% by weight of HNO3 and boiling at 393K. Photochemical decomposition occurs by above
reaction. Fuming HNO3 is orange owing to the presence of an excess of NO .
 Nitric Acid
Chemical Properties:

2. In aqueous solution, HNO3 acts as a strong acid which attacks most metals, often more rapidly if a trace of HNO2 is present. Exceptions are Au and the
platinum-group metals.

3. Only Mg, Mn and Zn liberate H2 from very dilute nitric acid. If the metal is a more powerful reducing agent than H2 , reaction with HNO3 reduces the
acid to N2 , NH3, NH2OH or NO. Others metals liberated NO or NO2 .

3Cu + 8HNO3(dil) → 3Cu(NO3)2 + 2NO + 4H2O

Cu + 4HNO3(conc.) → Cu(NO3)2 + 2NO2 + 2H2O

4Zn + 10HNO3(dil) → 4Zn(NO3)2 + 5H2O + N2O

Zn + 10HNO3(conc) → Zn(NO3)2 + 2H2O + 2NO2

4. Due to formation of passive film oxide on the surface of some metals like Cr, Al do not dissolve in concentrated nitric acid.

5. Conc HNO3 also oxidises non metals and their compounds.

I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O S8 + 48HNO3 → 8H2SO4 + 16H2O

C + 4HNO3 → CO2 + 2H2O + 4NO2 P4 + 20HNO3 → 4H3PO4 + 20NO2 + 4H2O

Brown ring test for nitrates:

This depends on the ability of Fe 2+ to reduce nitrates to nitric oxides, which reacts with Fe 2+ to form brown coloured complex.

NO3− + 3Fe 2 + 4H + → NO + 3Fe 2+ + 2H2O

[Fe(H2O)6]2+ + NO → [Fe(H2O)NO]2+ + H2O

 Allotropic form of Phosphorus

Crystalline white phosphorus contains tetrahedral P4 molecules in which the P-P bond distances (221 pm) are used to define rcov = 110 pm for a single bond.
White phosphorus is defined as the standard state of the element, but is actually metastable. The lower stability of the white form probably originates in
strain associated with the 60∘ bond angle.

White P4 Red Phosphorus (Hittorf Phosphorus) Black Phosphorus

 Allotropic form of Phosphorus

Properties White P Red P

State Soft waxy solid Brittle powder
Odour Garlic Odourless
Colour White (pure) Red
Melting point(Celsius) 44 Sublimes at 290
Solubility in water Insoluble Insoluble
Solubility in CS2 Soluble Insoluble
Reactivity Highly reactive Least reactive
Reaction with Cl2 PCl3, PCl5 (spontaneously) PCl3, PCl5 (upon heating)
Air (burn) P4O10 P4O10
White phosphorus is soluble in benzene, PCl3 and CS2 but is virtually insoluble in water, and is stored under water to prevent oxidation. In moist air, it
undergoes chemiluminescent oxidation, emitting a green glow and slowly forming P4O8 and some O3.

Black Phosphorus:

Black
Prepared when white P heated at P Prepared when red P heated in a
473K under high Pressure. sealed tube at 803K
β-black α-Black
Sublime in air

Does not burn in air upto 673K

Opaque monoclinic or rhombohedral crystal
 Phosphine
Preparation:

1. Laboratory, prepared by heating white P in with conc. NaOH in an inert atmosphere of CO2.

P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2

2. By action of calcium phosphide with water or dil HCl.

Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3

Ca3P2 + 6HCl → 3CaCl2 + 2PH3

3. The spontaneous flammability associated with PH3 is due to the presence of P2H4 or P4 vapours.

4. Phosphonium halides, PH4 X, are formed by treating PH3 with HX but only the iodide is stable under ambient conditions. The chloride is unstable above
243K and the bromide decomposes at 273 K. PH4+ ion is decomposed by water .

Physical Properties:

Phosphine is an extremely toxic, with rotten fish smell, colourless gas which is much less soluble in water than is NH3. The P-H bond is not polar enough to
form hydrogen bonds with H2O. In contrast to NH3 , aqueous solutions of PH3 are neutral, but in liquid NH3, PH3 acts as an acid.
 Phosphine
Chemical Properties:

1. Decomposition of PH3
light
PH3 + H2O Red P + H2

2. Reaction with metal salt solution:

3CuSO4 + 2PH3 → Cu3P2 + 3H2SO4

3HgCl2 + 2PH3 → Hg3P2 + 6HCl

3. PH3 is weakly base. PH3 + HBr → PH4Br

Uses:

Used in Holme’s signals due to spontaneous combustion of phosphine.

Used in smoke screen.

 PCl3 PCl5
Preparation: Preparation:

Δ Δ
1. P4 + 6Cl2 4PCl3 1. P4 + 10Cl2 4PCl5

2. P4 + 10SO2Cl2 → 4PCl5 + 10SO2

White
Properties:
2. P4 + 8SOCl2 → 4PCl3 + 4SO2 + 2S2Cl2
1. Yellowish white powder and undergo hydrolysis.
White PCl5 + H2O → POCl3 + 2HCl
Properties:
POCl3 + 3H2O → H3PO4 + 3HCl
1. Colourless oily liquid and hydrolyse in the presence of moisture.
2. Converts -COOH to -COCl and -OH to -Cl
PCl3 + 3H2O → H3PO3 + 3HCl
CH3COOH + PCl5 → CH3COCl + POCl3 + HCl
2. Converts -COOH to -COCl and -OH to -Cl CH3CH2OH + PCl5 → CH3CH2Cl + POCl3 + HCl

3CH3COOH + PCl3 → 3CH3COCl + H3PO3 3. With Finely divided metals to form Metal chloride.

3CH3CH2OH + PCl3 → 3CH3CH2Cl + H3PO3 2Ag + PCl5 → 2AgCl + PCl3

Sn + 2PCl5 → SnCl4 + 2PCl3

4. In solid state it exist as ionic solid [PCl4]+[PCl6]−.

 Oxoacids of Phosphorus

Name Formula O.S. Preparation

Hypophosphorus Acid (Phosphinic) H3PO2 +1 White P + alkali

Orthophosphorus Acid (Phosphonic) H3PO3 +3 P2O3 + water

Pyrophosphorous Acid H 4P 2O 5 +3 PCl3 + H3PO3

Hypophosphoric Acid H 4P 2O 6 +4 Red P + alkali

Orthophosphoric acid H3PO4 +5 P4O10 + water

Pyrophosphoric Acid H 4P 2O 7 +5 Heating H3PO4

Metaphosphoric acid (HPO3)3 +5 H3PO3 + Br2

In +3 OS, Phosphorous shows disproportionation.

4H3PO3 → 3H3PO4 + PH3

The acid containing P-H bond having strong reducing properties.

4AgNO3 + 2H2O + H3PO2 → 4Ag + 4HNO3 + H3PO4

 Group 16 (Chalcogen family)
During the fermentation process in the manufacture of wine, SO2 or K2S2O5 is added to the initial wine pressings to kill
microorganisms, the presence of which results in spoilage of the wine. Molecular SO2 is only used for large-scale wine
production, while K2S2O5 is the common additive in small- scale production.
 Occurence
• Dioxygen = It makes 21% of Earth’s atmosphere and 47% of earth crust(eg: water, limestone silicate, silica, bauxite and
haematite)
• Sulphur = occurs in deposits around volcanoes and hot springs, and sulfur-containing minerals include iron pyrites ( fool’s gold,
FeS2), galena (PbS), sphalerite or zinc blende (ZnS), cinnabar (HgS), realgar (As4S4), orpiment (As2S3), stibnite (Sb2S3),
molybdenite (MoS2), Chalcocite(Cu2S).
• Selenium, Tellurium = less abundant in nature.
• Tellurium = sylvanite(AgAuTe4)
 Properties of Group 16:
1. Electronic Configuration:

Valence Electron
Atomic Symbol Atomic No Atomic mass (u)
Configuration

Oxygen O 8 16.00 2s2 2p4

Sulphur S 16 32.07 3s2 3p4

Selenium Se 34 78.96 4s2 4p4

Tellurium Te 52 127.60 5s2 5p4

Polonium Po 84 209 6s2 6p4

2. Melting Point :

Order : Te > Po > Se > S > O

Element O S Se Te Po

[Link] (K) 55 393 490 725 520

3. Boiling Point :

Order : Te > Po > Se > S > O

Element O S Se Te Po

[Link] (K) 90 718 958 1260 1235

4. Atomic Size:

Element O S Se Te Po

Covalent radius
66 104 117 137 146
(pm)

Size increases due to increase in no. of shells

5. Electronegativity

Order : O > S > Se > Te > Po

Element O S Se Te Po

Electronegativity 3.50 2.58 2.55 2.01 1.76

6. Density:
Element O S Se Te Po

Density (g/cc) 1.32 2.06 4.19 6.25 -

Density increases due to increase in mass is more dominant over increase in size.

7. Ionisation Enthalpy: Generally IE decreases as size increases.( D-block contraction 3p → 4p , Lanthanoid contraction
5p → 6p , Actinoide contraction 6p → 7p)

Element O S Se Te Po

1st IE (KJ/mol) 1314 1000 941 869 813

IE decreases due toincrease in size.

8. Electron gain enthalpy:

Element O S Se Te Po

ΔegH -141 -200 -195 -190 -170

Chemical Properties of Group 16:
1. Oxidation states :
Element O S Se Te Po

Common O.S. -2, -1, 1, 2 -2, 2, 4, 6 -2, 2, 4, 6 -2, 2, 4, 6 2, 4

• Down the group of stability of O.S. +6 decreases, while stability of +3 O.S. increases due to inert pair effect.

• Bonding in +4 and +6 are covalent in nature.

2. Reactivity towards Oxygen:

Elements + Oxygen EO2 & EO3 (except oxygen element

• O3 and SO2 are gases while SeO2 is solid.

• Both types of oxides are acidic in nature.

• TeO2 is an oxidising agent.

3. Reactivity with Hydrogen:

Property H2O H2S H2Se H2Te

Decreases due to O-H bond is more stronger than Te-H so H2Te will dissociates
Thermal Stability
easily

BDE Decreases due to increases in size

Bond Angle Decreases due to Drago compound

Acidic Character Increases due to increase in size

Reducing Character Increases due to larger size and small BDE

Melting point : H2O > H2Te > H2Se > H2S

Boiling Point : H2O > H2Te > H2Se > H2S

Formation enthalpy (in KJ/mol): H2Te > H2Se > H2S > H2O (formation of Water and H2S is exothermic process)
3. Reactivity towards Halogen:

Group 16 elements + Halogen EX6, EX4, and EX2.

• Stability of Halide ion : F − > Cl − > Br − > I −

• Among hexahalides, hexafluoride are only stable halides. SF6 is exceptionally stable for steric reason. Hexafluorides are gaseous in nature.

• Among tetrafluoride, SF4 is gas, SeF4is liquid and TeF4 is solid.

• All elements except selenium form dichlorides and dibromides. They are sp 3 hybridised and have tetrahedral structure. Monohalides like
S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2 are dimeric in nature and undergo disproportionation.

2Se2Cl2 → SeCl4 + 3Se

 Simple Oxides

Neutral Oxides: Mixed Oxides:

Acidic Oxides: Basic Oxides:
• Neither Acidic nor basic.
• Two types A3O4,
• Non Metal Oxides are acidic • Non Metal Oxides are acidic
e.g. : CO, NO, N2O AB2O4.
• metals in higher OS show acidic character. • They combines with water to give base.
e.g. : Fe3O4, Pb3O4,
• They combines with water to give acid. e.g. : Na2O, CaO, BaO, MgO. MgAl2O4

e.g. : SO2, Cl2O7, CO2, P4O10, N2O5, Mn2O7, CaO + H2O → Ca(OH)2
CrO3, V2O5

SO2 + H2O → H2SO3

Amphoteric Oxides:

• Metal Oxides show dual behaviour of both acid as

well as alkali.

e.g. : Al2O3, ZnO, BeO, MnO2, Cr2O3, PbO, SnO

Al2O3 + 6HCl + 9H2O → 2[Al(H2O)6]3+ + 6Cl −

Al2O3 + 6NaOH + 3H2O → 2Na3[Al(OH)6]

 Dioxygen
Preparation:
1. Dioxygen is obtained industrially by the liquefaction and fractional distillation of air, and is stored and transported as a liquid.

2. Convenient laboratory preparations of O2 are the electrolysis of aqueous alkali using Ni electrodes, and decomposition of H2O2 .

2H2O2(aq) → 2H2O(l) + O2(g)

3. A mixture of KClO3 and MnO2 used to be sold as ‘oxygen mixture’.

Δ, MnO2
2KClO3 2KCl + 3O2

4. Thermal decompositions of many other oxo salts (e.g. KNO3, KMnO4 and K2S2O8 ) produce O2 .

2Ag2O(s) → 4Ag(s) + O2(g)

2HgO(s) → 2Hg(l) + O2(g)

2Pb3O4(s) → 6PbO(s) + O2(g)

2PbO2(s) → 2PbO(s) + O2(g)

 Dioxygen
Physical Properties: colourless gas, but condense to a
pale blue liquid or solid
Three stable isotopes
16
O, 17O, & 18O Odourless

Solubility in water is 3.08mL per O2 Tasteless

100mL at 298K

High BDE
Freezing point = 55K
Liquified temperature = 90K Paramagnetic

Chemical Properties:

Reaction with metal/Non metals:

2Ca + O2 → 2CaO, 4Al + 3O2 → 2Al2O3, P4 + 5O2 → P4O10,

V2O5
2ZnS + 3O2 → 2ZnO + 2SO2, CH4 + 2O2 → CO2 + 2H2O, 2SO2 + O2 2SO3,
CuCl2
4HCl + O2 2Cl2 + 2H2O
 Ozone
Preparation:

1. Ozone, O3, is usually prepared in up to 10% concentration by the action of a silent electrical discharge between two concentric metallized tubes
in an apparatus called an ozonizer. Electrical discharges in thunderstorms convert O2 into ozone. The action of UV radiation on O2, or heating O2
above 2750K followed by rapid quenching, also produces O3. In each of these processes, O atoms are produced and combine with O2 molecules.
Pure ozone can be separated from reaction mixtures by fractional liquefaction. The liquid is blue and boils at 163 K to give a perceptibly blue gas
with a characteristic ‘electric’ smell. Molecules of O3 are bent. Ozone absorbs strongly in the UV region, and its presence in the upper atmosphere
of the Earth is essential in protecting the planet’s surface from over-exposure to UV radiation from the Sun.

3O2 → 2O3 (10% formed). (ΔH298K = +142 KJ/mol)

Ozone is highly endothermic. The pure liquid is dangerously explosive, and the gas is a very powerful oxidizing agent.

The presence of high concentrations of alkali stabilizes O3 both thermodynamically and kinetically. Ozone is much more reactive than O2 (hence
the use of O3 in water purification.

O3 + S + H2O → H2SO4.

4O3 + PbS → PbSO4 + 4O2

O3 + 2I − + H2O → 2OH − + I2 + O2
 Ozone
Quantitative estimation of O3:

On reaction of O3 with excess KI buffered with borate buffer (pH = 9.2), I2 is liberated which can be liberated against standard sodium thiosulphate.

2KI + H2O + O3 → 2KOH + I2 + O2

• Nitrogen oxides (especially NO) emits from exhaust system supersonic jet aeroplanes might slowly deplete the conc of O3 in upper atmosphere.
NO + O3 → NO2 + O2

• Use of freons (in aerosol spray and refrigerant) can damage ozone layer

• Resonating Structure:
 Ozone
Physical Properties: Pale blue gas, dark blue liquid
and violet black solid

Thermodynamically unstable Characteristics smell

wrt Oxygen
O3

Small conc is harmless but >100ppm

Conversion to O2 is favourable breathing problems started.
 Allotropic form of Sulphur
1. Rhombic sulphur : (α-sulphur)

Soluble in CS2 Yellow Colour

Dissolve some extent in benzene,

α-sulphur Specific Gravity = 2.06
alcohol and ether

Insoluble in water [Link]. = 385.8K

Stable form at rt

2. Monoclinic Sulphur: (β-sulphur)

Both sulphur have S8

[Link]. = 393K
molecule. It is puckered
and has crown shape
β-sulphur

Stable above 369K and below Specific gravity = 1.98

369K α-sulphur is stable. So,
T= 369K is called transition At ≈1000K, S2 is more dominant species
temperature. and paramagnetic like O2
62
 SO2
Preparation:

1. S(s) + O2(g) → SO2(g)

2. In laboratory: SO32−(aq) + 2H + → H2O(l) + SO2(g)

3. Industrially, 4FeS2(s) + 11O2(s) → 2Fe2O3(s) + 8SO2(g)

Properties:

SO2 is colourless gas with pungent smell and is highly soluble in water. It liquifies at room temperature under pressure of 2atm and boils 263K.

SO2Cl2 Na2SO3 + H2O H2SO4, NaHSO3

CaHSO3
Petroleum
&
Cl
of
Preparation sugar
2
O H
N a
SO2

Anti-Ch
2+ Uses of SO2

lo
Fe air

r,
of in pr

disinfectant
V es
2O en Solvent
5 ce

Pre
SO3
Fe3+ + 2-

ser
SO4

v a tives
Bleaching of wool & Silk
 Oxoacids of Sulphur
[Link]. Formula Name Oxidation state
1 H2S2O4 Dithionous Acid +2
2 H2S2O3 Thiosulfuric acid +4, 0
3 H2SO3 Sulfurous acid +4
4 H2SO4 Sulfuric Acid +6
5 H2S2O7 Disulfuric acid +6
6 H2S2O8 Peroxydisulfuric Acid +6
 Sulphuric acid or Oil of Vitriol or King of Chemicals
Preparation:

Contact process: (Three step Process)

1. Burning of sulphur and sulphide ores in air to generate SO2.

The SO2 is purified by removing impurities such as arsenic compound.

2. Conversion of SO2 to SO3:

V2O5
2SO2(g) + O2(g) 2SO3(g) ΔH = -199.6 KJ/mol

Reaction is exothermic, reversible and forward reaction leads to decrease in volume. Therefore low temperature and high pressure are favourable
conditions. In practice, 720K and 2bar pressure is used.

3. Adsorption of SO3 in H2SO4 to give oleum:

SO3 + H2SO4 → H2S2O7

Finally dilution of oleum with water to gives H2SO4 of desired concentration. H2SO4 concentration is 96-98% pure.
 H2SO4
Physical Properties:
Colourless

[Link]. = 611K

Soluble in water and dissolution Dense, oily liquid

H2SO4
process is exothermic.

High but and viscosity indicate association in

Specific gravity = 1.84 structure due to H-bonding

Chemical Properties :

(1) Decomposition : H2SO4 → SO3 + H2O

(2) Acidic Nature: H2SO4 → H + + HSO4−

HSO4− → H + + SO42−
3. Reaction with Metal, Oxides and carbonates:

4. Dehydrating agent: 5. Oxidising Agent:

H2SO4 H2O + SO2 + [O]

12C + 11H2O

SO2
Sugar

ethyl alcohol HCOOH CO2 S8 H2O + Br2

H2SO4 CO + H2O
ethene + H2O C
HBr
Oxalic acid [O]
H 2S Cu

CO + CO2 + H2O H 2O + S CuSO4

5. Reaction with salts:

NaHSO4 + HNO3 NaHSO4 + HCl

Na
NO l
3 a C
N
H2SO4
)2 Ba
O3
Pb(N Cl
2

PbSO4 + 2HNO3 BaSO4 + 2HCl

electro white ppt white ppt

6. Uses of sulphuric acid:

• Fertilisers, manufacture of Rayon, in Storage batteries and lead accumulators, dehydrating agent, For pickling ( Cleaning of metal surface before
electroplating ).
 Group 17
Halogen Family

The French chemist Henri Moissan was the first person to isolate elemental fluorine. A reproduction of the U-shaped
electrolysis cell with which Moissan first isolated elemental fluorine in 1866 is shown with samples of cryolite (left) and
fluorspar (right). Fluorspar is the raw material from which anhydrous hydrofluoric acid (HF) is prepared. Cryolite is a rare
mineral that contains the fluoride ion.
 Occurence
• Fluorine = mineral Fluorspar(CaF2, fluorite), Cryolite (Na3 AlF6), fluoroapatite(Ca3(PO4)2 . CaF2)
• Chlorine = Rock Salt (NaCl), sylvite (KCl), Carnalite (KCl . MgCl2.2H2O).
−
• Bromine = Seawater Seawater is one source of Br2 , but significantly higher concentrations of Br are present in salt lakes and
natural brine wells.
• Iodine = It occurs as iodide ion in seawater and is taken up by seaweed, from which it may be extracted. Impure Chile saltpetre
(caliche) contains up to 1% sodium iodate and this has become an important source of I2 .
 Properties of Group 17:
1. Electronic Configuration:

Valence Electron
Atomic Symbol Atomic No Atomic mass (u)
Configuration

Fluorine F 9 19.00 2s2 2p5

Chlorine Cl 17 35.45 3s2 3p5

Bromine Br 35 79.90 4s2 4p5

Iodine I 53 126.90 5s2 5p5

Astatine At 85 210 6s2 6p5

2. Melting Point : Order : Cl2 > Br2 > I2 > F2

Element F2 Cl2 Br2 I2

[Link] (K) 54.5 381 347 305

3. Boiling Point : Order : I2 > Br2 > Cl2 > F2

Element F2 Cl2 Br2 I2

[Link] (K) 84.9 239 332.5 485.2

4. BDE : Order : Cl2 > Br2 > F2 > I2

Element F2 Cl2 Br2 I2

BDE (KJ/mol) 158.8 242.6 192.8 151.1

5. Atomic Size:

Element F Cl Br I At

Covalent radius
133 184 196 220 -
(pm)

Size increases due to increase in no. of shells

6. Electronegativity

Order : F > Cl > Br > I > At

Element F Cl Br I At

Electronegativity 4 3.2 3.0 2.8 2.2

7. Density:
Element F Cl Br I At

Density (g/cc) 1.5 1.66 3.19 4.94 -

Density increases due to increase in mass is more dominant over increase in size.

8. Ionisation Enthalpy: Generally IE decreases as size increases.( D-block contraction 3p → 4p , Lanthanoid contraction
5p → 6p , Actinoide contraction 6p → 7p)

Element F Cl Br I At

1st IE (KJ/mol) 1680 1256 1142 1008 -

IE decreases due to increase in size.

9. Electron gain enthalpy:

Element F Cl Br I At

ΔegH -333 -349 -325 -296 -

Physical Properties:
F2 = Yellow Gas

Cl2 = Greenish yellow gas

Br2 = Reddish liquid

I2 = Violet colour solid.

• The colour is due to adsorption of different quanta of radiation in visible region which result in excitation of outer electrons to higher energy level, thus
different colours are observed.

• Bromine & Iodine are sparingly soluble water but soluble in solvents like CHCl3, CCl4, hydrocarbon to give coloured solutions.

Chemical properties:

• Anomalous behaviour of Fluorine:

(1) small size

(6) Most reaction of fluorine are exothermic due to small size and high BDE
(2) high electronegativity
(7) HF is liquid below 293K due to stronger H-bonding while other HX are gases at rt
(3) low BDE (F-F)

(4) non availability of vacant d-orbital

(5) higher value of electrode potential

Chemical properties:

• Oxidation states:

Element F Cl Br I At

Common O.S. -1 -1, +1, +3, +5, +7 -1, +1, +3, +5, +7 -1, +1, +3, +5, +7 -1, +1

Due to absence of d -orbital, F can not show multiple OS.

• Chemical Reactivity:

All halogens are highly reactive. The react with metal & non-metal to form halides. Reactivity of halogen decreases down the group.

Halogens shows strong oxidising nature. F2 is the strongest oxidising agent in solution and in solid phase.

F2 + 2X − → 2F − + X2 (X = Cl, Br, I)

Cl2 + 2X − → 2Cl − + X2 ( X = Br, I)

Br2 + 2X − → 2Br − + X2 ( X = I)

Decreasing Oxidising ability of halogen in aqueous solution depends upon:

1 1
ΔH ∘
ΔH ∘
∘
ΔHhyd
X −(g) X −aq
diss
X2(g) 2
X(g)
2
• Chemical Reactivity:

F2 oxidises water to oxygen whereas Cl2 & Br2 reacts with water to form hypohalic acid and hypohalous acid.

2F2(g) + 2H2O(l) → 4H +(aq) + 4F −(aq) + O2(g)

X2 + H2O(l) → HX(aq) + HOX(aq) ( X = Cl, Br)

The reaction of I2 with water is non spontaneous. 4I −(aq) + 4H +(aq) + O2(g) → 2I2(s) + 2H2O(l)

• Reactivity towards Hydrogen:

Property HF HCl Her HI

Thermal Stability Decreases due to F-H bond is more stronger than I-H so HI will dissociates easily

BDE Decreases due to increases in size

Bond Angle Halogens does not form two bond to show bond angle

Acidic Character Increases due to increase in size

Reducing Character Increases due to larger size and small BDE

• Reactivity with Hydrogen:
Melting Point : HI > HF > HBr > HCl

Boiling Point : HF > HI > HBr > HCl

• Reactivity with Oxygen:

Element F Cl Br I

Oxides OF2, O2F2 Cl2O, ClO2, Cl2O6, Cl2O7 Br2O, BrO2, BrO3 I2O4, I2O5, I2O7

OF2 is thermally stable at

Are least stable halogen
298K. Both OF2 and O2F2 All are highly oxidising All are insoluble solids and
Properties oxides and exist only at
are strong fluorinating agent and tend to explode. decomposes on heating.
low temperature.
agent

O2F2 oxidises Pu to PuF6 ClO2 is used as bleaching

agent for paper pulp, They are powerful I2O5 is strong O.A. and
and used in removing Pu
textiles and in water Oxidising agent. used in estimation of CO.
from spent nuclear fuel.
treatment.
• Reactivity with Metal :

Metal in Higher OS will be more covalent than lower OS. SnCl4, PbCl4, SbCl5 and UF6 are more covalent than SnCl2, PbCl2, SbCl3 and UF4 respectively.

Ionic Character :

MF > MCl > MBr > MI (where M is monovalent metal)

Oxoacids of Halogens:

Halic (I) Acid HOF HOCl HOBr HOI

(hypohalous acid)

Halic (III) Acid - HOClO - -

(halous acid)

Halic (V) Acid - HOClO2 HOBrO2 HOIO2

(Halic acid)

Halic (VII) Acid - HOClO3 HOIO3 HOIO3

(perhalic acid)
Interhalogen Compounds:

Preparation:
473K
Cl2 + F2 2ClF
573K
Cl2 + 3F2 2ClF3

I2 + Cl2 → 2ICl

I2 + 3Cl2 → 2ICl3

Hydrolysis:

X − X′ + H2O → HX′ + HOX

Uses:

• Non aqueous solvents

• Fluorinating agents
235
• ClF3 & BrF3 are used in the production of UF6 in enrichment of U .

• U(s) + 3ClF3 → UF6(g) + 3ClF(g)



 Group 18
Noble Gas Family
Structure of Xenon hydrate, a Clatharate

For many years, it was thought that the only compounds the noble gases could form were clathrates. Clathrates are solid compounds in which a
gas, the guest, occupies holes in a lattice formed by a less volatile, chemically dissimilar substance, the host. Because clathrate formation does not
involve the formation of chemical bonds between the guest (Xe) and the host molecules (H2O, in the case of xenon hydrate), the guest molecules
are immediately released when the clathrate is melted or dissolved. In addition to the noble gases(Ar, Kr, Xe), many other species form stable
clathrates. One of the most interesting is methane hydrate, large deposits of which occur naturally at the bottom of the oceans. It is estimated that
the amount of methane in such deposits could have a major impact on the world’s energy needs later in this century.
 Properties of Noble Gas Family

Property He Ne Ar Kr Xe Rn

Atomic No. 2 10 18 36 54 86

Valence E.C. 1s2 2s2 2p6 3s2 3p6 4s2 4p6 5s2 5p6 6s2 6p6

Density(g/L) at
0.16 0.83 1.63 3.43 5.37 9.07
298K

Atomic radius(pm) 31 38 71 88 108 120

First I.E. (KJ/mol) 2372 2081 1521 1351 1170 1037

Normal O.S. - - - 0 (+2) 0 (+2, +4, +6) 0 (+2)

Electron gain
48 116 96 96 77 68
enthalpy (KJ/mol)

Melting point (/K) - 24.6 83.8 115.9 161.3 202

Boiling point (/K) 4.2 27.1 87.2 119.7 165 211

 Properties of Noble Gas Family

• Fractional distillation of liquid air is the only source of all the noble gases except helium. Although helium is
the second most abundant element in the universe (after hydrogen), the helium originally present in Earth’s
atmosphere was lost into space long ago because of its low molecular mass and resulting high mean velocity.
Natural gas often contains relatively high concentrations of helium (up to 7%), however, and it is the only
practical terrestrial source.

• Property He Ne Ar Kr Xe Rn

Product of reaction
- - - - - -
with O2

Type of oxide - - - - Oxide -

Product of reaction
- - - - - -
with N2

Product of reaction
- - - KrF2 XeF2, XeF4, XeF6 RnF2
with X2

Product of reaction
- - - - - -
with H2
 Reaction and Compounds of Noble Gas

• The widely held belief in the intrinsic lack of reactivity of the noble gases was challenged when Neil Bartlett, a British
professor of chemistry at the University of British Columbia, showed that PtF6, a compound used in the Manhattan
Project, could oxidize O2. Because the ionization energy of xenon (1170 kJ/mol) is actually lower than that of O2, Bartlett
recognised that PtF6 should also be able to oxidize xenon. When he mixed colorless xenon gas with deep red PtF6 vapour,
+ −
yellow-orange crystals immediately formed. Although Bartlett initially postulated that they were Xe PtF6 , it is now
generally agreed that the reaction also involves the transfer of a fluorine atom to xenon to give the XeF + ion:
+ −
Xe(g) + PtF6(g) → [XeF] [PtF5] (s)

• Xenon- Fluorine Compounds:

Xenon forms three binary fluorides by direct reaction.
673K, 1bar
(i) Xe(g) + F2(g) XeF2(s), (Xenon is in excess)
873K, 7bar
(ii) Xe(g) + 2F2(g) XeF4(s). (Xe : F = 1 : 5)
573K, 60−70bar
(iii) Xe(g) + 3F2(g) XeF6(s) (Xe : F = 1 : 20)
(iv) XeF4 + O2F2 → XeF6 + O2
 Properties of Xenon-fluorides

• XeF2, XeF4 and XeF6 are colourless crystalline solids and sublime readily at 298K.
• They are Powerful Fluorinating agents.

• They are readily hydrolysed even by traces of water. For example

Hydrolysis of XeF2: 2XeF2(s) + 2H2O(l) → 2Xe(g) + 4HF(aq) + O2(g)

Hydrolysis of XeF4: 6XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2
Hydrolysis of XeF6: XeF6 + 3H2O → XeO3 + 6HF
Partial Hydrolysis of XeF6: XeF6 + H2O → XeOF4 + 2HF
XeF6 + 2H2O → XeO2F2 + 4HF

• XeO3 is colourless explosive solid and has a pyramidal molecular structure. XeOF4 is colourless volatile liquid and has a
pyramidal molecular structure.

• Xenon fluoride reacts with fluorides ion:

+ − + −
XeF2 + PF5 → [XeF] [PF6] , XeF4 + SbF5 → [XeF3] [SbF6]
XeF6 + MF → M +[XeF7]− (M = Na, K, Rb or Cs)
END
 Quick Review of P-block Trends
Properties Group 13 Group 14 Group 15 Group 16 Group 17 Group 18

Melting Point B > Al > Tl > In > Ga C > Si > Ge > Pb > Sn As > Sb > Bi > P > N Te > Po > Se > S > O I2 > Br2 > Cl2 > F2 Rn > Xe > Kr > Ar > Ne > He

Boiling Point B > Al > Ga > In > Tl C > Ge > Si > Sn > Pb Sb > Bi > As > P > N Te > Po > Se > S > O I2 > Br2 > Cl2 > F2 Rn > Xe > Kr > Ar > Ne > He

IE1 ( KJ/mol ) B > Tl > Ga > Al > In C > Si > Ge > Pb > Sn N > P > As > Sb > Bi O > S > Se > Te > Po F > Cl > Br > I He > Ne > Ar > Kr > Xe > Rn

IE2 ( KJ/mol ) B > Ga > Tl > In > Al C > Si > Ge > Pb > Sn N > P > As > Bi > Sb - - -

IE3 ( KJ/mol ) B > Ga > Tl > Al > In C > Ge > Si > Pb > Sn N > P > As > Bi > Sb - - -

IE4 ( KJ/mol ) - C > Si > Ge > Pb > Sn

Density (g/mL) Tl > In > Ga > Al > B Pb > Sn > Ge > C* > Si Bi > Sb > As > P > N Te > Se > S > O I2 > Br2 > Cl2 > F2 Rn > Xe > Kr > Ar > Ne > He
(C* = diamond)

Atomic radius Tl > In > Al > Ga > B Pb > Sn > Ge > Si > C Bi > Sb > As > P > N Po > Te > Se > S > O I > Br > Cl > F Rn > Xe > Kr > Ar > Ne > He

Ionic Radius - - - Po > Te > Se > S > O I > Br > Cl > F ( X- /pm) -

Vanderwaal radius - - - - - Rn > Xe > Kr > Ar > Ne > He

Electrode Potential (SRP) (M(+3)/M = Tl > In > Ga > Al - - - I2 > Br2 > Cl2 > F2 -
( In volt ) (M(+1)/M = Al > In > Tl > Ga (acid) > Ga (alkali)

Negative Electron Gain Enthalpy - - - S > Se > Te > Po > O Cl > F > Br > I Ne > Ar = Kr > Xe > Rn > He
( + ve electron gain enthalpy)

Atomspheric content - - N > P > As > Sb = Bi - - Kr > Ar > He > Xe > Rn

Electronegativity B > Tl > In > Ga > Al C > Pb > Si = Ge = Sn - O > S > Se > Te > Po F > Cl > Br > I -

Hydration enthalpy - - - F > Cl > Br > I -

BDE - - - - Cl2 > Br2 > F2 > I2 -

Electrical resistivity - Si = Ge > Sn > Pb > C - - - -

Hydrides

Thermal stability - - NH3 > PH3 > AsH3 > SbH3 > BiH3 H2O > H2S > H2Se > H2Te HF > HCl > HBr > HI -

BDE - - NH3 > PH3 > AsH3 > SbH3 > BiH3 H2O > H2S > H2Se > H2Te HF > HCl > HBr > HI -

Basicity - - NH3 > PH3 > AsH3 > SbH3 > BiH3 - - -

Bond angle - - NH3 > PH3 > AsH3 > SbH3 > BiH3 H2O > H2Te > H2Se > H2S - -

Reducing Character - - BiH3 > SbH3 > AsH3 > PH3 > NH3 H2Te > H2Se > H2S > H2O - -

Melting Point - - BiH3 > NH3 > SbH3 > AsH3 > PH3 H2O > H2Te > H2Se > H2S HI > HF > HBr > HCl -

Boiling Point - - BiH3 > SbH3 > NH3 > AsH3 > PH3 H2O > H2Te > H2Se > H2S HF > HI > HBr > HCl -

Vap. Enthalpy - - NH3 > SbH3 > AsH3 > PH3 - - -

Formation enthalpy (released) - - NH3 > PH3 > AsH3 > SbH3 > BiH3 H2O > H2S > H2Se > H2Te - -

Dissociation constant - - - H2Te > H2Se > H2S > H2O HI > HBr > HCl > HF -