Chemistry

Session Objectives
1. Chemical properties of group 14 elements 2. Extraction and properties of silicon 3. Extraction of tin 4. Extraction of lead

5. Silicates and silicones

6. Glass 7. General properties of group 14 elements 8. Oxoacids of phosphorous

Action of Acids on group 14 elements

Non-oxidising acids do not attack carbon and silicon. Ge is not attacked by dilute HCl. However, when metal is heated in a stream of HCl gas, germanium chloroform is formed.

Ge 3HCl GeHCl3 H2
Tin dissolves slowly in dilute HCl but readily in Conc. HCl.

Sn 2HCl SnCl2 H2
Lead dissolves in Conc. HCl formig chloro-plumbous acid.

Pb 2HCl PbCl2 H2
PbCl2 2HCl H2PbCl4
(chloroplumbous acid)

Action of Alkalies
Carbon is unaffected by alkalies. Silicon reacts slowly with cold aq. NaOH and readily with hot solution to form silicate.

Si 2NaOH H2O Na2SiO3 2H2

Sn and Pb are slowly attacked by cold alkali but readily by hot alkali giving stannates and plumbates.

Sn 2NaOH H2O Na2SnO3 2H2 Pb 2NaOH H2O Na2PbO3 2H2

Oxides of group 14 elements

Carbon forms the oxides CO, CO2, C3O2, Si forms SiO2, which is solid at room temperature because it exists in the form of a three-dimensional network due to lack of formation of p bonds with oxygen. Three crystalline modifications of SiO2 are quartz, cristobalite and tridymite Pb forms a number of oxides like PbO, PbO2, Pb2O3, Pb3O4(red lead). Pb3O4 is actually 2PbO.PbO2 2Pb(NO3)2 -2PbO + 4NO2 + O2 6PbO + O2 2Pb3O4 Pb3O4 + 4HNO3 Pb(NO3)2 + PbO2 + 2H2O GeO2, SnO2 etc are also network solids. SnO2 is used as a polishing powder and also in the manufacture of glass and pottery

Halides of group 14 elements

React with halogens directly to form tetrahedral and covalent halides except C. CCl4 does not undergo hydrolysis due to non availability of d orbital. SiCl4 and the halides of heavier metals can undergo hydrolysis due to availability of vacant d orbitals. SiCl4 on hydrolysis gives silicic acid (H4SiO4).

PbBr4 and is PbI4 do not exist because Pb4 is a strong oxidant and Br- and I- are strong reductants.
Apart from tetrahalides, germanium, tin and lead form dihalides MX2. The stability of the dihalides increases steadily in the sequence CX2 < SiX2 < GeX2 < SnX2 < PbX2

Illustrative Example
Explain why PbCl4 is less stable than SnCl4? Solution In the 14th group, the stability of +4 oxidation state decreases down the group so Pb4+ is less stable than Sn4+.This is actually due to the inert pair effect as s-electrons do not participate in bond formation.

Extraction and properties of Si

By reduction of sand SiO2 with coke in an electric furnace(96-98% pure).
222732773 K SiO2 2C Si 2CO

Semiconductor grade silicon is prepared mainly by the reduction of SiCl4/SiHCl3 with H2 or by the pyrolysis of SiH4 At room temperature Si is unreactive towards all elements except flourine. Combines with halogens, N2 and O2 at high temperature. Forms carborundum(SiC) with carbon; extremely hard; used as abrasive and refractory material. With hot aqueous alkali liberates hydrogen.

Si 4OH (aq) SiO4 (aq) 2H2 4

Extraction of tin
Tin is commonly available as the mineral cassiterite, SnO2.

Ore is crushed and washed with water to remove impurities such as arsenic and sulphur as volatile oxides.
The roasted ore is heated with coal in a reverberatory furnace at 1500 K.

SnO2 + 2C Sn + 2CO
Tin is remelted on inclined surface to remove the impurities having higher melting point.

Properties of tin
Tin is a soft, silvery white metal. It is ductile and can be rolled into thin foils.

Tin is not attacked by air or water at ordinary temperatures: Heating with air or oxygen results in the formation of SnO2.
Tin is used as a coating on metals and in making various alloys like solder, bronze. It is also used for electroplating steel to make tin-plate. Tin plate is extensively used for making cans for food and drinks.

Lead
The ore is concentrated by froth-floatation and then roasted in a limited supply of air to give PbO which is reduced to the metal by heating with coke and limestone in a blast furnace. The molten lead is tapped from the bottom of the furnace. (i) 2PbS + 3O2 2PbO + 2SO2 (ii) PbO + C Pb + CO (iii) PbO + CO Pb + CO2 (iv) PbS + 2PbO 3Pb + SO2

Lead is mostly used in storage batteries, in alloy making and pigments/chemicals. PbCrO4 is used as a strong yellow pigment for road signs and markings. Lead compounds are also included in crown glass and cut glass, and in ceramic glazes.

Toxicity of Lead
Large amounts of lead in a child's blood can cause brain damage, mental retardation, behavior problems, anemia, liver and kidney damage, hearing loss, hyperactivity, developmental delays, other physical and mental problems, and in extreme cases, death.

Pb3(OH)2(CO3)2

Silicates
Orthosilicates : contain single discrete unit of SiO44 tetrahedra Pyrosilicates

Basic unit is (Si2O7)-6

Cyclic structure

Basic unit is (Si6O18)-12 Example is beryl, Be3Al2Si6O18

Linear silicate chain

Continuous single chain units of tetrahedra each sharing 2 oxygens. Basic unit is (SiO3)-2 or (Si2O6)-4.

e.g., pyroxenes; MgCaSi2O6.

Amphiboles
Continuous double chain units of tetrahedra each sharing 2 and 3 oxygens alternately. Basic unit is (Si4O11)-6 or (Si8O22)-12 e.g., asbestos; [Mg3(Si2O5)(OH)4]

Phyllosilicates
Continuous sheet units of tetrahedra each sharing 3 oxygens Basic unit (Si2O5)-2 e.g.Mica

3 D framework
Continuous framework of tetrahedra each sharing all 4 oxygen atoms. Basic units can be (SiO2) e.g. zeolites,feldspar

Silanes and Silicones

The hydrides of silicon are called silanes having general formula SinH2n+2

Polymeric organo-silicon compounds containing Si-O-Si bonds are called silicones. These have the general formula (R2SiO)n. Where R is CH3 group (majority cases) or C6H5 group.

Focus On Glassmaking
Glass is a mixture of sodium and calcium silicates.
1300 C CaO Na2CO3 6SiO2 Na2CO3 .CaSiO3 .4SiO2 CO2
o

Soda lime glass or Soft glass. Glass is not a true solid and dont have definite melting point. Small amounts of impurities impart beautiful colours. Fe2O3 green CoO blue Adding B2O3 gives, borosilicate glass (Pyrex) having low coefficient of thermal expansion and used in making laboratory glasswares. Lead-potash glass has high refractive index and used in lenses.

Group 15 elements
Nitrogen Phosphorus Arsenic Antimony Bismuth N P As Sb Bi [He] 2s2p3 [Ne] 3s23p3 [Ar]3d104s24p3 [Kr]4d105s25p3 [Xe]4f145d106s26p3

General trends of group 15 elements

The covalent radius increases down the group. All elements have nearly same and low electronegativity except nitrogen. P, As, Sb and Bi are solids under normal conditions. Ionisation energy

The value of ionization energy is quite high for the members of group 15 than the corresponding members of group 14. This is due to smaller atomic radii, increased nuclear charge and stable electronic configuration of half filled orbitals.

Illustrative Problem
Why nitrogen exists as N2 whereas phosphorous exists as P4

Solution :
Because d orbitals are not available in nitrogen.

Oxidation state
Stability of +3 oxidation state increases down the group while that of +5 oxidation state decreases down the group. Bi5+ salts are very rare and good oxidising agents As3+ salts are good reducing agents.

Oxidation Number 0

Nitrogen Compound N2

Phosphorus Compound P4

+3
+3 +5 +5 +5

HNO2 (nitrous acid)

N2O3 HNO3 (nitric acid) NaNO3 (sodium nitrate) N2O5

H3PO3 (phosphorous acid)

P 4O6 H3PO4 (phosphoric acid) Na3PO4 (sodium phosphate) P4O10

Hydrides: MH3
Down the group, covalent character, basicity and thermal stability decrease while reducing character increases. NH3 > PH3 93 48 > AsH3 91 48 > SbH3 91 18 > BiH3 90

107 48

Illustrative Problem
Explain why NH3 is a stronger base than PH3? Solution Since phosphorus is bigger in size as compared to nitrogen so, availabilty of lone pair is less. Thus PH3 is a weaker base than NH3

Illustrative Problem
Give the order of basicity and reducing character and stability for the following hydrides: NH3, PH3, AsH3, SbH3 Solution : Basicity Stability Reducing character NH3 > PH3 > AsH3 > SbH3 NH3 > PH3 > AsH3 > SbH3 NH3 < PH3 < AsH3 < SbH3

Oxides of nitrogen

Oxides of nitrogen

Illustrative Problem
Which oxide of nitrogen is coloured ? Solution : NO2 has unpaired electrons,so it is coloured.

Oxides
P, As, Sb and Bi form two types of oxides: M2O3 and M2O5 and exists as dimer due to reluctance for pp pp bonding.

Oxides of phosphorous P4O6 and P4O10

Both P4O6 and P4O10 are acidic oxides which dissolve in water to give phosphonic acid and phosphoric acid respectively.

Halides
Forms two series of halides; MX3 (pyramidal) MX5 (trigonal bipyramidal) Trihalides readily hydrolyse with water.

NCl3 4H2O NH4OH HOCl

AsCl3 3H2O H3 AsO3 3HCl

BiCl3 H2O BiO 3Cl 2H

PCl3 3H2O H3PO3 3HCl

SbCl3 H2O SbO 3Cl 2H

PCl5 is molecular in gas and liquid phases but exists as [PCl4]+[PCl6]- in the solid state .

Illustrative Example
Explain why PCl5 exists but NCl5 does not? Solution NCl5 is not formed because nitrogen does not have d-orbitals.

Illustrative Example
Solid phosphorous-pentachloride exhibits some ionic character, why?

Solution
This is because PCl5 exists as [PCl4]+ [PCl6]- in solid phase and hence exhibits ionic character.

Allotropy of P
White phosphorus: Waxy solid, insoluble in water, highly soluble in CS2 and benzene, highly reactive, highly toxic and glow in dark.

Stored in water because ignite spontaneously in air. Consist of discreate molecules P4.

Allotropy of P
Red phosphorus:
570 K White phosphorus red phosphorus

Amorphous and polymeric structure. Less reactive and nontoxic

Black phosohorus :
470 K, high pr. Most stable form White phosphorus Black phosphorus

Inert and has layered structure.

Oxy-acids of P
O P HO OH OH HO O P OH O O P OH OH H O P OH OH

H3PO4 Ortho phosphoric acid O P H H OH

Di phosphoric acid H4P2O7 O P OH O P O

H3PO3 Phosphoric acid O P OH O

HPO2 Hypophosphorus acid

O OH (HPO3)3 Cyclic phosphoric acid

Phosphatic fertilizers
Fertilizers usually contains N,P,K. Generally the ratio of N-P-K is written as 10-10-10 which indicates the percentage of N, P205, and K2O . Most important phosphatic fertilizer is the superphosphate of lime, Ca(H2PO4)2 which is produced from the treatment of phosphatic rock with sulphuric acid.

Ca3 (PO4 )2 2H2SO4 Ca(H2PO4 )2 2CaSO4

Triple superphosphate Ca(H2PO4)2.H2O

Ca5 (PO4 )3 F 7H3PO4 5H2O 5Ca(H2PO4 )2.H2O HF

Eutrophication
Eutrophication is the enrichment of an ecosystem with chemical nutrients, typically compounds containing nitrogen or phosphorus.

Thank you