THE p BLOCK ELEMENTS electronic configuration is ns

THE p -BLOCK ELEMENTS electronic configuration is ns 2 np 1 -6 (except for He) B. K. SHARMA

Session Objectives Group 13 elements Group 14 elements 1. properties of group 13 elements 1. properties of group 14 elements 2. Halides of group 13 elements 2. Extraction and properties of silicon 3. Hydrides of group 13 elements 4. Oxides of group 13 elements 3. Extraction of tin 5. Extraction of aluminum 4. Extraction of lead 6. Compounds and uses of 5. Silicates and silicones aluminum 7. Physical properties of group 14 elements 6. Glass 7. General properties of group 14 elements 8. Oxoacids of phosphorous

ATOMIC RADIUS Elements of group 13 • Increases down the group • Atomic radius (pm) B(88)<Al(143)>Ga(135)<In(167 )<Tl(170) • Ionic radius M+3 pm • B(27)<Al(53. 5)>Ga(62)<In(80)< Tl(88. 5) • Ionic radius M+pm • Ga(120)<In(140)<Tl(150) • (Higher nuclear charge and poor shielding by 3 d-electron) Elements of group 14 • Increases down the group C<Si<Ge<Sn<Pb Covalent radius M(iv)pm C(77)<Si(118)<Ge(122)<Sn(140 )<Pb(146) Ionic radius M+4 pm Si(40)<Ge(53)<Sn(69)<Pb(78)

IONISATION ENERGY Elements of group 13 Elements of group 14 • decreases down the group • B>Tl>Ga≈Al>In • C>Si>Ge>Sn<Pb

ELECTRONEGATIVITY Elements of group 13 Elements of group 14 • decreases down the group B(2. 0)>Al(1. 5)>Ga(1. 6) >Tl(1. 7)>In(1. 8) • Al Is most metallic and best reducing agent in the Boron family • C(2. 5)>Si≈Ge≈Sn (1. 8)<Pb(1. 9)

INERT PAIR EFFECT • The reluctance of ns 2 pair in the bond formation increases down the group

INERT PAIR EFFECT & OXIDATION STATES Elements of group 13 B<Tl<Ga<Al<In (+1) • B>Tl>Ga>Al>In (+3) Elements of group 14 • C<Si<Ge<Sn<Pb(+2) • C>Si>Ge>Sn<Pb(+4)

MELTING POINTS Elements of group 13 B(2453 K)>Al(933 K)>Ga(303 K)< In(430 K)<Tl(576 K) • `Ga MELTS IN HAND OF VERY POOR PACKING OF Ga 2 MOLECULES Elements of group 14 • C(4373)>Si(1693)>Ge(1218) >Sn(505)<Pb(600)

DENSITY Elements of group 13 B(2. 34)<Al(2. 7)<Ga(5. 9)<In(7. 31)<Tl(11. 85) • Unit In gcm-3 Elements of group 14 • C(diamond 3. 51)<Si(2. 34)<Ge(5. 32) <Sn(7. 26)<Pb(11. 34) • Unit In gcm-3

REACTIVITY TOWARDS AIR Elements of group 13 B is unreactive in crystalline form. Al forms a very thin oxide layer on the surface which protects the metal from further attack. Amorphous B and Al metal on heating in air form B 2 O 3 and Al 2 O 3 respectively. With N 2 at high temperature they form nitrides. B 2 O 3(a), Al 2 O 3(am), Ga 2 O 3(am), In 2 O 3(b), Tl 2 O 3(b) Elements of group 14 They form mainly two types of oxides, i. e. , MO and MO 2. Si. O only exists at high temperature. Oxides in higher oxidation states of elements are generally more acidic than those in lower oxidation states. Dioxides CO 2, Si. O 2 and Ge. O 2 (acidic), Sn. O 2 and Pb. O 2 (amphoteric) monoxides, CO, Ge. O is distinctly acidic, Sn. O and Pb. O amphoteric.

REACTIVITY TOWARDS WATER Elements of group 13 Except B Rest of elements of group 13 react with water at high. Elements of group 14 Carbon, silicon and germanium are not affected by water. Tin decompose steam to form dioxide and dihydrogen gas. Lead is unaffected by water probably because of a protective oxide film formation.

REACTIVITY TOWARDS HALOGENS Elements of group 13 • These elements react with halogens to form trihalides (except Tl I 3). Elements of group 14 (MX 2 and MX 4) Except C, other members react with X 2. MX 4 covalent , sp 3 , tetrahedral in shape. Exceptions are Sn. F 4 and Pb. F 4, ionic. Pb. I 4 does not exist. Ge to Pb are able to make MX 2. Stability of MX 2 increases down the group. Ge. X 4 is more stable than Ge. X 2, Pb. X 2 is more stable than Pb. X 4. Except CCl 4, other like Si. Cl 4 are easily hydrolysed by water.

REACTIVITY TOWARDS ACIDS & ALKALIES Elements of group 13 B does not react with acids and alkalies even at moderate temperature; but Al dissolves in mineral acids and aq alkalies and thus shows amphoteric character. Al dissolves in dilute HCl and liberates H 2 concentrated nitric acid renders Al passive by forming a Al 2 O 3 layer on the surface. Al also reacts with aqueous alkali and liberates H 2 Elements of group 14. Pb dissolves in water in the presence of oxygen to produce Pb(OH)2. It is called plumbosolvency. Pb+H 2 O+1/2 O 2 -- Pb(OH)2

ANOMALOUS PROPERTIES OF BORON • Reason: - Small Size, High IE, More Electronegativity, Absence of d orbitals. • (1) In the family only B shows allotropy. • (2) Max. covalency of B is 4(e. g. ) while for other it is 6 ( ). • (3)Pure B dose not react with water and HCl.

BORAX it contains the tetranuclear units Borax dissolves in water to give an alkaline solution. On heating, borax first loses water molecules and swells up. On further heating it turns into a transparent liquid, which solidifies into glass like material known as borax bead. The metaborates of many transition metals have characteristic colours and, borax bead test can be used to identify them in the laboratory. For example, when borax is heated in a Bunsen burner flame with Co. O on a loop of platinum wire, a blue coloured Co(BO 2)2 bead is formed.

Structure of Orthoboric acid H 3 BO 3

Orthoboric acid H 3 BO 3 white crystalline solid, with soapy touch. It is sparingly soluble in water but highly soluble in hot water. It can be prepared by acidifying an aqueous solution of borax. Boric acid is a weak monobasic acid. It is not a protonic acid but acts as a Lewis acid by accepting electrons from a hydroxyl ion: On heating, orthoboric acid above 370 K forms metaboric acid, HBO 2 which on further heating yields boric oxide, B 2 O 3.

Diborane, B 2 H 6(A fuel for super sonic rockets) Boron forms Bn. Hn+4(Nidoboranes), Bn. Hn+6(Arachno boranes) 1. prepared by treating boron trifluoride with Li. Al. H 4 in diethyl ether. 4 BF 3 + 3 Li. Al. H 4 → 2 B 2 H 6 + 3 Li. F + 3 Al. F 3 2. Lab method 2 Na. BH 4 + I 2 → B 2 H 6 + 2 Na. I + H 2 3. Industrial method

PROPERTIES OF DIBORANE 1. colourless, highly toxic gas, b. p. 180 K. 2. catches fire spontaneously upon exposure to air. It burns in oxygen releasing an enormous amount of energy. 3. Boranes are readily hydrolyzed by water to give boric acid. • B 2 H 6(g) + 6 H 2 O(l) → 2 B(OH)3(aq) + 6 H 2(g)

Diborane undergoes cleavage reactions with Lewis bases(L) 4. • • to give borane adducts, BH 3⋅L B 2 H 6 + 2 NMe 3 → 2 BH 3⋅NMe 3 B 2 H 6 + 2 CO → 2 BH 3⋅CO

Reaction of ammonia with diborane gives initially B 2 H 6. 2 NH 3 which is formulated as [BH 2(NH 3)2]+ [BH 4]– ; further heating gives borazine, B 3 N 3 H 6 known as “inorganic benzene” in view of its ring structure with alternate BH and NH groups. B 3 N 3 H 3 is isoster of benzene(12 atoms & 42 Electrons) • Borohydrides, are prepared by the reaction of metal hydrides • with B 2 H 6 in diethyl ether.

structure of diborane • Each B atom uses sp 3 hybrids for bonding. one is without an electron shown in broken lines. The terminal B-H bonds are (2 c-2 e) bonds but the two bridge bonds are (3 c-2 e) bonds or banana bonds

USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS 1. B fibres are used in making bullet-proof vest and light composite material for aircraft. 2. B-10 used in nuclear industry as protective shields and control rods. 3. Borax and H 3 BO 3 used as heat resistant glasses (e. g. , Pyrex), glass-wool. 4. Borax used as a flux for soldering metals. 5. H 3 BO 3 acid is generally used as a mild antiseptic. 6. Al forms alloys with Cu, Mn, Mg, Si and Zn. 7. The use of Al and its compounds for domestic purposes is now reduced considerably because of their toxic nature.

ANOMALOUS BEHAVIOUR OF CARBON • It is due to its smaller size, higher electronegativity, higher IE and unavailability of d orbitals. • C form pπ– pπ multiple bonds with itself and with other atoms of small size and high electronegativity. C=C, C ≡ C, C = O, C = S, and C ≡ N. • Heavier elements do not form pπ– pπ bonds because their atomic orbitals are too large and diffuse to have effective overlapping. • Carbon atoms have the tendency to link with one another through covalent bonds to form chains and rings. This property is called catenation. because C—C bonds are very strong. • C > > Si >Ge ≈ Sn. Pb does not show catenation. • Due to property of catenation and pπ– pπ bond formation, carbon is able to show allotropic forms.

ALLOTROPES OF CARBON • Carbon exhibits many allotropic forms; both crystalline as well as amorphous. Diamond and graphite are two well-known crystalline forms of carbon. • In 1985, third form of carbon known as fullerenes was discovered by H. W. Kroto, E. Smalley and R. F. Curl. For this discovery they were awarded the Nobel Prize in 1996.

Diamond (crystalline lattice) • Each C atom-sp 3 hybridization & linked to four other C-atoms by using tetrahedral fashion. produces a rigid 3 - dimensional network of carbon atoms. Diamond is a hardest substance on the earth. It is used as an abrasive for sharpening hard tools, in making dies and in the manufacture of tungsten filaments for electric light bulbs.

Graphite It has layered structure & held by vander Waals forces & distance between two layers is 340 pm. Each layer is composed of planar hexagonal rings of carbon atoms. Each C- atom in hexagonal ring undergoes sp 2 hybridization and makes 3 sigma bonds with 3 neighboring carbon atoms. Fourth electron forms a π bond. The electrons are delocalized therefore, graphite conducts electricity along the sheet. it is very soft and slippery. used as a dry lubricant in machines running at high temperature, where oil cannot be used as a lubricant.

structure of graphite

Fullerenes • Fullerenes are made by the heating of graphite in an electric arc in the presence of inert gases such as He or Ar. • The sooty material formed by condensation of vaporized Cn small molecules consists of mainly C 60 with smaller quantity of C 70 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. C 60 molecule has a shape like soccer ball and called Buckminsterfullerene.

It contains 20 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 hybridization. Each carbon atom forms three sigma bonds with other three carbon atoms. The remaining electron at each carbon is delocalized 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 HV of graphite is taken as zero. Δf HV values of diamond and fullerene, C 60 are 1. 90 and 38. 1 k. J mol– 1, respectively. 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.

structure of C 60 , Buckminsterfullerene

Carbon Monoxide • The mixture of CO and H 2 thus produced is known as water gas or synthesis gas. • a mixture of CO and N 2 is produced, which is called producer gas. • It highly poisonous because of its ability to form a complex with haemoglobin, • On small scale pure CO is prepared by dehydration of formic acid with concentrated H 2 SO 4 at 373 K

Carbon Dioxide

photosynthesis

dry ice • Carbon dioxide can be obtained as a solid in the form of dry ice by allowing the liquified CO 2 to expand rapidly. Dry ice is used as a refrigerant for ice-cream and frozen food.

Silicon Dioxide, Si. O 2

Silicones • They are a group of organosilicon polymers, which have (R 2 Si. O) as a repeating unit.

Silicates • silicates minerals exist in nature. Some eg. feldspar, zeolites, mica and asbestos. • The basic structural unit of silicates is Si. O 44–in which silicon atom is bonded to four oxygen atoms in tetrahedron fashion.

Zeolites • If Al atoms replace few silicon atoms in 3 -D network of Si. O 2, overall structure known as aluminosilicate, acquires a negative charge. Cations such as Na+, K+ or Ca 2+ balance the negative charge. e. g. feldspar and zeolites. • Zeolites are widely used as a catalyst in petrochemical industries for cracking of hydrocarbons and isomerization • ZSM-5 (A type of zeolite) used to convert alcohols directly into gasoline. • Hydrated zeolites are used as ion exchangers in softening of “hard” water.