‘P-BLOCK ELEMENTS: ° PROPERTIES : (i) Itexists in five forms, four of which are crystalline and one is amorphous. All erystalline forms are very hard made up of clusters of B,, units. All erystall forms are black in appearance and chemically inert. Melting, points are around 2300°C. But amorphous form is brown and chemically active. @ w 10) ) Reaction with sir: 4B+30, mee, 28,0, 2B+N, ™0C, 2BN; BN +3H,0 "EMEC, HBO. + NH Action of alkalies and acids 2B-+2NaOH +2H,0 —> 2NaBO, + 3H; 2B+3H,S0, "5 2H,BO, + 380, 2B + 6HNO, —“*» 2H,BO, + 6Nt Keaction with Mgand Ca: 3Mg+2B —> Mg,B, 3Ca+2B —>Ca,B, Mg,B, on consequent hydrolysis gives diborane Mg,B, + 6HCI "=> 3MgCl, + ByH, 5 BH, + 6H,0 —+2H,BO, + 61 Reducing properties: 38i0,+4B 28,0, +38i 3CO, +4B —, 2B,0, +3C decomposes steam liberating hydrogen gas 2B + 3H,0(steam) —+B,0, + 3H, USES : Boron is used in the construction of high impact-resistant stel and, since it absorbs neutrons, in reactor rods for controlling atomic reactions 2 COMPOUNDS OF BORON : 2 BORON TRIOXIDE (B,0,) : Q ° Lakshya Educare PREPARATION H.80, 070, HB0, “SS, H,8,0, ‘Ne 8.0, fone ce PROPERTIE: Itisa weakly acidic oxide and reacts with alkalies or bases to form borates. 3Na,0 + B,0, + 2Na,BO, (sodium orthoborate. Itreacts with water slowly t form orthoboric acid, When heated with transition metal sats it forms coloured compounds H,0 +B,0,2HBO,; HBO, + H,0 >H,BO, 3B,0; + Cr,(SO,), + 380, T + 2Cr(BO,),(green) 2B,0, + 2Cu(NO,), —*+ 4NO, t +0, P+ 2Cu(BO,), (blue) + P,0, <> 2BPO, ORTHOBORIC ACID (H,BO)) : Among the oxyacids of boron are‘P-BLOCK ELEMENTS Tet © PREPARATION : ()_Itisprecipitated by treating a concentrated solution of borax with sulphuric acid, Na,B,0, + H,SO, + 5H,O > Na,SO, + 4H,BO, J (From Colemanite: Powdered colemanite is suspended in water and excess SO, is passed through it On filtering and cooling the filtrate, white crystals of H,BO, are obtained. Ca,B,0,, +280; + 11H,0 — > 2Ca(H1S0,), + 6H, BO, QO PROPERTIES: (0 __Itisa weak monobasic acid and in aqueous solution the boron atom completes its octet by removing OH- from water molecules B(OH) (aq) + 2H,0(/) -> B(OH), (aq) + H,0"(aq). It, therefore, functions as a Lewis acid and not as.a proton donor. Itbchaves as strong acid when a polyhydroxy compound such as glycol or slycerol is added to its aqueous solution. The acidity is due tothe high stability of the conjugate bone chelate complex. Nl 1 1 wayor), 2 G4-OH GH-On | /O-GH] H+ AH,0 CH-OH ~ gr-07 No-cH T T Ethanol does not form similar complex but catechol, salicylic acids form similar complexes. COC) (CAD} ‘When heated it first forms metaboric acid (HBO, and then boron trioxide, Hp0, 0S, Heo, IC, 48.0, dhe Bo, Bote see Orthoboric acd is greasy to touch less soluble in cold water but more soluble in hot water. Ithas a layered structure in which planar BO, units are joined by hydrogen bonds. Lakshya Educare‘P-BLOCK ELEMENTS ‘TEST FOR BORATE RADICAL : ‘When boric acid is heated with ethyl alcohol, the evolved gas is burned forminga green edged flame. H,BO, + 3C,H,OH —> B(OC,H,), +3H,0 © ethyl borate (volatile) USES : Itisan antiseptic and its water solution is used as an eyewash. Itis also used in glass, enamel and pottery BORAX (Na,B,0,.10H,0) + PREPARATION: (@— FromCotemanite When colemanite powder is heated with Na,O, solution, the following renetion aceurs with the precipitation of CaC Ca,B,0,, + 2Na,CO, —> 2CaCO, J + Na,B,0, + 2NaBO,, The filterate is cooled when white crystals of borax are precipitated. The mother liquor on treatment with CO, converts NaBO, to Na,B ,O; which precipitates out on crystallization 4NaBO, + CO, —>Na,B,0, + NaCO, Gi) From orthoboric acid Borax is obtained by the action of Na,CO, on orthoboric acid, 4H,BO, + Na,CO, —»Na,B,0, + 6H,0 + CO, Itis found in nature but can also be prepared by the folowing methods. PROPERTIES: (Borax isawhite powder, less soluble in cold water, more soluble in hot water. (Irs aqueons solution is allealine hecanse ofits hydrolysis to weak acid H,RO, and strong alkali NaOH. Na,B,0, + 7H,0 —>4H,BO, + 2NaOH (ii) Action of heat. ‘When borax powder is heated, it first swells due to loss of water inthe form of steam but at 740°C itbecomes converted into colourless transparent borax bead, Na,B,0,10H,0 + —*+ Na,B,0, + 10 HOt Na:B,0, 2 , 2NaBO, + BO, (borax bead) (i) Action of acids Na,B,0, + 2HCI-+SH,O —» 2NaCI+4H,BO, (boric acid) On cooking, the white flakes of boricacid are obtained ()NaB,O, MO" )NaBO, "° 5 Na, [(OH), B(O-0), B (OH),] 6H,O F Correct formula of borax is Naz{B,0.(OH),] . 8H,0 BORAX-BEAD TEST : Boric anhydride reacts with certain metal salts such as, Ni, Co, Cri, Cu2*, Mn2* 2c. to form coloured metaborates. The colour of the metaborates can be used to ident the metallic ions (cations) in salts‘P-BLOCK ELEMENTS 163 Na,B,0,. 10H,0 — 3-3 Na,B,0, M* , 2NaBO, +8,0; ; CuO + B,O, —> Cu(BO,), (blue bead) sre Oo USES: Itisused (inborax bead test, Gi) in purifying gol, (ii) s ux during welding of metals and (iv) in production of glass. _DIBORANE @B,H, : Binary compounds of 8 with Hare called boron hydrides or boranes. These compounds form following two types of sores BH. -BlH, Bul, Bly, Bully, leg = — ByHjo» BsHyy» BH» Bulls ‘of diborane has aroused considerable interest because ofits usefulness in many synthetic reactions and also because the elucidation ofits structure helped to clarify the basic concepts about. the structure of electron deficient compounds. PREPARATION : @ 4BF,+3LiAIM, —s"_, 2B,H, +3LiF +3AIF, @ —2BC1,+6H, (excess) SL + BH, + HCL ) SBF, +6LiH —, B,H, + OLIBF, (jv) 2NaBH, +1, 4 BH, +2Nal +H, () 3NaBH, +4BF, —S5-> 3NaBF,+2B,H, (i Itean also be prepared by treating NaBH, with concentrated H,SO, or HPO, 2NaBH, + H,SO, —>B,H, + 2H, + Na,SO, 2NaBH, + 2H,PO, —> B,H, +2H, +2NaH,PO, (i) 2BF, + 6NaH — °K, B,H,,+6NaF (Industrial method) PROPERTIES ()_Diborane is a colourless gas (boiling point 183 K). (i Itisrapidly decomposed by water with the formation of H,BO, & H,; B,H, + 6H,0 —+2H,BO, + 6H, Gi) Mixtures of diborane with ir or oxygen inflame spontaneously producing large amount of heat Difborane has higher heat of combustion per unit weight of fuel than most other fuels. tis therefore used as a rocket ful BH, + 30) —+B,0, + 31,0 AH =~ 1976 ky mot! (iv) Pyrolysis oFB,H, in sealed vessels at temperatures above 375 K isan exceedingly complex process producing a mixture of various boranes, eg, B,H g- ByHs, BH, and B gH, (0) Diborane undergoes a facile addition reaction with alkenes and alkynes in ether solvents at room temperature to form organoboranes. This reaction is known as hydroboration reaction () BH, +HC] —>B,H,C1+H, (i) BAH, + 6McOH —» 2B(OMe), + 6H; Lakshya Educarero) (iy we CS) xi) ‘PBLOCK ELEMENTS Cleavage reactions (@) BH, + 2MeN —>2Me,NBH, () BAH, +2Me,P —> 2Me,PBH, (©) BH, +2CO 202 28m, 2BH,CO (borane carbonyl) B,H, + 2E1,S —+2Et,SBH, 3B,H,+6NH, ioe tree, BH, 2NHor[BHNH))} BH, 2° _, BINH, (boruzole)+ 12H, B,H, + 2KOH + 2H,0 —+2KBO, + 6H, (xv) BH, +6Cl, —>2BCl, + 6HCI B,H,+2LiH —>2LiBH, © ALUMINIUM (AD) EXTRACTION (HALL-HEROULT PROCESS): ‘The aluminium is extracted from ore bauxite (Al,0,2H,0). The ore is first purified by Bayere’s process ‘The anhydrous ALO, is mixed with Na,AIF, & CaF, & then fused. The fused mixture is subjected to electrolytic reduction when aluminiumis obi cs ° 0 @ (iy w 0 oi) oi) (vii) Lakshya Educare atcathode. ‘Aluminium is purified by Hoope's process PROPERTIES: Itisasilvery meta witha density of2.7g/ce, having a melting point of 660°C, andis a good conductor of heat and electricity. tis malleubleand ductile Action of air: Dry ras no action on aluminium, But moist air forms thin layer of AI,O.on its surface and it loses its Tuster. At very high temperatures itburns to form AI,O, and AIN. Reaction with halogens: When gaseous halogens are passed over aluminium, its halide are formed in an anhydrous form. 2A1 +3Cl, —> 2AICl, Action of alkalies: When warmed with concentrated NaOH, it liberates H, gas and a colourless solution of sodium aluminate is formed. 2AL + 2NaQH + 2H,O— 2NaAlO, + 3H, Action of acids: Aluminium reacts with dilute H,SO, and dilute HC! but concentrated HNO, does not react with aluminium because aluminium becomes passive by the aetion of concentrated HNO, forming protective oxide layeron the surface. 2Al + 3H,SO,—> AL,(SO,), + 3H,7 ; 2Al+6HCI—> 2AlCl, +3H,T Reaction with N,: When N, gas is passed over heated aluminium, aluminium nitride is formed. Hot aluminium thus acts as an absorbing agent for Np. 2Al+N, — 2AIN AIN reacts with hot water to form Al(OH), and NH, Reaction with water Aluminium dacs not react with cold watcr. tis very slowly attacked by boiling water or steam. 2A1+3H,0—> AIH), +3H,t Action of HgCl, solution: When aluminium is added to HgCl, solution mercury is liberated. SHgCl, + 2Al—> 2A1CI, + 3HgbPBLOCK ELEMENTS 165) Co) 2 0 ai) (ii) (iv) Reduction of oxides of metals: When oxides of less reactive metal than aluminium is heated with aluminium, the other metas liberated. 3MnO,+4Al+ 2, 2A10,+3Mn; C0, +2A1+ 2, Al, +2Cr USES isextensively used for manufacture of cooking and household utencis 2s aluminium plating fr tanks, pipes, ron bars and other stel objets to prevent corrosion. for manufacture of aluminium cables. for making precision al apparatus, aircraft bodies, rail coaches, motorboats, car COMPOUNDS OF ALUMINIUM : O ALUMINIUM OXIDE (A1,0)) : Hisalso called alumina, It occurs in nature inthe form of bauxite and corundum. Itis also found in the form ‘of gems, Some important aluminium oxide gems are: (A) Topaz-yellow, (B) Sapphire-blue, (C) Ruby-red, (D) Amethyst-violet,(E) Emerald-green © PREPARATION: Pure Al,O; i obtained by igniting ALSO), Al(OH), orammonium alum, AlySO)); ++ 44 Al0,+380,0 ;2AKOH), +A, ALO, +3H,07 (NH,),SO,.A1(SO,),.24H,0 —4- 2NH,* + Al,0, + 480, * + 25H,07 PROPERTIES itis a white amorphous powder insoluble in water but soluble in acid (forming eg, AIC) as well a alkalies (forming NaNlO,), Thus amphotericin nature. Its apolar covalent compound USES: usused (@fortheextration of aluminium. (_formakingarifcial gems. Gi) forthe preparation of compounds of aluminium. (iv) immaking fumace linings. Iisa efactory material (*) —asacatalyst in onganic reactions © ALUMINIUM CHLORIDE (AICI,.6H,0) : Inisacolourless crystalline solid, soluble in water. is covalent. Anhydrous AICI, isa deliqueseent white solid O PREPARATION : ()_Bydissolving aluminium, A1,0,,0rAKOH) indilute HCI 2AL+6HCL—+2AICI, +314; Al,0,+6HC1_—. 2aIC1, + 31,0; AKON), + 3HCI—+ ICL The solution obtsined is filtered and crystallized when the crystals of AICI, 6H,O are obtained, (@ Anhydrous AICI, is obtained by the action of Cl, on heated aluminium. Gi) Byheatinga mixture ofAJ,O, and coke and passing chlorine overt ALO; +3C + 3Cl, —> 2AICl, (anhydrous) +3CO7 ——— rts Bitecarew Gi) ww Ww i) Hydrated salt when heated strongly is converted to Al,0,, 2AICL,.6H,0 —4-+ 1,0, + 6HCIT + 91,0 Action of moisture on anhydrous AICI; ‘When exposed toair, anhydrous AICI, produces white fumes of HCL AICI, + 3H,0 © AIOH), + 3HCI7 Action of NHy Anhydrous AICI, absorbs NH, since the latter isa Lewis acid, AICI, + 6NH, ~ AICI, 6NH, (white solid) Action of NaOH solution: ‘When NaOH solution isadded dropwise to an aqueous AICI, solution, a gelatinous precipitate of AK(OH), i ist Formed which dissolves in excess of NaOH solution w give acolourless solution uf sodium aluminate AICI, +3NaOH > AI(OH) b+ 3NaCl;_AI(OH), + NAOH > NaAlo, + 2 This reaction is important a atest to distinguish between an aluminium salt from salts of Mg, Ca, Sr ‘nd Ba. (When NaOH solution isadded to ther salt solutions, a white precipitate of hydroxide forms which does not dissolve in excess of NaOH). Actionof NH OH solution: ‘When NH,OH solution is added to a solution of AICI,, a white precipitate of AI(OH), is formed Ive in excess of NH,OH. AICI, + 3NH,OH — Al(OH), 4 (white gelatinous) + 3NH,CI This reactions important asa testo distinguish an Al sal fom a Zn salt, (With precipitate of Zn(OH), is formed which dissolvesin excess of NH, OH solution), Hydrolysis with water: When AICI, is dissolved in water, it undenzoes hydrolysis rapidly to produce Al(OH), which sa ‘weak base and HCI which sa strong acid. Hence the solution is acidic to litmus. [AICH,0),]°* <=> [A(H,0), OH}? + H The compiex cation has a high tendency to get dimerised. oH 2[A(H,0),OHP* IMO) ALS, DANO) | “+ 2H,0 4LIH+AICL, —+ LiAlH, +3LiCl uses : itis used ) a catalyst for cracking of petroleum. i) as eatlyat in Friedel-Crafts reactions, (Gi) for preparing aluminium compounds. ALUMS ; M,S0,. M’, (S0,),- 24H,O OR MM’ (SO,),. 12,0 Alums are transparent crystalline solids having the above general formula where M isa univalent metal or positive radical and Misa trivalent metal. Some important alums are: (i)Potash alum K,S0,.Aly(SO,);-24H,0 (ii) Chrome alum K,S0, . Cr(SO,)s..24H,0 (iil) Ferric alum K,S0,.Fe,(S0,),.24H,0 _ (iv) Ammoniumalum (NH,),S0,.Al,(S0,),.241,0 ‘Aums are double salts which when dissolved in water produce metal ions(or ammonium ions) and the sulphate ions.werted by Total Image Converter - (no stamps are applied by registered ve POLL aOR 1 PBLOCK ELEMENTS 167, Q PREPARATION : ‘Alums can be prepared by fusing M,SO, & M’,(SO,), in I: | molarratio & the resulting mas dissolved into water, From the solution thus obtained, alums are crystallised. OQ USES: Itisused (@—_asamordantin dye industry (—_asagermicide for water purification (ii) as coagulating agent for precipi ting colloidal impurities from water. PB) GROUP 14 ELEMENTS : THE CARBON FAMILY Carbon (C) silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) are the members of group 14. Naturally occurring carbon contains two stable isotopes:“C and "°C. In addition to these third isotopes, “Cis also presents itis a raioacive isotope with halt. 5770 years. and used for radiocarbon dating. Silicon is a veryimpertant component of coramices, glass and cement. Germanium exists only in traces. Tin occurs mainly as cassierite, SnO, and lead as galena, PbS. Utrapure form of germanium and silicon are used to make transistors and semiconductor devices. Electronic Configuration : ‘The valence shel electronic configuration of these elements is ns?np* Covalent Radius ‘Theresa considerable increase in covalent radius from Co Si, thereatter from Sito Pb.a smallincrease in radius |s observed. This is due tothe presence of completey filed d and f orbitals in heavier members. lonization Enthalpy ‘The frat ionization enthalpy of group 14 members ie higher than the corresponding members of group 13. The influence of ner core electrons visible here also. In general the ionisation enthalpy decreases down the group.Small decreases in AH from Sito Ge to Sn and slightincrease in \H from Sn to Pb isthe consequence of poor shielding effects of intervening d and f-orbitals and increases in size ofthe atom. Electronegativity = ‘Due to smal size, the elements of this group are slightly more electronegative than group 13 elements. The clectronegativty value for elements from Sito Pb are almost the same. Physical Properties {All group 14 members are solids. Carbon and silicon are non-metals, germanium is metallold whereas tin and lead are sofl metals with low melting points. Melting points and boling points of group 14 elements are much higher than those of corresponding elements of group 13. Lakshya Educarewerted by Total Image Converter - (no stamps are applied by registered ve POLL aOR 1 168, ‘P-BLOCK ELEMENTS ATOMIC & PHYSICAL PROPERTIES Eecvon conven nan a [ra [m9 | pone" | a 6 ate pow a ee = = Chemical Properties + Oxidation states and trends in chemical reactivity : ‘The group 14 elements have four electrons in outermost shell. The common oxidation states exhibited by these elements are +4 and + 2, Carbon also exhibits negative oxidation states.Since the sum of tie firstfour ionization enthalpies is very high, compound in +4 oxidation state are generally covalent in nature. In heavier members the tendency to show +2 oxidation state increases in the sequence Ge < Sn < Pb. It is due to the inability of ns* electrons of valence shell io participate in bonding. The relative stabilities of these two oxidation states vary down, the group. Carbon cannot exceed is covalence more than 4. Other elements ofthe group can do so. Itis because Of the presence of ¢ orbital in them. Due to this, their halides undergo hydrolysis and have tendency to form complexes by accepting electron pairs from donor species. For example, the species like .SIF;> . [GeCi,}> [Sn(OH),}* exist (Reactivity towards oxygen : ‘Allmembers when heated in axygen form oxides. There are mainly two types of oxides, ie. monoxide and dioxide of formula MO and MO, respectively. SiO only exists at high temperature. Oxides in higher oxidation states of ‘elements are generally more acidic than those in lower oxidation state, The dioxides - CO, SiO, and GeO, are acidic, whereas SnO, and PbO, are amphoteric in nature. Among monoxides, CO is neutral, GeO is distinctly ‘acidic whereas SnO and PbO are amphoteric (i) Reactivity towarde water : Carbon , silicon and germanium are not affected by water. Tin decomposes steam toform dioxide and dihydrogen a8. Leads unaffected by water, probably becauses of a protective oxide flm formation. Reactivity towards halogen : ‘These elements can form halides of formula MX, and MX, (where X =F, CBr, I). Except carbon all other members react directly with halogen under suitable condition to make halides. Most of the MX, are covalent in nature, Exceptions are SnF, and PbF,, which are onic in nature . Pb, does not exist because Pb-! bond initially formed during the reaction does not release enough energy to unpair 6s electrons and excite ane of them to higher orbital tohave four unpaired electrons around lead atom, Heavier members Ge to Pb are able to make halides of formula MX,. Stabilty of dinalides increases down the group. Except CC, other tetrachlorides are easly hydrolysed by water because the central atom can accommodate the lone pai of electrons from oxygen atom of water molecules ind orbital Lakshya Educarewerted by Total Image Converter - (no stamps are applied by registered ve POLL aOR 1 PBLOCK ELEMENTS 169) IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF CARBON Like first member of other groups, carbon also differs from rest of the members ofits group. Itis due toits smaller size, higher electronegativily, higher ionisation enthalpy and unavailability of d orbitals. Accommodate only four pairs of electrons around t. This would limit the maximum covalence to four whereas other members can expand their covalence due tothe presence of d orbitals, Carbon also has unique ablity to form px-px multiple bonds with itselfand with other atoms of small size and high electronegatvity. Few example of multiple bonding are C= C, C =C, C=O C= S and C =N. Heavier elements do not form p-px bonds because their atomic orbital are too large and diffuse tohave 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. This is becauses C-C bonds are very strong. Down the group the size increases tendency to show catenation decreases. This can be clearly seen from bond enthalpies values. The order of caatenation is C > > Si > Ge = Sn. Lead does not show eatenation. Due to the pxoperty of catenation and pripr bonds formation carbon i able to show altropie forms, ALLOTROPES OF CARBON Carbon exhibits many allotropic forms; both crystallc 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.FCur. Diamond : Ithas a crystalline lattice. In diamond each carbon atom undergoes sp? hybridisation and linked to four other carbon atoms by using hybridised orbitals in tetrahedral fashion, The C-C bond length is 154 pm, The structure extends in ‘space and produces a raid three dimensional network of carbon aloms.In this structure directional covalent bonds are presents throughout the lattice. Iti very difficult to break extended covalent bonding and therefore, diamond isa hardest substance on the earth. It 's used as an abrasive for sharpening hard tools in making dyes and in the manufacture of tungsten filament for electric light buibs, Graphite : Graphite has layered structure. Layers are held by van der Waal’ forces and distance between two layers is 940, ‘om. Each layer is composed of planar hexagonal nas of carbon atoms. C—C bond enath within the laver's 141.5, [pm Each carbon atom in hexagonal ring undergoes sp hybridisation and make three sigma bonds with three ‘neighbouring carbon atoms. Fourth eleciron forms a x bond. The elecirons are delocalised over the whole sheet. Electrons are mobile and, therefore graphite conducts electricity along the sheet, Graphite cleaves easily between the layers and therefore, itis very soft and slippery. For this reason graphite is used as a dry lubricant in machines running at high temperature, where oll cannot be used as a lubricant Fullerenes Fullerenes are made by the heating of graphite n an electrical arc in he presence of inert gases such as helium or ‘argon. Fullerences are the oniy pure form of carbon becauses they have smooth structure without having ‘dangling bonds. Fulleren are cage Ike molecules. C,, molecule has a shape lke soccer ball and called Buckminsterfullerene. Itcontains twenty six-membered rings and twelve five membered rings. Asix membered rings fused with six or ve ‘membered rings but a five membered ring can only fuse with six membered rings. All the carbon atoms are equal {and they undergo sp? hybridisation. Each carbon atom forms three sigma bonds with other three carbon atoms, The remaining electron at each carbon atom is delocalised in molecular orbitals, which in tur give aromatic character tomolecule. This ball shaped molecule has 60 vertices and each one is occupied by one carbon ator and it also ‘contains both single and! double bonds with C — C distance of 143.5 pin ard 138.3 pm respectively, Spherical fullerenes are also called bucky balls in shor. tis veryimportant to know that graphite is thermodynamically most stable allotrope of carbon and, therefore, 4H" values of diamond and fullerene, C,, are 1.90 and 38.1 ki mot respectively Carbon black is obtained by burning hydrocarbons in a limited supply ofa Lakshya Educare170) ‘P-BLOCK ELEMENTS: Uses of carbon Graphite fibres embedded in plastic material form high strenath, lightweight composites. The composites are used in products such as tennis rackets, fishing ods, aircrafts and canoes. Being good conductor graphite is used for lectrodes in bateries and industria electrolysis. Crucibles made trom graphite are inert to dilute acids and alka- 3s. Being highly porous, activated charcoal is used in adsorbing poisonous gases; also used in water fiters to remove organic contaminators and in air conditioning system to contol odour. Carbon black is used as black Pigment in black ink and a5 filer in automobile tyres. Coke is used as a fuel and largely 28 a reducing agent in ‘metallurgy. Diamond isa precious stone and used in jewellery. itis measured in carats (1 carat = 200 mg.). © PROPERTIES OF CARBON : @ Carbon in any form will react with oxygen at asufficiently high temperature to give carbon dioxide; ina deficiency of oxygen, carbon monoxide is formed as well, Gi) C(s) +28(s) —>C8,1) Gil) Cals) + 2C(8) — CaCl) Gi) CIs) +2F.(g) — CFL) (iv) Itwill reduce steam, forming water gas, and many oxides of metals; these reductions are of industrial importance, C+ H,0(g) —25CO +H, ; Fe,0, + 3C —+2Fe + 3CO (0) Itismotattacked by dilute acids, but concentrated nitric acid and sulphuric acid are reduced if ‘warmed with carbon according to the equations: C(s) + 4HNO (aq) —> 2H, 0(1) + 4NO(g) + CO) + COs) »2H,0()+280,(@) © OXIDES OF CARBON CARBON DIOXIDE (CO) : © PREPARATION = (Inthe laboratory it ean be conveniently made by the action of dilute hydrochloric chips CO,"(aq) + 2H"(aq) —»CO,(g)+H,00) (i —_Industrally itis produced asa by-product during the manufacture of quicklime and in fermentation processes: CaCO 8} — CaS) + CO(g) 5 CH, ,O,{ag) {glucose} 2C,H,OH(aq) +260) PROPERTIES: © Itisacolourless, dourless and heavy gas which dissolves in its own volume of water at ordinary temperature and pressure. Like all gases it dissolves much more readily in water when the pressure js increased and this principle is used in the manufacture of soda water and fizzy drinks. (i) CO, iseasily liquefied (critical temperature = $1.1"C) and a cylinder ofthe gas under pressure isa convenient fire extinguisher. When the highly compressed gas isallowed to expand rapidly solid carbon dioxide (‘dry ice’) is formed. Solid carbon dioxide sublimes at -78'Cand, since no massy liquid is produced, it isa convenient means of producing low temperatures. Lakshya Educare‘P-BLOCK ELEMENTS a7 wy) o oa Carbon dioxide isthe acid anhydride of carbonic. steps.as follows: I,CO,(aq) + HO (1) (reversible) HCO, (aq) + H,0° (aq) HCO, (ag) + 1,0 (D (reversible) CO,* (aq) + 11,0" (aq) H,CO,/ HCO, buffersystem helps to maintain pH of blood between 7.26 to 7.42 A solution of carbonic avid in water will slowly tun blue fins red and when the solution is boiled, allthe CO, isevolved Carbon dioxide readily reacts with alkalies forming the carbonate and, if CO, hydrogen carbonate, This the basis of the lime-water test for CO, gas. Ca(OH) (aq) + CO.(g) > CaCO) + H,OClig) ; CaCO {s) + H,O(lig) + CO,(g) + CatlHCO,)(aq) ‘The above reaction accounts forthe formation of temporarily hard water. which isa weak dibasic acid and ionises into inexcess, the Carbon dioxide, which is normally present tothe extent of ~ 0.03% by volume in the atmosphere, is removed from it by the process known as photosynthesis. Itis the process by which green plants convert atmospheric CO, into carbohydrates such as glucose. The overall chemical change can be expressed as 6C0, + 1211.0 <> CH,.0, +60, + 61,0 By this process plants make food for themselves as well as for animals and human beings But the increase in combustion of fossil fuels and decomposition of limestone for cement manufaeturein recent years seem to increase the CO, content ofthe atmosphere. This may lead to inerease in «green house effect and thus, raise the temperature ofthe atmosphere which might have serious eommeyuences, Gaseous CO, is extensively used to carbonate soft drinks. Being heavy and non-supporter of ‘combustion it is used as fire extinguisher. A substantial amount of CO, is used to manufeture urea. 2 CARBON MONOXIDE (CO) : ° 0 @ Gi) wy) PREPARATION: It forms together with CO,, when carbon or carbonaceous matter is oxidized by air or oxygen. Itis also produced when CO, isreduced by red-hot carbon; this reaction i of mportance in metal extractions. Cs) +CO(@) — 20008) In the laboratory it can be prepared by dehydrating methanoic acid with concentrated sulphuric acid: HCOOH (lig) 5? CO(@) + 1,0 Ifoxalic acid is dehydrated in the same way, CO, is formed as well HC,0, "00 + 60, On commercial scale itis prepared by the passage of steam over hot coke. The mixture of CO and 1H, thus produced is known as water gas or synthesis gas.sss Lakshya Educare172, 0 wi 0) a @ @ (iy w ) oi ip Lakshya Educare CW+HOw® CO (g) + H.(g) (water gas). ‘When air is used instead of steam, a mixture of CO and N, is produced, which is called producer sas, 2C (5) +0,(¢) +4, (g) “> 2.CO(g) +4 N,(g) (Producer gas). ‘Water gas and producer gas are very important industrial fuels. Carbon monoxide in water gas or producer gas ean undergo further eambuistion forming carbon dioxide with the liberation of heat Zn+C€O, —+Zn0+CO K,Fe(CN), + 6H1,S0, (conc) + 6H,0 4 ,2K,SO, + FeSO, + (NH,),SO, + 6CO HCN + 2H,0 —+ HCOOH + 2NH, (absorbed by H,S0,) HCOOH —+H,0 +CO PROPERTIES + Carbon monoxide isa colourless, odourless gas which bums inair with ablue flame, forming CO, Itisexceedingly poisonous, combining with the haemoglobin in the blood more readily than oxygen, so that normal respiration is impeded very quickly. Ordinary gas masks are no protection against the eas, since it is not readily adsorbed on active charcoal. Inthe presence of ai, amixture of manganese (IV) oxide and copper(I) oxide catalytically oxidizes itto CO, and this mixed catalyst is used in the breathing apparatus wom by rescue teams in mine disasters Carbon monoxide isa powerful reducing agent, being employed industrially inthe extraction of ron and nickel: Fe,0,(8) + 3CO(g) —+ 2Fe(s) + 2CO,{) ; NiO{s) + CO(g) —+ Nils) +CO(g) Itreacts with many transition metal, forming volatile carbonyls; the formation of nickel carbonyl followed by its decomposition is the basis ofthe Mond’ process for obtaining very pure nickel: Nils) +4CO(2) + Ni(CO) (lia) °°S-+ Nis) + 4CO(2) Inaddition to reacting with oxygen, carbon monoxide combines with sulphur to give carbonyl sulphide and with chlorine in the presence of light to give carbonyl chloride (phosgene), used in the production of polyurethane foam plastics. Phosgene isan exceedingly poisonous gas. Ola) +S(s) —+ COS(S) (carbonyl sulphide); CO(g)+C1(g)—> COCL(g) (carbonyl chloride) Although carbon monoxide is nota true acid anhydride since it does not react with water to produce an acid, itreacts under pressure with fused sodium hydroxide to give sodium methanoate: NaOH(lig) + CO(g) —> HCOONa(s) “#2 HCOOH (aq) With hydrogen under pressure and inthe presence of zine oxide or chromium (Il) oxide catalystit reacts to give methanol; this reaction is of industrial importance CO(g) + 2H,(¢) —> CH,OH( 0 is eadily absorhed by nn ammoniaeal salution of capper (I) chloride to give CuCLCO 21.0. reduces an ammonical solution of silver nitrate to silver (black) and, inthe absence of other gaseous reducing agents, this serves asa test forthe gas, It can be estimated by reaction with iodine pentoxide, the iodine whichis produced quantitatively being titrated with standard sodium thiosulphate solution, SCO(g) + 1,048) —> 1 (6) + SCOX8)PBLOCK ELEMENTS 173) 2 CARBON SUBOXIDE (C0) : This isan evil-smelling gas and can be made by dehydrating propanedioic acid (malonic acid), of which itis the anhydride, with phosphorus pentoxide: 3. CH(COOH), + P,0,, —> 3C,0, + 4H,PO, When heated to about 200°C, it decomposes into CO, and C C04) —> COA) + 248) The molecule is thought to have linear structure: © =0. © CARBONATES (€0,*) AND BICARBONATES (HC0,”) Carbonic acid isa dibasic acids giving rise to two series of salts, carbonates (normal sats) and bicarbonates, (aia salts) due to successive removal ofthe replaceable hydrogens from H,CO, i,CO, + NaOH ——,NaHCO,+H,O; NaHCO, + NaOH —, Na,CO, + H,0 PREPARATION With NaOH 2NaOH + CO, —+Na,CO,; — Na,CO, + H,0 + CO, —_, 2NaHCO, (i Byprecipitation BaCl, + Na,CO, —» BaCO, | + 2NaC1 © CARBIDES : ‘The binary compounds of carbon with other elements (less electronegative or of similar electronegatiity) are called carbides. They are classified into following 3 categories (onic i) Covalent (Gi interstitial (ormetalic) ( Ionic carbides (or salt like carbides) : Generally formed by elements of I, I & Il group (Boron is exception). Based onthe product obtained on hydrolysis, they are further sub-classified nto three types. (a) Methanides These give CH, on reaction with H,O. ALC, + 12H,0 —+4A1(OH), +3CH, ; Be, + 41,0 —+2Be (OH), + CH, These carbides contain C* ions in their constitution. (by Acetylides These give C,H, on reaetion with HO. Cac, 2H,O —+Ca(OH),+C,H, ; Al, (C,), + 6H,O —>2AI (OH), +3CH, — Sr (OW), + C, Such compounds contain, (e)Allylides These give |-propyne on reaction with H,0. Mg,C, + 4H,O —»2Mg (OH), + CH,-C = CH ‘Such compounds contain, [|C-C-=C 4 ions. (Gi) Covalent carbides Compounds like CH, like SiC are also examples of cor ».CS, can be considered to be covalent carbides. Besides these, some giant molecules mnt carbides. Lakshya Educare174 ‘P-BLOCK ELEMENTS ‘Such carbides are formed by transition metals in which carbon atoms occupy interstitials inthe erystal structure of metals. Q CARBORUNDUM (SiC) : PREPARATION: sio, +3¢ > sic +2c0 © PROPERTIES : (@ __Itisaveryhard substance (Hardness =9.5 Moh) ( —_ Onbeating it does not melt rather decomposes into elements Gi) Notattacked by acids. However, it gives the following two reactions at high temperature. SiC +2NaOH +20, —*-+ Na,SiO, + CO, + H,0 ; SIC+4C1, 4 SiCI,+CCI, thas diamond ike structure in which each atom is sp hybridized. Therefore each atom is tetrahedrally surrounded by 4 atoms of other type. Q SILICON : Silicon is the second most abundant element occurring in the earth’s crust (about 28 percent by weight) as, the oxide, silica, ina variety of forms, g., sand, quartz and flint, and as silicates in rocks and clays. © PREPARATION : (@ —_Theelementis obtained from silica by reduction with carbon inan electric furnace: Si0,(6) + 2C(3) —+ Sif) +2CO(g) Extremely pure silicon is obtained from ‘chemically’ puresilicon by the method of zone refining. (SiO, +2Mg 5 2MgO+Si Q — PROPERTIE! Silicon isa very high melting-point solid with the same structure as diamond. The non-existence of an allotrope with the graphite structure clearly shows the inability of silicon atoms to multiple bond with themselves. In the massive form, silicon is chemically rather unreactive but powdered silicon isattacked by the halogens and alkalies: @ —Si(powdered) +2C1(2) — SiC (lig) Gi) Siqpowdered) + 20H (aq) + H,0(lig) — SiO,*Xaq) + 2H,(e) (ii) Itismotattacked by acids except hydrofluoric acid, with which it forms hexafluoresilici acid: Si(s) + 6HE(g) —> H.SiF (aq) +2H(g) (iv) Si+2KOH+H,0 —>K,Si0, + 2H, () — NaCO, + Si —++Na,Si0, +C (si) 2Mg+Si—+ Mg.Si (Magnesium silicide) © COMPOUNDS OF SILICON: icon Dioxide SiO, Silicon dioxide, commonly known as silica, occurs in several crystallographic forms. Quartz, cristobalite and tridymite are some of the crystalline forms of slica, and they are interconvertable at suitable temperature. Siicon sioxide is @ covalent, three-dimensional network sold in which each silicon atom is covalently bonded in a tetrahe- dral manner to four oxygen atoms. Each oxygen atom in tur covalently bonded to another silicon atoms. Each ‘comer is shared with another tetrahedron. The entire cxystal may be considered as giant molecule in which eightPBLOCK ELEMENTS 175) (a) (B) (c) ‘membered rings are formed with alternates silicon and oxygen atoms. Siica in its normal form is almost non- reactive because of very high Si-O bond enthalpy. It resists the attack by halogens, cihyrogen and most ofthe ‘acids and metals even at elevated temperatures. Howevers itis attacked by HF and NaOH. SIO, +2NaOH —+ Na,SiO, + HO. SIO, +4 HF ——> SiF,+2H,0 (Quartzs extensively used as a piezoelectric material; thas made possibie to develop extremely accurate clocks, ‘modern radio and television broadcasting and mobile radio communications, Sica gel used as a drying agent and {8 @ support for chromatographic materials and catalysts. Kieselghur, an amorphous form of slica is used in filtration plants. SILICATES : inary compouds of silicon with oxygen are calle silicates but they contain other metals also in their structures. 0 Si-O bond can be considered 50% ionic & Since thenegatvity difference bw 0 & Sis about 1.7, 50% covalent (i) If wecaluclate the radius ratio =~ =0.29 Itsuest tha the co-ordination no of silicon must be and from VBT point of view weeean say that iis sp* hybridized. Therefore silicate structures must be based upon SiO, * tetrahedral units (i) SiO tetrahedral units may exist as discrete units or may polymerse into larger units by sharing CLASSIFICATION OF SILICATES Orthosilicates : ‘These contain discrete [SiO,]* units ie., there isno sharing of comers with one another as shown is figure. e.g. Zircon (2rSi0,), Forsterite of Olivine (Mg,SIO,), Willemite (2n,Si0,) Pyrosilicate + Inthese silicates two tetrahedral units are joined by sharing oxygen at one comer thereby giving [Si,0.,]* units. P< (charge will be present onthe oxygen atoms which is bonded with one e, Thorteveitit (Se,Si,0,), Hemimorphite ZnSi,0,) Zn(OH)H,0) Cyclic silicates : Iftwo oxygen atoms per tetrahedron are shared to form closed rings such that the structure with general formula (Si0,*), or (SiO, ,2" is obtained, the silicates containing these anions are called cyclic silicates. $i,0,"" and Si,0,,"- anions are the typical examples of cyclic silicates. Lakshya Educarei176 ‘P-BLOCK ELEMENTS: sor sie (D) Chain silicates : (Chain siicates may be further classified into simple chain & double chain compounds. Incase of simple chains two comers of each tetrahedron are shared & they form along chain of | tetrahedron. Their general formula is also same asthe eyelie silicates ive, (SiO,)” Similarly, double chain silicates ean be drawn in which two simple chains are joined together by shared ‘oxygen, Such compounds are also known as amphiboles. The asbestos mineral isa well known example of double chain silicates, The anions of double chain silicates have general formula (Si,O,,),°°. 10,), Spondumene (LiAI(SiO.).), , ) Tremolite (Ca, Me,(Si,0,,), (OH), ), ete. Enstatite (MgSiO,), Diopside (CaMg( (E) Two dimensional sheet silicates = Insuch silicates, three oxygen atoms of each tetrahedral are shared with adjacent SiO,* tetrahedrals. Such sharing forms two dimension sheet structure with general formula (Si,0,) ©. Tale (Mg(Si,0,), Mg(OH), . Kaolin AL(OH),(Si,0,) (F) Three dimenstional sheet silicates : These silicates involveall four oxygen atom in sharing with adjacent SiO * tetrahedral units. 2, Quartz, Triéymite, Crystobalite Feldspa, Zeolite and Ultramarines. Lakshya EducarePBLOCK ELEMENTS 77, ¢ — smicones : Silicones are synthetic organosilicon compounds having repeated R, SiO units held by S These compounds have the gencral formula (R,SiO), winere R = alkyl orary group. The silicones are formed by the hydrolysis of alkyl or ary substituted chlorosilanes and their subsequent, polymerisation. The alkyl or ary substituted chloroslanes are prepared by the following reactions. ~O-Silinkages. (a) RCL+Si Se RSICI+R,SICI,+RSICI, (©) RMgCI+SiCI, —>RSiCI, + MgCl, 2RMgCI + SiCl, —>R,SiCI,+2MgCl,; 3RMgCI + SiC], —+R,SiCI-+ 3MgCl, After fractional distillation, the silane derivatives are hydrolysed and the ‘hydroxides’ immediately condense by intermolecular climination of water. The final product depends upon the numberof hydroxyl groups originally bonded tothe silicon atom: \ 7 20 NO" Y N YN on +2H01 Inthis manner several molcules may combine to form a long chain polymer whose both the ends will be occupied by -OH groups. Such compounds are generally represented from the following formula, R R R | | | On—B—0— 0-80 R ROR ‘The polymer chain depicted above is terminated by incorporating a small quantity of the monochlorosilane derivative into the hydrolysis mixture ® Silicones can be prepared from the folowing types of compounds only RSL GRSICL, —GiRSICI, Silicones from the pvt (4S (CH,), SiCl_40_, (CH,), Si(OH) cH, cH, CH CH. | | -H.0 | | CH—Si—oH + Ho—si—cH, —*9, csi osc, CH, cH, cH CH, ® Silicones from the hydrolysis ofa mixture of (CH,), SICI& (CH), SiCl, Lakshya Educare178 (P-BLOCK ELEMENTS ‘The dichloro derivative will form a long chain polymeras usual. But the growth ofthis polymer ean be blocked at any stage by the hydrolysis product of mono-chiloro derivative. ba, A bn, ® Silicones from the hydrolysis of tichlore derivative ‘When acompound like CH, SiCl, undergoes hydrolysis,a complex cross-linked polymer is obtained, ® —Thehytdrocarbon layer along the silicon-oxygen chain makes silicones water-repellent. Products having the physical properties of ols, rubbers, and resins can be produced using silicones. Silicone fluids (say as hydraulic systems of planes) are thermally stable and their viscosity alters very little with temperature, and silicone rubbers retain their elasticity at much lower temperatures than ordinary rubber. Silicone vanishes are such excellent insulators and so heat-resistant that insulating wiring with them enabled motors to work over-loads dof chemistry and technology, civilian as that would have set fre to the insulation formerly used. A whole new well as military, has been opened up by the development of silicones. Don anpieap: COMPOUNDS OF TIN : 2 STANNOUS OXIDE (nO) : PREPARATION: (@—_Byheating stannous hydroxide, Sr(OH).,inabsence o Su(OH), —+ Su0+H,07 i) Byheating stannous oxalate, SnC,O, in absence of at. SnC,0, —»Sn0 + COT + CO, > PROPERTIES: @ SnD isanamphoteric dark grey orblack solid oxide, insolulbe in water. I-dissolves in acids to form stannous sats SnO + 2HC| —+ SnCl, + 1,0; SnO + H,S0, —> SnSO, + H,0 {i Sn dissotvesin hot NaOH solution to form (soluble) sodium stamnite and water. SnO + 2NaQH —> Na,Sn0, + H,0 stannites are only known in aqueous solutions. Stannites absorb oxygen from air and are oxidised to stannato which are stable in nature. 2Na,Sn0, +0, —» 2Na,Sn0, USES : Forthe preparation of stannous chloride and stannous sulphate Q — STANNOUS CHLORIDE (SnC1;2H,0) Itisacolourless solid soluble in water Its solution becomes milky on standing due toitshydrolysis to Sn(OH), and HCI, taqueous solutions acidic to litmus. Itisa strong reducing agent. Itis soluble inaleoholand ether also Lakshya Educare‘P-BLOCK ELEMENTS 79 @ @ Gi) Q @ i) iy PREPARATION : @ — Sn+2HCK(concentrated) —+ SnCl,(ag) +H, i) SnO*2HC] —+ SnC (aq) + H,0 ‘The solution on crystallization gives colourless crystals of SnCl,-2H,0. PROPERTIES : Reaction with Hg,Cl, solution: When SnC, solution is added to an aqucous solution of mereuric chloride, a silky white precipitate of mercurous chloride, HCl, is formed which tums black due to further reduction of Hg,Cl, toblack mercury. 2HgCI, + SnCl, —> He,CLU4+SnC; —Hg,Cl, + SnC1, —+ 2Hgl+ Sac, Itreduces ferric chloride, FeCl, to ferrous chloride, FeCl. 2FeC (brown solution) + SnCl, —+ 2FeC, (colourless solution) +SnC, Itis hydrolysed with water to produce white precipitate of Sn(OH), SnCI, + 2H,0.¢> Sn(OH), (white) + 2HC1 Asi produces weak base and strong acid its aqueous solution i acidic, ts hydrolysis can be prevented by adding concentrated HCI to it during the process of its preparation, USES Indye industry asa reducing agent. For the test of mercuric sat. For the preparation of other stannous compounds. Q STANNIC OXIDE (Sn0,) : Q 0 ai) @ wo ) PREPARATIO! Bybuming Sn init Ssn+0,—> Sno, Byheating Sn with concentrated HNO, Sn +4HNO, —+ HSn0, + 4NO,? +H,0 ;H.Sn0, —*-+H,07 + Sn0, PROPERTIES : Iisa whitesolid insoluble in water. Itis weakly acidic Itdissolves in cone. H,SO, to form stannic sulphate, SnO, + 2H,SO, —+Sn(SO,), + 2H,0 Italso dissolves in cone. Alkalies to form alkali metal stannate solution. SnO, + 2NaOH —+ Na,SnO, (sodium stannate) + H,0 Q STANNIC CHLORIDE (SnCl) : Q @ ai) PREPARATION: By the action of Cl gas on heated Sn Sn-+2Cl, —+ SnCl, By theaction of CI, on stannous chloride SnCl, + Cl, — SnCI, Lakshya Educare° ‘P-BLOCK ELEMENTS Q PROPERTIES : (@ _Itisacolourless fuming liquid, Bp = 114°C. Itis covalent. (Action of moisture: It absorbs moisture and becomes converted into hydrated stannic chlorides, SnCl,'3H,O, SnCl,’SH,O, SnCl,6H,0, and SnC1,-8H,O. SnCl, .5 H,0 isknown as “butterof, tin” or“oxymercurate of tin”. (ii) Hydrolysis with water: Itcasily gets hydrolysed in water and produces strong acid HI, Henee its ‘aqueous solution is acidic to litmus. Ithydrolyses more rapidly than SnCl, SnCl, +4H,O—> H,Sn0 colloidal white precipitate) + 4HCL (iv) SnC I, isa Lewisacid. Hence ithas a tendency to accept lone pair of electrons from NH, PH, etc and form adducts such as SnC,-4NH, (8) Itdissolves in concentrated HCI forming H,SnCI, and in presence of ammonium chloride, it forms ammonium salts of this acid. SnCl, +2HC] —> H,SnCI, SnCl, +2 NH,Cl —> (NH)),SnCl, Q __ USES: For the proparation of stannic compounds. COMPOUNDS OF LEAD : LITHARGE (PbO) PDO is prepared by heating Pb at 180°C. Itisa volatile yellow compound. 2Pb +0, —*+ 2PbO It isan amphoteric oxide and dissolves in acids as wel ain alkalis, PbO + 2HNO,— 2+ PH(NO,), + HO; PbO-+2NaOH —*+Na,PDO, (sodium plumbate) + H,0 Itisused in rubber industry and inthe manufacture of flint glasses, enamels, and storage batteries. LEAD DIOXIDE (PbO,) ‘The fact that it does not liberate H,O, by the action of dilute HCI suggest the above formula (Itisa dioxide nota peroxide) Q PREPARATION : (@—PbO+ NaOCl > PbO, (insoluble) + NaCI ( —_-Pb,O, + 4HNO, (dilute —> 2Pb(NO,), + PbO, +2H,0 © PROPERTIES : (@ _Itisachocolate coloured insoluble powder. On heating at 440°C it gives the monoxide: 2P60, “°°, 2Pb0 + 0, (@ — Woxidizes HCIto Cl: PbO, + 4HCI—+ PbCI, + 2H,0+C1,? (i) Iedissolvesin cone. NaOH solution: PbO, + 2NaOH —> Na,PbO, (sodium plumbate) + H,0 (iv) Itoxidises Mn saltto permanganic acid: 2MnSO, + SPbO, + 6HNO, —> 2HMnO, + 2PbSO, + 3PA(NO,), + 2H,Caribe TTT es ‘P-BLOCK ELEMENTS 181 (0) Itreacts with SO, atred heat to form lead sulphate: PbO, + SO,—°-+ PbSO, (0) Itreacts with cone. HINO, to evolve oxygen gas. PbO, + 2HNO, —>PH(NO,), + 1/20, + 1,0 Oo uses Iris used in match industry for making ignition surface of match boxes and inthe preparation of KMnO,, RED LEAD (Pb,0) : O PREPARATION: Itis prepared by heating PbO at 450°C fora longtime. 6PbO + 0, 2+ 2Pb,0, © PROPERTIES + ()_Itisared powder insoluble in water but when heated with cone. HNO, itgives a red precipitate of PbO, Pb,O, + 4HNO, —> 2Pb(NO,), + PbO,L + 6H,O (When heated above 550°C, it decomposes into PbO Pb,O, —+ 6Pb0 + 027 Gil) roxidizescone. HCI to chlorine Pb,O, + 8HCl—> 3POCI, + 4H,0+C1,t (jv) Whenheated with conc. H,SO, itevolves oxygen 2Pb,0, + 6H,SO, —> 6PbSO, + 6H,O + 0,7 USES: Itis used as an oxidizing agent, for making red paint, for making special lead ecment and for making fin glass. LEAD CHLORIDE (PbCI,) : 2 PREPARATION: @ — Pb(NO,), +2HCI—+ PoCI,L +2HNO, (@—PRINO,), + 2NaCI—+ PhC1.L + 2NaNO, Gi) P(CH,COO), + HCI —> PbCl,d + 2CH,COOH (iv) PbO + 2HCI—> PbCLL +H,0 () — P(OH),+2HCI— Pec, +2H,0 (i) PH(OH),-PLCO, (basic lead earbonate) + 4HCI—> 2PbCI,L + C 2 prorertirs = Itisa white crystalline solid, insoluble in cold water but soluble in boiling water t dissolves in concentrated HCI forminga complex ion. 2 HCI + PCI, (reversible) H,PbCI,(chloroplumbous acid) QO USES: Itisused for making pigments for paints, + 3H,0 Lakshya Educare132, LEAD TETRACHLORIDE (PbCI) : ° @ @ PREPARATION: Itis prepared by the following methods By dissolving PbO, in cold cone. HCL PbO, + 4HCI— + PbCI, + 2H,0 PCI, dissolves in excess of HC! to forma stable solution of H, PCI, PCI, + 2HCl—> H,POCI, ‘When NH,Clisadded toa solution of chloroplumbic acd, a yellow precipitate ofammonium ciiloroplumbate is formed. H_POCI, + 2NH,Cl—>(NH)),PbCI,L + 2HCI ‘When crystals of ammonium chloroplumbate is added to ice cold cone, H,SO,, lead tetrachloride is formed and separates asa yellow oily liquid. (NH)),PbCI, + HSO,—> PbCl, + (NH,),SO, + 2HC1 By the action of CI, onasolution of PbCI, incone. HCL POCI, + Cl, — PCI, PROPERTIES Iisa yellow oily liquid which solidifies at 10°C and issoluble in organic solvents like ethanol and benzene, Rapid hydrolysis with water forms PbO, precipitate PbCI, + 2H,0—» PbO.J + 41IC1 USES = Itis used for making stannic compounds. Lakshya Educare