INORGANIC _CHEMISTRY P-BLOCK ELEMENTS GROUP IVwe Group IV ‘Types of Carbide @ —_ Tonicandssalt like: Classification on basis of (@)C, unit no. of carbon atoms { (b)C, unit present in hydrocarbon (©)Cyunit found on their hydrolysis unit: Al,Cy, Be,C Be,C + H,0 —> Be(OH), + CH, AL,C, + 12H,0 — 4A1(0H), + 3CH, Cy unit: CaC,, BaC, CaC, + 12H,0 —+ Ca(OH), + CI Cyunit: Me,C, Proposed struc. Me,C, +H,0 —> 2Mg(OH), + CH,-C=C:: Propyne ‘Dual show tautomerism, "G—-O Lseytindrical x bond (ii) Covalent carbide : SiC & B,C (Gi) Interstitial carbide : MC (Transition elementor inner transitional elements forms this kind of carbide) Acetelene Interstitial carbide formation doesn't affect the metalic lusture and electrical conductivity.(- no chemical bond is present, no change in property) Fe,C: Cementite Preparation 200010 10, +2 awe? Si+2C SiO, + 2C(coke) Saag? Sit 2COT Si+C ae sic diamond like structure colourless to yellow solid in room temp. Y when impurity is present Properties @ _Itis very hard ands used in cutting tools and abrassive powder(polishing material) @) tis very muchinert Gi) This notbeing affected by any acid except H,PO, Gv) _Itreacts with NaOH in presence of air SiC + 2NaOH + 0, —> Na,SiO, + CO, + H,O ‘P-Block elements-Group IV PIco —How to detect —Howto estimate — What are its absorbers @ — Howtodetect (a) bums with blue flame (b) CO is passed through PdCL, solution giving rise to black ppt. CO + PdCl, + H,O —> CO,f + Pdv + 2HCL Black metallic deposition (i) — Howtoestimate 1,0; + SCO —> I, + SCO, I, + $,03° —> 2h + $,0° (i) Whatareits absorbers (@) Cu,Cl, : CuCl + CO +2H,0 —> [CuCl(CO)H,0),] Uses: In the Mond's process of Ni - extraction COis the purifying agent for Ni Impure Ni + CO 75> Ni(Coy, "2 Ni+4CcO recycled Producer gas: CO +N, +H, Water gas: CO +H Water gas is having higher calorific value than producer gas. -: in water gas, both CO & H, bums while in producer gasN, doesn't burn. Teflon (CF, - CF} oat with ested Polymerisaton at _ CHCL, + HF orci, 7 CRHCL Zi, > CE ACE, oe agees? (CR) —CE 3g cals Mic Purpose ‘Temp. withstanding capacity upto 500-550°C (1* organic compound withstand this ........ ofhigh temp) SILICON Occurrence Siliconis the second most abundant (27.2%) element after oxygen (45.5%) in the earth's crust, It does not occur free in nature but in the combined state, it ocours widely in form of silica and silicates. All mineral rocks, clays and soils are built of silicates of magnesium, aluminium, potassium oriron. Aluminium silicate is however the most common constituent of rocks and clays. Silica is found in the free state in sand, flint and quartz and in the combined state as silicates like @ Feldspar-K,0. Al,0,, 6SiO, @_—_ Kaolinite—Al,0,. 28i0,.2H,0 Gi) Asbestos ~ CaO. 3MgO. 4810, a s—sS—ss P-Block clements-Group IV BI]Preparation ops ee . ! @ —_ Fromsilica (sand): Elemental silicon is obtained by the reduction of silica (SiO,) with high purity coke in an electric furnace, Si0,(s) + 2C(s) —> Si(s) + 2CO(e) ; Gi) _Fromsilicon tetrachloride (SiCl,)orsilicon chloroform (SiHCl,) Silicon of very high purty required for ‘making semiconductorsis obiained by reduction of highly purified silicon tetrachloride or silicon chloroform with dihydrogen followed by purification by zone refining. SiCI,()+2H,(g)—> Si(s) + 4HCI(g) SiHCL,(s) + H,(g)— Si(s) + 3HCl (g) PHYSICALPROPERTIES: @ Elemental siliconis very hard having diamond like structure. @__Ithas shining luster with a melting point of 1793 K and boiling point of about 3550 K. Gi) Silicon exists in three isotopes, ic.{$Si, 7{Si and 39Si but 28Si is the most common isotope. CHEMICALPROPERTIES: | Silicon is particularly unreactive at room temperature towards most of the elements except fluorine. Some important chemical reactions of silicon are discussed below. @ Action of air : Silicon reacts with oxygen of air at 1173 K to form silicon dioxide and with nitrogen of air at 1673 K to form silicon nitride,. Si(s) + 0,(g) UBK_, si0,(s) Silicon dioxide 38i(s) + 2N,(g) _1973K_, Si,NY(s) Siliconnitride (Action of steam : \tis slowly attacked by steam when heated to redness liberating dihydrogen gas, Si(s) + 2H,O(g) _=iness_, SiO, (s) + 2H,(g) (i)_—_-Reaction with halogens: It burns spontaneously in fluorine gas at room temperature to form silicon tetrafluoride (SiF,). Si(9) +2F,(g) —_Room Tenpersure_, SiP (J) However, with other halogens, it combines at high temperatures forming tetrahalides. Gv) Reaction with carbon : Silicon combines with carbon at 2500 K forming silicon carbide (SiC) known as carborundum, Si(9) +C(s) _250K_, Sic(s) Carborundum is an extremely hard substance next only to diamond. Itis mainly used as an abrasive and as arefractory material. usI @ Silicon is added to steel as such or more usually in form of ferrosilicon (an alloy of Fr and Si) to make it acid-resistant. High purity silicon is used as semiconductors in electronic devices such as transistors i) _Itisused in the preparation of alloys such as silicon-bronze, magnesium silicon bronze and ferrosilicon, COMPOUNDS OF SILICON: Silicates: Details about silicates are given in the topic " Soli What is silane. Si,H,,..9 (SiH) & Si,H, Only these two are found Higher molecules are not formed. +: Si can't show catanetion property State”, Hot Mg + Si-vap—> Mg,Si —“408°._, Mp, + SiH, + SiH, + - P-Block elements-Group 1V 7Ques. SiH, is more reactive than CH,, Explain Reasons @ si*-H& inc® =n C-clectro-ve than H Silesselectro-ve than H So bond polarity is reversed when Nu”attacks, it faces repulsion in C butnot in Si @ Silicon is having vacant orbital which is not in case of carbon Gi) Siliconis larger in size compared to C. By which the incoming Nur doesn't face any steric hindrance to attack at Si whereas CH, is lightly held fromall sides. Silicones Ttis organs silicon polymer CCl, +H,O—> no hydrolysis but CCI, + H,O —> COCI, + 2HCI super heated steam SiCl, + H,0 —> Si(OH), + 4HCI AD ts, =2H,0, SiO, R R R \ | } R,SiCL, +H,0 —aaq> R,Si(OH), ard + O-Si-O-Si-O-Si-O- a | | I R ROR silicon -H,0 9 RCCL, + H,0 aq R,C(OH), —"> | looses H,0 R-C-R read Silicones may have the cyclic structure also having 3, 4, 5 and 6 nos. of silicon atoms within the ring. Alcohol analoge of silicon isknownas silanol i wr ¥ \R not planar R,Sicl 22°, R,SioH EES R,Si0-SiR Silanol R R . i 4,0. H,0 | \ RISICL +RSICL gaia? eng” #-0-8i-— - R R This end of the chain can't lie extended hence P-Block elements-Group IVR,SiCliscalled as chain stopping unit, . Using R,SiC1 in acertain proportion we can control the chain length of the polymer | I o R 6 ' | | RSICl, + 1,0 —> R-Si(OH), —Y R -Si-O0-Si-O- i -O- I I o oO R | | sp? 3 dimensional network Itprovides the crosslinking among the chain making the polymer more hard and hence controling the proportion of RSiCI, we can control the hardness of polymer. Uses (1) Itcanbe used as electrical insulator (due to inertness of $i-O-Si bonds) Q) _Itisused as water repellant ("7 surface is covered) eg. car polish, shoe polish, massonary works in a G) __Itisused asantifoamingagentin sewage disposal, beer making and in coolingoil used to prepare potato chips. (4 Asalubricantin the gear boxes. SILICA Occurrence: Silica or silicon dioxide occurs in nature in the free state as sand, quartz.and flint and in the combined state as silicates like, Feldspar : K,O.A1,0,.6Si0,, Kaolinite : Al,0;. 2SiO,. 2H,O ete. PROPERTIES: (@ _ Puresilicais colourless, but sand is usually coloured yellow or brown due to the presence of ferric oxide asan impurity. Gi) Silicondioxideis insoluble in water and all acids except hydrofluoric acid. SiO,(s) + 4HF) — SiF,() +2H,00, Gi) __Italso combines with metallic oxides at high temperature giving silicatese-g. Si0,(s) + Ca0(s) —*> CaiO,(s) (iv) Whensilicais heated strongly with metallic sats, silicates are formed and the volatile oxides are driven offas vapours. SiO,(s) + Na,CO,(s) —> Na,Si0,(s) + CO,(g) SiO,(s) +Na,SO,(s) —> Na,Si0,(s) + SO,(@) 3Si0,(s) + Ca,(PO,),(s) —> 3CaSiO,(s) + P,0,(e) The first two examples quoted here are important in glass making, STRUCTURES OF SILICA : Silica has a three-dimensional network structure. In silica, silicon is sp*-hybridized andis thus linked to four oxygen atoms and each oxygen atom is linked to two silicon atoms forming a three-dimensional giant molecule as shown in figure. This three-dimensional network structure imparts stability to SiO, crystal and hence a large amount of energy is required to break the crystal resulting in high melting point. P-Block elements-Group IV 15USES: Sand is used in large quantities to make mortar and cement. Being transparentto ultraviolet light, large crystal of quartz are used for making lenses for optical instruments and for controlling the frequency of radio-transmitters. Gi) Powdered quartz is used for making silica bricks. Gv) Silica gel (SiO,.xH,0) is used as a desiccant (for absorbing moisture) and as an adsorbent in chromatography. TIN & ITS COMPOUND © — Sn—SES, Sn0, [Bums witha bright flame] cad, snCly SA sng. oom Wer reaction (@Sn+2H,0H,$n40 1 4110+20NOz+5H1,0 Metastannic acid fs Sn0, (v) Sn + 2NaOH + H,O —> Na,Sn0, + 2H,?. or KOE [In absence of air Na,Sn0, forms and in contact with air it readity convertsinto Na,Sn0,) ‘P-Block elements-Group IV 77a) Q) @) @) ©) ‘sone Oxides: SnO&Sn0, am Sn (White) <8 Sn +O, grey white SnC,0, <*> Sn0 (grey) +CO+ co, \___ H$n0 1.440 moe z a sacl, “5 sn(OH), Both are amphoteric in nature: SnO +H,SO,—> SnSO, + H,O SnO+2HCI—> SnCl, + H,0 SnO + 2NaOH or KOH _2!l_, Na,SnO, or K,Sn0, +H,0 Butconc. hot alkali behaves differently. 28n0 + 2KOH or NaOH —> K,SnO, or Na,SnO, + Sn+H,O Bi(OH), + [Sn(OH),*—> Bit + [Sn(OH),2> (black) SnO, + 2H,SO,—> Sn(SO,), + 2H,0 (Soluble only in hot conc. H,SO,) SnO,+ 2NaOH—> Na,$n0, + H,O SnO, + 48 + 2Na,CO, —> NaSnS, + Na,SO, + 2CO, (Insoluble inall acids even ifin aq. rigia) SnCl, & SnCl,: Sn+2HCI (hot conc.)—> SnCl, + Ht SnC1,.2H,0 __4_, Sn(OH)CI + HCI t+H,07 = Hence anh. SnCl, cannot be obtained. + SnO +HCIT {SnCl, + 4H,0—> Sn(OH), + 4HCI? fumes comes out} A piece of Snis always added to presence a solution of SnCl,. Explain. 6SnC1, +2H,0 + 0, —> 2SnCl, + 4Sn(OH)CH (white ppt) SnCl, +Sn—> 2SnCl, SnCl, + 41,0 —> Sn(OH),¢ (white ppt.) + 4HCL SnCL, +HCl—> HSnCl, #5 H, Sn, Chiorostainous ach SnCl, +2HCI—> H,SnCl,(Hexaopforo stannic (IV) acid) SnCl,;+ 2NH,CI—> (NH,), SnCk, (colourless crystalline compound known as" pink salt") Red Prop. of SnCl : Sn’? + 2Fe'} —> 2Fe*? + Sni# 2Cu"? + Sn? 2Cut + Sn" Hg’? + Sn*?—> Hg) +8n"4 PhNO, + SnCl, / HC—> PhNH, + Sn“* K,Cr,0, + SnCl, + HCL—> Cr*3 + Sn“ + KCI + H,0 Readily combines with L, => SnCl,1, => This reaction is used to estimate tin. P-Block elements-Group IV 73]< @ «i * @ Q) @) Formation of SnCl, Sn + Cl, (Excess) —> SnCl, Gi) 2HgCl, + Sn —> 2Hg 4 + SnCl, (molten) (dry) Sn + Aq, tigin —> SnCl, +NO + 1,0 SnCl,. SHO is known as butter of tin = used as mordant, (NHL), SCI, is known as'pink salt => used as calico printing. Mosaic gold : SnS, yellow crystalline substance : Sn+ 4NH,Cl—> (NH,), SnCl, +2NH, + H, 2(NH,), SnCl, +28 —> SnS, + 2NH,Cl + (NH,),SnCl, istinction of Sn‘? / Sn“: OHS Gi Hg? ii) Fe" + [K,Fe(CN),J —S*" 5 Blue ppt. COMPOUNDS OF LEAD Oxides of lead : @Pbo Gi) Pb,O, Red) (ii) Pb,O,(reddish yellow) (Sesquioxide) (iv) PbO, (dark brown) i (7vellow (Masscot) Bestest. Litharge PbO: \—+Redaish yellow (litharge) Laboratory Prep". : Pb(NO,), —> 2PbO + 4NO, +0, above 600°C. a H. eS PbQ, hot oxide 2, re FOO sted pbby 7 PD + HO Oda HH, orc, ¢ PbO! NE. pb +o Preparation of Pb,O,: 2PbLO + NaOCl —+ Pb,0, + NaCl i ae of iH Pb,O, + 2HNO, —> PbO, | + Pb(NO,), + H,O This reaction suggests that Pb,O, contains PbO, Pb,O, : 6PbO + 0, E> 2Pb,0, {In the same way, prove that its formula is 2PbO. PbO, } Pb,O, +4HNO, (cold.conc) or (hot dil.) —> 2Pb(NO,), + PbO, + 2H,0 But 2Pb,0, + 6H,SO, —> 6PbSO, + 6H,O +0, Pb,O, + SHC] —> 3PbCl, + 4H,0 + Cl, PbO, : Insoluble in water, HNO,, But reacts with HCl + H,SO, (hotcone.) and in hot NaOH / KOH. @ — Pb,O, + HNO, —> (i) Pb(OAc), + Caocnet +H,0—> PbO, [Brown(dark)] + CaCl, + 2CH,CO,H Excess bleaching powder is being removed by stirring with HNO, ‘P-Block elements-Group IV PIQ Sol. 0 @ Gi PO, + 4HCI—> PbCI, + Cl, + 2H,0 2PbO, + 2180, —> 2PbSO, + 211,0 + O, PbO, + 2NaOH —> Na,PbO, + 11,0 Reaction: ‘What happens when electrolysis is performed for hot NaCl solution containing PbO with stirring, NaCl 1 Nat +Cl. 1,0 1 1+ OH Atcathode : 2H* +2e—> Hy? Atanode : 2Cl-—> Cl, + 2e Cl, + 20H" 1 Clr + OCI + 1,0 PDO + OCI” (excess formed duc to electrolysis) —> PbO, + CI- PbO, : Powerful oxidising agent: PbO, + SO, —+ PbSO, [spontaneously] { PbS + O, —> PbSO, + 40, } PbS + 41,0, —> PbSO, + 4H,O PbO, + 2HNO, + (COOH), —> Pb(NO,),+ 2CO, + 2H,0 2MnSO, + SPO, + 6HNO; —> 3Pb(NO,), + 2PbSO,1 + 2HMnO, + 2H,0 PCI, : Exists as H,[PbCI,] PbO, + 4HC1—> PCI, + 2H,0 {ice cold conc. saturated with Cl,} POCI, + 2HCI— H,PbCl, Lead Tetraacetate : Pb:O, + 8ACOH(hot glacial) —> Po(OAc), +2Pb(OAc), + 4,0 Pb(OAe); is also converted into Pb(OAc), by passing into Cl, 2Pb(OAc), + Cl, —> PbOAc), + PCI, 4 Itisused as oxidising agent in org. chemistry to oxidise 1,2-diol to aldehydes and ketones. RCH(OH) RCH(OH) TetraEthylead : 4Na-Pb{alloy 10%-Na.) + 4C,H,Cl(vap.) —> 3Pb + PbE), + 4NaCl Itisantiknocking agent. Lead storage cell : —I2L, 2RCHO +H,0 diss Pb + PbO, + 2H,SO, SSZE= apps0, + 21,0 P-Block elements-Group IV 70]