Chapter 11 GROUP 13 ELEMENTS : THE BORON FAMILY Itincludes Boron 8) non-metal ‘Aluminium = (Al) metal Gallium Ga int) | mc Thalium a) Atomic and Physical Properties (Electronic Configuration Al these elements have three electrons in the outermost energy levels and their outer electronic configuration is « ‘The atomic radi aresmaller than group | and 2 elements due to increased nuclear charge. Atomic radius increases B to TI. The abrupt increase in the ‘atomic radius of Al is due to greater screening effect in Al ‘than in B. Atomic radius of Gas less than that of Al. This is, ‘due to presence of d-c"'s in Ga which have a poor shielding, ‘effect thus resulting in poor screening of outer e~! from nuclear charge. As @ result, size of Ga< Al. Tonization enthalpy Inspite ofthe large nuclear charge and small size, she first ionisation energies of these elements are less than the corresponding value of black elements. This is because p- ‘electrons are less penetrating and more shielded than s- ‘electrons, ie, they are farther from the nucleus and hence held les tightly than free s-electrons and thus can be easily removed. Electronegativity Down the group, clectronegativity first decreases from B to ‘Aland then increases marginally. This is due to difference in atomic sizeof the elements (8) Density : Density increases from B to TI due to increase in size ofthe atom. Aluminium has an extremely low density and hence used as an important structural material, Melting and boiling points : Melting points do not vary regularly due to structural changes in the elements. Boron has a very high melting point because it exists as a giant ‘covalent polymer in both solid and liquid states. The melting point decreases from B to Ga and then increases Dueto its unusually low m. pt. (303 K), Gacan existas liquid during summers, ii) tw) (i) The p-block elements (Group 13 and 14) Chemical Properties 0 @ iy ww) w Oxidation states Al forms AP ions. Down the group, stability of +3 OS. decreases while that of + 1 .S. increases. This is because of inert pair effet (i, due to poor shielding effect of intervening d-and Forbitals, the nse“ s becomes inert towards bonding) Tendency of forming ionic compounds The tendency of formation of ionic compounds increases from B to Tl. Boron forms only covalent compounds. This is ddue to its extremely high ionisation energy which is not compensated either by the lattice energies of its ionic ‘compounds or by the hydration energies of ions in aqueous solution ‘Trends in chemical reactivity In trivalent state, they form e~ deficient compounds. Thus, they show tendency to accept € pair and hence act as Lewis acids. This tendency decreases down the group, Be (@) BCI, accepts lone pair of e°s from NH to form BCL, Ni, (&) AICI, becomes stable by forming a dimer Al,Cly. In trivalent state, most oftheir compounds are hydrolysed in water. For ex: the trichlorides on hydrolysis form [M(on),] species Complex formation : On account of their smaller size and greater charge, these elements havea much greater tendency to form complexes than the s-block elements, Reactivity towards air: 4M(s)+302(g) > 2M30;(s) 2M(s)+ Nz (g)—*-> 2MN(s) (M= clement) ‘Aluminium forms a very thin oxide layer on surface which protect the metal from further attack, Boron trioxide is acidic. Aland Ga oxides are amphoteric and those of in and Tiare basic in their properties Crystalline boron is unreactive. Itis the amorphous boron which reacts with ic EB)‘The p-block elements (Group 13 and 14) (i), Reactivity towards acidsand alkalies: BB does not react with acids and alkalies. Al shows amphoteric character and reacts with both acids and alkalies. 2Al(s)+6HCI (aq) —+ 2AP*(aq)*6CT (aq)+3H,(8) 2Al(s) +2NaOH (ag) + 61,0() —> 2.Na* [AI(OH),} (09) +3H, (2) ‘Cone HINO, renders Al and Ga passive by forming a protective ‘oxide layer on the surface. (ii) Reactivity towards halogens: With halogens they form trihalides of formula MX, 2M (s)+3X, (g) —5 2MX, (5) (X=F,C1,Br,) Anomalous Behaviour of Boron Owing to its extremely small size, high electron density, high clectronegatvityand non-avilability of d-electrons, boron exhibits following anomalous properties © Boron is a typical non-metal, while other members of the ‘group are metals. forms only covalent compounds while other members ean form covalent as well as ionic compounds. The maximum covalency of Bis four while that of AL is six. Its oxides and hydroxides have acidic nature while that of ‘other members haveamphoteric and basic nature. IUshyurides are quite stable while that of other members are not so stable. Likenon-metals, it combines with metals to form metal borides (eg. MgB, while other members form alloy with metals. (Ga) It does not decompose steam while other members do 30, Trihalides of Boron: sh electronegativity of boron, all boron wo iy ww o Due to small size and halides are covalent, Boron atom, in BX,, has six electrons in the outermost orbit and thusit can accept a pair of electrons from a donor atom like N, O,, PorS to complete its octet. Hence boron halides function as very efficient Lewis act The relative lewis acid character of boron trihalides is found to follow the following order. BI, > BBr, > BCI,> BF, This anomalous behaviour can be explained on the basis of the relative tendency of the halogen atom to back donate its tunutilised electrons to the vacant p-orbitals of borom atom. Completely filled 2p Vacant 2p orbital orbital of fluorine ‘of boron me a Formation of ack bonding been boron and ‘orn BF, molecule Some Important Compounds of Boron Borax: Itisa white crystalline solid with formula Na,B,0,,10H,0. ‘contains tetranuclear units and the correct formula is therefore Nap[B,Os(OH),] 840 It dissolves in water to give an alkaline solution. Preparation: (From colemanite €a,B,0,,+2Na,CO, —> ‘Colematie 2CaC0, 4 +NagB,0; +2NaB0, posi eplons) (i) From borie acid: 411,BO, + Na,CO; —+Na,B,0, +6H,0+CO, Properties: © Aqueous solution of borax is alkaline due to hydrolytic decomposition which produces NaOH and H,B0,. 1NazB,O; + 7H;0 —> 2NaO1H +4113B03 )) On heating, borax loses water and swells into a white mass which on further heating melts to forms a transparent glassy solid called borax glass and borax bead, 123807. 1011;0 —*-+ NajB,0; —*-+ 2NaBO3+ B05 ‘Soa ee aoe ste earn ead ‘The metaborates of many transition metals have characteristic colours therefore borax bead testis used for qualitative analysis of various cation. Uses (Borax is used in the manufacture of enamels, glazes, pyrex lass Itisalso used asa cleansing and stiffening agent in laundry ‘work and in candle industry. It is used for glazing paper, playing cards and also as an antiseptic. (iv) Iti also used in water softening, Orthoboric Acid Itis white crystalline solid with a soapy touch, Preparation (From colemanite, «i, (iy Ca,B,0,, +280, +910 —+2CaS0, + 64,80, ) Ibis prepared by acidifying an aqueous solution of borax: NaB,0y +2HCI+SHj0 —> 2NaCl + 4B(OH), Properties (@ _Ttisa weak monobasic acid and acts asa Lewi B(0N),+ 21101 —s[B(0n),] +10" id(i) Action of heat: H,B0, Lore EEE HBO, +140 41Bo, —“S, 1,8,0, +H,0 Maton nie Teratone ae H,B,0, "5 28,0, +H,0 Trebor a ‘eon te Uses (this used as an antiseptic, as eye-wash (eye-lotion) and as a food preservative (i) Its used in the preparation of glass, glazes and enamels. (ii) Its also used in leather industry, Diborane Its formul Preparation: ABR; + 3LIAIN, —+ 2B Hg +3LiF + 3AIB, Billy 2NaBHy +1; —+ Bolg +2Nal + Hy (Labmethod) 2BF, + Nati °K 5 Botte + 6NAE (Industrial method) Properties: (Wis acotourles, highly toxie gas (i) Iteatches fire spontaneously on exposure to air. (ii) Action of oxygen (iv) Hydrolysis : Byllg(g)+61130(!)—+ 2B(ON1), (aq) + 6H13(g) ByHg +30; —+ B30, +310 (¥) Reaction with Lewis base Ball + 2NMey —> 2BHy. NMey Byllg +2CO—+2BH;,CO (i) Action of ammoni 32H, + 6NH1; —> 3[ BH (NH), |" [BH] Ay 2BNatly borasneo orale Cina bencc) + 12H Borazole has been called as inorganic benzene because itis very clase to benzene in structure and properties, Borazoleis isoeletronic with benzene Its planar molecule inwhich Band H atoms are sp" hybridized, The difference is that in borazole the x-bonding is dative and it arses from ‘overlap of empty p-orbitals of boran with filled p-orbitals of nitrogen. CHEMISTRY 4 | ~ N nc7 t' ww wt Hd oH BH y I 4 H Benzene Borzole Empty 2p orbital e ¢ ave Ne Ne ye 0 ite p orbital (i) Formation of complex borohydride 2MI+ByHg—>2M* [BH] (M = Lior Na) borhyride Uses of diborane (Its used as.a catalyst in polymerisation reactions (i) It is used as. reducing agent in organic reactions (ii) Its used for welding torches. (iv) Diborane is also used for prepari energy fuels and propellents. (9). Hydroboration is useful method for preparing hydrocarbons, alcohols, ketones and acids ‘Structure and bonding in diborane : Each B atom uses sp? hybrid orbitals for bonding. Two ofthe four sp? orbitals of cach of the boron atom overlap with 1 s orbitals of ‘wo terminal hydrogen atoms forming twonormal B-H ebonds. ‘One ofthe remaining sp? hybrid orbital ((ither filled or empty) of | ‘one of theboron atoms, the 1s orbital ofthe bridge hydrogen atom and one ofthe sp? hybrid orbitals (empty or filled respectively) of | the second boron atom overlap to form a delocalised orbital covering the three nuclei, Thus @ pair of electrons (one electron fiom B and other from H) acts as a bond between three atoms (centres); such bond is known as three-cenire two electron bonds (@Ge-2e bonds), The 3-centre ~ 2 €° bridge bonds are also referred to as banana bonds substances such as high EBD_7327(GROUP 14 ELEMENTS: THE CARBON FAMILYImportant Trends and Anomalous Behaviour of Carbon (Due to its smaller size, higher electronegativity, higher ionisation energy and unavailability of d-orbitals, carbon differs from rest ofthe members ofits group. Dueto absence of d-orbital, the maximum covalency of Cis 4 while for other members, it can be more than 4 due to presence of d-orbitals. Carbon forms px - px multiple bonds with itself and with ther atoms of smal sizeand high clectronegativity. Examples areC=C, C#C,C=0,C=SandC=N. Heavier elements do not form px-pn bonds because their atomic orbitals are too large and diffuse to have effective overlapping. Carbon shows the property of catenation ic. sel-linking of the atoms through covalent bonds. This is because C-C bonds are very trong. Down the group, catenation tendency decreases. Carbon remains unaffected by alkalies while other members reacts with alkalias| i, «iy tiv) o Si+2Na011+40;—+ NaSiO, +H 2 Sodium siicme Allotropes of Carbon Carbon exhibits many allotropic forms: both crystalline and. amorphous. Diamond, graphite and fullerenes are the allotropes of eatbon. Diamond Ithas a rigid 3D network of C-atoms. Ithhas directional covalent bonds throughout the lattice. Itis very difficult to break extended covalent bonding and hence diamond isthe hardest substance known. Its used asan abrasive for sharpening hard tools, in making dies and in the manufacture of tungsten filaments for electric light bulbs. In diamond all the electrons are used in bond formation, there is ‘nomobile electron in the system and hence the diamond erystals are non-conductor of electricity, Graphite It has a layered structure and the layers are held by van der Waals forces. The C atoms undergo sp* hybridisation, forming 3 o-bonds. The fourth forms a n- bond and is delocalised ‘over the whole sheet. Electrons are mobile and this makes graphite 4 good conductor of electricity, Iti soft and slippery and is thus ‘used asa dy lubricant in machines running at high temperature. Graphite is thermodynamicaly the mos stable allotrope of carbon and thus, 41° for graphite is taken to be zero, Graphite is used (i) in making electrodes and carbon ares, (Gi) as a lubricant, (it) in crucible, (iv) in lead pencils, and (v)asa moderatorin nuclear reactors. Fullerenes ‘Theyare made byheating graphite in an electric ae in presence of inert gases such as He or Ar. They are pure form of carbon, Fullerenes ae large cage like spheroidal molecules with general formula C,, (where n > 30). Two important member are Cy and Cyp- Ci flerenc looks like a soccer ball (socalled bucky ball). Cyy iscalled Buckminsterfullerene, ‘Some Important Compounds of C and Si Oxides of Carbon (Carbon monoxide (CO) (@) Preparation: 1. 2C(s)+02(¢)—*42C0%@) 2 HCOOH Sg + H0+C0 3 Cs)+1,0@) BE+ COV)+ Hae) Wer or syhesis s 4 2C(s)+02(g)+4N2(g) + 2001) +3No(e) a S$. CO;+C—+2C0; CO, +2n—+2n0+CO = K,Fe(CN), +6H;S0, + 611,0—+2K $0, + FeSO, 43(NH,)380, +600 (©) Properti 1. Itis colourless, odourless, water insoluble gas. 2. tis powerful reducing agent. 3. It combines with haemoglobin (Hb) in the blood thus forming carboxyhaemoglobin which decreases oxygen carrying capacity of Hb, 4. Asa reducing agent Fe,0,+3C0— 2-2" 2Fe+ 300, 6tearn) +CO MEE 5 HH, +CO} 1,0 (team) + CO MEME +H, +CO, 5. It behaves as an unsaturated compound and gives addition product with a number of substances. CHOH (nett co+ci, ae, Fem Caton cocl, lene here) Ni(CO), Sesame! Carbon monoxide is used asa fuel in the form of water ‘gas (CO+H1,) and producer gas (CO+N;) (i) Itisused in making carbonyls which in turn are used in the extraction ofiron and nickel Ni+4CO—+Ni(CO),;Fe +8SCO—+Fe(CO), (Gi) It is used in the manufacture of methanol, synthetic petrol and phosgene (Gv) tis used asa reducing agent in metallurgy of iron and in the manufacture of hydrogen Fe,0, + 3CO—> 2Fe +300, 1,0 (steam) + CO—*-4 11, CO, EBD_73.