UNIT 11 THE p -BLOCK ELEMENTS Objectives 4 «explain anomalous behaviour of boron and cat 4 describe allotropie forms of carbon: important con of boro} + list the important uses of group 13 and 14 elements and their ‘The variation in properties of the phlock elements due to the influence of d and f electrons in the inner core of the heavier elements makes their chemistry interesting In p-block elements the last electron enters the outermost orbital. As we know that the number of porbitals is three and, therefore, the maximum number of electrons that can be accommodated in a set of porbitals is six. Consequently there are six groups of p-block elements in the periodic table numbering from 13 to 18. Boron, carbon, nitrogen, oxygen, fluorine and helium head the groups. Their valence shell electronic configuration is ns np’ “(except for He). The inner core of the electronic configuration may, however, differ. The difference in inner core of elements greatly influences their physical properties (such asatomic and fonic radii, ionisation enthalpy. etc,) aswell as chemical properties. Consequently, a lot of variation in properties of elements in a group of p-block is observed. The maximum oxidation state shown by a p-block element is equal to the total number of valence electrons (ée., the sum of the s- and p-electrons). Clearly, the number of possible oxidation states increases towards the right of the periodic table. In addition to this so called group oxidation state, p-block elements may show other oxidation states which normally. but not necessarily, differ from the total number of valence electrons by unit of two. The important oxidation states exhibited by p-block elements are shown in Table 11.1. In boron, carbon and nitrogen families the group oxidation state is the most stable state for the lighter elements in the group. However, the oxidation state two unit less than the group oxidation state becomes progressively more stable for the heavier elements in each group. The occurrences of oxidation states two unit less than the group oxidation slates are sometime attributed to the ‘inert pair effect.308 Table 11.1 General Electronic Configuration 7 EMISTRY and Oxidation States of p-Block Elements Group 13, 14 15) 16 a7, 18 General electronic nsinp' | nstnp? | nsénp* | nsinp* ns? nstng configuration (0s! for He} First member of the B @ N ° F He group Group oxidation +3. +4 45 +6 +7 +8 state Other oxidation 4 43,3 | 4.42.2 [45.43.41 46. +4, 42 states ‘The relative stabilities of these two oxidation states — group oxidation state and two unit less than the group oxidation state- may vary from group to group and will be discussed at appropriate places. Itis interesting to note that the non-metals, and metaltoids exist only in the p-block of the periodic table, The non-metallic character of elements decreases down the group. In fact the heaviest element in each p-block group is the ‘most metallic in nature. This change from non- metallic to metallic character brings diversity in the chemistry of these elements depending on the group to which they belong. Ingeneral, non-metals have higher ontsation, enthalpies and higher electronegativities than the metals. Hence, in contrast to metals which readily form cations, non-metals readily form anions. The compounds formed by highly reactive non-metals with highly reactive metals are generally ionic because of large diflerences in their electronegativities. On the other hand. compounds formed between non-metals themselves are largely covalent in character because of small differences in their electronegativities. The change of non-metallic to metallic character can be best illustrated by the nature of oxides they form. The non-metal oxides are acidic or neutral whereas metal oxides are basic in nature, ‘The first member of p-block differs from the remaining members of thetr corresponding group in two major respects. First is the size and all other properties which depend on size. ‘Thus, the lightest p-block elements show the same kind of differences as the lightest s-block elements, lithium and beryllium. The second important difference, which applies only to the p-block elements, arises from the effect of d- orbitals in the valence shell of heavier elements (starting from the third period onwards) and their lack in second period elements. The second period clements of p-groups starting from boron are restricted to a maximum covalence of four (using 2s and three 2p orbitals). In contrast, the third period elements of p-groups with the electronic configuration 35’3p" have the vacant 3d orbitals lying between the 3p and the 4s levels of energy. Using these d-orbitals the third period elements can expand their covalence above four. For example, while boron forms only IBF,), aluminium gives [AIF,|” ion. The presence of these d-orbitals influences the chemistry of the heavier elements in a number of other ways. The combined effect of size and availability of d orbitals considerably influences the ability of these elements to form scbonds. The first member of a group differs from the heavier members in its ability to form pr- pr multiplebonds to itself (e.g, C=C, C=C,THE p-BLOCK ELEMENTS: and to other second row elements (e.g., C=O, C=N, C=N, N=O). This type of 1 - bonding is not particularly strong for the heavier p-block elements. The heavier elements do form x bonds but this involves d orbitals (dz ~ px or dx -dr). As the d orbitals are of higher energy than the porbitals, they contribute less to the overall stability of molecules than does px- pr bonding of the second row elements. However, the coordination number in species of heavier elements may be higher than for the Airsi element in the same oxidation state. For example, in 45 oxidation state both Nand P form oxoanions : NO, (three-coordination with x — bond involving one nitrogen p-orbital) and PO} (four-coordination involving s, pand orbitals contributing to the — bond). In this unit we will study the chemistry of group 13 and 14 elements of the periodic table, 11.1 GROUP 13 ELEMENTS: THE BORON FAMILY ‘This group elements show a wide variation in properties. Boron is a typical non-metal, aluminium is a metal but shows many chemical similarities to boron, and gallium, indium and thallium are almost exclusively metallic in character. Boron is a fairly rare element, mainly occurs as orthoboric acid, (H,BO,), borax, Na,B,0,-10H,0, and kernite, Na,B,0,-41,0. In india borax occurs in Puga Valley (Ladakh) and Sambhar Lake (Rajasthan), The abundance of boron in earth crust is less than 0.001% by mass. There are two isotopic forms of boron 'B (19%) and ''B (8196) Aluminium is the most abundant metal and the third most abundant element in the earth's crust (8.3% by mass] after oxygen (45.5%) and Si (27.7%). Bauxite, ALO, 21,0 and cryolite, Na,AIF, are the important minerals of aluminium, In India it is found as mica in Madhya Pradesh, Karnataka, Orissa and Jammu. Gallium, indium and thallium are less abundant elements in nature. The atomic, physical and chemical properties of these elements are discussed below. 309) 11.1.1 Electronic Configuration The outer electronic configuration of these elements is ns*np'. A close look at the electronic configuration suggests that while boron and aluminium have noble gas core, gallium and indium have noble gas plus 10 delectrons, and thallium has noble gas plus 14 electrons plus 10 delectrons cores. Thus, the electronic structures of these elements are more complex than for the first {wo groups of elements discussed in unit 10. This difference in electronic structures affects the other properties and consequently the chemistry ofall the elements of this group. 11.1.2 Atomic Radi On moving down the group, for each successive member one extra shell of electrons is added and, therefore, atomic radius Is expected to increase. However, a deviation can be seen. Atomic radius of Ga is less than that of Al. This can be understood from the variation in the inner core of the electronie configuration. The presence of additional 10 c-electrons offer only poor screening effect (Unit 2) for the outer electrons from the increased nuclear charge in gallium. Consequently, the atomic radius of gallium (135 pm) is less than that of aluminium (143 pm). 11.1.3 Ionization Enthalpy The lonisation enthalpy values as expected from the general trends do not decrease smoothly down the group, The decrease from B to Alis associated with increase in size. The observed discontinuity in the ionisation enthalpy values between Al and Ga, and between In and Tare due to inability of d-and _felectrons ;which have low screening effect, to compensate the increase in nuclear charge. The order of ionisation enthalpies, as expected, is 4,H, 8 _— / a7 \a é a Planer Terahedra AICI, achieves stability by forming a dimer a: act ris* ‘Tetrahedral In trivalent state most of the compounds being covalent are hydrolysed in water. For example, the trichlorides on hyrolysis in water form tetrahedral [M(OH),| species: the hybridisation state of element M is sp’. Aluminium chloride in acidified aqueous solution forms octahedral [Al(H,O), |" ton. In this complex ion, the 3d orbitals of Al are involved and the hybridisation state of Al is spc’. Problem 11.1 Standard electrode potential values, ES for Al’*/Al is -1.66 V and that of TI""/TI is +1.26 V. Predict about the formation of ‘M*™ ion in solution and compare the electropositive character of the two metals. Solution ‘Standard electrode potential values for two halfcell reactions that aluminium, has high tendency to make Al”"(aq) ions, whereas TI is not only unstable in sin solution but is a powerful oxidising agent also. Thus TI’ is more stable in solution than TI”, Aluminium being able to form +3 ions easily, is more electropositive than thallium, (Reactivity towards air Boron is unreactive in crystalline form. Aluminium forms a very thin oxide layer on the surface which protects the metal from further attack. Amorphous boron and aluminium metal on heating in air form B,O, and Al,O, respectively. With dinitrogen at high temperature they form nitrides. 2E(s) +30, (g)—*-> 2E,0, (8) 2E (5) +N, (g)—* >2EN(s) =element) ‘The nature of these oxides varies down the group. Boron trioxide ts acidic and reacts with basic (metallic) oxides forming metal borates. Aluminium and gallium oxides are amphoteric and those of indium and thallium are basic in their properties. (ii) Reactivity towards acids and alkalies Boron does not react with acids and alkalies: even at moderate temperature: but aluminium dissolves in mineral acids and aqueous alkalies: and thus shows amphoteric character. Aluminium dissolves in dilute HCL and liberates dihydrogen. 2Al(s) + GHC! faq) —> 2Al" (aq) + GCI faq) +3H,(@) However, concentrated nitric acid renders aluminium passive by forming a protective oxide layer on the surface. Aluminium also reacts with aqueous alkali and liberates dihydrogen. 2Al (s) +2NaOH faq) + 61,000) L 2Na‘[ALOH),| (aq) + SH,(g) Sodium tetrahydroxoaluminate(III) Reactivity towards halogens These elements react with halogens to form trihalides (except TI). 2E(s) + 3 X, (@ > 2EX, (5) (=F, CBr Dsi Problem 11.2 White fumes appear around the bottle of anhydrous aluminium chloride. Give Solution Anhydrous aluminium chloride is partially hydrolysed with atmospheric moisture to liberate HCl gas. Moist HC1 appears white in colour. 11.2 IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON Certain important trends can be observed in the chemical behaviour of group 13 elements. The tri-chlorides, bromides and iodides of all these elements being covalent in nature are hydrolysed in water Species like tetrahedral [M(OH),I and octahedral [M(H,0),J”", except in boron, exist in aqueous mecium ‘The monomeric trihalides, being electron deficient, are strong Lewis acids. Boron trifluoride easily reacts with Lewis bases such as NH, to complete octet around boron. FB +:NH, > FjBCNHy It is due to the absence of d orbitals that the maximum covalence of B is 4. Since the d orbitals are available with Al and other elements, the maximum covalence can be expected beyond 4. Most of the other metal halides (eg., AICL) are dimerised through halogen bridging (eg., AlCl). The metal species completes its octet by accepting electrons from halogen in these halogen bridged molecutes. Problem 11.3 Boron is unable to form BF,” ion. Explain. Solution Due to non-availability of dorbitals, boron {s unable to expand its octet. Therefore, the maximum covalence of boron cannot exceed 4 CHEMISTRY 11.3 SOME IMPORTANT COMPOUNDS OF BORON ‘Some useful compounds of boron are borax, orthoboric acid and diborane. We will briefly study their chemistry. 11.3.1 Borax It is the most important compound of boron. It is a white crystalline solid of formula Na,B,0,-10H,0, In fact it contains the tetranuclear units [B,O, (OH), |" and correct formula; therefore, is Na,{B,0,, (OH),|.8H,0. Borax dissolves in water to give an alkaline solution. Na,B,0, + 7H,0 > 2NaOH + 4H,B0, Orthoboric acid On heating, borax first loses water molecules and swells up. On further heating it ‘tums into a transparent liquid, which solidifies into glass like material known as borax bead. Na,B,0,.10H,0__4_,Na,B,O,_\_, 2NaBO, Sodium + B,O, metaborate Boric anhydride ‘The metaborates of many transition metals, have characteristic colours and, therefore, borax bead test can be used to identify them in the laboratory. For example, when borax is heated ina Bunsen burner flame with CoO on a loop of platinum wire, a blue coloured Co(BO,), bead is formed. 11.3.2 Orthoboric acid Orthoboric acid, H,BO, 1s a white crystalline solid, with soapy touch. Itis sparingly soluble in water but highly soluble in hot water, It can be prepared by acidifying an aqueous solution of borax. Na,B,0, + 2HCI + 5H,0 ~ 2NaCl + 4B(OH), Itis also formed by the hydrolysis (reaction with water or dilute acid) of most boron compounds (halides, hydrides, ete). It has a layer structure in which planar BO, units areTHE p-BLOCK ELEMENTS: joined by hydrogen bonds as shown in Fig. 11.1. Boric acid is a weak monobasic acid. It is not a protonte acid but acts as a Lewis acid by accepting electrons from a hydroxyl fon: B(OH), +2HOH — (B(OH), + H,0° On heating, orthoborie acid above 370K forms metaboric acid, HBO, which on further heating yields boric oxide, B,0,, H,B0,_4, HBO, 4, B,O, JH” Oo “HL BN oe iY H 0. 0. CHO Ng SHH Pte teeta ih NoPKo Hig Bio | H 4 Fig. 11.1 Structure of boric acid: the dotted lines represent hydrogen bonds Problem 11.4 Why is boric acid considered as a weak acid? Solution Because it is not able to release H’ ions onits own. It receives OH ions from water molecule to complete its octet and in turn releases H’ fons. 11.8.3 Diborane, B,H, ‘The simplest boron hydride known, is diborane. It is prepared by treating boron trifluoride with LiAIH, in diethyl ether. 4BF, +3 LiAIH, + 2B,H, + SUF + SAIF, ‘A convenient laboratory method for the preparation of diborane involves the oxidation of sodium borohydride with iodine. sis, 2NaBH, +1, > BH, +2Nal + H, ‘Diborane is produced on an industrial scale by the reaction of BF, with sodium hydride. 2BF, +6NaH 2°85, H, +6NaF Diborane is a colourless, highly toxic gas with a b.p. of 180 K. Diborane catches fire spontaneously upon exposure to air. It burns in oxygen releasing an enormous amount of energy. B,H,+30, >B,0, + 3H,0; AH? =-1976 kJ mol" Most of the higher boranes are also spontaneously flammable in air, Boranes are readily hydrolysed by water to give boric acid. B,H,@ + 6H,0() > 2B(OH), (aq) + Hg) Diborane undergoes cleavage reactions with Lewis basestl) to give borane adducts, BH,L B,H, +2 NMe, > 2BH, NM BH, +2 CO > 2BH,CO Reaction of ammonia with diborane gives. initially B,H,2NH, which is formulated as (BHNH,,I" [BH] ; further heating gives borazine, B,N,H, known as “inorganic benzene” in view of its ring structure with alternate BH and NE groups. 3B,H,+6NH, -+3/BH,(NH, },|"[BH,]° He2,98,N,H,+12H, The structure of diborane is shown in Fig 1 1.2(@). The four terminal hydrogen atoms and the two boron atoms lie in one plane, Above and below this plane, there are two bridging hydrogen atoms. ‘The four terminal B-H bonds are regular two cenire-two electron bonds while the two bridge (B-H-B) bondsare different and can be described in terms of three Fig.11.2(a) The structure of diborane. BH,sia centre-two electron bonds shown in Fig. 11.2 (0) Boron also forms series of hydrkdoborates: the most important oneis the tetrahedral [BH ion. Tetrahydridoborates of several metals are known. Lithium and sodium tetra- hyaridoborates, also known as borohydrides, are prepared by the reaction of metal hydrides with B,H, in diethyl ether. 2MH + BH, > 2M" (BH, aS) Hh H oT 6 ¢ ‘J Xe Fig.11.2{6) Bonding in diborane. Each B atom uses sp? hybrids for bonding. Out of the four sp? hybrids on each B atom, one is without an electron shown in broken lines. The terminal BAI bonds are normal 2-centre-2- electron bonds but the two bridge bonds are 3-centre-2-electron bonds. ‘The S-centre-2-electron bridge bonds are also referred toas banana bonds. Both LiBH, and NaBH, are used as reducing agents in organic synthesis. They are useful starting materials for preparing other metal borohydrides. (M=LiorNaj 11.4 USES OF BORON AND ALUMINIUM AND THEIR COMPOUNDS Boron being extremely hard refractory solid of high melting point, low density and very low electrical conductivity, finds many applications. Boron fibres are used in making bullet-proof vest and light composite material foraircraft, The boron-10 ("°B) isotope has high ability to absorb neutrons and, therefore, metal borides are used in nuclear industry as protective shields and control rods. The main industrial application of borax and boric acid is in the manufacture of heat resistant glasses (e.g. Pyrex), glass-wool and fibreglass. Borax is also used asa flux for soldering metals, for heat, scratch and stain resistant glazed coating to earthenwares and as constituent of medicinal soaps. An aqueous solution of CHEMISTRY orthoboric acid 1s generally used as a mild antiseptic. Aluminium is a bright silvery-white metal, with high tensile strength, It has a high electrical and thermal conductivity. On a weight-to-weight basis, the electrical conductivity of aluminium is twice that of copper. Aluminium is used extensively in industry and every day life. It forms alloys with Cu, Mn, Mg. Siand Zn. Aluminium and its alloys can be given shapes of pipe, tubes, rods, wires, plates or foils and, therefore, find uses in packing, utensil making, construction, aeroplane and transportation industry. The use of aluminium and. its compounds for domestic purposes is now reduced considerably because of their toxic nature. 11.5 GROUP 14 ELEMENTS: THE CARBON FAMILY Carbon (C}, silicon (Si), germanium (Ge), tin Sn) and lead (Pb} are the members of group 14. Carbon is the seventeenth most abundant element by mass in the earth’s crust. Ik is widely distributed in nature in free as well as in the combined state. In elemental state It is available as coal, graphite and diamond: however, in combined state it is present as metal carbonates, hydrocarbons and carbon dioxide gas (0.03%) in air. One can emphatically say that carbon is the most versatile element in the world. Its combination with other elements such as dihydrogen, dioxygen, chlorine and sulphur provides an astonishing array of materials ranging from living tissues to drugs and plastics. Organic chemistry is devoted to carbon containing compounds, It is an essential constituent of all living organisms. Naturally occurring carbon contains two stable tsotopes:'°C and ‘SC, In addition to these, third isotope, 'C is also present. ILisa radioactive isotope with half- life 5770 years and used for radiocarbon dating, Silicon is the second (27.7% by mass) most abundant element on the earth's crust and is present in nature in the form of silica and silicates. Silicon is a very important component of ceramics, glass and cement.THE p-BLOCK ELEMENTS Germanium exists only in traces. Tin occurs mainly as cassiterite, SnO, and lead as galena, PbS. Ultrapure form of germanium and silicon are used to make transistors and semiconductor devices. The important atomic and physical properties of the group 14 clemenis along with their electronic configuration are given in Table 11.2 Some of the atomic, physical and chemical properties are discussed below: 11.8.1 Electronic Configuration ‘The valence shell electronic configuration of these elements is ns’np’. The inner core of the electronic configuration of elements in this group also differs. 11.5.2 Covalent Radius ‘There is a considerable increase in covalent radius from C to SI, thereafter from SI to Pb a small increase in radius is observed. This is, 315 due to the presence of completely filled dand f orbitals in heavier members. 11.5.3 Ionization Enthalpy The first ionization enthalpy of group 14 members is higher than the corresponding members of group 13. The influence of inner coreelectronsis visible here also. In general the ionisation enthalpy decreases down the group. ‘Small decrease in A,H from Si toGe to Sn and slight increase in A\H from Sn to Pb is the consequence of poor shielding effect of intervening dand forbitals and increase in size oftheatom. 11.5.4 Electronegativity Due to small size, the elements of this group are slightly more electronegative than group 13 elements. The electronegativity values for elements from Si to Pb are almost the same. 11.5.5 Physical Properties All group 14 members are solids. Carbon and silicon arenon-metals, germaniumisa metalloid, Table 11.3 Atomic and Physical Properties of Group 14 Elements Element Property Carbon | Silicon | Germanium | Tin Lead c si Ge sn Pb ‘Atomic Number 6 14 32 50 82, ‘Atomic mass (g mol) 12.01 | 28.09 72.60 1s71 207.2, Blectronsc THel2s'2p* | INelas'sp? | larisd"asap" | Dkrlad’5¢ 5p | Delaj"'5a6 or" configuration Covalent radiue/pa| 77 16. 123, 140 146. Tonie radius M”/pm" = 40 53 69 78 Tonie radius M/pm™ 5 z 73 18 119) Tonvation | Aji, TORS 786 761 708 715 enthalpy/ | 41, 2352 1577 1587 14 1450 kJmor | af, 4620 | 3298 3300 2042 3081 an, e220 | 4354 4409 3929 4082 Blectronegativity™ 25 18 1s 18 18 Densily*/g em 3.51 2.34 5.32 7.207 11.34 Welling point/& 4375 T69s Tas 505 600 Bailing point/K = _|_ 3550 3125 2896 2024 Electrical resistivity/| 1010" 50 50 10° 2% 10" ohm em (293 K) “for M" oxidation state: ”6-coordination: “ Pauling scale; “203 K: “ for diamond; for graphite, density is 2.22: B-form (stable at room temperature)316 whereas tin and lead are soft metals with low melting paints, Melting points and boiling points ofgroup 14elementsare much higher than those ofcorrespondingelementsofgroup 13. 11.5.6 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 the first four ionization enthalpies is very high. compounds in +4 oxidation state are generally covalent in nature, In heavier members the tendency to show +2, oxidation slate increases in the sequence Ge> Si > Ge= Sn. Lead does not show catenation, Bond _Bond enthalpy / kJ mol c—c 348) si-si 297 Ge-Ge 260 Sn—Sn 240 Due to property of catenation and px- pr bond formation, carbon is able to show allotropic forms. 11.7 ALLOTROPES OF CARBON Carbon exhibits many allotropie 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 [Link], [Link] and [Link], For this discovery they were awarded the Nobel Prize in 1996. 11.7.1 Diamond It has 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 rigid three- dimensional network of carbon atoms. In this318 154 pm Fig. 11.3 The structure of diamond structure (Fig. 11.3) directional covalent bonds are present throughout the lattice. Itis very difficult to breakextended covalent bonding and, therefore, diamond isa 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. Problem 11.7 Diamond is covalent, yet it has high melting point. Why ? ‘Solution Diamond has a three-dimensional network involving strong C—C bonds, which are very difficult to break and, in tum has high melting point, 11.7.2 Graphite Graphite has layered structure (Fig.11.4) Layers are held by van der Waals forces and distance between two layers 1s 340 pm, Each layer is composed of planar hexagonal rings of carbon atoms. C—C bond length within the layer is 141.5 pm. Each carbon atom in hexagonal ring undergoes sp" hybridisation and makes three sigma bonds with three neighbouring carbon atoms. Fourth electron forms a xbond. The electrons are delocalised over the whole sheet. Electrons are mobile and, sgtsem Fig 11.4 The siructure of graphite 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 oil cannot be used as a lubricant. 11.7.3 Fullerenes Fullerenes are made by the heating of graphite in an electric arc in the presence of inert gases such as hellum or argon. The sooty material formed by condensation of vapourised "small molecules consists of mainly Cj, with smaller quantity of C,, 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. Coy molecule has a shape like soccer ball and called Buekminsterfullerene (Fig. 11.5). It contains twenty 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” hybridisation. Each carbon atom forms three sigma bonds with other three carbon atoms. The remaining electron at each carbon is delocalised inTHE p-BLOCK ELEMENTS: molecular orbitals, which in turn givearomatic 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. Fig.11.5 The structure of Cy, Buckminster: fallerene : Note that'molecule has the shape of @ soccer ball (football). Itis very important to know that graphite is thermodynamically most stable allotrope of carbon and, therefore, AyH” of graphite is taken as zero. AH’ values of diamond and fullerene, Cyp are 1.90 and 38.1 kJ mol ', 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 buming 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. 11.7.4 Uses of Carbon Graphite fibres embecided in plastic material form high strength, lightweight composites. ‘The composites are used in products such as tennis rackets, fishing rods, aircrafts and canoes. Being good conductor. graphite is used for electrodes in batteries and industrial electrolysis. Crucibles made from graphite are inert to dilute acids and alkalies. Being highly porous, activated charcoal is used in adsorbing poisonous gases; also used in water sig filters to remove organfe contaminators and in airconditioning system to control odour. Carbon black is used as black pigment in lack ink and as filler in automobile tyres. Coke is used as a fuel and largely as a reducing agent in metallurgy. Diamond is a precious stone and used in jewellery. It is measured in carats (I carat = 200 mg). 11.8 SOME IMPORTANT COMPOUNDS OF CARBON AND SILICON Oxides of Carbon ‘Two important oxides of carbon are carbon monoxide, CO and carbon dioxide, CO, 11.8.1 Carbon Monoxide Direct oxidation of C in limited supply of oxygen or air yields carbon monoxide. 2C{8) +O.) —4+ 2C01g) On small scale pure CO is prepared by dehydration of formic acid with concentrated H,SO, at 373 K i HCOOH a2 HS5? HLO+ CO On commercial scale it is prepared by the passage of steam over hot coke. The mixture of COand H, thus produced is known as water gas or synthesis gas. C(s) + H,0(g) 4712795, CO(g) + H, (8) Water gas When airis used instead of steam, a mixture of CO and N, 1s produced, which is called producer gi 2C(s) + 0, (8) + 4N,(g) 23 2cotg) + 4N,(g) Producer gas Water gas and producer gas are very important industrial fuels. Carbon monoxide in water gas or producer gas can undergo further combustion forming carbon dioxide with the liberation of heat. Carbon monoxide is a colourless odourless and almost water insoluble gas. It is a powerful reducing agent and reduces almost all metal oxides other than thoseof the alkali and alkaline earth metals, aluminium and a few transition metals. This property of