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P Block

This document discusses the p-block elements in the periodic table, focusing on their general trends, properties, and the unique behaviors of specific groups such as boron and carbon. It highlights the influence of electronic configurations on the physical and chemical properties of these elements, including oxidation states and reactivity. The document also covers the differences between lighter and heavier elements in the p-block, emphasizing the transition from non-metallic to metallic characteristics as one moves down the groups.

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11 views19 pages

P Block

This document discusses the p-block elements in the periodic table, focusing on their general trends, properties, and the unique behaviors of specific groups such as boron and carbon. It highlights the influence of electronic configurations on the physical and chemical properties of these elements, including oxidation states and reactivity. The document also covers the differences between lighter and heavier elements in the p-block, emphasizing the transition from non-metallic to metallic characteristics as one moves down the groups.

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prabhal2008
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Download as PDF or read online on Scribd
THE p-BLOCK ELEMENTS Objectives After studying this unit, you will be able to appreciate the general trends in the chemistry of p-block elements: describe the trends in physical and chemical properties of group 13 and elements: explain anomalous behaviour of, boron and carbon: describe allotropie forms of earbon: know the chemistry of some important compounds of boron, carbon and silicon; list the important uses of group 13. and 14 elements and their compounds. ‘The variation in properties of the p-block 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 porbital. As we know that the number of p orbitals is thre and, therefore, the maximum number of electrons that ean be accommodated in a set of p orbitals is six. Consequently there are six groups of p-block elements in the periodic table numbering from 13 to 18. Boron, carbon, nitroger 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 as atomic and tonic radi, ionisation enthalpy, ete.) as well 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 ts equal to the total number of valence electrons (ce., the sum of the s. and pelectrons). 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 progre: 2010.20 316 CHEMISTRY Table 11.1 General Electronic Configuration and Oxidation States of p-Block Elements Group 13 14 15 16 17 18 General electronic nstnp| | nstnpt | nsenp | nsinpt nstnp* nstnp! configuration (s*for He) First member of the B c N ° F He group Group oxidation 43 os 5 +6 +7 48 state ‘Other oxidation aot 43,-3 | +4, 42,2] 45, +3, 41,-1| 46, 44, 42 states The relative stabilities of these two oxidation slates 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. 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. Hence, in contrast to metals which readily form cations, non-metals readily form. 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 their 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 prblock 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 elements 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 3s’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 availability of d orbitals considerably influences the ability of these elements to form bonds. The first member of a group diflers from the heavier members in its ability to form pr- px multiple bonds to itself (e.g., C=C, C=C, 2010.20 ‘THE p-BLOCK ELEMENTS ) and to other second row elements (¢.g.. ), C=N, CaN, N=O). This type of x - bonding is not particularly stron, prlock elements. for the heavier However, the coordination number in species of heavier elements may be higher than for the first element in the same oxidation state. For example, in +5 oxidation state both N and 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, thallium and nihonium are almost exclusively metallic in character. Boron is a fairly rare element, mainly in India borax occurs in Puga 7 and Sambhar Lake (Rajasthan). The abundance of boron in earth crust is less than 0.0001% by mass. There are two isotopic forms of boron ““B (19%) and “'B (819%). 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, Al,O,. 2H, and eryolite, 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. Nihonium has symbol Nh, atomic number 113, atomic mass 286 ¢ mol! and electronic configuration [Rn] 5 6d’ 7s" 7p”. So far it has been prepared in small amount and half life ofits most stable 317 isotope is 20 seconds. Due to these reasons its chemistry has not been established. Nihonium is a synthetically prepared radioactive element. Here atomic, physical and chemical properties of elements of this group leaving nihonium are discussed below. 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 f electrons plus 10 delectron cores, Thus, the electronic structures of these elements are more complex than for the first two groups of elements discussed in unit 10. ‘This difference in electronic structures affects the other properties and consequently the chemistry of all the elements of this group. 11,1.2 Atomic Radii On moving down the group, for each successive member one extra shell of electrons is added and, therefore, atomic radius is expected to ‘The presence of additional 10 d-electrons offer only poor screening effect (Unit 2) for the outer electrons from the increased nuclear charge in gallium. Consequent!y [iia 11.1.3 Ionization Enthalpy ‘The fonisation 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. it ‘compensate the increase in nuclear charge. ‘The order of ionisation enthalpies, as pected, is AH, 2AI** (aq) + 6CT 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 (9) + 2NaOH(aq) + 6H,01) J 2Na"[AIOH),) faq) + 3H) Sodium tetrahydroxoaluminate() 2010.20 THALIUM DOESN'T SHOW TLI3 320 (iii) Reactivity towards halogens es Ty) 2E(s) + 3X, (> 2EX, (3) & Br, 1) Problem 11.2 White fumes appear around the bottle of anhydrous aluminium chloride. Give reason. Solution Anhydrous aluminium chloride is partially hydrolysed with atmospheric moisture to liberate HCI gas. Moist HCL 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 18 elements. The tri-chlorides, bromides and iodides of all these elements being covalent in nature are hydrolysed in water. Species like tetrahedral [M(OH),” and octahedral [M(H,0),|"", except in boron, exist in aqueous medium. ‘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. F,B +:NH, > F,BCNH, 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 (e.g., AICI,) are dimerised through halogen bridging (e.g., Al,Cl,). The metal species completes its octet by accepting electrons from halogen in these halogen bridged molecules. Problem 11.3, Boron is unable to form BF,” fon. Explain. Solution Due to non-availability of dorbitals, boron. is unable to expand its octet. Therefore, CHEMISTRY the maximum covalence of boron cannot exceed 4. 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 ILis the most important compound of boron. It is a white crystalline solid of formula QUBIORIONYO. tm fact it contains the tetranuclear units [B,O; (OH), |” and correct. formula; therefore, is Na,[B,; (OH),)-8H,0. Borax dissolves in water to give an alkaline solution. Na,B,0, *7H,0 >2NaOH + 411,BO, Orthoboric acid On heating, borax first loses water molecules and swells up. On further heating it turns intoa transparent liquid, which solidifies, into glass like material known as borax bead. Na,B,0,.10H,O__4_, Na,B,O,__4_, 2NaBO, Sodium +B,0, metaborate Borie anhydride ‘The metaborates of many transition metals have characteristic colours and. therefore, Na,B,O, + 2HC1 + 5H,O > 2NaCl + 4B(OH), Itis also formed by the hydrolysis (reaction with water or dilute acid) of most boron compounds (halides, hydrides, etc.) 2010.20 ‘THE p-BLOCK ELEMENTS Boric acid is a weak monobasic acid. It is not a protonic acid but acts as a Lewis acid by accepting electrons from a hydroxyl ion: B(OH), + 2HOH [B(OH),. + H,0° On heating, orthoboric acid above 370K forms metaboric acid, HBO, which on further heating yields boric oxide, B,O,, H,BO,_4, HBO, 4, B, Fig. 11. 1 Structure of boric acid: the dotted tines represent hydrogen bonds 11.3.3 Diborane, BH, ‘The simplest boron hydride known, is diborane. It 1s prepared by treating boron trifluoride with LiAlH, in diethyl ether. 4BF, +3 LIAIH, > 2B,H, + SLIF + 3AIF, A convenient laboratory method for the preparation of diborane involves the oxidation of sodium borohydride with iodine. 321 2NaBH, +1, > BH, + 2Nal +H, Diborane is produced on an industrial scale by the reaction of BF, with sodium hydride. 2bF, +6NaH —22%5p, 41, «6NaF Diborane is a colourless, highly toxic gas with a b.p. of 180 K. Diborane catches fire spontaneously upon exposure to air. [burns in oxygen releasing an enormous amount of energy. B,H,+30, >B,0, + 3H,O; AH? =-1976 kJ mot’ Most of the higher boranes are also spontaneously flammable in air. Boranes are readily hydrolysed by water to give boric acid. B,H,(g) + 6H,O() — 2B(OH),(aq) + 6H) Diborane undergoes cleavage reactions with Lewis bases(L) to give borane adducts, BHyL B,H, + 2. NMe, ~ 2BH,NMe, BH, +2 CO > 2BH,.CO Reaction of ammonia with diborane gives initially BH,.2NH, which is formulated as (BH,(NH,),I" [BH] ; further heating gives borazine, B,NjH, known as “inorganic benzene” in view of its ring structure with alternate BH and NH groups. 3B,H,+6NH, --3[BH, (NH,), [TBH] Heat, 95,NJH,+12H, ‘The structure of diborane is shown in Fig.11.2(a). The four terminal hydrogen atoms and the two boron atoms lie in one plane. Above and below this. planar? Fig.11.2(a) The structure of diborane, B,H, 2010.20 322 centre-two electron bonds shown in Fig.11.2 0). Boron also formsa series of hydridoborates; the most important one is the tetrahedral [BH] ion. Tetrahydridoborates of several metals are known. Lithium and sodium tetra- hydridoborates, also known as borohydrides, are prepared by the reaction of metal hydrides, with B,H, in diethyl ether. 2MH+B,H,> 2M" [BHD (M=LtorNa) p 5 H. EY H ‘ a XX, Fig.11.2(6) Bonding in diborane. Bach B atom uses sp? hybrids Jor bonding. Out of the four sp’ hybrids on each B atom, one is without an electron shown in broken lines. The terminal B-H bonds are normal 2-centre-2- electron bonds but the two bridge bonds are 3-centre-2-electron bonds. The 3-centre-2-electron bridge bonds are also referred o as banana bonds Both LiBH, and NaBH, are used as reducing agents in organic synthesis. They are useful starting materials for preparing other metal borohydrides. 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 applications | conductivity, finds many e boron 10 ("B) isotope has high ability to absorb neutrons and, therefore, meal borides are Used n nucleating ag protective shields and control rods. Borax is also used as a 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 )__ ee 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 everyday life. It forms alloys with Cu, Mn, Mg, Si and 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, silicon, germanium, tin lead and flerovium are the members of group 14. Carbon 1s the seventeenth most abundant element by mass in the earth's crust. It is widely distributed in nature in free as well as in the combined state. In elemental state itis 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 isotopes: “Cand "C. In addition to these, third isotope, '“C is also present. It is a 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 isa very important component of ceramics, glass and cement. Germanium exists only in traces. Tin 2010.20 ‘THE p-BLOCK ELEMENTS occurs mainly as cassiterite, SnO, and lead as galena, PbS. Flerovium is synthetically prepared radioactive element Ultrapure form of germanium and silicon are used to make transistors and semiconductor devices. Symbol of Flerovium is Fl. It has atomic number 114, atomic mass 289 gmol | and electronic configuration [Rn] 5f"'6d'°7s* 7p". It has been prepared only in small amount. Its half life is short and its chemistry has not been established yet. The important atomic and physical properties along with their electronic configuration of the elements of group 14 leaving flerovium are given in Table 11.3. Some of the atomic, physical and chemical properties are discussed below: 11.5.1 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. 23 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, due to the presence of completely filled d and 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 core electrons is visible here also. In general the ionisation enthalpy decreases down the group. Small decrease in 4,H from Si to Ge to Sn and slight increase in A,H from Sn to Pb is the consequence of poor shielding effect of intervening dnd 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 Sito Pb are almost the same. ‘Table 11.3 Atomic and Physical Properties of Group 14 Elements Element, Property Carbon | Silicon | Germanium | Tin Tead c Si Ge sn Pb [Atomic Number 6 rm 32 50 82 [Atomic mass (g mol} 12.01 28.09 72.60 1871 207.2 Electronic [Hel2s'2p’ | INelas*3p* | [Arisa!"4s"4p’ | 1krl4d"°5s’ Sp’ | [Xel4f""5d6s' 6p" configuration Covalent radius/pm"| 77 Ts 122 140 146 Tonic radius M"/pm = 40 58 69 78 Tonie radius M" /pmt = = 78. 118 119 Tonization | aH, 1086 786 761 708 715 enthalpy/ | 441, 2352 187 1537 141 1450 kimor' | aH, 4620 3228 3300 2042 3081 aH, 6220 4354 4409 3929 4082 Blectronegativity” 25 18 18 nn 19 Density'7e on? 35r 234 BaD 7.26" 71.34 Melting pomnt/i 4575 1655 Tas, 505 600 Boiling point/K = 3550 3123 2896 2024 Electrical resistivity/| 1010" 50. 50 10° 210" ohm em (293 K) “for M" oxidation state: ° 6-coordination: ° Pauling scale; “293 K; ° for diamond: for graphite, density is 2,22; '[Link] (stable at room temperature) 2010.20 24 11.5.5 Physical Properties All members of group 14 are solids. Carbon and, silicon are non-metals, germanium isametalloid, whereas tin and lead are soft metals with low melting points. Meltingpointsand boiling points ofgroup 14elementsaremuch higher than those ofcorrespondingelementsof group 13. 11.5.6 Chemical Properties Oxidation states and trends in chemical reactivity ‘The group 14 elements have four electrons in outermost shell ice the sum of the first four ionization enthalpies is very high, compounds in +4 oxidation state are generally covalent in nature, to participate in bonding. The relative stabilities of these two, oxidation states vary down the group. Carbon and silicon mostly show +4 oxidation state. Germanium forms stable compounds in +4 state and only few compounds in +2 state. Tin forms compounds in both oxidation states (Sn in +2 state is a reducing agent). Lead compounds in #2 state are stable and in +4 state are strong oxidising agents. In tetravalent state the number of electrons around the central atom in a molecule (e.g., carbon in CCl,) is eight. Being electron precise molecules, they are normally not expected to act as electron acceptor or electron donor species. Although carbon cannot exceed its covalence more than 4, other elements of the group can do so. It is because of the presence of d 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 , [GeCl,]”. [Sn(OH),|* exist where the hybridisation of the central atom is sp'd. @ Reactivity towards oxygen All members when heated in oxygen form oxides. There are mainly two types of oxides, Le., monoxide and dioxide of formula MO and CHEMISTRY MO, respectively Problem 11.5 Select the member(s) of group 14 that ( forms the most acidic dioxide, (11) Is commonly found in +2 oxidation state, (ii) used as semiconductor. Solution (carbon (ii) lead (ii) silicon and germanium. (ti) Reactivity towards water Carbon, silicon and germanium are not affected by water. Tin decomposes steam to form dioxide and dihydrogen gas. sn +2H,0 -% sno, +2H, Lead is unaffected by water, probably because ofa protective oxide film formation. iii) Reactivity towards halogen ‘These elements can form halides of formula MX, and MX, (where X= F, Cl, Br, Il. Except carbon, all other members react directly with halogen under suitable condition to make halides. Most of the MX, are covalent in nature. The central metal atom in these halides undergoes sp” hybridisation and the molecule {s tetrahedral in shape. Exceptions are SnF. and PbF,, which are ionic in nature. 2010.20 ‘THE p-BLOCK ELEMENTS Hydrolysis can be understood by taking the example of SiCl,, Itundergoes hydrolysis by initially accepting lone pair of electrons from water molecule in d orbitals of Si, finally Ieading to the formation of Si(OH), as shown 325, Carbon also has unique ability to form _px- prmultiple bonds with itselfand with other atoms of small size and high electronegativity. Few examples of multiple bonding are: GG] 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 because C—C bonds are very strong, Down the group the size increases and electronegativity decreases, and, thereby, tendency to show catenation decreases. This can be clearly seen from bond enthalpies values, The order of cateniation is C >> Si > Ge=\Sn. Lead does not show catenation. Silicic acid Bond Bond enthalpy / kJ mol * Problem 11.6 [Nc—c NO ~ 348 {SiF,? is known whereas [SICI,” not. | Si—Si Y 297 Give possible reasons. 260 Ss Se a3 ‘The main reasons are : () six large chloride ions cannot be accommodated around Si** due to limitation of its size. (i) interaction between Ione pair of chloride ion and Si“ is not very strong, 11.6 IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF CARBON Like first member of other groups, carbon also differs from rest of the members of its group. It is due to its smaller size, higher electronegativity, higher ionisation enthalpy and unavailability of d orbitals. In carbon, only s and p orbitals are available for bonding and, therefore, it can accommodate only four pairs of electrons around it. This would limit the maximum, covalence to four whereas other members can expand their covalence due to the presence of orbitals. Due to property of catenation and pa- px bond formation, carbon Is able to show allotropic forms. 11.7 ALLOTROPES OF CARBON Carbon exhibits many allotropic forms; both crystalline as well as amorphous. Diamond and graphite are two well-known crystalline forms of carbon. In 1985, third form of carbon known as fullerenes was discovered by [Link], [Link] and [Link]. For this discovery they were awarded the Nobel Prize in 1996, 11.7.1 Diamond 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 2010.20 154 pm Fig. 11.3. The structure of diamond structure (Fig, 11.3) directional covalent bonds are present throughout the lattice. Problem 11.7 Solution Diamond has a three-dimensional network involving SECT =essonas) which are very difficult to break and, in turn 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 is 340 pm. Each layer is composed of planar hexagonal rings of carbon atoms. C—C bond length within the layer is 141.5 pm. Fi hexagonal ring undergoe: ‘The electrons are delocalised over the whole sheet. Electrons are mobile and, CHEMISTRY Fig 11.4 The structure 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 inan electric are in the presence of inert gases such as helium or argon. The sooty material formed by condensation of vapourised C" small molecules consists of mainly Cy 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. Ce, molecule has a shape like soccer ball and called Buckminsterfullerene (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 2010.20 ‘THE p-BLOCK ELEMENTS molecular orbitals, ‘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. Fig.11.5 The structure of Cy, Buckminster fullerene : Note that molecule has the ‘shape of @ soccer ball (football) ‘A,H’ of graphite is taken as zero. AH values of diamond and fullerene, ‘eo 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 burning hydrocarbons in a limited supply of air. Charcoal and coke are obtained by heating wood or coal respectively at high temperatures in the absence of air. 11.7.4 Uses of Carbon Graphite fibres embedded in plastic material form high strength, lightweight composites. ‘The composites are used in products such as tennis rackets, fishing rods, airerafts 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 327 filters to remove organic contaminators and in airconditioning system to control odour. Carbon black is used as black pigment in black 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 ma). 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{s)+0,(g) 4 201g) On small scale pure CO is prepared by dehydration of formic acid with concentrated H,S0, at 373 K HCOOH =aycts0,? H,0 + CO Water gas When air is used instead of steam, a mixture of CO and N, is produced, which is called producer gas. 2CIs) + On(g) + 4No(g)— 29 2c 01g) + 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. ‘This property of 2010.20 328 CO is used in the extraction of many metals from their oxides ores. Fe,O, (s)+3CO(g)—*+ 2Fe(s)+3C0, (g) Zn0(s) +CO(g)—4>Zn(s) + CO, (g) In CO molecule, there are one sigma and two x bonds between carbon and oxygen, Because of the presence of a lone pair on carbon, CO molecule acts as a donor and reacts with certain metals when heated to form metal carbonyl: 11.8.2 Carbon Dioxide It ts prepared by complete combustion of carbon and carbon containing fuels in excess. ofair. (s)+0,(¢) —4400,(@) CH,(g) + 20,(g)—* 50, (g) + 2H, 0(8), In the laboratory it is conveniently prepared by the action of dilute HClon calcium carbonate. CaCO,{s) + 2HCI (aq) + CaCl, (aq) + CO, (@) + H,00) On commercial scale it is obtained by heating limestone. Iisa colourless and odourless gas. Its low solubility in water makes it of immense bio- chemical and geo-chemical importance. With water, it forms carbonic acid, HCO, which is a weak dibasic acid and dissociates in two steps: H,CO,{aq) + H,0() = HCO, (aq) + H,0"(aq) HCO, (aq) + H,0() = co? 5 +H, nf Carbon dioxide, which is normally present to the extent of ~ 0.03 % by volume in the CHEMISTRY it ol the es atmosphere, is removed from known as photosynthesis. peor hy. a 600, +12H,0— gb Cothz0p* 60, + 6H,O By this process plants make food for themselves as well as for animals and human beings. Unlike CO, it is not poisonous. But the increase in combustion of fossil fuels and decomposition of limestone for cement manufacture in recent years seem to increase the CO, content of the atmosphere. This may lead to increase in green house effect and thus, raise the temperature of the atmosphere which might have serious consequences. Carbon dioxide can be obtained as a solid {n the form of dry ice by allowing the liquified CO, to expand rapidly. \d non-supporter fire extinguisher, In CO, molecule carbon atom undergoes sp hybridisation. Two sp hybridised orbitals of carbon atom overlap with two p orbitals of oxygen atoms to make two sigma bonds while other two electrons of carbon atom are involved. in +. et - 0:<>:6=C=6:<9:05C-6 Resonance structures of carbon dioxide 11.8.3 Silicon Dioxide, SiO, 95% of the earth’s crust is made up of silica and silicates. Silicon dioxide, commonly known, as silica, occurs in several crystallographic forms. Quartz, cristobalite and tridymite are some of the crystalline forms of silica, and they are interconvertable at suitable temperature, Silicon dioxide is a covalent, three-dimensional 2010.20 ‘THE p-BLOCK ELEMENTS network solid in which each silicon atom is covalently bonded in a tetrahedral manner to four oxygen atoms. Each oxygen atom in tun covalently bonded to another silicon atoms as shown in diagram (Fig 11.6). Each corner is shared with another tetrahedron. The entire crystal may be considered as giant molecule in which eight membered rings are formed with, alternate silicon and oxygen atoms. | | Passe see Q fo 67 7 oa i 1 oO oO oO oO i 9 9 ee | | | | Fig. 11.6 Three dimensional structure of SiO, Silica in its normal form is almost non- reactive because of very high Si—O bond enthalpy. It resists the attack by halogens, dihydrogen and most of the acids and metals, even at elevated temperatures. However, it is attacked by HF and NaOH. SiO, + 2NaOH — Na,SiO, +H,0 SiO, + 4HF + SIF, + 2H,0 Quartz is extensively used as a piezoelectric ‘material it has made possible to develop extremely accurate clocks, modern radio and television broadcasting and mobile radio communications. Silica gels used as a drying agent and asa support for chromatographic materials and catalysts. Kieselghur, an amorphous form of silica is used infiltration plants. 11.8.4 Silicones ‘They are a group of organosilicon polymers, which have (R,SIO} as a repeating unit. ‘The starting materials for the manufacture of silicones are alkyl or aryl substituted silicon chlorides, R,SiCl,,_,. where Ris alkyl or aryl group. When methyl chloride reacts with silicon in the presence of copper as a catalyst, at a temperature 573K various types of methyl 529 substituted chlorostlane of formula MeSiCl,, Me,SiCl,, Me,SiCl with small amount of Me,Si are formed. Hydrolysis of dimethyl- dichlorosilane, (CH,),SiCl, followed by condensation polymerisation yields straight chain polymers. Cu powder acucr +si SPPMES cuy,sict, 70K +211,0 (CH).S1OH), SiG cu, cu, cu, 1 I ! HO-Si- 0H + HO~ Si OH + HO-Si- oH I I I cH, cH, cH, -11,0 Polymerisation cH, \ CH, i j 0+ Si- 0+ Si- f I cu, /,cH, silicone The chain length of the polymer can be controlled by adding (CH,), SiCI which blocks the ends as shown below : cH, cH, | | nHO— Si— OH + HO— Si— CH, | | cH, cH, “H,0 | potmessaton cH, cH, | | OF Si— OF SiI—CH, | | CH, /y CH, Silicone 2010.20 330 |. They have wide applications. They are used as sealant, greases, electrical insulators and for water proofing of fabrics. Being biocompatible they are also used in surgical and cosmetic plants. Solution l Simple silicones consist of fa o} chains in which alkyl or phenyl groups ‘occupy the remaining bonding positions on each silicon. They are hydrophobic (water repellant) in nature. 11.8.5 Silicates A large number of silicates minerals exist in nature, Some of the examples are feldspar, zeolites, mica and asbestos. The basic structural unit of silicates is SiO,* (Fig.11.7) in which silicon atom is bonded to four oxygen atoms in tetrahedron fashion. In silicates either the discrete unit 1s present or a number of such units are joined together via corners by sharing 1,2.3 or 4 oxygen atoms per silicate units, When silicate units are linked together, they form chain, ring, sheet or three-dimensional structures. Negative charge on silicate structure is CHEMISTRY + Silicon © Oxygen (b) (a) Tetrahedral structure of $10! anion: () Representation of S10; unit Fig. 11.7 neutralised by positively charged metal ions, If all the four corners are shared with other tetrahedral units, three-dimensional network is formed. Two important man-made silicates are glass and cement. 11.8.6 Zeolites Ifaluminium atoms replace few silicon atoms {in three-dimensional network of silicon dioxide, overall structure known as aluminosilicate, acquires a negative charge. Cations such as Na'K’ or Ca balance the negative charge. Examples are feldspar and zeolites. Zeolites are widely used as a catalyst in petrochemical industries for cracking of hydrocarbons and isomerisation, e.g., ZSM-5 (A type of zeolite) used to convert alcohols directly into gasoline, Hydrated zeolites are used as ion exchangers {in softening of “hard” water. ‘SUMMARY P-Block of the periodic table is unique in terms of having. all pes of elements ~ metals, non-metals and metalloids. There are six groups of p-block elements in the periodic table numbering from 13 to 18, Their valence shell electronic configuration is ns’np!* (except for He). Differences in the inner eore of their electronic configuration greatly Influence their physical and chemical properties, As a consequence of this, a lot of varfation in properties among these elements is observed. In addition to the group oxidation State, these elements show other oxidation states differing from the total number of valence electrons by unit of two. While the group oxidation state Is the most stable for the lighter clements of the group, lower oxidation states become progressively more stable for the heavier elements. The combined effect of size and availability of d orbitals considerably 2010.20 ‘THE p-BLOCK ELEMENTS 331 tnttuences the abilty of these elements to form s-bonds. While the lighter elements form pe-pa bonds, the heavier ones form dn-pr or de-dn bonds. Absence of d orbital in Beer elements nits thelr mexinmum covalcnce to 4 whie| Heaven txceed this mt ‘Boron isa typical non-metal and the other members are metals. The avalablity of 3 valence electrons (2s'2p') for covalent bond formation using four orbitals (2s, 2p, 2p, and 2p) leads to the oo called electron deficiency in boron compounds, This deflency tasks them good electron acceptor and thus boron compound behave as Lewis actA, Bteetsaras|coralent mclecular corpourca with dinjaregen sa barance! tho eimeated Which is diborane, B,H,, Diborane contains two bridging hydrogen atoms betwezn two Boron atoms; these bridge bonds are considered to be three-centre two-electron bonds, ‘The Important compounds of boron with doxygen are borle aeld and borax. Borie acid, IGE yjusieiwent: mencbecic acid; tacts as'a Lewis ac by sccpting eectronaltae hydrouy on, Borax isa while erysalline slid of formula Na,[8,0,(0F0,) SHO. The boraz bead teat gives characteristic colours of transition metals ‘Aluminium exhibits +3 oxidation state. With heavier elements #1 oxidation state gals Fegreasiclystabllecd on going down the group. This la a consequence af ab pated inert pair effect. (Carbon isa fypeal non-metal forming covalent bonds employing &tNa ur valenee electrons (2s°2p") Ht shows the property of catenation, the ability to form chains or tings, not only with C-C single bonds but also with muitiple bonds (C=C or C=C), The tendeney to eatenetion decreases us C>>SbGe = Sn > Pb, Carbon provides one of the best examples of allotropy. Three important allouopes of carbon are diamond, graphite thd fullerenes, ‘The members of the carbon family mainly exhibit +4 and #2 exidation alesis in $4 eridation sipioe WE generdly coe naturel Tig bac to show #2 oxidation state increases among heavier elements. Lead in #2 state fs stable whereas in +4 oxidation state iis a strong oxidising agent. Carbon also exhibits negative buidaion states, I forms two lmpérian oxide: CO ana C0, Cevbon monoxide ls neutral Feerees| CO) is scat ta natecarbon mmngithe Tgving lone pale of cecal forme metal carbonyls. It 1s deadly poloonous due 16 higher stabilty ofits haemoglobin complex as compared to that of oxyhacmoglobin complex. Carbon dioxide as such is not torte: However tnereased content of CO, in atmosphere due to combustion of fosll fuels and decomposition of liestone ts feared)to cause increase n green house effect Ths, Pept iaesitieltcmperatire of thd azbeephere and camcs|oeiouiereiares Sica, slleates and sllicones are important class of compounds and find applications in industry and technology. EXERCISES 11.1 Discuss the pattern of variation in the oxidation states of () BtoT1 and W)C to Pb 11.2 How can you explain higher stability of BCI, as compared to TICl, ? 11.3 Why does boron triflouride behave as a Lewis acid ? 114 Consider the compounds, BCI, and CCI,. How will they behave with water ? Justify, 11.5 Is borie acid a protic acid ? Explain, 11.6 Explain what happens when boric acid is heated . 11.7 Describe the shapes of BF, and BH. Assign the hybridisation of boron in these species. 11.8 Write reactions to justify amphoteric nature of aluminium, 2010.20 332 n ul rt n u rt u rT rt n rt u L 10 u 12 13, 4 15 7 18 19 20 21 22 23 24 25 CHEMISTRY What are electron deficient compounds ? Are BCI, and SiCI, electron deficient species ? Explain. Write the resonance structures of COZand HCO; . What is the state of hybridisation of carbon in (a) COZ (b) diamond (6) graphite? Explain the difference in properties of diamond and graphite on the basis of their structures, Rationalise the given statements and give chemical reactions : + Lead{tt) chloride reacts with Cl, to give PbCI,. + Lead(IV) chloride is highly unstable towards heat. + Lead is known not to form an iodide, Pbl, ‘Suggest reasons why the B-F bond lengths in BF, (180 pm) and BI (143 pm) differ. If B-Cl bond has a dipole moment, explain why BCI, molecule has 2er0 dipole moment. Aluminium trifluoride is insoluble in anhydrous HF but dissolves on addition of NaF. Aluminium trifluoride precipitates out of the resulting solution when gaseous BF, is bubbled through. Give reasons. Suggest a reason as to why CO is poisonous. How is excessive content of CO, responsible for global warming ? Explain structures of diborane and borle actd. What happens when (a) Borax is heated strongly. (0) Borie acid fs added to water, (c) Aluminium is treated with dilute NaOH, (@) BF, is reacted with ammonia ? Explain the following reactions {a) Silicon is heated with methyl chloride at high temperature in the presence of copper: {(b) Silicon dioxide is treated with hydrogen Muoride: (6) CO is heated with 2n0; (@) Hydrated alumina is treated with aqueous NaOH solution. Give reasons (Cone. HNO, can be transported in aluminium container. (i) A mixture of dilute NaOH and aluminium pieces is used to open drain. (it) Graphite is used as lubricant. {iv} Diamond is used as an abrasive. (©) Aluminium alloys are used to make aircraft body. (vi) Aluminium utensils should not be kept in water overnight. (ii) Aluminium wire is used to make transmission cables, Explain why is there a phenomenal decrease in ionization enthalpy from carbon to silicon ? How would you explain the lower atomic radius of Ga as compared to Al ? What are allotropes? Sketch the structure of two allotropes of carbon namely diamond and graphite. What is the impact of structure on physical properties of two allotropes? 2010.20 ‘THE p-BLOCK ELEMENTS 11.26 (a) Classify following oxides as neutral, acidic, basic or amphoterte: CO. B,0,. Si0,, CO,, Al,0,, PbO,. 1,0, {b) Write suitable chemical equations to show their nature, 11.27 In some of the reactions thallium resembles aluminium, whereas in others it resembles with group I metals. Support this statement by giving some evidences, 11.28 When metal X is treated with sodium hydroxide, a white precipitate (A) 1s obtained, which is soluble in excess of NaOH to give soluble complex (B). ‘Compound (A) is soluble in dilute HCI to form compound (C). The compound (A) when heated strongly gives (D), which is used to extract metal. Identify 09, (A). (B), (C) and (D). Write suitable equations to support their identities. 11.29 What do you understand by (a) inert pair effect (b) allotropy and (c) catenation? 11.80 A certain salt X, gives the following results, (@ Its aqueous solution is alkaline to litmus. () It swells up to a glassy material Y on strong heating (iii) When cone. 1,80, is added to a hot solution of X,white crystal of an acid Z separates out Write equations for all the above reactions and identify X.Y and 2. 11.31 Write balanced equations for: @ BF,+LH (i) BH, +H,0 > (ui) NaH + BH, > (iv) HBO, 5 (W) Al # NaOH (vi) BH, +N, > 11.82, Give one method for industrial preparation and one for laboratory preparation of CO and CO, each. 11.33 An aqueous solution of borax is (@) neutral {b) amphoteric (6) basic (@) actate 11.54 Borie aetd is polymeric due to {a) its acidte nature (0) the presence of hydrogen bonds {c) its monobasic nature (@)_ its geometsy 11.38. The type of hybridisation of boron in diborane 1s (@) sp () sp* (a sp* (a) dsp" 11.86 Thermodynamically the most stable form of carbon is (a) diamond () graphite (6) fullerenes (@) coal 11.87 Elements of group 14 {a) exhibit oxidation state of +4 only (b) exhibit oxidation state of +2 and +4 (©) form M® and M* fons (@) form ME and M* ions 11.88 If the starting material for the manufacture of silicones is RSICI,, write the structure of the product formed. 2010.20 333

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