UNIT 11 THE p -BLOCK ELEMENTS 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 14 elements; • explain anomalous behaviour of boron and carbon; • describe allotropic forms of carbon; • 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. influence of d and f electrons in the inner core of the heavier In p-block elements the last electron enters the outermost p orbital. As we know that the number of p orbitals is three and, therefore, the maximum number of electrons that can 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, nitrogen, oxygen, fluorine and helium head the groups. Their valence 2 1-6shell 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 ionic radii, ionisation enthalpy, etc.) 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 is equal to the total number of valence electrons (i.e., the sum of the sand 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 occurrence of oxidation states two unit less than the group oxidation states are sometime attributed to the ‘inert pair effect’. Table 11.1 General Electronic Configuration and Oxidation States of p-Block Elements Group 13 14 15 16 17 18 General electronic configuration ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 ns2np6 (1s2 for He) First member of the group B C N O F He Group oxidationstate +3 +4 +5 +6 +7 +8 Other oxidation states +1 +2, – 4 +3, – 3 +4, +2, –2 +5, + 3, +1, –1 +6, +4, +2 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. It is interesting to note that the non-metals and metalloids 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 nonmetallic to metallic character brings diversity in the chemistry of these elements depending on the group to which they belong. In general, non-metals have higher ionisation 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 differences 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 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 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 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 3s23p n 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 ]– ]3–[BF4, aluminium gives [AlF6ion. 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 π bonds. The first member of a group differs from the heavier members in its ability to form pπ - pπ multiple bonds to itself ( e.g., C=C, C≡C, N≡N) and to other second row elements (e.g., C=O, C=N, C≡N, N=O). This type of π - bonding is not particularly strong for the heavier p-block elements. The heavier elements do form π bonds but this involves d orbitals (dπ – pπ or dπ –dπ ). As the d orbitals are of higher energy than the p orbitals, they contribute less to the overall stability of molecules than does pπ - pπ bonding of the second row elements. 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 : NO3– (three-coordination with π – bond involving one nitrogen p-orbital) and PO43− (four-coordination involving s, p and d orbitals contributing to the π – 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, (H3BO3), borax, Na2B4O7·10H2O, and kernite, Na2B4O7·4H2O. In India borax occurs in Puga Valley (Ladakh) 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 10B (19%) and 11B (81%). 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, Al2O3. 2H2O and cryolite, Na3AlF6 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. 11.1.1 Electronic Configuration The outer electronic configuration of these elements is ns 2 np 1. 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 d-electrons, and thallium has noble gas plus 14 f-electrons plus 10 d-electron 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 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 electronic configuration. 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. Consequently, the atomic radius of gallium (135 pm) is less than that of aluminium (143 pm). 11.1.3 Ionization Enthalpy The ionisation enthalpy values as expected from the general trends do not decrease smoothly down the group. The decrease from B to Al is associated with increase in size. The observed discontinuity in the ionisation enthalpy values between Al and Ga, and between In and Tl are due to inability of d-and f-electrons ,which have low screening effect, to compensate the increase in nuclear charge. The order of ionisation enthalpies, as expected, is ΔiH1<ΔiH2<ΔiH3. The sum of the first three ionisation enthalpies for each of the elements is very high. Effect of this will be apparent when you study their chemical properties. 11.1.4 Electronegativity Down the group, electronegativity first decreases from B to Al and then increases marginally (Table 11.2). This is because of the discrepancies in atomic size of the elements. 11.1.5 Physical Properties Boron is non-metallic in nature. It is extremely hard and black coloured solid. It exists in many allotropic forms. Due to very strong crystalline lattice, boron has unusually high melting point. Rest of the members are soft metals with low melting point and high electrical conductivity. It is worthwhile to note that gallium with unusually low melting point (303K), could exist in liquid state during summer. Its high boiling point (2676K) makes it a useful material for measuring high temperatures. Density of the elements increases down the group from boron to thallium. 11.1.6 Chemical Properties Oxidation state and trends in chemical reactivity Due to small size of boron, the sum of its first three ionization enthalpies is very high. This prevents it to form +3 ions and forces it to form only covalent compounds. But as we move from B to Al, the sum of the first three ionisation enthalpies of Al considerably decreases, and is therefore able to form Al3+ ions. In fact, aluminium is a highly electropositive metal. However, down the group, due to poor shielding effect of intervening d and f orbitals, the increased effective nuclear charge holds ns electrons tightly (responsible for inert pair effect) and thereby, restricting their participation in bonding. As a result of this, only p-orbital electron may be involved in bonding. In fact in Ga, In and Tl, both +1 and +3 oxidation states are observed. The relative stability of +1 oxidation state progressively increases for heavier elements: Al > Si > Ge ≈ Sn. Lead does not show catenation. Bond Bond enthalpy / kJ mol –1 C—C Si —Si Ge—Ge Sn—Sn 348 297 260 240 Due to property of catenation and pπ– pπ 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 H.W.Kroto, E.Smalley and R.F.Curl. 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 3 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 Fig. 11.3 The structure of diamond structure (Fig. 11.3) directional covalent bonds are present throughout the lattice. It is very difficult to break extended covalent bonding and, therefore, diamond is a hardest substance on the earth. It is used as an abrasive for sharpening hard tools, in making dyes 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 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. Each carbon atom in hexagonal ring undergoes sp 2 hybridisation and makes three sigma bonds with three neighbouring carbon atoms. Fourth electron forms a π bond. The electrons are delocalised over the whole sheet. Electrons are mobile and, Fig 11.4 The structure of graphite therefore, graphite conducts electricity along the sheet. Graphite cleaves easily between the layers and, therefore, it is 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 helium or argon. The sooty material formed by condensation of vapourised Cn small molecules consists of mainly C60 with smaller quantity of C70 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. C60 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 2 hybridisation. Each carbon atom forms three sigma bonds with other three carbon atoms. The remaining electron at each carbon is delocalised in molecular orbitals, which in turn give aromatic 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 C60, Buckminsterfullerene : Note that molecule has the shape of a soccer ball (football). It is very important to know that graphite is thermodynamically most stable allotrope of carbon and, therefore, Δf HV of graphite is taken as zero. Δf HV values of diamond and fullerene, C60 are 1.90 and 38.1 kJ mol–1, 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, 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 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 (1 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, CO2. 11.8.1 Carbon Monoxide Direct oxidation of C in limited supply of oxygen or air yields carbon monoxide. 2C(s) + O (g) 2 ⎯⎯⎯Δ→ 2CO(g) On small scale pure CO is prepared by dehydration of formic acid with concentrated H2SO4 at 373 K 373KHCOOH ⎯⎯⎯⎯⎯ H O + CO →conc.H SO 224 On commercial scale it is prepared by the passage of steam over hot coke. The mixture of CO and H2 thus produced is known as water gas or synthesis gas. 473 1273K Cs + HOg ⎯⎯⎯⎯⎯⎯⎯CO g + H−→ g() () () 2 ()2 Water gas When air is used instead of steam, a mixture of CO and N2 is produced, which is called producer gas. 1273K 2C(s) + O (g) + 4N (g) ⎯⎯⎯⎯⎯2CO(g) 22 → + 4N (g) 2 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 those of the alkali and alkaline earth metals, aluminium and a few transition metals. This property of CO is used in the extraction of many metals from their oxides ores. ()+3CO g() ⎯Δ⎯ 2Fe s +3CO () FeO s ⎯→ () g23 2 () () ⎯Δ⎯Zn s +CO2 () gZnO s+ CO g ⎯→ () In CO molecule, there are one sigma and two π bonds between carbon and oxygen, :C ≡ O: . 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 carbonyls. The highly poisonous nature of CO arises because of its ability to form a complex with haemoglobin, which is about 300 times more stable than the oxygen-haemoglobin complex. This prevents haemoglobin in the red blood corpuscles from carrying oxygen round the body and ultimately resulting in death. 11.8.2 Carbon Dioxide It is prepared by complete combustion of carbon and carbon containing fuels in excess of air. C(s) +O (g)⎯⎯→Δ⎯ CO (g) 22 4 + 2 ⎯⎯→CO (g) + 2CH (g) 2O (g) Δ⎯2 2H O(g) In the laboratory it is conveniently prepared by the action of dilute HCl on calcium carbonate. CaCO3(s) + 2HCl (aq) → CaCl2 (aq) + CO2 (g) + H2O(l) On commercial scale it is obtained by heating limestone. It is a colourless and odourless gas. Its low solubility in water makes it of immense biochemical and geo-chemical importance. With water, it forms carbonic acid, H2CO3 which is a weak dibasic acid and dissociates in two steps: O+H2CO3(aq) + H2O(l) HCO3–(aq) + H3(aq) – 2–O+HCO3 (aq) + H2O(l) CO3 (aq) + H3(aq) H2CO3/HCO3– buffer system helps to maintain pH of blood between 7.26 to 7.42. Being acidic in nature, it combines with alkalies to form metal carbonates. Carbon dioxide, which is normally present to the extent of ~ 0.03 % by volume in the atmosphere, is removed from it by the process known as photosynthesis. It is the process by which green plants convert atmospheric CO2 into carbohydrates such as glucose. The overall chemical change can be expressed as: hν6CO +12H O ⎯⎯⎯⎯⎯⎯→CH O+ 6O 2 2 612 6 2Chlorphyll + 6H O 2 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 CO2 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 in the form of dry ice by allowing the liquified CO2 to expand rapidly. Dry ice is used as a refrigerant for ice-cream and frozen food. Gaseous CO2 is extensively used to carbonate soft drinks. Being heavy and non-supporter of combustion it is used as fire extinguisher. A substantial amount of CO2 is used to manufacture urea. In CO2 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 pπ– pπ bonding with oxygen atom. This results in its linear shape [with both C–O bonds of equal length (115 pm)] with no dipole moment. The resonance structures are shown below: Resonance structures of carbon dioxide 11.8.3 Silicon Dioxide, SiO2 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 network solid in which each silicon atom is covalently bonded in a tetrahedral manner to four oxygen atoms. Each oxygen atom in turn 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. Fig. 11.6 Three dimensional structure of SiO2 Silica in its normal form is almost nonreactive 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. SiO2 + 2NaOH → Na2SiO3 + H2O SiO2 + 4HF → SiF4 + 2H2O 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 gel is used as a drying agent and as a support for chromatographic materials and catalysts. Kieselghur, an amorphous form of silica is used in filtration plants. 11.8.4 Silicones They are a group of organosilicon polymers, which have (R2SiO) as a repeating unit. The starting materials for the manufacture of silicones are alkyl or aryl substituted silicon chlorides, R, where R is alkyl or arylnSiCl(4–n)group. When methyl chloride reacts with silicon in the presence of copper as a catalyst at a temperature 573K various types of methyl substituted chlorosilane of formula MeSiCl3, Me2SiCl2, Me3SiCl with small amount of Me4Si are formed. Hydrolysis of dimethyldichlorosilane, (CH3)2SiCl2 followed by condensation polymerisation yields straight chain polymers. The chain length of the polymer can be controlled by adding (CH3)3SiCl which blocks the ends as shown below : Silicones being surrounded by non-polar alkyl groups are water repelling in nature. They have in general high thermal stability, high dielectric strength and resistance to oxidation and chemicals. 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. 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 SiO44– (Fig.11.7) in which silicon atom is bonded to four oxygen atoms in tetrahedron fashion. In silicates either the discrete unit is 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 (a) (b) Fig. 11.7 (a) Tetrahedral structure of SiO44– anion; (b) Representation of SiO44–unit 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 If aluminium 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 Ca2+ 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. influences the ability of these elements to form π-bonds. While the lighter elements form pπ–pπbonds, the heavier ones form dπ–pπor dπ–dπbonds. Absence of d orbital in second period elements limits their maximum covalence to 4 while heavier ones can exceed this limit. Boron is a typical non-metal and the other members are metals. The availability of 3 valence electrons (2s 22p 1) for covalent bond formation using four orbitals (2s, 2px, 2py and 2pz) leads to the so called electron deficiency in boron compounds. This deficiency makes them good electron acceptor and thus boron compounds behave as Lewis acids. Boron forms covalent molecular compounds with dihydrogen as boranes, the simplest of which is diborane, B2H6. Diborane contains two bridging hydrogen atoms between two boron atoms; these bridge bonds are considered to be three-centre two-electron bonds. The important compounds of boron with dioxygen are boric acid and borax. Boric acid, B(OH)3 is a weak monobasic acid; it acts as a Lewis acid by accepting electrons from hydroxyl ion. Borax is a white crystalline solid of formula Na[BO(OH)]·8HO. The borax24542bead test gives characteristic colours of transition metals. Aluminium exhibits +3 oxidation state. With heavier elements +1 oxidation state gets progressively stabilised on going down the group. This is a consequence of the so called inert pair effect. Carbon is a typical non-metal forming covalent bonds employing all its four valence electrons (2s 22p 2). It shows the property of catenation, the ability to form chains or rings, not only with C–C single bonds but also with multiple bonds (C=C or C≡C). The tendency to catenation decreases as C>>Si>Ge ~ Sn > Pb. Carbon provides one of the best examples of allotropy. Three important allotropes of carbon are diamond, graphite and fullerenes. The members of the carbon family mainly exhibit +4 and +2 oxidation states; compouds in +4 oxidation states are generally covalent in nature. The tendency to show +2 oxidation state increases among heavier elements. Lead in +2 state is stable whereas in +4 oxidation state it is a strong oxidising agent. Carbon also exhibits negative oxidation states. It forms two important oxides: CO and CO2. Carbon monoxide is neutral whereas CO2 is acidic in nature. Carbon monoxide having lone pair of electrons on C forms metal carbonyls. It is deadly poisonous due to higher stability of its haemoglobin complex as compared to that of oxyhaemoglobin complex. Carbon dioxide as such is not toxic. However, increased content of CO2 in atmosphere due to combustion of fossil fuels and decomposition of limestone is feared to cause increase in ‘green house effect’. This, in turn, raises the temperature of the atmosphere and causes serious complications. Silica, silicates and silicones are important class of compounds and find applications in industry and technology. 11.1 Discuss the pattern of variation in the oxidation states of (i) B to Tl and (ii) C to Pb. 11.2 How can you explain higher stability of BCl3 as compared to TlCl3 ? 11.3 Why does boron triflouride behave as a Lewis acid ? 11.4 Consider the compounds, BCl3 and CCl4. How will they behave with water ? Justify. 11.5 Is boric acid a protic acid ? Explain. 11.6 Explain what happens when boric acid is heated . 11.7 Describe the shapes of BF3 and BH4 –. Assign the hybridisation of boron in these species. 11.8 Write reactions to justify amphoteric nature of aluminium. 11.9 What are electron deficient compounds ? Are BCl3 and SiCl4 electron deficient species ? Explain. 11.10 Write the resonance structures of CO32–and HCO3– . 11.11 What is the state of hybridisation of carbon in (a) CO32– (b) diamond (c) graphite? 11.12 Explain the difference in properties of diamond and graphite on the basis of their structures. 11.13 Rationalise the given statements and give chemical reactions : • Lead(II) chloride reacts with Cl2 to give PbCl4. • Lead(IV) chloride is highly unstable towards heat. • Lead is known not to form an iodide, PbI4. 11.14 Suggest reasons why the B–F bond lengths in BF3 (130 pm) and BF4– (143 pm) differ. 11.15 If B–Cl bond has a dipole moment, explain why BCl3 molecule has zero dipole moment. 11.16 Aluminium trifluoride is insoluble in anhydrous HF but dissolves on addition of NaF. Aluminium trifluoride precipitates out of the resulting solution when gaseous BF3 is bubbled through. Give reasons. 11.17 Suggest a reason as to why CO is poisonous. 11.18 How is excessive content of CO2 responsible for global warming ? 11.19 Explain structures of diborane and boric acid. 11.20 What happens when (a) Borax is heated strongly, (b) Boric acid is added to water, (c) Aluminium is treated with dilute NaOH, (d) BF3 is reacted with ammonia ? 11.21 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 fluoride; (c) CO is heated with ZnO; (d) Hydrated alumina is treated with aqueous NaOH solution. 11.22 Give reasons : (i) Conc. HNO3 can be transported in aluminium container. (ii) A mixture of dilute NaOH and aluminium pieces is used to open drain. (iii) Graphite is used as lubricant. (iv) Diamond is used as an abrasive. (v) Aluminium alloys are used to make aircraft body. (vi) Aluminium utensils should not be kept in water overnight. (vii) Aluminium wire is used to make transmission cables. 11.23 Explain why is there a phenomenal decrease in ionization enthalpy from carbon to silicon ? 11.24 How would you explain the lower atomic radius of Ga as compared to Al ? 11.25 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? 11.26 (a) Classify following oxides as neutral, acidic, basic or amphoteric: CO, BO, SiO, CO, AlO, PbO, TlO23 2223223 (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) is obtained, which is soluble in excess of NaOH to give soluble complex (B). Compound (A) is soluble in dilute HCl to form compound (C). The compound (A) when heated strongly gives (D), which is used to extract metal. Identify (X), (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? 11.30 A certain salt X, gives the following results. (i) Its aqueous solution is alkaline to litmus. (ii) It swells up to a glassy material Y on strong heating. (iii) When conc. H2SO4 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 Z. 11.31 Write balanced equations for: (i) BF3 + LiH → (ii) B2H6 + H2O → (iii) NaH + B2H6 → Δ(iv) H3BO3 →⎯(v) Al + NaOH → (vi) B2H6 + NH3 → 11.32. Give one method for industrial preparation and one for laboratory preparation of CO and CO2 each. 11.33 An aqueous solution of borax is (a) neutral (b) amphoteric (c) basic (d) acidic 11.34 Boric acid is polymeric due to (a) its acidic nature (b) the presence of hydrogen bonds (c) its monobasic nature (d) its geometry 11.35 The type of hybridisation of boron in diborane is (a) sp (b) sp2 (c) sp3 (d) dsp2 11.36 Thermodynamically the most stable form of carbon is (a) diamond (b) graphite (c) fullerenes (d) coal 11.37 Elements of group 14 (a) exhibit oxidation state of +4 only (b) exhibit oxidation state of +2 and +4 (c) form M2– and M4+ ions M2+(d) form and M4+ ions 11.38 If the starting material for the manufacture of silicones is RSiCl3, write the structure of the product formed.

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