chmeistry-part-2-book

THE s-BLOCK ELEMENTS 313 There is a regular trend in the physical and chemical properties of the alkali metal with increasing atomic numbers. The atomic and ionic sizes increase and the ionization enthalpies decrease systematically down the group. Somewhat similar trends are observed among the properties of the alkaline earth metals. The first element in each of these groups, lithium in Group 1 and beryllium in Group 2 shows similarities in properties to the second member of the next group. Such similarities are termed as the ‘diagonal relationship’ in the periodic table. As such these elements are anomalous as far as their group characteristics are concerned. The alkali metals are silvery white, soft and low melting. They are highly reactive. The compounds of alkali metals are predominantly ionic. Their oxides and hydroxides are soluble in water forming strong alkalies. Important compounds of sodium includes sodium carbonate, sodium chloride, sodium hydroxide and sodium hydrogencarbonate. Sodium hydroxide is manufactured by Castner-Kellner process and sodium carbonate by Solvay process. The chemistry of alkaline earth metals is very much like that of the alkali metals. However, some differences arise because of reduced atomic and ionic sizes and increased cationic charges in case of alkaline earth metals. Their oxides and hydroxides are less basic than the alkali metal oxides and hydroxides. Industrially important compounds of calcium include calcium oxide (lime), calcium hydroxide (slaked lime), calcium sulphate (Plaster of Paris), calcium carbonate (limestone) and cement. Portland cement is an important constructional material. It is manufactured by heating a pulverised mixture of limestone and clay in a rotary kiln. The clinker thus obtained is mixed with some gypsum (2-3%) to give a fine powder of cement. All these substances find variety of uses in different areas. Monovalent sodium and potassium ions and divalent magnesium and calcium ions are found in large proportions in biological fluids. These ions perform important biological functions such as maintenance of ion balance and nerve impulse conduction. EXERCISES 10.1 What are the common physical and chemical features of alkali metals ? 10.2 Discuss the general characteristics and gradation in properties of alkaline earth 10.3 metals. 10.4 10.5 Why are alkali metals not found in nature ? 10.6 Find out the oxidation state of sodium in Na2O2. Explain why is sodium less reactive than potassium. 10.7 Compare the alkali metals and alkaline earth metals with respect to (i) ionisation 10.8 enthalpy (ii) basicity of oxides and (iii) solubility of hydroxides. In what ways lithium shows similarities to magnesium in its chemical behaviour? 10.9 Explain why can alkali and alkaline earth metals not be obtained by chemical 10.10 reduction methods? Why are potassium and caesium, rather than lithium used in photoelectric cells? 10.11 When an alkali metal dissolves in liquid ammonia the solution can acquire different colours. Explain the reasons for this type of colour change. 10.12 Beryllium and magnesium do not give colour to flame whereas other alkaline 10.13 earth metals do so. Why ? 10.14 Discuss the various reactions that occur in the Solvay process. Potassium carbonate cannot be prepared by Solvay process. Why ? Why is Li2CO3 decomposed at a lower temperature whereas Na2CO3 at higher temperature? 2019-20

314 CHEMISTRY 10.15 Compare the solubility and thermal stability of the following compounds of the 10.16 alkali metals with those of the alkaline earth metals. (a) Nitrates (b) Carbonates 10.17 (c) Sulphates. 10.18 10.19 Starting with sodium chloride how would you proceed to prepare (i) sodium metal 10.20 (ii) sodium hydroxide (iii) sodium peroxide (iv) sodium carbonate ? 10.21 10.22 What happens when (i) magnesium is burnt in air (ii) quick lime is heated with 10.23 silica (iii) chlorine reacts with slaked lime (iv) calcium nitrate is heated ? 10.24 10.25 Describe two important uses of each of the following : (i) caustic soda (ii) sodium carbonate (iii) quicklime. 10.26 Draw the structure of (i) BeCl2 (vapour) (ii) BeCl2 (solid). 10.27 The hydroxides and carbonates of sodium and potassium are easily soluble in water while the corresponding salts of magnesium and calcium are sparingly 10.28 soluble in water. Explain. 10.29 Describe the importance of the following : (i) limestone (ii) cement (iii) plaster of paris. 10.30 10.31 Why are lithium salts commonly hydrated and those of the other alkali ions 10.32 usually anhydrous? Why is LiF almost insoluble in water whereas LiCl soluble not only in water but also in acetone ? Explain the significance of sodium, potassium, magnesium and calcium in biological fluids. What happens when (i) sodium metal is dropped in water ? (ii) sodium metal is heated in free supply of air ? (iii) sodium peroxide dissolves in water ? Comment on each of the following observations: (a) The mobilities of the alkali metal ions in aqueous solution are Li+ < Na+ < K+ < Rb+ < Cs+ (b) Lithium is the only alkali metal to form a nitride directly. (c) E for M2+ (aq) + 2e– → M(s) (where M = Ca, Sr or Ba) is nearly constant. State as to why (a) a solution of Na2CO3 is alkaline ? (b) alkali metals are prepared by electrolysis of their fused chlorides ? (c) sodium is found to be more useful than potassium ? Write balanced equations for reactions between (a) Na2O2 and water (b) KO2 and water (c) Na2O and CO2. How would you explain the following observations? (i) BeO is almost insoluble but BeSO4 is soluble in water, (ii) BaO is soluble but BaSO4 is insoluble in water, (iii) LiI is more soluble than KI in ethanol. Which of the alkali metal is having least melting point ? (a) Na (b) K (c) Rb (d) Cs Which one of the following alkali metals gives hydrated salts ? (a) Li (b) Na (c) K (d) Cs Which one of the alkaline earth metal carbonates is thermally the most stable ? (a) MgCO3 (b) CaCO3 (c) SrCO3 (d) BaCO3 2019-20

THE p-BLOCK ELEMENTS 315 UNIT 11 THE p-BLOCK ELEMENTS 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 After studying this unit, you will be In p-block elements the last electron enters the outermost able to p orbital. As we know that the number of p orbitals is three and, therefore, the maximum number of electrons that can • appreciate the general trends in the be accommodated in a set of p orbitals is six. Consequently chemistry of p-block elements; there are six groups of p–block elements in the periodic table numbering from 13 to 18. Boron, carbon, nitrogen, • describe the trends in physical and oxygen, fluorine and helium head the groups. Their valence chemical properties of group 13 and shell electronic configuration is ns2np1-6(except for He). 14 elements; The inner core of the electronic configuration may, however, differ. The difference in inner core of elements • explain anomalous behaviour of greatly influences their physical properties (such as atomic boron and carbon; and ionic radii, ionisation enthalpy, etc.) as well as chemical properties. Consequently, a lot of variation in properties of • describe allotropic forms of carbon; elements in a group of p-block is observed. The maximum oxidation state shown by a p-block element is equal to the • know the chemistry of some total number of valence electrons (i.e., the sum of the s- important compounds of boron, and p-electrons). Clearly, the number of possible oxidation carbon and silicon; states increases towards the right of the periodic table. In addition to this so called group oxidation state, p-block • list the important uses of group 13 elements may show other oxidation states which normally, and 14 elements and their but not necessarily, differ from the total number of valence compounds. 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’. 2019-20

316 CHEMISTRY Table 11.1 General Electronic Configuration and Oxidation States of p-Block Elements Group 13 14 15 16 17 18 ns2np1 ns2np4 ns2np5 General ns2np2 ns2np3 ns2np6 electronic (1s2 for He) configuration First member B CN O F He of the group Group +3 +4 +5 +6 +7 +8 oxidation state +1 +2, – 4 +3, – 3 +4, +2, –2 +5, + 3, +1, –1 +6, +4, +2 Other oxidation states The relative stabilities of these two oxidation The first member of p-block differs from the states – group oxidation state and two unit less remaining members of their corresponding than the group oxidation state – may vary from group in two major respects. First is the size group to group and will be discussed at and all other properties which depend on size. appropriate places. Thus, the lightest p-block elements show the same kind of differences as the lightest s-block It is interesting to note that the non-metals elements, lithium and beryllium. The second and metalloids exist only in the p-block of the important difference, which applies only to the periodic table. The non-metallic character of p-block elements, arises from the effect of d- elements decreases down the group. In fact the orbitals in the valence shell of heavier elements heaviest element in each p-block group is the (starting from the third period onwards) and most metallic in nature. This change from non- their lack in second period elements. The metallic to metallic character brings diversity second period elements of p-groups starting in the chemistry of these elements depending from boron are restricted to a maximum on the group to which they belong. covalence of four (using 2s and three 2p orbitals). In contrast, the third period elements In general, non-metals have higher ionisation of p-groups with the electronic configuration enthalpies and higher electronegativities than 3s23pn have the vacant 3d orbitals lying the metals. Hence, in contrast to metals which between the 3p and the 4s levels of energy. readily form cations, non-metals readily form Using these d-orbitals the third period anions. The compounds formed by highly elements can expand their covalence above reactive non-metals with highly reactive metals four. For example, while boron forms only are generally ionic because of large differences [BF4]–, aluminium gives [AlF6]3– ion. The in their electronegativities. On the other hand, presence of these d-orbitals influences the compounds formed between non-metals chemistry of the heavier elements in a number themselves are largely covalent in character of other ways. The combined effect of size and because of small differences in their availability of d orbitals considerably electronegativities. The change of non-metallic influences the ability of these elements to form to metallic character can be best illustrated by π bonds. The first member of a group differs the nature of oxides they form. The non-metal from the heavier members in its ability to form oxides are acidic or neutral whereas metal pπ - pπ multiple bonds to itself ( e.g., C=C, C≡C, oxides are basic in nature. 2019-20

THE p-BLOCK ELEMENTS 317 N≡N) and to other second row elements (e.g., isotope is 20 seconds. Due to these reasons its chemistry has not been established. C=O, C=N, C≡N, N=O). This type of π - bonding Nihonium is a synthetically prepared is not particularly strong for the heavier radioactive element. Here atomic, physical and chemical properties of elements of this group p-block elements. The heavier elements do form leaving nihonium are discussed below. π bonds but this involves d orbitals (dπ – pπ 11.1.1 Electronic Configuration or dπ –dπ ). As the d orbitals are of higher The outer electronic configuration of these energy than the p orbitals, they contribute less elements is ns2np1. A close look at the electronic configuration suggests that while to the overall stability of molecules than does boron and aluminium have noble gas core, gallium and indium have noble gas plus pπ - pπ bonding of the second row elements. 10 d-electrons, and thallium has noble gas plus 14 f- electrons plus 10 d-electron cores. However, the coordination number in species Thus, the electronic structures of these elements are more complex than for the first of heavier elements may be higher than for two groups of elements discussed in unit 10. This difference in electronic structures affects the first element in the same oxidation state. the other properties and consequently the chemistry of all the elements of this group. For example, in +5 oxidation state both N and P form oxoanions : NO3– (three-coordination 11.1.2 Atomic Radii with π – bond involving one nitrogen p-orbital) On moving down the group, for each successive and PO34− (four-coordination involving s, p and member one extra shell of electrons is added d orbitals contributing to the π – bond). In and, therefore, atomic radius is expected to increase. However, a deviation can be seen. this unit we will study the chemistry of group Atomic radius of Ga is less than that of Al. This can be understood from the variation in the 13 and 14 elements of the periodic table. inner core of the electronic configuration. The presence of additional 10 d-electrons offer 11.1 GROUP 13 ELEMENTS: THE BORON only poor screening effect (Unit 2) for the outer FAMILY electrons from the increased nuclear charge in gallium. Consequently, the atomic radius of This group elements show a wide variation in gallium (135 pm) is less than that of properties. Boron is a typical non-metal, aluminium (143 pm). aluminium is a metal but shows many chemical similarities to boron, and gallium, 11.1.3 Ionization Enthalpy indium, thallium and nihonium are almost exclusively metallic in character. The ionisation enthalpy values as expected from the general trends do not decrease Boron is a fairly rare element, mainly smoothly down the group. The decrease from occurs as orthoboric acid, (H3BO3), borax, B to Al is associated with increase in size. The Na2B4O7·10H2O, and kernite, Na2B4O7·4H2O. observed discontinuity in the ionisation In India borax occurs in Puga Valley (Ladakh) enthalpy values between Al and Ga, and and Sambhar Lake (Rajasthan). The between In and Tl are due to inability of d- and abundance of boron in earth crust is less than f-electrons ,which have low screening effect, to 0.0001% by mass. There are two isotopic compensate the increase in nuclear charge. forms of boron 10B (19%) and 11B (81%). Aluminium is the most abundant metal and The order of ionisation enthalpies, as the third most abundant element in the earth’s expected, is ∆iH1<∆iH2<∆iH3. The sum of the crust (8.3% by mass) after oxygen (45.5%) and first three ionisation enthalpies for each of the 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. Nihonium has symbol Nh, atomic number 113, atomic mass 286 g mol-1 and electronic configuration [Rn] 5f 14 6d10 7s2 7p2. So far it has been prepared in small amount and half life of its most stable 2019-20

318 CHEMISTRY elements is very high. Effect of this will be 11.1.6 Chemical Properties apparent when you study their chemical properties. Oxidation state and trends in chemical reactivity 11.1.4 Electronegativity Due to small size of boron, the sum of its first three ionization enthalpies is very high. This Down the group, electronegativity first prevents it to form +3 ions and forces it to form decreases from B to Al and then increases only covalent compounds. But as we move from marginally (Table 11.2). This is because of the B to Al, the sum of the first three ionisation discrepancies in atomic size of the elements. enthalpies of Al considerably decreases, and is therefore able to form Al3+ ions. In fact, 11.1.5 Physical Properties aluminium is a highly electropositive metal. However, down the group, due to poor Boron is non-metallic in nature. It is extremely shielding effect of intervening d and f orbitals, hard and black coloured solid. It exists in many the increased effective nuclear charge holds ns allotropic forms. Due to very strong crystalline electrons tightly (responsible for inert pair lattice, boron has unusually high melting point. effect) and thereby, restricting their Rest of the members are soft metals with low participation in bonding. As a result of this, melting point and high electrical conductivity. only p-orbital electron may be involved in It is worthwhile to note that gallium with bonding. In fact in Ga, In and Tl, both +1 and unusually low melting point (303 K), could +3 oxidation states are observed. The relative exist in liquid state during summer. Its high stability of +1 oxidation state progressively boiling point (2676 K) makes it a useful increases for heavier elements: Al<Ga<In<Tl. In material for measuring high temperatures. thallium +1 oxidation state is predominant Density of the elements increases down the group from boron to thallium. Table 11.2 Atomic and Physical Properties of Group 13 Elements Element Property Boron Aluminium Gallium Indium Thallium B Al Ga In Tl Atomic number 5 13 31 49 81 26.98 69.72 114.82 204.38 Atomic mass(g mol–1) 10.81 [Xe]4f145d106s26p1 Electronic [He]2s22p1 [Ne]3s23p1 [Ar]3d104s24p1 [Kr]4d105s25p1 170 Configuration 88.5 Atomic radius/pma (88) 143 135 167 150 Ionic radius (27) 53.5 62.0 80.0 589 1971 M3+/pmb 2877 1.8 Ionic radius - - 120 140 11.85 M+/pm 801 577 579 558 576 2427 1816 1979 1820 1730 Ionization ∆iH1 3659 2744 2962 2704 +1.26 enthalpy ∆∆iiHH32 2.0 1.5 1.6 1.7 –0.34 (kJ mol–1) Electronegativityc Density /g cm–3 2.35 2.70 5.90 7.31 at 298 K Melting point / K 2453 933 303 430 Boiling point / K 3923 2740 2676 2353 E/ V for (M3+/M) - –1.66 –0.34 E / V for (M+/M) - +0.55 –0.56 –0.18 -0.79(acid) –1.39(alkali) aMetallic radius, b 6-coordination, c Pauling scale, 2019-20

THE p-BLOCK ELEMENTS 319 whereas the +3 oxidation state is highly Solution oxidising in character. The compounds in +1 oxidation state, as expected from energy Standard electrode potential values for two considerations, are more ionic than those in half cell reactions suggest that aluminium +3 oxidation state. has high tendency to make Al3+(aq) ions, whereas Tl3+ is not only unstable in In trivalent state, the number of electrons solution but is a powerful oxidising agent around the central atom in a molecule also. Thus Tl+ is more stable in solution of the compounds of these elements than Tl3+. Aluminium being able to form (e.g., boron in BF3) will be only six. Such +3 ions easily, is more electropositive than electron deficient molecules have tendency thallium. to accept a pair of electrons to achieve stable electronic configuration and thus, behave as (i) Reactivity towards air Lewis acids. The tendency to behave as Lewis Boron is unreactive in crystalline form. acid decreases with the increase in the size Aluminium forms a very thin oxide layer on down the group. BCl3 easily accepts a lone pair the surface which protects the metal from of electrons from ammonia to form BCl3⋅NH3. further attack. Amorphous boron and aluminium metal on heating in air form B2O3 AlCl3 achieves stability by forming a dimer and Al2O3 respectively. With dinitrogen at high temperature they form nitrides. In trivalent state most of the compounds 2E (s) + 3O2 (g) ∆ → 2E2O3 (s) being covalent are hydrolysed in water. For 2E (s) + N2 (g) ∆ → 2EN (s) example, the trichlorides on hyrolysis in water (E = element) − form tetrahedral  M (OH )  species; the The nature of these oxides varies down the hybr 4 sp3. group. Boron trioxide is acidic and reacts with basic (metallic) oxides forming metal borates. idisation state of element M is Aluminium and gallium oxides are amphoteric and those of indium and thallium are basic in Aluminium chloride in acidified aqueous their properties. solution forms octahedral  Al (H2O)6 3+ ion. (ii) Reactivity towards acids and alkalies Boron does not react with acids and alkalies In this complex ion, the 3d orbitals of Al are even at moderate temperature; but aluminium dissolves in mineral acids and aqueous alkalies involved and the hybridisation state of Al is and thus shows amphoteric character. sp3d2. Aluminium dissolves in dilute HCl and liberates dihydrogen. Problem 11.1 2Al(s) + 6HCl (aq) → 2Al3+ (aq) + 6Cl– (aq) Standard electrode potential values, E for Al3+/Al is –1.66 V and that of Tl3+/Tl + 3H2 (g) However, concentrated nitric acid renders is +1.26 V. Predict about the formation of aluminium passive by forming a protective M3+ ion in solution and compare the oxide layer on the surface. electropositive character of the two Aluminium also reacts with aqueous alkali and liberates dihydrogen. metals. 2Al (s) + 2NaOH(aq) + 6H2O(l) ↓ 2 Na+ [Al(OH)4] –(aq) + 3H2(g) Sodium tetrahydroxoaluminate(III) 2019-20

320 CHEMISTRY (iii) Reactivity towards halogens the maximum covalence of boron cannot exceed 4. These elements react with halogens to form trihalides (except Tl I3). 11.3 SOME IMPORTANT COMPOUNDS OF 2E(s) + 3 X2 (g) → 2EX3 (s) (X = F, Cl, Br, I) BORON Problem 11.2 Some useful compounds of boron are borax, orthoboric acid and diborane. We will briefly White fumes appear around the bottle of study their chemistry. anhydrous aluminium chloride. Give reason. 11.3.1 Borax Solution It is the most important compound of boron. Anhydrous aluminium chloride is It is a white crystalline solid of formula partially hydrolysed with atmospheric moisture to liberate HCl gas. Moist HCl Na2B4O7⋅10H2O. In fact it contains the appears white in colour. tetranuclear units B4O5 (OH) 2− and correct 4 11.2 IMPORTANT TRENDS AND formula; therefore, is Na2[B4O5 (OH)4].8H2O. ANOMALOUS PROPERTIES OF Borax dissolves in water to give an alkaline BORON solution. Certain important trends can be observed Na2B4O7 + 7H2O → 2NaOH + 4H3BO3 Orthoboric acid in the chemical behaviour of group On heating, borax first loses water 13 elements. The tri-chlorides, bromides molecules and swells up. On further heating it turns into a transparent liquid, which solidifies and iodides of all these elements being into glass like material known as borax bead. covalent in nature are hydrolysed in water. OH)4]– Species like tetrahedral [M( boron, and octahedral [M(H2O)6]3+, except in exist in aqueous medium. Na2B4O7.10H2O ∆ → Na2B4O7 ∆ → 2NaBO2 The monomeric trihalides, being electron Sodium + B2O3 deficient, are strong Lewis acids. Boron metaborate Boric trifluoride easily reacts with Lewis bases such as NH3 to complete octet around boron. anhydride F3B + :NH3 → F3B ← NH3 The metaborates of many transition metals It is due to the absence of d orbitals that have characteristic colours and, therefore, the maximum covalence of B is 4. Since the d orbitals are available with Al and other borax bead test can be used to identify them elements, the maximum covalence can be expected beyond 4. Most of the other metal in the laboratory. For example, when borax is halides (e.g., AlCl3) are dimerised through halogen bridging (e.g., Al2Cl6). The metal heated in a Bunsen burner flame with CoO on species completes its octet by accepting electrons from halogen in these halogen a loop of platinum wire, a blue coloured bridged molecules. Co(BO2)2 bead is formed. 11.3.2 Orthoboric acid Problem 11.3 Orthoboric acid, H3BO3 is a white crystalline Boron is unable to form BF63– ion. Explain. solid, with soapy touch. It is sparingly soluble Solution in water but highly soluble in hot water. It can Due to non-availability of d orbitals, boron is unable to expand its octet. Therefore, be prepared by acidifying an aqueous solution of borax. Na2B4O7 + 2HCl + 5H2O → 2NaCl + 4B(OH)3 It is also formed by the hydrolysis (reaction with water or dilute acid) of most boron compounds (halides, hydrides, etc.). It has a 2019-20

THE p-BLOCK ELEMENTS 321 layer structure in which planar BO3 units are 2NaBH4 + I2 → B2H6 + 2NaI + H2 joined by hydrogen bonds as shown in Diborane is produced on an industrial scale Fig. 11.1. by the reaction of BF3 with sodium hydride. Boric acid is a weak monobasic acid. It is 2BF3 +6NaH 450K→B2H6 +6NaF not a protonic acid but acts as a Lewis acid by accepting electrons from a hydroxyl ion: Diborane is a colourless, highly toxic gas with a b.p. of 180 K. Diborane catches fire B(OH)3 + 2HOH → [B(OH)4]– + H3O+ spontaneously upon exposure to air. It burns On heating, orthoboric acid above 370K in oxygen releasing an enormous amount of forms metaboric acid, HBO2 which on further energy. heating yields boric oxide, B2O3. H3BO3 ∆→ HBO2 ∆→ B2O3 B2H6 +3O2 → B2O3 + 3H2O; ∆c H = −1976 kJ mol−1 Fig. 11. 1 Structure of boric acid; the dotted lines represent hydrogen bonds Most of the higher boranes are also spontaneously flammable in air. Boranes are Problem 11.4 readily hydrolysed by water to give boric acid. Why is boric acid considered as a weak acid? B2H6(g) + 6H2O(l) → 2B(OH)3(aq) + 6H2(g) Solution Because it is not able to release H+ ions Diborane undergoes cleavage reactions on its own. It receives OH– ions from water molecule to complete its octet and in turn with Lewis bases(L) to give borane adducts, releases H+ ions. BH3⋅L 11.3.3 Diborane, B2H6 B2H6 + 2 NMe3 → 2BH3⋅NMe3 The simplest boron hydride known, is diborane. It is prepared by treating boron B2H6 + 2 CO → 2BH3⋅CO trifluoride with LiAlH4 in diethyl ether. Reaction of ammonia with diborane gives 4BF3 + 3 LiAlH4 → 2B2H6 + 3LiF + 3AlF3 A convenient laboratory method for the i[nBiHti2a(lNlyHB3)22H]+ 6.[2BNHH4]3– which is formulated as preparation of diborane involves the oxidation ; further heating gives of sodium borohydride with iodine. borazine, B3N3H6 known as “inorganic benzene” in view of its ring structure with alternate BH and NH groups. 3B2H6 +6NH3 →3[BH2(NH3 )2 ]+[BH4 ]– Heat→2B3N3H6 +12H2 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 plane, there are two bridging hydrogen atoms. The four terminal B-H bonds are regular two centre-two electron bonds while the two bridge (B-H-B) bonds are different and can be described in terms of three Fig.11.2(a) The structure of diborane, B H 26 2019-20

322 CHEMISTRY centre–two electron bonds shown in orthoboric acid is generally used as a mild Fig.11.2 (b). antiseptic. Boron also forms a series of hydridoborates; Aluminium is a bright silvery-white metal, the most important one is the tetrahedral [BH4]– with high tensile strength. It has a high ion. Tetrahydridoborates of several metals are electrical and thermal conductivity. On a weight-to-weight basis, the electrical known. Lithium and sodium tetra- conductivity of aluminium is twice that of copper. Aluminium is used extensively in hydridoborates, also known as borohydrides, industry and everyday life. It forms alloys with Cu, Mn, Mg, Si and Zn. Aluminium and its are prepared by the reaction of metal hydrides alloys can be given shapes of pipe, tubes, rods, wires, plates or foils and, therefore, find with B2H6 in diethyl ether. (M = Li or Na) uses in packing, utensil making, 2MH + B2H6 → 2 M+ [BH4]– construction, aeroplane and transportation industry. The use of aluminium and its Fig.11.2(b) Bonding in diborane. Each B atom compounds for domestic purposes is now uses sp3 hybrids for bonding. Out reduced considerably because of their toxic of the four sp3 hybrids on each B nature. atom, one is without an electron shown in broken lines. The terminal 11.5 GROUP 14 ELEMENTS: THE CARBON B-H bonds are normal 2-centre-2- FAMILY electron bonds but the two bridge bonds are 3-centre-2-electron bonds. Carbon, silicon, germanium, tin lead and The 3-centre-2-electron bridge bonds flerovium are the members of group 14. Carbon are also referred to as banana bonds. is the seventeenth most abundant element by mass in the earth’s crust. It is widely Both LiBH4 and NaBH4 are used as distributed in nature in free as well as in the reducing agents in organic synthesis. They are combined state. In elemental state it is available useful starting materials for preparing other as coal, graphite and diamond; however, in metal borohydrides. combined state it is present as metal carbonates, hydrocarbons and carbon dioxide 11.4 USES OF BORON AND ALUMINIUM gas (0.03%) in air. One can emphatically say AND THEIR COMPOUNDS that carbon is the most versatile element in the world. Its combination with other elements Boron being extremely hard refractory solid of such as dihydrogen, dioxygen, chlorine and high melting point, low density and very low sulphur provides an astonishing array of electrical conductivity, finds many materials ranging from living tissues to drugs applications. Boron fibres are used in making and plastics. Organic chemistry is devoted to bullet-proof vest and light composite material carbon containing compounds. It is an for aircraft. The boron-10 (10B) isotope has high essential constituent of all living organisms. ability to absorb neutrons and, therefore, Naturally occurring carbon contains two stable metal borides are used in nuclear industry as isotopes:12C and 13C. In addition to these, third protective shields and control rods. The main isotope, 14C is also present. It is a radioactive industrial application of borax and boric acid isotope with half-life 5770 years and used for is in the manufacture of heat resistant glasses radiocarbon dating. Silicon is the second (e.g., Pyrex), glass-wool and fibreglass. Borax (27.7 % by mass) most abundant element on is also used as a flux for soldering metals, for the earth’s crust and is present in nature in heat, scratch and stain resistant glazed coating the form of silica and silicates. Silicon is a very to earthenwares and as constituent of important component of ceramics, glass and medicinal soaps. An aqueous solution of cement. Germanium exists only in traces. Tin 2019-20

THE p-BLOCK ELEMENTS 323 occurs mainly as cassiterite, SnO2 and lead as 11.5.2 Covalent Radius galena, PbS. Flerovium is synthetically prepared radioactive element There is a considerable increase in covalent radius from C to Si, thereafter from Si to Pb a Ultrapure form of germanium and silicon small increase in radius is observed. This is are used to make transistors and due to the presence of completely filled d and f semiconductor devices. orbitals in heavier members. Symbol of Flerovium is Fl. It has atomic 11.5.3 Ionization Enthalpy number 114, atomic mass 289 gmol-1 and electronic configuration [Rn] 5f 14 6d107s2 7p2. The first ionization enthalpy of group 14 It has been prepared only in small amount. members is higher than the corresponding Its half life is short and its chemistry has not members of group 13. The influence of inner been established yet. The important atomic core electrons is visible here also. In general the and physical properties along with their ionisation enthalpy decreases down the group. electronic configuration of the elements of Small decrease in ∆iH from Si to Ge to Sn and group 14 leaving flerovium are given in slight increase in ∆iH from Sn to Pb is the Table 11.3. Some of the atomic, physical and consequence of poor shielding effect of chemical properties are discussed below: intervening d and f orbitals and increase in size of the atom. 11.5.1 Electronic Configuration 11.5.4 Electronegativity The valence shell electronic configuration of these elements is ns2np2. The inner core of the Due to small size, the elements of this group electronic configuration of elements in this are slightly more electronegative than group group also differs. 13 elements. The electronegativity values for elements from Si to Pb are almost the same. 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–1) 12.01 28.09 [He]2s22p2 [Ne]3s23p2 72.60 118.71 207.2 [Ar]3d104s24p2 Electronic 77 118 [Kr]4d105s2 5p2 [Xe]4f145d106s26p2 configuration – 40 Covalent radius/pma – – 122 140 146 Ionic radius M4+/pmb 53 69 78 1086 786 73 Ionic radius M2+/pmb 2352 1577 118 119 4620 3228 761 708 715 Ionization ∆iH1 6220 4354 1537 1411 1450 enthalpy/ ∆iH2 3300 2942 3081 kJ mol–1 ∆iH3 2.5 1.8 4409 3929 4082 ∆iH4 3.51e 2.34 1.8 1.8 1.9 Electronegativityc 5.32 7.26f 11.34 Densityd/g cm–3 Melting point/K 4373 1693 1218 505 600 Boiling point/K – 3550 3123 2896 2024 Electrical resistivity/ 1014–1016 50 50 10–5 2 × 10–5 ohm cm (293 K) afor M IV oxidation state; b 6–coordination; c Pauling scale; d 293 K; e for diamond; for graphite, density is 2.22; fβ-form (stable at room temperature) 2019-20

324 CHEMISTRY 11.5.5 Physical Properties MO2 respectively. SiO only exists at high temperature. Oxides in higher oxidation states All members of group14 are solids. Carbon and of elements are generally more acidic than silicon are non-metals, germanium is a metalloid, those in lower oxidation states. The dioxides whereas tin and lead are soft metals with low — CO2, SiO2 and GeO2 are acidic, whereas melting points. Melting points and boiling points SnO2 and PbO2 are amphoteric in nature. of group 14 elements are much higher than those Among monoxides, CO is neutral, GeO is of corresponding elements of group 13. distinctly acidic whereas SnO and PbO are amphoteric. 11.5.6 Chemical Properties Problem 11.5 Oxidation states and trends in chemical Select the member(s) of group 14 that reactivity (i) forms the most acidic dioxide, (ii) is commonly found in +2 oxidation state, The group 14 elements have four electrons in (iii) used as semiconductor. outermost shell. The common oxidation states Solution exhibited by these elements are +4 and +2. (i) carbon (ii) lead (iii) silicon and germanium Carbon also exhibits negative oxidation states. (ii) Reactivity towards water Since the sum of the first four ionization Carbon, silicon and germanium are not enthalpies is very high, compounds in +4 affected by water. Tin decomposes steam to form dioxide and dihydrogen gas. oxidation state are generally covalent in nature. Sn + 2H2O →∆ SnO2 + 2H2 In heavier members the tendency to show +2 Lead is unaffected by water, probably oxidation state increases in the sequence because of a protective oxide film formation. Ge<Sn<Pb. It is due to the inability of ns2 (iii) Reactivity towards halogen electrons of valence shell to participate in These elements can form halides of formula bonding. The relative stabilities of these two MX2 and MX4 (where X = F, Cl, Br, I). Except carbon, all other members react directly with oxidation states vary down the group. Carbon halogen under suitable condition to make halides. Most of the MX4 are covalent in nature. and silicon mostly show +4 oxidation state. The central metal atom in these halides undergoes sp3 hybridisation and the molecule Germanium forms stable compounds in +4 is tetrahedral in shape. Exceptions are SnF4 and PbF4, which are ionic in nature. PbI4 does state and only few compounds in +2 state. Tin not exist because Pb—I bond initially formed during the reaction does not release enough forms compounds in both oxidation states (Sn energy to unpair 6s2 electrons and excite one of them to higher orbital to have four unpaired in +2 state is a reducing agent). Lead electrons around lead atom. Heavier members Ge to Pb are able to make halides of formula compounds in +2 state are stable and in +4 MX2. Stability of dihalides increases down the group. Considering the thermal and chemical state are strong oxidising agents. In tetravalent stability, GeX4 is more stable than GeX2, whereas PbX2 is more than PbX4. Except CCl4, state the number of electrons around the other tetrachlorides are easily hydrolysed central atom in a molecule (e.g., carbon in CCl4) 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 like, SiF62–, [GeCl6]2–, example, the species the hybridisation of the [cSenn(tOraHl )a6]t2o–mexiisstswp3hde2r.e (i) Reactivity towards oxygen All members when heated in oxygen form oxides. There are mainly two types of oxides, i.e., monoxide and dioxide of formula MO and 2019-20

THE p-BLOCK ELEMENTS 325 by water because the central atom can Carbon also has unique ability to form accommodate the lone pair of electrons from pπ– pπ multiple bonds with itself and with other oxygen atom of water molecule in d orbital. atoms of small size and high electronegativity. Few examples of multiple bonding are: C=C, Hydrolysis can be understood by taking C ≡ C, C = O, C = S, and C ≡ N. Heavier elements the example of SiCl4. It undergoes hydrolysis do not form pπ– pπ bonds because their atomic by initially accepting lone pair of electrons orbitals are too large and diffuse to have from water molecule in d orbitals of Si, finally effective overlapping. leading to the formation of Si(OH)4 as shown below : Carbon atoms have the tendency to link with one another through covalent bonds to Problem 11. 6 form chains and rings. This property is called [SiF6]2– is known whereas [SiCl6]2– not. catenation. This is because C—C bonds are Give possible reasons. very strong. Down the group the size increases Solution and electronegativity decreases, and, thereby, The main reasons are : tendency to show catenation decreases. This (i) six large chloride ions cannot be can be clearly seen from bond enthalpies accommodated around Si4+ due to values. The order of catenation is C > > Si > limitation of its size. Ge ≈ Sn. Lead does not show catenation. (ii) interaction between lone pair of chloride ion and Si4+ is not very strong. Bond Bond enthalpy / kJ mol –1 11.6 IMPORTANT TRENDS AND C—C 348 ANOMALOUS BEHAVIOUR OF Si —Si 297 CARBON Ge—Ge 260 Sn—Sn 240 Like first member of other groups, carbon also differs from rest of the members of its Due to property of catenation and pπ– pπ group. It is due to its smaller size, higher bond formation, carbon is able to show electronegativity, higher ionisation enthalpy allotropic forms. and unavailability of d orbitals. 11.7 ALLOTROPES OF CARBON In carbon, only s and p orbitals are available for bonding and, therefore, it can Carbon exhibits many allotropic forms; both accommodate only four pairs of electrons crystalline as well as amorphous. Diamond around it. This would limit the maximum and graphite are two well-known crystalline covalence to four whereas other members can forms of carbon. In 1985, third form of carbon expand their covalence due to the presence of known as fullerenes was discovered by d orbitals. 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 sp3 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 2019-20

326 CHEMISTRY Fig. 11.3 The structure of diamond Fig 11.4 The structure of graphite structure (Fig. 11.3) directional covalent bonds therefore, graphite conducts electricity along are present throughout the lattice. the sheet. Graphite cleaves easily between the layers and, therefore, it is very soft and slippery. It is very difficult to break extended covalent For this reason graphite is used as a dry bonding and, therefore, diamond is a hardest lubricant in machines running at high substance on the earth. It is used as an temperature, where oil cannot be used as a abrasive for sharpening hard tools, in making lubricant. dyes and in the manufacture of tungsten filaments for electric light bulbs. 11.7.3 Fullerenes Problem 11.7 Fullerenes are made by the heating of graphite in an electric arc in the presence of inert gases Diamond is covalent, yet it has high such as helium or argon. The sooty material melting point. Why ? formed by condensation of vapourised Cn small molecules consists of mainly C60 with smaller Solution quantity of C70 and traces of fullerenes consisting of even number of carbon atoms up Diamond has a three-dimensional to 350 or above. Fullerenes are the only pure network involving strong C—C bonds, form of carbon because they have smooth which are very difficult to break and, in structure without having ‘dangling’ bonds. turn has high melting point. Fullerenes are cage like molecules. C60 molecule has a shape like soccer ball and 11.7.2 Graphite called Buckminsterfullerene (Fig. 11.5). Graphite has layered structure (Fig.11.4). It contains twenty six- membered rings and Layers are held by van der Waals forces and twelve five-membered rings. A six membered distance between two layers is 340 pm. Each ring is fused with six or five membered rings layer is composed of planar hexagonal rings but a five membered ring can only fuse with of carbon atoms. C—C bond length within the six membered rings. All the carbon atoms are layer is 141.5 pm. Each carbon atom in equal and they undergo sp2 hybridisation. hexagonal ring undergoes sp2 hybridisation Each carbon atom forms three sigma bonds and makes three sigma bonds with three with other three carbon atoms. The remaining neighbouring carbon atoms. Fourth electron electron at each carbon is delocalised in forms a π bond. The electrons are delocalised over the whole sheet. Electrons are mobile and, 2019-20

THE p-BLOCK ELEMENTS 327 molecular orbitals, which in turn give aromatic filters to remove organic contaminators and in character to molecule. This ball shaped airconditioning system to control odour. molecule has 60 vertices and each one is Carbon black is used as black pigment in occupied by one carbon atom and it also black ink and as filler in automobile tyres. Coke contains both single and double bonds with is used as a fuel and largely as a reducing C–C distances of 143.5 pm and 138.3 pm agent in metallurgy. Diamond is a precious respectively. Spherical fullerenes are also called stone and used in jewellery. It is measured in bucky balls in short. carats (1 carat = 200 mg). Fig.11.5 The structure of C60, Buckminster- 11.8 SOME IMPORTANT COMPOUNDS OF fullerene : Note that molecule has the CARBON AND SILICON shape of a soccer ball (football). Oxides of Carbon It is very important to know that graphite Two important oxides of carbon are carbon is thermodynamically most stable allotrope of monoxide, CO and carbon dioxide, CO2. acCas6r0zbeaorrnoe.a1∆n.f9dH0,tahvneardleuf3eo8sre.o1,f∆kdfJiHammoooflng–1dr,aarpenhsdiptfeeucilstleitvraeeklnyee.n, 11.8.1 Carbon Monoxide Other forms of elemental carbon like carbon Direct oxidation of C in limited supply of black, coke, and charcoal are all impure forms oxygen or air yields carbon monoxide. of graphite or fullerenes. Carbon black is obtained by burning hydrocarbons in a limited 2C(s) + O2(g) ∆→ 2CO(g) supply of air. Charcoal and coke are obtained On small scale pure CO is prepared by by heating wood or coal respectively at high dehydration of formic acid with concentrated temperatures in the absence of air. H2SO4 at 373 K 11.7.4 Uses of Carbon Graphite fibres embedded in plastic material HCOOH con3c7.H32KSO→4 H2O + CO form high strength, lightweight composites. The composites are used in products such as On commercial scale it is prepared by the tennis rackets, fishing rods, aircrafts and passage of steam over hot coke. The mixture canoes. Being good conductor, graphite is used of CO and H2 thus produced is known as water for electrodes in batteries and industrial gas or synthesis gas. electrolysis. Crucibles made from graphite are inert to dilute acids and alkalies. Being highly C (s) + H2O (g) 473−1273K → CO (g) + H2 (g) porous, activated charcoal is used in adsorbing poisonous gases; also used in water Water gas When air is used instead of steam, a mixture of CO and N2 is produced, which is called producer gas. 2C(s) + O2(g) + 4N2(g) 1273K → 2CO(g) + 4N2(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 those of the alkali and alkaline earth metals, aluminium and a few transition metals. This property of 2019-20

328 CHEMISTRY CO is used in the extraction of many metals atmosphere, is removed from it by the process from their oxides ores. known as photosynthesis. It is the process Fe2O3 (s) + 3CO (g) ∆→ 2Fe (s) + 3CO2 (g) ZnO (s) + CO (g) ∆→ Zn (s) + CO2 (g) by which green plants convert atmospheric In CO molecule, there are one sigma and CO2 into carbohydrates such as glucose. The two π bonds between carbon and oxygen, overall chemical change can be expressed as: :C ≡ O: . Because of the presence of a lone pair on carbon, CO molecule acts as a donor and 6CO2 +12H2O hν → C6H12O6 + 6O2 reacts with certain metals when heated to form metal carbonyls. The highly poisonous Chlorophyll nature of CO arises because of its ability to form a complex with haemoglobin, which + 6H2O is about 300 times more stable than the oxygen-haemoglobin complex. This prevents By this process plants make food for haemoglobin in the red blood corpuscles from themselves as well as for animals and human carrying oxygen round the body and ultimately beings. Unlike CO, it is not poisonous. But the resulting in death. increase in combustion of fossil fuels and decomposition of limestone for cement 11.8.2 Carbon Dioxide manufacture in recent years seem to increase the CO2 content of the atmosphere. This may It is prepared by complete combustion of lead to increase in green house effect and carbon and carbon containing fuels in excess thus, raise the temperature of the atmosphere of air. which might have serious consequences. C(s) + O2(g) ∆→ CO2 (g) Carbon dioxide can be obtained as a solid CH4(g) + 2O2 (g) ∆→ CO2(g) + 2H2O(g) in the form of dry ice by allowing the liquified CO2 to expand rapidly. Dry ice is used as a In the laboratory it is conveniently refrigerant for ice-cream and frozen food. prepared by the action of dilute HCl on calcium carbonate. Gaseous CO2 is extensively used to carbonate soft drinks. Being heavy and non-supporter CaCO3(s) + 2HCl (aq) → CaCl2 (aq) + CO2 (g) + H2O(l) of combustion it is used as fire extinguisher. A On commercial scale it is obtained by substantial amount of CO2 is used to heating limestone. manufacture urea. It is a colourless and odourless gas. Its low In CO2 molecule carbon atom undergoes solubility in water makes it of immense bio- sp hybridisation. Two sp hybridised orbitals chemical and geo-chemical importance. With water, it forms carbonic acid, H2CO3 which is of carbon atom overlap with two p orbitals of a weak dibasic acid and dissociates in two oxygen atoms to make two sigma bonds while steps: H2CO3(aq) + H2O(l) HCO3–(aq) + H3O+(aq) other two electrons of carbon atom are involved HCO3– (aq) + H2O(l)  CO32– (aq) + H3O+(aq) in pπ– pπ bonding with oxygen atom. This results in its linear shape [with both C–O bonds H2CO3/HCO3– buffer system helps to maintain pH of blood between 7.26 to 7.42. of equal length (115 pm)] with no dipole Being acidic in nature, it combines with alkalies to form metal carbonates. moment. The resonance structures are shown Carbon dioxide, which is normally present below: to the extent of ~ 0.03 % by volume in the 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 2019-20

THE p-BLOCK ELEMENTS 329 network solid in which each silicon atom is substituted chlorosilane of formula MeSiCl3, covalently bonded in a tetrahedral manner to Me2SiCl2, Me3SiCl with small amount of Me4Si four oxygen atoms. Each oxygen atom in turn are formed. Hydrolysis of dimethyl- covalently bonded to another silicon atoms as shown in diagram (Fig 11.6 ). Each corner is dichlorosilane, (CH3)2SiCl2 followed by shared with another tetrahedron. The entire condensation polymerisation yields straight crystal may be considered as giant molecule in which eight membered rings are formed with chain polymers. alternate silicon and oxygen atoms. Fig. 11.6 Three dimensional structure of SiO2 The chain length of the polymer can be Silica in its normal form is almost non- controlled by adding (CH3)3SiCl which blocks reactive because of very high Si— O bond the ends as shown below : 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, RnSiCl(4–n), where R is 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 2019-20

330 CHEMISTRY Silicones being surrounded by non-polar (a) (b) alkyl groups are water repelling in nature. They have in general high thermal stability, Fig. 11.7 (a) Tetrahedral structure SoifOS44–iuOn44it– high dielectric strength and resistance to anion; (b) Representation of oxidation and chemicals. They have wide applications. They are used as sealant, greases, neutralised by positively charged metal ions. electrical insulators and for water proofing of If all the four corners are shared with other fabrics. Being biocompatible they are also used tetrahedral units, three-dimensional network in surgical and cosmetic plants. is formed. Problem: 11.8 Two important man-made silicates are glass and cement. What are silicones ? 11.8.6 Zeolites Solution If aluminium atoms replace few silicon atoms Simple silicones consist of in three-dimensional network of silicon dioxide, overall structure known as aluminosilicate, chains in which alkyl or phenyl groups acquires a negative charge. Cations such as occupy the remaining bonding positions Na+, K+ or Ca2+ balance the negative charge. on each silicon. They are hydrophobic Examples are feldspar and zeolites. Zeolites are (water repellant) in nature. widely used as a catalyst in petrochemical industries for cracking of hydrocarbons and 11.8.5 Silicates isomerisation, e.g., ZSM-5 (A type of zeolite) used to convert alcohols directly into gasoline. A large number of silicates minerals exist in Hydrated zeolites are used as ion exchangers nature. Some of the examples are feldspar, in softening of “hard” water. 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 SUMMARY p-Block of the periodic table is unique in terms of having all types 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 ns2np1–6 (except for He). Differences in the inner core of their electronic configuration greatly influence their physical and chemical properties. As a consequence of this, a lot of variation 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 elements 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 2019-20

THE p-BLOCK ELEMENTS 331 influences the ability of these elements to form π-bonds. While the lighter elements form pπ–pπ bonds, the heavier ones form dπ–pπ or dπ–dπ bonds. 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 (2s22p1) 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 Na2[B4O5(OH)4]·8H2O. The borax bead 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 (2s22p2). 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. EXERCISES 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. 2019-20

332 CHEMISTRY 11.9 What are electron deficient compounds ? Are BCl3 and SiCl4 electron 11.10 deficient species ? Explain. 11.11 Write the resonance structures of CO32–and HCO3– . 11.12 What is the state of hybridisation of carbon in (a) CO32– (b) diamond 11.13 (c) graphite? 11.14 Explain the difference in properties of diamond and graphite on the basis 11.15 of their structures. 11.16 11.17 Rationalise the given statements and give chemical reactions : 11.18 • Lead(II) chloride reacts with Cl2 to give PbCl4. 11.19 • Lead(IV) chloride is highly unstable towards heat. 11.20 • Lead is known not to form an iodide, PbI4. Suggest reasons why the B–F bond lengths in BF3 (130 pm) and BF4– 11.21 (143 pm) differ. 11.22 If B–Cl bond has a dipole moment, explain why BCl3 molecule has zero dipole moment. 11.23 11.24 Aluminium trifluoride is insoluble in anhydrous HF but dissolves on 11.25 addition of NaF. Aluminium trifluoride precipitates out of the resulting solution when gaseous BF3 is bubbled through. Give reasons. Suggest a reason as to why CO is poisonous. How is excessive content of CO2 responsible for global warming ? Explain structures of diborane and boric acid. 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 ? 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. 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. 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? 2019-20

THE p-BLOCK ELEMENTS 333 11.26 (a) Classify following oxides as neutral, acidic, basic or amphoteric: CO, B2O3, SiO2, CO2, Al2O3, PbO2, Tl2O3 (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 → (iv) H3BO3 →∆ (v) Al + NaOH → 11.32. (vi) B2H6 + NH3 → 11.33 Give one method for industrial preparation and one for laboratory preparation of CO and CO2 each. 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 (d) form M2+ and M4+ ions 11.38 If the starting material for the manufacture of silicones is RSiCl3, write the structure of the product formed. 2019-20

334 CHEMISTRY UNIT 12 ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES After studying this unit, you will be In the previous unit you have learnt that the element able to carbon has the unique property called catenation due to which it forms covalent bonds with other carbon atoms. • understand reasons for It also forms covalent bonds with atoms of other elements tetravalence of carbon and like hydrogen, oxygen, nitrogen, sulphur, phosphorus and shapes of organic molecules; halogens. The resulting compounds are studied under a separate branch of chemistry called organic chemistry. • write structures of organic This unit incorporates some basic principles and molecules in various ways; techniques of analysis required for understanding the formation and properties of organic compounds. • classify the organic compounds; • name the compounds according 12.1 GENERAL INTRODUCTION to IUPAC system of Organic compounds are vital for sustaining life on earth nomenclature and also derive and include complex molecules like genetic information their structures from the given bearing deoxyribonucleic acid (DNA) and proteins that names; constitute essential compounds of our blood, muscles and • understand the concept of skin. Organic compounds appear in materials like clothing, organic reaction mechanism; fuels, polymers, dyes and medicines. These are some of • explain the influence of the important areas of application of these compounds. electronic displacements on structure and reactivity of Science of organic chemistry is about two hundred organic compounds; years old. Around the year 1780, chemists began to • recognise the types of organic distinguish between organic compounds obtained from reactions; plants and animals and inorganic compounds prepared • learn the techniques of from mineral sources. Berzilius, a Swedish chemist purification of organic proposed that a ‘vital force’ was responsible for the compounds; formation of organic compounds. However, this notion • write the chemical reactions was rejected in 1828 when F. Wohler synthesised an involved in the qualitative organic compound, urea from an inorganic compound, analysis of organic compounds; ammonium cyanate. • understand the principles involved in quantitative analysis NH4CNO Heat → NH2 CONH2 of organic compounds. Urea Ammonium cyanate The pioneering synthesis of acetic acid by Kolbe (1845) and that of methane by Berthelot (1856) showed conclusively that organic compounds could be synthesised from inorganic sources in a laboratory. 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 335 The development of electronic theory of Thus, in H2C=CH2 molecule all the atoms must covalent bonding ushered organic chemistry be in the same plane. The p orbitals are into its modern shape. mutually parallel and both the p orbitals are 12.2 TETRAVALENCE OF CARBON: perpendicular to the plane of the molecule. SHAPES OF ORGANIC COMPOUNDS Rotation of one CH2 fragment with respect to 12.2.1 The Shapes of Carbon Compounds other interferes with maximum overlap of p The knowledge of fundamental concepts of orbitals and, therefore, such rotation about molecular structure helps in understanding carbon-carbon double bond (C=C) is and predicting the properties of organic restricted. The electron charge cloud of the π compounds. You have already learnt theories of valency and molecular structure in Unit 4. bond is located above and below the plane of Also, you already know that tetravalence of carbon and the formation of covalent bonds bonding atoms. This results in the electrons by it are explained in terms of its electronic being easily available to the attacking configuration and the hybridisation of s and reagents. In general, π bonds provide the most p orbitals. It may be recalled that formation and the shapes of molecules like methane reactive centres in the molecules containing (CH4), ethene (C2H4), ethyne (C2H2) are multiple bonds. explained in terms of the use of sp3, sp2 and sp hybrid orbitals by carbon atoms in the Problem 12.1 respective molecules. How many σ and π bonds are present in Hybridisation influences the bond length each of the following molecules? and bond enthalpy (strength) in compounds. The sp hybrid orbital contains more s (a) HC≡CCH=CHCH3 (b) CH2=C=CHCH3 character and hence it is closer to its nucleus Solution and forms shorter and stronger bonds than the sp3 hybrid orbital. The sp2 hybrid orbital (a) σ – C: 4; σ : 6; π :1; π C≡C:2 is intermediate in s character between sp and C C–H C=C sp3 and, hence, the length and enthalpy of the bonds it forms, are also intermediate between (b) σ C: 3; σC–H: 6; πC=C: 2. them. The change in hybridisation affects the C– electronegativity of carbon. The greater the s character of the hybrid orbitals, the greater is Problem 12.2 the electronegativity. Thus, a carbon atom having an sp hybrid orbital with 50% s What is the type of hybridisation of each character is more electronegative than that carbon in the following compounds? possessing sp2 or sp3 hybridised orbitals. This relative electronegativity is reflected in several (a) CH3Cl, (b) (CH3)2CO, (c) CH3CN, physical and chemical properties of the (d) HCONH2, (e) CH3CH=CHCN molecules concerned, about which you will Solution learn in later units. (a) sp3, (b) sp3, sp2, (c) sp3, sp, (d) sp2, (e) 12.2.2 Some Characteristic Features of π sp3, sp2, sp2, sp Bonds Problem 12.3 In a π (pi) bond formation, parallel orientation of the two p orbitals on adjacent atoms is Write the state of hybridisation of carbon necessary for a proper sideways overlap. in the following compounds and shapes of each of the molecules. (a) H2C=O, (b) CH3F, (c) HC≡N. Solution (a) sp2 hybridised carbon, trigonal planar; (b) sp3 hybridised carbon, tetrahedral; (c) sp hybridised carbon, linear. 2019-20

336 CHEMISTRY 12.3 STRUCTURAL REPRESENTATIONS Similarly, CH3CH2CH2CH2CH2CH2CH2CH3 OF ORGANIC COMPOUNDS can be further condensed to CH3(CH2)6CH3. For further simplification, organic chemists 12.3.1 Complete, Condensed and Bond-line use another way of representing the Structural Formulas structures, in which only lines are used. In this bond-line structural representation of Structures of organic compounds are organic compounds, carbon and hydrogen represented in several ways. The Lewis atoms are not shown and the lines structure or dot structure, dash structure, representing carbon-carbon bonds are drawn condensed structure and bond line structural in a zig-zag fashion. The only atoms formulas are some of the specific types. The specifically written are oxygen, chlorine, Lewis structures, however, can be simplified nitrogen etc. The terminals denote methyl by representing the two-electron covalent (–CH3) groups (unless indicated otherwise by bond by a dash (–). Such a structural formula a functional group), while the line junctions focuses on the electrons involved in bond denote carbon atoms bonded to appropriate formation. A single dash represents a single number of hydrogens required to satisfy the bond, double dash is used for double bond valency of the carbon atoms. Some of the and a triple dash represents triple bond. Lone- examples are represented as follows: pairs of electrons on heteroatoms (e.g., oxygen, nitrogen, sulphur, halogens etc.) may (i) 3-Methyloctane can be represented in or may not be shown. Thus, ethane (C2H6), various forms as: ethene (C2H4), ethyne (C2H2) and methanol (CH3OH) can be represented by the following (a) CH3CH2C|HCH2CH2CH2CH2CH3 structural formulas. Such structural representations are called complete structural CH3 formulas. (b) Ethane Ethene (c) Ethyne Methanol These structural formulas can be further (ii) Various ways of representing 2-bromo abbreviated by omitting some or all of the butane are: dashes representing covalent bonds and by indicating the number of identical groups (a) CH3CHBrCH2CH3 (b) attached to an atom by a subscript. The resulting expression of the compound is called (c) a condensed structural formula. Thus, ethane, ethene, ethyne and methanol can be written as: CH3CH3 H2C=CH2 HC≡CH CH3OH Ethane Ethene Ethyne Methanol 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 337 In cyclic compounds, the bond-line formulas (b) may be given as follows: Solution Cyclopropane Condensed formula: (a) HO(CH2)3CH(CH3)CH(CH3)2 (b) HOCH(CN)2 Bond-line formula: (a) Cyclopentane (b) chlorocyclohexane Problem 12.6 Expand each of the following bond-line Problem 12.4 formulas to show all the atoms including carbon and hydrogen Expand each of the following condensed (a) formulas into their complete structural formulas. (b) (a) CH3CH2COCH2CH3 (b) CH3CH=CH(CH2)3CH3 (c) Solution (a) (b) (d) Solution Problem 12.5 For each of the following compounds, write a condensed formula and also their bond-line formula. (a) HOCH2CH2CH2CH(CH3)CH(CH3)CH3 2019-20

338 CHEMISTRY 12.3.2 Three-Dimensional Molecular Models Representation of Organic Molecules Molecular models are physical devices that are used for a better visualisation and The three-dimensional (3-D) structure of perception of three-dimensional shapes of organic molecules can be represented on organic molecules. These are made of wood, paper by using certain conventions. For plastic or metal and are commercially example, by using solid ( ) and dashed available. Commonly three types of molecular ( ) wedge formula, the 3-D image of a models are used: (1) Framework model, (2) molecule from a two-dimensional picture Ball-and-stick model, and (3) Space filling can be perceived. In these formulas the model. In the framework model only the solid-wedge is used to indicate a bond bonds connecting the atoms of a molecule projecting out of the plane of paper, towards and not the atoms themselves are shown. the observer. The dashed-wedge is used to This model emphasizes the pattern of bonds depict the bond projecting out of the plane of of a molecule while ignoring the size of atoms. the paper and away from the observer. Wedges In the ball-and-stick model, both the atoms are shown in such a way that the broad end and the bonds are shown. Balls represent of the wedge is towards the observer. The atoms and the stick denotes a bond. bonds lying in plane of the paper are depicted Compounds containing C=C (e.g., ethene) can by using a normal line (—). 3-D representation best be represented by using springs in place of methane molecule on paper has been of sticks. These models are referred to as ball- shown in Fig. 12.1. and-spring model. The space-filling model emphasises the relative size of each atom based on its van der Waals radius. Bonds are not shown in this model. It conveys the volume occupied by each atom in the molecule. In addition to these models, computer graphics can also be used for molecular modelling. Framework model Ball and stick model Fig. 12.1 Wedge-and-dash representation of CH4 Space filling model Fig. 12.2 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 339 12.4 CLASSIFICATION OF ORGANIC (homocyclic). COMPOUNDS Cyclopropane Cyclohexane Cyclohexene The existing large number of organic Sometimes atoms other than carbon compounds and their ever-increasing are also present in the ring (heterocylic). numbers has made it necessary to classify Tetrahydrofuran given below is an example of them on the basis of their structures. Organic this type of compound: compounds are broadly classified as follows: Tetrahydrofuran I. Acyclic or open chain compounds These exhibit some of the properties similar to those of aliphatic compounds. These compounds are also called as aliphatic compounds and consist of straight or (b) Aromatic compounds branched chain compounds, for example: Aromatic compounds are special types of compounds. You will learn about these compounds in detail in Unit 13. These include benzene and other related ring compounds (benzenoid). Like alicyclic compounds, aromatic comounds may also have hetero atom in the ring. Such compounds are called hetrocyclic aromatic compounds. Some of the examples of various types of aromatic compounds are: Benzenoid aromatic compounds CH3CH3 Ethane Isobutane Benzene Aniline Naphthalene Non-benzenoid compound Acetaldehyde Acetic acid II Cyclic or closed chain or ring Tropone compounds (a) Alicyclic compounds Alicyclic (aliphatic cyclic) compounds contain carbon atoms joined in the form of a ring 2019-20

340 CHEMISTRY Heterocyclic aromatic compounds so because it is found in citrus fruits and the acid found in red ant is named formic acid Furan Thiophene Pyridine since the Latin word for ant is formica. These names are traditional and are considered as Organic compounds can also be classified trivial or common names. Some common on the basis of functional groups, into families names are followed even today. For example, or homologous series. Buckminsterfullerene is a common name given to the newly discovered C60 cluster (a form of 12.4.1 Functional Group carbon) noting its structural similarity to the geodesic domes popularised by the famous The functional group is an atom or a group of architect R. Buckminster Fuller. Common atoms joined to the carbon chain which is names are useful and in many cases responsible for the characteristic chemical indispensable, particularly when the properties of the organic compounds. The alternative systematic names are lengthy and examples are hydroxyl group (–OH), aldehyde complicated. Common names of some organic group (–CHO) and carboxylic acid group compounds are given in Table 12.1. (–COOH) etc. Table 12.1 Common or Trivial Names of Some 12.4.2 Homologous Series Organic Compounds A group or a series of organic compounds each containing a characteristic functional group 12.5.1 The IUPAC System of Nomenclature forms a homologous series and the members A systematic name of an organic compound is of the series are called homologues. The generally derived by identifying the parent members of a homologous series can be hydrocarbon and the functional group(s) represented by general molecular formula and attached to it. See the example given below. the successive members differ from each other in molecular formula by a –CH2 unit. There are a number of homologous series of organic compounds. Some of these are alkanes, alkenes, alkynes, haloalkanes, alkanols, alkanals, alkanones, alkanoic acids, amines etc. It is also possible that a compound contains two or more identical or different functional groups. This gives rise to polyfunctional compounds. 12.5 NOMENCLATURE OF ORGANIC COMPOUNDS Organic chemistry deals with millions of compounds. In order to clearly identify them, a systematic method of naming has been developed and is known as the IUPAC (International Union of Pure and Applied Chemistry) system of nomenclature. In this systematic nomenclature, the names are correlated with the structure such that the reader or listener can deduce the structure from the name. Before the IUPAC system of nomenclature, however, organic compounds were assigned names based on their origin or certain properties. For instance, citric acid is named 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 341 By further using prefixes and suffixes, the In order to name such compounds, the names parent name can be modified to obtain the of alkyl groups are prefixed to the name of actual name. Compounds containing carbon parent alkane. An alkyl group is derived from and hydrogen only are called hydrocarbons. A a saturated hydrocarbon by removing a hydrocarbon is termed saturated if it contains hydrogen atom from carbon. Thus, CH4 only carbon-carbon single bonds. The IUPAC becomes -CH3 and is called methyl group. An name for a homologous series of such alkyl group is named by substituting ‘yl’ for compounds is alkane. Paraffin (Latin: little ‘ane’ in the corresponding alkane. Some alkyl affinity) was the earlier name given to these groups are listed in Table 12.3. compounds. Unsaturated hydrocarbons are those, which contain at least one carbon- Table 12.3 Some Alkyl Groups carbon double or triple bond. Abbreviations are used for some alkyl 12.5.2 IUPAC Nomenclature of Alkanes groups. For example, methyl is abbreviated as Me, ethyl as Et, propyl as Pr and butyl as Bu. Straight chain hydrocarbons: The names The alkyl groups can be branched also. Thus, of such compounds are based on their chain propyl and butyl groups can have branched structure, and end with suffix ‘-ane’ and carry structures as shown below. a prefix indicating the number of carbon atoms present in the chain (except from CH4 to CH3-CH- CH3-CH2-CH- CH3-CH-CH2- C4H10, where the prefixes are derived from   trivial names). The IUPAC names of some straight chain saturated hydrocarbons are given in Table 12.2. The alkanes in Table 12.2 differ from each other by merely the number of -CH2 groups in the chain. They are homologues of alkane series. Table 12.2 IUPAC Names of Some Unbranched Saturated Hydrocarbons CH3 CH3 CH3 Isopropyl- sec-Butyl- Isobutyl- CH3 CH3   CH3-C- CH3-C-CH2-   CH3 CH3 tert-Butyl- Neopentyl- Branched chain hydrocarbons: In a Common branched groups have specific trivial branched chain compound small chains of names. For example, the propyl groups can carbon atoms are attached at one or more either be n-propyl group or isopropyl group. carbon atoms of the parent chain. The small The branched butyl groups are called sec- carbon chains (branches) are called alkyl butyl, isobutyl and tert-butyl group. We also groups. For example: encounter the structural unit, –CH2C(CH3)3, which is called neopentyl group. CH3–CH–CH2–CH3 CH3–CH–CH2–CH–CH3   Nomenclature of branched chain alkanes: We encounter a number of branched chain CH3 CH2CH3 CH3 alkanes. The rules for naming them are given below. (a) (b) 2019-20

342 CHEMISTRY 1. First of all, the longest carbon chain in separated from the groups by hyphens the molecule is identified. In the example and there is no break between methyl (I) given below, the longest chain has nine and nonane.] carbons and it is considered as the parent or root chain. Selection of parent chain as 4. If two or more identical substituent groups shown in (II) is not correct because it has are present then the numbers are only eight carbons. separated by commas. The names of identical substituents are not repeated, 2. The carbon atoms of the parent chain are instead prefixes such as di (for 2), tri numbered to identify the parent alkane and (for 3), tetra (for 4), penta (for 5), hexa (for to locate the positions of the carbon atoms 6) etc. are used. While writing the name of at which branching takes place due to the the substituents in alphabetical order, substitution of alkyl group in place of these prefixes, however, are not considered. hydrogen atoms. The numbering is done Thus, the following compounds are in such a way that the branched carbon named as: atoms get the lowest possible numbers. Thus, the numbering in the above example CH3 CH3 CH3 CH3 should be from left to right (branching at     carbon atoms 2 and 6) and not from right to left (giving numbers 4 and 8 to the CH3-CH-CH2-CH-CH3 CH3CCH2CHCH3 carbon atoms at which branches are 1 23 45 1 2 3 4 5 attached). CH3 1 2 3 4 56 78 9 C  C  C  C  C  C C  C  C 2,4-Dimethylpentane 2,2,4-Trimethylpentane  H3C H2C CH3 C CC   9 8 7 6 54 32 1 CH3CH2CHCCH2CH2CH3 C CCCCCCCC 1 2 3 4 5 6 7  CH3 C CC 3. The names of alkyl groups attached 3-Ethyl-4,4-dimethylheptane as a branch are then prefixed to the name of the parent alkane and position 5. If the two substituents are found in of the substituents is indicated by the equivalent positions, the lower number is appropriate numbers. If different alkyl given to the one coming first in the groups are present, they are listed in alphabetical listing. Thus, the following alphabetical order. Thus, name for the compound is 3-ethyl-6-methyloctane and compound shown above is: 6-ethyl-2- not 6-ethyl-3-methyloctane. methylnonane. [Note: the numbers are 1 234 5678 CH3 — CH2—CH—CH2—CH2—CH—CH2 —CH3  CH2CH3 CH3 6. The branched alkyl groups can be named by following the above mentioned procedures. However, the carbon atom of the branch that attaches to the root alkane is numbered 1 as exemplified below. 4 32 1 CH3–CH–CH2–CH–  CH3 CH3 1,3-Dimethylbutyl- 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 343 The name of such branched chain alkyl group Cyclic Compounds: A saturated monocyclic is placed in parenthesis while naming the compound is named by prefixing ‘cyclo’ to the compound. While writing the trivial names of corresponding straight chain alkane. If side substituents’ in alphabetical order, the chains are present, then the rules given above prefixes iso- and neo- are considered to be are applied. Names of some cyclic compounds the part of the fundamental name of alkyl are given below. group. The prefixes sec- and tert- are not considered to be the part of the fundamental 3-Ethyl-1,1-dimethylcyclohexane name. The use of iso and related common (not 1-ethyl-3,3-dimethylcyclohexane) prefixes for naming alkyl groups is also allowed Problem 12.7 by the IUPAC nomenclature as long as these Structures and IUPAC names of some are not further substituted. In multi- hydrocarbons are given below. Explain substituted compounds, the following rules why the names given in the parentheses may aso be remembered: are incorrect. • If there happens to be two chains of equal size, then that chain is to be selected which contains more number of side chains. • After selection of the chain, numbering is to be done from the end closer to the substituent. 5-(2-Ethylbutyl)-3,3-dimethyldecane 2,5,6- Trimethyloctane [and not 5-(2,2-Dimethylbutyl)-3-ethyldecane] [and not 3,4,7-Trimethyloctane] 5-sec-Butyl-4-isopropyldecane 3-Ethyl-5-methylheptane [and not 5-Ethyl-3-methylheptane] 5-(2,2-Dimethylpropyl)nonane Solution (a) Lowest locant number, 2,5,6 is lower than 3,5,7, (b) substituents are in equivalent position; lower number is given to the one that comes first in the name according to alphabetical order. 12.5.3 Nomenclature of Organic Compounds having Functional Group(s) A functional group, as defined earlier, is an atom or a group of atoms bonded together in a unique manner which is usually the site of 2019-20

344 CHEMISTRY chemical reactivity in an organic molecule. suffix. In such cases the full name of the Compounds having the same functional group parent alkane is written before the class suffix. undergo similar reactions. For example, For example CH2(OH)CH2(OH) is named as CH3OH, CH3CH2OH, and (CH3)2CHOH — all ethane–1,2–diol. However, the ending – ne of having -OH functional group liberate hydrogen the parent alkane is dropped in the case of on reaction with sodium metal. The presence compounds having more than one double of functional groups enables systematisation or triple bond; for example, CH2=CH-CH=CH2 of organic compounds into different classes. is named as buta–1,3–diene. Examples of some functional groups with their prefixes and suffixes along with some Problem 12.8 examples of organic compounds possessing Write the IUPAC names of the compounds these are given in Table 12.4. i-iv from their given structures. First of all, the functional group present Solution in the molecule is identified which determines the choice of appropriate suffix. The longest • The functional group present is an chain of carbon atoms containing the functional group is numbered in such a way alcohol (OH). Hence the suffix is ‘-ol’. that the functional group is attached at the carbon atom possessing lowest possible • The longest chain containing -OH has number in the chain. By using the suffix as given in Table 12.4, the name of the compound eight carbon atoms. Hence the is arrived at. corresponding saturated hydrocarbon is octane. In the case of polyfunctional compounds, one of the functional groups is chosen as the • The -OH is on carbon atom 3. In principal functional group and the compound is then named on that basis. The remaining addition, a methyl group is attached functional groups, which are subordinate at 6th carbon. functional groups, are named as substituents Hence, the systematic name of this using the appropriate prefixes. The choice of compound is 6-Methyloctan-3-ol. principal functional group is made on the basis of order of preference. The order of decreasing Solution priority for some functional groups is: The functional group present is ketone (>C=O), hence suffix ‘-one’. Presence of -COOH, –SO3H, -COOR (R=alkyl group), COCl, two keto groups is indicated by ‘di’, -CONH2, -CN,-HC=O, >C=O, -OH, -NH2, >C=C<, hence suffix becomes ‘dione’. The two -C≡C- . keto groups are at carbons 2 and 4. The longest chain contains 6 carbon atoms, The –R, C6H5-, halogens (F, Cl, Br, I), –NO2, hence, parent hydrocarbon is hexane. alkoxy (–OR) etc. are always prefix Thus, the systematic name is Hexane- substituents. Thus, a compound containing 2,4-dione. both an alcohol and a keto group is named as hydroxyalkanone since the keto group is preferred to the hydroxyl group. For example, HOCH2(CH2)3CH2COCH3 will be named as 7-hydroxyheptan-2-one and not as 2-oxoheptan -7-ol. Similarly, BrCH2CH=CH2 is named as 3-bromoprop-1-ene and not 1- bromoprop-2-ene. If more than one functional group of the same type are present, their number is indicated by adding di, tri, etc. before the class 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 345 Table 12.4 Some Functional Groups and Classes of Organic Compounds 2019-20

346 CHEMISTRY Solution (iii) Six membered ring containing a carbon-carbon double bond is implied by Here, two functional groups namely cyclohexene, which is numbered as ketone and carboxylic acid are present. shown in (I). The prefix 3-nitro means that The principal functional group is the a nitro group is present on C-3. Thus, carboxylic acid group; hence the parent complete structural formula of the chain will be suffixed with ‘oic’ acid. compound is (II). Double bond is suffixed Numbering of the chain starts from functional group whereas NO2 is prefixed carbon of – COOH functional group. The functional group therefore double bond keto group in the chain at carbon 5 is gets preference over –NO2 group: indicated by ‘oxo’. The longest chain including the principal functional (iv) ‘1-ol’ means that a -OH group is group has 6 carbon atoms; hence the present at C-1. OH is suffixed functional parent hydrocarbon is hexane. The group and gets preference over C=C compound is, therefore, named as bond. Thus the structure is as shown 5-Oxohexanoic acid. in (II): Solution (v) ‘heptanal’ indicates the compound to be an aldehyde containing 7 carbon The two C=C functional groups are atoms in the parent chain. The present at carbon atoms 1 and 3, while ‘6-hydroxy’ indicates that -OH group is the C≡C functional group is present at present at carbon 6. Thus, the structural carbon 5. These groups are indicated by formula of the compound is: suffixes ‘diene’ and ‘yne’ respectively. The CH3CH(OH)CH2CH2CH2CH2CHO. Carbon longest chain containing the functional atom of –CHO group is included while groups has 6 carbon atoms; hence the numbering the carbon chain. parent hydrocarbon is hexane. The name of compound, therefore, is Hexa-1,3- 12.5.4 Nomenclature of Substituted dien-5-yne. Benzene Compounds Problem 12.9 For IUPAC nomenclature of substituted benzene compounds, the substituent is Derive the structure of (i) 2-Chlorohexane, placed as prefix to the word benzene as (ii) Pent-4-en-2-ol, (iii) 3- Nitrocyclohexene, shown in the following examples. However, (iv) Cyclohex-2-en-1-ol, (v) 6-Hydroxy- common names (written in bracket below) heptanal. of many substituted benzene compounds are also universally used. Solution (i) ‘hexane’ indicates the presence of 6 carbon atoms in the chain. The functional group chloro is present at carbon 2. Hence, the structure of the compound is CH3CH2CH2CH2CH(Cl)CH3. (ii) ‘pent’ indicates that parent hydrocarbon contains 5 carbon atoms in the chain. ‘en’ and ‘ol’ correspond to the functional groups C=C and -OH at carbon atoms 4 and 2 respectively. Thus, the structure is CH2=CHCH2CH (OH)CH3. 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 347 Methylbenzene Methoxybenzene Aminobenzene Substituent of the base compound is assigned number1 and then the direction of (Toluene) (Anisole) (Aniline) numbering is chosen such that the next substituent gets the lowest number. The substituents appear in the name in alphabetical order. Some examples are given below. Nitrobenzene Bromobenzene 1-Chloro-2,4-dinitrobenzene (not 4-chloro,1,3-dinitrobenzene) If benzene ring is disubstituted, the position of substituents is defined 2-Chloro-1-methyl-4-nitrobenzene by numbering the carbon atoms of (not 4-methyl-5-chloro-nitrobenzene) the ring such that the substituents are located at the lowest numbers possible.For example, the compound(b) is named as 1,3-dibromobenzene and not as 1,5-dibromobenzene. (a) (b) (c) 1,2-Dibromo- 1,3-Dibromo- 1,4-Dibromo- benzene benzene benzene In the trivial system of nomenclature the 2-Chloro-4-methylanisole 4-Ethyl-2-methylaniline terms ortho (o), meta (m) and para (p) are used as prefixes to indicate the relative positions 3,4-Dimethylphenol 1,2;1,3 and 1,4 respectively. Thus, When a benzene ring is attached to an 1,3-dibromobenzene (b) is named as alkane with a functional group, it is m-dibromobenzene (meta is abbreviated as considered as substituent, instead of a parent. m-) and the other isomers of dibromobenzene The name for benzene as substituent is phenyl 1,2-(a) and 1,4-(c), are named as ortho (or just (C6H5-, also abbreviated as Ph). o-) and para (or just p-)-dibromobenzene, respectively. For tri - or higher substituted benzene derivatives, these prefixes cannot be used and the compounds are named by identifying substituent positions on the ring by following the lowest locant rule. In some cases, common name of benzene derivatives is taken as the base compound. 2019-20

348 CHEMISTRY Problem 12.10 different carbon skeletons, these are referred to as chain isomers and the phenomenon is termed Write the structural formula of: as chain isomerism. For example, C5H12 (a) o-Ethylanisole, (b) p-Nitroaniline, represents three compounds: (c) 2,3 - Dibromo -1 - phenylpentane, (d) 4-Ethyl-1-fluoro-2-nitrobenzene. CH3CH2CH2CH2CH3 CH3 Pentane  Solution CH3−CHCH2CH3 Isopentane (2-Methylbutane) (a) (b) CH3  CH3 C CH3  CH3 Neopentane (2,2-Dimethylpropane) (c) (d) (ii) Position isomerism: When two or more compounds differ in the position of substituent 12.6 ISOMERISM atom or functional group on the carbon skeleton, they are called position isomers and The phenomenon of existence of two or more this phenomenon is termed as position compounds possessing the same molecular isomerism. For example, the molecular formula but different properties is known as formula C3H8O represents two alcohols: isomerism. Such compounds are called as isomers. The following flow chart shows CH3CH2CH2OH OH different types of isomerism. Propan-1-ol  CH3−CH-CH3 12.6.1 Structural Isomerism Propan-2-ol Compounds having the same molecular (iii) Functional group isomerism: Two or formula but different structures (manners in more compounds having the same molecular which atoms are linked) are classified as formula but different functional groups are structural isomers. Some typical examples of called functional isomers and this different types of structural isomerism are given phenomenon is termed as functional group below: isomerism. For example, the molecular formula C3H6O represents an aldehyde and a (i) Chain isomerism: When two or more ketone: compounds have similar molecular formula but Isomerism Structural isomerism Stereoisomerism Chain Position Functional Metamerism Geometrical Optical isomerism isomerism group isomerism isomerism isomerism 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 349 O H understanding the reactivity of organic compounds and in planning strategy for their CH3−C-CH3 CH3−CH2—C= O synthesis. Propanone Propanal In the following sections, we shall learn (iv) Metamerism: It arises due to different alkyl some of the principles that explain how these chains on either side of the functional group reactions take place. in the molecule. For example, C4H10O represents methoxypropane (CH3OC3H7) and 12.7.1 Fission of a Covalent Bond ethoxyethane (C2H5OC2H5). A covalent bond can get cleaved either by : (i) 12.6.2 Stereoisomerism heterolytic cleavage, or by (ii) homolytic cleavage. The compounds that have the same constitution and sequence of covalent bonds In heterolytic cleavage, the bond breaks but differ in relative positions of their atoms in such a fashion that the shared pair of or groups in space are called stereoisomers. electrons remains with one of the fragments. This special type of isomerism is called as stereoisomerism and can be classified as After heterolysis, one atom has a sextet geometrical and optical isomerism. electronic structure and a positive charge and the other, a valence octet with at least one lone pair and a negative charge. Thus, heterolytic cleavage of bromomethane will give + 12.7 FUNDAMENTAL CONCEPTS IN and Br– as shown below. ORGANIC REACTION MECHANISM CH3 In an organic reaction, the organic molecule A species having a carbon atom possessing (also referred as a substrate) reacts with an appropriate attacking reagent and leads to the sextext of electrons and a positive charge is formation of one or more intermediate(s) and finally product(s) called a carbocation (earlier called carbonium + The general reaction is depicted as follows : ion). The CH3 ion is known as a methyl cation or methyl carbonium ion. Carbocations are Attacking classified as primary, secondary or tertiary OrganicReagent [Intermediate] Product(s) depending on whether one, two or three molecule carbons are directly attached to the positively (Substrate) Byproducts charged carbon. Some other examples of + carbocations are: CH3C H2 (ethyl cation, a + Substrate is that reactant which supplies primary carbocation), (CH3)2C H (isopropyl carbon to the new bond and the other reactant + is called reagent. If both the reactants supply cation, a secondary carbocation), and (CH3)3C carbon to the new bond then choice is arbitrary and in that case the molecule on (tert-butyl cation, a tertiary carbocation). which attention is focused is called substrate. Carbocations are highly unstable and reactive In such a reaction a covalent bond between two carbon atoms or a carbon and species. Alkyl groups directly attached to the some other atom is broken and a new bond is formed. A sequential account of each step, positively charged carbon stabilise the describing details of electron movement, energetics during bond cleavage and bond carbocations due to inductive and formation, and the rates of transformation of reactants into products (kinetics) is hyperconjugation effects, which you will be referred to as reaction mechanism. The knowledge of reaction mechanism helps in studying in the sections 12.7.5 and 12.7.9. The + observed order of carbocation stability is: CH3 + + + < CH3CH2 < (CH3)2CH < (CH3)3C. These carbocations have trigonal planar shape with positively charged carbon being sp2 + hybridised. Thus, the shape of CH3 may be considered as being derived from the overlap of three equivalent C(sp2) hybridised orbitals 2019-20

350 CHEMISTRY with 1s orbital of each of the three hydrogen headed’ (fish hook: ) curved arrow. Such atoms. Each bond may be represented as cleavage results in the formation of neutral C(sp2)–H(1s) sigma bond. The remaining species (atom or group) which contains an carbon orbital is perpendicular to the unpaired electron. These species are called free molecular plane and contains no electrons. radicals. Like carbocations and carbanions, [Fig. 12.3(a)]. free radicals are also very reactive. A homolytic cleavage can be shown as: Alkyl free radical Alkyl radicals are classified as primary, secondary, or tertiary. Alkyl radical stability increases as we proceed from primary to tertiary: Fig. 12.3(a) Shape of methyl carbocation Methyl Ethyl Isopropyl , free free free Tert-butyl The heterolytic cleavage can also give a species in which carbon gets the shared pair of radical radical radical free electrons. For example, when group Z attached to the carbon leaves without radical Organic reactions, which proceed by homolytic fission are called free radical or homopolar or nonpolar reactions. electron pair, the methyl anion is 12.7.2 Substrate and Reagent formed. Such a carbon species carrying a Ions are generally not formed in the reactions of negative charge on carbon atom is called organic compounds. Molecules as such carbanion. Carbon in carbanion is generally participate in the reaction. It is convenient to sp3 hybridised and its structure is distorted name one reagent as substrate and other as tetrahedron as shown in Fig. 12.3(b). reagent. In general, a molecule whose carbon is involved in new bond formation is called substrate and the other one is called reagent. When carbon-carbon bond is formed, the choice of naming the reactants as substrate and reagent is arbitrary and depends on molecule under observation. Example: Fig. 12.3(b) Shape of methyl carbanion (i) CH2 = CH2 + Br2 CH2 Br – CH2Br Substrate Reagent Product Carbanions are also unstable and reactive species. The organic reactions which proceed (ii) through heterolytic bond cleavage are called ionic or heteropolar or just polar reactions. Nucleophiles and Electrophiles In homolytic cleavage, one of the electrons Reagents attack the reactive site of the substrate. of the shared pair in a covalent bond goes with The reactive site may be electron deficient each of the bonded atoms. Thus, in homolytic cleavage, the movement of a single electron takes place instead of an electron pair. The single electron movement is shown by ‘half- 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 351 portion of the molecule (a positive reactive site) Problem 12.11 e.g., an atom with incomplete electron shell or the positive end of the dipole in the molecule. If Using curved-arrow notation, show the the attacking species is electron rich, it attacks formation of reactive intermediates when these sites. If attacking species is electron the following covalent bonds undergo deficient, the reactive site for it is that part of the heterolytic cleavage. substrate molecule which can supply electrons, e.g., π electrons in a double bond. (a) CH3–SCH3, (b) CH3–CN, (c) CH3–Cu Solution A reagent that brings an electron pair to the reactive site is called a nucleophile (Nu:) i.e., Problem 12.12 nucleus seeking and the reaction is then called nucleophilic. A reagent that takes away an Giving justification, categorise the electron pair from reactive site is called following molecules/ions as nucleophile electrophile (E+) i.e., electron seeking and the or electrophile: reaction is called electrophilic. During a polar organic reaction, a nucleophile attacks an electrophilic centre of the substrate which is that specific atom or part of the substrate which is electron deficient. Similarly, the electrophiles attack at nucleophilic centre, which is the electron rich centre of the substrate. Thus, the Solution electrophiles receive electron pair from the substrate when the two undergo bonding Nucleophiles: HS−,C2H5O−,( CH3 ) N:,H2N:− 3 interaction. A curved-arrow notation is used These species have unshared pair of to show the movement of an electron pair from electrons, which can be donated and the nucleophile to the electrophile. Some shared with an electrophile. examples of nucleophiles are the negatively charged ions with lone pair of electrons such + ++ as hydroxide (HO– ), cyanide (NC–) ions and E l e c t r o p h i l e s : BF3,Cl,CH3 −C = O,NO2 . carbanions (R3C:–). Neutral molecules such as etc., can also act as Reactive sites have only six valence electrons; can accept electron pair from nucleophiles due to the presence of lone pair a nucleophile. of electrons. Examples of electrophiles Problem 12.13 include carbocations ( + H3 ) and neutral Identify electrophilic centre in the following: CH3CH=O, CH3CN, CH3I. C molecules having functional groups like carbonyl group (>C=O) or alkyl halides Solution (R3C-X, where X is a halogen atom). The Among C H3HC*=O, H3C C* ≡ N , and carbon atom in carbocations has sextet H3C*–I, the starred carbon atoms are configuration; hence, it is electron deficient electrophilic centers as they will have and can receive a pair of electrons from the partial positive charge due to polarity of nucleophiles. In neutral molecules such as the bond. alkyl halides, due to the polarity of the C-X bond a partial positive charge is generated 12.7.3 Electron Movement in Organic Reactions on the carbon atom and hence the carbon atom The movement of electrons in organic reactions becomes an electrophilic centre at which a can be shown by curved-arrow notation. It nucleophile can attack. 2019-20

352 CHEMISTRY shows how changes in bonding occur due to 12.7.5 Inductive Effect electronic redistribution during the reaction. To show the change in position of a pair of When a covalent bond is formed between atoms electrons, curved arrow starts from the point of different electronegativity, the electron from where an electron pair is shifted and it density is more towards the more ends at a location to which the pair of electron electronegative atom of the bond. Such a shift may move. of electron density results in a polar covalent bond. Bond polarity leads to various electronic Presentation of shifting of electron pair is effects in organic compounds. given below : Let us consider cholorethane (CH3CH2Cl) (i) from π bond to in which the C–Cl bond is a polar covalent adjacent bond position bond. It is polarised in such a way that the (ii) from π bond to carbon-1 gains some positive charge (δ+) and adjacent atom the chlorine some negative charge (δ–). The (iii) from atom to adjacent fractional electronic charges on the two atoms bond position in a polar covalent bond are denoted by symbol Movement of single electron is indicated by a single barbed ‘fish hooks’ (i.e. half headed δ (delta) and the shift of electron density is curved arrow). For example, in transfer of shown by an arrow that points from δ+ to δ– hydroxide ion giving ethanol and in the dissociation of chloromethane, the movement end of the polar bond. δ− of electron using curved arrows can be δδ+ δ+ depicted as follows: CH3 →CH2→Cl 12.7.4 Electron Displacement Effects in 21 Covalent Bonds In turn carbon-1, which has developed The electron displacement in an organic partial positive charge (δ+) draws some electron molecule may take place either in the ground density towards it from the adjacent C-C bond. state under the influence of an atom or a Consequently, some positive charge (δδ+) substituent group or in the presence of an develops on carbon-2 also, where δδ+ appropriate attacking reagent. The electron symbolises relatively smaller positive charge displacements due to the influence of as compared to that on carbon – 1. In other an atom or a substituent group present in the words, the polar C – Cl bond induces polarity molecule cause permanent polarlisation of the in the adjacent bonds. Such polarisation of σ- bond. Inductive effect and resonance effects are bond caused by the polarisation of adjacent examples of this type of electron displacements. σ-bond is referred to as the inductive effect. Temporary electron displacement effects are This effect is passed on to the subsequent seen in a molecule when a reagent approaches bonds also but the effect decreases rapidly as to attack it. This type of electron displacement the number of intervening bonds increases and is called electromeric effect or polarisability becomes vanishingly small after three bonds. effect. In the following sections we will learn The inductive effect is related to the ability of about these types of electronic displacements. substituent(s) to either withdraw or donate electron density to the attached carbon atom. Based on this ability, the substitutents can be classified as electron-withdrawing or electron donating groups relative to hydrogen. Halogens and many other groups such as nitro (- NO2), cyano (- CN), carboxy (- COOH), ester (COOR), aryloxy (-OAr, e.g. – OC6H5), etc. are electron- withdrawing groups. On the other hand, the alkyl groups like methyl (–CH3) and ethyl (–CH2–CH3) are usually considered as electron donating groups. 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 353 Problem 12.14 be adequately represented by any of these Which bond is more polar in the following structures, rather it is a hybrid of the two pairs of molecules: (a) H3C-H, H3C-Br structures (I and II) called resonance (b) H3C-NH2, H3C-OH (c) H3C-OH, structures. The resonance structures H3C-SH (canonical structures or contributing Solution structures) are hypothetical and (a) C–Br, since Br is more electronegative individually do not represent any real than H, (b) C–O, (c) C–O molecule. They contribute to the actual structure in proportion to their stability. Problem 12.15 In which C–C bond of CH3CH2CH2Br, the Another example of resonance is provided inductive effect is expected to be the least? by nitromethane (CH3NO2) which can be represented by two Lewis structures, (I and II). Solution There are two types of N-O bonds in these Magnitude of inductive effect diminishes structures. as the number of intervening bonds increases. Hence, the effect is least in the However, it is known that the two N–O bonds bond between carbon-3 and hydrogen. of nitromethane are of the same length (intermediate between a N–O single bond 12.7.6 Resonance Structure and a N=O double bond). The actual structure of nitromethane is therefore a There are many organic molecules whose resonance hybrid of the two canonical behaviour cannot be explained by a single forms I and II. Lewis structure. An example is that of benzene. Its cyclic structure The energy of actual structure of the molecule containing alternating C–C single (the resonance hybrid) is lower than that of any and C=C double bonds shown is of the canonical structures. The difference in inadequate for explaining its Benzene energy between the actual structure and the characteristic properties. lowest energy resonance structure is called the resonance stabilisation energy or simply As per the above representation, benzene the resonance energy. The more the number should exhibit two different bond lengths, due of important contributing structures, the more to C–C single and C=C double bonds. However, is the resonance energy. Resonance is as determined experimentally benzene has a particularly important when the contributing uniform C–C bond distances of 139 pm, a structures are equivalent in energy. value intermediate between the C–C single(154 pm) and C=C double (134 pm) bonds. Thus, The following rules are applied while writing the structure of benzene cannot be represented resonance structures: adequately by the above structure. Further, benzene can be represented equally well by the The resonance structures have (i) the same energetically identical structures I and II. positions of nuclei and (ii) the same number of unpaired electrons. Among the resonance Therefore, according to the resonance theory structures, the one which has more number of (Unit 4) the actual structure of benzene cannot covalent bonds, all the atoms with octet of electrons (except hydrogen which has a duplet), less separation of opposite charges, (a negative charge if any on more electronegative atom, a positive charge if any on more electropositive atom) and more dispersal of charge, is more stable than others. 2019-20

354 CHEMISTRY Problem 12.16 Solution Write resonance structures of CH3COO– The two structures are less important and show the movement of electrons by contributors as they involve charge curved arrows. separation. Additionally, structure I Solution contains a carbon atom with an First, write the structure and put unshared pairs of valence electrons on incomplete octet. appropriate atoms. Then draw the arrows one at a time moving the electrons to get 12.7.7 Resonance Effect the other structures. The resonance effect is defined as ‘the polarity produced in the molecule by the interaction of Problem 12.17 two π-bonds or between a π-bond and lone pair Write resonance structures of of electrons present on an adjacent atom’. The CH2=CH–CHO. Indicate relative stability of effect is transmitted through the chain. There the contributing structures. are two types of resonance or mesomeric effect Solution designated as R or M effect. (i) Positive Resonance Effect (+R effect) In this effect, the transfer of electrons is away from an atom or substituent group attached to the conjugated system. This electron displacement makes certain positions in the molecule of high electron densities. This effect in aniline is shown as : Stability: I > II > III (ii) Negative Resonance Effect (- R effect) This effect is observed when the transfer of [I: Most stable, more number of covalent electrons is towards the atom or substituent bonds, each carbon and oxygen atom has group attached to the conjugated system. For an octet and no separation of opposite example in nitrobenzene this electron charge II: negative charge on more displacement can be depicted as : electronegative atom and positive charge on more electropositive atom; III: does not The atoms or substituent groups, which contribute as oxygen has positive charge represent +R or –R electron displacement and carbon has negative charge, hence effects are as follows : least stable]. +R effect: – halogen, –OH, –OR, –OCOR, –NH2, –NHR, –NR2, –NHCOR, Problem 12.18 – R effect: – COOH, –CHO, >C=O, – CN, –NO2 Explain why the following two structures, I and II cannot be the major contributors to the real structure of CH3COOCH3. 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 355 The presence of alternate single and double system or to an atom with an unshared bonds in an open chain or cyclic system is p orbital. The σ electrons of C—H bond of the termed as a conjugated system. These systems alkyl group enter into partial conjugation with often show abnormal behaviour. The examples the attached unsaturated system or with the are 1,3- butadiene, aniline and nitrobenzene unshared p orbital. Hyperconjugation is a etc. In such systems, the π-electrons are permanent effect. delocalised and the system develops polarity. To understand hyperconjugation effect, let 12.7.8 Electromeric Effect (E effect) + It is a temporary effect. The organic compounds having a multiple bond (a double us take an example of CH3 CH2 (ethyl cation) or triple bond) show this effect in the presence in which the positively charged carbon atom of an attacking reagent only. It is defined as has an empty p orbital. One of the C-H bonds the complete transfer of a shared pair of of the methyl group can align in the plane of π-electrons to one of the atoms joined by a this empty p orbital and the electrons multiple bond on the demand of an attacking constituting the C-H bond in plane with this p reagent. The effect is annulled as soon as the orbital can then be delocalised into the empty attacking reagent is removed from the domain p orbital as depicted in Fig. 12.4 (a). of the reaction. It is represented by E and the shifting of the electrons is shown by a curved Fig. 12.4(a) Orbital diagram showing arrow ( ). There are two distinct types of hyperconjugation in ethyl cation electromeric effect. (i) Positive Eelctromeric Effect (+E effect) In this This type of overlap stabilises the effect the π−electrons of the multiple bond are carbocation because electron density from the transferred to that atom to which the reagent adjacent σ bond helps in dispersing the positive gets attached. For example : charge. (ii) Negative Electromeric Effect (–E effect) In this effect the π - electrons of the multiple bond are transferred to that atom to which the attacking reagent does not get attached. For example: When inductive and electromeric effects In general, greater the number of alkyl operate in opposite directions, the electomeric groups attached to a positively charged carbon effect predominates. atom, the greater is the hyperconjugation interaction and stabilisation of the cation. 12.7.9 Hyperconjugation Thus, we have the following relative stability of carbocations : Hyperconjugation is a general stabilising interaction. It involves delocalisation of σ electrons of C—H bond of an alkyl group directly attached to an atom of unsaturated 2019-20

356 CHEMISTRY Problem 12.19 + Explain why (C+H3)3C is more stable than + CH3CH2 and C H3 is the least stable cation. Hyperconjugation is also possible in Solution + alkenes and alkylarenes. Hyperconjugation interaction in (CH3)3C is Delocalisation of electrons by + hyperconjugation in the case of alkene can be + the (CH3)3C depicted as in Fig. 12.4(b). greater than in as CH3 C H2 + has nine C-H bonds. In C H3 , vacant p orbital is perpendicular to the plane in which C-H bonds lie; hence cannot overlap with it. Thus, + lacks hyperconjugative stability. C H3 Fig. 12.4(b) Orbital diagram showing 12.7.10 Types of Organic Reactions and hyperconjugation in propene Mechanisms There are various ways of looking at the Organic reactions can be classified into the hyperconjugative effect. One of the way is to following categories: regard C—H bond as possessing partial ionic (i) Substitution reactions character due to resonance. (ii) Addition reactions (iii) Elimination reactions The hyperconjugation may also be (iv) Rearrangement reactions regarded as no bond resonance. You will be studying these reactions in Unit 13 and later in class XII. 12.8 METHODS OF PURIFICATION OF ORGANIC COMPOUNDS Once an organic compound is extracted from a natural source or synthesised in the laboratory, it is essential to purify it. Various methods used for the purification of organic compounds are based on the nature of the compound and the impurity present in it. The common techniques used for purification are as follows : (i) Sublimation (ii) Crystallisation (iii) Distillation (iv) Differential extraction and (v) Chromatography Finally, the purity of a compound is ascertained by determining its melting or boiling point. Most of the pure compounds have sharp melting points and boiling points. New methods of checking the purity of an organic compound are based on different types 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 357 of chromatographic and spectroscopic carefully. On boiling, the vapours of lower techniques. boiling component are formed first. The vapours are condensed by using a condenser 12.8.1 Sublimation and the liquid is collected in a receiver. The vapours of higher boiling component form later You have learnt earlier that on heating, some and the liquid can be collected separately. solid substances change from solid to vapour state without passing through liquid state. The Fig.12.5 Simple distillation. The vapours of a purification technique based on the above substance formed are condensed and principle is known as sublimation and is used the liquid is collected in conical flask. to separate sublimable compounds from non- sublimable impurities. Fractional Distillation: If the difference in boiling points of two liquids is not much, simple 12.8.2 Crystallisation distillation cannot be used to separate them. The vapours of such liquids are formed within This is one of the most commonly used the same temperature range and are condensed techniques for the purification of solid organic simultaneously. The technique of fractional compounds. It is based on the difference in the distillation is used in such cases. In this solubilities of the compound and the technique, vapours of a liquid mixture are impurities in a suitable solvent. The impure passed through a fractionating column before compound is dissolved in a solvent in which it condensation. The fractionating column is is sparingly soluble at room temperature but fitted over the mouth of the round bottom flask appreciably soluble at higher temperature. (Fig.12.6, page 358). The solution is concentrated to get a nearly saturated solution. On cooling the solution, Vapours of the liquid with higher boiling pure compound crystallises out and is point condense before the vapours of the liquid removed by filtration. The filtrate (mother with lower boiling point. The vapours rising liquor) contains impurities and small quantity up in the fractionating column become richer of the compound. If the compound is highly in more volatile component. By the time the soluble in one solvent and very little soluble in another solvent, crystallisation can be satisfactorily carried out in a mixture of these solvents. Impurities, which impart colour to the solution are removed by adsorbing over activated charcoal. Repeated crystallisation becomes necessary for the purification of compounds containing impurities of comparable solubilities. 12.8.3 Distillation This important method is used to separate (i) volatile liquids from nonvolatile impurities and (ii) the liquids having sufficient difference in their boiling points. Liquids having different boiling points vaporise at different temperatures. The vapours are cooled and the liquids so formed are collected separately. Chloroform (b.p 334 K) and aniline (b.p. 457 K) are easily separated by the technique of distillation (Fig 12.5). The liquid mixture is taken in a round bottom flask and heated 2019-20

358 CHEMISTRY column is called a theoretical plate. Commercially, columns with hundreds of plates are available. One of the technological applications of fractional distillation is to separate different fractions of crude oil in petroleum industry. Fig.12.6 Fractional distillation. The vapours of lower boiling Distillation under reduced fraction reach the top of the column first followed by pressure: This method is used vapours of higher boiling fractions. to purify liquids having very high boiling points and those, which decompose at or below their boiling points. Such liquids are made to boil at a temperature lower than their normal boiling points by reducing the pressure on their surface. A liquid boils at a temperature at which its vapour pressure is equal to the external pressure. The pressure is reduced with the help of a water pump or vacuum pump (Fig.12.8). Glycerol can be separated from spent-lye in soap industry by using this technique. vapours reach to the top of the fractionating Fig.12.7 Different types of fractionating columns. column, these are rich in the more volatile component. Fractionating columns are available in various sizes and designs as shown in Fig.12.7. A fractionating column provides many surfaces for heat exchange between the ascending vapours and the descending condensed liquid. Some of the condensing liquid in the fractionating column obtains heat from the ascending vapours and revaporises. The vapours thus become richer in low boiling component. The vapours of low boiling component ascend to the top of the column. On reaching the top, the vapours become pure in low boiling component and pass through the condenser and the pure liquid is collected in a receiver. After a series of successive distillations, the remaining liquid in the distillation flask gets enriched in high boiling component. Each successive condensation and vaporisation unit in the fractionating 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 359 Fig.12.8 Distillation under reduced pressure. A liquid boils at a temperature below its vapour pressure by reducing the pressure. Steam Distillation: This technique is 12.8.4 Differential Extraction applied to separate substances which are steam volatile and are immiscible with water. When an organic compound is present in an In steam distillation, steam from a steam aqueous medium, it is separated by shaking generator is passed through a heated flask it with an organic solvent in which it is more containing the liquid to be distilled. The soluble than in water. The organic solvent and mixture of steam and the volatile organic the aqueous solution should be immiscible compound is condensed and collected. The with each other so that they form two distinct compound is later separated from water layers which can be separated by separatory using a separating funnel. In steam funnel. The organic solvent is later removed by distillation, the liquid boils when the sum distillation or by evaporation to get back of vapour pressures due to the organic the compound. Differential extraction is carried liquid (p1) and that due to water (p2) out in a separatory funnel as shown in becomes equal to the atmospheric pressure Fig. 12.10 (Page 360). If the organic compound (p), i.e. p =p1+ p2. Since p1 is lower than p, is less soluble in the organic solvent, a very the organic liquid vaporises at lower large quantity of solvent would be required to temperature than its boiling point. extract even a very small quantity of the compound. The technique of continuous Thus, if one of the substances in the extraction is employed in such cases. In this mixture is water and the other, a water technique same solvent is repeatedly used for insoluble substance, then the mixture will boil extraction of the compound. close to but below, 373K. A mixture of water and the substance is obtained which can be 12.8.5 Chromatography separated by using a separating funnel. Aniline is separated by this technique from Chromatography is an important technique aniline – water mixture (Fig.12.9, Page 360). extensively used to separate mixtures into their components, purify compounds and also to test the purity of compounds. The name 2019-20

360 CHEMISTRY Fig.12.9 Steam distillation. Steam volatile component volatilizes, the vapours con- chromatography is based on the Greek word Fig.12.10 Differential extraction. Extraction of com- chroma, for colour since the method was first pound takes place based on difference used for the separation of coloured substances in solubility found in plants. In this technique, the mixture of substances is applied onto a stationary are two main types of chromatographic phase, which may be a solid or a liquid. A techniques based on the principle of differential pure solvent, a mixture of solvents, or a gas is adsorption. allowed to move slowly over the stationary (a) Column chromatography, and phase. The components of the mixture get (b) Thin layer chromatography. gradually separated from one another. The moving phase is called the mobile phase. Based on the principle involved, chromatography is classified into different categories. Two of these are: (a) Adsorption chromatography, and (b) Partition chromatography. a) Adsorption Chromatography: Adsor- ption chromatography is based on the fact that different compounds are adsorbed on an adsorbent to different degrees. Commonly used adsorbents are silica gel and alumina. When a mobile phase is allowed to move over a stationary phase (adsorbent), the components of the mixture move by varying distances over the stationary phase. Following 2019-20

ORGANIC CHEMISTRY – SOME BASIC PRINCIPLES AND TECHNIQUES 361 Column Chromatography: Column plate is then placed in a closed jar containing chromatography involves separation of a the eluant (Fig. 12.12a). As the eluant rises mixture over a column of adsorbent up the plate, the components of the mixture (stationary phase) packed in a glass tube. The move up along with the eluant to different column is fitted with a stopcock at its lower distances depending on their degree of end (Fig. 12.11). The mixture adsorbed on adsorption and separation takes place. The adsorbent is placed on the top of the adsorbent relative adsorption of each component of the column packed in a glass tube. An appropriate mixture is expressed in terms of its retardation eluant which is a liquid or a mixture of liquids factor i.e. Rf value (Fig.12.12 b). is allowed to flow down the column slowly. Depending upon the degree to which the Distance moved by the substance from base line (x) compounds are adsorbed, complete separation Rf = Distance moved by the solvent from base line (y) takes place. The most readily adsorbed substances are retained near the top and others come down to various distances in the column (Fig.12.11). Fig.12.12 (a) Thin layer chromatography. Chromatogram being developed. Fig.12.11 Column chromatography. Different Fig.12.12 (b) Developed chromatogram. stages of separation of components of a mixture. The spots of coloured compounds are visible on TLC plate due to their original colour. The Thin Layer Chromatography: Thin layer spots of colourless compounds, which are chromatography (TLC) is another type of invisible to the eye but fluoresce in ultraviolet adsorption chromatography, which involves light, can be detected by putting the plate under separation of substances of a mixture over a ultraviolet light. Another detection technique is thin layer of an adsorbent coated on glass plate. to place the plate in a covered jar containing a A thin layer (about 0.2mm thick) of an few crystals of iodine. Spots of compounds, adsorbent (silica gel or alumina) is spread over which adsorb iodine, will show up as brown a glass plate of suitable size. The plate is known spots. Sometimes an appropriate reagent may as thin layer chromatography plate or also be sprayed on the plate. For example, chromaplate. The solution of the mixture to amino acids may be detected by spraying the be separated is applied as a small spot about plate with ninhydrin solution (Fig.12.12b). 2 cm above one end of the TLC plate. The glass 2019-20

362 CHEMISTRY Partition Chromatography: Partition The spots of the separated colourless chromatography is based on continuous compounds may be observed either under differential partitioning of components of a ultraviolet light or by the use of an appropriate mixture between stationary and mobile spray reagent as discussed under thin layer phases. Paper chromatography is a type chromatography. of partition chromatography. In paper chromatography, a special quality paper 12.9 QUALITATIVE ANALYSIS OF known as chromatography paper is used. ORGANIC COMPOUNDS Chromatography paper contains water trapped in it, which acts as the stationary phase. The elements present in organic compounds are carbon and hydrogen. In addition to these, A strip of chromatography paper spotted they may also contain oxygen, nitrogen, at the base with the solution of the mixture is sulphur, halogens and phosphorus. suspended in a suitable solvent or a mixture of solvents (Fig. 12.13). This solvent acts as 12.9.1 Detection of Carbon and Hydrogen the mobile phase. The solvent rises up the paper by capillary action and flows over the Carbon and hydrogen are detected by heating spot. The paper selectively retains different the compound with copper(II) oxide. Carbon components according to their differing present in the compound is oxidised to carbon partition in the two phases. The paper strip dioxide (tested with lime-water, which develops so developed is known as a chromatogram. turbidity) and hydrogen to water (tested with The spots of the separated coloured anhydrous copper sulphate, which turns blue). compounds are visible at different heights from the position of initial spot on the chromatogram. C + 2CuO ∆ → 2Cu + CO2 Fig.12.13 Paper chromatography. 2H + CuO ∆ → Cu + H2O Chromatography paper in two different shapes. CO2 + Ca(OH)2 → CaCO3↓ + H2O 5H2O + CuSO4 → CuSO4.5H2O White Blue 12.9.2 Detection of Other Elements Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by “Lassaigne’s test”. The elements present in the compound are converted from covalent form into the ionic form by fusing the compound with sodium metal. Following reactions take place: Na + C + N ∆ → NaCN 2Na + S ∆ → Na2S Na + X ∆ → Na X (X = Cl, Br or I) C, N, S and X come from organic compound. Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused mass by boiling it with distilled water. This extract is known as sodium fusion extract. (A) Test for Nitrogen The sodium fusion extract is boiled with iron(II) sulphate and then acidified with 2019-20