Group 13 and 14 THE p -BLOCK ELEMENTS Objectives ‘After studying this unit, you will be ‘able to appreciate the general trends in the chemistry of p-block elements; esertbe the trends in physical and ‘chemical properties of group 18 and 14 element explain anomalous behaviour of ‘boron and carbon; deseribe allotropie forms of carbon: know the chemistry of some Important compounds of boron, carbon and silicon; list the important uses of group 13, and 14 elements and their ‘compounds. ‘The variation in properties of the p-block elements due to the influence of d and electrons in the inner core of the heavier elements makes their chemistry interesting In p-block elements the last electron enters the outermost potbital. As we know that the number of porbitals Is three and, therefore, the maximum number of electrons that can ‘be accommodated ina set of porbitals is six. Consequently there are six groups of p-biock elements in the periodic table numbering from 13 to 18. Boron, carbon, nitrogen, oxygen, fluorine and helium head the groups. Their valence shell electronie configuration is ns'np'(excep! for He). ‘The inner core of the electronic configuration may, however, differ. The difference in inner core of elements, ‘greatly influences thelr physteal properties (such as atomle and fontc radi, ionisation enthalpy, ete) as well as chemical properties. Consequently, a lot of variation in properties of elements ina group of p-block is observed, The maximum oxidation state shown by a p-block element is equal to the total number of valence electrons (ie., the stim of the and pelectrons). Clearly, the number of possible oxidation, slates increases towards the right of the periodic table. In addition to this so called group oxidation state, p-lock clements may show other oxidation states which normally, but not necessarily, difer from the total number of valence electrons by unit of two, The important oxidation states exhibited by p-block elements are shown in Table 11.1. In boron, carbon and nitrogen families the group oxidation slate is the most stable state for the lighter elements in the group. However, the oxidation state two unit less than the group oxidation state becomes progressively more stable for the heavier elements in each group. The occurrence of oxidation states two unit less than the group oxidation states are sometime attributed to the ‘inert pair effect.‘Table 11.1 General Electronic Configuration and Oxidation States of p-Block Elements ‘Group 13. 14 15 16 17 18. General electronic configuration nsinp! | nstnp | nsénp® nsénp* nsinp? nsingh (1s*for He) First member of the group F He Group oxidation state “ 5 “7 Other oxidation states 4 42-4 44, 42,-2 ]45, 43,41 46,44, 42, ‘The relative stabilities of these two oxidation states — group oxidation state and two unit less than the group oxidation state—_may vary from group to group and will be discussed at appropriate places. Itis interesting to note that the non-metals and metalloids exist only in the p-block of the periodic table. The non-metallic character of elements decreases down the group. In fact the heaviest element in each p-block group is the ‘most metallic in nature. This change from non- ‘metallic to metallic character brings diversity in the chemistry of these elements depending on the group to which they belong. In general, non-metals have higher fonisation enthalpies and higher electronegativities than the metals. Hence, in contrast to metals which readily form cations, non-metals readily form anions. The compounds formed by highly reactive non-metals with highly reactive metals are generally ionic because of large differences in their electronegativities. On the other hand, compounds formed between non-metals themselves are largely covalent in character because of small differences in their electronegativities, The change of non-metallic to metallic character can be best illustrated by the nature of oxides they form. The non-metal oxides are acidic or neutral whereas metal oxides are basic in nature. ‘The frst member of p-block differs from the remaining members of their corresponding group in two major respects. First is the size and all other properties which depend on size. ‘Thus, the lightest p-block elements show the same kind of differences as the lightest s-block elements, lithium and beryllium. The second {important difference, which applies only to the lock elements, arises from the effect of d- orbitals in the valence shell of heavier elements, (starting from the third period onwards) and their lack in second period elements. The second period elements of p-groups starting from boron are restricted to a maximum covalence of four {using 2s and three 2p orbitals). In contrast, the third period elements of p-groups with the electronic configuration. 8s'3p" have the vacant 3d orbitals lying between the 3p and the 4s levels of energy. Using these dorbitals the third period elements can expand their covalence above four. For example, while boron forms only IBF,[, aluminium gives [AIF,|* ion. The presence of these orbitals influences the chemistry of the heavier elements in a number ofother ways. The combined effect of size and availability of d orbitals considerably influences the ability ofthese elements to form bonds. The first member of a group dlffers from the heavier members in its ability to form ‘Pr pr multiple bonds to itself (e.g, C=C,‘THE p-BLOCK BLEMENTS ) and to other second row elements (€.f., (C20, C=N, C=N, N=O). This type of x - bonding is not particularly strong for the heavier block elements. The heavier elements do form x bonds but this involves d orbitals (dx ~ pr or dr ~de). As the d orbitals are of higher ‘energy than the porbitals, they contribute less to the overall stability of molecules than does pr- pr bonding of the second row elements. However, the coordination number in species of heavier elements may be higher than for the first element in the same oxidation state. For example, in +5 oxidation state both Nand P form oxoanions : NO; (three-coordination with x ~bond involving one nitrogen p-orbital) and PO? (four-coordination involving s, pand d orbitals contributing to the x ~ bond). In this unit we will study the chemistry of group 13 and 14 elements of the periodic table. 11.1 GROUP 13 ELEMENTS: THE BORON FAMILY This group elements show a wide variation in properties. Boron is a typical non-metal, aluminium is a metal but shows many chemical similarities to boron, and gallium, indium and thallium are almost exclusively ‘metallic in character. Boron is a fairly rare clement. mainly occurs as orthoborie acid, (H,B0,), borax, Na,B,0,-10H1,0, and kernite, NagB,0,-4H1,0. In India borax occurs in Puga Valley (Ladakh) and Sambhar Lake (Rajasthan). The abundance of boron in earth erustis less than 0.0001% by mass. There are two isotopic forms of boron '°B (19%) and ''B (81%). Aluminium is the most abundant metal and the third most abundant element in the earth's crust (8.3% by mass) after oxygen (45.5%) and Si 27.7%). Bauxite, AlO,, 2H,0 and eryolite, Na,AIF, are the important’ minerals of aluminium. In India it is found as mica in Madhya Pradesh, Karnataka, Orissa and Jammu. Gallium, indium and thallium are less abundant elements in nature. ‘The atomic, physical and chemical properties of these elements are discussed below. 00 11.1.1 Electronic Configuration ‘The outer electronic configuration of these elements is ns’np'. A close look at the electronic configuration suggests that while boron and aluminium have noble gas core, gallium and indium have noble gas plus 10 delectrons, and thallium has noble gas plus 14 f- electrons plus 10 d-electron cores. Thus, the electronic structures of these elements are more complex than for the first two groups of elements discussed in unit 10. ‘This difference in electronic structures affects the other properties and consequently the chemistry of all the elements of this group. 11.1.2 Atomic Radii ‘On moving down the group, for each successive member one extra shell of electrons is added and, therefore, atomic radius is expected to increase. However, a deviation can be seen, ‘Atomic radius of Ga is less than that of Al. This ‘can be understood from the variation in the inner core of the electronic configuration. The presence of additional 10 d-electrons offer only poor screening effect (Unit 2} for the outer electrons from the increased nuclear charge in gallium. Consequently, the atomic radius of gallium (135 pm) is less than that of aluminium (143 pm). 11.1.3 Ionization Enthalpy ‘The ionisation enthalpy values as expected from the general trends do not decrease smoothly down the group. The decrease from Bo Al is associated with increase in size. The observed discontinuity in the ionisation enthalpy values between Al and Ga, and between In and Tare due to inability of d-and _Felectrons ,which have low screening effect, to ‘compensate the increase in nuclear charge. ‘The order of ionisation enthalpies, as expected, is 4.H, a \~a1 = ca s Teatedral AICI, achieves stability by forming a dimer ‘Tetrahedral In trivalent state most of the compounds being covalent are hydrolysed in water. For example, the trichlorides on hyrolysis in water form tetrahedral [M(OH), | species: the hybridisation state of element M is sp’. Aluminium chloride in acidified aqueous solution forms octahedral [Al(H,0), |" ion. In this complex ion, the 3d orbitals of Al are involved and the hybridisation state of Al is spd’. [Probiem 11.1 Standard electrode potential values, E” for Al"*/Al is -1.66 V and that of TI" /TL is ¢1.26V. Predict about the formation of } ion in solution and compare the electropositive character of the two metals. Solution Standard electrode potential values fortwo halfcell reactions suggest that aluminium has high tendency to make Al"*(aq) ions whereas TI” is not only unstable in an Solution buts a powerful oxidising agent also. Thus TT’ Is more stable in solution than TI, Aluminium being able to form ++3 ons easily, is more electropositive than thallium, (@ Reactivity towards air Boron is unreactive in crystalline form. ‘Aluminium forms a very thin oxide layer on the surface which protects the metal from further attack. Amorphous boron and aluminium metal on heating in air form B,0, and Al,O, respectively. With dinitrogen at high temperature they form nitrides. 26 (s) +30, (4) +28, 0, (s) 2E(s)+N, (¢)—*>2EN(s) (E=element) ‘The nature of these oxides varies down the group. Boron trioxide is acidic and reacts with basic (metallic) oxides forming metal borates. Aluminium and gallium oxides are amphoteric and those of indium and thallium are basie in their properties. (i) Reactivity towards acids and alkalies Boron does not react with acids and alkalies even at moderate temperature; but aluminium dissolves in mineral acids and aqueous alkalies and thus shows amphoteric character. Aluminium dissolves in dilute HCI and liberates dihydrogen. 2Al(s) + BHC! (aq) > 2Al°* faq) + 6CY (aq) + 3H) However, concentrated nitric acid renders aluminium passive by forming a protective oxide layer on the surface. Aluminium also reacts with aqueous alkali and liberates dihydrogen. 241) +2NeO Hag + 64,00 2Na(ANOH),| Taq) + 3H Sodium tetrahydroxoaluminate(tI Gi) Reactivity towards halogens ‘These elements react with halogens to form trihalides (except TH). 2E(s) + 3 X, (@) > 2EX, (5) Ke * Cl, Br, 1)12 Problem 11.2 White fumes appear around the bottle of anhydrous aluminium chloride. Give Solution Anhydrous aluminium chloride is partially hydrolysed with atmospheric ‘moisture to liberate HCI gas. Moist HCL appears white in colour. 11.2 IMPORTANT TRENDS AND ANOMALOUS PROPERTIES OF BORON Certain important trends can be observed in the chemical behaviour of group 18 elements. ‘The tri-chlorides, bromides and iodides of all these elements being covalent in nature are hydrolysed in water. Species like tetrahedral [M(OH),l and ‘octahedral [M(H,0),)”", except in boron, exist in aqueous medium. ‘The monomeric trihalides, being electron deficient, are strong Lewis acids. Boron tuifluoride easily reacts with Lewis bases such as NH, to complete octet around boron, F,B 4:NH, > F,BCNH, It is due to the absence of d orbitals that the maximum covalence of B is 4. Since the d orbitals are available with Al and other elements, the maximum covalence can be expected beyond 4. Most of the other metal halides (e.g., AICl,) are dimerised through halogen bridging (e... Al,Cl,). The metal species completes its’ octet ‘by accepting electrons from halogen in these halogen bridged molecules. Problem 11.3 Boron is unable to form BF, ion. Explain. Solution Due tonon-availabllity of d orbitals, boron. is unable to expand its octet. Therefore, ‘the maximum covalence of boron cannot exceed 4. Borax It is the most important compound of boron, It is a white crystalline solid of formula Na,B,0,-10H,0. In fact it contains the tetranuclear units [B,O, (OH), |” and correct formula; therefore, is Na,{B,0, (OH),).8H,0. Borax dissolves in water to ‘give an alkaline solution. Na,B,0, +7H,0 > 2NaOH + 4H,BO, Orthoborie acid On heating, borax first loses water ‘molecules and swells up. On further heating it tums intoa transparent liquid, which solidifies Into glass like material known as borax bead Na,B,0,.10H,0__8, Na,B,0,_4_, 2NaBO, Sodium, + BOs metaborate Borie anhydride borax bead test can be used to identify them in the laboratory. For example, when borax is heated in a Bunsen burner flame with CoO on a loop of platinum wire, a blue coloured Co(BO,}, bead is formed.11, Match the following. Columnt Column tt Sam SS (Ores) (Formula) | | Semis | saunte 0 med (A) | Fluorspar | (p) | AleOs.2H:0 soem m0. (B) | Cryolite (q) | CaFo oe Fe00. (C)| Bauxite | (r) | MgCOs.Cacos wach Caco,/cuorn, (1) (A)-(8); (B)-(q); (C}-(r); D-(p) coon ah (2) (A(Q); (B)-(8); (Cp); De) 7 (3) (A}(0): (B)(a): (C48); D-(7) (4) (AY(a): (BH(S): (CHIN: Answer (2) Sol. (A) Fluorspar - CaF2 (B) Cryolite —— NasfAIFe] (C) Bauxite = = AlOs.2H20 11.5 GROUP 14 ELEMENTS: THE CARBON (D) Dolomite - MgCOs.Cacos ee Carbon (C}, silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) are the members of group 14. Carbon is the seventeenth most abundant clement by mass in the earth’s crust. It is widely distributed in nature in free as well as in the combined state. In elemental state it is available as coal, graphite and diamond; however, in combined state it is present as metal carbonates, hydrocarbons and carbon dioxide gas (0.03%) in air. One can emphatically say that carbon is the most versatile element in the world. Its combination with other elements such as dihydrogen, dioxygen, chlorine and sulphur provides an astonishing array of materials ranging from living tissues to drugs and plastics. Organic chemistry is devoted to carbon containing compounds. It is an essential constituent of all living organisms. Naturally occurring ¢arbon contains two stable isotopes:"*C and C. In addition to these, third isotope, “C is. also present. Itis a radioactive isotope with half- life 5770 years and used for radiocarbon dating, Silicon Is the second (27.7 % by mass) ‘most abundant element on the earth’s crust and is present in nature in the form of silica and silicates. Silicon is a very important component of ceramics, glass and cement.‘THE p-BLOCK BLEMENTS Germanium exists only in traces. Tin occurs mainly as cassiterite, SnO, and lead as galena, PbS. Ultrapure form of germanium and silicon are used to make transistors and ‘semiconductor devices. ‘The important atomic and physical properties of the group 14 elements along with their electronic configuration are given in Table 11.3 Some of the atomic, physical and chemical properties are discussed below: 11.5.1 Electronic Configuration ‘The valence shell electronic configuration of these elements is ns'np’. The inner core of the electronic configuration of elements in this group also differs. 11.5.2 Covalent Radius ‘There is a considerable increase in covalent. radius from C to Si, thereafter from Si to Pb a ‘small increase in radius is observed. This is, ais due to the presence of completely filed and f orbitals in heavier members. 11.5.3 Ionization Enthalpy ‘The first ionization enthalpy of group 14 members is higher than the corresponding members of group 13. The influence of inner core electrons is visible here also. In general the jonisation enthalpy decreases down the group. ‘Small decrease in A,H from Si to Ge to Snand slight increase in AH from Sn to Pb is the consequence of poor shielding effect of intervening dand forbitals and increase in size oftheatom. 11.5.4 Electronegativity Due to smalll size, the elements of this group are slightly more electronegative than group 13 elements. The electronegativity values for elements from Si to Pb are almost the same. 11.5.5 Physical Properties All group 14 members are solids. Carbon and siliconarenon-metals,germaniumisametalloid, ‘Table 11.3 Atomic and Physical Properties of Group 14 Elements Element rope Carbon Germanium | Tin Toad Property . = = [Atomic Number 6 32 82 [Atomic mass (g mor] 12.01 72.60 207.2 Electronic THel2s"2pF Tarlsd™4s ap ? | bxelaf"5a6s"6p" configuration Covalent radius/par| 7 na 122 140 146 Tonic radius M™/pai" = 40 53 69 78. Tonie radius Mpa = = 73 18 79 Tonization | a7, TO86 786 761 708 715 enthalpy/ | ay, 2352 | 1877 1537 wait 1450 kimor® | an, 4620 | 3228 3300 2942 3081 aH, 220 | 4354 4409 3929) 4082 Blectronegativity” 18 18 18 19 Density’/g em" 234 3.32 726 134 elting point 7 168s Tai8 505. 6007 Boiling point/ =| 3550. 3123) 2596, 2024 Electrical resistivity/] 10-10" 50 50 10° 2 10° ohm em (203 1)a16 whereas tin and lead are soft metals with low ‘meltingpoints, Meltingpointsand bollingpoints ofgroup 14 clementsaremuch higher than those ofcorrespondingelements of group 13. 11.5.6 Chemical Properties Oxidation states and trends in chemical reactivity “The group 14 elements have four electrons in outermost shell, Te common oxidation states exhibited by these elements are +4 and +2. Carbon also exhibits negative oxidation states. Since the sum of the first four ionization enthalpies is very high, compounds in +4 oxidation state are generally covalent in nature. In heavier members the tendeney to show +2 oxidation state inereases in the sequenc GecSnePb. It is due to the inability of ns’ electrons of valence shell to participate in bonding, The relative stabilities of these two oxidation states vary down the group. Carbon and silicon mostly show +4 oxidation state. Germanium forms stable compounds in +4 state and only few compounds in 42 state. Tin forms compounds in bath oxidation states (Sn in #2 state is a reducing agent). Lead compounds in 42 state are stable and in +4 slate are strong oxidising agents. In tetravalent state the number of electrons around the central atom in a molecule (e.g, carbon in CCL) {s 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 ean do so, ILis because of the presence of orbital in them. Due to this, their halides undergo hydrolysis and have tendency to form complexes by accepting electron pairs from donor species. For example, the species like, SiF?. [GeCl, [Sn(OH),]* exist where the hybridisation of the central atom is sp'e. @ Reactivity towards oxygen All members when heated in oxygen form oxides, There are mainly two types of oxides, ie,, monoxide and dioxide of formula MO and MO, respectively. SiO only exists at high temperature. Oxides in higher oxidation states of elements are generally more acidic than ‘CHEMISTRY those in lower oxidation states. The dioxides — CO,, SiO, and GeO, are acidic, whereas SnO, and PbO, are amphoteric in nature. Among monoxides, CO is neutral, GeO is distinctly acidle whereas SnO and PbO are amphoteric. Problem 11.5 Select the member(s) of group 14 that (i) forms the most acidie dioxide, (i) is ‘commonly found in +2 oxidation state, (ii) used as semiconductor. Solution (carbon (i) ead i silicon and germanium, Gi) Reactivity towards water Carbon, silicon and germanium are not affected by water. Tin decomposes steam to form dioxide and dihydrogen gas. ‘Sn + 2H,0 ++ Sn0, + 2H, Lead 1s unaffected by water, probably because ofa protective oxide lm formation. iii) Reactivity towards halogen ‘These elements can form halides of formula MX, and MX, (where X =F, Cl, Br, I. Except carbon, all other members react directly with halogen under suitable condition to make halides. Most ofthe MX, are covalent in nature. The central metal atom in these halides undergoes sp” hybridisation and the molecule Js tetrahedral in shape. Exceptions are SnF, and PDF, which are onic in nature. Pbl, does not exist because Pb—I bond initially formed during the reaction, does not release enough energy to unpair 6 electrons and excite one of them to higher orbital to have four unpaired tlectrons around lead atom, Heavier members Ge to Pb are able to make halides of formula MX, Stability of halides increases down the group, Considering the thermal and chemical Stablliy, GeX, is more stable than GeX,, whereas PDX, ismore than PbX,, Except CCl, other tetrachlorides are easliy hydrolysed by water because the central atom can‘THE p-BLOCK BLEMENTS accommodate the lone pair of electrons from oxygen atom of water molecule in dorbital Hydrolysis can be understood by taking the example of SiCl, It undergoes hydrolysis, by initially accepting lone pair of electrons from water molecule in corbitals of Si, finally leading to the formation of Si(OH), as shown below: ca a Ve. I Si st inc ie & | Sou ta u ca ou Si 07 | Son Ho Silcie actd Problem 11. 6 [SiF,)” is known whereas [SICI,J* not. Give possible reasons, Solution ‘The main reasons are: ( six large chloride fons cannot be accommodated around Si due to umitation of its size. i) interaction between lone pair of chloride ion and St*” is not very strong, 11.6 IMPORTANT TRENDS AND ANOMALOUS BEHAVIOUR OF ‘CARBON Like first member of other groups, carbon also differs from rest of the members of its group. It is due to its smaller size, higher electronegativity, higher lonisation enthalpy and unavailability of d orbitals. In carbon, only s and p orbitals are available for bonding and, therefore, it can accommodate only four pairs of clectrons around it. This would limit the maximum covalence to four whereas other members can expand their covalence due to the presence of dorbitals. air Carbon also has unique ability to form px- prmultiple bonds with itself and with other ‘atoms of small size and high electronegativity. Few examples of multiple bonding are: C=C, C=C, C=0,C=S, and C=N, Heavier elements do not form pr- pr bonds because their atomic orbitals are too large and diffuse to have effective overlapping. Carbon atoms have the tendency to link with one another through covalent bonds to form chains and rings. This property is called catenation. This is because C—C bonds are very strong, Down the group the size increases and electronegativity decreases, and, thereby, tendency to show catenation decreases. This can be clearly seen from bond enthalpies values. The order of eatenation is C >> Si > Ge» Sn. Lead does not show catenation. Bond Bond enthalpy / kJ mol co 348 si-si 297 Ge-Ge 260 Sn—Sn 240 Due to property of catenation and px px bond formation, carbon is able to show Notropic forms.The chemical formula of zeolite is Naz Alp Sig Og. xH2 O. Feldspar Formula KAISi308 Silicones are water repelling in nature, high thermal stability, high dielectric strength They have wide applications. They are used as sealant, greases, electrical insulators and for water proofing of fabrics. Being biocompatible they are also used in surgleal and cosmetic plants. Problem: 11.8 Solution ; chains in which alkyl or phenyl groups ‘occupy the remaining bonding positions ‘on each silicon. They are hydrophobie (water repellant) in nature, 11.8.5 Silicates A large number of silicates minerals exist in nature, Some of the examples are feldspar, zeolites, mica and asbestos. The basic structural unit of silicates is SiO," (Fig.11.7) in which silicon atom is bonded to four ‘oxygen atoms in tetrahedron fashion. In silicates either the diserete unit is present or a number of such units are joined together via corners by sharing 1,23 or 4 oxygen atoms per silicate units. When silicate units are linked together, they form chain, ring, sheet or three-dimensional structures. Negative charge on silicate structure is CHEMISTRY . + Silicon (© Oxygen @ © Fig. 11.7. (a) Tetrahedral structure of SO anion; (b) Representation of SiO; unit neutralised by positively charged metal fons. fall the four comers are shared with other tetrahedral units, three-dimensional network is formed. ‘Two important man-made silicates are lass and cement. 11.8.6 Zeolites Ifaluminium atoms replace few silicon atoms in three-dimensional network of silicon dioxide, overall structure known as aluminosilicate, acquires a negative charge. Cations such as Na’, K" or Ca** balance the negative charge. Examples are feldspar and zeolites. Zeolites are widely used as a catalyst in petrochemical Industries for cracking of hydrocarbons and isomerisation, e.g. ZSM-5 (A type of zeolite) used to convert alcohols directly into gasoline. Hydrated zeolites are used as ion exchangers in softening of hard” water. ‘SUMMARY 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 periodle lable numbering from 13 to 18. Their valence shell eleetronie configuration is ns'np!™ {except for Hel. Differences in the inner eore of their electronic configuration greatly {influence their physical and chemical properties. As a consequence of this, a lot of varfation in properties among these elements is observed. In addition to the group axidation ‘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 forthe lighter lements of the group, lower oxidation states become progressively more stable for the heavier elements. The combined effect of size and avatlabilty of d orbitals considerably‘THE p-BLOCK ELEMENTS influences the ability of these clements to form x-bonds. While the lighter elements form pr-px bonds, the heavier ones form dx-px or da-dx bonds. Absence of d orbital in Second period elements limits their maximum eovalence to 4 while heavier ones can exceed this limit Boron is a typical non-metal and the other members are metals. The availabilty of 3 valence electrons (2s'2p!) for covalent bond formation using four orbitals (2s, 2p, 2p, and 2p) leads to the so called electron deficiency in boron compounds. This deficleney ‘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, B,1i,. 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 borte aetd and borax. Borie acid. BIOM, Is a weak monobasic acid: it acts as a Lewis acid by accepting electrons from hydroxyl ion. Borax is a white crystalline sold of formula Na,{B,0,(0H),:8H,0. The borax bead test ives 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 8 a consequence of the so called inert patr effect. Carbon is a typical non-metal forming covalent bonds employing all its four valence electrons (2s"2p'). It shows the property of eatenation, 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 eatenation decreases as C>>Si>Ge = Sn > Pb. Carbon provides one of the best examples of allotropy. Three important allotropes of earbon are diamond. graphite and fullerenes. The members of the carbon family mainly exhibit +4 and +2 oxidation ‘States; compotds in +1 oxidation states are generally covalent in nature. The tendency to show 42 oxidation state increases among heavier elements. Lead in +2 state is stable whereas in +4 oxidation state it isa strong oxidising agent. Carbon also exhibits negative ‘oxidation states. It forms two important oxies: CO and CO,. Carbon monoxide is neutral whereas CO, is acidie in nature. Carbon monoxide having lone pair of electrons on forms metal earbonyls. It is deadly poisonous due to higher stability ofits haemoglobin complex as compared (o that of oxyhaemoglobin complex. Carbon dioxide as such is not toxie. However. inereased content of CO, 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, silieates and silicones arc important class of compounds and find applications in industry and technology. EXERCISES 11,1 Discuss the pattern of variation in the oxidation states of (WB toTl and (i) C to Pb. 11.2 How can you explain higher stability of BCI, as compared to TICl, ? 11.3 Why does boron tniffouride behave as a Lewis acid ? 11.4 Consider the compounds, BCI, and CCI, How will they behave with water ? Justify 11.5 Is boric acid a protic acid ? Explain, 11.6 Explain what happens when borie acid is heated, 11,7 Describe the shapes of BF, and BH,. Assign the hybridisation of boron in these species. 11,8 Write reactions to justify amphoteric nature of aluminium, aaaes 11.10 an az as naa 11.45 16 a7 11.18 11.19 11.20 aa 11.22 11.23 12a 11.28 ‘CHEMISTRY What are electron deficient compounds ? Are BCI, and SiCI, electron deficient species ? Explain Write the resonance structures of CO?and HCO; What is the state of hybridisation of carbon in (a) CO (b) diamond (6) graphite? Explain the difference in properties of diamond and graphite on the basis of thelr structures. Rationalise the given statements and give chemical reactions : + Lead) chloride reacts with Cl, to glve PbCI, + Lead\fV) chloride is highly unstable towards heat + Lead is known not to form an iodide, Poly Suggest reasons why the B-F bond lengths in BF, (130 pm) and BF; (145 pm difer IF B-Cl bond has a dipole moment, explain why BCl, molecule has zero dipole moment. Aluminium triluoride is insoluble in anhydrous HF but dissolves on addition of NaF. Aluminium trifluoride precipitates out of the resulting Solution when gaseous BF, is bubbled through. Suggest a reason as to why CO fs poisonous. How is excessive content of CO, responsible for global warming 2 Explain structures of diborane and borie actd. What happens when (a) Borax is heated strongly, (0) Borie acid is added to water, (6) Aluminium is treated with dilute NaOH, (@) BF, is reacted with ammonia ? Explain the following reactions (a) Silicon is heated with methyl chloride at high temperature in the presence of copper: (©) Silicon dioxide is treated with hydrogen fuoridk (6) CO Is heated with 2n0: (@) Hydrated alumina is treated with aqueous NaOH solution. Give reasons (Cone. HNO, can be transported in aluminium container. (A mixture of dilute NaOH and aluminium pieces is used to open ‘drain, (4) Graphite is used as lubricant, (iv) Diamond is used as an abrasive. (%) Aluminium alloys are used to make aircraft body. (i) Aluminium utensils should not be kept in water overnight. (vi) Aluminium wire is used to make transmission cables. Explain why is there a phenomenal decrease in fonization 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?‘THE p-BLOCK 11.26 a7 11.28 11.29 11.30 11.31 11.32. 11.33 11.34 1 1185 11.38 11.37 11.38 ELEMENTS 295 (a) Classify following oxides as neutral, acidic, baste or amphoterie: C0, B,0,,Si0,, CO, Al,0,, PbO,,TL0, (0) Write suitable chemical equations to show their nature. In some of the reactions thallium resembles aluminium, whereas in others it resembles with group 1 metals. Support this statement by giving some evidences. ‘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) Hl Compound (A) is soluble in dilute HC! to form compound (C). The compound ' (A) when heated strongly gives (D). which is used to extract metal. Identity (049, (4, (B}, (C) and (0). Write sultabte equations to support their identities, What do you understand by (a) inert pair effect (b) allotropy and (6) eatenation? A certain salt X, gives the following results. (@ ts aqueous solution is alkaline to litmus, (i) 1 swells up to a glassy material ¥ on strong heating. (ii), When cone. H,S0, is added to a hot solution of X,white erystal of an acid Z separates out Write equations for all the above reactions and identify X, ¥ and 2, Write balanced equations for: (0) BR,+Lin > (i) BAA, + H,0> (it) Nall + BH, Ww) HBO, 4s () Al + NaOH > (BH, +NH, > Give one method for industrial preparation and one for laboratory preparation of CO and CO, each. ‘An aqueous solution of borax is (@) neutral (0) amphoteric (6) baste (@) aciate Borie acid is polymeric due to (2) its acide nature (0) the presence of hydrogen bonds (6) its monobasie nature _—(@)_its geometry ‘The type of hybridisation of boron in diborane Is @sp Ws oe (0 dsp ‘Thermodynamically the most stable form of carbon is, (0) diamond (b) graphite (©) fullerenes (@) coal Blements of group 14 (a) exhibit oxidation state of +4 only (©) exhibit oxidation state of +2 and +4 (6) form MP and M* tons (@) form Me and M*+ions If the starting material for the manufacture of silicones is RSICI,, write the structure of the product formed.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Qu Discuss the pattern of variation in the oxidation states of (@)BtoTl (i) Cto Pb ‘Ans: @BtoTl Group 13 elements have their electronic configuration of ns® np’ and the oxidation state exhibited by these ‘elements should be 3. Apart from these two electrons boron and aluminium, other elements of this group exhibit both +1 and +3 oxidation states. Boron and aluminium show oxidation state of +3 due to the inert pair effect. The two electrons, which are present in the S-shell do not participate in bonding as they are strongly attracted by the nucleus. As we move down the group, the inert pair effect becomes more prominent. Therefore, Ga (+1) is unstable and T (+1) is very stable ‘On moving down the group, the stability of the +3 oxidation state gets decreased. Group 13 element Oxidation state B 43 Al +3 Ga, In, Ti 41,43 (i) Cto Pb The electronic configuration of group 14 elements is ns* np*. Hence, the most common oxidation state exhibited by them should be +4, Upon moving down the group, the +2 oxidation state becomes increasingly ‘common and the relatively higher oxidation states become less stable, This is because of the inert pair effect, Si and C mostly exhibit the +4 state, Although Sn, Ge and Pb show the +4 and +2 states, the stability of higher oxidation states decrease while moving down the group. Group 14 clement Oxidation state c 4 Si 4 Ge, Sn, PDNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Stability of +2 state increases qq“ > C Si Ge Sn Pb —— Stability of +4 state decreases Qn How can you explain the higher stability of BCI, as compared to TICI.? Ans: Thallium and boron belong to group 13 of the periodic table and +1 oxidation state becomes more stable as ‘we move down the group. Boron is more stable than thallium because +3 state of thallium is highly oxidizing and it reverts back to a more stable +1 state. Qi13 Why does boron trifluoride behave as a Lewis acid? ‘Ans: ‘The electronic configuration of boron is ns* np’. It contains 3 electrons in its valence shell. Thus, it can form only 3 covalent bonds which mean that there are only 6 electrons around boron and its octet remains incomplete. When tof the boron’s atom combines with 3 fluorine atoms, its octet (8) remains incomplete. Therefore, boron trifluoride remains electron-deficient and acts as Lewis acid. Sy oo prorbital i BIDS B—F 7 0 qi Consider the compounds, BCI: and CCL.. How will they behave with water? Justify. Ans: Since it is a Lewis acid, BCL readily undergoes hydrolysis to form boric acid. BCl; + 3H,0 + 3HCl+ B(OH);NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements On the other hand, CCI. does not undergo hydrolysis readily. Since carbon does possess any vacant orbitals, it cannot accept any electrons from water in order to form an intermediate. When CCl. and water are mixed, separate layers are formed. CCl, + H20 + NoReaction ans Is boric acid a protic acid? Explain. Ans: Boric acid isa weak monobasic acid which behaves as a Lewis ac B(OH)3+ 2HOH > [B(OH)i)” + H30* Itbehaves as a Lewis acid by accepting an electron par from the OH ion Qi6 Explain what happens when boric acid is heated Ans: So, itis not a protic acid. Upon heating orthoboric acid at a temperature of 370 K or above, itis converted into metaboric acid and, upon further heating, yields boric oxide (B:0:).. A A A 3 BOs. HBO: Fix 2 BsOr ed no?2O3 Metaboric Tetraboric Boric acid acid oxide Qu7 Describe the shapes of BF: and BH. Assign the hybridisation of boron in these species Ans: @ BF Boron tends to form monomeric covalent halides because of its small size and high electronegativity. These halides of boron usually have a planar triangular geometry, which can be explained by the overlap of three ‘sp* hybridized orbitals of boron with the sp’ orbitals of halogen atoms. It can be noted that boron is ‘sp* hybridized in BF,NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Polarbonde 6 6- Boron Trifluoride i) BHe BH. has a tetrahedral structure which is accounted for by the sp? hybridized orbitals. qe Write reactions to justify amphoteric nature of aluminium ‘Ans: Amphoteric substances are substances that exhibit both acidic and basic qualities. Since aluminium dissolves in both acids and bases, itis said to have an amphoteric nature. o 2Als) + CHOl(aq) > 2AM) + GCL + 3H(q o) 2Alp) + 2NaOH qq) + 6H20q) + 2Na*[AUOH)aliag + 3H) ans ‘What are electron deficient compounds? Are BCl,and SiCI, electron deficient species? Explain. Ans: Electron-deficient compounds are chemical compounds with incomplete octets that tend to acquire 1 or more electrons to complete their octet configurations. Bel,NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements BClis a good example of an electron-deficient compound. Since boron has three valence electrons, it forms 3 single bonds with chlorine, giving the boron atom a total of 6 electrons in the outermost shell. However, it is still short of 2 electrons to complete its octet. sich, Silicon has 4 valence electrons (its electronic configuration is 2s* 2p?). Its octet is completed after forming four single bonds with four different chlorine atoms. Therefore, SiCl. is not an electron-deficient compound. Qit.t0 Write the resonance structures of CO3 and HCOs . Ans: - For CO3 ‘There are only 2 resonating structures for the bicarbonate ion, For HCO; qi What is the state of hybridisation of carbon in (a) COs (b) diamond (c) graphite? ‘Ans: ‘The state of hybridization of carbon in: (@) corNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Cin COs is sp* hybriaized and is bonded to 3 oxygen atoms. (b) Diamond Each diamond carbon is hybridized by sp? and is bound to 4 additional carbon atoms. (©) Graphite Each carbon atom in graphite is hybridized with sp* and is bound to 3 other atoms of carbon. Qia2 Explain the difference in properties of diamond and graphite on the basis of their structures. Ans: Diamond Graphite Ichas a crystalline lattice Ithas a layered structure In diamond, each carbon atom is In graphite, each atom is sp2 hybridised and is bonded to p3 hybridised and bonded to four other carbon three other carbon atoms through a sigma bond. The atoms through a sigma bond. fourth electron forms a pi bond. thas a rigid covalent bond network which is Its quite soft and its layers can be separated easily. difficult to break. ‘The C-C bond length in diamond is 154 pm. The C-C bond length in graphite is 141.5 pm. [tacts as an electric insulator, Itis a good conductor of electricity. Q11.13 Rationalize the given statements and give chemical reactions: ‘+ Lead (ll) chloride reacts with Cl. to give PbCl.. + Lead (IV) chloride is highly unstable towards heat. ‘+ Lead is known not to form an iodide, Pbl. ‘+ Lead is a member of group 14 of the periodic table. The two oxidation statuses this group shows are +2 and +4, The + 2 oxidation state becomes more stable when moving down the group, and the oxidation status + 4 becomes less stable. This is due to the inert pair effect. So, PbCl.is significantly less stable than PbCL.. However, PbCI. formation occurs when the chlorine gas is bubbled through a PICl, saturated solution.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements PbCI,,, + Clg —* PbCl,, ‘+ Due to the inert pair effect, the higher oxidation state becomes unstable when moving down group v. PbCI,y, —* PBCly.) + Cl + Lead is not known for forming PbI4 In nature, Pb (+ 4) is oxidizing, and I reduce in nature. A Pb(WV) ‘and iodide ion combination are not stable. lodide ion reduces sharply in nature. Pb(IV) oxidizes I" to band reduces itself to Pb(I) Poly Pbk + Ih Qu.i4 ‘Suggest reasons why the B-F bond lengths in BF; (130 pm) and BF-(143 pm) differ. ‘Ans: In BF, the length of the BF bond is shorter than that of the B-F bond in BF. BF; is a species that has an electron deficiency. The fluorine and boron atoms undergo pn-pn back-bonding with a vacant p-orbital on boron to remove this deficiency. This endows the B-F bond with a double bond character. p - orbital yp - orbital pm- pr back bonding ‘This double-bond character causes a shortening of the bond length by BF: (130 pr). However, a change in hybridization from sp* (in BE) to sp* (in BF.) occurs when BF: coordinates with the fluoride ion. Boron now forms 4 sigma bonds and the character of the double-bond is lost. This represents the length of a 143 pm B- F bond in BF. ion,NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements F F oo r7 Ne Tetrahedral structure Qias If B-Cl bond has a dipole moment, explain why BCI: molecule has zero dipole moment. Ans: ‘The B ~ Cl bond is naturally polar because of the difference in the electronegativities of Cl and B. Yet the ‘molecule of BCI: is non-polar. That is because the shape of BCI is trigonal planar. The molecule is, ‘symmetrical. So the respective B ~ Cl bond dipole moments cancel each other, creating a zero dipole nee : cl ~~ : ———Cl B- cl g amas ‘Aluminium trifluoride is insoluble in anhydrous HF but dissolves when NaF is added. It precipitates out of the resulting solution when gaseous BF,(boron trifluoride) is bubbled through. Give reasons. Ans: Hydrogen fluoride is a covalent compound with a very strong intermolecular bonding to hydrogen. Thus, it does not provide ions and does not dissolve aluminium fluoride in it. Sodium fluoride is an ionic compound, and Alf dissolves when added to the mixture. This is because of the Free F- available, The reaction involved in the process is: ALF; + 3NaF > Nas[ALFs] When boron trifluoride is added to the solution, aluminium fluoride becomes precipitated out of solution. This is because the boron’s tendency to form complexes is much greater than that of aluminium, So, when boron trifluoride is added to the solution, B replaces Al of the complexes by the following reaction: Nas[AlF| + 3BF-> 3Na[BFi] + ALFyNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Qia7: ‘Suggest a reason as to why CO is poisonous. ‘Ans: Given its ability to form a complex with haemoglobin, carbon monoxide is highly poisonous. The former impedes binding with oxygen by Hb. Consequently, a person dies due to suffocation on not receiving oxygen ‘The complex CO ~ Hb is more stable than the complex O;-Hb. The CO ~ Hb complex is found to be roughly 200 times more stable than the O.-Hb complex. Q11.18 How is the excessive content of CO: responsible for global warming? ‘Ans: Carbon dioxide is a gas that is necessary for our survival. The increased CO: content in the environment, however, poses a serious threat. An increase in fossil fuel combustion, calcareous decomposition, and a decrease in the number of trees has resulted in higher carbon dioxide levels. Carbon dioxide has the property of trapping the heat that sun rays provide. The higher the carbon dioxide level, the greater the ‘amount of heat that is trapped. This leads to an increase in atmospheric temperature which causes global warming. Qi9 Explain the structures of diborane and boric acid. ‘Ans: (@) Diborane BH. is a compound that lacks an electron. B:H. only has 12 electrons ~ 6 eof 6H atoms and 3 eof 2B ‘atoms each. So none of the boron atoms has any electrons left after being mixed with 3 H atoms. X-ray Jiffraction studies showed the diborane structure as: H, |,= bridging hydrogen ‘Two boron and four-terminal atoms of hydrogen (H) lie in one direction, while the other two bridging atoms of hydrogen (H.) are on the surface perpendicular to the plane of boron atoms. Once, of the two atoms of hydrogen bridging, one atom of H lies above the plane, and the other below the plane. The terminal bonds are regular two-centre two-electron (2c ~ 2e-) bonds, while the two bridgings (B-H~B) bonds are three- centre two-electron (3c ~ 2e") bonds.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements (©) Boric acid Boric acid is structured ina layered form. Each planar unit BOS is connected by atoms H to each other. The H atoms form a covalent bond with a B03 unit whereas another B03 unit forms a hydrogen bond. The dotted lines, in the given figure, represent hydrogen bonds. 911.20 What happens when (a) Borax is heated strongly (b) Boric acid is added to water (©) Aluminum is treated with dilute NaOH (@) BF: is reacted with ammonia? ‘Ans: (a) Borax is heated strongly Borax undergoes various transformations when heated. itis losing molecules and swells of water at first. ‘Then it becomes a translucent liquid, which solidifies to form a glass-like material called a borax bead. Na:B.0;.10H:0 — Na,B.0;~+ 2NaBO; + BOs Borax Sodium Metaborate Boric anhydrideNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements (b) Boric is added to water When boric acid is added to water, it accepts electrons from -OH ion. B(OH)3 + 2H20 + [B(OH)4)" + H30* (©) Aluminum is treated with dilute NaOH ‘Aluminum reacts to sodium tetrahydroxoaluminate(tl) by forming dilute NaOH. In this process, hydrogen gasis liberated. 2Alia) + 2NAOH (aq) + GH2OW > 2Na*[AUOH)4\(4 + 3H2(9) (@) BF. is reacted with ammonia BF; (a Lewis acid) reacts with NH: (a Lewis base) to form a product. This results in a complete octet around Bin BF, BF;+ NH3—> [H3N > BF3] Qi Explain the following reactions igh temperature in the presence of copper; (®) Silicon dioxide is treated with hydrogen fluoride; (©) CO is heated with Zn0; (@) Hydrated alumina is treated with aqueous NaOH solution. Ans: {@) Silicon is heated with methyl chloride at high temperature in the presence of copper ‘A class of organosilicon polymers called methy-substituted chlorosilane MeSiCl, Me,SiCh, Me.SiCl, and Me.Si) are formed when silicon reacts with methyl chloride in the presence of copper (catalyst) and at a temperature of about §37 K. Cupowder renscisi 2+ (cHp,sich anc] 42H,0 (CH3)2Si(OH)2 cH Hy cu, | cH Polymersatia 1 nHO— Si— OH +HO — si—cry EE, _ ob sot si—cry I l “m0 I CH cH cy | cry Silicone © treated with hydrogen fluoride.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements When the hydrogen fluoride (HF) heats silicon dioxide (Si0,), it forms silicon tetrafluoride (SiF.). The Si - bond is usually a strong bond, avoiding any attack by halogens and most acids even at high temperatures. It is being attacked by HF though. SiO, + 4HF + SiFy+ 2H20 ‘The SiF. formed in this reaction can further react with HF to form hydro-fluorosilicie acid SiF, + 2HF > HpSiFy (c) CO is heated with ZnO ‘When CO reacts with ZnO, it reduces ZnO to Zn. CO acts as a reducing agent. ZnO (s) + COw + Zr + COrg) (d) Hydrated alumina is treated with aqueous NaOH solution ‘When sodium hydroxide is added to hydrated alumina, the former dissolves in the latter due to the sodium rmeta-aluminate formation AlO3.2H2O + 2NaOH ~» 2NaAlOz + 3H2O nize Give reasons: () Conc.HNO; can be transported in an aluminium container. (i)A mixture of dilute NaOH and aluminium pieces is used to open drain. (iii) Graphite is used as the lubricant. (iv) Diamond is used as an abrasive (v) Aluminum alloys are used to make aircraft body. (vi) Aluminum utensils should not be kept in water overnight. (vii) Aluminum wire is used to make transmission cables. Ans: ( Conc.HNO; can be transported in an aluminium container. {As it reacts with aluminium to form a thin protective oxide layer on the aluminium surface, concentrated HNO3 can be stored and transported in aluminium containers. Gi) A mixture of dilute NaOH and aluminium pieces is used to open the drain. ‘Sodium hydroxide and alumi im react to form sodium tetra hydro aluminate (ll) and hydrogen gas. 2Al+ 2NaOH + 6H2O > 2Na*[AOH)s)~ + 3H (iii) Graphite is used as the lubricant.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Graphite has a layered structure, and the forces of weak van der Waals bind different layers of graphite together. These layers may slide one over another. Graphite is slippery and soft. Graphite can, therefore, be utilized as a lubricant, (iw) Diamond i Carbon is sp3 hybridized in Diamond, With the help of strong covalent bonds, each carbon atom is bound to four other carbon atoms. These covalent bonds exist all over the surface, giving it a very rigid 3-D structure. ‘This extended covalent bonding is very hard to break and for this reason, diamond is the hardest known substance. Itis therefore used as an abrasive and for cutting instruments. (v) Alu used as an abrasive jum alloys are used to make aircraft body. ‘Aluminium alloys such as duralumin (aluminium-copper alloys) is light, tough and resistant to corrosion and hence is used to make aircraft body. (vi) Aluminium utensils should not be kept in water overnight. ‘The oxygen in water reacts to create a thin layer of aluminium oxide with aluminium. This layer prevents further reaction from aluminium. Nevertheless, some amount of aluminium oxide can dissolve in water if the water is held in an aluminium vessel for long periods of time. Water should not be stored overnight in ‘aluminium vessels because aluminium fons are harmful (vil) Aluminium wire is used to make transmission cables. Gold, copper, and aluminium are amongst the best electricity conductors. Silver is a costly metal and very delicate gold links. Copper is pretty expensive, and heavy too. Aluminium wires are good conductors of electricity and also itis cheap metal easily available, light in weight and also very good ductility. So itis used to make transmission cables. Q11.23 Explain why is there a phenomenal decrease in ionization enthalpy from carbon to silicon? Ans: Carbon ionizing enthalpy (the first element in group 14) is very high (1086 kJ / mol). That is expected because ofits small size. However, there is a sharp decrease in enthalpy (786 kJ) when moving down the ‘group to silicon. This is due to a considerable increase in the atomic sizes of elements when the group is moving down. Q11.24 How would you explain the lower atomic radius of Ga as compared to Al? ‘Ans: | Atomic radius (in pm) | Aluminium 143 | Gallium 1NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Although Ga has more than one shell than A, it is smaller in size than Al. This is because the 3¢-electrons have poor shielding effect. The shielding effect of d-electrons is very poor, and the effective nuclear charge ‘experienced in gallium by the valence electrons is far more than in Al. 911.25 What are allotropes? Sketch the structure of two allotropes of carbon namely diamond and graphite. What is the impact of structure on the physical properties of two allotropes? ‘Ans: Allotropy is the presence of an element in more than one form, having different physical properties but the ‘same chemical proper Allotropes of carbon l Crystalline allotropes Amorphous allotropes I | | Diamond Graphite Fullerenes Coal Charcoal Lamp black Diamond's solid 3-D structure makes it a really strong material. Diamond is probably one of the most difficult naturally occurring substances. It is used as an abrasive and as a tool for cutting.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Graphite Ithas hybridized carbon spi, structured in layer form. These layers are held together by the forces of weak van der Walls. These layers may slide over each other, making graphite slippery and soft. Consequently, itis used as a lubricant. 011.26 (@) Classify the following oxides as neutral, acidic, basic or amphoteric. 0, B.0,, Si0,, CO,, ALO:, PbO,, TO, (B) Write suitable equations to show their nature. rant Ans: an ry yo C0 = Neutral ve + B.0, = Acidic Being acidic, it reacts with bases to form salts. It reacts with NaOH to form sodium metaborate. B,O3 + 2NaOH + 2NaBO,+ H2O = sil \cidic Being acidic, it reacts with bases to form salts. It reacts with NaOH to form sodium silicate, SiO, + 2NaOH + 2Na,SiO3+ H2O + C0.= Acidic it reacts with bases to form salts. It reacts with NaOH to form sodium carbonate. Being acid CO,+ 2NaOH + Na,CO3+ H,O — ALO.= Amphoteric, "Amphoteric substances react with both acids and bases. AlO, reacts with both NaOH and H.SO. Al,O3 + 2NaOH -> NaAlOzNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements AlpO3 + 3H2SO4 > Alo(SOx)3 + 3H20 — PbO: = Amphoteric Amphoteric substances react with both acids and bases, PbO: reacts with both NaOH and H:SO.. PbO. + 2NaOH -+ NazPbO3 + H20 2PbO, + 2HySO,— 2PbSO4+ 2H. + Oy = ThO, = Basic Being basic, it reacts with acids to form salts. It reacts with HCI to form thallium chloride. TO; + 6HCL > 2TICls + 3H, Q11.27 In some of the reactions, thallium resembles aluminium, whereas in others it resembles with the group | ‘metals. Support this statement by giving some evidence. ‘Ans: ‘Thallium is a group 13 element. For this group, the most common oxidation state is + 3. Heavier members of this group, however, also display the state of oxidation + 1. This is due to the inert pair effect. Aluminium shows the state of oxidation + 3 and alkali metals show the state of oxidation + 1. Thallium demonstrates the oxidation state of both. Hence, itis similar to both aluminium and alkali metals. Thallium forms ‘compounds such as TICL and TI.0,, like aluminium. It also forms compounds like alkali metals such as TIO and TIC Q 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 HCI to form compound (C). ‘The compound (A) when heated strongly gives (D), which is used to extract the metal. Identify (X), (A), (8), (©) and (0). Write suitable equations to support their identities. ‘Ans: The given metal X gives sodium hydroxide to a white precipitate, and the precipitate dissolves exceeding sodium hydroxide. X must, therefore, be made of aluminium. The obtained white precipitate (compound A) is hydroxide from aluminium. Sodium tetrahydroxy aluminate(ll) isthe compound B formed when an excess of base is added.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements 2al + 3NaQH ———> A\(OH),|+ 3Na ‘Aluminium (x) Sodium hydroxide White ppt.(A) A(OH), + NaOH ———+ Na*[Al(OH), a ‘Sodium tetrahydroxoaluminate (i) (Goluble complex B) Now, when dilute hydrochloric acid is added to aluminium hydroxide, aluminium chloride (compound C) is obtained, AM(OH), + 3HCI—— AICI, + 3H,O (A) (ce) ‘As welt gives compound D when compound A is heated strongly. Uses this compound to extract metal X. Extracts aluminium metal from alumina. Therefore, alumina must be compound D. 2A(0H), —4. alo, + 3H,0 (A) (D) 911.29 What do you understand by (a) Inert pair effect (b) Allotropy and (c) Catenation? ‘Ans: (@) Inert pair effect ‘As one moves down the group, sblock electrons decrease their tendency to participate in chemical bonding. This effect is called the inert pair effect. The electronic configuration for group 13 elements is ns* np’, and its group valence is + 3. However, the oxidation state of + 1 becomes more stable when moving down the ‘group. This is because the ns* electrons are poorly shielded by the d- and f- electrons. The ns* electrons are held tightly by the nucleus as a result of poor shielding, and thus they can not engage in chemical bonding, (b) AllotropyNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Allotropy is the presence of an element in more than one form, having different physical properties but the ‘same chemical properties. The different forms of an element are called allotropes. Carbon occurs in three allotropical forms, for example, diamond, graphite and fullerenes. (©) Catenation ‘The atoms of some elements (such as carbon) may connect with each other via strong covalent bonds to form long chains or branches. This characteristic is known as catenation. itis most common in carbon and important in Si and S. 911.30 ‘A certain salt X gives the following results. () Its aqueous solution is alkaline to litmus. (i) It swells up to a glassy material ¥ on strong heating. (ti) When conc. H:S0. is added to a hot solution of X, a white crystal of an acid Z separates out. Write equations for all the above reactions and identify X, Y, and Z. ‘Ans: ‘The salt given to litmus is alkaline. X is, therefore, a salt with a strong base, and a weak acid. Once X is, heated excessively, it also swells to form material Y. Hence X has to be borax. When heated, borax loses water and swells in order to form sodium metaborate. When heating is continued, the forming of a glassy ‘material Y solidifies. Thus, ¥ must be a mixture of metaborate sodium and boric anhydride. Na,B,0, + 7H,O —““'+ 2NaOH + 4H,BO, Sodium ortoborc hydroxide acid A oe Na,B,0,.10H,0 > Na,B,0,-"> B,0,+2NaBO, Borax (X) Sodium Boric anhydride metaborate (Glassy material) When concentrated acid is added to borax, white crystals of orthoboric acid (2) are formed.NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Na,B40,. 10H,0 + H,SO, Na,SO, + 4H,BO,+5H,O Borax (X) Orthoboric acid (2) Q1131 Write balanced equations for: (Br. + (BH. + HO NaH + BAH, (wy HBO, (W)Al+ NaOH — (vi) BAH + NH ‘Ans: ()2BF, + 6LIH —+B,H, + GLIF settee yah ae (li) BH, + 6H,O —+ 2H,B0, + 6H, Dhorine Water Ontebeie — Hrdogen (ill) BH, + 2NaH —** 2NaBH, bonne agen cen, (iv) 48,80, “°+ 4HB0, 82+ H,8,0, 8+ 28,0, beteacd Tete am, (W) 2Al+2NaOH + 6H,O—> 2Na‘{AI(OH), Ii, + SH2 Stone ‘Sodium etahytonaumintt) (vi) 3B,H, +6NH, —> 3[BH,(NH,)/[BH,/ —+ 2B,N,H, + 12H, Carbon dioxide 0. canbe prepared inthe laboratory though the action of dur hyéochlre acd on ealetum carbonate ‘Their reacton a8 followsNCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements CaCO, + 2HCI,y —+ CaCl. + CO, + H,O CO; is commercially prepared by heating limestone. The reaction involved is as follows: caco, —4+cao + cot Carbon monoxide In the laboratory, CO is prepared by the dehydration of formic acid with conc. H:S0., at 373 K. The reaction involved is as follows: 373K HCOOH ~“conc.H,S0, H,O +CcOot ‘The CO is prepared commercially by passing steam over hot coke: a70-1279 K, Cu, + 4,0, co, + H, o lacay 911.33 ‘An aqueous solution of borax is (@)Neutral (b) Amphoteric (©)Basic (4) Acidic ‘Ans:NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements (b) Borax is a potent base salt (NaOH) and a weak acid (H.80,). Therefore, itis a basic fundamental in nature. 11.34 Borie acid is polymeric due to (@)Its acidic nature _(b) The presence of hydrogen bonds, (6)lts monobasic nature (d) Its geometry Ans: () Boric acid is polymeric due to the hydrogen bonds. The dotted lines in the given figure represent. hydrogen bonds. Neots ANH ‘ Hy BN nH HK Bg is 911.35 ‘The type of hybridization of boron in diborane is (a) sp (b)sp* (c) sp* (d) dsp ‘Ans: (€) Boron in diborane is sp* hybridized 911.36 ‘Thermodynamically the most stable form of carbon is (@) Diamond (b) Graphite (c) Fullerenes (d) Coal ‘Ans: (b) Graphite is thermodynamically the most stable form of carbon, 911.37NCERY Solutions for Class 11 Chemistry Chapter 11 ‘The p-Block Elements Elements of group 14 (0) exhibit oxidation state of +4 only (@) exhibit oxidation state of +2 and +4 (©) form Mand Mion (@ form Mand M* ions Ans: (b) Group 14 elements possess 4 valence electrons. Consequently, group oxidation status is + 4. However, the lower oxidation state becomes increasingly stable due to the inert pair effect, and the higher oxidation state becomes less stable, ‘Therefore, this group exhibits +4 and +2 oxidation states Group 14 element Oxidation state ic 44 Si 4 Ge, Sn, Pb 22,44