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Final P Block

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Aman Yadav
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UNIT 10: P- BLOCK ELEMENTS Group -13 to Group 18 Elements General Introduction: Electronic configu ration and g properties of elements across the periods and down the groups; element in each group. UNIT 20: PRINCIPLES RELATED TO PRACTICAL CHEMISTRY Detection of extra elements (Nitrogen, Sulphur, halogens) in organic compounds; Detection of the following functional groups; hydroxyl (alcoholic and phenolic), carbonyl (aldehyde and ketones) carboxyl, and amino groups in organic compounds. © The chemistry involved in the preparation of the following: The chemistry involved in the preparation of the folloy Inorganic compounds; Mohr’s salt, potash alum Organic compounds: Acetanilide, p-nitro acetanilide, aniline yellow, iodoform. The chemistry involved in the titrimetric exercises — Acids, bases, and the use of indicators, oxalic-acid vs KMnOs, Mohr’s salt vs KMnOs Chemical principles involyed in the fjualitative salt analysis: Chemical principles involved in the following experiments: 1. Enthalpy of solution of CuSO, No, ~ Noy 2. Enthalpy of neutralization of strong aci/And stithg base. 3. Preparation of lyophilic and lyophobic sols. 4. Kinetic study of the reaction of iodide ions with hydrogen peroxide at room temperature. Table 11.1 General Electronic Configuration and Oxidation States of p-Block Elements Group 13 14 15 16 17 18 General Scion KO) CD | em x |e lo |» | ge prt ®/@ @ eS First member 3) 43,-3 | 44, 42,-2 [45,493,411] 46.44.42 7 of the group Group oxidation state Other oxidation states Ma OS ©/@|* | Be 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 eens 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 ionisation enthalpies and higher electronegativities than the metals. Hence, in contrast to metals which readily form cations, non-metals readily form anions. The_ci reactive non-metals with. = ly reactive metals are generally ionic because of large Th. Qa meinen MAS BQ 7 Mtn unusually low melting point (303K), could existin Iga boiling point (: material for measuring hi, edu m: jakes it_a_use! Temperature: F,B 2NaCi + an action Ho — B 0 with water or dilute acid) of most boron compounds (halides, hydrides, etc.). It has a layer structure in which planar BO, units are ‘Na,B,0,.10H,0 ‘The metaborates of many transition-meta have characteristic colours and, therefore, 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 Toop of platinum wire. a blue colopred (CoBouzpeadisformed. (3 ao- " (8405 (oH) - Big0 2s * ae (a) joined by hydrogen bonds as shown in Fig. 11.1. Boric acid is a weak monobasic acid. 1Lis heating yields boric oxide, B,O,, H,B0,_4, HBO, 4, B,O, Bie APO AFOa y Q 11.3.3 Diborane(B,H, The simplest boron hydride known, is diborane. It is prepared by treatin; trifluoride with LiAIH, in diethyl ether. |B i 28 + SLIF + Sar, ‘convenient Tabor: method for the preparation of diborane involves the oxidation of sodium borohydride with iodine. Bi, — Rovome tin se Bie git OK by the reaction of BF, with sodium hydride. 2BF, +6NaH —°% BH, +6NaF Diborane is a colourless, with"a b.p. of . Diborane S fire spontaneously upon exposure to air, It bums in oxygen releasing an enormous amount of energy. Bet 90, oO 3H,0; A.H® =-1976 kJ mol" Most of the higher boranes are also foon\aneously flammable in air. Boranes are readily hydrolysed by water to give boric acid. B,H,{g) + 6H,0() > 2B(OH),(aq) + ee ee wih Lewis bascall to give hare adsusin Bi Some adda yi + 2NMe, 500 derco “Fetttin cfemaioni wth diborane gies sesualy Bye 2NFty which fs formulated aa [BH,(NH,),]" [BH,] ; further heating gives bordeine BiNtly known a “inasannie fete in ol a Fog atte as alternate Band NF groups. 9B, H,+6NH, 31611, (NH{7'IBH,T Ae nf Fig.11.2(a). The four terminal Hyessgen 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 deseribed in terms of three centre-two electron bonds shown in Fig. 11.2 (b). Boron also forms a series of hydridoborates; the most important one is the tetrahedral [BH ion. Tetrahydridoborates of several metals are known. Lithium and sodium tetra- hydridoborates, also known as borohydrides, are prepared by the reaction of metal hydrides with B,H, in diethyl ether. 2MH + B,H, > 2M" [BH,) (M = Lior Na) H H a SOR v5 z ac ef 11.5 GROUP 14 ELEMENTS: THE CARBON FAMILY Carbon (©), silicon (S9, germanium (Ge), tin (Sn) and lead (Pb) are the members of group 14. Carbon is the seventeenth most_abundant clement by mass ihe earth's crust. It is idely Gsicbuted mnataretn Tree asell 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 plasties. Organic chemistry is devoted to carbon containing ‘compounds. It is an essential constituent of all living organisms. Naturally occurring PC and ‘component of ceramics, glass and cement. Germanium exists only in traces, Tin occurs maint s (Cassiterite, SnO, and lead as ean PS ee “Tis ce form of and siffon are_used to make “transistors “apd semiconductordenices. PO: The important atomic and physfcal 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 Get@guration 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 due to the presence of completely filled dand f orbitals in heavier members. 11.5.3 IonizatigX Enthalpy The first ionizgffon enthalpy of group 14 members is##fgher than the corresponding members of group 13. The influence of inner core electronsis visible here also. In general the ionisation enthalpy decreases down the group. Small decrease in A.H from Sito GetoSnand slight increase in 37 from Sp-to-Pb isthe consequence Gi of onsequence of poor shiciding cftest inlervening dand Jorbitals and increase ins oftheatom. | 11.5.4 Electronegativity Due to small size, thé elements of this group are slightly more electronegative than group 13 elements. The electronegativity values. for elements from Sito Pb are almost the same. 11.5.5 Physical Properties All group 14 members are solids. Carbon and silicon arenon-metals, germaniumisametalloid, oe __w_“ueromew +4 ‘Table 11.3 Atomic and Physical Properties of Group 14 Elements Element qe eh as “for M" oxidation state; ° 6-coordination: “Pauling scale; * 293 K; * for diamond; for graphite, density is 2.22; 'f-form (siable at room temperature) whereas tin and lead are soft metals with low imeltingpor igpomtsan ‘points aremuch higher than those ofcorresponding elements of group 13. 11.8.6 Chemical Properties Oxidation states and trends in chemical reactivity ‘The group 14 elements have four electrons in outermost shell. The common oxidation states exhibited by these clements a Carbon also exhibits negative oxidation states. Since the sum of the first four ionization enthalpies is very high, compounds in +4 oxidation state are generally covalent in nature. In heavier members the tendency to show +2 oxidation_state increases in_the sequence GecSnePb_It is due _to the inabilityof 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 +2 state. Tin +4 agents. In tetravalent state the number of electrons around the central atom in a molecule (e.g., carbon in CCl.) is eight. Being electron precise molecules, they are normally not expected to act as electron acceptor or electron donor species. Although carbon cannot exceed its covalence more than 4, other elements of the group can do so. Itis because of the presence of dorbital 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, SiFy , [GeCl,J". (Sn(OH),)” exist where the hybridisation of the central atom is sp'd. 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 er electronegay In carbon, only s and p orbitals are available for bonding and, therefore, it can accommodate only four pairs of electrons around it. This would limit the maximum covalence to four whereas other members can expand their covalence due to the presence of dorbitals. cee 11.7 ALLOTROPES OF CARBON Carbon exhibits many allotropic forms; both, crystalline as well as amorphous. Diamor a a ncaa known oo Tallovehes was discovered by discovery they were awarded the Nobel Prize acon 11.7.1 Diamond ‘other carbon atoms by using hybridised orbitals in tetrahedral fashion. The CC bond length 1s 154 pm. The structure extends in space and produces a rigid three- dimensional network of carbon atoms. In this, Po Carbon also has unique ability to form pa prpuuiltiple bonds with itself and, Atop of small size and high electronegatwity. Few examples of multiple bonding are: C=C, C25, and CP Heavier elements afi bo ‘ause their atomic orbitals are too large and diffuse to have effective overlapping. Carbon atoms have the tendency tg ink ‘wit one another through covalent bonds to form chains and rings. This property is called. catenation “Th ie because © > § Ge = Sn. Lead does not show catenatk Bond Bond enthalpy / kJ mol” oc 348 sist — 297 os —260 Sn—Sa 240 ‘Due to property of catenation and pr- pr bond formation, carbon is able to show allotropic forms. Fig. 11.3 The structure of diamond structure (Fig. 11.3) directional covalent bonds are present throughout the lattice. ie dyes and in the manufacture of tungsten laments for electric light bulbs. Problem 11.7 Diamond is covalent, yet it has high ‘melting point. Why ? Solution Diamond has a three-dimensional network involving strong C—C bonds, which are very difficult to break and, in ‘tum has high melting point. 117.2 Graphite Graphite has layered structure (Fig.11.4) I ice Between two Tayers is 340 pm. Fach layer is composed of planar al ing ee erate 5 ‘arbon atom in hexagonal ring undergoes sp’ hybridisation and makes three sigma bonds with three neighbouring carbon atoms, Fourth electron forms axbond. The electrons are delocalised over the whole sheet, Blectrons are mobile and, ver Re whole shest, Blectrons are mobile and vaispm oF Fig 11.4 The structure of graphite therefore, graphite conducts electricity along the sheet. Graphite cleaves easily between the layers and, therefore, itis very soft and slippery. For this reason graphite 1s used as a dry lubricant _in_ machines running at_high ‘ERSTE Rete OO eMC SET as 0 jubricant. 11.7.8 Fullerenes a Rullerenes are made Inanclecinie are m The presence oft ‘Suchas Tellum orarion. The sooty material formed by Condensation of vapourised C small ‘molecules consists of mainly C,, with smaller quantity of Cry and traces of fullerenes consisting of even number of carbon atoms.up 0 or above, Fullerenes are the onk(pupy) ‘carbon because they have sino? etre ait are eee a ae ee aaa cage like molecutes. Coo QO ee called Buckminsterfullerene (Fig. 111.5). 6 lingua a ARREST WTSI or The membered ings taut s Sowensalscred mug ay aos ‘six membered rings, All the carhon atoms, gual and they undergo so" Ryaridiaion. C-C distances of 143.5 pm and 138.3 pm ssagy it alues conta Taleene, lee eee Coo Ae 1.90 and 38.1 kJ mol’, respectively. Other forms of elemental carbon like carbon black, coke, and charcoal are all impure forms of graphite or fullerenes. Carbon black is obtained by burning hydrocarbons in a limited supply of air. Charcoal and coke are obtained by heating wood or coal respectively at high temperatures in the absence of air. Theunadynonmi.— Thoumocremistry sims molecular orbitals, which in tum give aromatic character to molecule. This ball shaped (is very important to know that graphite molecule has 60 vertices and each one Is occupied by one carbon atom and it also is thermodynamic: 105 allotrope of contains both single and double bonds with on and, therefore. A, of, hite is taken as 60 7A Group 15 Group 15 includes nitrogen, phosphorus, arsenic, antimony and Element bismuth, As we go down the group, there is a shift from non-metallic to metallic through metalloidic character. Nitrogen and phosphamis are non-metals. arse! and at timony metalloids and bismuth is a typical metal. 7.1.1 Occurrence — Molecular nitrogen ises_ 78% J 0 . N In the earth's crust, it occurs as sodium nitrate, NaNO (called Chile | nm. gs and potassium nitrate (Indian saltpgtre). It is found in the A form of proteins in plants and animals. Phosphorus occurs in minerals . amekalloio 84 metollic of the apatite family,|Cao(PO,).. Ca Cag (POs ) which are the main components of phosphate rocks. Phosphorus is an essential constituent of animal and plant matter. It is present in bones as well as in living cells. Phosphoproteins are present in milk and eggs. Arsenic, antimony and bismuth are found mainly as sulphide minerals. The important atomic and physical properties of this group elements along with their electronic configurations are given in Table 7.1. Cag POa), Cok, =F, Cl or OH) (e.g., fluorapatite Table 7.1: Atomic and Physical Properties of Group 15 Elements ory cing 7 14.01 [He]2s"2p" 1402 2856 4577 3.0 70 g 63) 77.2" 0.879" 15 30.97 [Ne]3s°3p" 1012 1903 2910 2.1 110 212" 33 74.92 [Ar]3d"4s"4p’ 947 1798 2736 2.0 121 222" 1089" 888° 5.778" Atomic number Atomic mass/g mol* Electronic configuration Ionisation enthalpy — I (QH/(kJ mot") 0 Electronegativity Covalent radius/pm* Tonic radius/pm Melting point/K Boiling point/K Density/[g cm“(298 K)] * Bi single bond (E = element): ° E°; “E":" White phosphorus; * Grey a:form at 38.6 atm: ! Sublimation temperature; * At 63 K: "Grey a-form: * Molecular No. 7.1.2 Electronic The valence shell electronic configuration of these elements is ns*np*. The s orbital in these elements is completely filled and p orbitals are Qd UsUGS half-filled, making their electronic configuration extra stable. 7.1.3 Atomic and Covalent and ionic (in a particular state) radii increase in size Tonic Radii_ down the group. There is a considerable increase in covalent radius as Wuo} from_N to P. However, from As to Bi only a small increase in covalent radius is observed. This is due to the presence of completely filled d and/or f orbitals in heavier members. 7.1.4 Ionisation’ _onisation enthalpy decreases down the group due to gradual increase Enthalpy in atomic size. Because of the extra stable half-filled p orbitals electronic configuration and smaller size, the ionisation enthalpy of the group 15 elements is much greater than that of group 14 elements in the corresponding periods. The order of successive ionisation enthalpies, as expected is AH, < AH, < AH; (Table 7.1). 715 The electronegativity value, in general, decreases down the group with Electronegativity “increasing atomic size. However, amongst the heavier elements, the difference is not that much pronounced. 7.1.6 Physical All the elements of this gr Properties hile all others are solids. a e B Nitrogen and phi non arsenic and antimon ihetalloids anc uth is a metal. ‘in ionisation enthalpy and increase in atomic size. The boiling points. in general, from top to bottom in the group but the melting point increases upto arsenic and then decreases upto Bismuth Except nitrogen, all the elements show allotropy. ————— So 7.1.7 Chemical Properties Oxidation states and trends in chemical reactivity ‘The common oxidation states of these elements are -3, +3 and)+5. ‘The tendency To exhibit -3 oxidation state decreases down the group due to increase in si - In fact last member of the group, bismuth hardly forms any compound ir(—3 oxidation stat}. The stability of +5 oxidation state ‘down the group. The only well chara Srv compo are: Stability of +5 oxidation state deci id that of +3 state increasés (due to down the group. Nitrogen exhibits + I, + 2, + 4 oxidation states also when it reacts with oxygen. Phosphorus also shows +1 and +4 oxidation states in some oxoacids. In the case of nitrogen, all oxidation states from+1 to +4 tend to Similarly, in case Of phosphorus aay all intermediate oxidation states disproportionate into +5 and -3 both in alkali and acid. However +3 oxidation state in case of arsenic, antimony and bismuth becomes increasingly stable with respect to disproportionation. Nitrogen is restricted to a maximum covalency of 4 since only four (ones Sarea fing. The heavier elements have vacant orbitals in the outermost shell which can be used for bonding (covalency) and hence, expand their covalence as in PF;. HNQ,— He, + WO Anomalous properties.of nitrogen Nitrogen differs from the rest of the members of this group due to its small size, high electronegativity, high ionisation enthalpy and non-availability of d orbitals. Nitrogen has unique ability to form =? G. prepa imultipl/oonds with itself and with other elements having ¥—N small size and high el “ones (e.g., C, O). Heavier elements of this group do not me bonds as their atomic orbitals are so p__p large and diffuse that they cannot have effective overlapping. Thus, nitrogen exists as a diatomic molecule with a triple bond (one s and two p) between the two atoms. Consequently, its bond enthalpy (941.4 kJ mol”) is very high. On the contrary, phosphorus, arsenic and antimony form single bonds as P-P, As-As and Sb-Sb while bismuth forms metallic bonds in elemental state. However. the single N=N_bond is weaker_than_the single bond _hecause_of high interele cle nitroggy¥ Another factor which affects the chemistry of nitrogen is sence of d orbitals in its valence shell. Besides restricting its covalency to four, nitrogen cai form da—pzx, bi ier elements Can e.g., R,P = O or RP= = alkyl an ne arene Can form de —ga bond alsa wip transition metals when their compounds like P(C,H,); and As(C;Hs); act as ligands. () Reactivity towards hydrogen: All the elements of Group 15 form hydrides of the type EH, where E = N, P, As, Sb or Bi. Some of the properties of these hydrides are shown in Table 7.2. The hydrides show regular gradation in their properties. ‘The stabili Be : Conseques acter Chom." srmonia is ont Gondiry. strongest reducing teh SSeS Ses decreases in the orde ZA aa 40, ‘Table 7.2: Properties of Hydrides of Group 15 Elements x, 3 \y Gye Melting point/K OddiC Boiting point/K 4S, | (E-H-Distence¢pm, HEH angle () i FP /\s3, mol of oxides: E,Qy and E. of. the ae t is 1 Ege predominantly basic basic BPE BiB? LHe > Preparation Ammonia is present in small quantities in air and soil where it is formed by the decay of nitrogenous organic matter e.g., urea. NH,CONH, +2H,0 -> (NH, ),CO, = 2NH, +H,O +90) Z Ona small scale ammonia is obtained from ammonium salts which decompose when treated with caustic soda or calcium hydroxide. 2NH,Cl + Ca(OH), > 2H,0 + CaCl, (NH,), SO, + 2NaOH 2H,0 + Na,SO, On a large scale, ammonia is manufactured by Haber’s process. N,(g) + 3H,(g) = 2NHA(e): // A,H® = - 46.1 kJ mol In accordance with Le Chatelier’s principle, high pressure wold favour the formation of ammonia. The opt conditions for the production of ammonia are a pressure of Y a @aSe the rate of attainment of equilibrium. The ow chart lor the production of ammonia is shown in Fig. 7.1. Earlier, iron was used as a catalyst with molybdenum as a promoter. Properties Z Zz Ammonia is a colouiléss gas with a pungent odour, Its freezing and Q boiling points are “In the solid and liquid states, it is associated through hydrogen bonds as in the case SN of water and that accounts for its higher melting and boiling points % 4 _ than expected on the basis of its molecular mass. The ammonia molecule H is trigonal pyramidal with the nitrogen atom at the apex. It has three bond pairs and one lone pair of electrons as shown in the structure. fas is highly soluble in water. Its aqueous solution is weakly basic due to the formation of OH ions. NH,(¢) + H,O() = NH," (aq) + OH” fy ROD # NE PING It forms ammonium salts with acids, e.g., NH,Cl, (NH,),SO,, etc. As a weak base, it precipitates the hydroxides (hydrated oxides in case of Some metals) af many sactale Trobe Ther salt soliton is rom their salt solutions. ror example, Paso. ya) + 2NHQ(aq) > Zn(OH), (6)+ (NH), $04 (2a) 6 5 fp “8 Y Feclyga NH,OH Y Fe,03.xH,0°s, NH,CI aq n® Ys Frown poe brown ppt ‘The presence ata-lone pair of electrons on the nitrogen atom of the ammoni: iolecule make; is base. It donates the electron pair and forms. linkage ‘with metal ions and the formation of such complex compounds finds applicationgyin detection of metal ions such as Cu”, Ag’: DY Cu” (aq) + 4 NH,(aq) = [Cu(NH,),]”"(aq) A bblue) (deep blue) Ag’ (aq) (CI (ah) > AgCl(s) (colourless) (white ppt) AgCI(s) + 2NH, faq) > [Ag(NHs), ]Cl(aq) (white ppt) (colourless) Peet eee trey Centr Physical eee peer are Serer y vtec) Rees) pcerenmertts Za. colourless gas. Dinitrogen oxide neutral Nitrogen()) oxide] [=O Nitrogen monoxide [eolourless gas, [Nitrogentt) oxide] neutral sae ¢» Nitrogen dioxide [Nitrogen{IV) oxide] acidic sted ig east ng Si _colaurless solid |) Dinttrogen. pentoxide 4 INitrogen(¥) oxide} jaws oe Resonance Structures ed Nenad <>:nen-6 N-N-0 Tinea Nad: ov =d: Nod nSpm 6 ‘6 ©. 108° ° oS Ne UNS x i a EN 0 Z uF Po ©. heh S yee 4 No, ° No. No. 7.5 Nitric Acid Nitrogen forms oxoacids such as HN,O, (hyponitrous acid), HNO, (nitrous acid) and HNO, (nitric Sela) Rinonget theme 1 em HNO, is the most important Noy Preparation In the laboratory, nitric acid is prepared by heating KNO, or NaNO, and concentrated H,SO, in a glass retort. NaNO, +H,SO, - NaHSO, + HNO, On a large scale it is prepared mainly by This method is based upon catalytic oxidation of NH, by atmospheric oxygen. 4, ne Denguogecmaty 4NH, (2) + 502 (g —QageeeeGonoy} = +6H,0(g { J * peaks xo y { ) Nitric oxide thus formed combines with oxygen giving NO,. 2NOfg) + 9, (8) = 2NOK 8) * Nitrogen dioxide so formed, dissolvesamfater to give HNO,. # 2 ag fo) é s ig) NO thus formed is recycled and the aqueous HNO, can be concentrated by distillation upto ~ 68% by mass. Further concentration to 98% can be achieved by dehydration with concentrated H,S0,. Properties Itis a.colourless, gc. 231.4K and b.p. 355.6 K). Laboratory H €0 ‘gradenitric acid coftains ~ 68% of the HINO, by mass and has a a\02 SK _ specie gravity of 1.504. a is” In the gascous state, HNO, exists as a planar molecule ‘wooo \ cqequitinthe structure as shown. ‘o_In aqueous solution, nitric acid behaves as a strong acid giving hydronium and nitrate fons. HNO,(aq) +H,0() > H,0"faq) + NO, (aq) x Concentrated nitric acid is a strong oxidising agent and attacks most metals except noble metals such as gold and platinum. The oducts oF Oxdanon depemt-upon tie concentration of the acid, « tempsrative and the nature of the material upgergomng oxidation Cu + 4HINO,(conc.) + Cu(NO,), + 2NO;+ 2H.0 Zinc reacts with dilute nitric actd to give N,O and with concentrated acid to give NO,. o Gz) + figunowanate) > 4 22009, + 54.0 &) Zn + 4HINO,(conc,) + Zn (NO,), + 2H,0 + 2NO,, Some metal: do not dissolv ncentrated. acid because of the formation of © ‘oxide on The surface Concentrated nitric acid also oxidises non-metal and their compounds. Iodine is oxidised to iodic acid, carbon to carbon dioxide, sulphur to H,SO,, and phosphorus to phosphoric acid. gy Ny Ged}+ 8 HNO.(alute) + {CuNO)+ 2G + 411.0 ERA OLS MYRIQEK Me 10H > 2HIQZ + 10NQ7 + 4H,0 CA 4H NG > CO¢/+ 2H,0 + 40; CON > 8H,S0, + 486, + 16H,0 yn 20HNs, > anh + 20NGi+ 4H,0 Brown Ring Test: The familiar brown ring test for nitrates depends n the ability of Fe™ to reduce nitrates to nitric oxide, which reacts with Fe”’ to form a brown coloured complex. The test is usually carried out by adding dilute ferrous sulphate solution to an aqueous solution containing nitrate ion, and then carefully adding concentrated sulphuric acid along the sides of the test tube. A brown ring at the interface between the solution and sulphuric acid layers indicates the presence of nitrate ion in solution. 40, Qo,)+ 3Fe” + 4H" Re 3ie* + 2H,0 G JFe(Hz0)g)?* + NO — [Fe (H,0), (NO)? + H,0 (brown) 7.6 Phosphorus — Allotropic Forms Ve Fig. 7.2 White phosphorus Phosphorus is found in many allotropic forms, the important ones being white, red and black. JTBIS eee Eat sabe carbon eo and glows in dank insofuble in water but soluble in. carbon disulphide and glows in dark (chemiluminescence). It dissolves in boiling NaOH solution in an inert atmosphere giving PH; SS P, +3NaOH +3H,0 (PH, +3NaH,PO, pucen,, wven-mutal. (sodium hypoffosphite) White phosphorus is less stable and therefore, more reactive than the other solid phases under normal conditions because of angular strain. in the P, molecule where the angles are only 60°. It readily catches fire in air to give dense white fumes of P\O,o. Py +50, > P.O, It consists of discrete tetrahedral P, molecule as shown in Fig. 7.2. Red phosphorus ig obtained by heating white phosphorus at 573K in an inert atmosphere for several days. When red phosphorus is heated under high pressure, a series of phases of black phosphorus is formed. Wed-phosphorus possesses Tan grey Tus It is odausless. “hon. Reisonoos and —— well as_in_carbon disulphide. Chemically, red phosphorus is much less reactive than white phosphorus. It does not glow in the dark. It is polymeric, consisting of chains of P, tetrahedra linked together in the manner as shown in Fig. 7.3. Black phosphorus has two forms a-black phosphorus and f-black phosphorus. o-Black phosphorus is formed when red phosphorus is Fig.7.3: Red phosphorus heated in a sealed tube at 803K. It can be sublimed in air and has opaque monoclinic or rhombohedral crystals. It does not oxidise in air. §-Black phosphorus is prepared by heating white phosphorus at 473 K under high pressure. It does not burn in air upto 673 K. pee et ete Ceereree tty poet erend Peet eeer matt phosphorus number Hypophosphorous GPO, wb (Phosphinic) Orthophosphorous | (APO; +3 (Phosphonic) (HPO) ~ Pyrophosphorous Be Hypophosphoric LPO, ‘ Orthophosphoric HI we oe Pyrophosphoric (R07) oo we Metaphosphoric* (HPO), os> man = P-O-O-P p—s +5—+max — ke os= wax Po —4 man— 2 —+9us 06 < rom. P—P ° Ow— 2 — Rypous ° 0, 1 p TRPQR 4071 ~ rr RSex ee a g I | # O® Kors Didar oe ol Ortho @ 2 we © te f . cid Hypg 2 Cid -_ 4,700 7 Corr LEt Fig. 7.4 ae A a Bx Structures of some alO3. important oxoacids of —A— op phosphorus Cyclotrimetaphospho Af\_Polymetaphosphoric acid, (HPO), japhos Polymetaphosphoric 2 +s Hye PO, PO04.— ic —ly=0 am ioe ae e+ z= tS RAB tf, eg ° fi 46,902 —> Vo—~ ‘ 4s “\ /N 71 -@) 34a-4ed 178, OH monotare £40.) Ve 3 P e l+2-6<0 on No 0, wets — =P Axe g~G In oxoacids phosphorus is tetrahedrally surrounded by other atoms. All these acids contain at least one P=O bond and one P-OH bond. The oxoacids in which phosphorus has lower oxidation state (less than +5) contain, in addition to P=O and P-OH bonds, either P-P (e.g., in H.P,0)) or P-H (e.g,, in H,PO,Yonds but not both. These acids in +3 oxidation state of phosphoru tend to disproportionate to higher and lower oxidation states. For example, orthophophorous acid (or phosphorous acid) on heating disproportionates to give orthophosphoric acid (or phosphoric acid) and phosphine. 4H,PO, > aif, +P 7, The-actdls which contats 7 bond have strong reducing properties. a good reducing agent as it contains “AgNO, to metallic silver. + AHN, + HPO, role in basicity. Only those H atoms which are attached with oxygen in P-OH form are fonisable and cause the basicity. Thus, H,PO, and H,PO, are dibasic and tribasic, respectively as the structure of HjPO, has two P-OH bonds and H,PO, three. 7.10 Group 16 Elements 7.10.1 Occurrence Oxygen, sulphur, selenium, tellurium and polonium constitute Group 16 of the periodic table. This is sometimes known as group of . The name is derived from the Greek word for brass and points to the association of sulphur and its congeners with copper. Most copper minerals contain either oxygen or sulphur and frequently the other members of the group. en is the most abundant of son earth. Oxygen ae ant 46.6% hy mass of earth's crust. Dry air contains 20,946% oxygen by volume. However, the abundance of sulphur in the earth's crust is only 0 03-0.1%. Combined sulphur exists primartly as sulphates such as sum_CaSQ,.2H.0. epsam salt MgSO, ryte_BaSS. and ais ah a galena PbS. zi eKurFes,. ‘Traces of sulphur occur as hydrogen sulphide in volcanoes. Organic materials such as eggs, proteins, garlic, onion, mustard, hair and wool contain sulphur. Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores. Polonium occurs in nature as a decay product of thorium_ani jum minerals. je important atomic and physical properties of Group16 along with electronic configuration are given in Table 7.6. Some of the atomic, physical and chemical properties and their trends are discussed below. Bava 7.10.2 Electronic ‘elements of Group16 have six electrons in the outermost shell and Configuration /ave ns’np* general electronic configuration. 7.10.3 Atomic to increase in the number of shells, atomic and ionic radii increase and Ionic top to bottom in the group. The size of oxygen atom is, however, Radii cceptionally small. Enthalpy However, the elements of this group have lower ionisation enthalpy lues compared to those of Group15 in the corresponding periods. This is due to the fact that Group 15 elements have extra stable half- filled p orbitals electronic configurations. 7.10.5 Electron ‘ause of the compact nature of oxygen atom, it has less negative Gain fectron gain enthalpy than sulphur. However, from sulphur onwards Enthalp' the ie again becomes less negative upto polonium. 7.10.4 Tonisation Gation enthalpy decreases down the group. It is due to increase in valu 7.10.6 to fluorine, oxygen has the highest electronegativity value amongst Electronegativity fe elements. Within the group, electronegativity decreases with an increase in atomic number. This implies that the metallic character increases from oxygen to polonium. 7.10.7 Physical Properties 7.10.8 Chemical Properties Some of the physical properties of Group 16 elements are given in Table 7.6. Oxygen and sulphur are non-metals, selenium, jum metalloids, whereas polonium is a. |. Polonium is radioactive and is Short live Flite 13.8 days). All these elements exhibit allotropy. The melting and boiling points increase with an increase in atomic number down the group. The large difference between the melting and boiling points of oxygen and sulphur may be explained on the basis of their atomicity; oxygen exists as diatomic molecule (0,) whereas sulphur exists as oh ome Rene Sy ur exists as polyatomic molecule (Sq Oxidation states and trends in chemical reactivity ‘The elements of Group 16 exhibit a number of oxidation states (Table 7.6). The stability of -2 oxidation state decreases down the group. Polonium hardly shows -2 oxidation state. Since electronegativity of oxygen is very high, it shows only negative oxidation state as -2 except - ra Oo O. 16 onide cy 2,46) fe, in the case of opfvhere its cntdaoy/fe is + 2. Other elements of the group exhibit +2, + 4, + 6 oxidation states but + 4 and + 6 are more common. Sulphur, selenium and tellurium usually show + 4 oxidation state in their compounds with oxygen and + 6 with fluorine. The stability of + 6 oxidation state decreases down the group and stability of + 4 oxidation state increases (inert pair effect). Bonding in +4 and +6 oxidation states is arily covalent. oO Peroni & Of PFs VO eney Oo Aupa enidls.

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