elements of group VA nitrogen (7), phosphorus (is), Arsenic(33), Antimony,Sb(51). & Bismuth (83) > they are collectively called pnicogens which ‘means causing suffocation. > General electronic configuration—> ns? np? General characteristics 1. State: No Gas, Pa > Waxy solid, As > solid Sb & Bi — solids with lusters. 2. Category: N &P— Non-metals, As & Sb > Metalloids, Bi > Metal 3. Atomic radii, density and bpt gradually increases down the group. 4, Mpt — it increases from Nitrogen to Aresenic and then decreases. 5. Ionization energy > due to half filled P- orbitals they have higher ionization energy and it decreases down the group. 6. Electronegativity > it goes on decreasing order along the group due to increase in size of atom. 7. Allotropy:- > all elements except Bi shows allotropy > Nitrogen in solid exists in two allotropic forms a&B. + Allotrops of phosphorus are white, scarlet, black, red etc. > Arsenic exists in grey, yellow & black. > Antimony exists in yellow & brown 8. Nature of Bonding:~ > Maximum covalency of nitrogen is four as 2S & 2P are available for bonding e Other elements have covalency of 5 and maximum of 6 due to availability of d-orbitals e.g, 6 covalency in Ase", SbCle~ & Sb(OH)~ 9. Thermal and electrical conductivity: N & P > poor conductor As — Semi conductor Sb & Bi — good conductor 10. Oxidation states: —> These elements can exhibit -3 to +5 oxid states. i — Stability of +3 increases and that decreases from N to Bi and tendeney 3 decreases down the group, 7 11, Catenation:- To some extent N,P & as z property of catenation but less than tha gr. Element. 12. Formation of oxides:- The can form X204 & X20s nitrogen fors two neutral gy N20 and NO X203 > N203, P203, As20s, Sb20s, Bi20} X204 > N20s, P204, As204, Sb20s, BirOs X20s ~> N20s, P20s, AsiOs, Sbi0s, Biz; Acidic nature decreases ee eee eee, Stability decreases 13. Oxyacids: a. Oxyacids of nitrogen are -HNO», etc. b. Oxyacids of phosphorus are HP HsPOs, HsPOs, HPOs, HyP20; ete ce. Oxyacids of Arsenic are HsAsO HsAsOx 4d. Oxyacids of Antimony is H3Sb0: e. Oxyacids of Bismuth is HsBiOs Among the oxyacids, the strength & stabi order are HNO3 > H3PO4 > H3As04 > H35 14, Hydrides: they form covalent tibydi except ionic BiH3 NHy Ast, sol; Ammen hiottihe Aranne Steno B5 — Bond angle decreases down the group ( is electronegativity of central atom is 8 so reducing nature increases. 4 > Basic character decreases from NH © # They behave as Lewis base NH > PH; > AsHs > BiH 4 Although N is most electronegative it maximum tendency to donate elects Scanned with CamScannerZ ee SSS xr of boiling point Orde th > SbHs > NH > ASH > PH, s, Halides: ant Bi only can form trihalide but others can * form trihalides and pentahalides. Nitrogen doesn’t form pentahalide due to lack * cea-orbital , 4 Bi doesn’t form péniahalide ‘due to least stability of +5 state. | The trichalides of nitrogen family are sp3 hybridization while pentahalides have sp3d 4 Stability of halides NX3 < PX; < AsX3 < SbX3 < BiX; 4 Tendency to act as Lewis base decreases from NIB to NF3 Nb > NBr3 > NCL > NF + Except NF3_ & PF3 all trihalides gets hydrolysed NCls + 3H20 -+ 3HOCI + NH. AsCls + HO — HsAsOs + HCI PCh +3H20-> H3POs + 3HCI SbCl; + H20 > SbOCI + 2HCI BiCl + HoO — BiOCI + 2HCI + Heavier member's do not form pentachloride, pentabromide & pentaiodide due to inert pair éffect and greater reducing power of Br & I”. Pentahalides decomposes to lower stable halides PCL == PCh + Ch, PBrs == PBrs + Ch , PHOSPHORUS 4S phosphorus is active element it ocours in combined form * The important minerals of phosphorus are & Phosphotite > Ca(POs)2 Or Rock phosphate Chloroapatite > 3Ca(PO«)2.CaClz Fluoroapatite > 3Cax(PO,)a.CaF2 Vivianite > Fes(PO4)2.8H20 . p, Hydroxyapatite -» 3Cax(POs)2.Ca(OH)2 t oe is an essential constituent of bones conigin ood and nervous tissues. Bone ash '$ 80% of Ca3(PO4)2 b e q e > Although phosphorus is the element of nitrogen family (pnicogens) it has some dissimilarities with nitrogen i, Phosphorus is less electornegative than nitrogen ii, Phosphorus has d-orbital while nitrogen does not have iii, Phosphorus is not in diatomic form but in tetra atomic form while that of nitrogen is diatomic. iv. Phosphorus is active but nitrogen is almost inert V. Phosphorus forms pentahalide but not nitrogen vi. Phosphorus is solid but nitrogen is gas at ordinary temp. Extraction:- The phosphorus is obtained by heating phosphorte with sand and coke in an electric furnace at about 1770k. 2Ca(PO:)2+6Si0, —* > 6CaSiOs + PsO10 PsO1o + 106 —*-> Ps + 10CO ‘The vapours are condensed under water to get solid phosphorus. Thus formed phosphorus is purified by heating with acidified K2Cr,O; solution, where impurities are oxidized & removed. Allotrops of phosphorus 1. White or yellow phosphorus: > It is obtained by condensing vapors of phosphorus under water. > It is soft waxy solid with low ignition temperature (=35°C) > It-is oxidized & burnt on air easily which results glowing at night and the phenomenon is called phosphorescence, > It is extremely reactive & oxidized easily by air so it is stored under water. —> Phossy Jaw is diseases causing decay of bone caused by constant touch with white phosphorus. —> Molecular formula'-+ P4 , Shape of molecule > Tetrahedron Reactions a. With non-metals, O, P+ 02? Pie PO or P05 a Scanned with CamScannerb. c. a 2 5 Pe + 10Ch —*» apcis With metals: a Mg + Ps —~—> 2Mg;P2 4 6Na + Ps ——> 4NasP With alkali: Pst3NaQH+3H20 —*» 3NaH;POrt PEs? Sod.hypohosphite. White phosphorus explodes when rubbed with KCIO; or KNOs due to rapid oxidation Red phosphorus: it is obtained by heating white phosphorus at 250°C in presence of Ip catalyst in absence of air white phosphorus —¥°_» Red phosphorus. a > > is 3. it is dark red powder & non-poisonous in nature it is insoluble in water as well as CS: & doesnot show phosphorescence it ignition temp is 260°C. it is less active than white phosphorus P+0,;—°6 5 po, P+Ch —>Pcis P+Na —~>NasP scarlet Phosphorus: it is prepared by dissolving red phosphours in PBr; and boiling until” precipitation is complete. Physically it is more or less similar to red but chemically it is more active than red. Violet Phosphorus ‘Comparative properties of NH3 & PHs a > Uses of phosphorus: > = pre aay 1 2. it is preapared by heating white sealed tube at 530°C and conden vapours on the upper part ofthe tube a itis exystalling with mt 589°C ang pra are more or less similar to red, Black phosphorus Phospy this allotropic, form is prepared by white phosphorus at 200°C under y, pressure. It is in layered hexagonal structure and conductor of electricity, It is almost inert & gets ignited at 500% Red is mostly used in match industri make alloy called phosphorus bronze White is used in rat poisonous. Radioactive phosphorus is used P? for treatment of leukemia Black as conductor. Phosphine (PH) Phosphine is prepared by heating phosphorus with strong alkali. 3NaOH + Ps + 3Hz0—*>PHst + 3NalH:PO2 It can be obtained by hydrolysis of phosphide or treating with dil. Acids Ca3O2 + 6H20 ——>2PHs + 3Ca(0I AIP + 3HCl ——>PH; + AIC By action of alkali with phosphonium PHad + NaQH ——>PHs + Nal + Ht Properties NBs Pih : 1 Sate ‘& odour Colourless gas with pungent odour Colourless gas with rot : odour 2._ Solubility Highly soluble in water Feebly soluble 3. Physiological action | Non-Poisonous PolstOiS: 4. Stability More stable Less stable = 3. Combustibility ‘Only gets oxidized when strongly Itis combuste ee heated with On apusedos—29P.08 4NH3 + 302 ——2N> + 6H20 iors i . It fe Its with Weakly basic. & Basic character Basic nature. Te forms alts wi Wen Scanned with CamScanneraS OO HBr & HI NH; + HCl ——>NH,CI Gives, OH" in aqueous solution PH3 + HI ——>PHal ‘NH3 + HO = NHy*+OH- 77 Reaction with C2 | 8NHs + 3Cl> No + 6NHACI PHs + 3Ch PCI3 + 3HCI Excess PH; + 4Ch>PCls + 3HCI NH + 3Clp ~» NCly + 3HCI % Precipitation Metal hydroxides are precipitated with | Metal phosphide gets reactions metal salts solutions precipitated NH.OH + FeSO;->Fe(OH).v + 3CuSOs + 2PHs—> CUsP2t + (NH4)2S0s 3H2SOs 3AgNOs + PH3> AgsPY + 3HNOs However on boiling formation of ppt of metal occurs. It is also reducing behavior. 4 3AgNO3+ PHs + 3H20——> 6Ag + HsPO3 +6HNOs 9. Complex formation ‘CuSO; + NH; —>[Cu(NHs)4]SOx Excess deep blue It does not form complex with metal ions. Property AgCl + NHs> [Ag(NH3)2]Cl Excess coloursoluble 10. Bpt Higher bpt. Due to H-bond Less bpt.due to absence of H- bond. Il. Reaction with Na 2NH; + 2Na—*-2NaNEb + Ho (Nat 2PH;—*-)2NasP+3H2 12, Solvent property Tt is a non-aqueous solvent Tt doesnot act as a solvent ¢* Combustion of phosphorus in limited air, Ps430; — ->P4Oe Limited /s, ; fr Pet 6NgO PEs pag + 6Nz Vapours (/ciettes 7°, Slt waxy sold with garlic odout 1/,, Ruble in benzene, chloroform ete {P Oxidized by air forming PaOro DW disso ot OF Ov0 (4% issolves slowly in cold water giving He Ps a 1, Structure Pyramidal with bond angle 107.5 Pyramidal with bond angle 93° Oxides of Ph * P4Qg + 6H20 ——>4H3PO3 Ratha + With hot water formation of PHs & HsPOs occurs. POs + 6H20 ———> PH + 3H3POs 2, phosphorus pentoxide, PsOvo or P2Os ‘a. By complete combustion. of phosphorus on air. Py +502 ——> P,O10 Properties, —> White crystalline solid soluble in cold water forming metaphosphoric acid & — then phosphoric acid P10 + 2420 ——>4HPO; Scanned with CamScannerexcesswater PaO10 + 6H30 —SS_ 411,PO, ~ Due to great affinity with water, it is strong dehydrating agent and can dehydrate many compounds. P2010 + 24280 —* 4250; + 4HPO; PeO1o + 4HNO3 —* 42N205 + 4HPOs PeOto + 4CHsCOOH —*-9 2(CH;CO):0 + 4HPOs ‘Acie ‘cid anhride PsOQ1+4CHsCONH—* >CHSCN + 4HPO3 > With carbon PaO + 10C —* >, + 1000 Oxvacids of phosphorus 1. Hypophosphorus acid HsPO2: > Oxidation state of Po+1 > basicity1 H HO—p—o H 2. phosphorus acid HsPOs: > Oxidation state of P> +3 > Basicity +2 H H-O—p—eo O-H 3. Hypophosphoric acid, HPO. > Oxidation state of P> +4 > Basicity > 4 ’ OH OH O—- p—P-—o OH OH 4. ‘Orthophosphoric acid, H3POs —» Oxidation state of P> +5 > Basicity> 3 ° H-O—P— 0.4 oO I H 5. Pyrophosphoric acid, H.P.0, > Oxidation state of P +5 > Basicity > 4 OH OH Oo=—p— , —o OH OH 6. Metaphosphoric acid, HPO; > Oxidation state of P45 > basicity—>1 oe, O—H oO Phosphorus acid, HsPOs Preparations: By hydrolysis of PsOg as w PCh PCh + 3Hx0——> HPO; + 3HC] P4O¢ + 6H20 ——>4H5PO} Properties > white crystalline deliquescent solid solu water q a. acidic _strength:- Dibasic acid & fo series of salts HPO; —2& y+ HPOs, H:POx H* + HPOs~ Salts are NaH2PO3 b. Action of heat, 4HsPO0; 222» 34PO.+ PHS ©. Reducing action: it acts as reducing can reduce several metal ions such Ag’, Hg”, Mn™, C15" etc. CuSO«+HsPO3+H20 —? Cul +2808 AgNO) + HsPO; + HjO ——> 2Ag)+2HNOs* K:Cr0) + 41,80, + 3H3PO; —>K2S Crx(8O.)s + 3HsPOs+ 4420 Orthophosphoric acid HsPOs: Preparations: a. By hydrolysis of PsOvo Scanned with CamScannerThe chemical substances which are added to soil to supply necessary ingredients required for growth & development of plants are called fertilizers. Nitrogen, phosphorus & potassium are three main essential elements required for the plants. Nitrogen: nitrogen is responsible for growth, increasing protein content and production of green colouring matter. Phosphorus: phosphorus is responsible for proper development of plant its early maturity and arly ripening of fruits. Potassium:- it helps to develop healthy root system and produces resistance against disesase. It is also responsible for formation of albuminoids. p,O10 + 6120 —> 4HsPO: » BY action of conc. H2S04 on rock phosphate, cone 3H2SO« + Ca(POs)2 ——? 2H3POs + 3CaSO+ By hydrolysis of PCls: PCls + 4H20 ——? HsPOs + SHC! 4. By oxidizing phosphorus with conc.HNO3, pet cone NOs ——?4HsPOs + 20NOs + 440 Properties: Crystalline solid soluble in water 4 > Its conc. Solution is syrupy liquid due to H- bonds / 7 a . Acidic character:- Tribasic acid & triprotic | Pre-requisites for afertilizers, = al > Should be cheap & readily available Should be readily soluble in water Heo iene epic > HPO; = H+ HaPOs > Should contain essential elements. H;,PO, == H* + HPO. > Should be stable for long time of. artes BOs _5 Should be easily assimilated by plants. Three series of salts are formed, i.e. NaH2POs, | Fertilizers are classified into natural and ,_ NOHPOs & NaPOs artificial fertilizers. Action of heat: 1. Natural fertilizers: these are _ naturally substances such as vegetables or plant decaying maters, animals excreata, sewage etc, that contain essential nutrients to the 2HsPO, 25>, P20, + HO H.P:0, —2°°_> 2110; + H20 With AgNOs &BaCl 3AgNOs + HPO; ——> AgsPO«d + 3HNOs Yetow pat plants. 2. Artificial made chemical substances Nitrogenous fertilizers:- Nitrogen containing * fertilizers:- these are artificially fertilizers 3BaCh + 2E:PO,——> ‘Ba(PO.)2v + 6HCI White ppt. i. Urea: Oo é %, With bromide & iodide salts:- it is used to Prepare HBr & HI 3NaBr + H3PO, ——>NasPOs + 3HBr 3K1+ HsPO; ——>K5POs + 3HI With Mg salt: Meso, WSO. 1 1 a + HsPO, ——> Mg(NHs)POs + beg pals is used for the test of Mg** ion. tugs egg, MNUfacture fertilizers, detergensts i 2NHs + CO: 2 5 nH, ~C — NE +H:0 ii. Ammonium sulphate: —»+ ammonia gas is passed through a suspension of powdered gypsum in water till saturation and then CO2 is passed through it. 2NHs +CO2 + HO ——> (NH4)2CO; CaSO; + (NHs)xCOs —> (NH4)2S04 + CaCOst- —> By reaction of NHb with H2SO, 2NH; + H2SOq > Used ‘ettizerg Preservation of foods. (NH4)2SOx iii, Calcium cyanamide: Scanned with CamScanneree suc CaC2+Nz —_? CaCNa + C alum sbi violin ferlize ‘The calcium cyanamide is hydrolyzed to give ammonia Ca(CN); + 3H,0 ——> 2NHs + CaCO3 Ithas slow action and its effect on fertility is more permanent iv. Calcium ammonium nitrate itis called CAN or nitrolim stone — it is mixture of Ca(NOs)2 & NH:NOs is directly assimilated by plants v. Basic calcium nitrate. [Ca(NO3)2.Ca0] b. Phosphoric fertilizers: i. Superphosphate of lime: it is mixture of calcium dihydrogen phosphate and calcium sulphate dehydrate Cas(PO.)2 + 2H:SO, + 440 ——> Ca(H2PO4)2 + Soperhosphate of time 2CaSO4.2H20 + heat The active component is calcium dihydrogen phosphate & is water soluble. ii, Triple superphosphate:- it is concentrated superphosphate & is obtained as follows, more Cas(PO4)2 + 4H3POs + HO ——> 3Ca(H2POs4)2.H20 “Tepe sperposphate iii. Phosphatic —slag:- ._—- During manufacture of steel by basic process, slag formed is called Thomas slag which is used as fertilizer. 6CaO + PxO1o—2-4 2Ca(PO4)2 CaO + Si02 CaSiOs Thomas slag also contains CaSiO3 Mgs(PO2): is also formed as slag & called Gilchrist slag c. Potash fertilizers:= > the potassium salts eg. KCI (muriate of potash), K2SOz, K2CO3 (wood ashesh) & KNO; (salt petre) are used as potash fertilizers which supply potassium to plants. d. Mixed fertilizers :- these contain more ‘one essential nutrients. For eg. NPK fe is mixture of ammonium pho superphosphate and muriate of potash. Questior 1. Which of the following elements is metallic? a.P b.As c. Sb Bi 2. Pnicogens represent a. Group IA b. group IV c. group VA d. groupV1 3, Most reactive allotrop of phosphorus is a. White b. red c. black d. scarlet 4. Which of these is most stable hydride? a. NH3 ‘b. PHs c. ASH3 d. SbH; 5. Which is most acidic oxide? a. P20s b. As:0s c. N20s d. Sb20s 6. The correct order of bond angle of hydride a, NH3 > PHs > AsHs > SbHs b. SbHs > AsHs > PH; > NF c. NH3 > AsH3 > PH3 > SbHs d. PH; > NH3 >AsH3 > SbH3 7. Which of these has least bpt? a. NH b. PHS c. AsHs d. SbHs 8. Which is the most explosive? a.PCls b. NCI c. AsCh d. SbCls 9. | Nitrogen is comparatively inactive ¢l because a. It has low atomic radius b.Ithas high electro negativity ¢, Dissociation energy of its molecule is dall 10. H3PO2 is a a. Dibasic acid b. Monobasie acid ©. Tribasic acid d. None 11, The, product formed by heating phosphorus with caustic alkali is 2,P:05 b. NaP ©. PHs 4. HsPOs 12. Which of these is good condi electricity? a, Black phosphorus bared phos ¢. white d, none Scanned with CamScannerF “osphorescence is exhibited by fn ite phosphorus b red phosphorus ie black . scarlet c. rus ee ofthese is dibasic? 1 ae: b. HsPO, + HPO 4. H:PO; re used in Home’s, signal is? 15 Ma + CaCh b.CaCh + Cap, f cal + CasPe2 4. CaC. + Canny ‘The allotropic form of phosphorus used in rat ision is a. White phosphorus bred phosphorus c. black d.scarlet phosphorus 1, The structure of PCls is a, Tetrahedral b.Pentagonal ¢ octahedral d.trigonal bipyramidal Nitrolim is a. CaCNe b. CaCz c. CaCNa + C d. CaC> + CaCNy |. Which has highest percentage of nitrogen? a. Urea b. CAN ¢, ammonium nitrate d. Calcium nitrate 10. Thomas slag is .Cas(PO4)2 b. CaSiOs ©. FeSiOs d. both a &b . Superphosphate of lime contains a. Cax(PO.)2 b. CaHPOs ¢. Cax(POz)2 + H3PO4 d, Ca(H:PO:)2 Substance used in smoke screen is a. Zine phosphate b.calcium phosphide ¢.caleium phosphate d.calcium fluoride Increase in protein content in plants is due to 2. Phosphorus fertilizers b nitrogen fertilizer ©. potash fertilizer dal 34. Which is most basic? a.NHy b. PH % c ASH; d. SbH3 + Which is most stable? a. NCI; b. PCs ©. AsClh d. SbCl %6. Pals is Benerally kept in well stopped bottle because nL LL. a. Itis highly volatile b. It reacts with oxygen readily ©. It is explosive 4. It reacts readily with moisture 27. Whiel a. White phosphorus b. red phosphorus ©. P20s @.HsPO, On cooling vapors of phosphorus the type of phosphorus formed is a. Red b. black ©. white d. scarlet 29. The correct order of acidic strength of the following is a. H3PO4 > H2PO4- > HPO4— > PO4— b.PO4— > HPO > H204- > H3PO4 c. H2P04-> H3P04 > HPO4— > PO4— d. HPO4— > H2PO4- > H3PO4 > PO4— 30. Arsenic isa a. Non-metal b, metal c. metalloid d. none 31. Which is not allotrop of phosphorus ? b. white d. orange P 32. The reaction 4P + 3NaOH + 3H20 > 3INaH:PO; + PHs is a. Oxidation reaction b. reduction . neutralization reaction d. disproportion reaction 33. Which is of polymeric tetrahedral structure? a. Black phosphorus b. plastic phosphorus c. red phosphorus d. white phosphorus 34, Which is strongest reducing agent? 28. a. NH3 b. PHs c. AsH3 d. SbHs 35. Which is called muriate of potash? a. KCl b. K:8O, c. KNO; dal Answer I 2.¢ 3a 4a 5.¢ 6a |7.b 8.b 9. 10.b ine [ia [13a | 14d] 45.0 16.6 [17d [186 [19a | 20-4 2id [22.6 [23.0 [24a [25-4 26d [27.a | 28.¢ | 29.a | 30-c 31d [32d [33.¢ [34d [35a Fr Scanned with CamScanner