GROUPS 15 ELEMENTS - THE NITROGEN FAMILY COLLECTIVELY THESE ARE KNOWN AS PNICOGENS AND THEIR COMPOUNDS AS PNICTIDES. __| Electronic Configuration [Hej2s" 2p" i — = ING ap ees =e ey ____[fan3a™. 4s? 4p" = —_[IKnad™, 5s” 5p: [Xe]4f"", 5d", 68" 6p" CHARACTERISTIC OF NITROGEN FAMILY 24 244 24.2 24.3 241.4. 2.4.5. 24.6. 247. Physical Properti Electronic Configuration All these elements have general configuration of ns* np®. These are also p-block ‘elements since differentiating electron enters in p-block + fl Git Abundance Nitrogen is widely present in nature both in free as well as in the combined state. Phosphorus is an active element and thus, not found free in nature. It occurs as phosphates in the rocks and soil ; as phosphoproteins in all living beings (an essential constituent of bones, teeth, blood and nervous tissues). It is necessary for the growth of plants Non-metallic nature Like group 13 and group 14, there is a transition from non-metallic to metallic nature on moving down the group. N PAS Sb Bi wee Non-metals Semi-metals or metalloid Metal Melting point and boiling point The m.p. of pnicogens increases from nitrogen to arsenic and then decreases from arsenic to bismuth The lower values of Bi and Sb than As are explained on the basis of their more, tendency to show three covalent bonds instead of five covalent bonds due to inert pair effect. This brings in weak forces of attraction between their atoms in solid state leading to lowering in m.p. Morever, Bi being larger in size than antimony and thus, shows relatively weaker attractive forces between their atoms in solid state. The bp. of pnicogens, however, shows a regular trend as given below Element N Pe AS sb Bi bp. (K) 772 554 BBB 1860 1837 Physical state Nitrogen, the first element, is a gas while phosphorus, the second member, a soft waxy solid, however, can pass readily into vapour state. The remaining elements are solids. These all (except N and Bi) exist as discrete, tetraatomic, tetrahedral molecules. N exists as No in gaseous state and Bi as Bi, in solid state, Atomic radii Atomic radii increase with the increase of atomic number. The difference between N and P is comparatively high due to more effective shielding of 2s and 2p-orbitals in phosphorus. lonisation eneray The first ionisation energy decreases regularly on moving down the group. The ionisation energy of nitrogen is very high due to smaller size. The difference in ionisation energy between N and P is more but the difference afterwards between to consecutive members is small due to less shielding effect of d-electrons in As and Sb and of d and f-electrons in Bi2.4.10 Furthermore, it should be noted that first ionisation energies of group 15 members are much higher than those of eoresponding group 14,and group 16 elements, The higher values of IE, {group 14 elements are due to increase in nuclear charge. Extra stable ie haff filed configuration of p-subshell of group 15 elements accounts for the hhigher values of IE, than corresponding group 16 elements. Electronegativity ()—Electronegativity decreases gradually on moving down the group from N to Bi (i) N being most electronegative element of group 15 and shows more affinity to ‘show Non, (i) Bi having lowest electronegative nature and thus, shows ionic compound with most electronegative element, viz. , BiF has ionic lattice Oxidation state and valency ()All'these elements have two paired s-electrons and three unpaired p-electrons. in their valence shell and thus, exhibit three covalence involving sharing of | three electron pairs to attain stable noble gas configuration. (i) Except N, all have got vacant d-orbitals in their valence shell. One of the valence electron of s-orbital is excited to d-orbital to give five unpaired electron ‘and so the state of five covalency (except N which show + 5 oxidation state by co-ordinate bonding). | } ‘ie 7. Ground a ATA State Excited State Day (Except N) (ii) ‘The various oxidation state for each group members are } N=-3,-2,-1,41,42,43,44,45 Pa-3,43,44,45 As=-3,43,+5 Sb=-3,43,+5 =-3,43 (iv) Oxidation state Nitrogen 0 Ne 4 NH,OH (Hydroxylamine) 2 NoHe 3 NHs 4 NO 42 NO +4 ‘ No, +5 NOs (¥)_Allthese elements exhibit -3-oxidation state (covalency) in hydrides. (vi) The tendency to show - 3 ionic nature is not possible due to high-eneray considerations. However, nitrogen being smallest and most electronegative and thus, forms N™ ions in nitrides such as Mgs No, Ca:N:, etc. Rest all show - 3- oxidation state forming covaient compounds (wil) The +3 oxidation states are covalent and ionic both. The + 5 oxidation states are covalent as they cannot form M ions due to large amount of energy | involved therein (vil) The tendency to show M™ ionic state however, increases down the group due to inert effect. Sb and Bi form ionic compounds of + 3 oxidation state as SUF, _ ‘and iF. Most of the other compounds of + 3 oxidation state are covalent. e.g. NF5, PCly are covalent. Catenation It is a self linkage property of an element but itis in lesser extent in group 15 due to repulsion between lone pair HoN-NHz — Hydrazine H-N=N°=N° Hydrazoic acid2.4.14. 24.42. Ny" azide jon PoHy, AssHe Electrical and thermal conductivity Both these properties increase on moving down the group because of the increasing delocalization of electrons from nitrogen (N= N:) with a co-ordination number one to bismuth having metallic crystals with co-ordination number of six. Thus, nitrogen and phosphorus are non-conductors while bismuth is an excellent conductor of electricity Allotropy All these elements (except bismuth) show allotropy. Nitrogen exists in two solid allotropic forms, a-nitrogen (cubic, crystalline structure) and [-nitrogen (hexagonal, crystalline structure). Phosphorus exists in number of allotropic forms such as white fed, scarlet, a-black, p-black and violet. Arsenic exists in three allotropic forms, ie, yellow. black and explosive, Antinomy also exists in three forms, ie., yellow, black and explosive 2.2 Chemical properties : 2. A 2.2.2 Formation of hydrides : () Hydrides formed have YHs formula ~ (NH, PHs, AsH, SbHs, BiH) (i) Except NH, all hydrides are poisonous. (ii) NH neutralises protic acids as well as aprotic acids (Lewis acid), so, ammonia is strong base. ) PHo + Hi—> PH4I Phosphene Phosphonium lodide Phosphene is a weak base as compared to NHs and rest all have amphoteric nature. (v) NH will have high boiling point due to H-bond. (vi) Tendency of H-bonding and 8. P. NHs> PH < AsHs < SbH3 < Bills (vil) NH cannot acts as a reducing agent and BiH, is strongest reducing agent (vil) Stability decreases from NHs to Bits Size increases and so bond strength decreases (>) Hydrazine is used as propellant for rocket fuels, Itundergoes combustion releasing large amount of energy. (*) Ny is called azide ion -—> Has 4 lone pair Ba‘?N3 » Barium Azide (Ba(N; )2]. Formation of halid ()— Trihalides: All possible trihalides of all these elements are known except NCls, NBrs, and Nis Because Low polarity of the N~ X bond. ‘Weakness of N - X bond due to large size difference. Properties NCly +-3H20——> NH3 +3HOC! PCls +3H20——+ HgPO + SHC! SbCIg +H20—» SbOCI + 2HCI - (Stiony! Chloride) BIClz +H20-—> BiOCI + 2HCI (Bismithy! Chloride) When an aq. solution of BiCl; is prepared, after some time a turbidity appears in it which is milky in appearance and finally a white ppt. is formed due to formation of BiOC|, Lewis base order : NF3 PC + Cle DINITROGEN (N:) (i) Nitrogen is most abundant element in air (78% by volume) (ii) Itexists in the form of diatomic molecule, N; and is also called dinitrogen. )__ Dinitrogen can be prepared in the laboratory by the following reactions, NH,Cllaq) + NaNO. (aq) —“*"_yN,(g) + 2H,0(¢) + NaCKaq) (NHe)26r07 "+ Crg05(5) + 4H20(") + No(9) Armen eromate 2NH, + CuO —»2Cu + 3,0 +Np 2NH, + CaOCl; ——»3CaCl, +3H;0 +N; (9) ‘Commercial preparation of dinitrogen is carried out by liquefaction of air and its subsequent frac distillation. Dinitrogen (b.p. 77 K) cistills over first leaving behind liquid dioxygen (bp. 90 K). Dinitrogen| derived from ir does contain some traces of noble gases and dioxygen Properties of dinitrogen (i) Nitrogen is colourless, tasteless, odourless and non toxic gas. (i) Ithas very low solubility in water (23.2 em* per litre of water at 273 K and 1 atm.) (i) Its mop. and bp. are 63.2 K and 77 K respectively. ‘Chemical reactions of dinitrogen () Nitrogen has low chemical reactivity. It is stable because of N = N bond which has high bond: dissociation energy. Some of the chemical reactions are listed below. (ii) Highly electropositive metals react with Noto form respective nitrides 6Li + Np ——>2L.i,N;3Ca-+Nz —»CayN,3Mg + Ny ———>Mg,N, (ii) Non-metals tike H, and O; react at high temperature. BH, +Ny — F225 2H, +Ny 25, 3H on 050 es Cocca Mote (iv) Reaction with compounds like AlOs and calcium carbide (CaC.) 2100K 100K AO +Np+3C—2100K,2AIN +360 Cay +N °K, canon +c cane tre stan ‘unin a qenme Natrol 3.1. Fixation of Nitrogen The process of conversion of atmospheric nitrogen into its useful compounds is called fixation nitrogen. Fixation is brought about in following ways 3.1.1 Natural fixation. A large amount of atmospheric nitrogen is brought to the soil either lightening discharge or by symbiotic bacteria. Lightening discharge converts dinitrogen. and dioxygen of air into oxides of nitrogen which are eventually converted into nitric acid and nitrates in the soi ‘The process of conversion of dinitrogen into its useful compounds by natural or artificial meaning. Lightning Higtemp iscreated ” 2HNO3 + CaCO3——» CalNO3)p +H1z0 + CO eq. N2+O2 > HNO3 (Rainwater) from ran waters Ca(NO3}2 ——»Plant roots 184 _, proteins eed = oe urea+ amino acid —“**"°_, wasteproduct —A™°nfvtg P22", Ammoniumsalt Nitrosifyng bacteria nitrites inpbactera® Fifrates —Semmnyiing bacterle 5. (iroxi 0 “ ca) (iv) w 2 Artificial fixation. Nitrogen can be made to take part in chemical combination under Suitable conditions to form useful compounds (refer to chemical reactions) (Haber's process) () Na + 3Ha qa 2Mo ants 73K, (i) Np + 0p 923% yano(g) 22 sng M2 NOs (i) GLNy 4+ 2Lign unum tie (vy) 2AlsNp—2 DAN i - Aluminium nitride CaG2 +N2 ——»CaNCN + clu rae NIHON) 5 urea —"29 (NH, )2CO3 26 ides N,0 : laughing gas Highly poisonous gas, in very tte amount it will have hysteric effect. N=N-» 0, ithas linear geometry, 1. must be zero but itis more than zero because it has only ‘one polar bond. ‘Only NO and N2O are neutral oxides of N. Itis only N which forms paramagnetic oxide. Stability of oxides decreases with increasing atomic number. Thus, NzOs is stable while Bi,Os is not known. (vi) The acidic character of oxides decreases with decrease in OS. (vip (wi Nitrogen oxides 0 iy @w (w) N,O +1 = Neutral While NO; +4 = Acidic ) _SbaOs and BizOs are insoluble in water but dissolve in alkali Sb205 +6NaOH —-> 2NazSbO, +3H20 (Sodium Antimonate) i205 +6NaOH——> 2NagBiO, + 3H20 (Sodium Bismuthate) i) Types of Oxides: Element Types of Oxides [N PTAs SB, Bi X,0, N,O3 | P:03 | As:O3 | Sb,0; | Bi,05_| Ou N:O4 | P,0, | As;O, | Sb,0s | Bi,0« X,0: NOs | P70; | As,Os | Sb,0: Nitrogen also form NzO, NO, NO> oxides. The oxides show the wide range of oxidation numbers of N, from +1 to + 5. All the oxides are covalent ‘Aare gases at room temperature (except NzOs which is unstable sold at room temperature) The lower oxides are neutral and the higher ones are acidic, Oxides are summarised below, Oxidation | Physical Lewis Formula | Method of preparation Number of N | Appearance = 4 Célouriess gas | :N=N-2 56: | NHyNOs —"" N20 +220 if Pt ANHg +502 Pt ,4NO+6H20 Hs +802 sso0 * +2 Colourlessgas | :N =O In sold and fiquid states, itexists as loose gimer N02 +3. | Biuesota ea NO{g) + NOz(9)—22°S 5 ns05 ree nS[N2O. Dinitrogen +4 Colouriess liquid tetroxide NO; Nitrogen +4 Brown gas. dioxide | O. te ie Nos °. 0 | 4HNOs + P4010» Porcdie +5 Colourless YON 2N205 + 4HPOs ae Bs noephor o ‘o : phorshe 3.3.1. Nitrous oxide (N20) ()— NHyNOs 22°C N04 2450 (rnatten} (i) NHgOH+ HNO2 ——>N20+2+20 Gi) tis stable, relatively unreactive colouriess gas, itis a neutral oxide (iv) It's soluble in water (1 "1 by volume), but solution is neutral and the following equilibrium lies in left hand side N20 +H20 === HyN202 hyponitrous act ‘Therefore, it may be taken as anhydride of HNO: (v) _N,O is also used as an anaesthetic, particularly by dentists. It is also celled laughing gas, because its smell cause euphoria, francs wry at Nan 80 fe OHNO If we] |s v Ra tno] [ee] 3.3.2 Nitric Oxide (NO) (i) NO is an odd-electron molecule ; alternately we can say it is a free-rad Hence itis highly reactive 2NO +02 —>2NOp (brown fumes) 2NO +Cly ——»2NOCI ano 298°C 54,0 4NOz eee (i) Bohborder Is 2.5as described by MO, theory) anil ‘bond length Ws 1.18 which ntegndisabetenen srcoubie Solel and a irole fered bel Biogen snaitdgen ater333 (ii) thean be represented by the following resonance structures 11 valence electrons). itis paramagnetic. In Solid and liquid states it dimerises forming N;0: and paramagnetism disappears O-N-N-O o O-N-O-N (ny I is asymmetrical and is formed as a red solid in the presence of HC (iv) NO readily forms coordination complexes with transition metal ions. These complexes are called nitrosyls, [Fe(H0)sNO}" (brown ring) Net 0 HNO: Fe nrnon oO: Nojabe [Fe(HO)y (i) NOp molecule js angular with an O.N-O angle of 132° and N-1 bond length of 1.20 A (which is intermediate between a single and a double bond between nitrogen and oxygen atoms) (il) N:Oc has planar structure studied by X-ray. ON 184A, N o ° N-N bond lenath (1.64 A) in N:Os is about 20 % larger than the usual N-N single bond. We can think ofthe positive charge formed on the adjacent N atoms which Causes repulsion and thus increases the bond length (i) NOe soliciies at - 11.2°C ands colourless. AAs the temperature increases, proportion of brown NO, increases and the colour of the liquid darkens. At around 140°C, the mixture is almost entirely NOsPD(NOs)s Cu+ HNOs(cone) a = l= Tt J ao Wes ngs Neuse rise NO.F ZnCle Zn(NOsj2 + NOC! 3.3.4 Dinitrogen trioxide(N;0;) @___ itis an intensely blue liquid or @ pale blue solid. It exists only at low temperature and readily dissociates to give NO and NO2, N:O; == NO+NOz (i) The NOs molecule has an O2N - NO structure in the gas phase and at low temperature, with an extremely long (1.86 A) N- N_ bond which is consistent with its easy dissociation. Q 168 9 N72 198A 105" N. 4240 Two interconvertibie structures (in presence of light radiations of a particulat wavelength) are assigned to it ° NN IN == O=N NEO a SS INO + NO; won IE 40 NHANO2 fe N23 SHINO: NaOH an Not H:0 Nallo, 3.3.5 Dinitrogen pentoxide (N:Os) o 2HNO3 208 5 Nos +H20 Tow temp ‘Thus NzOs is the anhydride of HNOs (i) this colourless deliquescent solid and highly reactive (ii) Inthe gaseous phase: Nz05 —* »NO2 +NOs 02 No05 +03 ——>2NO3 +02 (wv) Insolid state: NoOs +H20 N2Os +Na——>NaNOs +NOz >2HNO3N2Os +NaCl--—>NaNO3 + NOC! (¥) With cone, H:S0,,itforms NO} (nitronium ion) which can attack benzene nucleus forming nitrobenzene N25 +3HSO, ——>2NO} : 3HSO4 + H20 Calg +NO} ——>CgHeNO2 +H! (vi) X-ray diffraction shows that solid NzOs is jonic, NO3NO3 (nitronium nitrate), In the solution and gaseous phase, itis covalent with structure: SNe we Each N atom is sp*-hybridised NOs HNOs, NO; + NO +O; Ho POs % Na ¥ NaNO + NO»<———{(in solid phase) |N2Os | (in gaseous phase) Neci NOs+NO; | 604 NaNOs + NO-CI pane : yO) tadean nos -———>(O) > 3.3.6 Nitrogen oxides and air pollution Collectively, nitrogen oxides are often given the symbol NOx. Two of them, NO and NO; are (of special importance in envionment chemistry, causing considerable amount of air pollution. ‘They are given off in automobile exhaust and when fossil fuels are bumt, as wall as being ‘made during thunderstorms. In each case, NO is made and then NO; Nz +02—> 2NO No+ fo2- —NO2 NO; is more unpleasant and gives rise to acid rain and also takes part in photochemical reactions forming smog. The photons making up sunlight can cause the NO2 molecules to decompose, releasing oxygen atoms. No, 5 NO+0 ‘Oxygen atoms are extremely reactive and will attack other molecules, especially those in car exhaust fumes. For examples hydrocarbons that escape combustion, can be ‘changed into aldehydes. The oxygen atoms can also react with Oto form Os NO; is also involved in the production of one of the most unpleasant of all chemicals, present in photochemical smog, Its known as PAN (peroxyacetyl nitrate) 0 chy ¢ ee -O-NOs Its presence in the atmosphere irritates eyes and lungs and generally makes breathing difficult, 4 2NH, + CO, == NH;COONH, == NH,CONH, + H20 arenin carbamate wea34 _Oxyacids of nitrogen = BO Se ere Hyponitrous acid HaN2O2 Nitrous acid HNO; (aa ee EN - HyN202 +H20 +N20 H2Nz Oz gives N2O (anhydride) only on heating but N,O when dissolved in H,0 will not form H> N2O2 3.4.1 NITRIC ACID ‘Chemical properties of nitric acid Decomposition 4HNO, (aq) —"**—»4NO, (g) + ©2(g) + 2H,0(1) Acidic nature. HNO (aq) + H2O(!) -» Hs" (aq) +NO3(aq) Oxidising agent. 2HNO, (conc. )-—»H,0 + 2NO; + [0] ; 2HNO,(dil)-—+H,0 + 2NO + 3{0} Oxidation of non - metals. (i) Carbon is oxidised to carbonic acid (H.CO3). 2HNOs > HO + 2NO> + [0] «2 C+ 2{0] + H,0 > HCO: (C+ 4HNO, -» HzCOs + H,0 + 4NO2 T (ii) Sulphuric is oxidised to sulphuric acid (H,S0.) 2HNOs -» HO + 2NO, + [0] « 24 Sq + 24[0] + 8H,0 > 8H,SO, S. + 48 HNO, —> BH,SO, + 48NO; + 16 HzO (il) lodine is oxidized to iodie acid (HIO,). 2HNOs ~» H;0 + 2NO> + [0] «5 b+ 5 [0] > 05 1,05 + H,0 > 2HIO; I, + 10 HNO; > 2HIO; + 10NO; + 4H;0 (iv) Phosphorus is oxidised to phosphoric acid (HsPO,) 2HNOs -» H,0 + 2NO2 + [0] x 10 Py + 1010] > PsOro P4O1o + GH:0 > 4HsPOs P+ 20HNO3 > 4HsPO, + 20NO; + 4H,0 (v) Arsenic is oxidised to arsenic acid (H AsO.) 2HNO, > H:0 + 2NO; + [0] «5 2As + 5[0] > As,0; ‘As,Os + 3H,0 > 2H 2As + 10 HNO, > 2H,ASO, * 210 + 10 NO, or As +5 HNOs > H,ASO, + H,0 + 5NO; ‘Arion sot Oxidation of compounds. Dilute as well as concentrated nitric acid oxidises a number of compounds. For examp! () Hydrogen sulphide is oxidised to sulphur With nane HNA.