chapter CoMPOUNDS OF S- ANp p-Biock ELEMENTs a THEIR CLASSIFICATION 1 -metals [except noble ga: “oh most of the metals and nor metal ble gases} t0 form obi wie on the basis of their physical and chemical properties me which are known 3S eg They are classified into three distinct types. | ee or salt-like hydrides. including the anions of complex hydrides, (i) Tonic or salt-like hy 3.1 HYDRIDES AND Hydrogen (ii) Covalent hydrides (Gi) Interstitial hydrides | may accept an electron to form hydride ion Hydrogen Hy) t& FH (gy This tendency of the hydrogen atom to form the negative ion is much lower than halogens fy example, 1 Ho) —2 Hy AH= 218 kJ mot! H,, + € —7 Hy AH = -67 kJ mol! The overall reaction is 1 SHyg + © —9 Hy) AH = 4151 kl mol! - 1 \ lef 5 Bry) +€ —> Bry, AH = 232 kJ mol''] Therefore, owing to the endothermic character of the H_ ion, only the most electropositive mets form ionic hydrides. Other elements of the main group generally form covalent hydrides. Classificaine of main group hydrides is given in Table 3.) —Comouning mnt aki % ahah Bro hie Table 3.1. Some hydrides of Main ¢ —__"" 2 14 15 che-""1 eH), BH, ch, Ny By | el { MgH, (Al. sins om “9 Ws en teen ee ‘ 45 3 . ' CoH, 1 Gay, Gen, ASH. ’ He | : iH V is ‘al StH, 1 tin Sn, Sbu _ ‘Br % al PoH re (8 HPo A ppanides of In and TI are not known as yet, 3.1.1 Jonic Hydrides its of s-block are highly electro, Positive, Therefore, nas tonic hydrides or saline know! hey combine wit Ce salt lke) hydrides, The noun imate tonic nature of the Jom yds led by their high conductance at their melting Points and also by the Observation ee hydrides is oftheir moiten salts, hydrogen is liberated at the anode, On electrolysis aration of Tonic Hydrides: Hydrides of Sroup | elements are ‘i veal and hydrogen under pressure at 423 to 1000 K. For example bY direct reaction 2Li + H, mK, 2 iH 2Na + Hy BK, ony In case of group 2 elements, Be and Mg do not directly combine With hydrogen to form ionic hydrides. BeH, and MgH, can be prepared by the thermal di . lecomposition of Be (C Mey)s and Met, respectively (where Me stands for CH,, Et stands for CHY). - BeH, can also be prepared by reducing BeCl, with LiH or Li AIH, as BeCl, + 2LiH _ehw , BeH, + 2HCI BeCl, + LiAIH, ate, Bet, + Lict +AlCl, The other elements of group 2 directly unite with hydrogen to torm ionic hydrides. For example, Ca +H, mK, can, Ba +H, Wak , Ball, Calcium hydride (Cal,) is commonly known as hydrolith, Properties of tonic Hydrides the ies whi cal of ionic () They are crystalline solids, white When pure and exhibit properties which are typical ‘subst ionic radi of Hr and F - Thelr properties resemble the corresponding fluorides because ionic mio W a (9 similar (140 and 136 pm respectively), rr Te atl eeTwoRGANIE (CHEMISTRY feist couple is abou rowing that | 7 vec ful reducing agents. They reduce Organic jy Tres act as DO W— RCHOW + Li ( se cooR + 2H p lio “ i ‘ sty with protonic solvents like water, alcoho! and liquig gone + CHO —> LOCH, + Hy T wt semen Nel + HO —> NaOH + HAT KH + NH,—> KNH, +H,T cal, + 20 + 2t bility of hydrides decre; i -_ gown a groups the Stability | Mea tis i (ay On goin ene ‘and hence weakening of the metal-hydrogen bong SM 10 increas i Es are employed to prepare complex hydrides ang hydride Me . Powerg, Acids to alee ing ‘ols, (v) These ie. 4H + AIC,—> LAH, + 3 Lic] hydride (LAIH,) is also a powerful reducing agent. of s-block Elements namely, LiH, NaH, RbH and CsH have Nac S of other Metals, p * Poe Lithium aluminum saractare of Hyanioet - of ‘group + : ~ a ve bydvide i a three-dimensional polymeric solid. I s I type structure, de up of ionic Be** and H” ion as thought of an formally ! It is quite j ionic in Nature nd may by cuohy i be considered to be an electron-defici A ively, it may be con: : de! ‘icient molecule pol; merized oe ‘ponds (as in diborane) and its structure is probably similar to that of Beth or BeMes centre Ib le, H, H, SO NN of’ Nw SH? NZ OO NZS (c) Mg H, has rutile structure (d) Call, StH, and Bal, are ionic solids containing M?* and H” ions. They have slightly distorted hep arrangement. 3.1.2 Covalent Hydrides ‘These are compounds like HF, HCI, CH,, NH, H,O, etc. where the bonds involving hydrogen atons are largely covalent. They are formed by boron (group 13), and elements of groups 14, 15, 16 and 17. Their properties depend upon the electronegativity difference between hydrogen and the slamCOMPOUNDS OF S= AND P-BLOCK Ei vag MENT % votatite, molecular hydrides. Along any given ry 2 they increasingly acidic as we move f > Of the Period me inet ¢ from left t ic Tab beco NH; > H,0— HF ° Fight these by base neutral — attic fi ned DY highly electronegative elements, such as HF, HO and Np for NH, exhibit hydrogen _ NHHy: HO, HF the X—-H bond becomes mo is os wrnoving from Cto F. This means thatthe Peart base Of the increasing vin e and therefore it becomes easier to ionise as a boron | acquires an increasn fo crease in acidity in moving from SiH, to HCI (via PH vu > We can similarly sy of X: Both CH, and SiH, do not behave as acids in water be 5) to increasing on ve very little polarity. ; cause the CH and bof a group, the acidity of the hydrides increases. Thi nd . sergies of the XH bonds. As the sizeof X ne Be oie in es of inborn oe from the nuclei that itis holding and so the bond bes electron density etext break the XH bond and the acid strength increases, Thue oe Thus it uF HCl and HBr compounds. Strongest acid ngths of the hydrides vary in just the opposite man ir basici we an icity depends on the availabilty of an washared ckston na 7 an Both CH, and SiH, do not have an unshared electron pair so they do not beh oe NH, #9 HF, the electronegativity of X increases which causes the unshared ‘clecron na i strongly and thus makes them less available for sharing with a proton. The oe. a des ; NH, is a base, water is a much weaker base and HF docs not bee we Tiga a size of the atom X and unshared pair becomes larger and less lend we a proton less strongly than a smaller and ‘more concentrated unshared pair. Thus we raxch weaker base than NH. Similarly, water is a much weaker base and H,S has no basic popes in water. 4.3 Interstitial Hydrides Many transition metals such as Ti, V, Pd, etc. absorb hydrogen to yield compounds in which hydrogen sons occupy interstitial (vacant) positions in the metal lattice. Their composition does not correspond ‘osimple whole number and, therefore, they are also known as nonstoichiometrie compounds. It is tot clearly understood whether the interstitial hydrides should be regarded as normal compounds or nieely considered as solutions of hydrogen in these metals. Theit composition generally varies with tovaation in their reaction conditions, Interstitial hydrides are also known as metallic hydrides. i Txerclse 3.1. Oxygen atom in H,O has two lone pairs whereas nitrogen in NH, bas only one unshared electron parbu sill NH, is a stronger base than H,0. =” ‘Ans, Base strength does not depend on the number of unshared pars but the availability ofthe unshared pat for awit one Although HO ona ro usted pss feta i as el PN 40" ln, The positive charge thus created attracts the remaining unshared pai and mak much less avallabe for ‘ig wih another proton, Thus the HO ion has never been observed,80 INorGanic CHEMISTRY, 1 Elements of group 13 do not react directly with hydro) Hydrides of Group 13 gen. However, b ‘ i Y USING indiren interesting hydrides of this group have been prepared. These hydrides are inn eCt Methods view of their structures. POtant from the te i Boron does not form simple monomeric species such as BH “a but a |; ci vey sd ‘arge numbe, compounds are known to exist. These compounds are divided into Wo distinct cate i" of Pol Ties: with the general formulae B,H,., and the other having formulae Bi the latter series are less stable. Some representative compounds of ‘the we senPounds belong ih BHy. BsH,). ByHjq» ByHy B gH, and ByH,q. Boron hydrides ae covalent in nes 2° BiH, pee called boranes by analogy with the alkanes. The simplest of these is diborane, Ba: They ares has been discussed in detail later on. ane, BH, and it cheng Aluminium forms only one high molecut " Recent structural investigations by X-ray ani surrounded octahedrally by six hydro; lar weight polymetric hydride (AIH. ich js \d neutron diffraction studies i me lle ag ne gen atoms. The structure consi: it ins Al On heating it decomposes into its elements. SS of network oF ALA wig Gallium is also known to form a hydride, GaH,—known as Ik ich i a T gallane which is an Unstable 2 oi, Indium hydride, (In H,), isa polymeric solid while thallium hydrides are extremely The elements of this group make use of the empty p-orbitals in the formation of ; Idrides such as Li‘[BH,), Li'TAIH,F, Li'[GaHiJl, Na*[BH,]-. The formate of thee i due to the hydride ion acting as an electron donor. Se hydride i BH, +H —> BH AIH, +H —> Ale These complex hydrides are prepared as follows: @ 4LiH_ + AIC, —28, Li[AlH,) + 3Licl Ether er (ii) Li + Al + 2H, —orsec? Li[AlH,] 250 atm Other complex hydrides can be prepared by similar methods. The stability of the complex hydrides increases when: (i) the extra electron can be completely stabiliszed by the anion. (ii) the polarizing power of the cation is maximum. / oo Thus, the alkali metal borohydrides are the most stable. Their stability increases with increasing tremely usefl size of the cation. These complex hydrides, particularly Li[AIH,] and aii aninil " ree reducing agents. They are used to reduce aldehydes and ketones to alcoho!COMPOUNDS OF 8 AND P-BLOCK ELevenry ELEMENT ade? of Group 14 . oup A 7 + ents of erbon has the unique capacity of forming an infinite numberof grouP- ‘where the limit of 7 is not known. Silicon and germanium fom Jong chain hydrides, CHa? é reduced energy of the M—M bond. In addition to saturated a limited umber of due 10 1 Varides such as alkenes and alkynes. hydrides carton aso te att ides), have the general formula Si jlicon hydrides), ula Si,H,,... but th janes. e roms. Silanes are prepared by the following metals: action of HCl on magnesium silicide. yoy he Mg,Si + 4HCI—> SiH, + 2Mgcl, 14 form covalent hydrides. The ease of their format ation decreases 38 we Move silicon-silicon chain is a SiH,, other silanes such as Si,H,, SiH, etc. are also fc . s wisition sonal distillation or by gas-liquid chromatograpy pened hi pylow ae action of LiAIH, on SiCI, in ether. w@By LiAIH, + SiCl,—> LiCl + AICI, + SiH, 5 hydrides called germanes such as GeH, (Germane), Gi i jum forms ee he eH, (Digermane) erat they ae prepared by addition of ala bore, MBH, w GeO inact, oth C ; form two hydrides; stannane, SnH, and distannane Sn,H,. SnH, is prepared by F nown to tn is SO% C1, with LiAIH, in ether at —30°. Lead is known to form only one hye rsaCl, ly \ydride plumbane, h are separated a us, it may Be concluded that the ease of hydride formation decreases as we move down the up. q ” suability of these hydrides. The stability of hydrides of group 14 elements decreases as we nove down the group. Since the electronegativities of carbon and hydrogen are about the same, fore, hydrogen cannot withdraw electronic charge by inductive effect and strength of the carbon- carbon bond is not effected. This makes the hydrocarbons stable compounds. Electronegativity of is 2.2 and that of silicon is 1.7, therefore, hydrogen atoms being more electronegative, "withdraw electronic charge, thereby weakening silicon-silicon bond. However for germanes, stannanes and plumbanes the decreasing trend in their stabilities is not due to the weakening of the metal-metal bond but primarily due to the weakening of metal-hydrogen bond. This may be attributed to the large {differences in sizes of metals and hydrogen and cannot remain united through a covalent bond due to poor overlap, (c) Reducing character. Since the thermal stability of hydrides decrease down the group, therefore, their ability to act as reducing agent increases. 4.1.6 Hydrides of Group 15 warns of this group form volatile hybrides of the general formula MH, The lige lene ato Hd es Of the type MGH, (uch as NjHy, PjH, and ASH) and nitrogen als forms hydazn HN,.A list of important hydrides of the elements of group 15 is given in Table 3.2.INORGANIC CHEMISTRY t Hydrides of the clements Some Important 1) °f Grog Table 3.2. § PS : NH Hydrazine HN, Ammonis e PA Diphosphine . “Ydrazoieg ‘'s Phosphint ed PH, arsine AsH; stibine oe Bismuthine ; type MH, Hydrides of the © from bit iy ; are prepared m inary meial commpounds @ epee be action of water or dilute acids as: tsh as Man, Cap, g or 2 - Mg,Sb Mg;N, + 6H,O—> 2NH, + 3Mg (On), “ CaP, + 6H,O —> 2PH, + 3cacony, Zayas, + GHC! —> 2ASH, + 3znc1, Mg,Sb, + 6HC] —> 2SbH, + 3MgCi, Mg,Bi, + 6HC] —> 2BiH, + 3Mgcl, structure of these trihydrides is described as pyrami: Sac iy tees than the ttrahdral value, This is de to the eae: The HN ammonia is stig he other three members of the group show a conn eenaion oF the lone However, nye is evident from Table 3.3, Siderable reduction font, 3.3. Important Parameters of the Hydrides of the Elemen: ts of Group 1 Atomic radius Bond angle —excrongtitiy emia Bondangie Bond enon oo Bond ener Bas (Umar pe24 P=110 93.7° : = 389 HH = 329 As=20 As =120 91.8° Sb =140 91.3° = 247 Sb=1.9 4 Sb—H = 255 It is obvious from Table 3.3, that smaller HMH angles occur in moles ts in cules with electronegativity of M. As the bonding electrons is MH, are drawn further away from Mt orden electronegativity), the bond pair-bond Pair repulsion decreases, thereby allowing the closing up of bond angles. This also leads to decrease in the lone pair-bond Pair repulsion. (©) Properties of MH, @ Base Strength. Ammonia is the strongest electron donor. Due to the small size of nitrogen atom the lone pair is concentrated over a small region. Increase in size of the central atom results in reduced electron density in the sp? hydrid orbitals as the electron cloud is now diffused over a large volume space and thus the electron donor capacity (i.e., base strength) decreases.COMPOUNDS OF S- AND P-BLOCK ELEMENT, % ivity difference between phosph e, The electronegativity een phos ature Tad hydrogen and is of opposite sign. Therefore, PH goa ss wert mim continues down the gFOup. TENS uch less polar is , pn sing: The structure and bond polarity (due oh yee ND orm hydrogen bridges. Thus, ammenia is high re HH H H 4 bot body UHAN..HON..HON..HAN,.HONS | | \ | | H oH H HoH igh electronegativi i ‘ ty of nitrogen ly associated inthe liquid sane, clsivelY high boiling point and heat of vaporization. As we move down the the nits et of te eeial atom decreases and there is no evidence of hydrogen bond i ion pont ides sli ' IL i i " 1 stability: ‘The thermal stability of group 15 hydrides falls "apidly with increasing M. NH;_PH;_AsH, SbH; BiH, ‘Decreasing stability n the group, the size of the central atom increases and thereby the sve 8 oo isis due to decreased overap with small hyérogn stom, abd cing Character. All these hydrides are strong reducing agents. Thermal stability dam 0 Seas cr down th group the M-—H bord weaken an edn chance oe ee ines 7 Hydrides of Group 16 ) Preparation. Elements of this group form volatile bivalent hydrides, H,O, H.S, H,Se, H,Te, H,Po. Westone’ by burning hydrogen in an atmosphere of oxygen while other hydrides are best prepared iy action of dilute hydrochloric acid on metal sulphides, selenides and tellurides. M;X(s) + 2HC] —> 2MCI + H,X(g) Hypo has ‘been prepared only in trace quantities by dissolving magnesium foil plated with Po in qaNHCl. (0) Properties of hydrides. Some important properties of hydrides are: (f) Volatile Nature. Water is a colourless, odourless liquid while hydrides of other elements of this group are colourless, poisonous gases with unpleasant odours. The volatility increases markedly frm water to hydrogen sulphide and then declines. Abnormally low volatile nature of water i tributed ‘ofydrogen bonding (caused due to its highly electronegative oxygen atom) which results in association \anumber of water molecules. As a consequence of this, water has high bling poin (and melting Print) as shown in Table 3.4.4 Re Iworcanic CHensry Table 3.4. Some Important Properties of Hydrides of Group 16 Flemeng —~ MO HS H,Se Boiling point, °c 100.00 payee ss * an ie -85.53 65.73 23 Electrolytic dissociation “ constant K 10*10 11107 2x 104 Bond length, HX (pm) 96 182 ir “ Bond angie 104.5 es oe " Hydrogen bond formation involving sulphur atoms is rare and is very weak, The is unassociated and is highly volatile. On moving down the group, the volatile mature ao HS 9 HLS to H,Se and to H,Te because of the increasing molecular weight and increasing ress fy forces, n der Wal, (é) Covalent Nature: The H—X bond lengths in HO, H,S, H,Se and HyTe ince as the size of the central atom increases. This increase can be correlated with eae Mata electronegativity difference between X and H. Therefore, as the degree of ionic cha © decteas: decreases, the length of the bond increases. ‘The nature of the bond in these hydrides can also be explained on the basis of Fajan ru to which as the size of the negative ion increases, the tendency to form covalent bond. ‘Since the size of the negative ion increases as we go down the group, therefore, the covalent increases in the hydrides increases. Charo, (iii) Acidity of hydrides. Aqueous solutions of hydrides behave as weak, diprotie acids HS == Ht + HS HS == H* + S> The acidic strength of the hydrides increases as we move from HS to H,Te as is evident dissociation constants listed in Table 3.4. The increasing acidic character reflects decreasing ra the electron donor ability of HS, HSe or HTe~ ions. As the charge density on the conus, decreases from OH- to HPo”, the proton is Jess tightly held in higher members and therefore ac character increases. i (iv) Reducing Charater and Stability of Hydrides, The thermal stability and bond decreases from H,O to H,Po. This is because the size of the negative ion increases from O* to Poh the charge is distributed over a large volume and this results in the instability of the hydride, dr consequence, the reducing power of these hydrides increases from H,O to H,Po. (v) Bond Angle. The data in Table 3.4 shows that the bond angle in H,S, H,Se and H,Te are much smaller than in H,O. As the bonding electrons in MH, IR are drawn further away from M because of the decreasing electronegativity of | 'Y M, the bond pair-bond pair repulsion will decrease, therefby allowing the closing 4 up of bond angles. This also leads to a decrease in the lone pair-bond pair repulsions. TACTr inthe gtComPounns OF S+ AND P-BLOCK ELemenrs q phides (Sulphanes) ly! , ysulphides beca few hydrogen poly use sulphur has , onl om bond. Some of the hydrogen polysulphides ce ee ends for gue! ame Structure Hydrogen disulphide nss4 Hydrogen trisulphide Hoss 5H ydrogen pentasulphide W355 554 aes of Group 17 vs 9810 ydrogen to form volatile yids, HX. The reaction of hare thn re with hydrogen react wil ace even in the dark; chlorine reacts wi takes PI : reacts with hydrogen in diffi ee avjrogen only on heating above SOO'C wile jodie ects ith HCI> pps expected from the order of decreasing clectronegativity of the halogens (F > C| > p, hich, (c) Heat of Formation. The heats of formation of hydrogen halides ine >), oy atomic mass of the halogen which indicates ing decrease in the quanti during the formation of hydrogen halides. Thus as we go down the group the a of; . halides should become more difficult which is in accordance with experimental frtion oth ke facts, Ng, (@ Reducing Properties. AS is evident from the heat of formation data, the ‘ Stabili as we move down the group. This HF and HC! ae stable upg ie O yy °C wh Tease it, ; halides decreases { ty dissociates slightly (126) and Hi dissociates at 440°C to 20%. This also impli Cw, character of the hydrogen halides increases as We gO down the group. plies that the me hy ‘ey Hl HBr _-HCl_HF : Diminishing reducing action course, has no appreciable reducing properties, ily oxi that even a dilute solution ote it, is liberated by i ‘ Ue to airy is li y the action of atmospheric oxygen: ‘oar ‘ig 4H + 0, —> 2H0 + 31, Hydrofluoric acid, of strong reducing agent, it is so eas ‘brown colour due to iodine which From the above discussion, itis evident that during reduction, oxidation of halide ion 2X 9X, + 2e takes The case of oxidation of the halide ion is expected to increase in the order of j the halide fons F, Cr, Brand 1. ‘The electron which is to be removed during vida eee the nucleus in F- and so should be the most difficult to remove, Therefore, I i ations close oem eden fo ea on 2H Seg 8 Pedy Jie Strength. Hydrogen halides are soluble in water and their aqueous solutions sis evident from ther dissociation constants, hydrogen fluoride even in fay dilute solvien a weak acid whereas the other three halides are strong acids, The strength of acids soi se my ens i of oe of H—X bonds. ‘Although the positive charge on H atom in HF molecule is greater than eee and HI molecules, the tendency for HF to release protons to water is less than that of HCl, =a This apparent anomaly becomes less surprising if the ionisation of hydrogen halide moleules en d solution is analysed in terms of the following cycle: : he HXg——P H+ Xa) @ @ | @ | a H@ Xo | | HX(aq) ———+ Haq) * x(a)CoMPOUNDS OF & AND P*BLOCK Exess a7 , +h ionisation is related t | eyele that su 10 @ number of yn this ration of HX molecules (Step 1), energy of dissin ant Meu ssociati BY nization enthalpy of H atom (step 3), electron affinity ihe gaseous HX 9 of HY and X° (step § and 6). A major factor in contribution ty (step 4), fe s igh bond dissociation energy. to the lower s HF gre ENTER BONDING IN ELECTRON DEFICIENT MOLECULES a ficient compound may be defined as one in which there is an insufficient mumb 5 cron er ete te octet of the central atom in term of its Lewis structure. These eon wee 10 ent number of electrons to form normal electron pair bonds (ie. ence Compounds (2 ae par of bonded atoms, For example, boron which es ‘ + 2-lecaron i lectronic i wee h ; oni 3 oe forms compounds which are described as electron deficient compounds, won ectrons but has four available orbitals 2s, 2p,, 2 i er members of boron family, namely aluminium, wales nh “ona ie heir valence electrons t0 form ionic MP species in their compounds, However born std oo Due to its very small size, the ionization energies are very high and the fomatk a woe Pyoes int take places. Boren thus adopts differen ots fl is funh maa ii bial, namely 7 @ pepe donation as observed in boron halides (BF, etc.) 7 donor-acceptor donation as in Me,N — BF,. a i a Ww Formation. of electron deficient compounds as in diborane (B,H,). i gtructure and Bonding of Diborane ee ae quite interesting from the point of view of ther suctures. The determination of Boron of boron hydrides was such an intricate problem that William Lipscomb was awarded a ote Prize in 1976 for elucidation of their structures. the siructure of diborane—the simplest boron hydride is quite interesting as there are not enough valence electrons to form ‘the expected number of covalent bonds. There are twelve valence electrons in - Bi three per boron atom and one for each H atom) and for the molecule to have an ethane type > ndtre 2 minimum of fourteen electrons are required as one electron pair is required to form each bond. age HL A : Hp a _ (Chis structure requires 14 valence electrons but only 12 valence electrons are avaiable) Boron has Therefore, we may conclude that diborane cannot have ethane type structure, Hence, hydrogen bidged structure for diborane was proposed based on the following evidence, vel (0 Based on electron diffraction studies, it was concluded that diborane has hydrogen bridge | slucture as shown in Fig, 3.1.TwoRGANIC CHEMISTRY Fig. 3.1. Structure of diborane Note. pm stands for picometer and it represents 10-!2 m, The above suucture depicts that there ae two type type which form normal covalent bonds with boron and H, . Sin boron atoms. The two-bridge hydrogen atoms are in a plane type Which fone. Therefore, there is no free rotation between the two boron aioe ‘ fom: (ii) Specific heat measurements also c boron atoms. onfirmed that there 4 is no free rotati ion ety, (ii) Raman and proton nuclear magnetic en the re hydrogen atoms in diborane are different than the other two foc MR) sp ‘ rogen atom: thant ees te of aiborane also confirmed that four hydrogen ane other drogen atoms as not more than four hydrogen ato: in diborane ate (CH), Bat ms ean be meta go The nature of the bonds involving bridgin; ® | ig, hydi is different bonds than the conventional two ‘electron. bonds These bridge a from the two boron atoms and one from each hydrogen atom. This at =o with only two electrons. srangri Ly OP Oe Ry GB) SUR 4H otek, Tetrahedral Tetrahedral H H N 7 7 tight ne ht angle to the ot vie ecta "2 confirmed thy fou i established, \ds involve one ek ent involves three Alo, BH3 BH used to form bonds to two terninl 3 hybrid orbitals, two of which are n atoms giving delocalised obits Each boron atom has four sp Jap with: Is orbital of hydroger hydrogen atoms and the other two over! covering all three nuclei.CCoMPOUNDS OF S AND P-BLOCK Etemants “ Y a oe) 4 \ B By SS HY 8 8 Fig. 3.2. Three centre bond in diborane. geseribed as having four two centre B—H bonds and ww js thus walent bonds having two electrons and therefore acco nn sign? feminal BH bonds are commonly referred to as 2¢— 0 three centre B14 unt for all the 12 valency pit con I ‘2e bonds. The i pel pec ee nucle and cotsing 2 pio ators cman eee nn sti ped (Se—Ze) oF banana Bor. Suche oF c—2 ade ae scanner ent compounds. 4 et essed that diborane, ByH, has four 2e—2e BH bonds and oo 3o—2e Bg i syetav®. : theory, a three centre B—HB linkage maybe epresented sa combination os wi br orbitals fom B and an s-orbital of esukingin tree molecule son tals “ nt cach bridging BHB bond contains two electrons in the y, bonding M.0, 39 HYDRIDES OF NITROGEN ‘The Important hydrides of nitrogen are: |, Ammonia NH, 2, Hydrazine, NoH, 3, Hydroxylamine, NH,OH 4, Hydrazoic acid, eH NLMINORGANIC CHEMISTRY 90 —— — - . ee A. Ammonia. The most common hydride of nitrogen is ammonia, = Preparation. |. It is prepared in the laboratory by heating a mixture of a . staked lime, Ca(OH). NONIUM chon. QNH,C] + Ca(OH), —> CaCl, + 2H,0 + 2NH, 3 2. Incan also be prepared in the laboratory by the action of water on magnesiu ™ nitri Mg.N, + 64,0 —> 3Mg(OH), + 2NH ride, Mp, 5 3. It is manufactured, on an industrial scale, by Haber’s Process which i : combination of nitrogen (1 vol.) and hydrogen G vol.) at about 425°C under 200, involves the di de along with small amounts of K,0 and Al,0, (as a catal "ee mre . bd St). Site in presence of iron oxi N, + 3H, == 2NH, + 93.6 KJ mot! ‘The reaction is exothermic is obtained by maintaining the following conditons: The reaction being exothermic, low temperat a ure ut at 400-500°C to maintain maximum yield SHOU be favcuny and is accompanied by decrease in volume. The . The most favoura ble yin (ij) Low temperature: However, the reaction is (i) High pressure: Since this reaction is accompained by decrease in volume, yield of ammonia is obtained at high pressure of 200 atmospheres. » the Taxing (it) High concentration: High concentrations of reactants (4e., Ny and H,) are mains maximum yield. ,) are maintained e (jv) Catalyst: To increase the reaction velocity, iron oxide along with small amounts K 0 ang {Al,O, is used as catalyst. Properties It is a colourless gas (bp. -33.35°C and a freezing point of -77.8°C) with strong pungent sm is highly soluble in water. It is lighter than air and causes tears in the eyes. Liquid amm el ag evaporation produces intense cooling and this property forms the basis of refrigeration plant al on 1. Basic Nature. Ammonia is quite basic and its aqueous solution turns red Jitmus blue. tts basi character in water is due to the formation of OH" ions.” J NH, + H,0. == [NH,'] + OH ne pair of electrons on nitrogen, ammonia acts as a Lewis base, Sine the lone pair of electrons is concentrated over a small region resulting As a Lewis base, ammonia forms complexes with many mel Due to the presence of a lo nitrogen atom has @ small size, in good basic character of ammonia. ions as: ag’ + 2NH, == [Ag(NH,),]° Cutt + 4NH, === [CuNH,),P* Ca + 4NH, <= (CA(NH) The white precipitate of silver chloride dissolves on addition of excess of ammonia. This is attribuel to the formation of a soluble complex-ion [Ag(NH,),I".COMPOUNDS OF S AND P-BLOCK ELemens AgCl + 2NH, —> [Ag(VH,),Ic1 Diammine silver (1) chloride through copper sulphate solution, at first a blui os anion n dissolves in excess of ammonia to form a bi ore i nys0s CuSO, + 2NH,OH —> Cu (OF), + (NHy,50, i i Breen precipitate of copper Solution due tothe formation Blue ppt. Hy * QNH,OH + (NH,),SO, —> [Cu(NH,),JS0, + 44,0 cHO”s Blue complex “ tetraamminecopper (il sulphate ectronegativity of nitrogen, ammonia is a polar molecule, The . tr " ; Presence of nitrogen pe? ws fo the formation of hydrogen bridges. As a result, ammonia is highly rte pond lead y assoc ef emyid 0 i H H H 4H 4 \ \ \ \ \ ees HON HON-- HON HONS HON, \ \ \ \ \ H H H H H ammonia has relatively high boiling point and high heat of vaporisation, Ammonia burns in air according to the reaction 4NH, + 30, —> 2N, + 6H,0 ia is oxidised by excess of air at about 800°C in presence of platinum gauze or consequently q,action of air. f, ammoni ae ~ ‘ion rhodium catalyst to form nitric oxide. ANH, + 50, —Wtare? INO + 6H1,0 ‘Tis reaction is very important industrially in the manufacture of nitric acid by Ostwald’s Process. i i ith halogens as shown in the following reactions. ons with halogens. Ammonia reacts with h " eee greenish-yellow flame in F, to given NF, Chlorine gives several products depending inconditions (NH,Cl, NHCI, NHCL, NCL, N, etc.). () ANH, +3F, > NF) +3NHF (Nk, +3Cl—> NCL, +3HCI Excess (i) NH, +3Cl, —> 6NH,CI +N, (b) 3Br, + 8NH, —> 6NH,Br + Ny Caution! (y) 31, +2NH,—> NHNI; + 3HI nitrogen triodide ammoniate92 IworGanic CHEMISTRY Pure NI, has not been obtained. This is a highly shock —— Only the ammonia adduct is obtained. “Sensitive compouny ound BNH,.NI, — SN, +9) a, % 4, Reaction"with methane (Andrussow 2 +9 + " ‘ process): 2 + 6N a for the industrial production of HCN by the Andrussow pr Feaction of yt . rocess, CH, + NH, + 1.50, ——R__ Me . . 2 Tam \ ‘The other process involving methane and ammonia is iow / HON + hg . as the c cl n De Het Nae OHCN GH, Phe 5. Reactions with other non-metal or thei i nom-metale or thei halides or oxides lead t0 4 numb Malis oF oxide, React . er of compounds as: MS of (i) C +2NH, —™%L, NH,CN +H, ws NA vig (ii) Py +4NH, ~———> 4PH, + 2N, (iii) 10S +4NH, ———> S,N, + 6H,S HLS further reacts with NH, to form ammonium sulphide. i») Metals react with ammonia to give nitrides : ! 3Me + 2NH, 5 Mon, + 34 : 3Ca + ONH, 2, ° 3 '3Ca(NI (0) Corrosion of Cu and brass by moist NH, air preclud BCANH — cay, « | Le les its use in "2 * 4NK, liquid or gaseous NH,. (vi PCL, + ONH, —> P(NH,), + 3NH,CI. (vii) P,Oj, reacts vigorously both with wet and dry NH, t ‘i ee ‘ , to form a range of products which ae used in industy for water softening because of th sii of winger sO: i ‘Ons, Pipes and valves fork, " it I HiNO—P—NH—P—ONH, ! ° ° | | ! H.NO—P--NH—P—ONH, (viii) 2PCl, + 16NH,(tig.) —> —{(H,N),P=N-PONH,),)" Cl + 9NH,CI (i) 68,Cl, + 16NH, = 5 S,Ny * 8S + 12NH,CI 6SCl, + 16NH, 9 —>_ SN, + 25 + 1ANH,CL Pure liquid ammonia is used as a nonaqeous solvent to cam which otherwise cannot be studied in aqueous solutions. ssolve alkali metals to form blue coloured, paramagrel, Lot of chemistry in liquid anna 6. Liquid ammonia as a solvent. cout several types of inorganic reactions, most important property is its ability to di and electrically conducting solutions containing solvated electrons. can be related to various reactions in water.COMPOUNDS OF S- AND P-BLOCK ELEMENTS % % —$<$<$<—<——— 5 oo . ammonia molecule is described as pyramidal or ter (Fig. 3.3)- rahedral with one Fig. 3.3. Structure of ammonia molecule (107.3°) in ammonia is slightly less than the tetrah angle (" lone pair of electrons while pushes the bond jon of w we ne uced below the tetrahedral angle of 109.5°. 5 ane on ued in the manufacture of 0 * qenonia ISS edral value. This is due to Pairs closer to each other. acl . ane for the synthesis of S,N, 118 Oe erarit . ee ectne of sodium carbonate (solvay process) 4 Py we in the manufacture of nitrogenous fertilizers such as ammonium nitrate. ammonium g itis tc. . . scab e, NH, Hydrazine, NH, may be considered to be derived from ammonia by NH, group. It is, therefore, expected to act base, which i tof @ gen atom by NH, ‘pect asa *» Which it gee * weaker base than NH. preparation 1) Rasehigs method. It is manufactured by oxidising aqueous ammonia ve hypochlorite, NaOCl in presence of glue or gelatine. 2NH, + NaOCl —> NH, + NaCl + H,0 Actually, the reaction praceeds in two steps: NH, + NaOCl —> NaOH +NH,Cl (Fast reaction) Present in large excess with Chloramine NH, + NH,Cl + NaQH —> NH, + NaCl + HO (Slow reaction) ‘The presence of gelatine assists the reaction between ammonia and chloramine to form hydrazine, wever, the role of gelatine in this Step is not completely understeood. 'naddition, there is another rapid but unwanted reaction in which hydrazine is destroyed. Ha NH, + 2NH,Cl 814 2NH,CI +N,os Trorcanic Cuemistry This reaction is catalysed by traces of heavy metal ions suct; is to suppress the above reaction by removing the metal ions. C8" and The resulting solution contains 63-70% of hydrazine whi “fe Pu y whi concentrated solution of hydrazine. Such a solution is disti ich on di of, is obtained as distillate. = distilled over NaOH or RoLe” Yield mu, (2) Reduction of nitric oxide. A solution of potassium sulphit 4 when pu eet © saturated y a in presence of sodium amalgam when hydrazine is formed. K,SO, + 2NO —-+> K,SO,.N K,SO,.N,0, So. Properties 1. Physical Properties. Anhydrous hydrazine is a fuming colourl constant, Some physica! properties of hydrozaine are given below. = "id with Some physical properties of hydrazine - @ high tle ie Physical property mp. CC) Value bp. CC) 20 density at 25° (g om™) 135 dipole moment (D) 1.00 cosity (centipoise) Las dielectric constant ¢ (25°C) “oo specific conductivity, K (ohm™ cnr!) at 25°C 317 G2, (25°C), kJ molt =25x106 AHS A25°C), ki molt 1492 506 ‘Stability. At room temperature pure hydrazine or its aqueous solutions with respect to decomposition despite the endothermic nature of the compound ey, tically sty energy of formation. and its positive ie Nog + 2Haig)—> NaH AH®, = 50.6 k3 mot AG®°, = 149.2 kS mol . Action of air on ignition (Oxidation). When igni i - in a ann ony large oroinon these lation). When ignited, hydrazine burns rapidly and compe, NH + On~)—> Nag) + 2420 AH =~621.5 kJ mot! One of the major uses of hydrazine and its methy! derivatives (CH) NHNH, and (CH,).N Nii as a rocket fuel in missiles, space shuttles etc. Ozone and hydrogen peroxide oxidise hydrazine to hydrazoic acid. HN; 3NH, + 50, —> 2HN, + 5H,O + 50; 2N,H, + 5H,0, — > 2HN, + 10H,OCompounds OFS AND P-BLOCK EuEmers zine decomposes on heating into ammonia and ni a SNH.NH, —> Ny © ANH, ind nitrogen, tium. In the absence of oxygen, it react . wth $0 'S with sodium to f form sodium 2NH,NH, + 2Na —> 2NH,.NHNa + H. L eo . It reacts with nitrous acid, gi itrous acid. |, giving hydrazoic aci : ion of NaH, + HNO, —> HN, + 2H,0 a6, HN, erties. It is powerful reducing agent. ‘ en mig clr oe sive rao sive and pic horde pau ol 4AuCl, + 3NJH, — 4Au +3N, + 12HCI 4AgNO, +NjH, —> 4Ag +N, + 4HNO PIC, +NH, —> Pt +N, + 4HCI , alkaline solution of ‘CuO (Fehling solution) to Cu,0. 4CuO +NjH, — 2Cu,0 +2H,0 +N, halogens to corresponding halogen acids. SS 2Cl, + NjH, — N, + 4HCI 2Br, + NjH, — N, + 4HBr renee 11H quantitatively in presnece of NaHCO, NH, +21, — N, +4HI mn reduces ferric salts to ferrous salts and iodates (10,) to iodides (I-). 4FeCl, + NjH, — 4FeCl, +4HCI +N, ANalO, + 3N,H, —> 2Nal + 6H,0 +3N, ¢pitredvees KMnO, in the presence of dilute H,S0,. oo 4KMnO, + 6H,SO, + SNjH, —> 2K,SO, + 4MnSO, + 16H,0 +SN, ‘The above reaction is used for the estimation of hydrazine and its salts. ° . (vi Itis readily oxidised by H,0, to free nitrogen and water. NyH\Q) + 2H,0,0) —> Ny) + 4H,O(g) + heat Because the products of reaction between these two liquids are both gases at the temperature of the reaction and the reaction is highly exothermic, therefore, there is a tremendous increase in the volume of the products. Hence hydrazine and hydrogen peroxide have been used in the propulsion of rockets. 8, Formation of complexes: As @ ligand, Since nitrogen atoms of hydrazine have a lone pair of clecrons, it can act as a ligand and form donor-acceptor complexes with metal ions such as Ni* and Co, eg, at reguoes a rede’ [Ni(NH,NHL),F* and (CotNH,NH - siruture, Is structure resembles that of hydrogen peroxide. Sine hydrazine PSS ‘on moment (1,85 D), the trans configuration can be ruled out.apne CHEMISTRY re as —— —4.N_NH, are expected 10 rotate mo = zi motectl rotation in NH. ne the jy N le ne that the inner le he x sin hi opserved thal | 1s 'S hinders. the NH grours pout it DAS beet dis roving against cach other: Consequent| ered sions mers as shown in Fig, 3.4, Fig. 3.4. Structure of N,H,. ofile (Fig. 3.5) that the rotation of NH, groups abou NAN beng s ear from the enerey PI mol either itis ol conformers in which H atoms (seen along the NN bond " ome ) are occurs through i ie conformation (¢) of hydrazine is much hi; cl ipsed cis con’ . igher (~ 20 ny lPted eo = errmation (8) is somewhat higher (~ 3 kJ mol’) in emery en (a) or (2). This is because the electron repulsions and hydrogen nuclear peace *s' hydrazine than in gauche-hydrazine. well as 17am aoe HDS (b) Trans, (staggered) H. H : a (Gauche) the gous "puso gp Energy, H H H H (a’) Trans (a) Trans. ( ° 90 180 270 360 Fig. 3.5. Energy profile of inner NH, rotation. Hydrazine energy profile shows fw minimas of the same energy at twist angles (a) of 100° and 260°, therefore, hydrazine, exists in a thermodynamic equilibrium of equimolar mixture of gauche conformers with mirror image rotamers (a) and (a‘) to one another.@) (a) ation of the two isomers requires a very small activation barri Pe we mgr toon temperate), Corseey te i ped sro aot 3 Cet ely Sl and NoH, molecules vibrate (with frequency ofthe order of 10! sexta Hy oe oe is at re) between qand a’ via trans configuration (6) (staggered). Ag OPT, NH,OF. It may be regarded as a derivative of NH, in which one jam on OH group. Its aqueous solution is less basic than ammonia or hy hydrogen ce NH,OH + H,O == NH,OH" + OH * [NH,OH" 087] Kye =~ [NH,OH] {NH OH] _ 5 mol 1 gf. Kis 7 NH 18x10 wait | 3 be by a number of methods. Anhydrous NH,OH i fon jt 80 u hy L,OH is thermally unstable i i kept in aqueous form or as its salt. The preparation of pure hydroxylamine is difficult 5 salts of hydroxalmine are prepared by one of these methods: synthesis involves the reduction of ammonium nitrite with SO, at 0°C and its = 6.6 x 10° mol 1! pestis ips ‘nino, + 4802 * INH, + 6H,0 = [NH,OH}S0, + (NH,),S0, + 2NH,HSO, par hydroxylamine is obtained by ammonolysis with liquid NH. [NH,OH],SO, + 2NH, = 2NH,OH + (NH, |));80,4 ‘Anmoniua sulphate being insoluble in liquid ammonia is removed by filtration. (ipitis prepared, jn the laboratory by the careful reduction of aqueous solution of nitrous acid or sum nitrite : with sodium or potassium bisulphite. HNO, + 2HSO,- + H,0* = [NH,OHI'HSO,'* HSO, Pue NH,OH is obtained by treating a suspension of| ‘hydroxyl ammonium sat wil ‘wovde) in butanol. HOHY'HSO, + NaQBu = NH,OH +NaHSO, + BuOH (i) itmay also be prepared by the hydrogenation of nitric oxide in acidic medium using platinum df Garo catalyst, e 2NO + 3H, + HS, —BE> (NH,OHDS% ith NaOBu (sodiumIWorcanic CHeMistRy * __—_——_ —_—_—~ wdroxylamine is thermally unstable and j — Properties. Pure hydrox) nd ts hyerosconie i. 33°C ind the solid d "lu, Sasbility. It is very unstable a solid decomposes slow), Te \ 1. Y 3NH,OH —> Ny + NH Y Above 15% Sy h +319 i 4NH,OH —+ NO + 2NHy + 34 It absorbs atmospheric oxygen in presence of an alkali to form itr 20 'NH,OH + 0, —> HNO, + H,0 OUS acig 2. Action of halogens: It explodes on contact with halogens INH,OH + 2CL—+ NO + 9 , tae 3. It also explodes with permanganate and dichromate, cl 4. Action of FINO, sad HNO, and hyponitrous acid (HN 0,) NHLOH when heated with nitric acid gives nitric oxide > 2°? o NH,OH + HNO,—+ 2NO + 2449 But with nitrous acd, it gives nitrous oxide, N,O ; Ww NH,OH + HNO, —+ NO + 211.0 di 2NH,OH + H,N;0,—+ 4H,0 + N, pate mas Nene ees tS 8 tig a, Ty base. NH,OH + HO = (NHOH)’ + on- money NHOH forms salts with acids which are formulated as additi hyGronyamine hydrochloride and hydroxylamine sulphate are oon coMPOIN, Fg (NH,OH),-H,50,, respectively, ated ay NH,O4, fi 6. Reducing properties: Hydroxylamine acts as @ powerful reducing agent in acidic medium, The basic 2NH;OH —+ NO + H0 + 44 (A) It reudces Fehling’s solution (CuO) to a red Precipitate of Cu,0, 2CuO + 2H —» Cu,0 + H,0 (if) It reduces AuCI, to Au (gold) AvCl, + 3H —» Au + 3HCI 4AuCI, + 6NH,OH —~> 4Au + 3N,0 + 12HCI + 3H,0 (if) Nt reduces iron (111) salts to iron (11) salts, 4FeCl, + 2NH,OH —> 4FeCl, + N,O + 411CI + 11,0 (iv) Halogens (X,) are reduced to halogen acids (HX). 2Cl, + NH,OH ——» NO + HO 4 4HCI 2Br, + NH,OH —» N,0 + H,0 + 4HBr (v) It reduces sodium bromate to sodium bromide, ANaBrO, 4+ 12NH,OH ——» 4NaBr 1 18H, + ON, 1 30) (vi) It reduces sodium iodate to sodium iodide. 4NalO, + 12NH,OH ——» 4Nal + 18H,0 + ON, + 30, equationCOMPOUNDS OF 8 AND P-BLOCK ELemearrs merouric chloride to mercury. iy eb acl, + 2NH,OH —> 2Hg + N,0 + AHCI + Ho : ac lds ! f res canal ac 3820 OXIIGINg AgeR in late ng vie prope NH,OH —» NH, +0 medium of 4 NayAsOs + NH,OH —» NaAsO, + NH, arsenite) Sodium arsenate) 0 ooivem + NH,OH +H,0—> 2Fe(OH), + NH, (ol), ae yponittOus acid forming N, Cg wit BY reo 2NH,OH + H.N,0,— 4H,0 + 2N, 5 with aldehydes and Ketones. It reacts with carbonyl compounds, ie, al ldehydes nfo oximes a8 pune { ' Oty —@ = [47] NOH —> CH,— Ca WOH Ho cH, cy —C= [OH] NOH —> otc beronsnp housed as an atloniant i photographic develope 9 for ducing Cal! to Cu! in the dyeing of acrylic fibres. aise form oxime with adhydes and Ketones ands ths fl i be prion pipe Se uh 2 910 siructure XH,0H exists s ols and trans Isomers. The N—-O distance of 147 pms cose wih se bond length NZ \Z N, / ~ (cle) (wens) D.Hydrazole Acid, HN, (Hydrogen azide), It may be considered as a hydride of nic but \ tar no relationship to the other hydrides of nitrogen, namely, NH, and N;H,. tacts as a weak ac lls aqueous solutions, comparable in strengths to acetic acid. ive ently Preparation, The anhydrous acid Isa colourless highly explosive igi is le pose (1H) = 269514 mol" at 254C) and fee energy of formation (80 #327 Uno" 25°C) mate ‘AHN, is unstable,Tworcanic CHEMISTRY 100 It is prepared by the oxidation of aqueous hydrazine with nitrous acid, NH; + HNO, —> HN, + HY + 21.6 —™ Nitric acid, hydrogen peroxide or K,S,O, can also be used as oxidizing agent, Properties: It is a colourtess voltile liquid; bp. = 37°C, mp, ~ -go°c 7 - are potential explosives and should be handled with care. It is a highly Poisonous its dilute Solu properties ‘ 1. Stability. It decomposes into N, and H, with the evolution of large am 2HN. . Unt Of heat, ; —> 3N, + H AH= ~51.5 2. Acidic behaviour. It is a weak acid, its strength is comparable to that of acet; wis ic acid, . HN sia —— Hag + Ny (aq) Ka= 1.8 x 19-5 3. Formation of azides. It forms salts with alkali hydroxides and active Metals lik; HN,,,, + NaQH —> NaN, + HO © Zn, Mg et, Mg + 2HN,., —> Me(N), + H, AIH, + 2HN, —““> AIN,), + 3H, M ad 3HNs..) — M;), + N, + NH, (M = Zan, Cu) HN, + AgNO,—> AsN, 4 + HNO, HN, +NH, — > NH,‘N, (Ammonium azide) HN, + NjH,—> N,H,* + N,- (Hydrazinium azide) Azides of beavy metals are highly explosive. Therefore, barium azide or lead azide are used in detonation caps. They explode on being struck by an object. Alkali metal azides are not explosive but decompose on heating to release nitrogen gas. 2NaN,—> 2Na + 3N,t 4, Reduction. Hydrazoic acid is reduced to NH, or NoH, by sodium amalgam or finely divide platinum. HN, + 4H,—> 2NH, 2HN, + 5H,—> 3NH,.NH, In acid solution, Ti(III), Cr(t1) and Sn(il) readily reduce the acid. Sn? + 3H? + HN, —> Snt + NH," + Na 5, Oxidation. Nitrous acid, Ce** and acidified KMnO, oxidise the 2 ‘can be used for the volumetric analysis. ° HN, + HNO, —> ee 2HN, + 0 (From acidified KMnO,)—* 3N2 My 5 rex id to Ny and thes + H,0ComPpounns OF S- AND P-BLOock Eizaeacts 191 composition HN, is decomposed by HCl, HI etc., giving N. 6D HN, + 2HCl —> NH, +N, + Cl, ture: ‘The three nitrogen atoms in HN, gas are collinear. struct H: Nc n——— 124pm 113 pm N <4, ion, N; is symmetrical and linear (both N—N) dist i spain " istances being 116 pm). Its electro ae may be represented in terms of valence bond theory as resonance hybrid of the ‘allowing pee structures: Itis isoelectronic with CO, and NO,*. The three nitrogen atoms in structure (1) use sp hybrid orbitals to form o-bonds Conc Boece Born) (N—N-N) (Formulation of sp-sp c-bond) Formation of two x-bonds in N, . Each ‘terminal Natom has a lone pair of electrons. 3.40) X0-ACIDS OF PHOSPHORUS \OrOUS: Phos horus 4 thse ger’ FMS two types of oxo-acids, name hosph« cids, ypes of oxo-acids, namely, the phosp! Hed po ha hosphores atom forms four sp? bonds and there i sme ltr) overlap bens? seg OF NEN with empty «orbitals of phosphors resting in pede baskbonig NE l cial OH and PH groups. The hydrogen atoms in p—OH sO ult: Howe 2 —H. groups are not ionizable. UP gi towever, hydrogen atoms in P—H gt IP oe shosphol ible 3 g °° ducing properties to these acids. A summary” oxo-acids of hosel and phosphoric series. In al rus is givenTworcatc CuraastRy ‘Table 3.6 Oxo-ackds of Phosphorus A. Hypophosphorous Acid, H.PO,{H,PO[OH)|* Preparatioa. It contains phosphorus in +1 oxidation state, It is p hypophosphite, Ba(H,PO,), with dilute sulphuric acid, repared by treating batuy Ba(H,PO,), + H,SO, —» BaSO,) + 2H,Po. ‘The precipitate of ‘BaSO, is filtered off and the filtrate . cooling yields white crystals of the acid, ets evaporated Under vacuum which oq Properties. 1. wobies ot oan allie solid M.p. 299.5 K. Iti i ™ es ox phos P. SK It is Soluble in water. its Salts are 2. Acidic mature. I: is a weak, monobasic acid and ionizes as H,PO, == H* + [H,P0,) K, = 1102 3. Action of heat. On heating, it decomposes to give phosphine 2H,PO,—> PH, + H. PO, 4. Action of nascent hydrogen. HPO, is reduced by nascent hydrogen (Zn +H ,80,) 10 phosphine H;PO, + 4H —> PH, + 2H,0 5. Reducing properties. It is a strong reducing agent. The reducing action is due 10 H,PO, + 2H,0 —> H,PO, + 4H (@) It precipitates silver from silver nitrate 4AgNO, + H,O + H,PO,—+ 4Agl + 4HNO, + H,P0) Similarly, it precipitates gold from its solution. (6) Mercuric chloride is reduced to mercurous chloride (calomel) and fi 4HgCl, + H,PO, + 2H,O—> 2Hg,Cl + 4HCI + _ 2Hg,Cl, + HPO, + 2H,O—> 4Hg + H;PO. * 44 nally to mercury: * Its recommended name is phosphonic acid.CoMPOUNDS OF S- AND P-BLOCK Elements 5 Cl and 1, to HCI and HI, respectively. feat 1, + 2H,O + 2X,—> 4HX + H,PO, f sas on warming with the acid yield cuprous hydride. “cus, + 3HPOs + OHO —» ACUH + 3H,P0, + 44,50, ‘ive metals (Zn, Hg etc.): Active metals react with the acid to give H,. Zn + 2H,PO, —> Zn(H,PO,), + H,) ? gone THe MERON Grace of he ai fe, pene ony Oe re. . ent WH 3 Sete a icing character is indicative of the presence of PH bonds, Keeping in ein, strongly red varacte ove properties along with evidence from Raman spectrum and X-ray analysis of its salts, ae pation o7 808 ia ged the following struct: j H | o=P—oH | H Phosphorous acid, HPO, {HPO(OH),|* rgaration. It contains phosphorus in +3 oxidation state. It is readily obtained by the hydrolysis of itsphorus trichloride in cold CCI, solution: PCI, +3H;0 —> HPO, + 3HCIT The resulting solution is heated to 453 K to drive out HCI and then allowed to cool when white ‘ysals of the acid separate out. ieee. 1. It is a white deliquescent crystalline solid, m.p. 343.1 K, having garlic odour. Its x hsouble in water and is dibasic, ic. it forms two series of sls such as M'H,PO; and M; HPO, "ore of the type M!,PO,. Thus it ionises as: HPO, <= H’ + HPO,» Ky = 1x10" dae H,PO,- == H+ HPOY .. K,=2* 19" "Action of heat, On heating, it gives phosphine according to equation: HPO, — 3H,PO, + PHs- agent though its reducing power is AR ‘edu : tay hs Properties. It also acts as a strong reducing at of H sPO,, ) Me reg HEeS mercuric chloride to mercurous chloride. dHCL + HsPOs a 2HgCl, + HPO, + HO — Heh + 2HCI + Hs Ks —— 2 5 Whendeg ‘d name is Phosphonie acid.Trorcantc CHEMISTRY 2 AgNO, + HPO, + H,0— 2 Ag + 2HNO, +H,PO, oper suphate reduced to metallic Copper ‘CuSO, + HsPOs + HO —> HPO, + Cu+ H,S0, (a Wreduces acidified KMnO, 2KMn0, + 3H,SO, +SH;PO; —> K,SO, + yt 4 PO, 4 + 2MnSO, + SHPO, +n @t reduces iodine to HI 1, + HPO, + H,0 —> H,PO, + 3H or reduces sulphur dioxide to sulphur 2H,PO; +SO,— 2H,P0,+S 1 4. Action on PCI,, It reacts with PCI; to give PCI, and POCI, H,PO, + 3PCl, —> PCI, + 3POCI, + 3HCI 5. Action of masceat hydrogen. It's reduced to phosphine by nascent hydrogen (Zn + 80) H,PO, + 6H —> PH, + 3H,0 Structure. Nuclear magnetic resonance spectroscopy of the acid, its salts and esters show tht there is only one hydrogen atom directly linked to phosphorus. This hydrogen is not ionised and cones reducing properties to it while the other two hydrogen atoms which are ionisable must be present as —OH groups. The diabasic nature of the acid has been confirmed from heat of neutralisation dat, H,PO, has been assigned the following structure: H i 07 | >on OH C. Hypophosphoric acid, H,P,O, st 1 a solu Preparation. It contains phosphorus in +4 oxidation state. It is prepared by pouring # $° Na,H,P,0, through a column of cation exchange resin in its hydrogen form. 2H(Resin) + Na,H,P,0,—> 2 Na (Resin) + H,P:0s sets iyi Properties. 1. It is a white crystalline solid containing two water molecules and ge! in presence of acids. rose H,P,0, + H,0 — HsPOs + H3PO4 ° H,P,06 2. It is a tetrabasic acid forming salts of the type Na,P20. and Na,H,F2''6(COMPOUNDS OF S- AND P-BLOCK ELEMENTS ee los ting above its melting point 335 K, i — cot esto” he 8 pol K, it decomposes into H,P0, and HPO, ye H,P;0,—+ HPO, + HPO, apove 453 K, PH, is evolved anti 4 H,P,0,— 3H,PO, + 4HPO, + PH, rotysts- ‘The acid undergoes hydrolysis on heating with mineral acids. " H,P20¢ + H,0 — HPO; + H,PO, oes not exhibit any reducing property. ths acid 0 ping in view the tetrabasic nature of the acid and its other properties, it has been ture. Keel ' ate following structure: OH OH o=P—P=0 OH OH theabove structure is supported by evidence from cryoscopic and Raman spectral data. » orthophosphoric acid: or phosphoric acid, H,PO, pation. 1. It is prepared industrially from a bone ash. Bone ash (obtained from the destructive iilaion of bones) is treated with concentrated H,SO, and heated. Calcium sulphate is filtered off ete filtrate contains phosphoric acid and is concentrated. Ca;(PO,) + 3HSO, — 3CaSO, 4+ 2H;PO, (bone ash) eee ash is oxidized with concentrated nitric acid. The entire ae fi acid. This liquid is treated with lead acetate which precipitates ‘Nrecovered by treatment with H,S gas: phosphorus content is oxidized lead phosphate. Phosphoric P+ SHNO,—» H,PO, + SNO, +#,0 (bone ash) (30-35%) 2H,PO, + 3(CH,COO), Pb —> Pd PO,), + ECH,COOH (impure) “ ~ Pb (PO,), + 3H,S—> apps + 2H:PO, "Ope (pure) / — i es It forms colourless glassy prisms. The erystals are detiguessent ~ em oa wi “el acid is = 83%. It is concentrated by £0 ing 7 we Me oil Benge Phosphoric acid also forms a her Hydrate HyPOs HO. Stall, ‘illite state, mp, 315.35 K.TworGanic CHEMISTRY Po, ‘with N/1O NaOH is shown below: Na,HPo, 44nd Ny a, wz st pH ‘| 0. 70 6 202 6 0 4 4 <— mio. MCI ml 0.1 MNaOH ——+ ‘The first inflexion, indicating the formation of NaH,PO, can be d by methyl the 2nd inflexion corresponding to Na,HPO,, is indicated by phenolphthalein, The orange indicaty, indi © thitd equivalence point cannot be detested by an indicator The pH changes very slowly withthe addition of arnt this is due to buffer action. Equimolar mixture of Na,HPO, and KH,PO, is an important bu Hand used in chemistry laboratories. fer solution H3PO,+ NaOH —-~ NaH,PO, + H,0 (primary salt) H,PO, + 2NaOH —> Na,HPO, + 2H,0 (secondary salt) H,PO, + 3NaOH —> Na,PO, + 3H,0 (tertiary salt) 2. Action of Heat. On heating to 523 K, it gives pyrophosphoric acid, H,P,0, 2H;PO, 22% 5 HyP,07 + H,0 . fe acids On further heating to 593 K, it loses one more molecule of water to give metaphosphoric a HPO, H,P,0, —224 4 2HPOs + H:0 When heated to red heat, it give phosphorus pentoxide, P,Os- 2HPO, FEHB» F205 * 120 omides and iodides wai? ic aci ith bi 3. Action on bromides and iodides. Phosphoric acid reacts with hydrobromic and hydroiodic acids, respectively. H,PO,+ 3NaBr—> Na3PO,+ 3HBr H,PO, + 3Nal— ‘Na3PO, + 3H!COMPOUNDS OF $+ AND P-BLOCK ELEMENTS HPO, + 3AgNO,—> Ag; 3HNO, dion barium chloride. A white precipitate of barium phosphate is produced which dissolves Leet il is 2H,PO, + 2BaCl, — Ba,(PO,), + 6HCI roperties- Phosphoric acid does not act as an oxidizing agent below 623 K. At ing PI « oxissing PFCP’ reactive towards metals and is reduced. sg emperatures+ magnesia mixture. H,PO, reacts with magnesia mixture (MgCl, - NH,OH) to Mine compound of ‘NH,MgPO,. spaetion om geste ost H_PO, + MgCl, + NH,OH—+ NH MgPO, + 2HCI~ H,0 monium molybdate. When phosphoric acid or phosphates are treated with Action om arm! sence of concentrated nitric acid, a yellow precipitate of ammonium exosium molybdate in pres jusinalybdate is obtained. HyPO, + 12(NH,)2 MoO, + 21HNO; —> (NH,)3 PO, . 12MoO; + 21NH,NO; + 12H,0 9, Acidic nature. It is a tribasic acid, the first hydrogen is ionized readily, second with difficulty adie third only in the presence of excess of strong alkalies: HPO, == HY + [H,POT [H,PO,y — H+ (HOT (HPO, == H' + (PO neta Keeping in view the tribasic mature of the acid, it has been edral structure, Ky= Lx 10 assigned the following _---Hydrogen Bond. ions which can be. derived different orthophosphate anions from 1 The stroctur =o stepwise removal of H” from OH groups are shown below. he Structure or corthophosphone * Uses L ic acid is of great commercial importance and is manufactured on a Mmultimill paneer ty the industry for the production of phosphate fertilizers, _ 2 important application of phosphoric acid is for metal treatment, cry git : i Le., dipping red hot metal in phosphoric acid—this imparts resistance to corrosion. Important application is chemical polishing of Al metal (which is replacing chrome plating), 3. Its salts are used in food, detergent and tooth-paste industries. E. Pyrophosphoric acid, H,P,0, Preparation. \t contains phosphorus in +5 oxidation state. It is prepared by heating orthophosphoric acid between 473 — 573 K. 2H,PO, —> H,P,0, + H,0 It is a white crystalline solid. It dissolves on heating in water to form orthophosphoric acid H,P,0, + H,0 —> 2H,PO, On strong It is a tetrabasic acid and forms two series of salts such as Na,P,O, and Na,H,P;0r heating, it forms metaphosphoric acid. H,P,0, —H_, 2HPO;+H,0 It does not possess any oxidising or reducing properties. «gram HPO, Hes remo! Structure, Its structure follows directly from its meiod of Prepaaonoi shape ne 5c aci whi of a water molecule from two orthophosphoric acid molecules pyrophosphoric acid has the following structure.COMPOUNDS OF S- AND PHBLock Ei 09 Structure of pyrophosphoric acid, H,P,0,, j.Metaphosphoric acid, HPO, peparation. It contains phosphorus in +5 oxidation state. (p tis prepared by heating orthophosphoric acid above 673 K. H3PO,—> HPO; +H,0 (ji) Its prepared by treating P.O, with a small amount of water. P,Oj9 + 2H,0—> 4HPO, Inmetaphosphoric acid, oxygen bridges are formed between adjacent phosphorous atoms to build wrings and chains in which there are four oxygen atoms linked to every phosphorus atom. 3y combining with each other, HPO, monomers polymerize into multiple units which may be represented bythe formula (HPO)... Properties. 1. It is a glassy semi-transparent solid and is commonly known as glacial phosphoric tid. Lis hygroscopic and dissolves in water forming orthophosphoric acid. HPO, + H,O—> H;PO, {ts sodium salt forms soluble complex with calcium ions and thus acts as a water softener. 2. Action on silver nitrate. It gives a white precipitate of silver metaphosphate, AgPO, i AgNO, + HPO, —> AgPO,+HNO; / vii ion on metal oxides, Alkali metal salts (like NaPO,) react with heavy metal oxides (0 give phosphates of different colours. NaPO, + CuO —> NaCuPO, . 4. Acti 3 , ra ‘ hate in vagal iY ON barium chloride Barium chloride yields a white prespita of barium phosphate Sralkatine solutions, BaCl, + 2HPO,—> Ba(PO,),+ 2HCI ., Mmonium molybdate test. This j Ss wht eg). Sve, 'S the only Phosphoric acid which coagulates egg albumin (the ve sah above MK by apres Stee HPO, is a monobasic and is formed by heating rhe “elimination of a Water molecule, therefore, its structure may This aci 'S acid also Bives aTWworGAnic CHEMISTRY a — me a , no _ HO—P——OW! a HO—p— 0 e 4 en 3 does not exist ag a disg in the polymerized form as a linear chain or as a cyclic ‘imetaphosphate, Tele uni but in the polymer 9 F 9 So | oN NAN JN / wT Nf ol 0 bo NK ‘Structure of finear metaphosphate ion Structure of cyclic trimety : Distinction between different oxo- ‘acids of Phosphorus Ortho-phosphoric acid {HxPO,) ‘White ppt. insoluble in acetic acid Noaction Noaction No action, White ppt. soluble in excess reagent White ppt. 3.5 OXOACIDS OF SULPHUR “4 Sulphur forms a maximum number of oxoacids some of which are very important both ee and industrial view Points. Those acids which have names ending in ous, their salts are its fsa Names ending in -ite, while those of acids ending in -ic have names ending in -ate. Oxoac ate listed in Table 3.7, by dissolving fi aiPhurous acid, H,S0,, contains sulphur in +4 oxidation site tis prepared by sulphur dioxide in water, S0,+H,O == SO; te 2 ateotie api and ionses ® not be ied in oes state, It js a diprotic acid H,SO, == H* +HSO, Hso,; == H'+80,2 This acid is unstable and canCOMPOUNDS OF S- AND P-BLOck ELEMENTS MW g agent and reduces halogens to halogen acids, permanganate to mangarious gle structure can be assigned to sulphurous acid because two isomeric ethyl part, NO SINE heen isolated. ot i acid ha’ Pca the ol reacts with thionyl chloride to yield symmetrical diethyi sulphite (b.p.. 434 K). alco yo pom OCH; 7 OH 2S — o=s ~ 2HC\ or ere] ocoHs oc: ri ‘Sym. diethyisulphite Thiony! ehlorie tbe 434K) Table 3.7. Some Oxoacids of Sulphur Formula Structure | ‘Name 9 4 | i \ sulphurous acid” H,SO, oe ‘On OH i Siphuric acid H,S0, 3 07 \™~ ‘oH ‘OH Peroxomonosulphuric acid H,S05 07 ‘Som Thiosulphuric acid H,8,03 oo it Dihionic acia s— 18:05 07 Yroe g a \ Dnuiphutic t acid H,S,0, oo . Perorodiey \ \| Iphuric acid Ss “ WSO A 07 No Nid dogy — L ‘OH ° NOt ex} SXiSt in the free state,InoRGANic CHEMISTRY pite to fo her dicthytsulphi aa with sodium sulphite to form anot yIsulphite Fahy seice 2 Sims ante dethyleulphite t= different from the fee gies 486 2 Sucet dicthyisulphite. The formation of wo different types of re Le sulphurous acid). namely. symmetrical sulphurous ett NShmemical suiphurous acid (having tetrahedral structure) are at, evident fro" Shae Be GNSS are cthyt dena Stace) anc unsy7m Unsymmetrical sulphurous acia ‘ich are always in in phosphorous acids which are reducing agents). The sutphite ion in its salts has pyramidal structure (similar to symmetrical s which all the S—O bends are of equal length (134 pm). The nature of bonding i 2s =e sammasse [TL] [TL] ITT as 22 somone. Fi | ulphurous acid), in Ssulphite ion may be se2-nyonazaton with Gne postion occupied By tone pair Bonding and structure of sulphite ion 2. Sulphuric acid. H,SO,. Containing sulphur in +6 oxidation state is manufactured by oxidation of sulphur dioxide by the lead chamber and contact processes. It is a strong and ionises as: SO, == H" + HSO, H+ sO, @ strong dehydrating agent. Structure @ Ms molecular formula is HzSO,.ComPounDs OF S- AND P-BLOCK ELemens W3 adi cid and forms two series of ns two di placeable hydrogens, oon and 1Na,SO. 7 yattSOe \ked to < re nyarouens A linked to oxygen atoms forming hydroxyl groups, ie. it cont ince it forms sulphuryl chloride on reaction with PCI, . it contains two cl. SO, hyn ( neo sit (HO) SOz a 4 ‘Sulphuric acid c ‘Sulpury! chloride re symmetrically arranged because only one type of organic derivative se hydroxyl BTOUPS 3 ° h has been isolated (compare it with HSO, which forms two types of 00 i CyH0800CrHs sulphites)- ; “ ve groups ar inked to sulphur as is evident fom the diferent shames used fr ihe seni of diethyl sulphone. (CHS —Peistions (CoH),S0, 2e_ cso, A 1,80, Diethyl sulphone (i Decision regarding the remaining two oxygen atoms in the molecule of sulphuric acid can be ated at by considering the bond lengths in the molecule which are suggestive of the presence of due bonds. ‘Thehigh boiling point and viscosity of concentrated sulphuric acid indicate association of molecules vahydrogen Bonding as shown below : Hydrogen bonded sulphuric acid molecules. ion ig tetrahedral and the SO bond lengths are all equal racter, The bonding can be explained as follows: 3s »® we analysis shows that the SO,>- pm) and have considerable double bond cha Ground state of sulphur atom Excited stated of | 8 sulphur atom —— o | NY Som red 2 © 8 spracasn a inthe Bonding and structure of $03 ion.NorGANIC CHEMISTRY acid H,SO, It is also known as Caro’s acid 3 oo een . conta ; prepared by reacting equimolar proportion of ing cain seen orHodoge erie nt acid. uh th, HO—S0,—0—H + H—-O—OH — HO080.0H + HO wisn cslie sal wich gute Sle tis a povertloxiing ape; ; sna The above me fi eparaon larty brings out consign St ty 4. Taipei acs H0,Coninng sulphur in +2 ovation ste te state though its stable salts are numerous, ‘specially sodium thiosulphate, The min be ‘thiosulphate can be proved from its method of preparation as: * eo NaO, Nao. SN, tens ERRRT/ NO ag/*\, 128! Secon suptite Sodus ‘Therefore, thiosuiphate in is structurally similar tothe sulphate of hehe seca by slr stom. This cones nO fen with radioactive sulphur which : vn have demonstrated the presence Of two dierent pes aie 2 i /\» a) Structure of $,02-ion. hen een tional soemticpans in photography to dissolve unreacted silver rome ina 5. Dithionie acid, H,8,0,, Containing sulphur in +5 oxidation state appar in a sono Sulphurous acid which is being oxidised by finely divided managanese dioxide, The dint consists of (0,S—S0,P~ with tetrahedral arrangement around each sulphur atom wit cosebe ‘Pied bonding in S—O bonds, Q 2F S- AND P-BLOCK ELEMENTS (ComPOUNDS 01 acids 5,0. Containing sulphur in +6 oxidation state is prepared by the addition ric acid. It is commonly known as oleum or fuming sulphuric acid ~ ulphu! J 6 Se ore anos air it releases white fumes). 7 en or oxidising agent and more powerful dehydrating agent than sulphuric acid. It forms B “i ni ° 1 with water” H,S,0, + HO — 2H,SO, jc acid May be considered as the dehydrated product of sulphuric acid: piso wo OH + H] ~ on ° ° Hox |_- wl + HO i ° ° Disuiphuric acid gaa structure of disulphuric acid. Containing sulphur in +6 oxidation state and is prepared by moles of chlorosulphonic acid as: This reaction proves the LPerdisulphuric acid, H,S,0, xing one mole of hydrogen peroxide with two ° ol ee —0-0— ao ° |e on wf Pw [70H HCI ‘ r 4 i” Perdisulphuric acid be agent. It is known as Marshall’s acid. By vi tue of the peroxy group, it is a strong oxidising Luareae 3, -2. Name and draw the structures of the following anions: $1032, $04 S:07 S208" $s I 4 fo b oy .8,02- Sthisulphate anion °i Tworcantc CHEMIsTRY 9 9 s,0¢ Githionate anion +4 N o To i 9 os i S,0; disulphate anion ~~ Pros g° hee { s,0,° peroxodisulphate anion o mS 4 0-07 TN Exercise 3.3. Gi . : " xercise ive two reactions for each of the followi i character (i) dehydrating properties (ii?) oxidising propeviee: PS © SUlphutic ai (hig ‘Ams. (i) Sulphuric acid ionises as a dibasic acid : “4 (ea) H,SO, === H’ + HSO, (bisulphate ion) uso, Na,SO, + H,0 + CO, (ii) Dehydrating properties When concentrated sulphuric acid is dropped on wood, sugar or paper, it absorbs moire a about charring. C20 —Eg6,? 12+ 1H,0 Sugar ‘ (absorbed by acid) Action with formic acid com } HCOOH —“22—> CO + HO WSO. (absorbed by acid) (iii) Oxidising properties ji sce oe Sulphuric acid acts as an oxidising agent since it undergoes . H,SO, —? H,0 + $0,+0 It oxidises carbon to carbon dioxide C+2H,SO,— CO, It oxidises phosphorus to phosphoric acid seo? ain P, + 10H,S0,— 4H;PO,* _- issociation to give ™ +20, + 2H20CCompounos OF S- AND P-BLock ELeMers 7 DS OF CHLORINE e known but only HCIO, (Perchloric acid), has been isolated as pure Iy in aqueous solution o in the form of thei sls. List of oxoacds of 1 properties are summarized in Table 3.8 cI 6 7 rine ar acids of chlorine see! ONT hers are stable on oll ° 700% with their Physical lorine along Table 3.8. Oxoacids of Chlorine tate | Name of acid Formula | Name ofsalt | Thermal stability Oxidizi onda | and acid strength power | ofct _ _ — Hypochiorous | HOC! Hypochlorite | > | ‘ Chlorous HOCIO Chiorite | zg 3 Chlorie Holo, | Chlorate | 8 a Pefchloric HOCIO, Perchlorate | s =a trends in the properties of the oxoacids and their salts are discussed below: ye A few get pro] () The acidic character of an oxoacid increases with increase in the oxidation number. For example. ing strength of the acids of chlorine is HCIO, > HCIO, > HCIO, > HCIO Eaplanation: It is a well-knwon fact that the strength of an acid is intimately related cts conjugate base, ie., stronger the acid, the weaker wit! be its conjugale base and vice versa. The the order of increasi to strength Oxidation +1 +3 +5 an dumb-bell bent- a aton pyramig Increasing charge detocalisation “Onjupate bases of Decreasing basicity eS OF . 7 Mechotine oan above oxoacids of chlorine are (clo,y, [Clo,), {ClO,F and [CIOT, respectively. ha "of oxygen ens in which the central atom has the highest oxidation number will have a maximum ets fa for participation in extension of the x-bond. Thereby, the charge oF the ion “the ion to be really stabilizes the ion and thus decreases its tendency 10 accept & Prolon ie, ne may be Very weak base with the result that the strength of the acid increases, ba roduced by extended Pointed : Out that in this series of ani “eet | (i) ne that in this series of anions delocalization of charge IS Pl ina gS the oxidati eTeagy jh tation number increas increases, the chlorine-oxygen bond becomes " © in th © oxidising : ing power and increase in thermal stability of the aci more covalent resulting id. For example, underInorcantc CHemistry 8 i lorites are stronger oxidisin, — 1 laboratory conditions, hypochlorite iB ABENIS than wad (ocr + Cr+ H,0)—, 2HOCT + 2¢- Solutions of the hypochlorite can be made by the disproportionation solution. cL. Ca(OCl), is used for cleani Ca(OH),.2H,0 is obtained by solution of NaOCl. Hypochlorous acid is quite weak and therefore solutions of hypochlorite are basic sinc te equilibrium lies well to the right. OF chlorine in cold aie + 20H" —> Cr +0cF 4 H,0 ing of swimming pool water. BI leaching. Powder Ca(OC!).c; the reaction of Cl, on slaked lime. sont Domestic bleach is about 510 Iti ocr +H,0 == HOC! + oH Hypochlorites are strong oxidizing agents, They oxidize: NH;—> NH,CI $o?2-—+ so? Mn* —+ Mno,- r— 10, Br— Br, The structure of hypochlorite ion is shown below:(COMPOUNDS OF S- AND p-Biock ELeMents 19 cid and Chlorites: Chlorous the least stable of the oxoacids of Jo! ed in pure form but is known only lute soli ) cH be isolat pure n solutions. Chlorites are known peal stable. HCIO, is prepared by treating an aqueous suspension of Ba(ClO,), with Oa 2 Nii oe OW, 4+ H,0 +2C10, > Ba(Cl0,), +2H,0 +0, Ba(ClO,), + H,S0,— BaSO, 1+ 2HCIO, ° ites are prepared by the reduction of aqueous solutions of CIO, in the presence of etal a ‘The reducing agent normally employed is a peroxide. gel hydroxide 2C10, + 07-—> 2C10; + 0, chlorite decomposes at 175°C to sodium chlorate and sodium chloride. = 3NaCIO, —> 2NaClO, + NaCl in use of NaClO, is in the bleaching action of textiles. It is also used as an oxidizing agent joe removing, oxides of nitrogen which act as pollutants. It is also used to oxidize certain toxic compound, mercaptans, H,S, HCN, thioethers etc. , ‘he C10; is non-linear. X-ray structure of AgClO, gives O—CI-O angle as 111° and C—O distance as 157 pm. The structure of chlorite ion is: ch The mai The chlorite ion is an angular AX,E, molecule. It can be represented by nwo resonance structures: ven below: . “Cle cl, for v\ ” ™ Zocio= 111° Cl-O = 187 pm ‘Sum of the single covalent radi of chlorine and oxygen is 165 Pm. @ ‘ . sym Chlorie acid and chlorates. Disproportionation of Cl, in hot alkaline solution has been used ze chlorates for a long time: ° fo 3Cl, + 60H —> ClO + Sct + 3H,0 then T exam - Adding Re KCIO, was prepared by bubbling chlorine gas through susPens to get less soluble KCI, on cooling. 6Ca(OH), + 6Cl,—> CaClO,), + 5CaCh * 6H,0 Chlorate ion fy Ca(ClO,), + KCL —> 2KCIO, + CaCl nt ClO,)2 4S @ pyramidal structure as shown on NeXt Page: ion of Ca(OH), and eet Tonic g, Snfiguration of chlorine atom.