Chemica gle eh til asst funtion tet (faa isle of Xd atoms 4 — Wisi We Ya Leto f neater ») ligase Seep Ef ee eonery 2 TT) stg eran ada meant tna ae ites p SU eee SY fox tht ¢ £ a. Ths . ey = aa ee eee Rint x Square f there cof} lewd ¢ ns Ds ye ee HH TCU Co ne Sth thts af oth wave function, — ES ute. dee od pusted Ooho.t ive o toby o Giseon He go stats on a Atahility.. lee a8 2 E BeVRT uroxr Sihpalacby Heitle A t E. london (m [997 | CES : Iqat,jssompuons of VET * / (Han Petre a + lose thes (doy dorms Ao wd . © f ~ oon Lo Cb ta Sa ‘ “tt ee wo Ra Sy dey Top alan tose ste ‘duce ae are! ox after bead covalent cri ss ae, 8 jee Ovbitot& tow Ht) ost iwn ys 5 est alts 2: ie as an 4 fied ovbitals wt i at o_eoutitab ( (4) Tv) Sie Ine emit be uA ton Soy ox tone of Oda hb jg sm xe dhe bend btw Wem owre UWNhe ely 0x8 ih “He bond tas 2 | ae Oc Bova — —— L ec, a | @ Move tis Hee Ate) Udy of Howl key Pence enous ia sete Wl (es Chawse, Suurty J [——__Co ni id pu 10 Hee Un enas alee v4 Ak Hyd Ha [ Hp LH fo Biter each whosto, form | Covalent bond » Te Va rtotd pbhoreon cH ond die Atlrathon pf —>s oe WA = nucleus, rare ie _ Rc pulsion Tr eat eae, —_ <— 2 te, > ¢, se ee oh Ha } bl =< th Hp, ty yo pulion a 4 Se a Wik hist } iw a H 4 A Attra troy He~ y Let cof tp as. do bay ashy Hg ah .2- By 44 Shs Sy Steen a Jropresent as bg, ~ 1 EL a HA Hp pet\othe Co amb toned trate fundion baa ASsyth Y= p(t) Wa 2) —_—G) + 1 Yoo 2, , =< aS x4 JF © ip 4 a So — foo 4 +E 4 =~ Yoo Ge ys ys ge mie 3 eet pe a bige ex peu moict ah bond © erst a- m q A Ke Gs, He wave fer nehen V at cal ciday Eq @ 1s mat comsect . “The. a — foes pu skhese opel by | eet ta —Lnnlpeave mend ’ Hp be Hp then (Me (An no J pac he fiyet stat Fd weil rey bo Sta Hes moutliur R. HK 9) Atast et Ose, pos s/ble State Hp Hp. State TT acct a |§ The, WHAve fon ch on Yor Stroke Dy Land) eee aa a Se ere SS [hic fo theowem 2] ae a it He Ltneok combination of Here | BE ousaue chun on ey Las ie — a ee

fil) fata 7] Rats] fees) talon 26 fe eas BS eas 2 a! mor]| an aawiore || er enarameeey “Omoxe. f. wAtctanhd cng ews canes | ie So Stem Bed nD, al Lotottsn ee sible [ae cleax | Ok. cable | 6 sof. bi 2 : aos in TW-bond dens reas thond , AR-t cn alas Se hear “Se bcties eal 2a bend [Wo eae ao wep Gitta ha formed bus a= Oo a fad Mi cob | Sie — foods obout le sat thsi te ae .Sey POTCUDs] CMa i... . pe iS 5 primiaMecion “a Yul) = -2 7 _ Mas Y-?d z Nis aah ue (e=+>)} Nit? adv Nits Wie iD Lia ~ ad g . a ee : Pi@) ds Pam Rypridi sation, c Re ee Goi tee ue OSS. tant Sas eee. ae ee a —— rr — a ce = lath tt 2 eee eats ie = DCO eee Lagornsl bb bipy aamidd OS= X+ ¢(-)\=- %= 673to only a few simple peory Ore cctully very dina ces ed is very dificyg My) iD dtl NCEP ance DOM ical SHC invol : valet e apr" satment eatment is ina ‘ATION’ of the ould be it Ea treat once Rae ee eee madeauay uMIT? mai a rennet female, ale hi) ‘The matt hereon" ‘ ve , Is. constituting the ij The valence gystems thor! ed pair consti 8 the inter, Most of eit cor thesbare Pye formation of coor] fave to use - trons oer inerefore, ster ms many sys gumes that ent tor od punds. s compounds 2 eo ent comPY ating structures and even |, ysl Mesonance hybrid of these struc it I explain all the structural featur 4. Forany thal : west spotecle of nye? re have elect, that molecule of ory the atoms ae more the molecule diamagnetic ay; es us theory Ha According 10 this theory is v i Nek 8H of two unpaired elect, city ® cating the presence on | pO ce M yeen molecule. ea a ands wi plicati is lain the i‘ i et it finds wide applications, jj Thi This theory fails to exP theory has some imitations, iy of molecules or ions, a Lone pair—Bond Pair > Bond pair—Bond ni ue to the presence of lone pairs besi d id ; b from be normal values in regular Hee Ps homes devieand bond Ff owever it Ba remembered thatitis the total ae Sf jalatom WE jetermines the type of hybridisation i of electron pairs in the valence shell ra “_ ‘Due to the presence of lone pairs in the anak irrespective of the number of bonded or jee gightly distorted and bond angles change Cae regular geometry ofthe is discuss geometries of some molecules containin a values in regular ces 4, stannous chloride molecule (SnCl,) ig bond pairs as well as lone pairs. ‘ound state electronic configurati thes unpaired electrons in ose jonof the central atom tin (2 =50) is [Kr] 4!°5s*5p, 5p, fwounp’ ie Sp-orbitals of tin and these are suffici (ii and, therefore, there is no need of promotion of ele Pe electrons. Then, the three orbitals In rine atoms of tin atom hybridise to give three sp? hybrid orbitals of equivalent energy, as shown. ey and.) fg ; ‘These three sp” hybrid orbitals adopt trigonal planar geomet it it tenina lone pair of electrons while the remaining Ea denaiald ie oe eaters Bae hybrid orbitals containing unpaired electrons overlap with 2p-orbitals of chlorine to form gpCl bonds as shown in Fig, 23 Thus, the central atom, Sn, ded by tiree orbitals, each containing a pair of jcrons, Two of these orbitals contain shared pairs while the third contains alone pair of laeaee Fig 23). The geometry of the molectile ‘should have been trigonal planar with bond angle of exactly (e sinBH, (Fig. 23). However, on account of the factthat Jone pair-bond pair repulsion is greater (a) Sn sule involving 5?” hybridisation. ortion in the molecule. The bond angle is e as shown in the figure. ion of SnCl, molec there is some dist ‘assumes V-shap Fig. 22. Formatis than bond pair-bond pair repulsion, slightly less than 120° and the molecule Lone pair sp? hybrid orbitals containing one lone pair i Fig. 23. Thr ' tals around tin, One of these ‘contain lone pair while other oo ee " ghape of SnCl; molecule: two contain single electronf repulsion betw i een two bond pai gt inthis molecule than in 7 ind pairs of el i ammonia. lectrons, Theref spot gnthe bond angle H—N—Hin See ects Tapio teres i V- 5 as OH ven Eaaaeeibes #8 V-shape been found tobe 1045°,Suchastructure Ft may Pe noted here that the central alone) ravolve 5P° hybridisation. Then ie atoms (C ne, there is no lone pair, NH, moleculeh e nthe total of four sp’ hybrid orbitals ( and H,O molecules have distorted ry of tetrahedron. Due to larger lone i ‘the bond angle is reduced from 09.8" de toe ‘Now, in case of HO, twolone pairs fo he |jn NH; S0 the bond angle decreases toa : regarded as V-shaped or angular, 4, Sulphur tetrafluoride (SF,) The central atom. S(Z = 16) has the electronic configuration : S: 1s? 2s? ap$ 3s*3p,? 3p,! 3p," Since sulphur forms four bonds in SFy one of the “3p, electrons is sforbitals on the excitation of atom [Fig. 26. These five orbitals (3s, 3p,, 3Py 3P_and 34) hybridise to give five sp'd hybrid orbitals which adopt trigonal bipyramidal geometry. The central atom is, therefore, surrounded by five hybrid orbitals. One of these contains a Jone pair of electrons while the other four contain one unpaired electron each. which overlap with p-orbitals of fluorine atoms to form four $_F bonds. However, due to the presence of a lone pair of electrons, there is distortion in the molecule and the bond angles are 89° and 177° instead of normal bond angles of 90° and 180° respectively. Such a structure is als o described as see saw shaped. @s ee Eg aa onan COCO : ie wm ® ODD GOCOO a | : on ENG : promoted to one of the @)S (Excited (0) SFa i lecule involving spd hybridisation. ‘The dotted arrows represent Fig, 26. Geometry of SF mol aval atm iri i ial position and notin axial irinSF, structures presentin equatorial position an« iti et ae Se e terms of stability of structure. We have learnt that in case of agonal a igeometry, the electron Pair present in axial postion experiences mor repulsion ee aie oa eee position. Therefore, in SE, molecule, if the lone pair is than the electron pair present in equal moe i ‘tion, it will have greater: sion and the structure ‘unstable. h prose on toda position, it will ‘experience comparatively less repulsion and the molecular structure will be stable. _— on(i) two tp-bp zepulsions at an angle the following repulsions; (i) one Ip-bp repulsion at an angle sbetweenneighbouring electron pairs decrease with cr Fepulsions between electron pairs at 120° may be neg 5, lering only the repulsions at 90° we observ ) while in structure (b), there are three Ip-bp rept on axial position, it will experience greater repulsion , r e (a) is stable and it has been experimentally verif dangles are89° and 117° instead of 90° and 120° res 5. Chlorine trifluoride (CIF) The central atom chlorine (Z = 17) has the outer e formation of CIF. lectronic configuration as : 3s? 3p. In the 's molecule, chlorine requires three halF-fil led orbitals to form three C ‘ctrons of 3p,-orbital to one of the vacant St ybridise to form five sp'd hybrid orbitals which adopt trigonal bipyramidal geometry (Fig. 28). Two of these hybrid orbitals are occupied by Jone pairs of electrons. The remaining three hybrid orbitale contain single electron each and oelione em three CF sigma bonds. Thus, in CIE,, the central chlorinea S surrounded by three bond pairs and two lone Pairs of electrons. Now, due to the presence ote juch a structure is alse ae bipyramidal structure and bond angle is 87.6° instead of Lone Pairs ff Fig. 28. Geometry of CIF, molecule involving sp'd hybridisation. _ |js molec to be li . Tm ccupied by lone pairs, "Ear OF trigonal bipyramidal with three outer electronic configuration of re ip. In the formation of XeF, mo Hf Jsas shown in Fig. 27. One Ss, three 5p and one 5; f the central ator mM, Xenon is; 2 Jpswhich adopt trigonal bipyramidal geometty ea hybridise to give five sp'4 hybrid gascontin lone Pairs of electrons whl the remaining two ye So nee oF these h atorial positions. Due tosymmetrical arran, q igementoflone Isions due to these are rea ‘Pairsaround the central xenon atom, ene repul ‘ese are zero. Therefore, the molecu : Xe iol le has linear structure. 5s 5p say” (4) ODD 0606) ‘ Xe cm © OBO OOOO state) XeF, t Linear Fig, 29. Formation of XeF, molecule by sp'd hybridisation. The dotted arrows represent electrons from F-atoms. 7. Xenon tetrafluoride (XeF,) In this case, the outer electronic configuration of the central atom, xenon, in the ground state (p*) is represented in Fig. 30. To account for four bonds in the formation of XeF,, two of the Spelectrons go to the 5d-orbitals so that there are now four unpaired electrons, as shown in Fig. 30. Thesix orbitals (one 5s, three 5p and two 5d) hybridise to form six sp'47 hybrid orbitals which adopt ‘ctahedral geometry. Two of these contain lone pairs of electrons. The remaining four contain y lone | unpaired electrons which are used in bonding with four atoms of fluorine as shown. The geometry ofthe molecule may be regarded as octahedral with two positions occupied by lone pairs or square atom | planar, | ‘sa oe ee © ®HD COCO =, ® O00 G0DCOO Yo (Excited tale) a LER | 5 EF FF zi molecule involving sp'd hybridisation. The dotted arrows ee eS Xora electrons supplied by fluorine atoms. 8. Iodine pentafluoride (IF,) aie | ‘The ground state electronic configuration of the central atom, iodine is: ntan 155.2 5p 57,Biss @ G00 COLCO F (Ground state) q @@® @DOOO NI (Pode state ® % x LEX! oe e “(Fs OOO ‘Square pyramidal Fig. 31. Square pyramidal structure of IF; molecule involving, oe hybridisation. This is shown in Fig. 31 (2). To account for five bonds in the formation of IF, two electrons from the doubly filled orbitals (5p, and 5p,) are promoted to the next Hosa Sd-orbitals. Then the si orbitals (one 5s, three 5p and two 5d) get hybridised to form six sp ‘i hybrid orbitals which adopt Gctahedral geometry. In this case, one of the positions is occupied by a lone pair of electrons, Te remaining five hybrid orbitals overlap with 2p-orbitals of fluorine atoms to form five I—Fbonds, Die to the presence of lone pairs, the molecule has distorted geometry. Its actual geometry may be regarded as square pyramidal. BrF, molecule has also similar geometry. Thus, it may be concluded from the above discussion that the actual geometry of a molecule containing one or more than one lone pairs of electrons is different from the geometry which is tobe expected from the type of hybridisation involved in the molecule. Structures of ions containing one or more coordinate bonds. The structures of ions containing coordinate bonds can be described on the basis of hybridisation. | For this, vacant orbitals equal to coordinate bonds are also hybridised. The coordinating group donates a lone pair of electrons to the vacant hybrid orbital. 1. BEy ion r One of the resonating structure of BF, ion is : | * B a | F ean ae ao configuration of boron atom (Z = 5) is 1s*2s?2p!. One of the electron} Dace dus ead he 2p orbital resulting three unpaired electrons. The 2s and three eres Siete form four sp> hybrid orbitals in which one orbital is vacant. The One Heinidaraes dy ontain one electron each are used for bond formation to three F atoms. a lone pair of electrons to the vacant sp’ hybrid orbital forming one coordinate bond. (Goole ® @CO ) i (Erte se) oO O06) Ale BF, © OOO) fe aa J iF | F ‘Tetrahedral FCS Banaue Fig. 32. Tetrahedral geometry of BF,- ion involving sp’ hybridisation. . |: tion, the one pond is coordinate bond (F B) : 2, PF, ion this ion, there are five o bonds and ; on F fgution of phosphorus atom (Z = 15) is (Ne] 3039) Tone bond. The ground state electronic ‘z electrons is promoted to 3d-orbital so that there : ee ieee bonds, one of tee 3p and i 3d (one vacant)] hybridise onic ee electrons. The six orbitals (Shedral geometry. Five ofthese contain = \ybrid orbitals, which adopt 1g one electron each are used for bonding wit th five F = One F- ion donates a lone pair of ae is octahedral as Sh else Bon to the vacant hybrid orbitals. The geometry of the Seometry of BF, ion is tetrahedral, el e lectrong, 3s s. Then fr! . oe 34 Tat tam OD OOD COOCO - elec [ ] —| F bonds P ee. O O00 @oCe® f spd” hybridisation 5 { PFE a y of amy : AO® OBOCO r Y whichistiy F FOFUF Fe Fig. 33. Formation of PF, ion involving sp*¢* hybridisation with one vacant orbital sf hybrid 3.SnCl, ion bonds. The ground state electronic ‘dinating ge It contains four covalent bonds and two coordinate “configuration of tin (Z = 50) is [Ar]4d!°5s* 5p! 5p,. To account for four covalent bonds, one of the | dectron from 5s orbital is prompted to a ‘3p orbital so that there are four unpaired electrons, “The six orbitals [one 5s, three 5p and two 5d (for coordinate bond)] hybridise to form six pe hybrid orbitals which adopt octahedral geometry. Four of these hybrid orbitals containing one ‘ms. Two CI ions donate lone pair of electrons election each are used for bonding with four Cl ator to the vacant hybrid orbitals forming two coordinate bonds. Thus, SnCI2- has octahedral re of | a ary ei The2s ce 5s Se al is vacatt (Ground State) @ @O0O COCce® & to three Oy / I i sO tom OD ODO CCOCO LK voridisation ai—— 4 wet __ oe a a | ot GF _ OOD QOL a antic er Fig. 34. Formation of SnCl" ion involving spf hybridisation with two vacant orbitals. F ‘ epECIPO PREG rRONECATIVITUON THE SHARES OF MOLECULES The clectronegativities of the atoms present in the molecule have also important effect on the shapes of the molecules. This effect can be easily studied by the following examples ==TAPPROAGH TO INORGANIC CHEMISTRY > S) tral atom tivity of the cent ange of electronega drides HO, H,S, Hg, (i) Bffect of ch hydrides of rOUP Vielements. The hydr ze 1 Se ang le of pairs: ; ind the central atom. But th. hy Take the examp! te ‘and two lone pairs) arow theirs have four electron pairs ease in the order: fa H,Se H,Te ra Ha 902 .6° 104.5° a electronegativities of the central atom as give, in terms of r ~ 8lVEN be Thismay be easily explained in Fhe central atom involves sp? hybridisation Inthe hydides of Group Oi pirsand twobond pairs Due tothe argerione py surrounded by four lctrn pai WORN PTT rced closer to each other and, therefore, i bonded electron pairs are force’ ¢ * 7 the boy hs normal tetrahedral angle of 109.5°. sess: fre from oxygen to tellurium, the size of the central atom Ba ee ouaie 2 tara decreasing, Consequently, the position thee increasing and its electronegativity goes on cecte : Of the bong pap hapy and more away from the central atom in moving from fj ine Preis iene ore pals in O—FIbond is closer to oxygen enol H,Te (Figure). For example, as shown, ie ‘ygen than the in SH bond, Asa result, the force of repulsion between the bonded pairs of s nae is more than that in H,S. In general, the force of repulsion between the bor electrons decreases as we move from H,0 to H,Te and, therefore, the bond angle the same order. nded pairs» also decteasesi, Se Bond pair of electrons lying 0.0 atom Bond pair of electrons 3 @: wa © ~ away trom S atom y 92.2° H larger repulsion bond ange ie Large distance, smaller more between bende repulsion bond angle is less between bonds Fig. 35. Similar behaviour is Shserved in the case of hydrides of group V elements as given below ren ere : ASH, SbH, 107 104° 92° 92° the basis of j f central | atom (ie. halogen atom), In these lectronegativity of the atom attached to the ceM || and one poston i occupa pp ee Tre es 9 hybridisation forming three sigmabone i move from PF, to PI, a Beometry may be described as pyramidal as "¢ | ample, as shown in figure the border Moves closer to the central atom as show". oan 318 away from P (closer to F) than the bond Pa! 2