sa — ut Che ermal Bonding the three electron bond is half as een nrrby oF dimer will be clove 10 that aP gi, election CP alted metallic bond. Ax DEA sD How the i Helectron bond is, a ion ton eg og ta electron pool oF électroa-gss: theory. This theory (ema cure ae, (OM (0) Bond tength of a ist ae bene po a econ ed” Brea, Fae tener tion nvm Za exe 6 Ut ee | seein re ieycavaem eee ea of a thrce-clectron bond is inter rete Seon ne ‘According Hind engi re tds He Seo ot ech iba Ri etl sea sie ge Sp acta ac 8 ae eyed ob, ugties ih Geson ool or The ie ive ‘2 able dstacess fe intermedi lively ci'hgve defile pesiionat measurable dune ioe, panered Pond length for a double bond (1-29 Ay ge, tween te | Feetrons but cryétal lattice. Since the valence-electrons are bond (= 1-06 A). 1 (=120 A) ana fare | eS Oo Soda od 10 any tadividéal gas or pairs of ions but belong fo Hot attached 10 1 iahcy are ive to. cove, threyghout the lattice Beeryal as a whole, WEcOne part of the crystal to the other a2 gas molecules “aeve MOLECULAR ORBITAL rH ELrcmnos nonDs 8 MON TREATMENT OF yap ore, canal ce We cea gr golds coe coniderint Hy* ion (onecleciron bona iar NO mined 7 F inotegrtaa._ Thu, cecrdlng fis theory, metal ai amo According. tos 41s (04,3! showing that one oy fie OT the,contiguratiny te, mobile electrons within lis sphcre of binds. metal fon 10 the mobi Of the bonding inolediaa Shuen Shs ha | Bauence te known as metlile bond. tig hale Mobi cre ae / a c - - 6 6--@ 1 i) NO molecule. According to MOT slectron species} has the following contpioy it Coat aoa Ps Go ah) ange In this configuration (rt) (nt)! a onfigur Tepresents @ three-eleciton bond P ovene IN METALS—METALLIC BOND Metals are good electrical and thermal oot is molecule (54.6201 ductors, they ate 2 Song pone sie ft actNe power, they had igh Ane boiling points, they. erystallise. with high onde nimbes 12 es Sich opens of Teta cana eect a basis of normal ions or covalent hoc oes ae Since ll the alors of a metal erytal are fda, sete ca fat ts bound together by fone Bonds a ace a ee bound together in an font crystal Tonic bond fey east sons of lllerenteleciconegativity. Van der Wook ee much t00 weak 40 account for high meling por fee ach om ina” metal erysal canna’ be bandera Hs Bor 14 neehbours by ordinary covslent ie ace a the numier of valence electrons i insutcen or te ea covaent hone wih all the ‘lose or elosest nelghboene a only one vatense clecwon.dLi==—> 13, 2 get atom Whe zien to form covalent bonds with 8 or 14 hear neghbts fy ferstal There is certainly no obviois way by whisk Li nome finm 8 or Té bonds fase iti ‘it. A schematic representation of sea * ffl, Amare eae ie ch dio Se re Soca heen (s (Attraction has bees hown by afrows) lectrou-poo! theory snd-metallic gtaperties, The electcon- fi se of i) Metallic tastre, ‘As a beam of lighit falls on the suctac ati12 chemical BOON! 20g a Thus when fight falls on a- mesa! st appears a8 iC UBL gjyt Dea: tp “ Bring rected. The surace therefor emirthe Pea e8 28 ray other peg alte Pay In quigQE of he meta, This proces is et Nicker heat transfe te ; rane the other ond of he imo MH oot ba a feystal 5, tilly. Since mobile deiccalised elec- i binding TOUNd each Kernel (Le actal ion, say M-) res tlding Ms ont aad eats tee Ha ond Song lt ree tation betwen fas 4 top and he Ualorm nal arecions ned there area 170 ey are joing the crystal Tater eta selva tak nah a Fe ena aue 108 119 Elec! Condatity, This raprty of eat ec pease "of mobile valence-clectrons. These electrons being omc, are ma position to move in an etctie field andthe © eRetricuy throush the metal (ee Fig. #12) & ©+8+0-0-0 +0 -0+070 | €.9. of HS Se chess 8 ei ir at 997997948 9-P "9-8 2 OO @ Y. E8556 2 Fit 12. Explanation of condction of eeticty ia iy Trail ctl on the Ess of lection poe te97- {ity Thersal Conductivity. This property is also due to Ut presence of abi Bs. When one part of a metal is heated, he electrons ia. that part. acquice a large amount of Kinet ene These eleciross, being ftee, move rapidly through the crystal ef vailable everyyye, Pefore shit ee i ing, sine deloealsed,eeetroos ach iz sate: Thus we see thar eile Wey pene siting e Postion wilh. expert toe neko na if Metical? ig yecets and cleciton eas surrounds: the kerael iP More chasted ea tt the positors, ‘The acaex neabboury cae 1 ease Wilk Which 2-234 Dew raetal bonds may be formed readily. tot ne, oes ty be Fred by moving te I son be atte ite to another i responsible forthe act "posi eee be beaten ata tee aese eee ah t gamete eS (le, ake ductile) by very Tle expos ture 09000 wm OOOO 22000. 00000 * shetauic kernel = y oxy Qo §'9'S @ ©9900 GO006 ©8000. 0000 tin dine pi edcetan centres asa Sap eA ema ace slong ‘the layer is shifted, G (@) High elasticity, The fact that fons can change position srihout brecking the metalic ctytal shows that rider a stress the may changed and attains the original position on strest isonk or Valence Bosd Theory. An alternative theory ‘ponding was introduced by Pauling. According te it bonding it estemially covalent in origin and meiclic Tinvolves resonance of electrowpair bonds (je. ordinary ‘etween each atom and its nearest neighbours. Fit 413. Cocddctiva of heat through metalic ‘rysias on the basis oFeletron-pool theory. sinters cones p25) iae Bs Chem ol “These hybrid orbitals which ate sing! ‘ponds, one With Li and other with Li ato Kets we have shown the electronic coctigura- “Tue orbitals shown in thick type ae those Let us consider the case of lithium metal bas Senet seihbours as shown be Xray aug dion of lithium aiom is 2% 20 showing thar Ang oe Malenceelectton which is insufficient (aie ve payin fing For, on br Fon of the oo eee vatent bond formation) ich bach ato ae conan sds between each atom of lithium and aif ge 21% rfel3s 2 h Iceoyqot (28 OS ipa js assumed that resonance tak Neigh. = are . iv ), (sp)* 2p,° 2p,°} guently ssrueed addres mee fakes place ra Cone -phich PF ig (15%. 282 —— LVL, (6p) (9)! 294° 2p") Rem sai Fetans ing Show on the resonance of pairs of bonds musi pit single ee, va tsigout he Aoi, Thyet ly Ma be agit et be shown as follovs "sions, vanoa| a Toms may Lids) Lidtst, 28) resonance forms ma u= u i ' — i + phus we fod that the fedutenent, in terms of valence bond Hou i Ths wet seig or te oration of retonaling cove et w= 1 - of imetipere should be orbitals, energetically not very diferent ey Hoods that er esiped orbitals tn the conguraton of the I be noted th heute Heri el e nr ae oy for ce sees ine ental and 8 neceimensional, = Es HOt | ae qyo. vacant omitals namely 2" ad. 20° on Lis, can resulting from this re tmeauetty electtons and! thie conttbae. to meulfe a ania) WOU ely ysesC® betwen | APLLM hese two 2p vacant orbilals are termed. sy mete catet bands chown above Would relate be" kanee beweca | ehyton. vjteroobl fron bess te arangnctal. dasa | Ste eter teeta Con kee ae ol eb (9) Moteclar Osbitel Theory—Baod Theory. This isthe quantum relatively more stable - inal reatment of the metallic crystal and is similar to mole. Bea to mechanical I heowy of covalent molecules, The elecitons fs a ati ud onder To Slne (the eral 35 = Wholeand ot ond — Ui sors any paits of atoms. According to this theory metalic a aay ridial of stom, the deloclsaton of the fee elec e bial t = Bm bi iif the atoms of a metal structure. \ oer te ue |; We have already sen tht when. diatomic moleul (a oo- wo vy enteo stem) is formed, two atomic orbitals of equal energy com, sclogether to give two’ molecular orbitals vis, one bondite mole: bested and one ant-bondiag moleular orbital,” Sully whey Sa or orale ofa tneeeeate stem combine ine se ae tase obtained vs bonding niceclar 9gial among cont lar orbital and non-bonding mélecular orbital, Foran ore Sore where mi ery large, we getn-moledlar orbitals In a'metllic crystal is generally @f the order of 10°. Thus it. 4 very large numberof atoins ofa metal say 10%, ave bought topther io form the metalic erysal, 10% moleolr orbitals are formes The > tecigies ofthese molecular orbitals are go closely"spaced tat. they fpper to be 9 contiouum, called a qpuscontinoos, energy, band, Wloce ths name band theoty. These molecular orbitals are loca, fed. these belonayo the etal as whole, ‘The eleti configuration of lithium som ve te2esppras sys ttt tie se eeu Spore’ Sea en eee dp ovals not very ures ye, he het fatale Seon an elestton om Secret ae Seen be trukos inva of thes iy une ee seinem io (cnet fe Lo a et ania edge Tic iam som Souttn , comgutin tomy Biol coment i” Li” ion withthe nig Terie Aree peat can ore erie be ant, cong Dee four ikem atoms as Lie Lash emeten! x nei Ber ceatons sonigunia wot age Al te Ae ceaton to Lato 36 tht Li comes Eee (aha ty span Li brome Li wi contests 1a, ane, Nou dan pe ers oobi nah A Let esos how tS olla obi (Le. enegy band ae fone ia 2 ihm exe Ekta canfgaate or eto Sons (9,3 2¢t I'm sons of hun mea ar aN Saino fra iio cys, they il frie Telnaes cau bandsMm chemical Dob lon oa {1, Seton This bande formed by he combina ty Arpmic orbitals af m lithium atoms and hence contalns from in ta Of hich are completely filed. Total number of electrons completely filled ts-band it 2vnmdn, Since 19 orbital hy vale pi steno he ence oer 104 Healton (vit. 2st-clectron) and does not appreciably InMerns hence i marrow atequitbrwm ineratome dirance, W-band ron-conducrt of rohcondan band seapintl (Uj Abad. This is called the valence-band. ‘ince 24 af bet xpleeetnern een hse ave very moc een ye onaig ony ane rnb, hugh aun ie aA fexelein 2ebond, These evel of 2-band have ner Of Doband i'n Conn neon cena, Bb hale The upper-haif of this bane ts empty while the tower half Ix complet edi ee ad S20 et pr ne cee Trot the lower-half can go 10 the ‘upper-half by energy available (til) Pp-band. 1 atoms of Lig solid will give~3n levels inp Land whose mario capecly to conain the electrons fe 23m eles Since 24 and 2p levels are near in energy, 2s and 2p band oveslap (er Pig. 413) a the. elegtons In. Deb thereto, ht Additional levels, differing very slightly in energy; to move about. ‘The portion where 26 and 2p bands -ovetlap fe called, overlap 200 anne contains electron, eit | ih filed, sae the rae sum eaparity of quasreontindovs band formed fom 2 and 2p bust fercontain the cecions i of Dnt Gnerd lection, ‘The electronic energy bands where te electons can move ait Ned the permitted bands, These are alto called Mellouln zone, Two Brillouin zones ate separated from. each other by emply band which are called forbidden zonea or Tonbldden energy gap, cg. tht filled Ve-band which isa noneandusting band is separated from te Aalstied hand by an empty zonemfobiddn tne oF fori rt fap, Thi on, the enetgy pap bien yan rb fs quite high and hence’ the promotion ‘ok elactrons from the lowet nonconducting ls-band to the igher ‘pond id pe vinted, The width of a Brillouo zone: depends on the overlapping of electron clouds, ‘The jevel below which al energy levels are fled fs termed Peal devel which may fl within a band own the ep rtwern tha bands. ‘Valence and conduction bands, As already stated a solid crytl ‘may be suppoted to contain efergy bands. nergy bands formed by the inner covagy levels afe very martow while thoteoblened fron the valence levels are quite wide and are. known as valence bands ‘The valence bands which are completely filed are called non-condoe 1c Dy ere Hey wr een oH of db im aha ‘ a mea ae ae Yo) & Nvecant upper {q- at eat LZ ot Lartiairaed Beat fee 25° ore ai Yee ecweton = Completery Filles "= band tNon~ conduction borat Eaee st ty, 2 38 2p czry bap inom ey. reat the xclsp die mete ted Bp bans filled are ealled conduction ye number of closely packed Fin 448. Porpaton oe ES Hon bonds while those wbich are pa lands 1n contagion bands there on ao tut aly 08 pysealproprtien of metal. [With the help of sen te ne pr me [ey hp ti aca) of ay ad ter are scone or ela to nora or emt-condustor etic) (Wf Conducts (Mens) Conductors are toe materials in seh Sty of ekewons ae aval for cet conduction. ih erg of rr ane evan baad ofa condor ipa iled sd esting eye number feels. Taese tars can be powoed oe aby vacant fees bese Sin by cece of ternal energy Gee Fa 16). Tisexpns bigh ele parent fort and hen {item from the attraction of euce Inet of nergy. bandy an isatg bas band, 1.¢. there are no electrons in this i sgl and thermal conduct (i) Non-condactos oF Teuttrs those obras in which vlene setae require ver Chemtct yayiine of the metas seal bound cv lrge lest ah gh 85 SPY consuctiot ‘BonecSnit ihe chery ep bch yt ch bend and) and the concen wey * commletely filled (now Sery large. (eee Fig Portally LD filled i i ond Yy Z/fA vost | Yoleree feonduction 316). bond Completely if), Wes word LLLL5 Sisters 18) Conductor (Mets) br intuatr (ooa- Pe Completely Y filles t Y; Is- bang BAND ENERGY Thus cherpy require ‘on from the completely-Giled valence-stel beg, mine 32 Esnduction band w vety high and el able» This explains that non-metals re ssa wction ban! d therefore, not novia ate sein ate Vecan bang ¥ (Coren sant Large Eneray Gap 77) canals Yi Conduction). & bongs | > ompletey | filedtone | $ thon ‘Conduct Sena [Completely filles Is-band (6) Nonsontictor or insulator (Noemie ip 10. Eneay Danan a (a) cancueor (metal) ane (2) nomeendoter cheeal Bond m ul St chet ce cretial PROPS Seincondctors ate in thei extesely pare are, eal ck semicon a aie et conducio' as of energy bands these have filled valence band (ron- rr a om cnsin Bae oe ee meni itera ie ey ns from Ones ow thermal conduetivny.. As he teapeatate Seen Ne typ Cammettad ee Becta th CELA ae ate a some more ctemperature increases the conduetivi ihe increase in tempe jn case of metallic conductors increase in tempera- Reentbthatin case of meta pe srieie condoctvity as the movement of eleetroas gute decreas ofthe kerk, sugared by aveatr vb Empty Conducton ‘Band |_— Electrons jumpee from Vatence-band 5 Energy CoP _ ___ Fermi Lever a e Posttvely charged = holes “Filled Valence- band iNon-Conduction ‘band! seconde xg a ric a ec OU een tnd Eng ane dana fran mtn cafcor arom eave 12" Fie ieee Bocee ns a ee ated into the10 chemical Borde Sometions substances, which are normally insulators, ce Rtade semiconductors when small amounts of impurities are added 19 then “Such sustnces recalled eats or import ae EoMductors. “Depending om the nature of impurity added exis Semiconductors are of two types ! (a) _ftspe extensicsemi-conductors, These are obtained whet an impurity atom to ‘he added has more external electrons thant arent insulator roms, e.g. when phosphorus, arsenic of antimony (all containing five vatence-electrons) atoms are added to pure silico? Of Sermanium (both containing four valence-electrons), We get N-YPE extrinsic semi-conductor. Each antimony atoth forms four covalent bonds with the suerounding four germaniom atoms by using ils our paeweerons and ish elccon i eft unused, Thus the i an extraccectton atthe lattice points occupied by antimony atoms compared to the Intice points cceupied By germanium atoms. TRE are as many extra electrons in the lattice points of dntimony. as thee are antimony atonss.. These extra electrons occupy, delocalised level (called donor impurity level) which is just below the empty conduc Mion band of germanium crystal (ce Pig. 4:18). These extra elections can easily be excited to the empty conduction band by the éppica- tion of electric Geld or by the iacrease in thermal energy and the crystal of germanium thereby becomes. semi-conductor. . In this case antimony is called adonor ioparity because it donaies an extra electron i the conduction baad ofpure germanium, Crystals of germanium arc semiconductors because of the presence of extra electrons in the donor impurities, hence the name itype (1 Used for negatively charged electrons) exttinsie semi-conductors, (0) type extraste semi-condactors. These ate obtained when aan impurity atom to be added has fewer external electrons than the Empty conduc Emply conduc- tion bond tion bond, Ie ‘Acceptor impurity level Containing positive holes QQOQO® ‘containing exiro electrons Bond Energy Filled Volence band Non-Conduction bend) Filled Valence - bond’ (Non Canduction bond) ° ey chemical Loring Uy e24 HSUIR6F atoms, eg, when be nium (voth contain- at ¢.g. when boron or aluminivm Panzer) eh drop sc rea: refon lucent 188 four valence-cleetrons), we get p-type"exiring Soe om eal this case three valenceclectrons of czch bore and yorm™ three covalent bonds with theee germanium sO nants fourth germanium atom is Sinzed with boron M00 scvmmaniyino™Plete bond containing only oie . electron (ore Tenn). Thus inthis bond. in the laltice there is a Te Termacte) Which creates a positive hole in ie valence samt crin cael There: areas. many positive holes as there aut hein Mom. “Positive Woles are the places where the elee- tron iy level) ie, THES Boles occupy the level (called acceptor Tr rad WReh exists close to the filed valence-band of germa~ i egeleciontiltom,-the filled valenee-baad can thermally be pane \¢ this eripty:acceptor impurity level af positive holes, vate tS gntenee ofan: applied potential an electron from_an sdjeF-ok 510m Moves inio'a hole and in turn i replaced by an elec 1 ee otter atom. Thus the molecule moves across the crystal ing tire-tion Which is opposite the direction of electron migration, Fire ho RUPEIBCUEN of as beng due fo the ation of the positive hole hence the name p-type (p used for positive holes) catisie Semiconductors, re ee ’ Releseness 4+ Ep Palen The nature ofthe Chemeal Bond, 34 eon, Comet inca Nr Ye el Pont 2. Deel and ahrn, Fundamental of Chemltry £ moder Inoue lon, Academie Tress, New York, 1970. ” 2. BE: Denis and DAL Mele, Concepts and Models of Ineganie herr, Bade ubliding Company, Waar, fas, USA 4+ CAs Cosltne, Yolence, Oops, New York, 1961 (2nd elitoo), 4S J:A-Daty, Generel Horgnle Chemstry, Lontrces Greeo 424 Co, Lid, London eo Neon 6 OK Rls Eearone since ond heel nding, McGraw New York 0.0" Z 7. GLE. Ryscbkenllewh, Chemical Bonding and the Geometry of Mole- cies Reh ee Ses nee ld 8. HB) Gray Becton and Chee Bonde, Bejan New York, 190, 9. Gable an 3. Gay tet Nate nMotesor Sih ee ee SNS 10. MC. Da Jen Sbl Theoret Cemiry. Rel BG RON “A. Caton a. Win, Aneel lnrane Chem Aikeydmencince, New Vote 190, 12 GE SEE Toa gle os alr Png ‘mer Langman 2B ara he) (ew cmpedtevaed eon ted PL, Rein, tates Chr. Beet RB Heap tad: Reblnee organ Cer