o DB Eleanon ue oumount of eutrgy selerred Bon a Mul atom im Hee baocus shie Gaines and Eada clecmo Prom a. megebodly changed tow, is woo ah elecwom aBtdaly., dhe proets may be depicted a0 A(g) + €C9) 9 A(a) + E (Aeeknow aPRmily) . she elechon aPtvily dloumines the Jenduncey ot an alow do ad om eabra— leclnow ond We Shenath willy teil me added elecnon choud i bound + Wo mucous . W Colablish tee Pack: elechon aPrrily ic the meverse Cane oP Jowizkion . fous’ Eledvon oPhrily indiedkes the provers xcay te —+ XGA), Waris exotic and ta magakive value idtecles te Process to bea exoltanm’e Owe tus tee Convention acepled im deBaing He electron aPhacht conladichs ta established convoukion in thoumedynomues, AlHough ‘exneay > Isaukkd to BA, i Some Cores eleewon absorbhon may alto o, : Byte —t he AN> - 828 Kilmet AR > Ogg Vamett Nge > Nay Aw + 203 ¥9 [uch BA + -20:3 Ka met™ “wus Aeon “Abily is Re Sorte prowess GP ionizahon ot 26). Keay —+ Kay t+ O@. A Possitive eleelmon aBhily imblies enanay is dened oom Wee alo _—— Gods a elocnove « Boietly Explin uy Fledwon aPrrlly is described an Zen Souizshion tuurgey”, Aun Elecnon @Pimily can be debmed as Me energy ot Vouizahiou of Reap iow, te, AU Tow He Procers Anca > ACA +e ; it deRvihion. eon veauine O Sign chomge , Because Wile Process 5 i. We louizebion Precers yinPrck one slep baceuand Prom We Fist lowization trove ot RQ), elecmow abtiuily cc somelines desoubed 00 4 Qmolk Tpwizdion EuerayFocton's giteding — Blecmon aPhinily s 2 \ — Size ot Sreetes Yr Gize ot te Shecies : 1) BPletie mucha dunaes BA of z* HW) Nature ot Re_ontilal into eBid re mend elednon Gels accomodabed » EA of Pevblrahion Pow oP onbétal. Cs>P24> e). Np, Nature of tue elechowte corRawuhon_, Speetes benring Wall -Bled om Rul Pied gubsholl axe very veh shlole due do bearing wrge exchauye Wis ode very mach sulucunk im ocenbuing Hae Tacomtnng energy vad added elecrom creates Hee el usrou. Om hea olturtand ff the menhy Bed on Rut BMed Sovel ther Ho process is Rwowred . Tus eleamon oPArly onda of ¢, Naud endo’. duond oP Vosdalion ot cleeMon «Paty along Foriod and beoup iy o's Nosumal Along Gop Cub to dont) > Size Twoenres — Eheewon aPHully decrees ui — decrvacing 2 * Alowg Yortod CLePh to sug’) > Size deosasts vith iwacing 24> Asewon— WD Expl cay Elecwon Attimity of Bad Pasod P blows chemmenls is Guenter. Yram —— 2ud period p bleu clomubs, ie, Fler, Os, NCPS BAL fury bu tis case He onden of elecion aPtndly Peltoris a severe oven — GR etedmomegelvity, A\Hwugh Second Period elements ome small sized and c alhacio om Outside elecwors towards mocleus is Wighin ton decwosbahi the added Seeomd period clomonts Hom tak of she stiocd pencd elements , Acco is under ax Wwekevrowreble sheng te elecwon- clectvon crepullon— wich 'S tonsidercily Wah Meare of Sualt steed Secowd Period clowonts . “This Swpulsive Foxeo is wot so Jarge i Cave OF Had Period clement .fhe valence Shell oP O amd 8") tho gobulsive baton mush be OvenwmZ . thus the Second elecmon a Phaily. ct Orygen- ond sulelun ts HVeand high. W Altisugh O-and S- har Sul Paes and oxides exPlum. “ve Second elechon rPrully tots of melts exirk an Aus: Sowization enogy and elednon aPtadly ane mol +2 omy Rrcbong pespousible for. Me shhility of a compound owned. Bw cooe of tonic Wmmpounds Ley acdkierd am exha shuaily, due to the sealeaoing LaWico_ energy Oybitch arises ou ot elied Pacung oF oprositcly urged tow ima. Cursblune latter « fon well sulpuides and onides, A) Hey hare very igh Vite onerdy Raw, Hay one Wigtty shable. BL and Be orbich ove has Wwetian eleckon Artidly amd shy 9 nal) 315 aie oe) Mee 4 1s? 28% | Ip bap Memablelely led 28 sublet grbile Be bao 25 subshelt | Cobleledy Bited, “us Li cam seceive elecwon ih iks 2s subshelt Be kao to iweb Wgtun 2P dort /subshalr fon accomodding entra | fuk From Re Concept of exchange eusray we enow met a filled | elecwou, + Swoshall. Beads to Some extna - shxbility due to Wah exch i ats foundion f Li to Li ts moow Bvowubte energi Heelly ree uk ot Be” trom “Be. : oreo, du cme oH, elechnon rao te be*fuceioued im Wietay penevang SS’ onbileL , wture is cue of Be, Atchon will move fo Me Rewer perabuhng Sp orbit. As 6S? elecdwon Wao mone Sadia dashailution Mean tos muctews ton Cp? owbilel, ebealmared! Llecwon aPtidly of Li will be Wau Hon Be. 2s ada 2P. “=: vein, ug sae tah log ane fo me ae OY ’ glut wich creales a bossi ye WAR Vaca d Ombitel. fo Medurg He cleckron-clecwon sapubblon— Hocough te peltd palin ot Y!-orlakls is Siguikeant fox kean'own Comgeuors. Hower. Sude wechonisi Bn seducing e-€ sepubion is mo} Possibte_ Ban Send poricd clomoly an Wey are Jacu of omy Cd!-orbihL. mo} ovly dus to A oobaleL tm MR vAlenely gh jwoused elecwow onsity this Possilailily Lalily ot dodochlizhor | | tdhy Yee elecnon oPtndly ot feo Post lantrauide elecamends are usualy wg ? ercdy shat Lirng ta Hae iuntone ePechive Mudecte Wh Due to tee Puesome a ta AP elechrons chowe experience d by tee valoney elechous ob Pork lanthanides becomevort Wah, ond Mas He Size ah Hee cements dectronres Contidennhlly Pecomes cluncst Some do the 4d Congeners, tts ds called Lawthavide Coulmachove - | fs sosulr ot tus Lautuuside CoubabHou—, the ouler omosh shett eleeroug enrodence WQhur clocmoskhic. atmachon ounrds Hee Mucus aBick Mureares ue. elecwon aPRndly Hpoern Meare ot latter Pock lanthanides (2-9. AX) Bleclror > vo otiviky —Hatun [mocennes by a large amount—due to ire delavislic, ePRecl- ubich moduces Arain Size considendity Gru oe due to iis waqh ceciron Prat, : : TA the Seed elecnon- aPrudly oP oreigen and sulehur is te osky 9 Aust MSharmodunamnielly cleclwon oPtinaly values ghatl be. expresse L wilh -ve Sign pak eleelwon abivly is woud Aerobed wilh a ave Sige [Ene - Av] Negolive eledron ablwwhes ane alsy vrown hich wnePons thal tthe eee. Crnurered decmol Live to have anny omnoe. elecwon. Rior Wee ewalion ot ov ond 55 Thue wank fo Aeoam exter— Fankun clecinon Wwko OT and sae Wetowing elacmow colt Real ee — eReck From We -ve ly changed. owtow 80, 40 ewkn eleemon—Goowp Blech onegeiaty > tis cedromgediay ot an clomonk, 1s mot il quo chowiod auvivonmenl te, onladron stoke > oR we Substihenks cbc. she guoups (6-0. ~ CHR, 7 CFs, ~ Mr, single eulities , ushiose clacwousgelivites depends OM Consktuauls eg. duc elechowsgehvily of tee avoups ~ CHS and-CFg *2_ door, tus Hue group elecwo magebivity (xe) om be Hecorrils lly _ Caleb by uring Hue atomic elecwomegekvityy ot the tovsthuent elements he grow eloerousgehiity cau be expressed im bows eb ibazemt group elaclronegetivity Cag) ond change to- ePricienk Panamskr, Coa) by Considering Wo touort of TePe~ Hinze cLecmouegehivily. es Aa +baSa © Za 2 bi eee =m Se + ois ™” ks tube pucpenty. It depends on — gleke of Wiladdizdi ow Od mature — ow ele) smay be Considered a0 we makure ot wr at tae constituent abome. ue ot tee Wunonk alow c Aecwourgehvity Cai) graeds Coo) of Meconslitunt alows ab fe Fount Hime, bar Aug chate -e! jwwetely propostional te he Mo. Gh couskhiont oko mg amore Woe paoroabiondty constant (5 ually avg ot ay values. A (avg & biveues), * 90, Og: bas sigue ot bo and ions Ohl + lange Co-eRicioul- parameter ba Can be deBued a ba Zt “Thus wilh unrenne 5 bo value deenenses . je Larger He Guoub gle fre bg value. the change cabadly fe change Sprosding orbacily js dineckty — Proboudkoucl to Hur mo. at aoushtuent atoms, of He anouh oshone_ ‘Chana Co-eRicient— iy inversely ProPorFond to. 7 Ths One OMe cL. ge a eoPertouk ot lowe damactn im ARB Bondy Rrackionat torte charaden > = ote (Xa-*B) 4 03S (4-48) Ty + 220 My 8-16 fiw Hey 16 (31g-2-2d) + segs ( S:lb-220) aasg © 18-67,‘ron Poriodic Table and Periodic Trends of Different Properties of Elements 491 4 = ~ 0.9 (soe Fig. 8,13.1.1). However, it is evident that QF depends on q (which may be fractional or integral). ft indicates that up to q =~ 0.9, AH for F is more negative compared {0 that of Cl, but after this, the process becomes more endothermic for F compared to that of ch Higher electron affinities of the heavier congeners of d-block elements : For the d-block elements, in moving down in a group, because of the d- and f-contraction, the size does not increase smoothly while it increases smoothly inthe case of the representative elements, Because of this fact, the general group trend is violated very often for the d-block elements. Because of the lanthanide contraction, the postlanthanides very often show the unusually high electron affinities (see Secondary Periodicity, Sec, 8.20). Let us consider the following elements (electron affinities are given in ki mot), CoC70) < Rh(120) < 1r(160); Ni(111) < Pad(160) < PH(205); CuI 18.3) < Ag(126) < 4u(223) {tis striking to note that gold is having the highest electron affinity (223 kJ mol!) among the metals. It is a consequence of ianthanide contraction. As a matter of fact, ionic aurighs (eg. Cs* Aur) are now well established (cf. Sec, 8.20.3). : ‘ 8.14 CONCEPT OF ELECTRONEGATIVITY Electronegativityis defined as the electron attracting power of an atom towards its nucleus when the atom is covalently bonded in a molecule. Thus the more electronegative element withdraws the bonding clectron cloud more towards its own nucleus giving rise to an accumulation of negative charge on it, From the definition, itis evident that he electronegativity ofan element is not an inherent property ofthe element. depends on its surrounding environment in the molecule in which the eletronegativity ofthe element is being considered. Thus the electronegativity of Sin the compounds, H,S, SF, and SF, is not the same and itis different in different compounds. Here it is worth mentioning that he lectronegativity of an element is not its inherent property but the electron affinity of an element te ‘ts inherent property. \t is understandable from their definitions From the standpoint of measurement of electronegativity, there are different scales which will be discussed below. 8.14.1 Pauling’s Electronegativity (x) 't gets its origin in the concept of valence bond theory (VBT). In the formation of a covalent bond 4-2, the ionic forms also contribute and the degree of contribution of the ionic forms depends on the clectronegativty difference between A and B. The wave function of the AB molecule in the light of VBT is given by : Vy Waa Mig OV as 8.14.1.1) Ifthe electronegativities of A and 2 are almost identical, then c, = cy < 1(B) then ¢5 > cy; and if, x(B) > 4(A) then e, > ey Because of the contribution of covalent-ionic resonance, the actual bond energy (E,_») of AB is always greater than that of the corresponding hyPothetical 100% covalent bond. This difference gives the measure of the contribution of covalent-ionic resonance energy. Thus, the covalent-ionic resonance ‘energy (A) = actual bond energy ~ energy of the corresponding 100% covalent bond492 Fundamental Concepts of Inorganic Chemistry 2 = AA ~B)= Ey Esa con ve (8.14.1.2) The energy of the corresponding 100% covalent bond can be theoretically calculated as the arithmatic mean as follows: Ex-a(eon = 9 (Eq.4* Egg) (8.14.13) where E, , and E, , denote the bond energies of A) and B, molecules Tespectively and these are measureable quantities. But by using the values of bond energy in this method, in some cases (e.g. LiHl, NaH, KH, etc.) the resonance energy (A) becomes negative which is not acceptable. To overcome this shortcoming, E,,g oy) has been defined as the geometric mean as follows : Ep-a¢co) =\ Esa) Es-a) w(8.14,1.4) O(A-B)= Ey 9 -f(Ex4) (Eg_g) (8.14.15) The resonance energy (A) arises due to the contribution of the ionic forms and it depends on the clectronegativity difference of 4 and B. From this consideration, Pauling proposed the following relationships : % of ionic character in 4 ~ B bond x(4) ~ 4(B) x JA(A~ B); and x(A)~ x(B) = 0.102, JA(4 = B) | where A is expressed in kJ mol, (8.14.1.6) Thus we get : Units of covalent-ionic resonance energy (A) Originally Pauling proposed that the electronegativity difference between the bonded atoms and Bis equal to VA, when’ A is expressed in eV. x(4) ~ x(B)=Vi, in ev If A is expressed in kJ mol-!, then by using the conversion factor, 1 eV per molecule = 96.5 kJ} mol"! we get : a (A) ~4(B)=,|4_ = 0.10208 UA) ~ 4(B) 65 Similarly, if A is expressed in kcal mol"! (1 eV. per molecule = 23.06 kcal mol~'), we get : a ~4(B)= 2084 x4) ~ x(B) 2306 A ‘To understand the basis of the relationship (Eqn. 8.14.1.6), we are to consider the following fact. In @ number of systems, it has been found that A is not an additive property but VA is an additive Property (at least approximately), i.e. A(A- B)+A(B-C)#A(A -C) but, [s(A~B) + JA(B—C) = fact C) ‘The above observation strongly indicates that the % of ionic character is linearly related with J not with A, i.e,1g of Different Properties of Elements 493 Periodic Table and Periodic Trend y(Ay~ x(a) VA BD ears as the proportionality constant in SL units. the electronegativity of one element is known be calculated and by repeating the process It leads to Eqn. 8.14.1.6 in which 0.102 apps in Eqn. 8.14.1.6, A isa measurable quantity. Hene® if then the electronegativity of the other involved element the electronegativity of all other elements can be ‘calculated. Pauling assigned an arbitrary value 4.0 for fluorine and calculated the efectronegativisies of ‘other elements. The Pauling’s values of Clectronegativities for different elements are given int Table 3.14.11 a perermination of electronegatvity from thermochemical data: By using some approximations, experimental parameter, i.e. enthalpy’ the cectronegatvity difference can be obtained by using another ¢ of formation. The basis of this technique is illustrated in the case of AB molecule. From Eqn. 8.14.1,6 we get : (8.14.1.7) _and Ey.p, We Bet (4 — B) = 96.51x(4) ~ KBP aay considering the Ey.» oy 28 the arithmatic mean (see Eqn. 8.14.1 3) of Ey 1 : A(A~B)= Egg 5 (Bana * Eno) wee (8.14.18) By combining Eqns. 8.14.1.7 and 8.14.1.8 we get = 96. ~ BYP = Ey - > 6.51x(A) ~ KCB = Ew Ena + Epp) (8.14.1.9) ee | = e 1 enthalpy of formation of AB in the reaction, — A, +> By = AB, is given by : : 1 _ AH(A-B)=Ey-~ (A-B)=Eyn qlEaa* Bea) we (8.14.1.10) Combining Eqns. 8.14.1.9 and 8.14.1.10 we get : (TAM A= B)= 96.544) ~ 1B? : [-AH (A= B) or, MA 0) reece 565 0.102 /— AH(A ~ B) (B.14.1.11) If the idea is generalised for th : \e compound, AB, th i enthalpy of formation of A —B bond are eid ae 2 oe AH(AB,) "= AH(A— n Ge) (B41 — AH = (AB, ) = 96.Snfy(A) ~ (BYP. A8.14.1.12) B6Sn Tr or, .(8.14.1.14)494 Fundamental Concepts of Inorganic Chemistry It should be remembered that Eqn. 8.14.1.14 is. applicable only when the total number of covalent bonds in the formation reaction, 4 +2, > AB, does not change and the conipound AB, does not contain any multiple bond. Table 8.14.1.1. Pauling elactronegativities (zp) of different elements (H BoC N OF to is 0} 25) 3.0 235 0 Na Mg Al Si soa 09 12 15 18 21 25 30 K Ca Vv Cr Mn Fe Co M Cu Zn Ga Ge 4s Se Br 08 1.0 16 16 15 18 18 18 19 16 16 18 20 24 28 Rb Sr Nb Mo Te Ru Rh Pd Ag Cd In Sn Sb Te [ 08 1.0 a0) 22 20 22 19 io ty te ie 21 215 cs Ba Ta W Re Os br Pt aw Hg Tl Pb Bi Po At 0.7 09 15 17 19 22 22 22 24 19 18 18 19 20 22 Fr Ra 0.709 Note : Electronegativity depends on oxidation states. The values given here refer to the most common oxidation states of the respective elements. However, a correction in Eqn, 8.14.1.14 is required when the rauitiple bonds exist in A, and/or By because in such cases all the bonds are not of the same energy. For example, Ey, yy = 945 kJ mol! > 3£ yyy) = 3 * 164 kJ mol. Thus, and O, are siabler than the hypothetical molecuics having three and two independent single bonds respectively. These extra stabilities are to be taken into consideration. The extra stabilities per nitrogen and oxygen atoms are 226( es 2) an 2 Ho 7s) kJ mol” respectively. By considering these factors, Eqn. 8.14.1.14 gets reduced ~ AH = 96.5 ¥ fx(A)~ 4(B)]? ~ 226 ny — 110% (18.14.1.15) ie. = AH = 96.50 (1,4 ~%p)* ~ 226 — 110mg where ny and mo give the number of single bonded nitrozen and oxygen atoms present in the molecule and the summation is taken over all the bonds in the molecule, Eqn. 8.14.1.15 assumes that the compound does not contain any multiple bond. Egn. 8.14.1.15 indicates that the compounds containing the single bonded nitrogen will have a tendency to have the positive values of heat of formation, if the electronegativity difference between nitrogen and the other element to which nitrogen is singly bonded is zero or very small. NCl; is an exampl: of this group and in fact, it is an unstable compound. This instability originates due to the extraordinary Strength of the triple bond W'=N. Similarly, the compounds like OF, ClO having x(4) ~ x(B) not so high are unstable, Thus o stabilise the compounds having single bonded nitrogen or oxygen, ionic resonance eneray, i.e. difference in electronegativity, should be high.Petiodic Table and > Let us illustrate the calculation of having the enthalpy of formati correction terms do not appear. HCD) ~ {2} Actually by using the enthalpy data, the electronegativities of the different elements are assuming the arbitrary value 7(F) = 4.0. Pauling’s electronegativities (based on thermochemical data) of different elements are given in Table 8.14.1.1 Note Pauling's original table of atom electronegativities was constructed mainly by using the covalent-ionic resonance energy (A). This original table had been revised by Allred (1961) by using extensive thermochemical data, Now these revised values are widely used. 3.14.2 Mulliken’s Orbital Electronegativity (x) 2.S. Mulliken (1934) proposed that the electronega! electron affinity of the sp by Hinze and Jaffe in 196 electron affinities and are lughly electronegati Mulliken proposed that the ~ bond will be pi and 4-B* contributes to the same extent and this is the same. The energy of A°3* depends on the io: Bwhile the energy of -B* is determined by the ionis: both the forms contribute equally, we g both the cases 4-B* and 4”B> is ident y is related wit both the ionisation energy and s under consideration, This originsl idea of Mulliken was further developed The atoms having high ionsation energies possess generally high covalent in nature if each of the species A° Jt é when the electronegativities of A and are gy (/) of 4 and electron affinity (4) of ion energy of B and electron affinity of A. When + the following condition, provided the Madelung energy in ai. IE, ~ Eag= IE, BA,, 01, IE, + EA, = 1Ey + EAy. Formation of A*B” is favoured when, /E, < ly and EA, < EAy: ie. IE, + EA, /E3+ EA,. Because of these facts, Mulliken defined the electronegativity of an element in terms of the sum of its ionisation energy and electron affinity. §f the electrer. affinity and ionisation energy are expressed in electron volts per atom, then 7, is expressed as : 1 zg . 1 a (A= UE a + Baie toy = 5 UE + EA) -(8.14.2.1) ‘The Pauling’s electronegativity (z,) and Mulliken’s electronegativity (1.4) are related as follows: hp = 0.168 UE ~ £41.23) = 0336, —0615)=0336%,, 02]... (8.14.2.2) (when FE and E4 ave given in €V/etom, i.e. 1, , is expressed in eV per atom). Thus, it is evident tis: pan, Groar relatioushiv.496 Fundamental Concepts of Inorganic Chemistry Units of IE and EA oy = : (JE + EA), when IE and EA are expressed in eV per atom. IS 1B and EA are expressed in kJ mol, then 7 2965 Similarly, if JE and EA are expressed in kcal mol-!, then, tu = (IE + EA) |, 1e¥ per molecule = 96,5 kJ mol Nac (IE + EA)| , leV per molecule = 23,06 kcal mol” 223.06 + Some workers have proposed the following relationship between , and 4, 13) * Here it should be pointed out that Pauling's original values of atom electronegativities have been revised by Allred (1961) by using the thermochemical data. These revised values of zp are related with the 4, values through the linear relationships discussed. Important features of Mulliken’s electronegativity : Mulliken argued that the ionisation energy and electron affinity depend on the nature of the orbital involved. For a particular element, depending on the nature of the orbital, the electronegativity may vary. Hence to define the electronegativity, the valence state of the species must be taken into consideration. Thus to define the elctronegativity, we should consider the valence state ionisation energy, ic. VSIE (JE,), and the valence state electron affinity ie. VSEA (EA,). Thus, x, is given by, 1 ) Yay = 3 (UE, + EA,), when the energies are expressed in eV per atom. Using the first ionisation energy and electron affinity of an atom X (i.e. EA of Xis JE of Xqy), we Bet the absolute electronegativity (x... [= (EA + IE)/2] which is related with the atsolute hardness (Mees) [= (IE - BA)/2] of X (cf. Fig, 14.15.3.1). LOF Lops =hua + IE), oF Nang =hUe - EA) The valence state energy parameters can be calculated and it is illustrated for Re when it is sp hybridised 2 15,1 JE, + (o296h 2a ly ot IE, + Be (Is'2s 2p) —“+ Be* (1s?2s'), and Be (1s?2s'2p!) —> Be* (Is' ; 1 ie, IB = UB, + 16,) Similarly, £4,, can be evaluated. 1 i Thus, ku (P) => (IE) + BA)Periodic Table and Periodic Trends of Different Properties of Elements 497 The electronegativigy increases in the sequence ns > np > nd and for the s—p hybridised orbitals, it is: : sp > sp?> sp° Values (in eV per atom) of ‘Ly for some elements are given below. H=72(s') Li 1(s!), 1.8 (p!); Be =4.8 (di?), 3.9 le"); B= 64 (07), 6.0 (te); C = 10.4 and 8.7 (di?x?9, 8.8 and 5.6 (er°n'), 8.0 (te); NN =15.7 and 7.9 (di?n?), 12.9 and 8.0 (tr'n!), 11.6 (10°); F = (Here, di = sp, tr = sp?, te = sp3) 1.3 (s!),12.2(p'). Comparison between Zp aid Zy,: 7p values calculated (by Eqn. 8.14.2.2) from %,, values are given below for some elements to reveal the effect of % of s-character on electronegativity. With the increase of character the electrovegativity increases. spp? spp sp C: 252 2.80 3.34 1.74 F: 104 3.95 Nz 3.74 418 5.14 252; Cl: 63 3.00 Thus,the accepted Pauling’s value of 2.5 for carbon corresponds to its sp? state, while the value of 3.0 for nitrogen involves the valence state between sp? and p. For, F(%,p= 4.00) and Cl(i» = 3.0), the p orbitals are considered. Thus, itappears that Mulliken’s idea of orbital electronegativity is more justified than the Pauling's empirical treatment, but the serious disadvantage with the Mulliken’s concept lies with the lack of the electron affinity data, Sometimes, it is also difficult to determine the exact state of hybridisation or jence state. For exemple, in transition metals both sp and sc? provice the same tetrahedral arrangement but the electronegativities of the two states widely differ. In such cases, the bond angle measurement cannot predict the state of hybridisation. 8.14.3 Jaffe-Hinze Etectronegat ities (known also as Mulliken-Jaffe electronegativity) Jaffe and Hinze extended (1962-63) the idea of Mulliken and showed that the electronegativity of a species depends not only on the nature of orbital, i, state of hybridisation, but also on the charge (9) of the species uncles consideration. Here we are te recall the quadratic equation (Eqn. 8.13.1.1) involving the ionisation energy or electron affinity and charge, g, ic. B= 0g + fq? ‘The slope of the curve, ie. Asi)/2y ~ a + 2g, gives the measure of electronegativity ‘Therefore, 1 = KAMVAg = 9. + 289 = a+ bq ofB.14.3.1) (putting a = a and b = 28) The relationship between the approach of Mulliken and Jaffe can be established by considering the suitable values of g. in the relationship, AH = ag + Bg?, for g = +1, the energy change gives the