Covalent 3.1 VALENCE BOND THEORY © The taain points of valence bond approach are as under: (@ Atoms retain their individuality in the molecule, (@) The bond is formed due to the interaction of valence electrons as the atoms approach eas Fe, the inner atomic orbits from each atom forming the bond are undisturbed. (i) When they form a bond, only valence electrons from each bonded atom lose their i i () The stability of the bond is explained by the fact that electrons forming the bond betwee ‘wo atoms undergo exchange between them. This method is based on two theorems which are stated as: (© 18%, and ¥, ate the wave functions for two isolated independent atoms, with energies, and Z,, respectively, then the total wave function y ofthe system can be written as a produc Of the wave functions of the two atoms W=¥,¥, (l) and energy of the system by E=E,+2, Q) (@ Ifa system can be represented by a number of w then the true wave function ¥ can be obtai wave functions, ave functions such as ,, ,, W. ined by taking a line: It may Y=NCG¥+G%+6%,4...) o pees Fi ted b where Nis the normalization constant and C,,C,, C,.....,are the Coefficients indicating the weightol Result th each of the ¥,’s. They are so adjusted as to give a staie of lowest energy. The squares of the coefficients a may the taken as a measure of the weights of each wave function to the total 3.1.1 Formation of the hydrogen molecule Letus now apply the concept of valence bond theory of the form “hydrogen atoms and consider the various forces of attraction and repui For two hydrogen atoms which are infinitely apart when there wave function of system is: wave function. ation of hydrogen molecule from Isions which may come into play. is no interaction between them Yawy, jand represent the wave functions fortwo hydro s Tespectively. Now. close together, .e., distance close enough for imeraction, the wave fanetion for: 2 can be written as : BB esp Di, (2) ‘ ydrogen atoms H1, and H0 Le, ae of all thes a e weightd soc flict ion. ecule fret > into pl’) veon thet the energy of the system consisting. m1 of internuclear distance aon by applying Schrodinger Ice ry may be shown graphically in © Positive (Repulsion) Exchange energy <—— Energy ——_> we — Internuclear distance, r, ———> er Fig. 3.2. Potential energy curves for hydrogen molecule. It may be noted that the total energy of the two isolated hydrogen atoms is taker the two atoms approach one another [without exchange of electrons, eq. (5). the electron 1 of His attracted by the nucleus of H,, and electron 2 of H, is similarly attracted to the nucleus of H, AS result there is weak attraction and consequently energy of the system starts decreasing, With decrease in distance between the two atoms, forces of attraction increase rapidly. Ultimately an equilibrium intemuclear distance (7,) is reached where the system has lowest energy, At distaness class: an this, stronger repulsion due to close proximity between the two nucle ses in and consequently the txepy of the system becomes positive (curve 1). The minima in curve | rebressaes, that a molecule formed but tre bond energy represented by wave function‘ (about 25-2 Imole) so taeatas sivabie Vimole (curve IV). One may thus conclude that the wave poorly with the experimental value of 431 4ks/m re NO eee finetion ¥, representing structure I is not correct, Certain np sa Y match the theoretical and observed valu (@) First Improvement : Exchange Energ, Halsthat electron |i associated wit 210 dad sr their atomic orbitals overlap and we are no ecule is Jo atoms come close togetler, ae bpiccatrn ea ier fe atoms retain thei individual electrons. We et note any oe leon iets te Shey eipe, it clearly states that we cannot ese yoni ility of findin} given. ‘ented by structure II. A careful examination of the wave function ¥ J electro’ 2 is associated with atom Hi, When aprobable representatic two wave functions. Rac ay, () al ii arebonetbuiod of wave fu TAs stad earlier in theorem I, the weigh ofits coefficients, So we have De =P (DY, 2) +¥, (2), 01) - 2)-¥,, 2), (1) Bee ect, combination as there is no change op stem calculated as a function of internuclegrag W, result ina significant lowering of energy and is represented by may is shown in curve Il and iS approximately 302.4 ki/mole and com racer pe adiionslowering in energy fe, 302.4259 = 99 King i trons between the two hydrogen atoms andie 'PProach each oe is the wave function wis eens PetrONs approach each other with opposite spins, Fig. 3.3 (aj.¢ Sach nuclei is always in possession of one electron at all times, Parallel h oth 8 shicra”® “inction can be improved by considering Sid one another by vatying extents trace the Mislear charge) rather thig & the ie ee unction W, (or W..,,)in-e4. (2 We have function, But so far we have. ‘assumed that ithe? 4 Situation may not always be true, There is cieto™H, oF H,, The wave funtion, ang gy oo, i ‘gnificance 9 structure eq. ( et these stry “Ted that Hye fraction of Ae sin, Sifficut gle s lesNDING | ext 80r t qe function may be Written ag iw ¥, (1) ®, a both elect , ions, Mon Pa ie F nce itrepresents a state in why ae ; ich ionie f i Noe yr Yon 0eter en the ah Hah conte acute tae © function may be written as ¥ =¥,(1) ¥, (2) 4 a , ‘aAl) Y, (2) Fo (2), (1) + ATW, (1), (2) 4 YL), (2, Spesisprsens the mixing coeficien. Ie tellg yy onus vate hci el ee ® Boe wave function Y. By applying the varianne method We ean ajo 1 eto lear dit ¢ lowest energy. This way w. Wwe can ad a lear distance iy guia the lowest energy. This way we can eAsure the extent of nie charaney e838 nted By cure fifa the value of 2 is about 0.17, andthe tonic contribution o the bonding one covalent ampares wel) piiimole fwe now calculate the energy ofthe system using, tate ie fate vowel ction as given by eg, (12 Toe ve ur eal Tie ney ssatdneane ren eA) dis knownas ) gdisan improvement over our earlier results and is uite close to the experimental value. ; STANCE r., wel This treatment which we ha combination heach othe, t referred to as method Bion wie e. “a. (7) that the atoms must approach one another with 33 (0), a esis of their electrons in “posite collection, It follows that the formation of covalent bond E 7 P Seplined by the lowering of the potential energy of the electrons, resulting from the increased Been density in the internuclear space M2 Resonance and resonance energy Sonetimes it is not possible to describe the Properties of a substance on the basis of a single Sur. Weexplain it by saying that the substance exists in a number of structures called resonating Btties The actual substance is then hybrid of these resonating structures. This phenomenon is semance. Each resonating structure makes a definite contribution, big or small, to the actaal Pte ofthe substance, This is explained with the help of resonating structures 1, Il, IIL of 4, H:H @ Hc @ HH (covalent) Gonie) saree if ii 1 a he Fog stutures can be represented by wave functions defined by 8 ©, 0), Ee 0) 7 ,_fcance of eq. (12) is that hydrogen bien cont ae Pann the | Shh 9, (7) or by the ionic structures a SiC LEVG HEDIS het Sa Bingen Mes structures indicate that they are ae ae eae it be Bald ab yeogea ean PES Mig, that 1, exhibits all of these three os Traction of time in some other form: The jletion of time in one form and for another tran OF aIponG3 Coaighay SE ve have laVe Single yhich cannot be desoribed in | e real structure is a resonance ea ienele structures w {not in the molecule. The Itch exhibits the ‘i i MMficulty lies i, es ion and not a nule which exhibits ‘here i Hig icity tes in the description equated (0 am can be iter ofthese Ben eee edit vem itis either ofthese, The resonance ine Aig et donkey and the horse, but ato moment itis ies ATE AIRS ; aa nce energy. re e of the contributing s eden ‘ pee tan ny one Of eer See eons with the most stable ae j #8 he all the resonating suc ajent bond The necessary conditions for ‘writing resonating structures are as follows ‘chy oom ee es Te nucle ofthe atoms iseach structure mustren Heed porons On eal aca ns may change, The ‘bond angles and bond lengths should be close! Only then th ea ificant For example, the Dey Sa ttnbution ofthat structure to the hybrid willbe significant. TO erica - ay struct structures of are less important than the Kekule structures beeause in posi 6 ‘Sone very long bond across the ring, BE sowie O-U &-2-0 Keke forms Dewar forms aa The following two structures of phosphorus acid (HPO,) are not resonance struct i aghen ‘of the displacement in the position of atoms. 190 fength of S id lone oxygen tr ie is shorter the ¥ oxide : cE nd. Howe H foratriple bon . fs dlength m “The two structure represent two different chemical species (Lautomers) which are in equilibriag, | gtance. Bond len: but are not resonance structures other structures, I Gi) Fach structure must have t Structures in which one form electrons. For example: one the same fiumber of unpaired electrons. We should not draw (Dipole moment Contains single unpaired electron and another contains two unpaid cottrbution. However, — saipartial negative cha e : i= 6 catton monoxide woul EN — 0: IN==0: andnot :N — 6: anton m: (ii) The contributing structures should all hat by taking the example of benzene. The ‘important than the more stable Kekule benzene, Wve similar energies Dewar structures have higher forms in the combination th . This rule may be illustrated energy and are, therefore, less But since oxygen lat represents the true structure of teck from carbon to th monoxide has very low zative charge resides on the most electronegative atoms and Positive charge on the most electropo sine atom willbe clases tthe ie stuctie Forse | *SOnating struct We may write the following resonating structures of HC] ltmay be represen Ce hae a ORond length, ¢ eT (ons (oni) I 1 ML Theres significant contribution from structure I (because of greater. lectronegative of chlorine). However, any contribution by structure Ill is not possible, " (») The-contributing structures should be so written that unlike charges reside on heighbouring | “lis, “Yble bong d atoms, Consider the resonance structures of HINO, . The lat structure dees na Contribute because Gee Theres, of +e charge on adjacent N atoms and double -ve change on the third nitrogen atom, » “OD, fore, =N=" Sees zeeVALENT BONDING A (vi) The greater the number o structures. For example, the double | ofan additional covalent bond. cr a the sontibution of the resonating Of BE, are important because of the formation f covalent bonds, bonded structures . Bt ee ©, 3 Ne Resonating structures for CO Following resonance structures can be wr iter = 80: Shy COD <> 20:0: <> 26:6 (covalent) Conic) for this molecule. : (i Bond length. The observed bond k ISI ond length between carbon and oxygen in CO is 113 pm. The ae aces 110 as Itis, therefore, obvious that the bond length in carbon digmahce Bond length measurements suggest that contribution fom resorance structure N donna over other structures, I and IIL. ne (Dipole moment. On the basis of bond length, we may say that strueture II makes sta partial positive charge on oxygen igen were the same, un PE contribution. However, we may note that this structure su; and partial negative change on carbon. If the electronegativities of carbon and ox carbon monoxide would have an appreciable dipole moment in the direction shown. eae lust frst ___ But since oxygen is more electronegative than carbon it, therefore, draws electron density rege back from carbon to the oxygen atom. This foree works inthe opposite direction and hence carbon monoxide has very low dipole moment (0.12 D). mst Resonating structures for carbon dioxide 10 = ce ‘o=c 3 (covalent) Gonic) I u 122 pm. The observed bond be some contribution from structures Il and Il wns from structures IL and III must be equa. I their contributions fipole moment. But CO, has zero dipole moment el s bond is 731.5 kJ/mole, Therefore, carbon - oxygen double bond is 7 {© (structure 1) should be about 1463.0 kl/mole, The 1601 ki/mole. The difference between these two values, quired due to contribution by structures I and I. It ‘nant form due to its symmetrical nature (ionie) ul jor oxygen double bond distance of distance is shorter than this value and is 115 pm, Therefore, there must out (ii) Dipole moment. Contributio" ait are unequal, the molecule will have ¢ (iii) Bond energy. The eneray of # heat of formation of the molecule o=Cc experimental value of heat of formation 1s die, 138 k/mole suggests the extra stability may be noted here that structure | is most domi: ruetures Land I, j hybrid of two resonance 8! izeable dipole moment for the mol a structures edicts a The low value (0.12 fiend Mie cancelling effect of dipole moments in s jons in structures I and I, ince structures of carbonate ion : eo ER The Lewis dot representation of carbonate jon contains @ able pond ana ms ies bong ‘between central C aoe atoms as shown below. Thi ahaa in oe See cain ‘oxygen bonds (C=O) should be shorter than the other two bonds. Also than the angle f. But this is contrary to observations. 808 313 ¢ o-c0V atomic ormed by . Bond Iv This has been explained by a combination of re Thus carbonate ion may be structures, | Example: Write down the resonance ‘sonance structures I, I and III for carbon dioxide Fepresented by structure IV which combination of these thr’ structures of agit () scy- le op i 0) No, (iii) HNO, Solution: @C1,07 Gg) NG ‘Ae three structures are equally important and result in the same bond order (* 2) for each bond in Ny “ oe NN INGEN S— C bond order is between 1.5 and 2 and C—N bond order is between 2 and 3. () NO, gle is 1y 3.13 (sigma) and x (pi) bonds e-covalent bond. Sigma bond is for ofatomic orbitals. This type of overlappin, formed by electron cloud havir (@)s—s overlap (b) s —p. overlap (Op—p, overlap sd by end-to-end overlap of any one of these combinations g results ina strong covalent bond. In these cases, bond is naximum density on the line connecting the centres of atoms, Bond formation between two hydrogen atoms to give H, results due to overlap of two Lsatomic orbitals. The covalent bond formed by the s-orbital electron cloud below is called a o-bond. O- GD Is End to end o-covalent overlap bond n dios Formation of H molecule, nese The formation of the HF may be visualized as an example of the overlap between 1s and 2p, atomic orbitals as shown wel End to end overlap -covalent i of s- 2p, orbitals bond Formation of HF The formation of F, molecule results by the overlap of 2p, atomic orbitals of fluorine atoms. This is shown in the figure below.Formation of Fy ax bond. x bond is formed by sideways or lateral overlap betwee! their lobes perpendicular to the molecular axi Beit "The sidewise overlap isnot efficient and results in a weak bond. Siem? than a pi-bond. 4 x fae - ee . | 4 B jis always strong ‘Sidewise overlap of p,—P, bits 3.1.4 Three-electron (odd-electron) bond Pauting in 1931 explained stability ofall odd molecules such as NO (nitric oxide) having no. of electrons 5 +6~ 11 to existence of three-electron bond between pairs of atoms. He suggested Thutthere are only fwo different arrangements (I & II) of accommodating three electrons into Be two orbitals. B o AB am i He suggested that calculation of energy for structure I alone shows repulsion between the twe atoms (+ve potential energy) and so structure (1) does not correspond to the formation of a stable ; bond. Similarly, structure (II) alone also leads to an unstable arrangement. Pauling suggested tha if two atoms A and B are identical or are very similar, so that the two structures 1 and II have very close energies, then resonance may occur between them, This resonance energy Will lead to attractot between two atoms (and lowering in energy) and will lead to the formation of a stable three-electra™ bond between the two atoms. The resonance between siruetutes I & II may be represented as ALB ALB This type of a three-electron bond is represented as A: - - B. Itis shown by Pauling that the three electron bond is about one-half as strong as an electron pair bond i. it corresponds to half bond. Paramagnetic nature of oxygen molecule can be explained with the help of three-elecy u Normally, we represent the bond between two oxygen atoms as oe ‘ 0:6: or O==0 But, this does not explain the paramagnetive nature of oxygen molecule. In the abo, of oxygen, all the electrons are in pairs, There is no unpaired electrons. Hence, parama ae remains unexplained. Pauling explained the paramagnetic nature of oxygen by Proposing ne a 0 three clectrons bonds between two oxygen atoms as shown below: some & rhreee! aiffere” found t xamP (Nitric 0% ele i) xois given O* sfunfavourable However, s between the tw The molec Sthree-clectro Molecule is d ouble ang a A the triple NiteALENT BONDING Sor OHO -electron bond corresponds Asathree-clectron bond corresponds to a hal bond, To remains 2, or [1 +(2 x 1/2)), al number of bonds between two. ‘oxygen of Tis structure accounts forthe presence of two unpaie ton hence the molecule of oxygen is paramagnetin "OMS One from each three-IN=0: The molecule can thus be assigned the following structure consisting of a double bond and N + 0: the er of the two structures I and Il, Thus faith #iiteeclectron bond, This structure is more stable than either ofthe two structures 1 and Tl, Thu ted! molecule is described as having 2 bond. It is expected to show bond length between that for a ve vt a tracti®’ double and a triple bond. The experimental value for bond length for NO is 115 pm, somewhat larger Ject™® than the triple bond value of 106 pm for NO i sned the following resonance structures, . (i) Nitrogen dioxide (NO,). It may be assigned th lowing n J jy, a> it fs i 118 pm which agrees well with the experimentally The NO bond distance was predicted to be Attemmined value of 119 pm by infrared spectroscopy nergy is defined as the energy needed of bond rupture ina molecule cule which is identical with fhe bond dissociation enerey ts atoms A & B. The process re cergy of a diatomic Mole 4 315 Bond Energy uel For a diatomic molecule, say AB: ! e (Gbsorbed) to break the molecule AB into i th "Sealled dissociation. Therefore, the bomlues of dissociation energy (F, inanenception As ied, the diatomic alkali metals have low values and hy‘ of dissociation energy. There iy no trend along a period, the dissociation eneray decreases as bond order decreases. In oth les, the bond dissociation energy decreases as bond length ae Bong peseigy OFF, is exceptionally low because of high repulsion between the non-l nding See Mena Hcaine ators (other halogens have longer bonds), issociation energy and bond energy terms are not identicy For polyatomic the bond Bseaitis ced caonroccte Bond dissociation energy (D) of a polyatomic molecule AB asthe energy required to break just one bond to form atom B and a group of atoms (radia, AB, _, Bond dissociation energies fora given bond are different for different structural and electron. "arrangements in the radical, - Although the bond dissociation energy of a given bond is not independent of the environments Butte variation is not very large. The bond dissociation energies may not change significantly wit Shange in environments around a given bond. Thus, it should be possible to characterise a bond by @n average bond energy (E) which is defined as the approximate energy required for breaking of the ond inany gaseous molecule, It does not include energies necessary for vaporization ot sublimation | ‘The distinction between bond dissociation energy (D) and average bond energy (E) shall beclest | The carbon in this Hom the following examples showing stepwise dissociation of saseous wate, sshybrid bonds. HLO@)—>H(@)+OH(~) —_D, (HOH) = 500K) Different types of 0G) 0,020) = ana ( sp type ame average bond energy (E) for 0-H bond isthe mean of the two separate bond dissociation | (ii) sp type energies (D, +D,)/2., that is, (500 +424)/2 — 462 KJ. The enthalpy change for the for mation of water ©) sp or &sp' molecule by the reaction is -926 kJ mol-! S21 sp hybridiz 2H (g) +0 @)—> H,0 (¢) fuoride ~ {tis negative because heats evolved in the formation of gaseous water. As expected, it is almost ‘twice the aoe. (E ~ 462) for an O-H bond and hence in close agreement with the | x ted to next ay 1 Presence of two O-H bonds in 1,0. However. the average bond energy (E) is quite different from | ju. wit avails the bond dissociation energy D, or D,. is ; Pd state ig 12 2 Example. The bond energy. OfLi, (113 kJ mol) is tess than that of H, (431 kJ mot ) though ) : : Eketronic configy both contain a c-bond, Solution. The bond enerey of a bond depends upon the bond len, th. Greater the bond length, trator Pond enerey-Li—Libondislargerthan t_ihors Heicehindaneagaetna that of nnd energy of Lip is smaller thanBONDING a pee ane ht henge ae at me raed tt frat The pom wanmen ich eh a ‘The equivalence of four bo ds can be explained by assuming U the 2v and three 2p orbitals are inte orbitals whieh orbitals t0 give equal number of symmetrically the available orbitals of carbon, 4 manner as to result in four equivalent 18 of regular tetrahedron, This mixing of atomic oriented orbitals of equal energy is referred to as OF the efi B¢ Significany aracteriseanes | for breaking ion or SUblimay BY (E) shall bed Fig. 3.4. Structure of metbane The carbon in this case is said to be sp? hybridized and carbon hyd as hybrid bonds, sn bonds are referred to Different types of hybridization are (sp type (ii) sp type bond dissociat (ii) sptype (iv) spd type ormation of (0) sp°d° or dsp" type (vi) sp? & type 3.2.1 sp hybridization or diagonal hybridization and the shape of beryllium fluoride Electronic configuration of beryllium in ground state is 1s? 2s*. One of the 2s electron: Promoted to next available empty orbital (ie., 2p,) and therefore electronic configuration of beryllium ected, it is alm reement with : mit fit i Excited state is 192, 25! te dif Is J mot!) thot i fy £ |] Berytum atom inground state ne bond lense 3 ‘ : , is smaller fi) ff TLL] motiumaom in excited sat fale beseech sp hybridisation fh] (i TT aslo From F atoms fel Now tnere are two half-filled orbitals, each having single unpaired electron, But they belong to iodifferent orbitals. One belongs tos and the other two p-orbital Theatr i set val Dons y 4 p fc ew & ler vitals whicl q 8€ 1Wo orbitals hybridise or get mixed up to form two new equivalent orbitals each o halts and half p character. i sella ital is ©ig. 3.5. sp hybridisation, : Rese 840 hybridized orbitals overlap separately with the p-orbitals of fluorine to form Be-F bonds, Sha ted as shown in Fig. 3.6. There are two bongs pe of BeF, molecule can be represente: Boro! ge copa Bonding ¢ X=Hor! f Fig. 3.6. Pictorial representation of BeF, Shape o! ; Shape lectron pairs. Therefore molecule is linear ‘with two orbitals at an angle of 180° to each CC 32.2. sp* hybridization or trigonal hybridization and the shape of BF, “an inshape. Electronic configuration of boron in ground state is 1s? 2s? 2p! One of the two 2s electrons Bets Promoted to next available vacant orbital (p,) The electronic configuration of boron in the exci Slates Is?2s! 2p! 2p! 2p. Configuration ofB atom in 8round state 2s 2p ; Configuration of B atom in excited state [4] ce Sp hybridisation my HW sia From F atoms the z Now there are three haltfilleg o1 different orbitals, To rbitals each having odd unpi be eo i . But they to equivalent : wired electrons. But they belong hybridised orbitals. In the abo 3 is / hy, ets eth « three orbitals hybridize to form thren ew equivatent | Shay, RY ‘ ization i eo WO orbitals net Ived to form three hybridised St orbitals. This type of hybridization therefore, known 357° yb iit ideation Boron forms sp? hybridised on, ‘idization or trigonal hybridization, | vt, Noomy Three sp? hybrid orbitals beng Fig. 3.7. Orientation of sp? hybrid orbitals Boron atom has now three sp” hybridised orbitals each having an odd unpaired electron. They are capable of forming three bonds by overlapping with, three half-filled orbitals of other atoms Bonding capacity of boron, therefore, is three. Boron forms compounds of type X — BO where X=HorCl ps Shape of BF, Shape of BF, molecule can be represented as shown in Fig, 3.8. There are three bonded electron pairs. The three bonds are equivalent and 120° apart. The molecule is, therefore, triangular and planar ect is shape er. lectra: F oe ‘a exci Fig. 3.8. Shape of BF, Exar i F, is triangular in shape while BeP, is linear, Seater, tnBers ee Tae hybridized. The sp hybrid orbitals are linearly oriented, That I 5 Suh the molecule of BeF,, is linear. InBeF., B atom is sp? hybridized. The sp’ f thecomers of a triangle. That is why the shape of BF ott) “Me ot Stannous chloride Molecule (SC1) ; i a is chloride i SV pete ey Jp santo electrons in the 5s orbital and two electrons in p-orbitals it Pilipae in isi an Ps Py noted that an orbital with pire eletrons ean participate in ridisation. etal a oft Whridsstion bot not in bond formation. Thus it is a case of sp” hybridisation, fc \d formation with two -most shell of tin are used for bon Fe gSHCl ope Se nn Tose edhe ‘ chlorine, while one electro! ‘ fe itis expected to be trigonal planar | « According to its hybridisation i r Tsp in ands na A ra dan Tce oe hybrid orbitals are oriented at an angle of 120° towards triangular. he tin (Sn) atom has electronic configuration,Fig, 39, Formation of stannous chlori 3.2.3 sp" hybridisation or tetrahedral hybridisation J When one s orbital and three p orbitals combine together to produce equivalent type of orbi ‘p* hybridisation takes place. Four sp® hybridised orbitals are produced which have the same: and shape and are oriented at an angle of 109°28" to one another. This is also. known as tetrahedry hybridisation because the hybridised orbitals are oriented towards the four corners of tetrahedr, with the nucleus occupying the centre of tetrahedron. In this position, hybridised orbitals experieng. minimum repulsive forces. This is illustrated in Fig. 3.10. pt ie eel od CS : ge Greate 2s 2p, 2w, 2p: inthe norm sp" hybridization Val Valenc oon VSEPR th scometries between th Four sp" hybrid orbitals Was propo: Fig. 3.10. sp* hybridisation the final st ‘this theo thenumber Hons, The fom one g Shape of methane molecule Atno. of carbon =6 Electronic conti 2 iguration of C in ground state = 1s? 2s? 2p 2p! 2p 2p}, 2p) Fig. 3.11. Shape of methane molecule.the ake place along the intemuciee te the Ls orbital yr Z HCH is 109° 28", clear axes. Hence four e of four hydrogen atoms. All these srbon-hydrogen o bondsare formed. Re inlay the molecule is ofthe type AB, withyp? hypeny tne < BAB eaual to 140°, : fleand three B at hybri jateral traingle a © B atoms occupy the y He AB, With p* hybridisation taking place the atoms A ge ee however the molecule : i 01 Bred big lof evahedron being occupied by B. This is bared cups the centre of tetaheal and enegelf H4, other due to similar charge and occupy yon tact that the hybridised orbitals TRY) pel €2 PY Positions in which there are minimum repulsive HS Lone pair of electrons. Another factor which d gfelectrons on the central atom, Certain elem fro detons on them which repel the share aoe ite nitrogen and oxygen contain lone pair or air of electron away from them. In such a case Iundangle changes from expected angle, Repulsion between the electrons isin the following order: Jone par, lone pair > lone pair, shared pair > shared pair, shared pair. Repulsion between the two lone pairs is maximum followed by that between a lone pair and a und pair followed by the repulsion between two shared paits of electrons. Greater the number of lone pairs of electrons on the central atom, greater is the distortion produced: jattenormal angle or shape. 425 Valence Shell Electron Pair Repulsion (VSEPR) Theory Valence shell electron pair repulsion theory (in short VSFPR theory) is the simplest theory for predicting the fpineties of molecules. It is based on the repulsive interactions Fetveen the electron pairs in the valence shell. This theory tis proposed by Sidgwick and Powell in 1940 and given th final shape by Gillespie and Nyholm (1957), According Ibis theory, the shapes of molecules can be determined by etumber of electron pairs in the valence shell of the central Hons These electron pairs experience electrostatic repulsions one another and the bonded atoms in a molecule adopt Nevil Sidgwick (1873-1952) Piticular arrangement in space around the central atom _ Nev Hovis RS wt Michkceps them on the average as far apart as possible ES See ig . 1 first yn if in poi i he theory of valency and chemical Main prints ‘of Valence Shell Electron Pair Repulsion Theory (VSEPR) the theory oa iemain points of VSEPR theory are as follows: iF i er Geometry of molecule depends upon te total mamber of valence shell electron Pars (bonded (aLotded) around the central atom in the colle clr sng sg) Repulsion between valence shell electron par SS a a aa electron-electron repulsion or to acquire @ ee lence shell i ‘as far apart as possible, Deteeponderenl electron pairs keep as ossible for a given number of Ft hh J arrangement is P ase more than one geometrical toes dance with the followin sin accordane ; ed pairs, then the most stable arrangement I "1" bond pair (ip-bp) repulsion which hat “Oe pair-lone pair (ip-ip) repulsion is greater LY ‘That is is bp) repulsion. Steater than bond pair-bond pait (DP: ae > ibp-bps it! (Four bond pairs) (Two bond pairs and two ‘Thus 4 Tone paits) a ape Thus, in methane, there are four pairs around carbon, while oxygen in red pis ne s fe n0. and two Tone pairs around it. According to VSEPR theory, it is the total num! Z Bipctror (Gonded as well as lone pairs) that determines the geometry of molecule. ee Regular and irregular geometries jn the 2 The moleciles in which the central atom is surrounded only by similar bonded electron Pairs form the bor have regular geometries while those in which the central atom is surrounded by bond pairs as well a sfisatior as lone pairs have irregular geometries. positions on 8 ore, have rezntar geometries because the cental amt these molecules are bonded to Molecules such as CHCl, and the molecules such as NH, Electronic confi Het, there i oiter two hy similar atoms and there are no lone pairs in these molecules. Be a5 2» CHCI, etc., in which the central atom is bonded to different atoms This is Bet and HO whieh have lone pairs as well as bond pairs, have irregular Teeny), Th Buration of nitrogen, 1s? 2s? 2p! 2, P|, 2ps ; level as there is no ¢, IS NO possibility of shifti from 2s level to 2p level as ‘mpty orbital 2¢ orb ty Of shifting of electron from A x bond or forming the bong , although i I ing or forming the bor ‘ Pond, is ion. This wil tie a hye shape. Hybridised orbitals are orienteg87 comers of a tetrahedron with one corner occupied by the lone pair of electrons from 2s esp? hybridived orbitals ‘overlap with the 1y orbitals of three hydrogen atoms (Fig. 3.12.). tan angle of 109° 28" between H— NH in tetrahedral geometry, Actually this angle contraction in angle takes place because the lone pair of electrons repels the shared pair jeotrons or bonded pair of electrons with a greater force (Fig. 3.12.) thereby reducing the angle. {Valence Shell Electron Pair Repulsion, VSEPR Theory), Lone pair Lone pair of electrons or simply S i, > ui if Bond pairs Fig, Thus it has pyramidal shape 12. Shape of ammonia molecule, Ond TOn pg Shape of water molecule ? At.no. of oxygen = 8 Electronic configuration = Is? 2s? 2p? 2p!, p! On Pa In the 2nd orbit there are four orbitals : 2s, 2p, 2p, and 2p,. Out of these 2s and 2p, cannot Sasi formthe bonds as they are paired. But they can participate in hybridisation. Hence it is case of sp" hybridisation. The hybridised orbitals are oriented along the comers of a tetrahedron. Two of the positions on the tetrahedron are occupied by lone pair of electrons from 2s and 2p, orbitals. The ato " ‘other two hybridised orbitals will overlap with the Is orbital of two hydrogen atoms to form a water ato molecule as shown in Fig. 3.13. We expect an angle of 109°28" in HOH. Actually the angle is 105 regiy _ Tisis due to stronger repulsion of two lone pair of electrons with shared pair of electrons (VSEPR Theory). Thus water is a V-shaped molecule. Lone btaint pairs Lone pair of electrons a Sow e m, Th Seen ble 7 Bond pairs Fig. 3:13. Shape of water molecule Structure of hydronium ion [H,0]” ous Inthe formation of hydrogen ion, coordinate, bond is involved. Here, oxygen stom in the water molecule is the donour while hydrogen ion is the acceptor. The formation of coordinate bond in H,0' may be represented as below pointing from the donor to the acceptor, as shown below in the soit mation of hydronium ion hat the coordinate covalent bond once formed is indistinguishable from important to note t covalent bond, SSFig. 414, Formation of hydronium ion. c r main tetrahedral because the : noted + of 1,0)" will continue to remain tetrahedral t iets co The Uirtence between H,O and H,0" is: while in H,0, two eee ae sermied by fone pis of electons itis only one tetrahedral position tha are ‘is occupied by loans pair of electrons in H,0". 3.2.6 dsp? square planar hybridisation nes This type of hybridisation takes place when one s, spape of two p (p, p,) and one d (d.2_,2) orbitals mix together fee to give four equivalent hybrid orbitals, These four hybrid configura orbitals keep their lobes directed towards the corners of asquare in the XY plane, ic. these hybrid orbitals point —_| away from the origin in the + and ¥ direction of X_/°—“"--J-=— and Y axes. The angle of maximum repulsion between their orbitals is 90° as shown in Fig. 3.15. Fig. 3.15. dsp? hybridisation. Shape of [Ni(CN),>- Pairing of single electrons in 3d orbitals in Ni?* takes place thereby creating one vacant 3d orbital. Electron pairs from four CN” ions are filled up in four hybrid orbitals obtained as a hybridisation as shown in Fig. 3.16. Delos areata Outer electronic configuration 2 a cu ofNiatom (3d°4s')in ground [HINT Tt Tt] [ty Electronic confi Ni* : Hestopeconiguration of" THT TTT atte Electronic confi Ni = Pe TH m 5 br Sul B bond. It may be noted that in BE, ion, boron ang completes its octet. Thus, the geometry of BF'-ion we iengnnny ; ‘ F, fon is tetrahedral ssshownin Fig 28. 4 rahedral pig, 3.28, Shape on BFP We Shape of PF,” ion ‘The phosphorus atom is the central atom epts . ‘4 phosphorus hexafluoride ion. The outer electronic czfgution of phosphomss (2 = 15) 3? pn order to form six bonds around phosphorus, we need six hybrid orbitals. This can be achieved by promoting the 3s electrons to the vacant higher energy 3d orbital followed by combination of one 3s, three 3p a eR ucere @ 3s, three 3p and two 3d orbitals to obtain six r site ace Nite - [efipeation of (Ground State) tt TRAE Configuration of P tT] 7 I (Gacited Stat) tt] [t sp° d” hybridisation PE; fh) EERE tht tet From F ion From F atoms The six spe? orbitals are directed towards the six comers ofan octahedron. Five of the sp'c-hybridised orbitals are half- filled while the sixth hybrid orbital is vacant. The half-filled hybrid orbitals overlap with the five 2p orbital of fluorine atoms toform five P—F bonds. The vacant sp’ hybrid orbital accepts pair of electrons from the fluoride ion, F and forms a dative F—+P bond. The geometry of PF, ion is octahedral as shown, in Fig. 3.29. Fig. 3.28, Shape on PF, ion Shape of SnCI2~ ion Snisthe central atom in SnC1- . The outer electronic configuration of tin (Z=50) Spl Spl n, there must be six hybrid orbitals. This can be achieved ‘inorder to form six bonds arounds tin atom 2 1 by promoting the 5s electrons into higher energy vacant Sp orbitals followed by combining the one 3 hybrid orbitals as shown below 58, three Sp and two Sd orbitals to give rise to six sp” Sp. 3d 5s Outer configuration of Sn tit pe ay ti) Outer configuration of Sn ca fietiate ah Be Sa 7) (eel) (oe i T From 2Cl ions Formation of SnCl,_ From 4 Cl atomspovbital of chlorine ator ofr Four Or spi ~ orbitals accept two pairs of ‘ons and form a pair ofdative “C1 ‘has a regular octahedral 180° ‘Tetrahedral geometry Diagonal molecular geometry ‘Trgonal planar geometry pe) As in CH,, BeF; (sp) Asin BF,(sp") ey | 2 Octahedral geometry ‘Trigonal bipyramidal geometry _ Pentagonal bipyramidal geometry fom molecular « Pn3) } v,andy,repres Asin SF, (d?5p") Asin PE,Gp") As in IE (sp) en SOLVED EXAMPLES tterefore, they c: volume @ Example I: Molecules CH, NH. they possess different geometry. Solution: One of the tetrahedral positions in NI ani, 0 vole the same kind of sp? hybridisation, yet SEE volume 2 sis occupied by lone pair of electrons. Similarly | “4lto the sun in the ease of water two positions are occupied by lone pair of electron Beleular orbit The epulsion between lone pai-bond pairis greater than that boty, Asa result Z HINH is decreased to 107°, There are sll yrenter the Z HOH is further decreased to 105° Example 2. Expla Solution: en bond pair and bond pair. ave function ¢ ?Pulsion in the case of water. Here 2 Crand C2 J} “owest ener case w, ig ne tiles Hetce lone pairs more aotive and mobile ineausing Wt _ i fe pair is more active ile in causing Coeff es fepulsion with other orbitals. Asa result, p-p repulsion is greater than Jp-bp repulsion which in turn fae is greater than bp-bp repulsion, that cas, 3. Givi ; Pxample 3. Giving reason pees ihe following molecules in order of inereasing bond angle. 0, NH, qT here win H,0 Overlap region ” of bonding and antibonding MO’s by ; atomic orbitals, 3.3.4 Formation of 1 orl Molecular orbitals which are i : obtaine, la i Overlaps containing th i strated by showing overlap of 2P, at0Mmic orbitals, antibonding MO te oe “leebraic signs yield bonding MO and those of opposite sign et bitalp by the lateral overlap of patoRmleoreltasni erlapy, ig: 3.37. Diagram showing the formation ‘of bonding and antibonding MO's Ping» by the overlap of 2p, atomic orbital, com rr ina ule orbital has (+) lobe above the z-axis and (- lobe below the pads, The edin ag, My Beans mints signs refer to the sign of wave function in the various lobes and not to nuclear or Sag) estan charges, The (+ve) sign (or upward direction) represenis one phase and Coe sign (or downvard direction) represents second phase of wave function. If we rotate this MO through 180° letanees sign (Fig. 3.38). A molecular orbital which is antisymmetric about the molecules axe ealleda x (pi) molecular orbital. The antibonding MO is also a 7 type M.O. They are labelled as = and 1, orbitals. The two 2p, atomic orbitals will overlap in a similar fashion to give mand ,. Both x, and ‘symoleoular orbitals are equivalent and have the same energy. These orbitals are said to be degenerate, ie, orbitals with same energy. das O36 ed aN eee) is designated rotation _—_— ilar axisanl ce s . Signs ofthe lobes are changed 3.38. Rotation of bonding MO. =F 435 Comparison of electron overlap in o and x molecular orbitals Inac-overlap, the overlap region is much greater than in a x—overlap. The difference arises tse in a c-overlap, two orbitals involve head-on overlap whereas in a n-overlap, the two fulti overlap laterally (or sideways) as shown in diagram (Fig, 3.39). Itis assumed that axis is ‘molecular axis, > es overlap Fig, 3.39. Comparison of «and t-overaps,Bi Plectron charge density £5 +p, and p, + p, will result in positive overlap, Variation of electronic charge with internuclear distance the molecular orbital wave functions Way, and W" yo, We can deter in the molecule. conbitals oftwoatomsa ‘Writing the wave functions of molecular orbitals in terms of those of Is atomic oF and. distribution of ‘Taking squares of both sides of the above equations Wino=[Vi,, Mig $2Vi, Vary) Bondit with the sa Viro =1V;,, +YVin, ~ Visa Yisg] tis observed that the bonding MO functions shows an increase in the electron charge density inthe overlap region by an amount 2), W;,, over that ofthe individual atoms as described by the functions v5, and v;,, 337 Rules for fill Thefilling of electre {) Electrons enter wilfist enter the lowest ‘This is represented graphically in Fig. 3.40. The dotted lines represent the charge densities of Andividual atoms and heavy lines represent the electron density for bonding MO. (@ Each molecular ‘este direction in acc t) In agreement wi BBY molecular o “to remain unpaire () Ele ®Raly reso wom? Electron charge density Ry 8 En i Intemnuclear Reo listance Fg 3 etey Je Bi, Fig, 340, Graph of electron density vs, distance results oO e ecient i in decrease in the charge density in the tia ype of a SAMO Yi, Vig. Thisis represented in Fig. 3.41. Itis also clear that bonding “oe! 2re ie ‘electron density ac ij Mirae ay la Brito decree Sensity a itis concentrated between the nuclel, whereas the antibonding Mo Mn p ‘density between the nuclei and concentrate itin regions on the indivigyg)Stribyy tig, ftwo, ge densis bed by 337 Rules for filling of electrons in molecular orbitals The filling of electrons in different molecular orbitals is done according to following rul nsities# _ Willfirst enter the lowest energy molecular orbital (Aufbau Principle). elem ectron charge density Fig. Electron density maps for bonding and antibonding ( Bonding MO (A's combined withthe same sign) Fi [pens stance 41. Graph of electron density vs. interme! oh, ne (9 Electrons enter molecular orbitals in the order of their increasi ar density and 6}, )MO’s are shown in Fig. 3.42. Antibonding MO (AO's combined with the opposite sign) 42, Flectron density map of Jj, and Gj, MO's 101 nergies, ie, the electron (i) Each molecular orbital can accommodate a maximum of to electrons with their spins in posite direction in accordance with Pauli’s exclusion principle, (iii) In agreement with Hund’s rule whenever two qual energy molecular orbitals are available, electrons prefer to remain unpaired, ((») Electrons (equal to the sum of the electrons Actually present in combining atoms) are placed one ttime into molecular orbital to obtain the electronic Configuration of the molecule. 438 Energy level diagram of molecular orbitals __ Energy level diagram of MO’s is shown in Fie. 3.43. Ih this type of diagram the combining ls are shown on two extremes and the r Molecular orbitals are represented in the middle limn. Atomic orbitals of same energy are shown at thesame level, The difference between the energies Blomic orbitals and the bonding ‘MO’s depend prea witen of overlap of atomic orbitals. A large over At a il result in greater lowering of bonding MC ene Srtesponding lange raise in the antibonding atomic esulting, Increasing energy Atomic sts Fig. 3.43. £1 Molecular bial ergy level diagram. Atom orbitalssand N. Here 282 ly to lighter elements like Bs Soe tee . , yen, The sequence in SUC ease W- IthenuniberoFeleetons in bonding MOSS areaerthanthe number ofslearms | MT ject On" in antibonding MO's then the motecule would be stable Borg 1s? 25 (NP =H? Ifthe numberof electrons in bonding ‘Mo's ae equal to the number of electrons is Oe four one picand it doesnot exist This is beoanse an elect i con in antibonding MO, then the molecule in am antibonding MO cancels out the stability gained © n th ber of covalent bon Bond order. It is defined as the numt Wy electron in the bonding MO dds present in a molecule. Iti} sjecttons als, do not inf The other fou moiated. Two of bonding molecula into o*2s antibs aFigure 3.45, Number of electrons in] number of electrons in antibonding MO's bonding MOS Bond order=4 calculated as Information conveyed by bond order (@ The mumber gives nature of @ bor Gi When the bond order comes ont to be 2er0 (ie., when the m sibonding MO’s), then the mol ., as bond order increases, bond J tewriten as vid whether it isa single, double or a triple bond umber of electrons in bonding sale does not exist ee Mo's is equal to the number of electrons in ant (iii) Bond order is inversely proportional to bond length, Jength decreases. (i) Fordiatomic molecules, bond dissociation ener () fall electrons in bonding and antibonding molecular orbitals are paired, the! diamagnetic. On the other hand, if there are unpaired electrons (or electrons), {mol are singly occupied, then the molecule is paramagnetic, mS 2y is directly proportional to the bond ode n the moleculeis lecular orbitals Bond order 3.3.10 Molecular energy level diagram for hydr olecule (H. Thebond Se, Pe ydrogen moll Hy) 33, is drogen moleculeis formed by the overtap of 1s atomic orbitals: I'shall ave two molecu SA ‘orbitals, one bonding (Gf, ) and the other antibonding ©, ). The H, molecule nce with Paul exlsion principle is shown in Fig, 3.44 has vo electrons and these can be accomm. inthe of, iodated in the Of, molecular orbital, In accord th ese electrons must have opposite spins, The energy level diagram of Ha ip 22-0) * lrie,, ont Th : round sat of H, is represented af, andthe bond ome is 77pm. o-bond. ati Bond dissociation energy in H, is 431.4 kl/mole and bond 1enzt®“COVALENT BONDING dN, Hey Case jd, 2 = B antip, = Ong = 7 D °d in the Pier cules 1 nil SS frome Atomic Molecular Atomic MS mole orbital orbitals, orbital % Fig. 344, Energy level diagram of Hy, o F Fela yfolecular energy level diagram for Be, ie The electronic configuration of beryllium (Z = a eS 4) atom is 15° 252. Number of electrons per beryl. s an elew jum atom are four and therefore, there are a total of eight electrons in the beryllium molecule to be polecule:lf accomodated in the molecular orbitals. Four of theelectrons that fill the 1s and o* 1 molecular orbitals, do not infact contribute to bonding. ‘The other four electrons are now to be accom- modated. Two of these electrons will go into 62s ® - bonding molecular orbital while the other two will — ond. Bointo o*2s antibonding molecular orbital as shown Re fo i inFigure 3.45, as in bond ig Fig. 3.45. Molecular orbital energy level .¢notei® The molecular orbital electronic configuration can clu, ba ses, HE WTitlen as rea: 4 Be, : KK (02s)? (8 2s)? » bond f 1 , molectl Bond order 7e-2)=0 a molecule does not exist The bond order is zero. Therefore stable Be ti pie +) 43.11 Energy level diagram for the feria SEN molecu Ht + configuration 1s?, 252, 2p%. We shall not take into account the “i ecular orbitals. ome, leetrons in c,, and o*,, molecular or teal ing ct TheN, motecute is well known, Its molecular orbital configuration may be writen as (KK. (93, i % fi « K shells ofthe combining atoms are full, Not taking EE ae ee cr aenmunteipet imi paras as eight electrons in bonding and two elec b le mr acOunt 6; and.o”,, orbitals, it has cae ding orbitals so the bond order in Ny is three, sa tals: Since there are six electrons et rformity with is Very high bond energy of 940 kl) Themolecule has 1c and 2x. bonds. Th Berrys aoe ban lngth of 110 pm. The energy level dagmum aban itty Very shor miIncreasing energy Is Atomic orbitals Fig 346, Molecular orbial energy level diagram of hypot thetical N, molecule, Nyion N."ion has one election less than N,. Its molecular orbital conti BRK (05,)*03,)*Cnb)?(n8)?(0%)!) iguration may be written as Thus the ion N3 is weaker than the molecule of N, for oxygen molecule (0,) a show PS O8¥EeN has electronic 7 20". The O, molecule is well known and The ves Patamagnetism (Fig, 3.47) “quivalent to that of tivo, “apaited electrons. The molecule has g the following configuration, Bey OPA ya ry, {Bond order ~ 36-14 5 lectrons in the nee bond theory had taitey ro Xe a tot, M ‘otal OPENS OE & aU ng iy, ular C3Is lecule, ay be writtens: nding orbitals Increasing energy Is Is Atomic orbitals Molecular orbitals Atomic orbitals Fig, 3.47. Molecular orbital energy level diagram of O,. 0} ion There are 12 ~ | = 11 electrons to be filled in the LL shells. 1 The bond order is= 1/2 (8 ~3)= 25 . Ths it has a stronger bond compared to oxygen. OF is Parumagnetic. The 03 jon will have the configuration: [KK(08,)? (oi? Co? CHE CP ORY °% ion ‘trons to be filled, Out of this, four electrons are filled in The x =I Tele ee tele x84) to be filled in LL molecular orbital, O} ion Molecular orbital. Thus 17 ~ 4 = 13 electrons are al f configuration a5 saan l4Ve molecular orbital ut Cota? (BY (a8 ERED2 ion will have ’ total of 14 electrons to be filed in LL molecular orbital oO; I ‘configuration as: Fay EKO, (5p) (OBE CBI CH PHP? Bond order= 418-6) Bond order in 0} is 1, itis therefore less stable than ©; and O,, SOLVED EXAMPLES Example 1. How does the MO theory account for the following? (@ Bond order in O} is more than in O, while. (Gi) Bond order in N; is less than in N, molecule. ‘Solution. (i) In 3, there are 11 valence electrons to be filled. The outer shell molecular orbital configuration is F . ; (a)? (525)? (Gaya)? (ays)® (apy)? (apn)! Bond order = $6-3=2 3 In O,, there are 12 valence electrons to be filled. The outer shells MO confi \guration is 2)" (35) (2p) ape) (apy) Cia)! (i) In Ni, there are 9 valence electrons to be filled. The Configuration is FR (62), )" (2 p.)* (tap)! 1 : Bond order= = (7-2) =2,5 TON, there are 10 electrons tobe filed The \¢ configuration is KK ,,)°(65, YO) ay) (Ory? 5 Bondorier= 4 (2). 5 N, does not con ‘wounpaired electr« () Bond orderoft 107 . higher th; ms Ascording to MO theory inthe cate of Ns noi heap: No.of electrons in bonding MO = g i ‘No.of electrons in antibonding Mo = > 1 Bond order > (8-2) =3 Incase of O, molecule No. of electrons in bonding MO = No. of electrons in antibonding MO = 4 1 Bond order= > (8-4) =2 Greater the bond order, greater the bond energy, Example 3. On the basis of MO theory, explain why? @N; molecule is diamagnetic while O, is paramagnetic. (i Bond ordes Nz is lower than that in N,. Solution. (i) The MO configuration of 'N, and O, can be written as N,: KK (6,,)°(6° 20) Tap)” apy) (Cape)? O32 KK (63,)°(03,)°(G2pe)” Cape)” (Gap) pu)! (yy)! N, does not contain unpaired electron, it is diamagnetic. Oxy en is paramagnetic as it contains twounpaired electrons. (i) Bond order in N3= Bond order in N, = $3.13 Molecular orbital energy level diagram of Ne,. 2-252 2p, The number of valence electrons The electronic configuration of neon atom (Z= 10) is 1s? 2s? 2p®. The num| Pérneon atom is 8. Thus, a total of 16 electrons in the neon molecule have to be placed in the LL Tolecila orbitals as shown in Fig. 3.48 een onfiguration of neon molecule ean be written as The molecular orbital electro 2 (nt 2p,)? (8 2p)? Nes KK (62592 (625)? (@ 2p,)? (2p) 1," (* 27.) CR" 2PY (2 2P Bond order 1/2 x (8-8) = 0 molecule does not exist. Bond order value of zero in case of Ne, molecule suggests that the nS olecule. It may wore to oxygen al Jose to nitrogen MO energy lev! Molecular Atomic orbitals Atomic obits orbitals Raitt valenc Fig. 3.48. Molecular orbital energy level diagram of Ne, Son (3, (6 33.14 MO energy level diagram for CO molecule 2 Solution In CO, the oxygen atomic orbitals ae lower in energy than the carbon atomic orbitals spills because oxygen is more electronegative than carbon, The 2s and 2p orbitals of oxygen have Bond ord 8 8 8 poll ofa, of carbon, Encrzy levels of cievent MLO co chown inthe figure. Due to this difference, the 03, ‘ a ti lis Paramagnet co pis orbital is higher in energy than the 6, orbital(Fig. 3.49). Carbon monoxide Possesses 10 valence electrons and, therefore, has a valence configuration Painiested by lectron), SIH on. we “tion, NO: Ni Mtrosy ion, NC (03,)°(64,,)*¢xt-x’ (03,2 ‘There are three net : Mee ccutar bonding Pairs (one le and one x) describing the molecule, | Nos, : KK (8 ; €O* ion i CO" ion i obtained by the loss of one : Alek from, M0. of CO moisa se” j MO. electonic configuration of coy are may be written as Ne bon{T BONDING 409 (OB, ) (35)? (ay)? yy)? (G, i ay order of CO’ ion = i0- 2) | Weexpect the bond dissociation energy of CO! to be iding values of CO. In fact itis not so. Rather the k 'ot so. Rather the bond order increases when CO changes 1€0* This can be attributed to removal of electron from the antibonding molecular orbital keeping faview the energy levels of carbon and oxygen atoms 3345 MO electrons configuration for rei 2 pitrogen oxide (NO) molecule {Toh oh The electronic configurations of N and O are ; Nile 2s°2p* : Is? 2s? 2p* There are five electrons in the valence shell of N ‘gndsix electrons in the valence shell of O. Thus a total filelectrons are to be accommodated in the M.O. of NO molecule. It may be noted that the bonding M.O. are close 0 oxygen atom whereas antibonding orbitals age close to nitrogen atom, MO energy level diagram of NO is shown in lower and bond length to be greater than Fig350 NO (11 valence electrons) has an electron configuration (63,)°(08 (0? xt! omic orbit i Cx, oxygen Bond order in NO = = (8-3) =2.5 sms oti 9, are shit q Fig. 3.50. Molecular orbital energy level Itis paramagnetic with a sit @_Thisismanifested by its easy ox: of electron) e unpaired electron. lation to NO* (by loss diagram of NO Nitrosyl ion, NO* Nitrosyl ion, NO* can be obtained if' we remove one electron from the nitric oxide molecule, NO—> NO*+e The molecular electronic configuration of NOt can be obtained by removing one electron from nite oxide NOP: KK (08, )2 (5 ,)? (hx)? (Rony)? (Me Bond order = —>~ Bond order in NO* is 3 which represents one & and two n-bonds, Since the bond order of NO’ is greater than that present in NO molecule, its bond disso Sey Breater and bond length smaller than that of NO._ 2 - nergy is less « the bond order of NO=is less than that of NO’, its bond dissociation et ag gth greater than that of NO. ‘The electronic configurations of carbon and nitrogen “atoms are = © 1825? 29? ON 1282p | Therearea total 9 electrons (4 electrons from carbon ‘atom and five electrons from nitrogen) that have to be accommodated in the molecular orbitals of CN. The molecular orbital diagram for CN molecule is shown in Figure 3.51 and the molecular orbital electronic ‘configuration for CN molecule may be written as CN:KK (6,7 (6)? (ty, Cp) 2,0)! It may be noted from the molecular orbital energy evel diagram that since the electronegativity of nitrogen __ is more than that of carbon, the 2s and 2p orbitals of nitrogen are lower in energy than the corresponding 2s and 2p orbitals of carbon. Bond Order = cr id ae Atomic Molecular Atomic jon is formed when CN molecule gai orbital septal) orbital electron inthe 0, MO. mS ONS Fig. 3:51 Molecular orbital energy level 2 } 0 ion lecular orialeleczonic configuration of CN- ee’. Xn ee IT Mg KK (04, (0%, ener, a )*(O34) (tap)? (yy) (Sag? Re Sectronie Bond order = 36-2) =3 tl : P : ” M ae aegis bend oreris CN- ion is greater than in CN molecule, its expected that CN. yi te Pltouigy 22° 3 : ‘Bond sissociation energy and wll hve a smaller bond length. : eat Orbitz hn orb We. ton Is aga lS of Teg Migin (Hion-bonding) because they en and 2pe orbital of fluorine. result from the combination of 1s orbital of hyo IG] The2p, and 2p, orbitals of tuorine yield no 7 pecause of their symmetry as they yi TERRY ig "-bording molecular orbitals atthe same energies ‘eld zero overlap wit h Ly orbital is obvious from Fig. 3.52 that atomic orbitals of elect ‘onegative fluorine are much lower in eseray than the 1s atomic orbital of hydrogen. M.O, electrons configuration of HF molecule may yy bewniten as ; KK(2s)* (6, (2px)? (apy)? MO diagram of hydrogen fluoride is shown in Fig, 3.52 H HF F ed 1 ‘om Bond order in HF = 1 ' “1 molecule eo 33.17 MO energy level diagram of HCI mo! chlorine atoms are The electronic configuration of hydrogen and chlorin H: Ist C1: 132252 2p6 352 3p* i a Molecular orbital energy ne cio afoaie o Se : pilpgen fluoride, The eneray of 3° and a ie orl a ratamic orbitals of the hydrogen atom TI asa very mmmetry and energy to interact Fite Isatomic orbital of H atom bees has proper sy pat “Satomic orbital. The 3p_ atomic orbital ie i ilar to that of chloride (Fig, 3.53) is simi drogen chlori ne atom is lower than that of ils of erie atom doesnot infer | of chlorine atomFig. 353. Molecular orbital encrBy evel diagram of HCI. SOLVED EXAMPLES Example 1.n the basis of MO theory, explain the magnetic characte 0 molecules. Aso give the bond order in each case. ~ Solution: (i) Molecular orbital configuration of N, is KK (0,)°(62,)° (rape) (pp) (Cape)? “As there is no unpaired electron, the molecule is diamagnetic 1 Bond oder = (1, ~n,) 1 5 B+2)=3 ‘orbital configuration of ©, is, KK (6,,)(05, )? 2) ,)*(02),)° (ap)? ayy)? ap ae lectrons, » the molecule is paramagnetic:'d electron 1 Bond order 7 B-a)<25 fp) Molecular orbital configuration of Cg is KK (2.)"pe)* (apg)? (ay (03,)2 Gs are no unpaired electrons, the molecule diamagnetic, Bond order = > (8-2) sear 2 Draw MO disgram for O%, 05 and OF yg Be the value of bond order in Mision. Moleculr orbital configuration of 02, Cs aut Oat written as under: KK (0,)°(63, (6, ©; :KK (63,)°(03,)°(o OK (2,)"(03,)7( Bondorder site I in 0; =— (8. in 0; =—(8-6)-1.0 Eunple 3. The bond energy of NO is 623 kJ/mol whereas that of NO* molecule ion is Mico Jus Man: NO KK (0,,)?(0. Bond order NO": KK (63,)?(6,)°(ar,)*(0, °C Bond order ree than NO, indenter NO’ justifies its higher bond energy ¢ paramagneth med, ie ‘molecular orbital configurations indicate p Keo He, nature of B, and in, He, (0,,)?(63,)? 222 Bond order = “5==0 z molecule. %° supports non-existence of heliump= KK (05,)2(05,)°(8)* (84) (n9) CH) CH)! 4 Bond order = = = 0$ :KK (of, )2(63,)*(02)2(08)? (4 °C)" _ 8-3 Bond order= = = 25 ’ bn" Unt)! 5 KK (0,)°(63,)" (62) (ee) Hy) () ; 8-5 ; Bond order = ror miss Because of decreasing bond order, the stability decreases as. 34 BOND Pz 3 > 0, > OF Covalent bonc gy, etc. These 3.3.18 Points of similarity and difference between valence-bond and molecular. ™paameters ar: orbital theory __ | Bond lengtt Points which are common to both theories: Trebond lengths ; (@) Both these theories are approximations. “ane are Very sr (Gi) Both interpret covalent bonds as orbitals embracing two atomic nuclei “etpicometers | (iii) Both require that the combining atomic orbitals should be of nearly equal energy : the? 1A .: should be capable of overlapping and the combining orbitals must have the same symmel (@) Both predict the concentration of electron density between the nuclei () Both can account for directed valency, (vi) Both predict the non-existence of helium molecule. Some points of difference between the two theories Valence bond theory Molecular orbital theory (@ Electrons in molecules are localized as if : It treats the nuclei of the molecule as they are in isolated atoms, polycentric and then construets one electron molecular orbital, (i) The total wave function in the valence bond treatment takes the contribution due to ionic terms. Molecular orbital theory overlapping. estimates the role of ionic terms in its {otal wave functions. 11 can easily explain the paramagnetism of ¢,. J(») Resonance is an integral part of valence | Resonance has no role in molecular orbital pond oy, theory. Ttis simple to apply, It is more difficult to apply. (i) eould not explain the paramagnetism of O,i : Hed an antibonding MO? The relative energies of TH, and Gi) are delettined by the energies of the atomic ‘ . from which they originate, The 6%, MO is ower in energy compared to the 2s atomic orbital s originated and is, therefore, calle, ‘da bonding orbital while the 61, MO is higher in dl rbital from which it originates and th © Brample 7. Draw a diagram showing the formation o cerita. Selation. Formation of c, bonding MO from atomic orbitals is shown in Fig 3.54 nucleus) hus called an antibonding MO. fa 6, bonding MO from atomic Fig. 3.54. Formation of o,, orbital 34 BOND PARAMETERS Covalent bonds are associated with certain characteristics like bond length, bond dissociation fap, etc. These characteristics help us to arrive at certain decisions regarding their reactivities. Tiepanmeters are discussed in some detail as under LBond length. It is defined as the distance between the centres of two bonded atoms ina molecule Thebond lengths are experimentally determined with the help of spectroscopic methods. The value s@hincare very small. It was expressed in Angstrom units (A) earlier. But S.. units encouraged the Eetipicometers (pm). The relation between the two units can be established as under: 1A = 108cm = 107°m 1pm = 10-? m where pm stands for picometer Tnsalength of 1 A would correspond to a length of 100 pm. Bond length is equal to the sum of the radii of atoms forming the bond. The radius of the hydrogen #0537 pm, therefore, the distance between the centers of the two hydrogen atoms in a hydrogen ale aS. 37 pm + 37 pm =74 pm se bond lengths items aus bonds are given in Table 3.1. It is important to note that the Mbl¢bond is shorter than the double bond, which in turn is shorter than a single bond, Table 3.1. Single and multiple bond lengths of some common bonds (pm) Bond length Bond length 154 74 234 92 244 280 (contd)Family increase With INE “Aperusal ofthe Table 3.1 reveals that the bond lenaths in a BiVeR I creases in the order {n atomic number. For example, the HX distance in the hydrogen ha! HOF Br— ite sizeof the second atom (other than H) increases in the ord!ofeteotrom® With 1s due to stronger repulsion of wo Fone Pale 8 ronal bipyrarnidal, *, Molecule involves dip? hybridisation and its shape is 180" ‘ion BEY, all the BF bonds are dative. sora) (028) 804 the ‘orbital electronic configuration for Be, can be written as KK bond onder is one. @ o raw the 3. enemy of the pure cov: Ds peach sr ae 7.10 kal ° cE ally A zero. S. one half 6.2.5 What do “& sp, octahedral 9, sp angular planar 6 i Discuss Bees b> b- bp > do bp write a short n Multiple choice questions 5) a 4 5. (d isa thre 1(@) 2@) 3d) 4d) _ a §, What is at 6 (0) 7. a. 0).(0) 8 (a) 9. (a) 5 9, (a) What do 3 True-False statements | cause of i 1, Tue 2. False 3. True 4, True 5. False t. @) Write sho 6. Tre 7. True 8, False 9. False 10. False Resonan¢ Shors Answer Questions sy i Give two 1. State three main points of valence bond theory. ’ H if 2 With the help ofa diagram, indicate various forces of attraction and repulsion is a molecule of ©). N,0 is lin | fs hydrogen. (ce), Why is C 4. List three necessary conditions for writing resonating structures 1, What is hydrog 4 White the resonating structure of (i) N,O and (ii) CO?> ion, sxample, i > Explain with the help ofa diagram how two p-orbitals overlap () endsto end and (ii) laterally tse valence bo Which bonds ae formed in the two cases M What is hy rial & Define hybridisation of orbitals, Name different kinds of hybridisation and the shapes of moh ecules obtained from such hybridisations. On thet P > the basis o 2 Name two factors that determine the shapes of molecules Briefly discuss one of them, a 8 Which type of hybridisation is involved inthe formation of a molecule of Xe F,? What isthe | 1 shape of this molecule ? EP NSON' ab Ob iF Discus, Discuss the 9. Bond enerey of N, molecule ‘shigher than that of ©,. Explain oy 3nd p snap e MO energy level cisgram af hydrogen tune Using vs General Questions D Oxep, «. 1 (@) What is valence bond theory of bonding? 1 senianta, °) Wh SF is bonding ina hydrogen mote nein How does valence bond theory account fo 0) HY is the (6) What do i ‘Ve the ) a othe following structure of hydrogen molecule signify: Pollo se DY awe Ik Ing p ; 2 Ve the various Fesonating structures for carbon monoxide molecule, Wh: at » (a) Menge oy cic egdaah Ls acs Suey the foie the wy lo p,°Wing ap, A '