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    Chapter 1 Inorganic

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    THEORIES OF CHEMICAL BONDING 2.1 Concept of Covalent Bond Formation: The formation of a covalent. bond is due to sharing of electrons, between atoms of 494-1, elements. In order to understand it, let us look at the H — H bond in the H molecule. As two hydrogen atoms come closer together, electrostatic interactions : FS ra Oz) begin to develop between them. The two positively charged nuclei repel each other and the two negativity charged electrons also repel each other. Each nucleus attracts both electrons Figure (2.1). There are four attractive forces. It ihe attractive forces (=3uSL A. uy are stronger than the repulsive forces, a covalent bond is formed. - In this way the two atoms join together and the two shared electrons occupy the region (Ueber ii) between the nuclei The shared electrons (: together into an H, molecule, zn 72) act as a kind of “glue (7) to bind the two nuclei o Nucleus 3 . Attraction Se Attraction 4—}—— Repulsion -—> atracion «> 3 Oo Nucletis oa H, Hy Fig, (2.4) Various interactions between two H atoms. \ There are four attractive forces and two repulsive. | Both nuclei are simultaneously attracted oe ‘Ut=huith) to the same electrons and are” therefore held together. * ‘The values of the various attractive and repulsive forces between nuclei and electrons ina covalent bond depend on, how close the atoms are. If the hydrogen atoms are too far apart, the attractive forces are small and no bond exists. If the hydrogen atoms are too close together, the repulsive interaction (V3 Jisé_/s5) between the nuclei becomes so strong that it pushes the atoms apart. There is an optimum distance (-6--t) between nuclei called the bond length where net attractive forces are maximized. (tst»45< m4). Here the H — H molecule. is most stable Fig. (2.2). In the H, molecule, the bond length is 74 pm. ‘On a graph of energy versus internuclear distance, the bond length corresponds to the minimum-energy (xf =( Sse Ure deer ps: This is the situation of most stable arangement : ‘ 59 60 ati ILMI Inorganic Chemi ergy (kJ/mol) —————> ———_ ex A = R > 0 74pm Internuclear distance (pm) > (H-H bond length) : - Fig. (2.2) Potential energy profile as a function of the distance between the nuclei of the hydrogen atoms, As the atoms approach each other (right side of graph), the energy decreases until the distarice reaches to bond distance and then begins to increase again due to repulsions. Theories of Chemical Bonding Various theories of chemical bonding have been put forward, They are being discussed ‘one by one. “2.2. Valence Bond Theory (VBT); Quantum Mechanical Treatment This theory was given by L. Pauling. The main points of valence bond theory are as follows. a Atoms retain (4,/'e) their individuality (<9) in the molecule. (il) The bond is formed due to the interaction of valence electrons as the atoms approach each other. The inner atomic orbits from each atom not forming the bond remain undisturbed (Ler) ILA), (il) ‘When atoms form a bond, only the orbital having valence electrons (si from each bonded atom lose their identity (=5¢2), (iv) The stability (1) of the bond is due to the fact that electrons forming the bond between two atoms undergo exchange (tz. /UxUsi) between them, Before going into the details of this theory, we should understand the concept of wave function of electron in an orbital of an atom. The wave functions of various orbitals, which have certain electrons in an atom have their mathematical expressions, These expressions are Obtained from’ solution 98 6dr Schrodinger wave equation for H-atom. The expression of Wy, is z @ > and Wo, IS. + i ‘wv zr ‘ q (Zz Zh ae . @) [: - zl 226, The wave functions of 1s and 2s are independent of @ and @. Angle 0 is called azimuthal angle and @ is called zenith angle, GL us Spbss) _ . . eorles of Chemical Bonding 61 eel co Erwin Rudolf Josef Alexand i 42 August 1887, Vienna, craiieen citizenship Austtia, reland nat Nationality Austrian Fields Physics i ; institutions University of Breslau, University ‘of Zirich, Humboldt University of Berlin, Univer Oxford, University of Graz, Dublin ote : Advanced Studies, Ghent University known for Schrédinger equation, Schvédinge’s cal, Schrédinger method, Schrédinger functional, ~S + Schrédinger group, Schrédinger pictu Erwin Schrodinger Schrddinger-Newton equations, Schrésinger field, Rayleigh-Schrddinger perturbation, ‘Schrédinger logics, Cat state ; ; Notable awards Nobel Prize in Physics (1833), Max Planck Medal (1937) Died 4 January 1964 (aged 73) Theorems of Valence Bond Theory: . There are two theorems on which VBT in based: ) cI, and Yi are the wave functions (GE 4) for two isolated independent atoms (L Auto sk), with energies E, and E,, respectively, then the total wave function w of the system can be writen as a product ofthe wave functions ofthe two atoms W=¥, Py ® and energy of the system by E=E,+E, (i) (i) Ifa system can be represented by a number cof wave functions such-as ‘#4, ‘Va, ‘Fs, then * the true (y-) wave function or actual (&) wave function, W can be obtained by taking a linear combination of all these wave functions. iy ‘ WP = (Cy + CoP2 # CPs Fd (i) where Nis the normalization constant and Cy, Cz, Cz. are the coefficients (en LoL 7) indicating the weight of each of the ,'s. They are So adjusted (A) 2s 10 give a state of lowest ~ energy. The squares of the coefficients Gh CG sone may be taken as a measure of the weights of each wave function to the total wave function. Keeping these theorems (24/7) in view, molecule from two H-atoms. . Formation of the Hydrogen Molecule : Now ‘let us apply the concept of valence bond theory (VBT) of the formation of hydrogen molecule from hydrogen atoms. For this we have to consider the various forces of attraction and repulsion which. may come. into play. When two hydrogen atom combine to make a covalent bond then amount of energy evolved in 431.4 kd mol". This is bond formation energy. This is the amount of energy lowered and is experimental value. i Now, we try to construct (tt) the wave functions of H, from two wave ms of H-atoms. The new wave functions are also called trial wave functions (22 2 LI LRP”). we are going to discuss the formation of Hy 62 ILMI Inorganic Chemi When two hydrogen atoms are infinitely apart (6 x ) then there is no interact, * between them ; ery, (iv) Let ‘7, and ‘Y, represent the ‘wave functions for two hydrogen atoms of Hy and 4, respectively. 4 Now, if we bring two H-atoms Close together, at a distance close enough for interaction, thy New wave function with wave function Ei. 4 . i Py Y, (1). (2) ) 1 The newly constructed wave function ¥, ', Of Hy molecule is represented in Fig (2.3), H, and are two hydrogen atoms and the electrons as 1 and 2. Pi (1) means that electron ‘1° Of atom means that electroh '2' of H, revolves around its own can be obtained from solution ; Ab Aierfiire . ery, Ce HSE hese i(tjor Schrodinger wave equation, The wave function, the Wave function of two atoms as given by equation (v). The energy of th Hydrogen atoms may be calculated, For this purpose we need internucl Schrodinger wave Equation. The form of. ‘Schrodinger wave equation use: first trial wave function (wiuset = Gs, 4g), is the combined system consisting of tho lear distance.r,, by applyi cd al Fig. (2.3) at this stage is SvHvae ! aes (i) ‘a EMEA Bcf Wut. Fle LU SF, A(hebL- H= Hamiltonian Operator (it involves Laplacian Operator V2. Please consult ‘Schrodinger Wave equation for this purpose) j c= Volume element of electronic cloud ‘ : eb Tei Me ture Fy 2S) ‘¥; = Resulting wave function Which we have constructed in equation (v). Here we have Constructed , in equation (v) : ’ . Do you know that! The celebrated Schrodinger wave equation in terms of Cartesian Co-ordinates is BY PY LY Br2m E ae Of art RR IE-Pyy =o E= Total energy of system P= Potential energy w= Wave function : %, ¥, 2 ate cartesian co-ordinates If we substitutes equation (v) for Y; energy lowering will be calculated by Here in Schrodinger wave equation (vi) then the value of Theories of Chemical Bonding eS S YAY, de ; Since ¥,='¥, (1) ¥, (2) S Ye of YN) YQ) AY,(1) (2) de e--—______"_" SP) YQP ae The energy changes as a function of distance /, may be shown graphically in Fig. (2.3) (curve |) It should be remembered that electrons ‘1’ and '2’ have not been allowed to exchange. They are satisfying their own nuclei even coming close to make a bond. (re SP pif ete ph SE seh ge se i(2)ol yA) So, wii A.curve showing only forces of repulsion, © Positive (Repulsion) «— Energy —> energy Obeys equation (VID) Obeys equation (XIII) Negative (Attraction) Obeys equation (XVII) “ — : © fe Internuclear distance, 74, > Fig. (2.3) Potential energy curves for hydrogen molecule, 2 Itis a’ convention (<- Ip-bp > bp-bp (b). _Repulsion between electron pairs at vertices (51x74) greater than 115° apa can be neglected. In the formation of a bond, the central atom shares its valence electrons with the surrounding atoms. Born 31 May 1838, Skipton, Yorkshire Era : 49th-century philosophy Region Western Philosophy School Utilitarianism Main interests Ethics, Politics Notable ideas Ethical Hedonism, paradox of hedonism Died 28 August 1900 (aged 62), Cambridge Henry Sidgwick Concept of Bond Angle: The bond angle is the angle formed by two surrounding atoms with the central atom at the vertex. Ideal angles are observed when all the bonds around a central atom are identical and are connected to the same type of atom. When ‘this is not the case, such as when multiple bonds, lone pairs, or different surrounding atoms are present, the bond angles deviate (ts 37’) from the ideal angles. 68 ILMI Inorganic Chemis We use the VSEPR model to explain the molecular shapes, bond angles and bong lengths. We observe them through various types of spectroscopy. VSEPR predictions are in accordance with our observations. 2.3.4. Molecular Shape with Two Electron Groups (Linear Arrangement): AX, Type Comounds. When two electron groups repel each other, they lie on opposite sides of the central atom in a straight line. The linear arrangement (qz7tefUL)) of electron groups results in a linear molecular shape and a bond angle of 180°. | seni he Molecular shape {all electron groups are burry in bonding) BeCl,: Gaseous beryllium chloride (BeCl,) is an example of a linear molecule (AX,). 180° Be co,: In carbon dioxide, the central carbon is surrounded by two double bonds: 180” Each double bond acts as a separate electron group and sta) ys 180° away from the other, so CO, is linear. Similarly CS,, HCN, BeF, etc, have linear structure. “ Remember that! of CO; or on the Cl atoms of BeCl; are not involved in the molecular. shape. Only the valence electron groups around the central atom influence :the molecular shapes. The lone pairs on the O atoms 2.3.2 Molecular Shapes with Three Electron Groups (Trigonal Planar Arrangement) (a) AX; Type Compounds: Three electron groups around the central atom repel each other. They lie at the comers of an equilateral triangle (qi is s¥L- 12). This is the trigonal planar arrangement, and the ideal bond angle is 120°. Trgonal planar TRIGONAL PLANAR AX; type Theories of Chemical Bonding : a 89 Examples are: S. aes o %o structure of BF3: When the three electron groups are bonding groups, the name of the molecular shape is also trigonal planar (v2 ut*Lidisu3 v2). Boron tituoride (BF,) has six electrons around the central B in ~ three single bonds to F atoms. The molecule is flat with all four atoms lying in a plane. : fF: b 120° Resonance in no? and co? lons: The nitrate (No,°) and carbonate (co®) are polyatomic ions, They have trigonal planar shapes. Each of them shows three resonance structures (.x YUP Lien Seer Shh). The resonance hybrid has three identical 4 bonds, so the ideal bond angle of 120° is observed: Look at three resonance structures of No,° jon, 9 9 0:6 & 3: ° DR Aa AN o= 9 OP C09 “UO (eu oEN= Out —OdUugate acd GHN - 0,7) Formaldehyde (HCHO): When the surrounding atoms or the electron groups are not identical, nonideal (x 2Ut.2) bond angles occur. Consider formaldehyde (CH,0). Its trigonal planar shape is due to two types of ‘surrounding atoms (O and H) and two types of electron groups (single and double bonds): The actual bond angles differ from the ideal ones. The reason is that the four electrons in the double bond repel the two electrons in each of the two single bonds more strongly than they repel each other. Four electrons of a double bond occupy more space. 70 _ ILMI Inorganic Chemistry 2 ST. _ lO OOO'= (b) _AX,E Type Compounds: - : Positions of atoms define a shape (er “Lav P), so when one ut the Hb oe bine is a lone pair represented by E in (AX,E), the molecule is bent (@)or V shaped. nts. thelone pair,” : = shape of gaseous (ut =e Su) tin (ll) chloride (SnCI,) has the three electron groups ina trigonal plane, with the lone pair at one of the triangle’s ‘comers. * Bent (V shaped) = ‘ Since a lone pair is held by only one nucleus, it'exerts a stronger repulsion than a bonding Pair. Thus, a lone pair repels bonding pairs more strongly than bonding pairs repel each other. This repulsion increases the angle (< Gsl-% wsli< 3 FL /@.) between lone pair and bonding pair, which decreases the angle between bonding pairs. Note the large decréase from the ideal 120° to 95° angle in SnCl,: Some other examples in this respect are as follows: 0. Pr Sn, mm ee TOO cecl men 2.3.3 Molecular Shapes with Four Electron Groups (Tetrahedral Arrangement) (2) AX; Type Compounds. (Structure of CH,) All molecules or ions with four electron groups around a central atom, adopt the tetrahedral arrangement. Perspective drawings for CH, is as shown, 7 - ads o” “oc H ee 109.57 H aoe <7 Methane H (The effect of bond-pair repulsions on bond angle of a perfect tetrahedral.) ‘The normal lines represent electron groups in the Plane of the page, one wedge is the bond of a group lying towards you above the Page, and the other is the bond of a group lying away from you below the page. When the four electron groups are involved in bonding, the molecular shape is ¢alled tetrahdedral (AX,). This is an extremely common geometry in organic molecules, The molecules of V-A group as ¢C, 14Si, Ge, s0Sn and g2Pb give such structures as SiHy, SIX, GeX,, Sry, SnX,, PbCl, etc, ; : Theories of Chemical Bonding 741 o) AXE Type Compounds (Structure of NH). When one of the four electron groups in the tetrahedral arrangement is a lone pair, the molecular shape Is that of a trigonal pyr: ramid (AXE). This is a tetrahedron with one point "missing". As expected, the measured bond angle is slightly less than the ideal 109.5°. In ammonia.(NH), for example, the lone pairs forces the N—H bonding pairs together, and the H—-N—H bond angle is 407.3? instead of 109.59, Swe Ammonia Some other examples are BH,, AsH.,, SbH,, BiH, PCL, NF, AsCl, ete.- When NH and H® form an ammonium ion, for example, the lone pair on trigonal pyramidal INH, forms a covalent bond coordinated to H® to form tetrahedral NH,°. In NH,® the HN—H bond angle expands. The reason is that the repulsions due to the lone pair decrease, because another bonding pair is developed. The status of four electron pairs is equal and all bond angles in NH,° are 109.5° each, H . \ A i @) +HO ON 17] un] H H (©) AX,E, Type Compounds [Structure of (H,0)]: When the four electron groups around the central atom include two bonding and two nonbonding groups, the molecular shape is bent or V shaped (AXE). 6 eE Bent (V shaped) AXE, Some other compounds are H,8, OF», SCl, etc. 2.3.4 — Molecular Shapes with Five Electron Groups (Trigonal Bipyramidal Arrangement) (a) AX, Type Compounds: [Structure of PCI} ; When ‘five electron groups maximize their separation, they form the trigonal bipyramidal of Londo ttt z120%—s/ ce) arrangement, ie, two trigonal pyramids sharing the same base. Note that there are two positions for surrounding electron groups and two ideal bond angles, 72 ILMI Inorganic Chemis 2 Three equatorial groups (utut ots) lie in a trigonal plane that includes the central atom. Two axiay groups (4 ,LfL (ls!) lie above and below this plane. Therefore, 120° bond angles separaty equatorial groups, and a 90° angle separate axials from equatorials. In general, the greater the bong angle, the weaker the repulsions, so ‘equatorial-equatorial (120°) repulsions are weaker than axia), toi i is below. equatorial (90°) repulsions. The structure of PCI, is given ; : ie arialnclby tet Wequitoriauis Lretturt le Spratt Lolnatteth itlee al “Axial @ Equitorial 0 a ‘TRIGONAL BIPYRAMIDAL AX, There aré no lone pairs on P and As in PCl, and AsFs., i {b) AXE Type, Compounds [Structure of Sulphur Tetrafluoride (SF). Lone pairs exert stronger repulsive forces than bonding pairs, so to minimize repulsions (LELIFFE,23), the lone pairs occupy equatorial positions. With one lone pair present at an equatorial position, the molecule has a seesaw shape (AX,E). Sulphur tetrafluoride (SF,), has this Shape. Note the ideal bond angles and actual bond angles. The equatorial lone pair repels all fur boriding pairs to lower the actual bond angles, Avi | Ideal bond angles Actual bond angles a Ideal and actual bond angles in SF, Tepulsions, the single Ione pair in SF, occupies an equatorial poston of tte | trigonal bipyramic. The lower actual bond angles result from lone-pairrepulsions ofthe bonding pairs, Some other examples are 2SCI,F,,IF,°,10,F,°, | (6) AXE, Type Compounds [Structure of Bromine Tiflouride (rf), | The tendency of lone pairs to occupy equatorial positions causes Molecules with three bonding groups and two lone pais to have a T shape. Bromine triuoride(BrF), has tis shape andthe To minimize 90° yy eonesof chemical Bonding |B redicted angles decrease from the ideal 90°.F—Br—F bond angle: is chlorine Prune CIF, (@ for equatorial and a for axial) ther camels nr a E he o= “ E + Tshaped Qo AXE, T-shaped The molecular shapes of the trigonal bipyramidal dale mu? arrangement. @ AX,E, Type, Compounds [Structure of lodate lon (|; Oy, Molecules. with two bonding groups have three. lone pairs in, equatorial postions. The a bonds are in axial positions, giving the molecule a linear shape. For example, the tri-iodide ion (|; ©), which forms, when I, dissolves in aqueous 1© solution is linear: Linear An other example is XeF,. Xe has three lone pairs and molecule is linear. 23.5 Molecular Shapes with Six Electron Groups (Octahedral Arrangement) AX, Type Compounds: : Six electron groups point to the comers of an octahedron (pF ub 21). It is an eight- sided regular polygon with six equidistant vertices. The six positions are equivalent, So all the groups have a 90° ideal bond angle. Three important molecular shapes are within this arrangement. Sulphur Hexafluoride (SF): With six bonding groups, the molecular shape is ‘octahedral (AX,). When seesaw-shaped SF, for example, reacts with additional Fp, the central S-atom expands its valence shell (eeu SE us) further to form sulphur hexafluoride (SF): } Octahedral ” »..Octahedral SFe (AX) (AXe) : it eS Similarly, the compounds of AX,E having one lone pair and five bond pairs are fire» and XeOF, Te £ i a e e e a E 5 ‘Square pyramidal (AX;E) Square planar (AX,E,) The molecular shapes of the octahedral electron-group arrangement. Some other compounds of type AX,E, are XeF, and 1c1,°. af Limitations of VSEPR Theory: : (i) VSEPR theory is applicable to covalent compounds only and cannot be applied jonic compounds. (i) | This theory does not make any distinction between s, p, d and f orbitals, (iii) The theory does not help in the prediction of shapes of coordination compounds (iv) VSEPR theory simply predicts that molecules such as NH3, H,0, CHCl, etc, ae distorted from the regular geometrical shapes but does not quantify (tt: +) the extent of distortion (wo S24). ‘ 2.4 Hybridization of Orbitals: (Valence Bond Theory) The mixing of atomic orbitals to give equal number of symmetrically hybridized orbitals is referred to as hybridization. . ne 2.4.1 Structure of BeF,: Let us discuss the structure of BeF, molecule. One of electrons of 2s is promoted to say 2p, orbital. 2s! and 2p,' hybridize to give two sp hybridized orbitals. An sp orbital has 50% s character and 50% p character. . sp-Hybridization: Electronic configuration of Be = [tt] [b] [oToTo] —> [7] [4] Co 0 0] . ; 1s? 28? 2pf2py 2p 1s? 2s! 2p! 2p) 2p, Electroyic configuration of >F = 1s? 2s? 2p? Opp 2pr sp hybridization These two hybridized orbitals overlap separately (Ebi Uiieyre fib) with the i electron each to form two Be-F bonds. Shape of BeF. molecule cat ule is lines rbitals of fluorine having one : : resented as shown in Fig: (2.9). There’are two bonded electron pairs. Therefore molec 2 i le of 180° to each other. The-overlap-for o-bond is due to j i it [ fu) with two orbitals at an ang! oon (aLigiLesafie) op of Be and p, of F-atom. — meories of Chemical Bonding ji oe f 180X” F Be F Linear Linear Fig. (2.5) Molecular shape of the linear electron-group arrangement. 242 Hie Hybridization or Trigonal Hybridization: e en one s and two p-orbitals combine together to prod i it e hybridization fakes place. gether to produce equivalent type of orbitals, 2424 Structure of BF: Let us discuss the structure. of BF. Electronic configuration of boron in ground state is 18? 2s? 2p). one ofthe two 2s electrons gels prommted (ut Zt & Li) to next available vacant (x 2 te Ue) oybtal say 2p,. The electronic configuration of boron in the excited state is 1s* 2s! 2p, 2py 2P>- (Remember that promoted electron of 2s can go to any of the 2p orbital ie., 2p,or 2p,). Now, the electrons belong to tw diferent types of orbitals jie., one is 2s, and two are 2p. To get equivalent bonds these three orbitals hybridize to: form three new equivalent (i) hybridised atbitals. In this case one 2s and two 2p orbitals are involved (tsr.2*) to form three hybridised orbitals. This type of hybridization is, therefore, known as ‘sp? hybridization or trigonal hybridization. Ithas 33.3% sand 66.6% p-character. These three orbitals lie in one plane and are directed towards the three corners of an equilateral triangle wf ‘Jiss-1), 80 that the angles between them are 120°. ee sp” hybridisation 5, 120° GAY ‘Three sp” hybrid orbitals ls _28 » Electronic configuration of sB atom in ground state = 4] [te] Tele . Is. 2s 2p, Electronic configuration of sB atom in excited stte= [44] [t] CALtle : “sp hybridization Electronic configuration of »F afom = 1s?2s? 2p? 2p? 2p! (nsiznyt bore entnd oe Witte A-0eF ) Three F-atoms share three electrons of their 2p; orbital with electrons of 2p? hybridized orbitals. oma: ~ ILMI Inorganic Chem, (H 2 «!8 sp? hybridization Boron atom is capable (- ¢) of toring three bonds by overlapping with, three Pay orbitals of other atoms. The overtap i is between sp? of B-atom and p-orbitals of F atoms. Configuration of 8 atom after making bonds with three F-atoms. ' Trigonal planar Fig. (2.6) The two molécular shapes of the trigonal planar electron-group arrangement. Shape of BF; molecule can be represented as shown in Fig. (2. o The other examples are * $0, BCl;, no®, co” ete, 24.2.2 Structure of Stannous Chloride (SnCI,): In stannous chloride the tin (,,Sn) atom has electronic configuration as Ss Sp Sd Electronic configuration of ,,Sn atom in ground state=[t4] [t] +[0]- Lo[o[o]o]o] In order to make SnCl, there is no need for the’ promotion of electrons and three orbitals hybridize as such with 4-electrons in them: +4] [¢[*To] [o[oTopoyo sp” hybridisation E ess than 120° V-Shaped structure Fig. (2.7) Formation of stannous chloride. In SnClp, two unpaired electrons in outermost shell of tin (Sn) are Used for bond formation with two atoms of chlorine. One electron pair is left unused as lone pair. Thus there are three electron paits, two bond pairs and a lone pair. According to its hybridization, it is expected to be trigonal planar Fig. (2.7). One of the three positions is occupied by lone pair of electrons. The expecteq angle is 120°. But the actual angle is less than 120°, This is because of a greater repulsion bétween the bond i (o) and lone pair (Ip) than between the bond pair (bp) and bond pair (bp). The other examples sa $0. PbCI, etc. Bent (V shaped) theories of Chemical Bonding : 77 eee oom Pb, - ON 7 X%, 1 So: aa The bonds are produced in SnCl, and PBC, by head on overlap ofp orbitals of Cl-atoms' and sp” of Sn and Pb. SiAspotetebo tpe fe the dat: W583 nttiSnCl, A — AMCLYSnA 24.3. sp* hybridization or Tetrahedral Hybridization: ‘ When one s orbital and three p orbitals combine together to produce equivalent type of orbitals, sp? hybridization takes place. : 243.1 Structure of CH,: “Four sp hybridized orbitals are produced which have the same energy and shape Cidade? e-bnu Li”) and are oriented (ta: uuu) at an angle of 109°28' fo one another Fig (2.8). This is also known as tetrahedral (Wi, 3-4) hybridization, because the hybridized orbitals are oriented towards the four comers of a tetrahedron. The nucleus of carbon atom occupies the centre of tetrahedron. In this position, hybridized orbitals experience minimum repulsive forces, Electronic configuration of carbon (¢C) in ground state = AU} (il Aj 1} 0 1 s° 2s -2p,.2py 2p. And carbon (¢C) in excited state = [71] [7 47114 Is | 28 py 2p, 2p, sp hybridization There are four orbitals having unpaired electrons. These 2s, 2p,, 2p, and 2p, orbitals wil fist of all hybridize. Four sp? hybridized orbitals produced are arranged tetrahedrally and are shown in Fig. (28). TETRAHEDRAL Tetrahedral “Y Fig. (2.8) The molecular shapes of the tetrahedral electron-group arrangement. All the four hybridized orbitals overlap with the 1s orbitals of four hydrogen atoms. All these Overlappings take place along the internuclear axes. Hence, four carbon-hydrogen o bonds are formed. - These bonds are due to s-sp* overlapping. Other examples are CCI, CBr,, SiH, SiCI,,GeH,, GeCl,, SnCl,, PbCl, etc, 78 ILMI Inorganic Che; API ALLL Lute ipL iu lus 2Pb aiSn; Ge, Si, CAVE Agr Le eet. (edt Ope Lvgite STL MOH AU -BLKIAL Rul Seity 2.4.3.2 Structure of Ammonia (NIH,): Electronic configuration of nitrogen (N) in ground state = 2s? 2p, 2p, 2p, sp hybridization Here, there is no possibilty of shifting of electron from 2s level to 2p level as there is NO empty 2p orbital. 2s orbital, athough incapable of overtapping participates in hybridization. This will give rise g ‘sp? hybridization, 2 Hybridized orbitals are oriented towards the corners of a tetrahedron. Three sp? hybridzeg Orbitals overlap with the 1s orbitals ‘of three hydrogen atoms. The fourth comer is occupied by lone pair We expect an angle of 109°28" (109.59) between H_— N — H in tetrahedral geometry. Actually this angle is 107.5°. This contraction Gy in angle takes place because the lone pair of electrons repels the shared pair of electrons or bonded pair of electrons with a greater force, thereby reducing the angle Fig (2.9). Methane Ammonia Trigonal pyramidal Fig, (2.9) The effect of lone-pair repulsions on bond angle in NH, in comparison to CH, Similarly we can justify the shapes of PH,, SbH, and BiH,, Pel, BBry SbCl, Bicl, cio$, H,0°. : , (Ur esLUP Ay cle tite 2.4.3.3 Structure of Water Molecule © Electronic configuration of oxygen (,0) atom = [1L] [7] (1477) ; Is? 2s? 2p, 2p, 2p, There is no promotion of-electrons, so electronic configuration of ,0 is, 111] 1s? , 2s? 2pt 2p! 2p! eet sV VAS Se gp bhyl) : sp hybridization These outermost orbitals having six electrons can participate (tL. ») in hybrid A rbitals hybridize and two of the positions on the tetrahedron are. occupied by lone pairs i 7 ae The other two hybridized orbitals will overlap with the 1s orbitals of two hydrogen atoms electrons. Theories of Chemical Bondin 79 a form a water molecule in Fig angle is 1045. This ae fs Fig. (2.10). We expect an angle of 109°28’ in HOH. Actually, the {o stronger repulsion of two lone pairs of electrons with shared pair of electrons. nO 104.5 Bent (V shaped) Fig, (2.10) In H.0 Fig. (2.10) In HG two lone pairs cause greater repulsions and the bond angle is decreased to 104.5°, Similarly we can discuss the structures of H,8, H,Se, H,T¢ 2.4.3.4 Structure of Hydronium ton [H,0]° i ee of coordinate covalent bond in H,O® may be represented as follows. fe covalent bond results when an empty obrital (Jt;.7 ué) present in the other atom accommodates (¢!_* -ty) a lone pair of an ot ther atom, It is important to note that the ee coyglent bond once formed is indistinguishable (Eb Sebi ticstSc?) from a covalent ee ; ion has an empty s orbital which overlaps with one of the orbitals of oxygen atom ga lone pair of electrons forming hydronium ion, HO®: This is llustrated in Fig. (2.11). This lone pair of oxygen is present in an sp? orbital, 4 yon! BF Heat Fig, (211) The geometry of HO© ion, One ofthe lone pair of O-atomis at the fourth corner of tetrahedron. * (eho wT vil Uf Se Pel sta LLM) itty Z EHO) The shape of Ha? will continue to remain involved remains sp. In H,0, two tetrahedral positions are in H0® only one tetrahedral position is occupiet still there on the fourth corner of positive oxygen. 2.4.4 sp*d Hybridization: Mixing of one s, three p an process is called sp'd hybridization. These five spd orbitals are directec Fig, (2.12a). They form three coplanner bond remaining two bonds are at right angles to this pl of PF, in this case. done d atomic orb Compare H,0 and H,0° tetrahedral because the hybridization occupied by lone pairs of electrons but xd by loan pair of electrons and this lone pair is jitals gives five sp?d hybrid orbitals and .d towards the comers of @ trigonal bipyramid as shown in ds Gtbek Lhestu ci) with bond angles of 120°, Jane one above and other below. Let us take example 80 7 is given.» OM on re oat ieee eye 4 ects eet hyb sa to ove fe ue ae ed ata Ca ') for combination = permi Of fives covalent bons with fhe fue ae ste = 1s228227° ath aph sph 3p! 33a? 3030 340 Electronic configuration of ,,P in g 29,2 93s 3ph 3, apt 3d! 3a°3a"3a%3q0 Electronic configuration of ;sP in exited state = Is sp'd hybridization. TRIGONAL BIPYRAMIDAL fe ~ 990° e en 1z20° e@ 2 'e . Trigonal bipyramidal a (a) (b) Fig. (2.12) The ie molecular shapes of the asa bipyramidal electron-group arrangement. But all the hybridised orbitals -are not equivalent (u%’ 1). Three of these are oriented towards the three comers of an equilateral triangle making an angle of 120° between them. The bonds formed by these orbitals are known as equitorial bonds. Remaining two orbitals are oriented at right angles to the plane of first set.of three orbitals. Thus PF, has trigonal bipyramidal shape as shown in Fig. (2.12) : 5 The other molecules as PCI,, PBrs, AsCl, etc. can be similarly explained. ALITA ALE L Asp ne SutdSod Lig edtisevLVAcS , 2.4.4.2. Structure of SF, Molecule: : F _ 3s 3p 3d oo Electronic configuration of -( Mom sulphur (,)S) atom in ground state. I Sulphur (,,S) atom in excited state. = ty tn sp'd hybridization To have four unpaired electrons, one electron from 3p, orbital is unpaired and promoted to a orbital. Thus five orbitals are used, four contain shared or bonded pairs of electrons-and one contains @ one pair. sp°d hybridization occurs, giving an expected trigonal bipyramidal shape, Actually the four fluorine atoms are joined tetrahedrally to sulphur atom in an imegular manne! (= 4 A274-) due to presence of alone pair Fig. (2.13) Ideal bond angles ‘Actual bond angles Fig. (2.13) Distorted trigonal bipyramid structure of SF,. 2.4.43 Structure of tcl) lon: : ey i IClz'ion has been found to be linear in shape. This can be explained by assuming sp°d hybridization of the orbitals of iodine. spd hybridization leads to trigonal bipyramidal shape. Two chlorine atoms occupy. axial (a) positions because the repulsions will be the minimum in this arrangement. One CI° ion will enter one of the sp'd hybrid orbitals which is vacant. It will make a o-bond. Another spd hybrid orbital containing single electron will overlap with one p-orbital of one é 3 ° chlorine atom to form one bond, Thus, in actual appearance (=| J’) the ICI, ion will have linear shape because the three base positions (ur uf UES Lul+) of the triangular bipyramid will be occupied by lone pairs of electrons as shown in Fig. (2.14) Ground state electronic configuration of iodine ysl =... Spy Spy" Spl Sd? «Py SP. Hybridization without excitation ,,1= {1 | tb | 1b 1)0 Ssp'd orbitals, cl oesheree C1® goes here, °° The other examples are XeF,,1,, IF, etc. Linear Fig. (2.14) Linear geometry of ICI, ion, 24.4.4 Structure of Cl '3 Molecule: : 7 a The outer electronic configuration of chlorine in ground state is 3s? 3p 3p; 3p,. In the formation of CIF, molecule, one of the paired electrons in 3p orbital is promoted to 3d orbital. : : volving one three p and one q yybrric five orbital The promotion of 3p electron is followed by hy m is therefore surrounded by f I, the, chlorine ator bee pair of electrons. Orbitals to give sp°d hybridization. , Th Containing a pair of electrons while the other hg contain oer 3s Electronic configuration of ra chlorine (, Cl) atom in ground state. Electronic configuration of PEt chlorine (,,Cl) atom in excited state, aoe : pd hybridization 82 a F i 87.6° é . ‘cl Fe —— 7.6° o= é e e iF . “T-Shaped a AXE, @ ® Fig. (2.15) Structure of CIF, molecule, As two positions of the trigonal bipyramid are occupied by lone. pairs, the molecule has a T-shape. The angle F —Cl—F expected from this geometry is 90° Fig. (2.15) However, actual angle _is 87.6°. This is due to repulsion from lone pairs which result in contraction of angle.’ The other examples are CIF, and BrF, Fig. (2.15). i 2.4.5 sp%d? Hybridization A combination of one s, three p and two d atomic orbitals gives six equivalent sp'd° hybrid orbitals directed octahedrally. This type of combination is known as sp3d? hybridization. Hybrid orbitals are oriented towards the comers of an octahedron (Avda). Let us discuss a few examples. : 2.4.5.1 Structure of Sulphur Hexafluoride (SF,): Outer electronic configuration of sulphur atom in the ground state is 3s2 3p! 3p} 3pl. To get the requisite number of half-filled orbitals for hybridization purposes, one of the 3s and one of 3p, electrons are made to jump to two of the 3d empty orbitals. Now six unpaired electrons are available in six orbitals. : Eishor (8) dground site = G) GO) fepepototo . Electronic configuration of «te ePs3P:'” Sd Bd 3d 3a 3a sulphur (gS) in excited state = ' | fo (terete 6spd? orbitals Theories of i Theories oftchemical Bonding § The six hybrid:orbitals are now directed towards (ut /A%1<-) the comers of a regular oct " +. ss ap ard six hybrid orbitals overip withthe p-oritalsof six fuorine atoms, So SF; molecule n octahedral structure as shown in Fig (2.16). The other example is IOF, OCTAHEDRAL : s — Fi Octahedral ig. (2.46) The molecular shapes of the octahedral electron-group arrangement, Octahedral shape of SF, molecule, 24.5.2 Structure of lodine Pentafluoride {iF,): The outer electronic configuration of iodine (,,l) in the ground state is = [i] GT) (ofofofolo Ss 5p, 5Py 5p: Sd Sd Sd Sd Sd and of iodine (,,1) in excited state= [4] (4 [ 111 i[1Jololo 3s .5p Sp 5p. Sd Sd 6sp'd? orbitals In the excited state two electrons from 5p orbitals are excited to 5d orbitals, thereby giving five single electrons. 5s, 5p,, 5Py. 5p, and two d-orbitals hybridize to give six equivalent orbitals oriented octahedrally. Each of them is sp°c’. However one position is occupied by a lone pair. Therefore actual shape is square pyramidal (SF SEO) Fig. (2.17) o~= ‘Square pyramidal Fig, (2.17) Square pyramidal shape of IF 2.4.5.3. Structure of Xenon Tetrafluorine XeF,: seicon tod li igurati i is the excited state, two of The outer electronic contiguration of Xe in the ground state is given. Int tale, the 5p electrons go to ‘the 5d-orbitals sc that there are now four unpaired electrons, The central atom, Xe, is surrounded by six orbitals resulting from sp°o’ hybridization. , * . \ Ground state electronic configuration of Xenon (4Xe) atom. Excited state electronic - mo ont _ Configuration of Xenon (,,Xe) atom. : ; pik hybridization : The hybrid orbitals are oriented octahedrally (api sd Lec P Woes Fi. 210) Four of these orbitals contain shared pairs while the remaining two contain fone pair of electrons. “ ya Square planar tha Fig. (2.18) Different ways to sketch the square planar structures of XeF, molecule. As the vertex positions are occupied by lone pairs, the actual shape is square plannar (G14) as represented in Fig. (2.18) 2.4.6 sp*d° Hybridisation Here we mix one’s, three p and three d atomic orbitals to give seven sp°d? lnybrid orbitals. They are directed towards the comers of a pentagonal bipyramid (Ze Lina Aceh se Sur Luss LS sui suschs!), These are not equivalent (F220, 212) hybrid orbitals. Five of “them point towards the vertices of a regular pentagon while others are. perpendicular to the plane. 2.4.6.1 Structure of lodine Heptafluoride (IF;): * The outer electronic configuration of iodine atom in the ground state and excited states are given. ; Todine (,,1) in the ground state = tL wit Ol o}o}o}o 3s Sp Sp Sp Sd 5d Sd Sd Sd Iodine (,,l) in the excited stae= [1] []i11] [LT 1fo[o 3s__ 5p Sp Sp__Sd Sd SdJ5d Sd ‘Tsp°d? orbitals To create half-filled orbitals for hybridization purposes, unpairing of Ss as well.as of 5p, and 5p, electrons takes place. Thus seven unpaired electrons are available for bond formation to give rise to IF, molecule. The resulting molecule acquires pentagonal bipyramidal shape shown in Fig (2.19) In this case all the seven hybrid orbitals are not equivalent. Five of them are directed towards t fit 72° ther, the rest of two are oriented at es of a regular pentagon giving an angle:72° with one another, ie to the a of the first set of five orbitals. Thus the bond angles in the molecule are of wm and 90°. Theories of Ch ‘ Theories of Chemical Bonding 7 ¥ Fig. (2.19) Formation and structure of IF, molecule, 2.5. Shapes of Molecular lons 2.5.1 — Structure of Nitrate lon (no$): In nitrate ion, nitrogen is the central atom and i i ; nit it has 5 electrons in outermost shell (2s? 2p°), ‘ while oxygen atom has six electrons (2s 2p), The nitrate ion carries a unit negative charge. It means be one of the oxygen atoms carries an extra electron and comes in the form of 0° to give noe o- atoms. * : ie Actually this extra electron is of H-atom. Whien HNOs (HONO;) is dissociated it gives NOS and H™ ions. j i" The bond formation in nitrate ion can be shown in Fig. (2.20 a). There are two O-atoms and one O-ion. We write it three times around one N-atom in following diagram. 2 Electronic configuration of O-Atom= [44] [tH] t¥ te) [eelre td * Stor, ‘2s 2s zy ~ extra tects fe electro covalent <é ‘bon: 25 ps Electronic configuration of N-Atom= [+4] [+ | t | ta 7s (Unhybridized) sp? hybridisation 7 ‘o-bond ap 8/7 o-atom= [#4] [HALAL +] a oe)? Fig, (2.20 a) Formation of nitrate fon from two neutral O-atoms and one negative oxygen. The 2p, orbital of nitrogen is left unhybridized and itis involved in 7 bond formation. In the rest of orbitals of N-atom one sp? has electron pair. Two have single electrons, Unhybridized 2p, orbital of * nitrogen has single electron. pEINS EOL VE wo thybLeu! Porites? Stet Liste Sty) sph iN) (Posin lS Se etn ENE r Prunpaltedse(* OLi-c-tt.21c0-ordinate covalent “<7 (ee dedto Ki Sf ed PALNle Ar LitetOOU 2 Lah o Covalent o-bond vt cor i od oO i Jlanar. (2.20 susie of Ho} fon wih igi NO® are three’ and Fig. ( king NO 3 ‘and ny Total number of electron pairs used for init tie is sp”. Thus the Fy : So the of otbitals required are three i.e., aed ee own in Fig. (220 b). molecule is trigonal planar with bon 2.52 Sucka of Cranats in. 9s : 2 in ground sae while in excited state itis 1, a 2 Electronic configuration of carbon is 15 2s? 2p ions. 1d two 0° : 2s!, 2p, 2p 2p) as described below. We take one 0- aa 7] FTI Carbon (C)'in ground s| 5 HH Py cited state = [44] [4 GT] p Carbon (OD in ex ; oF is t ° t : oe Carbon in excited state Tay : and after hybridizations = [1 hybridisation em eo oo Fig. (2.21) Formation and structure of co, ion. In carbonate ion carbon atom shares four electrons forming four bonds. Out of these three are sigma (a) and one pi (x) bond. Remember that x bonds are excluded (txt) from bybeicizeigy and therefore co,© ion has triangular planar shape Fig. (2.21). As carbonate ion has two negative charges. It is implied that two oxygens have an extra a electron: while the third oxygen is normal. The half-filled unhybridized orbital of Carbon (COA LG tod auf Azz ee L x8) forms a m bond with that of ongen atom having no extra electrons and thus bonded by a double-bond to carbon atom. The bond angle is 120°. However carbon atom has no lone pair of eto and ee be molecule has a regular geometry. FL the APA Mie 120° Uy ut 0 Ut hyb tes Lie tA hyb) spcsieut ted aly ato lidL EMER NIELS An Leste AinE0 ur sotl sell Cee trt crit nce (iy S26 tilt turin col) ae tee = meories of Chemical Bonding : : . 87 —_—_.v—0.0©0—0—0— ae ee a 253 Structure of Sulphate ion (80,8) "The outer eledtronic configuratic 1 sf sulphur atom is 3s 3p!. The shape of molecule suggests that it is a case of sp° hybridization, To have the requisite (Lt'; 2) number of halt-filed orbitals one * electron from s and one electron from p oribtals are excited to d-orl als as shown in Fig. (2.22). Sulphur (68) atom inground state= [A] [A] 1] 4 ofolojofo . 3s. 3p, 3p, 3p, 3d Bd Bd dB Sulphur (,,8) atom inexcited stte= Ct] [Tt Tt) (*Lto]o[o 3 __ 3p wh. RISA 3d 3d Bd Form four o bonds to Excluded from four oxygen atoms hybridization and form sp* hybridisation _ T bonds to two oxygen atoms, which are O. Two are O and other two are O° 3 f ; ‘NY J Fig. (2.22) Tetrahedral structure of SOO. Out of four oxygen atoms two have extra electron and are O°. That is why the net charge on 802 is -2. nother words two oxygen atoms are neutral with two unpaired electrons each as on 1 How tis 20= 25 2p,2p,2P, 40° =28 2p,2p,22, and two oxygen atom are O-', They have one unpaired electron in their p-orbitals which makes one z-bond, Sulphur combines with four oxygen atoms forming four bonds, thus using four pairs of o-bond. Also sulphur atom has no non-bonded electron pair. The number of hybrid orbitals used are four viz., one's and three p orbitals as per sequence. The two half-filled d-orbitals form m bonds with two oxygen atoms, having no extra electron. filer AHOe suze An L ty Ade urcrespts- eso ) tarsi son eS re Meet zhOn tl tiotitin dE sp? (LF 2 A hyd) ya er UW te TnL dds 2.5.4 . Structure of Chlorate lon (clo2): \ . Chlorine combines with three atoms of oxygen using three of its electrons. Thus it forms ‘three single o bonds with oxygen using three of its electrons. Here two electrons 88 3d 3s 3p aE] a c= fr] [t[ +] t [lt m hybridization 0&4 oe uy Excluded from hye ygons Form three bonds FX yonds to fooxygen atoms _ ve 80 ‘SP hybridization te} i 103). Fig, (2.23) Structure of Chlorate ion (cl03 ‘t participate in hybridization but'form from 3p, and 3p, are excited fo 3d orbitals which don't pitt aa ol give 5} ht with we Sine dine without extra electron. 35 ma ts ected pel rami we ith 0 ing three orbitals. : bee oe He cu an be aed! Its expected geometry is Se as comer position occupied by a lone pair ae cca with two oxygen atoms ue hybridization is involved, The two half-filled ete, os bonded to chlorine by double bonds as shown in| ig. io ithe Uretesp'FWChECIO) rr LFA yc tut Alot : Peace ee : Z ~ 89 Lota c to tiF< 0° Lisp fiutLttitiersL ett Onsen a - (eel tsp hint (Si 5 fe, 2.5.5” Structure of Perchlorate ion (cio?) woo at The outer electronic configuration of Clatom is 352 32, 3Py, 3P,. peeeee a from, + 38, and 3p, are excited to 3d orbitals. Single electron in 3s, 3p, 3p, and 3p, hybridize in p* mann; ene : give tetrahedral shape, Electrons in 3d orbital form m bonds. CIOS Ton is tetrahedral. Chlorine has ny non-bonded electron pair in the excited state. Three half-filled d-orbitals form bonds with three Oxygen atoms without extra electron and thus bonded by double bonds to chlorine as shown in Fig. (2.24)... Chlorine (Cl) atom in ground state = 4 Wi} 1 O;o}o Oo}0 35 3p, 3p, 3p, 3d 3d 3d 3d 3d 1 Py 3p, 3s 3p 3d Chlorine (;,Cl) atom in excited state = [4] [> tlt it tht L ] —— ae m four m bonds with four oxygen atoms sp hybridization Je EX Fig. (2.24) Tetrahedral shape of perchlorate ion (cl09), Form three x bonds with three oxygen atoms a theories of Chemical Bonding : 89 Ofna tte 220% cee -— J Bo GOOG wtb BOL sug utd 13UCIO,) ateeiatd 2.6 Molecular Orbital Theory (MOT) The main points of molecular orbital theory (MOT) put forward by F. Hund and R.S. Mulliken in 1930 are as follows. ; ()) Electrons belonging to two ‘boniding atoms are controlled by the entire molecule (abd = Ufte), The electrons will occupy molecular orbitals which belong to the entire molecule. eb fJhle vrutlb uModini /Ar (ii) In an atom there are s, p, d..... atomic orbitals. These orbitals are determined (tL \/24*) by various values (U2? ) of quantum numbers. In a molecule we have a set of molecular orbitals o, Tyo (iil) Like an atomic orbital, molecular orbital can contain a maximum of two electrons. (iv) The various electrons occupy different orbitals according to Hund’s’ rule of maximum ‘Tnultiplicity as in the case of atomic orbitals. 2.6.1 Linear Combination of Atomic Orbitals (ua: Here we need a very simple, reasonable (cuts) and a satisfactory (o* P) model of chemical bonding. It is obtained if it is assumed (¢/U7) that atomic orbitals of constituents (L21») combine, in a linear additive fashion to form molecular orbitals. Consider two atoms A and Bute. fy fu LIL (21), Each of them possesses a single valence electron. Let w., and ‘Wg fepresent the wave functions of atoms A and B. Now atomic orbitals A and B having valence electrons overlap. The. valence electrons will be in region where the orbitals overlap. Therefore, they can be associated with either nucleus (7U-£ ue xiif" wr). Consequently (G), the valence electrons have a much larger volume available for their movement as compared with that available in each isolated atom. The electrons can be thought of as moving in a molecular orbital whose total volume is approximately equal to the sum of the volume of atomic orbitals of A and B. In this way, the wave function of molecular orbitals can be expressed as a linear combination of atomic orbitals (LCAO) (ebb ¥ te). pg is the wave function of molecular orbital and will be written as Waa = Ca Wat Co We Here C, and Cg are the mixing coefficients (Lr KouL viz Afvxct), Value of C, and Cpis ~ $0 chosen as to get a molecular orbital of lowest energy (Utz4/ Lund iéa A). When we consider the bonding in two similar atoms, then the magnitude (5) .of the Coefficients-C, and Cg must be same. In that case a= or C,=+ In this way there will be two molecular orbitals as a result of two types of combinations as given below. : 0 : . © w=y,t Ve : WV Ye __‘ItValues of Cy and Cy are taken as unity aa One molecular ott (ys obtained BY 200 by stands for bonding. The other molecular orbital (y") the atomic orbitals. As discussed earlier that the nu of atomic orbitals involved in bonding. ye function of two atomic orbitals the subtraction of wave funcieny r I to the n rbitals is always equal to the nun, ber of tin ‘of atomic orbitals to give rise to sy molecular orbitals requires: a cotrcaente te tity a fe a ei wd) XK wapte : () +. Symmetry (ef tee =£i) and relative energies (<3 Le Lida) of along vd yg must be close to each other. + orbitals, y, and Wp or (i) Extontof overlap (w SLT Lents te) and yp should be large. (iii) ‘Momic orbitals of same sign should overlap. 2.6.2 Bonding and Antibonding Molecular Orbitals: = A : The molecular orbital that is obtained by the addition overlap of two atomic orbitals i termed as bonding molecular and is represented as y?. ye FwatWe Some features (4) of bonding molecular orbitals (BMO) are: : () __BMO possesses lower energy than the atomic orbitals from which itis formed. (i), BMO has high electron density (c¢1,6U £ wi /#) in the region between the two nucki and this is the reason for stabiity of bond (2521). (iii) BMO is formed when lobes of the combining atomic orbitals have same sign. The magnitude of ty” is numerically bigger than wy, oF Wg. (iv) Every electron in a BMO contributes (¢/u1-2°) to attraction (~) between two atoms. Antibonding Molecular Orbital (ABMO): The molecular orbital obtained by the subtraction of overlap of two atomic orbitals is termed the antibonding molecular orbital and is represented as w*. WE WA Vp Some features of ABMO are: (i) ABMO possesses higher energy than the atomic orbitals from which it is formed. (i) The probability (4) of finding the electron in between the nuclei is. negligible (EeEF 3747) in ABMO (iil) ABO is formed when the lobes of combining atomic orbitals’ have opposite signs. vy" & numerically (< #024) smaller than wy, OF Yip (iv) Every elgctron in an ABMO contributes to repulsion (‘411 -2> 23_/8.) between two atoms 2.6.3 Combination of s Orbitals to Give Molecular Orbitals (MO): % Consider two hydrogen atoms with their s-orbitals. They have one electron each. Using LCAO approach the two atomic orbitals will overlap to give two molecular orbitals. The first combination is yetween the charge clouds of Ys theories of Chemical Bonding o1 oblained by the addition of two atomic orbitals, The pictorial representation (¢/ pU < st L U*) is shown in Fig. (2.25) : WPMO= NW, + Vis) Where Nis a normalizing constant. The valve of N may be taken as 4 for simplicity (<1+1es1-). “ The electron in this MO will.spend most of its time between the two nuclei Hg and Hp. The electron is now stabilized (241) by two nuclear charges instead of one in an atomic orbital, The resulting MO is of lower energy than the 1s orbital. That is why it is called a BMO. ‘The second possibility (w&11~23) of linear combination is obtained by subtracting the two; atomic orbitals and is shown in Fig. (2.25) 5 4 ‘Antibonding MO, o;, Node (1s—1s) @-@ H, H, Isolated H atoms Tis + 13) Bonding MO, 6,, . _ Fig, (2.25) Bonding and antibonding M.O due to s-s overlap. Thé resulting molecular orbital has zero electron density (bor 2¥es SL Ut L ew Aly ~ between the nuclei. The region of zero electron density is called nodal plane (secu! Pity uth). The neteffect is to push the nuclei apart (Lb weet zuss) rather than to hold them together. The resulting molecular orbital is of higher energy than the isolated 1s atomic orbital. The molecular orbitals discussed above have cylinderical symmetry (Lev sU 10> S44) and are called c (sigma) molecular orbitals just like the combination of two 1s atomic orbitals: The combination of 2s atomic orbitals also gives rise to c-molecular orbitals. The only difference is that their sizes are different. , ~ 26.4 Formation of o Molecular Orbitals From p-orbitals Overlapping Along the Internuclear Axis: Sigma type molecular orbitals are also formed when p, atomic orbitals of two atoms combine with each other. We are now assuming that the intemuclear axis (UtZsSweuss»2U7 e/ln) is the 2- axis. This is illustrated in a diagram shown in Fig. (2.26) Subtract Node F J (antibonding) @:3 ‘OD P P, 6,,MO ‘ Add (bonding) Pe* Pe Fig, (2.26) Formiation o M.O due to head on overlapping of two p-orbitals. verlap of 2p, atomic orbital is desing i the subtraction of 2p; atomic ori... | irical symmetry around the as a (2.30) irr The molecular orbital formed by the aditio : 5 3 ital formed by ‘2p, OF simply as ob; The molecular of ‘tals also have cytind designated as cz, oF simply oz. These orbitals also orbitals Fig. axis and hence they are also classified as o-moleculat 2.6.5 Formation of x orbitals: obt lp itals which are ; i i a oe Pee a ee py orbitals are designated as x (pi) molecular Orbital, Li t3Le pu» LBL) of Py ee This is illustrated by showing overlap of 2p, atomic orbitals. ; Of Opposite son « Ovetiaps containing the same algebraic signs yield BMO and those of opposite sig, ABMO Fig, (2.27). ined by the lateral or sidewise OV pune 3; MO 2p, = 2, (antibonding) 0 f ye 2 2, ‘Add 4g (boring) zt Papp, Fig. (2.27) Formation of 7: M.O due to parallel overlapping of two p,-orbitals, (CIEL polo TZ tbr) The bonding molecular has (+) lobe above the z-axis and (-) lobe below the z-axis, The pls and minus signs refer to the sign of wave function in the various lobes and not to nuclear OF electronic chargés. The (+ve) sign or Upward direction represents one phase and (-ve) sign or downwar direction represents second phase of wave function. (CE etn Fe AG Liturionteus The two 2py atomic orbitals will over molecular orbitals are equi SF Dyip, L Aine) ‘2p ina similar fashion to give my and m, Both m, ant, valent and have the same energy. These orbitals are said to be degenerate Table (2.1): Comparison of BMO and ABMO, Bonding Molecular Orbitals (BMO) Anti-bonding Molecular Orbitals (ABNO] (i) Bonding “molecular orbitals (BMO) are ()Antibonding molecular orbitals (ABNO| 8 Obtained when two atomic orbitals combine obtained when two atomic orbitals combine together in such a way that their lobes with together in such a way that their lobes wi ++ sign overlap. Itis a+ + overlap, +=sign overiap. Itis a+ —overlap. ii) The probability of finding the electron in] (i) Th ili L (ii) iesteign ee eee cre (ii) he Probability of finding the electron the ‘region between the nuclei of te Combining atoms is very high and hence combini oe a stable molecule is formed ing aloms is negligible, (ii) The energy of bonding molecular orbial (il) The energy of antibonding moleouar oti is less than that of both the combining is more ‘han that ato ti atomic orbitals and bes ts formation atomic orbitals and hence the formation? of bonding molecular orbital leads to the an uc formation of a stable bond, antibonding molecular orbital prod Tepulsion between the combining atoms. |

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