CHAPTER OG Chemical Bonding and Molecular Structure Achemical bond is kind of attraction which holds two or more constituents faioms, molecules or ions) together. The process of their combination is called chemical bonding. For an clement, bond formation is valency dependent phenomenon. The valency is defined as the combining capacity of an eleme: Insimpler words, the number of bonds formed by an clement with the other similar species is called the valency of that element. The formation of a chemical bond is always accompanied by release of energy Asa matter of fact all the attractive forces constituting a chemical bond are electrostatic in nature. Depending upon different situation, different names are assigned to them, An outline of all such bonds is given below J Kosset-tewis approach Chemica bons J = ‘Sctemicet bonding Ocean t. L lonic bond (electrovalent bond) f 1 Covalent bond strong bons Wk bans Covelont character lonie dimeric) titer mca) bens Fajr a (Een 200 Hole) (Energy » 2-42 kJ/mole) Polarity of covalent bonds | 1 = Dipole mor [ T T 1 i ] Coordinate bond a @ o o © wo Formal charge Tonic Covalent Coordinate Metallic Hydrogen van der Waals Bond parameters bond “bond bond bond ond (8-2 kj) bond (2-8 Kk) = Bond angle = Bond enthalpy KOSSEL-LEWIS APPROACH TO « Valence bond theory (VBT) CHEMICAL BONDING : OCTET RULE ~Types of overlapping and In 1916, Kossel and Lewis theory was the first explanation of a chemical bond in pvarilicstcn ‘terms of electrons that was accepted. ~ Types of hybridisation According to this theory, ( Valence shell electron pair ') Outer most electrons (valency el y i ieiascic uses en etter lency electrons) play a fundamental role in (Gillespie theory) {9 lonie bonding involves to anche 8 involves the transfer of one or more electrons from one atom Molecular orbital theory (MOT) (iid Cov = Types of molecular orbitals ~ Energy level tor MOs en two atoms. syeivaroaen Eonding |= Types of nya alent bonding involves sharing of electrons betwes ogen bonding144 (iv Electrons are transferred or shared such that each atom attains electronic configuration of a noble gas c. having 8 outer shell (valency) (W) The above arrangement is called octet rule. Lewis symbols * In the formation of a mole: electrons take part in chen electrons are cule, only the outer shell I combination, These known as valence electrons. The inner shell electrons are well protected and are generally not involved in the combination process. Lewis introduced simple notations to represent valence electrons of an atom. These notations are called Lewis symbols, eg. Alll the valence (outer-shell) electrons of the Lewis structure are represented by the dots « the symbol. urrounding Significance of Lewis symbols ‘The common valency of the number of dots in Lewis symbols or 8 minus the of dots. e.g. Li, Be, B have 1, 2, 3 valency resp while N, O, F have 8 minus number of dots, 1 valency respectively, element is either e 3, 2 and Limitations of octet rule The octet rule, though useful in explaining the formation of a large number of compounds but there are some Limitations which are discussed below {0 Incomplete octet molecules (or electron deficient molecules) Some stable molecules exist in nature tn which central atom has less than 8 electrons in their ‘outer most or valence shell ©. BeF,, BF, AICls, LiCl, BeH, ete. "Note Being lectron deficient these have higher tendency to accept ‘lecron pai. Tha's why these molecules arava called i seid (i Odd electron molecules Some molecules or ions Possesses odd number of electrons in their outermost shell. These are paramagnetic in nature, e.g. NO.NO., OBJECTIVE Chemistry Voy, ome molecules have jectron rich molecules So w Heo aaee thar'd clectrons in the vatenee shell of centray Mlorne"This ts called super octet or expanded acter oot, oe S—F bonds having all 12 electrons in the valence shell of sulphur, Other, e4g, are PClay I (iv) Formation of compounds of 1 Octet rule suggested that noble gases are inert but Xe and Kr take part in bonding to form compounds with elements like fluorine XeF 2, XeFy, XeOF,, XeOF,, KrF, ) Other deawhacks ble gases and oxygen + This theory does molecules. + Wdoes not ex; molecules, + Tewas not able to that take place d IONIC BOND (ELECTROVALENT BOND) The slectrostatie force of attractioy h Sas a y element), a hot account for the shape of plain the relative stability of the fell about the ing bond for energy changes ie bond J when ansfers one or om (highly cleet 3 electronegative m Na ae, (Clectropositiy 7 : electrot) a =o Wes a cation: Song ativg The number of uni tom ans an elect uit eh i Siicttevatence of caer TE) Progen, "2° becomer ser salon chee # that ion, Te On the inn : n is the tion of pe pray Rae:Chemical Bonding and Molecular Structure Factors affecting the formation of ionic bond Some basi factors that affect the formation of ionic bond are (9 Tonisation energy In the formations of ionic bond, cations are formed from metals through the loss of electrons, This loss of clectrons depends upon ionisation energy. Smaller the value of ionisation ‘enthalpy, greater is the tendency of the atom to form cation, Therefore, alkali metals and alkaline earth ‘metals easily form cations due to their low ionisation ‘energies, {i Electron affinity The tendency to form an anion by the atom depends upon its electron affinity. Greater the (-)ve value of A.,H more be the energy released during this process. As a result, the formation of an anion becomes easier. In other words, high electron affinity of a non-metal favours the formation of an anion, This is generally in cases where octet is incomplete. F — Telectrons 0 = 6electrons N = 5electrons (i Lattice enthalpy The amount of energy released when free fons join together to form one mole of a cxysal is called lattice enthalpy. The higher the magnitude of the lattice energy, the greater is the tendency of the formation of an ionic bond. M*(g)+X"(g)—> MX(s); AH = -U Latce Factors affecting lattice enthalpy The value of lattice enthalpy depends upon the following factors (0 Charge on the ions Greater the charge on the ions, larger will be the force of attraction and hence, higher is the value of lattice enthalpy, lattice enthalpies of NaCl < CaCl, < MgO 788K) mat! 22544) mol! -3932 &f wot (Size of the ions Larger the size of ions, greater is the internuclear distance and smaller will be the force of attraction, hence lower will be the value of lattice enthalpy, lattice enthalpies of NaCl > NaBr, LiF > Lit ‘The main consequences of lattice enthalp + Greater the lattice enthalpy, more the stab ionie compound, + The lattice enthalpy is greater for small and highly charged ions. “a AH gation Both lattice energy and h with increase in ionic + Ifthe anion and the cation are of comparable size, the cationie radius will influence the lattice energy. Since lattice energy decreases much more than the hydration energy with increasing ionie siz, solubility will increase as we go down the group. (BeOH), DICH CH,O#)> D(CH,OCH,) Hence solubility of ionic solid (say NaCl) in H,0 > CH,CH,OH > CH,OCH, * Greater the interionic distance (r butween positive and negative ions, smaller the force of attraction between positive and negative ions hones solubility in the gi Greater the ven solvent, CHECK POINT 4] 1. The formal charge of the O-atoms in the ion uS—n=—8n° fa) 2 (by 2. Among the compounds; Which of the follo electrons ? (a) Coandso, (©) G0, and co wo (ayn NO,CO,ClO,N 5,50, ando,, owing pairs has odd number of (b) So, ando, (a) Noandcio, 3. Which of the following compo ra, tre, “ Insts os ome cnet tons Baas te) gam OBJECTIVE Chemistry yy ui Ld LiBr_ bt Tnterionie distance increases LiF NaF KF RDF GF (maximum towa Fd the disco fap (max) << force of attraction increases (max) solubility in water increases i s is very big, the solul However, if one of the ions is very T increases with decreasing size of the other ion, CSF > CsCl > CsBr > CsI Lil > Nal > KI > Cst LINO, > NaNO; > KNO5 > CsNO4 (very big anion) Also, greater the charge the greater the force of between positive and negative ions, hence tendency of the ions to go into the solubility bility (very big cation) (very big anion) attraction smaller the the solution hence smaller Na* cr Ba cr apy cr (Nac) (Bac) AIC; charge increases ae max ¢_Solublity increase Na Ch Nat SOT Nat Poy < : acl NaS, Na,PO, charge increases max max <—Sclubility increases Phot ong hasan ey ler tin acne lectrovatent linkage ? (o) ger a sic © An atom of an elem i 7 beatae ote AN thre eecrony in its outers form othe eB Wd tM in ts outermost obi (@) ap, nd Petivcen these uve will be (©) ant (by a3, 7. The higher lati wo as (2 sao MS eneey con ls to ©) Sr (0) cao 8.183" ita han ft BO b Ker than Aug? 1 Mich ote at ME on ange fon is larger tha? {ty Soin tone Mowing wan be stable salt in water?Chemical Bonding and Molecular Structure Pe T BOND (ii) High charge on the cation or anion Higher the COVALEN charge on the cation, greater i its polarising power. iris 11 poe ee Lv sy . Hee, covalent character of the chlorides follow the 3 erm covalent bond, The force of attraction order : ae ang atoms is called the covalent bond. This bond is {ener formed between two electronegative, i penemetal atoms, larly, greater the charge on the anion, more easily it gets polarised, Hence, covalent nature of LiF < Li;O< LisN Staring occurs between the electrons of the outer most Since, size of F" Lich > LF nature, Therefore, many of covalent compounds show isomerism,148 Example 4.1 Which of thermally. more stable? Explain, Sol tg? IN: 20 stanjago Mg hay Boble gas electron, V-clectrons cont Polatising power the same size Breater than More stable, configu igWation of the vale of Zn?* on an anion and charge. Thy hat of Meco, on wi nd thus, ZnC0, Difference bet atoms, on the followin "ween electronegaty lls in polaisabitty of basis of potari Ng two types (0 Non-polar coy; ities of he coval Ys covalent bonds cova atoms having 7 eit ele on-polar covalent Such molecules, the shared pair qually attracted by 4 las he two atoms, eg. Hence, a covaler character as a res clectronegativities of the sto ‘covalent bond, Dipole moment The magnitude of ionic character in a pol: is measured through a quantity called dip, is Usually Tepresente, Dipole Moment is defined as the of the charge and the distance Positive and negative charges, Mathematically, it is expressed as Dipole moment (1) = charge iq) x distance Dipole moment is expressed in debye (D), Product of the between the Y the compounds MgCOy and: 2nCO, is Expl hile Zn?" has an hell. Thus, is larger than a cation of lattice energy of ZC, is 1 is thermally Participating lent bond. Thus, are of the lent bond £10 oF almost “tronegativites is called bond, I bs Fas Bray ete, In of electrons is 'F Covalent bond, ‘ole moment, |, magnitude centres of of sepay OBJECTIVE Chemistry \ SlA=1x 19% " esuandd =1A cm ola a x 1x 10% = 4.8x 19-18 Suey then ecule will have a dipole moment FL Deby m i arated by a g Ox 10°" esu are sep; ya sta if changes of 1. Fs s 1.0x 10° esuem = 10D h a 1 D= 3.336x 10 C-m (when change + In Sl unit, = 3.336% 10 Cand d =1%10- yp), ' Also, -602x 10° €)x (19-10 m) 602x 10 Com = 4.8 5 8 ©, Dipole moment of HCI is .03x10-!8, stem and is expressed as 1.03 D, Dipole moment is a vector quantity well as magnitude, The direction represented by a small arrow entre and head pointing t The dipole Moment of HC] a Awa! Y as it has direction Of the dipole moment With talon the positing wards the negative centre ee | may be represented ag Ne is used to indicate the ft. ecules wag xg molecule with angle 6, resultant “1OF Summation of the vector ‘°F Moment Of the side AB. Mrestans 2 egg 0 al 2 8 the Value Smaller the value of jt les witho one pair of electrons Rem +f, “=, mH, net = Hy +p =O Ha sy) tn, ,Chemical Bonding and Molecular Structure In this case resultant jt of H—B—H on the left is cancelled by py; of the right. c=0 0 = 180°, neo H H H 6 =120% planar, p= 0 H H H a a Ch 8 =60° a = 6 120 t = 180° ortho meta para ‘Theoretical 4» =6.30D » = 3.80 D pn =0.00D Experimental p=6.00D w=3.79D 2 =0.00D In this case pt (o-isomer) > jt (m-isomer) > 41 (p-isomer) but experimental value of o-isomer < theoretical value. This is due to dipole-dipole repulsion in o-isomer that increases bond angle greater than 60° and p decreases. Unsymmetrical molecules with lone pair of electrons have some dipole moment as lone pair of electron also possesses some dipole moment. 1 10 a ue y fw NSH ‘Aramonia y= 1.47 D) Water (= 1.85 D) Hyp © =104.5°)> py, = 107°) Hs0, © = 120°) Dipole moment of NH, is greater than that of NF. This is because, in case of NH, the orbital dipole of lone pair is in the same direction as the resultant dipole moment of the N—Hbonds whereas in NF}, the orbital dipole is in the direction ‘opposite to the resultant dipole moment of the three N—F bonds. Ol INS PAN W T f F if F H F Hag ® 4.902107 ein Hyer = 0-80*107% mn. By using dipole moment, the percentage ionic character of polar bond (4—B) can be calculated as: For the molecule to be 100% ionic, each end should carry charge ‘equal to one unit, i.e. 48x10"! esu. 14 % ionic character in a molecule __ observed value of fe 100 theoretical value of y- HCl > HBr > HI % ionic character of HF > 394% 16.0% 108%" 4.7% Table 4.1 summarises relation between geometry of molecules and dipole moment. Table 4.1 Relationbetween molecular geometry and dipole moment Formula Molecular geometry Dipole moment AX oe AX Trigonal planar zero Trigonal pyramidal an be non-zer0 ____Tshaped eam be non-zero __ AX, Tetrchedral zero Square planar 2er0 Seesaw can be non-26r0 All X atoms are assumed to be identical. Example 4.2 The dipole moment of HBr is 2.60x 10° Cm and the interatomic spacing is 1.41 A. What is the per cen ionic character of HBr? Sol, ‘Theoretical value of dipole moment of a 100% ionic character = ex d (1.60x 10719 €) (1.4L 107% 2.26 10° Cm Observed value of dipole moment =2,60% 10" Cm per cent ionic character = —2bserved value observed value 109 theoretical value 2.60% 10 2.26 10 = 115% x 100 Example 4.3 A diatomic molecule has a dipole moment of 1.2 D. If its bond distance is 1.0 A, what fraction of an electronic charge exists on each atom? Sol, For a diatomic molecule dipole moment p =e xd 107 esu em 1.0% 10 em = 1.2x 107° es theoretical value of electronic charge = 4.8% 10°'? esu 1.2x 107° 8x 10% £. Electronic charge Fraction of the electronic change = 0.25150 CHECK POINT 4.9 1. Which is the most covalent? (a) Cor tb) co. te) Cos () CBr 2. The ruinber of electrons involv molecules is fay red in the bond formation of Ny (oy4 (6 (a) 10 3. Which has maximum covalent character? {ay sic (b) Mgcl; {e) Nac (a) acl, 4. The order of resultant dipole moment i (a) SF, HS> HO LH He dioxide molecule is linear. The The cabo eso Cand O are 2.5 and 35 rpc coe a ease values and on consideration of Molec ten nature of C—O bond and the molecule geometry, respectively are (a) polar polar (6) polar, non-polar (b) HEH SoHo (d) HE>HO0,>H0; (b) 0, > 1,0, > 0, (©) 0, > HD, >0, (a) HO, > 0, > 0; VALENCE BOND THEORY (VBT) This theory was put forward by Heitler and London in 1927. It was based on quantum mechanical model and concept of atomic orbital overlapping. It was further extended by Pauling and Slater in 1931. Postulates (i Overlapping of two distinct atomic orbital, each having an unpaired electron, results in formation of covalent bond, (i This process of overlapping completes with release in energy. This make the resulting bond stable. Hence, overlapping results decrease in energy, (i) The overlapping of two atomic orbitals form a single merged orbital. This newly formed orbital is called bond orbital or a localised mote cular orbital, (iv) The electrostatic attraction between the o cloud and the nuclei of atoms acts binding force of th ‘ectron as the major bond, (0) Opposite spin of the two electrons, neutralises their spin magnetic moments. This further contributes ta the covalent bonding. covalei 1 rc fasing (C—O) bond length of ne correct order of increas 1g (C—O) bor ath of Cc 5, The con ‘coyand CO; is (a) Co} H,O >PH, >HS (b) Nit, >PH, >H1,0 21S (c) NH SHS >PH, 2H0 (d) PH, >H,S>NH, >H,0 7, Resonance structures can be written for (a) 0, (b) NH, (c) CH, (a) HO 8, Inwhich of the following compounds, resonance does 1 occur (i) HO (ii) SiO. (ili) SO, (iv) CO, ‘The correct answer is, (a) Both (i) and (iv) (b) Both (i) and (ii) (c) Both (iii) and (ivy (4) (i), Gi) and (iv) The extension suggested by Pauling and Slater @ The stent of chemical bond formed depends of thew ate omic overlapping. Greater is the lapping, stronger werlapping to take place. _, Stommie orbital must have ooo (iid Overt are (id For overt the Participating valence . a electrons, als, wit i cae with directional electron M1) results in stronge Hy m drogen rereeule as per VBT hei nucle} ly and Hy are in them are rag we Na a ae kinds of new fae Tepresented ie! 7 act dace by (0 Attractive force eB thi Structure of Consider two hy each oth presen t bond. approachi ee and electrons 2 and ey. Differen approac * Nucleus of one ae Between ’ one aton Nfs aN, OBB ts Oy, * Nucleus of ong ! ul one ay Tae om a , Aen and ye 884 elegy, (iO Repulsive forces pvt 48 OF other atom, * Electron ¢ 0 electrons CS areChemical Bonding and Molecular Structure Attractive forces tend to bring the combining atoms close to each other. On the other hand repulsive forces tend to push them apart. a 8 He Ms ic forces, a ® New forces Axtractive forces, Ropulsve forces Fig. 4.4 Forces of attraction and repulsion during ‘the formation of Hy molecule “The magnitude of new attractive forces is more than the new repulsive forces. As a result, two atoms approach ‘each other and potential energy decreases. Ultimately, a state is reached where attractive forces, just balance the repulsive forces. This state is reached when the atoms are at critical distance rp. ‘Ata distance greater than ry, the attractive forces are dominant whereas at a distance smaller than ry. the repulsive forces dominant over the attractive forces which leads to increase of potential energy. Masimum lowering of energy takes place at critical distance ry. “The lowering of PE as a function of inter-nuclear distance has been shown in figure 4.5 below Fig 4.5 Variation of potential energy (PE) Itis clear from the curve that, the energy of two H-atoms when they are held at a distance ro is smaller than the energy of individual H-atoms. Therefore, the H-atoms constitute a stable grouping called hydrogen molecule. ‘The critical distance rg corresponding to minimum energy is called bond length. Experiments have shown that the value of rg is 74 pr The energy corresponding to the minimum in the curve is called bond energy/enthalpy. If this much energy is supplied from outside, the bond will break and the molecule will dissociate into atoms. H,(g) + 4358] mol! —> Hig) + Hig) 155 Directional properties of bonds When two atoms approach each other to form bonds, atomic orbitals overlap. The overlap between the ator drbitals can be positive, negative or zero depending upon the characteristics of the orbitals participating to overlap, Positive overlap involves the overlap of the lobes of same signs. It leads to attractive interactions. Negative overlap involves the overlap of the lobes of opposite It leads to repulsiv tions. Zero overlap implies inability of any kind of interactions. The various arrangements of s and p-orbitals resulting in positive, negative and zero overlap are depicted in figure below a Negative or ot of pase ovelap Positive 0 in| CED O~ Combination of 2p, atomic enitals tw © Combination of 2p, and 2 s atomic onbitals 4 PP ‘Combination uf 2p, atomic orbitals Py Pe a ty Combination of 2p, atomic orbitals Pe MP 0 w Zero onerap (Zero overlap out of phase due to different orientation direction of approach) Fig. 46 Positive, negative and zero overlaps of sand patomie orbitals The criterion of overlap of atomic orbitals of combining atoms is the main factor for the formation of ‘covalent bonds: ‘both in homonuclear as well as in heteronuclear diatomic molecules and polyatomic molecules. In case of polyatomic ‘molecules like CH, NH; and HO, the VBT should be taken into consideration for their characteristics shapes. ‘As we know the shapes of CHy,NH, and H,0 molecules are tetrahedral, pyramidal and bent respectively. Their shapes can be described in terins of the orbital overlaps.156 Types of overlapping and nature of covalent bonds Based on types of overlapping, covalent bonc! of wo distinct natures are formed, as discussed below Sigma (c) bond This type of covalent bond is formed by head-on overlap, i.e. end-to-end overlap along the internuclear axis. The clectron density of a sigma bond is concentrated between the nuclei of the bonding atoms (along the inter-nuclear axis). The electrons constituting sigma bond are called sigma electrons, Sigma bond can be formed by any one of the following types of combinations of atomic orbitals. (des overlapping When two half-filled overlap along the inter-nuclear axis, itis s-s overlapping. O-O-@ -sorbital orbitals, led orbital ss overlapping (i0 sp overlapping When half-filled s-orbital of one atom overlaps with half-filled p-orbitals, ie. p., Py OF p, of the other atom along the internuclear axis It is, called s-p overlapping. The bond thus formed is called s-p sigma bond. orbital peotbital (i p-p overlapping When half-filled p-orbitals of one atom overlaps with half-filled p-orbitals of other atom coaxially it is called p-p overlapping. The bond as formed is called p-p sigma bond. CO. CO — CODO postal prbital Pp overlapping Note The strength of bond formed as a result of different types of overlapping are as follows ‘-s overlapping <5-p overlapping axial p-p} overlap (0 neal pov [tenner apt iT] CUD 2p Pe Py Pe Pe Py Pr 2s{h Lj2s isi] [B]is «+ InNH, molecule, three o-bonds are by (s-p) overlap of H and N-atoms. i ij ih 1s(H) x DN overlap CHECKPOINT 4.4, 1. On the basis of VB theory, the formation of H, molecule 4. The molecule of hydrogen atom is formed due to the F 7 werlapping of orbitals of two hydrogen atoms. Which of from two H-atoms invol overlapping 8 {ay the overlap of eacant is orbtal ofthe to H-atoms the following types of overlapping takes place in the {b) the lowering of potential energy of the system as the two formation of H, molecule Heatoms come neat to each other. - {c) stabilization of the molecule when the nuclel are brought oe: © S5-« Sill loser to each other from the equilibrium internuclear os ” distance (2) the maixmum energy of the system at the equilibrium © es a ee internuclear distance. TP 2. Inwhich of the following pairs attractive force work? 5. Number of = c-bonds in the following structur sg, Range: ste ‘umber of x-bonds and o-bonds in the following structur v ‘a im ea Na—Nov Cate v a Here, Nand Ng represent two nuclei and e, and eg refer to a oH electrons surrounding N , and Ng nuclei aA H (a) L Mand vi (b) IIL TV and V S (c) Lit Mandy (a) Vand VI ag 3. Consider the following graph " a = HOH i (a) 619 (b) 420 (e) 5,19 (ty 5,20 2 6. Which orbital is used by oxygen atom to form a sigma bor 2 swith other oxygen atom in 0; molecule ? & (a) pure p-orbital (b) sp?-hybrid orbital 2358 (€) sp?-hybrid orbital (a) sp-bybrid orbital 7. Two hybrid orbitals have a bond angle of 120°. The percentage of s character in the hybrid orbital is nearly Th above potential energy curves given for the formation (a) 25% (b) 33% (ey SOK (dk) 66% off, molecule as a function of internuclear distance of 8. Diagonal hybrid ema gueer & hunetion at tatercien ds sgonal hybridisation is the another name of teatoms. atwhat pa curve Hy is found in the (3) 9 hybridisation (b) ap? hybridisation wa one ee ann (€) 5 hybridisation (4) All of these ———_————zZ 158 HYBRIDISATION valence We cnsidr formation of CH lee basta ale od approach, To account for tetravatent na bond Para imexeited state in which there ae (OF Cupaired electrons and four CH o-bonds are uPPor be by overlap of $~55~ Py oS ~ Py and s— Px sof H 1s 1 1s 1 Ground state Excited state What do you think about these (C—H) bonds? « are these equivalent? «« are these having different bond lengths and bond energies (due to different types of overlap)? our answer is These are equivalent as there is hybridisation taking place. + These have equal bond energy and bond length. This is due to the formation of new orbitals before overlapping takes place, by a process called hybridisation, ‘This concept was put forward by Pauling, Hybridisation is defined as the process of intermixing of valence shell atomic orbitals of slightly different enengies in an atom to generate a set of new atomic orbitals of equivalent energy. New orbitals formed are called hybrid orbitals. This phenomenon is referred as hybridisation, Salient features of hybridisation ‘The main features of hybridisation are as follows (0 The number of hybrid orbitals generated is equal to the number of the atomic orbitals that get hybridised. (io The hybridised orbitals are of equivalent energy and similar shape. (ii) The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals. (iv) These hybrid orbitals are arranged in space in such a direction so that there is minimum repulsion between electron pairs. This gives a stable arrangement of electron. Thus, different types of hybridisation show different types the geometry of the molecules. Important conditions for hybridisation (0 The orbitals present in the valence shell of the stom are hybridised. (i0 The orbitals taking part in hybridisation must have a small difference of energies. oBsective Chemistry Vo), f electron (© me Le ee 2D. -omotion of eetFON Ty hy - ag Pro condition PY palf-filled orbitals cy that 0 cases, even | sa ja) Te is not neces i co cipate : Gf valence oF vacant orbitals take pay filled orbitals in hybridisation- jdisation | hybridisat Types i, hybridisation are sp-nybr ae one p-orbital hybridise 10 produc | inthis type one $C ital. The two sphybsd | two equivalent Pen a straight line making an angle o oral are ojcue possesses linear geometry. jtals has 50% s-character and Each of hybrid orbi | 50% p-character. s 2s 2 °& Bey : 7 (Linear Be Ground=[] Lb | rmolecile) state) 4, 5 Op Be (Excited=[ Wa state) 1s _sp sp 2p 2p | Belt, (Molecule)=[11] [T«[1= | (Hybridsed state) AB | sp-hybridised orbital | +> eof H The two halffilled A and B sp-hybrid orbitals form ¢-bonds with half-filled s-orbitals of two H-atoms by (69-5) overlap thus, forming two Be — H bonds. 7 x 180° . keer» : 2— 4GoSov Crear ‘tal ofBe ap,orbital of Be sp-nybrid : 15(H-atom) (Crear sp-hybrcisation) ion and two p Ve three sp*-hybridisati (P, and p, ) orbitals of a” quivalent sp?-hybrid These th ee ap? the three “hybrid ost; angle of 13908 Fan caus are directed towards This a Silatera molecule, Earp S8i¥eS a tree tl triangle with an 22.93%) ga ' bra ‘eangular aw tothe *racter ang 9 /..e Pitas hi nd as 1/3rd (or *d (or 66.7%) p-character:Chemical Bonding and Molecular Structure ¢.g, BF), BCly, BH, AICI,, carbon containing double bond, Ike CH, =CHa, S02,S05,CO5° ete. an te Is 2s 2p cignal planar *BGroindstare[0] C0} [7 wee) 1s 2s ap B (Excited satel-[h] [1] [T]t Is spt Oy Bal, Molecule)=[1] [x [ix [x ry (?-hybridised state) AB sp?-hybridised orbitals x9 eof Cl ‘The three half-filled A, Band C sp?-hybrid orbitals form o-bonds with half-filled p-orbitals of three Cl-atoms by (p?-p) overlap and give trigonal planar geometry. sp?-hybridisation Inthis type, one s and three p-orbitals internist for four sp’-hybrid orbitals of equivalent energy. These four sp*-hybrid orbitals are directed towards the four corners ‘Table 4.3 Hybrid orbitals and their geometric orientations 159 of a tetrahedron separated by an angle of 109° 28. sp?-hybrid orbitals have 1/4th (or 25%) s-character and 3/Ath (or 75%) p-character. ee cH, Is 28 2p Cerahédrat °C Ground stte)=[B] (8) (117 rinecle) eee Scercnedsae-ft]} (1) GOT 1s sis phe cory eotecster=[E] [bel] bx] ABCD sp'-hybridised orbitals ‘The four half-filled A, B, C and D sp*-hybrid orbitals form, «6-bonds with half-filled s-orbitals of four H-atoms by (sp’-s) overlap and gives tetrahedral gcometry. Tetrahedral sp'-hybridisation Note the sizeof different hybrid orbitals increases as pp csp! ee Predicted bond angle Shape of motecule Beto cA, Ont 10" neat Wi) three) BF CyHy,S0.S03 120° Trigonal planar Gi) =p (lou (Clg, CoH. CClyy SiC, NH 109° 28 Gv) dsp? (four) ‘Square planar [Nuc ‘90° ‘Square planar (PANE), 90° ‘Square planar a ve) 7 idal_ PCL PF, 120° andl 90° Trigonal bipyramidal Wi Gin Shes 90" Octahedeal [FelH1,0\)" 90" ‘Octabedtal Wap Oahedal FRC 0" Gaabodrl [CoNH)e]” 90° Octabiedral iF bevel m Re Pemtagonal bipyramidal Pentagonal bi Hybridisation of elements involving d-orbitals The involvement of d-orbitals in hybridisation takes place when d-orbitals are lying vacant or partly filled. Electrons in s and p-orbitals of the outermost shell can Uwe d-orbitals of the outer shell as well as d-orbitals of the jon depending upon the nature of molecule, colved in hybridisation with 3s and 3p and also with 4sand 4p. This is because the energy of the 3d-orbitals are comparable ‘and 3p-orbitals and also with 4s and to the energy of the 3 Aprorbitals.160 hybridisation are as follows Some of the examples of thi (Formation of PCy ee P Ground state) = (Ne} [1h] (7TA 11 L sap sd P Excited stare) = (Nel [1] [LTDA ad PCIs = INe} [ix] ix] x] 1] | webb Here, x denotes electrons of CI” atoms. The five orbitals undergo hybridisation and give a set of five sp*d-hybridised orbitals. These are {irected towards the five comers of a trigonal bipyramidal. a a a ‘cl cl ‘1's. 4.7 Trigonal bipyramidal geometry of PCl, molecule IPCs, the five sp°d-orbitals of phosphorus overlap occupied electrons in p-orbitals of Saine atom to form five P—Clsigmn bond Ga Plane at an angle of 120° with each othe. These bonds are termed as equatorial bonds, The cahen n ee P—Cl bonds, one lie above nnd tive other lie below the equatorial plane, making an 2ufle of 90° with the plane. These wo hake are called axial bonds, Svmmetrical structures are usually more stable than, asymmetrical ones. Thus, PCly is highly unstable, and in the solid state it splits into (PCi]* and [PCIg]~ ions, 2PCly — [Pcl] + (PCI, )- moma Eat Gest crea OBJECTIVE Chemistry y, ml. (i Formation of SF, 3p WEL MoT WEn mon bP Cy (Ground state) = [Ne] S (Excited state) = [Ne] SFg = [Ne] Ix] 1x] 1% sp'a? -hybridisea Here, x denoted electrons of F~atoms, The sp*d?-hybridised orbitals of Soverlap with singly occupied electrons in orbitals of fluorine atoms to form six SF sigma bonds, Thus, Sit nolecule has a regular octahedral geometyy, F Fil. 4.8 Octahedral geometry of Sk, molecule ion of IF, HGround sate) = [7] (it Form: amo MExched sate) = [7] Gomory "(GH or ae SPE hyrbridived Here, x denotes electrons of F-atoms, The seven half-filled sp*d°-hybridised orbitals of I overlap Pith half-filled orbitals of F-atoms to form seven pyri bonds. Thus, IF, is pentagonal bipyramidal in which five 1 F hon tre in one Plane at angle of 72° and two 1 — 9 poms ne Perpendicular to the plane of equitorial bonds F = 7 ii Regular Pentayon ie 4.9 Pentagonal bipyramidal geomemry If, moleculececal Bonding and Molecular Structure 161 gicting the hybridisation This number comes out to be ra shapes of molecules 2 = sp hybridisation i, ‘ne need to know the numbers of lone pairs (by use 3. => sp” hybridisation AVSEPR theory). 4 => sp" hybridisation or dsp” hybridisation jweadopt tO methods for the study of type of hybridisation (decided by way of orbital used) ited 1 Count number of atoms directly attached to 5 => sp°d hybridisation Mei} atom + Jone pairs + single electrons 6 = sp°d® hybridisation or d®sp" hybridisation Mead 1 Count -bonds + —> (coordinate) bonds 7 => sp'd?-hybridisation ter d or inner d-orbitals are used). + lone pairs + single electrons (based on Table 4.4 Method of determination of type of hybridisation Central olecale oF ion Central Number of electrons attached to central atom Total hybrid orb ‘Atoms bonds Ip Single Method | Method tt @ ( — lectron(d) Bonde) laterd) Oterdee) a _ 7 = 4 e S 4 a ” 5 5 5 = 6 6 wt 1 3 3162 Central fe eh p Single toms bonds ip electron (d) po a one See iched to centeal atom, electrons atta Number of | "Method i Ore dae VALENCE SHELL ELECTRON EORY shape of Beximum possible distances between them, °R theory provides 4 simple method The 1 Pulsive interaction between the electron pairs decrease 10 predict the shapes of covalent Molecules, This inthe order theory, "85 Proposed by Sidgwiek and Powell in Xi (P-Lone ait (p) > Jone bond pair (bp) » 1940. It was further developed by Gillespie ang bond pair (bP)-bon pale MSPS pond pi ° Nyholm in 1957, his theory, Provides a simple NS repulsive off 'S results in ¢ from idealised «0 Beet the shapes ap alco fects resy it deviations from idealise recedure 19 predict 1 hapes of co ent molecu shapes and alterations in bond angi, The main postulates of PR theory are as follows Cometic (9 The shape of a motecute depends upon the qunnber of valence shell electro isles in molecules SHiBeS of molecular can be identifie, Help of VSEpR ap FY. Te je nient to de® ” Pairs (bonded as centra ded) around the cd with the divide the molecule Categories as al atom, is conven iN Which the Which the StL AION has no lone cen atom ha pair, or more Jone pairs a8 oneyemical Bonding and Molecular Structure d 163 cs of molecules based on the numb na ametties Ne number of bond pairs of electrons and the shape and hybridisat ‘he 0G by the Following table d pairs of elect ud the shape and hybridisat ‘ace Table 4.5 The effect of bonding and lone pair on geometry and bond angle ae Number of oe Orbitals on Theoreti zc ea EI le central atom — shay VSEPR Bond angle pea a ee re notation — ® Bond patra Lone pairs CE stands for eS - tone"patr i - SG, AX; 180 we Wiangle 3 ° AX, 120" Plane Wiongle Axe ie: Arulor ‘Tetraedrat ao e AX, 109° 28" Tetrahedral Tetrahedral E AXE tor 48° Trigonal : dake pyramidal 3 pee AXE 102° 35" Pyramidal ms. 2 AXE 104° 27 Angular = a ANE, 102" Angular 2 2 AXE, oo" “Angular Trigonal 3 ° AX 120° and 90° Triganal Dipsramidal Uipseamidal Trigonal 4 1 AXE 1OF 36'and Irregular bipyramidal 6°39 forbear ae AX Es T-shaped e 3 Trigonal ec arse Tshaped —_________dipramigat_ Trigonal AXE, 180" Linear bipyramidal = octahedral AX, 207 Octahedeal ~Ostahedeal E 4° 20" Saqware pyramidal Octahedral 4 AXE 90" Square planar Pentagonal 7 AX, 72°, 90° Pentagonal bipyramidal : bipyramidal Example 4.6 Explain abnormal behaviour in the following (#0 Sulphur tetrafluoride (SE,) There are four bond pairs structures based on VSEPR mode. and one lone pair. To minimise the repulsive forces the oar sr, 0 5 lone pair occupies ain equatorial position ail are located at the other four vorticns $0 (0 Chlorine trifluoride (CIF) There are three bond pairs : and two lone pairs. As a general rule, if lone pairs occur . 18 trigonal bipyramidal they will be located in the {auatorial positions (round the middle) rather than th etial (op and bottom), since this arta Iminimises the repulsive forces. F re (f) 1 fon is made up of an Ty molecule with an T bonded to it by means of a coordinate bond “ A in which I is Tone pair acceptor (Lewis acid) and T the lone pair donor (Lewis base). Ther re two bond164 pairs and three lone pairs in the outer shell of central ‘To minimise the repulsive forces the three lone ator. To mini ition, The ion is therefore torial position. The os + the equa pairs occupy linear in shape with a bond angle of exactly 180°, GF + Fr ler Lewis tase Lewis bse CHECK POINT 4.5 1. The isostructural pair of species (i.e. having same shape and hybridisation) is (a) BC, and BrCl, (b) Nit and NO; (c) NF, and Br, (4) BEy and Nir 2 The hybridisation of 5 in $0, is (a) sp (cp * Which one ofthe following species has a linear shape 2 (2) 0, (©) $0, (0) be-tp> Ip-bp > Ipulp (9) tobe > Ip-lp > bp-ty § The shape of X (a) 90° (b) 120 (c) 180° (a) 109 11, The d-orbital involved in. spd hy bridisation is dss (b) a, (oa! (a) "ments is not correct? (2) Hybridisation is the mixing of atomic orbitals prior to thet Sombining into molecular urbinne (0) sp? hybrid orbitals are form; and one s-orbital (©) asp? hybrid orbitals ore directed towards the corners of regular octahedron, (4) sp? hybrid orbitals are all at 90° to one another. led from two p-atomic orbitalsChemical Bonding and Molecular Structure MOLECULAR ORBITAL THEORY (MOT) Irwas given by Hund and Mulliken in 1932. According to this theory, when two atomic orbitals combine or overlap, they lose their identity. As a result of it these form new orbitals called molecular orbitals which are not associated with a particular atom but belong to the molecules as a whole. Salient features of MOT (0 The electrons in a molecule are various molecular orbitals, (i The atomic orbitals of comparable energies and proper symmetry, combine to form molecular orbitals. present in the (ii A molecular orbital is influenced by two or more nuclei depending upon the number of atoms in the molecule, (io) The number of molecular orbitals formed is equal to the number of combining atomic orbitals, ¥ two atomic orbitals combine, two molecular orbitals are formed. These molecular orbitals are named as bonding MO (Y, ) and antibonding MO Wa) (0) The bonding MO has lower energy. Hence, it has greater stability than the corresponding anti-bonding molecular orbitals, (v9 The probability distribution of electrons around a group of nuclei in a molecule is given by a molecular orbital. (vi The molecular orbitals are filled in accordance with Aufbau principle and Hund’s rule. Linear combination of atomic orbitals (LCA0) To yield qualitative picture of molecular orbitals in a molecule we use # quantum method named as linear combination of atomic orbitals, This method is used because the Schrodinger wave equation is too difficult ‘o apply on the systems containing more than one electron as these electrons are moving in the field of several nuclei LCAO isa method of superposition of atomic orbitals quantum mechanically as shown below. According to this method wave functions () of individual atomic orbitals linearly combined and form molecular orbitals. Here, two cases can be generated. 165 Formation of bonding and antibonding molecular orbitals by LCAO Case 1 When two waves are in phase, the waves adds up and constructive interference occurs. ‘The amplitude of new wave is, Wyo or, = Vi, +P, (Bonding MO). Here, Yio is also called P,, je. GERADE MO corresponding to increased electron density between the two nuclei due to in phase overlap, Case It When two waves are out of phase, the wave are subtracted from each others and destructive interference occurs. The amplitude of new wave is “ii or Y, =¥y —fy (Anti-bonding MO) Types of molecular orbitals Just as the atomic orbitals are designated as s, p, d or f. the molecular orbitals of diatomic molecules are named, 6 (sigma), api) etc. o-molecular orbitals ‘The molecular orbitals which are cylindrically symmetrical around the inter-nuclear axis or bond axis are called sigma, o-molecular orbitals, e.g. the molecular orbitals formed by addition of ls-orbitals is designated as ols and the molecular orbital formed by subtraction of Is-orbitals is designated as 6's. Similarly, combination of 2s-orbitals results in the formation of two sigma molecular orbitals designated as 62s and o* 2sas illustrated in figure below ee O-O— x S @& -C—_—. wy yo Fig. 4.10 Molecular orbitals formed by addition and subtraction of 2s-orbitals Among 2p-orbitals as the 2p,-orbitals is assumed to lie along inter-nuclear axis, therefore the molecular orbital formed by the addition overlap of 2p,-orbitals is designated as. 2p, while the molecular orbital formed by the subte of 2p, -orbitals is action overlap signated of o* 2p, (see figure below), Q-O-Or. G y+ €.)— (tering ae condone it 2D, 2, Fig. 4.11 Molecular orbitals formed by addition and subtraction overlap of 2p, orbitals166 -molecular orbitals hapa ‘The molecular orbitals which are formed by lateral ov st) of prorbitals are called pi (x) molecular orbitals. Thee molecula ‘orbitals are not cylindrically symmetrical around a inter-nuclear axis or bond axis because of the prese se positive lobes above and negative lobes below the mole % plane, e.§ ° result in the formation of k2p, and x* 2p, mole and addition and subtraction overlap of 2p, orbitals result in the formation of x2p, and x” 2p, molecular orbitals respectively as illustrated in figure below lar orbitals DA 2 Ww Ca) Pinole ebie) 2 2 2p, D.O—__9lp Sy TLS sresoung ‘moles tals) Fig, 4.12 molecular orbitals formed by addition and subtraction of 2p, oF 2p,-orbitals A mbonding molecular orbital has large: above and below the inter-nuclear axis, molecular orbital has electron density The x” anti-bond anode between the nuclei, Table 4.6 Following MOs are formed when atomic orbit tals overlap olecular orbitals Atomic orbitals —__Molecular orbital Bor 2p, + 2p, - 2p, + 2p, 2p, The potential energy of the orbitals are in order BMO < at ¢ orbitals < ABMO Anti-bonding Mo (subteactionty,~ y, Ih) Nets outing MO taditiony ie, (¥y9¥y) Finds Energy level diagram diferent M05 the addition and subtraction overlap of 2p,,-otbitals OBJECTIVE Chemistry Yo, ve can say that BMO has lower energy, ea nan vivore stability than the corresponding woo. Pint BMO are filled, then ABMO starts fil haar. MO has lower encrgy than that of ABM ifferences between bonding and ae aig molecular orbitals Bonding MO MO (BMO} S.N (ABMOs 1 Bonding molecular orb is formed by the additio overlap of atomic orbitals. Anti-bonding molecular orgy is formed by the subtraction overlap of atomic orbital, ea the nucle of bonded a 3. Inhibit elecon In this orbital electron dens is less in between the mice, Electrons it this orbital leads repulsion between atoms ity is more in be the nuctei, Electrons in this orbital lead to attraction between atoms. Ins energy is more than the ‘energy of the atomic orbitals. Iis energy is less than the ‘energy of the atomic orbitals Conditions for the combination of atomic orbitals Fos the atomic orbit formation of molecu als to combine resulting in the ular orbitals the main conditions (0 The combining at tomic orbitals should have al Sime chergies, e.g. in case of homonuclear diatomic molecules Is-orbital of one atom can Combine with Is-orbital of the other atom bit {s-orbital of one atom cannot combine with 2s-orbital of the other atoin beeative the ene 2s-orbital ppreciably higher than that of Is-orbital, (10 The extent of overlap between the atomic of of the two atoms should be lane Greater the &xtent of overlap the greater will be the ggton-density between the maclel of H combinin, same symmet orbital of one of the other Which me; i The # atomic orbitals should have th TY about the molecular axis. % Hom can combine with 2p,-0! atom but not with the 2p, orbit! “ns if atomic orbitals have same oF WY the same en parca * have the same syinmetry. * Moted that 2a cling ty 0 not have Je Ae env xis is taken as the inter-t™ modern conventions.Che ‘al Bonding and Molecular Structure Energy levels for MOs The energy levels of these above listed molecular orbitals ee et oth hd ler ahi molecular orbitals of different homonuclear diatonic molecules of second period of the periodic table follows + For Op and Fy : (more than 14 el are as ’ lectrons or above Ny) Gls Nyy it indicates a stable molecules and if the value of BO is negative or zero (ie. N, < NV, or N, =Nq)it indicates an unstable molecuile. (4 Bond dissociation energy is directly proportional to bond order. Greater the bond order, greater is the bond dissociation energy (or bond enthalpy). (ii Bond length of the molecule is inversly proportional to the bond order of the molecule. Thus, greater the bond order, shorter will be the bond length (iv) Bond order of molecule is equal to the number of covalent bond between the atoms in the molecule. Thus, for O», 03, 03, OF", bond length increases on moving left to right. On the other hand, bond order and bond energy decrease on moving left to right. The molecule with same number of electrons wi have same MO and same bond order. eg. Np and O} contained 15e”, thus, both have same MO and same bond order. Magnetic behaviour If all the electrons in a molecule are paired, the inolecule is diamagnetic [i.c. repelled by magnetic field] and if there re unpaired electrons in a molecule, the molecule is paramagnetic, In Oy, % 2p, and % 2p, each orbital has one electron in degenerate levels (of equal energy) hence, itis paramagnetic Molecule Total Electronic configuration, Ny Ny Bond Magn orion number of ——— —— order electrons als Gis 925 Gas Rr 2p, 2p, 10 Db 0s P 00 > 05 Lo > 00 > 10 P 20 dD 30 D 30 Dorer a lcetronic configuration ek eR be RM Hy Oe ok gts 2 G2 oO D ee - 20 D foame as) 3420 D = foe Ga) tao b a Goame aN) = Game a8 Na) *P = paramagnetic, D = diamagnet Table 4.9 MO electron oe yn, Bond Magee Toa a aoe order nature dietrons Sk 0262 02%, way nlp, £9, 2p, 62p, — “ae p 1 108 P ae 10 25 P = 107 1s Sirerte ee oF rm 7 aT ary Pee) | Sg ae lo hey ao HYDROGEN BONDING Seige bn exits hacen the Haxomof The cont ofthe hyagen boning was nated by Molecule andthe F-atom of ane her molecule, Tatimer and Rodebush (1920), These are the special wpe of dipole-dipole interactions existing between the srecules containing hydogen atom in the neighbourhood of highly electronegative atoms like F, O or N. Cause of formation of hydrogen bond sidered that n, Hat drogen atom is bonded covalently to some other “iOleion, ‘lipole-dip, ighly electronegative atom (F, O, N) then due tern large ‘ iletence, in their eletronegativty the bond par of is i 8. of H-bond is similar to that of ole or dipole nduced dipole ASH. ae bg displaced towards the electronegative atom, t isa slight Bor AN Heng ie Fini charge develops on H-atom while slight noyaths (Ris the o hatte develops on an electronegative atom. Hencees Condit: ‘He por of the moecule dipole is developed. Onditions fo stan ail hydrogen at os positive plead the aiher Fr effeane Ming (OEM Bonding atom as negative pole. (0 Hvdogen atom atom his hydrogen stom experiences electrostatic force of Stet onegatig oe ition from another highly electronegative ste, on 0.) presen in its vicinity. Ths eleewosnan Torce of attraction is termed as hydrogen bonding, tions are rete «boned to highly *O or N, Greater th Breater is the “Feo > Omn "ON. See OBJECTIVE Chemistry yy Bond Magnetic go>(i The size of electronegative atom should be small. If the size of electronegative atom is lange, the attractive force with H-atom would be less and consequently, strength of H-bond would be less. eg. Although electronegativity of N and Cl is same but still H— Cl does not form any H-bond because of the large size of Cl-atom, Types of hydrogen bonding There are two types of hydrogen bonding Intramolecular H-bonding This type of H-bonding occurs when polar H and high electronegative atom are present in the same molecule. eg. CANS 5 ae ohydroxy benzaldehyde OV (a ‘i. nz? L 6 o-nitro phenol & & O-H-O (io \ | O-H—O Be Nickel dimethyl glyoximate (a chelate) The necessary conditions for the formation of intramolecular hydrogen bonding are * The ring formed as a result of hydrogen bonding should be planar. * A5 or 6 membered ring should be formed. * Interacting atoms should be placed in such a way that » there is minimum strain during the ring closure. In case of anti-form of pyridine-2-carboxyl dioxime, there is intramolecular hydrogen bonding. On the other hand, H-bonding is not seen its syn-form. Syoet Sw Pee il I BHyy-N a sm Intermolecular H-bonding This type of H-bonding takes place between H and highly electronegative element present in the different molecules of the same substance (as in between HO and HO) or different substances (as in between HO and NHj). e.g. (0 In water molecule Due to polar nature of H,O, there is sociation of water molecules through H-bonding this gives a liquid state of H,O with abnormally high boiling point. fe be me Om np .H. ee Hp. - no Hy Hye Hye If we observe, one water molecule is joined to four other water molecules ~ hwo with Heatoms and other two with O-atoms. Thus, coordination number of water molecule in water is four. Hg. Hn | fi-o Hs o oF 5 He SO. OH OK ? Aa sel oH H 3. MH (i In hydrofluoric acid (HF) However in the gaseous state, several polymeric forms of the HF molecules exist. In these monomers are held together through H-bonding. A pentagonal arrangement of H—F molecules is shown below 101 pon Dy Similar H-bonding also occurs in alcohol (A-OH), ammonia (NH,) and phenol (C,H,OH) molecules. id dimerises in gaseous state due to 160 pm 100 pm il & |e [ H 0.0. H—C—C7 e—c —H TN H ‘OH... 0" H170 Consequences of the hydrogen-bonding (0 Due to H-bonding boiling points of water, ammonia, hydrofluoric acid are abnormally high, CHECKPOINT 4G 7 Which of the following is paramagnetic and has the bond order? @N. (Hy (0, wr 2. Which of the following is paramagnetic? (OF) NO Ke) CO (ay eX ‘3 In the formation of NO* from NO, the electon will be removed from (a) a-x orbital (b) ox” orbital (©) a-corbital (2) ee" orbital ‘4 When N3 is formed from N, bond-order 0} is formed from 0, bond-order (2) increases (0) decreases (6) Increases, decreases (a) decreases, increases ‘5. Which of the following have identical bond order? LCN" 1.0; ML NOW. cN* Choose the correct option. (2) Both t and tnt (©) land it “and when (b) Both itand ty (2) Both rand wv . Bond order of 0,,03,03 and OBJECTIVE Chemistry, ‘ing point order Boiling Poi HO» HE > NHy > CH, jing point order Melt Feng» Ni > HF > CH, ao Solubility of the organic compounds in water 4 to H-bond formation. (ii) Due to hydrogen bonding, viscosity (n) ofthe liga sases as given below (in centipoise (CP), CH,OH CH,OH I CHOH oH | Gans cH,OH | CH,OH oo ase n= 1070¢ (@) 05 <0! In which oS eee the following substances will ‘hydrogen bood! (ay ner tt tag Hs Which of the following is cor = 2) Hsu, Dg I coect onder for meling (0) HOH " (Ho: : (4) HO. ft