CHEMICAL BONDING INTRODUCTION (Most of the elements exist as molecules which are cluster of atoms. How do atoms combine to form molecules and why do atoms form bonds. Such doubts will be discussed in this chapter. (@ — Amolecule will only be formed if it is more stable and has a lower energy, than the indi atoms. CHEMICAL BOND @ A force that acts between two or more atoms to hold them together as a stable molecule. (i _Itisunion of two or more atoms involving redistribution of clectron among them. Gii) This process accompanied by decrease in energy. Gs) Decrease in energy « Strength of the bond. () Therefore molecules are more stable than atoms. Cause of Chemie: 1. Tendency to acquire minimum energy": Combination ¥ (distance) FF, @ When two atoms approaches to cach other. Nucleus of one atom attracts the electron of another atom. (According to quantum theory when two atoms of element approach each other then there will be force of attraction as well as force of repulsion between the bonded atoms. At the minimum distance where these forces becomes equal is called bond formation condition (equilibrium state) and atom of the clements get stabilized by bond formation phenomena by lowering their energy. Gi) ~—_If net result is attraction, the total energy of the system (molecule) decreases and a chemical bond forms. (@) So, Attraction « energy « Stability. () Bond formation is an exothermic process 2. Tendency to acquire noble gas configuration : @ Atom combines to acquire noble gas configuration. (Only outermost electron i.e. ns, np and (n-1)d electrons participate in bond formation. @ Inert gas elements do not participate, as they have stable electronic configuration and hence minimum energy. (Stable electronic configuration ; 1s* or ns*np%)CHEMICA, BONDS ‘STRONG BOND WEAK BOND (inter atomic) (Inter Molecutar) lonic Covalent Co-ordinate Metalic Hydrogen Vander waal's bond bond bond bond bond ‘bond Lewis Octet Rule @ Every atom has a tendency to complete its octet. (i) Hydrogen has the tendency to complete its duplet. (i To acquire inert gas configuration atoms loose or gain electron or share electron. (@v) The tendency of atoms to achieve eight electrons in their outer most shell is known as Lewis octet nile. ¢g., HO molecule eg, BeCl, Molecule Cade) aGe Qe) Obeys octet rule Doesn't obeys octet rule Exception of Octet Rule = (a) Incomplete oétet: molecules : oF (electron deficient molecules) or Hypovalent molecules Compound in which octet is not complete in outer most orbit of central atorn. Examples - Halides of IMA groups, BF, AICI;, BCI,, hydride of III A/13* group ete. in BCly } [Boron has only 6 electrons| Other examples - BeCl, (4 electron), ZnCI,(4 electron), Ga(CH;); (6 electron) (©) Expansion of octet or (electron efficient molecules) or Hypervalent molecules Compound in which central atom has more than 8 electron in outermost orbits. Example - PCl,, SFg, IF;, the central atom P, S and I contain 10, 12, and 14 electrons respectively. E® eee Electron dot formula of PCI, (© Pseudo inert gas configuration : Cations of transition metals, which contains 18 clectrons in outermost orbit Examples = Ga*?, Cut, Ag*, Zn*?, Cd", Sn*4, Pb“ etc. Electronic configuration of Ga- 1s?, 2s*2p®, 3s?3p°3d", 4s*4p! Electronic configuration of Ga‘? - 1s, 2s? 2p®, 3s73p'3d"° 18 electron@ Odd electron molecules : - Central atom have an unpaired electron or odd number (7 electron, 11 electron, cte) of electrons in their outer most shell. Examples : NO, NO C1O,, CIO, ete. 6 c.g NO moiccule 7 electron 8 electron CO-ORDINATE BOND (DATIVE BOND) @) @) It is a covalent bond in which the shared ¢lectron pair come from one atom is called coordinate bond. Necessary conditions for the formation of co-ordinate bond arc- (@) Octet of donor atom should be complete and should have atleast one lone pair of electron. (b) Acceptor atom should have a deficiency of at least one pair of electron. eg. ‘Atom which provide clectron pair for sharing is called donor. Other atom which accepts electron pair is called acceptot. Thai is why it is called donor-acceptor or dative bond 4 F HN fg Rp aD er, H F BF, is clectron deficient compound. Example: NH,’ : ' HON +H HONGH H H (Bronsted - Lowry acid) (electron acceptor) HON H, \ 0° fH > 10H H 4 O; NOIMPORTANT LEWIS ELECTRON DOT/CROSS STRUCTURES ‘Compound Structure Electron dot/Cross formula LM ‘Sodium Sulphide (Na,S) 2(Na")S-~ 2. | Calcium Hydride (Call,) ca*2(11") Fi: cat 3. | Hydrogen Peroxide(H1,0,) | H-O-O-11 4. | Phosphine(PH,) whe 5. | Carbon mono-oxide(CO) 6. | Carbon di-oxide (CO,) 7. | Hydrogen Cyanide (HCN) HOC=N 8. | Potassium Isocyanide(KNC) | Neo 9. | Sodium Hydroxide@NaOH)™"} §46—H 10, | Nitrotfoxide(N,O) U1. | Nitric oxide (NO orN,0;) O=N—N=0 ° 12, | Dinitrogentrioxide(N,0;) ontin=o 90 13. | Dinitrogentetaoxide (NO) | o=t—t=o O° oO 14. | Nitrogen Pentacxide(Nj0,) | o=mA—o—=0 15. | Nitrousacid (HNO,) H—O—N=O ° 16.| Nitricacid (HNO,) Ho-teo12 19, 20. 2. 22. 24. 25. Nitrate lon (NO;-) I "7 Ammonium Chloride (NII,C1) ft afr Carbonate lon (CO,-~) o-t-0 ‘Sulphur di-oxide(SO,) o+s=0 9° ‘Sulphur Tri-oxide (SO3) o+dio 9 Sulphite Ion (SO,-~) oko 3 Sulphate lon (SO,-~) oFo ° Phosphoric Acid (H,PO,) H0-f-0-HPhosphorous acid (H3PO,) Phosphate fon (PO,-—-) of the following species are hypervalent? . +2. BF, 3. SO?,4. CO;> (A)1,2,3 (B)1.3 (€)3,4 (D) 1,2 Ans, (B) Sol. Hypervalent : Central atom of thecompound having more than 8¢. Exericse L The octet tule is not obcyed in : (A) co, (8) Bal, © rely (0) siF, Ans. (B),(C) rv Towhich of the following species octet ruleis not applicable: (A) Bs (B) SF. IF, (co Ans. (A),(B),(©) COVALENT BOND @ A covalent bond is formed by the mutual sharing of electrons between two atoms to complete their octet. (Except H which completes its duplet). 0; molecule N; molecule (i The shared pair of electrons should have opposite spins, and are localised between two atoms concemed.Shairing of electrons may occurs in three ways — ‘No. of electrons shared Electron pair Bond between two atoms 2 T Single bond (—) 4 2 Double bond ¢ 6 3 Triple bond (=) Examples— H—H—H Three single bonds (not triple bond) 4 NEN, Triple bond. (not three single bond) $} =. Double bond (Not two single bond) H =H, (Two single bonds.) Orbital concept of covalent bond : @ Onc orbital can accomodate at the most 2 electrons with opposite spins [11] @ Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its orbitals. (ii) Tendency to complete orbital or t6 pair the electron is an essential con Completion of octet is not the essential'condition of covalent bond. (i) Covaleney =\It is defined as thenumber of electrons contributed by an atom of the element for shairing with other atoms fo achieve noble gas configuration. () Ifthe outermost orbit has empty orbitals then covalent bonds are formed in exicted state. n of covalent bond. Variable valeney in covalent bonds : @ Variable valencies are shown by those elements which have empty orbitals in outermost shell. (@ Lone pair clectrons gets excited in the subshell of the same shell to form the maximum number of unpaired electrons. Maximum covalency is shown in excited state. Gi) The energy required for excitation of electrons is called promotion energy. (®) Promotion rule — Excitation of electrons in the same orbit. Example : @ Phosphorus -» Ground state fy) GE) Covaleney 3 (PCl;) 3s 3» Phosphorus -» Excited state 4] Go] GLI Covalency — 5 (PCI,)(6) Sulphur + Ground state. ff) Gol) CLI Covalency — 2 (SF;) 3s ‘3p 3d Sulphur + Excited state excited state [tL] G [114] GET I Covalency — 4 (SF,) 3s 3p 2 excited state [7 11114] Go Covalency — 6 (SF,) 3s RD 3d So variable covalency of S is 2, 4 & 6. (c) _lodine has three lone pair of electrons Groundstaey Fit] FETT] CLL) 55 5p 5d So it shows three excited states - Maximum number of unpaired electrons = 7 Variable Valencies are 1, 3, 5,7 Applications of Variable Valency = To cxplain existence of molecules : NCI, - exists NCI, — doesn’t exists (due to absence of d-orbitals in Nitrogen.) While PCI, and PCI both exist because 34 orbitals are presént.in phosphorus. OF, —,exists, but OF and OF¢ doesn’t exists due to absence of d-orbitals, while SF, and SF, exists dueto presence of d-orbital, present in its valence shell. Note : Compound in which Ionic, covalent and co-ordinate bonds are present arc following NH,Cl, CuSO,, K,[Fe(CN),], KNC, Na,PO,, KNO,, ete. Wave mechanical concept of chemical bonding - (Overlapping) To explain the nature of covalent bond two theories based on quantum mechanics have been proposed. (1) Valence bond theory (VBT) 2) Molecular orbital theory (MOT) VALENCE BOND THEORY (twas presented by Heitler & London to explain how a covalent bond is formed. It was extended by Pauling & Slater. (i) The main points of theory are - (a) To form a covalent bond overlapping occurs between half filled valence shell orbitals of the two atoms. (b) Resulting bond acquires a pair of electrons with opposite spins to get stability. (©) Orbitals come closer to each other from the direction in which there is maximum overlapping (d) So covalent bond has directional character. (©) Extent of overlapping « strength of chemical bon(0 Extent of overlapping depends on two factors. () Nature of orbitals — p, d and f are directional orbitals -» more overlapping s-orbitals -> non directional — less overlapping (i Nature of overlapping — Co-axial overlapping - extent of overlapping more. Collateral overlapping - extent of overlapping less Order of strength of Co - axial overlapping — P-p>s-p>s-s —— —_ —.~ & (@ As the value of n increases, bond strength decreases. 1-1>1-2>2-2>2-3>3-3 (h) If is same bond strength order will be following 2p - 2p > 2s - 2p > 2s - 2s 1s - 2p > 2s - 2p > 38 - 3p @ Electron which is already paired in valency shell can enter into bond formation, it they can be unpaired first and shifted to vacant orbitals of slightly higher energy of the same énergy shell. @ This point can explain the trivalency of boron, tetravaleriey of €arbon, penta-valency of phosphorus etc. (k) Two types of bonds are formed on account of overlapping, (A)Sigma(o)bond ——_(B) Pi (x) bond (A)Sigma (c) bond : (Bond formed between ‘two atoms by the overlapping of half filled orbitals along their axis (end to end ovérlap) jis called sigma bond. (i) bond do not take part in resonance. Gi) Free rotation is possible about a single c bond. (jv) Maximum overlapping is possible between electron clouds and hence it is strong bond, () There can be only « bond between two atoms. Sigma bond are formed by four types of overlapping (a) s-s overlapping (H,) - Two half filled s-orbitals overlap along the internuclear axis. bond QO O —M® 1s. 1s 1s 1s (18 orbital of hydrogen) (1s orbital of hydrogen) (Formation of H, molecule) (b) s- p overlapping (Formation of HF) ~ When half fill s-orbital of one atom overlap with half filled p-orbital of other atom. O-: SD Oe ‘1s orbital of Hydrogen 2p orbital of Fluorine(© p-p overlapping — (Coaxial) — It involves the coaxial overlapping between half filled p-orbitals of two different atoms. eg. Formation of Cl,, Fy, Bry Cone + Coe — CO DD Porbital Porbital Pp overlapping (B) Pi (x) bond @ The bond formed by sidewise (lateral) overlapping are known as x bonds. @ Lateral overlapping is only partial, so bonds formed are weaker and hence more reactive than bonds (Repulsion between nucleus is more as orbitals have to come much close to each other for = bbond formation) “7 Formation of ©, molecule — see Eet Atomic 0 Atomic orbital ‘of oxygen of oxygen Only py and p, of oxygen atom haye unpaired electron in each orbital for bonding. Electronic configuration of oxygen is ~"1s?2s?2p,? 2p,!2p,! Gii) Free rotation aboutia bond is not possible. Gv) x bond is’Weaker than o bond (Bond energy difference is 63.5 KJ or 15 K cal/mole) (¥) x bond takes part in resonance. (si) x bond formed by pure or unhybrid orbitals. Ilustration When 2s-2s,2p-2p and 2p —2s orbitals overlap, the bond strength decreases in the order: (A) p-p>s-s> p-s (B)p-p> p-s>5~s(C) s-s> p-p> p-s (D) 5—s> p-s>p-p Ans. (B) Sol. _ Bondstrength« directional property of orbitals. Exercise 1. Which of the following has been arranged in order of decreasing bond length? (A) P-0>CI-0>s-0 (B) P-0>5-0>CI-0 (©) s-0>C1-0>P-0 (D) c!-0>5-0>P-0 Ans. (B) 2. Ax-bondmaybetween two p, orbitals containing one unpaired clectron cach when they approach each other appropriately alon; (A)x-axis By: (C)z-axis (@)B&C Ans. (D)44 HYBRIDISATION der an example of Be compound :- formed without hybridisation then - ci&*Be®=Pcr both the Be-Cl bonds should have different parameters and p-p bond strength is greater than s-p bond strength. Practically bond strength and distance of both the Be-Cl bonds are same. This problem may overcome if hybridisation of s and p-orbital occurs. Hybridisation : @ @ Itis introduced by pauling, to explain equivalent nature of covalent bonds ina molecule. Definition : Mixing of different shapes and approximate equal energy atomic orbitals, and redistribution of energy to form new orbitals, of same shape & same energy. fp - bp>bp-bp (ii) The directional propertics in hybrid orbital is more than atomic orbitals. Therefore hybrid orbitals form stronger sigma bond. The directional property of different hybrid orbitals will be in following. order. sp bond pair ~ bond pair. (©) Two sigma bonds & two lone pair electrons : (This condition is shown by following compounds and ions. 1,0, OCI, OBr,, OF, ete.49 i) Inall above examples, the central atom showing sp? hybridisation, angular shape and bond angle will be either less then 109°28" or more than 109°28". YZ VF Ps <% ‘Molecular angular orbital of HO. ‘Structure of H,O (Angular) In H,0 the hybridisation on © atom is sp3, but due to presence of two lone pair electrons they repell each other and then repell their adjacent bond pair electron. These repulsion will be in following order. Lp. Lp. > Lp. — bp. > bp. = bp. L.p.= fone pair electron bip. = bond pair electron Examples on sp? Hybridisation Example | bond lone pair Hybridisation |” Shape electron CH, 4 = sy Tetrahedron Ba, 4 - sp* ‘Tetrahedron & 1, 4 - sp ‘Tetrahedron 4 - sp Tetrahedron 4 : sp Tetrahedron 4 = sp Tetrahedron 3 1 sp Pyramidal NCH), 3 1 sp Pyramidal i, 3 1 sp* Pyramidal Ho 3 1 sp Pyramidal XeO, 3 1 * Pyramidal Su, 2 2 sp’ Angular (V-shaped) clo 2 2 sp Angular(V-shaped) scl, 2 2 sp* Angular(V-shaped) Diamond 4 - sp* Tetrahedron SiO, 4 - sp Tetrahedron sic 4 sp Tetrahedron20 sp'd Hybridisation : @ In this hybridisation one s orbitals, three p-orbital and one d orbital are mixed to give five new hybrid orbitals called as sp*d hybrid orbitals. ( Out of these five orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are perpendicular to the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes is trigonal bipyramidal. For example, PF, showing sp°d hybridisation as 3p 3d P (ground state) fi] Gt) CCT I ad P* (excited state) G I Patom share with fveeore CELE TH TT I five sp'd hybrid-otbitals, Malcom bpm! ia (PF, Gai) In this hybridisation d, » orbital is hybridised with s and p orbitals, In this way five spd hybrid orbitals form five sigma bond with five F atoms and givea molecule of PF,, shape of this molecule is trigonal bipyramidal. Axial two P-Cl bonds are longer than equatorial three P-CI bond due to repulsion between 3 equatorial bond pair of electron and 2 axial bond pair of electron. In above hybri ition there are four conditions (a) Five sigma bonds and zero lone pair electron : The following examples represent this conditions. PFs, PCls, PBrs, Ple, ASF, AsCl,, SbCly, SbF, etc.@) 24 (Trigonal bipyramidal) ‘Molecular trigonal bipyramidal orbital of PC1, The shape of all above molecules is trigonal bipyramidal. Four sigma bonds and one lone'pair of electron : ‘The following examples represent this condition, SF,, SoPy. TePy POF, )PF,-\'SbE,, SCl,, SeCl,, TeCl, ete. The shapef all above cxamples will be irregular tetrahcdron/sce saw. Examples SF, 3s 2p Ed S ground state 1) GOT) CLT I 3s 3p 3d S excited state fi) GOT) GI I ab [ab [av] ah I rT five sp'd hybrid orbitals S atom share with four electron of F© @ sp'd? Hybri Mekecar sere rita of SF Three sigma bonds & two lone pair of electrons : ‘The following examples represent this condition, CIF,, BrF, IF,, BrCl,, ICI, ete, The shape of all above compounds is *T” shape. ‘Structure of CIF, (T-Shaped) Malena Taped ita CF, ‘Two sigma bonds & three lone pair of electrons : The following examples represent this condition. ICL,>, 1Br,", CIF", IF, BrF,", XeF, 15. Bry The geometry of above examples will be linear @ Inthis hybridisation, one s-orbital, three p-orbitals & two d-orbitals are mixed to give six new hybrid orbitals known as sp'd? hybrid orbitals. (i) The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral. (i) The angle between all hybrid orbitals will be 90°. Example : SF,, AlF3, PF, ICI, XeF,, XeOF,, IC1-, iv) Two “4” orbital participates in the hybridisation are d,2_,2 and d,2,23 SF: 3s » ] S (ground state) a) (414) CT ] . 3s 3 3d S (excited state) fom Goo aeeteyare) CTT) S (after hybridisation) ‘six sp'd? hybrid orbitals sp'd? Hybridisation: " (@_ Inthis hybridisation, one s-orbital, three p-orbitals & three d-orbitals are mixed to give seven new (@ In this hybridisation d-orbitals used are d,,.'d,3),2 & d,2 orbitals. These seven sp3d? orbitals/are configurated in pentagonal bipyramidal shape. Gv) Five bond-angles ate of,72° & two hybrid orbitals are perpendicular to the plane of five hybrid orbitals that és pentagonal planar, the shape of molecule becomes pentagonal bipyramidal. (¥) The following examples showing sp*d° hybridisation : IF, & XeFg Mlustration. 1. Which ofthe following statement isnot correct? (A) Hybridizationis the mixing of stomic orbitals (B) sp? hybrid orbitals are formed from two p- atomic orbitals and one s-atomic orbitals (C) dsp* — hybrid orbitals are at 90° to one another (D) asp! —hybrid orbitals are directed towards the comers of a regular octahedron Ans. (A) Sol. Hybridization is the mixing of atomic orbitals having comparable energy.24 2. Thecorrect order of increasing s-character (in percentage) in the hybrid orbitals of following molecules! ionsis: () coe (Il) XeF, (yy (IV)NCI, — (V) BeCl, (A)Isill sp? Yscharacter=33.3% — spd? 16.6% > sp'd 20% — sp =25% > sp 50% | Which of the following statementis incorrect ? (A) NH shows sp? — hybridisation whereas N#1z shows sp? —hybridisation (B) A(OH); hasa regular tetrahedral geom (C) sp? hybridized orbitals have equal s-and p- character (D) Usually hybridized orbitals form o- bonds © 2. Whichiscorrect statement? Asthes-character of a hybrid orbital decreases (1) Thebond angle decreases (if)Thebond strength increases (U1) The bond length increases: (IV) Size of orbital increases, (A) (D, (HU) and (LY) °B)(11)y(M) and (IV) (C) (1) and (it) (D)Allarecomrect Ans. (A) HYBRIDISATION IN SOLID STATE / AQUEOUS STATE OF MOLECULES Hybridization of covalent specie which exist in ionic form in solid state, Gaseous State |Hybridization [sotid state __| Hybridization (Cation) Hybridization (Anion) PCls [rci.]* + [PCI Br, [PBr,J* + Be IXeF,, [XeF,]* + FT INO, INo,]* +[NO,- INO, INO]? + [NO IN,O5 INO]? + [NOT BrF [BrF,]* +[BrF,)” MF UF)" +E.” ici [cn +f1c- C1,0, [clo +{c10,- 1,05 Pr +[l05); 1,Clyry fC} 4[1C1,- ty Oy +07" cn UCN} +10), spdMlustration 1, Thecationic part of solid Cl,0, ishaving the”. * shape. (A)linear (B)angular (C)Tetrahedron —_(D) undefined Ans. (B) Sol. CLO [Cost +(clo.r wen Exercise 1, Whatisthe state ofhybridisation of Xcin cationic part of solid XeF. Aspe? (B) spt (©sp'd (D)sp* Ans. (B) GLESSPIE AND NYHOM THEORY OR VSEPR THEORY (Valence shell electron pair repulsion theory) (@ Ifthe central atom possess only bonded pairs of electroris alongwith identical atoms then shape of the compound is symmetrical and according 16 Sidgwick & Powel eg. BF, - 120° = rrigonal planar CH =109°28".) > tetrahedral €O, 180° = linear Gi) Ifthe central atom possess bonded pair of electrons as well as lone pair of electron, then shape of the molecule will be unsymmetrical ic. the original bond angle will disturbed due to repulsion between lone pair of electrons. Similarly on having different type of side atoms, molecule becomes unsymmetrical due to unequal force of repulsion between electron. Order of repulsion is — ¢.p, - -p > Gp — bp. > bp. — bp. 1 Bond angle = No of fone pair of electron Gii) By increasing one lone pair of electron, bond angle is decreased approx by 2.5°. eg. CH, NH; H,0 — sp? hybridisation 109? 107, 105° Gv) In the different molecules if central atom have same number of lone pair of clectron then bond angle will depend on electronegativities of A & B. In AB, type of molecules if side atoms are same Electronegativity of central atom increases, then bond angle increases. rm x a sero bes reousiontoto creepy 10> Hecronegaiyf Bond angle - NH, > PH, > AsH26 In AB, type molecules, if central atoms are same and the Electroncgativity of side atoms increases then bond angle decreases. eh * a a ™ lectronegativty of ucrine is greater than chlorine PF, < PCI, H,0 Wis aN Mlustration 1. Arrangethe following in order of decreasing NV - 0 bond length’: NO; ,'NO;, NO; (A)NO; > NO} > NO; (B) NO; >NO; >.NO3(C) NO; >NO; > NO;(D) NO; > NO; > NO; Ans. (B) L Sol, Bondorder= Bondjongih No,* No,- No,- Bondorder 2 1s 1.33 Exercise 1. Commentonthe ZCNC and ZHNN in CH,NCS and HN, respectively. (A) less than 120° and less than 120° (B) Greater than 120° and less than 120° (C)less than 120° and greaterthan 120° (D) Greater than 120° and greater than 120° Ans. (B) 2. Thecorrect order of decreasing x -O-X bondangleis (X= H,F oC) : (A) H,0>Cl,0> F,0 (B) Cl,0> H,0> F,0 (C) F,0>Cl,0> H,0 (D) F,0>H,0> C10 Ans. (B) DRAGO'S RULE According to Drago, when central atom of the compound is of 3rd period or below this of periodic table then lone pair is present in stereo chemically inactive s-orbital and bonding will take place through pure p-orbitals. But electronegativity of the surrounding atom must be less than or equal 10.2.5. Then there is no hybridization and bond angle is nearly 90°. NH; (107.8%), PH, (93.6°), Asi, (91.8°), SbH, (91.3°)27 Mlustration 1 Ans. Sol. Among the following, the correct statement is: (A) Between NH, and PH,, NH; isa better electron donor because the lone pair of electrons occupies spherical ‘s’ orbital andis less directional (B) Between NH, and PH, PH, isa better electron donor because the lone pair of electrons occupies sp? orbital and is more directional (©) Between NH, and PH,, NH, isa better electron donor beeause the lone pair of electrons occupies sp’ orbital and is more directional (D) Between NH, and PH,, PH, isa better electron donor because the lone pair of electrons occupies spherical ‘s" orbital andis less directional © NII, —+ sp? hybridisation (directional property), PH,— No hybridisation Sothe NH, isa better lewis base than PH, Exercise 1, Thebondanglein Pi, (A)Much lesser than NH, (B) Equal to thatin NH, (C)Much greater than in NH (D)Slightlymorethan in NH, Ans. (A) RESONANCE @ _Thecoficept of resonance was introduced by Heisen berg (1920) , and later developed by pauling and ingold, toexplain the properties of certain molecules, (i) _Ithasbecn found that the observed properties of certain compounds cannot be satisfactorily explained by writingasingle lewis structure. The molecule is then supposed to have many structures, each of which canexplain mostof the properties ofthe molecule but none can explainall the properties of the molecules. ‘The actual structure isin between ofall these contributing structures and is called resonance hybrid and the different individual structures are called resonating structures or canonical forms. This phenomenon is calledresonance. (ii) Letusdiscuss resonance in ozone, according to its resonating structure it should have one single bond (O—O = 1.48A) but experiments show that both the bonds are same which can be proved by its resonance hybridas shown below. A So = 50 Resonance hybrid To calculate bond order in the polyatomic molecule or ion use following formula : Total number of bonds in a molecule Bond order = Resonating Structures 0a CO Bond order=4= 133 ¢ =P" PO Bond order= i o28 CIO Bond order=2=1.75 (A)benzyl chloride (B)cthyl chloride (C)chlorobenzene —_(D) allyl chloride Ans. (©) Sol. _Boththemolecule shows resonance Exercise lL Which of the following option is incorrect? (DAI C-O bonds in CO} are equal but not in H,CO,. (I)AIC-O bonds in HCO} are equal but not in HCO,H (Ill) C-O bond length in HCO} is longer than C-O bond length in CO". (I1V)C-O bond length in HCO and C-O bond length in CO? aréequal/ (A) IME IV (B) EM (MEI, (@)1e1v Ans. (A) 2, Resonance does not occur duc to the (A) delocalization of alone pairofelections . (B)dclocalization of sigma clectrons (C) delocalization of piclectrons (D) None ofthese Ans. (B) BENT RULE When all hybrid orbitals equivalent. Ex. sp, sp? (1) Ifthe more EN atom present in hybrid orbital, %s character decreases. to compensate decrement of %s character these %s character increases on that orbital which have less EN atom bonded. Example-1 " " F " t Jot [+ pst ZI™ sLoyat wel eS Althave se ta character rn o © ch C-Hbondlength a>b>c>d HCFbondangle b b > c (X = Central atom) Ithybrid orbital are not equivalent Lip. acquire place where %s character are higher Example-3 sf pd s —s For ex. of pd apd SF, CIF, XeF; F F Kl al De oF F | oq More EN atom aquire place where %s character are less Example4 PCF. i i i i Ch a F Sra “Na Nr Nror | | | a] ca F F F PFCI, PR.CI, PCI PECL30 Bond length comparison Example-S Kyte nel re Ne iw oO Nu N-N bond length a b Ilustration 1. Comment onthe effect of lone pairon axial and equatorial borid angles of SF,- F tov Sol CD>S@)103° F Asexpeeted axial bond should distort more than equitorial but actually duc to loan pair has tendency to goes with more % character available bond angle decreases more than axial one. Equatorial F—S—F angle will be 120° butit is 103°) 2. Axial B.A. in (GF,)>CH,=SF,. Why? F mn k F € Sef f Soh aval [ae Vas 0" Equsoral 105" 10 7 Exercise L ‘The strongest P-O bond is found in the molecule (A) F,PO (B)C1,PO (C)Br,PO (D)(CH),PO Ans. (A)34 BACK BONDING ‘The one sided sharing of electron pair present in the outer orbital of an atom with the empty orbital present in the adjacent atom. It leads to the formation of a x coordinate bond. Condition for back bonding Effects of back bonding L 2 3. 4. The donor atom must have localized donatable electron pair. In general these are later half , second period P - block elements (F, O, N and C). The acceptor atom must have low energy empty orbital which generally are np or nd orbitals. Small and similar sized orbitals favour overlap. always leads to an increase in bond order between the participating atoms. It always leads to an increase in bond strength between participating atoms. It always leads to a decrease in bond length between participating atoms. It decreases the lewis acid character of the acceptor atom as the low energy empty orbital is now filled and not available for accepting the electron from a lewis base. This is eVident in case of boron halides. Boron and fluorine are the members of the same périod and hence have orbitals having similar size and energy. This allows fluorine to effectively donate the electrons from its filled p orbitals to the empty unhybridized orbital of boron. This makes BF, much weaker lewis acid than BCI, which intum isa weaker lewis acid than BBry. Structural formula of boron trifluoride, BF, showing ? bonding involving filled fluorine 2p orbitals (formally lone pairs) overlapping with the empty 2p orbital on boron and donating electron density to relieve boron's clectron deficiency. This can casily be explained by the increase in size of the halogen atom, its orbitals and decreased capacity to donate electron towards back-bonding as we move down the group. The Lewis acidity scale of boron trihalides BX, (X=F, Cl, Br, 1) and character of the boron-halogen bonds have been studied by means of DV-Xm approach. Present results show that the acid strength of boron ttihalides increases in the order BF; BCI, > BBr, > Bl, (B) BI, > BBr, > BCI,> BF, (C) BF, > BI, > BCI, > BBr, (D) BF,> BCI, > Bl, > BBr, Ans. (B) SILICATES ‘The way in which the (SiO,)* tetrahedral units are linked together provides a convenient classification of the many silicate minerals.fot +-» ‘Tto'sl [02+ “itors| £5.0.<0 (.0+-«'forsl] 7 snes) 20, OAML alos) to's) 2u -H’ors] to's) o1oy DR afour Paps aay poaeys #209105 aamanig Aejnunog Tesuay | ejauoyyesauag | 0, J0°ON Josadsy, S24DIIIIS JO UO}yDIIJISSDID34 wn-170°S] aunyonaig [202 + unI0%s)] biG=U ont 0%] Lot+-, To's] “eh =U ~~-<' Fors) g=uyt parHsay J vnus0g persue qnuuog per2025 ‘onaajour ad puns: 10,10 °ON, SOLES, Josadlsy,== iL —¥-o0-— & *Cors) “Cors) Oy stafuigo tou = tt ose Loworpsoppipa] ---<'fors| u 0.6 | ayvois ways az aynsojour 4og paiwys soreoIES eyo perauas) Jost36 POSES J enunod jexu95 yuo g ex919 ‘ojnasjour Jad pacys: 40,J0"ON. sarcoms josadsyMlustration 1 The following pictures represent various silicate anions. Their formulae are respectively: YAK, me (A) SiO; Si, (B) Sioy Si,OfG (©) sio> Si,0 (D) ios SiO} Ans. (B) Sol. (1) —_Orthosilicateis SiO, (HI) Ist & last are chain terminating unit. So the molecular formula is SiO, 2° + siO- +Si0, > 2. Si,0,anion is obtained when (A)no oxygen of a SiO, tetrahedron is shared with another SiO, tetrahedron, (B)one oxygen ofa SiO, tetrahedron is shared with another SiO, tetrahedron. (C)two oxygen ofa SiO, tetrahedron are shared with another SiO, tetrahedron. (D) three or all four oxygens ofa tetrahedron are shared with other SiO) tetrahedron. Ans. (B) Sol. — Pyrosilicate > no. of oxygen shared in cach tetrahedronis 1. Exercise 1. Si,O$ (having three tetrahedral) is represented as: (A) AY ® KY \ (C)both (D)none Ans. (B) 2. Thesilicate anion in the mineral kinoite is a chain of three SiO, tetrahedra that share comers with adjacent tetrahedra. The mincral also contains Ca** ions, Cu** ions,and water molecules ina 1:1:1 ratio mineral is representedas: (A) CaCuSiO,'H,0 (B) CaCuSi,0,2H,0 (C) Ca,Cu,Si,0,;2H,0(D) none of these Ans. (©) BRIDGE BOND Whena species scems to be exceeding its valence in abid to join two specie the bond is termed as the bridge bond. ‘Themain reason for the formation of the bridge bond is to complete the octet. This is the main but not the only reason. There could be specie which have octet already exceeded and still they try to gain more electrons by the formation of the bridge bond. It seems that the reason is just the availability of low energy empty orbitals. The first preference of every species is to satisfy the valency within the molecule. That is the back bonding. The bridge bond is formed when a species cannot satisfy the electron deficiency by back bonding.38 The bridge bonds are of two types: 1, Theelectron deficient bridge bond. It is formed by hydrogen, alkyl or boron. 2. Coordinate bridge bonds. These are formed by the species which have an extra donatable electron pair in their valence shell. These are generally formed by halogens. Planar /NonPlamar | Structure Hybridisation Compound] Bridge Al{CHy, | 30-26"dD dD _D IY mA! N A Y Q suryduon | b= ds- cs | _ap-9¢] _(pqos) ous SOS, yp” Spm (aso j uop aay) PO: seu | _popmayion |__oy -9¢ Sigteg dunyquon | _ — ds— ds |__ap- 96 p—- aD <3 maya | sm @s- 9&6 | _ov of hota Jwuyquon | b~ ds cds | _ay-96 gt svurjg uN ampnng| acura | —_ueyosuasy | __a8pugq| _punodinoa40 Iustration 1. Thetypeof overlap inthe ridge bond existingin Al (CH,),is (A) sp'—sp'd—sp* (B) sp'-sp*-sp>_ (C) sp—s—sp* (D) sp? —sp?—sp* Ans. (D) mt ie Ci said Sol. ne~, be Sen, mW VP |. Themolecular shapes of diborane is shown: Consider the following statements for diborane: Wo a 1. Boron is approximately sp" hybridised Ww CoN, 2.B-H-Bangleis 180° 3. There are two terminal B-H bonds for each boron atom 4. Thereare only 12 bonding electrons available Ofthese statements: (A) 1,3and4 are correct (BY1, 2and 3 are correct (C)2,3 and 4 are correct (D)1,2and 4 are correct Ans. (A) HYDROLYSIS Hydrolysis is a chemical process in which a certain molecule is split into two parts by the addition of amolecule of water. One fragment of the parent molecule gains a hydrogen ion (H+) from the additional water molecule. The other group collects the remaining hydroxyl group (OH-). Ilustration le ‘Select correct statement about hydrolysis of BCI, and NCI, (A) NCI, ishydrolysed and gives HOCI but BCI, isnot hydrolysed. (B)Botli NCI, and BCI, on hydrolysis gives HCT (C)NCI, on hydrolysis gives HOCI but BCI, gives HCI. (D) Both NCI, and BCI, on hydrolysis gives HOCI. Ans. Sol. NCI,+3H,0-NH,+HOCI; BCI, +3H,0 > H,BO, + 3HCI Exercise 1. Which of the following halides cannot be hydrolysed? (TeF, (ll) SF, (Ui) NCI, (IV) NF, Choose the correct code : (AVI&IV (B)LU& Ml (LUeIV (Dav ‘Ans. (D)a4 lone “(HON “(HOPI dur “ost Peds ‘pes | ENS] ¥ ENS] ENS] IDHE “Or Pes * FE apes | ENS] 9 ENS] —— [wonewonrodoxisicr Peds ‘pes | ENS] 9 ‘ENS] pads ‘pds | Ens) 9 ‘ins) € =Ayowseg ‘Ho POTD (uoyn joaynss 04 pads1 | ayuozo4y unsy Gpysog Sy yoysnd Sw puposd 1 ‘orn “os"t Ens] fost e=Anaseg ‘H 2y21diuI0 z FNS) *o%dH z= Anjoysea ‘H a1ardwod 9 YENSI fora Z=Anased “Hy a1e1du0D 1 SENS] ‘o's*H ¢=Anaseg ‘H 291d) 9 ENS] Sora COC) ZeAyaseg ‘H a191dU0D z ENS] *o's'H = 1 Opa SyeN H ajapditto> £ ‘HN TDOHE ENS) ‘ON Z=Anoqsuel ‘1 aapditiod z] tone “Goad *FNs) joea arsequt_[*(HO) e=Anaseg Y a1eydI0D £ lone“ “Esl Son] POUED (wow yosnesa 01 r29ds04 | 3yn290] uns) Crprsog ‘1 yoyod | DMA puposd awypauuayiy opsy aaduoy) young | —_ fo vn | _s0 wnpoig uns |uruowospuasT wuspmnpayy punodwo3 4243 MOLECULAR ORBITAL THEORY VBT (Valence bond theory) was unable to explain eg. Paramagnetic nature of ©, molecule, as per VBT (:0: should be diamagnetic. Definition: The atomic orbital lose their identity during molecule formation (overlapping) and form new orbitals termed as molecular orbitals. Characteristic of molecular orbitals: 0 @ iil) @) ” Molecular orbital formed by overlapping of atomic orbital of same energy ‘Number of molecular orbital formed = number of atomic orbital involved in overlapping Half of the molecular orbital have lower energy are called Bonding molecular orbital. Half are of higher energy is termed as Antibonding molecular orbital Electronic configuration in various molecular orbital are governed by same three rules. (9) Aufbau'’s rule (b) Hund’s rule (©) Pauli’s exclusion principle ‘Comparison of Bonding molecular orbital & Antibonding molecular orbital : Bonding molecular orbital (BMO) Antibonding Molecular orbital (ABMO) Bonding MO is the result ofthe linear ‘ABMO is result of linear combination of AO combination of AO when their wave when their wave function are substracted function are added Y=, +4, Y=%,—%y Generally yt does not have node. Italwayshavea node between two nuclei of bondedatom. Charge density increase between two Charge density decrease in between two nuclei, nuclei resulting attraction between two leads to repulsion between twoatoms. atoms Energy of BMO is less, hense stable Energy of ABMO is high, hence unstable Notation of molecular orbitals: As atomic orbitals are known by letters s, p, d and f depending on their shapes. Similarly for molecular orbital, For bonding molecular orbital- 0, 2,8 etc. For antibonding molecular orbital- 0+, x*, 5+ etc. are used for different shapes of electron cloud.44 Energy Level Diagram of molecular orbital : On the basis of Aufbau’s rule - increasing order of energics of various molecular orbitals is- © (Is) < o* (1s) <9 (25) <0 (25) , F,, Ney aeaeten? 2p VE ® Y@_@. Having two unpaired Ca rer te Cake o(2p,) @ (2s) (25) ® oO” ™~_@ is ™. a 1s Atomicerital “S_@ "atomic orital of oxygen atom (15) of oxygen atom Molecular orbital of oxygen Molecule Bond order = 2 For 0, molecule Increasing energy Stability order— 0; > 0,> 0;> OF Bond length O20; > 0,> 0;45 Energy level diagram for B,, C, and N, molecules — 9 (1s) <0* (Is) <6 (2s) N, :thenmolecute exist NyCO* Exercise 1. Duringthe formation ofa molecular orbital from atomic orbitals, probability ofelectron density is: (A) minimum in the nodal plane (8) maximum inthe nodal plane (©)zero in the nodal plane (D) zero onthe surface of the lobe Ans. (C) 2. Pickouttheincorreet statement? (AYN, has greater dissociation energy than N,* (B) O, has lower dissociation energy than 0,” (C)Bond length in N,* is lessthan N, (D) Bond length in NO* is less than in NO. Ans. (©) 3. Whichofthe following species is paramagnetic’? (A)NO™ (B) 02> (c)cN™ (p)co Ans. (A) 4. Bond order of &¢ l (B)2 (3 (@)o Ans. (D)48 Characteristic of Covalent Compound : 0 @ Gi) ) w) oi) Physical state :~ Covalent compounds are found in all the three states - Gas, Solid & Liquid. Separate molecules — In gaseous state Associate molecules — In liquid & solid state (Duc to strong vander waal’s force and hydrogen bonding among the molecules.) As the molecular weight increases, physical state changes : cg. FrandCl, Br, ly gs liquid solid —___, Top to bottom in a group, Vander waal’s force increases between the molecules. Covalent solid : Those solids in which atoms are linked together by covalent bonds, forms infinite three dimensional giant structure. ¢.g. Diamond, Graphite, AfN, SiC, SiO, ete. Molecular solid : Discrete (separate) molecules are formed by covalent bonds and then the molecules associated due to intermolecular force of attraction. (Vander-waal’s force) eg. Solid I, dry ice (Solid CO,) ete. Conductivity : Mostly covalent compounds are bad conductor of dlectricity, But few polar covalent compounds duc to self ionisation can conduct clectricity.¢,g°H,0, lig. NH, ete. H,0 + H,O = H,O* + OHA 2NH, =? NH\t +)NH,~ Free ions are formed which ean conduetelectricity. Exceptions: Graphite, HCIin water, Solubilitys’Non polar compound are soluble in non polar solvents. Non polar compounds forms ‘Vander-waal’s bond with non polar solvent molecules. Isomerism : Covalent bond is rigid and directional, so it shows isomerism. eg. Organic compounds. Reaction : Reaction between covalent compounds are slow. Because it involves breaking of old bonds and formation of new bonds ELECTROVALENT OR IONIC BOND 0 The chemical bond formed between two or more atoms as a result of the complete transfer of one or more electrons from one atom to another is called Ionic or electrovalent bond. Electro positive atom loses electron (group IA to IIIA) Electro negative atom gains electron (group VA to VIIA) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond. Electronegativity difference « nature of ionic bond. Example 1A and VIIA group elements form maximum ionic compound. Na + Cl > Na + oo 281 287 28 2.8.8 Xe % (Ne configuration) (Ar configuration)49 ”) «i ii) ai More the distance between two elements in periodic table more will be ionic character of bond. Total number of clectron lose or gained is called electrovalency. Example — @ electrovalency of Mg = 2 electrovalency of O= 2 electrovalency of Ca=2 (b) electrovalency of Cl © 2002 eloctrovalency of Ca= 2 electrovalency of O= 2 The force of attraction is equal in all direction, so ionic bond is non-directional, Ionic compound do not have molecular formula, [bhas only empirical formula. eg. NaCl is the empirical formula of sodium chloride. Conditions for Forming Ionic Bonds : @ @) © Formatioft of Ionic bond depends upon these three factors : Ionization energy : Amount of energy required to remove an electron from the outermost orbit of an isolated gaseous atom to form the positive ion or cation. (energy absorbed) Lesser Ionisation energy -> Greater tendency to form cation. “o were oN sue } Cationformationtendency Electron affinity ‘Amount of energy released when an electron is added to an isolated gascous atom to form negative ion (i.e. : anion). Higher electron affinity -» Greater tendency to form anion eg Ch>F>Br>r F>O?>N3 Lattice energy - Amount of energy released when one mole of crystal lattice is formed. Higher lattice energy -» Greater will be the stability or strength of ionic compound. Factors affecting lattice energy : () Magnitude of charge : Lattice energy (U) « 2* 2° (Ionic charges of cation and anion)50 Lattice energy Magnitude of charge NaF MgF, AI Nat Met? ne — Lattice energy increases, Size of cation decreases. (W Size of Cation : Lattice energy * += “a NaCl Kel RCL CsCl a Size of cation increasing —Size of anion is constant ~ Lattice energy decreases Representation of formula of compounds : @) © © Write the symbols of the ions side by side in such a way that positive ion isat thelef and negative ion is at the right as A°B- Write their electrovalencies in figure at the top of each symbol as A*BY, Now apply criss cross rule as AS™BL i.c formulaA,B,e Examples : Calcium chloride'caS"Gid| = CaCly Inert Pair Configuration, The heavy elements of IITA, IV A and V A groups form cations having charge equal to group number and two less thin group number, e.g. Ti", In‘, Sn'2, Pb". In these elements due to more penetration power of s orbitals, the atom generally does not lose ¢- present in ns orbital, so only np electrons are lost by the atom. This effect is called “inert pair effect”. Mlustras 1. Amongthe following, the clement which show inert-pair effect are: () 87 (Sn (uu Pb aye (A&I (B)1& (naiv (DLN&M Ans. (B) Sol. _Inaheaviourp-block elements lower oxidation becomes more & more stable due to the inert pair effect. Sothestability of Pb‘? > Pb“# Bi? > Bis Exercise 1. Whichof following stability orders incorrect duc to inert pair effect. (A)Hg?> Hg"* (8) B?*> Bis (C)Pb*>Pb* = (D) Fe?" < Fe* Ans. (D)84 POLARIZATION (Fajan’s Rule) (Covalent nature in ionic bond) (@ — Whena cation approaches an anion closely the positive charge of a cation attract the electron cloud of the anion towards itself, due to the electrostatic force of attraction between them. (@ —_Atthe same time cation also repel the positively charge nucleus of anion. (ai) Due to this combined effect, cloud of anion is bulged or elongated towards the cation. This is called distortion, deformation or Polarization of the anion by the cation and anion is Polarized. Polarization Power The ability of cation to polarise a nearby anion is called Polarization power of cation. © @©® — exp Polarizability : (Ability of anion to get polarised by the cation. (i) Polarization of anion causes some sharing of electron between the ions $0ionic bond acquires certain covalent character. (ii) Polarisation « Covalent-character (iv) Magnitude of polarization depends upon a number of factorssuggested by Fajan and are known as Fajan's rule. FAJAN'S RULE + (FACTORS AFFECTING POLARIZATION) (a) Size of cation ; Polarization of the anion increases as the size of cation decreases. Polarization = Se salon In a group— BeCl, MgCl, | - Size of cation increases CaCl, | - Covalent character decreases SrCl, | = onic character increases Bat Greatest polarizing power of Be?*, shows its maximum covalent character in BeCl,. In a period — ‘Na’, Mg”, AI®, Sit —__, - Size of cation decreases - Covalent character increases ) Size of anion If the size of the anion increases for a given cation, the covalent character increases Polarization = size of anion. CaF, CaCl, | - Size of anion increases CaBr, | - Covalent character increases Cal, | - Ionic character decreases52 © ‘Charge on cation and anion ; => Polarisation = charge on cation / anion @ Charge on cation x Polarisation (covalent character) eg. NaCl MgCl, AICI, SiCl, Nat Met ae sit ~ Charge on cation increases = Covalent character increases = Ionic character decreases (Melting Point decreases) , scati 1 CCharge on anion = polarisation = covalent nature « === (@) Electronic configuration of cation : Ifthe size of cations in different compounds are same than that of cation having inert gas configuration, polarization capacity of cation having pseudo inert gas configuration is high. CuCl (Melting Point = 442°C) —> Cut (2,8, 18) (Covalent) NaCl (Melting Point = 800°C) —> Nat (2, 8)_— (onic) Cut and Na* both the cation (Pscudo & inert) have same charge and siz€ but polarizing power of Cu* is more than Na* because Z¢ of ns*p® (inert) < Z.gof ns*p%d" (pscudo). Nat < cut onic) (Covalent) ‘So, CuC! has more covalent character than NaCl. 1, Amongst LiCl, RbCl BeCl, and MgCl, ,the compounds with the greatest and the Ieast ionic character, respectively are: (A) LiCland RbCl (B) RbCland BeCl, (C) RbCland MgCl, (D) MgCl, and BeCl, Sol. (B) ‘According to the fajans rule 1 Covalent character « polarisation power °: 5 >— oF cation polarisability «size ofanion Exercise 1. Themelting point of AIF, is 1291° Cand that of SiF, is- 77°C (itsublimes) because : (A) there is a very large difference in the ionic character of the Al-F and Si-F bonds (B)in AIF, AP interacts very strongly with the neighbouring F~ ions togivea three dimensional ‘structure but in Sif, no such interaction is possible (C)the silicon ion in the tetrahedral Sif, isnot shielded effectively from the fluoride ions whereas in AIF, the AP? ionis shielded onall sides (D)theattractive forces betwoen the Sif, moleculesare strong whereas those between the AIF, molecules are weak Ans. (B)53 Properties of ionic compounds : @) ©) © @ © @ @ Physical state : onic compounds are hard, crystalline and brittle due to strong electrostatic force of attraction. Brittleness - (Same charged ions comes nearer. So they repell each other) Isomorphism : @ Two compounds are said to be isomorphous if they have'similat number of electrons i.esimilar electronic configuration of their cation andanion, Gi) They have similar erystal structure. Example - ‘Na* F Mg” oO? Valency, +1 -l +2, -2 Clectronie configuration 2,8, 2,8 28 2,8 ‘similarly Ca*? 2crt 2Ktt s? 2.8.8) (28,8) 28,8) 2,8, 8) Boiling point and melting point : Tonic compounds have high boiling point and melting point due to strong electrostatics force of attraction among oppositely charged ions, Conductivity : It depends on ionic mobility. In solid state - No free ions - Bad conductor of electricity. In fused state or aqueous solution Duc to free ions - Good conductor of electricity. conductivity order : Solid state < Fused state < Aqueous solution, Solubility : Highly soluble in water (Polar solvents) Example : NaCl in water ‘The Na* ions get associates with negatively charged ‘O° of water And CI- ions associates with positively charged *H’ of water.54 (ii) Thus charge on Na* and Cl- decreases and electrostatics force of attraction also decreases which leads to free ion. (iw) The energy released duc to interaction between solvent and solute is called solvation energy. If water is used as solvent it is called hydration energy. (%) Foran ionic compound to be soluble in water Hydration energy > Lattice energy 1 Lanice energy = Soupmay Hydration energy = Solubility. 1 {r, & r_are radius of cation and anion} not Hydration energy (H) (v)) Hydration energy mainly depends on the cation radius because the value + is negligible in < 1 comparison to —. t (si) Down the group both the lattice energy & hydration energy deéreases) if decreases in lattice is greater than hydration energy, solubility increases down the group and vice versa. Allustration 1, Thehydration ofonic compounidsinvolves:, (A) Evolution ofheat (B) Weakening of atractive forces (C) Dissociation into ions (D)Allofthese Sol. (D) TheoryBased Exercise 1. Thecorrectorder of hydration energy is (A) Be? < Lit (B) Na*> Mg? (C)Na* < Mg*? (D)AI3 CH,OH > CH,CH,OH > CH,COCH, > CH,OCH, > CH, {) Ionic compounds are more soluble in the solvents, having high dielectric constant. (©) __H,SO, and H,0, have high dielectric constant but these are not a good solvent due to oxidising nature.@) Size of Ion: (a) Keeping size of cation constant, the lattice energy decreases with the increases of anionic radius. Hence, order of solubility of LiX in water is LiF < LiCl < LiBr Lattice Energy, therefore Li is more soluble in water. (©) Keeping size of anion constant, the hydration energy decreases with the increase of cationic radius. Hence order of solubility of MSO, will be - BeSO, > MgSO, > CaSO, > SSO, > BaSO, (Exception of Fajan’s rule) (@)__Msize of cation and anion is very large, solubility decreases from top to bottom, As, solubility « (©) Solubility decreases in a period (as ionic nature decreases and covalent nature increases) NaCl > MgCl, > AICI, 1, Whichof the followingis/are incorrect about solubility trend ingroup I S11? Least solublein water . {Most solublein water (A) Hydroxides LioH CsOl (B)Carbonates Cs,COs Li,co, (CNitrate Ba(NO})y Be(NO,), (D)Sulphates Baso, BeSO, Sol. (B) Conreet solubility order Li,CO, H-Cl > H-Br > H-I dipole moment (y) = 0 for H-H, F-F, CI-Cl, Br-Br, O-O For polyatomic molecules dipole moments (1) depends on the vector sumof dipole moments of all the covalent bonds. For PCI; and SF,, etc. dipole moment (1) = 0 due to their regular geometry. Benzene, naphthalene, biphenyl have dipole mofnents (1) = 0.due to planar structure. Ifthe vector sum is zero, than compound is non-polar compound or symmetrical compound (and it is not essential that individual dipole momients (1) of every bond should be zero). Example ; (A) BX;.'CCl,, SiCly, CH,, CO,, CS,, PCI, SiH, ete. In thes@ examples the bond B-F, CCl, C-H, C-O, P-Cl etc. are polar even though compounds are non-polar. we Pa, s ‘NH, NF, bys Me 4 wyF oe Sn ove, @ FA NX, aot Ne yt Ececronagabity ot P= sa Dipole moment of HO is 1.85 D which is resultant dipole moment (1) of two O-H bonds. oO ZS, wo dipole moment (,) of H,O is more than dipole moment (u) of H,S because electronegativity of oxygen is higher than sulphur. Angular structure of molecule have greater dipole moment. Application of dipole moment : 0 To determine polarity and geometry of molecule : If dipole moment (x)= 0 compound is non polar and symmetrical eg. CO,, BF,, CCl, CH,. BeF, ete.