CHEMICAL BONDINGDISCLAIMER “The content provided herein are created and owned by various authors and licensed to Sorting Hat Technologies Private Limited (“Company”). The Company disclaims all rights and liabilities in relation to the content. The author of the content shall be solely responsible towards, without limitation, any claims, liabilities, damages or suits which may arise with respect to the same.”Chemical Bonding Force of attraction between two or more than two atoms to hold them together is called chemical bond. = Atoms combine to gain stability by decrement in energy. Example : Formation of H, molecule H(g) + H(@) ——> H,(g) + 435.5 kJ/mol H = -495.5 kd/mol = - g & x Potential Energy —>% + H(e) Internuclear distance ———> Tendency to acquire minimum energy: 1 When two atoms approach to each other-electrons of one atom attracts the nucleus of another atam. 2 Two electrons and nucleus of both the atoms repel each other's. 3, Total energy of system decreases if net result is attraction. When the net energy of the system is least a chemical bond is formed. 4, Energy released in bond formation is called bond energy. 5. Bond formation is an exothermic process. 6. Bond dissociation is an endothermic process. Repulsion AttractionEnergy | Energy 1 Stability | Stability | Exothermic Endothermic P.-e,, P,-e, e@-€,. P,P, Internuclear distance at the time of bond formation is called bond length Qo « Bond | Internuclear Energy y distance Oar r rso Bond length H, =D, R>A R=A AR Bond Energy H, O>F [Strength « More electronegativity of donor ator] Intramolecular Hydrogen Bonding : H-Bond formation between two or more molecules of either the same or different compounds known as intermolecular H-bonding. wo Ho Xe Kom He Xe‘These are two types: (b) (a) Homo-intermotecular :- Hydrogen bond between molecules of same compounds. Examples: (i) Hydrogen fluoride: HF is a polar molecule, with the fluorine atom acquiring a slight negative charge and the hydrogen atom acquiring an equal positive charge. The electrostatic attraction between the oppositely charged ends results in hydrogen bonding as shown below. HOP see HOF aa HF (i) Water : The high boiling point of water compared to that of hydrogen sulphide is due to molecular association through hydrogen bonding. The crystal structure of ice shows a tetrahedral arrangement of water molecules. Each oxygen atom is surrounded tetrahedrally by 4 others. Hydrogen bond link pairs of oxygen atoms together as shown in Fig. The arrangement of water molecules in ice is a very open structure and this explains the low density of ice. When ice melts, the structure breaks down and the molecules pack more closely together so that water has a higher density; this packing goes to a maximum up to a temperature of 4°C. 6: HOH Hetero intermolecular: Hydrogen bond between molecules of Example: ()) Alcohols and water : Lower alcohols and phenols are associated due to intermolecular hydrogen bonding. Methanol, ethanol and phenol have relatively much higher boiling points than methane or chloromethane, ethane or chlaroethane, benzene or chlorobenzene respectively.o_H_o_H_o_W LLld aces wae aoe, 2. Order of strength of H-bon ¢ HAF >H,0> NH, © OHO > NOH een > N=H © 7,0 >D,0>H,0 For Better H-bonding [Extent of H-bonding « Number of hydrogenbond = bond strength] ‘Some Examples of intermolecular hydrogen bonding 4 is N ww (Homo int ermolecular) 4 H H .O_H (eto intermolecular) qi) (wy) (2) Application of intermolecular H-bonding 1. Boiling point f)(Hel NH, > HF Boiling point H,0 > HF > NH, Dimerization: CH,COOH exist as a dimer in vapour phase Observed molecular mass = 2 x 60 = 120, due to intra molecular H-bonding dimerization is observed NH,-linear H-bonding ys i s Cone Con NH \ x \ 4 4 iH = HCY, HBr; HG] not exist In case of HCL: wet, +) stage se © In case of K’F, due to similar size of F> : 2KOR +H-F SF PH—FTK® or KTHFD ‘Symmetrical H-bonding 6. _ p-nitrophenol a. ont oy 7 ppt ved O-nitrophenol BP? _vPU (O.2 Whyiee floats on water? 177 Pm ff recant space Sol. 47 Density of ice is less than water. Due to cage like structure of Ice, it has vacant space inside making it less denser. © Maximum density of H,0 at 4°C (277 K)Density |~ g/m? —Temperature (k)—> Order of M.P and B.P in amines IRNH, > R,NH > R,N er i 3 Viscosity « Number of Hydrogen bonding Solubility «< Number of Hydrogen bonding (5 Gorrect order of solubility in water @ 1° amino > Alcohol Gi) Glycerol > ethyl glycol > ethanol ii) CH,CH,CH,>CH,CH,OH > CH,-O-CH, Sol. w (8) Glycerol > ethyl glycol > ethanol Application of intermolecular H-bonding Chelation or intramolecular hydrogen bonding (with in a molecule) Sometimes hydrogen bonding may take place within a molecule; this is known as intramolecular (or internal) hydrogen bonding. it may lead to the linkage of two groups to from a ring; such an effect is known as chelation, Examples: @) Nitrophenolsiii) (iv) ™) a os = we £ \ \ , . | a, ‘o-nitrophenol m-nitrophenot p-nitrophenol less soluble in water ——~__~commmmcaivvoreuune Because of the proximity of -OH and -NO, groups in o-nitrophenol there is intramolecular hydrogen bonding which prevents intermolecular hydrogen bonding between two or more molecules. Since molecular association cannot take place, the boiling point of o-nitrophenol is lower than that of the other two. Because of the distance between -OH and -NO, groups in m- and p-nitrophenols there is no possibility of intramolecular hydrogen bonding. Intermolecular hydrogen bonding may take place to a certain extent which cause some degree of molecular association; this is responssible for the higher boiling points of the two nitrophenols. Further the formation of intramolecular hydrogen bonding in o-nitrophenol prevents it from entering into intermolecular hydrogen bonding with water and this explains its reduced solubility. o-hydroxybenzaldehyde, o-chlorophenol and o-hydroxybenzoic acid. °. °. f° (Ox 7 (ox ; (L ss ; <# ct ° I 1 H ° SH Chloralhydrate CCl,.CH(OH), “8 + Anions of Caro’s acid (H,SO,) O, 0-H Hu >< “ %, PY 1 % So-o-H of “o-b* Urea 10.oO Ring formed is 4- membered It is having angle strain Weaker H-bond cannot tole rate that C-C covalent bonds can do, so cyclo propane and cyclobutene exist. Which of the given statements is/are true? (a) H,S is gas while H,0 is liquid. (b) Ethanol has higher boiling point than diethyl ether. (©) Both (a) and (b). (d) None of these. Sal. © .5 o-Nitrophenol is (a) less volatile than p-nitrophenol (b) equally volatile as p-nitrophenol (©) more volatile than p-nitrophenol (d) none of these. Sol, © o-Nitrophenolis more volatile than p-nitrophenol as it has lower boiling point than p-nitrophenol due to intramolecular hydrogen bonding while p-nitrophenol has stronger intermolecular hydrogen bonding. (0.6 Among the following pairs, the pairs which are having dipole-induced dipole interaction are (a) HCl — He, H20 — alcohols, Clo — CCla (b) HCL — He, H20 — Xe, H20 — C02 (©) H20 — alcohols, Sif — He, H20 — Xe (d) SiF4 — He, Cly — CCl4, H20 — CO2 Sol. © 1.HCl — He, H20 — Xe, H20 — CO2 -) Arrange in increasing order of boiling @ HF, HCl, HBr, HI Gi) —-H,0, HF, NH, (ii) PH,, H,S, HC1 (iv) H,0, CH,OH, CH,OCH, Sol. @ Hel < HBr < HI < HE (i) NH, < HF < H,0 (iii) PH, < H,S < HCI (iv) CH,OCH, < CH,OH < H,0 Q.8 Why chloral hydrate is a stable molecule ? Sol. Chloral hydrate a is stable due to H-bonding (intramolecular) lH Me cic—cOn chloral hydrate 0.2 Explain, why cis-maleie acid is stronger acid than trans-fumaric acid? Sol, cis -Maleic acid is stronger acid than trans -fumaric acid because conjugate base of maleic acic is stable due to intramolecular H-bonding. 29 9 i i H H Sc7 on co" So foo ll ll o i) Stable conjugate base of maleic acid _£00H fi Hooc“H Fumaric acid (No-intramolecular H-bonding) O50 Which structure of HF is correct ? F F y ¥S \ HOH Fr Sof ‘ ‘ @ F Gi # Gi) H-F --H-F --He-Fe-H-F-- (iv) None Sol. F has 3 lone pair hence linear structure around F is not possible. Hence correct option is (i). (0.0) Heat of vapourisation of water is higher than HF, However strength of H-Bond in HF is higher than water.Sol. H,0 is surrounded by 4 other H,O molecules whereas HF is surrounded by only 2 molecules. Due to this, extent of hydrogen bonding in H,0 is more, hence Heat of vapourisation of water is higher. (0.52 Experimental molecular weight of acetic acid is just double than theoritical molecular weight. Why ? 0---HO Sol. CHy—-Co Zo—CH, OH--~ Observed molecular weight = 120 Due to intermolecular, H-Bonding (QS KHF, exists but KHBr, & KHI, does not. Why ? Sol. KHF,9 K* + HF,” [Fu... H-F] H-bonding KHBre + K’ + HBr [not stable} No hydrogen bonding KHL, K+ Hi; [not stable} 0.14. echydroxybenzatdehyde is liquid while p-hydroxybenzaldehyde is solid at room temperature? Why? Sol. Intramolecular intermolecular H-bonding H-bonding Due to intramolecular hydrogen bonding in p-hydroxybenzaldenyde. 14.2 Molecular forces : Strength : ion-ion attraction forces > ion-dipole attraction forces > dipole-dipole attraction forces > ion-induced dipole attraction forces > dipole induced dipole attraction forces > Instantaneous dipole induced dipole attraction forces Weak intermolecular attraction forces : fo) @ 3. 1 ton-dipole attraction Polar molecules are attracted by attracted by the anion. ns. The -ve pole is attracted by cation and +ve pole ‘Strength depend on @ Charge density of ion Gi) Polarity of polar molecule (Lit + H,0), (Cl + HCD), (NO," + CH,OH), (KCL + H,0) ton-induced dipole attraction When non polar molecules come in contact with ions, its electron cloud gets polarized and the oppositely charged end of it is attracted by the ion Van der Waal's forces : These are the weakest type of forces that happen amongst the chemical species which bring a considerable change in physical properties = These are non-valence cohesive forces, non-directional. These attractive forces being played among the 2 molecules, are independent of the presence of other molecules. = Solid, liquid or gaseous states of many molecules are described on the basis of inter molecular forces other than metallic, covalent, ionic bonds. Although inert gases do not form any type of bond but may exist in liquid and solid states. This shows that the atoms of inert gases are attracted by each other through some type of intermolecular forces. These intermolecular forces are called Vander Waals forces. Dipole-dipole attraction forces (Keesom forces) The oppositely charged poles of two polar molecules (for example: H,S, HCI, PH, etc.) is known as dipole-dipole attraction. 15.2. Dipole induced-dipole attraction forces This is force occurs in a mixture of polar and non-polar molecules. For example, force of attraction between Cl, and H,0. © Size of non polar molecules increases then interaction between molecules increases. 6 WN a 8 Debye force Hediecarctrek . Solubility of noble gases in water and formation of noble gas hydrates like AL6H,0, Xe.6H,O . He and Ne do not form clathrate compound. 3. _ Instantaneous dipole induced dipole attraction forces. / London dispersion forces The weakest intermolecular forces operating in similar non polar gaseous molecules are known as London forces. These forces are very weak in nature and exists only at low temperature. For example, weak intermolecular forces in F,, CL N,, molecules and in nobal gases. Example : Non-polar atoms, molecule and compound like, He, Ne, Ar, Kr, Xe, F,, Cl Br,,1,, and Benzene, CCl,, CO,, CS, etc. ® ©— AB nstantanenus Induced dipole dipole 15 Dispersion force is present between (A) polar + polar (8) non polar + non polar (C) polar + non polar (0) alt Sol. © 16,0.16 Which of the following order of density is incorrect ? (A) H,0(s) < H,0()) (B) Ga(s) < Ga(l) (©) Bis) < BI) (0) D,0(s) < D,0() (E) 0,0(s) Na> K> Rb > Cs Ina period : Metallic bond strength « Number of electron participating in metallic bona For d-block In group [Metallic bond strength « Z,, 3d < 4d < Sd (Heat of atomisation) 1 metallic bond strength Softest ‘s-block metal — Cs Hardest ‘s-block metal — Be — Metals are malleable and ductile — Metallic lustre is due to oscillation of surface mobile electron by absorption of light energy. ISoftness « 7— Metals are good conductors of heat and electricity Conductivity order > Ag > Cu> Au > AL (b) the number of valence electrons per atom {c) both (a) and (b) none of these. Sol.:© The conductivity of metal is determined by the electronic concentration and the mobility of free electrons and the number of valence electrons per atom. (0.10 Metallic solids are characterised by (b) low conductivity of heat and electricity (c) low melting point (d) paired electrons (c) bright lustre. Sol.:@ Metallic solids are characterised by bright lustre, hardness, high melting point, ability to resonate sound and excellent conductivity of heat and electricity. (0.95 Metals are malleable because when struck, one plane of metal atoms (a) can slide past another plane without breaking bonds (b) cannot easily move out of the way (cl moves in a way that maximizes the repulsive forces wit (¢) bonds to the plane directly beneath it. jin the metal Sol.:@ Metals are malleable because when struck, one plane of metal atoms can slide past another plane without breaking bonds. (0.2.0, In motallic crystal, the (a) kernels as well as the electrons move rapidly {b) electrons float freely around metal atom 8.(c) electrons are immobile (3) valence electrons are not available. Sol. :© Valence electrons float freely around the metal atom in metallic solid. 2. tonic bond/electrovalent bond lonic bond formed between metal and non metal. lonic bond is a electrostatic force of attraction between cation and anion which have been created by complete removal and acceptance of electron respectively during its formation. Example: wah nat 08) » Nat eet Nact Example: na] Caf, —>Ca ce cat = Caf, 8 Example: lonic compound of Li, Be, Mg, Al, LiF, Li,O, Li carbides, LiH MgF, MgO Mg,C, AIF, ALO, ALC, Bec © Metals salt having poly atomic anion are ionic in nature. Electrovalency : Number of electron donate and gain to achieve inert gas configuration. Na>1 F2771 Mg —> 2 O 2,62] Fornon metal Al> 3 N 2,5>3 12,Example : Mg + 0 ——>Mg? 40" 282 26 ae} electrovalency of Mg = 2 electrovalency of O = 2 Mgo Example: Ca + Cl ——4¢a" + 2¢I" = CaCl, 2.882 2,87 4 One e- cl 2,8,7 4 One e electrovalency of Ca = 2 electrovalency of Ci 9.2) The compounds containing electrovalent bonds are called {a) covalent compounds {b) ionic compounds (c) coordinate compounds (d) complex compounds. Sol, : (b) ‘The compounds containing electrovalent bonds are called electrovatent compounds or ionic compounds. 9.25 inelectrovatent compounds, the electrovalency is equal to the (a) number of unit charges on the ion (b) number of p-orbital electrons. (¢) period number (4) none of these. Sol. :@ Electrovalency is equal to the unit charges on the ion. 20..25 In the formation of ionic bond in KNO3, how many electrons gets transferred by potassium atom? (@) 2 ® 1 @3 @ 0 Sol, © In formation of ionic bond in KNO3, loses only one electron to get inert gas stability. (2.4 tn the formation of NaCl, the type of force generated in this ionic compound is (a) van der Waals’ forces (b) hydrogen bonding (0) electrostatic attraction (d) none of these. Sol. :© In formation of NaCl, Na atom gains one positive charge and chlorine gains one negative charge. The force which attract the opposite ions together is electrostatic force. 0.25 The easec of atom to form ionic bond dependson (a) high ionisation enthalpy (b) low ionisation enthalpy (¢) low electron gain enthalpy (@) both (a) and (c). Sol. © Lesser the ionisation enthalpy of an atom, greater is the ease of losing the valence electron. 26 All atkatine earth metals have valence electrons and form ionic bond by gaining charge. @) 2,42 © 44 ©) 2-20 Wd) 1-1 Sol.:@) All the alkaline earth metals have two electrons in their valence shell, so they lose two electrons te form cations with + 2 charge a.Energy steps involved in ionic bond formation : Born Haber's Cyele A whole series of energy changes are involved when one starts from the elements and finishes with an ionic crystal. These changes are shown in the Born-Haber cycle. Ms) +2 x) > arx(6) tel [saree mie) Xe) a ee athe mig) Ke) v here, SE = heat of sublimation of Na(s) IE = ionisation enthalpy of Nae) BDE = bond dissociation energy of Cl,(e) EG = electron gain enthalpy of Cl(g) LE= lattice energy AH, eat of formation of NaCi(s) Hess Law: 1 AHF = Ala # Ae + 5 AHgoe + AHge + AM, AH, = -ve AH, <0 AH, = AH 4 AH, + EAH + (Hy + AHO) aa oe Required Released energy energy Released energy > Required energy © It is a necessary condition for formation of ionic bond Favorable condition for ionic bond formatior (Low SE. of metal Gi) Atom forming cation should have low ionisation energy (ii) Atom forming anion should have high electron gain enthalpy (iv) LE(released amount of LE) should be highQ.27 sol. “ Q.28 sol. 9.29 Sol.:@) Lat Q.30 Sol.:© Select the correct formula of magnesium oxide : (a) mgo (©) Mg,0, (c) Mgo, ©) Mg,0 If the formula of a metal sulphuric is MSO, then what could be the formula of metal phosphate. MPO,), MPO.) Lattice energy is inversely proportional to sum of radii of (a) anion (b)eation —(c)ions {¢) both (a) and (b). ice energy is inversely proportional to interatomic distance of anion and cation. Which of the following statements is incorrect regarding Lattice enthalpy? (a) Lattice enthalpy becomes more negative as interionic distance decreases. (b) Lattice enthalpy is directly proportional to the product of ionic charges. (c) Crystal with high lattice enthalpy metts at low temperature usually. (d) None of these Usually crystal with high lattice enthalpy melts at high temperature. 23,©.5) Born-Haber cycle is an energy cycle for (a) aqueous solution (b) solid compounds (0 ionic compounds (4) gaseous compounds. Sol.: © Born-Haber cycle is used to calculate the lattice energy of the ionic compound. (92 Select the incorrect statement from the following optio (2) Every pure solid crystalline substance has a characteristic and unique melting point. (b) Impure sample of substance has different melting point. (©) Two different pure substances have same melting points. (a) Melting point serves as the criteria of purity of a solid substance. Sol.: 0 Two different pure substances have different melting points. All the other options are correct. Every pure solid crystalline substance has a characteristic and unique melting point and impure sample of substance has different melting point. Melting point serves as the criteria of purity of a solid substance. (95 The correct order regarding the solubility of alkaline wat (a) BeCla < MgCly < Cala < SrClg < Bala (b) MgCl > BeCly > BaCly > SrCly > Cala (e) Bacla > MgClz > CaClz > BeCly > SrCl2 (d) BeCla > MgCl > CaCla > SrClo > BaCla Sol. :@ Solubility decreases down the group of alkaline earth metal halides in water. So, correct order here is BeClp > MgCl > CaCly > SrCly > BaCl (20 The ionic radius of cation will be smaller and more efficient in polarizing (a) carbonate ion (b) carbonate molecule (c) hydrogen ion (d) water. 24,Sol.:@ The ionic radius of cation will be smaller and more efficient in polari carbonate ion. 0.95 Soy-x=6-2=4 The following compounds have been arranged in order of their increasing thermal stabilities. Identify the correct order KqCO3 (1) MgCO3 (I!) CaCOs (Il!) BeCO3 (IV) @isicmcs Vv (Vcc 1 (@iwencic @ucivemet Sol.:©) On increasing the size of alkaline earth metal ions, stability of their carbonate salts increases due to increasing polarity. Alkali metal carbonates are more stable than carbonates of alkaline earth metals due to their higher polar characters, Thus, correct order of stability BeCO3(.) < MECO3(,) < CaCO3(<) < KQC03(q) fe, IVC ICI NaClo3 > KCIO3 > RbClO3 > CsClO3 (b) Liclo3 < NaClo3 CsClo3 < Liclo3 NaF > KF > RbF > CsF AH. = -ve MF > MCL > MBr > MI AN, = -ve LiX < NaX < KX < RbX < CsK (<= cl Brit 25.Properties of onic compound : 1. lonic compound are non-directional in nature. 2. Due to non-directional nature of band ionic compound do not show stereoisom erism 3. Due to strong electrostatic attraction ionic compound exist in the form of solid So, these have high melting point. 4. lonic compound show conductivity in molten and aqueous medium due to presence of free ions but not in solid state. 5. lonic compound are more soluble in polar solvent. 6. The reaction of ionic compound is fast. 7. lonic compound show isomorphism. 8. lonic compound have crystalline structure. 9. These are hard and brittle in nature. 10. In ionic compound, only ions are present not atoms. Propertie: Isomorphism : If two ionic compounds have same crystalline structure then they are isomorphous. Condition : © Both ionic compounds have same number of ions. © Both cations should be isoelectronic or have same shape (Hybridisation) OR If ionic compounds have crystalline water then they should have same general formula. (0.27 Pair of compounds which are not isomorphous (A) NaF and Mgo (8) NaNO, and Mgco, (C) KMnO, and BaSO, (O) KI, and TU, (E) Na,SO, and MgcO, sol. © Number of ions different. (0.25 Which of the following is not isomorphous with others? (A) White vitriol — 2nS0,.7H,0 (8) Epsum salt — MgSO,.7H,0 (C) Green salt — FeSO,.7H,0 (D) Washing salt — Na,CO,.10 H,0 sol, (0) 26.Lattice energy: Amount of energy required to break one mole ionic lattice into its gaseous cation and anion is called lattice energy and vice-versa also defined as lattice energy. NaCl(s) —Encovermic _, Nar(g) + Cl-(g) ‘AH,, = #ve Nar(g) + Cl-(g) —fxothermie _, NarCl + Energy (solid) AH,, = ~ve Lattice energy « —*—*— GH) Where K is pocking constant Lattice energy depends upon following three factors : 1. Change on ions 2. Size of ions 3. Packing of cations and anion (Data based) © Charge factor more dominant factor Example: NaF < MgF, < AIF, LiF < Li,0 < Li,N LiF > NaF > KF > RbF > CsF KF > KCL > KBr > KI NaF < MgO Hydration Energy: Amount of energy released when one mole of gaseous cation and anion are completely dissolved in water is called hydration energy. (a) Always carries negative sign Na’ 4 xH,O—> fla (H,0, or Na* (aq) + energy AH, = -ve ct (g) + yH,0 —>ct (H,0)y or Cl + energy AH, (Ar) = -ve Net hydration energy = ~(AHye + AHye) co Hye > AB ct A Hydration energy of ion «x charge density of ionsCharge on ion charge density = 2S" o" Oe < Se See he te In hydration energy, cation contribute more than anion due to small size. hydrated size of Li'(aq) > Hydrated size of Na‘(aq) HE= 1 lonic mobility of i ee onic mobility of lons « 7 crated size of ions © Order of size @ Lit < Nat Na‘(aq) > K*(aq) > Rb*(aq) > Cs*(aa) Gil) F-(aq) > Cl{aq) > Brac) > (aq) @v) Fel Rb*(aq) > Cs*(aq) i) F(aq) < Cl(aq) < Br(aq) < (aq) Al"(aq) < Mg(aq) < Na‘(aq) Electrical conductivity of ions In aqueous solution, It depends upon following two factors () Charge carrying capacity of ions Gi) lonic mobility of ions Li(aq) < Na‘(aq) < K’(aq) < Rb*(aq) F-(aq) < Cl-(aq) < Br(aq) < I-(aq) Na‘(aq) < Mg"*(aq) < Al'(aq) © Charge carrying capacity is given by preference over ionic mobility. Alum : (M,SO,.M,(SO,),.24H,0 Where, M is monovalent cation Mis trivalent cation (Cr?, AL, Fe") K,SO,.AL(SO,),.24H,0 (Potash alum) K,S0,.Cr,(S0,),.24H,0 (Crome alurn) Ail alums are isomorphous © Aqueous solution of alum is acidic in nature K,SO, —*° > 2KOH+H,SO, Neutral SB. SA 28.AL,(SO,), —#2-> AUOH), +H,S0, Acidic SB. S.A Species present in aq. solution/solid state of alum are 2[M(H,0),]" + 2(0(H,0),]”? + HSO,** lon-dipole attraction > distance| > M has vacant orbital > coordinate bond => 10 layer of incoming H,0 = Hydrated ion Li does not form alum as its covalency = 4 On heating alum converts into amorphous solid (dead alum) due to removal of water molecule. Pseudo alum : MSO,.M,"(SO_),.24H,0 bivalent 0.55. Which of the following show conductivity (1) AIF (molten) (2) Alcl, (3) Held) (4) Graphite (5) Na(s) (6) H,S0,(aq) (7) Nano, (8) KNO,(aq) (9) MgCl,(aq) (10) CuSO,,5H,0 Sol. (AIF, Graphite, Na(s), H,SO,, KNO, MgCl, CuSO, 5H,O ©. £0. Solubility of Ktis maximum in (A) CH,OH (E: (C) C,H,-0# € 4) (8) CH,-0-CH, (Er = 4.) =27) (D) H,C—G—CH, (Er = 21) ° Sol. @)cH,on Solvent HF H,S0, H,0, H,0 0,0 Er 120 102 98 BI 7) Acidic Oxidising Universal Polarisation : . No compound exists as 100% ionic . No bond is 100% ionic. It has some covalent character. . Calculation of covalent character in ionic bond is practically impossible. So, they can be compared by phenomena of polarisation. 29.Polarisation (Covalent character in ionic bond) When two opposite charge attract to each other than ionic bond is formed and cation attract electron cloud of anion. So. symmetrical anion become unsymmetrical distortion of anion by cation is called polarisation due to polarisation electron are shifted toward cation. So, ionic character decreases, covalent character increases. Isolated anion 100% ionic Shifting or transfer or electron nic character |, Covalent character + Sharing of electron [, Fajan’s Rules All the covalent bonds have some partial ionic character, the ionic bonds also have partial covalent character. The partial covalent character of ionic bonds was discussed by Fajan’s rules: . The smaller the size of the cation and the larger the size of the anion, the greater the covalent character of an ionic bond. «The greater the charge on the cation, the greater the covalent character of the ionic bond. . For cations of the same size and charge, the one, with electronic configuration (n-1)d* ns®, typical of transition metals, is more polarising than the one with a noble gas configuration, ns? np®, typical of alkali and alkaline earth metal cations. * The cation polarises the anion, pulling the electronic charge toward itself and thereby increasing the electronic charge between the two. This is precisely what happens in a covalent bond, ie., buildup of electron charge density between the nuclei. The polarising power of the cation, the polarisability of the anion and the extent of distortion (polarisation) of anion are the factors, which determine the per cent covalent character of the ionic bond. © Polarisation power of a cation is usually called ionic potential or charge density. Charge on cation Size of cation lonic potential (phi 30,1 Size of cation : +5. “15 Polarisation of electron “O- cloud of anion by cation +3 Cation Anion Example : CsCl < RbCl < KCl < NaCl < LiCl 2. 3. Size of cationec ———_—__| Polarisation [Polarisability « Size of anion| Size of anion: Ability of anion to polarise towards cation is called polarisability. lPolarisability « Size of anion| Polarization « Charge on anion Example : NaF < NaCl < NaBr < Nal CaF, < CaCl, < CaBr, < Cal, PbF, < PbCl, < PbBr, < Pbi, ARF << AgCl < AgBr < AbI Sie ofanentect Fcc carci ‘Grcer oF polarisabiity Charge density of cation Chare Size Polarising power ~ $< covalent character llonic potential(4) = Period — 6 1 covalent character} Group — 6 | covalent character | a.n period Example : UicteBect, Bect, or ne) «i NaCl MgCl, BeCl, < MgCl, < CaCl, < BaCl, ‘qheovalent characterl ionic coharacter? > 1 Covalent character’ 4. Pseudo Inert gas configuration = ns?np*nd® Example Au’, Bis, Pb’*, Sn'*, Ag’, Cu’, Zn'?, Cd", Hg AgCl > KCL AuCl>Rbcl __| llonic character = order of covalent character cur Nav >= 0.96 = 0.95 cuct > NaCl 2, 8, 182, 8 Cur = 1s? 2s? 2p? 3s? 3p? 3d" 4s' (ns? np® nd") 5. Non inert gas configuration : ns? np nd? (n + 1)s° Example: — Tl’, Pb", Bi”? PbCl, > MgCl, BiCl, > CaCl, ‘Covalent Character? 32.Pedh Noninert >inertgas ->Covalent Example Zn"? < Cd"? < Pb? Hg’? > Pb? Zn"? < Cd"? < Hg? Cur < Ag’ < Au" Zn"? < Cd"? < Hg? Tl < Pb? < Bi? Some order of pola @ Be"? CC. PPT Charge < Size < PP. < ai) li Mg? Size > Charge < PP, < Polarisability x Charge on anion « size of anion| Peck <8rS?>Cl FS2> O07 =F >Br> Cl > F As polarisation increases transition of electron from anion to cationt intensity] darkness | 33.cucl, CuBr Cul_| white Pbcl, PbBr, Ager Pbi, + Yellow Agi Agcl Hg,Cl, Hg.Br, | Hg,l > green Hgl, > Scarlet red Bil, + Black/brown Yellow . All phosphide are in black colour . Mostly sulphide are black coloured Cds — yellow ZnS — white Mns — Fink AS prey Sn? on Yellow Orange Brown Yellow Application of polarisation 1. Covalent character/ionic character : As polarisation 1, Sharing tendency 1 , Covalent character | , lonie character | Covalent bond Covalent > lo! Conduct onic > Covalent 34,Covatent t Ber, Becl, BeBr, Bel, COL) Tae] [atch ater, All ict MEF.) | MecL = MEBr, = MEI. | covalent > tonic but lattic ionc LiF Licl Libr Lil NaF NaCl Nar _—Nal v lonic > Covalent 2) The dogree of polariz: (a) charge density of cations only {b) charge density of anions only {c) charge density of cations and polarizability of the anion (4) all of these. Sol. :©) Polarizing power depends on the tendency of cation to polarize and the polarizability of the anion. 9.42, Many ionic compounds have some covalent characters due to () ion polarization (b) charge polarization (¢) proton polarization (6) electron polarization. Sol. : @) As the charge on the ion increases, the electrostatic attraction of the cation for the outer electrons of the anion also increases, with the result its ability for forming the covalent bond increases. (45 Even though the crystal radii of both K* and Ag’ are almost same, the melting point of AgCl is only 455°C, while that of KCl is 776°C. The best explanation is (a) Agcl has more ionic character than KCl due to greater polarizing power of potassium ion{b) KCL has more ionic character than AgCl due to greater polarizing power of potassium ion (c) AgCl has more covalent character than KCl due to greater pol: power of silver ion (a) KCL has more covalent character than AgCl due to greater polarizing power of silver ion. Sol.:© The K’ ion has octet configuration in the outer shell (3s?3p°). Therefore, it has less polarizing power and hence KCl is more ionic. Whereas, in Ag’ ion, there is pseudo. octet configuration (4s’4p*40") in its outer shell. Therefore, it has greater polarizing power due to ineffective shielding of nuclear charge by d-electrons. (44 The order of covalent nature for aluminium halides is AUF3 < AICl3 < AlBr3 < All, The best explanation according to Fajans’ rule is {a) AL* is larger in size and hence it has greater polarizing power {b) the polarizability of halide ions increases with increase in their size and hence the covatent nature also increases {c) the polarizability of halide ions decreases with increase in their size and hence the covalent nature decreases {d) the given order of covalent nature is due to greater polarizing power of AD" ion, Sol.:() The polarizability of halide ions increases with increase in their size and hence, the covalent nature also increases. (0.45 The correct order of covalent nature of alkali metal chlorides is fa) LiCl < NaCl < KCL NaCl > Kel > RbCL> CsCl (4) LiCl = NaCl = KCl = RbCl < CsCl Sol. :© The covalent nature decreases with increase in the size of cation since the polarizing power decreases with increase in the size.2 Thermal stability : Stability towards heat/temperature compound having high thermal stability means high temperature required to decompose. (@) _T.S of compound having only covalent bonds Thermal stability « BE x number of covalent bonds| NH, PH, BE > TS > PH, HS Hel BE < TS > > (b)__T.S of ionic compound having mono atomic anion and cation CO*, SF, Cl, Br, |*, Hr. N73, P) Example : NaCl Only ion’ bond present [Thermal stability « Lattice Energy] LiH > Nal > KH > RbH > CsH. TST Ls (©) TS of ionic compound having polyatomic anion (OH, 0,2, 0,7, Ny C CO, Oxyanion) % > HE lSotubitity ot Mainlys - block compounds Note (1) If common ion is smaller like F*, O-?, OH*, Lit, Na’, Ba’? MA cation — L.€. + dominant LEY st Noto (2) If common ion is larger like |", 8°, Cs", Rb’, Polyatomic anions HE — dominantNote 3 Note 4 Note 5 di) 1 Solubility « —_____1_| '"Y * Bolarisation / covalent character Applicable for Be-halide, p and d-block compounds Solubility decide by ionic character 1A — Carbonate, sulphate bicarbonate Solubility ion organic y polarisation or C.C Examples a LiF < NaF < KF < RbF < CsF (LE) BeCO, > MgCO, > CaCO, > SrCO, > BaCO, BaF, < BaCl, < BaBr, < Bal, (LE) BeCl, > MgCl, > CaCl, > SrCl, > BaCl, BeSO, > MgSO, > CaSO, > SrSO, > BaSO, Li,0 < Na,0 < K,0 < Rb,0 < Cs,0 LiClO, > NaClO, > KCLO, > RCIO, > CsClO, Be(OH), < Mg(OH), < Ca(OH), < Sr(OH), BeF, > BeCl, > BeBr, > Bel, AgF'> AgCI > AgBr > Agi FbF, > PbCl, > PbBr, > Pbl, HgF, > HeCl, > HgBr, > Hel, NaS > CuS < ZnS U____] s-block PP 4 Cation T Solubility T pol. sol. T INa,S > Zns > Cus Licl > NaCl in acetone/pyridine covalent] tonict AgO > AgS NaF < Sncl, Nav small + LE —- ON sizel LEL 39.SaCl, > Sncl, charge t pol. T solution Fe(OH), > Fe(OH). Mgr, < MgCl, < MgBr, < Mgl, ay LICL > NaCl > KCI < RbCl < CsCl (xiv) LL cl larger cl-Smaller Important points regarding solubility : @ All alkali metal salts are water soluble except Lif, Li,CO,, Li,C,0,, Li,PO, fi) All metal nitrates are water soluble. Gil) All metal sulphates are water soluble except SrSO,, BaSO,, HgSO,, Ag,SO,, PbSO, Gv) __s-block metal sulphides are water soluble, rest are insoluble. () II Acarbonate are insoluble in water (i) hydroxide and Ba(OH), are water soluble. Rest hydroxide are insoluble or sparingly soluble. (il) Generally, metal halides are water soluble except Cl’, Br, I of Ag, Hg, Pb (0.6 Which of the following is least soluble in water. (A) Na,co, (8) KNO, {c) sso, (0) Bacl, sol, © (O47 Incorrect solubility order : (A) CH,OH > C,H,OH > C,H,OH (8) CH,OH > CH,-O-CH, > C,H,-0-C,H, (C) C,H,OH < CH,OH < CH-OH (0) 0-nitrophenol > p-nitorphenol HOH CH—-OH H Sol. (©) Solubility + inter motecular H-bonding > Intramolecular H-bonding 40.Melting point and Boiling point : M.P. - Diamond(s) > NaCl(s) > H,0(s) > CO,(s) 4000°C ionic H-bond VW. M.P. of Metalic + Non-metalic compound : () — MP&LE] applicable for Na’, K*, Pb’, Cs*, Al, or F-, 07, Ho, No? 1 re IMP « ——_____| (iy Polarisation] for others MP -> lonic > Covalent| (iii) Except giant molecule like diamond, silica borazone (BN),, Carborundem (SiC) Norbide (8,C) = Hardness — Diamond > B,C > SiC > ALO, (uaa ae ¥ natural Artificial Corundum Example: () Bec, < MgCl, < CaCl, < SrCl, < Bact, (PP) (i) CaF, > CaCl, > CaBr, > Cal, (LE) (ii) NaF’< MgF, < AIF, (LE) (iv) NaCl > MgCl, > AlCl, (P.P) (¥) _Na,O < MgO'< ALO, (LE) * 4 a NaCl > CuCl > CuCl, (vii) NaCl > KCL > RbCl > CsCl > Lict Covalent (villi) MgF, > CaF, > SrF, > BaF, > BeF, 126.3°C 1418°C Covalent (ix) CaF, > MgF, > SrF, > BaF, > Bef, Metal fluoride < Metal oxide () Sn, > snct, (cl) ALF, > alcl, (xii) NaF < MgO < SCN < Tic Charget Let a.Melting point of non metal compound Intermolecular force « M.P x B.P «TS « Viscosity « ——\ _« 1 CH,-O-CH, < HOH Volatility “ VP (vwa) H-bond CH,-N, < HN, cVWE H-bond H, < CO, < H.0 BP CHOW < H,0 1S H,0 < 0,0 BP HCl < HNO, < H,PO, MP wr Extent of H-bonding CH,0H < GH2OH < CHyrOH . CH,OH CH—-OH CH,-OH 0, <8, < Se, < Te, H,> He BP Melting point of metals IMP « Metal bond strength @) — Li> Na>K> Rb>Cs. Size} M.B.S0 Wi) 3d<4d<5d Zyl M.8.80 . Zn > Cd > Hg (volatile metal) Number of paired electron | Inter electron repulsion between pairs 1, MBS| interatomic distancet SizeT No unpaired electron here So, this can't be related with others as every where number of unpaired electron | but number a 3d Number of Number of unpaired eS unpaired electron Number of paired T Se Zn (Min) Be >Ca>Sr>Ba>Mg Innerd is vacant © High participation of resonation structure (delocalizing) there, which increasestability (Pauling theory) Mg doesnot have vacant d. $0, it is less stable @ less MP, Be has Size | + MBS | Minimum M-P in all elements — He Minimum M-P in all elements — C (Diamond) Minimum M.-P in all metal — W Minimum M.P in all metal — Hg Minimum M.P in Boron family — Ga Minimum M.-P in all Boron family — 8(Covalent) Applications of Fajan Rule: Heating effect 1 @ In polyatomic compound like CO,, SO,, NO,", HCO," C,0,”", CH,COO", OH", 0,*, 0,7, ClO,", 0,7 with increase in % ionic character, thermal stability increase. CO," (carbonate ion) : Thermal decomposition of carbonate Metal carbonate —*—> Metaloxide + CO, Exception : Na,CO,, K,CO,, Rb,CO,, Cs,CO, possess high thermal stability and they do not decompose even when heated up to red hot rather than melt. Na,CO, — Soda ash K,CO, ~ Pearlash gco, —*-+ go + €0,1 Magnestic znco, —-» zn0 +€0,} Calamine Caco, —*-+ CaO + C0, Calcite Pbco, —+—+ pbo + CO, | Corrusite FecO, —*-+ FeO + CO, 1 Siderite CuCO,,.Cu(OH), —* 2Cu0 + CO, + H,0 Molacite (gree) black (basic copper carbonate) 2PbCO, Pb(OH), —Y—» 3PbO + 2CO, + H,0 white leadbasic lead carbonate PbO — letharge Pb,0, — Red lead or sindoor Cu, Hg, Ag, Au, Pt — Very less reaction metal Ag,cO, —2-+ Ag +CO, + 40, HgCO, —->H#g + CO, +o, t + 4 Diamagnetic paramagnetic WH Colourless sedansh Na,CO, 10,0 £22" _5Na,co, HO +> Na,cO, hashing haraon | No decomposition (i) Sulphate (SO,?-) Metal sulphate —““""_, metal oxide + $O,1 Metal sulphate —“°*_» Metal oxide +50, +40, Except Na,SO,,K,SO,,Rb,SO,,Cs,SO, MgSO, "5 MgO + SO, + 40, t Pps, PbO + SO, + 30, ZnSO, > Zn0 +0, + 30, Li,S0, "411.0 +0, T +30, + ‘Some important reaction of sulphate 1. FeSO,7H,O—*2°5 >FeSO, “5 _» Fe“, + SO, + 3, aa,Example of intramolecular redox reaction Fe, (SO,), —— Fe,0, + SO, Non Redox reaction Fare miphate row beta snso, —.+Sn0,+S0, sarnoce isha Intramolecular Redox reaction Sn0 +80, Good R.A. Good 0.A CaSO, 2H,0 —"**_+caso, JH0+ 3 2H0 "+ caso, cad+S0, +40, a=! CuSO, 5H,0 —*""_, CuSO, 8H,0 S75 > CUSO,H,O -2,0 | 100°¢ Cuso,H,0 cud + $0, H 40 | 220°C ON cu,0 +50, + to, «22 —cuso (white) as.Symmetrical [cu(#,0), ]so,4,0 H-bonding (ii) Nitrate (NO;):- Water of Crystallization Thermal decomposition reaction of nitrates Metalnitrate ——> Metal oxide + NO, + 0, (row cow cxeutass Sense’ singe oy Exception MNO, ——> MNO, +0, (M =Na,k,Rb,G) QI Stable oxide donot form NaNO, ——> NaNO, +0, kNO, ——+kNO, +0, RbNO, ——>RDNO, +0, l2Mn0, 5 >M,0 + N, + =O, | | IM=Na,k,Rb,G — diamgnetic _ Paramagnetic’ 2NaNO, —"Z=_4Na,O +N, +0, LINO, ——i,0+NO, +0, Mg(NO,), ——>Mg0+NO, +0, Cu(No,), ——>Cu0 + NO, +0, 46.Pb(NO,), —> PbO+NO, +0, ‘AgNO, ——>2Ag + 2NO, + to HgNO, ——+Hg+NO, + 30: ©.1.5 Which of the s-block metal nitrate give brown colour NO, gas on heating (A) Lino, (B) NaNO, (C) kNO, (D) CsNO, Sol. 4 Example (@)2n$0,7H,0 —2#*_42n50,H,0 == +2050, #2470 + 80, + 40, (vb) Na,SO,10H,0 ——+Na,SO,H,0 ——+Na,so, ——> X Gv) HCO @iearbonate) 2MHCO, —,>M,Co, +CO, +H,0 M = Na. k, Rb, G Example 2NaHCO, ——>Na,CO, + CO, 7 +H,0 ‘stay ated LIHCO, exist in liquid state Metal hydroxide (OH )——> Metal oxide + H,0 () Perchlorate (clO;) IMclo, —M,0 +Cl, + 30, 4a.(vi) Superoxide (0;) 3 MO, —7M,0+ 50, where M is k, Rb, Cs * Aqueous solution of metal hydride are basic in nature MH’ + H'OH” ——+MOH +H, fT NaH +H"OH——+ NaOH +H, T CaH, + 2H°OH ——»Ca(OH), +H, T ere ‘nda ret od (vii) Nitrides (N?-) LIN > Na.N>k,N N= > highly exothermic NH, —"+NH; ——+NH* —> N2 BaCN—+5Ba +3N, ‘2NaN, —*— 2Na(s) + 3N, * Pure nitrogen gas can be obtained by heating metal ozide because no other gas eous product is formed. * NaNO, is used in motor car air bags 9.59 Anhydrous MgCl, ean be obtained by (A) merci, or,0— a meet, +Hett 140 (B) MgCl, 6H,0 <*> MgCl, + HCl T +H,0 (C) Mg + ditHCL—+>MgCl, +H, (D) MgO +C + Cl, ——>Mgcl,+co Tt rested (a) sengarocs Sol. ® 48.Which of the following contain two s-block metals? Q.50 (A) superphosphate CaSO,, + Ca(H,PO,),, (8) Microcosmic salt Na(NH), HPO, 4H,0 (C) Lithophone -> (Zns + BaSO,) (0) Fu: n mixture (Na,CO, +k,CO, ) Sol. ° Soda lime + NaOH + Cad Aqueous solution of Ca(OH), = lime water Suspension of Ca(OH), = milk of magnesia CaO +H,0 Calon), Inert pair effect In P-block elements (group n0.13 to 16), on moving down the group lower oxidation state becomes more stable as compare to higher oxidation state due to inertness of electron pair of 6s orbital is called inert pair effect. This electron pair of 6s orbital do not participate in bonding as it is strongly attracted towards nucleus due to poor shielding effect of inner d and f orbitals. Tl, Xe] 4F*Sd6s?6p! Pb,, [xe] 4f“ 5d 6s 6p” i,, [Xe] 4f*5d"6s* 6p" ep"? 49,43 1a" 15" a+ co +4 N345 +3 +4 45 a“ sf aq 5 : 7 - Stability Z y y ability of | of higher Ga Ge AS lower 0.ST | oxidation Na Ny “ya state 3 +4 +5 i sn so “Na “a “ea Th+H1 Pb > +2 Bi+3 Stablity of oxidation state 1 > Th 13" Pb? > Pb’ 1a | group Bi? > Bi 15 Order of stability: Tl’ > In" > Ga” (due to inert pair effect) Order of stability: Pb'? > Sn“? > Ge? (due to inert pair effect) Application of inert pair effect 1 Salt of Tl, Pb and Bi** are good oxidising agent. TH? +2e Tr Pb“ + 2e° ——>Pb* Bi" +2e° +B" PbI, doesnot exist because Pb" is a strong oxidising agent and I” is strong reducing agent. Pb + 2e° Pb? [Pb + a > Pb? +1,Fcc PbBr, + Br, Pbcl, —%2-+PbCl, + Cl, PbF, exist at room temperature Pb“'(aq) + 47, —*\—>PbF, (00) owen a, TU, exist in TL’ and & in aqueous medium TI? +27 ——+TU' +1, Ler— (riety ie .—on Sn? —_steHten_ Sat $n* work as reducing agent Order of stability: sn? < sn‘ Example to show reducing nature of SnCl, ‘2HgCl, + SnCl, ——>Hg, Cl, + Sncl, Hg,Cl,+SnCl, _——> Hg +Sncl, calor weveet 2BiCl, + 35nCl, —> 2Bi 1+ 3Sncl, 2AuCL, + 3SNCL, ——> 2Au 4+ 3SnCl, Felon et Ge"? < Ge (order of stability) aU? 4 37 9 Tl? 4 3 mt TU 4 TU +R does not exist st.* Cul, does not exist Cu (aq) + 2), > Cul + i * Fel, ——> does not exist Few, +31, —Fel, +21 ean * Sow etal ~» Cur Fer. (2 AUZL, exhibit oxidising character Stability of TI halide TIF, > TICL, > Tier, > TU, Stability of TI" halide TU, > TIBr, > TICL, > TIF, + does not exist It is mainly applicable for 13", 14%, 16 and 16” group In general, elements are stable in their higher oxidation state. But in p-block elements from group no. 13 to 16 on moving down the group, lower oxidation state gradually becomes stable and higher oxidation state become less stable and last element of each group is stable in lower oxidation state rather than higher oxidation state due to inertness of ns-electrons towards bonding due to poor shielding of 4f subshell is called Inert pair effec 51 Correct order of stability of metal cation is are: (A) Al? < sb? 4 bonds). However, if the central atom belongs to third or lower period it can have > 8 electrons. At last verify the covalency of central atom. Lewis Structure of ions : Distribute the negative charge on surrounding atom in such a way that octet of none of the surrounding atom is complete before the bond formation with central atom. If however, the octet of surrounding atom is complete by making it uni-negatively charged (particularly in case of halogen which contains seven valence electron), then such surrounding atom will attach itself with central atom through a co-ordinate covalent bond. cory AL. N, 67 8 37 Sa But the above structures of NO,- is incorrect as the central nitrogen belongs to second period, it can never form five covalent bond ie., it can't have more than 8 electrons, so its actual structure is :16 L 20: Be Nos 07 sen-:- * Drawbacks of Lewis Theory /Octet rule 1. Electron deficient species / hypovalent compound : The covalent compound in which central atom having less than 8 valence electron. e.g. BeH,, BeCl,, AICI,, B,H,, ZnCl, BF, etc, 2. Super octet / hyper valent compound : The covalent compound in which central atom having greater than 8 valence electron e.g. PCI, SF, PF, XeF,, SF, etc. 3. Alllodd electron species e.g. NO, NO,, CH,, CIO, CIO, OF ete. * all electron species are paramagnetic 4. Existence of compound of Xe, e.g. XeO,, Xe,0,, Xe0,, XeF,, XOF,, XeF, 5. \t could not tell anything about bond parameters like bond energy. bond length etc. 6. it could not give any idea about shape of the compound55 Which of the following statements about covalent bend i (2) Covalent bond is formed between two similar atoms. (b) Covalent bond is formed between two dissimilar atoms. (¢) Both of these. (4) None of the: @ correct? Sol.:0 Covalent bend can be formed between two similar or dissimilar atoms. (5. Which of the following compounds is covalent? (a) Ha {b) Cao {e) KCL (d) Nags Sol: Hg is a covalent compound. Rest all are ionic compounds. ().55 Which one of the following violates the octet rule? (a) Pcl (b) Brg () NF (a) Asks Sol. @ The electronic configuration of As : [Arl4s°3d%4p?. t has vacant 4d orbital. These vacant orbitals can get involved in the hybridisation process which allows arsenic to have an expanded octet. Therefore, AsFg violates the octet rule. 56. The formation of compounds PFs, SFg, BCl3 are not according to the rule of (@) octet (b) doublet (triplet (@) none of above Sol:@ The octet rule states that atoms tend to form compounds in ways that give them eight valence electrons and thus, have the electronic configuration of a noble gas.Q.57 Sol: @ 9.58 Sol: NaCl gives white precipitate with AgNO3 solution but CClq does not. This is because (a) NaCl is a covalent compound and gives Cl: ions in the solution (b) CCl is an ionic compound and does not give Cl’ ions in the solution. (c) NaClis an ionic compound and does not give Cl- ions in the solution. (d) CClg is a covalent compound and does not give Cl- ions in the sol NaCl is an ionic compound and gives Cl’ ions in the solution. These Ct ions react with Ag’ ions given by AgNO3 to form while precipitate of AgCl. However, CCly is a covalent compound and does not give Cl ions to react with Ag’. Which of the following statements is correct? (a)A double bond is stronger than triple bond. (b)A triple bond is shorter than double bond. (c)A triple bond is less reactive than double bond. (d)A double bond is less stable than triple bond. A triple bond is shorter than double bond. Q.59 Sol? In C309, there are (a)2 C-C double bonds and 2 C-0 double bonds. (b)2 C-C double bond and 3 C—O double bonds. (c)1 C-C triple and 3 C—O double bonds (d)3 C—O double bonds. Carbon suboxide i.e., C302 has structure O=C=C=C=0. Formal charge :In any polyatomic ion charge is present on the complete ion and not on any individual atom e.g. NH,", 50,7, Po,?. To calculate charge on any individual atom, concept of formal charge introduces. This concept is. helpful during draw of Lewis dot structure. “It is defined as difference of valence electron available on atom and number of electrons available with the atom in given structure”. Formal charge = (V.E.) - [N.B.E. + (B.E./2)] Where number of valence electron jon-bonded electron jonde¢ electron Examples : formal charges on every element on HNO, The H atom : It has one valence electron, zero lone pair (or zero nonbonding electrons), and forms one bond (two bonding electrons). Substituting in Eq. (i), we write FC = (1) - (0) -% (2)=0. The O atom bonded to H: It has six valence electrons, two lone pairs (or four nonbonding electrons), and form two bonds (or four bonding electrons). Hence, we write FC = (6) - (4) -% (4) = 0. The N atom: It has five valence electrons, zero lone pair (or zero nonbonding electrons), and forms four bonds (or has eight bonding electrons). Thus, we write FC = (5) - (0) -% ()= 41 The end © atom in N=0: It has six valence electrons in the free state but in the Lewis structure (| or !!), it has two lone pairs (or four nonbonding electrons) and forms two bonds (or has four bonding electrons). Thus, we can write FC = (6) - (4) -%2 (4) =0 The end O atom in N-O: it has six valence electrons in the free state but in the Lewis ‘structure (I or |!), it has three lone pairs or six nonbonding electrons and forms one bond (or has two bonding electrons). 59.thus, we write FC = (8) ~ (6) -¥%2(2)=—-1 We can now write the Lewis structures (| and I!) for nitric acid molecule including the formal charges AG. ~ or H-6- Si ' u Molecule Structure Formal charge 1 fa) O(1) = 6 - 2 -Y2 (6) = 2 3 0Q)=6-4-% (4) Os 127 a 0(3)= 6-6 - % (2) ,7 ~~ S=6-2-%x6=41 so 2g Qo ow =6- 6 “x 2=-1 , 0(2)= 6- 4-/Ax4=0 _ 4-2-%% 65-1 £0. O=6-2-Ax6=+1 4-2-¥x6=-1 CN" 5-2-"x6=0 H! ie: | N=5-2-“%(8)=+1 NH N On each H = 1-0 - ¥2 (2) No,0.60) The format charge on sulphur in HS0- @ #2 (b) -2 era @-4 Sol.:@ Lewis dot structure of HSO- is (6) The formal charge on double bonded O-atom in carbonate ion is @o HH © -2 (ay +2 Sol.!) Lewis dot structure of CO,”*is 1: pe i ot & O. Formal charge on double bonded © - atom 1 =V-L-3 8=6- x4=6-6=0 15 of Covalent Compound 1. Physical State: Generally, Covalent compounds exist in liquid or gases state. Some compounds having high molecular masses exist as soft solid Example S,.P, and |, * This is due to presence of weak force of attraction (van der waal's forces) be tween the molecule Exception: Diamond, SiC, SiO, are solid due to their polymeric nature 2. In covalent compound, atom and molecule are present but not ions. 3. Generally, they are bad conductor of electricity some polar compound such as HCI in aqueous solution conduct electricity. 4. Graphite is a covalent compound but conduct electricity due to presence of mobilexe” which is delocalised between hexagonal layer of graphite. ist Layer 1 |_| Vander Waal s force | of attraction I i and Layer ce ff TAT) morite xe — sp* Graphite is also known as black lead or plumbago Covalent compound are directional in nature, therefore it shows stereoisomerism. Covalent compound are soluble in non-polar solvent (Organic solvent like C,H,.CCL,.CS,.ether etc. (due to concept like dissolve like) Covalent compound exhibit molecular reaction and these are slow than ionic reaction, [Nature of oxidising —> F, > Cl, > Br, >) IF, cur, « err, * (52 The Lewis structure of chleric acid contains single bonds, double bonds and Lone pairs of electrons are respectively (a) 3,2,5 (b) 2, 0,7 22,7 (4) 2, 3,80.65 How many electrons are involved in bonding in Lewis structure of $0. ion? (a)22— (6) 20 @18 @12 So. @ No. of covalent bonds = 6 -, Total no. of electrons involved in bonding = 6 x 2 = 12 4 Which of the following statements is correct according to Sidgwick- Powell theory? (a)If there are two pairs of electrons in the valence shell of the central atom, the orbitals containing them will be oriented at 120° to each other. (b)If there are three electron pairs on the central atom, they will be at 120° to each other, giving plane triangular structure. (c)For four electron pairs the angle is 107° and the shape is tetrahedral. (AIL of these Sol. :® According to Sidgwick-Powell theory, if there are three electron pairs on the central atom, they will be at 120°, giving triangular structure. (G5 According to Sidgwick-Powell theory prediction, the bond angle of a molecule containing 6 electron pairs in outer shell, will be (a) 90° (b) 180° (c) 120° (d) 90°, 120° Sol.:@ 63.For a molecule with 6 electron pairs, the bond angle will be 90° and the shape is octahedral. ‘Sudgen Concept of Singlet linkage According to Sudgen octetrule is never violated and he gave the concept of singlet linkage and explained the thermal decomposition of PCI, by this concept. Pcl, ——>PCl, +Cl, ‘ a ok a [Number of sin glet bond = Total number of electron in bonds - 8] Example: IF,=14-8=6 * But in case of SF,, this concept is failed. So, it has been discarded. SF, — iu Example: IF, i ams F F Types of Orbital 1. S-orbital Spherical, Non-directional gerade 2 P-orbital Electron density lies along the axis.Coma" Py Nodal plane - yz ungerade Nodal plane = xz Pz Nodal plane = xy d-orbitals > gerade, directional ——_, Along the axis Between the axis (Axial) (Non-axial) dy de ds Nodal Plane=2 — Nodall Plan at 45° of xandy Nodal lin axis yz, x2 65.Between axis in the plane 1.4, 24, 3.4 ny ie Go. Qo» Ge. HW A BW Centre of symmetry with respect to phase and electron density Absent Valency Bond Theory (VBT) Given by Heitler and London. It was extended by Pauling and Slater. According to valence bond theory, atom of an element form bond only to pair up its unpaired electron present in ground state or excited state This pairing of unpaired electron will take place by overlapping of half filled atomic orbi each having unpaired electron with opposite spin. This combination of atomic orbitals named as overlapping OR According to this theory, valency shell electron participate in bond format ion. It has two parts 1. Overlapping theory Theory which expiain formation of covalent bond 2 Hybridisation Theory which explain shape of molecule and bond parameters (bond angle, bond length and bond energy. (1) Overtapping theory ‘Overlapping means common area sharing. 5D+G>e— overlapping A partial interpenetration is observed when atoms at minimum energy state while forming bond. This interpenetration of orbitals is called overlapping of orbital as result pairing of electrons take place. The strength of a covalent bond is a function of extent of overlapping. Internuclear axis: Axis on which nucleus of bond forming atom present. 6s.internuclear axis, for AB > x Internuctear axis, For AC > y Directional Properties of covalent Bonds: With the help of overlap and hybridization of atomic orbitals, the directional nature of binds in poly atomic species is explained in VBT. For instance directional bonds in CH, NH, , and H,0 ete Condition for overlapping 1. In homonuclear molecular species, atomic orbital of same energy level undergo overlapping while in heteronuclear molecular species, atomic orbital of comparable energy level undergo overlapping. 2. Combining atomic orbital must be in same phase and phase difference between them should be zero. Overlapping and Nature of Covalent Bonds Based on overlapping covalent bonds can be (@) sigma (s) bond (ii) pi (x) bond lassified as ii) detta (8) bond Sigma (0) bond: Bonds formed due to axial overlapping are called Sigma (a) bonds. ‘A sigma bond can be formed by the following types of combinations of atomic orbitals. -s overlapping: When two half filled s-orbitals approach along their internuclear a» e * e- @ S-orbital $- orbital S-S overlappingPoints to remember © 3-p overlapping: When one half filled s-orbitals ap .phosphorus exist as P, but p-orbital. Nitrogen exist as N, “Oxygen exist in O, but S=S not possible at room temperature. ee &eo @@ s- orbital p- orbital s—p overlapping p-p overlapping : When two half filled p-orbitals approach along their internuclear axis os Os -@eesPa p-orbital p- orbital Pp -poverlapping pi(x) bond The bonds formed due to side wise overlapping of atomic orbitals ie. when axes of overlapping orbitals stay parallel. The electro density gets split above and below bonding axis like two saucer type electro clouds. (@) pr- pe p-orbital p-orbital —_p-p overlappingP.+P, yorz x @r-pr) Pj+P, xorz s P,+P, xory * Any other p-p overlapping is not possible : % p-orbital d-orbital p, -d, orbital © d.-d. x : * d- orbital d- orbital d, - 4, overtaping Py + Py y x - py + Py - % - Pz + dxz x is‘ x dxz + dxz 2 y z x z 2 ss = x 5 z y Comparison of s bond strength: 1 If shell number of orbitals are same [Bond strength = Extent of overlapping = directional pro 2p-2p > 2s-2p > 2s-2s > 2p-2p € Bond Strength Axial axial axial Colateral caps wo © paial(o-p) Asialle-p) vials) Colateral (p-p) 2. When value of n is different 1s-1s > 2s-2p > 2p-2p oo 4 Pond strength « Fail number of orbitals 18-2p > 18-3p > 1s-4p Example 70.HOF > Hel > HBr > Ho C=C > NN > 6G: >: Si-Si< P—p <:8—8: HoH > ete [Catenation property of element « a —bond strength] ca.Lc>s>p [E>S>Si>P>N50] ‘Comparison of p bond strength [2px - 2px > 2pn - 3dn > 2px - 3pr| ronan? sable er weak 4 bond strength e ————______________ i th « internuclear dis tance (Bond length) Bond Energy — |Cl, > Br, > F, >I, loxidising property of covelant oxides / oxyanion « a IReducing property of covelant hydride « Example ClO > ClO, > ClO; > Clo, eames Oxidising T-st property T Example CH, 18-2p > 18-28 > 2p-2p > 2s-2p > 28-25 > 2s-3p > 28-35 > 3p-3p > 3s-3p > 3s-3s Hint: If internuclear distance is incomparable than B.S, « Bond distance If internuclear distance is comparable than B.S. « Extent of overlapping (directional of nature) 2. Hybridisation - by Pauling It was introduced by Pauling and Slater, to explain equivalent nature of covalent bonds in a molecule. Consider an example of Bet ctP=SpeP-P cy f it is formed without hybridisation then ~ both the Be-Cl bonds should have different parameters and p-p bond strength should be greater than s-p bond strength. But experimentally bond parameters of both the Be-Cl bonds are same. This can be explained by the concept of hybridisation. Hybridisation : Phenomena of intermixing of atomic orbitals of same or nearly same energy and thus producing hybrid orbitals of same energy and same shape is called as hybridisation. Now after considering s-p hybridisation in BeCl, bond strength of both the bonds will be equal clPTSP pe SPP cy Understanding Formation of methane (CH,) can also help us understand hybridizatio 73.es, Ce Ti 1s-2s 15-2 overlapping BE Hybrid orbitals are directional in nature and form o bond. > Generally « bond is formed by hybrid orbital while x bond is formed by pure orbitals. a In benzyne x bond is formed by sp’ hybrid orbitals. 1.4 4 4 H K (> Ip sin en Cl sHo wy a QZ Benzyne HW 4 | 4 1 Size/Energy/directional property of hybrid orbitals «<= sp spi spt 50% s 33% 6 25% 50% p 67% p 75% p p-character?, size t, Energy? , directional property? . ‘Types of Hybridisation : 2 Pa sp, /sp, /SP, Linear 180° 3 sp P,P, /SP,P,/SP,P, _Trigonal planar 120° 4 sp ei Tetrahedral 109°28" Trigonal bi- « goe780° § spd sP,P,P.4,, pyramidal 10720780 75.7 spd? SP.PSP. spid? SP.PPdy 4 edaby Some examples of hybridization a @ @ @ ® ‘sp-hybridisation — line: Bond angle 180° Example : C,H,.BeCl,.Co,,C,0,,CdCl, HgCl, ‘sp? hybridisation Angle 120° Trigonal planar (s+P. +R) Example: BCI,,AICL,,C,H,,BF,,NO;,Graphite,erc ‘Sp? hybridisation Angle 109°28" Tetrahedral Example : CCL,.NH;,SO%.ClO;, ,0.NH, diamond, ‘Sp°d hybridisation : Angle = 90,120 Example : PCI, SF,,CIF,,XeF, Sp'd?/d’sp?—> S+PX+PY4PZ+4, » +d, Octahedral 90° Pentagonal bipyramidal 72°,90°,180° a % “tf 76.1D Bond angle = 90°, 180° Example : SF, (6) spd? hybridisation : 18+ 3p +3d(d,, +4,,, +d, + 7hybrid oribitals Bond angle -> 72°,90° Geometty—> Pentagonal bipyramidal So Example : |F, Example Value of bond angle No. of B.A. Becl, 180 1 er, 120 3 cH, 109,28 6 120 3 Pcl, 180 1 90,90 612 ste 180 3 n 5 'F, 90 10 180 1 Calculation of Hybridisation :