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Chapter04 - Chemical Bonding Typ PDF
Chapter04 - Chemical Bonding Typ PDF
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 4243 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 Ny CO* 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 decreases52 © ‘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.87 If dipole moment (ji) * 0 compound will be polar and unsymmetrical. cg. HO, SO,, NH, Cl,0, CH,Cl, CHCI, ete. (i) Tocalculate % ionic character : Experimental value of dipolemoment(u) 99 % Ionic character =- Theoritical value of dipolemoment(u) (ii) To distinguish cis form or trans form:~ (a) Dipole moment of cis isomers is normally higher than trans isomers. cg. - — eH oan cH HCO wt ans neo 1=0 @s-form ‘Trans-form Polar (#0) Non Polar ( (b) If two groups have opposite inductive effeet than trans-isomer will have greatér dipole moment- eg. 4 © HO \Z NZ ‘ Y I c JN 7® H H @ (iv) To locate position of substituents in aromatic compounds. 1 Dipolemoment (n) «a (a) If'same substituents are present in the symmetrical position dipole moment (m) of benzene ring compounds will be zero. a a a, o& a smo - (b) As angle between substituents decrease valuc of dipole moment (1) increase Some important orders of dipole moments (p) HF > H,O > NH, > NF; H,0 > H,S CH,CI > CH,F > CH,Br > CH,I BF, < NF; < NH, HF > H,O > SO, > NH, H,0 < H,0,58 Mlustration 1, Whichhasmaximum dipole moment? a ca a c ch cl “ “or oS © “wo © Oo a a a Sol. (A) Due to the symmetrical structure dipole moment of (C) &: (D) are zero & (A) having maximum dipole moment. Exercise. 1. Whichof the following has been arranged in order of decreasing dipole moment ? (A) CHC1> CH3F> CH,Br > CHI (B) CH,F > CH,C1> CHyBr > CHyt (C) CH,C1> CH3Br>CHj1> CHF (D) CHF > CH,C1 > CH,1>CH,Br Ans. (A) 2. Theexperimental value of the dipole moment of HCl is 1.03 D. Théllengiti‘of the HC! bond is 1.27544. The percentage of ionic character in HCI (A)43 (B21 © (D7 Ans. (QC) VANDER WAAL'S FORCES (a) Thistype of attractive forces occurs in case of non-polar molecules suchas H,0>,Cly,CH,,CO, tc. () — Theexistence of weak attractive forees among the non-polar molecule was first proposed by dutch scientist J.D. Vander Waal (© Vanderwaal’sforce oc molecularweight Atomic weight Boilingpoint Types of Vander Waal’s force : - @ —_Dipole-Dipole attraction or Keason force =I as HF and HCI ea cS HE HCl (i) Dipole - Induced dipole attraction or Debye force : In this case a neutral molecule is induced as a dipole by another dipole as shown in fig. eg. HCL Before induction = <> After induction <>Gii)Induced dipole - induced dipole attraction or London or dispersion force between two non polar molecules as in Cl,, He etc. a IMlustration |. Thestrongest force among the followings (A) London force (B)lon-dipole interaction (©)Dipole-induced dipole interaction (D) Dipole-dipole interaction Sol. (B) For ion-dipole interaction 1 E« r 2. Selectthecorreet statement : (A) Boiling point of NF, is greater than NMe,. (B) Greater the dipole moments in molecule, greatétwill bethe dipole-dipole interaction between the molecules. (©) London dispersion force increases with decreasing number of electrons. (D) Boiling point of hydrides of earbon family decreases down the group. Sol. (B) Surface area & molecular weight of NMe, is greater than NF,, so the boiling point of NMe, > NF; Exercise 1. Xecanbeliquified dueto’ "within molecules: (A)ion-dipole interaction (B) dipole-dipole interaction (C)dipole- induced dipole interaction (D) instantaneous dipole induced dipole interaction Ans. (D) HYDROGEN BOND It is an electrostatic attractive force between covalently bonded hydrogen atom of one molecule and an electronegative atom (F, O, N) @ __Itisnot formed in ionic compounds Gi) Hydrogen bond forms in polar covalent compounds, (not in non-polar) () _Itisalso known as dipole-dipole attraction or ion-dipole interaction. HY — Fr... Ho — FF... HOt — FRMain condition for Hydrogen bonding : 0 @ i) @) “a ®) Hydrogen should be covalently bonded with high electronegative element ike F,0,N. Atomic size of electronegative element should be small. Decreasing order of atomic siz N > O > F Decreasing orderof electronegativity is— Fo> > N (4.0) G5) (3.0) 1 Strength of Hydrogen bond « Electronegativity of clement « Siomic sine of element Hydrogen bonding occurs in HCN, due to (~C = N) triple bond (sp hybridisation), clectronegativities of carbon and nitrogen increases. H—-C=N%....... SH-CEN®....... SH-C=N ‘Types of Hydrogen Bonding Inter Molecular Intra Molecular 4 Homo Inter Molecular Hetero Inter Molecular Intermolecular Hydrogen bond Hydrogen bond formation betwecn two or more molecules of cither the same or different compounds known as Inter molecular Hydrogen bonding These are two types. @ Homointermotecular :- Hydrogen bond between molecules of same compounds. ce oH ~ NONE NE | OS 7H LN SL \/ \ 7 a rr e Fe (i) Hetro intermolecular :- Hydrogen bond between molecules of different compounds. eg. alcohol, water Poy H” ae ‘O—H" &, 2 ® Water alcohol «== Water Intra molecular Hydrogen bond :- It takes place within the molecule. @ Hydrogen bonded with electronegative elements of a functional group, form Hydrogen bond with another electronegative element present on nearest position on the same molecule. (@ This type of Hydrogen bond is mostly occured in organic compounds. (ii) It result in ring formation (Chelation).64 es t Or ot I Qe He war Ct aa § Salcylaldehyde o-luorophencl 2, 6-cihydroxyl benzoate Effect of Hydrogen bond on physical properties : @ Solubility = (A) Inter molecular Hydrogen bonding (a) Few organic compounds (Non-polar) are soluble in water (Polar solvent) due to Hydrogen bonding. eg. alcohol, acetic acid ete. are soluble in water, Other examples-Glucose, Fructose etc, dissolve'in, water, (b) Ketone, ether, alkane etc. are insoluble (na Hydrogen bond) (©) Solubility order- CH,OCH, < CH, OH. Primary amine >'secondary amine > tertiary amine (B) Intra molecular Ilydrogen bonding: (a) It decreases solubility as it form chelate by Hydrogen bonding, so Hydrogen is not free for other molecule. (b) It can not form H-bond with water molecule so can not dissolves. NAS. (Salicylaldehyde) (©) Inter molecular Hydrogen bond O—H*—-“O=C—H It-can form Hydrogen bond with water molecule so it can dissolved62 @ Vise Hydrogen bond associates molecules together, so viscosity increases fon ‘CH, —OH CHOH << | < pon ‘CH, OH CH,— OH HO > CH—OH > CH—O—CH, water alcohol ether (iil) Melting point and boiling point (a) Duc to intermolecular Hydrogen bond Melting Point & Boiling Point of compounds increases. H,0 > CH,OH > CH, — O—CcH, (b) Trihydric alcohol > dihydric alcohol > monohydic alcohol ‘Monocarboxylic acid form stronger Hydrogen bond than alcohol of comparable molecular weight. Therefore Boiling Point of carboxylic acid is higher than alcohol. (©) Decreasing order of Melting Point & Boiling Point isomer amincs- °-amine > 2°-amine > 3°-amine R R—NIl, > R—NHRIR— NR (no hydrogen with nitrogen atom) (@) Boiling points of VA, VIA; VIIA hydrides decreases on decreasing molecular weights, va VIA VIIA NH; 1,0 HF boiling point HF > HI> HBr > HCI PH; HS Hal H,O > TeH, > ScH, > H,S AsH, Sell, HBr NH; > SbH, > Ast > PH, SbH, TH, = (©) But sudden increase in boiling point of Ni1,, 11,0 and HF is due to Hydrogen bonding H,0 > HF > NH, Intramolecular Hydrogen bonding gives rise to ring formation, so the force of attraction among these molecules are vander waal’s force. So, Melting Point and Boiling Point are low. (iv) Moleeular weight : Molecular weight of CH,COOH is double of its molecular formula, due to dimer formation occur by Hydrogen bonding Gon —O fo Ne —R R- No—w*0F (s) Physical state : H,O is liquid while H,S is gas. Water and Ice:- Both have Hydrogen bonding even then density of ice is less than water. Volume of ice is more because of open cage like crystal structure, from by association of water molecules with the help of Hydrogen bond.63 HO becomes solid (Ice) duc to four hydrogen bond among water molecule are formed in tetrahedral SES Zt Wt H (i) Base strength CHNH,, (CH), NH, (CH,)3 N, form Hydrogen bond with water. So, less hydrolysis ic. it gives OH" ions. While (CH,), N* OH” (ammonium compound) will give OH- ion in large amount due to no Hydrogen bonding. H l = cHy— — H+ OH H + fe (Ammonium compound.) CH—N — CH, NO Hydrogen atom bondéd directly with Nitrogen atom 4, ‘sono hydrogen bonding occurs, Effect of intramolecular H-bonding @ Strength of acid (@) The formation of intramolecular H-bonding in the conjugate base of an acid gives extra stability to conjugate base and hence acid strength increases eg. Salicylic acid is stronger than benzoic acid and 2, 6~ dihydroxy benzoic acid > salicylic acid. H ws, Kh ; +H 2, 6-dihydroxy! benzoate ion (b) C,H,SH is more acidic than C,H,OH. In C,H,OH, Hydrogen bond forms, so H* is not free (©) HF is weaker acid than HI, due to Hydrogen bond in H - F, H* is not free64 (i) Stability of chloral hydrate:- Iftwo or more OH group on the same atom are present it will be unstable, but chloral hydrate is stable (due to Hydrogen bonding). aSe—clH ‘Chloral hydrate 0 (il) Malcic acid (cis) is stronger acid than fumaric acid (trans). ° oO H 4 y N\ NN NN i og, — Tf &ote c. iC. 9 SN /\c/ F i i i ° ° (Maleic acid) ‘Stable conjugate base of maleic acid H sor ql ZN ‘HOOC H Fumati¢’acid (No-intramolecular Hydrogen bonding) Note: The relative strength of various bonds is as follows Ionic bond > Covalent bond > Metallic bond > Hydrogen bond > Vander waal’s bond Mlustration 1. Ethanol hasa higher boiling point than dimethyl ether though they have the same molecular weight. This isdueto: (A)resonance (B) coordinate bonding (C) hydrogen bonding (D) ionic bonding So. (© 48 R-O--m H-O-—= 11-0 hook ok R05 |” Hydrogen bonding is not possible. R Exercise 1. Arrange the followingin order of decreasing boiling point : (n-Burane (Q)n-Butanol (U1) n-Butyl chloride (IV) Isobutane (A) W>m>i>t (BW >M>m>1 (C)1>u>m>w (D) t>M>1>Vv Ans. (D)METALLIC BOND @) ) © @ © oO The constituent particles of metallic solids are metal atoms which are held together by metallic bond. In order to explain the nature of metallic bond Lorentz proposed a simple theory known as electron {gas model or electron sca model. ‘A metal atom is supposed to consist of two parts, valence electrons and the remaining part (the nucleus and the inner shells) called kemel. The kemels of metal atoms occupy the lattice sites while the space between the kemel is occupied by valence electrons. Duc to small ionization energy the valence electrons of metal atoms are not held by the nucleus firmly. Therefore, the electrons leave the field of influence of one kernel and come under the influence of another kernel. Thus the electrons are not localised but are mobile. The simultaneous attraction between the kemels and the mobile electrons which hold the kernel together is known as metallic bond. Propertics of metals and their explanation by electron sea model ? 1 @ b) @) ) © @ @) ) ) ) Metallic lusture : is due to presence of delocalised mobile electrons These loosely bonded clectrons vibrate due to.energy photon of incident light and radiates energy immediately. Electrical conductivity: is due to’mobile electrons. These electrons flow equally in all direction. While applying a potential difference across a metal, there will be a directed flow of electrons towards the positive clectrode. The directed flow of electrons carries the electric current from one point to another and therefore, the metals are known to be good conductors. ‘Thermal conductivity : It can also be explained on the basis of electron gas model. While heating a metal kinetic energy of electron increases and propagates through collisions. Malleability and ducti This property is duc to non directional nature of metallic bond. Basically the keels can slip over each other when a deforming force is applied. High tensile strength : It is due to positively charged kemels and the mobile valence electrons.POINTS TO REMEMBER @) 0) © @ © 0 () (h) o «) (a) ) (0) Bond energy of a diatomic molecule is enthalpy change to dissociate one mole of the diatomic gascous molecule to form the respective gaseous atoms. Strong metallic bonding is favoured by smaller size of kernel. Band theory is related with metallic nature The resonance structure do not have independent existence. ‘The hydration of ionic compounds involves evolution of heat, weakening of attractive forces and dissociation into ions ‘The maximum covalency is equal to the actual number of s-clectron and p-clectrons in the outermost shell Many ionic crystals dissolve in water because water decreases the interionic attraction in the erystal lattice due to solvation. Hydrogen bond stabilizes the secondary structure of proteins, Isoelectronic molecular species have similar molecular orbitalsand similar structure according to isoelectric principle The amount of energy required to break oné'tiole of the bonded atom and separate the bonded atoms in the gascous state is known as bond dissociation energy The average angle betwech the bonded ofbitals is known as bond angle (0). Bond lefigth may be defined as the average distance between the centres of nuclei of two bonded atoms. Polymorphism (Allotropy) is a term used when one and the same substance can erystallise in more than one forms. In SO,, there is px - px bonding as well as px - dx bonding due to overlap of filled px orbitals of oxygen with the vacant 3d orbitals of sulphur. H,SO, exists in two forms which are always in equilibrium with one another H | JIN 108 Kod :0: H (Symmetrical sulphurous acid) (Unsymmetrical sulphurous acid) ‘The unsymmetrical form containing SH bond explains the reducing character of H,SO,.67 (9) Theanion of H,SO, icc. SO, has a pyramidal structure with S atom in sp* hybridization and all the S - O bonds are of equal bond length (134 pm) (@ _Inthe gaseous phase, SO, is a planar triangular molecule with sulphur atom in sp? hybridization state In order to account for the equivalency of all the S — O bonds and short S — O distance of 143 1pm, SO, may be considered as a resonance hybrid involving px-px S - O bonding along with additional pr-px bonding. (©) Inthe solid phase, SO, polymerizes to puckered rings or the more stable layer'structure as shown. oO ° 3 oO PANN" —F—~o IN AINZIN, ric SSN S. Ss. oN ons %o Ring Structure Layer Structure68 SOLVED EXAMPLES Q.1_Anatomofelement A has three electrons in its outer shell and B has six clectrons in its outermost shell. ‘The formula of the compound formed between these will be- AB, (B)A,B, (A,B, (D)A,B Ans. (B) Sol. _ Inthis case the valence electron in the atom Ais three and hence its valency is generally3. Intheatom B the number of valence electron is six. Hence its valency is usually2, Hence the formula ofthe molecule formed from Aand B could be ABs. An example of two such elements are Al and O and the formula of Aluminium oxideisAl,Os. Q2__ oHydroxy benzaldchyde isa liquid at room temperature while p-hydroxy benzalchye is ahigh melting solid Sol. _o-Hydroxy benzaldehyde show intramolecular H-bonding or chelation, which are weaker than intermolecular H-bonding in p-hydroxy benzaldehyde. OF oe VT” I Hq Q3 Compare thebond angle in (axial bond angle) oO Re | - Wie] . x7 | nec | OR oO o ay Sol. — ductoring strain B.A. in second will be more than (I) QA Using VSEPR theory, draw the shape of PCI, and BrF. ly SY ‘/ ON ‘cl FE SoL cl a Q5___ Indicate the type of hybridization of each carbon atom in the following compounds (A)CHCN (B)CH,CH=CH, (C)H,C-CaC-CH, (D)HC=C-CH=CH, Sol. (A)sp?andsp (B)sp*,sp, sp? (C) sp, sp,sp. sp? (D) sp, sp, sp*, sp”Q6 Sol. Qi Ans. Q8 Ans. Sol. 69 ‘Among the following compounds/species write the order 0-O bond length in O,.0,(AsF,].K[O,] oO; O,[AsF,] or 03[ASF,]_ K[O,] or K*o; ‘The bond length decreases with increasing bond order Species 0; 03 03 Bond order 2.0 25 1s Bond length 03 < 0, < Oo ‘Twoclements X and Y have following electronic configuration X Is?, 2s?, 2p®; 3s?, 3p; 4s? Y Is?, 252, 2p; 3s, aps ‘The expected compound formed by combination of X and Y will be expressed as- (A)XY; (B)X,Y, (OX3Ys (D)XY, “w Valency of element X is 2(2 electrons in the outermost shell) while that of element Y is 1(1 electron required in the outermost shell to complete octet) So the formula ofthe compound between X and Y is XY, 2. 4 ee Y XY, ‘The compound MX, is tetfahderal. The number of e gas % 100 = 11S CO, isisostructural with (aycH, (B)SnCl, OneCl, (D)NO, oO The structure of CO, is linear O=C=O, similarly the structures of HgCl, is linear (Cl-Hg-Cl). SnCl, H and NO, have angularstructuesand CH, has tetrahedral structure | 1 nH Mn Identify the correct sequence of increasing numberof n-bondsin the strictures of the following molecules: (H,S,0, (ll) H,S0, (ui 1,8,0, (A) LL I (B) 1,1 OnLm (D)1, ULL @)ma Sol. Q16 Ans. Sol. Qi7 Ans, Sol. Q.18 Ans. tg H,S,0, HO—SS—OH — 4z-bonds 00 H,SO, wot In-bonds OH ll H,S,0, wo ow 3a-bonds o Enol form of acetone contains the following: (A) 9o-bond, I n-bond and two lone pair of electrons. (B)80-bond, 2 x-bond and two lone pair of electrons (C) 10c-bond, 1 x-bond and one lone pair of electrons (D)9<-bond, 2 x-bond and one lone pair of electrons @) Enol form of acctonc is ae [9 cand 1 xbondand 2rp) The decreasing order of solubility ofsilver halide is (A)Agl>AgBr>AgCl>AgF (B)AgF>AgCl>AgBr>Agl (C)AgCI>AgF>AgBr>Agl (D)AgBr>AgF>Agl>AgCl (8) ‘Agi has maximum covalent character [-+ “isa large anion}, while A gF has minimum covalent character, ‘Therefore, ithas more solubility ‘The atomic number of Sn is 50. The shape of gaseous SnC1, molecule is: (A)CI-Sn-Cl @) « SO D) X @ AN O gt Om A @) Sn[Z=50}. [Kr] sp?—hybridisation :72 Q9 Q20 Q21 Sol. Q22 Sol. Inwhich case hydrogen bond will not be observed (A) H,03 (B)H,O (C) H,03 (D)H,0* (@) 1,03 species ° HOH () |o-H-0- @) dd H (©) H,03(H-bonding) (D)H,0"(n0 H-bonding) H: * ‘H: * [ipowoct [f>o-4] Which of the following statements is correctin the context of theallene molecule, CjH,? (A) The central carbon is sp hybridized (B) The terminal carbon atoms are sp* hybridized (©) The planes containing the CH, groups are mutually perpendicular to permit the formation of wo separate 1-bonds. (D)Allcorrect @) ” =c=c~ H “ C: u~ aH Prove that dipole moment of C,H,Cl and m-C,H,Cl, are same. cl C oO BR eX Hq = 2x cos 60 x05 Thus both have jy =x Maleicacid is more acidic than fumaricacid. Why? 9 ° i KA, . Neg eo Nm An Malcic acid Anion is: sab Invomolecalar 1 boaingQ.23 Sol. Q24 Q2s Sol. 73 Glycerolis more viscous than ethanol. Explain. CH,-O-H ba-o-n | cHroH tu, -on + Due to presence of 3-OH groups higher no. of H-bonding, Glycerol is more viscous than ethanol Ithas been observed that %'s' character in Sb-H bond in SbH, is 0.5%. Predict the %'s’ character in the orbital occupied by the lone pairis. (A) 99.5% (B)99.0% (C)98.5% (D) 98.0% 1) Total %s-character in three Sb-H bond pairs = 0.5 +0.5 +0.5= 1.5% hence % s-character in (.p.= 100 1.5= 98.5% ‘The dipole moment of NH, is more than that of NF, Q Q Dipole moment vectors <= i N= Dipole moment vectors ‘are counter acting Ss ra IN, are reinforcing pe wall i My one another + + "1 Hy WS AlsoPolatityof _ N—————F bond >Polarityof | N—————H_ bond (EN=3.0) (EN=4.0) (EN 0) (EN=2.1)