‘Unit Ft Unit Three I hemical Bonding and structure Chemical bonding is a force that holds two or More ato; \ ms together, There are three types of chemical bonds. These are:- 1 Ionic bond 2. Covalent bond 3. Metallic bond 1. Ionic bond e Itisalso called electrovalent bond ¢ It is formed by complete transfer of electrons e It is formed between elements that have low i ionization energy (metals) and high electronegativity (non -metals) 7e M + xX ————> Mx metal non-metal e The strong electrostatic force of attraction between cation (positive ion) and anion (negative ion) is termed as ionic bond. © Compounds formed by ionic bond are called ionic compounds Example: a) K + Clo — Kcr [Arkh [Nej3s°3p° {Ar][Ne]3s°3p" SRE a * KCl is ionic compound b) 2Na + o- Nato2~ [Ne]3s! Sesion! giNellNe] “. Na)O is ionic compoundds nic compoun 8 Propents) of is Eserisial ions _ a are all crystalline solids bn have high boiling points and melting They have high density They are resistant to heat but many will break bey They are hard and brittle / They are usually soluble in polar solvent i.e, Water insoluble in non-polar solvents such as benzene, toly They transmit electricity in aqueous or molten State, “4 e They are non-volatile Illustrative Example T. What is an ion? How it is formed? | Sotution: , * Anion is charged atom or group of atoms. It is when a neutral atom gains or loses electrons ¢ Anions are formed when atoms gain electrons wh are formed when atoms lose electrons. 2. What type of electrons participate in bond formation? Sofutian: Valence electrons 3. State the octet rule The octet rule states that during the formation of a chemica\ bond, each atom has an octet (8) electrons in its valence shell gaining, losing or sharing of valence electrons. A complete a is very stable because all orbitals are full 4. Which of the following is ionic compound? A. HCI B. NaCl C.H:0 2! D. CH, Solution: Sodium chloride (NaCl) is ionic compound because itis formed between sodium (metal) and chlorine (non-metal) by transfer of electrons, 5. All of these are Characteristics of most ionic compounds in te solid phase except (UEE 2003 E.C) A. high melting point B. Solubility in water oH high electrical conductivity D. insolubility in organic solvents Points formed De catUnit Fhrec: - 116 Chemical Bonding and Satution: Ionic compounds do not conduct electricity in solia jh because ions are not move freely to carry charge Phase Answer C 6. which of the compounds below is most likely to be ionic? A. CCl B. NOz €.ScCh Dd. clo, Solution candium is transition metal that combines with chlorine and form jonic compound, Answer C 7. Four elements A, B, C and D have atomic numbers Z-Lzz+] and z+ 2, respectively. Ifz is 9, then the bond between which pair of elements will be ionic? (UEE)" A. Aand C C. Band D B. Cand D D. Band C Sakution: Element Atomic number Electron configuration A z-1=9-1=8 z=9 z+1=9+1=10- z+2=9+2=11-- . Metals usually have 1 to 3 valence electrons while non-metals have 5 to 7 and noble gases except helium have 8 valence electrons, = Aand B are non-metals = Cis noble gas => Dis metal 0O Dy, 28,1 + lonic bond is formed either between D and A or D and B. Answer C . - wo 8. Which of the following compounds is unlikely to contain ionic bonds? (UEE, 2004 E.C) ACO B. NaF, C. LiCl, D. MgBro Solution: The bond Between carbon and Oxygen in CO is not ionic because both are non-metals. Answer A"7 ait Shree Chemical Bonding ug | 9. Which of the statement below best explains why atoms regg, chemically with each other? (UEE 2004 F.C) \ ‘A. When atoms react, they gain proton and are more stabye B. When atoms react, they lose all their electrons and they become more stable ° CC. When atoms reac, they lose, gain of share electrons ang ag then less stable 1, When atoms react, they lose, gain of shate electrons to any, full outer energy level and are then more stable Salutien: In ordinary reactidns. only valence electrons are lost ‘gtined or shared by atoms to be more stable Answer D 10. Which of the following form tonic bond with fluorine and why Magnesium, Boron, Oxygen and Carbon - Salution: Only magnesium will form jonic bond with Nuorine because boron is metalloid and oxygen and e: metals Note: Metalloids form covslent bond with non-metals 11, How many ionic bonds result from the formation of a) NaCl b) MgCl; ¢) LisN ‘Selutian: a) One ionic bond since only one electron is transferred from sodium to chlorine. +) two ionic bonds because two electrons are transferred from Magnesium to chlorine. ¢) Tree ionic bonds since three electrons are transferred from lithium to nitrogen. 12. What role does electron affinity play in the formation of an ios bond? Setutien: Electron affinity is exothermic process th and plays a role in making the ion more stable than the sepa" . tom in the formation of ionic bond. bon are non. releases bea! i “hnit Shree: Chemicol Banding and stouctre us, Lewis clectron-dot symbols stecrron-dot symbol is the representation of valence ews i a ree sas dots around the symbol af etemeat, The se symbol represents the nycTeus ang its Inner electrons deer symbol far epresentative elements (A : soup able 3. Lew iat mia’ FIVA TVA TEN | VUA | Vita Taj ma jo torr vp 1 asap | nS Ap { | | ' | | jas re ee sw the Lewis symbol for period three elements. Ro Se SO he Solution: N @ Lonis elects on-dot symbol is used to show electron transfer from metals ta non-metals in ionic band formation Naser ——» a fe! Example: “ ‘ oe a cee ediafey @ Cafe] to show the electron transfer is electton-dot foray and write the formula of the ionte compound between 8) potsssiuma and bromine ©) Aluminum and Oxygen __ calcium and nitrogen d) Lithium and Sulphur Selatan: a) Potassiam tas one valence electron and bromine has sew en valence, electrons. as Nie efi Formula: KBr Name: Potassium bromideFormula: Cay Name: Calcium nitride ¢) Aluminum has three valence electron and oxygen has 6 vale electrons mee Formula: Al,Oy Name: Aluminum oxide 4d) Lithium is monovalent and sulfur has 6 valence electrons. Formula: Li) Name: Lithium sulphide 14, Use sub shell notation and Lewis electron-dot symbol to Tepresent the election configuration of the following. a)Na* b)p® c) AP* dyo* Solution: unit Thece: Chemical Bonding and stwsctant Lewis symbol {Na} fey ray" fey shell and Lewis symbol opt or (Nel 29s opt orl : 25 A rjerence between SUD. difference bet Pe 5 nw reir representation of clectron spin vedo not sosatian in Oe TE IHLA, and [VA, the Lewis symbols ror groups HA, 1 = » elec Solutio? acon pat However, in ground-state electron show the ele fon, there is no unpaired guration, there is 20 P| paar vec in group (HA and two unpaired electrons in anpaired ele 8 15, What is Jectrons in group IA, one group IVA si consider Mg, Aland Si. ee [NoJ3s", has fulfilled 3s sub shell i.c. paired. Mg: 15 25° 2p°3s pat.in Lewis electron - dot formula, there are two unpaired a, in Lewis el ! Fore ip’ = [Ne]3s°3p' has one pairedand one > unpaired electrons in 3s and 3p respectively. But, not paired electrons in Lewis electron — dot formuta i.c -®! Si: Is? 2s? 2p"3s"3p} 3p! 3p? = [Ne]3s°3p! 3p) 3p? has one Paired and two unpaired electrons. But, in Lewis electron-dot formula, there are four unpaired electrons i.e, 5! 3° Forgroup IA, VA, VIA, VIIA and VIA they have similar ~ ‘Rotations, 2 S 6 s 7 Formation of ionic bonding * Formation of ionic bond is affected by: * 1 Ionization energy . Electron affinity Latice energyV4 Unit Three: ry ret electrons from isolated gascous atom to : Is) favour the formatioi OF og, le \. lonization energy (IE) is the eners: with low ionization energy (meta! bo ond. ray released when atoms for, affinity (non-metals) favou, iy (EA) is the energy anions. Elements with high electron the formation of jonic compounds. 3. Lattice energy (U) ~ is the energy rel ) cations and one mole of mole of ionic compound. It is also the energy requt ~ascous ions. 2. Electron affinity . in to isolated g: Icaffects strength, melting por ionic compounds. e The higher the lattice energ melting point and hardness ionic compounds. Lattice energy is affect by i) Size of ions ii) The magnitude of the charge © The smaller the size, the hig Example: Lattice energy of LiCl > NaCl because Lithium has smaller size than sodium ¢ The larger the magnitude of the charge, the higher ts the lattice energy. Example: Lattice energy of MgCly > NaCl because the charge of Mr is +2 while that of Na’ is +1 eased when one Mole ot | anions combine red to break one mole of ionic salig | | t. hardness and solubility of the higher is the bond strengp, but the lower the solubility of her is the lattice Chemical Bonding and quired to FEMOVE Valery, form cation. El eng together to form one _—| s’s Law through the | * Hess law states rr i ~ states that enthalpy change AH doesn’t depend ap Path taken by the reactants as they proceed to form 4 product = 4H = AH, + AH) + AHee Unit Fixe: jder formation of LiF : | Cons mn ae step 1; Vaporization of Litlium Li(s) 7 Lil), AHsu = 155k3 grep 2: Decomposition of F2(g) V4Fx(@) 7 F(B)» AHaiss = 79k] step 3: Removal of valence electron from lithium atém Lig) > Li'(g) + ©, OH, = +520ks step 4. Addition of an electron to fluorine atom P(g) te > F(g), AH, = -333kI step 5: Bringing together one mole of Li'(g) and F(g) to ‘ form I mol of LiF Li'(g) + F(g) — LiF(s), U = -1349kJ (< steps 1, 2, and 3 are endothermic while 4 and 5 are exothermic processes. These five steps involved in the formation of LiF is represented by the Born-Haber cycle as follows - buy Li(s) + ‘“AFx(g) ———> LIiF(s) AHgiss U +1e7 AHys FQ) FC) » FO) HEA ~le ———_——* Lil) AHIE, . Fig. 3.1. The Born-Haber cycle for LiF According to Hess’s law: AH r= AHayy + AHyise + AH ze + AHea + U AH; ~ enthalpy of formation AH, ~ enthalpy of sublimation Heiss — enthalpy of dissociation Li(g) a_ 123 anit Fhree: Chemicat Belg ang | AH: — enthalpy of first jonization cnersy \ AH,:, — enthalpy of electro affinity U = Lattice energy U AL ~ Allin + AH gigs + ABE * Ata U ; J+ 79k) + 520k! 1 (333K) + (-1349kJ) lattice ene NaCl. LiC Salutian: RDC al in KCI, RbCl KCI < NaCl = LiCI, because fatti decreasing ionte radii (Li « Na’ _ RbI(s) Asus, fa U MEA Allure» Ig) Ig) : t+le~ ~ + Rb(g) ———__, ae F g) jsi -le 18, Using the following d . chloride (CaCl) lata, determine the lattice energy of calei™®Unit Three: Chemical Bonding and stuicture 90kJ/mol 145kJ/mol AH a An, ot Cla(g) ——— CaC(s) Cals. AHgiss U DHEA 3 atte Alar — 2C1(8) ®) + HIE: . Aiier : Calg) — 7? Ca'(@) > Ca?"(g) a8) he —le- Clg) + ¢ 7 CI(g), AHea = -349kI/mol = For 2Cl(g) + 2e° 9 2CI(g), AHr4 = 2x(-349) = -698kJ/mol Ifyou change the epetticients of a given reaction, the value of ‘ q ge also changes. a aa w AFlge AF Ale + AHgigt AHea + U Hy; — (SHsup + AHgiss + AH tr + AHie2 + AHA) =-795.8 — (178.2 + 243.4 + 590 + 1145 + (-698)) = -2254.4kJ/mol 19. Which of the following compounds would be expected to have the highest melting point? (UEE, 2002 E.C) A. BaF B.BaCl C.BaBr D. Bal, Solution: BaF, > BaCl, > BaBr2 > Bal, because the atomic radii F Cay M2 = Ca’M? => M has two valence i.e. gained 2 electrons to have an octeti| its valence shell. The valence electrons of M are 6 => Mis found in group VIA c) MoS3: M2 Ss: M's? => M has 3 valence electrons and found in d) KyM: K? M, = K'M? = M gained 2 electrons and has 6 electrons i.e. found in group Ve Ionic Compounds that violate the octet rule ions of ionic compounds wi 2 | 1, Cations of ionic comp with less than ei, it outer most shell ight electrons in the group [IIA . + Compounds of lithiy 3 Example: M such as : . Li' (@=3) SLIP, LiCl, LisO ete ge4- {=2>91s=“Unit 5 free: Chemical Banding and structure 126 . transition and post transition elements have more 2. The cations of in their valence shell. than a compounds of such metals violate the octet tule. Je: FeCl, CuO, ZnF2 ete Exam? Fe"'(z = 26) x -=26-3= < nfiguration: 1872s’2p° 3s°3p%3d°, the number of electrons Ff shell is equal to 11 that is above eight in the ecu (z= 29) e=29-2=27 2762976 3.22.64 49 on configuration: 1s°2s°2p” 3s°3p°3q", the number of electrons oe thi shell are equal to 17 i.c. above 8. 2 n lons with completely filled subshells that are represented by ns’ np° nd” valence shell configuration show Pseudo noble gas configuration. They follow the rule of 18. mple: Zn’ (2 = 30) Examp! [Nc] 3573p"? « Cu (z= 29) ‘6 [Ne] 3s* 3p° 3d’ © Ag’ (z=47) 6 1s'2s°2p°3s"3p°3d'°4s"4ps°4q"? Illustrative Example 23. Which of the following ionic compounds doesn’t violate the octet tule? A)NaCIB) CuO C) Sno D) LiF Sofution: NaCl doesn’t violate the octet rule because there are 8 electrons in outer atomic shell Na(@=I1):e= 11-1 =10 15726796. 296 . 8'2s'2p": [He] 2s 2p", valence electrons in the second shell =246=8 Answer A 4. Write three cati, . - uodo-noble.gas configuratio. a ce cations that show Pseuodo-nobl gas configuration a (2=31); 18728996 352 3p%3d!? ae = 50): 18°262op8 382 3p°3d!°4s4p%aq!° @= 48): 1822529p6 3.2 3p°3d!°4s"4p%4d"® electron127 Ante Sees Cheon Oreo tag | 25. Which of the following ionic compound does not obey the 4 rule? A)MgOB) KPC) AIF D) ZnF2 Solution: Mg?" (z= 12) 1s'2s*2p" has 8 electrons in the valence g, it obeys ’ K' (z= 19): Is? 382 3p’, has 8 electrons in the oute, shell. It obeys. AD’ (z= 13): 2p" has 8 electrons in the valence shel} | d!° has 18 electrons in the | Zn? (z = 30); 132s°2p" 38° 3p"3 valence shell. It violates the octet rule and obeys the 18- rule, Answer: D 2. Covalent bonding Covalent bond is formed when the bonded atoms share ° electrons in the internuclear region e When one pair of electrons (two electrons) are shared, single covalent bond is formed Example: * “HHH or HH Ch $C Gh or:G]—Cr: e If two pairs of electrons (four electrons) are shared, double pond is formed Example: +070 6: oF :6== 6: e If three pairs of electrons (six electro . ms) are she ‘ covalent bond is formed ) are shared, triple Re REO ENEINE OF Ns Example: = Nr The shared electrons are termed as . d electrons b e, Onding pairs and the unshare are called Non-bondin 8 Pairs (Lone pairs) -” 6‘Untt Free: Chemical Bonding and a le: ExampP H+: CE ry > Now-bording pais ( Lone pars) Bonding pair 5 structure for covalent compounds wii . . Le’ ¢ following rules to draw the Lewis structure of covalent Follow th compounds. . |, Find the total valence electrons and pair them. 2. Identify the central atom. The more electro Positive element or the one that has larger size is central atom. 3, Draw the skeletal structure 4, Fulfill the octet of terminal atoms except hydrogen 5, Place any remaining lone pairs on the central atom 6. Make multiple bond (double or triple) by using lone pair on the terminal atoms to fulfill the octet of the central atom if necessary. ple: Draw the Lewis structure of a) NF3 b) PH’, c) NOy Sotution: a) NF3: Find the total valence electrons. To do this multiply the valence electron of each atom by its subscript and add N(z= 7): 1872s?2p? Valence electrons = 2 +3=5 F(z= 9): 1s72s?2p° Valence electrons = 2 + 5 =7 N: subscript x 5=1 x 5S=5 F; subscript x 7=3 X 7=21 Total valence electrons = 26 Pairs = =13 * The central atom is N because it has larger size than F * Draw skeletal structure F—N—F | FE Fulfill the octet of terminal atoms Exam|129 bp = bonding pairs Lp = Lone pairs Note: The sum of bp and Lp must valence electrons. b) PHS: P: Lx 5=5 H:4x 1=4 | be equal to the total pairs of Change = -1 Total valence electrons = 8 H - H—-N—H H . _8 Pairs = rt 4 For positive polyatomic ions, subtract their charge from total valence electrons since positive charge implics loss of electrons ¢ Central atom = P ¢ Skeletal structure: * No extra lone pair of electrons * Use bracket to show its charge.+ ry wba bp=4 | - OF=N: 1x 5=5 aN 0:3 X6=18 ome =+] Total iad electrons = 24 =12 Pairs = For negative polyatomic ions, add their charge to the total valence electrons, because negative implies gain of electrons. « Central atom = N « Skeletal structure: Ze O—N | ° * Fulfill the octet of the terminal atoms 2 NH vl HE PN —H—>| H—— rT b) H* + H,0 + H,0' He —H—+fa—o * ct dative bond c) BF; + NH; > F;BNH, 7 - H Fs # it " BY +:N—| ONE a136 Trt Tee: Chemisad Being and stactang Iustrative Example ide whether the following substances contain coordi, inate . 33. Dec! covalent bond or not. 3ycoe ~—«Y)HNOs «CO d) NH c) POCI; Solution: Draw the Lewis structure to know whether they posses dative bond or not. a2 +O; COF p O: 2- vO rane Poul worn coveiert Dons or draw the skeletal structure for COZ and fulfill the octet of the So terminal atoms t , then you make double bond by NG using one lone pair of either of the three 0 atoms coordinate covalent ° 2 - Sl bond is formed «C03 _ has coordinate covalent bond. b) HNO;, Draw the skeletal structure by finding the total g valence electrons ano Total valence electrons = 1+5+3x6=24 . ~ Pairs = & =12Anit Three: Chemical Banding and ou make doubie bond by Usig ir of electrons Cithee y 137 , Now y' onc of the lone pa the two 0 atoms. >6 Ae. ° 1H covalent bond C=O: t bond rdinate covalent bong => INO; has coordinate c) by the above method: = CO has coordinate covalent! , has no coo’ —H | Dye 1 H 0: e) POCI; , has coordinate covalent bond _ “:6-—P—Ch Ck 34. Which of the following molecules doesn’t have a coordinate covalent bond? (UEE, 2000 E.C) A. H30°B. NHS C. BF;NI D. COz Satution: CO, has no coordinate covalent bond. Resonance Structure | Resonance is a condition occurring when more than one valid Lewis structure can be written for a particular molecule. The various Lewis structures are called the resonance structure. The resonance structure differ in distribution of electrons only. * The actual species that occurs is resonance hybrid Answer D Example: a) SO;Unit free: Chemical Bondi, 138 — Bonding and cteucture resonance resonance resonance structure I structure II structure SII 7 Lye 0 ¢ resonance resonance resonance structure 1 structure I] hybrid of & II Formal charge Formal charge is a hypothetical charge the atom has in the molecule or ion / Formal charge of an atom = valence electrons — associated electrons 1 Associated electrons = number of unshared clectrons + — number of shared electrons Thus, Formal charge of an atom = valence electrons — [number of unshared 1 5 electrons + — number of shared electrons] 2 Three general points govern the most reasonable (possible) Lewis structure based on formal charges: 1 Smaller formula charges (weather positive or negative or zero) are preferable to large ones. Like charges on adjacent atoms are not desirable. A more negative formal charge should reside on a more electronegative atom. The formula charges must sum up to the actual charge on the Species: zero for a molecule and the ionic charge for an ion. * Itis used to determine the most plausible Lewis structures when more than one possibility exists for a compound. 4, 3.139 ) ») 2 «the two forms are: The formal charges in the Wo Structure (a) Oo! [6-4- al=0 ot jo-2-2)=*1 I 36-6--Q) =! 0' [6-6-5 Structure (b) 1 16 -6-—(Q)]=-l 0! [6-6 7! ] 1 SS a =41 O° [6-2 5 1 o' [6 -4- A) =0 Structures aand b are symmetrical and each has the same forma | charges but on different atoms of oxygen. So they contribute equally to the resonance hybrid. b) Determine the formula charge of each atom in nitrate ion (NO;). Explanation: Draw the Lewis structure for. 2.5 20: [3 1, NSO O44 = Formal charge for:a te Unit Ffiree: Chemicat Bending and stuucture = —x2)=-1 o' [6 6+5 a) offs 6+ 5x 2)=-1 of6- +5 *4]=0 1 nt (5-(O+ >" B=+1 Therefore, the formal charges are: +1 (N atom), +1 (singly bonded oxygen atoms) and 0 (doubly bonded © atom). The sum of the formal charges = (-1) + (-1) + (0) + (+I)=-1 is equal to the overall charge on the nitrate ion (NO;). c) Determine the formal charges and use them to determine the overall charge if any, on the species represented by the following Lewis structure. Formal charges for: O atoms: Valence electrons = 6 Unshared electrons = 6 Shared electrons = 2 0: [6- (6+ sx2N=-1 S atom: Valence electrons = 6 Unshared electrons = 2 Shared electrons = 6 1 $:{6-(2+ —x6)]= 1 Q+>x6]=+ The sum of formula charges = (-1) + (-1) + (-1)+ I= ~2. Therefore, the overall charge of the given species is —2.4 ghnce: Chemical DONelng and 4 SS e octet ru le Covalent Molecules that less than ef; he 1 viola! 5 ms have iS eleetrg, 1. Molecules whose central Example: Ho, BeCl BCls, AICI ete setihn es 2. Matecutes whose © entr ms have greater than cight electron c,, Sa BrFss ICIs ete mber of valence electrons 3. Molecules Example: NO, NO}, ClO2 ete Illustrative examples 35. Draw the resonance structures of a) NOZ b) HNO, 6) 93 d) CsHe e) NO.F Solution: Draw the Lewis structure first oC 0Unit Ginee: Chemical Banding and. otwucti fy the atoms in PF, PCls, OF2, BC]; and SiF, which do not 36. Identi obey Sela I or not the octet rule, given molecule. the octet rule. tn order to know whether a given atom in a molecule obeys we have to draw the Lewis structure for a , both P and F obey the octet lure => The molecule obeys the octet rule , P violates the octet rule while Cl obeys = The molecule violates the octet rule , Both O and F obey the octet rule => The molecule obeys the “er: octet rule BCh: Y , B violates but Cl obeys the 0 octet rule C c = The molecule violates the octet rule 37. In which pattern does A obey the octet rule? | he AAS « 4 ™ PFs: B.A 0. .A=Se€ution: When there are cight electrons around A, such patter Answer D obcy the octet rule. 5 not obe! 38. Which molcenle has Lewis structure that docs y the oy rule? (UEE, 2004 E.C) A.NO BCS: Salution: Molecules that do no! central atom violate the oct 143 C. PFs D. HCN t have eight electrons around their et rule. You know this by drawing i Lewis strugture. n=O NO: ° , has 7 electrons on N Sy, SOS has 8 electrons on C PF: -—P—F | has 8 electrons on P =N;, has 8 electrons on C HCN: H = Answer A 39. Draw all the resonance structure of N2Ox. Solutions 6: o \s o — on \ 40. Which one has more resonance structures, HNO; or N03? Sofution: NOS has three resonance structures while HNO; has two resonance structures. Polar and Non-polar covalent molecules Non-polar covalent bond is formed when electrons shared equally. * {occurs when the shared electrons is at equal distance from both of the bonding atoms A + Bee Unit Three: Chemical Bonding and ot 144 The electronegativity difference between bonding atoms is almost Zero. The molecules formed by non-polar bond are non polar molecules CH, COs, Cs, 2, by, Fe "02, CS, ete + Hy, Ox, Cla, by Fay CHa, CO2, CS2, ete. example polar covalent bond is formed between two atoms of different electronegativity. tis formed when electrons are shared unequally. As’ + B®, the bonding electrons are attracted toward the more electronegative atom. As a result, a partially positive charge (5+) is formed on less positive atom and a partially negative charge (6-) The molecules formed by polar bond are polar molecules » The measure of polarity of a molecule is called dipole moment. The dipolar character of a molecule is often represented by an arrow. This arrow points toward the negative charge center. magnitude of distance Dipole moment (u)= separted x between charges (q) their centers(d) b+ 8 HF: H-F 6+HA H,0: —0 25 SI unit of = coulomb: meter 6+H other unit = Debye (D) 1D =3.33 x 10°Cm Illustrative Example 7 a - wane in increasing order of polarity: HF, HI, HCI, HBr olution: HI < HBr < HCl < HF, since the electrongativeity di : . ference Increases in the order listed145 anit Fhrce: Chemical Bonding and , a dipole moment without polar bg, aid d and no dipole ne? here a molecule with t What about a molecule with a polar bon moment? / Safutian: There is no molecule without polar bond that has dipoy moment. However, there are polar bonds ve wncelhed ay as in CF, and CO, the effects of one bond is by the h | effects of the other bond. FS 4 Cry F2=*C= F , polar bond : , dipole moment = zero F 5 &- 26: & CO2: Q= oe 9 , polar bond , dipole moment = 0 42. Which one has higher boiling point, l; or ICI? Solution: Polar covalent molecules have higher boiling point tha non-polar covalent molecules because, polar bond is Strong than non-polar bond. [2 is non-polar while IC] is polar. Answer IC] 43. Classify the following molecules as polar or non-pol molecules. a) CHC; c) NF; ce) HBF, b) BCI; d) SO; f) SOz Solution: HS a) | net dipole moment Lt— CaCl. = It is polar Os b) Ct » It is symmetric molecule with no f dipole moment Bs = It is non-polar ro CkUnit Ffivee: Chemica Bonding and otusctur 146 net dipole moment 3) ef = Itis polar Pa , Itis symmetric molecule with out a dipole moment => It is non-polar net dipole moment = Itis polar . | iret dipole moment eo = It is polar 44, Which bond between the following groups of elements will be the most polar? (UEE, 2003 EC) A.S-F B.S-Cl C.S-Br D.S-I Solution: The most clectronegative element is fluorine. Therefore, the electronegativity difference between S and F is the highest. Asaresult, the S—F bond is the most polar. Answer A 45. Dichloro ethylene, C2H2Cl, has the following Lewis structures. Which one has a dipole moment of Zero? (UEF, 1998 E.C) J il Ut St ALS aa c=. i cl i “a ‘\ Ad B.Il C. Wand 1 D, 1H Solution: * Structure IY has no net dipole moment. Answer D -147 Unit Féree: Chemical Bonding ang , 46. Arrange the following molecules decreasing order OF Pola based on the given values of thei dipole moment. Molecule Dipole Moment (D) HCl ee 2,0 i NF; 0.23 co 0.12 NH; 1.47 Sofution: The targer the value of dipole moment, the more polar jg the molecule. = H,0 > NH; > HCI > NF; > CO 47, Which of the following molecule is non-polar? (UEE) A. CS2 B. SOz C.CHCl —D. SF, Answer A Properties of Covalent Compounds ¢ Covalent compounds are generally liquids or gases at ordinary conditions. Some covalent molecules like iodine», solids. Example: Water (H,O) lian liquids Ethanol (C:HsOH) Ammonia (NH3) Hydrogen chloride (HCI) ( are gases Hydrogen sulphide ¢ Covalent compounds have lower boiling point and melting point compared to tonic compounds © = They are volatile . Re arc usually soluble in non-polar solvents ! ion-pola ~ eo ay ovale compounds are non-electrolytes al y t generate ions that carry charge Some polar covalent compounds are electrolytesTENE 3 Unlt Three: Chemical Banding and. stusctare IHustrative example the following is not true about covalent compounds? covalent molecules have higher boiling point than non- t compounds are molecules but all molecules are not ry covalent compounds nt is the measure of a polar covalent bond. junds have higher boiling point than ionic —— _ Covalen neces _ pipole mome p, Covalent comp “compounds lution: Covalent compounds are molecules but molecules such as Solution nydrogen (Hz). Oxygen (O2), fluorine (F,) are not compounds because they are made of the same atom. Answer D 49, Which of the following contains both ionic and covalent bond? (UEE, 1999 EC) . acaco; BPCh =. Mg... CHO Selution: Compounds that contain metal ion or ammonium and polyatomic anion contain both ionic and covalent bond. CaCO; has Ca” (metal ion) and CO$~ (polyatomic ion) = has both ionic and covalent bond Note: Ammonium ion (NH#) and non-metal anion also posses both bonds Example: NH,Cl has both ionic and covalent bond. 50. All of the following when added to water will produce electrolytic Sefution except (UEE. 2004 E.C) A.N,(g) B.Nal(s) C. HCI(g) _D. KOH(s) Solution: Ny is non-polar molecule that doesn’t form any ion when it is added to water. It is non-electrolyte. Nal is ionic compound that dissolvels in water and generates Na’ and I ions as charge carrier. It is electrolytes. HCl is polar covalent compound and dissolves in water to form HO" and CI that are used as charge carrier. KOH is ionic compound and it is electrolyte when dissolved in Water, Answer: AUnit Three tg no ectton Pat, nce shell Electron Pai; Molecular Geometry and the Vale —s Repulsion force (VSEPR) tay a very important rol; © = The structure of molecules play iy f erties. ining their propertle / = ‘ ‘or model is used as a tool to explain y, y * VSEPR theory 0 istorted rather than as predictive tga given structure §S we is that the structure around a ty main idea of this a minimizing repulsion between Vo atom is SE Tae means, the bonding and non-bongj, electron ee jiyen atom are positioned as far apart gs pairs around a BIN VSEPR theory. possible. According to VS ; - f ~ pair > Lone —pair ~ bonding > bonding-pair. Lone-pair ~Lone pa 5 Igion bonding pair p repulsion pair repulst Duis, © The VSEPR theory can be used to convert the dimensional Lewis structures in to three dimensig, geometry. « Electron pair arrangement is the set of electrons bonding and Lone pairs around the central atom. « Molecular shape is the relative positions of the atoy nuclei. Predicting the shape of molecules 1. Molecular shapes with two electron sets © AX) - type © Bonding pairs = 2, Lone pair = 0 « Arrangement = linear « Shape = linear * Bond angle = 180° Example: CO,, CS», BeCh, CoH», HCN ete BeCly: ‘Cl. Be 6 _ SOF Bee . 180° + One single bond One double bond = j one set of One triple bond electrons One lone pairUnit FAree: Chemicat 150 Bonding and strscture If there js no lone pairs of electrons on the central atom, f molecular shape and electron arrangement are same. shape with three clectron sets d Molecular i) AX type / « Bonding pairs * 3, lone pairs = 0 @ = Shape = electron arrangement = trigonal planar Bond angle = 120° Cla AICI, SOs, COZ~, NOF ete Example: B gp Be, , i ree: dS ie ii, AXE type e Bonding pairs = 2, lone pairs = | e electron arrangement = trigonal planar «shape = bent or angular i) AX, type © Bonding pairs = 4, lone pai 0 ¢ Shape = electron agangement = tetrahedral * Bond angle = 109.5° Example: CH,, PH?, NH}, SO”, PO}, etc Lal l t hot a x [oa 50 . or il) AX;E type E. Bonding pair = 3, Lone pair = 1 number of lone pair of electrons151 Unit Fhree: Chemical Bonding and . { tea | e Electron arrangement = tetrahedral © Molecular shape = trigonal pyrapmid ¢ Bond angle = 107° Example: NH, PHs, H,0', ete iii) AX2E type e Bonding pairs = Electron arrangement: tetrahe t or angu 2, Lone pairs = 2 dral ° lar or v-shape e Molecular shape: ben e Bond angle: 104.5° Example: HzO, SO2, 03, OF. H2S, SnBrz etc H,0: ann 4, Molecular shapes with five electron sets i) AXs type e Bonding pairs = ¢ Electron arrangement = bipyramid » Bond angle 90°, 120° Example: PCls, SiFs’, etc 5, Lone pairs = 0 molecular shape = trigonal ii) AX4E type © Bonding pairs = 4, Lone pair = | © Electron arrangement: trigonal bipyramid . Molecular shape: see-sawNG Cir trcccrine , XeO2F2, OFF etc SFa: 1 axsbs YPC i ANS onding pairs = 3, Lone pair = 2 Flectron arrangement: trigonal bipyramid lar shape: T-shape Molecu! rape: BF ICh, CIF, ete gxampie $—Br—F , BrF, ct | pis bye” BrF3: e iv) AXES type Bonding pairs = 2, Lone pair =3 . Electron arrangement: trigonal bipyramid « Molecular shape: linear Example: XeF), ly, [Fz , etc XeF2: 6. Molecular Shape with six electron sets i) AX type + Bonding pairs = 6, Lone pair = 0 « Electron arrangement = shape = octahedral « Bond angle = 90° Example: SFs, PC1g etc it) AXsE type . * Bonding pairs = 5, Lone pair = 1 . BI Electron arrangement = octahedral * Molecular shape: square pyramidalanit Toner ns, 153 xeOFs ete Example: BrFs, Tels + By ve Bs / Xe fF 3 iii) AXGE: typ vgs = 4p Lone pair = 2 « Bonding pairs = “> aipedral Electron arrangement = octal Molecular shape: square planar Example: Xek a, Che ee | f | : Sel : | XeFs: we NE Note: The molecular shape of molecules with more than one centyy atom is predicted with respect to each central atom Consider methanol (CH;OH) It has two central atom, C and O. H H—C—ON | H There are four bonding pairs and no lone pair around C. therefore, the molecular shape with respect to C is tetrahedral. ¢ There are two lone pairs and two bond pairs around 0. Asé result the shape is bent with respect to 0 Mustrative Ex SI. Use the VSE ane se the VSEPR theory to predict the elect molecular shape of the following sub ee nwemen ™ : il subs a) C10; c) Pelt e) a b) ShCIE d) CHT ‘ f) AsH3“You begin by drawing the Lewis structure and based “pove 6? neral sets predict the electron arrangement and 7 ae ape of ane given series . 4) 6102 lo ‘J Mees ore are 2 bp and 2 Lp on the central atom. rr shape: bent or angular or v-shape se tw. a Moleculal vp flectron arrangement: tetrahedral “Ck x OK | ye p) SaCls /\ sé Cl gp <> There are 6 bp and no lone pair around the central atom. = Molecular shape: Electron arrangement: octahedral f - —Gi PCIe , Be Ck = There are 4 bp and no lone pair around the central atom. > Molecular shape: Electron arrangement: tetrahedral a) cHe # F ee .* bp =3 Lp=Q > Molecular shape: Electron arrangement: trigonal planar eR, pre 4 7\ we _ C— é A/a +e I} p=4 T a x F} Lp =2(on central atom) > i" aa shape: square planar clon arrangement: octahedralinit Shree: Chemical Bonding and , 155 f) AsH, H—As—H H 4 «trigonal pyram | => Molecular shape: trigon4 al arrangement: tetral f the mo clow with respect jg ni => Electron §2. Predict the shape @! ral carbon atoms Iecule given b cach cent CHy cH=cH-C2C CH | | ‘ ‘ : ct . | Solution: Draw the detail Lewis structure: H | | nffnd ome iF 4 | | H H = There are 4 bp and zero lone pair around C ~ land C- 6. | Therefore, the molecular shape with respect to Ct and C-~65 | tetrahedral | = There are 4 bp and zero fone pair around C - 4 and C ~ 5 but one double bond is considered as one set of electrons. As a result, te shape with respect C — 4 and C — 5 is trigonal planar. = There are 4 bp and zero lone pair around C - 2 and C — 3 but om triple bond is one set of electrons. Therefore, the shape with Tespect to C -2 and C 3 is linear 53. Which of the following species has the smallest H — X — H bor! angle where X is the central atom? (VEE, 2004 E.C) A.OH2 B. NH C.CH 3 . CH. ). BH Solution: Draw the Lewis Structurc redict of the structure and predi shape of the cule ind predict the shape I OH, = H,0: -_ N\ H bent shapes , bond angle =104,5!Unit Féivce: Chenicat Banding anc strcte ES , trigonal pyramidal shape bond angle = 107" , tetrahedral shape bond . angle = 109.5° , tetrahedral shape bond H—-B—H angle = 120" BH: = HO has the smalles bond while BH; has the largest bond angle. Answer A 54, NF; BFs and CIF; all have molecular formulae of the type XF3. Which molecule (s) has (have) trigonal pyramidal molecular acometry? (UEE, 2003 E.C) ‘A. NF; and BF; C. NF; and CIF; B. BF, and CIF D.NEs Sedution: Draw the Lewis structure for cach and predict the molecular shape NFs Te » trigonal pyramidal shape S op oO , trigonal planar shape Os: , T~ shape 58. What is th i Te, B.C is ¢ molecular geometry of O3? (UEE 2003 E.C) B. ea Planar C. Trigonal pyramidal Bent D. TetrahedralEu Unit Stee: Chemical Bonding ang | ructure of Os Solution: Draw the Le oO On: 7% 3 bp and [Lp of electrons are found around thy sl atom. However, one double bond et of electrons. Therefore Answer 3 centr considered as one S| shape of O; is bent. owing is NOT probable shape ofa Molecule hy 56. Which of the fotl (VEE, 2002 E.C). A. tetrahedral, GeCls B. A bent, HCN Safution: C. A trigonal bipyramid, PC\, D. A T-shape, BrF; Ch GeCl: <é}—Ge—Cl , tetrahedral shape “Cr HCN: H-~C™=N: two sets of electron around the central atom. It is linear Ct \—P—Ch : . \ , trigonal bipyramidal shape “C BrF 5: PEE shape ok 57. What is the H-N~H bond angle in the teen 5 2 ; NH and NH} Tespectively? ae Sefution: Ny: | OM | 4 » ithas bent shape with 104.5” bondUnit Stree: Chemical Bondi any SS —H ie aa » its molecular shape is trigonal 4 . Pyramid with bond angle 107° i ith jt . » thas tetrahedral shape with b i: ps ond NAG? | 1 angle 109.5° H sg. Which reaction involves a change in the clectron pair poorietty for the under lined atom? (UEE ABE +P" BFy C280; + 0, 280, BNI tH! NAS DLO +H > HOt Solatian: Electron pair gcometry means electron arrangement around the central atom Lewis structure molecular geometry electron pair geometry =. trigonal planar trigonal planar | tetrahedral tetrahedral NHy: 4#—N—H (igonal pyramidal _ tetrahedral H ' + NHFJH— Ny tetrahedral tetrahedral HE- Unit Three: Chemical Bending and, trigonal planar bent trigonal planar ey trigonal planar g — strahedral Ho: 4 SH bent te { ; a ahedral 1,0"; [HOH] trigonal planar tetrahi - Answer A H 59. What are the three aspects that minimize the repulsion betwee, valence shell electron pairs? Solution: * Bonding pair and bonding pair * Bonding pair and lone pair «Lone pair and lone pair 60. Write the causes of distortions of molecules Solution: « Repulsions between electrons in a lone-pair and other clectrons ¢ Difference in electronegativity between atoms ¢ Triple bond, double bond and single bond. Triple bond causes more distortion than double bond and single bond. Intermolecular forces in covalent compounds © There are two types of electroste ic forces 1. intramolecular force : 2. intermolecular force‘Unit Sfirce: Chemical Bonding and structure 160, .e between intermolecular and intramolecular forces. able Lae mie Intermolecular forces rae particle * cxist between particles ~ sexist with | ica property. © affect physical property « affect chem * weak ¢ (Tog Example cs covalent bond and Dipole-dipole force, London wali ‘eat force and Hydrogen bond. Fpole-dipote interactions » They exist in polar molecules. In a polar molecules there are permanent dipole moment Fig. Dipole - dipole interactions in HBr molecules Hydrogen bond “ Itisaspecial type of dipole — dipole force « Itis the strongest intermolecular force « Stis formed when a hydrogen atom in one molecule is bonded to one of the highly electronegative atom (F, O or N) in other molecule. « Itis found in water, ammonia, hydrogen fluoride, alcohols, carboxylic acids, proteins, DNA etc. ~ SF WY Ny / Fr H. yeeF Fig. London, eto bonding in hydrogen flouride i po called dispersion force Sccurs between all atoms and molecules.161 ie i a unit Force: Chemical Bonding anc, se. n noble gases and nop, © Itis only force that exists betwee! ta molecules. — IL is the weakest intermolecular fo Londen force aneous and induced dipoles Fig. Instant ases, the strength Of Londgp -polar molecu les incre: A e of a non force also increases. Illustrative Example 61, Which molecule in each pair has stronger London forces? Explain a) F, or Bry Sotation: 2) Br2 has stronger Lon polarized duc to its larger size. b) Kr has stronger London force bee: easily due to its larger size. (molar mas c) CoH, has stronger London force 62. Nz and CO are isoelectronic, which substance would you expect to have higher boiling point? Explain Solution: CO has higher boiling point since it is polar molecule. In polar molecule, dipole-dipole force occurs which ts stronger tha London force in non-polar molecules 63. Arrange the following in increasing order of hydrogen bond strength NH3, H.O, HF Setation: NH3 < H:0 < HF, as electronegativity difference betwett drogen and other atom increases, the strength of hydrogen bond also increases. 64. Which type of intermolecular force is dominant in the follow! b) Ne or Kr c) CH, or CoHe don force than F2, Br2 is more easi, ¢ it forms induced dipok ) substances? a) {Cl d) Cly g) CH;COO C 12 3 H b) CHy e) HI h) MeCl, c) CHOH 1) CH;NH; i) PCI,162 $$ ee Roading and otuacture . g) dipole-dipole force, because it j solution 2) Mondon-force since it is TiGiispolke im c) Hydrogen bond d) London force Pm) dipole-dipole force 0 Hydrogen bond 2) Hydrogen bond h) lon-dipole force because it is ionic compound i) dipole-dipole force There is a strong covalent bond between the N atoms i gas, Nz, Why, then does nitrogen have such a low boiling point jr 196°C? (UEE, 2004 E.C) A. The bond between the N-atoms is triple B. Nis very electronegative, only next to F and O C. The strong bond, an intramolecular one determines the boiling point of the substance. D. Boiling point is determined by intermolecular force, which in this case is weak as the molecule is non-polar. Solution: Boiling point is determined by intermolecular force. No is non-polar and the weakest intermolecular force, London force holds N> molecules together. As a result, N2 has low boiling point. Answer D 66. Which of the following explains, why at room temperature, L is a solid, Br2 is liquid and C), is a gas? (UEE, 2004 E.C) A. Jonic bonding C. Hydrogen bonding B. Hybridization D. London dispession forces Solution: 1, Br: and Cl; are non-polar molecules. As molecular mass increases strength of London force increases in non-polar molecules. That is why Iz is solid, Bro is liquid and Cl. is gas. Answer D 67. Of Brs, Ne, HC] and No, which is likely to have the largest London dispersion forces? (UEE, 2003 G.C) A.Bn B.Ne C. HCI D. No Solution: The largest London dispersion force occurs in Br; because ithas the largest molecular mass (size). The dominant force in HClis dipole-dipole force. Answer A 65. in nitrogen1s3 Unit Ghree: Chemical Bonding ang, 68. Solid water (ice) is lighter than liquid water. aie. why? Satution: The hydrogen bond in ice holds the "occupied Tat : rigid but open structure and more ramuabeth we Ce ate means the molecules of water are far apa ore densetien water. That is why liquid water at OVC is m an cg, Metallic bond © Ibis formed when the val attract each other. e The clectron-sea model is a co metal atoms in a sample of me! form a delocalized sea of clectron: s envelopes the positively charged metal ions. -@-@ -@-@<——_ metal ion @- @-@ -@ -<—— eelocalized electron -®-@-@-@ ®-0-8-@- Fig. Electron-sea model for metals The strength of metallic bond is affected by: 1. Number of valence electrons 2. Size (packing arrangement of the metal atoms) « Asnumber of valence electrons increase and size decrease, the strength of metallic bond increases. Illustrative Examples 69. State some properties of metals related to the concept of metalli bonding. Solution: ¢ Malleability (hammed into sheet) ¢ — Ductility (drawn in to wire) : ane (transmit heat and electricity) 8) ‘ing and boiling points * Strong and durable 10. inne has higher ee Explain Safution: a a a or K ‘as smaller size than K Jence electrons of metal and metal ion ncept used to describe how all y. tal contribute their electrons tg s. This sea of electrons (_ kernel)‘Unit Three: Chemical Banding and steuctuie 64 — I “metallic bonding different from ionic bonding and is 1. How bonding? 1 valent bot Hic bonding no transfer of electrons like ionic bond. co s sort: 12. Oo covalent bond, metallic bond does not involve any ontra air of metal atoms that is bonded through any particular ae of electrons. Instead, the valence electrons are tocalized P fthe atoms in the substance. The substance is held all o! 5 tal te the attraction that exists between the positively 7 .q metal and the mobile, free electrons. chare® reater metallic character? | 72, Which = has 8 c) Bor Al ec | ae K d) Ca or Ga | ) . Metallic character is described in terms of ease of losing ‘As size increases metallic character also increases. { electrons. . 5 . ize than Be and loses its valence electron 3) Li because it has larger s\ easily . b) K has larger size c) Al has large size . @) Cahas high tendency to lose its valence electrons. 73, Which one of the following is NOT true of metallic bonding? | (UE, 2002 E.C) | A. Itgives rise to excellent electrical conductivity. B, Electrons are free to move throughout the structure C. The strength of metallic bond increases down a group D. The strength of metallic bond affects the boiling point of metals. Solution: As size increases metallic bond strength decreases while metallic characters increases. Answer C 74. Which of the following element has the highest melting point? (UEE, 2004 E.C) A. odine C. Mercury B. tungsten D. bromine Solution: {n, general, metals have higher melting point than non- rade AOmetallic bond. However, metals have a wide range g Points, from -39°C (mercury) to 3410°C. (tungsten) Answer Balnit Shree: Chemical Bonding ang 165 icity i id state? 75. Which one transmit electricity oF a C. sodium chlori ee D. sulphur B. copper Satution: Mctals conduct electricity in the three states of Matter Answer B i i als 16. List some properties of solid meta Solutian: «= They are malleal «They have high elect e They have high density, ble and ductile 7 (ectrical and thermal conductivity melting point and boiling point They are shiny «They are sonorous (have deep sou! «They are reducing agent They are hard Chemical bonding Theories There are two commonly used theories of chemical bonding baseq on the concept of quantum mechanics. These are 1. The valence bond theory (VBT) | 2. The molecular orbital theory (MOT) L 1. The Valence Bond Theory (VBT) According to VBT, two atoms form a bond when both of the following conditions occur i) There is orbital overlap between two atoms. Half-filled orbitals | overlap to form covalent bond. ii) A maximum of two electrons of opposite spin, can be present in the overlapping orbitals. Example: HH + H->H-H, Lewis theory Is — 1s overlap . ee to VBT, the greater the overlap, the stronger is ¢ Sigma (8) bond is formed when orbitals overlap in head !@ head or end to end or linear overlap. | nd when hit) ¢ The electron density of sigma bond is greatest along the axis) s~sand s~ P will always overlap along the nuclear axis al hence result only sigma bond.1h er i et Overlap region oe: o ee &- bond axis ' s S-S Overlap a) @:O— @ 1s. 1s 1s- 1s overlap b) CH OSD? OM O.. P-Poverlap ¢) Fig. sigma bond formation a) P —P overlap S-S overlap. b) S-orbital overlaps along the nuclea: P—~ orbital. c) P — orbital overlaps axis P- orbital. Pi(m) bond is formed when P-orbitals overlap in side-to-side or parallel overlap. I bond has two regions of electron density, one above and the other, below the nuclear bond axis. ( ox Fig P_p side way overlap for m bond formation * Note: i) Ail single bonds are sigma bonds because their clectron density is concentrated along the bond axis. ») A double bond has one sigma and one pi bond. i) A triple bond has one sigma and two pi bonds.