Basic Concepts of Chemical Bonding Lewis Symbols and lonic Bonding 84 82 83 84 85 86 (@) Valence electrons are those that take part in chemical bonding, those in the outermost electron shell of the atom. This usually means the electrons beyond the core noble-gas configuration of the atom, although itis sometimes only the outer shell electrons. (&) —_N: [He} 2s%2p* A nitrogen atom has § valence electrons. Ls valence electrons. (©) _18%2s*2p* 38%? The atom (Si) has 4 valence electrons. L fr [Ne] valence electrons (2) Atoms will gain, lose or share electrons to achieve the nearest noble-gas electron configuration. Except for H and He, this corresponds to eight electrons in the valence shell, thus the term octet rule. (©) S: [Ne]3s"3p* A sulfur atom has 6 valence electrons, so it must gain 2 electrons to achieve an octet (©) 18#2s%2p*=[Hel2s*2p? The atom (N) has 5 valence electrons and must gain 3 electrons to achieve an octet. P: 18*2s*2p*3s*8p”. A 3s electron is a valence electron; a 2s (or 1s) electron is a non-valence electron. The 3s valence electron is involved in chemical bonding, while the 2s or 1s non- valence electron is not. Sc: 18°2s"2p%3s"3p"4s"3d!" = [Arj4s*3d'. Scandium has three (3) valence electrons. These valence electrons are available for chemical bonding, while the core electrons do not Participate in bonding, @) c& +B (a) «Mg. (0) 17087 88 89 8.10 att 8.12 8.13 814 815 Chemical Bonding Solutions to Exercises Potassium has a single valence electron, which it tends to lose to achieve a completed octet. Calcium has two valence electrons, which it tends to lose to achieve a completed octet. Thus, K loses a single electron while Ca loses two electrons when reacting with Cl. Removing one electron from the core of either K* or Ca®* would be energetically unfavorable, because the core electrons are stabilized by a strong electrostatic attraction for the nucleus. Even a large lattice energy is not enough to promote removal of a core electron. Bromine does not accept more than one electron, because the additional electron(s) would have a higher principle quantum number than the valence electrons in the completed octet of, Br. Electrons beyond the n = 4 level in a bromine anion would be substantially shielded from the nucleus by the core electrons and are further from the nucleus than the other electrons. In other words, the energy of the 5s orbital in Bis sufficiently high that Br or other anions with a negative charge greater than -1 do not form. @ AIF, ) KS ©) Y,0; (8) MO.Ne (a) Rb,O- (b) Bal, =) LO (d) MgCl, (a) ‘Sr**: [Kr], noble-gas configuration (b) Ti: [Arj3d* (0) Se: [Ar|4s*ad!%4p* = [Kr], noble-gas configuration (4) Nf [ANd © Br-: [Arj4s?3d"°4p* = [Kr], noble-gas configuration (Mn: [Arja* (a) Zn?*: [Arj3d" —_(b) Te*: [Kr]5s"4d"°5p® = [Xe], noble-gas configuration (©) _Se™: [Ar|4s®3d"4p" (This is a very unlikely ion. A more stable and commonly-found ion would be Sc™.) Sc™: [Ar], noble-gas configuration (6) Ru: (Krldd® ——(e) TI: [Ke]6s%4f"5d" —(f) Au'[xXe}4f"*5d"? (@) Lattice energy is the energy required to totally separate one mole of solid ionic ‘compound into its gaseous ions. (©) The magnitude of the lattice energy depends on the magnitudes of the charges of the two ions, their radii and the arrangement of ions in the lattice. The main factor is the charges, because the radii of ions do not vary over a wide range. 1718 Chemical Bonding _ Solutions to Exercises 8.16 NaF, 910 ki/mol; MgO, 3795 kJ/mol ‘The two factors that affect lattice energies are charge and ionic radii. The Na-F and ‘Mg-O separations are similar (Na* is larger than Mg®*, but F- is smaller than O°). The charges on Mg* and O* are twice those of Na’ and F-, so according to Equation 8.4, the lattice energy of MgO is approximately four times that of NaF. (0) MgCl, 2326 kJ/mol; SrCl,, 2127 kJ/mol The two factors that affect lattice energies are charge and ionic radii. The ionic charges are the same in the two compounds. The ionic radius of Mg** is smaller than that of Sr* so the Mg-Cl distance is slightly smaller than the Sr-Cl distance. Since lattice energy is inversely proportional to the ion separation, the lattice energy of MgC, is slightly larger than that of SrCl,. 8.17 KF, 808 ku/mol; CaO, 3414 ki/mol; ScN, 7547 ki/mol The sizes of the ions vary as follows: Sc™ K* and Br~> Cr, the difference between Cs* and K* must be approximately equal to the difference between Br~ and Cr. This is somewhat surprising, since K* and Cs* are two rows apart and CI” and Br” are only one row apart. 820 (a) _In MgO, the magnitude of the charges on both ions is 2; in MgCl,, the magnitudes of the charges are 2 and 1. Also, the CI” ion is larger than the O* ion, so the charge: separation is greater in MgCl,. Thus, the lattice energy of MgO is greater, because the product of the ionic charges is greater and the ion separation is smaller. (b) The ions have +1 and -1 charger in all three compounds. In NaCI the cationic and anionic radii are smaller than in the other two compounds, so it has the largest lattice energy. In RbBr and CsBr, the anion is the same, but the Cs cation is larger, so CsBr has the smaller lattice energy. 1728.21 8.22 8.23 8.24 Chemical Bonding Solutions to Exercises (2) In BaO, the magnitude of the charges of both ions is 2; in KF, the magnitudes are 1 Charge considerations alone predict that BaO will have the higher lattice energy. The distance effect is less clear, O* and Fare isoelectronic, so F°, with the larger Z, has ‘a slightly smaller radius. Ba’ is two rows lower on the periodic chart than K’, but it has a greater positive charge, so the radii are probably similar. In any case, the ionic separations in the two compounds are not very different, and the charge effect dominates, Equation 8.4 predicts that as the oppositely charged ions approach each other, the energy of interaction will be large and negative. This more than compensates for the energy required to form Ca and O* from the neutral atoms (see Figure 8.4 for the formation of NaCl). Cals) > Ca(g); Bra(l) > 2Br(g); Calg) > Ca'(g) + te; Car(g) > Ca*(g)+ 16% 2Br(g) +2e° > 2Br(Q), exothermic; Ca*(g) + 2Br-(g) > CaBr,(s), exothermic RbCi(s) > Rb*(g) + Cr(g) OH (lattice energy) = ? By analogy to NaCl, Figure 8.4; the lattice energy is DH, = -AH, RbCKs) + AH, Rb(g) + AH, Cilg) +1, (Rb) +E (Cl) = -(-430.5 kJ) + 85.8 kd + 121.7 kd + 403 kd + (-349 kd) = +692 kd This value is smaller than that for NaCl (+788 kJ) because Rb" has a larger ionic radius than Na’. This means that the value of din the denominator of Equation 8.4 is larger for RbCI, and the potential energy of the electrostatic attraction is smaller. By analogy to Figure 8.4: H,, =-AH, CaCl, + AH, Ca(g) + 24H; Ci(g) +1, (Ca) + I, (Ca) + 2E (Ci) = -(-795.8 kJ) + 179.3 kd + 2(121.7 ku) + 590 kd + 1145 kJ + 2(-349 kJ) = +2256 kd From Table 8.2, the lattice energy of NaCl, +788 kJ/mol, is considerably less than that of CaF,. The 2+ charge of Ca* leads to much greater electrostatic attractions and a higher lattice energy. Covalent Bonding, Electronegativity and Bond Polarity 8.25 8.26 (a) A covalent bond is the bond formed when two atoms share one or more pairs of electrons, (b) __Anysimple compound whose component atoms are nonmetals, such as H,, SO,, and CC\,, are molecular and have covalent bonds between atoms. (©) __ Ionic because it is a gas even below room temperature. Kand Ar. Kis an active metal with one valence electron. It is most likely to achieve an octet by losing this single electron and to participate in ionic bonding. Ar has a stable octet of valence electrons; it is not likely to form chemical bonds of any type. 1738 Chemical Bonding Solutions to Exercises 827. 8.30 831 8.32 Analyze/Plan. Follow the logic in Sample Exercise 83. Solve: Check. Each pair of shared electrons in SiC, is shown as a line; each atom is surrounded by an octet of electrons. {b) double bond is required because there are not enough electrons to satisfy the octet rule with single bonds and unshared pairs. (©) The greater the number of shared electron pairs between two atoms, the shorter the distance between the atoms. If O, has a double bond, the O-O distance will be shorter than the O-O single bond distance, S=c=s The C-S bonds in CS, are double bonds, so the C-S distances will be shorter than a C-S single bond distance, (a) Electronegativity is the ability of an atom in a molecule (a bonded atom) to attract, electrons to itself. (b) The range of electronegativities on the Pauling scale is 0.7-4.0, (€) Fluorine, F, is the most electronegative element. (4) Cesium, Cs, is the least electronegative element that is not radioactive. (a) The electronegativity of the elements increases going from left to right across a row of the periodic chart. (b) _Electronegativity decreases going down a family of the periodic chart. (©) Generally, the trends in electronegativity are the same as those in ionization energy ‘and opposite those in electron affinity. Thattis, the more positive the ionization energy {and the more negative the electron affinity (omitting a few exceptions), the greater the electronegativity of an element. 1748.34 8.35 8.36 837 8.38 Chemical Bonding Solutions to Exercises Plan. Electronegativity increases going up and to the right in the periodic table. Solve: @ S ()C (AS (Mg Check. The electronegativity values in Figure (8.9) confirm these selections. Electronegativity increases going up and to the right in the periodic table. @o MOA OA WF The bonds in (a), (b) and (d) are polar because the atoms involved differ in electronegativity. ‘The more electronegative element in each polar bond is: (a)O (b) F (d) O ‘The more different the electronegativity values of the two elements, the more polar the bond, (a) O-F ) Plan, Isoelectronic species have the same number of valence electrons and the same electron configuration. Solve: ‘A single O atom has 6 valence electrons, so the neutral ozone molecule O; is isoelectronic with NO;-. G=0-G > 38 Check. The octet rule is satisfied. 1798.48 8.49 8.50 Chemical Bonding Solutions to Exercises (©) Since each N-O bond has partial double bond character, the N-O bond length in NO, should be shorter than in species with formal N-O single bonds. (@) 16, 8° pairs [He | | (b) More than one correct Lewis structure can be drawn, so resonance structures are needed to accurately describe the structure. (©) _NO,*has 16 valence electrons. Consider other triatomic molecules involving second- row nonmetallic elements. O,?* or C; are not ‘common’ (or stable). CO, is common and matches the description (as does N°, azide ion). Plan/Solve. The Lewis structures are as follows: ‘The more pairs of electrons shared by two atoms, the shorter the bond between the atoms. ‘The average number of electron pairs shared by C and O in the three species is 3 for CO, 2 for CO, and 1.33 for CO,*. This is also the order of increasing bond length: CO < CO, < co". The Lewis structures are as follows: Se pairs 9e pairs _ ~ [mo [ee ™ aks851 852 Chemical Bonding Solutions to Exercises The average number of electron pairs in the N-O bond is 3.0 for NO*, 1.5 for NO; and 1.33 for NO,”. The more electron pairs shared between two atoms, the shorter the bond. Thus the 'N-O bond lengths vary in the order NO* < NO,” < NO,~ @ (b) @) (b) © ‘Two equally valid Lewis structures can be drawn for benzene. 4 4 H H xe H H H H Each structure consists of alternating single and double C-C bonds; a particular bond is single in one structure and double in the other. ‘The concept of resonance dictates that the true description of bonding is some hybrid or blend of the two Lewis structures. The most obvious blend of these two resonance structures is a molecule with six equivalent C-C bonds, each with some but not total double-bond character. If the molecule has six equivalent C-C bonds, the lengths of these bonds should be equal. ‘The resonance model described in (a) has 6 equivalent C-C bonds, each with some double bond character. That is, more than 1 pair but less than 2 pairs of electrons, is involved in each C-C bond. This model predicts a uniform C-C bond length that is shorter than a single bond but longer than a double bond. Hq a H H HH SOG ee H H H H H ‘The resonance model of this molecule has bonds that are neither single nor double, but somewhere in between. This results in bond lengths that are intermediate between C-C single and C=C double bond lengths. OO 1818 Chemical Bonding Solutions to Exercises Exceptions to the Octet Rule 853 854 8.55 8.56 857 (2) The octet rule states that atoms will gain, lose or share electrons until they are surrounded by eight valence electrons. (&) The octet rule applies to the individual ions in an ionic compound. That is, the cation has lost electrons to achieve an octet and the anion has gained electrons to achieve an octet. For example, in MgCl,, Mg loses 2 6” to become Mg with the electron configuration of Ne. Each Ci atom gains one electron to form Cr with the electron configuration of Ar. Carbon, in group 14, needs to form four single bonds to achieve an octet, as in CH,. Nitrogen, in group 15, needs to form three, as in NH,. If G = group number and n = the number of single bonds, G +n = 18 is a general relationship for the representative non-metals. Check: O as in H,0 (G = 16) + (n = 2 bonds) = 18 ‘The most common exceptions to the octet rule are molecules with more than eight electrons ‘around one or more atoms, usually the central atom. Examples: SF,, PF, In the third period, atoms have the space and available orbitals to accommodate extra electrons. Since atomic radius increases going down a family, elements in the third period land beyond are less subject to destabilization from additional electron-electron repulsions. ‘Also, the third shell contains d orbitals that are relatively close in energy to 3s and 3p orbitals (the ones that accommodate the octet) and provide an allowed energy state for the extra electrons. (a) 246", 126° pairs 2 CO,* has three resonance structures, but all obey the octet rule. (0) 6 e, Se" pairs, impossible to satisfy (c) 226°, 11° pairs ‘octet rule with only 6 valence electrons eH Ci-E] H 6 electrons around B 10 e° around central I 1828 chemical Bonding 8.58 8.59 @) @) © 6=8—O: x S35 @ (b) © Solutions to Exercises 326°, 16 & pairs 480°, 24° pairs ‘obeys the octet rule 12 €° around As; three nonbonded pairs on each F have been omitted 11.67, 5.5 &" pairs; (vb) 226° 11 "pairs odd electron molecule ( ‘The odd electron is probably on N 10 & around central I because itis less electronegative than O. [3-1-4] 186°, 9" pairs (6) 246, 126° pairs Ges: Cl: Structures with expanded octets ~ around S can be drawn, but are 6 e around B not preferred (Section 8.7). ‘Structures such as the one below can be drawn, but are not likely 366", 186° pairs because of high formal charges on i Band Cl 12 €* around the central Xe (F cannot expand beyond an octet.) ch-—-Be—Cl 166. Be pairs This structure violates the octet rule; Be has only 4 e~ around it. C= Be=Cl <—> :G}-Be=Cl:<—> C= Be-El ‘The formal charges on each of the atoms in the four resonance structures are: :G-Be—Gt G=Be=G :G+-Be=Cl: :C=Be—Cit 0 0 0 4 2 4 0 2 2 42 2 0 ‘Since formal charges are minimized on the structure that violates the octet rule, this form is probably most important. 1838 Chemical Bonding 8.60 (a) (e) © Solutions to Exercises 19 @°, 9.5 e° pairs, odd electron molecule BC EG. > DGS: None of the structures satisfies the octet rule. In each structure, one atom has only 7 € around it. If a molecule has an odd number of electrons in the valence shell, no Lewis structure can satisty the octet rule. BGS: > 13-.-G > -D-GS: 484 440 a4 Formal charge arguments predict that the two resonance structures with the odd electron on © are most important. This contradicts electronegativity arguments, which would predict that the less electronegative atom, Cl, would be more likely to have fewer than 8 e" around it. Bond Enthalpies 861 8.62 Analyze. Given: structural formulas. Find: enthalpy of reaction. Plan. Count the number and kinds of bonds that are broken and formed by the reaction. Use bond enthalpies from Table 8.4 and Equation 8.12 to calculate the overall enthalpy of reaction, ‘AH. Solve: (@) (o) © (a) (b) © OH = 2D(0-H) + D(O-0) + 4D(C-H) + D(C=C) ~ 2D(0-H) - 20(0-C) - 4D(C-H) - D(C-C) MH = D(0-0) + D(C=C) - 2D(0-C) - D(C-C) = 146 + 614 - 2(358) - 348 = -304 kJ ‘AH = 5D(C-H) + D(C =N) + D(C=C) - SD(C-H) - D(C=N) - 20(C-C) = D(C=C) - 2D(C-C) = 614 - 2(848) = -82 kJ ‘AH = 6D(N-Ci) - 3D(Ci-Cl - DIN=N) = 6(200) - 3(242) - 941 = -467 kJ AH = 3D(C-Br) + D(C-H) + D(CI-CI) - 3D(C-Br) - (C-Cl) - D(H-Cl) = D(C-+H) + D(CI-Cl) - D(C-Cl) - D(H-Cl) OH = 419 + 242 - 328 - 431 = -104 kJ AH = 4D(C-H) + 2D(C-S) + 20(S-+H) + D(C-C) + D(H-Br) -4D(S-H) - D(C-C) - 2D(C-Br) - 4D(C-H) = 2D(C-S) + D(H-Br) - 20(S-H) - 2D(C-Br) ‘BH = 2(259) + 366 - 2(339) - 2(276) = -346 kJ BH = 4D(N-H) + D(N-N) + (CHC) - 4D(N-H) - D(N-Ci) = D(N-N) + D(CH-CI) - D(N-Ci) ‘BH = 163 + 242 - 200 = 205 kd 1848.64 Chemical Bonding Solutions to Exercises Plan. Draw structural formulas so bonds can be visualized. Then use Table 8.4 and Equation 8.11. Solve: @ 2 ore + 3F-F ——» 2 Four + 3 Br—Br Br F ‘AH = 6D(N-Br) + 3D(F-F) - 6D(N-F) - 3D(Br-Br) = 6(243) + 3(155) - 6(272) - 3(193) = -288 kJ H (oe) C=O + 2H-H ——> po H AH = D(C=0) + 20(H-H) - 3D(C-H) - D(C-0) - D(0-H) = 1072 + 2(436) - 3(413) - 358 - 463 = -116 kJ i © HOSTH +3 FF Foor + BHF F ‘AH = 2D(S-H) + 3D(F-F) - 4D(S-F) - 20(H-F) = 2(339) + 3(155) - 4(927) - 2(567) = -1299 kJ Plan. Draw structural formulas so bonds can be visualized, (a) H—C—H + H—N——H—® — H—C==N—H + H—O—H AH = D(C=0) + 2D(C-H) + SD(N+H) - D(C=N) - 2(C-H) - 2D(N-H) - 20(0-H) D(C=0) + D(N-H) - D(C=N) - 2D(0-H) 99 + 391 - 615 - 2(463) = -351 kd a a H HoH . t ©) H—Si—H + oo pt +H—C H H oH MH = 30(Si-H) + D(Si-Ci) + 4D(C-H) - SD(Si+H) - 3D(C-H) - D(Si-C) - D(H-Cl) D(Si-Cl) + D(C-H) - D(Si-C) - D(H-Cl) BH = (464) + 413 - (301) - 431 = 145 kd (©) Plan. Use bond enthalpies to calculate AH for the reaction with S,(g) as a product. Then, 185