878 8.79 Chemical Bonding Solutions to Exercises (b) —Te-I. Both are in the fifth row of the periodic chart and have the two largest covalent radii among this group of elements. (©) Tel. Teneeds to participate in two covalent bonds to satisfy the octet rule, and each atom needs to participate in one bond, so by forming a Tel, molecule, the octet rule can be satisfied for all three atoms. a (6) _B,0,. Although this is probably not a purely ionic compound, it can be understood in terms of gaining and losing electrons to achieve a noble-gas configuration. If each B atom were to lose 3 &° and each O atom were to gain 2.6", charge balance and the ‘octet rule would be satisfied. P,0,. Each P atom needs to share 3 6” and each O atom 2 &” to achieve an octet. ‘Although the correct number of electrons seem to be available, a correct Lewis structure is difficult to imagine. In fact, phosphorus (II!) oxide exists as P,O, rather than P,O, (Chapter 22). Use the method detailed in Section 8.5, A Closer Look, to estimate partial charges from ‘electronegativity values. From Figure 8.6, the electronegativity of Fis 4.0 and of Cl is 3.0. F has 4.0// (3.0 + 4.0) = 0.57 of the charge of the bonding e- pair. Cihas 3.0 / (3.0 + 4.0) = 0.43 of the charge of the bonding &” pair. ‘This amounts to 0.57 x 2e = 1.14@ on F or 0.14e more than a neutral F atom. This implies a -0.14 charge on F and +0.14 charge on Cl. From Figure 7.5, the covalent radius of is 1.70A. 0.71 Aand of Clis 0.99 A. The FCI separation 110m . 1D 3.34% 10 Cem Clearly, this method is approximate. The estimated dipole moment of 1.1 D is within 30% of the measured value of 0.88 D. b=Qr=0.14ex xA70Ax 1.60% 10° °C 44D e Formal charge (FC) = # valence e* - (# nonbonding e” + 1/2 # bonding e-) (2) 186", 96° pairs Seb > ROS FC for the central O -[2+12(@)=+1 (b) 486", 246° pairs iy le FC for P=5 - [0+ 1/2 (12)]= 1908 Chemical Bonding Solutions to Exercises © @ 880 (a) (o) ©) 881 (a) The three nonbonded pairs on each F have been omitted. 17 €; 86° pairs, 1 odd = =o oo The odd electron is probably on N because it is less electronegative than O. ‘Assuming the odd electron is on N, FC for N= 5 -[1+ 1/2 (6)| = +1 If the odd electron is on O, FC for N=5-[2 + 1/2 (6)] 286, 146 pairs (©) 3267, 16 6 pairs ¢i—F—ci | FC for 1=7 -[4+ 1/2 (6)]=0 140", 7 € pairs 827, 16 &° pairs [:6-3: | oH 16-0-0: FC on Ci=7 - [6 + 1/2(2)] FC on Cl ~[0+ 1/2(8)) 8 ‘The oxidation number of Cl is +1 in CIO and +7 in CIO, ‘The definition of formal charge assumes that all bonding pairs of electrons are equally shared by the two bonded atoms, that all bonds are purely covalent. The definition of oxidation number assumes that the more electronegative element in the bond gets all of the bonding electrons, that the bonds are purely ionic. These two definitions represent the two extremes of how electron density is distributed between bonded atoms. In CIO” and CiO,;, Clis the less electronegative element, so the oxidation numbers have a higher positive value than the formal charges. The true description of the electron density distribution is somewhere between the extremes indicated by formal charge and oxidation number. IN=SN—O: <—> :h-N=0: <—> titen=d: ow 4 2a 14100 In the leftmost structure, the more electronegative O atom has the negative formal charge, so this structure is likely to be most important. 1918 8.82 8.83 8.84 Chemical Bonding Solutions to Exercises (b) In general, the more shared pairs of electrons between two atoms, the shorter the bond, and vice versa. That the N-N bond length in NO is slightly longer than the typical NN indicates that the middle and right resonance structures where the N ‘atoms share less than 3 electron pairs are contributors to the true structure. That the N-O bond length is slightly shorter than a typical N=O indicates that the middle structure, where N and O share more than 2 electron pairs, does contribute to the true structure. This physical data indicates that while formal charge can be used to Predict which resonance form will be more important to the observed structure, the influence of minor contributors on the true structure cannot be ignored. 1," has a Lewis structure with an expanded octet of electrons around the central I. F cannot accommodate an expanded octet because it is too small and has no available d orbitals in its valence shell ‘BH = 8D(C-H) - D(C-C) - 6D(C-+H) - D(H-H) = 2D(C-+H) - D(C-C) - D(H-H) = 2(413) - 348 - 496 = +42 kJ AH = 8D(C+H) + 1/2 D(0=0) - D(C-C) - 6D(C+H) - 20(0-H) = 2D(C-+H) + 1/2 D(O=0) - D(C-C) - 20(0-H) = 2(413) + 1/2 (4985) - 948 - 2(463) = -200 kJ ‘The fundamental difference in the two reactions is the formation of 1 mol of H-H bonds versus the formation of 2 mol of O-H bonds. The latter is much more exothermic, so the reaction involving oxygen is more exothermic. (@) AH =5D(C-H) + D(C-C) + D(C-0) + D(O-H) - 6D(C-H) -20(C-0) (C-C) + D(O-H) - (CH) - (C-0) = 848 kd + 463 kJ - 413 kJ - 358 kd ‘AH = +40 kJ; ethanol has the lower enthalpy (b) AH = 4D(C-H) + D(C-C) + 20(C-0) - 4D(C-H) - D(C-C) - D(C=0) = 2D(C-0) - D(C=0) = 2(858 kJ) - 799 kd ‘AH = -83 kd; acetaldehyde has the lower enthalpy (©) AH =8D(C-H) + 4D(C-C) + (C=C) - 8D(C-H) - 2D(C-C) - 2D(C=C) = 2D(C-C) - D(C=C) = 2(848 kJ) - 614 kd ‘AH = +82 kJ; cyclopentene has the lower enthalpy8 Chemical Bonding | Solutions to Exercises (@) AH =30(C-+H) + D(C-N) + D(C=N) - 30(C-H) - D(C-C) -D(C=N) = D(C-N) - D(C-C) = 293 kJ - 348 kd (MH =-55 kJ; acetonitrile has the lower enthalpy 4 4 4 885 (a) 4 1p} —— _ 6 N=N+ 120=c=0 9 ? ? + 10H—O—H + O=O0 oy oN oS ritogtcerne (MH = 20D(C-H) + 8D(C-C) + 12D(C-O) + 24D(O-N) + 12D(N=O) = [6D(N=N) + 24D(C=0) + 20D(H-O) + D(O=0)) AH = 20(413) + 8(348) + 12(358) + 24(201) + 12(607) = [6(941) + 24(799) + 20(463) + 495) = -7129 kd AMOICSHNO, . -7429kd BTAGC HNO, 4moiCH.NO, (©) 4C,H,N,O,(s) 6N,(g) + 7CO,(g) + 10H,0(9) + 21C(s) 1.00 g C,H,N,O, x = 7.85 kdlg CH.N,O, 8.86 Bond Enthalpy (kJ) 1.0 aw 12 13 14 15 16 Bond Length ‘When comparing the same pair of bonded atoms (C-N vs. C=N vs. C=N), the shorter the bond the greater the bond energy, but the two quantities are not necessarily directly proportional. ‘The plot clearly shows that there are no simple length/strength correlations for single bonds. alone, double bonds alone, triple bonds alone, or among different pairs of bonded atoms (all C-C bonds vs. all C-N bonds, etc.) 1938.87 Chemical Bonding Solutions to Exercises (a) (b) () @ ‘S-N =1.77 A (sum of the bonding atomic radii from figure 7.5). ‘S-O = 1.75 A (the sum of the bonding atomic radii from figure 7.5.) Alternatively, halt of the S-S distance in S, (1.02) plus half of the O-O distance from Table 8.5 (0.74) is 1.76. ‘Owing to the resonance structures for SO, (see Solution 8.58(c)), we assume that the ‘S-O bond in SO, is intermediate between a double and single bond, so the distance of 1.43 A should be significantly shorter than an S-O single bond distance, 1.75 A. 546°, 27 & pair ‘The observed S-O bond distance, 1.48 A, is similar to that in SO,, 1.43 A, which can bbe described by resonance structures showing both single and double S-O bonds. Thus, S,O must have resonance structures with both single and double S-O bonds. ‘The structure with the S=O bond has 5 6” pairs about this $ atom. To the extent that this resonance form contributes to the true structure, the S atom bound to O has more than an octet of electrons around it. Integrative Exercises 8.88 8.89 (a) ©) (o) (@ Ti: (Arad? ; Ca: [Arl4s*. Yes. The 2 valence electrons in Ti and Ca are in different principle quantum levels and different subshells. According to the Aufbau Principle, valence electrons will occupy the lowest energy ‘empty orbital. Thus, in Ca the 4s is lower in energy than the 3d, while in Ti?*, the 3d is lower in energy than the 4s. ‘Since there is only one 4s orbital, the 2 valence electrons in Ca are paired. There are 5 degenerate 3d orbitals, so the 2 valence electrons in Ti® are unpaired. Ca has no unpaired electrons, Ti** has 2. Sr(s) > Sr(g) ‘BH; Sr(g) (OH,5, S(s)] S19) > Srig) +16" 1,Sr Sr(g)> SPQ) +167 Sr Cig) > 2CK9) 2H, Clg) [D(C] 2C\(g) +2" > 2Cr(g) 2E, Cl SrCi,{s) > Sr(s) + Ci,(9) “AH; Srl, SrCi,(s) > SP*(g)+2Cr(9) AH: 1948.90 891 8.92 Chemical Bonding Solutions to Exercises (0) BH, SiOL(s) = AH, Sig) + 1(S0) + 1(S0) + 20H, CXg) + 2E(CI) - AHye SrCl, rCL,(S) = 164.4 kJ + 549 kd + 1064 kJ + 2(121.7) kd + 2(-349) kJ - 2127 kJ = 804k) ‘The pathway to the formation of K,O can be written: 2K(s) > 2K(g) 2AH; K(Q) 2K(g) > 2K*(g) +267 21K) 1/2. 0,9) > O(g) AH, O() 0@) +16 > O1@) EO) O@+t1e > O'@ £0) 2K"(g) + O*(@) > K,0(8) “bias K,0(8) 2K(s) + 1/2 0,9) > K,0(s) AH, K,0(s) AH, K,O(s) = 20H, K(g) +2 1,(K) + BH, O(g) + E,(0) + E,(0) - AH, K0(6) E,(O) = AH; K,O(s) + AH, K,0(s) - 2H, K(g) -21(K) - AH, (9) - E,(0) E,{O) = -363.2 kJ + 2238 kJ - 2(89.99) kJ - 2(419) kJ - 247.5 kd - (-141) kd (= +750 kd (a) Assume 100 g. 14.529 C x10! 1.209 mol C; 1.209 / 1.209 = 1 12011gC 1.83gHx Tag 816 mol H; 1.816 / 1.209 = 1.5 643090 = 1.814 mol Cl; 1.814 / 1.209 = 1.5 1935 9 0x5 55g 5 = 1.209 mol O; 1.209 / 1.209 = 1.0 Multiplying by 2 to obtain an integer ratio, the empirical formula is C3H,ClO,, (©) The empirical formula weight is 2(12.0) + 3(1.0) + 3(35.5) + 2(16) = 165.5. The ‘empirical formula is the molecular formula. (©) 446,226 pairs + tO—H | eH CI Or Ib (2) Gy 1067, 56° pair Nz 106", 5 6° pair 2NS=Nz 1958 Chemical Bonding Solutions to Exercises (b) ) @) e) 8.93 () © N, is an extremely stable, unreactive compound. Under appropriate conditions, it can be either oxidized (Section 22.7) or reduced (Sections 14.6 and 15.1). C,H, is a reactive gas, used in combination with O, for welding and as starting material for ‘organic synthesis (Section 25.4). 2N,(g) + 50.(9) > 2N,0,(9) 2C,H,(9) + 50,(9) > 4CO,(g) + 2H,0(a) AH fq (N:) = 20H; N,O,(Q)- 20H; N,(Q) - SAH, O,(9) = 2(11.30) - 2(0) - 5(0) = 22.60 kJ 1.30 kJ/mol N, H ain (CzH,) = 40H; CO,(g) + 20H, H,O(g) - 24H; C.H,(9) - 5AH; 0,(9) = 4(-393.5 kJ) + 2(-241.82 kJ) - 2(226.7 kd) - 5(0) = 2511.0 1255.5 kJ/mol C,H. AHS on DHS (GH, The oxidation of C,H, is highly exothermic, which means that the energy state of the combined products is much lower than that of the reactants. The reaction is “down hill" in an energy sense, and occurs readily. The oxidation of N, is mildly endothermic (energy of products higher than reactants) and the reaction does not readily occur. This is in agreement with the general reactivities from part (b). Referring to bond enthalpies in Table 8.4, when the C-H bonds are taken into ‘account, even more energy is required for bond breaking in the oxidation ot C,H, than in the oxidation of N,. The diference seems to be in the enthalpies of formation of the products. CO,(g) and H,0(g) have extremely exothermic. AH; values, which cause the oxidation of C,H, to be energetically favorable, N,O,(g) has an endothermic AH; values, which causes the oxidation of N, to be energetically unfavorable. Assume 100 g. 62.04 g Ba x—1™0l__ _ 9.4518 mol Ba; 0.4518 /0.4518 = 1.0 137.3398a 1 mol 37.96 gNx—1MOl_ _ 2.710 mol N;2.710/ 0.4518 =6.0 ON *Tg007gN 71m The empirical formula is BaN,. Ba has an ionic charge of 2+, so there must be two 1- azide ions to balance the charge. The formula of each azide ion is Nj. 16 e, 8° pairs [:Wenesiie] <—> [ sn fir] "<—> [finns] AH O+1 2 2+ 0 The left structure minimizes formal charges and is probably the main contributor. 1968.94 Chemical Bonding Solutions to Exercises @ @ (o) ‘The two N-N bond lengths will be equal. The two minor contributors would individually cause unequal N-N distances, but collectively they contribute equally to the lengthening and shortening of each bond. The N-N distance will be approximately 1.24 A, the average N=N distance. ‘Assume 100 g of compound 69.69 Sx IMIS -217mos 32.079 80.4.9 Nx JOIN _ 9.17 moi N 14.019 S and N are present in a 1:1 mol ratio, so the empirical formula is SN. The empirical formula weight is 46. /FW = 184.3/46 = 4 The molecular formula is S.N,. 44 6°, 22 €* pairs. Because of its small radius, N is unlikely to have an expanded ‘octet. Begin with alternating S and N atoms in the ring. Try to satisfy the octet rule with single bonds and lone pairs. At least two double bonds somewhere in the ring are required. a oN, ‘These structures carry formal charges on S and N atoms as shown. Other possibilities include: 7 ‘These structures have zero formal charges on all atoms and are likely to contribute to the true structure. Note that the S atoms that are shown with two double bonds are not necessarily linear, because S has an expanded octet. Other resonance structures with four double bonds are. In either resonance structure, the two ‘extra’ electron pairs can be placed on any pair of S atoms in ring, leading to a total of 10 resonance structures. The sulfur atoms altemately carry formal charges of +1 and -1. Without further structural information, itis not possible to eliminate any of the above structures. Clearly, the S,N, molecule stretches the limits of the Lewis model of chemical bonding. 1978 Chemical Bonding _ 8.95 8.96 © @) (@) (b) © fa) (o) © Solutions to Exercises Each resonance structure has 8 total bonds and more than 8 but less than 16 bonding e* pairs, so an “average” bond will be intermediate between a S-N single and double bond. We estimate an average S-N single bond length to be 1.77 A (sum of bonding atomic radii from figure 7.5). We do not have a direct value for a S-N double bond length. Comparing double and single bond lengths for C~C (1.34 A, 1.54 A), N-N (1.24 A, 1.47 A) and O-O (1.21 A, 1.48 A) bonds from Table 8.5, we see that, ‘on average, a double bond is approximately 0.23 A shorter than a single bond. Applying this difference to the S-N single bond length, we estimate the S-N double bond length as 1.54 A. Finally, the intermediate S-N bond length in S,N, should be between these two values, approximately 1.60-165 A. [The measured bond length is 1.62 A) SAN, > 48(g) + 4N(Q) MH = 40H; S(g) + 40H, Ng) - AH; SN, DH = 4(222.8 kJ) + 4(472.7 kd) - 480 kJ = 2302 kJ This energy, 2302 kJ, represents the dissociation of 8 S-N bonds in the molecule; the average dissociation energy of one S-N bond in SWN, is then 2302 kJ/8 bonds = 287.8 kJ. HF(g) > Hig) + Fig) O(H-F) 567 kd Hig) > HYg)+ te I (H) 1312 kd Fg)+1¢ > Fig) E(F) ~328 kK HF(g) > H"(g) +F(g) AH 1551 kJ (AH = D(H-Cl) + I(H) + E(Cl) BH = 431 kd + 1312 kd + (-349) kJ = 1394 kJ AH = D(H-Br) + I(H) + E(Br) DH = 366 kJ + 1312 kd + (-325) kJ = 1353 kJ CH4(a) > 6H(Q) + 8C(9) ‘AH’ = 60H; Hig) + 64H, C(g) - AH; C.H4(9) DH = 6(217.94) kJ + 6(718.4) kJ - 82.9 kJ = 5535 kJ CiH,(g) > 6CH(Q) C.Hy(g) > 6H(a) + 6C(Q) OH 5535 kJ 6H(g) + 6C(g) > 6CH(Q) “BD(C-H)_-6(413) kd CcHe() > BCH(a) 3057 kJ 3057 kd is the energy required to break the 6 C-C bonds in C,H,(g). The average bond dissociation energy for one carbon-carbon bond in C,H,(g) is soe - 509.5 kJ. 1988.97 Chemical Bonding Solutions to Exercises @ (a) (b) © @ The value of 509.5 kJ is between the average value for a C-C single bond (348 kJ) and a C=C double bond (614 kJ). It is somewhat greater than the average of these two values, indicating that the carbon-carbon bond in benzene is a bit stronger than we might expect. Br,(I) > 2Br(g) ‘AH’ =2AH; Br(g) =2(111.8) kJ = 223.6 kd CCI) > Cig) + 4C1(9) AH = AH; Cig) + 40H, Ci(g) - AH; CCl) = 718.4 kJ + 4(121.7) kd - (-139.3) kJ = 1344.5 1944.5kI ‘C= Cibonds H,0,(I) > 2H(g) + 20(g) 2H(g) + 20(a) > 20H(g) = 336.1 kJ H,0,(l) > 20H(g) D(0-0}() = 20H; Hig) + 20H; O(g) - AH, H,0,(1) - 20(0-H)(g) 2(217.94) kJ + 2(247.5) kJ - (-187.8) kJ - 2(463) kJ = 193k The data are listed below. bond D gas kJ/mol D liquid ki/mot Br-Br 193 223.6 cl 328 336.1 o-0 146 192.7 Breaking bonds in the liquid requires more energy than breaking bonds in the gas phase. For simple molecules, bond dissociation from the liquid phase can be thought of in two steps: molecule (!) > molecule (9) molecule (g) > atoms (g) ‘The first step is evaporation or vaporization of the liquid and the second is bond dissociation in the gas phase. Average bond enthalpy in the liquid phase is then the ‘sum of the enthalpy of vaporization for the molecule and the gas phase bond dissociation enthalpies, divided by the number of bonds dissociated. This is greater than the gas phase bond dissociation enthalpy owing to the contribution from the enthalpy of vaporization. 1998 Chemical Bonding _ 8.98 (b) (© @) © Solutions to Exercises Assume 100 g, A: 87.7 gIn/ 114.82 = 0.764 mol In; 0.764 / 0.384 = 2 12.39 S/ 32.07 = 0.384 molS; 0.384/0.384=1 B: 78.2gIn/ 114.82 = 0.681 mol In; 0.681 / 0.680 = 1 21.89 S/ 32.07 = 0.680molS; 0.680/0.680 C: 705g In/ 114.82 = 0.614 molin; 0.614/0.614 295gS/ 32.07 = 0.920molS; 0.920/0614=1.5 A: nS; B: InS; C: In,S, AS In());— B: In(l); Cz Incl) In(l) : [Kr}Ss*4d"°; In(It) : [Kr]5s'4d"°; In(ill) : [Krj4d"? None of these are noble-gas configurations. The ionic radius of In* in compound C will be smallest. Removing successive electrons from an atom reduces electron repulsion, increases the effective nuclear charge experienced by the valence electrons and decreases the ionic radius. The higher the charge on a cation, the smaller the radius. Lattice energy is directly related to the charge on the ions and inversely related to the interionic distance. Only the charge and size of the In varies in the three compounds. In(1) in compound A has the smallest charge and the largest ionic radius, so compound A has the smallest lattice energy and the lowest melting point. In(lt!) in compound C has the greatest charge and the smallest ionic radius, so compound C hhas the largest lattice energy and highest melting point.