MO model correctly predies that NO™ is paramagnetic. Bond en ‘ergy: NO- = NO < NO"; bond length: NO” < Ni - O «™ O H Oo » @ O OB x ag oy a ase Oo Oo o Oo Ground state Excited state Lewis structure shows no unpaited electrons. The ground-state MO diagram for O; has two unpaired electrons, I takes enerby t0 pair clectrons in the same crbital, The MO diagram with no unpaited leetrons is at a higher energy and is an excited stare. S94, cy i eon, aN: ‘Trigonal planae polar 120% sp? b Can also bes iS ? F F Polar Nonpoler ‘V-shaped about both N atoms; ~120% 92, “These are distinctly diferent molecules pl o=ces) a Linear; polars 18 ‘Teshapeds polar; = 90°; dep? 461. a, The NNO structure is corset. Prom the Lewis structures we ‘would predict both NNO and NON to be linear, but NON would be nonpolar. NNO is polar bNeN=0 > NEN A1410 0 41-12 41 +1 Formal charges ‘The central N is p hybridized, We can probably ignore the third resonance structure on the basis of formal charge. c. sp hybrid orbitals from the center N overlap with atomic orbials (or bybe ‘orbitals fom the other two atoms to form the rw sigma bonds “The semaining p orbitals from the center N overlap with p orbitals from the other N to form the two bonds. 63.2. Ns, Ne", Ny and N” wail al be present, assuming excess Nb. Light with wavelengths in the range of 8533 nm <2 = 127 am will produce NN but no ions. c. Consider the MO enersy-level diagram for Ns (see Figs 14.49 and 14.41). The electron removed from Ns isin the ap MO, which is lower in energy than the 2p atomic orbital from which the electron in atomic nitrogen is removed. Since the electron removed from Nz is lower in energy than the electron in IN, the ionization energy of No is greater than for N. 65. The —N-Nso ‘Answers to Selected Exeicises ASS ‘complete Lewis structure follows. All but two ofthe carbon atoms ze sp" hybridized. Tre tw carbon atoms thae contain the double bond are sp” hybridized (see), cay st cs eae Pan bs 6 oe one |) ne EAL al | | HO’ [No mott ofthe cathons are nor in the same plane since a maiority ‘of carbon atoms exhibit a tetrahedral structure, Note: CH, CH, and CH ate shorthand for earbor atoms singly bonded to hydeo- fen atoms. 67-2. The CO ond is pola with the negative end fround the more clectronegatve oxygen atom, We would expect ‘metal cations to be attracted to and bond to the oxygen end of CO fon the basis of electronegasviy. b. 1C==O% FC (carbon) = ~Is FC (oxygen) = +1. From formal charge we would expect metal cations to bond to the carbon (with the negative formal charge) €. In MO theory, only orbitals with proper syminetry overlap form bonding orbitals. The metals that form bonds ro CO are wo: ally transition metals, all of which have outer electrons in he d of bitals. The only MOs of CO thar have proper symmetry to overlap ‘with d orbitals are the may* orbitals, whose shape is similar to the d orbitals (se Fig. 14.36), Since che antibonding MOs have more ‘carbon characte, one would expect the bond to form through c bon. 69. A157 237 kJimol (caleulated); there isa 154 kj disrep- ancy, Benzene is more stable (lower in energy) by 154 k] than we ‘expect from bond energies. Two equivalent Lewis structures can be ‘drawn for benzene. The bonding system implied by each Lewis, structure consists of three localized 7 bonds. This, however, does not adequately explein the six equivalent C—C bonds in benzene. “To explain the equivalent C—C bonds, the = electrons ate said to be delocalized over the ene surface ofthe molecule (See Section 14.5). The large discrepancy berween che AH] values is because the cifect of a delocalized = bonding system was not considered when P. Ina mechanism, the rate of the slowest step determines the rate of the reaction. The activation energy forthe slowese step will be the largese energy barvier that the reaction must, overcome. Since the second hump in he diagram is atthe highest ‘energy, thea the second step (I —» P) has the largest activation en= ergy and will be the eate-dereemining step (the slow step). 67. pos- itive AE value 69. A catalyst increases the eate ofa eeaction by providing reactans with an alternate pathway (mechanism) t0 con= vert ro products. This altemace pathway has a lower acivation ‘energy, thus ineeasing the rate of the reaction. A heterogenous ‘catalyst ii. diferent phase than the reactants. The catalyst is usually a solid, although @ emalysein a quid phase can act as a heterogeneous catalyst fo some gas-phas# reactions. Since the cat- alyzed reaction basa different mechanism than the uncatalyzed re- action, the catalyzed reaction most likely will have a different rate law 71 Since the chlovine atom-caalzed reaction hs lower aerition energy then the Cheatajaed rate is faster Hence, Cl is smote efective catalyst. 73. At high (Js the erayme i completely serurated with substrate. Once the enzyne completely saturated, the ate of decomposition of ES can 20 longer increase and the Kr y0 Tor) * 60.571 77.3, untested: k= 0.465 day”! desing agent: k= 0.659 day amtiondarn, k= 0.779 day” bs No, the Sle degrades more rapidly withthe additives. unteed in = 149 day, dealing agent: fy = 1.05 day antioxidant tin = 0.890 day 79. The rate depends onthe number of reactant tnolecules adsorbed on the surface of the catalyst. This quantity i proportional robe concentration of reactant. Howevet, wheo all ‘he catalyst surface sites are occupied he eae becomes indepen dent of the concentration of reactant. ee = DEITYOS] © HINOCII 5 rhe energy level 1 Rare = ARITUOGEL MEUCCEL 93 The eerrevel diagram would look Something like the second diagram in Eeteise 65), Forming the chombic (yellow) ets requzes a solr activation ener than forming the resagoal (orange) exystals Therefore, the rhombi ryt fxm firs. The tetragonal crystals ae thrmodynamically more stable than the chombic xy: tals ie, AE is nepaive for Hay (thombic)—> Hal ts2gor). “The major eeason High (tetragonal) does’ form fists that the activation energy is Fate age fr this process it 10 slow). ‘Once enough sme has elapsed, then rhe thermedyeamizally stable fora of Hl is present. 85.8, Second order; by 17.15 20 4.6 5= 30s 6. 475 6 31 kfol 87. 28.8 kjmol ‘ate remains constant, 75, Rate = 89,2. 53.9 kjmol B83 chirps per minae per inset ECC TR kimin) 42+ 0.80 0H 2507078 78 203 as as or 73 ga 0, or 30 $8088 SOF “The rule of vu appears oe fay accurate, about 21°, ‘ee dICh , AisINO.C Eqenne 91. Rate = SO = FINO.) + HINO 88% Re A{CHIXD, B= 0.93 8-4 b. 8.80 x 10! hy c. 3.0% 10? kymol, 4. The activation energy is close to the CX bond energy. A plau- sible mechanism is CH — Cy +X CH +¥ — cH (slow) (fase) 95, rate = KAIIBP,, k= 1.4 x 10°? L? mol“* s“* 97. Rate = =dIN.O3) _ 2A; KIMIINO, dt LM} + 2h chapter 16 11, Dipole forces act between polar molecules. The electrostatic at- traction berween the postive end of ove polar molecule and the neg sive end of another isthe dipole force. Dipole forces are erally weaker than hydrogen bonding, Both of these forces are due to di- ‘pole moments in molecules. Hydrogen bonding i given 8 separate name fom dipole forces because hydrogen bonding is = paniulaly| strong dipole force. London dispersion forces can be referred 10 as instantaneous induced dipole fores. As the sizeof the molecule i "seas, the strength ofthe London dispersion forces increases. As the number of electrons in a wolecule ges large i is easier fr the elec-