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- Many compounds of the transition-metal elements containdirect bonds between metal atoms. We will assumethat the z-axis is defined as the metal–metal bond axis.(a) Which of the 3d orbitals (Figure 6.23) is most likely tomake a σ bond between metal atoms? (b) Sketch the s3dbonding and σ*3d antibonding MOs. (c) With reference tothe “Closer Look” box on the phases of orbitals, explain whya node is generated in the σ*3d MO. (d) Sketch the energyleveldiagram for the Sc2 molecule, assuming that only the3d orbital from part (a) is important. (e) What is the bondorder in Sc2?Carbon tetrafluoride gas, CF4(g), is used as arefrigerant. It is very stable when released into theatmosphere and is a known potent greenhousegas. Calcium fluoride, CaF2(s), is the main sourceof the world’s supply of fluorine. It is used in theproduction of specialized lenses and windowmaterials. K/U(a) Describe the bonding in a molecule of carbontetrafluoride.(b) Compare and contrast the bonding of carbontetrafluoride and calcium fluoride.Sketch the distribution of electron density in the bonding and antibonding molecular orbitals formed from two s orbitals and from two p orbitals.
- Discuss the nature of the bonding in the nitrate ion (NO3) . Draw the possible Lewis resonance diagrams for this ion. Use the VSEPR theory to determine the steric number, the hybridization of the central N atom, and the geometry of the ion. Show how the use of resonance structures can be avoided by introducing a de-localized MO. What bond order is predicted by the MO model for the NO bonds in the nitrate ion?A paper published in the research Journal Science in 2007 (S. Vallina and R. Simo, Science, Vol. 315, p. 506, January 26, 2007) reported studies of dimethylsulfide (DMS), an important green-house gas that is released by marine phytoplankton. This gas represents the largest natural source of atmospheric sulfur and a major precursor of hygroscopic (i.e., cloud-forming) particles in clean air over the remote oceans, thereby acting to reduce the amount of solar radiation that crosses the atmosphere and is absorbed by the ocean. (a) Sketch the Lewis structure of dimethylsulfide, CH3SCH3, and list the bond angles in the molecule. (b) Use electronegativities to decide where the positive and negative charges lie in the molecule. Is the molecule polar? (c) The mean seawater concentration of DMS in the ocean in the region between 15 north latitude and 15 south latitude is 2.7 nM (nanomolar). How many molecules of DMS are present in 1.0 m3 of seawater?Discuss the nature of the bonding in the nitrite ion (NO2) . Draw the possible Lewis resonance diagrams for this ion. Use the VSEPR theory to determine the steric number, the hybridization of the central nitrogen atom, and the geometry of the ion. Show how the use of resonance structures can be avoided by introducing a de-localized MO. What bond order does the MO model predict for the NO bonds in the nitrite ion?
- Two variations of the octahedral geometry (see Table 4-1) are illustrated below. Which of the compounds/ions Br3, ClF3, XeF4, SF4, PF5, ClF5, and SF6 have these molecular structures?Calculate the lattice energy of AgBr(s) using the following thermodynamic data (all data is in kJ/mol). Ag(s) ΔHsublimation = 265 kJ/mol Ag(g) Ionization energy = 711 kJ/mol Br-Br(g) Bond energy = 173 kJ/mol Br(g) Electron affinity = -345 kJ/mol AgBr(s) ΔH°f = -120 kJ/mol ______________ kJ/molEstimate cryvstal structure type for CaF: ionic radii for Ca:0.1nm and F:0.133nm
- The phosphorus trihalides 1PX32 show the following variationin the bond angle X¬P¬X: PF3, 96.3°; PCl3, 100.3°;PBr3, 101.0°; PI3, 102.0°. The trend is generally attributedto the change in the electronegativity of the halogen.(a) Assuming that all electron domains are the same size,what value of the X¬P¬X angle is predicted by the VSEPRmodel? (b) What is the general trend in the X¬P¬Xangle as the halide electronegativity increases? (c) Usingthe VSEPR model, explain the observed trend in X¬P¬Xangle as the electronegativity of X changes. (d) Based onyour answer to part (c), predict the structure of PBrCl4.(a) The nitric oxide molecule, NO, readily loses one electronto form the NO+ ion. Which of the following is the best explanationof why this happens: (i) Oxygen is more electronegativethan nitrogen, (ii) The highest energy electron inNO lies in a p2*p molecular orbital, or (iii) The p2*p MO in NOis completely filled. (b) Predict the order of the N¬O bondstrengths in NO, NO+, and NO-, and describe the magneticproperties of each. (c) With what neutral homonuclear diatomicmolecules are the NO+ and NO- ions isoelectronic(same number of electrons)?Carbon monoxide, CO, is isoelectronic to N2. (a) Draw aLewis structure for CO that satisfies the octet rule. (b) Assumethat the diagram in Figure 9.46 can be used to describethe MOs of CO. What is the predicted bond order forCO? Is this answer in accord with the Lewis structure youdrew in part (a)? (c) Experimentally, it is found that thehighest energy electrons in CO reside in a σ-type MO. Isthat observation consistent with Figure 9.46? If not, whatmodification needs to be made to the diagram? How doesthis modification relate to Figure 9.43? (d) Would you expectthe π2p MOs of CO to have equal atomic orbital contributionsfrom the C and O atoms? If not, which atom wouldhave the greater contribution?