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Chemistry 121 Third midterm exam November 19, 2009
Rules: 1. The time limit is 1 hour and 30 minutes. The exam ends at 9:15 a.m. 2. This exam is closed book and closed notes. You may use a calculator. If you need a physical constant or unit conversion factor that is not provided, you may ask the proctor. This exam must represent your own work! 3. Sign your exam with the honor pledge below: Scores:
Question 1 2 3 4 5 6 Total points
Points possible 25 20 20 25 30 30 150
then during hybridization the new sp hybrid orbital will become slightly higher in energy than the original 2s orbital and so the energy of the electron in that orbital will be raised. why does C hybridize in this molecule? The energetic costs of hybridization include the energy necessary to promote 1 electron in the 2s orbital to a 2p orbital. In other words. a) Draw a Lewis structure for this molecule and predict its molecular geometry.1) (25 pts) Consider the bonding in the covalent C2H2 molecule. and therefore the energy of the electron in that orbital will be lowered during hybridization. However. This decrease in potential and kinetic energy offsets all of the energy necessary for electron promotion and hybridization. The2s and 1 2p orbitals combine to form 2 new sp hybrid orbitals c) Using your understanding of orbitals. the electrons in the new molecular orbitals will experience a lower potential energy than in their initial atomic orbitals or hybrid orbitals because they will experience coulombic interactions of two nuclei. explain the energetic costs and benefits of orbital hybridization. In addition the new molecular orbital will be larger than the original atomic or hybrid orbitals and therefore the kinetic energy of the electrons in the molecular orbitals will also decrease. Once hybridization is complete and bonding has occurred. The molecule will be linear b) Draw an electron configuration diagram (orbital‐filling diagrams in MF terminology) of the C atom before and after hybridization. . Name the type of new hybrid orbital formed. the 2p orbital involved in hybridization will lower in energy.
The first sentence is incorrect: the valence electrons are loosely held in metals because of their relatively low core charge and therefore are also easily ionized. what are the characteristics of a good fuel molecule: a few weak bonds. 2s. many weak bonds. In potassium the 4s and 3p orbitals would combine to form a band that would be 1/8 filled while in chromium the 4s and 3d orbitals would combine to form a band that would be ½ filled. The more atoms there are in the molecule. Hence. The sea of electrons model of metallic bonding says that because metals have low electron affinities. but in neutral metals ionization doesn’t occur. There is long range order in metals. all of their electrons are weakly held to the nucleus and can be readily be ionized. 3p and 4s bands while chromium has 1s. during reaction. so there is no order in metallic solids and that’s why metals are malleable. Because this results in charged nuclei floating in a sea of electrons. the more bonds can be formed in the products. reaction of this molecule will be exothermic. which requires formation of strong bonds in the products. but they are not free to move around. Metals are malleable because these interactions are not dependent on orientation. In the third sentence the modern band theory of metals says that the valence orbitals form bands that are filled with valence electrons. . provide the correct information where needed. 2p. 4s and 4d bands. 2p. Because Cr has more bands than K. The more modern band theory of metallic bonding says that the electrons form bands. release a significant amount of energy. they pack to maximize favorable electron/nucleus interactions and minimize unfavorable electron/electron and nuclear/nuclear interactions. Thus.e. Electron affinity has nothing to do with anything In the second sentence the metallic nuclei retain their core electrons. the nuclei of the atoms are free to move around. and explain whether the reasoning is logical or not. the fuel molecule should have weak bonds. The larger number of electrons filling bonding orbitals in Cr results in stronger interactions and therefore it is a harder metal with a higher melting point. a few strong bonds. 2s. i. so more bonds in the reactant molecule implies more energy release during reaction. 3s. and potassium has 1s. Hess’ law requires that the energy of the reaction must equal the energy absorbed to break all the bonds in the reactants minus the energy released in forming all the bonds in the products. which cost a small amount of energy to break. and provide logical reasoning where needed. The energy of breaking the bonds in the fuel molecule acts against this energy release.” Per molecule. and apply Hess’ law in your explanation. it is a harder metal with a much higher melting point.2) (20 pts) Assess the following analysis of the birth of atomic theory. they are held in place by the delocalized electrons. 3p. a good fuel molecule will have many weak bonds. A high energy fuel molecule will. 3s. 3) (20 pts) Fuels are often described as containing “high energy molecules. In your assessment. or many strong bonds? Explain your reasoning in terms of bond energies. you must determine what information is correct or incorrect. only on distance. although the electrons do become delocalized into a ‘sea’ of electrons.
McHale used calcium carbide in her exploding pumpkin demonstration. Explain this stability using your MO diagram. label the molecular orbitals and fill in the valence electrons. c) What is the bond order of the carbide anion? the bond order is (8‐2)/2 = 3.4) (25 pts) Dr. a) Draw a molecular orbital diagram of the carbide anion. C22‐ . The highest occupied orbital will be a σ2p orbital made from the overlap of 2pz orbitals and will look something like this: . so in C23‐ the additional electron in antibonding orbitals will be more destabilizing than the lack of an electron in a bonding orbital in C2‐ e) Draw a picture of the highest occupied molecular orbital in C22‐.5) <C23‐ (bond order = 2. (the π2p molecular orbitals will be lower in energy than the σ2p orbital) b) Despite the fact that carbon does not have a very high electron affinity.5). This results in a net stabilization of the anion which is greater than anticipated. d) Rank the bond length of the C2‐. Electron affinities are measures of a single atoms tendency to accept an additional electron and therefore don’t account for the stabilization that can occur upon formation of molecular orbitals. C22‐ and C23‐ anions from shortest to longest C22‐(bond order = 2) <C2‐ (bond order =2. the carbide anion is fairly stable. resulting in a net lowering of their energy. and a greater stabilization than would be predicted by electron affinities. The additional electrons went into bonding orbitals. Remember antibonding orbitals go up in energy more than bonding orbitals go down.
36 kJ per mole of CH4 ΔHrxn2 = (2 mol)ΔHf(CO) +(4 mol) ΔHf(H2O) – [(2 mol)ΔHf(CH4) + (3 mol)ΔHf(O2)] ΔHrxn2 = (2 mol)(‐110.83 kJ/mol ΔHrxn1 = (1 mol)ΔHf(CO2) +(2 mol) ΔHf(H2O) – [(1 mol)ΔHf(CH4) + (2 mol)ΔHf(O2)] ΔHrxn1 = (1 mol)(‐393. a) Write two balanced equations for the reaction of methane gas with oxygen to produce each of these products.83 kJ/mol)– [(2 mol)(‐74.5) (30 pts) Burning methane (CH4) in oxygen can produce mixtures of different carbon containing products.5 kJ/mol.5 kJ/mol. In each case assume H2O(l) is the only other product Reaction 1) CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Reaction 1) 2CH4(g) + 3O2(g) 2CO(g) + 4H2O(l) b) Determine the standard enthalpies for the reactions in part (a) given the following standard enthalpies of formation: ΔHfo CH4 (g) = ‐74. ΔHfo CO(g) = ‐110.83 kJ/mol)– [(1 mol)(‐74.5 kJ/mol) +(2 mol)(‐285. is CO2(g) the predominant carbon‐containing product in the combustion of methane? Reaction 1 is more exothermic than reaction 2.8 kJ/mol) + (2 mol(0 kJ/mol)] ΔHrxn1 = ‐890. the reactants in reaction 1 have been lowered in energy more by conversion to products that they were in reaction two. Therefore. when the oxygen suppy is adequate. and ΔHfo H2O(l) =‐285. more strongly bonded products than reaction 2 and therefore CO2 should be the predominant product as long as there is sufficient oxygen.36 kJ for 1 mole of CH4 c) Why.8 kJ/mol.5 kJ/mol) +(4 mol)(‐285.72 kJ per 2 moles of CH4 or ‐607. . including CO(g) and CO2(g). ΔHfo CO2 (g) =‐ 393.8 kJ/mol) + (3 mol(0 kJ/mol)] ΔHrxn2 =‐1214. Therefore reaction 1 results in more stable.
which are lustrous and therefore wouldn’t be clear and transparent and they feel cold because metals are excellent heat conductors due to the loosely held. Solids 1 and 3 are metals. The material in bottles 4 and 5 are brittle and break with much less force than the solid in bottle 2. What conclusions can you make about solids 1 and 3 based on these properties? State your reasons briefly. low melting solid. . Calcium oxide (CaO). a) You examine the bottles visually. Silver (Ag). In CaO both ions have a +2 charge. Bottles 4 and 5 must contain ionic solids because those lattices are held together by electrostatic forces and changing alignments of the lattice can easily result in repulsions which cleave the crystal. and determine that the material in bottle 5 has a melting point about twice that of the solid in bottle 4. Calcium oxide and sodium oxide are the only possibilities left. Bottles 2. boron nitride (BN). Use this information to determine the identities of the contents of bottles 4 and 5. A co‐worker has collected the labels and asks you to match labels to the contents of the bottles using your superior knowledge of chemistry. The 6s and 5d orbitals will combine to form a new molecular orbital band which can hold 12 electrons per atom will be ½ filled. What conclusions can you draw? State your reasoning briefly. When you touch the contents. Bottle 5 requires a great deal of force which suggests it is a covalent network crystal like diamond. State your reasoning briefly in terms of electron configurations and molecular orbital theory W has an electron configuration of [Xe]6s24f145d4. transparent solids. Therefore bottle 3 is W and bottle 1 is Ag. so the electrostatic forces holding the lattice together should be much stronger than in Na2O. As has an electron configuration of [Kr]5s14d10 and the 5s and 4d orbitals will combine to create a band that will be 11/12 full with most of the antibonding orbitals populated resulting in a soft. 4 and 5 contain clear. Therefore CaO should have a higher melting point and will be the solid in bottle 5. and therefore might be expected to form a diamond‐like solid. so W should have a very high melting point. solids in bottles 1 and 3 feel cold. This will completely fill the bonding orbitals. delocalized valence electrons b) You determine that the melting point of the solid in bottle 3 is much higher than that of the solid in bottle 1. c) You take samples of the contents of bottles 2. and Sodium oxide (Na2O). but not the antibonding orbitals. BN is a solid with the same number of valence electrons as C. therefore bottle 2 is BN d) You measure the melting points of the solids in bottles 4 and 5. The 5 labels are: Tungsten (W). while bottle 4 will be Na2O.6) (30 pts) In lab you find five bottles containing solid crystals that have lost their label. non‐transparent solids. while bottles 1 and 3 contain shiny. Use this information to determine the identities of the contents of bottles 1 and 3. 4 and 5 and strike them. Identify the solid in bottle 2. State your reasoning briefly.
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