CHEMISTRY 2070 PRELIM II ANSWERS

Your Name:
(P lease print) Last F irst CORN ELL N etID

November 8, 2012

Day and Time of Your Lab Section: Lab TA: Complete academic integrity is expected of all students of Cornell University at all times, whether in the presence or absence of members of the faculty or teaching sta. Understanding this, I declare that I shall not give, use, or receive unauthorized aid in this examination. Your Signature: There are 6 (multipart) questions and a total of 13 pages (including this cover sheet, a blank page after all the questions, a page of potentially useful facts and a periodic table at the end). Make sure that your examination booklet is complete. The prelim is not designed with the idea that all, or necessarily any of you, will complete each and every question. Work strategically; if you nd a problem that seems to require a large amount of time, you should probably work on other questions rst. . . and when you return, try a dierent approach! Write your answers directly on these sheets. Use the blank page, or if necessary the backs of pages, but clearly indicate on the problem page where work can be found. If you need to include additional pages, please attach them securely to the rest of the test book. Be brief, concise, and neat. Proctors are not allowed to interpret questions for you. No additional formulas, or values of fundamental constants, are required to answer these questions; if you believe that there is missing information, please check to make sure that you have taken advantage of any information provided to you in the problem. You may leave when you are nished, except in the nal minutes of the exam. Please do so quietly after turning your paper. Question 1. Question 2. Question 3. Question 4. Question 5. Question 6. Total (32) (32) (34) (28) (21) (28) (175)

Show your work! (Unless you dont care to receive partial credit).

1. (a) (22 points) Below is drawn a skeletal Lewis structure for the molecule carvone, which you snied in class. i. Add bonds and/or lone pairs as required so that the picture represents a Lewis structure indicating bonding patterns in the molecule carvone. ii. How many bonds (most easily, classied by the atoms connected, as indicated) and how many bonds (of any kind) are found in this molecule? iii. If this molecule exists in distinct stereoisomers, indicate by placing a star () next to the relevant optical center(s). (Please do not infer any information from the lengths or orientations of bonds in the skeletal structure; they are drawn solely to indicate connectivities!).

(b) (10 points) There are 10 C atoms in the skeleton of carvone show above. For the molecule as you have drawn it, count the number of sp, sp2 and sp3 hybridized centers (at the C atoms, only!). # sp centers # sp2 centers # sp3 centers zero 5 5

2. (a) (2 points) You are told that a given triatomic molecule has a measured bond angle of about 120 . What can you tell about the steric number in this compound? A triatomic molecule corresponds to CN 2 about the central atom. 120 bond angles are found in either SN 3, or perhaps SN 5 structures. But CN 2 and SN 5 corresponds to a linear molecule, because the lone pairs prefer to occupy the three equatorial positions. So the only choice is SN 3. (b) (6 points) You are told that a given triatomic molecule is linear; that is, the only bond angle is 180 . What can you tell about the steric number in this compound? A triatomic molecule corresponds to CN 2 about the central atom. 180 bond angles are found in either SN 2, SN 5 or SN 6 structures; we need to analyze each separately to see if the substitution pattern leaves the last two bond pairs at 180 ; in all three cases, the molecule is linear. So the SN may be 2, 5 or 6.

OOPS! As several of you have pointed out, for SN 6 the molecule would have to be an absurd species, like XeF2 , that would almost certainly not be bound. 2 Too many lone pair electrons. So a better answer would be SN may be 2 or 5 only.
(c) (24 points) For the following ions, nd the steric number (SN), the coordination number (CN) and using those values predict the molecular geometry. XeF+ 3

BrF+ 2

CCl 3

3. Consider the molecules N2 O, N2 , N2 F2 and N2 H4 . All contain an N to N bond. (a) (10 points) Draw Lewis structures appropriate to each. Include reasonable resonance structures and/or isomers where appropriate; make sure that you indicate lone pair electrons as required.

(b) (6 points) Based on your Lewis structures, in which molecule(s) is the N-N bond order greater than 2?

N2O and N2

(c) (6 points) Based on your Lewis structures, in which molecule(s) is the N-N bond longest?

N2H4

(d) (6 points) Based on your Lewis structures, in which molecule(s) is there an N-N bond dipole (i.e. the nitrogen to nitrogen bond has a positive and negative end)?

N2 O

(e) (6 points) Based on your Lewis structures, in which molecule(s) is there a molecular dipole moment?

N2O

and

4. (a) (16 points) Below are shown 4 MOs associated with a homonuclear molecule. The MOs show are all the result of combinations of AOs on the two atoms with n = 2; the signs of the individual portions of the wave function are indicated by the regions with heavy dark lines (negative) or unshaded (positive). Describe the MOs shown as corresponding to 2s , 2p or 2p bonds, and as bonding, nonbonding or antibonding.

5. An MO diagram describing the molecule BeN is shown below. Only the electron orbitals associated with the n = 2 valence shell are shown.

(a) (4 points) Identify which atom (Be or N) corresponds to atom A. Be. . . because its AOs are higher in energy than N

(b) (4 points) Label according to the conventional labeling scheme each of the atomic orbitals (AOs) and molecular orbitals (MOs) by entering the label names into the diagram. As shown

(c) (4 points) Assign electrons to the ground state of the molecule BeN by lling the appropriate MOs in the slots provided in the MO diagram. Indicate spin state with and symbols. As shown

(d) (3 points) Identify your BeN molecule as either paragmagnetic or diamagnetic, and give the bond order you predict. Molecule has one unpaired electron; its paramagnetic. 3 There are 5 bonding electrons, 2 antibonding, so the net bond order is . 2

(e) (6 points) Consider the isoelectronic species BC. Describe any dierences in the MO diagram for BC from that shown for the BeN molecule. B has one more electron in its AOs than does Be; so there would a single electron in one of the 2p orbitals of atom A. C has one less electron than does N in its AOs; therefore there will only be two electrons in two of the three 2p orbitals of atom B. The C AO energy levels would be somewhat higher than those of the N AOs; the B AOs lower than those of Be (but still higher than those of C). In the molecule, the electron density in the bonding MOs would be more nearly equal than in BeN (though still heavier at the C than the B); the antibonding orbitals, heavier at B than at C.

6. Below are listed the ionization energies (in some cases, 1st and 2nd), electron anities (in some cases, 1st and 2nd), and ionic sizes of some atoms in the periodic table, and a calculated value for Zef f , the net nuclear charge felt by the last electron added to the atom. Below are listed the ionization energies (IE) and electron anities (EA) for a series of Group 1, 2, 16 and 17 atoms. All energies are given in aJ/atom; positive energies mean that energy is required to produce that state. In addition, we have listed the Zef f derived from the 1st ionization energy, in units of the proton charge. Weve also included ionic radii for the ion in its natural state (i.e. with its valence shell either full (if an anion) or empty (if a cation)), in pm.

Metal

Group 1st

IE 2nd

Cation Radius 90 59 102 72 138 100

Zef f

non- Group Metal F O Cl S Br Se 17 16 17 16 17 16

EA 1st 2nd

Anion Radius 133 140 181 184 196 198

Zef f

Li Be Na Mg K Ca

1 2 1 2 1 2

0.86 1.49 2.92 0.83 1.23 2.41 0.70 0.98 1.90

1.3 1.9 2.5 3.3 3.5 4.4

-0.58 -0.23 1.30 -0.59 -0.33 0.98 -0.55 -0.32 1.00

5.1 4.5 6.1 5.5 9.0 8.3

(a) (6 points) The 1st ionization energy of the Group 2 elements is consistently signicantly larger than the 1st ionization energy in Group 1. Why? As we go right across the periodic table from Group 1 to Group 2, the eective nuclear charge felt by a valence s electron increases by less than a full charge; as a percentage, the increase is something like 40% for Li/Be and 20 For very large (probably unmeasurably large!) atoms, wed expect the two values to converge to something more nearly the same. (b) (6 points) The ionic radii decrease regularly as we go from Group 1 to Group 2 (for the same period) yet increase for Groups 16 and 17. Why? As we go right across the periodic table from Group 1 to Group 2, the eective nuclear charge felt by a valence electron(s) increase regularly; so where two ions have the same electron conguration we expect that the one with larger nuclear charge would be smaller in radius, diameter and/or volume. But when we compare ions from the left and right hand sides of the periodic table, were comparing cations whose last electrons are in the (n 1)th shell to anions whose last electrons are in the nth shell. So the anions are likely to be largereven though Zef f is increasing as we move across the period. (c) (4 points) The second electron anities of the Group 16 elements are always positive. Why? 1st EA refers to the energy gained when an electron is captured by the neutral atom. 2nd EA requires that we attract an electron to an already negatively charged speciesthe Coulomb interaction always objects to that process. So 2nd and subsequent EAs are always unstable with respect to the free electron and anion. (Of course, when brought together in a lattice of positive charges the net may be favorable!)

(d) (6 points) In the text you were told that the lattice energy of diatomic NaCl (i.e. the energy released when the separated ions came to their equilibrium distance) was -0.82 aJ. Without doing any calculations, suggest which pair of ions (other than, of course, Na+ and Cl ) from the table above should have a lattice energy most nearly the same as that found for NaCl. Explain your choice. For similarly charged ions the lattice energy diers only because r, the distance between nuclei, diers. So wed look for a pair of 1 ions with the same total ionic size as NaCl. The sum of their radii is 102 + 181 = 283 pm; LiBr is the closest in size (90 + 196 = 286 pm).

(e) (6 points) You are asked to design a system with twice the lattice energy of NaCl; conveniently enough, Ca2+ is about the same size as Na+ . When the lattice energy of the molecule CaCl2 is measured, it seems to be far from the desired value; after a little thought, your error becomes clear. Do you predict the actual value to be higher or lower? Assess the various contributions to the lattice energy of the process 2Cl (g) + Ca2+ (g) CaCl2 (g)

so as to clarify the design aw. Actual lattice energy will be somewhat larger. There are two main errors; the rst is that we have two anions, and so we need to count two anion-cation interactions each of which will be about double the lattice energy of NaCl. That gets us to four times the NaCl lattice energy...but were not done. We also need to account for the Cl-Cl repulsion; that will be less than the NaCl attraction because the distance is a lot further away (as we have two cation radii in between the two anions....so the center-to-center distance will be way long. Id imagine that the entire lattice energy would be something more than 3.5 times as large in CaCl2 than in NaCl. Of course none of these values match tabulated valueswhich describe crystals, not isolated ionic molecules. . .

10

This page is intentionally left blank

11

Some possibly useful facts:

IEn, = 2.18 aJ can be taken as a denition of Ze .

Coulombs law states that for two ions of charge Q1 and Q2 separated by a center-to-center distance r12 the electrostatic energy of interaction is Q1 Q2 E = 231 (aJ pm) r12 Negative values of E correspond to an attractive interaction. (p)(x) = h 4

h mv The mass of the neutron is mn = 1.675 1027 kg The mass of the proton is mp = 1.673 1027 kg The mass of the electron is me = 9.109 1031 kg 6.022 1023 amu = 1 gram (exactly) Ephoton = h = h = 6.626 1034 Joulesec hc c = 2.998 108 meter/sec

1 watt = 1 Joule/sec

12

13