CHEMISTRY 3810

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Problem Set #7

Topic: Chemistry of the Group 17 and 18 Elements. You are responsible for Ch. 12 of Shriver-Atkins
1.

Preferably without consulting reference material, write out the halogens and noble gases as they appear in the periodic table,
and indicate the trends in (a) physical state (s, l, or g) at room temperature and pressure, (b) electronegativity, (c) hardness of
the halide ion, and (d) colour.

2.

Describe how the halogens are recovered from their naturally occurring halides and rationalize the approach in terms of
standard potentials. Give balanced chemical equations and conditions where appropriate.

3.

Sketch the chlor-alkali cell. Show the half-cell reactions and indicate the direction of diffusion of the ions. Give the chemical
equation for the unwanted reaction that would occur if OH migrated through the membrane and into the anode compartment.

CHEMISTRY 3810

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Problem Set #7

4.

Sketch the form of the vacant s* orbital of a dihalogen molecule and describe its role in the Lewis acidity of the dihalogens.

5.

Nitrogen trifluoride, NF3, boils at -129C and is devoid of Lewis basicity. By contrast the lower molar mass compound NH3
boils at -33C and is well known as a Lewis base. (a) Describe the origins of this very large difference in volatility. (b)
Describe the probable origins of the difference in basicity.

CHEMISTRY 3810

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Problem Set #7

6.

Based on the analogy between halogens and pseudohalogens: (a) Write the balanced equation for the probable reaction of
cyanogen (CN) 2 with aqueous sodium hydroxide. (b) Write the equation for the probable reaction of excess thiocyanate with
the oxidizing agent Mn0 2(s) in acidic aqueous solution. (c) Write a plausible structure for trimethylsilyl cyanide.

7.

(a) Use the VSEPR model to predict the probable shapes of IF6+ and IF7. (b) Give a plausible chemical equation for the
preparation of [IF6][SbF6].

CHEMISTRY 3810

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Problem Set #7

8.

Predict whether each of the following solutes is likely to make liquid BrF3 a stronger Lewis acid or a stronger Lewis base: (a)
SbF5, (b) SF6, (c) CsF.

9.

Predict whether each of the following compounds is likely to be dangerously explosive in contact with BrF3, and explain your
answer: (a) SbF5, (b) CH30H, (c) F2, (d) S2Cl2.

CHEMISTRY 3810

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Problem Set #7

10. The formation of Br 3 from a tetraalkylammonium bromide and Br 2 is only slightly exoergic. Write an equation (or NR for no
reaction) for the interaction of [NR4][Br3] with excess I2 in CH2Cl2 solution, and give your reasoning.

11. Explain why CsI3 (s) is stable with respect to the elements but NaI3 (s) is not.

12. Write plausible Lewis structures for (a) ClO2 and (b) I205 and predict their shapes and point groups.

CHEMISTRY 3810

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Problem Set #7

13. (a) Give the formulas and the probable relative acidities of perbromic acid and periodic acid. (b) Which is the more stable?

14. (a) Describe the expected trend in the standard potential of an oxoanion in a solution with decreasing pH (b) Demonstrate this
phenomenon by calculating the reduction potential of ClO4 at pH = 7 and comparing it with the tabulated value at pH = 0.

CHEMISTRY 3810

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Problem Set #7

15. With regard to the general influence of pH on the standard potentials of oxoanions, explain why the disproportionation of an
oxoanion is often promoted by low pH.

16. Which oxidizing agent reacts more readily in dilute aqueous solution, perchloric acid or periodic acid? Give a mechanistic
explanation for the difference.

17. (a) For which of the following anions is disproportionation thermodynamically favourable in acidic solution: ClO, CIO2 ,
ClO3 and ClO4? (if you do not know the properties of these ions, determine them from a table of standard potentials.) (b) For
which of the favourable cases is the reaction rate very low at room temperature?

CHEMISTRY 3810

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Problem Set #7

18. Which of the following compounds present an explosion hazard? (a) NH4ClO4, (b) Mg(ClO4)2, (c) NaCI0 4, (d)
[Fe(OH2)6][ClO4]2. Explain your reasoning.

19. Explain why helium is present in low concentration in the atmosphere even though it is the second most abundant element in
the universe.

CHEMISTRY 3810

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Problem Set #7

20. Which of the noble gases would you choose as (a) the lowest temperature liquid refrigerant, (b) an electric discharge light
source requiring a safe gas with the lowest ionization energy, (c) the least expensive inert atmosphere?

21. Give the formula and describe the structure of a noble gas species that is isostructural with (a) ICl 4, (b) IBr 2, (c) BrO3, (d)
CIF.

CHEMISTRY 3810

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Problem Set #7

22. (a) Give Lewis formulas and formal charges for ClO, Br 2, and XeF+. (b) Are these species isolobal? (c) Describe the chemical
similarities as judged by their reactions with nucleophiles. (d) Rationalize the trends in electrophilicity and basicity.

CHEMISTRY 3810

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Problem Set #7

23. By means of balanced chemical equations and a statement of conditions, describe a suitable synthesis of (a) xenon difluoride,
(b) xenon hexafluoride, (c) xenon trioxide.

24. (a) Give a Lewis structure for XeF7. (b) Speculate on its possible structures by using the VSEPR model and analogy with other
xenon

25. Given the bond lengths and angles in I5+, describe the bonding in terms of two-center and three-center s bonds and account for
the structure in terms of the VSEPR model.
26. Until the work of K.O. Christe (Inorg. Chem. 25, 3721 (1986)), F2 could be prepared only electrochemically. Give chemical
equations for Christe's preparation and summarize the reasoning behind it.
(see the original article provided)

CHEMISTRY 3810

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Problem Set #7

27. Predict the line-patterns in the 19F NMR spectrum of the following halogen fluorides. Assume that the axial position(s) is(are)
deshielded more, and that there is no chemical exchange: a) ClF3
b) BrF5
c) IF7

CHEMISTRY 3810

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Problem Set #7

28. Provide an MO interpretation of the bonding in ClF3. Treat the F atoms as simple spheres (pseudo s orbitals), but consider all
the valence s and p orbitals of the central atom, as usual.

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Problem Set #7

CHEMISTRY 3810

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Problem Set #7

CHEMISTRY 3810

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Problem Set #7

29. The Se 2I42+ cation in [Se 2I4][Sb2F10]2 has the unusual shape shown below. Like many halogen compounds, it is extremely
electron rich. This means that there are many electrons per nucleus. One bonding model for SeI2+ involves the p bonds
indicated at the right. Use these p orbitals as a basis set to construct an MO description of the dimer in Se 2I42+. It is not
necessary to provide symmetry labels for the dimer orbitals, but provide an energy-level diagram and orbital topologies. Is your
model consistent with the very weak bonding between the two halves of the dimer indicated by the observed bond distances?
(Reference: T. Klapotke and J. Passmore, Acc. Chem. Res. (1989) 22, 234-240).

CHEMISTRY 3810

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30. Provide an MO description of the bonding in XeF4. Use the example done in class for BrF5 as a guide.

Problem Set #7

CHEMISTRY 3810

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Problem Set #7

31. The structure of XeF6 has been the subject of continuing discussion and debate among chemists. It is not an easy molecule to
study! Describe the idealized VSEPR and actual gas phase structures of XeF6. What structure does XeF6 adopt in solution
(NMR evidence) and in the solid state? Reference: K. Seppelt, Acc. Chem. Res. (1979) 12, 211-216.

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Problem Set #7

CHEMISTRY 3810

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Problem Set #7

32. Interpret the NMR spectra of the C5F5N-Xe-F+ cation. (a) shows the 19F signal for the Xe-F fluorine atom only, while (b)
shows the 129Xe spectrum. C5F5N is a pentafluoropyridine molecule, attached to Xe via the N atom. The nitrogen is natural
abundance.

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Problem Set #7

33. Interpret the 125Xe NMR spectrum of OXe(OTeF5)4 shown below. The structure resembles that of OXeF4, with the OTeF5
groups replacing the fluorine ligands. OTeF5 has the structure indicated below. Each of the larger lines in spectrum is split
into quintets by 4 Hz. The separation between the quintets is 55 Hz, while the separation between the centres of the three
clusters is 640 Hz.

CHEMISTRY 3810

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Problem Set #7

34. Is the poorly resolved 125Xe NMR spectrum shown below consistent with the proposed structure Of C6F5X+?

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