Welcome to Rickards Test!

Please submit your answers to these questions in Scilympiad under the

appropriate question number.

This test was written by Yash Shah and Vy Le.

Part I: Redox Titration!

Dr. Jones is a retired chemist and has found a bottle of ethanol in his home. He wants to determine
its concentration.

However, it has been many years since Dr. Jones has spent time in the lab, so his knowledge is a bit
rusty. Help him as he performs a redox titration!

Dr. Jones chooses to use potassium dichromate, K2 Cr2 O7 , to oxidize ethanol, C2 H5 OH. He correctly
remembers that his reaction will yield ethanoic (acetic) acid and trivalent chromium cations.

1. Let’s begin with determining oxidation states. What are the oxidation states of chromium in dichromate
and carbon in ethanol?
2. What are the oxidation states of chromium in the reduced chromium ion and carbon in the ethanoic
acid?

3. Describe the color change as the reaction proceeds.

4. Dr. Jones recalls that the balanced oxidation half-reaction for his procedure will be as follows:

C2 H5 OH (aq) + H2 O (l) −−→ CH3 COOH (aq) + 4 H+ (aq) + 4 e− (1)

Help him out by providing the balanced reduction half-reaction. Don’t forget to include states of matter!
5. Given the above equations, how many moles of electrons are transferred per 1 mole of reaction?
A. 9 moles
B. 4 moles
C. 12 moles
D. 10 moles
6. Combine the half-reactions and provide the balanced full reaction. Integral coefficients only!
7. Dr. Jones correctly chooses to carry out his reaction in acidic medium. Why wouldn’t the reaction
proceed under alternate conditions?
A. Medium pH would lead to the deprotonation of ethanol, so rendering the reaction unfeasible.
B. Cr2 O7 2 – can only exist in acidic solution.
C. The conventional cadmium catalyst in this reaction can only exist in acidic solution.
D. High pH would promote the unwanted side reaction of the reduction of hydronium reduction.
Dr. Jones creates his analyte by taking a 10.0 mL sample of ethanol solution and diluting to 100. mL
with distilled water. He uses a 0.398 molar solution of K2 CrO7 .

The results of his titration are summarized below in the table. Remember that readings of the titrant
are recorded by a burette!
 Initial K2 Cr2 O7 , mL Final K2 Cr2 O7 , mL Analyte, mL
Trial 1 34.3 49.7 100.
Trial 3 30.1 45.3 100.
Trial 3 24.6 39.6 100.

8. What is the average volume of K2 CrO7 used?

9. What is the concentration of ethanol in the ORIGINAL, non-diluted solution?

Part II: Some more general redox chemistry! The below problems explore topics not usually seen in
SciOly tests. Assume pH = 0 unless otherwise stated.

Assume T = 298.15 K for all problems.

Below is an incomplete Latimer Diagram of Uranium.

+0.06 V xV
UO2 2+ −−−−−→ UO2 + −−→ U4+

Source: Housecroft & Sharpe’s Inorganic Chemistry, 5th Edition

4+
10. Given that the voltage of the UO2 2+ /U redox couple is +0.33 V, determine the value of x in volts.
11. Given your answer to the above, is UO2 + susceptible to disproportionation?
12. Provide the equilibrium constant, K, for the single electron disproportionation of UO2 + . Hint: if your
answer to the above was yes, K > 1, if your answer was no, K < 1.

13. The reduction of Ag+ to elemental silver has a voltage of +0.80 V.

However, the silver (I) cation may be removed from solution by the addition of the Cl – anion. The
ksp of AgCl is 1.77 · 10−10 .

What is the potential of the Ag+ /Ag couple in a solution where the concentration of free Cl – is main-
tained at 1.00 M?
14. Consider the single electron reduction of Mn3+ to Mn2+ at pH = 0:

Mn3+ (aq) + e− −−→ Mn2+ (aq) E ◦ = +1.54 V

However, in base, both Mn3+ and Mn2+ precipitate out as insoluble salts of the formulas Mn(OH)3
(ksp = 10−36 ) and Mn(OH)2 (ksp = 2 · 10−13 ), respectively.

Calculate the potential of the Mn3+ /Mn2+ couple if the pH were to be maintained at 14.

Part III: Periodic trends (everybody’s favorite subtopic!). Unless otherwise indicated, assume all atoms
in this section to be in their gas phase and ground state.

15. What is the correct complete electron configuration of copper?

16. What is the correct noble gas electron configuration of tin?

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17. Which halogen (for the purpose of this test, F, Cl, Br, and I) is the most electronegative?
18. Which binary hydrogen halide (for the purpose of this test, HF, HCl, HBr, and HI) is the most acidic
in aqueous solution? Justify your answer! Hint: Consider conjugate bases.
19. Nitrogen has only one well-known allotrope: dinitrogen, or N2 . Briefly describe the structure of 2
allotropes of its heavier congener, phosphorus, and account for the fact that phosphorus does not form
triple-bonds. Hint: Consider orbitals.
20. Aluminum and magnesium are the 3rd and 7th most abundant elements in the Earth’s crust, respectively.
Which of the two have a higher first ioniziation energy and why?
21. Molecular nitrogen and oxygen account for a combined 99% of the earth’s atmoshpere. Intriguingly,
atomic nitrogen has a higher first ionization energy than atomic oxygen. Account for this unexpected
result.
22. Thallium and indium are so soft that they can be cut with a knife at standrad conditions. Explain why
thallium (Group 13, Z = 81) has a higher first ionization energy than indium (Group 13, Z = 49).

23. Transition metal ions are known to produce vibrant colors in aqueous solution. However, zinc is an
exception to this rule. Explain why aqueous solutions of Zn2+ are colorless.

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24. Consider the curves of potential energy vs. internuclear distance for three different types of carbon-carbon bonds.

Which of the following could be the correct identities of the bonds X, Y, and Z?

a. X is C≡C; Y is C=C; Z is C-C.

b. X is C≡C; Y is C-C; Z is C=C.
c. X is C-C; Y is C=C; Z is C≡C.
d. X is C=C; Y is C-C; Z is C≡C.
e. X is C=C; Y is C≡C; Z is C-C.
25. Consider the curve of potential energy vs. internuclear distance for the two homonuclear diatomic compounds F2
and Cl2.

In a deviation from the expected trend, the bond strength of F2 is less than that of Cl2. Which of the following
best explains this unexpected observation?

a. Fluorine is a smaller atom, and Coulomb’s law states that there is a weaker attraction between two
particles with smaller radii compared to particles with larger radii.
b. Since chlorine has a larger effective nuclear charge than fluorine, chlorine holds its electrons closer to its
nucleus, making its bonding interactions unusually favorable due to extra electrostatic attractions.
c. The bond length of Cl2 is larger than that of the F2 bond, and Coulomb’s law predicts that bond length is
directly proportional to the observed bond strength.
d. Due to fluorine’s high number of electrons relative to its small atomic radius, the F-F bond experiences
additional destabilizing electron-electron repulsions which are not present in the Cl-Cl bond.
e. This observation is not unexpected; the data in the graph above follow the expected trend for bond
strength down a group in the periodic table.

26. Using crystal field theory, rank the following ligands from strong field to weak field: H2O, Cl-, CO.

27. Consider the two coordination complexes [CoF6]3- and [Co(CN)6]3-.

A. What is the molecular geometry of each complex?
B. Which one of the two complexes above is likely to have the higher field splitting energy?
C. Predict the t2g and eg electron configurations of both [CoF6]3- and [Co(CN)6]3-.
D. Based on your answer to part (c), predict the crystal field stabilization energy of both [CoF6]3- and [Co(CN)6]3- in
terms of the octahedral field splitting energy, ΔO, and the pairing energy, P of the complexes.
Part III. Periodic Trends! This section will be more integrative with conceptual
understanding, so make sure you use any fundamental concepts you know for any
explanations! Use the PDF to answer Questions 28-53!

Let’s talk about VSEPR and bond angles!

28. What is the bond angle between each C-H bond in methane?
29. What is the bond angle between each S-F bond in sulfur hexafluoride?
30. Explain the difference between electron domain geometry and molecular
geometry.
31. Identify the electron domain geometry and molecular geometry of water.
32. Based on this information, would the bond angle of water or NO2 be larger, and
why?

Luffy is having some trouble wrapping his mind around effective nuclear charge, so let’s
dive in a bit about them.
33. Luffy is arguing that the effective nuclear charge of a sodium atom for the valence
electron is +11, but that isn’t the right amount as you tell him. What should the
number be?
34. Luffy is still confused as to why that is the case, since Coulomb’s Law states that
the charge of the nucleus is +11 and the electron is -1, so the electron will be
attracted to the +11 nucleus charge. What is the problem?
35. Alright, Luffy is starting to understand what is going on, but in order for him to
understand the concept better, he wants a little more information on periodic
trends for him to understand what’s going on. Which of the following element(s)
will have a larger effective nuclear charge on a given valence electron compared to
the sodium atom? Select all that apply.
a. Lithium
b. Potassium
c. Magnesium
36. Luffy questions, “If the sodium ion were to be generated from the sodium atom,
will that make the effective nuclear charge of the valence electron(s) larger?”
Answer the question and explain why.
37. Now, Luffy finally proposes that neon should have a lower effective nuclear charge
compared to the sodium ion. Is he right about that, and why?
One of the most useful concepts in organic chemistry is electronegativity, since it helps to
explain how certain reagents can react with each other. This question will focus a bit
more on electronegativity.
38. What is the most electronegative element?
39. What is the least electronegative element?
40. How does the electronegativity change within the alkaline earth metals?
41. Should magnesium, aluminum, or sulfur have the highest electronegativity?
Explain why using periodic trends.

A scientist is currently trying to study atomic and ionic radii and how they change over
the periodic table. The diagram below will be useful for parts c. and d. of this question.

42. Which of the following has the largest atomic radius?

a. Phosphorus
b. Cobalt
c. Strontium
d. Silver
43. What concept can best explain why helium would have the smallest atomic radius
while rubidium would have one of the largest atomic radii?
44. If the three elements in this diagram are the noble gasses helium, neon, and argon,
which letter is associated with each element?
a. A -
b. B -
c. C -
45. What do all of the relative maxima mean on this graph, and how would this look in
terms of atomic theory?
 46. Order the following based on smallest to largest size: S2-, Ar, Ca2+, Cl-. Explain how
you know the order.

This question will go over some other periodic trends that are good to know.
47. Does the first ionization energy of each element in the same period increase or
decrease?
48. Why does aluminum’s 4th ionization energy require a substantial amount of energy
compared to the 3rd one?
49. For the alkali metals, what is the general crystal structure at standard temperature
and pressure?
50. From what corner to its opposite end would usually show the largest increase in
metallic character?
51. What is the difference between the crystal lattice and crystal structure?
52. Despite the typical periodic trends for melting point, what element has the highest
melting point of any element (Hint: Diamonds)?
53. If metallic bonds are not that strong compared to ionic or covalent bonds, why do
metals have higher melting points than nonmetals?