Electrochemistry Questions:

1. A concentration cell is made up of the Cu/Cu2+ couple, where the Cu2+ concentrations
are 1.0 M and 0.10 M. Which of the following statements best describes the operation of
this cell?

a. The anode compartment contains a 0.10 M Cu2+ solution, which decreases in

concentration as the cell operates, and the cathode compartment contains a 1.0 M
Cu2+ solution, which also decreases in concentration as the cell operates.

b. The anode compartment contains a 0.10 M Cu2+ solution, which increases in

concentration as the cell operates, and the cathode compartment contains a 1.0 M
Cu2+ solution which decreases in concentration as the cell operates.

c. The anode compartment contains a 0.10 M Cu2+ solution, which decreases in

concentration as the cell operates, and the cathode compartment contains a 1.0 M
Cu2+ solution which increases in concentration as the cell operates.

d. The anode compartment contains a 1.0 M Cu2+ solution, which decreases in

concentration as the cell operates and the cathode compartment contains a 0.10 M
Cu2+ solution which increases in concentration as the cell operates.

e. The anode compartment contains a 1.0 M Cu2+ solution, which increases in

concentration as the cell operates and the cathode compartment contains a 0.10 M
Cu2+ solution which decreases in concentration as the cell operates.
ANSWER: B

2. Which of the following is the strongest reducing agent?

Cl2 + 2e- → 2 Cl- E° = 1.36 V

Mg2+ + 2e- → Mg E° = -2.37 V
2H+ + 2e- → H2 E° = 0.00 V

a) Cl2 b) H2 c) Mg d) Mg2+ e) Cl–

ANSWER: C

3. a. Suppose one wished to make a battery based on the two half cells:

[Pt(Cl)6]2- + e– → [Pt(Cl)6]3- E°R = +0.45V vs. SHE

[PtIV(Cl)5]– + e– → [PtIII(Cl)5]2– E°R = +0.25V vs. SHE
If [Pt(Cl)6]2- is present in 1M concentration, [Pt(Cl)6]3- is present in 1M concentration,
[PtIII(Cl)5]2– is present in 1M and [PtIV(Cl)5]– is present in 0.001M concentration, what
" RT % 0.059
would the single cell battery potential be at 25˚C where $2.303 ' = ?
# nF & n
∆E=(0.45-0.25) - 0.059(log[[Pt(Cl)6]3-•[PtIV(Cl)5]–/ [Pt(Cl)6]2-•[PtIII(Cl)5]2–]

!
b. Consider a cell that contains two half cells each having 1M [Pt(Cl)6]2-. What will be the
measured voltage of this cell? What happens when one of the half cells is illuminated
with light that [Pt(Cl)6]2- absorbs generating [PtIII(Cl)6]2–?
THE CELL POTENTIAL WILL INITIALLY BE ZERO. UPON IRRADIATION A
CONCENTRATON CELL IS FORMED SINCE THE CONCENTRATION OF [Pt(Cl)6]2-
WILL NOT BE THE SAME IN BOTH HALF CELLS AND VOLTAGE IS OBSERVED

c. Circle all correct answers: A photoelectrochemical cell has:

a. two metal electrodes and a light sensitive electrolyte.
b. at least one electrode that is a metal electrode
c. two semiconductor electrodes
d. at least one semiconductor electrode.

ANSWER: C&D

4. 1) How many electrons are required to reduce NO3– to NH3?

ANSWER: 8

Inorganic chemistry questions:

1. The octahedral complex, [Pt(Cl)6]2- is yellow in color. The sodium salt of this complex
easily dissolves in water, and irradiation of the dissolved complex by visible light
causes photoaquation (the light induced replacement of a ligand by a water ligand) to
occur forming the product [Pt(Cl)5(H2O)]–.

a. What is the oxidation state of the platinum center of the starting complex and
how many d-electrons does it contain?
b. Draw the d-orbital splitting diagram for [Pt(Cl)6]2-, label each orbital and
show the electron occupancy.
c. What color light does the complex absorb?
d. It has been suggested that the mechanism of the photoaquation reaction is:

1. [Pt(Cl)6]2- + hν ""
k1 III
# [Pt (Cl)6]
2–

2. [PtIII(Cl)6]2– ""
k2 III 2–
# [Pt (Cl)5] + Cl•
Keq
! ]2– + [Pt(Cl) ]2-
3. [PtIII(Cl) [PtIV(Cl)5]– + [Pt(Cl)6]3-
5 6

!
 4. [Pt(Cl)6]3- ""
k4 2–
# [Pt(Cl)5] + Cl
–

5. [Pt(Cl)5]2– + H2O ""

k5
# [Pt(Cl)5(H2O)]
2–

6. [Pt(Cl)5(H2O)]2– + O2 ""
k6
# [Pt(Cl)5(H2O)]
–
!
!
# d [ Pt(Cl) ] 2" &
6
Write a rate law for this
! mechanism in terms of "%% (( assuming that
$ dt '
step (1) is the rate determining step.

e. [Circle the correct answer] This reaction

! contains a chain reaction in which:
1. Steps (1) and (2) represent the chain.
2. Steps (2) and (3) represent the chain.
3. Steps (2), (3) and (4) represent the chain.
Steps (3) and (4) represent the chain.

2. Consider the complex ions Co(NH3)63+, Co(CN)63–, and Co(F)63–. The color of absorbed
electromagnetic radiation for these compounds is (in no specific order) red, blue, and
UV. Match the complex ion to its color in aqueous solution

Complex Ion Observed Color

Co(NH3)63+

Co(CN)63–

Co(F)63–

3. Which complex has a larger value of 10Dq?

a. [PtCl6]2- or [NiCl4]2-
b. [Cr(CN)6]3– or [WF6]3–
Fill in the table
Complex Geometry d-orbital Splitting Hybridization of the
diagram Valence Shell Orbtals

[Fe(CN)6]4–

[FeCl4]2–

[Pt(CN)4]2–

V(CO)6–

Kinetics
1. 210Bi has a half life of 5 days while 222Ra has a half life of 3.8days. If one starts with a
sample that is a 50:50 mix of 210Bi and 222Ra what will the ratio of Bi to Ra be after 10
days?

2. ) Consider a reaction which is zero-order in A and first-order in B,

A + B → Products Rate = k[A][B]
What are the relative rates of this reaction in the vessels shown below.
Note: each vessel has the same volume.
 = A molecule = B molecule

I II

III IV

a) III > I = IV > II b) I > III > II > IV c. IV > II > III > I
d. II > IV > I > III e. I = III > = IV

2. Indicate the units on the rate constant for the following situations
a. The reaction is a third order reaction.
2
"d [ A] [ A]
b. The observed rate law is of the form: = kobs 2
dt [C ][ B ]
c. The reaction is a bimolecular reaction.
3. The current vs. time graph for a particular electrochemical reaction (run at 25˚C)
shows that the current drops off to!¼ its initial value after 60 minutes. What is the
half-life for this reaction? Increasing the cell temperature from 25˚C to 35˚C causes
the current to drop off to ¼ of its initial value in 30 minutes. What is the activation
barrier for the reaction?
Acids and Bases

1. Addition of sodium acetate to an acetic acid solution at equilibrium will cause:

a) no change in H3O+ concentration.

b) H3O+ concentration to decrease.

c.) H3O+ concentration to increase.

d) concentrations of all species to increase.

e) a decrease in hydroxide concentrations.

2. Glycine amide and glycine amide hydrochloride are commonly used reagents for the
preparation of buffer solutions. The dissociation reaction for glycine amide
hydrochloride is shown below.

O O

Cl H 3N C H 2O H 3O H 2N C Ka = 6.3 x 10-9
C NH2 C NH2
H2 H2
Glycine amide hydrochloride Glycine amide
C2H7ClN2O C2H6N2O
Mol. Wt. = 110.54 g/mol Mol. Wt. = 74.08 g/mol

A. How many grams of glycine amide should be added to 5.01 g of glycine

amide hydrochloride to give 500.0 mL of solution with a pH of 8.00? Show work.

B. What would be the pH of the solution prepared in part (a) after it was mixed
with 5.00 mL of 1.00 M HCl? Show work.

C. What would be the pH of the solution prepared in part (b) after it was diluted
to a total volume of 650.0 mL with distilled water?

Solution Questions:

1. A solution with strong intermolecular forces will have a:

a. low temperature freezing point
b. low temperature boiling point
 c. high boiling point
d. a low density
2. a. Calculate the molality of an aqueous solution that has a boiling point elevation of 1.5˚C.
Assume no dissociation of the solute.
b. How could one explain a von Hoft factor of 0.5 for a solute that was a strong hydrogen
bonder in a solvent that could not hydrogen bond? (acetic acid in H2CCl2 for example)

3. An aqueous salt solution is found to generate an osmotic pressure of 10Atm. At what

temperature will this solution freeze? The freezing point constant for water is 1.86˚CKg/mole.