CHEM 17 PROBLEM SET 3

First Semester, AY 2015-2016

TOTAL:60/60

MULTIPLE CHOICE. Write the letter of the best answer [2 pt each]

For numbers 1 to 3, consider the case below.
The table shows the observed colors of iron complexes with ligands Q, R and X in aqueous solution.
Metal complex

FeQ64

FeR64

FeX64

Observed color

blue green

orange

Violet

1. What is the oxidation state of iron in the complexes above?

A.
B.

+1
+2

C.
D.

+3
+4

2. Which of the following sequences arrange the given ligands in order of increasing field strength?
A.
B.

Q < R < X
R < Q < X

C.
D.

Q < X < R
R < X < Q

3. When the complexes shown above are converted to their analog FeL63 complex (L = ligand), one appeared
red, one appeared green, while one appeared colorless. Which complex appeared colorless?
A.

FeQ63

B.

FeR63

C.

FeX63

4. Which metal ion forms a cherry-red precipitate with dimethylglyoxime?

A.
B.

Mn2+
Cr3+

C.
D.

Cu2+
Ni2+

5. Which is a major product when sulfite is reacted with permanganate in basic conditions?
A.
B.

Mn2+(aq)
Mn(OH)4

C.
D.

MnO2(s)
MnO42(aq)

For numbers 6 to 7, refer to the Latimer diagram below for sulphur species under standard-state conditions
and pH = 12.

6. Which species will disproportionate spontaneously under the above conditons?

A.
B.

SO32
SO42

C.
D.

S
S2O32

7. What is the standard reduction potential for the reduction of SO42 to S2O32 under the above conditions?
A.
B.

1.512
0.756

C.
D.
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0.360
0.180

8. Which of the following statements are TRUE about the electrolysis of KI?
I.
II.
III.
IV.
A.
B.

H2 is generated at the cathode.

I2 is generated at the cathode.
O2 is generated at the anode.
I2 is generated at the anode.

I and III
I and IV

C.
D.

II and III
II and IV

For numbers 9 to 11, consider the electrochemical cell below. The graphite electrode used has surface area of
1.0 cm2. The measured Ecell for this cell is 0.46 V.
Cu(s) | Cu2+(0.05 M) || Fe3+ (0.05 M), Fe2+ (0.05 M) | C(s)
9. What will happen to the measured Ecell at equilibrium when the 0.05 M Fe2+ and Fe3+ solutions in the cell
above were both replaced with 0.10 M solutions?
A.

Ecell < 0.46 V

B.

Ecell > 0.46 V

C.

Ecell = 0.46 V

10. What will happen to the measured Ecell at equilibrium when the 0.05 M Cu2+ solution in the cell above was
replaced with 0.10 M solution?
A.

Ecell < 0.46 V

B.

Ecell > 0.46 V

C.

Ecell = 0.46 V

11. What will happen to the measured Ecell at equilibrium when the graphite electrode above was replaced with
one which has a surface area of 2.0 cm2?
A.

Ecell < 0.46 V

B.

Ecell > 0.46 V

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C.

Ecell = 0.46 V

PROBLEM SOLVING. Show complete solutions and box the final answer in answering each problem.
1. Colorful complex. A student prepared a complex, with the formula [Co(NH3)5NO2]Cl2 by mixing suitable
amounts of Co(II), NH3, NaNO2 and H2O2 in ethanol and crystallizing it in an ice bath. The resulting product is
light red in color. However, when this product was left standing in ambient temperature, its color changes to a
bright orange. Elemental analysis of these two differently colored solids showed that they still have the same
elemental compositions. X-ray studies also revealed that the coordination number of the Co center is also the
same for both forms.
[1-1]

Using crystal field theory, propose a mechanism that could account for the observed color change.
Draw relevant structures of the complexes.
[6 pt]

[1-2]

This complex cannot be considered thermochromic since its color changes are not reversible with
heating/cooling. Based on your proposed mechanism, explain why this complex did not exhibit
thermochromism, as compared to the complex we synthesized in the lab. [4 pt]

2. Redox chemistry of chlorine. Given below is the Frost diagram for chlorine species under acidic and basic
conditions.

[2-1]

Identify the most thermodynamically stable form of chlorine under acidic conditions.

[1 pt]

[2-2]

Identify the most thermodynamically stable form of chlorine under basic conditions.

[1 pt]

[2-3]

Under which conditions (CHOOSE: acidic OR basic) is perchlorate a stronger oxidant?

[3 pt]

Chlorine dioxide, ClO2, is a major disinfectant used in water treatment. Depending on the contaminant it
attempts to neutralize, it may act either as an oxidizing or reducing agent.
[2-4]

Chlorine dioxide, by itself, is unstable and will disproportionate spontaneously. Write a balanced
chemical equation for the disproportionation of ClO2.
[3 pt]

[2-5]

The versatility of ClO2 as a disinfectant is best observed in slightly alkaline conditions, as compared to
acidic conditions. Account for this observed activity.
[5 pt]

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3. Determination of Kb. The cell below:

Pt(s) | H2 (g, 1 bar) | RNH2 (aq, 0.10 M), RNH3Cl (aq, 0.050 M) || HCl (aq, 1 M) | H2 (g, 1 bar) || Pt(s)
has a potential of 0.490 V. Given E0(H+/H2) = 0.00 V
[3-1].

Write the balanced equation for the cathodic half-cell reaction. [1 pt]

[3-2].

Write the balanced equation for the anodic half-cell reaction [2 pt]

[3-3].

Calculate the standard reduction potential for the reduction half reaction: RNH3+(aq) ! RNH2(aq) +
H2(g). [6 pt]

[3-4].

Calculate Kb for the organic base RNH2. [6 pt]

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