Chemistry 17 (Third Long Exam)

I. Modified True or False: Read the following statements carefully, and then write TRUE if the statement is
true. Otherwise, change the underlined word to make the statement true.
1. Zn can be substituted by Mg as an oxidizing agent in Experiment # 14 (Selected Redox Reactions).
2. A certain voltage is applied in an electrolytic cell to make a non-spontaneous reaction spontaneous.
3. A yellow precipitate, Zn3[Fe(CN)2], is produced if K4Fe(CN)6 is added to a Zn2+ solution.
4. The charge of Co in the complex [CoCl(NO2)(NH3)4]+ is +4.
5. The cell reaction of a primary battery can be reversed by passing electricity through the battery.
6. Cr3+ interferes with the formation of the red lake in the prescence of NH4OAc and aluminon reagent.
7. The coordination number of Pt(en)2I2C2O4 is 4.
8. Electrons flow from anode to cathode in an electrolytic cell.
9. NH4+ is the only cation that did not form a precipitate with 3.0 M NaOH.
10. Only NO2-, NO3- and CrO42- give positive result in the test for strong reducing anions.

II. Multiple Choice: Choose the letter of the best answer.

1. What is the cell reaction for a charging lead battery?
A. PbO2(s) + Pb(s) + 2H+(aq) + 2HSO4-(aq) → 2PbSO4(s) + 2H2O(l)
B. PbO2(s) + 4H+(aq) + 2HSO4-(aq) + 4e- → PbSO4(s) + H2(g) + 2H2O(l) + SO42-(aq)
C. 2PbSO4(s) + 2H2O(l) → PbO2(s) + Pb(s) + 2H+(aq) + 2HSO4-(aq)
D. PbSO4(s) + H2(g) + 2H2O(l) + SO42-(aq) → PbO2(s) + 4H+(aq) + 2HSO4-(aq) + 4e-

2. The following anions interfere with the formation of a brown ring in the confirmatory test of Nitrate:
A. Chloride, Thiocyanate, Nitrite C. Iodide, Thiocyanate, Oxalate
B. Thiocyanate, Nitrite, Bromide D. Bromide, Nitrite, Sulfate

3. Which of the following complexes are diamagnetic?

A. [CoF6]3- B. [Fe(CN)6]3- C. [Co(H2O)6]2+ D. [Co(NH3)6]3+

4. Calculate the equilibrium constant at 25 ˚C for the reaction:

Pb2+(aq) + Sn(s) → Pb(s) + Sn2+(aq) (E0Pb2+/Pb = -0.126 V, E0Sn2+/Sn = -0.14 V)
A. 0.34 B. 9.7 x 108 C.2.97 D. 1.0 x 10-9

5. Which of the following is not a characteristic of the complex [Fe(CN)6]3-?

A. Pairing energy is greater than splitting energy
B. Low spin complex
C. Produces large crystal field splitting.
D. Strong-field complex
 III. Qualitative Analysis.
A. Determine Cations A to E and compounds F and G.

Cations A, B, C, D and E

6.0 M HCl

White ppt F from Cation A Cations B, C, D and E

6.0 M NH3

White ppt from NVR for

Cation B and C Cation D and E

X’s NH3 3.0 M NaOH

White ppt of White ppt of C White ppt due Pungent

B dissolves undissolved to Cation D colorless gas G
due to Cation E
Test
Yellow-green
Flame
B. Determine anions H-L and compounds M-R.

Cations H, I, J, K and L

FeCl3
K3Fe(CN)6

Blue ppt M due to Anion H and I Anions J, K and L

Acidified AgNO3 Acidified AgNO3

NVR due to H Yellow ppt N White ppt O NVR due to K and L

due to anion I due to anion J
6M H2SO4 AgNO3
1M FeSO4 X’s NH3
Brown solution Colorless solution White ppt NVR due to L
due to Fe(NO)2+ due to K
6M H2SO4
6M H2SO4
Acid R that has a
Effervescence Q vinegar smell
IV. Problem Solving

1. a. Determine the standard reduction potential of Cr3+(aq) + 3e- → Cr(s) given the E˚red of E˚Cr2+/Cr = -0.91V
and E˚Cr3+/Cr2+ = -0.41V.
b. Using Cr3+(aq) + 3e- → Cr(s) as the anode with [Cr3+] = 1M, determine whether the reaction is
spontaneous or not, and if Pb(s) can be plated out from the following cathodes:
i. PbSO4(s) + 2e- → Pb(s) + SO42-(aq) E˚red = -0.356
ii. Pb (aq) + 2e → Pb(s)
2+ - E˚red = -0.126
Note: The concentrations of all aqueous species are 1M.
c. Solve for the equilibrium constant for the reactions in (b) which is/are spontaneous.

2. Consider the frost diagram for Vanadium in acidic medium.

Frost Diagram, Vanadium, pH = 0

0 V

VO2+
-1
NE0red (V)

-2 V2+ VO2+

V3+

-3
0 1 2 3 4 5
Oxidation Number (N)

a. Which vanadium series is the most stable?

b. Which species is the strongest oxidizing agent?
c. Which species is the strongest reducing agent?
d. Will V3+ disproportionate to V2+ and VO2+?
e. Will VO2+ and V3+ comproportionate to VO2+?

3. a. Determine which complex is high-spin and which is low-spin between [Ni(H2O)6]2+ and [Ni(CN)4]2-.
b. What is the charge of Ni in the low-spin complex? Write its electronic configuration. Draw the orbital
diagram of the complex if it is diamagnetic.
c. Name the high spin complex in (a).
d. Write the water dissociation reaction of the high spin complex in (a).
e. From the reaction in (d), name the conjugate of the high-spin complex.