Oxidation States of Vanadium From

the Reduction by Zinc and Oxidation

by Permanganate

Michele Dubé M.S.

Date Performed: November 13, 2019
Date Submitted: November 20, 2019

I have neither given nor received unauthorized aid on this assessment:

Jay-Ho Chung
Results

Mass of NH4VO3 (g) 1.6005

Molarity of Vanadium Stock Solution (M) 0.054720

Table 1. Data For Vanadium Stock Solution

Observations from Table 1 illustrated the data used for the preparation of the vanadium stock

solution (the molarity of vanadium stock solution was calculated under Figure 6). (The mass of

NH4VO3 was included after the approval of lab TA Charles Quinn and Alden Harring because it

provided information utilized in the calculations illustrated under Figure 6).

Further Observations

During the preparation of the VO2+ solution, there was a color change from colorless to aureate

yellow as illustrated in Figure 1.

Figure 1. Aureate Yellow Color of the Vanadium Stock Solution

Figure 1 demonstrated the aureate yellow color after the preparation of the vanadium stock

solution.
 Volume of Vanadium Stock Solution (mL) 25.00

Initial Solution Color Tyrian purple

Final Solution Color Aurora blue

Initial KMnO4 Buret Reading (mL) 0.00

Final KMnO4 Buret Reading (mL) 39.95

Volume of KMnO4 Added (mL) 39.90

Concentration of KMnO4 0.02001

Table 2. Data From Reduction by Zinc

Observations from Table 2 provided the data collected from the reduction of the vanadium stock

solution by zinc and informed the data for Table 3. (This data was included after the approval of

lab TA Charles Quinn and Alden Harring because it provided information utilized in the

calculations illustrated under Figure 7).

Further Observations

After the decanting of the zinc solution, the initial solution color was colorless (Figure 2). After

the addition of sulfuric acid and vanadium stock solution, the solution turned tyrian purple

(Figure 3). After the addition of the reduced vanadium solution to the vanadium stock solution,

the resulting solution was aurora blue (Figure 4). After the titration of this solution, the color

changed from seafoam green (Figure 5) to yellow to yellow-orange. Note, furthermore, that the

volume of KMnO4 was after the endpoint (indicated by a yellow-orange color) by roughly 0.05

mL which is why the volume of KMnO4 added is recorded as 39.90 mL instead of 39.95 mL.
Figure 2. Initial Color of Zinc Solution

Figure 2 illustrated the color of the zinc solution after decanting.

Figure 3. Tyrian Purple Color of Reduced Vanadium Solution

Figure 3 illustrated the tyrian purple color of the zinc solution after adding the vanadium stock

and sulfuric acid.

Figure 4. Aurora Blue Color of Reduced Vanadium and Vanadium Stock Solution

Figure 4 demonstrated the aurora blue color of the solution after adding the reduced vanadium

solution to the vanadium stock solution.

Figure 5. Seafoam Green Color of Solution

Figure 5 demonstrated the seafoam green color of the protected vanadium solution upon titration

with permanganate solution.

 Moles KMnO4 Used 7.9840×10-4

Moles Vanadium Used 0.001368

Oxidation State of Vanadium After Zinc 2+

Reduction
Table 3. Results of Reduction by Zinc

Observations from Table 3 provided an understanding of the oxidation state of vanadium after

the reduction by zinc (the moles of vanadium KMnO4 and vanadium used were calculated in

Figure 7 and the oxidation state of vanadium after zinc reduction was calculated in Figure 8).

Color Oxidation State

Aureate Yellow 5+

Aurora Blue 2+
Table 4. Oxidation States of Vanadium Solutions

Observations from Table 4 provided the oxidation states of vanadium solutions and this was

calculated under Figure 8.

Discussion Questions

1. Describe any deviations from the manual instructions or any unusual observations during

the experiment.

One deviation from the manual instruction was during the titration with permanganate.

The titration was supposed to occur at a temperature between 60 and 80 degrees celsius to

prevent a side reaction to create the formation of MnO2, but this was not the case. The

temperature dropped to roughly 55 degrees celsius roughly two to three times, but it did not

appear as though a side reaction occurred. Regardless, in the case that a side reaction occurred,

this would lead to error. A side reaction would result in less vanadium solution to titrate. This

would result in less permanganate used to reach the endpoint color, thereby resulting in a

calculation that indicates less moles of permanganate were used. This could have then resulted in

a calculated oxidation state that was higher than the actual value due to this deviation.

Some additional error could include titration error as well. While titrating, there could

have been an error while reading the buret during titration as well. Furthermore, during the

titration, some permanganate ended up on the sides of the Erlenmeyer flask. While diluted water

was added to the sides to obtain all of the permanganate added, there could have been some

permanganate that did not return. Within the calculations, this would have resulted in a higher

volume of permanganate added from the buret and therefore a higher number of moles of

permanganate. As seen from the calculations (Figure 8), if the moles of permanganate added

were actually less than what was recorded, the error of leaving some permanganate could result

in a lower oxidation state and therefore some error.

 2. Give the five balanced equations for the reaction of zinc and pervanadyl ion (VO2+) and

the oxidation states of vanadium species with permanganate.

(Reduction by Zinc Calculation)

1. Oxidation Reaction (Unbalanced): VO2++3e-⇌V2+ (oxygens are not balanced)

a. Balanced Oxidation Half-Reaction: VO2++4H++3e-⇌V2++2H2O (oxygens are

balanced by adding water on right side)

2. Reduction Half-Reaction: Zn⇌Zn2++2e-

3. Combining reactions: 2(VO2++4H++3e-⇌VO2++2H2O) + 3(Zn⇌Zn2++2e-) [Coefficients are

to balance electrons]

a. 2VO2++8H++3Zn+6e-⇌2V2++4H2O+3Zn2++6e-

i. 2VO2++8H++Zn⇌2V2++Zn2++4H2O

Reduction by Zinc (Balanced): 2VO2++8H++Zn⇌2V2++Zn2++4H2O

(Oxidation by Permanganate Calculation)

1. Oxidation Reaction (Unbalanced): V2+⇌VO2++3e-

a. Balanced Oxidation Half-Reaction: V2++2H2O⇌VO2++4H++3e- (oxygens are

balanced by adding water on the left side)

2. Reduction Half-Reaction: MnO4-+8H++5e-⇌Mn2++4H2O

3. Combining reactions: 5(V2++2H2O⇌VO2++4H++3e-) + 3(MnO4-+8H++5e-⇌Mn2++4H2O)

a. 5V2++10H2O+3MnO4-+24H++15e-⇌5VO2++20H++3Mn2++12H2O+ 15e-

i. 5V2++3MnO4-+4H+⇌5VO2++3Mn2++2H2O

Oxidation by Permanganate (Balanced): 5V2++3MnO4-+4H+⇌5VO2++3Mn2++2H2O

 3. Why does it not affect the titration results when the zinc-reduced vanadium is added to a

large quantity of vanadium stock solution before titration with permanganate?

The titration results are not affected when the vanadium stock solution is added because it

is the reduced vanadium (oxidation state of 2+) that reacts with the permanganate. The stock

solution vanadium has an oxidation state of 5+, and the oxidation state cannot go any higher than

5+. As a result, the titration results are not affected as the stock solution does not react with the

permanganate thereby ensuring that only the 2+ reaction will react with the permanganate while

protecting the unstable 2+ solution from oxidation by oxygen in the surrounding area.

4. What would be the effect on the results if a few granules of zinc fell into the vanadium

stock solution before titration with permanganate?

If a few granules of zinc fell into the vanadium stock solution before titration with

permanganate, then the zinc could start to reduce the vanadium stock solution before titration.

This will result in more 2+ vanadium solution, and will thereby result in more permanganate

needed to reach the endpoint color of yellow-orange. This means that, if more permanganate is

used, then it will be calculated as though more number of moles of permanganate were used.

This will result in a calculated oxidation state that is lower than the actual oxidation state as a

result of this error.

Calculations Section

Figure 6. Calculation of Molarity of Vanadium Stock Solution

Figure 7. Calculation of Moles of Vanadium Used and Moles of Permanganate Used

Figure 8. Calculation of Moles of Electrons and Oxidation State of Aurora Blue (Reduced

Vanadium) Solution

Acknowledgements

I would like to sincerely thank Professor Dubé for her assistance and patience, especially

due to the difficulty I had while determining the endpoint color of the solution. I would also like

to thank my lab TA Natalie Davis for answering any questions during lab and checking over my

notebook and work, along with my lab partners Abe Hoffman and Asif Islam for sticking with

me and working cohesively with me to execute the lab and cleaning up thoroughly. Finally, I

would like to thank the other lab TAs Meg Haberle, Alden Harring, and Charles Quinn for their

tireless and extremely helpful assistance during the lab help sessions.
 Works Cited

Department of Chemistry and Biochemistry, Middlebury College. Advanced General Chemistry

Laboratory Manual, Fourth Edition (CHEM 107); Academx Publishing Services, Inc:

Sagamore Beach, MA, 2019.