G.

De Vera

Post Lab Discussion

SELECTED REDOX REACTIONS

DATA AND RESULTS

A. Na2C2O4 + KMnO4 (Neutral Media)
-

Slight / complete decolorization of permanganate solution with BROWN precipitate

Redn: 3e- + 2H2O + MnO4- MnO2(s) + 4OHOxidn: 4OH- + C2O42- 2CO32- + 2H2O + 2e4OH- + 2MnO4- + 3C2O42- 2MnO2(s) + 6CO32- + 2H2O

DATA AND RESULTS

B. Na2C2O4 + KMnO4 (Acidic Media)
-

Formation of colorless to faint pink due to Mn2+ (evolution of gas may be observed)

Redn: 5e- +8H+ + MnO4- Mn2+ + 4H2O Oxidn: C2O42- 2CO2 + 2e-___________ 16H+ + 2MnO4- + 5C2O42- 2Mn2+ + 10CO2 + 8H2O

DATA AND RESULTS

C. Na2C2O4 + KMnO4 (Basic Media)
-

Formation of emerald-green solution due to MnO42-

Redn: e- + MnO4- MnO42Oxidn: 4OH- + C2O42- 2CO32- + 2H2O +2 e4OH- + 2MnO4- + C2O42- 2MnO42- + 2CO32- + 2H2O

DATA AND RESULTS

D. FeCl3 + KSCN - Formation of blood red solution (Fe3+ + SCN- FeSCN2+) E. FeSCN2+ + Zn(s) - Decrease in the color intensity of FeSCN2+ (blood-red) solution. (Dissolution of some Zn metal) Redn: e- + FeSCN2+ Fe2+ + SCNOxidn: Zn(s) Zn2+ + 2eZn(s) + 2 FeSCN2+ Zn2+ + 2Fe2+ + 2SCN-

DATA AND RESULTS

F. FeCl3 + K4Fe(CN)6 - Formation of Prussian-blue ppt - 4Fe3+ + 3[Fe(CN)6]4- Fe4[Fe(CN)6]3(s) G. Fe4[Fe(CN)6]3(s) + Zn - Decrease in the amount of Prussian-blue ppt Redn: 4e- + Fe4[Fe(CN)6]3(s) 4Fe2+ + 3[Fe(CN)6]4Oxidn: Zn(s) Zn2+ + 2e2Zn(s) + Fe4[Fe(CN)6]3(s) 2Zn2+ + 4Fe2+ + 3[Fe(CN)6]4-

DATA AND RESULTS

G. Fe4[Fe(CN)6]3(s) + Zn
-

A white ppt may be observed due to the reaction of Zn2+ with [Fe(CN)6]4-

Redn: 4e- + Fe4[Fe(CN)6]3(s) 4Fe2+ + 3[Fe(CN)6]4Oxidn: Zn(s) + 2[Fe(CN)6]4- Zn4[Fe(CN)6]2(s) + 8e4Zn(s) + 2Fe4[Fe(CN)6]3(s) Zn4[Fe(CN)6]2(s) + 8Fe2+ + 4[Fe(CN)6]4-

ANSWERS TO QUESTIONS
1. Oxidation of [Co(NH3)6]2+ to [Co(NH3)6]3+ with H2O2 as RA Oxidn: [Co(NH3)6]2+ [Co(NH3)6]3+ + eRedn: 2e- + H2O2 2OH2[Co(NH3)6]2+ + H2O2 [Co(NH3)6]3+ + 2OH-

ANSWERS TO QUESTIONS
2. Balanced RedOx reactions: a. 6K3Fe(CN)6 + Cr2O3 + 10KOH 2K2CrO4 + 6 K4Fe(CN)6 + 5H2O b. 2Cu(NH3)4Cl2 + 7 KCN + H2O 2K2Cu(CN)3 + KCNO + 6NH3 + 2NH4Cl + 2 KCl c. CoCl2 + 7KNO2 + 2HCl K3Co(NO2)6 + NO +H2O + 4 KCl d. 2[Cr(Cl)6]3- + Zn 2Cr2+ + [ZnCl4]2- + 8Cl-

ANSWERS TO QUESTIONS
3. E0cell = E0red + E0oxid

a. Water oxidation:
2 H2O(l) O2(g) + 4H+ (10-7M) + 4eEoxid = -0.815V

E0cell = E0red + E0oxid > 0

* E0red > -E0oxid > 0.815 V

- All Co3+ species with E0red value greater than 0.815 V can oxidize water. b. Water reduction
2H2O(l) + 2e- H2(g) + 2OH-Only Co(CN)63- can reduce water. E0red = -0.828 V

ANSWERS TO QUESTIONS
5. Suppose oxalic acid was used instead of oxalate salt:

a. Equation: 6H+ + 2MnO4- + 5H2C2O4 2Mn2+ + 10CO2(g) + 8H2O

b. Physical / Chemical changes: -Decolorization of purple solution (formation of colorless to faint pink solution) c. How one could make the reaction at a reasonably rapid speed? - Addition of MnSO4 may catalyze the reaction (recall autocatalysis experiment)

ANSWER TO QUESTIONS
6. Consider Part B and Part C of the experiment: a. Role of Zn reducing agent b. Reagents that can replace Zn: Any metal above Zn in the activity series

LATIMER AND FROST DIAGRAMS

convenient sources of understanding complex redox chemistry of any element in its various oxidation states

LATIMER AND FROST DIAGRAMS

Example of a Latimer Diagram

LATIMER AND FROST DIAGRAMS

LATIMER DIAGRAMS
a. From L to R, the species of the element towards right are in LOWER oxidation state. b. The std electrode potential value for the redn half rxn involving any pair of the species joined by an arrow is shown above the arrow. c. For generation of E0 value for a combination of processes:

d. Separate diagrams for different media.

LATIMER DIAGRAMS

Latimer Diagram for Fe

LATIMER DIAGRAM
Exercise: Draw a Latimer Diagram for copper

LATIMER DIAGRAM

LATIMER DIAGRAM

LATIMER DIAGRAM

LATIMER DIAGRAM

FROST DIAGRAMS

FROST DIAGRAM

FROST DIAGRAM
Exercise: Draw a Frost Diagram for Cu.

FROST DIAGRAM

FROST DIAGRAM
a. Oxidation state increases from L R b. Slope of the line joining 2 pts = Std Potential value of the couple formed by the 2 species c. *steeper line corresponds to higher potential and more spontaneity:

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM

FROST DIAGRAM
Identify the following: a. Strongest oxidizing agent b. Strongest reducing agent c. Unstable towards disproportionation d. Tends to form via comproportionation e. Most stable Cr species

QUIZ
Construct a Frost diagram for titanium in acidic, aqueous solution from the data on the Latimer diagram.

a. Which is the most stable form of titanium under these conditions? b. Does any species on the diagram disproportionate under these conditions? If so, what are the products of its disproportionation? c. Calculate the standard reduction potential for the half reaction:

QUIZ