SELECTED REDOX REACTIONS

R. J. V. CUERQUIS
DEPARTMENT OF MINING, METALLURGICAL AND MATERIALS ENGINEERING, COLLEGE OF ENGINEERING UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES MAY 15, 2013 MARO PEA

RESULTS AND DISCUSSION A redox reaction occurs if the reactants undergo a change in oxidation number. Reduction describes a decrease in oxidation number resulting from the gain of electrons while oxidation is an increase in the oxidation number as a result of electron loss. In this experiment, three redox reactions involving simple compounds as well as complexes were investigated. Reaction Between Sodium Sulfite and Potassium Permanganate in Different Media In this part of the experiment, the reaction between sodium sulfite and potassium permanganate were observed in different media, particularly with varying hydrogen ion concentration. MnO4-, which is purple in color, is a strong oxidizing agent. It yields a variety of reduction products depending on the medium in which its reduction took place. Some of these products include Mn2+, MnO42-, and solid MnO2. In this system, SO32- served as the reducing agent. Its activity is strongly dependent on the hydrogen ion concentration. If made basic, its power as a reducing agent increases. As a reducing agent, it is oxidized into colorless SO42-. The reaction between the two was first carried out in a neutral medium. A dark brown precipitate was observed in this

reaction which indicated the reduction of MnO4- to solid MnO2. The overall redox equation for this reaction is: Re: 2[3e- + 2H2O(l) + MnO4-(aq) MnO2(s) +4OH-(aq)] (1) 2Ox: 3[2OH (aq) + SO3 (aq) SO42-(aq) + H2O(l) + 2e-] (2) Net: H2O(l) + 2MnO4-(aq) 3SO32-(aq) 3SO42-(aq) + 2MnO2(s) + 2OH-(aq) (3) Another reaction was carried out in an acidic medium. This was done by acidifying the sulfite solution with excess H2SO4 before adding the permanganate solution. A colorless solution was then observed, indicating the reduction of MnO4- to Mn2+. The Mn2+ is actually pale pink in color but is almost colorless in very dilute solutions. The overall redox equation for this reaction is: Re: 2[5e- + 8H+(aq) + MnO4-(aq) Mn2+(aq) +4H2O(l)] (4) 2Ox: 5[H2O(l) + SO3 (aq) SO42-(aq) + 2H+(aq) + 2e-] (5) Net: 6H+(aq) + 2 MnO4-(aq) + 5SO32-(aq) 5 SO42-(aq) + 2Mn2+(aq) + 3H2O(l) (6) Lastly, the reaction was carried out in a basic medium. This was done by adding excess NaOH to the sulfite solution before adding the permanganate solution. Right after the addition of KMnO4, a green solution was observed, indicating the reduction of MnO4- to MnO42-. After some time, the green solution turned murky brown. The overall redox equation for this reaction is:

Re: 2[e- + MnO4-(aq) MnO42-(aq)] (7) Ox: 2OH-(aq) + SO32-(aq) SO42-(aq) + H2O(l) + 2e- (8) Net: 2OH-(aq) + 2MnO4-(aq) + SO32-(aq) SO42-(aq) + 2MnO42-(aq) + H2O(l) (9) Reaction of Ferric Chloride + Potassium Thiocyanate with Zinc The system investigated here is the reaction between Fe3+ and SCN- producing the bloodred thiocyanatoiron(III) complex , FeSCN2+. Fe3+(aq) + SCN-(aq) FeSCN2+(aq) (10)

With the addition of Zinc dust into the Prussian blue solution, a decrease in the amount of Prussian blue precipitate was observed. It has also been accompanied by the dissolution of zinc metal. Again, basing on the activity series of metals, zinc is a more reactive metal than iron so it has the capability to displace the iron from the complex. Zinc served as a reducing agent in this reaction. The Fe3+ in the complex was reduced to Fe2+ and zinc metal was oxidized to Zn2+. The overall redox equation for this reaction is: Re: 4e- + Fe4[Fe(CN)6]3(s) 4Fe2+(aq) + 3[Fe(CN)6]4-(aq) (14) Ox: 2[Zn(s) Zn2+(aq) + 2e-] (11) Net: 2Zn(s) + Fe4[Fe(CN)6]3(s) 4Fe2+(aq) + 3[Fe(CN)6]4-(aq) + 2Zn2+(aq) (15) CONCLUSION AND RECOMMENDATION In this experiment, three redox reactions involving simple compounds as well as complexes were investigated: (1) reaction between sodium sulfite and potassium permanganate in different media; (2) reaction of ferric chloride and potassium thiocyanate with zinc; and (3) reaction of ferric chloride and potassium ferrocyanide with zinc. The first system demonstrated how MnO4yields a variety of reduction products depending on the medium in which its reduction took place, coupled with the oxidation of SO32- to SO42-. In neutral medium, MnO4- was reduced to the brown MnO2 solid; in acidic medium, the MnO4- was reduced to the colorless Mn2+; and in basic medium, it was reduced to the green MnO42-. The last two systems involved the redox reaction of iron complexes. Zinc reduced Fe3+ from both complexes to Fe2+. This shows that zinc has a much stronger reducing property compared to iron.

With the addition of zinc dust into the bloodred solution, there has been a decrease in the color intensity of FeSCN2+ solution, from redblood to grayish-green solution. It has also been accompanied by the dissolution of solid zinc. Zinc is a more reactive metal than iron basing on the activity series of metals. Therefore, it has the capability to displace iron from the complex. Zinc served as a reducing agent in this reaction. The Fe3+ ion in the complex was reduced to Fe2+ and solid zinc was oxidized to Zn2+. The overall redox equation for this reaction is: Re: 2[e- + FeSCN2+(aq) Fe2+(aq) + SCN-(aq)] (10) Ox: Zn(s) Zn2+(aq) + 2e(11) Net: 2 FeSCN2+(aq) + Zn(s) 2Fe2+(aq) + Zn2+(aq) + 2SCN-(aq) (12)

Reaction of Ferric Chloride + Potassium Ferrocyanide with Zinc The system under observation here is the reaction between Fe3+ and [Fe(CN)6]4- ions to produce the Prussian blue Fe4[Fe(CN)6]3 precipitate. 4Fe3+(aq) + 3[Fe(CN)6]4-(aq) Fe4[Fe(CN)6]3(s) (13)

The following recommendations can be used to extend the experiment: 1. the use of oxalate or other reducing agents aside from sulfite in the reduction of permanganate; 2. the use of other metals with higher reducing property than zinc in the redox reactions of complexes.