Prepared by: ENGR. RENA P.

MORA 1
Oxidation-Reduction Methods

Model 1: Theory

• Oxidation-reduction methods of analysis involve a change in valence of the reacting substances.

• When one substance is oxidized, some other substance must be correspondingly reduced, and, conversely,
when one substance is reduced, some other substance must be correspondingly oxidized.
• Faraday’s law: A change in charge of one is equivalent to the gain or loss of 96,500 C of electricity for each
formula weight of element or group of elements involved.
• Since in every oxidation-reduction reaction the charge lost or gained by one substance must necessarily be
gained or lost by another, it follows that there is always a transfer of electrons in oxidation-reduction reactions.
• The reactant which loses electrons in an oxidation-reduction reaction is the reducing agent and can be
identified in the equation for the reaction as the reactant containing a constituent atom or atoms converted to a higher
state of oxidation, e.g.,
𝐹𝑒 2+ → 𝐹𝑒 3+ + 𝑒
2𝐼 − → 𝐼2 + 2𝑒
• The electrons lost by the reducing agent are gained by the oxidizing agent, the reactant containing a
constituent atom or atoms which are converted to a lower state of oxidation, e.g.,
𝐶𝑒 4+ + 𝑒 → 𝐶𝑒 3+
𝐹𝑒 3+ + 𝑒 → 𝐹𝑒 2+
• The equivalent weight of a reducing agent is that weight which loses electrons equivalent to 96,500 C, and it
can be calculated by dividing the gram-molecular weight by the number of electrons lost by each molecule; e.g., the
equivalent weight of ferrous sulfate oxidized to ferric sulfate, Fe 2+  Fe3+ + e, is 151.91 g.
• An equivalent weight of an oxidizing agent is that weight which gains electrons equivalent to 1 faraday, or to
the electrons gained by 1 gram-ion of hydrogen ions, 2H+ + 2e  H2. It can be calculated by dividing the gram-molecular
weight by the number of electrons gained by each molecule: e.g., the equivalent weight of ceric sulfate, Ce 4+ + e Ce3+ is
332.24 g, and that of potassium permanganate, MnO4- + 5eMn2+, is 1/5 gram-molecular weight or 31.61 g.
• The oxidation number of Mn in KMnO4 is:
▪ Oxidation state of potassium ion is always 1+
▪ Oxidation state of oxygen ion is always 2- except for peroxide, O22-, which is 1-.
▪ Since KMnO4 is neutral compound (no charge in the chemical formula), sum of all oxidation
states of elements in the formula must equal to 0. Therefore, the oxidation number of Mn in
KMnO4 is
+1 (K) + x (Mn) + (4 x 2-) = 0
x = 7+

Study Guide Questions

1. What is a reducing agent? An oxidizing agent?
2. What is an oxidation-reduction method of analysis?
3. Ferrous sulfate is an oxidizing agent.
4. What is the oxidation number of S in Na2S2O3?

Model 2: Standard Solutions (Oxidizing Agents)

• Ferric ammonium sulfate

• Potassium permanganate
o Permanganate ion  manganous ion
MnO4- + 5e  Mn2+
o 1 equivalent = 158.03/5 = 31.61 g
• Potassium dichromate
o Dichromate ion  chromous ion
o Cr2O72- + 6e  2Cr3+
o 1 equivalent = 294.18/6 = 49.03 g
• Potassium bromate
o Bromate ion  bromide ion
o BrO3- + 6e  Br-
o 1 equivalent = 167.01/6 = 27.83 g
• Potassium iodate
• Potassium ferricyanide
 Prepared by: ENGR. RENA P. MORA 2
Oxidation-Reduction Methods

• Ceric sulfate
o Ceric ion  cerous ion
o Ce4+ + e  Ce3+
o 1 equivalent = 332.24/1 = 332.24 g
• Iodine
o Iodine  iodide ion
o I2 + 2e  2I-
o 1 equivalent = 253.80/2 = 126.90 g
• Bromine

Study Guide Questions

5. What are the standard solutions used as oxidizing agent?
6. T or F: One mole of dichromate ions gains a total of 6 electrons when converted to chromous ion.

Model 3: Standard Solutions (Reducing Agents)

• Ferrous ammonium sulfate

o Ferrous ion  ferric ion
o Fe2+  Fe3+ + 1e
o 1 equivalent = 392.14 g
• Oxalic acid
o Oxalate ion  carbon dioxide
o C2O42-  2CO2 + 2e
o 1 equivalent = 126.07/2 = 63.035 g
• Potassium arsenite
o Arsenite ion  arsenate ion
o AsO2- + H2O  AsO3- + 2H+ + 2e
o 1 equivalent = 49.46 g
• Titanium trichloride
o Titanous ion  titanic ion
o Ti3+  Ti4+ + 1e
o 1 equivalent = 154.26 g
• Sodium thiosulfate
o Thiosulfate ion  tetrathionate ion
o 2S2O32-  S4O62- + 2e
o 1 equivalent = 248.17 g

Study Guide Questions

7. What are the standard solutions used as reducing agent?
8. What is the gram-equivalent weight of sodium oxalate (134)? Hint: See above for the number of electrons lost or
gained for oxalate ion. Then divide the molecular weight of sodium oxalate to number of electrons lost or gained.
Answer: 67.

Model 4: Permanganate Methods

• Potassium permanganate solution can be standardized easily, and it retains its concentration over long
periods of time when proper precautions are observed in its preparation and preservation. It also serves as an indicator in
titrations where it is used, since a very slight excess of permanganate imparts to solutions a distinct pink color.
• Standardization of Potassium Permanganate
o Sodium oxalate is the best standard to use in the standardization of potassium permanganate.
o To calculate the normality of KMnO4 solution
1000 𝑥 𝑊
𝑁=
𝑉 𝑥 67.00
Where W = weight of sodium oxalate sample in grams
V = volume of KMnO4 solution used in milliliters
 Prepared by: ENGR. RENA P. MORA 3
Oxidation-Reduction Methods

Study Guide Questions

9. What is the indicator used in standardization of potassium permanganate?
10. What is the standard used in standardization of potassium permanganate?
11. A 0.2295-g sample of sodium oxalate (97.8% Na2C2O4) required 35.12 ml of a potassium permanganate solution in
a titration. What was the normality of the permanganate solution? Hint: Find first the weight of sodium oxalate in
the sample then apply the above formula. Answer: 0.0954 N

Model 5: Direct Titration Methods

• Assay of Hydrogen Peroxide Solution

o Standard – Potassium permanganate
o Indicator – Potassium permanganate
o Each milliliter of 0.1 N potassium permanganate is equivalent to 1.701 mg of H2O2
o To comply with U.S.P. definition, a solution of hydrogen peroxide should contain not less than 2.5 g
and not more than 3.5 g of H2O2 per 100 ml.

Model 5: Indirect Titration Methods

• The indirect method of permanganate oxidation is employed with those compounds that can be converted
through chemical reactions to an equivalent amount of oxalate, which in turn can then be quantitatively
oxidized by permanganate. In the assay for the malic acid content of cherry juice the malic acid is converted to
an equivalent amount of calcium salt, which is converted to insoluble calcium oxalate; the oxalate is then
liberated and oxidized with permanganate.
• Assay of Cherry Juice for Malic Acid
o Standard – Potassium permanganate
o Indicator – Potassium permanganate
o Each milliliter of 0.1 N potassium permanganate is equivalent to 6.704 mg of C4H6O5
• Assay of Manganese Dioxide, Precipitated
o Standard – Potassium permanganate
o Indicator – Potassium permanganate
• Assay of Titanium Dioxide
o Standard – Potassium permanganate
o Indicator – Potassium permanganate

Study Guide Questions

12. What are the substances that can be assayed by using indirect permanganate oxidation method?

Model 6: Residual Titration Methods

• The residual titrations in the official assays with potassium permanganate solutions are of two types, viz.: (1)
titration in which an excess of standard potassium permanganate solution is employed to oxidize a substance,
and the amount in excess is determined by reduction with (a) excess standard oxalic acid or (b) excess ferrous
ammonium sulfate and back titration with more standard potassium permanganate; (2) titration in which an
excess of standard oxalic acid solution is added to the substance and the excess oxalic acid is titrated with
standard potassium permanganate.
• Standard solution – Oxalic acid
o Oxalic acid reduces potassium permanganate and neutralizes sodium hydroxide.
• Assay of Sodium Nitrite
o Standard solution – Potassium permanganate and oxalic acid
o Indicator - Potassium permanganate
o Each milliliter of 0.1 N potassium permanganate is equivalent to 3.450 mg of NaNO2

Study Guide Questions

13. What is the most effective chemical substance in removing stains of potassium permanganate?

Model 7: Ceric Sulfate Titration Methods

 Prepared by: ENGR. RENA P. MORA 4
Oxidation-Reduction Methods

• Standard solution – Ceric sulfate (Standardization)

o Standard – Arsenic trioxide
o Indicator – Orthopenanthroline TS
o Calculation for the normality of ceric sulfate solution:
𝑤𝑡 𝑜𝑓 𝑎𝑟𝑠𝑒𝑛𝑖𝑐 𝑡𝑟𝑖𝑜𝑥𝑖𝑑𝑒
𝑁= 𝑚𝑙 𝑥 0.04946
• Indicator is Orthophenanthroline TS
• The base orthophenanthroline dissolves readily in aqueous solutions of ferrous salts, three molecules
combining with one ferrous ion to form complex ions (Ferrous phenanthroline), known as ferroin, which have
an intensely red color.
• Assay of Ferrous Sulfate Tablets
o Standard – Ceric sulfate
o Indicator – Orthopenanthroline TS
o Each milliliter of 0.1 N ceric sulfate is equivalent to 27.80 mg of FeSO4.7H2O
• Assay of Ascorbic Acid

Study Guide Questions

14. What is another name of ferroin?
15. What is the standard used in standardization of ceric sulfate?