Redox Methods

Oxidimetry and Reductimetry

• Titration of an oxidizing agent with a standard
solution of a reducing agent or the titration of a
reducing agent with a standard solution of an
oxidizing agent

• Oxidation – the increase in the positive direction

of the electrical valence or oxidation number of
an element or radical

• Reduction – the decrease in electrical valence or

oxidation number of an element or radical
• To find the equivalent weight of an oxidizing or
reducing agent, take that fraction of its formula
weight so that in the oxidation or reduction
process there will be involved the equivalent of a
transfer of one electron
– By dividing the formula weight of the substance by the
total change in oxidation number involved in the
oxidation-reduction process
– By dividing the formula weight of the substance by the
number of electrons transferred per formula weight of
substance
• mL x N = number of gram-milliequivalents
• mLs x Ns x meq wt.x = gramsx

• How many grams of the following reducing

substances constitute the gram-equivalent weight
in each case:
– FeSO42H2O : Fe2+  Fe3+ + e-
– SnCl2 : Sn2+  Sn4+ + 2e-
– H2C2O42H2O :
• C2O4=  2CO2 + 2e-
• 5C2O4= + 2MnO4- + 16H+  10CO2 + 2Mn2+ + 8H2O
– KHC2O4H2O
– KHC2O4 H2C2O42H2O
– H2S (oxidized to S) and (oxidized to H2SO4)
– Na2S2O35H2O
• 2S2O3=  S4O6= + 2e-
• 2S2O3= + I2  S4O6= + 2I-
– H2O2
• 5H2O2 + 2MnO4- + 6H+  5O2 + 2Mn2+ + 8H2O
• How many grams of the following oxidizing substances
constitute the gram-milliequivalent weight in each case:
– K3Fe(CN)6
• Fe(CN)63- + e-  Fe(CN)64-
– KMnO4
• MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
• MnO4- + 5Fe2+ + 8H+  Mn2+ + 4H2O + 5Fe3+
• In alkaline solution, MnO4- + 8H2O + 3e-  MnO2 + 4OH-
– K2Cr2O7
• Cr2O7= + 14H+ + 6e-  2Cr3+ + 7H2O
• Cr2O7= + 6Fe2+ + 14H+  2Cr3+ + 7H2O + 6Fe3+
– I2
• I2 + 2e-  2I-
– KBrO3 (reduced to bromide)
• BrO3- + 6H+ + 6e-  Br- + 3H2O
– H2O2
• H2O2 + 2H+ + 2e-  2H2O
 Permanganate process
• Potassium permanganate is extensively used
as an oxidimetric standard.
• It serves as its own indicator
• A normal solution contains 1/5 the gram
molecular weight per liter if used in the
presence of acid.
• What is the percentage of iron in a sample of
iron ore weighing 0.7100 g if, after solution
and reduction of the iron with amalgamated
zinc, 48.06 mL of KMnO4 (1.000 mL =
0.006700 g Na2C2O4) is required to oxidize the
iron? How many grams of KMnO4 are
contained in each milliliter of the solution?
 Dichromate process
• Oxidizing substances can be determined by
the dichromate process by the addition of a
measured excess of a ferrous salt and the
titration of the excess with the standard
solution.
• What is the percentage of Fe2O3 in a sample of
limonite ore if the iron from a 0.5000-g
sample is reduced and titrated with 35.15 ml
of a potassium dichromate solution of which
15.00 mL is equivalent in oxidizing power to
25.00 mL of a potassium permanganate
solution which has an iron value of 0.004750
g?
 Ceric Sulfate or Cerate process
• Cerium in the 4-valent state is a very powerful oxidizing
agent, the yellow ceric or complex cerate ions being
reduced to colorless 3-valent cerous ions, Ce4+ + e- 
Ce3+

• What weight of limonite should be taken so that after

solution in HCl and reduction of the iron, the volume of
standard ceric solution required for titration will be
one half the percentage of Fe2O3 in the sample (6.000
mL of the ceric solution = 2.000 mL KHC2O4 solution =
3.000 ml of 0.08000 N NaOH)?