Redox Titration

Prepared by:
Engr. John Kristoffer S. Robleza
A. Equivalent Weights of Oxidizing and
Reducing Agents
To find the equivalent weight of an oxidizing or reducing agent we must, therefore,
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. This will be
accomplished (1) by dividing the formula weight of the substance by the total
change in oxidation number involved in the oxidation-reduction process, or (2) by
dividing the formula weight of the substance by the number of electrons
transferred per formula weight of substance.
How many grams of the following reducing substances constitute the gram
equivalent weight in each case:
(a) FeSO4.7H2O
(b) SnCl2
(c) H2C2O4.2H2O (oxalic acid)
(d) KHC2O4.H2O (potassium binoxalate)
(e) KHC2O4.H2C2O4.2H2O (potassium tetroxalate)
(f) H2S (oxidized to S)
(g) H2S (oxidized to H2SO4)
(h) Na2S2O3.5H2O (oxidized to Na2S4O6)
(i) H2O2
reducing substances – oxidation process takes place
(a) FeSO4.7H2O
Fe2+ (+2) → Fe3+ (+3) + e- f=1
277.85 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 277.85 𝑔/𝑒𝑞
1 𝑒𝑞/𝑚𝑜𝑙

(b) SnCl2
Sn2+ (+2) → Sn4+ (+4) + 2e- f=2
189.9 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 94.95 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙

(c) H2C2O4.2H2O
C2O42- (C+3) → 2CO2 (C+4) + 2e- f=2
126 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 63 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙
(d) KHC2O4.H2O
C2O42- (C+3) → 2CO2 (C+4) + 2e- f=2
146 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 73 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙

(e) KHC2O4.H2C2O4.2H2O
2C2O4-2 → 4CO2 + 4e- f=4
254 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 63.5 𝑔/𝑒𝑞
4 𝑒𝑞/𝑚𝑜𝑙

(f) H2S (oxidized to S)

S2- (–2) → S0 (0) + 2e- f=2
34 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 17 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙
(g) H2S (oxidized to H2SO4)
S2- (–2) → S6+ (+6) + 8e- f=8
34 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 4.25 𝑔/𝑒𝑞
8 𝑒𝑞/𝑚𝑜𝑙

(h) Na2S2O3.5H2O (oxidized to Na2S4O6)

2S2O32- (+ 2) → S4O62- (+2.5) + 1e- f=1
248 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 248 𝑔/𝑒𝑞
1 𝑒𝑞/𝑚𝑜𝑙

(i) H2O2 (as a reducing agent, oxidizes to free O)

H2O2 (–1) → O20 (0) + 2e- f=2
34 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 17 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙
How many grams of the following oxidizing substances constitute the gram
equivalent weight in each case:
(a) K3Fe(CN)6 (d) I2
(b) KMnO4 (e) K2Cr2O7
(c) KBrO3 (reduced to bromide) (f) H2O2

oxidizing substances – reduction process takes place

(a) K3Fe(CN)6
Fe(CN)63- (Fe+3) + 1e- → Fe(CN)64- (Fe+2) f=1
328.85 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 328.85 𝑔/𝑒𝑞
1 𝑒𝑞/𝑚𝑜𝑙
(b) KMnO4
** when reduced in the presence of an acid, permanganate forms
manganous ions
MnO4–1 (+7) + 5e- → Mn2+ (+2) f=5
158 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 31.6 𝑔/𝑒𝑞
5 𝑒𝑞/𝑚𝑜𝑙

** in alkaline solution, permanganate is reduced to MnO2

MnO4–1 (+7) + 3e- → Mn2+ (+4) f=3
158 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 52.6667 𝑔/𝑒𝑞
3 𝑒𝑞/𝑚𝑜𝑙
(c) KBrO3 (reduced to bromide)
KBrO3 (+5) + 6e- → Br- (–1) f=6
167 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 27.8333 𝑔/𝑒𝑞
6 𝑒𝑞/𝑚𝑜𝑙
(d) I2
I2 (0) + 2e- → 2I- (–1) f=2
254 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 127 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙

(e) K2Cr2O7
Cr2O72- (+6) + 6e- → 2Cr3+ (+3) f=6
294 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 49 𝑔/𝑒𝑞
6 𝑒𝑞/𝑚𝑜𝑙
(f) H2O2 (as an oxidizing agent, reduce to H2O)
H2O2 (–1) + 2e- → H2O (–2) f=2
34 𝑔/𝑚𝑜𝑙
𝑒𝑞 𝑤𝑡 = = 17 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙
B. Calculations of Oxidation and Reduction
Processes
1. A ferrous solution contains 1.176 g of FeSO4.(NH4)2 SO4.6H2O (ammonium ferrous
sulfate)in 30.00 mL; a dichromate solution contains 0.2940 g of K2Cr2O7 in 20.00
mL. Find (a) the normality of the ferrous solution as a reducing agent, (b) the
normality of the dichromate solution as an oxidizing agent, (c) the volume of the
dichromate equivalent to 1.000 mL of the ferrous solution.

1.176 𝑔
𝑁𝐹𝑒𝑆𝑂4 ∙ 𝑁𝐻4 2 𝑆𝑂4 ∙6𝐻2 𝑂 = = 0.1000 𝑒𝑞/𝐿
392.1308 𝑔/𝑚𝑜𝑙 30 𝑚𝐿
×
1 𝑒𝑞/𝑚𝑜𝑙 1000 𝑚𝐿/𝐿
0.2940 𝑔
𝑁𝐾2 𝐶𝑟2 𝑂7 = = 0.3000 𝑒𝑞/𝐿
294 𝑔/𝑚𝑜𝑙 20 𝑚𝐿
×
6 𝑒𝑞/𝑚𝑜𝑙 1000 𝑚𝐿/𝐿
 𝑚𝑒𝑞𝑜.𝑎. = 𝑚𝑒𝑞𝑟.𝑎
𝑚𝑒𝑞𝐾2 𝐶𝑟2 𝑂7 = 𝑚𝑒𝑞𝐹𝑒𝑆𝑂4∙ 𝑁𝐻4 2 𝑆𝑂4 ∙6𝐻2 𝑂
𝑉𝐾2 𝐶𝑟2 𝑂7 𝑁𝐾2 𝐶𝑟2 𝑂7 = 𝑉𝐹𝑒𝑆𝑂4 ∙ 𝑁𝐻4 2 𝑆𝑂4∙6𝐻2 𝑂 𝑁𝐹𝑒𝑆𝑂4 ∙ 𝑁𝐻4 2 𝑆𝑂4 ∙6𝐻2 𝑂
0.1000 𝑁 1.0 𝑚𝐿
𝑉𝐾2 𝐶𝑟2 𝑂7 = = 0.3333 𝑚𝐿
0.3000 𝑁

2. From the following data, calculate the normality ratio of the HNO3 as an oxidizing
agent to the tetroxalate solution as a reducing agent (assuming reduction of HNO3
to NO):
1.000 mL of HNO3 ≈ 1.246 mL NaOH
1.000 mL KHC2O4.H2C2O4.2H2O ≈ 1.743 mL NaOH
1.000 mL NaOH ≈ 0.06000 mmol H2C2O4.2H2O
*consider acid-base titration
𝑚𝑒𝑞𝐻2 𝐶2 𝑂4 ∙2𝐻2 𝑂 = 𝑚𝑒𝑞𝑁𝑎𝑂𝐻
2 𝑚𝑒𝑞
0.0600 𝑚𝑚𝑜𝑙 ×
𝑁𝑁𝑎𝑂𝐻 = 𝑚𝑚𝑜𝑙 = 0.12 𝑚𝑒𝑞/𝑚𝐿
1.0 𝑚𝐿

𝑚𝑒𝑞𝐾𝐻𝐶2 𝑂4 ∙𝐻2 𝐶2 𝑂4 ∙2𝐻2 𝑂 = 𝑚𝑒𝑞𝑁𝑎𝑂𝐻

1.743 𝑚𝐿 0.12 𝑚𝑒𝑞/𝑚𝐿
𝑁𝐾𝐻𝐶2 𝑂4 ∙𝐻2 𝐶2 𝑂4∙2𝐻2 𝑂 = = 0.2092 𝑚𝑒𝑞/𝑚𝐿
1.0 𝑚𝐿

𝑚𝑒𝑞𝐻𝑁𝑂3 = 𝑚𝑒𝑞𝑁𝑎𝑂𝐻
1.246 𝑚𝐿 0.12 𝑚𝑒𝑞/𝑚𝐿
𝑁𝐻𝑁𝑂3 = = 0.1492 𝑚𝑒𝑞/𝑚𝐿
1.0 𝑚𝐿
*consider redox titration
Oxidation of potassium tetroxalate
2C2O4-2 (C +3) → 4CO2 (C +4) + 4e- f = 4 (as reducing agent)
𝑓𝑟.𝑎.
𝑁𝑟.𝑎. = 𝑁𝑎𝑐𝑖𝑑 ×
𝑓𝑎𝑐𝑖𝑑
𝑚𝑒𝑞 4 𝑚𝑒𝑞
𝑁𝑟.𝑎. = 0.2092 × = 0.2789
𝑚𝐿 3 𝑚𝐿
Reduction of nitric acid
NO3-1 (N +5) + 3e- → NO (N +2) f=3 (as oxidizing agent)
𝑓𝑜.𝑎.
𝑁𝑜.𝑎. = 𝑁𝑎𝑐𝑖𝑑 ×
𝑓𝑎𝑐𝑖𝑑
𝑚𝑒𝑞 3 𝑚𝑒𝑞
𝑁𝑜.𝑎. = 0.1492 × = 0.4476
𝑚𝐿 1 𝑚𝐿
 𝑚𝑒𝑞
𝑁𝑜.𝑎. 0.4476 𝑚𝐿
= 𝑚𝑒𝑞 = 1.6049
𝑁𝑟.𝑎. 0.2789 𝑚𝐿
C. Oxidation with Potassium Permanganate
(Permanganate Process)
Potassium permanganate is a strong oxidant with an intense violet color. In strongly
acidic solutions , it is reduced to colorless .

𝑀𝑛𝑂4− + 8𝐻+ + 5𝑒 − ↔ 𝑀𝑛2+ + 4𝐻2 𝑂

(manganous ion)
In neutral or alkaline solution, the product is the brown solid, 𝑀𝑛𝑂2 .
𝑀𝑛𝑂4− + 4𝐻 + + 3𝑒 − ↔ 𝑀𝑛𝑂2 𝑠 + 2𝐻2 𝑂
(manganese dioxide)
In strongly alkaline solution (2 M NaOH), green manganate ion is produced.
𝑀𝑛𝑂4− + 𝑒 − ↔ 𝑀𝑛𝑂42−
(manganate ion)
For titrations in strongly acidic solution, KMnO4 serves as its own indicator because
the product, Mn2+, is colorless. The end point is taken as the first persistent
appearance of pale pink MnO4-. If the titrant is too dilute to be seen, an indicator
such as ferroin (orthophenanthroline) can be used.
3 ways to use KMnO4 solution:
a. It is used in the presence of acid in the direct titration of a large number of
oxidizable cations and anions

Substance Oxidized to Substance Oxidized to

Fe2+ Fe3+ H2O2 O2
Sn2+ Sn4+ Mo3+ MoO32–
VO2+ VO3– Ti3+ TiO2+
C2O42– CO2 U4+ UO22+
NO2– NO3– As3+ AsO43–
SO3 2– SO42–
b. It is used in the presence of acid in the indirect titration of a large number of
reducible substances. In each case a measured amount of a reducing agent (e.g., a
ferrous salt or an oxalate) is added, and, after reduction is complete, the excess
reducing agent is titrated with standard permanganate

Substance Reduced to
MnO4 – Mn2+
Cr2O72 – Cr3+
MnO2, Mn3O4 Mn2+
PbO2, Pb2O3, Pb3O4 Pb2+
Ce4+ Ce3+
c. It is used in neutral or alkaline solution in the titration of a very few substances.
In these cases, the permanganate is reduced to MnO2, which precipitates. The
permanganate, therefore, has an oxidizing power only three-fifths of what it has
when used in the presence of acid

Substance Oxidized to
Mn2+ MnO2
HCOOH (formic acid) CO2
PROBLEMS
1. What is the normality of a solution of potassium permanganate if 40.00 mL will
oxidize that weight of potassium tetroxalate, KHC2O4.H2C2O4.2H2O, which requires
30.00 mL of 0.5000 N sodium hydroxide solution for its neutralization, and what is
the value of 1.000 mL of the KMnO4 in terms of grams As2O3 in the titration of As3+
to H3AsO4 in the presence of acid?
2. 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) are required to oxidize the iron? How many grams
of KMnO4 are contained in each milliliter of the solution?
3. How many grams of H2O2 are contained in a solution that requires for titration
14.05 mL of KMnO4 of which 1.000 mL ≈ 0.008378 g Fe (i.e., will oxidize that
amount of iron from the divalent to the trivalent state)? How many grams and how
many milliliters of oxygen measured dry and under standard conditions are evolved
during the titration?
4. What is the percentage of MnO2 in a pyrolusite ore if a sample weighing 0.4000 g
is treated with 0.6000 g of pure H2C2O4.2H2O and dilute H2SO4 and after reduction
has taken place (MnO2 + H2C2O4 + 2H+ → Mn2+ + 2CO2 + 2H2O), the excess oxalic
acid requires 26.26 mL of 0.1000 N KMnO4 for titration? If pure As2O3 were used
instead of oxalic acid, how many grams would be required in order for the other
numerical data to remain the same?
5. What is the milliequivalent weight of Pb3O4 and of Pb in the calculation analysis
of red lead (impure Pb3O4) Pb3O4(s) + H2C2O4 + 3SO42- + 6H+ → 3Pb2+ + CO2 + 4H2O
6. A steel containing 0.90% Mn is analyzed by the three standard methods:
Bismuthate, Chlorate (Williams)and Volhard, in each case with a 2.50 g sample,
0.0833 N KMnO4 and 0.100 N FeSO4 solutions. Calculate the volume of KMnO4
required in each case.
7. What is the normality of KMnO4 solution in relation to its use in slightly alkaline
solution (i.e., when reduced to MnO2) if each mL will oxidize 0.1000 mmol As2O3 in
the presence of acid? How many mmols of K4Fe(CN)6 will each mL of the
permanganate oxidize (to ferricyanide) in the presence of acid?
8. A sample of pyrolusite weighing 0.6000 g is dissolved in a solution containing
5.00 mL of 6.00 N H2SO4 and 0.900 g of H2C2O4.2H2O. The excess oxalate then
requires 24.00 mL of KMnO4 solution for titration. If each mL of the KMnO4 will
oxidize the Fe(II) in 0.03058 g FeSO4.7H2O, what is the oxidizing power of the
sample in terms of MnO2?
D. Oxidation with Potassium Dichromate
(Dichromate Process)
In acidic solution, orange dichromate ion is a powerful oxidant that is
reduced to chromic ion:

𝐶𝑟2 𝑂72− + 14𝐻+ + 6𝑒 − ↔ 2𝐶𝑟 3+ + 7𝐻2 𝑂

K2Cr2O7 is a primary standard. Its solutions are stable, and it is cheap.

Because Cr2O72- is orange and complexes of range from green to violet, indicators
with distinctive color changes, such as diphenylamine sulfonic acid or
diphenylbenzidine sulfonic acid, are used to find a dichromate end point.
Alternatively, reactions can be monitored with Pt and calomel electrodes.
K2Cr2O7 is not as strong an oxidant as KMnO4 or Ce4+. It is employed chiefly
for the determination of Fe2+ and, indirectly for species that will oxidize Fe2+ to Fe3+.
PROBLEMS
1. 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 K2Cr2O7 solution of which
15.00 mL is equivalent in oxidizing power to 25.00 mL of KMnO4 solution which has
an “iron value” of 0.004750 g?
2. Fusion with Na2O2 oxidizes the chromium in a 0.2000 g sample of chromite ore to
chromate. The addition of 50.0 ml pipetful of ferrous sulfate solution reduces this
in acid solution to chromic ions (Cr2O72- + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O) and
the excess ferrous ions are titrated with 7.59 mL of 0.1000 N K2Cr2O7. Each pipetful
of ferrous solution is equivalent to 47.09 mL of the standard K2Cr2O7 solution. What
is the percentage of Cr in the sample? What weight of sample of the chromite ore
should be taken so that the number of milliliters of standard 1.000 N K2Cr2O7 that
are equivalent to the ferrous solution added, minus the number of milliliters of
K2Cr2O7 used in the titration, will equal the percentage of Cr2O3 in the sample?
3. How many mL of K2Cr2O7 containing 25.00 g of the salt per liter would react with
3.402 g of FeSO4.7H2Oin dilute acid solution? What is the normality of the
dichromate solution as a potassium salt?
4. How many grams of pure K2Cr2O7 must be weighed out, dissolved,
and diluted to exactly 700 mL to make a solution which, when used in the titration
of iron in a sample of ore, shall be of such a strength that four times the number of
milliliters used with a half-gram sample will represent one-half the percentage of
FeO in the sample?
5. One hundred milliliters of K2Cr2O7 solution (10.0 grams per liter), 5.00 mL of 6 N
H2SO4 , and 75.0 ml. of FeSO4 solution (80.0 grams FeSO4.7H2O per liter) are mixed
and the resulting solution is titrated with 0.2121 N KMnO4. Calculate the volume
required.
E. Oxidation with Ce4+
(Ceric Sulfate or Cerate Process)
Reduction of Ce4+ to Ce3+ proceeds cleanly in acidic solutions.

𝐶𝑒 4+ + 𝑒 − → 𝐶𝑒 3+

Ce4+ is yellow and Ce3+ is colorless, but the color change is not distinct enough for
cerium to be its own indicator. Ferroin and other substituted phenanthroline redox
indicators.
F. Methods Involving Iodine
(Iodimetric Process)
When a reducing analyte is titrated directly with iodine (to produce ), the method is
called iodimetry. In iodometry, an oxidizing analyte is added to excess to produce
iodine, which is then titrated with standard thiosulfate solution.

𝐼2 𝑎𝑞 + 𝐼− ↔ 𝐼3−

The fundamental reaction in this process is that between iodine and sodium
thiosulfate, with starch (or sometimes chloroform) as the indicator.

𝐼2 + 2𝑆2 𝑂32− → 2𝐼− + 𝑆4 𝑂62−