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Chapter 2: Volumetric methods

Part 5: Redox Titration
• Definitions
Physical and chemical methods •
•
Nernst equation
Equilibrium constant
for food analysis 1 • Factors affecting on potential (Further reading)
• Redox Titration
1. Principle
By: Dương Hữu Huy 2. Titration curve
3. Indicator
• Permanganate method
• Dichromate method
• Iodine method (or thiosulfate method)

What is Oxidation—Reduction Reactions Nernst equation

• Oxidation-Reduction Reactions = Redox reaction • Half-reaction: Ox + n.e⁻ → Re

0.0591 [𝑂𝑥]
• Redox reaction: An electron-transfer reaction 𝐸 / =𝐸 / + 𝑙𝑜𝑔
𝑛 [𝑅𝑒]
Sn2+ + Fe3+  Sn4+ + Fe2+ • Example: Fe3+ + 1.e⁻ → Fe2+
0.0591 [𝐹𝑒 ]
• Reducing agent: A species that donates electrons to another species: Sn2+ 𝐸 / =𝐸 / + 𝑙𝑜𝑔
1 [𝐹𝑒 ]
• Oxidation: A loss of electrons: Sn2+ - 2e⁻ → Sn4+ •𝐸 / is standard-state potential (25 °C, 1 atm, and [H+] = 1 M)
• Oxidizing agent: A species that accepts electrons from another species: Fe3+
• Reduction: A gain of electrons: Fe3+ + 1e⁻ → Fe2+
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Example: write Nernst equations for half-reactions:

• Cu2+ + 2.e⁻ → Cu Equilibrium constant of redox reaction
• MnO4⁻ + 8H+ + 5.e⁻ → Mn2+ + 4H2O
• Cl2 + 2.e⁻ → 2Cl⁻ aOx1 + bKh2 = aKh1 + bOx2
• 5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O • Equilibrium constant:

• Half-reactions:
aOx1 + n1.e  aKh1 => E01
bOX2 + n2.e  bKh2 => E02
• At equivalence point: E1 = E2

n(E − E )
lgK = n = n1*n2
0.0591

Example: Calculate K for reaction:

Ce4+ + Fe2+ = Ce3+ + Fe3+ Direction of redox reaction
• Standard-state potential: 𝐸 = 1.55 𝑉 𝑎𝑛𝑑 𝐸 = 0.77 𝑉
/ / aOx1 + bKh2 = aKh1 + bOx2 (1) K: equilibrium constant
• K > 1: Reaction (1) is in forward direction
• K < 1: Reaction (1) is in back direction
In redox reaction, we rarely use K. E is used more common
• ∆E = E01 - E02 > 0: Reaction (1) is in forward direction
• ∆E = E01 - E02 < 0: Reaction (1) is in back direction
Example: Mixing two solutions: 𝐸 / = 0.77 V and 𝐸 / = 0.15 V.
Write a correct reaction.
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Potential at equivalence point Redox Titration

• Half-reactions: 1. Principle
aOx1 + n1 .e  aKh1 => E0 1 2. Titration curve
bOX2 + n2.e  bKh2 => E02 3. Indicator
• At equivalence point: E01 = E02 = Eeq 4. Permanganate method
. . 5. Dichromate method
E =
6. Iodine method (or thiosulfate method)
Example: Calculate Eeq for the reaction:
Ce4+ + Fe2+ = Ce3+ + Fe3+
Standard-state potential: 𝐸 / = 1.55 𝑉 𝑎𝑛𝑑 𝐸 / = 0.77 𝑉

Redox Titration Redox Titration

Principle Titration curve

• Based on redox reaction • Construct E vs V of titrant or analyte added

• Titration reaction: aOx1 + bKh2 = aKh1 + bOx2

• Example: 5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
• Standards: Ox or Kh, and Analytes: Ox or Kh
• Redox indicator: The oxidized and reduced forms differ in color.
• Common titrants: H2C2O4.2H2O, KMnO4, K2Cr2O7, Na2S2O3.5H2O …
• Using the equivalence concentration for calculating the results
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Redox Titration Redox Titration

Redox indicator Redox indicator
• Also reducing - oxidizing reagents: In(Ox) + n.e⁻ → In(Re) • Three types of redox indicator
• Oxidized and reduced forms depend on the solution’s electrochemical potential.
• Titrant is indicator, such as KMnO4. MnO4⁻ (purple) → Mn2+ (colorless)
• The oxidized and reduced forms differ in color.
• Indicators do not participate in the redox titration. During titrating, when 1 drop of MnO4⁻ is in excess => solution’s color return pink.
• Example: Directly titrating Fe2+ with titrant K2Cr2O7 in strong acidic condition, • Indicators indicate the presence of a specific oxidized or reduced species, such as starch,
using diphenylamine. Note: diphenylamine in reducing form is colorless but that starch forms a complex with I2 having a blue.
in oxidizing form is dark purple.
• Titration reaction: 6Fe2+ + Cr2O72 + 14H+  6Fe3+ + 2Cr3+ + 7H2O Before equivalence point, solution is dark blue due to a presence of I2-starch complex, when
• When 1 drops of K2Cr2O7 is in excess meaning that solution is oxidizing 1 drop of reducing reagent is in excess => all I2 are consumed => solution return colorless.
condition, diphenylamine changes to oxidized forms leading solution’s color • Indicators have different color between oxidized and reduced forms such as
return red-purple.
diphenylamine

Redox Titration
Redox indicator Permanganate method

• Titrant: KMnO4
• Analytes: reducing agents such H2C2O4, Fe2+,
NO2⁻ …
KMnO4 C; V • Indicator: KMnO4
• Conditions: strong acidic solution (adjusted
by H2SO4 6N)
X: Co; Vo
Strong acidic solution
Indicator: KMnO4
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Permanganate method
Principle
• Based on strong oxidation of KMnO4 in acidic condition.
MnO4- + 8H+ + 5.e⁻ 5Fe3+ + Mn2+ + 4H2O E0 = 1.51 V
• When 1 drop of MnO4⁻ is in excess, solution’s color return pink => end point
Notes
1. Adjust to acidic condition by H2SO4 (don’t use HCl, HNO3 and …)
2. Reaction is slow at the beginning, then is fast due to the presence of Mn2+
as catalyst
3. Heating to 60 – 70 °C to accelerate the reaction at the beginning.

Zimmermann solution KMnO4 preparation

• KMnO4 (M = 158 g/mol) => z = 5 => CN = 5.CM

• Dissolve KMnO4 in distilled water and stored in dark bottle. => Standardized by H2C2O4
• Aqueous solutions of permanganate are not entirely stable because of water oxidation:
4MnO4- + 2H2O → 4MnO2(s) + 3O2(g) + 4OH⁻
• Permanganate solutions are moderately stable provided they are free of manganese
dioxide and stored in a dark container. => Remove MnO2 by glass filter after 24 hrs of
When matrix sample contains a large amount of Cl⁻, we use Zimmermann solution preparation or heating solution to remove organic compounds
• Mn2+: catalyst • Permanganate solutions oxidize chloride ion: 2MnO4⁻ + 10Cl⁻ + 16H+ ⇄ 2Mn2+ + 5Cl2 +
8H2O
• H2SO4: acidic medium • The permanganate end point is not permanent because excess permanganate ions react
• H3PO4: form a colorless complex with Fe3+ slowly with the relatively large concentration of manganese(II) ions present at the end
point, according to the reaction: 2MnO4⁻ + 3Mn2+ + 2H2O ⇄ 5MnO2(s) + 4H+
The rate at which this equilibrium is approached is so slow that the end point fades only
gradually over a period of perhaps 30 seconds.
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• Example: Tính lượng KMnO4 (P=99,5%; M = 158 g/mol) cần thiết để pha được 1
lít dung dịch KMnO4 0.02N. Cho phản ứng : MnO4- + 8H+ + 5.e⁻ 5Fe3+ + Mn2+
+ 4H2O
Common application of permanganate method

Direct titrations
• Determination of H2C2O4
H2C2O4 + MnO4⁻ + H+ → Mn2+ + CO2 + H2O
• Determination of Fe2+
5Fe2+ + MnO4⁻ + 8H+ 5Fe3+ + Mn2+ + 4H2O
• Example: Số mL KMnO4 1N cần lấy để pha 100 mL KMnO4 0.05N là: • Determination of H2O2
H2O2 + MnO4⁻ + 8H+ Mn2+ + O2 + H2O

Displacement titrations
Back titration
• Strong reducing analytes such as: Cu+, Sn2+, Ce3+ ..
1. Step 1: Sn2+ + Fe3+ → Sn4+ + Fe2+ • When analytes such as S2⁻, NO2⁻… slowly react with KMnO4, direct
2. Step 2: 5Fe2+ + MnO4⁻ + 8H+ 5Fe3+ + Mn2+ + 4H2O titration can not be applied.
• Determination of RCHO (carbohydrate analysis of food sample => Bertrand method)
• Determination of S2⁻ as an example
1. RCHO + Cu2+ + OH⁻ → RCOOH + Cu2O + H2O
2. Cu2O + Fe3+ → Cu2+ + Fe2+ • Step 1: Reacting with known and excess amount of KMnO4
3. 5Fe2+ + MnO4⁻ + 8H+ 5Fe3+ + Mn2+ + 4H2O
S2⁻ + MnO4⁻ excess + H+ → Mn2+ + SO42⁻ + H2O
• Determination of metal ions which form oxalate precipitate such as: Ca2+, Ba2+ …
1. Step 1: Precipitating Ca2+ + (NH4)2C2O4 → CaC2O4 + 2NH4+ • Step 2: Titrating excess amount of KMnO4 by Fe2+
2. Step 2: Filtering, cleaning and dissolving a precipitate
5Fe2+ + MnO4⁻ + 8H+ 5Fe3+ + Mn2+ + 4H2O
CaC2O4 + H2SO4 → CaSO4 + H2C2O4
3. Step 3: Titrating H2C2O4
H2C2O4 + MnO4⁻ + H+ → Mn2+ + CO2 + H2O
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Iodine method (Thiosulfate method) Important notes

• Based on reaction: I2 + 2.e⁻ → 2I⁻ E0 = 0.54 V • Room temperature

• Back or displacement titration using Na2S2O3 (Thiosulfate) as titrant and • Slight acidic condition adjusted by CH3COOH
or diluted H2SO4
starch as indicator in slight acidic medium (CH3COOH or diluted H2SO4)
• Adding starch indication when solution’s color
• Titration reaction: I2 + 2Na2S2O3 → 2NaI + Na2S4O6 is light yellow
• Indicator: Starch
• At endpoint: I2-Starch complex (blue-black) → starch (colorless)
• Notes: Direct titration using standard I2 solution (IO3⁻ solution) can be
applied

Starch indicator Na2S2O3 standard

• 0.5 – 1 % • Na2S2O3.5H2O (M = g/mol) => z = 1 => CN = CM

• Starch-I2 complex => blue-black color (C)
• Standardizing by K2Cr2O7 (displacement titration)
• Very sensitive until 10-5 M of I2 solution
• Solution is not stable due to O2 and bacteria
• Complex not stable at high temperature (>50 °C)
• Adding indicator to solution when light yellow • Dissolve in boiling water (cooling to room temperature) which is free from
color O2 and CO2.
• Preparation: 0.5 g + 100 mL hot water =>
• Store in closed and dark bottle.
heating 2 min until transparent solution
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Application 1 Application 1

• Determination of reducing analytes such as Sn2+, S2O32⁻, SO32⁻ … • Determination of oxidizing analytes such as Fe3+, O2, Cr2O72⁻, MnO4⁻ …
• Back titration • Displacement titration
• Step 1: • Step 1:
Re + I3⁻excess → 3I⁻ + Ox Ox + KI → I3⁻
• Step 2: Titrating with standard Na2S2O3 using starch indicator • Step 2:
I3⁻excess + S2O32⁻ → 3I⁻ + S4O62⁻ I3⁻ + S2O32⁻ → 3I⁻ + S4O62⁻

• A 25.00 mL sample of a liquid bleach was diluted to 1000 mL in a volumetric flask. A 25

• The amount of Fe in a 0.4891 g sample of an ore was determined by a redox titration with
mL portion of the diluted sample was transferred by pipet into an Erlenmeyer flask and
K2Cr2O7. The sample was dissolved in HCl and the iron brought into the +2 oxidation
treated with excess KI, oxidizing the OCl⁻ to Cl⁻, and producing I3⁻. The liberated I3⁻ was
state using a Jones reductor. Titration to the diphenylamine sulfonic acid end point
determined by titrating with 0.09892 M Na2S2O3, requiring 8.96 mL to reach the starch
required 36.92 mL of 0.02153 M K2Cr2O7. Report the iron content of the ore as % w/w
indicator end point. Report the % w/v NaOCl in the sample of bleach.
Fe2O3.
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• The amount of ascorbic acid, C6H8O6, in orange juice was determined by oxidizing the
ascorbic acid to dehydroascorbic acid, C6H6O6, with a known excess of I3⁻, and back
titrating the excess I3⁻ with Na2S2O3. A 5.00 mL sample of filtered orange juice was
treated with 50.00 mL of excess 0.01023 M I3⁻. After the oxidation was complete, 13.82
mL of 0.07203 M Na2S2O3 was needed to reach the starch indicator end point. Report the
concentration of ascorbic acid in milligrams per 100 mL.