Chapter 3: Determination of Percentage Total Com-
bined Manganese in Multi-Phase Oxide Systems (The
Mohr’s Salt / Permanganate Method)
This chapter details a classic, robust visual titrimetric procedure for determining total
combined manganese in complex ores. Commercial manganese ores (such as pyrolusite
or manganese fines) are typically multi-phase systems containing Manganese Dioxide
(M nO2 ), Manganese(III) Oxide (M n2 O3 ), and Hausmannite (M n3 O4 ).
To determine total manganese without relying on complex indicators or instrumen-
tation, the Mohr’s Salt Indirect Titration Method is the standard metallurgical
approach. This technique operates on a ”reduction-back-titration” principle, avoiding
the issues of managing dark precipitates during visual endpoints.
3.1 The Chemistry and Phase-Transformation Logic
When an ore sample contains multiple high-valence oxidation states of manganese (M n3+
and M n4+ ), direct visual titration is challenging. The chemical strategy here is to use a
measured excess of a standard reducing agent to bring all high-valence manganese down
to stable M n2+ , followed by titrating the leftover reducing agent.
1. The Selective Reductive Dissolution Stage
Instead of using Hydrochloric acid (which drives off variable amounts of chlorine gas and
ruins the stoichiometric calculations), the multi-phase powder is digested in an acidic
medium containing a precise, known excess of Mohr’s Salt (Ferrous Ammonium Sul-
phate, [N H4 ]2 F e[SO4 ]2 · 6H2 O).
The F e2+ ions from Mohr’s salt reduce all high-valence manganese phases down to
the stable divalent state (M n2+ ) in a sulphuric acid environment:
• Manganese Dioxide (M nO2 ): The M n4+ is reduced to M n2+ via a 2-electron
transfer.
M nO2 + 2F e2+ + 4H + → M n2+ + 2F e3+ + 2H2 O
• Manganese(III) Oxide (M n2 O3 ): The M n3+ is reduced to M n2+ via a 1-electron
transfer per manganese atom.
M n2 O3 + 2F e2+ + 6H + → 2M n2+ + 2F e3+ + 3H2 O
• Hausmannite (M n3 O4 ): Treated as a mixed-valence network (M nO·Mn2 O3 ), the
higher-valence portion is smoothly reduced.
M n3 O4 + 2F e2+ + 8H + → 3M n2+ + 2F e3+ + 4H2 O
Following this digestion step, 100% of the manganese from all initial phases is
unified into the soluble divalent state (M n2+ ).
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2. The Back-Titration Logic
Because an exact, excess quantity of Mohr’s salt (F e2+ ) was added at the start, some
F e2+ will remain unreacted after all the manganese oxides are fully reduced.
We determine this unreacted remnant by performing a back-titration with standard
Potassium Permanganate (KM nO4 ) under strongly acidic conditions:
M nO4− + 5F e2+ + 8H + → M n2+ + 5F e3+ + 4H2 O
3. Clear Visual Endpoint Mechanics
Unlike Volhard’s method, which generates a confusing brown precipitate, this solution
remains perfectly clear throughout the titration.
• As KM nO4 is dropped into the flask, it is instantly reduced to colorless M n2+ by
the residual F e2+ .
• The moment the last remaining F e2+ ion is oxidized, the next single drop of KM nO4
has no partner left to react with. It remains intact, tinting the entire clear solution
with a permanent, faint pink color. This acts as its own highly sensitive indicator.
3.2 Stepwise Procedure
Step 1: Preparation of Standard Reagents
1. 0.02 M Potassium Permanganate (KM nO4 ): Standardize carefully against
primary standard sodium oxalate (N a2 C2 O4 ) as outlined in Vogel Section 10.93.
2. Standard Mohr’s Salt Solution: Dissolve an accurately weighed mass (≈ 9.8 g)
of A.R. grade Ferrous Ammonium Sulphate in 100 mL of 1 M H2 SO4 and dilute to
250 mL in a volumetric flask.
3. The Blank Run: Pipette 25.0 mL of this Mohr’s salt solution into a clean flask,
add 20 mL of 1 M H2 SO4 , and titrate with your standard KM nO4 . Note this
volume as Vblank . This establishes exactly how much permanganate matches your
unreacted reducing agent.
Step 2: Reductive Digestion of the Ore
1. Accurately weigh 0.50 g (w) of the finely powdered, dried Manganese ore into a
250 mL conical flask.
2. Pipette exactly 50.0 mL of your standard Mohr’s salt solution into the flask con-
taining the ore.
3. Add 30 mL of 1:4 Sulphuric Acid (H2 SO4 ).
4. Place a small watch glass over the neck of the flask to act as a reflux cap, and
heat gently on a hot plate under a fume hood. Maintain a gentle simmer for 15–20
minutes.
5. Observation: Digestion is complete when all dark, gritty oxide particles disappear,
leaving behind only a faint, white sandy residue of insoluble silica (SiO2 ).
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Step 3: Back-Titration
1. Cool the flask down completely to room temperature under running tap water.
Justification: Hot acid solutions can cause a slow reaction between atmospheric
oxygen and residual F e2+ , skewing your data.
2. Dilute the solution with approximately 50 mL of de-ionised water.
3. Titrate the cool solution immediately with the standard 0.02 M Potassium Per-
manganate (KM nO4 ) from your burette.
4. Swirl smoothly until a single drop imparts a faint pink hue that persists across
the clear solution for at least 30 seconds. Note this volume as Vsample .
3.3 Calculations and Stoichiometry
The math tracks how much reducing agent was eaten by the manganese oxides.
Since 50.0 mL of Mohr’s salt was added to the sample, it is equivalent to double your
blank volume (2 × Vblank ). The volume of permanganate representing the manganese
alone (VM n ) is the difference between what the reducing agent was worth originally and
what was left over:
VM n = (2 × Vblank ) − Vsample
From the electron balance:
• 1 mole of KM nO4 ≡ 5 moles of F e2+ (5-electron change)
• 1 mole of M nO2 ≡ 2 moles of F e2+ (2-electron change)
Therefore, 1 mole of KM nO4 ≡ 2.5 moles of Manganese.
VM n × MP × 2.5 × 54.94
% Total Combined Manganese =
10 × w
Where:
• VM n = Calculated equivalent volume of KM nO4 reacted with the manganese (mL).
• MP = Molarity of the standard Potassium Permanganate titrant (0.02 M).
• 2.5 = Stoichiometric equivalence factor (2.5 moles of Mn per mole of KM nO4 ).
• 54.94 = Atomic weight of Manganese (g/mol).
• w = Initial dry mass of the multi-phase ore powder sample (grams).
• 10 = Mathematical constant combining unit conversions (mL to L) and percentage
scaling.