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Advance Stoichiometry Based on Redox Reactions

ChemistryRedox ReactionsFor NEET aspirants

Redox stoichiometry turns a redox reaction into numbers: how much oxidant reacts with how much reductant, and what volume of titrant reaches the end point. It has two routes, the mole method (from the balanced equation) and the equivalent method (from n-factors, with no balancing). This page builds n-factor, equivalent weight, normality and the law of equivalence, then applies them to permanganate and dichromate titrations, iodometry, back titration and the volume strength of . Redox stoichiometry numericals appear every year in JEE Main and as one-step problems in NEET.

On this page1Two routes2n-factor3Equivalents and normality4Law of equivalence5Redox titrations6Iodometry and iodimetry7Back titration8Volume strength of
Key Formulas - Quick Reference
  1. ★ Must learnn-factor (redox) electrons lost or gained per formula unit (change in ON) (atoms that change); add if two elements change.
  2. ★ Must learnEquivalent weight ; gram equivalents moles .
  3. ★ Must learnNormality (molarity); milliequivalents (mL).
  4. ★ Must learnLaw of equivalence: meq of oxidant meq of reductant, so , or .
  5. Disproportionation: , with , the electrons per mole in the two directions.
  6. Iodometry: eq of oxidant eq of liberated eq of ( for → ).
  7. Back titration: meq(sample) meq(excess reagent added) meq(back-titrant).
  8. ★ Must learnVolume strength of (litres of at STP from 1 L).

1. Two Routes to Redox Stoichiometry

Every redox calculation asks the same thing: how many moles of electrons does the reductant give, and how much oxidant is needed to take them? You can answer it with the mole method (balance, then use the mole ratio) or the equivalent method (count electrons per formula unit and equate equivalents). Both always agree.

Mole method and equivalent method for a redox titration give the same answer The same permanganate and iron(II) problem solved two ways. The mole method balances the equation and uses the 1 to 5 mole ratio. The equivalent method multiplies molarity by n-factor and equates milliequivalents. Both give 20 millilitres. How many mL of 0.02 M KMnO4 oxidise 20 mL of 0.1 M FeSO4 in acid? Mole method 1 balance: MnO4− + 5Fe2+ + 8H+ → ... 2 Fe2+ = 20 × 0.1 = 2 mmol 3 MnO4− = 2 ÷ 5 = 0.4 mmol 4 V = 0.4 ÷ 0.02 = 20 mL Equivalent method 1 n-factors: KMnO4 5, Fe2+ 1 (no balancing) 2 meq Fe2+ = 1 × 0.1 × 20 = 2 3 meq KMnO4 = 5 × 0.02 × V = 0.1V 4 0.1V = 2, so V = 20 mL same answer: 20 mL
Figure 1: The mole method needs the balanced equation; the equivalent method needs only the n-factors (5 for , 1 for ). Both give 20 mL.
Mole method

Needs the balanced equation. Best when the products matter or one reagent is limiting, as in + → + .

Equivalent method

Needs only n-factors. Fastest for titrations, mixtures, back titration and multistep problems; no balancing at all.

2. n-Factor

The n-factor of a species in a redox reaction is the number of electrons it loses or gains per formula unit, that is, per mole. Find it as (change in oxidation number per atom) (number of atoms that change).

The n-factor is a property of the reaction, not of the compound. Permanganate gives three different values in three media, and thiosulphate gives 1 with iodine but 8 with chlorine.

n-factors of common oxidants and reductants used in redox titrations Horizontal bar chart of electrons per formula unit: permanganate 5 in acid, 3 in neutral, 1 in strong base; dichromate 6; hydrogen peroxide 2; iodine 2; iron(II) sulphate 1; oxalic acid 2; ferrous oxalate 3; thiosulphate 1 with iodine and 8 with chlorine; copper(I) sulphide 8. electrons per formula unit (n-factor) 0 1 2 3 4 5 6 7 8 KMnO4 → Mn2+ (acid) 5 KMnO4 → MnO2 (neutral) 3 KMnO4 → MnO42− (strong base) 1 K2Cr2O7 → Cr3+ (acid) 6 H2O2 → H2O (oxidant) 2 I2 → I− 2 FeSO4 → Fe3+ 1 H2C2O4 → CO2 2 FeC2O4 → Fe3+ + CO2 3 H2O2 → O2 (reductant) 2 Na2S2O3 → S4O62− (with I2) 1 Na2S2O3 → SO42− (with Cl2) 8 Cu2S → Cu2+ + SO2 8 oxidants (gain e−) reductants (lose e−)
Figure 2: The n-factor belongs to the reaction, not the compound: is 5, 3 or 1 by medium, and thiosulphate is 1 with but 8 with .

2.1 Two elements changing, and disproportionation

If two parts of a formula change, add their electrons: ferrous oxalate loses 1 from Fe and 2 from oxalate, so . For a species that both gains and loses electrons, combine the two directions: .

Special n-factors: two elements oxidised in ferrous oxalate, and chlorine disproportionating Ferrous oxalate loses one electron from iron and two from the oxalate carbons, so its n-factor is 3 and equivalent weight 48. Chlorine in hot alkali gains 2 and loses 10 per molecule in the two directions, so its n-factor is 20 over 12, five thirds, and equivalent weight 42.6. Two parts oxidised: FeC2O4 = 3 e− Fe2+ → Fe3+: 1 e− C2O42− → 2CO2: 2 × 1 = 2 e− n = 1 + 2 = 3 E = 144 ÷ 3 = 48 (M of FeC2O4 = 144 g mol−1) Disproportionation: Cl2 in hot alkali Cl2 → 2Cl− gains n1 = 2 Cl2 → 2ClO3− loses n2 = 10 n = n1n2 ÷ (n1 + n2) = 20 ÷ 12 = 5/3 check: 3Cl2 move 5e−, so 5/3 per Cl2 E = 71 ÷ (5/3) = 42.6
Figure 3: When two parts of one formula change, add their electrons (: ). For a disproportionating species, (: ).
n-factor in acid-base and salt reactions (used with the same equivalent rules): acids, the number of replaced (basicity: 2, 3, 2, 1); bases, the replaced ( 2); salts, the total charge on the cations ( 6).
Exam Trick 5-3-1, then 6. takes 5 electrons in acid, 3 in neutral, 1 in strong alkali; takes 6. Thiosulphate gives just 1 with iodine. These five numbers solve most titration questions.
JEE Advanced One compound, two n-factors. Oxalic acid is 2 as an acid and 2 as a reductant. is 1 as an acid but 2 as a reductant. Potassium tetroxalate, , has 3 replaceable H (n = 3 with NaOH) and two oxalate units (n = 4 with ). So equal moles of it need volumes of 0.1 M NaOH and 0.1 M in the ratio . Always ask which reaction the question is about.
Key idea
n-factor = electrons per formula unit for this reaction. Change the medium or partner and the n-factor can change.

3. Equivalents, Equivalent Weight and Normality

Equivalent weight is the mass that gives or takes one mole of electrons. One equivalent of any oxidant reacts exactly with one equivalent of any reductant. Normality is the number of gram equivalents per litre: molarity.
Equivalent map: converting mass, moles and solution data to gram equivalents Hub diagram with gram equivalents at the centre. Mass divided by equivalent weight, moles times n-factor, normality times volume, and n-factor times molarity times volume all give gram equivalents. In titrations milliequivalents equal normality times volume in millilitres. mass w (g) moles solution: N × V (L) solution: n × M × V (L) gram equivalents = moles of e− moved ÷ E (E = M ÷ n) × n N = n × M in titrations use milli-units: meq = N × V(mL) = n × M × V(mL)
Figure 4: Every quantity in a redox problem turns into equivalents, and one equivalent means one mole of electrons transferred. Equal equivalents of oxidant and reductant always react.
Reagent (reaction) / g moln-factor / g
(acid, → )158531.6
(neutral, → )158352.7
(acid, → )294649
(→ )2781278
Mohr's salt, 3921392
Oxalic acid, (→ )126263
(either role)34217
(→ )2542127
(with )2481248

4. The Law of Equivalence

In any reaction the equivalents of all reacting species are equal. For a titration, meq of oxidant meq of reductant.

The law needs no balanced equation, works for unbalanced and multistep changes, and simply adds up for mixtures: meq of a mixture is the sum of the meq of its parts. If 20 mL of 0.05 M oxalic acid needs 20 mL of in acid, then and M, the same as from the balanced equation

Exam Trick Stay in milli-units. meq mL mL, and mmol mL. You never convert to litres, and a mass in grams becomes meq as .
Flowchart for solving any redox titration problem with equivalents Flowchart: identify oxidant and reductant, find n-factors, convert quantities to milliequivalents, subtract the back-titrated amount if an excess was added, equate milliequivalents and convert the answer to the quantity asked. yes no Identify the oxidant and the reductant Find each n-factor (check the medium) Turn every quantity into meq: N × mL, n × M × mL, 1000 w ÷ E Excess reagent added first? meq(sample) = meq(added) − meq(back-titrated) meq(oxidant) = meq(reductant) Solve, then convert to mass, %, molarity or volume strength
Figure 5: Five moves solve every redox titration. The branch handles back titration; the most common error is a wrong n-factor at the second step.
Key idea
Equal equivalents react, not equal moles. Moles react in the ratio of the inverse n-factors: 1 (n = 5) per 5 (n = 1).
Quick Recall: tap to check
n-factor of with acidified ?
3 (Fe 1 + oxalate 2); .
Normality of 0.1 M in acid?
N.
Equivalent weight of in neutral medium?
.

5. Redox Titrations

Just as acid-base titrations use a pH indicator, redox titrations find the strength of an oxidant or reductant with a redox-sensitive end point. Three situations are common.

5.1 Permanganate: a self-indicator

Intensely purple is decolourised as long as a reductant ( or ) remains, because is almost colourless. The first lasting pale pink marks the end point; the eye detects it at only about mol L of , so the overshoot beyond the equivalence point (where oxidant and reductant are equal in mole stoichiometry) is negligible. Oxalate titrations are run warm (about 60 °C) because the reaction is slow in the cold.

Permanganate titration: potassium permanganate is its own indicator A burette of purple potassium permanganate drips into a conical flask of iron(II) or oxalate in dilute sulphuric acid. During the titration each drop is decolourised as manganese two plus forms; at the end point the first permanent pale pink appears. KMnO4 (purple, titrant) Fe2+ or C2O42− in dil. H2SO4 stopcock During titration each purple drop turns colourless (Mn2+) End point first permanent pale pink pink at only about 10−6 mol L−1 MnO4−, so the overshoot is negligible oxalate: warm to about 60 °C
Figure 6: is a self-indicator: purple while it is used up, pale pink at the first drop in excess (about mol L). The medium is dilute .

5.2 Dichromate with an indicator

Orange gives green , a change too weak to see clearly, so it is not a self-indicator. A redox indicator, diphenylamine, is oxidised by the first drop of excess dichromate after the equivalence point and turns an intense blue (blue-violet).

5.3 Choosing the acid

The acid must not react with the titrant. Dilute is used for permanganate. HCl is avoided because ( V) oxidises ( V) to , wasting titrant; dichromate ( V) does not, so it can be used in HCl. is avoided with both because it is an oxidant itself.

Which acid to use: permanganate needs dilute sulphuric acid, dichromate tolerates hydrochloric acid Matrix of acids against titrants. Dilute sulphuric acid suits both. Hydrochloric acid is avoided with permanganate because 1.51 volt exceeds 1.36 volt for chlorine, but it is safe with dichromate at 1.33 volt. Nitric acid is avoided with both because it is itself an oxidant. KMnO4 titrant K2Cr2O7 titrant dil. H2SO4 ✓ use no side reaction ✓ use no side reaction HCl ✗ avoid Cl− oxidised: 1.51 > 1.36 ✓ use Cl− safe: 1.33 < 1.36 HNO3 ✗ avoid itself an oxidant ✗ avoid itself an oxidant E° / V 1.51 MnO4−/Mn2+ 1.36 Cl2/Cl− 1.33 Cr2O72−/Cr3+
Figure 7: An acid must not react with the titrant. (1.51 V) oxidises (1.36 V), so HCl wastes permanganate; (1.33 V) does not.

6. Iodometry and Iodimetry

Iodine reactions give a third way to see the end point. Iodine forms an intense blue complex with starch, and it reacts quickly and cleanly with thiosulphate. Iodine is barely soluble in water, but it stays dissolved in KI solution as ().

In iodometry an oxidant that can oxidise , such as , is treated with excess KI. The liberated iodine is titrated with standard thiosulphate. Starch is added near the end (when the solution turns pale yellow), and the blue colour vanishes when the last iodine is used up.

Iodometry and iodimetry: titrations built on iodine and thiosulphate Iodometry: an oxidant such as copper two plus liberates iodine from excess potassium iodide and the iodine is titrated with sodium thiosulphate using starch near the end point. Iodimetry: a standard iodine solution titrates a reductant directly. Iodometry (indirect): an oxidant is estimated oxidant Cu2+, Cr2O72−, Cl2, H2O2, MnO4−, IO3− + excess KI I2 liberated (held as I3−, brown) Na2S2O3 2I− + S4O62− starch near the end: blue → colourless 2Cu2+ + 4I− → Cu2I2 + I2 I2 + 2S2O32− → 2I− + S4O62− eq of oxidant = eq of I2 = eq of S2O32− Iodimetry (direct): a reductant is estimated standard I2 (burette) I2 + 2e− → 2I− reductant: S2O32−, SO32−, AsO33−, Sn2+, H2S end point: first permanent blue with starch
Figure 8: In iodometry iodine is only a messenger: the oxidant, the liberated and the thiosulphate have equal equivalents. In iodimetry a standard solution titrates a reductant directly.
Iodometry (indirect)

Estimates an oxidant. Oxidant + excess KI → ; titrate with . End point: blue → colourless.

Iodimetry (direct)

Estimates a reductant with a standard solution. End point: the first permanent blue with starch.

Key idea
In iodometry, iodine is only a messenger: eq of oxidant = eq of = eq of thiosulphate, with for each and each .
Quick Recall: tap to check
Why is not titrated in HCl?
(1.51 V) oxidises (1.36 V) to , so extra titrant is used.
Why is starch added only near the end in iodometry?
At high iodine concentration the starch-iodine complex forms too firmly and the end point becomes sluggish.
Indicator for dichromate titration of ?
Diphenylamine, which turns intense blue just after the equivalence point.

7. Back Titration

When the sample reacts slowly, is insoluble or cannot be titrated directly (for example in pyrolusite ore), add a known excess of a reagent, let it react completely, and titrate the left-over excess.

Back titration: the sample's equivalents equal those added minus those left over Bar of ten milliequivalents of oxalate added to manganese dioxide ore. Eight are used by the sample and two are left over, measured by titration with twenty millilitres of 0.02 molar permanganate. 50 mL of 0.1 M H2C2O4 added to MnO2 ore (excess oxalate) 8 meq used by MnO2 (the sample) 2 meq total added: 2 × 0.1 × 50 = 10 meq left over: titrated by 20 mL 0.02 M KMnO4 = 2 meq meq(sample) = meq(added) − meq(back) = 10 − 2 = 8
Figure 9: In a back titration a known excess reagent is added and the left-over part is titrated. Here meq of , i.e. 4 mmol, since for .

8. Volume Strength of Hydrogen Peroxide

bottles are labelled in volumes. " volume" means that 1 L of the solution gives L of at STP when it decomposes:

Two moles of give one mole of , 22.4 L at STP. So 1 L of an molar solution gives litres. With , :

Volume strength of hydrogen peroxide: 20 volume solution converted to molarity, normality and percentage A bottle of 20 volume hydrogen peroxide: one litre releases twenty litres of oxygen at STP on decomposition. Its molarity is 20 divided by 11.2, 1.79 molar; normality 3.57; strength 60.7 grams per litre or 6.07 percent weight by volume. H2O2 20 V 1 L of solution 2H2O2 → 2H2O + O2 on heating 20 L O2 at STP from 1 L M = 20 ÷ 11.2 = 1.79 mol L−1 N = 2 × 1.79 = 3.57 N strength = 1.79 × 34 = 60.7 g L−1 = 6.07% (w/v) 2 mol H2O2 → 1 mol O2 = 22.4 L at STP, so volume strength = 11.2 × M = 5.6 × N
Figure 10: "20 volume" means 1 L gives 20 L of at STP. With , it is 1.79 M, 3.57 N and 6.07% (w/v).

is usually estimated by titration with acidified , in which it acts as a reductant ():

Exam Trick 11.2 and 5.6. Volume strength . Quick checks: 10 V ≈ 3%, 20 V ≈ 6%, 100 V ≈ 30% (w/v). Exams use 22.4 L for STP unless they say otherwise; with 22.7 L (1 bar) the factor becomes 11.35.
Key idea
" volume" = L of at STP per litre, so and .
Quick Recall: tap to check
Molarity of "11.2 volume" ?
1 M (); normality 2 N.
In a back titration, which meq equals the sample?
Total meq of reagent added minus meq of the back-titrant.
n-factor of with acidified ?
2: O goes from to 0 in .

8.1 The whole concept at a glance

Mind map of redox stoichiometry Mind map with six branches: n-factor, equivalents and normality, law of equivalence, redox titrations, iodometry and iodimetry, and volume strength of hydrogen peroxide with back titration. Redox stoichiometry n-factor e− per formula unit KMnO4 5 / 3 / 1 K2Cr2O7 6, FeC2O4 3 Equivalents E = M ÷ n N = n × M meq = N × mL Law of equivalence meq oxidant = meq reductant no balancing needed n1M1V1 = n2M2V2 Titrations KMnO4 self-indicator Cr2O72−: diphenylamine dil. H2SO4, not HCl Iodine methods iodometry: oxidant → I2 iodimetry: I2 titrant starch near the end H2O2 strength V = 11.2 M = 5.6 N 10 V ≈ 3% back titration: total − back
Figure 11: The whole concept on one page. Revise from the centre outwards.

9. Solved Examples

Solved Example 1
What volume of 0.1 M (acidic) is needed to oxidise 1.52 g of ()?
Solution:

meq of . Normality of N.

, so mL. (Mole check: 10 mmol need mmol , i.e. mL.)

Solved Example 2
The equivalent weight of () in acidic medium is
(A) 294
(B) 147
(C) 49
(D) 98
Solution:

Answer: (C). Each Cr falls from to , and there are two Cr: . .

Solved Example 3
20 mL of 0.05 M oxalic acid needs 20 mL of a solution in dilute . Find the molarity of .
Solution:

: , so M (normality 0.1 N).

Solved Example 4
How many grams of Mohr's salt () react with 25 mL of 0.1 N in acid?
Solution:

meq of dichromate . Mohr's salt has ( → ), so .

Mass g.

Solved Example 5
A 0.5 g sample of a copper ore is dissolved. The liberates iodine from excess KI, and the iodine needs 25 mL of 0.1 M . Find the percentage of copper ().
Solution:

Iodometry: meq meq meq thiosulphate . Copper has ( → Cu(I)), so 2.5 mmol Cu.

Mass of Cu mg; percentage .

Solved Example 6
A sample of is labelled "20 volume". Its normality is
(A) 1.79 N
(B) 3.57 N
(C) 5.6 N
(D) 0.89 N
Solution:

Answer: (B). N (molarity M; strength g L, about 6.1% w/v).

Solved Example 7
25 mL of an solution needs 20 mL of 0.04 M in acid. Find the molarity and the volume strength of the .
Solution:

meq = meq . With , mmol , so M.

Volume strength volume.

Solved Example 8
0.5 g of pyrolusite ore is warmed with 50 mL of 0.1 M oxalic acid in dilute . The excess oxalic acid needs 20 mL of 0.02 M . Find the percentage of ().
Solution:

meq oxalic acid added . meq (back) . So meq .

has (Mn ): 4 mmol, mass mg. Percentage .

Solved Example 9
Find the equivalent weight of () in + → + + .
Solution:

Per : to 2 it gains ; to 2 it would lose .

Check: 3 transfer 5 electrons, i.e. per .

.

Solved Example 10
1 mmol of potassium tetroxalate, , is titrated separately with 0.1 M NaOH and with 0.1 M in acid. Find each volume.
Solution:

As an acid it has 3 replaceable H: meq , so mL.

As a reductant its two oxalate units give : meq , and gives mL.

Practice Questions
  1. Show with three examples that a reductant in excess gives a lower oxidation state product and an oxidant in excess gives a higher one.Answer: C + : excess C gives CO, excess gives . + : excess gives , excess gives . Na + : excess Na gives , excess gives .
  2. Why does thiosulphate react differently with iodine ( + → + ) and bromine ( + + → + + )?Answer: is a stronger oxidant than : it takes S to ( per ), while only reaches (S , ).
  3. In the Ostwald process, + → + . What is the maximum mass of NO from 10.00 g and 20.00 g ?Answer: 0.587 mol needs 0.734 mol , but only 0.625 mol is present, so is limiting: NO mol g.
  4. Find the equivalent weight of () in its titration with acidified .Answer: , .
  5. What volume of 0.1 N oxidises 50 mL of 0.15 N ?Answer: , mL.
  6. Find the volume strength of 1.5 N .Answer: volume.
  7. What is the normality of 0.1 M used in neutral medium, and how many electrons does each take?Answer: 3 electrons ( forms), so 0.3 N.

Common Mistakes to Avoid

Watch out
  • Writing for a redox titration. Use (or normalities).
  • Taking for in every medium (it is 3 in neutral and 1 in strongly alkaline solution).
  • Taking for thiosulphate with iodine (it is 1 per ) or for (it is 2).
  • Treating n-factor as a fixed property of a compound: is 1 as an acid but 2 as a reductant.
  • Titrating permanganate in HCl or instead of dilute .
  • In a back titration, equating the sample to the back-titrant instead of to (added back-titrated).
  • Mixing units: meq mL, but gram equivalents L.
  • Adding starch at the start of an iodometric titration rather than near the end point.

Frequently Asked Questions

What is n-factor in redox reactions?

The n-factor is the number of electrons lost or gained by one formula unit of a species in a given reaction. It equals the change in oxidation number per atom times the number of atoms that change. KMnO4 has n equal to 5 in acid, 3 in neutral and 1 in strongly alkaline medium.

What is the law of equivalence?

The law of equivalence says that in any reaction the equivalents of all reacting species are equal. In a redox titration the milliequivalents of oxidant equal those of reductant, so N1V1 = N2V2, or n1M1V1 = n2M2V2. It works without a balanced equation and for mixtures.

Why is the equivalent weight of KMnO4 different in acidic, neutral and basic media?

Equivalent weight is molar mass divided by n-factor, and the product of permanganate depends on the medium. It gains 5 electrons in acid (Mn2+), 3 in neutral (MnO2) and 1 in strong alkali (MnO4 2-), so its equivalent weight is 31.6, 52.7 or 158.

What is the difference between iodometry and iodimetry?

Iodometry is indirect: an oxidant liberates iodine from excess potassium iodide and the iodine is titrated with sodium thiosulphate. Iodimetry is direct: a standard iodine solution titrates a reductant such as sulphite or thiosulphate. Starch shows the end point in both.

Why is KMnO4 called a self-indicator?

Permanganate is intensely purple, while its reduction product Mn2+ is almost colourless. As long as reductant remains each drop is decolourised; the first drop in excess gives a permanent pale pink at about 0.000001 mol per litre, so no separate indicator is needed.

What does 20 volume hydrogen peroxide mean?

It means one litre of the solution gives 20 litres of oxygen at STP on decomposition. Since 2 moles of H2O2 give 22.4 litres of O2, volume strength equals 11.2 times molarity, so 20 volume H2O2 is 1.79 M, 3.57 N and about 6 percent weight by volume.

Which redox stoichiometry questions are asked in NEET?

NEET asks one-step problems: molarity or normality from titration volumes, equivalent weight of KMnO4 or K2Cr2O7, volume strength of H2O2, and the mole ratio of oxidant to reductant from a balanced equation, plus NCERT facts on KMnO4 as a self-indicator and starch in iodometric titrations.

How do JEE Main and JEE Advanced test redox titrations?

JEE uses n-factors that change with the medium, back titration of ores such as pyrolusite, iodometric estimation of copper, mixtures titrated by two reagents, compounds like tetroxalate with different acid and redox n-factors, disproportionation n-factors and volume strength conversions, often as integer-answer questions.

Previous year questions on Advance Stoichiometry Based on Redox Reactions

13 questions from past papers, each with a step-by-step solution.

Show all 13 questions

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