Ch. 1 | Some Basic Concepts of Chemistry0/14

Percentage Labelling of Oleum

Decode the SO₃ content of fuming sulphuric acid and calculate its H₂SO₄ yield

🖼 Image PendingIndustrial storage of oleum (fuming sulphuric acid) with rising acidic mist

AI Generation Prompt

Ultra-wide cinematic banner (16:5 ratio). A dark industrial scene at night — large metallic storage tanks of oleum with faint orange safety lighting, thin white acidic fumes curling upward from valve fittings. In the foreground, a sealed glass ampoule holding a deep amber liquid with fine white mist rising off its surface. Conveys chemical potency and industrial scale. Photorealistic, dark cinematic atmosphere, orange accent lighting. No text.

Real Life Hook

Walk into a Contact Process sulphuric acid plant and the air itself stings. That sting is oleum — sulphuric acid so concentrated that it holds dissolved sulphur trioxide, which grabs moisture from the air instantly to form a white acidic mist.

Oleum is not a lab curiosity. It is the working intermediate in the industrial manufacture of almost all the world's HX2SOX4\ce{H2SO4}, and it is potent enough that its containers must stay sealed at all times. Its other name — fuming sulphuric acid — is completely literal.

What oleum is. Oleum is a solution of free sulphur trioxide (SOX3\ce{SO3}) dissolved in 100% sulphuric acid (HX2SOX4\ce{H2SO4}). It is loosely written as HX2SX2OX7\ce{H2S2O7} (pyrosulphuric acid), but the real composition depends on how much SOX3\ce{SO3} was dissolved — it is not a fixed compound.

Oleum is made in the Contact Process by absorbing excess SOX3\ce{SO3} gas into concentrated HX2SOX4\ce{H2SO4}. Dissolving SOX3\ce{SO3} straight into water is avoided — that reaction is so violently exothermic that it shatters glassware and throws up a dangerous acid mist. Oleum is the controlled route to ultra-concentrated HX2SOX4\ce{H2SO4}.

The Dilution Chemistry

What happens when oleum is diluted. Add water to oleum and the free SOX3\ce{SO3} reacts with it to make more HX2SOX4\ce{H2SO4}:

SOX3+HX2OHX2SOX4\ce{SO3 + H2O -> H2SO4}

Treating the whole oleum as one unit: HX2SOX4+SOX3+HX2O2HX2SOX4\ce{H2SO4 + SO3 + H2O -> 2H2SO4}

Dilution is continued until every bit of free SOX3\ce{SO3} has converted to HX2SOX4\ce{H2SO4}. Notice the mass bookkeeping: 80 g of SOX3\ce{SO3} takes in 18 g of HX2O\ce{H2O} to give 98 g of HX2SOX4\ce{H2SO4} — heavier than the SOX3\ce{SO3} you started with. The total mass of the solution grows during dilution, and that growth is exactly what the % labelling number records.

🖼 Image PendingComposition breakdown of 118% oleum into SO3 and H2SO4 fractions before and after dilution

AI Generation Prompt

Infographic-style diagram on a dark background. Left: a labelled flask "100 g Oleum (118%)" split into two coloured bands — 80 g SO₃ (orange, upper) and 20 g H₂SO₄ (blue, lower). A horizontal arrow labelled "+ 18 g H₂O" points right. Right: a labelled flask "118 g H₂SO₄" as a single unified blue band. Beneath the arrow, the equation SO₃ + H₂O → H₂SO₄ with masses 80 g + 18 g → 98 g. Dark background (#0a0a0a), orange and blue accent labels, clean technical illustration style.

📸 118% oleum: a 100 g sample holds 80 g free SO₃ + 20 g H₂SO₄. Adding 18 g water converts all the SO₃ into 98 g H₂SO₄, giving 118 g total.

What % Labelling Actually Means

The definition. The % labelling of oleum = the total grams of HX2SOX4\ce{H2SO4} you obtain when exactly 100 g of the oleum is diluted with just enough water to convert all the free SOX3\ce{SO3}.

118% oleum — worked through. 100 g of it needs 18 g of HX2O\ce{H2O} for complete dilution. Moles of HX2O\ce{H2O} = 1, so moles of SOX3\ce{SO3} that reacted = 1 — meaning 80 g of free SOX3\ce{SO3} was present. The other 20 g was already HX2SOX4\ce{H2SO4}. After dilution: 20 g (original) + 98 g (from SOX3\ce{SO3}) = 118 g HX2SOX4\ce{H2SO4}

Patterns worth locking in:

  • % labelling is always greater than 100 for oleum (you add water, so the HX2SOX4\ce{H2SO4} mass overshoots 100 g)
  • Pure 100% HX2SOX4\ce{H2SO4} → exactly 100% labelling
  • Water needed for full dilution (g) =(%100)= (\% - 100)
  • Free SOX3\ce{SO3} in a 100 g sample =8018(%100)=409(%100)= \frac{80}{18}(\% - 100) = \frac{40}{9}(\% - 100) g
mSO3=40(x100)9 g,mH2O=(x100) gm_{\ce{SO3}} = \frac{40\,(x - 100)}{9}\text{ g}, \qquad m_{\ce{H2O}} = (x - 100)\text{ g}

Composition of x% Oleum (per 100 g sample)

Both follow from SO₃ + H₂O → H₂SO₄ stoichiometry. Check for 118%: m(SO₃) = 40×18/9 = 80 g, m(H₂O) = 18 g.

Example 1
SOLVED

Calculate the composition (mass of free SOX3\ce{SO3} and mass of HX2SOX4\ce{H2SO4}) of 109% labelled oleum.

Example 2
SOLVED

0.5 g of fuming HX2SOX4\ce{H2SO4} (oleum) is dissolved in water and neutralised completely by 26.7 mL of 0.4 N NaOH. Find the percentage of free SOX3\ce{SO3} in the sample.

JEE / NEET Exam InsightJEE / NEET
Labelling is not purity. % labelling > 100 means "grams of HX2SOX4\ce{H2SO4} you can make from 100 g," not "grams of HX2SOX4\ce{H2SO4} already inside." Mixing these up is the most common trap.
The one formula to anchor everything: water needed (g) =%100= \% - 100. From it, mSOX3=409(%100)m_{\ce{SO3}} = \frac{40}{9}(\% - 100) and mHX2SOX4=100mSOX3m_{\ce{H2SO4}} = 100 - m_{\ce{SO3}}.
Titration problems — use equivalents. When dissolved oleum is titrated against a base, both the HX2SOX4\ce{H2SO4} and the SOX3\ce{SO3} react: meq(HX2SOX4\ce{H2SO4}) + meq(SOX3\ce{SO3}) = meq(base). Equivalent weight of SOX3\ce{SO3} = 40, because its n-factor is 2 (it turns into dibasic HX2SOX4\ce{H2SO4}).
Quick Check

Q1.A bottle is labelled "112% H₂SO₄". What does this mean?