Chemistry · Some Basic Concepts of Chemistry

Percentage Composition & Empirical Formula

When a new or unknown compound is handed to a chemist, the first question is always the same: what is its formula, and in what ratio are the elements present? NCERT Section 1.9 answers this through mass percent composition and the empirical formula. This subtopic builds the complete bridge — from the mass percent of each element, to the simplest whole-number ratio of atoms, to the exact molecular formula via $n = M / M_{\text{emp}}$. It is one of the most reliably tested calculation areas in NEET.

Mass Percent Composition

Mass percent composition expresses how much of the total mass of a compound is contributed by each constituent element. For a pure substance the composition is fixed — this is a direct consequence of the law of definite proportions — so the mass percent of any element is a characteristic constant of that compound. Comparing the measured composition of a sample against the theoretical value is the standard way to check the purity of a substance.

The defining relation, taken directly from NCERT Section 1.9, is straightforward. The mass of an element in one mole of compound is divided by the molar mass of the whole compound and scaled to a percentage:

$$\text{Mass \% of an element} = \frac{\text{mass of that element in one mole of compound}}{\text{molar mass of the compound}} \times 100$$

The numerator is found by multiplying the number of atoms of that element in the formula by its atomic mass. Because the percentages of all elements in a compound must add to 100, the last element's percentage can often be obtained by subtraction rather than by a separate calculation — a useful time-saver in the examination hall.

QuantityMeaningHow to obtain it
Mass of element in 1 molContribution of one element to the molar mass(number of atoms in formula) × (atomic mass)
Molar mass of compoundSum of atomic masses of all atoms in the formulaAdd every atom's atomic mass
Mass percentFraction of total mass from that element$\dfrac{\text{element mass}}{\text{molar mass}}\times 100$
CheckAll percentages must total 100%Sum of all mass percents = 100

Worked Examples — Percent Composition

The cleanest illustration is water, $\ce{H2O}$, whose molar mass is $18.02\ \text{g mol}^{-1}$. Water contains two hydrogen atoms (mass $2 \times 1.008 = 2.016\ \text{g}$) and one oxygen atom (mass $16.00\ \text{g}$). Applying the definition gives the two percentages, which sum to 100 as required.

Worked Example 1

Calculate the mass percent of hydrogen and oxygen in water, $\ce{H2O}$.

$$\text{Mass \% of H} = \frac{2.016}{18.02}\times 100 = 11.18\%$$

$$\text{Mass \% of O} = \frac{16.00}{18.02}\times 100 = 88.79\%$$

The two values add to $99.97\%$, i.e. $100\%$ within rounding — a built-in check that the composition is internally consistent.

A second NCERT example, ethanol $\ce{C2H5OH}$, extends this to a three-element compound. Its molar mass is $(2\times 12.01 + 6\times 1.008 + 16.00) = 46.068\ \text{g}$. The carbon mass is $2\times 12.01 = 24.02\ \text{g}$, the hydrogen mass is $6\times 1.008 = 6.048\ \text{g}$, and the oxygen mass is $16.00\ \text{g}$.

Worked Example 2

Find the mass percent of C, H and O in ethanol, $\ce{C2H5OH}$ (molar mass $46.068\ \text{g}$).

$$\text{Mass \% of C} = \frac{24.02}{46.068}\times 100 = 52.14\%$$

$$\text{Mass \% of H} = \frac{6.048}{46.068}\times 100 = 13.13\%$$

$$\text{Mass \% of O} = \frac{16.00}{46.068}\times 100 = 34.73\%$$

Total $= 52.14 + 13.13 + 34.73 = 100.00\%$.

NEET Trap

Atoms, not molecules, in the numerator

For hydrogen in water the mass to use is $2 \times 1.008 = 2.016\ \text{g}$, accounting for both hydrogen atoms — not a single atom's mass of $1.008\ \text{g}$. A common slip is to forget the subscript multiplier and halve the hydrogen percentage.

Always multiply the atomic mass by the number of atoms of that element in one formula unit before forming the ratio.

Empirical vs Molecular Formula

Two distinct kinds of formula describe a compound, and NEET frequently tests whether candidates can tell them apart. An empirical formula represents the simplest whole-number ratio of the various atoms present in a compound. A molecular formula shows the exact number of atoms of each element present in one molecule of the compound. The molecular formula is therefore always an integral multiple of the empirical formula.

This relationship is captured by a single equation that underpins the entire subtopic, where $X$ is the empirical formula and $n$ is a whole number:

$$\text{Molecular formula} = (\text{Empirical formula})_n = X_n$$

Empirical formula CH₂O × n n = 6 Molecular formula C₆H₁₂O₆ Glucose one real molecule Same C : H : O ratio of 1 : 2 : 1 — only the absolute atom count differs.
Figure 2. The molecular formula is the empirical formula scaled by a whole number n. Glucose has the empirical formula CH₂O, but each molecule actually contains six such units, so the molecular formula is C₆H₁₂O₆ (n = 6). Both formulas preserve the identical 1 : 2 : 1 ratio of carbon, hydrogen and oxygen.
CompoundMolecular formulaEmpirical formulan
Glucose$\ce{C6H12O6}$$\ce{CH2O}$6
Hydrogen peroxide$\ce{H2O2}$$\ce{HO}$2
Benzene$\ce{C6H6}$$\ce{CH}$6
Water$\ce{H2O}$$\ce{H2O}$1
Sucrose$\ce{C12H22O11}$$\ce{C12H22O11}$1

When the subscripts of the molecular formula are already in their simplest ratio and cannot be reduced to smaller integers, the empirical and molecular formulas coincide and $n = 1$. Water, ammonia $\ce{NH3}$, carbon dioxide $\ce{CO2}$ and sucrose are standard examples. For ionic compounds such as $\ce{NaCl}$, $\ce{KCl}$ and $\ce{MgO}$, only an empirical (simplest-ratio) formula is meaningful, since these solids do not exist as discrete molecules.

The 5-Step Method for the Empirical Formula

If the mass percent of every element in a compound is known, its empirical formula can be derived by a fixed algorithm. The molecular formula follows whenever the molar mass is also supplied. The schematic below shows the full pipeline that this subtopic asks you to master.

Mass % composition Moles of each (÷ atomic mass) Empirical (÷ smallest) Molecular (× n) n = molar mass ÷ empirical formula mass
Figure 1. The complete pipeline. Mass percent data is converted to moles, reduced to the simplest ratio (the empirical formula), and finally scaled by the integer n to give the molecular formula. The last step requires the molar mass.
StepOperationOutput
1Assume a 100 g sample; each mass percent becomes that many gramsMass of each element (g)
2Divide each mass by the element's atomic massMoles of each element
3Divide every mole value by the smallest mole valueProvisional mole ratio
4If ratios are not whole numbers, multiply all by a small integer; write subscriptsEmpirical formula
5Compute $n = M / M_{\text{emp}}$ and multiply the empirical formula by $n$Molecular formula

The assumption of a 100 g sample in Step 1 is purely a convenience. Because the empirical formula depends only on the ratio of atoms, the chosen sample size cannot affect the answer; taking 100 g simply makes each percentage equal to a mass in grams.

Build the foundation

Every step here rests on converting mass to moles. If that conversion is shaky, revisit Mole Concept & Molar Mass first.

Worked Example — NCERT Chlorinated Compound

NCERT Problem 1.2 is the canonical application of all five steps at once, and several NEET items are direct variants of it. A compound contains $4.07\%$ hydrogen, $24.27\%$ carbon and $71.65\%$ chlorine, with a molar mass of $98.96\ \text{g}$. The table tracks Steps 1 to 3 in one view.

ElementMass % → mass in 100 gMoles (÷ atomic mass)÷ smallest (2.021)
H4.07 g$\dfrac{4.07}{1.008} = 4.04$$\dfrac{4.04}{2.021} = 2$
C24.27 g$\dfrac{24.27}{12.01} = 2.021$$\dfrac{2.021}{2.021} = 1$
Cl71.65 g$\dfrac{71.65}{35.453} = 2.021$$\dfrac{2.021}{2.021} = 1$
Worked Example 3

Determine the empirical and molecular formulas of the compound above.

Step 4 — empirical formula. The ratio $\text{H} : \text{C} : \text{Cl} = 2 : 1 : 1$, all whole numbers, so the empirical formula is $\ce{CH2Cl}$.

Step 5 — molecular formula. Empirical formula mass: $12.01 + (2\times 1.008) + 35.453 = 49.48\ \text{g}$.

$$n = \frac{M}{M_{\text{emp}}} = \frac{98.96}{49.48} = 2$$

Multiplying every subscript by $n = 2$ gives the molecular formula $\ce{C2H4Cl2}$.

Molecular Formula from Empirical Formula

Once the empirical formula is known, recovering the molecular formula is a two-stage arithmetic exercise. First, the empirical formula mass $M_{\text{emp}}$ is obtained by summing the atomic masses of every atom in the empirical unit. Second, the integer multiplier $n$ is the ratio of the experimentally known molar mass to that empirical formula mass.

$$M_{\text{emp}} = \sum (\text{atoms in empirical unit}) \times (\text{atomic mass}), \qquad n = \frac{M}{M_{\text{emp}}}$$

The value of $n$ must round to a whole number; a small deviation (such as $5.97$ or $2.04$) reflects rounding in the atomic masses or the percentages and should be taken as the nearest integer. Multiplying each subscript of the empirical formula by $n$ then yields the molecular formula.

NEET Trap

When ratios are not clean integers

In Step 3 a ratio may emerge as $1 : 1.5$ or $1 : 1.33$. Do not round these to whole numbers prematurely — multiply every ratio by the smallest integer that clears the fraction. A $1.5$ requires multiplying by 2 (giving $2 : 3$); a $1.33$ ($\approx 4/3$) requires multiplying by 3 (giving $3 : 4$).

Rounding 1.5 down to 1 changes the compound entirely. Clear the fraction first, then round only genuine measurement noise.

Worked Example — Iron Oxide

The NCERT exercise on an oxide of iron tests the same method with a two-element compound where one percentage is found by subtraction. The oxide contains $69.9\%$ iron, and the remaining $30.1\%$ is oxygen (atomic masses $\ce{Fe} = 55.85$, $\ce{O} = 16.00$). For a 100 g sample this is $69.9\ \text{g}$ Fe and $30.1\ \text{g}$ O.

ElementMass in 100 gMoles÷ smallest (1.252)×2 (clear 0.5)
Fe69.9 g$\dfrac{69.9}{55.85} = 1.252$$1.00$$2$
O30.1 g$\dfrac{30.1}{16.00} = 1.881$$1.50$$3$
Worked Example 4

Find the empirical formula of the iron oxide (69.9% Fe, 30.1% O).

Dividing by the smaller mole value gives $\text{Fe} : \text{O} = 1 : 1.5$, which is not whole-number. Multiplying both by 2 clears the half: $\text{Fe} : \text{O} = 2 : 3$.

The empirical formula is therefore $\ce{Fe2O3}$ — haematite — consistent with iron in its $+3$ oxidation state.

This example also demonstrates the subtraction shortcut for the final percentage: only iron was measured, and oxygen was obtained as $100 - 69.9 = 30.1\%$. The same arithmetic, applied with the molar mass of the oxide ($159.7\ \text{g}$ for $\ce{Fe2O3}$), would confirm $n = 1$ since the empirical and molecular formulas of this oxide are identical.

Quick Recap

Percentage Composition & Empirical Formula

  • Mass % of an element $= \dfrac{\text{mass of element in 1 mol}}{\text{molar mass}} \times 100$; all percentages sum to 100.
  • Empirical formula = simplest whole-number atom ratio; molecular formula = exact atom count per molecule.
  • Relationship: molecular formula $= X_n$, where $n = M / M_{\text{emp}}$ is a whole number.
  • Five steps: 100 g sample → moles → divide by smallest → clear fractions to subscripts → multiply by $n$.
  • Worked anchors: $\ce{CH2Cl} \to \ce{C2H4Cl2}$ ($n=2$); iron oxide $1:1.5 \to 2:3 \to \ce{Fe2O3}$.
  • When the molecular subscripts are already simplest, empirical = molecular and $n = 1$ (e.g. $\ce{H2O}$, $\ce{CO2}$).

NEET PYQ Snapshot — Percentage Composition & Empirical Formula

Empirical-formula and percentage-composition items from recent NEET papers, solved with the 5-step method.

NEET 2024 · Q.100

A compound X contains 32% of A, 20% of B and the remaining percentage of C. The empirical formula of X is (atomic masses $A = 64$, $B = 40$, $C = 32\ \text{u}$):

  • (1) $\ce{A2BC2}$
  • (2) $\ce{ABC3}$
  • (3) $\ce{A2B2C}$
  • (4) $\ce{ABC4}$
Answer: (2) $\ce{ABC3}$

C is $100 - 32 - 20 = 48\%$. Moles: $A = 32/64 = 0.5$, $B = 20/40 = 0.5$, $C = 48/32 = 1.5$. Dividing by smallest (0.5): $A : B : C = 1 : 1 : 3$, giving $\ce{ABC3}$.

NEET 2021 · Q.82

An organic compound contains 78% (by wt.) carbon and the remaining percentage of hydrogen. The empirical formula of this compound is (atomic wt. C = 12, H = 1):

  • (1) $\ce{CH4}$
  • (2) $\ce{CH}$
  • (3) $\ce{CH2}$
  • (4) $\ce{CH3}$
Answer: (4) $\ce{CH3}$

H is $100 - 78 = 22\%$. Moles: $C = 78/12 = 6.5$, $H = 22/1 = 22$. Dividing by smallest (6.5): $C : H = 1 : 3.38 \approx 1 : 3$, giving $\ce{CH3}$.

Concept · Empirical → Molecular

A compound has the empirical formula $\ce{CH2O}$ and a molar mass of $180\ \text{g mol}^{-1}$. Its molecular formula is:

  • (1) $\ce{CH2O}$
  • (2) $\ce{C2H4O2}$
  • (3) $\ce{C6H12O6}$
  • (4) $\ce{C3H6O3}$
Answer: (3) $\ce{C6H12O6}$

Empirical formula mass of $\ce{CH2O} = 12 + 2 + 16 = 30\ \text{g}$. $n = 180/30 = 6$. Multiplying subscripts by 6 gives $\ce{C6H12O6}$ (glucose).

FAQs — Percentage Composition & Empirical Formula

Common doubts on mass percent, the empirical–molecular distinction and the n-multiplier.

What is the difference between empirical formula and molecular formula?

An empirical formula represents the simplest whole-number ratio of the various atoms present in a compound, whereas the molecular formula shows the exact number of different types of atoms present in one molecule of the compound. The molecular formula is always an integral multiple of the empirical formula, that is molecular formula = n × empirical formula, where n is a whole number. For example, the empirical formula of glucose is CH2O while its molecular formula is C6H12O6, so n = 6.

How do you calculate the mass percent of an element in a compound?

Mass percent of an element equals the mass of that element in one mole of the compound divided by the molar mass of the compound, multiplied by 100. For example, in water (H2O) the molar mass is 18.02 g, so the mass percent of hydrogen is (2.016 / 18.02) × 100 = 11.18% and the mass percent of oxygen is (16.00 / 18.02) × 100 = 88.79%.

What are the steps to determine an empirical formula from percentage composition?

Step 1: assume a 100 g sample so each percentage becomes that many grams. Step 2: divide each mass by the element's atomic mass to get moles. Step 3: divide every mole value by the smallest mole value to get the mole ratio. Step 4: if the ratios are not whole numbers, multiply all of them by a suitable small integer to clear fractions, then write the formula using these numbers as subscripts. Step 5: if molar mass is given, compute the molecular formula.

How do you find the molecular formula from the empirical formula?

First find the empirical formula mass by adding the atomic masses of all atoms in the empirical formula. Then compute n = molar mass ÷ empirical formula mass, where n is rounded to the nearest whole number. Finally, multiply every subscript in the empirical formula by n. For example, for empirical formula CH2Cl (empirical formula mass 49.48 g) with molar mass 98.96 g, n = 98.96 / 49.48 = 2, so the molecular formula is C2H4Cl2.

Can the empirical formula be the same as the molecular formula?

Yes. When the subscripts in the molecular formula are already in the simplest whole-number ratio and cannot be reduced to smaller integers, the empirical and molecular formulas are identical and n = 1. Water (H2O), ammonia (NH3), carbon dioxide (CO2) and sucrose (C12H22O11) are examples where the two formulas coincide.

Why do we assume a 100 g sample when finding an empirical formula?

Assuming a 100 g sample is a convenience: when the data is given as mass percent, each percentage value directly becomes the number of grams of that element in the 100 g sample. This removes the need for an actual mass and lets us convert straight to moles. Because the empirical formula only depends on the ratio of atoms, the assumed sample size does not affect the final answer.