AQA A-Level Physical Chemistry 3.1.2 Amount of Substance Empirical and Molecular Formulae
3.1.2

Empirical and Molecular Formulae

Learn the definitions of empirical and molecular formulas and master how to calculate them from experimental data.

Analytical techniques, such as combustion analysis or mass spectrometry, allow chemists to determine the relative amounts of elements in a compound. We use this data to find the empirical and molecular formulas of the substance.

Definitions

Empirical Formula

The simplest whole number ratio of atoms of each element in a compound.

Molecular Formula

The actual number of atoms of each element in a compound.

🔑 Key Principle

A molecular formula is always a simple whole-number multiple of the empirical formula. For example, the empirical formula of glucose is \( \text{CH}_2\text{O} \), while its molecular formula is \( \text{C}_6\text{H}_{12}\text{O}_6 \) (which is exactly \( 6 \times \text{CH}_2\text{O} \)).

How to Calculate Empirical Formula

When given the percentage composition or masses of elements in a compound, follow these four structured steps:

Steps to Calculate Empirical Formula Step 1: Masses / % Assume 100g sample so % = mass in grams Step 2: Find Moles Divide each mass by its atomic mass (Ar) Step 3: Find Ratio Divide all mole values by the smallest value Step 4: Scale Ratio Scale to whole numbers (e.g. multiply 1.5 by 2)
✏️ Worked Example 1: Basic Empirical Formula
A compound contains 40.0% carbon, 6.7% hydrogen, and 53.3% oxygen by mass. Calculate the empirical formula of the compound.

Assume we have a 100 g sample of the compound. Write down the mass of each element:

  • Mass of Carbon (\( \text{C} \)) = \( 40.0 \text{ g} \)
  • Mass of Hydrogen (\( \text{H} \)) = \( 6.7 \text{ g} \)
  • Mass of Oxygen (\( \text{O} \)) = \( 53.3 \text{ g} \)

Step 1: Convert masses to moles using \( n = \frac{m}{A_r} \).

\[ n(\text{C}) = \frac{40.0}{12.0} = 3.33 \text{ mol} \]

\[ n(\text{H}) = \frac{6.7}{1.0} = 6.70 \text{ mol} \]

\[ n(\text{O}) = \frac{53.3}{16.0} = 3.33 \text{ mol} \]

Step 2: Divide all moles by the smallest value (\( 3.33 \)).

\[ \text{C} = \frac{3.33}{3.33} = 1.0 \]

\[ \text{H} = \frac{6.70}{3.33} = 2.01 \approx 2.0 \]

\[ \text{O} = \frac{3.33}{3.33} = 1.0 \]

The simplest whole number ratio is \( 1 : 2 : 1 \).

Therefore, the empirical formula is \( \text{CH}_2\text{O} \).

📝 AQA Examiner Tip

Sometimes the mole ratio will not resolve directly to whole numbers. Do not round numbers such as 1.5, 1.33, or 1.25. Instead, multiply the entire ratio to make them whole:

  • If ratio ends in .5, multiply all values by 2 (e.g. \( 1 : 1.5 \to 2 : 3 \))
  • If ratio ends in .33, multiply all values by 3 (e.g. \( 1 : 1.33 \to 3 : 4 \))
  • If ratio ends in .25, multiply all values by 4 (e.g. \( 1 : 1.25 \to 4 : 5 \))

How to Calculate Molecular Formula

To find the molecular formula, you must be given the relative molecular mass (\( M_r \)) of the compound along with either its empirical formula or the data to calculate it.

  1. Calculate the relative formula mass of the empirical formula.
  2. Divide the molecular \( M_r \) by the empirical mass to find the multiplier.
  3. Multiply all numbers of atoms in the empirical formula by this multiplier.
✏️ Worked Example 2: Finding Molecular Formula
A compound has the empirical formula \( \text{CH}_2 \) and a relative molecular mass of 84.0. Find its molecular formula.

Step 1: Calculate the empirical formula mass of \( \text{CH}_2 \).

\[ \text{Empirical mass} = A_r(\text{C}) + 2 \times A_r(\text{H}) = 12.0 + 2 \times 1.0 = 14.0 \]

Step 2: Divide the molecular mass by the empirical mass.

\[ \text{Multiplier} = \frac{\text{Molecular } M_r}{\text{Empirical mass}} = \frac{84.0}{14.0} = 6.0 \]

Step 3: Multiply the empirical formula by the multiplier.

\[ \text{Molecular Formula} = 6 \times (\text{CH}_2) = \text{C}_6\text{H}_{12} \]

The molecular formula of the compound is \( \text{C}_6\text{H}_{12} \).

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