Gen Chem 1Composition and Mass Spectra

Combustion Analysis

Burn a compound, weigh the CO₂ and H₂O, and work back to its empirical formula.

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To find a new compound's formula you need its mass percent of each element, as in Empirical Formulas. For compounds of carbon and hydrogen (and often oxygen), the classic way to get those percents is to burn a weighed sample and weigh what comes out, a careful use of Mass-to-Mass Stoichiometry.

The sample burns in a stream of pure oxygen. Every carbon atom ends up in $\mathrm{CO_2}$ and every hydrogen atom in $\mathrm{H_2O}$. The gases pass through two tubes: one soaks up the water and the other the carbon dioxide. Each tube is weighed before and after, and the gains are the masses of $\mathrm{H_2O}$ and $\mathrm{CO_2}$ formed.

Key idea

$$m_\text{C} = m_{\mathrm{CO_2}} \times \frac{12.01}{44.01}, \qquad m_\text{H} = m_{\mathrm{H_2O}} \times \frac{2(1.01)}{18.02}, \qquad m_\text{O} = m_\text{sample} - m_\text{C} - m_\text{H}.$$ Then change each mass to moles and find the smallest whole-number ratio.

Why it works

Atoms are conserved. All the carbon in the $\mathrm{CO_2}$ came from the sample, since the oxygen gas has none, and the fraction of $\mathrm{CO_2}$'s mass that is carbon is $12.01/44.01$. The same goes for hydrogen in water, with 2 H atoms per molecule. Oxygen is different: the products' oxygen came partly from the sample and partly from the $\mathrm{O_2}$ it burned in, and we cannot tell which atoms came from where. So the sample's oxygen is whatever mass is left over.
From grams of $\mathrm{CO_2}$ to moles of carbon: one carbon atom per $\mathrm{CO_2}$ molecule. For hydrogen, the second factor is 2 mol H per mol $\mathrm{H_2O}$.

Worked example: A hydrocarbon

Burning $0.440\ \text{g}$ of a hydrocarbon (only C and H) gives $1.317\ \text{g}$ of $\mathrm{CO_2}$ and $0.7190\ \text{g}$ of $\mathrm{H_2O}$. Find the empirical formula.
  1. Moles of C: $\dfrac{1.317}{44.01} = 0.02993\ \text{mol CO}_2$, so $0.02993\ \text{mol C}$ (mass $0.3594\ \text{g}$).
  2. Moles of H: $\dfrac{0.7190}{18.02} = 0.03990\ \text{mol H}_2\text{O}$, times 2 is $0.07980\ \text{mol H}$ (mass $0.0806\ \text{g}$).
  3. Check: $0.3594 + 0.0806 = 0.440\ \text{g}$, the whole sample, so there is no oxygen.
  4. Ratio: $\dfrac{0.07980}{0.02993} = 2.67$, so C : H = 1 : 2.67. Multiply by 3: 3 : 8.

Answer: $\mathrm{C_3H_8}$

Worked example: Oxygen by difference

A $0.2000\ \text{g}$ sample of a compound of C, H and O burns to $0.3995\ \text{g}$ of $\mathrm{CO_2}$ and $0.1636\ \text{g}$ of $\mathrm{H_2O}$. Its molar mass is about $88\ \text{g/mol}$. Find the empirical and molecular formulas.
  1. C: $0.3995 \times \dfrac{12.01}{44.01} = 0.1090\ \text{g}$, which is $0.1090/12.01 = 0.009077\ \text{mol}$.
  2. H: $0.1636 \times \dfrac{2.02}{18.02} = 0.01834\ \text{g}$, which is $0.01834/1.01 = 0.01816\ \text{mol}$.
  3. O: $0.2000 - 0.1090 - 0.01834 = 0.07264\ \text{g}$, which is $0.07264/16.00 = 0.004540\ \text{mol}$.
  4. Divide by the smallest (0.004540): C 2.00, H 4.00, O 1.00. Empirical formula $\mathrm{C_2H_4O}$, mass $44.06\ \text{g/mol}$.
  5. $88/44.06 = 2$, so the molecular formula is $\mathrm{C_4H_8O_2}$.

Answer: Empirical $\mathrm{C_2H_4O}$; molecular $\mathrm{C_4H_8O_2}$.

Common mistake

Taking the sample's oxygen from the products' oxygen. In the second example the $\mathrm{CO_2}$ and $\mathrm{H_2O}$ hold $0.4357\ \text{g}$ of oxygen in all, six times the $0.0726\ \text{g}$ that was really in the sample; most of it came from the $\mathrm{O_2}$. Find oxygen only by subtraction. Check: if C + H already add up to the sample's mass, the compound has no oxygen.
When a ratio comes out near 1.5, 1.33 or 1.25, multiply every number by 2, 3 or 4. Round only when a number is within about 0.1 of a whole number; 2.67 is not "about 3".

Practice

Pass with 3 right answers, the last 2 in a row. Each right answer earns 3 XP.

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This is one of the top rungs of General Chemistry 1.

Sources and further reading

  • OpenStax Chemistry 2e, 4.5 Quantitative Chemical Analysis
  • OpenStax Chemistry 2e, 3.2 Determining Empirical and Molecular Formulas
  • College Board, AP Chemistry Course and Exam Description (effective fall 2024), Unit 1: Atomic Structure and Properties
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