Doc Brown's Advanced A level theoretical chemistry revision notes

 Part 8.5 The Theory and Practice of Steam Distillation

[Author ©  Dr Phil Brown PhD: Doc Brown's Chemistry exam revision notes suitable for advanced A level chemistry students studying pre–university/college advanced level theoretical–physical chemistry courses:  steam distillation  [page updated May 2nd 2026 *]

8.5 Extraction using steam distillation of immiscible liquids

(NOT fractional distillation of miscible liquids involving water e.g. fractionally distilling fermented sugar solution to extract ethanol)

What is steam distillation? Why is steam distillation useful for thermally unstable compounds?

What apparatus do you need? How do you do a steam distillation?

A steam distillation calculation to theoretically predict the composition of the distillate are fully explained.

We consider its advantages over conventional fractional distillation and how it used to extract organic compounds from complex from reaction mixtures - natural or synthetic

• The technique of steam distillation is a very useful method for extracting molecules with a high boiling point, which under normal distillation conditions might thermally decompose.
  • i.e. the kinetic energies of the molecules at the boiling point may be sufficient to overcome the activation energies of possible reactions such as decomposition into smaller molecules or transformation into another molecule of similar size.
• As has been stated earlier, when a liquid is heated, the vapour pressure rises, and when it equals the ambient pressure the liquid boils i.e. bubbles of vapour can form in the bulk of the liquid.
• If a mixture of two immiscible liquids (or solutions) is heated, BOTH molecules can contribute to the vapour pressure and BOTH will express their full saturated vapour pressure because being immiscible, the two liquids act independently..
  • so at a given temperature
  • P_tot = p_A + p_B, and is irrespective of the actual ratio of the volumes of liquids.
  • or P_tot = p_H2O + p_roduct, where P_product is the vapour pressure of the (usually organic) material extracted since we are dealing with steam distillation.
  • If the larger proportion of Ptot is from water vapour, you can then distil over substances at ~100^oC which might normally only distil over at much higher temperatures of say 150–300^oC.
  • This means you can predict two things from vapour pressure tables data:
    • (1) the temperature at which the mixture will distil over i.e. at normal pressure in the laboratory
      • i.e. when P_tot = p_H2O + p_product = 760 mmHg (101 kPa)
      • In the calculation procedure below to theoretically calculate the percentage by mass of water and desired product by mass:
      • p = partial pressure, n = mol, m = mass in g, M or M_r = relative molecular mass
    • (2) the composition of the distilled mixture if you know the distillation temperature
      • you do this calculation from the vapour pressure ratio as follows, because the vapour pressure ratio is also the mol ration (assuming ideal gas behaviour)
      • Think of the product as the desired organic compound extracted from the mixture by steam distillation.
      • p_product/p_H2O = n_product/n_H2O where n = number of moles of each component
        • this assumes mole ratio and vapour pressure ratio are identical, which is strictly speaking only true for ideal gases, but accurate enough in this context.
      • So, bringing in relative molecular masses and mols n = m/M_r
      • P_product/P_H2O = (m_product/M_product) / (m_H2O/18)
      • and carefully rearranging gives the product mass ratio
      • m_product/m_H2O = (P_product x M_product) / (P_H2O x 18)
      • to give the mass ratio in the distillate
      • from the mass ratio numbers you can then calculate
      • % m_product = (m_product x 100) / (m_product + m_H2O)
      • See the example calculation at the end.
• In practice the vapour pressure due to water often far exceeds that of the extracted material but there are several advantages to using steam distillation as a mixture separation technique e.g.
•  USES and advantages of using steam distillation compared to conventional distillation.
• (i) It is important to realise is that a thermally unstable organic material can then be distilled over at a temperature much lower than its decomposition or transformation temperature - avoids thermal decomposition which might occur at its normal boiling point.
• (ii) You can extract a (not very) volatile organic compound from a complex and often messy reaction mixture, as long as everything else is not volatile apart from water.
• (iii) Steam distillation is used to extract perfume compounds from naturally occurring plant materials.
• Below is shown the experimental technique for extracting phenylamine from a nitrobenzene reduction in section 8.5 Organic Redox reactions
• 
• The technique is widely used in the extraction of molecules from natural products e.g.
  • In the perfumery industry, perfume molecules like those from lavender can be extracted from natural plant materials using steam distillation – an unforgettable 'odour' experienced from the rural distilleries of Provence whilst driving in France! – not that the 'kids' where interested back in those days!
• Vacuum or reduced pressure distillation is a superior method BUT is not always as convenient? or practical? or cheap? in the context of a rural industry!

WHAT NEXT?

Part 8 sub–index: 8.1 Vapour pressure, nature, origin and examples explained * 8.2.1 Introduction to the types of intermolecular forces and examples explained (index) * 8.2.2 Detailed comparative discussion of boiling points of 8 organic molecule of similar molecular mass * 8.3 Boiling point plots of six organic homologous series - graphs and explanation * 8.4 Other case studies of boiling points related to intermolecular forces * 8.5 Steam distillation – theory and practice * Evidence and theory for hydrogen bonding in simple covalent hydride * 8.7 Solubility of covalent compounds, miscible and immiscible liquids

Advanced Equilibrium Chemistry Notes Part 1. Equilibrium, Le Chatelier's Principle–rules * Part 2. K_c and K_p equilibrium expressions and calculations * Part 3. Equilibrium and industrial processes * Part 4. Partition, solubility product and ion–exchange * Part 5. pH, weak–strong acid–base theory and calculations * Part 6. Salt hydrolysis, Acid–base titrations–indicators, pH curves and buffers * Part 7. Redox equilibria, half–cell electrode potentials, electrolysis and electrochemical series