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Hydrocarbons

Free radical substitution and the photochlorination of alkanes

  • 3 things to know
  • Components 1 and 2

Overview

Type of mechanism by which methane reacts with chlorine, condition required for methane and chlorine to react together and three stages of a free radical substitution mechanism.

What you need to know

Answer each one before you reveal it.

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Key term

State the condition required for methane and chlorine to react together.

Key term

Write the equation for the initiation step in the chlorination of methane, and name the type of bond fission involved.

Key term

Explain why ultraviolet light breaks the Cl—Cl bond rather than the C—H bond of methane.

Questions from this subtopic

Each one with the model answer underneath.

  1. 1

    Name the type of mechanism by which methane reacts with chlorine.

    Model answer

    It reacts by free radical substitution.

  2. 2

    State the condition required for methane and chlorine to react together.

    Model answer

    Ultraviolet light is required to start the reaction.

  3. 3

    Name the three stages of a free radical substitution mechanism.

    Model answer

    They are initiation, propagation and termination.

  4. 4

    Write the equation for the initiation step in the chlorination of methane, and name the type of bond fission involved.

    Model answer

    Cl₂ → 2Cl•, and the fission is homolytic, with each chlorine atom taking one electron of the shared pair.

  5. 5

    Explain why ultraviolet light breaks the Cl—Cl bond rather than the C—H bond of methane.

    Model answer

    The Cl—Cl bond enthalpy is only about 242 kJ mol⁻¹, well below the 413 kJ mol⁻¹ of the C—H bond, so the ultraviolet photons carry enough energy to break the first but not the second.

  6. 6

    Write the two propagation steps in the chlorination of methane.

    Model answer

    Cl• + CH₄ → •CH₃ + HCl, and then •CH₃ + Cl₂ → CH₃Cl + Cl•.

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