Thermodynamic Terms

01Thermodynamic Terms

Enthalpy of formation and atomisation

This section covers standard enthalpy of formation and standard enthalpy of atomisation, including their equations and sign conventions.

Standard enthalpy of formation

Standard enthalpy of formation, ΔfH\Delta_\mathrm{f}H^\circ, is the enthalpy change for producing exactly one mole of a compound directly from its constituent elements, with all substances in their standard states under standard conditions.

For this course, standard conditions are 298 K and 100 kPa. An equation representing an enthalpy of formation must therefore produce exactly one mole of the compound.

Na(s)+12ClX2(g)NaCl(s)\ce{Na(s) + 1/2Cl2(g) -> NaCl(s)}    ΔfH=411 kJmol1\Delta_\mathrm{f}H^\circ = -411\ \mathrm{kJ\,mol^{-1}}

By convention, an element in its standard state has ΔfH=0\Delta_\mathrm{f}H^\circ=0. Formation enthalpies of compounds may be positive or negative.

Standard enthalpy of atomisation

Standard enthalpy of atomisation, ΔatH\Delta_\mathrm{at}H^\circ, is the enthalpy change for converting an element in its standard state into exactly one mole of gaseous atoms under standard conditions.

Atomisation requires particles in an element to be separated into individual gaseous atoms, so it is an endothermic process and its enthalpy change is positive.

Element in its standard state Atomisation equation Key requirement
Potassium, solid K(s)K(g)\ce{K(s) -> K(g)} Forms 1 mol of K(g)\ce{K(g)} atoms
Mercury, liquid Hg(l)Hg(g)\ce{Hg(l) -> Hg(g)} Starts from mercury's standard state
Chlorine, gas 12ClX2(g)Cl(g)\ce{1/2Cl2(g) -> Cl(g)} The 12\frac12 coefficient gives 1 mol of atoms

Worked example: writing atomisation equations

Question: Write equations representing the standard enthalpy of atomisation of potassium and mercury.

Potassium: its standard state is solid, and one mole of gaseous atoms must be produced:

K(s)K(g)\ce{K(s) -> K(g)}

Mercury: its standard state is liquid, so the starting state must be Hg(l)\ce{Hg(l)}:

Hg(l)Hg(g)\ce{Hg(l) -> Hg(g)}

Exam Tip: In a formation equation, check that exactly one mole of compound is formed. In an atomisation equation, check that exactly one mole of gaseous atoms is formed and that the element starts in its standard state.

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