The enthalpy of formation (ΔH°f) is the heat change when one mole of a compound is formed from its constituent elements in their standard states at 298 K and 1 atm pressure. Standard enthalpies of formation for elements in their most stable form are defined as zero. These values are tabulated and used extensively with Hess's Law to calculate enthalpy changes for any chemical reaction.
ΔH°_rxn = Σn·ΔH°f(products) − Σm·ΔH°f(reactants)
LaTeX: \Delta H^\circ_{\text{rxn}} = \sum n \, \Delta H^\circ_f(\text{products}) - \sum m \, \Delta H^\circ_f(\text{reactants})
| Symbol | Meaning | Unit |
|---|---|---|
| ΔH°_rxn | Standard enthalpy of reaction | kJ/mol |
| n, m | Stoichiometric coefficients | dimensionless |
| ΔH°f | Standard enthalpy of formation | kJ/mol |
Problem
Calculate ΔH° for the combustion of methane: CH₄(g) + 2O₂(g) → CO₂(g) + 2H₂O(l). Given: ΔH°f[CH₄(g)] = −74.8 kJ/mol, ΔH°f[CO₂(g)] = −393.5 kJ/mol, ΔH°f[H₂O(l)] = −285.8 kJ/mol, ΔH°f[O₂(g)] = 0 kJ/mol.
Solution
Step 1: Apply the formation enthalpy equation. ΔH°_rxn = [1×(−393.5) + 2×(−285.8)] − [1×(−74.8) + 2×0] Step 2: Calculate products sum: −393.5 + (−571.6) = −965.1 kJ/mol. Step 3: Calculate reactants sum: −74.8 + 0 = −74.8 kJ/mol. Step 4: Subtract: ΔH°_rxn = −965.1 − (−74.8) = −965.1 + 74.8 = −890.3 kJ/mol.
Answer
ΔH° = −890.3 kJ/mol (exothermic)
| Compound | Formula | State | ΔH°f (kJ/mol) |
|---|---|---|---|
| Water | H₂O | Liquid | −285.8 |
| Carbon dioxide | CO₂ | Gas | −393.5 |
| Methane | CH₄ | Gas | −74.8 |
| Ammonia | NH₃ | Gas | −46.1 |
| Glucose | C₆H₁₂O₆ | Solid | −1274.0 |
| Ethanol | C₂H₅OH | Liquid | −277.7 |
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Hess's Law states that the total enthalpy change of a chemical reaction is independent of the pathway taken, depending only on the initial and final states of the system. This principle allows chemists to calculate enthalpy changes for reactions that are difficult or impossible to measure directly by combining known thermochemical equations. It is a direct consequence of the First Law of Thermodynamics, making enthalpy a state function.
Standard enthalpy refers to the enthalpy change of a process measured under standard conditions: 298.15 K (25 °C) and 1 bar (approximately 1 atm) pressure, with all substances in their standard states. Standard enthalpy values provide a universal reference for comparing thermochemical data across different reactions and sources. The symbol ΔH° (read "delta H naught" or "delta H standard") denotes a standard enthalpy change.
Gibbs free energy (G) is a thermodynamic potential that measures the maximum reversible work a system can perform at constant temperature and pressure, and determines the spontaneity of a process. A negative ΔG indicates a spontaneous reaction, a positive ΔG indicates a non-spontaneous reaction, and ΔG = 0 indicates a system at equilibrium. It combines enthalpy and entropy into a single criterion for spontaneity, making it one of the most powerful tools in chemical thermodynamics.
From Greek 'enthalpein' (to heat within) and Latin 'formatio' (a shaping or forming). The concept was systematized in the late 19th century following the work of Julius Thomsen and Marcellin Berthelot.