If the reaction of a known amount of substance X, n(X), is carried out in a calorimeter and the temperature change measured, the enthalpy change for that reaction (written with 1 mole of X in the equation) can be calculated as the actual heat transferred is given by
Note the negative sign because if the temperature of the calorimeter rises (ΔT positive) energy has been transfered from the reaction system to the calorimeter (the surroundings) and the reaction is exothermic.
Heat of formation of a substance: Symbol ΔfH, the heat (enthalpy) change when one mole of that substance is formed from its elements in their standard states.
By convention an element in its most stable form at 100 kPa pressure and 25 oC (298 K) is said to be in its standard state and to have an enthalpy of formation, ΔfH, of zero
Example:
we can also write this equation as:
Heat of combustion of a substance: Symbol ΔcH, the heat given out when one mole of that substance reacts with dioxygen to give the most oxidised products.
Example:
ΔcH(CH4) is the enthalpy change for the reaction
From the appropriate equation above it can be seen that ΔcH(H2) = ΔfH(H2O).
Hess's law (of constant heat summation): The enthalpy change for a reaction is independent of the way the reaction is carried out (i.e. it depends only on the initial conditions of the reactants and the final conditions of the products). Put another way if a reaction is carried out in a number of steps the enthalpy change is the sum of the enthalpy changes for each individual step.
It follows from Hess's law that for the general reaction
where Σ means "the sum of". This is a very useful expression because the enthalpy change for any reaction can be calculated from tables of heats of formation of the compounds involved.
Bond enthalpy (strength): The energy needed to break a chemical bond, with the bonding electrons being evenly divided between the fragments
Example: The oxygen-oxygen bond strength of dimethyl peroxide, CH3O-OCH3, is Δ r H for the reaction:
.