Hess’s Law
There are two ways to determine the amount of heat involved in a chemical change:
measure it experimentally, or calculate it from other experimentally determined enthalpy
changes. Some reactions are difficult, if not impossible, to investigate and make accurate
measurements for experimentally. And even when a reaction is not hard to perform or
measure, it is convenient to be able to determine the heat involved in a reaction without
having to perform an experiment.
This type of calculation usually involves the use of Hess’s law, which states: If a process
can be written as the sum of several stepwise processes, the enthalpy change of the total
process equals the sum of the enthalpy changes of the various steps. Hess’s law is valid
because enthalpy is a state function: Enthalpy changes depend only on where a chemical
process starts and ends, but not on the path it takes from start to finish. For example, we
can think of the reaction of carbon with oxygen to form carbon dioxide as occurring either
directly or by a two-step process. The direct process is written:
In the two-step process, first carbon monoxide is formed:
Then, carbon monoxide reacts further to form carbon dioxide:
The equation describing the overall reaction is the sum of these two chemical changes:
Because the CO produced in Step 1 is consumed in Step 2, the net change is:
According to Hess’s law, the enthalpy change of the reaction will equal the sum of the
enthalpy changes of the steps.
Before we further practice using Hess’s law, let us recall two important features of ΔH.
1. ΔH is directly proportional to the quantities of reactants or products. For example,
the enthalpy change for the reaction forming 1 mole of NO2(g) is +33.2 kJ:
When 2 moles of NO2 (twice as much) are formed, the ΔH will be twice as large:
In general, if we multiply or divide an equation by a number, then the enthalpy change
should also be multiplied or divided by the same number.
2. ΔH for a reaction in one direction is equal in magnitude and opposite in sign to
ΔH for the reaction in the reverse direction. For example, given that:
Then, for the “reverse” reaction, the enthalpy change is also “reversed”:
Example 1
What is ΔH for the following reaction
given the following reactions
Example 2
Calculate ΔH for the process:
from the following information:
Example 3
Chlorine monofluoride can react with fluorine to form chlorine trifluoride:
Use the reactions here to determine the ΔH° for reaction (i):
Example 4
Aluminum chloride can be formed from its elements:
Use the reactions here to determine the ΔH° for reaction (i):
