A thermodynamic principle states that the enthalpy change of a reaction is independent of the pathway taken between initial and final states. This means that if a reaction can occur via multiple routes, the total enthalpy change will be the same regardless of the specific steps involved. Consequently, the heat of reaction can be determined by summing the enthalpy changes for individual steps, even if those steps are hypothetical. For example, the enthalpy change for the formation of carbon dioxide from carbon and oxygen can be determined directly by burning carbon in oxygen, or indirectly by first reacting carbon to carbon monoxide and then reacting the carbon monoxide with more oxygen to yield carbon dioxide. The total enthalpy change will be the same in both cases.
This principle provides a powerful tool for determining enthalpy changes of reactions that are difficult or impossible to measure directly. This is particularly useful in cases where a reaction proceeds too slowly, produces unwanted side products, or involves unstable intermediates. By using known enthalpy changes of other reactions, it is possible to calculate the desired enthalpy change, providing valuable thermodynamic data. Historically, this principle played a significant role in the development of thermochemistry and continues to be essential in various fields like chemical engineering, materials science, and environmental science.