Reversing a thermochemical equation changes the direction of the chemical process, so its enthalpy change must also reverse sign. An endothermic change becomes exothermic when represented in the opposite direction, and the numerical magnitude remains the same. This adjustment ensures that each equation contributes the correct energy change when equations are combined to reach the target reaction.
Multiplying every coefficient in a thermochemical equation by the same factor also multiplies its enthalpy change by that factor. The equation then represents a proportionally larger or smaller chemical change, so its energy change must scale accordingly. Applying this relationship allows known reactions to be adjusted before they are added in a Hess’s law calculation.
Intermediate substances appear in the equations used to construct a target reaction, but they must cancel when the equations are added. Their cancellation shows that the combined equations reproduce the desired reactants and products rather than introducing extra chemical species. This algebraic arrangement connects measured thermochemical equations with a reaction whose enthalpy change is being determined indirectly.
First, write the target reaction and compare it with the available thermochemical equations. Reverse any equation whose direction is unsuitable, changing the enthalpy sign, and multiply equations when their coefficients need scaling, multiplying the enthalpy value as well. Finally, add the adjusted equations and their enthalpy changes to obtain the value for the target reaction.
After adjusting the available equations, add the chemical species on both sides and cancel substances that occur in opposite directions. The remaining reactants and products should match the target equation, including their coefficients. The enthalpy values must be added using the same reversals and multipliers applied to the equations; otherwise, the calculated reaction enthalpy will not correspond to the assembled reaction.
Hess’s law is useful when the enthalpy change of a reaction is difficult to measure directly but related thermochemical equations are available. Chemists can combine equations involving combustion, formation, or other energy changes to obtain the target reaction enthalpy. This approach extends thermochemical analysis to chemical systems that cannot be evaluated conveniently through one direct measurement.