Hess's Law states that the total enthalpy change of a reaction is the same, regardless of whether the reaction occurs in one step or multiple steps. This principle is based on the idea that enthalpy is a state function, meaning it depends only on the initial and final states of a system and not on the path taken to achieve that change. This law allows chemists to calculate enthalpy changes for reactions that are difficult to measure directly by using known enthalpy changes from other reactions.