Hess's Law states that the total enthalpy change for a reaction is the sum of the enthalpy changes for individual steps, as enthalpy is a state function. The discussion centers on why Hess's Law may not appear to be obeyed in real-world scenarios. Participants suggest that the law is generally valid under ideal conditions, but can be violated when the actual quantities of reactants do not match the stoichiometric ratios required for the enthalpy changes to apply. This discrepancy can lead to situations where the observed enthalpy change is less than expected, as it only reflects the amount of reactants that actually participate in the reaction. The conversation emphasizes the importance of ensuring correct molar proportions in reactions for Hess's Law to hold true.