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Unlike many other functions of state, entropy cannot be directly observed but must be calculated. Absolute standard molar entropy of a substance can be calculated from the measured temperature dependence of its heat capacity. The molar entropy of ions is obtained as a difference in entropy from a reference state defined as zero entropy.
Despite the foregoing, there is a difference between the two quantities. The information entropy Η can be calculated for any probability distribution (if the "message" is taken to be that the event i which had probability p i occurred, out of the space of the events possible), while the thermodynamic entropy S refers to thermodynamic probabilities p i specifically.
It is the difference between the enthalpy after the process has completed, i.e. the enthalpy of the products assuming that the reaction goes to completion, and the initial enthalpy of the system, namely the reactants. These processes are specified solely by their initial and final states, so that the enthalpy change for the reverse is the ...
In thermodynamics, a departure function is defined for any thermodynamic property as the difference between the property as computed for an ideal gas and the property of the species as it exists in the real world, for a specified temperature T and pressure P. Common departure functions include those for enthalpy, entropy, and internal energy.
There are multiple approaches to deriving the partition function. The following derivation follows the more powerful and general information-theoretic Jaynesian maximum entropy approach. According to the second law of thermodynamics, a system assumes a configuration of maximum entropy at thermodynamic equilibrium.
The entropy is thus a measure of the uncertainty about exactly which quantum state the system is in, given that we know its energy to be in some interval of size . Deriving the fundamental thermodynamic relation from first principles thus amounts to proving that the above definition of entropy implies that for reversible processes we have:
Figure 1. A thermodynamic model system. Differences in pressure, density, and temperature of a thermodynamic system tend to equalize over time. For example, in a room containing a glass of melting ice, the difference in temperature between the warm room and the cold glass of ice and water is equalized by energy flowing as heat from the room to the cooler ice and water mixture.
Entropy is one of the few quantities in the physical sciences that require a particular direction for time, sometimes called an arrow of time. As one goes "forward" in time, the second law of thermodynamics says, the entropy of an isolated system can increase, but not decrease. Thus, entropy measurement is a way of distinguishing the past from ...