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Fundamental thermodynamic relation

physical science Maturity 11-13 Next article →

The fundamental thermodynamic relation consists of four essential equations in thermodynamics. These equations demonstrate how important thermodynamic quantities depend on variables that scientists can control. In a laboratory, researchers can measure these variables experimentally. Using these relations, scientists can determine sought-after values like enthalpy (H) or Gibbs free energy (G). These equations are essentially equations of state. They describe the relationship between the different properties of a physical system.

To understand the mechanism, we look at a closed system in thermal equilibrium. The most common expression describes a microscopic change in internal energy (U). This change is expressed in terms of changes in entropy (S) and volume (V). We also include absolute temperature (T) and pressure (P). The relation shows that a change in internal energy is equal to the temperature multiplied by the change in entropy, minus the pressure multiplied by the change in volume. This specific form assumes the process is reversible. However, the relation also holds for non-reversible changes. This is because U, S, and V are state functions. This means they depend only on the initial and final states of the process.

Thermodynamics uses different variables to express these relations through various thermodynamic potentials. One way to express the relation is using enthalpy (H). Another way uses the Helmholtz free energy (F). A third way uses the Gibbs free energy (G). The math changes depending on which variables are being used. If the system contains different chemical components, the relation must generalize. In these cases, we add chemical potentials (mu) for each particle type. If the system has more external parameters, we use generalized forces (X). For example, if the parameter is volume, the force is pressure.

These relations can be derived from the two laws of thermodynamics. The first law of thermodynamics defines heat. It states that heat is the change in internal energy not caused by external parameters. The second law of thermodynamics relates to entropy. For a reversible process, the heat supplied is equal to the temperature multiplied by the change in entropy. By substituting this into the first law, we arrive at the fundamental relation. This provides a bridge between heat, work, and the internal energy of a system.

We can also derive these relations using statistical mechanics. This field looks at the microscopic world of particles. Entropy is defined by the number of microstates in a small energy interval. A microstate is a specific way the tiny parts of a system can be arranged. Entropy measures our uncertainty about which microstate the system is actually in. In the thermodynamic limit, which means an infinitely large system, the specific entropy does not depend on the energy interval. This allows us to connect tiny, microscopic movements to large, macroscopic properties.

Statistical mechanics uses the idea that all states at a particular energy are equally likely. This is known as the equal a priori probability postulate. Using this, we can define temperature based on how entropy changes with energy. We can also define generalized forces by looking at how energy levels change when an external parameter is adjusted. For instance, if we change a parameter like volume, the energy levels of the system move. This movement causes a change in the number of available states. This change is what we perceive as work or force in the macroscopic world.

Finally, the fundamental thermodynamic relation is deeply connected to the Boltzmann distribution. The Boltzmann distribution describes the probability density of a microstate. This distribution is linked to the partition function, which is a normalization factor. Scientists have shown that the fundamental relation and certain postulates can build the entire theory of statistical mechanics. This connection proves that the laws of physics are universal. They apply to any system, whether it is a small group of atoms or a massive gas.

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