Heat Transfer in Solids, Liquids, and Gases

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The Little Heat Engine:
Heat Transfer in Solids, Liquids and Gases

The question now is wherein the mistake consists and how it can be removed.

Max Planck, Philosophy of Physics, 1936.

While it is true that the field of thermodynamics can be complex,1-8 the basic ideas behind the study of heat (or energy) transfer remain simple. Let us begin this study with an ideal solid, S1, in an empty universe. S1 contains atoms arranged in a regular array called a "lattice" (see Figure 1). Bonding electrons may be present. The nuclei of each atom act as weights and the bonding electrons as springs in an oscillator model. Non-bonding electrons may also be present, however in an ideal solid these electrons are not involved in carrying current. By extension, S1 contains no electronic conduction bands. The non-bonding electrons may be involved in Van der Waals (or contact) interactions between atoms. Given these restraint, it is clear that S1 is a non-metal.

Ideal solids do not exist. However, graphite provides a close approximation of such an object. Graphite is a black, carbon-containing, solid material. Each carbon atom within graphite is bonded to 3 neighbors. Graphite is black because it very efficiently absorbs light which is incident upon its surface. In the 1800's, scientists studied objects made from graphite plates. Since the graphite plates were black, these objects became known as "blackbodies". By extension, we will therefore assume that S1, being an ideal solid, is also a perfect blackbody. That is to say, S1 can perfectly absorb any light incident on its surface.

Let us place our ideal solid, S1, in an imaginary box. The walls of this box have the property of not permitting any heat to be transferred from inside the box to the outside world and vice versa. When an imaginary partition has the property of not permitting the transfer of heat, mass, and light, we say that the partition is adiabatic. Since, S1 is alone inside the adiabatic box, no light can strike its surface (sources of light do not exist). Let us assume that S1 is in the lowest possible energy state. This is the rest energy, Erest. For our ideal solid, the rest energy is the sum of the relativistic energy, Erel, and the energy contained in the bonds of the solid, Ebond. The relativistic energy is given by Einstein's equation, E = mc2. Other than relativistic and bonding energy, S1 contains no other energy (or heat). Simplistically speaking, it is near 0 Kelvin, or absolute zero.

That absolute zero exists is expressed in the form of the 3rd law of thermodynamics, the last major law of heat transfer to be formulated. This law is the most appropriate starting point for our discussion. Thus, an ideal solid containing no heat energy is close to absolute zero as defined by the 3rd law of thermodynamics. In such a setting, the atoms that make up the solid are perfectly still. Our universe now has a total energy (Etotal) equal to the rest mass of the solid (ETotal = Esolid = Erest= Erel + Ebond.

Now, let us imagine that there is a hypothetical little heat engine inside S1. We chose an engine rather than a source to reflect the fact that work is being done as we ponder this problem. However, to be strictly correct, a source of heat could have been invoked. For now, we assume that our little heat engine is producing hypothetical work and it is also operating at a single temperature. It is therefore said to be isothermal. As it works, the little heat engine releases heat into its environment.

It is thus possible to turn on this hypothetical little heat engine and to start releasing heat inside our solid. However, where will this heat go? We must introduce some kind of "receptacle" to accept the heat. This receptacle will be referred to as a "degree of freedom." The first degrees of freedom that we shall introduce are found in the vibration of the atoms about their absolute location, such...
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