THERMODYNAMICS The universe is made up of bits of matter, and the bits of matter have mass and energy.

Neither mass nor energy may be created or destroyed, but in some special cases interconversions between mass and energy may occur. The things that happen in nature occur because matter is trying to gather to itself as much mass as it can (gravity) and to release as much of its energy as it can (the Sun, for example). This gathering of mass and loss of energy requires a price to be paid - the price of freedom. It seems that mass, energy, and freedom are the coins of the universe. Mass and energy must be conserved: if one part of the universe gathers more "wealth" as mass or energy, those must come from somewhere else in the universe, so there is always competition in the trading of these commodities. Freedom, on the other hand, is not conserved. However, there are some strange restraints on freedom. The freedom of the universe can take many forms, and appears to be able to increase without limit. However, the total freedom of the universe is not allowed to decrease. The energy or the mass of a part of the universe may increase or decrease, but only if there is a corresponding decrease or increase somewhere else in the universe. The freedom in that part of the universe may increase with no change in the freedom of the rest of the universe. There might be decreases in freedom in the rest of the universe, but the sum of the increase and decrease must result in a net increase. There can be a decrease in the freedom in one part of the universe, but ONLY if there is an

equal or greater increase in the rest of the universe. Most of us have a general idea of what mass and energy are, and we may have a fair understanding of how we can quantify them, or to say how much of them we have. Freedom is a more complicated concept. The freedom within a part of the universe may take two major forms: the freedom of the mass and the freedom of the energy. The amount of freedom is related to the number of different ways the mass or the energy in that part of the universe may be arranged while not gaining or losing any mass or energy. We will concentrate on a specific part of the universe, perhaps within a closed container. If the mass within the container is distributed into a lot of tiny little balls (atoms) flying blindly about, running into each other and anything else (like walls) that may be in their way, there is a huge number of different ways the atoms could be arranged at any one time. Each atom could at different times occupy any place within the container that was not already occupied by another atom, but on average the atoms will be uniformly distributed throughout the container. If we can mathematically estimate the number of different ways the atoms may be arranged, we can quantify the freedom of the mass. If somehow we increase the size of the container, each atom can move around in a greater amount of space, and the number of ways the mass may be arranged will increase.

Now let us turn to the freedom of the energy within the container. If the mass is in the form of atoms flying around, energy is only

in the form of the kinetic energy of these atoms, and the energy of the electrons in the atoms moving around their nucleus (and sometimes we have to consider the neutrons, protons, and other stuff moving around in the nucleus). An atom's kinetic energy is related to its mass and its velocity. The energy in the container is the sum of the kinetic energies of all of the atoms, but the velocity is not the same for each atom, and the atoms are continually exchanging this energy through collisions with each other and through collisions with the walls. In the same way that the mass may have freedom in the number of ways the atoms may be arranged in space, the energy may have freedom in the number of ways that the velocities and directions of the atoms may be arranged. The velocities of the molecules are closely related to the temperature. The energy and freedom of gaseous atoms appear only in velocities and directions, and is called translational energy and translational freedom. In the case of molecules (a molecule is a group of two or more atoms held together by chemical bonds) there are additional freedoms and additional forms of energy. Bonds between atoms act as springs allowing the atoms to vibrate within the molecule, so that the molecules may contain different levels of vibrational energy and vibrational freedom. Additionally, the entire molecule may rotate on different axes, allowing different levels of rotational energy and rotational freedom.

temperature. An increase in the temperature of a gas leads directly to an increase in energy, and this can only occur if there is a decrease in energy somewhere else in the universe. We say that energy is transferred to the gas and the container (we will call that the "system")) from somewhere in the remainder of the universe (we will call that the "surroundings"). The increase in energy is accompanied by an increase in the energetic freedom of the system. The thermodynamic term for quantifying freedom is entropy, and it is given the symbol S. Like freedom, the entropy of a system increases with the temperature and with volume. The effect of volume is more easily seem in terms of concentration, especially in the case of mixtures. For a certain number of atoms or molecules, an increase in volume results in a decrease in concentration. Therefore, the entropy of a system increases as the concentrations of the components decrease. The part of entropy which is determined by energetic freedom is called thermal entropy, and the part that is determined by concentration is called configurational entropy. The units of entropy are the same as those of heat capacity and of the gas law constant. The product of entropy (or a change in entropy) and the absolute temperature has the same units as energy (or a change in energy

While the freedom of mass is related to the volume in which the mass is distributed, the freedom of energy is related to the