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Thermodynamics is the science of heat and temperature and, in particular, of the laws governing the conversion of thermal energy into mechanical, electrical, or other forms of energy. It is a central branch of science that has important applications in chemistry, physics, biology, and engineering. Thermodynamics is a logical discipline that organizes the information obtained from experiments performed on systems and enables us to draw conclusions, without further experimentation, about other properties of the system. It allows us to predict whether a reaction will proceed and what the maximum yield might be.

Thermodynamics is a macroscopic science that deals with such properties as pressure, temperature, and volume. Unlike quantum mechanics , thermodynamics is not based on a specific model, and therefore it is unaffected by our changing concepts of atoms and molecules. By the same token, equations derived from thermodynamics do not provide us with molecular interpretations of complex phenomena. Furthermore, thermodynamics tells us nothing about the rate of a process except its likelihood.

Applications of thermodynamics are based on three fundamental laws that deal with energy and entropy changes. The laws of thermodynamics cannot be derived; their validity is based on the fact that they predict changes that are consistent with experimental observations.

The first law of thermodynamics is based on the law of conservation of energy, which states that energy can neither be created nor destroyed; therefore, the total energy of the universe is constant. It is convenient for scientists to divide the universe into two parts: the system (the part of the universe that is under study—for example, a beaker of solution) and the surroundings (the rest of the universe). For any process, then, the change in the energy of the universe is zero. Chemists are usually interested only in what happens to the system. Consequently, for a given process the first law can be expressed as

Δ U = q + w          (1)

where Δ U is the change in the internal energy of the system, q is the heat exchange between the system and the surroundings, and w is the work done by the system or performed on the system by the surroundings. The first law is useful in studying the energetics of physical processes, such as the melting or boiling of a substance, and chemical reactions—for example, combustion . The heat change occurring as part of a process is measured with a calorimeter. For a constant-volume process, the heat change is equated to the change in the internal energy Δ U of the system; for a constant-pressure process, which is more common, the heat change is equated to the change in the enthalpy Δ H of the system. Enthalpy H is a thermodynamic function closely related to the internal energy of the system, and is defined as

H = U + PV          (2)

where P and V are the pressure and volume of the system, respectively.

The first law of thermodynamics deals only with energy changes and cannot predict the direction of a process. It asks, for example: Under a given set of conditions of pressure, temperature, and concentration, will a specific reaction occur? To answer the question we need a new thermodynamic function called entropy S. To define entropy, we need to use a quantum mechanical concept. The entropy of a system is related to the distribution of energy among the available molecular energy levels at a given temperature. The greater the number of energy levels that have significant occupation, the greater the entropy.

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