We begin our study of physical chemistry with
thermodynamics. Thermodynamics (from the Greek words for “heat” and “power”) is
the study of heat, energy, work, and the changes they produce in the states of
systems. In a broader sense, thermodynamics defines the relationships between
the macroscopic properties of a system. A key property in thermodynamics is
temperature, and thermodynamics is sometimes defined as the study of the
relation of temperature to the macroscopic properties of matter.
We shall be studying equilibrium thermodynamics, which deals
with systems in equilibrium. (Irreversible thermodynamics deals with non-equilibrium
systems and rate processes.) Equilibrium thermodynamics is a macroscopic
science and is independent of any theories of molecular structure. Strictly
speaking, the word “molecule” is not element of the vocabulary of
thermodynamics. However, we won’t adopt a purist attitude but will often use
molecular concepts to help us understand thermodynamics. Thermodynamics does
not apply to systems that contain only a few molecules; a system must contain
a great many molecules for it to be treated thermodynamically. The term
“thermodynamics” in this book will always mean equilibrium thermodynamics.
Thermodynamic Systems
The macroscopic part of the universe under study in
thermodynamics is called the system. The parts of the universe that will
interact with the system are known as the surroundings.
For example, to study the vapor pressure of water as a
function of temperature, we might put a sealed container of water (with any air
evacuated) in a constant-temperature bath and connect a manometer to the
container to measure the pressure.
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