- those so rapid that, in the time frame of the process of interest, the atomic states rapidly bring system to its own state of internal thermodynamic equilibrium;
- those so slow that, in the time frame of the process of interest, they leave the system unchanged.

**Introduction**

The term ‘thermodynamics’ refers to a macroscopic description of bodies and processes. The qualified term ‘statistical thermodynamics’ refers to descriptions of bodies and processes in terms of the atomic constitution of matter, mainly described by sets of items all alike, so as to have equal probabilities. Thermodynamics arose from the study of two distinct kinds of transfer of energy, as heat and as work, and the relation of those to the system’s macroscopic variables of volume, pressure and temperature. Transfers of matter are also studied in thermodynamics.

Thermodynamic equilibrium is one of the most important concepts for thermodynamics. The temperature of a thermodynamic system is well defined, and is perhaps the most characteristic quantity of thermodynamics. As the systems and processes of interest are taken further from thermodynamic equilibrium, their exact thermodynamical study becomes more difficult. Relatively simple approximate calculations, however, using the variables of equilibrium thermodynamics, are of much practical value. In many important practical cases, as in heat engines or refrigerators, the systems consist of many subsystems at different temperatures and pressures. In engineering practice, thermodynamic calculations deal effectively with such systems provided the equilibrium thermodynamic variables are nearly enough well-defined.

Central to thermodynamic analysis are the definitions of the system, which is of interest, and of its surroundings. The surroundings of a thermodynamic system consist of physical devices and of other thermodynamic systems that can interact with it. An example of a thermodynamic surrounding is a heat bath, which is held at a prescribed temperature, regardless of how much heat might be drawn from it.

There are four fundamental kinds of physical entities in thermodynamics, states of a system, walls of a system, thermodynamic processes of a system, and thermodynamic operations. This allows two fundamental approaches to thermodynamic reasoning, that in terms of states of a system, and that in terms of cyclic processes of a system.

A thermodynamic system can be defined in terms of its states. In this way, a thermodynamic system is a macroscopic physical object, explicitly specified in terms of macroscopic physical and chemical variables that describe its macroscopic properties. The macroscopic state variables of thermodynamics have been recognized in the course of empirical work in physics and chemistry. Always associated with the material that constitutes a system, its working substance, are the walls that delimit the system, and connect it with its surroundings. The state variables chosen for the system should be appropriate for the natures of the walls and surroundings.

A thermodynamic operation is an artificial physical manipulation that changes the definition of a system or its surroundings. Usually it is a change of the permeability or some other feature of a wall of the system, that allows energy (as heat or work) or matter (mass) to be exchanged with the environment. For example, the partition between two thermodynamic systems can be removed so as to produce a single system. A thermodynamic operation usually leads to a thermodynamic process of transfer of mass or energy that changes the state of the system, and the transfer occurs in natural accord with the laws of thermodynamics. Besides thermodynamic operations, changes in the surroundings can also initiate thermodynamic processes.

A thermodynamic system can also be defined in terms of the cyclic processes that it can undergo. A cyclic process is a cyclic sequence of thermodynamic operations and processes that can be repeated indefinitely often without changing the final state of the system.For thermodynamics and statistical thermodynamics to apply to a physical system, it is necessary that its internal atomic mechanisms fall into one of two classes:

The rapid atomic mechanisms account for the internal energy of the system. They mediate the macroscopic changes that are of interest for thermodynamics and statistical thermodynamics, because they quickly bring the system near enough to thermodynamic equilibrium. “When intermediate rates are present, thermodynamics and statistical mechanics cannot be applied.” Such intermediate rate atomic processes do not bring the system near enough to thermodynamic equilibrium in the time frame of the macroscopic process of interest. This separation of time scales of atomic processes is a theme that recurs throughout the subject.

For example, classical thermodynamics is characterized by its study of materials that have equations of state or characteristic equations. They express equilibrium relations between macroscopic mechanical variables and temperature and internal energy. They express the constitutive peculiarities of the material of the system. A classical material can usually be described by a function that makes pressure dependent on volume and temperature, the resulting pressure being established much more rapidly than any imposed change of volume or temperature.

This introduction to thermodynamics takes a gradual approach to the subject, starting with a focus on cyclic processes and thermodynamic equilibrium, and then gradually beginning to further consider non-equilibrium systems.

Thermodynamic facts can often be explained by viewing macroscopic objects as assemblies of very many microscopic or atomic objects that obey Hamiltonian dynamics. The microscopic or atomic objects exist in species, the objects of each species being all alike. Because of this likeness, statistical methods can be used to account for the macroscopic properties of the thermodynamic system in terms of the properties of the microscopic species. Such explanation is called statistical thermodynamics; also often it is referred to by the term ‘statistical mechanics’, though this term can have a wider meaning, referring to ‘microscopic objects’, such as economic quantities, that do not obey Hamiltonian dynamics.

**THE HISTORY OF THERMODYNAMICS**

The history of thermodynamics as a scientific discipline generally begins with Otto von Guericke who, in 1650, built and designed the world’s first vacuum pump and demonstrated a vacuum using his Magdeburg hemispheres. Guericke was driven to make a vacuum in order to disprove Aristotle’s long-held supposition that ‘nature abhors a vacuum’. Shortly after Guericke, the physicist and chemist Robert Boyle had learned of Guericke’s designs and, in 1656, in coordination with scientist Robert Hooke, built an air pump. Using this pump, Boyle and Hooke noticed a correlation between pressure, temperature, and volume. In time, Boyle’s Law was formulated, stating that for a gas at constant temperature, its pressure and volume are inversely proportional. In 1679, based on these concepts, an associate of Boyle’s named Denis Papin built a steam digester, which was a closed vessel with a tightly fitting lid that confined steam until a high pressure was generated.

Later designs implemented a steam release valve that kept the machine from exploding. By watching the valve rhythmically move up and down, Papin conceived of the idea of a piston and a cylinder engine. He did not, however, follow through with his design. Nevertheless, in 1697, based on Papin’s designs, engineer Thomas Savery built the first engine, followed by Thomas Newcomen in 1712. Although these early engines were crude and inefficient, they attracted the attention of the leading scientists of the time.

The concepts of heat capacity and latent heat, which were necessary for development of thermodynamics, were developed by professor Joseph Black at the University of Glasgow, where James Watt worked as an instrument maker. Watt consulted with Black on tests of his steam engine, but it was Watt who conceived the idea of the external condenser, greatly raising the steam engine’s efficiency. Drawing on all the previous work led Sadi Carnot, the “father of thermodynamics”, to publish Reflections on the Motive Power of Fire (1824), a discourse on heat, power, energy and engine efficiency. The paper outlined the basic energetic relations between the Carnot engine, the Carnot cycle, and motive power. It marked the start of thermodynamics as a modern science.

The first thermodynamic textbook was written in 1859 by William Rankine, originally trained as a physicist and a civil and mechanical engineering professor at the University of Glasgow.The first and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin).

The foundations of statistical thermodynamics were set out by physicists such as James Clerk Maxwell, Ludwig Boltzmann, Max Planck, Rudolf Clausius and J. Willard Gibbs.

From 1873 to ’76, the American mathematical physicist Josiah Willard Gibbs published a series of three papers, the most famous being “On the equilibrium of heterogeneous substances”. Gibbs showed how thermodynamic processes, including chemical reactions, could be graphically analyzed. By studying the energy, entropy, volume, chemical potential, temperature and pressure of the thermodynamic system, one can determine if a process would occur spontaneously. Chemical thermodynamics was further developed by Pierre Duhem, Gilbert N. Lewis, Merle Randall, and E. A. Guggenheim, who applied the mathematical methods of Gibbs.

**INDEPENDENT BRANCHES OF THERMODYNAMICS: **

Thermodynamic systems are theoretical constructions used to model physical systems that exchange matter and energy in terms of the laws of thermodynamics. The study of thermodynamical systems has developed into several related branches, each using a different fundamental model as a theoretical or experimental basis, or applying the principles to varying types of systems.

**1. CLASSICAL THERMODYNAMICS:**

Classical thermodynamics accounts for the behavior of a thermodynamic system in terms, either of its time-invariant equilibrium states, or else of its continually repeated cyclic processes, but, formally, not both in the same account. It uses only time-invariant, or equilibrium, macroscopic quantities measurable in the laboratory, counting as time-invariant a long-term time-average of a quantity, such as a flow, generated by a continually repetitive process. In classical thermodynamics, rates of change are not admitted as variables of interest. An equilibrium state stands endlessly without change over time, while a continually repeated cyclic process runs endlessly without a net change in the system over time. In the account in terms of equilibrium states of a system, a state of thermodynamic equilibrium in a simple system is spatially homogeneous.

In the classical account solely in terms of a cyclic process, the spatial interior of the ‘working body’ of that process is not considered; the ‘working body’ thus does not have a defined internal thermodynamic state of its own because no assumption is made that it should be in thermodynamic equilibrium; only its inputs and outputs of energy as heat and work are considered. It is common to describe a cycle theoretically as composed of a sequence of very many thermodynamic operations and processes. This creates a link to the description in terms of equilibrium states. The cycle is then theoretically described as a continuous progression of equilibrium states.

Classical thermodynamics was originally concerned with the transformation of energy in a cyclic process, and the exchange of energy between closed systems defined only by their equilibrium states. The distinction between transfers of energy as heat and as work was central.

As classical thermodynamics developed, the distinction between heat and work became less central. This was because there was more interest in open systems, for which the distinction between heat and work is not simple. Alongside the amount of heat transferred as a fundamental quantity, **entropy** was gradually found to be a more generally applicable concept, especially when considering chemical reactions. Massieu in 1869 considered entropy as the basic dependent thermodynamic variable, with energy potentials and the reciprocal of the thermodynamic temperature as fundamental independent variables. Massieu functions can be useful in present-day non-equilibrium thermodynamics. In 1875, in the work of Josiah Willard Gibbs, entropy was considered a fundamental independent variable, while internal energy was a dependent variable.

All actual physical processes are to some degree irreversible. Classical thermodynamics can consider irreversible processes, but its account in exact terms is restricted to variables that refer only to initial and final states of thermodynamic equilibrium, or to rates of input and output that do not change with time. For example, classical thermodynamics can consider time-average rates of flows generated by continually repeated irreversible cyclic processes. Also it can consider irreversible changes between equilibrium states of systems consisting of several phases, or with removable or replaceable partitions. But for systems that are described in terms of equilibrium states, it considers neither flows, nor spatial inhomogeneities in simple systems with no externally imposed force fields such as gravity. In the account in terms of equilibrium states of a system, descriptions of irreversible processes refer only to initial and final static equilibrium states; the time it takes to change thermodynamic state is not considered.

**2. LOCAL EQUILIBRIUM THERMODYNAMICS:**

Local equilibrium thermodynamics is concerned with the time courses and rates of progress of irreversible processes in systems that are smoothly spatially inhomogeneous. It admits time as a fundamental quantity, but only in a restricted way. Rather than considering time-invariant flows as long-term-average rates of cyclic processes, local equilibrium thermodynamics considers time-varying flows in systems that are described by states of local thermodynamic equilibrium, as follows.

For processes that involve only suitably small and smooth spatial inhomogeneities and suitably small changes with time, a good approximation can be found through the assumption of local thermodynamic equilibrium. Within the large or global region of a process, for a suitably small local region, this approximation assumes that a quantity known as the **entropy** of the small local region can be defined in a particular way. It may be said that it is entirely derived from the concepts of classical thermodynamics; in particular, neither flow rates nor changes over time are admitted into the definition of the entropy of the small local region. It is assumed that the instantaneous global entropy of a non-equilibrium system can be found by adding up the simultaneous instantaneous entropies of its constituent small local regions. Local equilibrium thermodynamics considers processes that involve the time-dependent production of entropy by dissipative processes, in which kinetic energy of bulk flow and chemical potential energy are converted into internal energy at time-rates that are explicitly accounted for. Time-varying bulk flows and specific diffusional flows are considered, but they are required to be dependent variables, derived only from material properties described only by static macroscopic equilibrium states of small local regions. The independent state variables of a small local region are only those of classical thermodynamics.

**3. GENERALIZED OR EXTENDED THERMODYNAMICS**

Like local equilibrium thermodynamics, generalized or extended thermodynamics also is concerned with the time courses and rates of progress of irreversible processes in systems that are smoothly spatially inhomogeneous. It describes time-varying flows in terms of states of suitably small local regions within a global region that is smoothly spatially inhomogeneous, rather than considering flows as time-invariant long-term-average rates of cyclic processes. In its accounts of processes, generalized or extended thermodynamics admits time as a fundamental quantity in a more far-reaching way than does local equilibrium thermodynamics. The states of small local regions are defined by macroscopic quantities that are explicitly allowed to vary with time, including time-varying flows. Generalized thermodynamics might tackle such problems as ultrasound or shock waves, in which there are strong spatial inhomogeneities and changes in time fast enough to outpace a tendency towards local thermodynamic equilibrium. Generalized or extended thermodynamics is a diverse and developing project, rather than a more or less completed subject such as is classical thermodynamics.

For generalized or extended thermodynamics, the definition of the quantity known as the entropy of a small local region is in terms beyond those of classical thermodynamics; in particular, flow rates are admitted into the definition of the entropy of a small local region. The independent state variables of a small local region include flow rates, which are not admitted as independent variables for the small local regions of local equilibrium thermodynamics.

Outside the range of classical thermodynamics, the definition of the entropy of a small local region is no simple matter. For a thermodynamic account of a process in terms of the entropies of small local regions, the definition of entropy should be such as to ensure that the second law of thermodynamics applies in each small local region. It is often assumed without proof that the instantaneous global entropy of a non-equilibrium system can be found by adding up the simultaneous instantaneous entropies of its constituent small local regions. For a given physical process, the selection of suitable independent local non-equilibrium macroscopic state variables for the construction of a thermodynamic description calls for qualitative physical understanding, rather than being a simply mathematical problem concerned with a uniquely determined thermodynamic description. A suitable definition of the entropy of a small local region depends on the physically insightful and judicious selection of the independent local non-equilibrium macroscopic state variables, and different selections provide different generalized or extended thermodynamical accounts of one and the same given physical process. This is one of the several good reasons for considering entropy as an epistemic physical variable, rather than as a simply material quantity. According to a respected author: “There is no compelling reason to believe that the classical thermodynamic entropy is a measurable property of nonequilibrium phenomena.”

**4. STATISTICAL THERMODYNAMICS**

Statistical thermodynamics, also called statistical mechanics, emerged with the development of atomic and molecular theories in the second half of the 19th century and early 20th century. It provides an explanation of classical thermodynamics. It considers the microscopic interactions between individual particles and their collective motions, in terms of classical or of quantum mechanics. Its explanation is in terms of statistics that rest on the fact the system is composed of several species of particles or collective motions, the members of each species respectively being in some sense all alike.

**5. THERMODYNAMIC EQUILIBRIUM**

Equilibrium thermodynamics studies transformations of matter and energy in systems at or near thermodynamic equilibrium. In thermodynamic equilibrium, a system’s properties are, by definition, unchanging in time. In thermodynamic equilibrium no macroscopic change is occurring or can be triggered; within the system, every microscopic process is balanced by its opposite; this is called the principle of detailed balance. A central aim in equilibrium thermodynamics is: given a system in a well-defined initial state, subject to specified constraints, to calculate what the equilibrium state of the system is.

In theoretical studies, it is often convenient to consider the simplest kind of thermodynamic system. This is defined variously by different authors. For the Principal Engineer, the following definition is convenient, as abstracted from the definitions of various authors. A region of material with all intensive properties continuous in space and time is called a **phase**. A simple system is defined as one that consists of a single phase of a pure chemical substance, with no interior partitions.

Within a simple isolated thermodynamic system in thermodynamic equilibrium, in the absence of externally imposed force fields, all properties of the material of the system are spatially homogeneous. Much of the basic theory of thermodynamics is concerned with homogeneous systems in thermodynamic equilibrium.

**6. QUASI-STATIC SIMPLE THERMODYNAMIC SYSTEMS**

Most systems found in nature or considered in engineering are not in thermodynamic equilibrium, exactly considered. They are changing or can be triggered to change over time, and are continuously and discontinuously subject to flux of matter and energy to and from other systems. For example, according to Callen, “in absolute thermodynamic equilibrium all radioactive materials would have decayed completely and nuclear reactions would have transmuted all nuclei to the most stable isotopes. Such processes, which would take cosmic times to complete, generally can be ignored.” Such processes being ignored, many systems in nature are close enough to thermodynamic equilibrium that for many purposes their behavior can be well approximated by equilibrium calculations.

Quasi-static transfers between simple systems are nearly in thermodynamic equilibrium and are reversible. It simplifies theoretical thermodynamical studies to imagine transfers of energy and matter between two simple systems that proceed so slowly that at all times each simple system considered separately is near enough to thermodynamic equilibrium. Such processes are sometimes called quasi-static and are near enough to being reversible.

Natural processes are partly described by tendency towards thermodynamic equilibrium but are in fact irreversible. If not initially in thermodynamic equilibrium, simple isolated thermodynamic systems, as time passes, tend to evolve naturally towards thermodynamic equilibrium. In the absence of externally imposed force fields, they become homogeneous in their local properties. Such homogeneity is an important characteristic of a system in thermodynamic equilibrium. Many thermodynamic processes can be modeled by compound or composite systems, consisting of several or many contiguous component simple systems, initially not in thermodynamic equilibrium, but allowed to transfer mass and energy between them. Natural thermodynamic processes are described in terms of a tendency towards thermodynamic equilibrium within simple systems and in transfers between contiguous simple systems. Such natural processes are irreversible.