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Thermodynamics

Thermodynamics is the branch of physics that deals with heat and temperature, and their relation to energy, work, radiation, and properties of matter. The behavior of these quantities is governed by the four laws of thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, chemical engineering and mechanical engineering, but also in fields as complex as meteorology.

A description of any thermodynamic system employs the four laws of thermodynamics that form an axiomatic basis. The first law specifies that energy can be exchanged between physical systems as heat and work. The second law defines the existence of a quantity called entropy, that describes the direction, thermodynamically, that a system can evolve and quantifies the state of order of a system and that can be used to quantify the useful work that can be extracted from the system.

With these tools, thermodynamics can be used to describe how systems respond to changes in their environment. This can be applied to a wide variety of topics in science and engineering, such as engines, phase transitions, chemical reactions, transport phenomena, and even black holes. The results of thermodynamics are essential for other fields of physics and for chemistry, chemical engineering, corrosion engineering, aerospace engineering, mechanical engineering, cell biology, biomedical engineering, materials science, and economics, to name a few.

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.

During the years 1873-76 the American mathematical physicist Josiah Willard Gibbs published a series of three papers, the most famous being On the Equilibrium of Heterogeneous Substances, in which he showed how thermodynamic processes, including chemical reactions, could be graphically analyzed, by studying the energy, entropy, volume, temperature and pressure of the thermodynamic system in such a manner, one can determine if a process would occur spontaneously. Also Pierre Duhem in the 19th century wrote about chemical thermodynamics. During the early 20th century, chemists such as Gilbert N. Lewis, Merle Randall, and E. A. Guggenheim applied the mathematical methods of Gibbs to the analysis of chemical processes.

Classical thermodynamics is the description of the states of thermodynamic systems at near-equilibrium, that uses macroscopic, measurable properties. It is used to model exchanges of energy, work and heat based on the laws of thermodynamics. The qualifier classical reflects the fact that it represents the first level of understanding of the subject as it developed in the 19th century and describes the changes of a system in terms of macroscopic empirical (large scale, and measurable) parameters. A microscopic interpretation of these concepts was later provided by the development of statistical mechanics.

Equilibrium thermodynamics is the systematic study of transfers of matter and energy in systems as they pass from one state of thermodynamic equilibrium to another. The term 'thermodynamic equilibrium' indicates a state of balance. In an equilibrium state there are no unbalanced potentials, or driving forces, between macroscopically distinct parts of the system. A central aim in equilibrium thermodynamics is: given a system in a well-defined initial equilibrium state, and given its surroundings, and given its constitutive walls, to calculate what will be the final equilibrium state of the system after a specified thermodynamic operation has changed its walls or surroundings.

An important concept in thermodynamics is the thermodynamic system, which is a precisely defined region of the universe under study. Everything in the universe except the system is called the surroundings. A system is separated from the remainder of the universe by a boundary which may be a physical boundary or notional, but which by convention defines a finite volume. Exchanges of work, heat, or matter between the system and the surroundings take place across this boundary.

Boundaries are of four types: fixed, movable, real, and imaginary. For example, in an engine, a fixed boundary means the piston is locked at its position, within which a constant volume process might occur. If the piston is allowed to move that boundary is movable while the cylinder and cylinder head boundaries are fixed. For closed systems, boundaries are real while for open systems boundaries are often imaginary. In the case of a jet engine, a fixed imaginary boundary might be assumed at the intake of the engine, fixed boundaries along the surface of the case and a second fixed imaginary boundary across the exhaust nozzle.

Once in thermodynamic equilibrium, a system's properties are, by definition, unchanging in time. Systems in equilibrium are much simpler and easier to understand than are systems which are not in equilibrium. Often, when analysing a dynamic thermodynamic process, the simplifying assumption is made that each intermediate state in the process is at equilibrium, producing thermodynamic processes which develop so slowly as to allow each intermediate step to be an equilibrium state and are said to be reversible processes.

A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. It can be described by process quantities. Typically, each thermodynamic process is distinguished from other processes in energetic character according to what parameters, such as temperature, pressure, or volume, etc., are held fixed; Furthermore, it is useful to group these processes into pairs, in which each variable held constant is one member of a conjugate pair.

A thermodynamic reservoir is a system which is so large that its state parameters are not appreciably altered when it is brought into contact with the system of interest. When the reservoir is brought into contact with the system, the system is brought into equilibrium with the reservoir. For example, a pressure reservoir is a system at a particular pressure, which imposes that pressure upon the system to which it is mechanically connected. The Earth's atmosphere is often used as a pressure reservoir. If ocean water is used to cool a power plant, the ocean is often a temperature reservoir in the analysis of the power plant cycle.