Thermodynamics |
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In thermodynamics, a quasi-static process, also known as a quasi-equilibrium process (from Latin quasi, meaning ‘as if’ [1] ), is a thermodynamic process that happens slowly enough for the system to remain in internal physical (but not necessarily chemical) thermodynamic equilibrium. An example of this is quasi-static expansion of a mixture of hydrogen and oxygen gas, where the volume of the system changes so slowly that the pressure remains uniform throughout the system at each instant of time during the process. [2] Such an idealized process is a succession of physical equilibrium states, characterized by infinite slowness. [3]
Only in a quasi-static thermodynamic process can we exactly define intensive quantities (such as pressure, temperature, specific volume, specific entropy) of the system at any instant during the whole process; otherwise, since no internal equilibrium is established, different parts of the system would have different values of these quantities, so a single value per quantity may not be sufficient to represent the whole system. In other words, when an equation for a change in a state function contains P or T, it implies a quasi-static process.
While all reversible processes are quasi-static, most authors do not require a general quasi-static process to maintain equilibrium between system and surroundings and avoid dissipation, [4] which are defining characteristics of a reversible process. For example, quasi-static compression of a system by a piston subject to friction is irreversible; although the system is always in internal thermal equilibrium, the friction ensures the generation of dissipative entropy, which goes against the definition of reversibility. Any engineer would remember to include friction when calculating the dissipative entropy generation.
An example of a quasi-static process that is not idealizable as reversible is slow heat transfer between two bodies on two finitely different temperatures, where the heat transfer rate is controlled by a poorly conductive partition between the two bodies. In this case, no matter how slowly the process takes place, the state of the composite system consisting of the two bodies is far from equilibrium, since thermal equilibrium for this composite system requires that the two bodies be at the same temperature. Nevertheless, the entropy change for each body can be calculated using the Clausius equality for reversible heat transfer.
An adiabatic process is a type of thermodynamic process that occurs without transferring heat or mass between the thermodynamic system and its environment. Unlike an isothermal process, an adiabatic process transfers energy to the surroundings only as work. As a key concept in thermodynamics, the adiabatic process supports the theory that explains the first law of thermodynamics.
Entropy is a scientific concept that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the microscopic description of nature in statistical physics, and to the principles of information theory. It has found far-ranging applications in chemistry and physics, in biological systems and their relation to life, in cosmology, economics, sociology, weather science, climate change, and information systems including the transmission of information in telecommunication.
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. 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, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology.
The second law of thermodynamics is a physical law based on universal empirical observation concerning heat and energy interconversions. A simple statement of the law is that heat always flows spontaneously from hotter to colder regions of matter. Another statement is: "Not all heat can be converted into work in a cyclic process."
The first law of thermodynamics is a formulation of the law of conservation of energy in the context of thermodynamic processes. The law distinguishes two principal forms of energy transfer, heat and thermodynamic work, that modify a thermodynamic system containing a constant amount of matter. The law also defines the internal energy of a system, an extensive property for taking account of the balance of heat and work in the system. Energy cannot be created or destroyed, but it can be transformed from one form to another. In an isolated system the sum of all forms of energy is constant.
Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In thermodynamic equilibrium, there are no net macroscopic flows of matter nor of energy within a system or between systems. In a system that is in its own state of internal thermodynamic equilibrium, no macroscopic change occurs.
An isentropic process is an idealized thermodynamic process that is both adiabatic and reversible. The work transfers of the system are frictionless, and there is no net transfer of heat or matter. Such an idealized process is useful in engineering as a model of and basis of comparison for real processes. This process is idealized because reversible processes do not occur in reality; thinking of a process as both adiabatic and reversible would show that the initial and final entropies are the same, thus, the reason it is called isentropic. Thermodynamic processes are named based on the effect they would have on the system. Even though in reality it is not necessarily possible to carry out an isentropic process, some may be approximated as such.
An isothermal process is a type of thermodynamic process in which the temperature T of a system remains constant: ΔT = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and a change in the system occurs slowly enough to allow the system to be continuously adjusted to the temperature of the reservoir through heat exchange (see quasi-equilibrium). In contrast, an adiabatic process is where a system exchanges no heat with its surroundings (Q = 0).
In thermodynamics, a reversible process is a process, involving a system and its surroundings, whose direction can be reversed by infinitesimal changes in some properties of the surroundings, such as pressure or temperature.
The classification of internal processes in thermodynamic systems is introduced
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of chemical reactions.
The laws of thermodynamics are a set of scientific laws which define a group of physical quantities, such as temperature, energy, and entropy, that characterize thermodynamic systems in thermodynamic equilibrium. The laws also use various parameters for thermodynamic processes, such as thermodynamic work and heat, and establish relationships between them. They state empirical facts that form a basis of precluding the possibility of certain phenomena, such as perpetual motion. In addition to their use in thermodynamics, they are important fundamental laws of physics in general and are applicable in other natural sciences.
Thermodynamics is expressed by a mathematical framework of thermodynamic equations which relate various thermodynamic quantities and physical properties measured in a laboratory or production process. Thermodynamics is based on a fundamental set of postulates, that became the laws of thermodynamics.
In thermodynamics, a thermodynamic state of a system is its condition at a specific time; that is, fully identified by values of a suitable set of parameters known as state variables, state parameters or thermodynamic variables. Once such a set of values of thermodynamic variables has been specified for a system, the values of all thermodynamic properties of the system are uniquely determined. Usually, by default, a thermodynamic state is taken to be one of thermodynamic equilibrium. This means that the state is not merely the condition of the system at a specific time, but that the condition is the same, unchanging, over an indefinitely long duration of time.
Classical thermodynamics considers three main kinds of thermodynamic processes: (1) changes in a system, (2) cycles in a system, and (3) flow processes.
A thermodynamic cycle consists of linked sequences of thermodynamic processes that involve transfer of heat and work into and out of the system, while varying pressure, temperature, and other state variables within the system, and that eventually returns the system to its initial state. In the process of passing through a cycle, the working fluid (system) may convert heat from a warm source into useful work, and dispose of the remaining heat to a cold sink, thereby acting as a heat engine. Conversely, the cycle may be reversed and use work to move heat from a cold source and transfer it to a warm sink thereby acting as a heat pump. If at every point in the cycle the system is in thermodynamic equilibrium, the cycle is reversible. Whether carried out reversible or irreversibly, the net entropy change of the system is zero, as entropy is a state function.
Thermodynamic work is one of the principal processes by which a thermodynamic system can interact with its surroundings and exchange energy. This exchange results in externally measurable macroscopic forces on the system's surroundings, which can cause mechanical work, to lift a weight, for example, or cause changes in electromagnetic, or gravitational variables. The surroundings also can perform work on a thermodynamic system, which is measured by an opposite sign convention.
In classical thermodynamics, entropy is a property of a thermodynamic system that expresses the direction or outcome of spontaneous changes in the system. The term was introduced by Rudolf Clausius in the mid-19th century to explain the relationship of the internal energy that is available or unavailable for transformations in form of heat and work. Entropy predicts that certain processes are irreversible or impossible, despite not violating the conservation of energy. The definition of entropy is central to the establishment of the second law of thermodynamics, which states that the entropy of isolated systems cannot decrease with time, as they always tend to arrive at a state of thermodynamic equilibrium, where the entropy is highest. Entropy is therefore also considered to be a measure of disorder in the system.
A Carnot cycle is an ideal thermodynamic cycle proposed by French physicist Sadi Carnot in 1824 and expanded upon by others in the 1830s and 1840s. By Carnot's theorem, it provides an upper limit on the efficiency of any classical thermodynamic engine during the conversion of heat into work, or conversely, the efficiency of a refrigeration system in creating a temperature difference through the application of work to the system.
In thermodynamics, heat is the thermal energy transferred between systems due to a temperature difference. In colloquial use, heat sometimes refers to thermal energy itself. Thermal energy is the kinetic energy of vibrating and colliding atoms in a substance.