Entropy production

Entropy production (or generation) is the amount of entropy which is produced in any irreversible processes such as heat and mass transfer processes including motion of bodies, heat exchange, fluid flow, substances expanding or mixing, anelastic deformation of solids, and any irreversible thermodynamic cycle, including thermal machines such as power plants, heat engines, refrigerators, heat pumps, and air conditioners. 
In the dual representation entropy-exergy for accounting the second law of thermodynamics it can be expressed in equivalent terms of exergy disruption.
Short history.
Entropy is produced in irreversible processes. The importance of avoiding irreversible processes (hence reducing the entropy production) was recognized as early as 1824 by Carnot. In 1865 Rudolf Clausius expanded his previous work from 1854 on the concept of “unkompensierte Verwandlungen” (uncompensated transformations), which, in our modern nomenclature, would be called the entropy production. In the same article in which he introduced the name entropy, Clausius gives the expression for the entropy production (for a closed system), which he denotes by "N", in equation (71) which reads
Here "S" is the entropy in the final state and the integral is to be taken from the initial state to the final state. From the context, it is clear that "N" = 0 if the process is reversible and "N" > 0 in case of an irreversible process.
First and second law.
The laws of thermodynamics system apply to well-defined systems. Fig.1 is a general representation of a thermodynamic system. We consider systems which, in general, are inhomogeneous. Heat and mass are transferred across the boundaries (nonadiabatic, open systems), and the boundaries are moving (usually through pistons). In our formulation we assume that heat and mass transfer and volume changes take place only separately at well-defined regions of the system boundary. The expression, given here, are not the most general formulations of the first and second law. E.g. kinetic energy and potential energy terms are missing and exchange of matter by diffusion is excluded.
The rate of entropy production, denoted by formula_2, is a key element of the second law of thermodynamics for open inhomogeneous systems which reads
Here "S" is the entropy of the system; "T"k is the temperature at which the heat flow formula_4 enters the system; formula_5 represents the entropy flow into the system at position "k", due to matter flowing into the system (formula_6 are the molar flow and mass flow and "S"mk and "s"k are the molar entropy (i.e. entropy per mole) and specific entropy (i.e. entropy per unit mass) of the matter, flowing into the system, respectively); formula_7 represents the entropy production rates due to internal processes. The index "i" in formula_7 refers to the fact that the entropy is produced due to irreversible processes. The entropy-production rate of every process in nature is always positive or zero. This is an essential aspect of the second law.
The ∑'s indicate the algebraic sum of the respective contributions if there are more heat flows, matter flows, and internal processes.
In order to demonstrate the impact of the second law, and the role of entropy production, it has to be combined with the first law which reads
with "U" the internal energy of the system; formula_10 the enthalpy flows into the system due to the matter that flows into the system ("H"mk its molar enthalpy, "h"k the specific enthalpy (i.e. enthalpy per unit mass)), and d"V"k/d"t" are the rates of change of the volume of the system due to a moving boundary at position "k" while "p"k is the pressure behind that boundary; "P" represents all other forms of power application (such as electrical).
The first and second law have been formulated in terms of time derivatives of "U" and "S" rather than in terms of total differentials d"U" and d"S" where it is tacitly assumed that d"t" > 0. So, the formulation in terms of time derivatives is more elegant. An even bigger advantage of this formulation is, however, that it emphasizes that "heat flow" and "power" are the basic thermodynamic properties and that heat and work are derived quantities being the time integrals of the heat flow and the power respectively.
Examples of irreversible processes.
Entropy is produced in irreversible processes. Some important irreversible processes are:
The expression for the rate of entropy production in the first two cases will be derived in separate sections.
Performance of heat engines and refrigerators.
Most heat engines and refrigerators are closed cyclic machines. In the steady state the internal energy and the entropy of the machines after one cycle are the same as at the start of the cycle. Hence, on average, d"U"/d"t" = 0 and d"S"/d"t" = 0 since "U" and "S" are functions of state. Furthermore they are closed systems (formula_11) and the volume is fixed (d"V"/d"t" = 0). This leads to a significant simplification of the first and second law:
and
The summation is over the (two) places where heat is added or removed.
Engines.
For a heat engine (Fig.2a) the first and second law obtain the form
and
Here formula_16 is the heat supplied at the high temperature "T"H, formula_17 is the heat removed at ambient temperature "T"a, and "P" is the power delivered by the engine. Eliminating formula_17 gives
The efficiency is defined by
If formula_21 the performance of the engine is at its maximum and the efficiency is equal to the Carnot efficiency
Refrigerators.
For refrigerators (fig.2b) holds
and
Here "P" is the power, supplied to produce the cooling power formula_25 at the low temperature "T"L. Eliminating formula_17 now gives
The Coefficient Of Performance of refrigerators is defined by
If formula_21 the performance of the cooler is at its maximum. The COP is then given by the Carnot Coefficient Of Performance
Power dissipation.
In both cases we find a contribution formula_31 which reduces the system performance. This product of ambient temperature and the (average) entropy production rate formula_32 is called the dissipated power.
Equivalence with other formulations.
It is interesting to investigate how the above mathematical formulation of the second law relates with other well-known formulations of the second law.
We first look at a heat engine, assuming that formula_33. In other words: the heat flow formula_16 is completely converted into power. In this case the second law would reduce to
Since formula_36 and formula_37 this would result in formula_38 which violates the condition that the entropy production is always positive. Hence: "No process is possible in which the sole result is the absorption of heat from a reservoir and its complete conversion into work." This is the Kelvin statement of the second law.
Now look at the case of the refrigerator and assume that the input power is zero. In other words: heat is transported from a low temperature to a high temperature without doing work on the system. The first law with "P" = 0 would give
and the second law then yields
or
Since formula_42 and formula_43 this would result in formula_38 which again violates the condition that the entropy production is always positive. Hence: "No process is possible whose sole result is the transfer of heat from a body of lower temperature to a body of higher temperature." This is the Clausius statement of the second law.
Expressions for the entropy production.
Heat flow.
In case of a heat flow formula_45 from "T"1 to "T"2 (with formula_46) the rate of entropy production is given by
If the heat flow is in a bar with length "L", cross-sectional area "A", and thermal conductivity κ, and the temperature difference is small
the entropy production rate is
Flow of mass.
In case of a volume flow formula_50 from a pressure "p"1 to "p"2
For small pressure drops and defining the flow conductance "C" by formula_52 we get
The dependences of formula_54 on ("T"1−"T"2) and on ("p"1−"p"2) are quadratic. 
This is typical for expressions of the entropy production rates in general. They guarantee that the entropy production is positive.
Entropy of mixing.
In this Section we will calculate the entropy of mixing when two ideal gases diffuse into each other. Consider a volume "V"t divided in two volumes "V"a and "V"b so that "V"t = "V"a+"V"b. The volume "V"a contains "n"a moles of an ideal gas "a" and "V"b contains "n"b moles of gas "b". The total amount is "n"t = "n"a + "n"b. The temperature and pressure in the two volumes is the same. The entropy at the start is given by
When the division between the two gases is removed the two gases expand, comparable to a Joule-Thomson expansion. In the final state the temperature is the same as initially but the two gases now both take the volume "V"t. The relation of the entropy of "n" moles an ideal gas is
with "C"V the molar heat capacity at constant volume and "R" the molar ideal gas constant.
The system is an adiabatic closed system, so the entropy increase during the mixing of the two gases is equal to the entropy production. It is given by
As the initial and final temperature are the same the temperature terms plays no role, so we can focus on the volume terms. The result is
Introducing the concentration "x" = "n"a/"n"t = "V"a/"V"t we arrive at the well known expression
Joule expansion.
The Joule expansion is similar to the mixing described above. It takes place in an adiabatic system consisting of a gas and two rigid vessels (a and b) of equal volume, connected by a valve. Initially, the valve is closed. Vessel (a) contains the gas under high pressure while the other vessel (b) is empty. When the valve is opened the gas flows from vessel (a) into (b) until the pressures in the two vessels are equal. The volume, taken by the gas, is doubled while the internal energy of the system is constant (adiabatic and no work done). Assuming that the gas is ideal the molar internal energy is given by "U"m = "C"V"T". As "C"V is constant, constant "U" means constant "T". The molar entropy of an ideal gas, as function of the molar volume "V"m and "T", is given by
The system, of the two vessels and the gas, is closed and adiabatic, so the entropy production during the process is equal to the increase of the entropy of the gas. So, doubling the volume with "T" constant, gives that the entropy production per mole gas is
Microscopic interpretation.
The Joule expansion provides an opportunity to explain the entropy production in statistical mechanical (i.e., microscopic) terms. At the expansion, the volume that the gas can occupy is doubled. This means that, for every molecule there are now two possibilities: it can be placed in container (a) or (b). If we have one mole of gas, the number of molecules is equal to Avogadro's number "N"A. The increase of the microscopic possibilities is a factor of 2 per molecule, so in total the factor is 2"N"A. Using the well-known Boltzmann expression for the entropy
with "k" Boltzmann's constant and Ω the number of microscopic possibilities to realize the macroscopic state, gives
So, in an irreversible process, the number of microscopic possibilities to realize the macroscopic state is increased by a certain factor.
Basic inequalities and stability conditions.
In this section we derive the basic inequalities and stability conditions for closed systems. For closed systems the first law reduces to
The second law we write as
For adiabatic systems formula_66 so d"S"/d"t" ≥ 0. In other words: the entropy of adiabatic systems cannot decrease. In equilibrium the entropy is at its maximum. Isolated systems are a special case of adiabatic systems, so this statement is also valid for isolated systems.
Now consider systems with constant temperature and volume. In most cases "T" is the temperature of the surroundings with which the system is in good thermal contact. Since "V" is constant the first law gives formula_67. Substitution in the second law, and using that "T" is constant, gives
With the Helmholtz free energy, defined as
we get
If "P" = 0 this is the mathematical formulation of the general property that the free energy of systems with fixed temperature and volume tends to a minimum. The expression can be integrated from the initial state i to the final state f resulting in
where "W"S is the work done "by" the system. If the process inside the system is completely reversible the equality sign holds. Hence the maximum work, that can be extracted from the system, is equal to the free energy of the initial state minus the free energy of the final state.
Finally we consider systems with constant temperature and pressure and take "P" = 0. As "p" is constant the first laws gives
Combining with the second law, and using that "T" is constant, gives
With the Gibbs free energy, defined as
we get
Homogeneous systems.
In homogeneous systems the temperature and pressure are well-defined and all internal processes are reversible. Hence formula_76. As a result the second law, multiplied by "T", reduces to
With "P"=0 the first law becomes
Eliminating formula_45 and multiplying with d"t" gives
Since
with "G"m the molar Gibbs free energy and "μ" the molar chemical potential we obtain the well-known result
Entropy production in stochastic processes.
Since physical processes can be described by stochastic processes, such as Markov chains and diffusion processes, entropy production can be defined mathematically in such processes.
For a continuous-time Markov chain with instantaneous probability distribution formula_83 and transition rate formula_84, the instantaneous entropy production rate is
The long-time behavior of entropy production is kept after a proper lifting of the process. This approach provides a dynamic explanation for the Kelvin statement and the Clausius statement of the second law of thermodynamics.