The Thermodynamics of Phase and Reaction Equilibria

Chapter 1

Review of the First and Second Laws of Thermodynamics

The purpose of this chapter is twofold: (i) to summarize the definitions and concepts used in thermodynamics and (ii) to explain what the first and second laws of thermodynamics are and to show how to simplify the equations expressing these laws for various systems.

1.1 Definitions

1.1.1 System

Any region that occupies a volume and has a boundary is called a system. The volume outside the boundary is called the surroundings of the system. The sum of the system and its surroundings is called the universe. Thermodynamics considers systems only at the macroscopic level. It is convenient to distinguish between three general types of systems:

• Isolated system: These are the set of systems that exchange neither mass nor energy with the surroundings. For example, the universe is an isolated system.

• Closed system: These are the set of systems that exchange energy (in the form of heat and work) but not mass with the surroundings.

• Open system: These are the set of systems that exchange both mass and energy with the surroundings.

The equations available to analyze closed and open systems are different from each other. Therefore, one should properly define the system before solving the problem.

1.1.2 Property and State

In order to describe and analyze a system, some of the quantities that are characteristic of it must be known. These quantities are called properties and comprise volume, mass, temperature, pressure, etc. Thermodynamic properties are considered to be either intensive or extensive. When the property is proportional to the mass of the system, the property is extensive, i.e. volume, kinetic energy, potential energy. On the other hand, when the property is independent of the mass of the system, the property is intensive, i.e. viscosity, refractive index, density, temperature, pressure, mole fraction.

Specific (or molar) properties are extensive properties divided by the total mass (or total moles) of the system, i.e.

(1.1-1)

represents any extensive property, then Eqn (1.1-1) is expressed as

(1.1-2)

where m and n are the total mass and moles, respectively. Note that all specific (or molar) properties are intensive.

A complete list of the properties of a system describes its state. Consider a function

(1.1-3)

is dependent, and x are independent. In thermodynamics we would say that "the state of the system, , is fixed when the thermodynamic properties x and y are specified. Note that the mathematical term point is equivalent to the thermodynamic term state."

The number of independent intensive properties needed to fix the state of a system is called the degrees of freedom, for a given system at equilibrium and is expressed in the form¹

(1.1-4)

is the number of components.

Therefore, the state of a single-phase, single-component system can be specified by two independent intensive properties. Two properties are independent if one property can be varied while the other one is held constant. For example, temperature and density (or specific volume) are always independent properties, and together they can fix the state of a single-phase, single-component system.

A change of state is called a process, which can occur in a number of ways. Work and heat can occur only during processes and only across the boundary of the system. The path followed in going from one state to another is known as the process path.

1.1.3 Equilibrium

It is important to differentiate between the concepts of steady-state, uniform, and equilibrium:

• Steady-state: does not change as a function of time, i.e.

(1.1-5)

• Uniform: is not a function of position, i.e.

(1.1-6)

• Equilibrium: A system is in equilibrium if both the steady-state and uniform conditions are met simultaneously. This implies that the variables associated with the system, such as temperature, pressure, and density, are constant at all times and have the same magnitude at all positions within the system. A difference in any potential that causes a process to take place spontaneously is called a driving force. Driving force(s) turns out to be zero for a system in equilibrium. Thus, no work can be done by a system in equilibrium.

It should be kept in mind that thermodynamics considers systems only at equilibrium. By examining the system in its initial and final equilibrium states, it is possible to determine the heat and work interactions of the system with its surroundings during this process. Thermodynamics, however, does not consider the time it takes for the system in going from an initial equilibrium state to a final equilibrium state.

1.2 Concepts of the Abstract World of Thermodynamics

The steps followed in the solution of a thermodynamic problem are shown in Fig. 1.1. The first step is to transform the real problem into the abstract world of thermodynamics in which necessary equations are provided for solving it. Once the problem is solved in the abstract world, then it is transformed back into the real world.

Fig. 1.1 The path followed in the solution of thermodynamics problems ( Prausnitz, 1986 ).

In the abstract world of thermodynamics, the two concepts, i.e. state/path function and reversible process, play a vital role in the solution of problems.

1.2.1 State and Path Functions

If a system is caused to undergo a process, any property of the system whose value at the final state is the same no matter what path is used to carry out the process is called a state function.² On the other hand, if a property is a path function, its value at the final state will depend on what path is used and will be different for every path.

The quantities encountered in thermodynamics are all state functions except heat and work. The only exception to this statement is the work done by body forces, i.e. work done against a gravitational force. Body forces are conservative forces.³

is called an exact differential for which this expression is the total differential , i.e.

(1.2-1)

to be expressed as a total differential is that

(1.2-2)

1.2.2 Reversible Process

A process executed by a system is called reversible if the system and its surroundings can be restored to their initial states and leave no net effects at all on the physical world. Another term for reversible may be completely erasable. In the real world, all processes are irreversible. Processes are considered reversible only if they are executed very slowly, i.e. the driving force for the process is very small.

1.2.3 General Approach Used in the Solution of Thermodynamics Problems

Once the concepts of state/path function and reversible process are understood, the elaboration of is independent of the path followed during the process, i.e.

(1.2-3)

Fig. 1.2 A hypothetical path replacing an actual path.

1.3 Work

In thermodynamics, work can be broadly classified as expansion and non-expansion type of work. Expansion (or contraction) work is related to the change in the volume of system. Non-expansion work, on the other hand, includes shaft work, flow work, chemical work, electrical work, etc. By convention, work done on the system is considered positive.

In differential form,⁴ the work associated with the volume change is given by

(1.3-1)

, and Eqn (1.3-1) becomes

(1.3-2)

indicating that the work done by a system is a function of the properties of the system only when the work is done reversibly.

The shaft work, is the work done on the system by external means through a rotating shaft. Reversible shaft work in a steady-state flow process with negligible changes in kinetic and potential energies is given by

(1.3-3)

The work associated with moving the fluid into and out of an open system is known as the flow work. The flow work done by a tangential stress (or shear stress) is usually considered negligible by choosing the boundaries of the system perpendicular to the flow direction. On the other hand, the flow work done by a normal stress, i.e. pressure force, is given by PV.

1.4 Paths Followed During a Process

In going from one state to another, a system may follow various paths. Depending on the path followed, the process may be:

• Isometric/isochoric (constant volume).

• Isobaric (constant pressure).

• Isothermal (constant temperature).

• Adiabatic.

An isothermal process is usually confused with an adiabatic process. An isothermal process is one in which the temperature of the system does not change throughout the process,⁵ i.e. Tsys = constant. An adiabatic process. The adiabatic and isothermal processes are often opposite extremes and real processes fall in between.

It should be kept in mind that heat transfer is a slow process and can be considered negligible in processes taking place very rapidly. Since slow and rapid are relative terms, there is no clear-cut recipe to differentiate slow processes from rapid ones. One should use engineering judgement in the analysis of a given problem. For example, consider the following two cases in which a rigid tank filled with a high-pressure gas at ambient temperature is evacuated by:

(i) Punching a tiny hole in the surface of the tank.

(ii) Opening a large valve placed on the top of the tank.

Suppose that the tank is not insulated and it is required to find how the gas temperature within the tank changes with pressure. Since process (i) is rather slow, it allows heat transfer between the tank contents and ambient air to take place. Thus, the gas remaining in the tank may be considered to undergo an isothermal process. On the other hand, evacuation of the tank is very rapid in process (ii). Over the time scale of the evacuation process, heat transfer between the tank contents and ambient air is almost negligible. As a result, the gas remaining in the tank may be assumed to undergo an adiabatic process even though there is no insulation around the tank.

1.5 The First Law of Thermodynamics

The first law of thermodynamics is a statement of the conservation of energy, i.e. although energy can be transferred from one system to another in many forms, it can neither be created nor destroyed. Therefore, the total amount of energy available in the universe is constant. Consider an open system exchanging heat and work with its surroundings as shown in Fig. 1.3. The conservation statement for energy is expressed as

(1.5-1)

In differential form, Eqn (1.5-1) takes the form

(1.5-2)

where H, EK, EP, and U represent enthalpy, kinetic energy, potential energy, and internal energy, respectively.

Fig. 1.3 An open system exchanging mass and energy with its surroundings.

In terms of molar quantities, Eqn (1.5-2) is written as

(1.5-3)

The internal energy is the sum of the kinetic energy (translational, rotational, and vibrational) and potential energies of attraction at the molecular level. Since thermodynamics is concerned with systems at macroscopic level, it is not concerned with the origin of internal energy but states that internal energy is extensive, i.e. its value is dependent on the extent or size of the system, and it is a state function.

The enthalpy is a made-up variable defined by

(1.5-4)

In an open flow system, enthalpy can be interpreted as the amount of energy transferred across a system boundary by a moving flow. In Eqn (1.5-4), the term PV represents the flow work.

The term W in Eqns (1.5-2) and (1.5-3) is the sum of the shaft work and the work associated with the volume change.

1.5.1 Simplification of the Energy Balance

1.5.1.1 Isolated System

, Eqn (1.5-3) reduces to

(1.5-5)

In an isolated system, energy is converted from one form to another but the total energy is always constant.

1.5.1.2 Closed System

and nsys = constant, Eqn (1.5-3) reduces to

(1.5-6)

Integration of Eqn (1.5-6) gives⁶

(1.5-7)

1.5.1.3 Steady-State Flow System

. Therefore, Eqn (1.5-3) reduces to

(1.5-8)

or⁷

(1.5-9)

1.6 The Second Law of Thermodynamics

The second law of thermodynamics introduces a new property called entropy, S, which is an extensive property of a system. The entropy change of a closed system is equal to the heat added reversibly to it divided by the absolute temperature of the system, i.e.

(1.6-1)

can be interpreted as the integrating factor.

To determine the absolute value of entropy, it is necessary to define a reference state. Otherwise, only changes in entropy can be determined. The reference state of entropy is a perfect crystal at 0 K. Entropy of this reference state is arbitrarily fixed to 0 J/K. In this way, an absolute entropy can be attributed to every substance at specified conditions like temperature and pressure.

Although the second law of thermodynamics can be expressed in many ways, these statements are equivalent to each other. One of the statements of the second law of thermodynamics is that "any spontaneous process in any isolated system always results in an increase in the entropy of that system." Since the universe is an isolated system, this statement is mathematically expressed in the form:

(1.6-2)

.

The second law of thermodynamics can also be expressed in terms of the Clausius and Kelvin-Planck statements:

• Clausius statement: As shown in Fig. 1.4, it is impossible to construct a device that, operating in a cycle, will produce no effect other than the transfer of heat from a cold body to a hot one.

Fig. 1.4 Schematic representation of the Clausius statement.

• Kelvin-Planck statement: As shown in Fig. 1.5, it is impossible to construct a device that, operating in a cycle, will produce no effect other than converting heat completely into work.

Fig. 1.5 Schematic representation of the Kelvin-Planck statement.

The energy can be thought of as the ability of the system to perform work. The entropy, on the other hand, is a measure of how much this ability has been devaluated.⁸ An increase in entropy implies, (i) decrease in the ability of energy to do useful work, (ii) depreciation of energy, and (iii) increase in disorder.

While the generation of entropy is either equal to or greater than zero, the entropy of a system may decrease, increase, or remain the same. Therefore, a decrease in the entropy of a system does not necessarily imply the violation of the second law of thermodynamics. In general, the entropy of a system decreases as it changes to a more orderly state. Some examples are:

• During phase transformation to a more orderly state, i.e. Liquid →  Solid or Gas →  Liquid.

• As the temperature of a substance decreases.

• As the pressure of a gas increases.

It is important to note that there is no such thing as the conservation of entropy. Real processes always generate entropy and, as a result, entropy of the universe always increases. The change in the entropy of a system can be calculated from the following expression:

(1.6-3)

For an open system as shown in Fig. 1.3, the differential form of Eqn (1.6-3) becomes

(1.6-4)

Rearrangement of Eqn (1.6-4) gives

(1.6-5)

which is also known as the entropy balance.

In terms of molar quantities, Eqn (1.6-5) becomes

(1.6-6)

1.6.1 Simplification of the Entropy Balance

1.6.1.1 Isolated System

, Eqn (1.6-6) reduces to

(1.6-7)

1.6.1.2 Closed System

, and nsys = constant, Eqn (1.6-6) reduces to

(1.6-8)

1.6.1.3 Steady-State Flow System

. Therefore, Eqn (1.6-6) reduces to

(1.6-9)

References

1. Prausnitz JM. J Non-Equil Thermodyn. 1986;11:49–66.

¹ The easiest way to remember Gibbs phase rule is to use the formula: Police + Forces = Cops + 2.

² A property that is defined as the combination of other state functions is also a state function.

, is called conservative .

⁴ Since W rather than dWin the later stages.

⁵ If the initial and final state temperatures are the same, this does not necessarily imply an isothermal process.

⁶ For any state function :

For any path function :

implies out − in.

⁸ While inflation degrades money, conversion from one form to another degrades energy.

Chapter 2

Thermodynamic Properties of Real Substances

Thermodynamics deals with the work and heat interactions of the system with its surroundings as it undergoes a process. These quantities can be estimated once the changes in various state functions, namely, internal energy, enthalpy, and entropy, are known. The purpose of this chapter is to develop general expressions to calculate changes in internal energy, enthalpy, and entropy.

2.1 Work Functions

For a closed system undergoing a reversible isothermal process, integration of Eqn (1.6-8) gives

(2.1-1)

The use of Eqn (2.1-1) in Eqn (1.5-7) leads to

(2.1-2)

in which the changes in kinetic and potential energies are considered negligible. Rearrangement of Eqn (2.1-2) results in

(2.1-3)

is called the Helmholtz energy and is defined by

(2.1-4)

Since U, T, and S are all state functions, Helmholtz energy is a state function. It is also an extensive property. As can be seen from Eqn comes from the German word Arbeit, meaning work.

For a steady-state flow system undergoing a reversible isothermal process, combination of Eqns (1.5-9) and (1.6-9) yields

(2.1-5)

in which the changes in kinetic and potential energies are considered negligible. Rearrangement of Eqn (2.1-5) gives

(2.1-6)

is called the Gibbs¹energy and is defined by

(2.1-7)

Since H, T, and S are all state functions, Gibbs energy is a state function. It is also an extensive property. As can be seen from Eqn (2.1-6), the decrease in the Gibbs energy indicates the maximum work that can be obtained from a steady-state flow system under isothermal conditions. Helmholtz and Gibbs energies are sometimes referred to as work functions.

Examination of Eqns " can be interpreted as a measure of unavailable energy.

2.2 Thermodynamic Properties of a Single-Phase System

2.2.1 Fundamental Equations

In differential form, the first law of thermodynamics for a closed system is given by

(2.2-1)

If the process is reversible, substitution of Eqns (1.3-2) and (1.6-1) into Eqn (2.2-1) gives

(2.2-2)

The definition of enthalpy is given by

(2.2-3)

The differential form of Eqn (2.2-3) becomes

(2.2-4)

Substitution of Eqn (2.2-2) into Eqn (2.2-4) gives

(2.2-5)

The definition of Helmholtz energy is given by

(2.2-6)

The differential form of Eqn (2.2-6) becomes

(2.2-7)

Substitution of Eqn (2.2-2) into Eqn (2.2-7) gives

(2.2-8)

The definition of Gibbs energy is given by

(2.2-9)

The differential form of Eqn (2.2-9) becomes

(2.2-10)

Substitution of Eqn (2.2-5) into Eqn (2.2-10) gives

(2.2-11)

It is also possible to express Eqns (2.2-2), (2.2-5), (2.2-8), and (2.2-11) in terms of mass or molar quantities, i.e.

(2.2 - 12)

(2.2 - 13)

(2.2 - 14)

(2.2-15)

These equations are called fundamental equations. Note that fundamental equations consist of only properties and their differential changes. These properties and their changes are state functions and are not dependent on the path or process involved. Therefore, once the initial and final states are specified, the expressions given in Eqns (2.2-12)–(2.2-15) hold for all processes (reversible or irreversible) and for a change of state in either a closed system or a steady-state flow system.

2.2.2 Maxwell Relations

, expressed in the form

(2.2-16)

the following relationship holds:

(2.2-17)

, are all state functions, application of Eqn (2.2-17) to the expressions given in Eqns (2.2-12)–(2.2-15) leads to

(2.2-18)

(2.2-19)

(2.2-20)

(2.2-21)

These equations are known as the Maxwell relations.

2.2.3 Internal Energy Change

For a single-phase and single-component system, the Gibbs phase rule, Eqn (1.1-4), gives the number of degrees of freedom as two. Hence, the state of such a system is specified by two independent intensive properties. The dependence of internal energy on temperature and volume, i.e.

(2.2-22)

leads to a convenient relationship to use in calculating the internal energy change.is given by

(2.2-23)

in terms of measurable quantities, differentiation of Eqn constant gives

(2.2-24)

The use of Eqn (2.2-20) in Eqn (2.2-24) yields

(2.2-25)

Thus, substitution of Eqn (2.2-25) into Eqn (2.2-23) gives the change in internal energy as

(2.2-26)

2.2.4 Enthalpy Change

The dependence of enthalpy on temperature and pressure, i.e.

(2.2-27)

leads to a convenient relationship to use in calculating the enthalpy change.is given by

(2.2-28)

in terms of measurable quantities, differentiation of Eqn constant gives

(2.2-29)

The use of Eqn (2.2-21) in Eqn (2.2-29) yields

(2.2-30)

Thus, substitution of Eqn (2.2-30) into Eqn (2.2-28) gives the change in enthalpy as

(2.2-31)

2.2.5 Entropy Change

Before deriving the equations to calculate the change in entropy, it is necessary to express heat capacities at constant volume and pressure in terms of partial derivatives of entropy.

, is defined by

(2.2-32)

The use of Eqn (2.2-12) in Eqn (2.2-32) leads to

(2.2-33)

, is defined by

(2.2-34)

The use of Eqn (2.2-13) in Eqn (2.2-34) leads to

(2.2-35)

Entropy may be expressed as a function of temperature and volume, i.e.

(2.2-36)

, is given by

(2.2-37)

The use of Eqns (2.2-20) and (2.2-33) in Eqn (2.2-37) gives the change in entropy as

(2.2-38)

It is also possible to express entropy as a function of temperature and pressure, i.e.

(2.2-39)

, is given by

(2.2-40)

The use of Eqns (2.2-21) and (2.2-35) in Eqn (2.2-40) gives the change in entropy as

(2.2-41)

2.2.6 Relationship Between Partial