c 2011 Ismail Tosun

Chapter 1 Review of the First and Second Laws of Thermodynamics

The purpose of this chapter is twofold: (i) to summarize the denitions and concepts used in thermodynamics, (ii) to explain what the rst 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 dierent from each other. Therefore, one should properly dene 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. Specic (or molar) properties are extensive properties divided by the total mass (or total moles) of the system, i.e., Specic property = Extensive property Total mass Molar property = Extensive property Total moles (1.1-1)

If represents any extensive property, then Eq. (1.1-1) is expressed as b= m and e= n (1.1-2)

where m and n are the total mass and moles, respectively. Note that all specic (or molar) properties are intensive. A complete list of the properties of a system describes its state. Consider a function w = f (x, y ) (1.1-3)

in which there are three variables: w is dependent, and x and y are independent. In thermodynamics we would say that "the state of the system, w, is xed when the thermodynamic properties x and y are specied." Note that the mathematical term "point" is equivalent to the thermodynamic term "state". The number of independent intensive properties needed to x the state of a system is called the degrees of freedom. The Gibbs phase rule species the number of degrees of freedom, F , for a given system at equilibrium and is expressed in the form1 P +F =C +2 (1.1-4)

where P is the number of phases and C is the number of components. Therefore, the state of a single-phase, single-component system can be specied 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 specic volume) are always independent properties, and together they can x the state of a single-phase, singlecomponent 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 dierentiate between the concepts of steady-state, uniform, and equilibrium. Steady-state: The term steady-state means that at a particular location in space the dependent variable does not change as a function of time, i.e., =0 (1.1-5) t x,y,z Uniform: The term uniform means that at a particular instant in time the dependent variable is not a function of position, i.e., = = =0 (1.1-6) x y,z,t y x,z,t z x,y,t 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 dierence in any potential that causes a process to take
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The easiest way to remember Gibbs phase rule is to use the formula: Police + Forces = Cops + 2

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 nal 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 nal equilibrium state. 1.2 CONCEPTS OF THE "ABSTRACT WORLD" OF THERMODYNAMICS The steps followed in the solution of a thermodynamic problem are shown in Figure 1.1. The rst 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.
Abstract world of thermodynamics

Real world Problem Solution

Figure 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 nal state is the same no matter what path is used to carry out the process is called a state function2 . On the other hand, if a property is a path function, its value at the nal state will depend on what path is used and will be dierent 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 forces3 . The term "state function" in thermodynamics corresponds to the term "exact dierential" in mathematics. The expression M (x, y) dx + N (x, y ) dy is called an exact dierential if there exists some = (x, y ) for which this expression is the total dierential d, i.e., M (x, y) dx + N (x, y ) dy = d(x, y ) (1.2-1)

A necessary and sucient condition for the expression M (x, y ) dx + N (x, y ) dy to be expressed as a total dierential is that N M = (1.2-2) y x x y
A property that is dened as the combination of other state functions is also a state function. A force, F, is called conservative if the work done by the force is a state function. In mathematical terms, F = 0.
3 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 eects 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 Figure 1.1 can be carried out as follows. Although all processes taking place in nature are irreversible, all thermodynamic properties are state functions. Thus, it is always possible to replace the path of a real process by a convenient hypothetical reversible path(s) as shown in Figure 1.2. As long as the initial and nal states are the same, the change in the state function is independent of the path followed during the process, i.e., ()actual irreversible path = ()hypothetical reversible path
Hypothetical Path (Reversible) P

(1.2-3)

Actual Path (Irreversible)

Figure 1.2 A hypothetical path replacing an actual path.

1.3 WORK In thermodynamics, work can be broadly classied as expansion and non-expansion type of work. Expansion (or contraction) work is related to the change in the volume of system. Nonexpansion work, on the other hand, includes shaft work, ow work, chemical work, electrical work, etc. By convention, work done on the system is considered positive. In dierential form4 , the work associated with the volume change is given by W = Pex dVsys (1.3-1)

where Pex represents the external pressure. Work is always done against an external force, i.e., there must be some resistance against which the force operates. Otherwise, no work is done. For example, the work done by a closed system in expanding into a vacuum is zero. For a reversible process, the dierence in the driving force is very small, i.e., Psys ' Pex , and Eq. (1.3-1) becomes Wrev = Psys dVsys (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.
Since W is a path function, it is expressed in dierential form as W rather than dW . Heat, in dierential form, will also be expressed as Q in the later stages.
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The shaft work, Ws , is the work done on the system by external means through a rotating shaft. Reversible shaft work in a steady-state ow process with negligible changes in kinetic and potential energies is given by Ws,rev = Vsys dPsys (1.3-3)

The work associated with moving the uid into and out of an open system is known as the ow work. The ow work done by a tangential stress (or shear stress) is usually considered negligible by choosing the boundaries of the system perpendicular to the ow direction. On the other hand, the ow work done by a normal stress, i.e., pressure force, is given by P V . 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 process5 , i.e., Tsys = constant. An adiabatic process, on the other hand, is one in which there is no exchange of heat between the system and its surroundings, i.e., Q = 0. 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 dierentiate 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 lled 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 nd 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 rst 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 Figure 1.3. The conservation statement for energy is expressed as
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If the initial and nal state temperatures are the same, this does not necessarily imply an isothermal process.

m in

SYSTEM

m out

Figure 1.3 An open system exchanging mass and energy with its surroundings. Energy in Energy out = Change in the energy of the system In dierential form, Eq. (1.5-1) takes the form h i bP bP b +E bK + E b +E bK + E dmin + Q + W H H
in

(1.5-1)

where H , EK , EP , and U represent enthalpy, kinetic energy, potential energy, and internal energy, respectively. In terms of molar quantities, Eq. (1.5-2) is written as i h eP e +E eK + E eP e +E eK + E dnin + Q + W H H
in

dmout i bP b +E bK + E =d m U
out

sys

(1.5-2)

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 dened by H = U + PV (1.5-4)

dnout h i e +E eK + E eP =d n U
out

sys

(1.5-3)

In an open ow system, enthalpy can be interpreted as the amount of energy transferred across a system boundary by a moving ow. In Eq. (1.5-4), the term P V represents the ow work. The term W in Eqs. (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 Simplication of the Energy Balance Isolated system Since there are no inlet and outlet streams, i.e., dnin = dnout = 0, and no exchange of heat and work, i.e., Q = W = 0, Eq. (1.5-3) reduces to i h eP e +E eK + E = dEsys = 0 Esys = constant (1.5-5) d n U
sys

In an isolated system energy is converted from one form to another but the total energy is always constant. 6

 Closed system Since there are no inlet or outlet streams, i.e., dnin = dnout = 0, and nsys = constant, Eq. (1.5-3) reduces to e +E eK + E eP (1.5-6) Q + W = nsys d U
sys

Integration of Eq. (1.5-6) gives6

Steady-state ow system
sys

eP e+W f = U e + E eK + E Q

(1.5-7)

dnout = dn, W = Ws (boundaries of the system are xed in space) and In h this case dnin = i e e e = 0. Therefore, Eq. (1.5-3) reduces to d n U + EK + EP or7 Q Ws e eP eP eK + E e +E eK + E + = H +E H dn dn out in e + E eK + E eP e+W fs = H Q (1.5-8)

(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., dS = Qrev T (1.6-1)

Note that although Qrev is a path function Qrev /T is a state function. Therefore, 1/T can be interpreted as the integrating factor. To determine the absolute value of entropy, it is necessary to dene a reference state. Otherwise, only changes in entropy can be determined. The reference state of entropy is a perfect crystal at zero Kelvin. Entropy of this reference state is arbitrarily xed to zero Joules per Kelvin. In this way, an absolute entropy can be attributed to every substance at specied 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 dSuniverse = dSsys + dSsurr 0
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(1.6-2)

For any state function

For any path function

f inal state initial state

d = f inal initial =
f inal state

=
initial state

In the case of a steady-state ow system, implies "out in".

Note that the change in the entropy of the universe also gives the generation of entropy associated with the irreversibilities, i.e., Suniverse = Sgen . The second law of thermodynamics can also be expressed in terms of the Clausius and Kelvin-Planck statements: Clausius statement: As shown in Figure 1.4, it is impossible to construct a device that, operating in a cycle, will produce no eect other than the transfer of heat from a cold body to a hot one.
TH QH TH > TC QH = QC QC TC
NOT POSSIBLE

Figure 1.4 Schematic representation of the Clausius statement. Kelvin-Planck statement: As shown in Figure 1.5, it is impossible to construct a device that, operating in a cycle, will produce no eect other than converting heat completely into work.
TH QH Wnet QH = Wnet
NOT POSSIBLE

Figure 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 devaluated8 . 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.
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While ination degrades money, conversion from one form to another degrades energy.

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: Entropy in Entropy out + Entropy generation = Change in the entropy of the system (1.6-3) For an open system as shown in Figure 1.3, the dierential form of Eq. (1.6-3) becomes bout dmout + Sgen = d(mS b)sys bin dmin + Q S (1.6-4) S T Rearrangement of Eq. (1.6-4) gives b)sys + S bout dmout S bin dmin Sgen = d(mS Q 0 T (1.6-5)

which is also known as the entropy balance. In terms of molar quantities, Eq. (1.6-5) becomes

1.6.1 Simplication of the Entropy Balance Isolated system

e)sys + S eout dnout S ein dnin Q 0 Sgen = d(nS T

(1.6-6)

Since there are no inlet and outlet streams, i.e., dnin = dnout = 0, and no exchange of heat, i.e., Q = 0, Eq. (1.6-6) reduces to dSsys 0 (1.6-7) Closed system Since there are no inlet or outlet streams, i.e., dnin = dnout = 0, and nsys = constant, Eq. (1.6-6) reduces to e esys Q 0 dS (1.6-8) T Steady-state ow system e)sys = 0. Therefore, Eq. (1.6-6) reduces to In this case dnin = dnout = dn, and d(nS e ein Q 0 eout S S T

(1.6-9)

REFERENCE Prausnitz, J.M., 1986, J. Non-Equilibrium Thermodynamics 11, 49-66.

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