Chapter 3

Entropy and the Second Law

Heat and Microscopic Reversibility
Consider the following system. A ball is dropped from a height d. From experience we know that with each successive bounce the ball will reach a height lower than its previous height. Microscopically, we d see that each impact converts some of the uniform motion of the falling ball into chaotic motion of the atoms in the ball and the ground and consequently that the temperature of the ball and the ground increases. This process is said to thermalize the energy of the collision such that a portion of the work done on the ball and ground during impact is converted into heat. In our experience we encounter no circumstances where the disorganized motion of the atoms in the ball or ground that we associate with the thermal energy of the two bodies is completely converted back into the organized motion of macroscopic motion of the ball. For example, balls to not bounce higher than their original height (there is no such material as ubber!). Here we see that there is a natural direction for the process of a ball bouncing from a given height; the ball bounces lower with each successive bounce and the work done on the ball and ground is converted into heat. 33

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Entropy and the Second Law

Reversibility and Spontaneous Processes

Other events demonstrate this natural direction as well, for example temperature gradients naturally dissipate in materials. A material at a uniform temperature doesn t spontaneously develop a macroscopic temperature gradient across its length. Likewise, a burning candle never reverses itself, reforming the wick, lifting the melted wax back up the candle and solidifying. The molecules in the gas occupying our lecture hall do not spontaneously all being to move in the same direction. These examples show the connection between the directionality of a process, reversibility and spontaneity. Let s discuss in some detail here. Spontaneous Processes Let s be more concrete about what we mean by an event being spontaneous. De nition 10 A spontaneous process is one which proceeds without an external driving force. All processes occurring in nature without the interference of an externally directed force are spontaneous. Heat naturally ows from a region of high temperature to a region of low temperature. No external force is needed to move heat down a temperature gradient. Likewise, a drop of dye placed on the surface of water naturally mixes with the water without any stirring from an external force. If the individual molecules in the dye move randomly with no bias in any direction the drop still disperses and the process leads to mixing with no external driving force causing the molecules in the dye to move away from each other. Similarly, gas molecules spontaneously move from regions of high pressure to regions of low pressure. The pressure gradient itself drives the mass transfer with no external driving force. The reverse of these processes do not occur without some external action. Unmixing the dye from the water is not a spontaneous process. The dye molecules once mixed into the water are dispersed and purifying the water or dye is an eort against entropy. If the dye spontaneously separated itself from the water into a small drop it would mean that the randomness (or entropy) of the unmixed system is higher than the randomness (entropy) of the mixed system, which is not the case (assuming that the dye and water molecules are not immiscible). Sometimes processes appear to spontaneously move towards a decrease in randomness (the unmixing of oil and water, for example), although closer inspection reveals that this is not the case. We ll discuss this paradox in more detail later. Notice that all these processes have a natural direction. If we video taped these processes

Entropy and the Second Law

35

and showed them to you in reverse you would immediately know that the tape was being played backwards. In other words, these processes are not reversible. Reversibility A reversible process is one which reverses itself with an in nitesimal driving force. No in nitesimal driving force is going to unmix the dye from the water, nor will a minute change in the conditions of my system cause heat to ow back up a temperature gradient it just owed down. Since the driving forces in the spontaneous processes described above are all nite, an in nitesimal driving force to oppose the spontaneous process cannot overcome the natural progression of the process. The concept of reversibility here is somewhat abstract since it is only in the ideal sense that we could ever apply an in nitesimal driving force. For example, if the temperature gradient I create in my bar of iron is in nitesimally small, heat will ow very slowly from the higher temperature end to the lower temperature end. If I then apply an in nitesimal driving force to create a temperature gradient in the reverse direction, heat will ow in the reverse direction. That is, the original process of heat owing down a temperature gradient is reversible if the original driving force is very small. Notice too that this process becomes very slow when it is reversible because the in nitesimal driving force causes the process to proceed very slowly. Using these principles we can then mentally test whether a process is spontaneous, or reversible by these two rules: If the process appears natural in reverse, then it is not spontaneous. If the process can be reversed by application of an in nitesimal external driving force, then it is reversible. An additional handy mental test might be this: If the process is proceeding at a nite rate it is not reversible.

Entropy and Disorder

The last section on spontaneous processes and reversibility was difcult to write without using the concept of entropy. However, I was able to write those sections without using the word entropy by using terms such as disorder, randomness, and chaotic. This illustrates

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Entropy and the Second Law

just how useful the concept of entropy is since it allows us to develop a precise theory about randomness, reversibility and spontaneous processes. In fact we are going to use the concept of entropy as the foundation for stating the Second Law of thermodynamics. The natural way to proceed is to be more precise about what we mean by entropy.

Entropy and Disorder

What is the entropy? It is a measure of the disorder in the system. An increase in entropy of a system means that its randomness has increased. A solid crystal is more ordered than its liquid since the crystal atoms are arranged in a well de ned pattern. The atoms of the liquid move about randomly. Likewise, the vaporization of the liquid results in a higher entropy phase because the motion and con guration of the atoms of the liquid were more ordered than the motions and con guration of the atoms in the gas. The entropy of the a drop of dye placed in a glass of water increases as the dye diuses and the system mixes. As heat ows down a temperature gradient, entropy increases because energy is dispersed in the system more randomly. Although all this is correct, we haven t said anything quanti able yet or anything that can help us solve a thermodynamics problem. To do this we ll have to develop more of the connection between entropy, disorder, reversibility and spontaneous processes, and then we can get back to developing the quantitative rules associated with entropy. Let s be more precise by what we mean by disorder. Disorder Disorder is related to the degree to which energy, atomic con guration, and motion in a system are not ordered. For example, if the atoms in a solid all move together in a uniform way, there is no disorder in their motion. On the other hand, if each atom follows a trajectory which appears independent of the other atoms in the system then the motion of the atoms is disordered, and random. One way to see how much disorder is in a system is to analyze how much detail is required to specify the microscopic state of a system. An ordered system requires very little data to describe it. For example, the location of atoms in a perfect crystal can be speci ed with the lattice type, basis and lattice constants. On the other hand, the exact structure of a disordered alloy would be impossible to specify. We connect the concepts of disorder and spontaneity by noticing that the amount of order tends to naturally decrease as a process proceeds.

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37

Spontaneity is naturally associated with processes which increase the disorder or entropy of the universe. The entropy of the ball and ground is higher on the nth bounce than it was on the (n-1)th bounce because some of the energy of the ball was converted into the disordered motion of the atoms in the ball and the ground. The entropy of the mixture of dye and water increases with time since at any given point in time our knowledge of the location of the dye decreases. The direction of processes is associated with disorder increasing with time. Furthermore, if processes do not lead to overall decreases in the amount of disorder in the universe, then a process cannot be reversed if it increased the disorder of the universe because in order to reverse it we would have to somehow create the original amount of order from the state of increased disorder. Let s state an axiom here which will make a more precise statement about the entropy and reversibility of processes. Entropy Axiom 2 There exists a property of systems called entropy S, which is functionally related to the measurable coordinates which characterize the system and which is an intrinsic property of the system related to the degree of disorder within the system. For a reversible process, changes in the entropy are given by: dS =
q . T

This relationship between the heat of the process, the temperature and the dierential change in entropy of the process only holds for reversible processes. Note also that since the entropy is functionally related to the measurables that characterize the system it must be a state function. We ll discuss this in more detail later. Let s now state another axiom having to do with entropy.

The Second Law

Axiom 3 The Second Law of Thermodynamics states that the change in entropy of the universe (that is the system and its surroundings considered together) is positive and approaches zero for any process which approaches reversibility. Stotal 0

with the equality holding when the process is reversible.

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Entropy and the Second Law

In other words, a process increases the entropy (disorder) of the universe, unless it is reversible in which case it leaves the entropy of the universe unchanged. Remember, that a process is said to be reversible if its direction can be reversed at any given point in time by an in nitesimal change in the external conditions of the system. So if a process is reversible it must have not been creating entropy since once it has created entropy that entropy cannot be destroyed. This is again because if entropy has increased, then disorder has increased. To return to the state of order from a state of higher disorder would require creating order from disorder, which is impossible, as is implicitly stated by the Second Law. Notice then that the Second Law also implies that a process must be proceeding in nitesimally slowly to not be creating entropy. That is, if the driving forces for the process are nite, then an in nitesimal force cannot reverse them. Since the process cannot be reversed by the in nitesimal driving force then it must be creating entropy so a process which proceeds at a nite rate is not reversible. For example, if I am melting ice by adding heat very slowly, I can reverse the melting, that is I can refreeze the water by removing heat slowly from the system. This process can be reversed because if it is done slowly it is kept very close to its equilibrium condition because the driving forces for the process are kept in nitesimally small. If I heat the ice too rapidly, then some of the heat might lead to causing the liquid water to heat up, which would cause the molecules to move quickly and dissipate their energy in ways other than in melting the ice. Another example is the isothermal expansion of a gas. Lowering the pressure on the gas slightly allows the gas to expand slowly. Increasing the pressure again causes the gas to compress back to its original state. If the pressure is lowered more than an in nitesimal amount then the gas will expand rapidly, creating temperature and pressure gradients and heat ow and dissipation of the energy of the gas. Another statement of the Second Law, which can either be viewed as a result of our statement of the 2nd Law or as an alternative statement for it is: No process is possible in which the sole result is the adsorption of heat from a reservoir and its complete conversion into work. Some heat is always discarded during the process to a cold sink which increases the entropy of the cold sink. This is again related to the fact that order cannot be created from disorder. Creating ordered motion (work) from disordered motion (heat) can be done, but the overall process produces entropy.

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39

Microscopic Description of Entropy

We ll discuss entropy in a statistical mechanics context later, but here we ll brie y describe the microscopic point of view to help facilitate our understanding of the entropy. Consider an alloy of fty percent copper and fty percent gold. You can imagine that there are various ways to arrange the individual atoms in the system including some con gurations which are precise, ordered and perfect. That is where we know exactly the position of each atom in the system. Likewise, there are many con gurations of the atoms which follow no pattern and which are highly disordered. The patterned arrangements have high order and thus low entropy whereas the disordered systems are of higher entropy. In addition to the entropy associated with the congurations of the atoms in the system we also have entropy associated with the ways we distribute energy within the system. Each microscopic degree of freedom in the system can have quanta of energy in that particular motion. The more quanta of energy in the various motions of the atoms the more random the motion and the higher the temperature of the system.

Entropy and Reversible Processes

For a reversible process we noted that dS = Tq , thus to determine the change in entropy of a system for a reversible process we just integrate dS
2

S = S2

S1 =
1

q T

the entropy change of the surroundings is just the negative of the entropy change of the system for a reversible process. This is because during a reversible process the only heat involved is the transfer of energy between the system and the surroundings via heat. No additional random motion is generated, either in the system or in the surroundings so this random motion is not transferred between the system and the surroundings through heat. Because entropy is an state function we know that the change in entropy for a process which returns the system to its original state (say a cyclic process) leaves the entropy of the system unchanged. The entropy of the surroundings will be left unchanged as well, as long as the cycle was performed reversibly. Notice that the entropy change of a system during a reversible process is just the heat ow into the system divided by the temperature at which the heat is transferred into the system. So at low temperatures, say 10 kelvin 10 joules of heat transfer results in one J/K of entropy increase. This same amount of heat transfer to a sys1 tem at room temperature, 300K results in an entropy change of 30

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Entropy and the Second Law

J/K, which is much smaller than the entropy change from the same amount of heat transfer at low temperature. This results from the fact that systems at higher temperatures are already more random so a heat transfer to the higher temperature system results in less of an impact. A sneeze won t get you much notice in the crowd at a heavy metal concert, but we d notice it in the relative quite of a thermodynamics lecture.

Entropy Production
Note that for any process the entropy of a system may decrease. This must be accompanied by an entropy transfer to the surroundings equal to or greater than the decrease in entropy of the system. For a reversible process the equality holds, that is all entropy changes in the system are due only to entropy transfers between the system and the surroundings. This is the result of the fact that the entropy of the universe can never decrease. For a system we can say that any entropy change is associated with either a transfer of entropy from the surroundings or from entropy generated within the system: dSsys = dStrans + dSprod The entropy transferred to or from the system is positive or negative, but the entropy production is always positive. This relates to our earlier discussion that we don t produce order from disorder. Example 2 What is the entropy change for an ideal gas undergoing an isothermal compression?
2

S=

1 T

dqrev
1

dqrev =
2

dw = P dV = nRT dV V
2 nR dV = nR ln V V V1

S=
1

So the expanded gas has a higher entropy. This is because the expanded gas has more room accessible to it. If I pick any unit of volume of the cylinder the probability that a particular gas molecule is in that volume element is lower for the expanded gas. I consequently know less about the system and its randomness has increased. If a process is not reversible, some heat is generated in the process and the change in entropy of the system is not matched by an equal and opposite change in the entropy of the surroundings as it was in the reversible case. The dierence between the entropy change in the system and the change in the surroundings is just the entropy produced by the irreversible process. During an irreversible cyclic

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process heat is generated which is then transferred to the surroundings which results in a net increase in entropy for the surroundings during each cycle of the process. The entropy change in the system however is zero at the end of each cycle since any entropy generated during the cycle must be transferred to the surroundings because the entropy of the system must not change when the system is returned to its initial state because entropy is a state function. Remember that if a process is performed very slowly such that it is never far from its equilibrium state the process is reversible and thus there is no production of entropy. Again, this is because processes that are carried out very slowly dissipate very little energy and thus have a minimal entropy production. To dissipate no energy at all the process has to be carried out in nitely slowly. If the process is carried out with nite driving forces, that is away from its equilibrium condition we nd that the system proceeds at a nite rate and thus dissipates more energy than one that proceeds with smaller driving forces. For example, if a gas is allowed to freely expand into a vacuum we know that the ow of the gas produces large pressure and temperature gradients which cause ordered energy to be converted into disordered motion, which dissipate energy and create entropy. The process cannot be reversed by just closing the valve on the vessel and the produced entropy once produced cannot be destroyed.

Combined First and Second Laws

The rst law states the conservation of energy as dU = q + w whereas the second law says that for a reversible process we can write dS =
q T

If we only consider reversible processes and mechanical work w = P dV we can combine these two statements into the expression dU = T dS P dV

which is one of the most important equations in thermodynamics and we will use it extensively to derive relationships among the thermodynamic variables later in this course. Here we might ask when does dU = T dS P dV ? Because we used the restriction that the process be reversible to state that dS = Tq and w = P dV we might be under the impression that this combined statement of the rst and

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Entropy and the Second Law

second laws only holds for reversible processes. However, noting that dU , dS , dV are all exact dierentials and that dU just gives the change in U when S S + dS and V V + dV , that is: dU = U (S + dS, V + dV ) U (S, V )

Since U is a state function its value only depends on the system conditions, not on the process by which that state was obtained. Therefore, the change in U, that is dU in going from State 1 (S, V ) to State 2 (S + dS, V + dV ) is path independent and dU is not associated with any process. We conclude then that dU = T dS P dV always holds true as is dU = q + w. What isn t always true is that we can equate the rst terms and second terms from these two expressions for dU. That is the relations dS = Tq and w = P dV are true only when the process is reversible. What the combined rst and second laws says is that U is a function of S and V. U = U (S, V ) and that since U is a state function we can write the total dierential as dU = U dS + U dV V S S V and if a process is carried out reversibly then the dierential coecients U =T S V and U = P V S are the temperature and pressure, respectively. If the process is not carried out reversibly, then the coecients are not temperature and pressure (which often are not even well de ned for a irreversible process). What makes all this discussion mute is that even if the process is carried out irreversibly, because U is a state function all we have to do is nd a reversible process that connects the same two states and dU will be the same for this reversible process as it was for the irreversible one and the dierential coecients are simply the temperature and pressure. In this discussion we noticed that by writing the combined statements of the rst and second laws as dU = T dS P dV what we imply is that U is a function of S and V , U (S, V ). In other words, that entropy and volume are the natural variables of the internal energy. Unfortunately, entropy and volume are not very convenient variables to have as our natural variables. For example, it is common in an experiment to hold one of the natural variables xed. If we choose volume then we must carry out our experiments in a constant volume bomb which is not very convenient. On the other hand, if we choose to hold the other natural variable of U constant, S then what kind of

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experiment must we conduct? The conclusion is that entropy is not a very practical natural variable and it would be useful if we could nd a way to change variables so that we could have more convenient natural variables to work with. Before we actually make a change of variables to something more convenient than entropy S and volume V, let s discuss a general mathematical procedure for making changes of variables. This method is known as Legendre Transformations . Legendre Transformations Consider a state function Y (X1 , X2 , . . . Xn ) which is a function of the n independent variables X1 , X2 , . . . Xn . Remember that for an exact function we can write the total dierential of this function as dY (X1 , X2 , . . . Xn ) = C1dX1 + C2 dX2 + . . . + Cn dXn where the coecients Ci =
Y Xi Xj =i

We now can derive a set of new functions which replace any combination of the independent variables with their respective conjugate pairs. = Y C1X1 C2X2 2 (X1 , C2 , X3 , . . . , Xn ) = Y ( ) = X , X , . . . , C Y C n n n Xn 1 2 C1 X1 C2 X2 1,2 (C1 , C2 , X3, . . . , Xn ) = Y C1X1 C2 X2 . . . Cn Xn 1,2,...,n (C1 , C2 , . . . , Cn ) = Y We then have several dierent choices for which variables we have as our natural variables of the new function where we can replace any variable of the function Y with its conjugate pair. We ll being the next chapter on Thermodynamic Variables and Relations with an application of Legendre Transformations on the internal energy function.
1 (C1 , X2 , . . . , Xn )

Chapter 3 Main Points

1. A spontaneous process is one which occurs with no external driving force and produces entropy. 2. A reversible process is one which reverses itself with an in nitesimal driving force. This process involves no production of entropy and occurs in nitely slowly.

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Entropy and the Second Law

3. The natural direction of processes is the direction that leads to increases in the entropy of the universe. 4. There exists a property of systems called entropy, which is a function related to the state of the system and which is an intrinsic property of the system related to the degree of disorder within the system. For a reversible process, changes in the entropy are given by: dS =
q . T

1. The Second Law of Thermodynamics states that the change in entropy of the universe is positive and approaches zero for any process which approaches reversibility. 2. The entropy of a system may decrease for a given process if an entropy transfer to the surroundings is greater than the decrease in entropy of the system. 3. The combined First and Second Laws of thermodynamics: dU = T dS P dV