Entropy and the Second Law of Thermodynamics: Disorder and the Unavailability of Energy

Entropy and the Unavailability of Energy to Do Work

What does a change in entropy mean, and why should we be interested in it? One reason is that entropy is directly related to the fact that not all heat transfer can be converted into work. The next example gives some indication of how an increase in entropy results in less heat transfer into work.

Example 15.7

Less Work is Produced by a Given Heat Transfer When Entropy Change is Greater

(a) Calculate the work output of a Carnot engine operating between temperatures of 600 K and 100 K for 4000 J of heat transfer to the engine. (b) Now suppose that the 4000 J of heat transfer occurs first from the 600 K reservoir to a 250 K reservoir (without doing any work, and this produces the increase in entropy calculated above) before transferring into a Carnot engine operating between 250 K and 100 K. What work output is produced? (See Figure 15.35.)

Strategy

In both parts, we must first calculate the Carnot efficiency and then the work output.

Solution (a)

The Carnot efficiency is given by

$${\text{Eff}}_{\text{C}}=1-\frac{T_{\text{c}}}{T_{\text{h}}}\text{.}$$

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Substituting the given temperatures yields

$${\text{Eff}}_{\text{C}}=1-\frac{\text{100 K}}{\text{600 K}}=0\text{.}\text{833}\text{.}$$

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Now the work output can be calculated using the definition of efficiency for any heat engine as given by

$$\text{Eff}=\frac{W}{Q_{\text{h}}}\text{.}$$

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Solving for $W$ and substituting known terms gives

$$\begin{array}{lll}W& =& {\text{Eff}}_{\text{C}}{Q}_{\text{h}}\\ & =& (0.833)(\text{4000}\text{J})=\text{3333 J.}\end{array}$$

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Solution (b)

Similarly,

$${\text{Eff}\prime }_{\text{C}}=1-\frac{T_{\text{c}}}{{\text{T′}}_{\text{c}}}=\text{1}-\frac{\text{100 K}}{\text{250 K}}=\mathrm{0.600,}$$

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so that

$$\begin{array}{lll}W& =& {\text{Eff}\prime }_{\text{C}}{Q}_h\\ & =& (0.600)(\text{4000 J})=\text{2400 J.}\end{array}$$

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Discussion

There is 933 J less work from the same heat transfer in the second process. This result is important. The same heat transfer into two perfect engines produces different work outputs, because the entropy change differs in the two cases. In the second case, entropy is greater and less work is produced. Entropy is associated with the unavailability of energy to do work.

Figure 15.35 (a) A Carnot engine working at between 600 K and 100 K has 4000 J of heat transfer and performs 3333 J of work. (b) The 4000 J of heat transfer occurs first irreversibly to a 250 K reservoir and then goes into a Carnot engine. The increase in entropy caused by the heat transfer to a colder reservoir results in a smaller work output of 2400 J. There is a permanent loss of 933 J of energy for the purpose of doing work.

When entropy increases, a certain amount of energy becomes permanently unavailable to do work. The energy is not lost, but its character is changed, so that some of it can never be converted to doing work—that is, to an organized force acting through a distance. For instance, in the previous example, 933 J less work was done after an increase in entropy of 9.33 J/K occurred in the 4000 J heat transfer from the 600 K reservoir to the 250 K reservoir. It can be shown that the amount of energy that becomes unavailable for work is

where $T_0$ is the lowest temperature utilized. In the previous example,

as found.

Heat Death of the Universe: An Overdose of Entropy

In the early, energetic universe, all matter and energy were easily interchangeable and identical in nature. Gravity played a vital role in the young universe. Although it may have seemed disorderly, and therefore, superficially entropic, in fact, there was enormous potential energy available to do work—all the future energy in the universe.

As the universe matured, temperature differences arose, which created more opportunity for work. Stars are hotter than planets, for example, which are warmer than icy asteroids, which are warmer still than the vacuum of the space between them.

Most of these are cooling down from their usually violent births, at which time they were provided with energy of their own—nuclear energy in the case of stars, volcanic energy on Earth and other planets, and so on. Without additional energy input, however, their days are numbered.

As entropy increases, less and less energy in the universe is available to do work. On Earth, we still have great stores of energy such as fossil and nuclear fuels; large-scale temperature differences, which can provide wind energy; geothermal energies due to differences in temperature in Earth’s layers; and tidal energies owing to our abundance of liquid water. As these are used, a certain fraction of the energy they contain can never be converted into doing work. Eventually, all fuels will be exhausted, all temperatures will equalize, and it will be impossible for heat engines to function, or for work to be done.

Entropy increases in a closed system, such as the universe. But in parts of the universe, for instance, in the Solar system, it is not a locally closed system. Energy flows from the Sun to the planets, replenishing Earth’s stores of energy. The Sun will continue to supply us with energy for about another five billion years. We will enjoy direct solar energy, as well as side effects of solar energy, such as wind power and biomass energy from photosynthetic plants. The energy from the Sun will keep our water at the liquid state, and the Moon’s gravitational pull will continue to provide tidal energy. But Earth’s geothermal energy will slowly run down and won’t be replenished.

But in terms of the universe, and the very long-term, very large-scale picture, the entropy of the universe is increasing, and so the availability of energy to do work is constantly decreasing. Eventually, when all stars have died, all forms of potential energy have been utilized, and all temperatures have equalized (depending on the mass of the universe, either at a very high temperature following a universal contraction, or a very low one, just before all activity ceases) there will be no possibility of doing work.

Either way, the universe is destined for thermodynamic equilibrium—maximum entropy. This is often called the heat death of the universe, and will mean the end of all activity. However, whether the universe contracts and heats up, or continues to expand and cools down, the end is not near. Calculations of black holes suggest that entropy can easily continue for at least ${\text{10}}^{\text{100}}$ years.

Order to Disorder

Entropy is related not only to the unavailability of energy to do work—it is also a measure of disorder. This notion was initially postulated by Ludwig Boltzmann in the 1800s. For example, melting a block of ice means taking a highly structured and orderly system of water molecules and converting it into a disorderly liquid in which molecules have no fixed positions. (See Figure 15.36.) There is a large increase in entropy in the process, as seen in the following example.

Figure 15.36 When ice melts, it becomes more disordered and less structured. The systematic arrangement of molecules in a crystal structure is replaced by a more random and less orderly movement of molecules without fixed locations or orientations. Its entropy increases because heat transfer occurs into it. Entropy is a measure of disorder.

In another easily imagined example, suppose we mix equal masses of water originally at two different temperatures, say $\text{20.0º C}$ and $\text{40.0º C}$. The result is water at an intermediate temperature of $\text{30.0º C}$. Three outcomes have resulted: entropy has increased, some energy has become unavailable to do work, and the system has become less orderly. Let us think about each of these results.

First, entropy has increased for the same reason that it did in the example above. Mixing the two bodies of water has the same effect as heat transfer from the hot one and the same heat transfer into the cold one. The mixing decreases the entropy of the hot water but increases the entropy of the cold water by a greater amount, producing an overall increase in entropy.

Second, once the two masses of water are mixed, there is only one temperature—you cannot run a heat engine with them. The energy that could have been used to run a heat engine is now unavailable to do work.

Third, the mixture is less orderly, or to use another term, less structured. Rather than having two masses at different temperatures and with different distributions of molecular speeds, we now have a single mass with a uniform temperature.

These three results—entropy, unavailability of energy, and disorder—are not only related but are in fact essentially equivalent.

Life, Evolution, and the Second Law of Thermodynamics

Some people misunderstand the second law of thermodynamics, stated in terms of entropy, to say that the process of the evolution of life violates this law. Over time, complex organisms evolved from much simpler ancestors, representing a large decrease in entropy of the Earth’s biosphere. It is a fact that living organisms have evolved to be highly structured, and much lower in entropy than the substances from which they grow. But it is always possible for the entropy of one part of the universe to decrease, provided the total change in entropy of the universe increases. In equation form, we can write this as

Thus $\mathrm{\Delta }{S}_{\text{syst}}$ can be negative as long as $\mathrm{\Delta }{S}_{\text{envir}}$ is positive and greater in magnitude.

How is it possible for a system to decrease its entropy? Energy transfer is necessary. If I pick up marbles that are scattered about the room and put them into a cup, my work has decreased the entropy of that system. If I gather iron ore from the ground and convert it into steel and build a bridge, my work has decreased the entropy of that system. Energy coming from the Sun can decrease the entropy of local systems on Earth—that is, $\mathrm{\Delta }{S}_{\text{syst}}$ is negative. But the overall entropy of the rest of the universe increases by a greater amount—that is, $\mathrm{\Delta }{S}_{\text{envir}}$ is positive and greater in magnitude. Thus, $\mathrm{\Delta }{S}_{\text{tot}}=\mathrm{\Delta }{S}_{\text{syst}}+\mathrm{\Delta }{S}_{\text{envir}}>0$, and the second law of thermodynamics is not violated.

Every time a plant stores some solar energy in the form of chemical potential energy, or an updraft of warm air lifts a soaring bird, the Earth can be viewed as a heat engine operating between a hot reservoir supplied by the Sun and a cold reservoir supplied by dark outer space—a heat engine of high complexity, causing local decreases in entropy as it uses part of the heat transfer from the Sun into deep space. There is a large total increase in entropy resulting from this massive heat transfer. A small part of this heat transfer is stored in structured systems on Earth, producing much smaller local decreases in entropy. (See Figure 15.37.)

Figure 15.37 Earth’s entropy may decrease in the process of intercepting a small part of the heat transfer from the Sun into deep space. Entropy for the entire process increases greatly while Earth becomes more structured with living systems and stored energy in various forms.