11.

1 SPONTANEITY
Every process has a preferred direction, which is referred to in thermodynamics as the spontaneous direction. Left to itself, a process follows its spontaneous direction. For example, the spontaneous direction for water movement is downhill, from higher altitude to lower altitude. A spontaneous process can be reversed only by the action of some outside force. Water runs uphill only if an external agent, such as a pump, forces it to do so. A process may be spontaneous, and yet the process may not occur. Extending our water example, water can be stored behind a dam for a very long time unless a spillway is opened. A chemical example is the reaction of methane and oxygen to form carbon dioxide and water:

Methaneoxygen mixtures can be stored indefinitely, but a spark will cause the mixture to burst into flames. A process that does not appear to occur may be spontaneous but very slow, or it may be nonspontaneous. Water does not run uphill, even when a spillway is present, without the action of a pump, because this is the non-spontaneous direction. Water and carbon dioxide do not rearrange into methane and molecular oxygen, even in the presence of a spark, because this is the nonspontaneous direction:

Notice that the word spontaneous has a different meaning in thermodynamics than it does in everyday speech. Ordinarily, spontaneous refers to an event that takes place without any effort or premeditation. For example, a crowd cheers spontaneously for an outstanding performance. In thermodynamics, spontaneous refers only to the natural direction of a process, without regard to whether it occurs rapidly or slowly. This chapter deals with the spontaneity of chemical change, which refers to the direction that a process will take if left alone and given enough time. Chemical kinetics, which we introduce in Chapter 12, describes the factors that determine the speed of that change. Chapter 13 deals with equilibrium, which is the state that the chemical reaction (eventually) arrives at.

Dispersal of Matter
To gain some insight into why processes have preferred directions, consider some large-scale events that go in one particular direction: 1. A bag of marbles dropped on the floor will scatter, but the marbles will not roll spontaneously back into the bag. 2. An untended wooden fence eventually falls apart, but piles of wood will not assemble spontaneously into fences. 3. A student's dormitory room naturally gets messy, but (unfortunately) does not spontaneously

clean itself up! Each of these processes has a spontaneous direction, in which matter becomes more spread out or dispersed. Another way to describe these processes states that each reduces the constraints on the objects. The marbles in a bag, the boards of a fence, and the books and clothing in a tidy dorm room are restricted, or constrained, in their positions. We can summarize these observations in a common-sense law: things tend to become dispersed. Does this common-sense law also apply to events at the molecular level? Consider the two glass bulbs shown in Figure 11-1. One bulb contains nitrogen dioxide, a red-brown gas, and the second bulb is empty. When the valve that connects the bulbs is opened, the red-brown gas expands to fill both bulbs. The opposite process never occurs spontaneously. That is, if both bulbs contain NO2 at the same pressure, opening the valve never causes the pressure to rise in one bulb and fall in the other. Figure 11-1

Courtesy of Patrick Watson

When the valve is opened between two bulbs, one of which is empty and the other filled with a gas, gas molecules move spontaneously from the filled bulb until the gas molecules are dispersed equally between the bulbs. The reverse process never occurs spontaneously.

The second part of Figure 11-1 shows a molecular view of what happens in the two bulbs. Recall from Chapter 2 that the molecules of a gas are in continual motion. The NO2 molecules in the filled bulb are always moving, undergoing countless collisions with one another and with the walls of their container. When the valve between the two bulbs is opened, some molecules move into the empty bulb, and eventually the concentration of molecules in each bulb is the same. At this point, the gas molecules are in a state of dynamic equilibrium. Molecules still move back and

forth between the two bulbs, but the concentration of molecules in each bulb remains the same. This state is discussed in detail in Chapter 13. The gas molecules escaping from a bulb behave similarly to marbles rolling out of a bag. Molecules, like marbles, tend to become more dispersed, filling a larger volume. The opposite process, in which gas molecules become more constrained by all moving into one bulb, never occurs spontaneously. Thus, our common-sense law applies to this molecular example. For a second example, consider Figure 11-2, which shows sugar dissolving in coffee from a molecular perspective. Before the solid sugar dissolves, the sugar molecules are organized in a crystal. As the molecules dissolve, they become dispersed uniformly throughout the liquid coffee. The opposite process, in which the molecules become more constrained by forming sugar cubes from sweet coffee, does not occur. Once again, the direction of spontaneous change at the molecular level conforms to the common-sense law. Sugar molecules are more dispersed when they are dissolved in coffee than when they are part of a solid crystal. A sugar cube is the molecular equivalent of a tidy dorm room. Sugar molecules disperse, destroying the compact molecular organization of a sugar cube as the cube dissolves in coffee. Figure 11-2

Pelana/Shutterstock.com
Sugar dissolving in coffee involves dispersal of molecules. Sugar molecules are distributed more widely in solution than they are in the solid crystal.

Energy Dispersal
Processes that do not involve obvious dispersal of matter may nevertheless have preferred directions. For example, Figure 11-3 shows that when a hot block of metal is placed in a cold glass of water, the metal block cools and the water warms. This process continues until the two are at the same temperature. Whenever two objects at different temperatures contact each other, the object at higher temperature transfers energy to the object at lower temperature. Figure 11-3

Courtesy of Andy Washnik

When a hot object contacts a cold object, heat always flows from higher to lower temperature.

The molecular views shown in Figure 11-3 show that this is an example of energy dispersal. Recall from Chapter 3 that higher temperature means larger average thermal energy. The metal atoms in the hot block have higher thermal energies than the water molecules in the glass. When the two objects contact each other, the hotter atoms transfer energy to the colder molecules until the average thermal energy of each object is the same. Figure 11-4 shows another example of energy dispersal. When a baseball pitcher throws a fastball, all the molecules of the ball move together through space. This represents an energy constraint. In addition to their random thermal energies of motion, all the molecules making up the ball have a portion of their kinetic energies that point in the same direction. As described in Chapter 3, when the ball comes to rest in the catcher's glove, the conversion of kinetic energy to thermal energy causes an increase in the temperature of the glove. The molecules in the glove move with larger average speeds. Moreover, these increased molecular speeds point randomly in all directions. In other words, the constrained, directional character of the kinetic energy of the ball has been dispersed into randomly directed energy of molecules in the glove. Figure 11-4

As a thrown baseball is caught, its kinetic energy is dispersed from the organized kinetic energy of the ball to randomly oriented kinetic energies of many individual molecules in the catcher's glove.

Energy and Spontaneity

Spontaneous processes result in the dispersal of matter and energy. In many cases, however, the spontaneous direction of a process may not be obvious. Can we use energy changes to predict spontaneity? To answer that question, consider two everyday events, the melting of ice at room temperature and the formation of ice in a freezer. As diagrammed in Figure 11-5, ice melts spontaneously if a mixture of water and ice at 0 C is placed on a table at 25 C:

Recall from Section 8.6 that a phase change from solid to liquid requires energy to overcome the intermolecular forces holding molecules in place in the solid. In this spontaneous process, the waterice system gains energy as ice melts. The enthalpy change of the system also is positive. Figure 11-5

Schematic view of the spontaneous process for a water and ice mixture on a table. The

energy-absorbing process, melting, is spontaneous under these conditions.

Now consider what happens if the same mixture is placed in a freezer at 15 C. Water freezes spontaneously, as shown schematically in Figure 11-6:

This process is the reverse of melting. To form a solid from a liquid, we must remove enough energy to allow the molecules to stick together in the solid phase. In this spontaneous process, the waterice system releases energy as water solidifies, and the enthalpy of the system also decreases. Figure 11-6

Schematic view of the spontaneous process for a water and ice mixture in a freezer. The energy-releasing process, freezing, is spontaneous under these conditions.

Both these everyday processes are spontaneous, but whereas one process is endothermic, the other is exothermic. The energy and enthalpy of the system increase in one process, but these quantities decrease in the other process. This simple example demonstrates that analyzing energy and enthalpy changes alone is not enough to predict whether a process will occur spontaneously. We need a property other than energy and enthalpy if we hope to use thermodynamics to determine when a process will be spontaneous.

Opposing Dispersal Trends

Liquid water contains molecules that are free to move about through their entire volume, whereas the water molecules in ice are held in a highly structured three-dimensional lattice. Thus, when water freezes, the spontaneous conversion leads to more constraint within the system. This seems like a violation of the common-sense law, but to complete our analysis we need to consider the energy change that accompanies freezing. As Figure 11-7 illustrates, water releases energy as it freezes. Energy is dispersed in the freezer as a result of the energy transfer. Freezing constrains matter but disperses energy.

Figure 11-7

When water freezes, its molecules become more constrained, but the energy released in this process becomes more dispersed in the surroundings.

The melting of ice is the reverse of the freezing of water. Energy becomes more constrained as it is transferred from the air in the room to the melting ice. At the same time, the molecules in the ice cube become less constrained, because they are free to move about in the liquid phase. Melting disperses matter but constrains energy. If the common-sense law of dispersal is correct, then the freezing and melting processes both must have a net increase in dispersion. In freezing, the energy dispersal caused by the heat flow must be larger than the molecular constraints created by the fixed positions of the ice molecules. In melting, the dispersal of matter that results from releasing molecules from their fixed positions must be larger than the energy constraints created by absorbing energy from the surroundings. The spontaneity of any process must therefore be evaluated in terms of the dispersal of both energy and matter. In Section 11.2, we define a new thermodynamic function that allows us to do such evaluations.

SECTION EXERCISES
11.1.1 Explain the following observations in terms of dispersal and constraints: (a) untended fences eventually fall down; (b) a plate is easy to break but difficult to mend; and (c) a wine cooler beverage does not spontaneously separate into alcohol, water, and fruit juice.

Answer: (a) A fence is constrained; when it falls down, it becomes more dispersed; (b) a plate has a relatively constrained structure, which becomes dispersed when the plate breaks; and (c) forming a solution from pure substances involves dispersal of the components throughout the solution. 11.1.2 Solid sugar can be recovered from coffee by boiling off the water. (Coffee candy can be made in this way.) Sugar molecules become more constrained in this process. What else must occur for total dispersal to increase? Answer: Constraining one substance (formation of sugar crystals) must be accompanied by even greater dispersal elsewhere. In this example, the water molecules that boil away are much more dispersed than water molecules in the liquid. 11.1.3 Draw molecular pictures of liquid water and water vapour that show what happens to the constraints among H2O molecules when water evaporates. Answer:

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