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Home Physical Chemistry Equilibrium and the Second Law of Thermodynamics Spontaneous Mixing  
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Spontaneous MixingAuthor: John Hutchinson
We begin by examining common characteristics of spontaneous processes, and for simplicity, we focus on processes not involving phase transitions or chemical reactions. A very clear example of such a process is mixing. Imagine putting a drop of blue ink in a glass of water. At first, the blue dye in the ink is highly concentrated. Therefore, the molecules of the dye are closely congregated. Slowly but steadily, the dye begins to diffuse throughout the entire glass of water, so that eventually the water appears as a uniform blue color. This occurs more readily with agitation or stirring but occurs spontaneously even without such effort. Careful measurements show that this process occurs without a change in temperature, so there is no energy input or released during the mixing. We conclude that, although there is no energetic advantage to the dye molecules dispersing themselves, they do so spontaneously. Furthermore, this process is irreversible in the sense that, without considerable effort on our part, the dye molecules will never return to form a single localized drop. We now seek an understanding of how and why this mixing occurs. Consider the following rather abstract model for the dye molecules in the water. For the glass, we take a row of ten small boxes, each one of which represents a possible location for a molecule, either of water or of dye. For the molecules, we take marbles, clear for water and blue for ink. Each box will accommodate only a single marble, since two molecules cannot be in the same place as the same time. Since we see a drop of dye when the molecules are congregated, we model a "drop" as three blue marbles in consecutive boxes. Notice that there are only eight ways to have a "drop" of dye, assuming that the three dye "molecules" are indistinguishable from one another. Two possibilities are shown in subfigure 1.1 and subfigure 1.2. It is not difficult to find the other six.
By contrast, there are many more ways to arrange the dye molecules so that they do not form a drop, i.e., so that the three molecules are not together. Two possibilities are shown in subfigure 1.3 and subfigure 1.4. The total number of such possibilities is 112. (The total number of all possible arrangements can be calculated as follows: there are 10 possible locations for the first blue marble, 9 for the second, and 8 for the third. This gives 720 possible arrangements, but many of these are identical, since the marbles are indistinguishable. The number of duplicates for each arrangement is 6, calculated from three choices for the first marble, two for the second, and one for the third. The total number of nonidentical arrangements of the molecules is 720/6 = 120). We conclude that, if we randomly place the 3 marbles in the tray of 10 boxes, the chances are only 8 out of 120 (or 1 out of 15) of observing a drop of ink. Now, in a real experiment, there are many, many times more ink molecules and many, many times more possible positions for each molecule. To see how this comes into play, consider a row of 500 boxes and 5 blue marbles. (The mole fraction of ink is thus 0.01.) The total number of distinct configurations of the blue marbles in these boxes is approximately 2×10^{11}. The number of these configurations which have all five ink marbles together in a drop is 496. If the arrangements are sampled randomly, the chances of observing a drop of ink with all five molecules together are thus about one in 500 million. The possibilities are remote even for observing a partial "droplet" consisting of fewer than all five dye molecules. The chance for four of the molecules to be found together is about one in 800,000. Even if we define a droplet to be only three molecules together, the chances of observing one are less than one in 1600. We could, with some difficulty, calculate the probability for observing a drop of ink when there are 10^{23} molecules. However, it is reasonably deduced from our small calculations that the probability is essentially zero for the ink molecules, randomly distributed into the water molecules, to be found together. We conclude from this that the reason why we observe ink to disperse in water is that the probability is infinitesimally small for randomly distributed dye molecules to be congregated in a drop. Interestingly, however, when we set up the real ink and water experiment, we did not randomly distribute the ink molecules. Rather, we began initially with a drop of ink in which the dye molecules were already congregated. We know that, according to our kinetic theory, the molecules are in constant random motion. Therefore, they must be constantly rearranging themselves. Since these random motions do not energetically favor any one arrangement over any other one arrangement, we can assume that all possible arrangements are equally probable. Since most of the arrangements do not correspond to a drop of ink, then most of the time we will not observe a drop. In the case above with five blue marbles in 500 boxes, we expect to see a drop only once in every 500 million times we look at the "glass". In a real glass of water with a real drop of ink, the chances are very much smaller than this. We draw two very important conclusions from our model. First, the random motions of molecules make every possible arrangement of these molecules equally probable. Second, mixing occurs spontaneously simply because there are vastly many more arrangements which are mixed than which are not. The first conclusion tells us "how" mixing occurs, and the second tells us "why." On the basis of these observations, we deduce the following preliminary generalization: a spontaneous process occurs because it produces the most probable final state.


Home Physical Chemistry Equilibrium and the Second Law of Thermodynamics Spontaneous Mixing 