Chemical Thermodynamics

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The Second Law of Thermodynamics

The second law of thermodynamics states that in any spontaneous process the entropy of the universe will increase. What does this mean? It means that all spontaneous processes must increase the number of available micro-states. The number of available micro-states after any event will always be greater than the number of available micro-states before the event. Because atoms form large objects like boulders, large objects must also obey the second law.

   The second law can be stated in a very intuitive way. The uncertainty of the universe increases with time. This is why it is more difficult to predict what will happen far in the future. Weather is a great example. The weatherman may be able to forecast rain tomorrow, but he cannot forecast rain a month in advance.

   Consider a bicycle that is turned upside down. The back wheel is spun until it is moving very fast. The second law explains why the wheel will not turn for long. The atoms that make up the wheel are moving very fast, so these atoms have lots of energy. As the wheel spins some of this energy is transferred as heat to the air around the wheel and to the frame that holds the wheel. This increases the air temperature which in turn increases the number of micro-states available to the air molecules. The entropy of the air molecules increases. Since the frame also heats up, its atoms are free to occupy more micro-states. Eventually all of the energy in the wheel will be dissipated as heat. The wheel’s entropy decreases as it slows. The entropy of its surroundings increases. The increase is more than enough to offset the decrease. Thus, the entropy of the universe as a whole increases.

Figure 6.8: System vs. Surroundings

system.GIF (29015 bytes)

The equation that must always be satisfied is as follows:

entropy change of the system + entropy change of the surroundings =
entropy change of the universe > 0.


The entropy of any system can decrease as long as the entropy of the surroundings increases, and the increase is greater than the decrease.
       

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