Once the mean free path decreases below a limiting value, measured property values do not change any more.
As the number of molecules is increased, the distance that a molecule on an average can travel between collisions (which is termed as the mean free path, denoted usually by λ) decreases as the collision frequency increases. We can intuitively understand that, in both these experiments, when the number of molecules is less, the molecules travel freely for a considerable distance before encountering another molecule or a wall. He summarizes the three laws of thermodynamics in the following manner: For readers who are interested in the philosophical aspects of the laws of thermodynamics, I strongly recommend the two books by Peter Atkins that are given in the Suggested Reading list. These may quite rightly be viewed as statements of the Principle of Increase of Entropy, which we will discuss later. For instance, everyone can relate to statements like For something to become cleaner something else must become dirtier and Left to themselves things tend to go from bad to worse from the popular Murphy’s laws. The second law has a particularly special place in our minds because it seems to explain so many occurrences in our daily life. They are now applied in diverse areas such as financial markets, cosmology, computing, bio-technology and agriculture, to name a few. Today, thermodynamics is almost synonymous with mechanical engineering! The laws of thermodynamics, based on experiments, have now come to be regarded as being among the fundamental laws of the Universe.
The quest to improve the efficiency of devices that convert heat into useful work led to the evolution of engineering thermodynamics. Thermodynamics originated as a subject in mechanical engineering at the start of the industrial revolution when, steam generated from burning coal was utilized to run machinery.
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