Thermodynamics of Fluids at Meso and Nano Scales

Department of Chemical Biomolecular Engineering and Institute for Physical Science Technology, University of Maryland, College Park, MD 20742, U.S.A. and The Petroleum Institute, Abu Dhabi, U.A.E. 

Traditionally, the thermodynamics of fluids used in engineering is essentially macroscopic. Fluids are treated as homogeneous molecular structure and fluctuations are ignored. Size and surface effects disappear in the thermodynamic limit in which the volume V and the number of particles N tend to infinity while the molecular density of the substance, p = NjV, remains finite. Macroscopic thermodynamics often eliminates the size of the system by reducing the extensive thermodynamic properties by the number of particles, mass, or volume. The actual scale is restored only in the stage of engineering design. 

Edited by A. R. H. Goodwin, J. V. Sengers and C. J. Peters International Union of Pure and Applied Chemistry 2010 Published by the Royal Society of Chemistry, www.rse.org 

These approximations are usually sufficient, even, for instance, when considering a 1 mm of water, which contains 3-10 molecules. 

However, there are at least three categories of popular systems in which these assumptions may breakdown  

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Thermodynamics of Fluids at Meso and Nano Scales Inequality (7.17) means that the fluctuation can be neglected when... 

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