On the thermodynamical admissibility of the triphasic theory of charged hydrated tissues.

The triphasic theory on soft charged hydrated tissues (Lai, W. M., Hou, J. S., and Mow, V. C., 1991, "A Triphasic Theory for the Swelling and Deformation Behaviors of Articular Cartilage," ASME J. Biomech. Eng., 113, pp. 245-258) attributes the swelling propensity of articular cartilage to three different mechanisms: Donnan osmosis, excluded volume effect, and chemical expansion stress. The aim of this study is to evaluate the thermodynamic plausibility of the triphasic theory. The free energy of a sample of articular cartilage subjected to a closed cycle of mechanical and chemical loading is calculated using the triphasic theory. It is shown that the chemical expansion stress term induces an unphysiological generation of free energy during each closed cycle of loading and unloading. As the cycle of loading and unloading can be repeated an indefinite number of times, any amount of free energy can be drawn from a sample of articular cartilage, if the triphasic theory were true. The formulation for the chemical expansion stress as used in the triphasic theory conflicts with the second law of thermodynamics.