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The Gibbs–Donnan effect is a name for the behaviour of charged particles near a semi-permeable membrane that sometimes fail to distribute evenly across the two sides of the membrane. The usual cause is the presence of a different charged substance that is unable to pass through the membrane and thus creates an uneven electrical charge. For example, the large anionic proteins in blood plasma are not permeable to capillary walls. Because small cations are attracted, but are not bound to the proteins, small anions will cross capillary walls away from the anionic proteins more readily than small cations.

Thus, some ionic species can pass through the barrier while others cannot. The solutions may be gels or colloids as well as solutions of electrolytes, and as such the phase boundary between gels, or a gel and a liquid, can also act as a selective barrier. The electric potential arising between two such solutions is called the Donnan potential.

The effect is named after the American physicist Josiah Willard Gibbs who proposed it in 1878 and the British chemist Frederick G. Donnan who studied it experimentally in 1911.

The Donnan equilibrium is prominent in the triphasic model for articular cartilage proposed by Mow and Lai, as well as in electrochemical fuel cells and dialysis.

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