Ma. Adeliza F.

Mortalla February 21, 2012 Nernst Distribution Law

BSChE-4 Physical Chemistry 2 Dr. Dahlia H. Pescos

When a solute is taken up with two immiscible liquids, in both of which the solute is soluble, the solute distributes itself between the two liquids in such a way that the ratio of its concentration in the two liquid phases is constant at a given temperature provided the molecular state of the distributed solute is same in both the phases. This statement is a Nernst Distribution Law (1891) or Partition Law i.e. the law that determines the relative distribution of a component that is soluble in two liquids, these liquids being immiscible or miscible to a limited extent. This law is one of the laws applying to ideal dilute solutions. It was discovered by Walther Herman Nernst in 1890. The Nernst distribution law states that, at equilibrium, the ratio of the concentrations of a third component in two liquid phases is constant. The law may be expressed in the form

where are the molar equilibrium concentrations of the solute in two phases. is called distribution coefficient or partition coefficient, which is temperature dependent. Strictly, this equation is valid only with pure solvents. In practice, the solvents are always saturated with molecules of the other phase; e.g., water in the organic phase. Further, the solute A may be differently solvated in the two solvents. Nevertheless, the equation above may be considered valid, if the mutual solubilities of the solvents are small, say <1%, and the activity factors of the system are constant. For example, Iodine a violet cyrstalline solid when added to a mixture of two immiscible liquids water and carbon tetrachloride, distributes in both of them. The value of K in this case is 85 at room temperature i.e. 298 K. There are basically two limitations. They are: 1. The solute which is to be distributed should not react with any of the solvents. 2. The solute should not undergo any change in its molecular state in the solvents i.e. it should neither dissociate nor associate.

(A)

When solute undergoes association in one of the solvents, we have:

where n =order of association. (B) When solute undergoes dissociation, we have:

where

= on degree of dissociation.

(C) When solute is to be extracted from solution by another suitable solvent, we have: Amount left unextracted = where W =Initial amount present in solution, V =volume of solution, volume of extracting solvent, = Distribution coefficient, n = Number of extraction operations. Applications Solvent Extraction The ability of a solute (inorganic or organic) to distribute itself between an aqueous solution and an immiscible organic solvent has long been applied to separation and purification of solutes either by extraction into the organic phase, leaving undesirable substances in the aqueous phase; or by extraction of the undesirable substances into the organic phase, leaving the desirable solute in the aqueous phase. Partition Chromatography Chromatography is a physical method of separating mixtures of organic compounds, biomolecules, organic and inorganic salts, etc., by distribution or partition between two phases. One of the phases is the stationary phase and the other is the mobile phase. These two phases are in contact with each other and the mobile phase moves through stationary phase. The compounds in the mixtures have different values of partition or distribution coefficients, and the separation is based on this difference in partition coefficients.

Problem Solving Find the total amount of butyric acid extracted from an aqueous solution with benzene. 12 g of butyric acid is dissolved in 300 ml of water. The distribution coefficient of butyric acid between benzene and water is 3 at 18C. In one experiment, 300 ml of benzene was used for single extraction. In another experiment, three 100 ml portions were used for extraction. Find the amount of butyric acid extracted by the two methods.

During a single extraction, 9,0 g of butyric acid is obtained. For the first partial extraction, Wo = 12 g, [ ]

Amount of solute still present after the first extraction is 3.25 g. For the second partial extraction, Wo = 3.25 g, [ For the third extraction, Wo = 0.88 g, [ ] ]

Thus, the total amount of solute extracted in three extractions is 11.77 g, giving an extraction percentage of 98%.

References: http://oscience.info/chemistry/distribution-law/ http://fch.upol.cz/skripta/fcc_and_zvem_english/FCH/Nernst%20Distribution %20law.htm Date Retrieved: February 20, 2012