Partition equilibrium

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Partition equilibrium is a special case of chemical equilibrium. The most common chemical equilibrium systems involve reactants and products in the same phase - either all gases or all solutions. However, it is also possible to get equilibria between substances in different phases, such as two liquids that do not mix (are immiscible). [1] Partition equilibria are described by Nernst's distribution law.

Contents

Example

For example, ammonia (NH3) is soluble in both water (aq) and the organic solvent trichloromethane (CHCl3) - two immiscible solvents. If ammonia is first dissolved in water, and then an equal volume of trichloromethane is added, and the two liquids shaken together, the following equilibrium is established:

Kc = [NH3(CHCl3)]/[NH3 (aq)]      (where Kc is the equilibrium constant)

The equilibrium concentrations of ammonia in each layer can be established by titration with standard acid solution. It can thus be determined that Kc remains constant, with a value of 0.4 in this case.

Partition coefficient

This particular kind of equilibrium constant measures how a substance distributes or partitions itself between two immiscible solvents. [2] It is called the partition coefficient or distribution coefficient.

Partition equilibrium chromatography

Partition equilibrium chromatography is a type of chromatography that is typically used in gas chromatography (GC) and high performance liquid chromatography (HPLC). The stationary phase in GC is a high boiling liquid bonded to solid surface and the mobile phase is a gas.

See also

Related Research Articles

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In chemical analysis, chromatography is a laboratory technique for the separation of a mixture into its components. The mixture is dissolved in a fluid solvent called the mobile phase, which carries it through a system on which a material called the stationary phase is fixed. Because the different constituents of the mixture tend to have different affinities for the stationary phase and are retained for different lengths of time depending on their interactions with its surface sites, the constituents travel at different apparent velocities in the mobile fluid, causing them to separate. The separation is based on the differential partitioning between the mobile and the stationary phases. Subtle differences in a compound's partition coefficient result in differential retention on the stationary phase and thus affect the separation.

<span class="mw-page-title-main">Solubility</span> Capacity of a substance to dissolve in a solvent in a homogeneous way

In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.

Solubility equilibrium is a type of dynamic equilibrium that exists when a chemical compound in the solid state is in chemical equilibrium with a solution of that compound. The solid may dissolve unchanged, with dissociation, or with chemical reaction with another constituent of the solution, such as acid or alkali. Each solubility equilibrium is characterized by a temperature-dependent solubility product which functions like an equilibrium constant. Solubility equilibria are important in pharmaceutical, environmental and many other scenarios.

<span class="mw-page-title-main">High-performance liquid chromatography</span> Technique in analytical chemistry

High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify specific components in mixtures. The mixtures can originate from food, chemicals, pharmaceuticals, biological, environmental and agriculture, etc, which have been dissolved into liquid solutions.

In chemistry, a dynamic equilibrium exists once a reversible reaction occurs. Substances transition between the reactants and products at equal rates, meaning there is no net change. Reactants and products are formed at such a rate that the concentration of neither changes. It is a particular example of a system in a steady state.

In physical chemistry, Henry's law is a gas law that states that the amount of dissolved gas in a liquid is directly proportional to its partial pressure above the liquid. The proportionality factor is called Henry's law constant. It was formulated by the English chemist William Henry, who studied the topic in the early 19th century.

Ammonia solution, also known as ammonia water, ammonium hydroxide, ammoniacal liquor, ammonia liquor, aqua ammonia, aqueous ammonia, or (inaccurately) ammonia, is a solution of ammonia in water. It can be denoted by the symbols NH3(aq). Although the name ammonium hydroxide suggests an alkali with the composition [NH+
4
][OH
]
, it is actually impossible to isolate samples of NH4OH. The ions NH+
4
and OH do not account for a significant fraction of the total amount of ammonia except in extremely dilute solutions.

In the physical sciences, a partition coefficient (P) or distribution coefficient (D) is the ratio of concentrations of a compound in a mixture of two immiscible solvents at equilibrium. This ratio is therefore a comparison of the solubilities of the solute in these two liquids. The partition coefficient generally refers to the concentration ratio of un-ionized species of compound, whereas the distribution coefficient refers to the concentration ratio of all species of the compound.

<span class="mw-page-title-main">Absorption (chemistry)</span> Chemical process

In chemistry, absorption is a physical or chemical phenomenon or a process in which atoms, molecules or ions enter some bulk phase – liquid or solid material. This is a different process from adsorption, since molecules undergoing absorption are taken up by the volume, not by the surface.

<span class="mw-page-title-main">Liquid–liquid extraction</span> Method to separate compounds or metal complexes

Liquid–liquid extraction, also known as solvent extraction and partitioning, is a method to separate compounds or metal complexes, based on their relative solubilities in two different immiscible liquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer of one or more species from one liquid into another liquid phase, generally from aqueous to organic. The transfer is driven by chemical potential, i.e. once the transfer is complete, the overall system of chemical components that make up the solutes and the solvents are in a more stable configuration. The solvent that is enriched in solute(s) is called extract. The feed solution that is depleted in solute(s) is called the raffinate. Liquid-liquid extraction is a basic technique in chemical laboratories, where it is performed using a variety of apparatus, from separatory funnels to countercurrent distribution equipment called as mixer settlers. This type of process is commonly performed after a chemical reaction as part of the work-up, often including an acidic work-up.

Aqueous biphasic systems (ABS) or aqueous two-phase systems (ATPS) are clean alternatives for traditional organic-water solvent extraction systems.

The distribution constant (KD) is the equilibrium constant for the distribution of an analyte in two immiscible solvents.

A solvated electron is a free electron in a solution, in which it behaves like an anion. An electron's being solvated in a solution means it is bound by the solution. The notation for a solvated electron in formulas of chemical reactions is "e". Often, discussions of solvated electrons focus on their solutions in ammonia, which are stable for days, but solvated electrons also occur in water and many other solvents – in fact, in any solvent that mediates outer-sphere electron transfer. The solvated electron is responsible for a great deal of radiation chemistry.

Countercurrent distribution is an analytical chemistry technique which was developed by Lyman C. Craig in the 1940s. Countercurrent distribution is a separation process that is founded on the principles of liquid–liquid extraction where a chemical compound is distributed (partitioned) between two immiscible liquid phases according to its relative solubility in the two phases. The simplest form of liquid-liquid extraction is the partitioning of a mixture of compounds between two immiscible liquid phases in a separatory funnel. This occurs in five steps: 1) preparation of the separatory funnel with the two phase solvent system, 2) introduction of the compound mixture into the separatory funnel, 3) vigorous shaking of the separatory funnel to mix the two layers and allow for mass transfer of compounds in and out of the phases, 4) The contents of the separatory funnel are allowed to settle back into two distinct phases and 5) the two phases are separated from each other by draining out the bottom phase. If a compound is insoluble in the lower phase it will distribute into the upper phase and stay in the separatory funnel. If a compound is insoluble in the upper phase it will distribute into the lower phase and be removed from the separatory funnel. If the mixture contains one or more compounds that are soluble in the upper phase and one or more compounds that are soluble in the lower phase, then an extraction has occurred. Often, an individual compound is soluble to a certain extent in both phases and the extraction is, therefore, incomplete. The relative solubility of a compound in two phases is known as the partition coefficient.

<span class="mw-page-title-main">Miscibility</span> Ability of two substances to form a homogeneous solution when mixed regardless of concentration

Miscibility is the property of two substances to mix in all proportions, forming a homogeneous mixture. The term is most often applied to liquids but also applies to solids and gases. An example in liquids is the miscibility of water and ethanol as they mix in all proportions.

Partition chromatography theory and practice was introduced through the work and publications of Archer Martin and Richard Laurence Millington Synge during the 1940s. They would later receive the 1952 Nobel Prize in Chemistry "for their invention of partition chromatography".

In chemistry, binding selectivity is defined with respect to the binding of ligands to a substrate forming a complex. Binding selectivity describes how a ligand may bind more preferentially to one receptor than another. A selectivity coefficient is the equilibrium constant for the reaction of displacement by one ligand of another ligand in a complex with the substrate. Binding selectivity is of major importance in biochemistry and in chemical separation processes.

Equilibrium chemistry is concerned with systems in chemical equilibrium. The unifying principle is that the free energy of a system at equilibrium is the minimum possible, so that the slope of the free energy with respect to the reaction coordinate is zero. This principle, applied to mixtures at equilibrium provides a definition of an equilibrium constant. Applications include acid–base, host–guest, metal–complex, solubility, partition, chromatography and redox equilibria.

<span class="mw-page-title-main">Countercurrent chromatography</span>

Countercurrent chromatography is a form of liquid–liquid chromatography that uses a liquid stationary phase that is held in place by inertia of the molecules composing the stationary phase accelerating toward the center of a centrifuge due to centripetal force and is used to separate, identify, and quantify the chemical components of a mixture. In its broadest sense, countercurrent chromatography encompasses a collection of related liquid chromatography techniques that employ two immiscible liquid phases without a solid support. The two liquid phases come in contact with each other as at least one phase is pumped through a column, a hollow tube or a series of chambers connected with channels, which contains both phases. The resulting dynamic mixing and settling action allows the components to be separated by their respective solubilities in the two phases. A wide variety of two-phase solvent systems consisting of at least two immiscible liquids may be employed to provide the proper selectivity for the desired separation.

References

  1. Rudrapal, Mithun; Kothawade, Aniket P.; Ezzat, Shahira M.; Egbuna, Chukwuebuka (2022), "Bioanalysis: methods, techniques, and applications", Analytical Techniques in Biosciences, Elsevier, pp. 1–24, doi:10.1016/b978-0-12-822654-4.00002-6, ISBN   978-0-12-822654-4 , retrieved 2024-02-01
  2. Kwon Y (2001). "4.2.4: Partition and Distribution Coefficients". Handbook of Essential Pharmacokinetics, Pharmacodynamics and Drug Metabolism for Industrial Scientists. New York: Kluwer Academic/Plenum Publishers. p. 44. ISBN   978-1-4757-8693-4.