what is distribution coefficient in solvent extraction
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(3) and (4), respectively. So, after n-th extraction, the quantity left behind would be: If the entire quantity of the extracting solvent is used in one lot, the unextracted amount x will be: Let's work through a sample problem to understand solvent extraction. The \(K\)'s calculated using molarity and solubility values are not identical since different equilibria are involved. As you shake the sep funnel its normal for a gas to build up- for example, some solvent evaporates, or youre using sodium bicarbonate and carbon dioxide forms. Youre going to use a 0.020 M solution of benzoic acid (BzOH) in water and a 0.020 M solution of sodium hydroxide (NaOH). 9YS1h Ratio of concentrations in a mixture at equilibrium, "4.2.4: Partition and Distribution Coefficients", "Chapter 15: General Anesthetic Pharmacology", "Chapter 3: Free Energy and Phase Diagrams", "The partition of organic compounds. Alberta Education Diploma - Chemistry 30: Exam Prep & Study Guide, Psychological Research & Experimental Design, All Teacher Certification Test Prep Courses, What Is Distillation? Liquid-liquid extraction involves the exchange of certain com- pounds between two solvents that are immiscible or only partially miscible. Its like a teacher waved a magic wand and did the work for me. Upon shaking, these separate into two layers. Uncharged metal Chelate complex formation. [11]:57ff,69f[12] M is used to indicate the number of ionized forms; for the I-th form (I = 1, 2, , M) the logarithm of the corresponding partition coefficient, Both diethyl ether and benzene at first glance appear to be poor choices for extraction because caffeine is more soluble in water than in either solvent (if a gram of caffeine dissolves in \(46 \: \text{mL}\) water, but \(100 \: \text{mL}\) of benzene, caffeine is more soluble in water). [36], In metallurgy, the partition coefficient is an important factor in determining how different impurities are distributed between molten and solidified metal. and an aqueous solution of a weak base such as sodium bicarbonate. than they are in water. After the ether boils away you are left with solid compound A. Salts, or anything with a charge, is going to dissolve in the aqueous phase. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. Organic compounds are generally much more soluble in organic solvents, like benzene, chloroform, and ether, than in water and these solvents are immiscible with water. E9e%75S3`fPEug
(Solution 1 ORGANIC BASES IN METHYLENE CHLORIDE). The partition coefficient is the ratio of the compound's concentration in the organic layer compared to the aqueous layer. (It should be less than after one 10.0 mL extraction) Compare the actual amount of benzoic acid remaining with what you expect from the Kd calculation. The coefficients a and b were obtained by slope analysis. :^ BWLgQG >stream
It can be calculated, %E=100 x millimoles of solute extracted/ total millimoles of the aqueous phase. [5] Partition coefficients can also be defined when one of the phases is solid, for instance, when one phase is a molten metal and the second is a solid metal,[6] or when both phases are solids. The distribution or partition coefficient, K d, measured at equilibrium, is a useful concept that expresses the relative affinity for a sorbate in solution to sorb to a particular solid. flashcard sets. 0000005551 00000 n
Second extraction: extract 50.0 mL aqueous benzoic acid with two 5.0 mL portions of DCM. { "01_Liquid-Liquid_Extraction" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "02_Chromatography_\u2013_Background" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "03_Broadening_of_Chromatographic_Peaks" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "04_Fundamental_Resolution_Equation" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "05_Liquid_Chromatographic_Separation_Methods" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "06_Gas_Chromatographic_Separation_Methods" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "07_Appendix_1:__Derivation_of_the_Fundamental_Resolution_Equation" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()" }, { "01_In-class_Problems" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "02_Text" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "03_Learning_Objectives" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "04_Instructor\'s_Manual" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "05_Out-of-class_Problems" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "06_Laboratory_Projects" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "07_Specialty_Topics" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()", "08_Vignettes" : "property get [Map MindTouch.Deki.Logic.ExtensionProcessorQueryProvider+<>c__DisplayClass228_0.b__1]()" }, [ "article:topic", "showtoc:no", "license:ccbyncsa", "licenseversion:40", "authorname:asdl", "author@Thomas Wenzel" ], https://chem.libretexts.org/@app/auth/3/login?returnto=https%3A%2F%2Fchem.libretexts.org%2FBookshelves%2FAnalytical_Chemistry%2FSupplemental_Modules_(Analytical_Chemistry)%2FAnalytical_Sciences_Digital_Library%2FCourseware%2FSeparation_Science%2F02_Text%2F01_Liquid-Liquid_Extraction, \( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}}}\) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash{#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\), status page at https://status.libretexts.org. [51][53][54] In order to get reasonable correlations, the most common elements contained in drugs (hydrogen, carbon, oxygen, sulfur, nitrogen, and halogens) are divided into several different atom types depending on the environment of the atom within the molecule. The log P of a solute can be determined by correlating its retention time with similar compounds with known log P values. of S in solvent A)/(conc. hd0U7vE|{T;+n9Jr(nkdnFBG,gWtll(jJ"}R.PVZG!Wy_.^mlP"E7AzTEIZ#I2y5`8)'~}Z`!-&}
Molecule mining approaches apply a similarity-matrix-based prediction or an automatic fragmentation scheme into molecular substructures. The less dense phase will be the top layer- most organic solvents are less dense than water. So if we have a solution of benzoic acid in water, which is the more efficient way to extract it: doing a single extraction using 10 mL of DCM, or two extractions, each using 5 mL of DCM? But its charged sodium salt is soluble in water. 0000000016 00000 n
How does solvent extraction work by temmary.com, This equilibrium constant is known as partition coefficient Kpc. After draining the organic layer from the first extraction, fresh solvent can be added to the aqueous layer remaining in the funnel to begin the second extraction (Figure 4.17b). 0000002730 00000 n
Acid-Base Extraction | Overview, Purpose & Applications. There are many situations where prediction of partition coefficients prior to experimental measurement is useful. [10]:275ff[11]:6 The defined precedent is for the lipophilic and hydrophilic phase types to always be in the numerator and denominator respectively; for example, in a biphasic system of n-octanol (hereafter simply "octanol") and water: To a first approximation, the non-polar phase in such experiments is usually dominated by the un-ionized form of the solute, which is electrically neutral, though this may not be true for the aqueous phase. 0000009232 00000 n
The effectiveness of our approach was compared with the . [citation needed]. [35] In the field of hydrogeology, the octanolwater partition coefficient Kow is used to predict and model the migration of dissolved hydrophobic organic compounds in soil and groundwater. (I just wrote them out an scanned them in rather than typing it up). Because the numerator is large and the denominator is small, Kd should always be more than 1. Thus, a two-stage extraction is more efficient. The partition coefficient \(K\) is the ratio of the compound's concentration in the organic layer compared to the aqueous layer. The round bottom flask shouldnt be more than ~40% full of solvent or else you will get bumping (solvent slashing around- youll lose product this way). This result means that \(0.12 \: \text{g}\) is extracted into the diethyl ether in the second extraction and \(0.09 \: \text{g}\) remains in the aqueous layer \(\left( 0.21 \: \text{g} - 0.12 \: \text{g} \right)\). In addition, Hammett-type corrections are included to account of electronic and steric effects. [10]:2804 Hence, a single experiment can be used to measure the logarithms of the partition coefficient (log P) giving the distribution of molecules that are primarily neutral in charge, as well as the distribution coefficient (log D) of all forms of the molecule over a pH range, e.g., between 2 and 12. The distribution coefficient for GPA (K) was defined by Eq. Its solubility data is shown in Figure 4.13b. Water and organic solvents should not be miscible to each other. Actual partition coefficients are experimental, but can be estimated by using solubility data. Step 2: Remove the water layer from step (1), adjust the pH back to a value of 13 using a concentrated solution of sodium hydroxide, shake against methylene chloride, and we now have a solution of the organic bases in methylene chloride. Vibrational Spectroscopy Overview & Types | What is Vibrational Spectroscopy? The value is greater than one if a substance is more soluble in fat-like solvents such as n-octanol, and less than one if it is more soluble in water. How do you get it out? , is defined in the same manner as for the un-ionized form. (ii) Now let's use 100 cc of ether in two successive extractions, using 50 cc each time. endstream
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The partition coefficient is the ratio of the moles of solute in the two phases, and is a more effective means of measuring whether you have achieved the desired goal. [citation needed]. In most solvent extraction procedures the extraction of solute from an aqueous phase to an immiscible organic phase such as dichloromethane, hexane, and benzene. =NPFWk(](h)g#|d_I_
AD2[o":NNaxqgiUi6 This law gives the best results when employed under the following conditions. Failure to do this is a safety hazard; the cap would burst off your sep funnel. [12] For example, in octanolwater: which sums the individual partition coefficients (not their logarithms), and where Its working mechanism is based upon Nernst distribution law. A: The dissociation constant is defined as the ratio of the amount of compound in the organic phase to the amount of compound in the aqueous phase. 0000051499 00000 n
The values listed here[67] are sorted by the partition coefficient. Create your account, 14 chapters | You will probably have to make the benzoic acid solution yourself, but the NaOH solution will be provided for you. However, P is also the concentration ratio of the un-ionized species of compounds. If "\(x\)" is the gram quantity of hyoscyamine extracted into the diethyl ether layer, then "\(0.50 \: \text{g} - x\)" would remain in the aqueous layer after equilibrium is established. I feel like its a lifeline. between higher alcohols and water", "OctanolWater Partition Coefficients and Aqueous Solubilities of Organic Compounds", "OctanolWater Partition Coefficients of Simple Organic Compounds", "Chapter 2.2: Pharmacokinetic Phase: ADME", "What determines the strength of noncovalent association of ligands to proteins in aqueous solution? In other words, in two extractions using the same 100 cc ether we can separate (2/3 + 2/9), or 88.9%, of the original amount of the compound. It is also known as n-octanol-water partition ratio. Step 1: Lower the pH of the water using concentrated hydrochloric acid. Generally, after the purification of WPA by solvent extraction, the content of P2O5 in . Ht;o0{-)R\\AK C:$uB-I[@~Y{h;H*,~
&_dVtJH#wh@XHz(GM"+o*@gm>i IY'(_G~b ?%8IadOdJ4 )7i This result means \(0.04 \: \text{g}\) remains in the aqueous layer \(\left( 0.09 \: \text{g} - 0.05 \: \text{g} \right)\) after the third extraction. This website helped me pass! How can you use extraction to separate them? [29][30] Likewise, hydrophobicity plays a major role in determining where drugs are distributed within the body after absorption and, as a consequence, in how rapidly they are metabolized and excreted. Solvent extraction is somehow different from distillation. \[4.07 = \dfrac{\left( \dfrac{x}{50 \: \text{mL ether}} \right)}{\left( \dfrac{0.21 \: \text{g} - x}{150 \: \text{mL water}} \right)}\]. 0000004979 00000 n
Some common masking agents are 8-quinolinol for Fe3+, CN(cyanate), Tartarate, etc. Actinides Properties & Characteristics | What are Actinides? The widely used anions are oxion, triphenylphosphine, and some inorganic anions such as FeCl4-, MnO4, 2. Salting out is the method by which electrolytes are added to enhance the extractability of complexes. or estimated by calculation based on a variety of methods (fragment-based, atom-based, etc.). Another consideration when choosing a solvent for extraction is toxicity: chloroform is carcinogenic and therefore is probably not the best option despite its excellent solvation ability. For most moderately polar to non-polar organic compounds the distribution coefficient, K, will have a value between 0.5 to 10 for distribution between an organic solvent and . Hence there is a need to prioritize the remainder for testing. After the second extraction drain off the lower DCM layer and once again titrate the aqueous layer to determine how much benzoic acid remains. One way to solubilize this anion in the organic phase is to add a cation with similar properties. Valence Bond Theory of Coordination Compounds, Adsorption Chromatography: Definition & Example. In physical science, partition coefficient (P) or distribution coefficient (D) is a ratio of a compound's concentrations in the mix of two immiscible solvents at the equilibrium. In general, three extractions are the optimal compromise between expended effort and maximizing the recovery of material. The extraction solvent is usually a volatile organic liquid that can be removed by evaporation after the desired component has been extracted. countercurrent distribution, in chemistry, a multistage solvent-extraction process, one of many separation methods that can be employed in chemical analysis. So if we add an aqueous solution of sodium bicarbonate to deprotonate the benzoic acid, the resulting sodium salt (the conjugate base of benzoic acid) will stay in the water layer. For example, morphine has a \(K\) of roughly 2 in petroleum ether and water, and a \(K\) of roughly 0.33 in diethyl ether and water.\(^2\) When the \(K\) is less than one, it means the compound partitions into the aqueous layer more than the organic layer. In the first stage: In the first extraction 2/3 (that is, 66.7%) is extracted. The given solid must be much more soluble in the organic solvent than in water. What are the advantages of solvent extraction? Since organic compounds have their distribution ratio largely in favor of the benzene phase, more of them would pass into a non-aqueous layer. Furthermore, there exist also approaches using maximum common subgraph searches or molecule kernels. A conventional method for predicting log P through this type of method is to parameterize the distribution coefficient contributions of various atoms to the overall molecular partition coefficient, which produces a parametric model. Get unlimited access to over 88,000 lessons. After shaking the sep funnel for a moment, compound A will dissolve in the organic layer and salts B and C will dissolve in the water layer. However, since the value of log P is determined by linear regression, several compounds with similar structures must have known log P values, and extrapolation from one chemical class to anotherapplying a regression equation derived from one chemical class to a second onemay not be reliable, since each chemical classes will have its characteristic regression parameters. This quantity can be approximated using the solubility data. The distribution coefficient (K) is a measure of how well a given solvent will extract and hold in the organic phase a constituent from the aqueous feed liquor. I highly recommend you use this site! Water also dissolves in organic solvents: ethyl acetate (3 %), diethyl ether (1.4 %), dichloromethane (0.25 %) and chloroform (0.056 %). The SFPE procedure combined with LC-MS/MS analysis was used for the first time to prepare a clinical sample containing the drugs mentioned above from different therapeutic groups. - Definition, Process & Apparatus, What is Fractional Distillation? [53], The most common of these uses a group contribution method and is termed cLogP. Solubility data can therefore be used to choose an appropriate solvent for an extraction. A related value, D, does not distinguish between different species, only indicating the concentration ratio of the substance between the two phases. in these circumstances, the separation is calculated as the partition coefficient ratio of two solutes. thus, the metal ion is extracted in the aqueous phase. \[\begin{align} K &\sim \dfrac{\text{organic solubility}}{\text{water solubility}} \\[4pt] &\sim \dfrac{\left( 1.44 \: \text{g hyoscyamine}/100 \: \text{mL diethyl ether} \right)}{\left( 0.354 \: \text{g hyoscyamine}/100 \: \text{mL water} \right)} \\[4pt] &\sim \textbf{4.07} \: \text{(approximate} K \text{)} \end{align}\]. It has been shown that the log P of a compound can be determined by the sum of its non-overlapping molecular fragments (defined as one or more atoms covalently bound to each other within the molecule). For example, benzoic acid is much more soluble in organics than it is in water. As we will see shortly, this distribution of a solute between two immiscible phases forms the basis of chromatographic separations as well. \(^3\)From: The Merck Index, 12\(^\text{th}\) edition, Merck Research Laboratories, 1996. %PDF-1.4
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\[\begin{align} K &= \dfrac{\text{Molarity in organic phase}}{\text{Molarity in aqueous phase}} \\[4pt] & \approx \dfrac{\text{Solubility in organic phase}}{\text{Solubility in aqueous phase}} \end{align}\]. In this method the solid particles present into the two immiscible liquids can be easily separated by suspending those solid particles directly into these immiscible or some what miscible liquids. When extracting with either of these solvents, the \(K\) would be less than one (see calculation below) and it would be an "uphill battle" to draw out the caffeine from the water. They also provide guidance in choosing the most efficient way to conduct an extractive separation . Observe the different colours formed in the two solvents. Hydrophobic insecticides and herbicides tend to be more active. To understand the distribution of solute in two solvents, Let us consider an example of ammonia dissolved in two immiscible solvents. In the context of pharmacodynamics (how the drug affects the body), the hydrophobic effect is the major driving force for the binding of drugs to their receptor targets. HlTn0+hb46aWfVdmSlU("PGqEb
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eOm+Yd5CsLw{2Nj(A^Xm#mBPGdfIk c.#!; The formation of a mixture of 1:1 and 1:2 complexes with 2-hexylpyridine is indicated. If a substance is present as several chemical species in the partition system due to association or dissociation, each species is assigned its own Kow value. Most organic solvents are immiscible with water. The "partition coefficient, (K)" defines the solubility differences for a given compound between two immiscible solvents at equilibrium. The partition coefficient, abbreviated P, is defined as a particular ratio of the concentrations of a solute between the two solvents (a biphase of liquid phases), specifically for un-ionized solutes, and the logarithm of the ratio is thus log P.[10]:275ff When one of the solvents is water and the other is a non-polar solvent, then the log P value is a measure of lipophilicity or hydrophobicity. QSAR equations, which in turn are based on calculated partition coefficients, can be used to provide toxicity estimates. Later on, in 1940 this process get real importance because of its use in extracting rare earth metals. The distribution coefficient, log D, is the ratio of the sum of the concentrations of all forms of the compound (ionized plus un-ionized) in each of the two phases, one essentially always aqueous; as such, it depends on the pH of the aqueous phase, and log D = log P for non-ionizable compounds at any pH. It can be seen that high SLR is beneficial to solid-liquid extraction of GPA, but excessive solvent can inhibit the dissolution of GPA from EUMF cell tissues. {Hd85 j|p=mB[f"DSAm+q^diDQ}N72vVTNw4A4):9D*}5mQJ.Xt+l}>FD3KXqmME]yn>IT ~Jzxp(5) viwj(S,-1oGfB4:Mc=\zDghQEYE=]]rL*2p;7WvVfFzTg#n-)1!>.6:*2f
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"8rGEZQRcjVW]..CYlTe+wVV3esNylslVk+T,T^[CK98. This is because of the like dissolves like rule. The metal atom with positive charges aggregates themselves with negative charges to form neutral complexes. This equilibrium constant is known as partition coefficient Kpc. Chromatography Phases, Types & Uses | What is Chromatography? They can be separated through two main methods, It is best suitable for electrically neutral metal atom extractions. In areas such as drug discoveryareas involving partition phenomena in biological systems such as the human bodythe log D at the physiologic pH= 7.4 is of particular interest. (
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Jp$k(VaE= Solvent extraction, also called liquid-liquid extraction (LLE) and partitioning, is a method to separate compounds based on their relative solubilities in two different immiscible liquids.. Using this data you can calculate Kd. If the solute A is initially soluble in one . endstream
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As the aqueous layer is returned to the separatory funnel, the residual \(0.21 \: \text{g}\) is the quantity to be further extracted, which alters the calculation for the second extraction by replacing the \(0.50 \: \text{g}\) value. Activity Coefficient Equation & Uses | What is an Activity Coefficient? When using equal volumes, a \(K\) of \(\sim 6\) means there will be six times as many morphine molecules in the organic layer as there are in the water layer. [38][39] The most common method of measuring the distribution of the solute is by UV/VIS spectroscopy. 8)", "Water-oil partition profiling of ionized drug molecules using cyclic voltammetry and a 96-well microfilter plate system", "A new access to Gibbs energies of transfer of ions across liquid|liquid interfaces and a new method to study electrochemical processes at well-defined three-phase junctions", "Quantitative analysis of biochemical processes in living cells at a single-molecule level: a case of olaparibPARP1 (DNA repair protein) interactions", "The toxicity data landscape for environmental chemicals", "Lipophilicity--methods of determination and its role in medicinal chemistry", "Atomic Physicochemical Parameters for Three-Dimensional Structure-Directed Quantitative StructureActivity Relationships I. Partition Coefficients as a Measure of Hydrophobicity", "Computation of octanol-water partition coefficients by guiding an additive model with knowledge", "Simple method of calculating octanol/water partition coefficient", "A review of methods for the calculation of solution free energies and the modelling of systems in solution", "A comparison of log Kow (n-octanolwater partition coefficient) values for non-ionic, anionic, cationic and amphoteric surfactants determined using predictions and experimental methods", "Octanol-Water Partition Coefficient Measurement by a Simple, "Determination of liquid-liquid partition coefficients by separation methods", "Chapter 3: Solubility and Lipophilicity", List of boiling and freezing information of solvents, https://en.wikipedia.org/w/index.php?title=Partition_coefficient&oldid=1140367721, Short description is different from Wikidata, Articles with unsourced statements from June 2021, All articles needing additional references, Articles needing additional references from March 2016, Articles with unsourced statements from March 2016, Wikipedia articles needing factual verification from March 2016, Articles lacking reliable references from March 2016, Wikipedia articles needing page number citations from March 2016, Creative Commons Attribution-ShareAlike License 3.0, This page was last edited on 19 February 2023, at 19:59.
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