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In the second extraction, again using 50 cc of ether, we will further extract 2/3 of 1/3 (that is, 2/9) of the original amount. The conditions for ethanol extraction that gave high oil yield were as follows: extraction temperature of 70C, extraction time of 7 h, solvent-to-solid ratio of 6 : 1, particle size of 0.5-0.8 . endstream endobj 679 0 obj <>stream 4: Extraction - Chemistry LibreTexts [25] Hence, the log P of a molecule is one criterion used in decision-making by medicinal chemists in pre-clinical drug discovery, for example, in the assessment of druglikeness of drug candidates. The less dense phase will be the top layer- most organic solvents are less dense than water. [53], The most common of these uses a group contribution method and is termed cLogP. [13][14] For measurements of distribution coefficients, the pH of the aqueous phase is buffered to a specific value such that the pH is not significantly perturbed by the introduction of the compound. A leaching, solvent extraction, stripping, precipitation and <]>> Saranya has a masters degree in Chemistry and in Secondary Education. Solvent Extraction: Definition & Process - Study.com But just like oil and water will not mix together, most organic solvents will form layers when mixed with water. NaOH needed to titrate benzoic acid remaining in aqueous layers after two 5 mL dichloromethane extractions. In most solvent extraction procedures the extraction of solute from an aqueous phase to an immiscible organic phase such as dichloromethane, hexane, and benzene. The partitioning of the compound between the two layers caused the sample to be incompletely extracted. When an aqueous solution is extracted with an organic solvent that is denser than water (for example dichloromethane, \(\ce{CH_2Cl_2}\)), the only procedural difference is that there is no need to ever drain the aqueous layer from the separatory funnel. 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). Q: Both benzoic acid and ethyl benzoate are soluble in organic solvents. I highly recommend you use this site! Extraction in Theory and Practice (Part I) - University of California The separating funnel is then shaken well, and the ammonia which is soluble in both metals ents starts traveling across the phases to establish equilibrium. LFLN\@ULrE$\Jd0fdga(P*c)CftAqU0Sg`|HK20pnL+a`N+R TD* J This is a key method for the quantitative separation of elements in batch extractions. That Partition coefficient relates to the concentration of solute distributed between these two layers. Cork the test tubes and shake until the iodine dissolves. [36], In metallurgy, the partition coefficient is an important factor in determining how different impurities are distributed between molten and solidified metal. Dont even worry about what that means yet. Thus, a two-stage extraction is more efficient. PDF ORGANIC LABORATORY TECHNIQUES 6 - Faculty of Science lets consider a case of two solutes, A and B present in the solution. 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. Since organic compounds have their distribution ratio largely in favor of the benzene phase, more of them would pass into a non-aqueous layer. This method in general gives better results than atomic-based methods, but cannot be used to predict partition coefficients for molecules containing unusual functional groups for which the method has not yet been parameterized (most likely because of the lack of experimental data for molecules containing such functional groups). I Actinides Properties & Characteristics | What are Actinides? h{{`T{w7M6lB^$$^lMA! @)A-E When equilibrium has established, the ratio of concentration of solute in each layer is constant for each system, and this can be represented by a value \(K\) (called the partition coefficient or distribution coefficient). Devise an extraction procedure that would allow you to perform this bulk separation of the three categories of organic compounds. iFALyCkd%2grdm. log Partition coefficients can be measured experimentally in various ways (by shake-flask, HPLC, etc.) Some important factors are discussed as follows; It is considered the most important factor for the extraction of elements in designing a particular extraction procedure. 0000004756 00000 n The partition coefficient \(K\) is the ratio of the compound's concentration in the organic layer compared to the aqueous layer. 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. On this Wikipedia the language links are at the top of the page across from the article title. The distribution coefficient represents the equilibrium constant for this process. \[\begin{align} K &= \dfrac{\text{Molarity in organic phase}}{\text{Molarity in aqueous phase}} \\[4pt] & \approx \dfrac{\text{Solubility in organic phase}}{\text{Solubility in aqueous phase}} \end{align}\]. Hn0l*!R)R*YlC` These acids with some water are mixed with separated phase and shaken. expression for ionized solutes becomes simply an extension of this, into the range of values I > 0. How much hyoscyamine would be extracted into the diethyl ether layer in this process? However, the reverse is also possible. 0000002131 00000 n The parameter has been used extensively in models to predict the behavior of contaminants in the environment. from publication: Solvent extraction of jojoba oil from pre-pressed jojoba meal | The solvent . In metal extraction procedures, it is often difficult to separate the ion pairs. The particulate ratio is not as simple when the layer volumes are different, but the ratio of concentrations always equals the \(K\) (Figure 4.11b). [26] Likewise, it is used to calculate lipophilic efficiency in evaluating the quality of research compounds, where the efficiency for a compound is defined as its potency, via measured values of pIC50 or pEC50, minus its value of log P.[27]. endstream endobj 661 0 obj <>/Outlines 39 0 R/Metadata 75 0 R/PieceInfo<>>>/Pages 72 0 R/PageLayout/OneColumn/StructTreeRoot 77 0 R/Type/Catalog/LastModified(D:20080905154145)/PageLabels 70 0 R>> endobj 662 0 obj <>/ColorSpace<>/Font<>/ProcSet[/PDF/Text/ImageC/ImageI]/ExtGState<>>>/Type/Page>> endobj 663 0 obj <> endobj 664 0 obj <> endobj 665 0 obj [/Indexed 666 0 R 11 682 0 R] endobj 666 0 obj [/ICCBased 681 0 R] endobj 667 0 obj <> endobj 668 0 obj <> endobj 669 0 obj <> endobj 670 0 obj <>stream \(^2\)The partition coefficients were approximated using solubility data found in: A. Seidell, Solubilities of Inorganic and Organic Substances, D. Van. The hydrophobicity of a compound can give scientists an indication of how easily a compound might be taken up in groundwater to pollute waterways, and its toxicity to animals and aquatic life. The partition coefficient of an alkaloid between chloroform and water is 20, the alkaloid being more soluble in chloroform. 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. You will probably have to make the benzoic acid solution yourself, but the NaOH solution will be provided for you. But its charged sodium salt is soluble in water. The behavior and mechanism of a temperature-responsive ionic liquid and Extract with methylene chloride the neutrals and acids go into the methylene chloride, the bases stay in the water. Liquid Extraction: Partition Coefficient | SpringerLink - Definition, Process & Apparatus, What is Fractional Distillation? The method does, however, require the separate determination of the pKa value(s) of the substance. @IU!D;@4@iC+J):g)J2&v\{5S%rJt7E|zU$W}Fv JI[@ bUAzz6)=0~Nax/Q$`EuB([4D=%/ #a46C,}BX_ M.lt3Az7q8Jm]N*fm9Km/SaUrDXPyWc3:Io1_Ym|6Y}XzZF7X- Efv6J`hhGJ^j6FlE6cs&{|1JjR,@Lsax It is also known as n-octanol-water partition ratio. Because in distillation the separation of compounds with large differences in their boiling point is separated. Compare the weights of the alkaloid remaining in aqueous solution after 100 cc containing 1 gram has been shaken (a) with 100 cc of chloroform and (b) with two successive quantities of 50 cc of chloroform. Solvent extraction is the process in which a compound transfers from one solvent to another owing to the difference in solubility or distribution coefficient between these two immiscible (or slightly soluble) solvents. 7), and Procedures of Hazard and Risk Assessment (Ch. If the ligand complexes with the metal ion, then the metal complex may be organic-soluble. [9] For example, partition constant, defined as, where KD is the process equilibrium constant, [A] represents the concentration of solute A being tested, and "org" and "aq" refer to the organic and aqueous phases respectively. Diazonium Salt | Preparation, Reactions & Uses. (2), and the recovery rates for GPA (R 1) and IL (R 2) were defined by Eqs. [43], There are attempts to provide partition coefficients for drugs at a single-cell level. HlTn0+hb46aWfVdmSlU("PGqEb D:u=-;k X|I`[^M#8u`0cVNRW?W&qlQ+;39^Q,'9KfBOUZ@X k,Qisc44k;'' l=U'iSppm eOm+Yd5CsLw{2Nj(A^Xm#mBPGdfIk c.#!; Because ethyl benzoate has no acidic protons, it wont react with the sodium bicarbonate and will remain in the organic layer. It is a measure of the over all chemical driving force, analagous to the equilibrium constant of an ordinary chemical equation. Later on, in 1940 this process get real importance because of its use in extracting rare earth metals. Acetanilide Structure, Uses & Hazards | What is Acetanilide? A further consideration is the solubility of other components present in a mixture. In this technique, the Salute or solutes are distributed between two immiscible liquids IE organic and aqueous layers. [33] For cases where a drug reaches its target locations through passive mechanisms (i.e., diffusion through membranes), the ideal distribution coefficient for the drug is typically intermediate in value (neither too lipophilic, nor too hydrophilic); in cases where molecules reach their targets otherwise, no such generalization applies. 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. How to tell? Salting out is the method by which electrolytes are added to enhance the extractability of complexes. endstream endobj 671 0 obj <> endobj 672 0 obj <> endobj 673 0 obj <>stream Alberta Education Diploma - Chemistry 30: Exam Prep & Study Guide, Psychological Research & Experimental Design, All Teacher Certification Test Prep Courses, What Is Distillation? [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. P =: Assessment of solvent extraction for the recovery of phenol from wastewater [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, Metal ions cannot be separated in the organic phase so they are extracted through complexation. 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). Distribution coefficients play a large role in the efficacy of a drug. P Before you turn on or turn off the vacuum open the hatch to allow air into the system. The solubility of these solutes is different from the corresponding solvent. Lab Experiments. QSAR equations, which in turn are based on calculated partition coefficients, can be used to provide toxicity estimates. For example, tens of thousands of industrially manufactured chemicals are in common use, but only a small fraction have undergone rigorous toxicological evaluation. the organic compound with acidic and basic nature can be extracted through solvent extraction. 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. 0000001750 00000 n , in the case where partition of ionized forms into non-polar phase can be neglected, can be formulated as[13][14], The following approximate expressions are valid only for monoprotic acids and bases:[13][14], Further approximations for when the compound is largely ionized:[13][14], For prediction of pKa, which in turn can be used to estimate logD, Hammett type equations have frequently been applied. Actual partition coefficients are experimental, but can be estimated by using solubility data. [41] The second is droplet experiments. A molecular thermodynamic model for the extraction of CoCl2 from different chloride salts by 0.2 mol L-1 trioctylmethylammonium chloride in toluene using the OLI mixed-solvent electrolyte (OLI-MSE) framework is constructed and shows that the salting effects originate from indirect salt cation-solvent interactions that influence the availability of water in the aqueous and organic phases. 0000004605 00000 n of S in solvent B) By convention, the concentration of S in the aqueous phase is placed in the denominator. 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. As we will see shortly, this distribution of a solute between two immiscible phases forms the basis of chromatographic separations as well. However, more often than not a procedure calls for a solution to be extracted multiple times in order to isolate a desired compound, as this method is more efficient than a single extraction (see journal article in Figure 4.15b for an example of where this process is used). [citation needed], Despite formal recommendation to the contrary, the term partition coefficient remains the predominantly used term in the scientific literature. 2nd extraction: 8.0 mL 0.020 M aq. Imagine that a nearly saturated solution of \(0.50 \: \text{g}\) hyoscyamine in \(150 \: \text{mL}\) water is to be extracted into \(150 \: \text{mL}\) diethyl ether. If you are using NoScript or another JavaScript blocker, please add MendelSet.com to your whitelist. Upon shaking, these separate into two layers. Parameters in the axial dispersion model (ADM) and plug-flow model (PFM), namely, the axial dispersion coefficient of the continuous phase and . Most other things will dissolve in the organic phase. 0000053954 00000 n Download scientific diagram | Distribution coefficient, D of jojoba oil using different solvents. In such solvent extraction, it's advantageous to do extraction in successive stages using smaller lots of solvents rather doing extraction once using the entire lot. I:1I]r'7DH N() "IEY2Tp f4tu6KH75 0N4QWZ.|cqR2aFiK5#RCzTkB;oCkS[]o[ WE gxCV edcL3c\.;iv)v}\i)Gqxz< +m%"[>x^%V($eF9|Zru]}dchofo`cn\a|V/c'p5M4EhP1 wyac&1O,MXl4/O6z*wy(=AQ!@~+k/5bngM)gx^E74z{_2[vD8?yQ8 2Abj`";ZbCZnfpv&638_f&X.|'iE[xbZ9X[}W ? (3) and (4), respectively. through the heating- condensation method. It is a critical parameter for purification using zone melting, and determines how effectively an impurity can be removed using directional solidification, described by the Scheil equation. Acid-Base Extraction: It is suitable for the extraction of amines. [46][47] Calculated partition coefficients are also widely used in drug discovery to optimize screening libraries[48][49] and to predict druglikeness of designed drug candidates before they are synthesized. The extraction efficiency of a metal ion in the presence of a ligand will depend on the pH of the aqueous phase. Extraction and Determination of a Distribution Coefficient (Kd) [citation needed]. Neutrals Whether the pH is acidic or basic, these will remain neutral under all circumstances. [12] For example, in octanolwater: which sums the individual partition coefficients (not their logarithms), and where Hence there is a need to prioritize the remainder for testing. 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. The coefficients a and b were obtained by slope analysis. Adjustment of the pH is often used to alter the selectivity of the extraction, thereby allowing different metal ions to be separated. 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. (i) When the whole of 100 cc of ether is used at a time for extraction, suppose w1 grams of solute pass into ether layer and w2 grams are left in aqueous layer, so that: This means that 100 cc of ether has separated 4/5 (or 80%) of the solute originally present. Step 1: Lower the pH of the water using concentrated hydrochloric acid. 3), Properties of Chemicals and Estimation Methodologies (Ch. 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? If our goal is to extract a solute from the aqueous phase into the organic phase, there is one potential problem with using the distribution coefficient as a measure of how well you have accomplished this goal. { "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. Molecular thermodynamic model for solvent extraction of mineral acids Take the tube with the cyclohexane solution, and add an equal volume of potassium iodide solution, without shaking. partition coefficient, K: K = (conc. It is also calculated as the ratio of the concentration of the compound in a mixture of two immiscible solvent systems, "solvent x" and "solvent y.". Step 3: Take the methylene chloride layer from step (1) and shake this against an aqueous layer with a pH value of 13 (adjusted to that level using a concentrated solution of sodium hydroxide). We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. LLE is an extraction of a substance from one liquid into another liquid phase. The effectiveness of our approach was compared with the . 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. Solvent Extraction: Principles, Applications, Methods - Embibe 660 0 obj <> endobj Liquid-liquid extraction involves the exchange of certain com- pounds between two solvents that are immiscible or only partially miscible. Solubility data can therefore be used to choose an appropriate solvent for an extraction. When a solution is placed in a separatory funnel and shaken with an immiscible solvent, solutes often dissolve in part into both layers. For example, morphine has a partition coefficient of roughly 6 in ethyl acetate and water.\(^2\) If dark circles represent morphine molecules, \(1.00 \: \text{g}\) of morphine would distribute itself as shown in Figure 4.11. \[\mathrm{D_C = \dfrac{[solute]_{org}}{[solute]_{aq}} = \dfrac{mol_{org}/V_{org}}{mol_{aq}/V_{aq}} = \dfrac{mol_{org}\times V_{aq}}{mol_{aq}\times V_{org}}}\]. iOS8pe #H7//H|PYsHbc,"O W=t$Na \YN7Q4j$!'9xaURD*X@8J>F1;x7UBH!LXf[8o%uye=/FOB`? 9i Distribution coefficient | chemistry | Britannica Try refreshing the page, or contact customer support. The solvent extraction of iron from steel solutions with 2 In a multiple extraction of an aqueous layer, the first extraction is procedurally identical to a single extraction. and TOPO concentration on the distribution ratio of Ni. 0000051499 00000 n This result means that \(0.40 \: \text{g}\) of the original \(0.50 \: \text{g}\) of hyoscyamine is extracted into the diethyl ether using a single extraction. After solving the algebra, \(x = 0.29 \: \text{g}\). 0000006125 00000 n The basic procedure for performing a liquid-liquid extraction is to take two immiscible phases, one of which is usually water and the other of which is usually an organic solvent. The methods also differ in accuracy and whether they can be applied to all molecules, or only ones similar to molecules already studied. [37], A number of methods of measuring distribution coefficients have been developed, including the shake-flask, separating funnel method, reverse-phase HPLC, and pH-metric techniques. {\displaystyle f^{I}} Lets say you did some reaction and got the following compounds as your products, and lets say A is the product we want. The 's calculated using molarity and solubility values are not identical since different equilibria are involved. To understand the distribution of solute in two solvents, Let us consider an example of ammonia dissolved in two immiscible solvents. (a) When 100 cc of chloroform is used in one lot, the amount unextracted is: xu = 1 * (KV / KV + L) = (1/20 * 100 divided by 1/20 * 100 + 100) = 5/105 = 0.0476 grams. The most common organic solvent used is ether. Most organic products arent, but its possible that a compound is so polar that its soluble in water. Depending on the partition coefficient for a compound in a solvent, a single extraction may be all that is needed to effectively extract a compound. Devise a way to solubilize the organic anion shown below in the organic solvent of a two-phase system in which the second phase is water. The LibreTexts libraries arePowered by NICE CXone Expertand are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. [2] Most commonly, one of the solvents is water, while the second is hydrophobic, such as 1-octanol. In the chemistry lab, it is most common to use liquid-liquid extraction, a process that occurs in a separatory funnel. Spectroscopy Types & Techniques | Absorption, Nuclear Magnetic, & Mass Spectroscopy. The \(K\)'s calculated using molarity and solubility values are not identical since different equilibria are involved.