The solubility of these solutes is different from the corresponding solvent. (ii) Now let's use 100 cc of ether in two successive extractions, using 50 cc each time. 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. 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. After solving the algebra, \(x = 0.05 \: \text{g}\). 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. and an aqueous solution of a weak base such as sodium bicarbonate. [7] The partitioning of a substance into a solid results in a solid solution. Liquid-liquid extraction involves the exchange of certain com- pounds between two solvents that are immiscible or only partially miscible. Im going to go through all of the math after I describe the procedure. You will probably have to make the benzoic acid solution yourself, but the NaOH solution will be provided for you. The two phases are put into a device called a separatory funnel, and compounds in the system will distribute between the two phases. 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). 9YS1h Because in distillation the separation of compounds with large differences in their boiling point is separated through the heating- condensation method. This compound will align itself right along the interface of the two layers. 0000000873 00000 n iOS8pe #H7//H|PYsHbc,"O W=t$Na \YN7Q4j$!'9xaURD*X@8J>F1;x7UBH!LXf[8o%uye=/FOB`? 9i This is used extraction ion and purification of the analyte. Create your account, 14 chapters | In the chemistry lab, it is most common to use liquid-liquid extraction, a process that occurs in a separatory funnel. or estimated by calculation based on a variety of methods (fragment-based, atom-based, etc.). startxref are generally water-soluble but not organic-soluble. \[\mathrm{D_M = \dfrac{mol_{org}}{mol_{aq}}}\], \[\mathrm{D_C = \dfrac{mol_{org}\times V_{aq}}{mol_{aq}\times V_{org}} = D_M\left(\dfrac{V_{aq}}{V_{org}} \right )}\]. [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. This equilibrium constant is known as partition coefficient Kpc. The partitioning of the compound between the two layers caused the sample to be incompletely extracted. h{{`T{w7M6lB^$$^lMA! @)A-E [2] Most commonly, one of the solvents is water, while the second is hydrophobic, such as 1-octanol. [6], Many other industries take into account distribution coefficients for example in the formulation of make-up, topical ointments, dyes, hair colors and many other consumer products. (Solution 1 ORGANIC BASES IN METHYLENE CHLORIDE). E9e%75S3`fPEug These metal ions are complicated first with bulky organic anionic groups. There is a problem at the end of this chapter to demonstrate that more extractions are better than one larger extraction. ( ia\ T,=x9s87}:; = 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. In this example, a single extraction resulted in extraction of \(80\%\) of the hyoscyamine \(\left( 100\% \times 0.40 \: \text{g}/0.50 \: \text{g} \right)\) from the aqueous layer into the organic layer. The key to understanding how to do this separation relates to the effect that pH will have on the different categories of compounds. 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. Since we really want as much of the solute in the organic phase as possible, this system has not yet achieved that outcome. The distribution coefficient for GPA (K) was defined by Eq. Likewise, most salts are much more soluble in water than they are in organic solvents. If one of the solvents is a gas and the other a liquid, a gas/liquid partition coefficient can be determined. All other trademarks and copyrights are the property of their respective owners. 0000004605 00000 n &Tgz*/3"I,YJ/sW"r'` WW-dp}}}@?be \D`K{/ RfrrsCVP'gCVKmof(T$|#hdMvs_khthC5m]BH;~9;jTwciX0'qu_1QjWX~jwO$lqC:X Jp$k(VaE= In common practice, the solute often exits in different molecular conditions in two immiscible phases due to polymerization ionization, and complexation, therefore partition coefficient is used to define the ratio. The partition coefficients reflect the solubility of a compound in the organic and aqueous layers, and so is dependent on the solvent system used. [42] Here a reaction at a triple interface between a conductive solid, droplets of a redox active liquid phase and an electrolyte solution have been used to determine the energy required to transfer a charged species across the interface. a,#z/A#PKgDFxPRz l>kd}E b"~'PnP):u}QZ#J,C?M`_h&r}1zNXbv/ew=c/WG|x2R^xmM+*Ju8s3./N?k\$m9wR6`}]x'uzGK If a substance is present as several chemical species in the partition system due to association or dissociation, each species is assigned its own Kow value. The IUPAC further recommends "partition ratio" for cases where transfer activity coefficients can be determined, and "distribution ratio" for the ratio of total analytical concentrations of a solute between phases, regardless of chemical form.[9]. HlTMo@W@R+E[xa,68mn0y$N,.@+ vZ"l{p0WEPIn!M 5AhaB'!O%Fys{2,& $:cG(T OtI/&v|]0Atd4QzYNeNB^k$HFXh6bs78^ aO Zhm(4g HAKzt//O/O!K33,8)>=j92W98_ w9s.8 cW0[YR Pl8a^*/OSikFgW6OI7.bF42x]\sd}.IlX%sx -%XQz?k/n4EMN3z9W#Iu+7:xC>.vJ$Fy!V+ .Fp endstream endobj 679 0 obj <>stream This is a key method for the quantitative separation of elements in batch extractions. If the distribution coefficient, K, for a given solvent extraction is 169: (a) What is the molar concentration of the analyte found in the extracting solvent if the concentration in the original solvent after the extraction is 0.027 M? Immiscible liquids are ones that cannot get mixed up together and separate into layers when shaken together. This page titled 4.5: Extraction Theory is shared under a CC BY-NC-ND 4.0 license and was authored, remixed, and/or curated by Lisa Nichols via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request. How does solvent extraction work by temmary.com, This equilibrium constant is known as partition coefficient Kpc. [citation needed]. ", "Transport, Accumulation and Transformation Processes (Ch. The metal atom with positive charges aggregates themselves with negative charges to form neutral complexes. Distribution coefficients play a large role in the efficacy of a drug. Next we want to examine some general types of extraction procedures that are commonly used. \[K = \dfrac{\text{Molarity in organic phase}}{\text{Molarity in aqueous phase}}\]. How do you get it out? \(^3\)From: The Merck Index, 12\(^\text{th}\) edition, Merck Research Laboratories, 1996. the two solvents, called the distribution coefficient, is characteristic of the compound and of the solvent pair. The values listed here[67] are sorted by the partition coefficient. Its solubility data is shown in Figure 4.13b. A related value, D, does not distinguish between different species, only indicating the concentration ratio of the substance between the two phases. 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. Failure to do this is a safety hazard; the cap would burst off your sep funnel. 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. Coordination Compounds Applications & Importance | What is Coordination Compound? endstream endobj 675 0 obj <>stream Since the organic layer from the first extraction had already reached equilibrium with the aqueous layer, it would do little good to return it to the separatory funnel and expose it to the aqueous layer again. The distribution coefficient is the ratio of the concentration of solute in the organic phase over the concentration of solute in the aqueous phase (the V-terms are the volume of the phases). In the context of pharmacokinetics (how the body absorbs, metabolizes, and excretes a drug), the distribution coefficient has a strong influence on ADME properties of the drug. Dont even worry about what that means yet. Other prediction methods rely on other experimental measurements such as solubility. Most organic solvents are immiscible with water. (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. endstream endobj 680 0 obj <>stream xb```b``e`e``Kc`@ fd;#ThhD QB3$t^/P.%"TR2!X"|QDuE(li@utt4 2` :( I8@iu@h& The calculation for the third extraction is as follows: \[4.07 = \dfrac{\left( \dfrac{x}{50 \: \text{mL ether}} \right)}{\left( \dfrac{0.09 \: \text{g} - x}{150 \: \text{mL water}} \right)}\]. Most other things will dissolve in the organic phase. Enrolling in a course lets you earn progress by passing quizzes and exams. (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. If you see a charge or if you see a row I metal (Li, Na, K) then its a salt. Now titrate the aqueous layer with NaOH to determine how much benzoic acid remained in the water. In metal extraction procedures, it is often difficult to separate the ion pairs. At the end of this guide I'll show you the sample calculations involving the distribution coefficient, Kd. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. [44][45] This strategy requires methods for the determination of concentrations in individual cells, i.e., with Fluorescence correlation spectroscopy or quantitative Image analysis. This is a greater quantity than was obtained using a single extraction of \(150 \: \text{mL}\) diethyl ether, which resulted in only \(0.40 \: \text{g}\) of hyoscyamine extracted (\(80\%\)). (b) When 50 cc of chloroform is used in each of two stages, the amount unextracted is: xu = 1 * (KV / KV + L)2 = (1/20 * 100 divided by 1/20 * 100 + 50)2. Organic compounds are then quite easily separated from the mixture with inorganic compounds in aqueous medium by adding benzene, chloroform, etc. As a first step to this problem, show what might happen to this compound when added to such a two-phase system. A: By doing an extraction with an organic solvent (ether, DCM etc.) Knowing the value of \(K\), the value of \(x\) can be solved for using the equation below. Pour a 2 cm depth of cyclohexane into one test tube and a 2 cm depth of potassium iodide solution into the other. 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.". Activity Coefficient Equation & Uses | What is an Activity Coefficient? The 's calculated using molarity and solubility values are not identical since different equilibria are involved. [41] The second is droplet experiments. Step 4. Diazonium Salt | Preparation, Reactions & Uses. 0000003679 00000 n ABSTRACT Mass transfer experiments were carried out in an annular pulsed disc-and-doughnut column (APDDC) using 30% (v/v) TBP-kerosene + uranium nitrate + nitric acid + water system (uranium nitrate system) for both extraction and stripping processes. The problem relates to the relative volumes of the phases. f Hence it is advisable to make the drug as hydrophilic as possible while it still retains adequate binding affinity to the therapeutic protein target. The combined organic phases from several extractions (containing extractant) are treated with a fresh aqueous layer to remove the impurities. Ht;o0{-)R\\AK C:$uB-I[@~Y{h;H*,~ &_dVtJH#wh@XHz(GM"+o*@gm>i IY'(_G~b ?%8IadOdJ4 )7i P distribution coefficient partition coefficient K=C1/C2=g compound per mL organic solvent/g compound per mL water K=1.5 any organic compound with an equilibrium distribution coefficient greater than 1.5 can be separated from water by extraction with a water insoluble organic solvent changing the solubility with acid base chemistry Solvent extraction is acknowledged as the most promising method for metal separation and purification especially in industrial production due to . Taking the ratio of the compound's solubility in diethyl ether compared to water gives an approximate \(K\) of 4. [citation needed], Values for other compounds may be found in a variety of available reviews and monographs. 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. First extraction: in a sep funnel add 50.0 mL of the aqueous benzoic acid solution and 10.0 mL dichloromethane (DCM). {\displaystyle f^{I}} So now youre left with a solution of compound B in ether. 0000009232 00000 n If the \(50 \: \text{mL}\) diethyl ether extracts are combined in this example (Figure 4.19), there would be a total of \(0.46 \: \text{g}\) of hyoscyamine in the combined organic extracts. Accessibility StatementFor more information contact us atinfo@libretexts.orgor check out our status page at https://status.libretexts.org. It is also known as n-octanol-water partition ratio. 3), Properties of Chemicals and Estimation Methodologies (Ch. To do an extraction you need to use an organic solvent that is not miscible with water, or else you wont get any layers to separate. While this method is generally the least accurate, the advantage is that it is the most general, being able to provide at least a rough estimate for a wide variety of molecules. {\displaystyle f^{0}} [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. 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.. I HlTKo0WB1Am{*!`MB)k>diek U]0J a / 6` 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. 0000000016 00000 n Valence Bond Theory of Coordination Compounds, Adsorption Chromatography: Definition & Example. succeed. HS[o0~G8OyMd&V-euf$#1[kQbwizc9'@^B@qA-,`'Z>mb `-[s. OL.1"1D6c'XtM0!Zai=,TE These acids with some water are mixed with separated phase and shaken. CHEM 2423 Resources. Hn0l*!R)R*YlC` After solving the algebra, \(x = 0.12 \: \text{g}\). [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. Lets say you did the extraction above using ether. 0000008032 00000 n It is a simple and easily performable classical technique. The neutrals stay in the methylene chloride layer. The two systems are related however, and \(K\)'s derived from solubility data should be similar to actual \(K\)'s. 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). In general, three extractions are the optimal compromise between expended effort and maximizing the recovery of material. She has taught high school, AP chemistry for 2 years and is teaching undergraduate college chemistry for 3 years. 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. By the rule the correct answer will keep you in orgo lab longer, its the second choice- two 5 mL extractions. The most common use of the distribution principle is in the extraction of substances by solvents, which are often employed in a laboratory or in large scale manufacturing. (I just wrote them out an scanned them in rather than typing it up). [2]:551ff[21][pageneeded][22]:1121ff[23][pageneeded][24] Critical discussions of the challenges of measurement of logP and related computation of its estimated values (see below) appear in several reviews. 0000001282 00000 n [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. 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. Solubility data for caffeine is shown in Table 4.2. Since organic compounds have their distribution ratio largely in favor of the benzene phase, more of them would pass into a non-aqueous layer. SNDc%Aqw_|/ZX&lCJb|Q[lnl)6=acT*/7]g8 0000003345 00000 n 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). Solvent extraction is a process in which a substance can be separated from its matrix. In analytical applications, solvent extraction may serve the following three key purposes of analyte characterization; In analytical chemistry, it is a useful tool for extraction. Compounds that have dissimilar molecular structures usually have widely different distribution coefficients, and mixtures of such compounds can be separated satisfactorily by one or a few transfers between a suitable solvent pair in One way to solubilize this anion in the organic phase is to add a cation with similar properties. What is the use of solvent extraction in chemical engineering? Hydrophobic drugs with high octanol-water partition coefficients are mainly distributed to hydrophobic areas such as lipid bilayers of cells. [citation needed], Despite formal recommendation to the contrary, the term partition coefficient remains the predominantly used term in the scientific literature. :^ BWLgQG >stream If the same 100 cc of solution is used in four or five lots, a still greater proportion could be extracted. CHEM 1305, CHEM 1405, CHEM 1413, CHEM 1411 (CHEM 1311, CHEM 1111), CHEM 2423 & CHEM 2425 Resources. In multiple extractions, the organic layers are combined together,as the goal is to extract the compound into the organic solvent. xbbr``b``3 1x4> s the can be separated in the organic layer. Vibrational Spectroscopy Overview & Types | What is Vibrational Spectroscopy? In addition, Hammett-type corrections are included to account of electronic and steric effects. I 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. [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. Solubility data can therefore be used to choose an appropriate solvent for an extraction. The extraction efficiency of a metal ion in the presence of a ligand will depend on the pH of the aqueous phase. endstream endobj 674 0 obj <>stream {\displaystyle \log P_{\text{oct/wat}}^{I}} Spectroscopy Types & Techniques | Absorption, Nuclear Magnetic, & Mass Spectroscopy. Neutrals Whether the pH is acidic or basic, these will remain neutral under all circumstances. f To understand the distribution of solute in two solvents, Let us consider an example of ammonia dissolved in two immiscible solvents. Legal. Adjustment of the pH is often used to alter the selectivity of the extraction, thereby allowing different metal ions to be separated. The given solid must be much more soluble in the organic solvent than in water. endstream endobj 686 0 obj <>/Size 660/Type/XRef>>stream 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. 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. 0000002730 00000 n such organic products which have low boiling points or are thermally unstable are preferably separated or refined by this process, The principle of solvent extraction next line works on the principle of Nernst distribution law or partition law which states that when a solute particle is distributed in the two solvents is also distributed in a fixed ratio irrespective of the solute present. {\displaystyle \log P_{\text{oct/wat}}^{I}} Masking agents are metal complexing agents, introduced here to improve the separation factor. The partition coefficient is the ratio of the compound's concentration in the organic layer compared to the aqueous layer. To unlock this lesson you must be a Study.com Member. In most solvent extraction procedures the extraction of solute from an aqueous phase to an immiscible organic phase such as dichloromethane, hexane, and benzene. 0000004979 00000 n 0000003429 00000 n This is essentially an equilibration process whereby we start with the solute in the aqueous phase and allow it to distribute into the organic phase. Because in distillation the separation of compounds with large differences in their boiling point is separated. thus, the metal ion is extracted in the aqueous phase. For example, EDTA is the most useful masking agent for anionic complex formation with several metal ions under specific conditions. Parameters in the axial dispersion model (ADM) and plug-flow model (PFM), namely, the axial dispersion coefficient of the continuous phase and . This quantity can be approximated using the solubility data. 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.#!; Actinides Properties & Characteristics | What are Actinides? [3] Hence the partition coefficient measures how hydrophilic ("water-loving") or hydrophobic ("water-fearing") a chemical substance is. The product you want to isolate cant be soluble in water ether. 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. BivL)`tU.g=&]kR|+/?Oo~3xzBu~mo#O G~mJ'A2 <0 [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. Give it a try! Usually it helps to form a neutral metal complex. 660 0 obj <> endobj In practice this is accomplished by use of an apparatus in which the solution to be extracted is continuously treated with fresh solvent. 660 28 If the solute A is initially soluble in one . [citation needed], 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. R ,dxay 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 coefficient is very low, by repeated extractions with small volumes of solvent. We can use these facts to our advantage to purify the products of a reaction. of extractions performed, K is the distribution coefficient, V A is the volume of solvent A and V B is the volume of solvent B. The results of the calculations in this section are summarized in Figure 4.18. 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. 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). Percent efficiency is calculated for every used solvent and method to get the max possible yield. 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