Anda di halaman 1dari 4

The importance of separation. To isolate the compound because sample may be to complex to be analyzed directly.

Removal of only interfering compounds/ interferents(chemical species that causes a systematic eror by enhancing the analytical signal or the background. Principles of separation Complete

separation

and

Partial Separation.

Reaction Quotient, Q = [products]m/[reactants]n Eqm constant, k = [products]meqm/[reactants]neqm If [Q < K][Q/K < 1] [ln Q/K < 0] the rxn go right (G < 0) fwd is Spon. If [Q > K][Q/K > 1] [ln Q/K > 0] the rxn go Left (G > 0) fwd nonSpon If [Q = K][Q/K = 1] [ln Q/K = 0] the rxn @ eqm (G = 0) G = RT ln Q/K = RT ln Q RT ln K ; G = RT ln 1 RT ln K = 0 (Q=K) Go = -RT ln K ; K = exp(-G0/RT) G = RT lnQ RT lnK = G0 + RT InQ = G0 + RT In{aA(org)/aA(aq)} = 0 (eqm) Go = -RT ln {aA(org)/aA(aq)} ; KD = exp(-G0/RT) = {aA(org)/aA(aq)}
ratio of activities for A in the two phases will be constant and independent of A at any given temp

*Distribution ratio is affected by side dissociations. Purpose of KD is to find most efficient way to extract/separate; and also to calculate [remaining analyte] in the (aq)soln after certain no. extractions. Fraction extracted in the org phase if FA and that the fraction remaining in (aq)phase(G) after 1 cycle of extraction

Extraction involving Acid-Base Equilibria When a weak monoprotic acid HA is ectracted from water to org solvent : 1)Dissociation of weak monoprotic acid HA in (aq)phase only 2)Partition of HA in [aq] and [org] phase

Extraction Techniques Solid-Liquid extraction (SLE) : Like the brewing of tea, the lower MW polar cmpds dissolve in hot water are removed from hiugh MW water insoluble cellulose,protein and lipid materials. Liquid-Liquid extraction (LLE) : common method used in org lab to separate the desired cmpd and unwanted material (work up of a rxn before purification). It is based on the difference in distribution/solubility of solute in two immiscible liquids (hexane/water) . The distribution of the two immiscible phases in eqm is governed by the Nernst distribution law. : A(aq) A(org) Ideal Extraction Solvent used in LLE needs to have good extracting where it has low solubility in water;moderate volatility; Hi-Stability; Lo-Reactivity; Loflammability; Lo-Toxicity; Inexpensive & readily available in req purity. -Less Dense than water = Diethyl ether, ethyl acetate, hydrocarbons -More Dense than water = Dichloromethane Gibbs free energy (measure of max amt of useful work from a system) (state function) G = H-TS. For a change occuring at constant T & P; G= nG(pdt)-nG(rxts)=[nH(pdt) nH(rxts)]T.[nS(pdt) nS(rxts) ]=H T S

D in terms of fraction of HA in (aq)phase. When extraction of HA is done into an [org]solvent, it is more effective at a low pH where D increases. Extraction of Base is more effective at hi-pH. Opposite applies for extraction into [aq]solvent.

Extracting Inorganic species (Metal Ion) Mn+(aq) + nHL(org) MLn (org) + nH+(aq) Metal ion in [aq]phase can be extracted to the [org]solvent when it is complexed with a ligand or chelates (attach to metal via >1 atom) 1. Mn+: Free metal ion will be found in [aq] phase only 2. HL: Ligand (HL) is partitioned between [aq] and org phase 3. MLn : Metal complex formed will be partitioned btwn [aq] &[org] phases 4. H+: Dissociation of ligand occurs in [aq] phase only

1) Choice of Solvent : Solvent differs in physical ppts (polarity;density) and should be able to remove matrix interferent 2) Treament of Emulsions ( due to mixing at interfacial surface) : [surfactant] or mutual solubility or Surface tension = emulsion Ways to get rid of it, Time&patience to separate; if water one of the solvent, add c.NaCl to dehydrate org layer or detergent to remove org layer; if total Vol<13ml, centrifudge; Gravity filtration via cotton 3) Stripping and Backwashing

Separations of Metal Ions by extraction The separation is better if the pH1/2 of the 2 metal ions differ by 3 pH units (1000 x) or more. Otherwise the quantitative separation cannot be achieved. When the extraction curves of the 2 metal ions are separated by less than 3 pH units, it is necessary to mask one of the ions to maintain selectivity and quantitative separation of the desired metal over the other. Masking: to prevent one species from interfering in the analysis of another. Masking can be done by adding another chelating agent capable of binding to the unwanted ion(s) = masking agent. Since the unwanted ion(s) now is invisible, it will not be extracted into organic layer. The masking agent has to selective to the undesired ion, and be more stable than the metal chelating agent complex. It must also be charged and water soluble to stay in the [aq]phase ~contrast to the extracting agent (into org)

Small Summary

Kinetics Of Extraction : Rate of formation of complex may be slow. When mass transfer of not very rapid, it is possible to separate using difference in speed of formation of complexes. This is mostly possible in extraction of orgniac species(metal ion) using chelating agents. Parameters to consider in LLE Acidifying the medium : Relatively volatile analyte may be lost my evaporation. To overcome this problem, addition

of acid may be requires to promote the salt formation so that the analyte will remain in the aqueous phase. Batchwise single stage extraction : Suitable if F>0.99 or DRv>100; usually perfoemd in small scale chemistry labs using a separating funnel. Successive batch extarction to improve fraction extraction.

2) Liquid enter the Soxhlet chamber and immersion of the permeable cellulose extraction thimble that holds the solid sample occurs. 3) The solvent extracts the compounds of interest and leaves the solid mass behind. (Indication: Solvent may change color) 4) As the solvent level rises, the solution is forced through the small inner tube and the chamber is flushed due to a siphoning effect. 5) The solvent resutrs to the RBF taking the extracted compounds with it. 6) After many cycles the desired compound is concentrated in the RBF. The extracting solvent is removed via rotary evaporator, yielf the extracted compound. Limitations of LLE : Large volumes of solvent is consumed and has to be disposed, labor intensive and slow. Solid-phase Extraction (SPE)/ Solid-liquid Extraction : the analyte is extracted from liquid medium has it is flowed through the solid extracting phase (sorbent). This uses way lesser amount of solvent as compared to LLE and can be automated and provides faster extraction time when pressurerised so liquid is pushed/pulled through the solvent. Successful SPE : Rapid sorption, high and reproducible %solutes taken up by sorbent. and that solutes must be easily and completely removed later. The Sorption-desoription process must be reversible and so sorbent is hydrophobic and oleophillic Aproaches : analyte of interest retained in sorbent cartridge or the other way around. Before sorbent cartridge is used, it has to be conditioned ( remove any adsorbed material using a range of solvents) Elution is started with weak solvent, impurities having weak interactions with the sorbent will be aluted out. Now the solven str/polarity can be increase to elute out solutes that are moderately retained by sorbent ( bit by bit approach) Types of interaction in SPE : Intermolecular hydrogen bonding between polar analytes & un/modified silica sorbents. Analyte may/may not interact with solid phase sorbent via IMF; ionic, or even reacting with it. Solid-phase micro extraction (SPME) : Instead of liquid passing through the sorbent, the sorbent immersed into liquid sample, A fused(amorphous non crystalline) silica fiber coated with a non volatile solid polymer adsorbent thin film used to extract organic analytes from aq samples. This is a SAMPLE prep extraction technique and is generally used for an analyte collection for determination by gas chromatograpy(GC). It allows the combi of analyte prep and pre-concentration in a single step. Approaches : Extraction of volatile / non-volative extraction Extraction is complete when the [analyte] reaches distribution eqm between sample matrix & fused silica fibre absorbent thin film coating. To speed up :agitate Adsorption-Desorption SPME is used for analyte prep and pre[] for GC. Followng adsorption, the analyte is usually thermally desorbed directly in the injection port of a GC for analysis. The most common adsorbent thin film is Polydimethylsiloxane (PDMS). Various polymeric coatings for various types of analytes are commercially available. SPME Advantage : Solventless extraction; integrates extration, analyte preparation & pre[] in a single step; Fast simple and easy to automate; great potential for field app (on site sampling). When properly stored, the loaded firbre can be transported to the lab and analysed days later without significant loss of analytes. Fibre is reusable. SPME Limitations : Fibre is fragile; loss of analyte during transfer to GC injection port. Other extraction techniques. 1) Extraction using super critical fluid (CO2) : Diffusion constant is in between gas and liquid phases. Density of SCF is close to that of liquid. Good solvating power(like liquid) so analyte can be non volatile. Viscosity, minimal surface tension(like gas). High diffusity, rapid mass tranfer and can penetrate better the pores

Multistage countercurrent continuous process : Suitable if fraction extracted is low, small DRv. Used for rare metal extraction in dustry. Many extraction stages are required. Solvent distileld from extract-colelction flask, contacted with aqueous phase and resutrned to flask in a continuous manner. Soxlet Extraction (Continuous) Solid-Liquid Extraction where analyte is extracton from a solid medium. Only required where the desired compound has a limited solubility in a solvent and the impurity is insoluble in that solvent. Choose solvent that will extract the analyte only and repeat extraction due to the limited solubility. If the solubility os the desired compound and the impurities are significantly different, then simple filtration can be used. 1) Heating solvent in round bottomed flask, vapors form and condense.

Extraction is fast and high efficiency The extracted material is easily recovered by simply depressurizing, allowing the SCF to return to gas phase and evaporate.

the resin. Ion exchange resins are high molecular weight polymers that contain lalrge number of ionic function groups. They are porous and are essentially insoluble solids.

Common SCF : CO2 , modifier can be added to adjust the polarity of SCF which improves the extraction efficiency of analyte. However, CO2 is not a good medium for extraction of highly polar compounds as it is non polar Extraction using SCF is done to facilitate the extraction of organic material from solid samples.

Decaffeination Process (due to health issues of caffeine) Causes aroma and flavor losses. SCF CO2 has been used to extract the aroma and flavor before decaffing and is returned to the coffee beans/tea leaves therafter (1)Swelling raw beans with water (2) extrating caffeine fro beans with organic solvent (3) steam stripping to remove all residual solvent from the beans (4) drying the decaff-ed beans. **Many solvent have been used : Benzene, methylene chloride.. Microwave assisted Extraction (MAE) When microwave radiation is applied to gas it will absorb the energy and change the mass rapid transfer rate. In liquids and solids, the molecules do not rotate freely and has to be heated. Heating process is due to the ionic conduction(movement of ions generating heat via friction) and dipolar polarization( reorientation of dipoles under microwave). dipole moment vigorous oscillation Up to 40 samples simultaneously extracted and have contactless temp/pressure control. The system uses 90% less solvent than Soxhlet (environmentally friendly technique) Solid sample placed into vessel w extracting solvent and heated up to 10000C in 2min. Pressure-relief lid will release vapor if it exceeds set limit. Application : Microwave Decomposition/pressure digestion of oragnic substances @TP, leaving behind only the inorg components. If process is done in (l):_______________ (g):______________ Advantages of MAE : process economics (extraction yield/purity); energy costs/time; products (extract selectivity heat degradation, potential for unique products) Environmentally Responsible (green house gas emission/pollutants solvent usetoxicity Limitations of MAE : Potential explosion hazard; Higher instrument costs; limited to small scale extraction. Ultrasonic extraction : Uses altrasonic vibration to ensure contact between sample and extractin solvent. It is fast but extraction efficiency is not as high as some other techniques. Ion Exchange : Ions held on an ion exchange are exchanged for ions in a solution brougth into contact with

Anda mungkin juga menyukai