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Experiment 4: Extraction

• Pulling a compound (or compounds) out of one phase into another solid/liquid ! making a cup of tea liquid/liquid ! most common in lab liquids must be immiscible • Used for the isolation, purification, and/or separation of compounds

Part A: Separation of Acidic, Basic and Neutral Substances Part B: Isolation & Analysis

- isolation of potential therapeutics from natural sources - remove water soluble impurities from an organic reaction mixture typically inorganic salts means of preliminary purification (wash) - separate two organic compounds bearing different functional groups • Terminology - extract: pulling out what you want - wash: removing what you don't want both are effectively the same process • This technique is based on solubility differences

Reading: Mohrig, Hammond & Schatz Ch. 11 pgs 113-132 Ch. 12 pgs 132-141 Ch. 20 pgs 277-310 Carey Ch. 13 pgs 574-581 watch the technique video on the course website!

Extraction: How Does it Work
• Organic compound in a separatory funnel with two immiscible liquids - two layers - typically an organic solvent & water - relative solvent densities will determine which layer is which (e.g. top or bottom) • Layers are mixed by inverting funnel gently; will separate on standing • Compound (x) will distribute (partition) itself between the layers (phases) - equilibrium based on rel. solubility of x in each layer - organic layer will contain neutral organic compounds - aqueous layer will contain organic & inorganic salts • Drain lower layer out the bottom; Pour upper layer out the top separatory funnel x x x x x x x x
less dense layer more dense layer

Organic vs. Aqueous Layer: Top or Bottom?
• Consider the solvent density vs. water Densities of Some Common Extraction Solvents solvent
less dense (top layer)

density 0.672 0.713 0.879 1.000 1.198 1.335 1.498 "

hexanes diethyl ether benzene


water saturated NaCl (aq)

more dense (bottom layer)

dichloromethane chloroform

• If don't know densities add a few drops of water to the separatory funnel - water will join the aqueous layer!

will be difficult to extract the compound from water K= ! • What if extraction efficiency is poor?? . K ! 4 .05 K= = = 7 K gives us information about extraction efficiency General Principles # start with a mixture of compounds dissolved in an organic solvent # Extract With water H2O acid HCl Removes polar.saturate the aqueous layer with NaCl ("salting out") shift the equilibrium (change K) • How can we use extraction to separate two (or more) organic compounds? .35 0.If K < 1.modify solubility? • If know solubility's.increase number of extraction steps more efficient to carry out multiple small extractions than 1 large one even if K ! 4 so 3 x 5mL extraction better than 1 x 15mL extraction!! .For an efficient extraction (water ! organic solvent). can calculate K If for compound X: solubility in water is 5g/100 mL "solubility in an organic solvent is 35 g/100 mL 35g/100mLB 5g/100mLA 0.Distribution Coefficient (K) • Ratio of concentrations of a compound [X] in the layers is known the distribution coefficient (K) [X] in organic solvent [X] in water solubility of X in organic solvent solubility of X in water Extraction • Extraction Efficiency: . low MW compounds inorganic acids & bases polar organics with <5 carbons basic compounds inorganic bases R-NH2 strongly acidic compounds inorganic acids R-CO2H (pKa ! 5) acidic compounds OH O R OH Separation of a Mixture by Extraction Why? solubility R NH2 HCl H R NH2 Cl weak base NaHCO3 strong base NaOH Na2CO3 NaHCO3 R O O Na OH NaOH O Na (pKa ! 10) .

4-dimethoxybenzene will remain in the organic layer .7) Experiment 4: Extraction A. inorganic salts ! readily hydrate • Typical drying agents include: Drying Agent calcium chloride calcium sulfate magnesium sulfate potassium carbonate sodium sulfate CaCl2 CaSO4 MgSO4 K2CO3 Na2SO4 Capacity high low high medium high Speed medium fast fast medium slow Applications hydrocarbons generally useful not for very acid sensitive cmpds not for acidic cmpds generally useful Next Week (October 3 .benzoic acid (carboxylic acid) organic base . Your mixture contains the following components (dissolve in ether) Extraction Technique: The Basic Setup • separatory funnel set in a ring (be sure it is the right size) • stopper & stopcock should fit avoid leaks • stopcock should be closed! • collection flask below "just in case" • add solution slowly avoid spills .filter or decant solution away from drying agent Lab Reports are due at the beginning of your regular lab session Extraction Overview 1. The benzoic acid (a carboxylic acid) is separated upon extraction with base Ar-CO2H + NaOH ! Ar-CO2.Na+ 4.4-chloroanaline (amine) neutral substance . Separation of a 3-Component Mixture by Extraction strong organic acid .4-dimethoxybenzene (ether) B. Isolation & Analysis recover compounds by neutralization/filtration or evaporation evaluate success of separation by TLC & melting point confirm identity of separated components by IR Exp 4 Notebook: Research Plan MUST be a flowchart use the entire page for the flowchart.swirl.1. drying agent should be free flowing (not clumped).Drying Agents • Used to remove final traces of water from organic solutions • Typically anhydrous. Separation of the 4-chloroaniline (an amine) is achieved by extracting the mixture with acid Ar-NH2 + HCl ! Ar-NH3+ Cl 3. avoid excess . The 1.let stand (swirl occasionally) for 5-15 minutes .add a small amount of solid drying agent to the organic solution .use a funnel • solution must be cool avoid large pressure build up ring stand stopper metal ring stopcock should be closed!!! note that the tip of the funnel is below the rim of the flask! empty flask or beaker funnel (optional) 2. experimental section will follow on a new page DUE: Distillation Lab Report (exp 3) • Procedure .

use a little extra solvent to complete transfer 3. Separate layers as before .will contain amine salt (flask #1) . Add NaOH to separatory funnel.deprotonation of benzoic acid is a bit slow 7. then drain lower layer ! aqueous layer . Dissolve in ether ! transfer resulting solution to the separatory funnel . Separate layers . Repeat steps 3-4 .let sit for 5-10 min (keep busy while you wait!) decant liquid into tared roundbottom flask concentrate using the rotary evaporator .more is not better .Na+ + HCl ! Ar-CO2H ($) cool & collect crystals Flask 1: . then drain lower layer ! aqueous layer . Add HCl to the separatory funnel.REMEMBER: multiple extractions using smaller amounts of reagent are more efficient than a single extraction with the same reagent volume! hold stopper securely! Experimental Details 6.50g!) 2.wait for separation to occur.vent frequently to prevent pressure build-up 4.+ NaOH ! Ar-NH2 ($) cool & collect crystals Flask 2: basic extracts. Repeat steps 6 & 7 .organic layer remains .be sure you know which layer is which! .wait for separation to occur.record accurate weight (does not need to be 1. stopper and invert sep funnel to mix . stopper and invert separatory funnel to mix .pour top layer out through top of sep funnel (flask #3) ! will contain 1. Obtain approximately 1. should be some free-flowing solid . make basic with concentrated NaOH (check pH) Ar-NH3+ Cl .drain lower layer out through bottom (set aside to discard later) . vent gases point funnel away from yourself & others • repeat several times DON'T SHAKE! avoid emulsions • set funnel back into ring • allow layers to separate be sure you know which layer is which! • remove stopper so funnel will drain! • drain lower layer through stopcock keep tip of funnel below rim of container • pour upper layer out through top avoid contamination Experimental Details • Separation CAUTION! escaping gases 1.5g compound mixture (1:1:1 ratio by weight) .4-dimethoxybenzene Experimental Details • Isolation of Components Flask 3: organics. make acidic with concentrated HCl (check pH) Ar-CO2. Wash organic layer with saturated NaCl (aq) . dry over anhydrous Na2SO4 swirl to mix.Extraction Technique: Separation • add appropriate aqueous reagent to the solution • stopper the funnel and invert hold on to the stopper! • vent carefully release pressure.mix thoroughly -.will contain benzoic acid & 1.preliminary drying .HINT: place flask with organics in back of hood and do something else while you wait for the rotavap! acidic extracts.will contain carboxylic acid salt (flask #2) .4-dimethoxybenzene layer remains .4-dimethoxybenzene ensure complete extraction of the amine from the organic layer .to ensure complete extraction of the carboxylic acid from the organic layer sand baths! Fire Hazard! .will contain 1.

emulsions will take a long time before layers separate • Vent frequently .sep funnel could explode • During isolation.Experimental Details • Finishing Up 1. for C-H bond H C H Infrared Spectroscopy • Absorption in specific region in IR spectrum corresponds to specific types of molecular vibrations: FREQUENCY (cm-1) 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 Bon ds t o H tr ip l e bon ds do ubl e bon ds fi nge rp ri nt re gi on O-H. C-O.don't shake . invert funnel gently much of each compound can you expect to recover? 3. first press between two pieces of filter paper.000 nm #: 1. then dry under vacuum (be sure side arm test tube is clean!!) NOT dip paper into solution. dry samples .5 4.avoid pressure build up . evaluate success of separation by TLC .0 5 6 (MICRON S ) 7 8 9 10 11 12 13 14 16 symmetric stretch asymmetric stretch scissoring (in plane bending) . determine melting point of each compound 4.keeps emulsions from forming . Get IR spectra from your TA .2 x 1014 Hz • Photon energies associated with this region are weak . be sure solutions are acidic/basic (check with pH paper) .can induce vibrational excitation of covalently bonded atoms & groups • Exact frequencies of vibrations determined by the strength of the bonds involved and the masses of the connected atoms • Wide variety of vibrational motions.easy to get confused if you're not clear on what you're doing .MIX THOROUGHLY after each addition of HCl or NaOH • Come prepared . et c .use to confirm identity of each component Some Pointers: • Label your flasks! . weigh samples (& calculate % recovery) . etc .5 3. C-H C= O C-C.1. C !N C ! initial 1:1:1 mixture.g.500-16. plus 3 isolated components .0 3.once discarded.not large enough to excite electrons . commonly talk about "stretching & bending" e.9 x 1013 .H C ! Erlenmeyer/beaker looks pretty much like the next • NEVER throw anything away until you're absolutely sure you don't need it .must write a flow sheet for the pre-lab research plan (use the entire width of the page) Infrared Spectroscopy (IR) • Infrared region of electromagnetic spectrum ": 2. N. it's tough to get it back! • When extracting. use a boiling stick or glass rod .you can always dispose of it later . can you tell if separation was successful? 5.developing solvent is chloroform (use in the hood!) .samples #1 & 2 will be very wet. C=C C= N Ar-H H C H C H H 2.

none of the above . pg 579) • Carboxylic acids .minor absorbances will be present in acid & amine spectra as well IR spectrum of tert-butylbenzene SDBS Database National Institute of Advanced Industrial Science and Technology.NH stretch (ca.may be diffuse . can determine what types of functional groups are present in a molecule Identification of Mixture Components Distinguishing features by IR spectroscopy (see Carey.Infrared Spectroscopy • Plot light absorbsed/transmitted as a function of frequency. 3000 cm-1) . 11/7/07 Infrared Spectrum of a Carboxylic Acid O R OH Infrared Spectrum of an Amine (RNH2) R-NH2 OH stretch C=O stretch NH stretch % NO C=O .C=O stretch (ca. 3400 cm-1) .broad OH stretch (ca.2 bands for a NH2 group C-H stretch • Ethers . 2850-3150 cm-1) C-O stretch (ca. 1000-1250 cm-1) .will likely see minor FG absorbances C-H stretch (ca. 1710 cm-1) • Amines .

what conclusions will you reach? .Percent Recovery % recovery = amount distillate recovered (mL) amount of original solution (mL) x 100 discuss differences in % holdup and % recovery relates to the efficiency of the two processes .make a general statement about distillation techniques you studied . volume graph (equiv to temp vs. what does the temperature change indicate? are the drops pure? does purity vary? report % recovery and % holdup will show minor FG absorbances only C-H stretch % NO NH % NO C=O Writing the Lab Report: Exp #3 Distillation ! Results & Discussion .Percent Holdup amount of material retained by the distillation apparatus amount liquid left in flask(mL) amount of original solution (mL) % holdup = x 100 .a brief recap of your findings .technique experiment: what will you learn? .Infrared Spectrum of an Ether OR Writing the Lab Report: Exp #3 Distillation ! Purpose .Decide which method is better for the separation of cyclohexane & toluene clearly explain why you made this choice (based on your results) do your findings agree with your expectations? again.should be brief (2-3 sentences) ! Appendix A: Calculations .Compare the two distillation techniques compare how well the two components separated in each case what data can you use? bp recorded vs known bp Temp vs.Evaluate data ! simple distillation discuss temp vs.a general discussion of theory/expected results is not a purpose! ! Results & Discussion .g. time!) compare to theory (what do you expect to see)? C-O stretch do your results agree with your expectations? explain! what does plot tell you about composition of drops over time? e. Vol plots Writing the Lab Report: Exp #3 Distillation ! Conclusion . first must decide what you expect to see your expectations shouldn't influence interpretation of your data .Evaluate data ! fractional distillation discuss same topics as for simple distillation .Plot data for both simple & fractional distillations (include graphs) these are essentially temp vs time plots as discussed in class raw data (# drops vs temperature) does not belong here! .