ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 1 Stereochemistry Stereochemistry is the study of the three-dimensional configuration that makes up a molecule and the ways in which this arrangement affects the physical and chemical properties of molecules. Isomerism is the main concern of stereochemistry. Isomers are sets of chemical compounds with identical molecular formulas but different structural properties. There are two types of isomers, structural isomers and stereoisomers. Structural isomers are subdivided into two: position and functional isomers. Position isomers occur among substituted hydrocarbons. The substituents are attached to different positions on the carbon chain. ex. CH3CH2CH2OH 1-propanol CH3CH(OH)CH3 2-propanol

Functional isomers, on the other hand, have very different chemical properties because differences in the structures give rise to different functional groups. ex. CH3CH2OH ethanol CH3OCH3 dimethyl ether

Stereoisomers are molecules which have the same basic arrangement of atoms in their molecules but differ in the way the atoms are arranged in space. There are three basic types of stereoisomers such as conformational isomers, geometric isomers and optical isomers. Molecules that exhibit free rotation about a single bond give rise to conformational isomerism. This is usually illustrated by alkanes due to their C-C single bond. It is usually represented using the Newman projection.

eclipsed

staggered

anti-staggered

gauche-staggered

chair

boat

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

The second type of stereoisomerism is geometric isomerism which is common in alkenes. Geometric isomers differ in physical properties such as melting points and boiling points. ex. cis (same side) trans (opposite side)

For alkenes where cis-trans configuration does not apply, the geometry of the alkene may be designated by E ( entgegen, opposite) or Z (zussamen, together). This is applied by determining which of the two groups of atoms, attached to the carbon of the double bond, acquire the higher priority according to the Cahn-Ingold-Prelog rules. If the two groups with higher priority are located at the same side of the double bond, the isomer is said to be Z. If they are located on the opposite sides of the double bond, then the isomer is of the Etype. ex. Z-3-chloro-2-pentene E-3-chloro-2-pentene

The last type of stereoisomerism is optical isomerism. When planepolarized light is passed through an optical isomer, it is rotated into a different plane of polarization. Optical isomers exhibit this optical activity in varying degree. These isomers have similar properties and differ only in the direction in which they rotate light. Molecules that are non-superimposable mirror images are called enantiomers. They are also known as optical isomers. They rotate the plane-polarized light in opposite directions but with the same magnitude. All enantiomers have chiral centers and are considered chiral molecules. Chiral centers are carbon atoms that bear four different atoms or groups of atoms. If one or more atoms or group of atoms are the same, they are considered achiral. Steroisomers that are not mirror images of each other are called diasteriomers.
H C Cl OH CH 3 H H3C Cl OH M I R R O R HO Cl HO H3C H CH 3 H C Cl

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

PROCEDURE 1. Draw all the possible structural isomers of a compound with the molecular formula C4H8O. a. How many are positional isomers? Functional group isomers? 2. Make a model of butane. Examine the internal bonds and carefully rotate the single bond. a. Draw the Newman projection of the different conformations of butane. b. Which is the most stable conformer? Why? c. Which is the least stable? Why? 3. Draw all possible structural isomers of the compound C2H4FBr. a. Label whether the isomer is a chiral or achiral molecule by putting an asterisk (*) on the chiral center. b. Make a model of the chiral compound and its mirror image. Draw their structures. c. Are these two molecules superimposable? d. Are they enantiomers? e. Are enantiomers stereoisomers? 4. Determine whether each of the following is optically active. a. CH3CH(OH)COOH b. CH3CH2CHOHCH3 c. CH3CH2CH2CH3 5. Construct a model of a cylcohexane molecule (C 6H12) a. Draw the chair conformation of the molecule. b. Draw the boat conformation of the molecule. c. Which is a more stable conformer? 6. Construct a model of methylcyclohexane in the chair form. a. Is the methyl group in the axial or equatorial position? b. Flip the model to convert it to the other chair conformation. This is done by holding carbons 2, 3, 5 and 6 firmly and flipping carbons 1 and 4. c. What is the position of the methyl group in the resulting conformation? d. Considering the positions of the methyl group, which is more stable? axial or equatorial? 7. Construct a model of the different stereoisomers of CH 3CHOHCHOHCH3 and draw the Newman projection. a. Which compounds are enantiomers? b. Which compounds are diasteriomers?

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

REFERENCES Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004 Institute of Chemistry. Laboratory Manual in Basic Organic Chemistry UP Los Baos. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 2 SOLUBILITY BEHAVIOR OF ORGANIC COMPOUNDS An organic compound exhibits one important property that is related to its structure, its solubility. The solubility of a solute is the maximum quantity of solute that can be dissolved in a certain quantity of solvent or quantity of solution at a specified temperature. There are several solvents used and these include water, ether, 5% sodium hydroxide, 5% sodium bicarbonate, 5% hydrochloric acid and concentrated sulfuric acid. Like dissolves like this rule of thumb is commonly used in determining whether a solute is soluble in a given solvent. Nonpolar solutes dissolve in nonpolar solvents and polar solutes dissolve in polar solvents. Chemical reactions may also exist between the solvent and the solute causing the dissolution of the solute in the given solvent. Intermolecular forces of attraction between molecules are the main factors that are responsible for the solubility of compounds in a given solvent. These include dipole-dipole interaction, ion-dipole interaction or van der Waals force of attraction. Dipole-dipole interactions exist between polar molecules. Ion-dipole interactions, on the other hand exist between ionic and polar molecules. Van der Waals forces of attraction, also known as the London dispersion force, exist in all molecules but are prevalent in nonpolar compounds, especially high molecular weight-organic compounds. Water-soluble and water-insoluble organic compounds are grouped into the following classes: water-soluble (S1), ether soluble (S2), strong acid (A1), weak acid (A2), base (B), neutral (N), miscellaneous neutral (M), and inert (I).

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Organic compound
H2O (+) soluble + ether (-) (+) (-) + 5% HCl (+) B with N or S Miscellaneous M Neutral compound (+) N Neutral Basic compound + H2SO4 (+) (-) A1 A2 Acidic compound S1 S2 water-soluble compound (-) insoluble + 5% NaOH (+) + 5% NaHCO3

(-) I Inert

MATERIALS AND APPARATUS Test tube and droppers Solvents: Distilled water Ether 5% NaHCO3 5% NaOH 5% HCl Conc. H2SO4 PROCEDURE Test the solubility of each compound in water by adding 1 mL of the solvent to 6 drops of a liquid or a pinch of a solid test compound. If the compound is dissolved, record it as soluble (+). If it does not dissolve, record it as insoluble (-). Compounds that are liquid are soluble if they form homogeneous solution with the solvent. To the compounds that gave positive result in water, test their solubility in ether by doing the same procedure as above. Record the solubility. Test Compounds: hexane benzamide acetone ethyl alcohol benzyl alcohol aniline toluene sucrose benzaldehyde benzoic acid phenol

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

To the water-insoluble test compounds, test their solubility in 5% NaOH. The substance may be considered soluble even if not all of it dissolves, as long as it is more soluble in the solvent than in water. Record the solubility. To the test compounds that are soluble in 5% NaOH, test their solubility in 5% NaHCO3. Record the solubility. Test the solubility in 5% HCl of the test compounds that did not dissolve in 5% NaOH. Record the solubility. To the test compounds insoluble in the above solvents that do not contain nitrogen or sulfur, test their solubility in concentrated H 2SO4. Manifestations of a reaction such as production of heat, change of color, formation of a precipitate, or evolution of gas mean that they are soluble. QUESTIONS 1. What are the types of intermolecular forces present in solutions formed due to solvent-solute interactions? 2. Write the balanced chemical equations of the solvent-solute combinations that formed solutions due to chemical reactions. 3. On the basis of solubility behavior, show how each of the following pairs of compounds may be distinguished from each other. a. CH3NHCH3 and CH3(CH2)5CH2NH2 b. Ethanal and hydroxyethanal c. Benzyl amine and benzyl alcohol REFERENCES Dalton, David and Mei Tak Yip. Organic Chemistry in the Laboratory. New York: D. Van Nostrand Company. 1979 Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 3 ESTERIFICATION OF SALICYLIC ACID: PREPARATION AND CHARACTERIZATION OF ASPIRIN AND OIL OF WINTERGREEN

Esterification is a process wherein esters, , are formed from either carboxylic acid or its derivatives and an alcohol. This reaction is usually catalyzed by an acid. The mechanism of esterification using carboxylic acids generally involves the following steps:

Salicylic acid, a difunctional organic compound with a carboxyl and hydroxyl group both attached to a benzene ring, can undergo two different esterification reactions. It can both act as a carboxylic acid and as an alcohol. In this experiment, two derivatives of salicylic acid will be synthesized, the acetyl salicylic acid and methyl salicylate. Acetylsalicylic acid or aspirin is the most widely used medicine in the world. It has the ability to reduce fever, pain and to act as an anti-inflammatory agent. In the preparation of aspirin, the salicylic acid acts as an alcohol and it reacts with acetic anhydride in the presence of sulfuric acid as a catalyst. Methyl salicylate, also called oil of wintergreen, is prepared from the reaction of salicylic acid and methanol, CH 3OH. It is used in perfumes and as a flavoring agent in candies, gums and foods. This compound is also used by athletes to soothe muscle aches. The methyl salicylate undergoes hydrolysis with water to form salicylic acid, which is responsible for the relief of muscle pains.

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

The general reaction for the preparation of these two salicylic acid derivatives is Acetylsalicylic acid

Methyl salicylate

Another important process involved in the preparation of acetylsalicylic acid is recrystallization. This is a method of purifying solid organic compounds. By this method, the impure solid compound is dissolved in a warm solvent, the warm solution is filtered and then crystals are allowed to reform as the solution cools. Recrystallization is an easy and effective process of purification and can be done in a micro-scale experiment as long as the solvent chosen satisfies the following criteria: It should readily dissolve the solute at elevated temperatures and sparingly at lower temperatures. It should dissolve the desired solute and not the impurities. It should be chemically inert to the solute. It should allow the solute to give well-formed crystals upon cooling. It should be highly volatile to permit easy removal from the purified crystals. In this experiment, aspirin is prepared through esterification of salicylic acid and acetic anhydride. It is then recrystallized to obtain a pure aspirin. Formation of crystals can be induced in two ways. The first one is by seeding which involves the addition of a pure solid compound with the same composition as that of the compound to be crystallized. The second one is by scratching the walls of the container to induce the formation of crystals. The recrystallized aspirin is then characterized and compared to crude aspirin and to commercial aspirin.

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

MATERIALS and APPARATUS Salicylic acid Acetic anhydride 85% phosphoric acidic Aqueous NaHCO3 125 ml E-flask Droppers Filter papers Watch glass PROCEDURE A. Preparation of acetyl salicylic acid (aspirin) 1. Place 3 g of salicylic acid in a 125 ml Erlenmeyer flask. 2. Add cautiously 7.5 ml of acetic anhydride and drops of 85% phosphoric acid. 3. Mix well and heat the flask in a boiling water bath for 10 minutes. 4. Allow the flask to cool to room temperature and then place it in an ice bath. 5. Add 15 ml of an ice water mixture to the contents of the flask. 6. If oil separates during the cooling process, induce crystallization by scratching the side of the flask with a stirring rod. 7. Collect the crude crystals by suction filtration. 8. Wash the crystals several times with small portions of cold water. 9. Transfer the crystals to a weighed watch glass and air dry. 10. Weigh the crude dry aspirin and calculate the percentage yield of crude products. B. Recrystallization of aspirin 1. Set aside a small quantity of crude aspirin for characterization. 2. Transfer the rest of the crude aspirin to a 125 ml E-flask containing a minimum volume (10-15ml) of diethyl ether. Then add an equal volume of petroleum ether t the flask. Mix contents by swirling rapidly. 3. Complete the recrystallization process by cooling the flask in an ice bath. 4. Collect the crystals by suction filtration. 5. Allow the crystals to dry then weigh and calculate the percentage yield. 6. Transfer the aspirin to a vial and label properly. petroleum ether methanol toluene diethyl ether capillary tubes stirring rod 50 ml beaker Bunsen burner conc. H2SO4

thermometer cooking oil wire gauze ice

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

C. Characterization of aspirin 1. Melting point Determination a. Pulverize the sample by placing the crude and recrystallized aspirin on a watch glass and crush them with a metal spatula or the end of the test tube b. Mound up the pulverized sample and press the open end of the melting point capillary tube into the sample against the surface of the watch glass. Lightly tap the sealed end of the tube on the tabletop. (Caution: capillaries are fragile) Introduce more samples to the tube until the sample fills about 2-4 mm height. c. Place 25 ml of oil in a dry 50 ml beaker. Insert a thermometer through a cork near the top of the top of the thermometer. Attach the capillary tube with the sample to the thermometer by means of a thin strip of rubber band. d. Heat the oil bath strongly with constant stirring until the temperature is 10-15C below the known melting point. Afterwards, use a very low flame so that the temperature of the bath rises at a rate of 3C per minute. e. As soon as a droplet of liquid forms in the tube (start of melting), record the temperature; as soon as the last trace of the solid has liquefied (end of melting), record the second temperature reading. f. Allow the bath to cool and make another trial of fresh samples. 2. Solubility test a. Grind a tablet of commercial aspirin in a mortar and pestle. Add about 0.1 g of aspirin to a test tube with 2.5 ml each of the solvent (water, aqueous NaHCO3 and toluene). b. Mix by thorough agitation. c. Examine and record your observations. d. Do the same for the crude and recrystallized aspirin. 3. Test for Phenolic group a. Dissolve few crystals of salicylic acid in 5 ml of water, then add a drop of 1%FeCl3 solution and note the color. (Note: a color change ranging from red to violet results because of the formation of the ironphenol complex) b. Repeat test with the commercial, crude and recrystallized aspirin. c. Record the results. D. Preparation of methyl salicylate (oil of wintergreen)

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

1. Place 1 g of salicylic acid in a test tube. 2. Add 5 ml of methanol and 3 drops of conc. H 2SO4, then heat the mixture in a boiling water bath for about 15 minutes. 3. Note the odor of the liquid that remains in the test tube. 4. Add a drop of ferric chloride solution. Is there any observable change of color? Record observations.

QUESTIONS 1. What is the purpose of the ferric chloride in the characterization of aspirin? 2. Was the recrystallized aspirin pure? Explain why or why not. What are the possible sources of errors? 3. How do you account for the smell of vinegar when an old bottle of aspirin is opened? 4. Will a color change result when FeCl 3 is added to oil of wintergreen? Why/why not?

REFERENCES Dalton, David and Mei Tak Yip. Organic Chemistry in the Laboratory. New Yorl: D. Van Nostrand Company. 1999. Organic Chemistry Group, UP Diliman. Organic Chemistry Laboratory Manual. Salesiana Publishing, Inc. 2003. UP Open University. Experiments in Chemistry. 1998.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 4 CHROMATOGRAPHY OF PLANT PIGMENTS Separating impure mixtures into pure substances is among the most important and fundamental of skills which must be learned by a chemist. The study of pure substances requires that the chemist learn many different techniques of separation so as to pursue the study of properties of pure substances and their reactions. It was Alexander Tswett, a Russian botanist, who first found that he could extract pigments from plants. This extraction was done by grinding the leaves in an organic solvent. He then poured the solvent extract containing the mixture of dissolved pigments through a tube full of powdered chalk (CaCO 3, or calcium carbonate). The various pigments separated into colored bands as the extract penetrated down through the powdered chalk. He carefully removed the column of chalk from the tube and separated the colored bands. Extraction of the different colored bands with the solvent produced solutions of separated pigments for study. Many common materials around us are made up of mixtures of compounds. Examples are: gasoline, ink, cosmetics, dyes, and pigments. It is often very difficult to separate these mixtures, especially if the components are chemically very similar. One way to do this takes advantage of the slight differences in the components' solubilities, which are due to slight differences in their chemical structure. This separation method is called thin layer, or paper, chromatography. Paper chromatography is a method used to separate very small quantities of substances from each other. The identity of these separated substances can also be determined. In paper chromatography, a small sample of a mixture is placed on porous paper which is in contact with the solvent. The solvent moves through the paper due to capillary action and dissolves the mixture spot. The components of the sample start to move along the paper at the same rate as the solvent. Components of the mixture with a stronger attraction to the paper than to the solvent will move more slowly that the components with a strong attraction to the solvent. The differences in the rates with which the components travel along the paper lead to their separation. Particular mixtures will have chromatographic patterns that are consistent and reproducible as long as the paper, solvent, and time are constant. This makes paper chromatography a qualitative method for identifying some of the components in a mixture. Different solvents will change the patterns of component separation. Colored spots on the finished and dried chromatogram can be cut out of the paper with scissors and redissolved to obtain a pure sample of one component of the mixture.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Quantitative analysis of chromatographic data includes the calculation of retention factors, or retardation factors (R f). This gives the quantitative measure of a components properties in a mixture. The Rf value is calculated as Rf = Distance traveled by solute/Distance traveled by solvent This applies when chromatograms are made with the same solvent and developed for the same amount of time, Rf values are identical Objectives: 1. To separate pigments from the leaves of spinach; 2. To identify the different pigments present in spinach leaves; 3. To compute the approximate rates of flow (Rf values) of each of the component pigments of the leaves. MATERIALS AND APPARATUS Whatman #1 filter paper (pre-cut into a cylindrical shape to fit a 400 ml beaker without touching the sides of the glassware) petroleum ether diethyl ether ordinary filter paper stapler or scotch tape acetone spinach leaves (or watercress or any leafy vegetable that is in season) mortar & pestle funnel aluminum foil PROCEDURE A. Preparing the crude chlorophyll extract 1. Obtain about 15 mature leaves of spinach & macerate them using mortar and pestle. Add a pinch of fine sand to get better results. 2. Add 5 ml of acetone in portions to 1 ml. 3. Collect the extract using ordinary filter paper in a funnel. B. Paper chromatographic separation of chloroplast pigment 1. Test the fitness of the pre-cut filter in the beaker. Hold the paper on the sides only. Be sure the paper does not touch the side of the beaker but it should reach the bottom of the glassware. 2. Remove the filter paper strip from the beaker. About of an inch from the bottom draw a horizontal line lightly using a pencil. Use the line as a guide to apply the pigment extract from A using a capillary tube. 14

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

3.

4. 5. 6. 7. 8.

Allow this to dry. Then make a second, a third and even a fourth application of the pigment, allowing the paper to dry in between applications. Staple the two ends of the paper or tape them with a narrow piece of scotch tape. Pour the solvent (40:10:50 mixture of acetone and petroleum ether and diethyl ether) into the beaker to about half an inch level. Make sure that the solvent does not splatter on the sides of the beaker. Cover the beaker with a piece of aluminum foil and let it stand for 3-5 minutes. Carefully lower the filter paper into the beaker so that the bottom half inch or so is in the solvent and the line of pigment extract is above it. Allow the solvent to rise in the filter paper undisturbed. When the solvent front reaches around a centimeter before the top of the paper, remove the chromatogram from the beaker. Allow it to dry in air. Measure the distance traveled by each pigment and the solvent. Compute the Rf values of each pigment.

QUESTIONS 1. How many separate bands of color appeared in the chromatogram? 2. In what order did the bands of color appear in the chromatogram? 3. Compute the approximate Rf values of each pigment using the following formula: Rf = distance traveled by solute (pigment) Distance traveled by solvent 4. Submit the chromatogram together with your report.1

REFERENCES Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000. Todd, D. Experimental Organic Chemistry, Prentice-Hall Inc., N.J. 2001.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 5 ISOLATION OF ESSENTIAL OIL BY STEAM DISTILLATION A special type of distillation which is usually used to separate sensitive materials like natural aromatic compounds is steam distillation. This is one way of obtaining essential oils from herbs, flowers, leaves, roots and wood. Steam distillation is a valuable technique for the separation of volatile compounds from nonvolatile compounds. This involves the co-distillation of a mixture of water and a volatile organic compound that is immiscible with water. Steam distillation occurs at temperature less than 100C. Many complex organic compounds tend to decompose at sustained high temperatures. Separation by normal distillation would then not be an option, so water or steam are introduced into the distillation apparatus. By adding water or steam the boiling point of the compounds is depressed, allowing them to evaporate at lower temperatures, preferably below the temperatures at which the deterioration of the material becomes appreciable. If the substances to be distilled are very sensitive to heat, steam distillation can also be combined with vacuum distillation. After distillation the vapors are condensed as usual, usually yielding a two-phase system of water and the organic compounds, allowing for simple separation. Steam distillation is employed in the isolation of essential oils and in the manufacure of perfumes. In this method steam is guided over the plant material containing the desired oils. It is also employed in the synthetic procedures of complex organic compounds. Essential oils are mixtures of volatile organic compunds that are obtained from plants and are immiscible with water. They provide the characterisric odors of plants from which they came from. The major constituent of essential oils are terpenes and their oxygenated derivatives. Terpenes are structurally composed of isoprene units confined in a head-to-tail fashion. Limonene is the most widely distributed cyclic terpenes in plants. It is obtained from orange peels and constitutes as much as 1% of the weight composition of the peels. The structure of limonene is
CH 3

C H3C

CH 2

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

In the experiment, aside from the isolation of limonene by steam distillation, hydrocarbons will be characterized and their reactions will be compared. Hydrocarbons are organic compounds that contain carbon and hydrogen atoms. They are classified into three: the saturated, unsaturated and the aromatic hydrocarbons. Saturated hydrocarbons include alkanes and are generally inert towards many chemical reagents. Unsaturated hydrocarbons, on the other hand, contains a double or tirple bonds as in alkenes and alkynes, respectively. These unsaturations have weak pi () bonds whose electrons are loosely held and are susceptible to electrophiles, species that are electron defiecient. Alkenes are more reactive than alkynes. They both undergo electrophilic addition. Aromatic hydrocarbons are compounds which also have unsaturations, however, they are not as reactive as alkenes and alkynes. This is beacause aromatic hydrocarbons are more stable. The simplest aromatic compound is benzene. Benzene exhibits resonance, where in the electrons of the conjugated double bonds are delocalized within the ring. Due to their stabilty, they react via electrophilic aromatic substitution. Different chemical reagents will be used to distinguish the reactions of these three hydrocarbons. These include an alkyl halide with AlCl 3, bromine in water and Baeyers reagent. Limonene, a terpene with 2 unsaturations, will be used to represent the unsaturated hydrocarbons. This will be compared with hexane and benzene. MATERIALS AND APPARATUS n-hexane Benzene t-butyl chloride 0.05 M KMnO4 anhydrous Na2SO4 anhydrous AlCl3 0.05 M Br2 in water Saturated NaCl solution Orange peels (or peels from calamansi & other citrus fruits in the Cordillera that are in season) Steam distillation set up: 500 ml round bottom flask burner clamps Separatory funnel Aluminum foil condenser iron stand stoppers balance droppers E-flasks iron ring evaporating dish spot plate

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Steam Distillation set-up PROCEDURES A. Isolation Of Essential Oil

Separatory Apparatus

Cut the samples and weigh 150 grams. Place the sample into a 500 ml round-bottom flask filled with distilled water. Prepare the steam distillation set up similar to the figure shown on the board. Rapidly distill the mixture until 150 ml of distillate is collected. Add 15 ml of saturated NaCl solution to the distillate, and then extract the essential oil from the mixture using three 20-ml portions of hexane as extracting solvent. Dry the extract by adding a pinch of anhydrous sodium sulfate. Allow the extract to stand for 10 minutes and decant. Evaporate the hexane using a steam bath until 6-10 ml of the extract is left. Determine the boiling point of limonene. B. Physical Properties of Hydrocarbons Examine the physical state of the essential oil. Record the color, its solubility in water, and the density with respect to water. Compare the results with hexane and benzene. Record your observations. Place 8 drops each of hexane, limonene and benzene in three separate evaporating dishes. Ignite the solution using an open flame. Observe the

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

appearance of the flame whether it is smoky or clear. Record your observations. C. Chemical Properties of Hydrocarbons 1. Reaction with t-butyl chloride and AlCl3

Into three clean and dry micro test tubes, place 4 drops each of hexane, limonene and benzene. Add 8 drops of t-butyl chloride to each test tube and mix thoroughly. Incline the test tube at a 45 angle and place a small crystal of anhydrous AlCl3 near its mouth. Using a cork, stopper the test tube while in this position taking care that the crystals do NOT fall into the solution. Wet the crystals by letting the solution touch them. Observe the change in the color of the crystal. Repeat the procedure using the rest of the test solutions. 2. Reaction with bromine in water a. In the absence of light Into three separate dry test tubes, place 8 drops each of hexane, limonene and benzene. Wrap each test tube with a carbon paper or with an aluminum foil making sure the solution is not exposed to any light source. Add 3 drops of bromine in water to each. Shakes the test tubes well and place inside your locker for 10 to 15 minutes. Record your observations b. In the presence of light Into three separate dry test tubes, place 8 drops each of hexane, limonene and benzene. Add 3 drops of bromine in water to each. Shake the test tubes well and expose to direct sunlight for 10 to 15 minutes. Record your observations. Into three separate dry test tubes, place 8 drops of hexane, limonene and benzene. Add 8 drops of 0.05 M KMnO 4 solution. Shake the test tube well and observe any discoloration. Record your observations.

QUESTIONS Write all the equations for all the tests giving positive results. Classify whether the reaction is substitution or an addition reaction.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

REFERENCES Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004 Matta, M.S., A. C. Wilbraham and D.D. Staley. Introduction to General, Organic And Biological Chemistry M.A. D.C. Heah Co., 1996. UP Open University. Experiments in Organic Chemistry

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 6 ALCOHOLS AND PHENOLS Alcohols and phenols are organic compounds with the hydroxyl (-OH) functional unit. Alcohols have the general formula ROH where R is any alkyl group. Phenols, on the other hand, have the general formula ArOH where Ar is an aryl group or an aromatic hydrocarbon. Alcohols can generate hydrogen bonds with each other and with water that is why they have higher boiling points than corresponding hydrocarbons. They are also soluble in water provided they have 5 carbons or less. Phenols are more acidic than alcohols but are less soluble in water. Alcohols undergo three general reactions: cleavage of the OH bond (acidity) cleavage of the CO bond (nucleophilic substitution) oxidation Alcohols have similar properties with water. They are weak acids that can react with electropositive metals to form metal alkoxides. This reaction is called a redox reaction. ROH + M RO-M+ + H2 The order of acidity of alcohols is CH3OH > 1 > 2 > 3. An alcohol can also act as a Lewis base since it is amphoteric like water. It can react with Lewis acids in the presence of a catalyst. One general test to distinguish the different classes of alcohols is Lucas test. In this test, alcohols react with Lucas reagent (HCl and ZnCl 2 as catalyst). Tertiary alcohols form immiscible layers almost immediately with Lucas reagent. Secondary alcohols, on the other hand, form two layers within 5 to 10 minutes upon addition of the reagent. Primary alcohols almost exhibit no reaction with Lucas reagent. This is an example of a reaction wherein the CO bond is cleaved and the OH group is replaced by a halide (-X). Primary alcohols are easily oxidized to aldehydes and further into carboxylic acids. Secondary alcohols are oxidized to form ketones. Tertiary alcohols are unreactive to oxidizing agents since they have no hydrogen atoms attached to the carbon with the hydroxyl group. Oxidizing agents include potassium dichromate (K2Cr2O7), chromic acid (H2CrO4) and potassium permanganate (KMnO4). Phenols are organic compounds with one or more hydroxyl groups attached to an aromatic ring. They are stronger acids than alcohols due to the stability caused by the resonance of the phenoxide anion. They are, however,

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weaker acid than carboxylic acids since they cannot be dissolved in weak bases like sodium bicarbonate. Phenols react with a neutral solution of ferric chloride to give purple colored iron-phenol complex. This is a characteristic reaction of enols, an -OH group that is adjacent to an unsaturated carbon (-C=C-OH). The OH of phenol is considered as an electron-donating substituent. This is because the OH activates the benzene ring towards reactions with electrophiles. It is, therefore, an ortho- and para- director. At room temperature, bromine water reacts with phenols to form insoluble tribrominated products.
O

Phenoxide anion

MATERIALS AND APPARATUS 10 ml each of the following: ethyl alcohol tert-butyl alcohol phenol Na metal 10% K2Cr2O7 8 N NaOH 10% FeCl3 test tubes PROCEDURE A. Solubility 1. Introduce 0.5 ml of the following in seven separate test tubes using a calibrated dropper: ethyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, benzyl alcohol, glycerol and 0.5 g each of phenol, p-nitrophenol and p-methylphenol. 2. Add 1 ml (20 drops) of water using a calibrated dropper to the tube containing ethyl alcohol. n-butyl alcohol benzyl alcohol isopropyl alcohol glacial acetic acid Lucas reagent I2 in KI thermometers conc. H2SO4 6 N H2SO4 Br2 in water droppers sec-butyl alcohol glycerol

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

3. Shake the tube after each addition. If cloudiness results, continue adding water dropwise until a homogeneous system is obtained. 4. Note the total volume of the water added. If no cloudiness results upon adding 2 ml of water, record it as completely soluble. Do the same procedure with the remaining test compounds. Reserve the contents of the test tubes for B1. B. Reactions of the OH Group 1. a. To each of n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 0.5 g phenol in four separate test tubes, add a small pellet of sodium. b. Compare the rate of the gas evolution. Unreacted sodium metal must be destroyed by adding ethyl alcohol until it dissolves. CAUTION: Unreacted sodium metal is very reactive in water and may result to a violent reaction when the test tube is cleaned after the experiment is completed.

2. a. Warm a mixture of 5 drops of an ethyl alcohol and 5 drops of glacial acetic acid with 1 drop of conc. H2SO4. b. Note the odor of the product. c. Perform the same procedure with a few drops of phenol. 3. Lucas Test a. Place 10 drops of n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol separately in three test tubes. b. Into each test tube, add 3 ml Lucas reagent. c. Allow the mixture to stand for 10 minutes. Note the time required for the separation of the two layers. C. Oxidation 1. To 5 drops of n-butyl alcohol, add 10 drops of dilute sulfuric acid and two drops of 10% K2Cr2O7 solution. 2. Warm gently. Note the color of the solution and the odor of the product. 3. Repeat the experiment with sec-butyl alcohol and tert-butyl alcohol. D. Iodoform Test 1. To 5 drops of ethyl alcohol in 1 ml of water, add 5 drops of 8 N NaOH. 2. Add dropwise a solution of iodine in KI until a pale yellow color persists. 3. Warm the mixture in a water bath at 60C. 4. Set aside for 5-15 minutes and observe.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

E.

Reactions of Phenol 1. Reaction with Br2.H2O a. Dissolve a few crystals of phenol in 1 ml water in a test tube. b. Shake and warm the solution. c. Allow to cool and add bromine water dropwise. 2. Test for the enol group in phenols a. Place 5 drops of 10 % FeCl 3 solution in 2 test tubes, add 3 drops of an alcohol to one test tube and a crystal of phenol to the other. b. Observe and compare the results. 3. Reaction with aqueous neutral KMnO4 a. Place 5 drops of phenol solution in a clean, dry test tube. b. Add a drop of aqueous neutral KMnO4. c. Observe for the decolorization of potassium permanganate.

QUESTIONS 1. Write all pertinent equations and balance them. 2. Give the mechanism of the reaction of alcohols with Lucas reagent. REFERENCES Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004. Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 7 ALDEHYDES AND KETONES Aldehydes and ketones both contain the carbonyl (C=O) group. These two groups of compounds differ only in the number of alkyl groups attached to the carbonyl carbon. In aldehydes, an alkyl group and a hydrogen atom are attached to the carbonyl carbons, while in ketones two alkyl groups are attached. The presence of the electronegative oxygen atom allows them to form hydrogen bonds with water. Low molecular weight aldehydes and ketones are soluble in water and they have higher boiling points than corresponding hydrocarbons. However, they have lower boiling points than alcohols since they cannot generate hydrogen bonds with each other. Due to the difference in the electronegativity values between the carbon and oxygen of the carbonyl group, the characteristic reaction of aldehydes and ketones is nucleophilic addition. Nucleophiles, or electron-loving species, are easily attracted to the carbonyl carbon and from an sp 2 hybridized carbon, it is transformed to an sp3 hybridized carbon. These nucleophiles include derivatives of ammonia and the hydroxyl substituent. Nucleophilic addition may be acidcatalyzed if the nucleophile is very weak.

Nu C O Nu H C O

Nu C O

Aldehydes are easily oxidized to carboxylic acids even by weak oxidizing agents like silver ions or copper ions. Ketones are less susceptible to oxidation primarily because of steric hindrance. One example of such oxidation reacvtions is the Tollens test which is a general test for the presence of aldehydes. Tollens reagent is composed of silver nitrate complexed with ammonia {ammoniacal silver nitrate, Ag(NH3)2+}. Silver ions oxidize both aliphatic and aromatic aldehydes. Two other reagents, Benedicts reagent (solution of copper ions complexed with citrate in sodium bicarbonate) and Fehlings reagent (solution of copper ions complexed with tartrate and sodium hydroxide) can also be used to oxidize aldehydes. However, these two oxidizing agents can only oxidize aliphatic aldehydes. Aldehydes can also be distinguished from ketones using Schiffs test. Schiffs reagent is a pink fuchsine dye which decolorizes with sulfurous acid. When this reagent reacts with aldehydes, a purple-violet colored solution is observed. Iodoform test is the test for the presence of a methyl group attached to the

25

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

carbonyl group of the ketone. Methyl ketones, , undergo exhaustive halogen substitution followed by the cleavage of the carbonyl carbon. Iodoform, a yellow solid is formed when methyl ketones react with iodine in the presence of a base.
O R-C-CH 3

+ 3I2 + 4 OH-

+ CHI3 + 3H2O + 3Iyellow solid iodoform

MATERIALS AND APPARATUS Formalin (40% HCHO in H2O) 10% NaOH Acetone I2 in KI Benzaldehyde 95% ethyl alcohol Solid 2,4-dinitrophenylhydrazine Schiffs reagent reagent 2,4-Dinitrophenyl hydrazine-hydrochloride solution Droppers test tubes 250 mL beakers PROCEDURE 1. Reaction with 2,4-dinitrophenylhydrazine Place 1 ml 95 % ethyl alcohol in 3 separate test tubes. To one tube add 2 drops acetone and to the other 2 drops of benzaldehyde. To each of the three test tubes add 1 ml of 2,4-dinitrophenylhydrazine-hydrochloride solution. If no precipitate forms immediately, allow to stand for a few minutes. 2. Tollens Test In 3 separate test tubes, place 1 ml of Tollens reagent. To one tube add a drop of formalin, to the other a drop of acetone and to the third a drop of benzaldehyde. Mix thoroughly. If no reaction occurs at room temperature, warm in hot water bath. Aromatic aldehydes may require heating. A silver mirror will be formed. After the reaction, pour out the contents of the test tube in a waste jar and rinse with water. 3. Schiffs Test In 3 separate test tubes, place 5 drops of Schiffs reagent. To one tube add a drop of formalin, to the other a drop of acetone and to the third a drop 0.1 M HCl 1.0 M HCl 0.1M HOAc Benedicts Tollens reagent Burner

26

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

of benzaldehyde. Shake and observe the color developed in three to four minutes. 4. Benedicts Test In 2 separate test tubes, place 1 ml of Benedicts solution. To one tube add 5 drops of formalin and to the other 5 drops of benzaldehyde. Place the test tubes in a hot water bath. Note the time it takes for a red-brick precipitate to appear. 5. Iodoform Test In 2 separate test tubes, place 1 ml of 10% NaOH. To one tube add 4 drops of acetone and to the other 4 drops of ethyl alcohol. To each, add iodine in KI dropwise with shaking until the solution becomes yellow. Shake the test tube after each addition of the iodine solution. Warm the solution in a water bath. If the solution becomes colorless after heating, add more I 2 in KI and note if the solution turns yellow again. Record the color of the solution after each addition of I2 in KI before and after heating. 6. Effect of Acid Concentration on the Rate of Addition of 2,4dinitrophenylhydrazine Preparation of the reaction mixture for the whole class by an assigned group: Dissolve 0.3 g of 2,4-dinitrophenylhydrazine in 30 ml of acetone contained in a 250 ml beaker. Place 10 drops of the above solution in each of four test tubes. Keep one tube as standard. To one tube add 2 drops of 0.1 M acetic acid, to the other add 2 drops of 0.1 M HCl and to the last tube, add 2 drops of 1.0 M HCl. Immediately record any change observed. Note the time of mixing and the time when crystals appear. Observe for about 20 minutes. QUESTIONS 1. Cite some industrial uses of the Tollens test. 2. Explain the results observed in the procedure #6. 3. Briefly state how the following pairs of compounds can be distinguished by giving the reagent and the visible results. a) phenyl methyl ether and phenylethanol b) CH3CH2CHO and c) benzaldehyde and

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

REFERENCES Doyle, Michael and William Mungall. Experimental Organic Chemistry. New York: John Wiley and Sons. 2000. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000. Todd, D. Experimental Organic Chemistry, Prentice-Hall Inc., N.J. 2001.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 8 CARBOXYLIC ACID AND DERIVATIVES Carboxylic acids are organic compounds which contain one or more carboxyl group (-COOH). Hydrogen, alkyl or aryl groups can be attached to the carboxyl group. They are soluble in water due to hydrogen bonding and they have the highest boiling point. Carboxylic acids are the most acidic organic compounds because of the stability of the carboxylate anion as a result of resonance.
O RCO O RC O

Electron-withdrawing groups can increase the acidity of carboxylic acid. They are soluble in strong bases like NaOH and even in weak bases like sodium bicarbonate, NaHCO3. Carboxylic acids can be attacked by several nucleophiles to form the following acid derivatives:
O R C NH 2 R O C O O C R R O C OR' R O C X

Amide

anhydride

ester

acyl halide

Acid chlorides are the most common acid derivatives that are used to prepare other acid derivatives due to the high reactivity of the chloride atom. Esters and amides are the most important derivatives of carboxylic acids since they are the principal linkages in most natural products like fats and proteins. Anhydrides can also be used to prepare other derivatives and are obtained through dehydration of two carboxylic acids. Hydrolysis is a process wherein the parent acid is regained from its derivatives. This can be acid or base catalyzed.
O R C NH 2 catalyst R O C OH

+ H2O

O R C OR'

+ H2O

catalyst R catalyst

O C OH

O R C X

+ H 2O + H2O catalyst

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

+ H2O

Carboxylic acids react with ferric chloride to give colored complexes. Benzoic acid reacts with FeCl 3 resulting to a flesh-colored precipitate, Fe(C6H5COO-)3. Acetic acid gives a red solution, Fe(OH)2(CH3COO-), with FeCl3. MATERIALS AND APPARATUS PROCEDURE Glacial acetic acid 5% NaHCO3 conc. H2SO4 25% NaOH 0.1 M HCl benzamide 10 % NaOH Bunsen burner Watch glass 125 ml Erlenmeyer flasks 1. Solubility in 5% NaHCO3 Place 3 drops of acetic acid and a pinch of benzoic acid in two separate test tubes. Then add 3 ml of 5% NaHCO 3 solution. Record any observable change. 2. Reaction with FeCl3 a) Test for acetic acid benzoic acid 95% ethanol ethyl acetate dilute Sulfuric acid acetic anhydride 0.1% KMnO4 formic acid litmus paper evaporating dish ethyl acetate in ether alcoholic NH2OH.HCl alcoholic KOH acetylsalicylic acid benzoyl chloride 0.1 M FeCl3 oxalic acid test tubes 50 ml beakers

To 3 ml of 10% NaOH in a test tube, add acetic acid until the solution is slightly acid to litmus paper. Add a few drops of FeCl 3 solution. Note the formation of a red-colored solution. b) Test for benzoic acid

To a test tube containing 2 ml of water add a pinch of benzoic acid. Heat gently as the solid dissolves. Cool. Add 10% NH 3 until the solution is slightly basic to litmus. Boil off excess ammonia. Add 2 drops of FeCl 3 solution. Observe the formation of a flesh-colored precipitate. 3. Formation of Esters

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

a) b)

From carboxylic acids: To 10 drops of acetic acid, add 1 ml of ethanol and 5 drops of concentrated H 2SO4. Warm. Note the sweet smell of the ester formed. Reserve the product for #5. From acyl halides (Schotten-Baumann Reaction): Into a test tube, place 1 ml of ethanol and 3 ml of water. Then add carefully 5 drops of benzoyl chloride. Stopper with a cork and shake. To this solution, add gradually with vigorous shaking, 3 ml of 20% NaOH. Observe the odor.

4. Reducing Property of Some Acids In two separate test tubes, place 1 ml each of formic acid and oxalic acid. Add 2 ml of dilute sulfuric acid and then warm gently. Add 0.1 % KMnO 4 solution drop by drop, shaking the solution, until the decolorization of the permanganate solution stops. Record your observations. 5. Hydrolysis of Acid Derivatives a) Acetic anhydride. Into a test tube, place 2 ml of water. Add carefully 1 ml of acetic anhydride. Observe the evolution of heat. Test the mixture by holding over the test tube a piece of moist blue litmus paper. Amides. Into a test tube, place a pinch of benzamide and add 5 ml of 10% NaOH. Heat. Note the odor of the gas evolved and test its reaction by holding over the test tube a piece of moist red litmus paper. Ester. To 2 ml of ethyl acetate in a test tube, add 5 ml of 6.0 M NaOH. Reflux for 30 minutes. Observe the disappearance of the pleasant smell of the ester. Neutralize the resulting mixture with 6.0 M HCl. Observe the emergence of the sour smell of the carboxylic acid formed.

b)

c)

QUESTIONS 1. Write the chemical equations involved in all tests that yielded positive results. 2. Why would acyl halides give higher yields of amides compared to carboxylic acids or esters on reaction with ammonia? 3. Why should excess alkali be avoided in the FeCl 3 test for CH3COOH and benzoic acid? REFERENCES

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 9 AMINES Amines are organic derivatives of ammonia in which one or more hydrogen atoms have been replaced by an alkyl or aryl group. They are classified into primary (one alkyl or aryl group), secondary (two alkyl or aryl groups or a combination thereof), and tertiary (three alkyl or aryl groups or a combination of these groups) amines. RNH2 RNH2 ArNH2 1 R2NH (Ar)RNH Ar2NH 2 R3N (Ar)R2N or (Ar)2RN Ar3N 3

Amines are considered basic because of the presence of an unshared electron pair in the nitrogen atom. This unshared pair of electrons enables amines to act as Lewis bases or as a nucleophile. The more available the electron pair, the more basic the amine is. Thus, the order of basicity in amines is 1 > 2 > 3. Amines also activate an aromatic ring towards electrophilic aromatic substitution and are ortho- and para- directors. Primary amines react with chloroform, CHCl 3, and alcoholic potassium hydroxide to form isocyanide, a compound which has a characteristic fishy smell. This reaction is called carbylamine test. The equation for this reaction is RNH2 + CHCl3 RN+C- + HCl isocyanide The reaction is reversible; however, KOH is used to neutralize the hydrochloric acid produced in the reaction to force the reaction to go forward. Amines can be distinguished as primary, secondary or tertiary through the Hinsberg Test. The amine is shaken with benzene sulfonyl chloride in the presence of aqueous potassium hydroxide. Primary and secondary amines form insoluble substituted sulfonamides while tertiary amines do not. Upon addition of KOH, primary amines yield a clear solution while insoluble secondary sulfonamides are unaffected by the addition of the base.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

MATERIALS AND APPARATUS aniline diethylamine triethylamine benzenesulfonyl chloride pH papers chloroform concentrated HCl PROCEDURES 1. Basicity of Amines Place three pieces of pH paper in a clean watch glass. Determine the pH of the three amines by adding a drop of aniline, benzyl amine and diethylamine separately into three pH papers. Record the pH. 2. Carbylamine Test In a clean and dry micro test tube, place 2 drops of aniline and then add 6 drops of chloroform and 20 drops of alcoholic KOH. Warm for a few seconds. Note the odor of the solution (NOTE: isocyanide is toxic). Before discarding the solution, add 1 ml concentrated HCl. 3. Salt Formation Put 2 drops of aniline in a micro test tube and add concentrated H 2SO4 drop by drop until a visible change is observed. Record you observations. 4. Hinsberg Test To 2 drops of aniline in a micro test tube, add 2 drops of benzenesulfonyl chloride, then mix. If a residue is formed, add 1.0 mL 10% KOH solution. Stopper the test tube and shake the mixture vigorously (Note 1). Test the pH of the solution to make sure that it is alkaline. Cool the solution and filter or decant from any residue. Label the residue as A. Note whether residue A is a solid or a liquid. If it is a liquid, note whether it is lighter or heavier than the alkaline solution. Test the solubility of residue A in water and in 5% HCl (Note 2). 10% NaOH solution 5% HCl droppers test tubes with stoppers benzyl amine alcoholic KOH concentrated H2SO4

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Acidify the clear filtrate from the mixture of aniline and benzenesulfonyl chloride with 5% HCl. Scratch the sides of test tube with a stirring rod to hasten crystallization of product B. Repeat procedure 4 using diethylamine and triethylamine. Some secondary amines react slowly, and it is occasionally necessary to warm the reaction. NOTES 1. If the reaction mixture heats up considerably, it should be cooled. Certain N,N-dialkylanilines produce a purple dye if the mixture becomes too hot. This may be prevented by carrying out the reaction at 15C to 20C. 2. The solubility of A in HCl indicates that the original reaction mixture contains tertiary amine. The sodium salts of certain sulfonamides of high molecular weight may be insoluble in the alkaline solution. Usually they are soluble in water. QUESTIONS Show by means of a diagram how the above procedure allows for distinguishing primary, secondary and tertiary amines. REFERENCES Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004 Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 10 SYNTHESIS OF 1-PHENYLAZO-2-NAPHTHOL One common reaction of amines is their reaction with nitrous acid. Different classifications of amines give different products with this reaction. Primary amines give diazonium salts. Aromatic primary amines yield brightly colored azo dyes. Secondary amines form yellow, neutral nitrosamines and tertiary amines produce solutions containing ammonium nitrites. In this experiment, 1-phenylazo-2-naphthol, Sudan 1, is synthesized from a primary amine, particularly aniline and -naphthol. The synthesis of Sudan 1 consists of 2 reactions. First, the reaction of aniline with nitrous acid, which is called diazotization; and second, coupling reaction, the reaction of a diazonium salt and -naphthol to form the azo dye. Diazotization is the formation of diazonium salts. In this reaction, primary aromatic amines react with nitrous acid. Diazonium salts are the most versatile intermediates in organic synthesis since they can still undergo two kinds or reaction: replacement and coupling reaction. In coupling reactions, the positively charged diazonium ions serve as electrophiles toward highly activated aromatic compounds like phenols and anilines, to give coupling products. This reaction is important in the synthesis of dyes that are usually used as indicators in acid-base neutralization reactions. These coupling products can also be used as staining agents on plants and as textile dyes. Dyes are highly colored because they absorb light in the visible region of the spectrum. Chromophores or color-bearers are the species that are responsible for the absorption of light. In azo dyes, it is the N=N which links two aromatic rings together that is responsible for the absorption of light. Aside from chromophores, dyes also have color-deepeners or enhancers called auxochromes which intensify the color of the dye. These auxochromes include aromatic rings with NHR, -NR2, -OH and-OR substituents Fabric dyeing is of two kinds: direct and ingrain dyeing. In direct dyeing, dyes are directly attached to the fabric via chemical interactions called salt linkages. However, there are dyes that are not suitable for some fabrics. One example is cotton. Cotton fiber lacks functional groups that are capable of forming chemical interactions with the dye. However, dyes can be developed in the cotton and this is what we call ingrain dyeing. In this method, the dye is synthesized inside the fabric. Cotton fabrics have pores and spaces between the fibers that become the site of reaction between the two components of the dye. When reaction occurs, the dye is trapped within the fibers. The synthesis of 1-phenylazo-2-naphthol involves the following reaction mechanism:

36 +

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL NH 2

NaNO2, HCl 0C

N=N

N N

+
OH

MATERIALS AND APPARATUS Aniline -naphthol NaNO2 crystals 5% aqueous NaOH conc. HCl PROCEDURES A. Preparation of phenyldiazonium chloride solution Combine 0.2 ml aniline, 0.35 ml water and 0.5 ml concentrated HCl in a 50 ml Erlenmeyer flask. Cool the contents to 4C (Note 1) and then add approximately 1 ml of ice cold distilled water. To the resulting cold mixture, add gradually spatulaful NaNO2 crystals. Keep the temperature of the mixture below 5C (Note 2). B. Preparation of -naphthol Solution Dissolve 0.35 g -naphthol in 4.5 ml of 5% aqueous NaOH in a 50 ml beaker. Cool to 4C. ethanol rock salt 2 mL pipette 50 ml E-Flask 50 ml beaker ice 100% cotton fabric (2x3cm) Bunsen burner

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

C. Ingrain Dyeing Place the fabric to be dyed in the cold -naphthol solution, still immersed in the ice bath. Allow the fiber to soak for 2-3 minutes. Remove the fabric from the bath and pat it between filter papers. Immerse the fabric in the phenyldiazonium chloride solution for several minutes, remove from the solution and rinse well with running water. Note the result. D. Synthesis of Sudan 1 After completing the ingrain dyeing, add slowly, with stirring, the remaining phenyldiazonium chloride solution to the cold -naphthol solution. Allow the reaction mixture to stand at 4C for 1-5 minutes. Filter the product and wash it with several small portions of cold water. Recrystallize the crude product (use steam bath) using a minimum amount of hot ethanol (Note 3). NOTES 1. Rock salt can be added to ensure that the temperature in the ice bath is maintained. 2. The temperature of the phenyldiazonium solution must be kept below 5C at all times to prevent decomposition, which will form undesirable side products. 3. Usually about 10 ml of hot ethanol will be required to dissolve the product. In case some solids remain undissolved after 20 ml of hot ethanol has been added, filter off the undissolved solids and let the filtrate cool to recrystallize. QUESTIONS 1. Give the amine and the coupling component that can be used as starting materials for the synthesis of the following dyes:

a.

butter yellow

b.

methyl red 38

ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

2. Give two possible conditions that could lead to the formation of side products. Write chemical equations for these side reactions. 3. What are the two properties of a good dye? Define each.

REFERENCES Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004 Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 11 Analysis of Unknown Organic Compounds I. Preliminary Examination A. Physical State B. Color C. Odor Determination of Physical Properties A. Determine the Melting Point B. Ignition Test Solubility Class Determine the solubility of the given compound in different solvents. (Refer to Experiment 2) Elemental Analysis Carbon, hydrogen and oxygen are predominant elements found in organic compounds. Other elements commonly found in organic compounds are nitrogen, sulfur, fluorine, chlorine, bromine and iodine. The less common elements are phosphorous, arsenic, antimony, mercury and other metals. The covalent nature of the bonding of these elements in organic compounds does not allow direct test for the presence of each. Since most organic compounds do not ionize in solution, it is necessary to convert them to ionizable compounds. In this way, the presence of these elements can be shown for testing for the ions in solution. The usual procedure is to break up the organic molecule through fusion by heating the substance at a high temperature with metallic sodium or a mixture of anhydrous potassium carbonate and powdered magnesium. The transformation to ionizable inorganic substances through fusion with sodium is represented by the following equation: Organic compound containing C,H, O, N, S, X + Na NaCN + Na 2S + NaOH + After fusion, the ionic tests used in inorganic qualitative analysis are applied in order to show the presence of each element. PROCEDURES A. Sodium Fusion With DRY tongs or pincers, take a small piece of sodium metal (about 2 mm3) and press between layers of DRY filter paper. Place a pinch of the powdered test sample into a watch glass and roll the sodium metal in it. Place the sodium metal, now covered with the powder test

II.

III.

IV.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

sample, into a bubblet. Hold the bubblet with clean crucible tongs and heat in a flame slowly at the start. Gradually increase the heat until the end of the tube is red hot for about a minute. Drop the bubblet into a beaker containing 25 ml distilled water. Make sure that the bubblet breaks. Otherwise, repeat the procedure. Heat to almost boiling and filter. The clear filtrate is used as a test solution for some elements specified below. B. Test for Sulfur Acidify 2 ml of the test solution with dilute acetic acid. Add a few drops of lead acetate solution. A black precipitate indicates the presence of sulfur. C. Test for Halogen Acidify a 2 ml portion of the alkaline fusion solution with dilute nitric acid and boil briefly to expel any HCN that may be present. The appearance of distinct white or yellow precipitate on the addition of silver nitrate indicates the presence of halogen. A yellow color suggests bromide or iodide. To differentiate the halogens in the event of a positive silver halide precipitate, acidify another 2 to 3 ml portion of the original solution and add about 0.3 ml toluene. Then add a few drops of fresh chlorine water or a few mg of calcium hypochlorite. Be sure the pH remains acidic. A yellow-orange color of the toluene layer indicates bromine; a violet color, iodine. D. Test for Nitrogen Add two drops of FeSO 4 solution to 2 ml of the colorless filtrate from the sodium fusion. Add 0.50 ml NaOH to produce a distinct alkalinity. Heat to boiling and then filter to remove the precipitate. Acidify the filtrate with dilute sulfuric acid and add two drops of FeCl 3 solution. Let stand for 10 minutes. The formation of greenish to Prussian blue solution indicates the presence of nitrogen. E. Ferrox test for Oxygen In a dry test tube grind together, with a stirring rod, a crystal of iron (III) ammonium sulfate {or iron (III) chloride} and a crystal of potassium thiocyanate. Iron (III) haxathiocyanate (III) will adhere to the stirring rod. Dissolve the adhering solid using drops of the sodium solution placed in another test tube.

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

If the compound contains oxygen, the salt will dissolve to give a red purple solution. The salt will not dissolve in hydrocarbon solvents, such as toluene, or halogenated solvents alone. Moreover, diphenyl ether does not give a positive test. V. Functional Group Test Functional group tests may be done directly or indirectly on the unknown compound itself, or the compound may be dissolved in a suitable solvent. Ethyl alcohol is generally a good solvent for most organic compounds. This solvent may be used in all of the functional group tests except for alcohols. Other solvent commonly used are diethyl ether, chloroform and benzene. It is a good practice to perform a control test and a blank test side by side with the functional group test of the unknown compound. A control test may be done by adding the same reagents and performing the same operations as the test compounds on a compound that has the functional group being detected. This serves as a standard positive result for that particular functional group test. A blank test, on the other hand, is done by adding the same reagents and performing the same operations on a solution that does not have the functional group being detected (i.e. distilled water or the solvent used). This serves as a standard negative result for that particular functional group test.

REFERENCE Institute of Chemistry. Organic Chemistry Laboratory Manual UP Diliman, 2004

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Special Experiments

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

Experiment 12 DYES AND DYEING Dyeing is a process of applying various colors to materials through infusion of coloring substances into them. These colored substances are called dyes. Dyes may be classified into three categories: vegetable and animal dyes, mineral dyes and synthetic dyes. Vegetable and animal dyes are natural colored substances that are obtained from vegetables and animals. An example of a vegetable dye is indigo. The most important and common dye is the synthetic dye which is obtained from the reaction of aniline with nitrous acid and a compound with a highly activated aromatic ring. There are three groups of atoms that can be associated to dyes giving their characteristic colors. These are chromophores, auxochromes and sulfonic acids. Chromophores are color producing groups present in all dyes. An example is N=N-, which is the chromophore of azo dyes. The auxochromes are color intensifiers. These are the groups of aromatic compounds with ortho- and para-activating substituents like OH, -NH 2 and OCH3. Sulfonic acids are compounds that attach the dye molecules into the fabric. MATERIALS AND APPARATUS dye powder or extract stirrer large glass vessel or basin paraffin fabric (cotton, linen, wool) iron ring PROCEDURE I. Basic Dyeing A. Various tie-dyeing patterns 1. Twisting Gather a length of fabric and hold one end tight while twisting the other until the length twists back on itself. Then tie the fabric and dye for all-over pattern. 2. Circular Pattern Pull materials up towards the center like a closed umbrella and bind downwards at intervals. To obtain distinct and disconnected circular lines, tie off each section with individual rubber bands or cords. vinegar needle thread/string/rubber band brush burner thermometer NaCl scissors beeswax iron stand push pins

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ELEMENTARY ORGANIC CHEMISTRY LABORATORY MANUAL

3. Pleating Accordion-fold the fabric and tie with continuous cord up and down for muted stripes. For definite stripes, make individual ties at desired distances on the folded fabric. Resulting lines will be clean-cut stripes. 4. Stitching Draw any pattern on the fabric and outline by stitching. Running stitches and whipping stitches are commonly used. Pull the sewn threads from both sides and tie the ends together; designs can cross one another. They can also be regular or irregular. The fabric can be used in single layer or doubled over. 5. Marblelizing Bunch and twist the cloth then tightly tie in random fashion with cords or rubber bands. 6. Tying Up Objects Tie up objects like marbles or coins in the fabric by knotting or stringing. These may be dyed separately or bunched together. B. Dyeing Method 1. Dissolve 1 teaspoon dye in 1 pint boiling water. Stir well. Lightcolored dyes are generally used first. 2. Stir in 2 tablespoons of salt (direct dye for cotton and linen) or 1 tablespoon vinegar (acid dye for silk or wool). 3. Wet tied fabric in plain water and immerse in the dye bath. If necessary, add enough water to cover the fabric. 4. Remove fabric and rinse in cold water until water is clear. 5. When dry, untie. Second color may now be dyed over the first. 6. Retie the fabric. Prepare next dye and repeat the whole process. 7. Submit tie-dyed material to your instructor. II. Batik Designing 1. Wash the fabric first with mild detergent before dyeing. Press until dry and free from wrinkles. 2. Stretch the fabric on a frame, securing it in place with push pins. Lay the frame flat on a table top. 3. Design directly on the fabric, or work from a sketch. Draw design lightly on the cloth with a pencil, or with a brush and pale tint watercolor.

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4. Melt the wax in a water bath. Melted wax is extremely inflammable so it must never be melted directly over an open flame. Wax is ready for use when it darkens the fabric to which it is applied. Test by dipping a pointbrush into the melted wax and then dabbing it onto the fabric. If the wax does not darken, heat it a little more. The waxed parts remain the color of the fabric and the un-waxed cloth becomes the dyed area. 5. Paint your design rapidly, returning the brush frequently to the wax pot. It is essential that the wax resist be hot and flowing. 6. Remove the fabric from the frame. Allow the wax to cool. Crush the parts of waxed design to give a crackle look. When less crackle look is desired, beeswax may be added to the paraffin. 7. Prepare the dye bath. Follow the directions on the package of the dye. Add salt or vinegar as directed. 8. Rinse the fabric in lukewarm water. Place the fabric gently in the dye bath with a temperature of about 90F. Leave it completely submerged for 20-30 minutes. Stir occasionally. 9. Remove the fabric from the dye bath and rinse in lukewarm water to remove the excess dye. Hung the fabric to dry. 10. Lay the dried fabric on several sheets of newspaper. Place one sheet of paper on top of the fabric and press with hot iron. Change the papers frequently and press until all the wax is removed.

REFERENCES Bell, C.E., A. Clark, D.F. Tader and O. Rodig. Organic Chemistry Laboratory N.Y. Saunders College Puiblishing, 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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Experiment 13 SYNTHESIS OF NYLON POLYMERS Polymerization is a process of reacting a monomer molecule together in a chemical reaction to form linear chains or a three-dimensional network of polymer chains. There are many forms of polymerization and different systems exist to categorize them. Addition polymerization involves the linking together of molecules incorporating double or triple bonds. These unsaturated monomers have extra internal bonds which are able to break and link with other monomers to form repeating chains. Examples of polymers prepared in this method of reaction are polyethylene, polypropylene and polyvinyl chloride. Chain growth-step growth system categorizes polymers based on their mechanism. In a chain growth polymerization reaction, polymers are formed by the reaction of monomers with a reactive center. Condensation polymerization occurs when monomers bond together through condensation reaction. Typically, these reactions can be achieved through reacting molecules incorporating alcohols, amines or carboxylic acids. Condensation reactions are characterized by a removal of a water molecule. One of the most important polymers synthesized today is nylon. Nylon is made of repeating units with amide linkages between them. Hence, it is frequently called polyamide. One of the most common example is nylon 6,6 or polyamide 6,6 (PA66). This polymer is prepared from condensation polymerization of equal parts of a diamine and a dicarboxylic acid. This process is the same as the formation of peptide bonds in amino acids. Nylon 6,6 is a semi-crystalline polyamide commonly used in fiber applications such as carpeting, clothing, and tire cords. It is also used as an engineering material in bearings and gears due to its good abrasion resistance and self-lubricating properties. MATERIALS AND APPARATUS aqueous solution of 0.5 M 1,6-diaminohexane and 0.5 M NaOH 0.30 M adipoyl chloride in cyclohexane 5% aq. NaHCO3 phthalic anhydride ethylene glycol glycerol test tube filter paper

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PROCEDURE I. Preparation of Nylon 6.6 (Interfacial polymerization)

Into a 18x150-mm test tube, add 8 mL of an aqueous solution that is 0.50M 1,6-diaminohexane and 0.50M sodium hydroxide. Carefully add 8 ml of a 0.30M solution of adipoyl chloride in cyclohexane to the test tube by slowly pouring the adipoyl chloride solution down the wall of the slightly tilted tube. (NOTE 1) Two layers should form, and there should be immediate formation of a polymer film at the liquid-liquid interface. Using a piece of steel wire with a hook bent into one end, hook the polymer mass near the center and slowly raise the polymer mass so that a continuous rope of polymer is formed. (NOTE 2) Transfer the polymer rope directly into a beaker containing 50 ml of 5% aqueous sodium bicarbonate. Rinse the rope several times with water, and then place the polymer on a piece of filter paper to dry. Vigorously stir the remainder of the reagents in the test tube to form additional polymer. Decant the cyclohexane and aqueous solution from the solid polymer, and discard the liquid in the waste container that is provided. Thoroughly wash the solid polymer with 5% aqueous sodium bicarbonate and then with water. Dry the polymer on a piece of filter paper. Weigh the two batches of dry polymer and calculate a percentage yield. A small amount of this washed and dried polymer can be melted in a test tube by gentle heating. A nylon fiber can be drawn from the melt by touching the surface of the melted polymer with a clean glass rod and then slowly withdrawing the rod with the fiber attached. II. Preparation of Polyester

Place 3.0 g of phthalic anhydride in each of two 18 x 150-mm test tubes. To one tube add 1.3 g (1.2 ml) of ethylene glycol, and to the second add 1.3 g (1.0 ml) of glycerol. Clamp both tubes so that they may be heated with a flame simultaneously, and then heat the tubes gently to 150 to 180C. Vapor will evolve during the heating process. Continue heating an additional 5 minutes, and gradually raise the temperature to ~200C during this heating period. Allow the tubes to cool and then determine the physical properties (appearance, softening point, and solubilities) of the 2 polymers. NOTES 1. Adipoyl chloride and 1,6-diaminohexane are both toxic and should neither be inhaled nor allowed tocome in contact with your skin.

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2. Do not handle the polymer with bare hands. It may contain unreacted reagents. REFERENCES Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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Experiment 14 SOAPS AND DETERGENTS MATERIALS AND APPARATUS ethanol HCl 0.5% CaCl2 beakers coconut oil PROCEDURE A. Saponification of coconut oil (Soap formation) 1. Mix 10 ml ethanol with 15 ml 6 M NaOH in a 400 ml beaker. 2. Add 15 ml coconut oil and mix by swirling. 3. Add boiling chips then cover with a watch glass and heat the mixture gently with intermittent swirling over a small burner flame or a hot plate, until the mixture is viscous (about minutes) 4. Allow the mixture to cool then salt-out the product by stirring in 50 ml saturated NaCl solution. 5. Collect the precipitated soap by suction filtration. 6. Wash the soap twice with 15 ml portions of ice-cold distilled water. Allow the suction to continue until no more liquid drains from the funnel. 7. Save a tablespoonful of soap for Part B. 8. Place the remaining soap in an evaporating dish or 250 ml beaker, heat in a hot plate and stir in enough distilled water to make a thick solution. (OPTIONAL: you may add remaining essential oils from Experiment 5). 9. Allow the soap to cool. It should resemble a cake of commercial soap (Use with caution: it may contain some NaOH) B. Chemical Properties of soaps and synthetic detergents Dissolve a tablespoon of the soap sample and powder detergent in 30 ml warm distilled water. Use the resulting mixtures for the following tests. 1. Hydrolysis Test the mixtures with small piece of red and blue litmus paper. 2. Reaction with acid Slowly add 10 ml of 0.05 M HCl to 5 ml of the test mixture. Record any changes you observe. Add 4 ml of dichloromethane to each mixture and shake vigorously. Record your observations. NaOH dichloromethane 0.5% FeCl3 blue/red litmus paper hot plate satd NaCl kerosene 0.5% MgCl2 ice suction filtration apparatus

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3. Reaction with hard water To 5 ml of test mixture, add 1 ml of 0.5% calcium chloride solution and shake vigorously. Repeat using 0.5 % ferric chloride and 0.5 % magnesium chloride. Record you observations. 4. Emulsifying action Place 8 drops of kerosene in three separate dry test tubes. Add 5 ml soap solution to the first test tube, 5 ml detergent mixture to the second, and 5 ml distilled water to the last tube. Shake each tube vigorously for three minutes then examine. Allow the test tube to stand for 5 minutes then repeat the examination. REFERENCES Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993. Palleros, D.R. Experimental Organic Chemistry N.Y. John Wiley & Sons, Inc. 2000.

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Experiment 15 WINE-MAKING Wines are the alcoholic fermentation products of the juice of grapes and other fruit extracts through the aid of yeasts, mostly Saccharomyces cerevisiae. Yeasts are unicellular fungi that reproduce asexually by budding or fission. The reaction by which these wines are produced is generally referred to as fermentation and may be summarized as: Yeast + Glucose Alcohol (Ethanol) + CO2 In this reaction, the enzyme zymase present in yeasts act on the dissolved sugar, changing it to ethyl alcohol and carbon dioxide. This reaction is also important in baking bread, but the desired product is then the carbon dioxide rather than alcohol. The production of alcohol occurs best in the absence of oxygen. However, from the yeast's point of view, alcohol and carbon dioxide are waste products, and as the yeast continues to grow and metabolize in the sugar solution, the accumulation of alcohol will become toxic when it reaches a concentration between 14-18%, thereby killing the yeast cells. This is the reason why the percentage of alcohol in wine and beer can only be approximately 16%. In order to produce beverages (liquor) with higher concentrations of alcohol, the fermented products must undergo distillation. MATERIALS AND APPARATUS fruit extracts cheesecloth mortar and pestle sterilized bottles PROCEDURE A. Extraction of the Fruit Juice 1. Wash the fruit and remove the peels. 2. Cut into small pieces and boil the fruits with an equal amount of water. 3. Extract the juice by pressing and straining through a cheese cloth. 4. Measure the volume of the extracted juice then add cup of sugar to every cup of the extract. 5. Heat the sweetened extract for 10 to 15 minutes then cool. sugar cotton beakers yeast graduated cylinder

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B. Fermentation 1. Weigh 2 grams of the yeast for every cup of the extract. 2. Macerate the yeast in a mortar to make a smooth paste. Add this to the previously boiled extract. 3. Transfer the mixture into a sterilized container and loosely stopper the mouth with cotton. 4. Set aside for at least one week or longer for complete fermentation. C. Pasteurization 1. Decant or filter the wine through cheesecloth. 2. Place the mixture in a clean bottle and heat in a water bath for 30 minutes. Keep the temperature of the bath at 60C. 3. Cool the mixture. 4. Place an airtight cover and age for 10 days or more. Make sure that the bottle is filled to capacity with the mixture. Egg white may be added in the proportion of one egg white for every ten cups of extract to assist in the precipitation and clarification of the prepared wine. QUESTIONS 1. Enumerate the conditions essential to alcohol fermentation. 2. What other materials in addition to egg whites may help in the clarification of wines? 3. What variants of wine are commercially available and how are these obtained, for ex. red wine vs. white wine, etc.? REFERENCES Bell, C.E., A. Clark, D.F. Tader and O. Rodig. Organic Chemistry Laboratory N.Y. Saunders College Puiblishing, 1993. Neal Carmichael, L. Laboratory Chemistry Ohio, Merrill Publsihing Co., 1993. Organic Chemistry Committee. Experiments in Organic Chemistry. Manila: Salesiana. 1993.

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