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Practical Organic Chemistry


First Year

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Calculation of Percentage Yield


The yield in a reaction is the mount of product of acceptable purity actually obtained the percentage yield is the ratio of this amount to that theoretically obtainable x 100, and it is usually calculated from the equation of the reaction Example: In the esterfication reaction of Succinate : ( 5gr. ) of the acid is heated with 100 ml ethanol and ( 6.2 gr. ) ester is produced .
HO-CO-CH 2 CH 2 -CO- OH + 2C 2 H 5 OH H+ C 2 H 5 O-CO-CH 2 CH 2 -CO-OC 2 H 5 + 2H 2 O

Succinic acid

ethanol

diethyl Succinate

5gr. Succinic acid ( Mol.wt= 118 ) , ethanol ( 100 ml ) d= 0.79 g/ml No. Of mole =
5 = 0.042 Sucinic acid 12

Weight of ethanol = 100 ml x 0.79 g/ml = 79 grams. No. of mole =


79 = 1.72 ethanol 46

From experiment work we have 6.2 gr. Ester (mol.wt. 174) so: No. of moles = So, yield % =
6.2 = 0.036 ester 174

Exp. produced 0.03 100 = 100 = 85% Theoritical produced .042

General Procedure For Laboratory Report


1. Name of Experiment 2. Aim Of Experiment Example: Oxidation reaction or substitution reaction or determine on the physical properties 3. Theory and Equations Write the chemical equation and the mechanism of the reaction and any calculation equations required. 4. Apparatus and material Draw the equipments used in the experiment and write the materials used showing their purity and

manufactures name. 5. Calculations and Results Write the procedure of calculation of yield or any results. 6. Discussion Write the reasons to make the experiment successes and that increase the yield.

Experiment No. 1
"Melting Point"
A pure crystalline organic compounds has in general , a define and sharp melting point , that is the melting point range ( The difference between the temperature at which the collapse of the crystals is first observed and the temperature at which the sample becomes completely liquid ) does not exceed about 0.5 c . The experimental method in most common use is to heat a small amount ( about 1mg. ) of the substance in a capillary tube inserted into suitable melting point apparatus , and to determine the temperature at which melting occurs .

Procedures 1- Place a small amount of the finally powered substance (unknown) in a capillary tube, after you had closed one end of the tube by using Bunsen burner (by inserting it horizontally into the extreme edge of a small Bunsen flame for a few seconds, and the caspillary tube related mean while; the formation of the glass bead of the tube should be avoided). 2- Connect the capillary tube with graduated thermometer by using a rubber band (Fig.1).

3- Dip the capillary tube and thermometer in liquid paraffin in suitable container. 4- Start heating gradually using Bunsen burner (1-2 c / ml). 5- Determine the melting point when the solid start to melt. The temperature at which the substance commences to liquefy and the temperature at which the solid has disappeared, i.e. the melting point is observed. For pure compound, the melting point range should not exceed 0.5 1c , it is usually less .

Figure (1), Capillary tube with graduated thermometer. Discussion: 1- Define the melting point and the field that is used for. 2- What the effect of impurities on melting point? 3- Type of path used? And Why? 4- Why it most cooling the path before it used again to calculate the melting point?

5- Why it must the thermometer and the capillary tube must at the same level? 6- Why must substance in capillary tube be pushed together and no more 2-3m m height?

Experiment No. 2
"Boiling point-Criteria of purity of Liquids Simple Distillation"
Boiling point of liquid is reached when the vapor pressure of the liquid equals that of the atmosphere. It is usually determined by simple distillation. A pure liquid (which distils without decomposition) will have a sharp B.P. which will remain constant until the whole of the liquid has boiled off, leaving no residue. Unlike the m.p. , this B.P. whilst remaining sharp , may very in value over a range of several degrees , owing to fluctuations in the barometric pressure . The B.P. of an impure liquid will depend largely on the physical nature of the impurities. If all the impurities are nonvolatile, the liquid will have a sharp B.P and the solid impurities will remain behind when the liquid has evaporated. If the

impurities are volatile , then the B.P. of the liquid may ( a ) remain constant or ( b ) rise steadily as the liquid boils or ( c ) rise in a series of definite steps , according to the nature and quantity of impurities present . Although a pure liquid has a sharp B.P does not always indicate a pure liquid, but may be caused by a constant boiling mixture of two or more liquid, eg. : a mix of 20.2 % of HCL and 79.8 % water boils steadily at 100/760 mm. .

Simple Distillation

Distillation is the process of vaporizing a substance condensing the vapor, and collecting the condensate in another vessel. The basic elements of a distillation apparatus are boiling flask a thermometer, consider and a receiver.

Procedure 1- Assemble the apparatus (Fig. 3) 2- Place the liquid in the flask. Put some small fragments of unglazed porcelain (boiling chips).

3- Place the thermometer in position; heat the flask either on water bath if the liquid has low B.P. or else directly over wire gauze.

Important point to be noticed with Regard to simple Distillation 1- Pragments of unglazed porcelain should always be added whenever a liquid is boiled in order to provide nuclei for the formation of bubbles of the vapor and thus ensure steady gentle boiling, if the boiling chips are omitted the liquid may becomessuper heated, and then suddenly boil with great evidence. 2- A water condenser can be used for any liquid the boiling of which does not exceed 140c. Above this temp an air condenser should be used. 3- Low boiling liquids are usually distilled from a water bath for additional safety. Generally, most liquids of boiling points below 80oC, may be distilled in this way, for liquids of higher B.P. a sand bath, or direct heating on gauze, is necessary.

Figure (3)

Experiment No. 3
"Separation on of liquids

Fractional Distillation"
In the distillation of a pure liquid, vapor from the boiling flask , rises and condenses until the apparatus in thermal equilibrium and the thermometer registers the which will remain constant as long as liquid and vapor we both present . Distillation of a mixture of two miscible liquids can be illustrated by the vapor liquid phase diagram in (Fig.4). The B.p of pure components A & B are T a & T b . The lower curve gives the B.p of various mixtures of A & B and the upper curve, the condensation temperature of mixture of gaseous A &B . These two lines do not coincide at given temp. (And press) and the composition of the liquid apron phases in equilibrium differ. If an equimolar mixture of liquids A & B (composition x 1 ) heated to its B.p (temp T i ) the vapors leaving the liquid will have the composition x 2 which is enriched in the lowering boiling component. If a sample of this vapor is remove the composition of the remaining liquid shifts to the right on the diagram i.e. the relative amount of B increases , and the axis has a higher B.p continued distillation from the mix. Provides distillation progressively enriched in B, but each reaction of it will contain both components. If the condensed vapor of composition x 2 , are equilibrated at temperature T 2 the a vapor will now have a composition x 3 which is even more in reached in the low boiling component A. If the equilibrate on can be repeated several times, it is possible to obtain final distillate

which is nearly pure A. This process, termed "Fractional Distillation", is accomplished by distilling through a column with a large surface area at which repeated exchange of molecules between liquid and a vapor phases occurs. The phase diagram in (Fig.4) is typical of a mixture of similar compounds which ideal or nearly ideal solution as defined by Raoult's law: xA + PB xB P total = P A + P B = P A
R R R R R R R R R R R R R

x: are the vapor pressure and mole fractions respectively of P, A & B. In a distillation at atmospheric pressure P total =760 mm
R R

Hg.

Figure (4) With mixture of dissimilar compounds, such as an alcohol and a hydrocarbon, association of one component occurs in the liquid, and the solution usually does not follow this relationship. At some composition, in this case here will be a minimum in the vapor liquid diagram (Fig.5) such system is called an

azeotrope, and a liquid of composition x will distill completely at temperature Tx as constant Bp mixture. Fractional distillation of a mixture of A & B of any other composition will provide distillate of composition x until only one component remains in the liquid. A common sample of this type of azeotrops is ethanol water (95: 5).

Figure (5) In fractional distillation the fractionating column is inserted vertically between the flask containing the boiling liquid and the condenser (Fig. 6). The principle of fractionating column is that as the vapors ascend the column from the boiling mixture below, the higher boiling components are condensed and returned to the flask, the ascending column of vapor being thus steadily Scrubbed by the descending column of liquid condensate .

Figure (6)

Procedure :
1. Prepare three flasks and label them A, B of C. 2. Place 40 ml of mix. of equal volumes of benzene & toluene in the boiling flask, put few boiling chips. 3. Assemble the apparatus (Fig. 6). 4. Heat the flask with a burner placed so that the chip of the lame touches or is just below the wire gauze. 5. As soon as the mixture starts to boil and the refluxing Vapors have reached the thermometer, regulate the flame so that distillation continues steadily at a rate of only a bout one drop every 1 2 seconds . 6. Collect the fractions (A) [2085] oC, (B) [85 107]oC, (C) [107-111]oC. These fractions should have volumes about 19, 2 and 17 ml respectively.

7. Continue distillation until a bout 1 or 2 ml of liquid remain in the flask.

ExperimentNo . 4
"Steam Distillation"
Many water insoluble compounds may be readily purified by distillation in a current of steam, provided that he compound is volatile, and the impurities non volatile, under these condition.

Procedure :
1. Place the material to be distilled in a distilling flask (A) (Fig. 7).

2. Meat the water in container (C) and let the steam current passes over the material in (A) the mixture in (A) is thus rapidly heated.

Figure (7), Steam Distillation Apparatus

Experiment No. 5
"Preparation of Acetic Acid" Ethanol, being a typical primary alcohol containing CH 2 OH group , gives on oxidation first acetaldehyde and then acetic acid .

[O] -2H CH 3 + CH 2 OH CH 3 CH(OH) 2 CH 3 COOH -H 2 O CH3CHO Acetaldehyde The oxidizing agent used is a mixture of sodium dichromate and sulpharic acid. To prepare acetic acid aqueous ethanol is added gradually to that mixture of aqueous sodium dichromate and sulphuric acid. Procedure : 1. Assemble the apparatus shown in the Figure (8) below. 2. Add 10 ml of distilled water in a distilling flask, and then add slowly 35 ml of conc. H 2 SO 4 with continuous stirring. 3. Add 35 gm of sodium dichromate to the mixture, shake well for complete dissolving. 4. Place in a dropping funnel 1.5 ml of alcohol with 6 ml of water add the mixture drop wise through the condenser to the distilling flask (notice the change in the color ). Shake the distilling flask during the addition. 5. When the addition is complete and the reaction is subsided heat the mixture for 20 minutes using water bath. 6. Assemble the apparatus for simple distillation collection 8 ml of distillate which is agueous acetic acid.

Figure (8)

Tests :
1. With litmus paper. 2. With NaOH. 3. With ethanol (notice the odor of ethylacetat ester).

Experiment NO. 6
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"Preparation of Cyclohexene" "Elimination Reaction " Alkenes can be formed by the acid catalyzed dehydration of alcohols. Cyclohexene is prepared by the dehydration of cyclohexanol (a secondary alcohol) in the presence of H 2 SO 4 :
R R R R

OH

H OH H H+

H+

Procedure :
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1. Place (20gm) cyclohexanol and (2 ml) of H 2 SO 4 in a


R R R R

distilling flask. 2. Add 23 pieces of boiling chips, attach the flask to a fractional distillation assembly, and slowly heat the contents of the flask to boiling and distill the product. The . temperature should be kept under 90 3. Collect 810 ml of distillate, transfer to a separating funnel and remove the water layer. 4. Transfer the upper layer (the cyclohexane) into a conical flask, add 23 gm of a drying inorganic salt MgSO 4 or
R R

CaCl 2 . Shake well for 10 minutes. Leave for 24 hours to


R R

dry.

5. Filter through a fluted paper, and distill by simple distillation apparatus, the distillation rate should be 5 drop per minute

Determine : 1. B.p of fractional distillates. 2. Calculate the percentage yield. 3. Test for unsaturation (either by KMnO 4 or Br 2 water).

Experiment NO.7:
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" Saponification reaction"


Hydrolysis of esters under alkaline conditions, saponification, Is a chemicalreaction that has been carried out for centuries as a means of making soap.Heating triglyceride fats or oils with aqueous alkali (sodium carbonate or sodiumhydroxide) results in hydrolysis of the triglyceride esters forming "soaps",sodium salts of the fatty acids. Since the fat or oil starting materials are not soluble in water, the saponificationreaction proceeds very slowly unless some provision is made for bringing thefatty ester and base into the same phase. One method is to use alcohol as asolvent to solubilize the fat and base together and then the alcohol is removed atthe end to isolate the soap. Another approach is to use a tetraalkylammoniumsalt as a phase transfer catalyst to bring the base into the oil phase therebyspeeding up the hydrolysis. In this experiment, partially hydrogenated vegetable shortening will besaponified using aqueous sodium hydroxide with tetrabutylammonium bromideas a phase transfer catalyst.

Procedure:
Partially hydrogenated vegetable shortening (2.0 g) is placed in a 50 mL beakeralong with 2 mL of 25% aqueous sodium hydroxide and 0.020 g oftetrabutyammonium bromide. The mixture is heated on steam bath withoccasional stirring for 20 minutes, or until the oil phase has disappeared and only soap solids and a clear aqueous phase remain. The mixture is allowed to cool toroom temperature then cooled in an ice bath while 5 mL of ice cold water isslowly added. The suspension of soap solids is stirred while keeping it in the icebath, then suction filtered using a Buchner funnel. The soap solids are rinsedwith a few mL of ice cold water and air dried in the Buchner funnel.

Testing the Solubility and Foaming Properties of the Soap in Soft and HardWater
A small amount of the soap on the tip of a spatula is dispersed in about 20 mL ofdistilled water in a clean 50 mL beaker. The soap dispersion is transferred to a 60mL separatory funnel and shaken vigorously. The solubility and foamingproperties of the resulting solution are observed and recorded. The procedure is repeated using 20 mL of regular tap water. How do the solubility and foamingproperties of the soap in the hard water compare to the distilled water?

Experiment NO.8: "prepare Caffeine"


Caffeine is a minor constituent of tea, coffee, and other natural plant materials.The major constituent of tea is cellulose which is not water soluble. Caffeine is water soluble but so are some tannins and gallic acid which is formedin the process of boilingtea leaves. The latter two components can be converted to their calcium salts which are insoluble in water. The caffeine can then be extracted from the water by methylenechloride in almost pure form. Some chlorophyll is often extracted at the same time.

Procedure:
Place 15 g of tea leaves, 5 g of calcium carbonate powder and 200 mL ofwater into a 600 mL beaker. Boil the solution on a hot plate for 20 minutes withoccasional stirring. Cool the solution but, while it is still warm, vacuum filter through aBuchner funnel using a fast filter paper, if available. Normally, hot solutions are notvacuum filtered. Rinse the leaves with 50 mL of water. Carefully press out as muchfiltrate as possible since

the caffeine is in the aqueous layer. Rinse again with 50 mL ofwater. Cool the solution to room temperature and pour it into a 500mL separatoryfunnel. Extract with 35mL of methylene chloride. In a departure from normal procedure,it will be necessary to vigorously shake the separatory funnel in order to extract thecaffeine. First, relieve the pressure buildup as soon as you mix the two liquids. Thenshake vigorously for 10 seconds and relieve pressure, repeat the shaking two more times.An emulsion will probably form.To break the emulsion formed in the methylene chloride layer, slowly drain themethylene chloride layer through a small amount of anhydrous magnesium sulphate in apowder funnel with a loose cotton plug (a tight plug will prevent drainage). Extract the aqueous solution once again with a 35 mL of methylene chloride,repeating the steps above to collect the lower layer. Combine the methylene chlorideextracts and, if necessary, dry further with additional anhydrous magnesium sulphate. The methylene chloride solution will be stripped on a rotoevaporator. Tare weigha 100-mL rb flask and transfer the dried methylene chloride solution to it. Be certain that there is no magnesium sulphate in the solution. Stripping this solution to dryness will takeless than 5 minutes. You will be left with a small amount of residue with a greenish tinge.Obtain the weight of crude caffeine by difference.Add 5-8 mL of hot acetone to dissolve the crude caffeine and transfer the solution

to a 50 mL Erlenmeyer flask for recrystallization. Add a few drops of petroleum etheruntil you reach the cloud point (caffeine is less soluble in this mixed solvent and is justbeginning to precipitate) and then cool the solution. If you donot get a precipitate, youmay have used too much acetone, carefully boil off the excess on a steam bath using aboiling stick for ebullation. Suction filter the caffeine using a small Hirsch funnel and petroleum ether as atransfer/rinse solvent. A second crop of caffeine may form in the filtrate as the solventevaporates. This second crop can also be collected by vacuum filtration but keep itseparate from the first crop. After air drying, weigh each crop and record your % caffeinerecovered from tea.