PREPARATION OF RAYON BY CUPRAMMONIUM PROCESS Introduction Cellulose is the chief structural component to which plants owe their rigidity

and form. Cellulose is natural polymeric material having fibrous structure. It is the principal component of the covering of plant cells. Cellulose represented by the formula (C6H10O5) is a linear polymer containing glucose units. Wood, cotton and other plant materials are the main sources of cellulose. In the pure form cellulose is present in cotton(98%) while in wood it is about 50% of the mass of dry wood. Cellulose can be converted into cupra silk, acetate rayon and viscose rayon depending upon the method of treatment it undergoes while forming rayon. Between 1890 and 1895, German scientists Fremery and urban developed the manufacture of rayon from cellulose. They based their process on the observation that cellulose is soluble in ammoniacal copper oxide and can be regenerated from solution by adding acid. Cellulose is an insoluble material; however it is found to dissolve in cuprammoniam complex..[Cu(NH3)4](OH)2, known as Schweitzers reagent. It is regenerated from solution by adding sulphuric acid. Thus rayon is regenerated cellulose and it is used for making fabrics like stockings, shirts etc. Aim of the projects The main objective of the project is to illustrate the preparation of rayon by the cuprammonium process. Instead of wood pulp as the cellulose source, attempt is done to make use of raw cellulose products such as waste paper(un-printed), filter paper etc. Apparatus and chemicals Beakers(250 ml.) Conical flask(250ml.) Filter flask Funnel,glass rod Sodium hydroxide solution Copper sulphate 50% Ammonia solution Filter paper strips Syringe Procedure until a precipitate is formed. Add NaOH solution to complete precipitation. Filter off the precipitate and wash it with water two or three times until the washing does not give a precipitate with barium chloride solution. Tranfer the precipitate into a beaker and add 50 ml.

of liquid ammonia.. The precipitate dissolves giving a deep blue transparent solution. This is known as Schweitzers reagent. Cut few filter paper strips (about 1g) intosmall pieces and add them into the cuprammoniam reagent taken into a conical flask. Close the flask with a cork and keep it over night. When all the pieces of filter paper have dissolved, the solution will be viscous(called viscose). The viscous solution is drawn into a syringe. Keeping the nozzle of a syringe inside 5M sulphuric acid solution taken in a beaker, the solution in the syringe is forced into the acid solution. Move the nozzle of the syringe in the acid solution continuously to form long filaments of rayon in the acid solution. The beaker containing rayon fibers is allowed to stand undistributed until the blue colour of the rayon filaments disappears and becomes white. Remove the rayon threads from the acid bath, wash with water and dry using filter paper. Result Mass of filter paper strips used = ..g Mass of rayon thread formed = ..g

Aim

To prepare a sample of cuprammonium rayon threads from filter paper

Apparatus Required a) Conical flask (preferably 250 ml) b) Funnel c) Glass rod

d) Beaker (preferably 250 ml) e) f) Water bath Filter paper (Whatman paper or ordinary filter paper sheets. Preferably, Whatman)

Chemicals Required a) CuSO4

b) NaOH solution c) d) e) f) Liquor ammonia solution Dilute H2SO4 Whatman Paper Distilled H2O

Background

Rayon is a synthetic fiber produced from cellulose. Developed in an attempt to produce silk chemically, it was originally called artificial silk or wood silk. Rayon is a regenerated fiber, because cellulose is converted to a liquid compound and then back to cellulose in the form of fiber. For example, cuprammonium rayon is made by dissolving cellulose in an ammoniacal copper sulphate solution. The characteristics of rayon fibers are: s s s s They are highly absorbent, Soft and comfortable, Easy to dye & Drape well.

Introduction Cellulose is natures own giant molecule. It is the fibrous material that every plant from seaweed to the sequoia makes by baking glucose molecules in long chains; the chains are bound together in the fibers that give plants their shape and strength. Wood has now become the main source of cellulose. Since it contains only 40% to 50% cellulose, the substance must be extracted by pulping. The logs are flaked, and then simmered in chemicals that dissolve the tarry lignin, resins and minerals. The remaining pulp, about 93% cellulose, is dried and rolled into sheets-raw material for paper, rayon and other products. It can be obtained in 2 ways:

1. Viscose Process: Cellulose is soaked in 30% caustic soda solution for about 3 hrs. The alkali

solution is removed and the product is treated with CSi. This gives cellulose xanthate, which is dissolved in NaOH solution to give viscous solution. This is filtered and forced through a spinneret into a dilute H2SO4 solution, both of which harden the gum like thread into rayon fibers. The process of making viscose was discovered by C.F.Cross and EJ.Bevan in 1891. 2. Cuprammonium Rayon: Cuprammonium rayon is obtained by dissolving pieces of filter paper in a deep blue solution containing tetra-ammine cupric hydroxide. The latter is obtained from a solution of copper sulphate. To it, NH)OH solution is added to precipitate cupric hydroxide, which is then dissolved in excess of NH/. Reactions: CUSO4+ 2NH4OH Cu(OH)2+ (NH4)2S04 Pale blue ppt Cu(OH) 2 + 4NH4OH [Cu(NH3) 4](0H) 2 + 4H2O [Cu(NH3) 4](0H) 2 + pieces of filter paper left for 10-15 days give a viscous solution calledVISCOSE. Procedure A. Preparation of Schweitzers Solution: a) Way20gofCuSO).5H20.

b) Transfer this to a beaker having 100ml distilled water and add 15ml of dilute H2SO4 to prevent hydrolysis of CuSO). c) Stir it with a glass rod till a clear solution is obtained. Add 11ml of liquor ammonia drop by drop with slow stirring. The precipitate of cupric hydroxide is separated out. d) Filter the solution containing cupric hydroxide through a funnel with filter paper.

e) Wash the precipitate of cupric hydroxide with water until the filtrate fails to give a positive test for sulphate ions with barium chloride solution. f) Transfer the precipitate to a beaker that contains 50ml of liquor ammonia or wash it down the funnel. The precipitate when dissolved in liquor ammonia gives a deep blue solution of tetra-ammine cupric hydroxide. This is known as SCHWEITZERS SOLUTION. B. Preparation of Cellulose material a) After weighing 2g of filter paper divide it into very fine pieces and then transfer these pieces to the tetra-ammine cupric hydroxide solution in the beaker. b) Seal the flask and keep for 10 to 15 days, during this period the filter paper is dissolved completely. C. Formation of Ravon Thread a) Take 50ml of distilled water in a glass container. To this add 20ml of conc H2SO4 drop by drop. Cool the solution under tap water. In a big glass container pour some of the solution. b) Fill the syringe with cellulose solution prepared before.

c) Place the big glass container containing H2SO4 solution produced before in ice (the reaction being spontaneous results in excess release of energy in the form of heat which makes the fibers weak and breaks them). d) Immerse the tip of the syringe in the solution and press gently. Notice the fibers getting formed in the acid bath. Continue to move your hand and keep pressing the syringe to extrude more fibers into the bath. e) f) Leave the fibers in solution till they decolorize and become strong enough. Filter and wash with distilled water.

Precautions a) Addition of excess NH/ should be avoided.

b) Before taking the viscose in the syringe make sure that it does not contain any particles of paper, otherwise, it would clog the needle of the syringe. c) Addition of NH/ should be done in a fume cupboard and with extreme care. The fumes if inhaled may cause giddiness. d) Use a thick needle otherwise the fibers wont come out.

Materials 3.0 g salicylic acid 6 mL acetic anhydride* 5-8 drops of 85% phosphoric acid or concentrated sulfuric acid* distilled water (about 50 mL) 10 mL ethanol 1% iron III chloride (optional, to test purity) *Use extreme caution when handling these chemicals. Phosphoric or sulfuric acid and acetic anhydride can cause severe burns.

Equipment filter paper (12.5 cm) ring stand with funnel two 400 mL beakers 125 mL Erlenmeyer flask 50 mL buret or measuring pipet 10 mL and 50 mL graduated cylinder fume hood, hot plate, balance dropper stirring rod ice bath wash bottle

1. Accurately weigh 3.00 grams of salicylic acid and transfer to a dry Erlenmeyer flask. If you

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4. 5.
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7. 8. 9.

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will be calculating actual and theoretical yield, be sure to record how much salicylic acid you actually measured. Add 6 mL of acetic anhydride and 5-8 drops of 85% phosphoric acid to the flask. Gently swirl the flask to mix the solution. Place the flask in a beaker of warm water for ~15 minutes. Add 20 drops of cold water dropwise to the warm solution to destroy the excess acetic anhydride. Add 20 mL of water to the flask. Set the flask in an ice bath to cool the mixture and speed crystallization. When the crystallization process appears complete, pour the mixture through a Buckner funnel. Apply suction filtration through the funnel and wash the crystals with a few milliliters of ice cold water. Be sure the water is near freezing to minimize loss of product. Perform a recrystallization to purify the product. Transfer the crystals to a beaker. Add 10 mL of ethanol. Stir and warm the beaker to dissolve the crystals. After the crystals have dissolved, add 25 mL of warm water to the alcohol solution. Cover the beaker. Crystals will reform as the solution cools. Once crystallization has started, set the beaker in an ice bath to complete the recrystallization. Pour the contents of the beaker into a Buckner funnel and apply suction filtration.

11. Remove the crystals to dry paper to remove excess water. 12. Confirm you have acetylsalicylic acid by verifying a melting point of 135C.

Here are some examples of follow-up activities and questions which may be asked upon synthesizing aspirin: You can compare the actual and theoretical yield of acetylsalicylic acid based on the initial quantity of salicylic acid. Can you identify the limiting reactant in the synthesis? You can compare the quality of the synthesized aspirin with commercial aspirin and salicylic acid. Add one drop of 1% iron III chloride to separate test tubes containing a few crystals of each substance. Observe the color: Pure aspirin would show no color, while salicylic acid or traces of it in impure aspirin will show a purple color. Examine the aspirin crystals under a microscope. You should see white small-grained crystals with obvious repeating units. Can you identify the functional groups in salicylic acid? Can you predict how these groups affect the properties of the molecule and how the body reacts to it? Salicylic acid has an -OH group (an alcohol) and a carboxyl group -COOH (an organic acid). The acid portion of the molecule is one of the factors that causes irritation in the stomach. In addition to irritation caused by acidity, aspirin causes stomach irritation by inhibiting the production of prostaglandins, hormones responsible for slowing gastric acid production.

Here are some additional questions relating to aspirin synthesis: Can you explain what happened to the -OH group in the salicylic acid when the acetic acid was added? The -OH group from the salicylic acid combined with the acetic acid, producing water and an ester group. Can you see what effect this had on the end product? This reduced the strength of the acid and made the aspirin easier to ingest. Why do you think the aspirin was washed with distilled water? How did this affect the end product? How did this affect the actual product yield? Washing the aspirin removed most of the unreacted salicylic acid and acetic anhydride to yield a purer product. Some product was dissolved and lost in the washing process. Cold water was used to miminize dissolving the product. How did the synthesis use different temperatures to affect solubility of aspirin? At higher temperatures (warm water), molecules have more kinetic energy and collide with each other more often to interact with water molecules, increasing the solubility of the aspirin. The ice bath slowed the molecules, allowing them to more easily stick together and "fall out" of solution or crystallize.

Safety Considerations This procedure uses flammable substances and generates heat and toxic fumes. Please wear safety glasses and skin protection, work in a well-ventilated area, and be familiar with the safety data for your chemicals. Ferrofluid can stain skin and clothing. Keep it out of reach of children and pets. Contact your local poison control center if you suspect ingestion (risk of iron poisoning; carrier is kerosene). Materials household ammonia oleic acid (may be found in some pharmacies, craft, and health food stores) PCB etchant (ferric chloride solution) - from an electronics store or you can make your ferric chloride or ferrous chloride solution or you can use magnetite or magnetic hematite powder if you have either of those minerals handy (magnetic hematite is an inexpensive mineral used in jewelry) steel wool distilled water a magnet kerosene heat source 2 beakers or measuring cups a plastic syringe or medicine cup (something to measure 10 ml) filter papers or coffee filters

The magnetic particles in this ferrofluid consist of magnetite. If you aren't starting with magnetite, then the first step is to prepare it. This is done by reducing the ferric chloride (FeCl3) in PCB etchant to ferrous chloride (FeCl2). Ferric chloride is then reacted to produce magnetite. Commercial PCB etchant is usually 1.5M ferric chloride, to yield 5 grams of magnetite. If you are using a stock solution of ferric chloride, follow the procedure using a 1.5M solution. 1. Pour 10 ml of PCB etchant and 10 ml of distilled water in a glass cup. 2. Add a piece of steel wool to the solution. Mix the liquid until you get a color change. The solution should become bright green (green is the FeCl2). 3. Filter the liquid through filter paper or a coffee filter. Keep the liquid; discard the filter. 4. Precipitate the magnetite out of the solution. Add 20 ml of PCB etchant (FeCl3) to the green solution (FeCl2). If you are using stock solutions of ferric and ferrous chloride, keep in mind FeCl3 and FeCl2 react in a 2:1 ratio. 5. Stir in 150 ml of ammonia. The magnetite, Fe3O4, will fall out of solution. This is the product you want to collect. The next step is to take the magnetite and suspend it in the carrier solution. The magnetic particles need to be coated with a surfactant so that they won't stick together when magnetized. Finally, the coated particles will be suspended in a carrier so the magnetic solution will flow like a liquid. Since you are going to be working with ammonia and kerosense, prepare the carrier in a well-ventilated area, outdoors or under a fume hood. 1. Heat the magnetite solution to just below boiling.

2. Stir in 5 ml oleic acid. Maintain the heat until the ammonia evaporates (approximately an hour). 3. Remove the mixture from heat and allow it to cool. The oleic acid reacts with ammonia to form ammonium oleate. Heat allows the oleate ion to enter solution, while the ammonia escapes as a gas (which is why you need ventilation). When the oleate ion binds to a magnetite particle it is reconverted to oleic acid. 4. Add 100 ml kerosene to the coated magnetite suspension. Stir the suspension until most of the black color has been transferred into the kerosene. Magnetite and oleic acid are insoluble in water, while oleic acid is soluble in kerosene. The coated particles will leave the aqueous solution in favor of the kerosene. If you make a substitution for the kerosene, you want a solvent with the same property: the ability to dissolve the oleic acid but not uncoated magnetite. 5. Decant and save the kerosene layer. Discard the water. The magnetite plus oleic acid plus kerosene is the ferrofluid.

Castor oil is used as a source of vegetable oils which, on reaction with warm concentrated alkali, form soaps. The vegetable oils in castor oil also contain hydroxy-groups (OH) which will react readily with concentrated sulfuric acid, forming a long chain molecule with an ionic sulfonate group on the end. Such molecules behave as detergents. Only small quantities of reagents are required, reducing the risks associated with the use of such hazardous reagents. Read our standard health & safety guidance

Lesson organisation
These two class experiments are suitable for reliable students, able to handle concentrated acids and alkalis responsibly, safely and with sufficient skill. The experiments will take about 45 minutes.

Apparatus and chemicals

Each working group will need: Eye protection: goggles (Safety spectacles are NOT suitable) Test-tubes, 4 Boiling tubes, 3 (see note 1) Test-tube rack Test-tube holder Cork, to fit test tube Dropping pipette Measuring cylinders (10 cm3), 2 Beakers (100 cm3), 2 Beaker (250 cm3) Glass rod Spatula Bunsen burner, Tripod and gauze Heat resistant mat Access to Boiling water from an electric kettle (see note 4) Ice-bath (optional) (see note 4) Filter flask, funnel, filter papers, and pump (see note 5) Castor oil, about 5 cm3 (see note 2) Ethanol (IDA, Industrial Denatured Alcohol) (Highly flammable, Harmful), 5 cm3 Sodium hydroxide solution, 5 mol dm-3 (Corrosive), 10 cm3 Sodium chloride (Low hazard), 10 g Concentrated sulfuric acid (Corrosive), 2 cm3 (see note 1) Purified water (distilled or deionised)

Technical notes
Ethanol (IDA, Industrial Denatured Alcohol) (Highly flammable, Harmful) Refer to CLEAPSS Hazcard 40A Sodium hydroxide solution (Corrosive) Refer to CLEAPSS Hazcard 91 and Recipe Card 65 Sodium chloride (Low hazard) Concentrated sulfuric acid (Corrosive) Refer to CLEAPSS Hazcard 98A 1 A large (150 x 25 mm) test-tube 2 Castor oil is the best oil for making soap in the school laboratory, but reasonable results can be obtained from olive oil and rape-seed oil. For making detergent by sulfonation, the hydroxy-group on the carbon chain is essential, and castor oil is necessary. 3 At least two electric kettles, strategically situated around the laboratory, will be needed to allow students to fill their water-baths (250 cm3 beakers or larger, or a small metal waterbath). These should be pre-heated to boiling at the start of the lesson so that a rapid re-heat is possible when students have to fill their water baths. It may be safer for students to take the electric kettles to their working places than to carry beakers of boiling water around the laboratory. 4 An ice-bath will help to speed up the precipitation of the soap produced. Again, two or more placed around the laboratory will probably be necessary. 5 The solid soap needs to be filtered off using a pump. Four water-pumps set up around the laboratory, with filter flasks (100 cm3) and either small Buchner or Hirsch funnels, will allow the class to filter their products efficiently. Filter papers should be available to size for each funnel. If water pumps are not available, other types of suction pump can be used.

Procedure

HEALTH & SAFETY: Wear goggles at all times throughout these experiments. You are using 5 mol dm-3 sodium hydroxide and, in the second part, concentrated sulphuric acid, both very corrosive liquids. If you spill either of these on the skin, wash off at once in the sink with plenty of running water. Similarly, quickly mop up any spills on the bench with a damp cloth and then rinse it thoroughly. Making soap a Place about 2 cm3 of castor oil in a 100 cm3 beaker using a dropping pipette, followed by 5 cm3 of ethanol. Stir with a glass rod to mix. b Add 10 cm3 of sodium hydroxide solution.. c Prepare a waterbath containing near-boiling water from an electric kettle so that you can safely lower the small beaker into it without spillage. A 250 cm3 beaker may be used as the waterbath. Do not use too much water, as the small beaker needs to be supported without risk of the water coming over the top. d Stir the mixture in the beaker with a glass rod for 5 minutes. If the water bath cools too much, you may need to renew with fresh boiling water. e Meanwhile in a boiling tube make a saturated solution of sodium chloride by shaking solid sodium chloride with 10 cm3 of water until no more will dissolve. Allow to settle. f After 5 minutes, add the saturated sodium chloride solution to the small beaker and stir. g Cool the mixture by changing to a cold water bath (or an ice bath if available). h Soft, white lumps of the soap will gradually form in the mixture. Leave for a few minutes to improve the yield. During this time the soap may rise to the surface and form a soft crust on cooling. i Using a pump, with a fresh filter paper damped down in the funnel, filter off the soap, breaking up the crust with a glass rod if necessary j Allow the soap to drain on a paper towel do not touch it with your fingers, as it may still contain sodium hydroxide. k Use a spatula to transfer a little of the soap to a test-tube, and add a few cm3 of purified water. Shake well! What happens? You have made a soap! Making a detergent a Add 4 cm3 of concentrated sulfuric acid to a boiling tube (your teacher may do this for you). b Using the dropping pipette, add 2 cm3 of castor oil very carefully to the boiling tube, swirling gently to mix. Does the test-tube become hot? c Add 10 cm3 of cold water to a boiling tube (about 3 - 4 cm depth), then carefully pour the reaction mixture from the first tube into the water. The liquid may be very slow-flowing (viscous) and contain concentrated acid, so be careful and take your time over this. d Stir to remove the excess of acid into the water and then decant (pour off) the water down the sink, leaving a pinkish-grey sludge. Wash the product again with two more portions of water. e Use a spatula to transfer a small quantity of the product to a clean test-tube. Add a few cm3 of water, and shake well. What happens? You have made a detergent!

Teaching notes

As these experiments involve the use of two very corrosive reagents, the reliability of the class in terms of both manipulative skills and behaviour is important. However, the quantities actually used are small, and risks can be minimised by advance preparation of reaction vessels with these reagents already measured out. If the teacher is uncertain about the reliability of the class, the experiments may be performed as demonstrations, but should not be scaled up. The use of a flexicam or similar to project onto a screen may help with visibility of a demonstration. Castor oil is an example of a triglyceride, in which three long hydrocarbon chains (typically around 16 carbon atoms in length) are all linked through oxygen atoms to one 3-carbon chain at the end. The latter is derived from glycerol hence the name triglyceride. A simple triglyceride structure looks like this:

For castor oil, the carbon chains are each 18 carbon atoms long. However, part way along each chain there is carbon-carbon double bond, with a hydroxygroup nearby. The double bond means that the chains do not pack well together, so this triglyceride is a liquid rather than a solid a vegetable oil rather than a fat. When boiled with sodium hydroxide, the glycerol end group is split off, and the long chains pair up with the sodium ions to form sodium ricinoleate, which is the soap. The three hydroxy-groups on the carbon chains react with concentrated sulfuric acid to form a sulfonic acid group, OSO2OH. These groups are watersoluble, but the hydrocarbon chains are not. It is this conflicting pair of properties that makes such substances good detergents, with the hydrocarbon chains mixing with greasy dirt and the sulfonic acid groups dissolving in water. The detergent formed from castor oil is called Turkey Red oil. This was the first synthetic detergent to be made, and is still used in some bath oils.