Lab+Manual+2014 Cbe 2207

The University of Western Ontario
Faculty of Engineering Science DEPARTMENT OF CHEMICAL AND BIOCHEMICAL ENGINEERING
INDUSTRIAL ORGANIC CHEMISTRY II
CBE2207 LABORATORY MANUAL
Prepared by P. Charpentier, E. R. Gillies and J. Herrera 8th Edition
CBE2207 Laboratory Manual
Edited by J. Herrera, 2014
TABLE OF CONTENTS
1 1.1 1.2 1.3 1.4 1.5 1.6 INTRODUCTION.................................................................................... 3 CONVERSION FACTORS .................................................................... 3 COMMON ITEMS OF GLASSWARE AND APPARATUS ...................... 5 A NOTE TO THE STUDENT................................................................... 9 SAFETY GUIDELINES........................................................................... 9 GENERAL HOUSEKEEPING AND LABORATORY WORK ................. 14 GUIDELINES FOR PREPARATION OF LABORATORY REPORTS.... 16
LABORATORY 1 - AN ATTEMPT AT THE SYNTHESIS OF A SECONDARY ALCOHOL: THE UNCERTAIN REDUCTION OF A KETONE .......................22 LABORATORY 2- REACTIONS OF ALCOHOLS: SYNTHESIS, PURIFICATION AND STRUCTURE ELUCIDATION OF AN ORGANOLEPTIC MOLECULE......27 LABORATORY 3 - THE ALDOL CONDENSATION - SYNTHESIS OF BENZYL AND DIBENZYLACETONES...............................................................32 LABORATORY 4- ALDOL CONDENSATION, BENZYNE FORMATION AND THE DIELS-ALDER REACTION : A MULTI-STEP REACTION SEQUENCE39 APPENDIX ..47
INTRODUCTION 1.1 CONVERSION FACTORS FOR SOME COMMONLY USED UNITS OF MEASUREMENT
Acceleration Area ft/s2 3.281X100 g (accel. of gravity) 1.020X10-1 m2 ft2 1.076X101 inch2 1.550X103 2 yard 1.197X100 kg/m2 g/cm 1.000X10-3 lb/gallon 8.345X10-3 lb/ft3 6.242X10-2 J btu 9.484X10-1 calorie 2.387X10-1 (thermochemical) erg 1.000X107 ft-lb 7.375X10-1 kW-hr 2.778X107 N dyne 1.000X105 pound force 2.248X10-1 J/kg*K btu/lb*oF 2.390X10-4 2.390X10-4 cal/g*oC m 1.000X1010 in 3.937X101 ft 3.281X100 micron 1.000X106 mile 6.213X10-4 yard 1.094X100 kg ounce 3.527X102 lb 2.205X100 W btu/hr 3.414X100 btu/sec 9.484X10-4 cal/sec 2.390X10-1 ft-lb/sec 7.376X10-1 horsepower 1.341X10-1 (550 ft*lb/sec) Pa atm 9.869X10-6 (76cm Hg) bar 1.000X10-5 cm of Hg 7.506X10-3 2 dyne/cm 1.000X101 in of Hg 2.961X10-4 2 kg force/cm 1.020X10-5 m/s2 3.048X10-1 9.807X100 9.290X10-2 6.452X10-4 8.361X10-1 1.000X103 1.198X102 1.602X101 1.054X103 4.184X100 1.000X10-7 1.356X100 3.600X10-6 1.000X10-5 4.448X100 4.184X103 4.184X103 1.000X10-10 2.540X10-2 3.048X10-1 1.000X10-6 1.609X103 9.144X10-1 2.835X10-1 4.536X10-1 2.929X10-1 1.054X101 4.184X100 1.356X100 7.457X102 1.013X105 1.000X105 1.333X103 1.000X10-1 3.337X103 9.807X104
Density
Energy (includes work)
Force Heat capacity (includes entropy) Length
Mass Power
Pressure
CONVERSION FACTORS FOR SOME COMMONLY USED UNITS OF MEASUREMENT CONTD lb/in2 (psi) torr (mm of Hg) ft3 in3 gallon (U.S.) L ounce (U.S.) 1.450X10-4 7.501X10-3 3.531X101 6.102X10-1 2.642X102 1.000X103 3.381X104 6.895X103 1.332X102 2.832X102 1.639X10-5 3.785X10-3 1.000X10-3 2.957X10-5
Volume (includes capacity)
m3
psig = pounds per square inch gauge psia = ponds per square inch absolute
1.2 COMMON ITEMS OF GLASSWARE AND APPARATUS

Most of the apparatus used will be familiar to you, but the following notes may help you in identifying and using specific pieces. The ERLENMEYER or CONICAL FLASK is used for handling solutions, and for titrations. It is designed with a narrow neck to minimize loss of solution through splashing or evaporation. The FILTER or BUCHNER FLASK is used in conjunction with the Buchner funnel for vacuum-assisted filtration. It is heavy-walled to give pressure resistance; for this reason, a Buchner funnel should never be used to heat a solution. Attach it to the vacuum line or water aspirator with heavy-wall rubber tubing. For any operation involving vacuum, always use heavy walled rubber tubing never use soft tubes like Tygon. If a water aspirator is used, an empty flask should come between the filter and the pump to avoid suck-back if the water pressure falls. The Buchner assembly is top-heavy and should be supported when in operation. The BUCHNER FUNNEL is used for filtration. It fits through a rubber bung or cone into the Buchner flask. To use, assemble the flask and funnel, place a filter-paper flat across the perforated porcelain plate, and wet the paper with the solvent being used (usually distilled water). Turn on the vacuum and make sure the paper is correctly seated in the funnel; the filter paper should be cut slightly smaller than the funnel, but make sure it covers all the holes. Stir the suspension to be filtered and quickly pour it onto the center of the paper, using a glass rod to guide it. Filtration will go more quickly if you keep liquid in the funnel. If all of the liquid is filtered off, the residual solid will pack down into a solid cake, slowing filtration. To empty the funnel after the solid cake has
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been washed and sucked as dry as possible, loosen the cake around the edge with a spatula, carefully invert the funnel onto a watch-glass and tap it gently. The EVAPORATING DISH is used to provide a large surface area to speed up evaporation. It can be heated on the steam-bath but should never be heated with a direct flame. The BURETTE accurately measures volumes to 0.1ml accuracy. When titrating, always fill the burette to the zero milliliter marking. Your eye should be level with the bottom of the meniscus in order to take a proper reading of the liquid level.
The TRANSFER PIPETTE accurately delivers one volume (e.g. 5 or10 or25ml).
The PASTEUR or DROPPING PIPETTE is for transferring a few drops.
The SEPARATORY FUNNEL is used for the separation of liquids with differing densities and for washing. The funnel should have a properly working stopcock and a stopper of the correct size. The solution to be separated is poured into the funnel with the stopcock closed and the funnel stoppered. It is then shaken vigorously with two hands; one holding the bottom of the flask between first and second fingers and the other on the stopper so it does not fall out. This maneuver is performed with the flask upside down and the stem directed away from people standing by in case of any splashing. The pressure which may build up inside the flask is released by holding the funnel upside down and opening the stopcock. Next, the funnel is placed in a proper size support ring.
Enough time is given for the solutions to separate into two distinct layers after which the bottom layer can be removed and the procedure repeated until necessary. (It is assumed that one knows which layer is to be kept!) GAS CYLINDERS with the safety cap off need to be securely strapped to the wall or a desk in order to prevent them from falling. There is considerable pressure in these cylinders and care must be taken to control the flow of gases from them. The main cylinder or tank valve should be closed when not in operation. This valve measures the pressure present in the tank (i.e. how much gas is left in the tank). The control valve, usually the second one, gives the pressure reading present in the line connected to the tank. This is usually a backwards valve, meaning that to reduce pressure it needs to be turned in the counterclockwise direction. A BUBBLER is usually inserted in the gas line between the cylinder and the connection to the apparatus to be filled with the gas. This is advantageous for two reasons: 1) the flow of gas is actually seen as it bubbles through the oil in the bubbler and 2) this is an outlet for the gas if the pressure becomes too high so that it exits via the bubbler rather than blowing the glassware or connecting tubes. When working with gas cylinders it is very important that you know and understand how everything is connected and what function each piece of equipment has. There are many different shapes of
CONDENSERS available for use. All of them serve the same purpose in conjunction with distillation apparatus. Their purpose is to cool the vapors inside the condenser usually with water as coolant. The condenser is placed before and is tilted toward the receiving flasks. The glass is blown so that the cooling liquid is separated from the vapors which are to be condensed. To have good cooling cold water should flow through the condenser at
all times. This is achieved by connecting the water inlet to the bottom end of the condenser and the outlet to the top so the water flows from the bottom up the condenser and out the top.
ERROR DATA Volumetric flasks Volume (ml) 10 25 50 100 Error 0.04 0.06 0.10 0.16 Volumetric pipettes Volume (ml) 1 2 5 10 Error 0.006 0.006 0.01 0.01
1.3
A NOTE TO THE STUDENT
The objective of this laboratory is to introduce the student to basic organic reactions and analytical instrumentation, as used in industrial operations and processes. By performing the prescribed experiments the student will become familiar with a typical organic chemical laboratory and the operation of typical analytical instruments. She/he will also obtain a feeling and routine for generation of analytical results and the technical capabilities of various instruments. The generated knowledge will enable the student to better understand the basic chemical principles and control of industrial processes, which is essential for proper operation of individual units in the plant and the management of processes for optimum performance and product quality, and environmental effects. Whether in management, processing, design or laboratory, an engineer should have good knowledge and understanding of the chemistry, measurements and instrumentation being used in the plant. The important decisions and modifications that an engineer must make in industry will be based on the results obtained from the laboratory. A good understanding of possible errors in procedures and instruments is also required and particularly a good understanding of variables that could affect a result. A lack of this understanding very often results in erroneous judgments that can affect considerably both production and quality of the final product.
1.4
SAFETY GUIDELINES
Although this laboratory does not involve extensive manipulation of hazardous chemicals, some of the materials that will be used are often flammable and volatile as well as toxic. Each student must therefore follow strictly all safety procedures and not perform any unauthorized manipulations with these chemicals prior to consultation with the instructor or the demonstrator. Although most of laboratory safety is common sense, this is a general guideline, and therefore may be incomplete. If you are ever unsure about safety, please ask.
Remember: ACCIDENTS ARE CAUSED AND CAN BE PREVENTED! VIOLATION OF ANY OF THE REGULATIONS DESCRIBED BELOW WILL MEAN THAT YOU WILL NOT BE PERMITTED TO WORK IN THE LABORATORY AND THEREFORE RECEIVE A MARK OF ZERO FOR THE LABORATORY REPORT. 1.4.1 Laboratory Apparel Rules -Safety goggles are required in the laboratory AT ALL TIMES! Eyes are extremely sensitive and delicate to minimum amount of most chemicals. You are responsible to provide your own goggles. -Contact lenses should not be worn in the laboratory. Goggles protect the eyes from spill hazards, but do nothing to protect them from fumes, which can easily dry or dissolve contact lenses and may result in the necessity of eye surgery for their removal. Moreover contact lenses can also absorb chemicals from the air (especially those breathable lenses), concentrate and hold them against the eye, and/or prevent proper flushing of the eye should a chemical be splashed into the eyes. -Laboratory coats must be worn at all times inside the laboratory. If you need to step outside the laboratory for a while, your coat must be removed and left behind in the laboratory. -Sandals, open-toed shoes and high heels are not permitted in the lab. Shorts or skirts cut above the knee are not permitted either. If a spill occurs, your clothing will protect you from direct exposure. Open toe and shorts or skirts are prohibited to protect your feet from splashes and spills. The restriction on high heels is for balance. If you must wear some of this gear for a later appointment or situation you should consider carrying with you a pair of sneakers and sweat pants to wear during the lab.
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- Careful consideration should be given before wearing any jewelry into the lab. Some chemicals can get beneath a ring, watch or some other form of jewelry, this prevent them from evaporating and hold them against the skin increase the risk of injury. If you decide to wear jewelry to the laboratory be particularly mindful of itching, burning or any other irritation under or around your jewelry. Some gems and precious metals might be easily damaged by the laboratory environment (for instance silver and opal jewelry). If you decide to ear jewelry you do it at your own risk. - Never wear clothes that hang, such as loose sleeves. Ties and scarves must be tucked inside your laboratory coat - A good suggestion is to wear only very old clothes to the laboratory. Some students might consider bringing lab-suitable clothing with them in a gym bag and change right before and after lab. If you have a very tight schedule (must be documented) and decide to change into suitable clothes before the lab we can arrange for 10 minutes for you to change clothes. - Long hair is to be constrained at all times. 1.4.2 Safety rules - Eating and drinking in the laboratory is strictly forbidden. - No radios, tape players, CD players, iPods or any other devices of this type will be permitted in the laboratory at any time. -Use of cell phones is not permitted in the laboratory. -Identify all of the laboratory safety equipment, and keep their location in
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your mind at all times. We might ask you to close your eyes any time during a lab and point to such safety equipment as the fire extinguisher, the emergency eyewash stations, the safety shower, the nearest exit etc. This exercise might save you from a big injury. For instance if you were to splash a chemical in your eyes, you'd better be able to find that eyewash station without your eyes well before permanent damage can occur (which can be seconds depending on the nature of the chemical). - Develop good working habits. Keep your area clean and tidy. Your working area reflects your working habits and also the quality of your work and results. A clean and tidy environment decreases the probability of a laboratory accident. - ALL FLASKS, BEAKERS AND CONTAINERS WITH ANY CHEMICALS OR SYNTHESIS PRODUCTS THAT YOU LEAVE BEIND AFTER A LABORATORY SESSION MUST BE CLEARLY LABELED WITH THE NAME OF THE CHEMICAL, THE OWNER AND DATE! UNLABELED VIALS CONTAINING CHEMICALS WILLL BE DISCARDED.
1.4.3 Handling Chemicals and Equipment Students will work in groups of two or three and enough time will be provided to finish all the prescribed experiments. If any piece of equipment fails or does not function properly, students are required to report the problem immediately to the demonstrator or the instructor and are not allowed to attempt to fix the instrument on their own. 1. Do not taste chemicals. 2. Do not pipet any chemicals by mouth. Use rubber bulb (propipette). 3. Do not pour liquids that are flammable or that do not mix with water into sinks. Pour them into the provided and labeled containers.
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4. Do not mix incompatible chemicals. If you do not know their compatibility ask. 5. Do not heat flammable liquids with an open flame. 6. Operations involving volatile or toxic materials are to be conducted in the fume hood. 7. Dispose of solid wastes in garbage pails. Do not use the sinks. 8. Clean up spills (solid or liquid) at once. 9. Return chipped or broken glassware to the laboratory TAs or technician. 10. Be sure the apparatus is placed properly. Do not move instruments without proper consultation with the laboratory TAs or technician. 11. When heating a test tube make sure that it is not pointing towards yourself or other people in the vicinity, so no damage will result if the contents suddenly dump out. 12. Never apply force to any glass apparatus. Many serious cuts are caused by the sudden fracture of glass under strain from misuse. In particular, never use force in an attempt to push a thermometer or glass tube through a hole in a cork or rubber. 13. Never heat a tightly sealed flask even if it is empty-----it will explode. 14. Do not attempt to buttress a laboratory assembly with makeshift supports such as books, pencils and the like. Use several ring stands if necessary. Round
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bottom flasks cannot stand freely on the bench----use a special cork support or place the flask into a beaker. 15. Do not attempt to break up a solid in the bottom of a flask by punching the solid with a glass stirring rod. The rod may either fracture in your hand or puncture the bottom of the flask. 16. Avoid shortcuts! If you have an idea for an improvement talk it over with your demonstrator; if no objections, try it; if it is successful, tell us about it, you will get extra marks. 17. There are certain necessary precautions associated with particular chemicals or experiments. Your demonstrator will point these out when required. 18. If you are not familiar with a piece of apparatus or an experimental procedure ask for help. Dont just try to muddle through without knowing what you are doing. 19. Chemical waste should be disposed of in the labeled waste containers provided. Halogenated chemicals must be disposed of separately from nonhalogenated chemicals. Nothing should go down the drain! Dispose of all chemicals in the bottles marked for the specific lab.
1.5
GENERAL HOUSEKEEPING AND LABORATORY WORK
ALL STUDENTS MUST HAVE A LABORATORY BOOK IN WHICH TO RECORD ALL LAB DATA DURING THE LABORATORY PERIOD. The lab book used in
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industry is a legal document. Loose papers for recording of data or comments are not allowed and will be removed from the lab. Each student must read the instructions for the particular experiment PRIOR to coming to the laboratory. He/she should understand the whole procedure and what must be done in the experiment. This knowledge will be checked periodically by the instructor or the demonstrator and it will be evaluated. Equations for all reactions should be written out in your lab notebook before coming to the laboratory. Also, any calculations required (e.g. theoretical yield, preparation of solutions) should be written in full in your laboratory notebook before coming to the laboratory. Record all observations in the lab book including any color changes, unexpected events, smells, etc. The notebook will be marked from time to time during the term. Plan your working time in the laboratory! By doing this your laboratory will be a useful and pleasant experience rather than a frustrating one. ALL LABORATORY EXPERIMENTS MUST BE DONE DURING THE ALLOCATED TIME PERIOD. THERE WILL BE NO EXTENSION OF THE LAB AND NO ADDITIONAL TIME PERIOD AVAILABLE FOR THE EXPERIMENTS, except under special circumstances such as illness verified by a doctors note.
1. Keep benches clean and orderly and sinks clean. You must leave your portion of the bench and all glassware and equipment clean at the end of the lab period. 2. Aisles and floors are to be kept free of obstructions. Keep cupboard doors and drawers closed when not in use. 3. Hang coats on the rack. No coats are permitted on tables or benches. 4. Laboratory doors MUST be unlocked during lab period.
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1.6
GUIDELINES FOR PREPARATION OF LABORATORY REPORTS
Laboratory reports should be written as though they were short technical reports. Thus Tables and Figures should always be referred to in the prose text of the report, i.e. they should not appear on their own. The report should be written in the past tense, since it is a description and a correlation of past observations. The present tense may be used in referring to laws of nature, properties of materials etc. which are independent of time. Thus, for instance, in a particular experiment The ambient temperature equaled 22 C; on the other hand, The ambient temperature equals about 20 C .
TITLE PAGE Title of experiment Name of person writing the report Name of experimenters Date when the experiment was performed All Formal reports must be TYPED ABSTRACT The Abstract should summarize the entire report. It should state clearly and briefly the objectives, methods, results and conclusions of the lab. Objective: Method: Results: State the objective or purpose of the lab In one or two sentences, summarize the methods, including scientific and common names of chemicals and techniques used. Summarize what was found in the study
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Conclusions:
State the significance of the results in relation to the objective.
INTRODUCTION The Introduction should describe the scope and the purpose of the lab and include any background information necessary to understand the experiment. State the general problem. Give a brief statement of why the general topic is relevant and important. Define any specialized terms or concepts (e.g. the concept of distillation) likely to be encountered later in the lab report. Supply sufficient background (historical and theoretical) information to allow the reader to evaluate and understand the results of the study without needing to refer to other publications. The introduction to each experiment in this manual can be used as a guide but must not be copied and cannot be used as the backbone of the introduction in the report. State the specific objective or purpose of the lab and the approach to be used. The purpose states what you are investigating and why; how you perform the investigation should be described later in the Methods and Materials.
MATERIALS AND METHODS The Methods section should describe what was done and how it was done. It should be written in the past tense with active voice, and in paragraph form. The Materials and Methods section should provide only enough detail to permit a competent worker to evaluate the validity of the experiment and to repeat it, if necessary. It should not be simply a recipe of all the steps involved. State the names (IUPAC if possible) of the chemicals used, the instruments, equipment and pattern of
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replication. Describe any unusual numerical calculations and state the statistical technique used to analyze the data. RESULTS The Results section should present the data collected in a summarized form and describe only the key features of these data, emphasizing trends or patterns that are relevant to the hypotheses being tested. Interpretation of the data is reserved for the discussion section. Do not present the same data in both a table and figure i.e. place table of raw data in an appendix and place figure in the results section. Titles of tables and figures should contain enough information to understand the contents without reference to the text. The number and title are placed at the top of a table, and at the bottom of figure. Guide the reader through your figure (s) and table (s) in a logical and systematic manner, pointing out trends and differences that pertain to the objective (s) of the report. Simply state what you found in your study, without inference or reference to "expected" results. DISCUSSION The Discussion section should provide an explanation and interpretation of your results and indicate the significance of the results to the hypothesis being tested. Results of previous studies on the same topic should be compared with yours, with an explanation of why your results are different from previous studies, if necessary. State how and why your results either support or do not support the objectives and hypotheses. REMEMBER: results are results, they are never wrong simply by being different from either your expectations or from other investigations.
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CONCLUSIONS Draw conclusions about the hypotheses (objectives) of your study, based on all data available in the current studies. APPENDIX Includes all raw experimental data, e.g. time vs. temperature data points, sample calculations, and any other information or data used for the experiment and calculations. REFERENCES The Reference section should be a list of all books, journals, and other materials cited in the body of the paper. Please notice that all reference sources must be peer reviewed and scientifically validated. Wikipedia or other non-refereed materials available on the World Wide Web are not acceptable as reference sources in a technical report. The surname of the author(s) and the year of publication should be inserted in the text at an appropriate place: "Smith (1991) compared..." or "... have been recently compared (Smith, 1991)." If the reference has more than 2 authors, include only the surname of the first author, followed by "et al." "Smith et al. (1991) compared..." or "... have been recently compared (Smith et al., 1991)."
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When listing more than one citation at a given point in the text, list them in chronologically by first author, but for 2 (or more) papers, published in the same year, list these alphabetically: "(Jones, 1978; Black et al., 1989; Smith, 1989; Jones and Smith, 1991)" If an author or group of authors has published more than one article in a given year, you can distinguish between these articles by placing a letter postscript after the publication year: "(Black and Smith, 1990a; Black and Smith, 1990b)" List all references in alphabetical order, sorted by the author(s)' last name(s). In cases where the same author or group of authors has/have published multiple papers that you have cited, then arrange these references in chronological order.. All authors must be given in the reference list - the abbreviation "et al." Is used only in the text. The following are examples of the punctuation, style and abbreviations that may be used for references (note: the headings given here are not to be included in your reference list). Journal article: Jones, R.S., E.J. Gutherz, W.R. Nelson and G.C. Matlock. 1989. Burrow utilization by yellowedge grouper, Epinephelusflavolimbatus, in the northwestern Gulf of Mexico. Env. Biol. Fish. 26: 277-284. Chapter in a Book: Gross, M.T. 1984. Sunfish, Salmon and evolution of alternative reproductive strategies and tactics in fishes. Pp. 55-57. In: G.W. Potts and R.J. Wooten (eds.) Fish reproduction: strategies and tactics. Academic Press, London.
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Book: Siegel, S. 1956. Nonparametric statistics for the behavioral sciences. McGraw-Hill, New York. pp. 312.
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LABORATORY 1 AN ATTEMPT AT THE SYNTHESIS OF A SECONDARY ALCOHOL: THE UNCERTAIN REDUCTION OF A KETONE
(2 lab periods) ABSTRACT During this laboratory session you will attempt to reduce a ketone. Some groups will be using sodium borohydride and some sodium chloride. Sodium chloride is not a reducing agent so the ketone will not transform into the alcohol. However, even if sodium borohydride is used the reaction should be carefully carried out to obtain the alcohol. You will find out whether your synthesis was successful using IR spectroscopy. INTRODUCTION As you have learned in class, aldehydes and ketones can be converted to alcohols by a process known as reduction. In this case the reduction process involves the creation of a new set of C-H and O-H bonds.
O CH3 CH2 C H O CH3 C CH3 CH3 CH2 CH2 OH OH CH3 CH CH3 (2) (1)
There are several reagents available for this reaction. For example, lithium aluminum hydride (LiAlH4) is a commonly used reducing agent; however, it is extremely reactive with water and rapidly decomposes in air, making it difficult to handle. Sodium borohydride (NaBH4) is also a commonly used reducing agent and is easier to handle safely. The reaction of sodium borohydride with water is sufficiently slow at room temperature to allow its use as a reducing agent in an aqueous medium. However, many organic compounds are insoluble in water, so it is frequently necessary to use ethanol as a solvent.
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Sodium borohydride serves as a source of H- (hydride, a very powerful nucleophile), which attacks the electrophilic carbon of the carbonyl group in the ketone. However, sodium borohydride does react to some extent with the solvent ethanol and it is therefore necessary to use excess sodium borohydride to overcome this effect so that the reducing agent does not become the limiting factor in this experiment. The product benzhydrol is soluble in the ethanol-water mixture which was used for the reaction but is insoluble in water. Thus, if the reaction mixture is diluted with cold water the product precipitates. However, if the reaction was unsuccessful unreacted benzophenone will precipitate as well. Sodium borate remains in solution since it is a salt and is very soluble in water. Following the precipitation of your reaction product, you will purify it further by recrystallization (Appendix 1A). In order to evaluate the success of your experiment, you will use infrared spectroscopy. The most important aspect to understand is that the bonds in the molecules stretch and bend and that this stretching and bending is linked to the absorption of infrared light. The wavelength of the infrared light absorbed in these processes depends on the specific atoms and bonds (ie. single, double, or triple) involved. The absorbed wavelengths for a given sample can be determined using an instrument called an infrared spectrometer and plotted to provide a spectrum. As different functional groups absorb light of characteristic wavelengths, leading to characteristic peaks in the spectrum, this technique can be very useful in determining which functional groups are present in a molecule. This aids in verifying the identity of the compound. More details on infrared spectroscopy can be found in the text (Wade Ch. 12-1 12-12) and your lecture notes. MATERIALS 125mL Erlenmeyer flask Ceramic Boiling chips 50mL, 500mL beakers
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Buchner funnel and filtering flask Whatman #4 Filter paper Disposable Pasteur pipette 6.0 g Benzophenone 50mL 96% EtOH (ethanol) 0.60 g of Reactant A or B (these will be either sodium borohydride or sodium chloride but you will not know the exact identity of the reactant you are using).
5mL 6N NaOH Hot Plate/ Magnetic stirrer FT-IR Spectrophotometer
METHODS Lab One 1. In a 125 ml Erlenmeyer flask dissolve 6.0 g of benzophenone in 50 ml of ethanol. You will need to use a magnetic bar and stir plate. 2. In a 50 ml beaker dissolve 0.6 g of Reactant A or B in 25 drops of distilled water, and using a Pasteur pipette add this solution drop-wise, with stirring, to the solution of benzophenone. Continue stirring the reaction for 15 minutes. 3. Using a 10ml graduated pipette add 4 ml of a 6N NaOH solution and a boiling chip to your flask, and boil the reaction mixture on a hot plate for 10 minutes. 4. Being cautious, pour the reaction mixture into 400 ml of cold water and ice and stir with a glass rod until the ice is all melted. Collect the resulting precipitate on filter paper using a Buchner funnel. 6. Wash the crude product with 100ml cold H2O, and let the product sit on the filter for 5 minutes to remove as much water from the crude product as possible. Using a metal spatula carefully transfer your product to a tared plastic weighing boat and place it in the dessicator until next lab period.
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Lab Two 1. Weigh your dried crude product and assuming a successful synthesis determine the percentage yield. 2. Weigh out 1.0g of your crude product and recrystallize it using an appropriate solvent (ask your TA which one to use) Do this recrystallization in a 250 ml Erlenmyer flask. Suspend your product in approximately 50 mL of solvent, heat it gently using a hot plate (do not boil) and swirl until complete dissolution. You will need to add more solvent (use 10 mL aliquots) until the solid is dissolved. Be patient. After cooling, first at room temperature and then on ice, filter your recrystallized product on a Buchner funnel, air dry the crystals for 10 minutes on the filter paper, weigh the product to calculate yield and do a melting point determination. 3. Obtain an infrared spectrum of your purified final product (benzhydrol if the synthesis was successful), compare it with the one of bezophenone provided.
PRE LAB QUESTIONS Week 1 1. Draw Lewis structures for benzophenone, benzhydrol, and sodium borohydride. 2. Draw the reaction mechanism (arrow diagram) for the reduction benzophenone to benzohydrol. 3. Calculate the theoretical yield of benzohydrol assuming 100% reduction of benzophenone. You should include your calculations.
PRE LAB QUESTIONS Week 2
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1. What do you expect to be the main change in the infrared spectrum as you go from the benzophenone starting material to the benzhydrol product? 2. What was the purpose of using 6N NaOH during the benzophenone reduction experiment last week? SUMMARY OF SPECIFIC REQUIREMENTS FOR THE REPORT 1. Assuming a successful synthesis, show calculations of the % yield for the crude and recrystallized product. 2. Compare the infrared spectra of the starting material benzophenone and that one of your product. Which peaks are common and which are different? Using the data in the text book (Wade sec 12-1 12-12) assign the major peaks that correspond to the functional groups in benzophenone and benzhydrol. Does the spectrum indicate that your reaction was successful or unsuccessful? 3. Establish the identity of Reactants A and B. 4. Propose and discuss (using a minimum of 200 words) another way, besides any form of spectroscopy, to evaluate whether your reaction was successful.
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LABORATORY 2 REACTIONS OF ALCOHOLS: SYNTHESIS, PURIFICATION AND STRUCTURE ELUCIDATION OF AN ORGANOLEPTIC MOLECULE.
( 2 lab periods ) ABSTRACT During this laboratory session you will run a common reaction of alcohols to synthesize a molecule that is used in the food and flavours industry. You will elucidate the structure of the molecule using IR and NMR. INTRODUCTION Organoleptic substances are commonly used in the industry to fabricate consumer products. In general an organoleptic material is defined as a substance that has sensory properties, such as odour, colour, taste or feel. Specifically in the food industry organoleptic refers to substances used to improve or impart odours and flavours to materials, making the product more appealing to consumers. While a wide range of organoleptic substances are used in the flavours and fragrances industry (for instance, orange extract or lavender oil); it is more desirable to use single molecules with strong organoleptic properties rather than the very expensive and complex mixture obtained as oil extract from a natural product. During this laboratory you will synthesize a molecule with high organoleptic properties. The procedure in based on an equilibrium reaction involving a carboxylic acid and an alcohol. Since this is an equilibrium reaction, an excess of reactants is required to drive the reaction to completion. In our case the carboxylic acid will be used in excess since it is less expensive than the alcohols we are using and more easily removed from the reaction mixture. In the isolation procedure, the excess acetic acid and the unreacted alcohol is removed by extraction with water since the product has a low water solubility. Any remaining acid is removed by extraction with
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aqueous sodium bicarbonate (NaHCO3). Na2SO4.
The resulting product is dried over
MATERIALS AND METHODS An alcohol (you will not know the structure of the alcohol you are using). Either one of these acids: Glacial Acetic Acid Formic Acid H2SO4 (conc.) Sodium Sulfate (anhydrous) 5% aqueous Sodium Bicarbonate Saturated NaCL solution 100 ml Round bottom boiling flask Reflux condenser Short path Distillation head with thermometer and condenser Boiling stones Heating mantle 250 ml separatory funnel Glass funnel and filter paper Sample vial (CAUTION : highly corrosive )
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Synthesis and purification steps 1. Place 15 ml of the alcohol in a 100 ml RB flask and add 20 ml of the carboxylic acid 2. Swirl to mix and carefully add 4 ml of conc. H2SO4. 3. Add a few boiling stones, attach a reflux condenser, start the cooling water, and reflux the mixture for 1 hour. Cool to room temperature. 4. Transfer the mixture to a separatory funnel and add 55 ml of cold water. Rinse the 100 ml RB flask with 10 ml of cold water and add it to the contents of the separatory funnel. Mix the two phases by inversion 20 30 times. If you shake the mixture too vigorously it will form an unbreakable emulsion. 5. Allow the phases to separate and drain off the lower aqueous layer. 6. Add 25 ml of 5% NaHCO3 to the separatory funnel. Do this carefully as there will be gas evolved. Mix by inversion, drain, and check the pH of the aqueous phase with litmus paper. If it is not basic you will have to repeat the 5% NaHCO3 washing step. 7. A final extraction with 20 ml of saturated NaCl will remove residual water from the product. 8. Fold a piece of filter paper, put it in a glass funnel, and add 1 g of anhydrous Sodium Sulfate ( Na2SO4 ) to the filter. Clean, dry, and weigh a 100 ml RB flask and filter your product into it. The Na2SO4 will complete the drying process. Weigh your product and then seal the flask with a stopper and some parafilm and label it clearly. Week 2 - Spectroscopic analysis of the product.
1. Obtain the infrared spectrum of your product. 2. Obtain the 1H-NMR of your product. (These will be provided). 3. Obtain the MS of your product. (These will be provided) 4. Using the spectroscopic information and the synthesis protocol used, elucidate the structure of your product. You must solve this structure before
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leaving the lab. Feel free to bring any reference materials you think will help you in this task.
PRE-LAB QUESTIONS Week 1 1. Provide an example of an organoleptic molecule used in the food insdutry 2. Which gas in evolving during step 6 of the synthesis and purification protocol? PRE-LAB Questions Week 2 1. What will be the position of the infrared O-H stretching band for carboxylic acid and the alcohol. Would you expect to see a difference between the two bands? 2. What are the typical MS fragmentation patterns of alcohols and acetic acid? How would those differentiate form the MS fragmentation pattern of your product? SUMMARY OF REQUIREMENTS FOR YOUR LAB REPORT 1. Show step by step how you elucidated the structure of the molecule you synthesized. These should include assignment of each 1H-NMR peak and main infrared bands. Indicate how the MS spectrum contributes to structure elucidation. 2. Clearly identify the reaction and mechanism involved in the synthesis procedure. 2. Calculate your yield. Suggest possible reasons why your yield might be less than 100%. 3. Sulphuric acid is also a strong oxidizing and dehydrating agent, what do you predict as by products of the reaction between the alcohol and sulphuric acid? Will
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all these by-products remain in liquid phase? Propose an analytical technique to identify these.
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LABORATORY 3 THE ALDOL CONDENSATION - SYNTHESIS OF BENZYL AND DIBENZYLACETONES

INTRODUCTION The Aldol condensation is perhaps one of the most important and versatile organic reactions that leads to the formation of a new carbon-carbon bond. In it simplest form the aldol condensation combines two carbonyl compounds (ketones and/or aldehydes) to yield a new -hydroxy- aldehyde or ketone (know also as aldol)
Under the basic conditions required to run the condensation reaction the aldol product normally undergoes water elimination, to yield the final , unsaturated aldehyde or ketone:
The mechanism for the aldol condensation requires the formation of the enolate ion of the ketone or aldehyde under strong basic conditions. This step involves the abstraction of a proton (H+) from the alpha position in the carbonyl compound. The resulting ion is resonance stabilized in the form of an enolate:
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Enolate ions are strong nucleophiles and will add to a molecule containing a carbonyl group:
The resulting aldol undergoes base-catalyzed dehydration
In this experiment we will perform a cross-aldol condensation. A cross condensation is a reaction in which one aldehyde or ketone adds to the carbonyl group of a different compound. It is very important that for a cross aldol condensation the electrophile (the carbonyl compound being attacked by the enolate) cannot form enolate ions itself. Otherwise a mixture of products can be obtained.
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To avoid a mixture of products usually one of the reactants chosen should not have the ability of forming an enolate ion. In other words, the reactant should not have protons available in the alpha position. Another complication arises when the resulting product has also protons available in the alpha position, in this case a double condensation can occur:
In this experiment you will use acetone as the enolate forming nucleophile and benzaldehyde as the electrophile. As in the previous example, acetone has alpha hydrogen on both sides of the carbonyl group, so acetone can add either one or two molecules of benzaldehyde to yield benzalacetone (4 phenyl -3 penten-2-one) or dibenzalacetone (1,5-diphenyl-1,4 petadien-3-one) respectively.
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You will synthesize both products and characterize them using UV spectroscopy and melting point measurements. MATERIALS AND METHODS 95 % Ethanol Acetone Benzaldehyde 600 ml beaker to use as an ice bath 125 ml Erlenmyer flask 16 x 100 test tube Pasteur pipette Thermometer Buchner funnel, filter paper, and vacuum flask Melting point apparatus UV spectrophotometer Week 1 Synthesis of dibenzal acetone.
1. Half fill a 600 ml beaker with crushed ice 2. In a 150 mL Erlenmeyer mix 30mL of Ethanol (95%) and 40mL of a 10% NaOH. Put a thermometer into the reaction mixture and place the flask into the ice bath. Stir the mixture occasionally by swirling. 3. In a 16 x 100 test tube mix 4mL of benzaldehyde and 1.5mL of acetone, mix. 4. Using the Pasteur pipette add the benzaldehyde acetone mixture to the ethanolic NaOH solution drop by drop stirring frequently. The addition should be done over a period of 20 min. Keep track of the temperature of the reaction mixture. By moving back and forth between the ice bath and the bench you can keep the mixture greater than 20 C but less than 28 C.
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Cloudiness of the solution indicates formation of the product. If cloudiness is not observed let the mixture reach room temperature. 5. After finishing the addition stir manually for 10 minutes and then let the reaction mixture stand for 10 minutes at room temperature. Slowly add 2 ml of ice water to the mixture to force precipitation of product. Put the reaction mixture in the ice bath for 10 more minutes. 6. Filter the reaction mixture using a Bchner funnel and vacuum, wash the mixture with cold water until the pH of the filtrate is neutral (basic pH will interfere with recrystallization), and continue to draw air through your product to partially dry it. 7. Weight your crude product 8. Recrystallize your product from ethanol. You should obtain yellow , needlelike crystals. 9. Weight your recrystallized product and determine its melting point. 10. Use a single crystal dissolved in 20mL of ethanol to obtain the UV spectra (400 to 200nm). This solution might be too concentrated for the UV so it might be necessary to dilute in ethanol even more. Week 2 Synthesis of benzal acetone.
1. Half fill a 600 ml beaker with crushed ice 2. In a 150 mL Erlenmeyer mix 30mL of Ethanol (95%) and 40mL of a 10% NaOH. Put a thermometer into the reaction mixture and place the flask into the ice bath. Stir the mixture occasionally by swirling. 3. In a 16 x 100 test tube mix 4mL of benzaldehyde and 6mL of acetone, mix. 4. Using the Pasteur pipette add the benzaldehyde acetone mixture to the ethanolic NaOH solution drop by drop stirring frequently. The addition should be done over a period of 20 min. Keep track of the temperature of the reaction mixture. By moving back and forth between the ice bath and the bench you can keep the mixture greater than 20 C but less than 28 C. White cloudiness of the solution indicates formation of the product. If the
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mixture begins to turn brown this indicates product decomposition and that the reaction temperature is too high. If cloudiness is not observed let the mixture reach room temperature. 5. After finishing the addition stir manually for 10 minutes and then let the reaction mixture stand for 10 minutes at room temperature. Slowly add 2 ml of ice water to he mixture to force precipitation of product. Put the reaction mixture in the ice bath for 10 more minutes. 6. Filter the reaction mixture using a Buchner and vacuum. Discard the liquid filtrate and rinse the vacuum flask. 7. Using 100mL of 50 % Ethanol wash the precipitate. In this step we are extracting benzalacetone (that becomes an oily suspension) and goes to the filtrate from the dibenzalacetone (that remains as solid in the Buchner). Benzalacetone has low melting point (close to 40, 42oC) therefore it is very difficult to recrystallize. We will extract it to get the UV spectra 8. Take 5mL of the aqueous oily suspension and put it in a 16 x 100 test tube . 9. Add 3mL of chloroform and vortex the mixture to extract the oily suspension into the organic phase. 10. Take one drop of the chloroform phase (bottom phase), mix it with 5mL of EtOH, and obtain the UV spectra of this mixture (400 - 200 nm ). Dilution or concentration might be required to get good quality spectra. PRE-LAB QUESTIONS Week 1 1. Do you think is possible to run the Aldol condensation in acidic instead of basic conditions? 2. Write four possible products that can result from an attempt to run a crossed aldol condensation between acetone and 2-propanal.
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Week 2 1. In the last step, chloroform is used to extract benzalacetone from water. Do you anticipate that the organic phase (chloroform) will sit above or below the aqueous phase? Justify your answer. 2. Recrystallization of benzalacetone is very difficult due to its low melting point, suggest another method of purification for the product. Justify your answer SUMMARY OF REQUIREMENTS FOR YOUR LAB REPORT 1. Calculate your yield of dibenzalacetone. Suggest possible reasons why your yield might be less than 100%. 2. Based on the scientific literature (available in the library and the web) propose a method for the isolation from the reaction mixture and purification of benzalacetone . 3. The UV/Vis spectrum of Benzaldehyde is shown below. Compare this spectrum with the spectra you obtained for your products, discuss the differences and similarities in terms on conjugation of pi systems.
benzaldehyde
6
benzaldehyde
4 Absorbance
0 200
220
240
260
280
300 w avelength (nm)
320
340
360
380
400
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LABORATORY 4 ALDOL CONDENSATION, BENZYNE FORMATION AND THE DIELS-ALDER REACTION : A MULTI-STEP REACTION SEQUENCE
( 2 lab periods ) ABSTRACT In this laboratory experiment you will run an Aldol condensation reaction to synthesize Tetraphenylcyclopentadienone. Then, you will use tetraphenylcyclopentadienone in a Diels-Alder reaction to obtain 1,2,3,4tetraphenylnaphthalene. Since this is your last laboratory, you are expected to clearly understand the chemistry involved on each of the synthetic steps and be familiar with all techniques. These will be evaluated during the laboratory session. There will not be written report required for this laboratory; instead you will be evaluated on your knowledge of reactions and procedures involved and the final yield of your product.
INTRODUCTION In this laboratory experiment you will again utilize the Aldol condensation to synthesize a highly coloured organic molecule; Tetraphenylcyclopentadienone. Then, you will use this compound in a Diels-Alder reaction to obtain 1,2,3,4tetraphenylnaphthalene. During this last step you will be constructing a new aromatic ring structure utilizing benzyne, an unusual and unstable reactant that must be generated in situ. In the first part of this experiment you will use diphenylacetone as the enolate forming nucleophile and benzil as the electrophile. Diphenyl acetone has alpha hydrogens on both sides of the carbonyl group, while benzyl has two carbonyl groups. If the stoichiometry and reaction conditions are carefully controlled, a cross
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double Aldol condensation takes place, and the product obtained is a highly substituted cyclopentadienone:
Notice that in his case a very strong base is needed (potassium ethoxide). The resulting product is an aldol, however under the very strong basic conditions the aldol undergoes dehydration to yield the unsaturated, highly conjugated ketone. In the second part of the experiment you will react the tetraphenylcyclopentadienone obtained with benzyne in a Diels Alder reaction to form 1,2,3,4tetraphenylnaphthalene. Since benzyne is very unstable it is necessary to generate it in situ. Our strategy will be then to form benzyne from the unstable diazonium salt of anthranilic acid:
Diazonium salt of anthranilic acid
To obtain the diazonium salt of anthranilic acid it is necessary first to run a diazotization reaction on anthranilic acid. Diazotation reactions often involve the use of sodium nitrite and HCl to generate nitrous acid (HONO). HONO protonates and loses water to give the nitrosonium ion (NO+) used as electrophile that attacks the
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amino group to yield the diazonium salt. In this case, however we will use isopentyl nitrite to form the nitrosonium ion:
Then, the sequence for the formation of the diazonium salt is:
Once the diazonium salt is formed, it rapidly undergoes decomposition, losing CO2 and N2 to yield benzyne:
Benzyne is a very reactive molecule and extremely difficult to isolate. In our case benzyne will react with the tetraphenylcyclopentadienone obtained in the first part of the laboratory session. The process is a DielsAlder reaction that in turns gives another unstable intermediate:
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The intermediate readily loses carbon monoxide (CO) to yield the fully aromatized 1,2,3,4-tetraphenylnaphthalene:
Please refer to the next page for a full synthetic pathway for this experiment. In the first part of the experiment you will synthesize tetraphenylcyclopentadienone, characterize it by FTIR, UV and melting point measurement. In the second part you will synthesize 1,2,3,4-tetraphenylnaphthalene through a Diels Alder reaction between tetraphenylcyclopentadienone and benzyne. You will characterize the product by by FTIR, UV and melting point measurements.
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Figure 9.1 Synthetic diagram for the synthesis of 1,2,3,4-tetraphenylnaphthalene.
tetraphenylcyclopentadienone
MATERIALS AND METHODS Benzil 1,3-Diphenyl Acetone Ethanol (anhydrous) Anthranilic acid 1,2-Dimethoxyethane ( DME ) Isoamyl Nitrite Methanol Dichloromethane 1.25 % KOH in Ethanol 50 and 100 ml RB flasks Reflux condenser Claisen adapter Heating mantle and controller Hirsh funnel and vacuum flask Screw cap vials Melting point apparatus FT IR and UV/VIS spectrophotometers
Part 1 1.
Synthesis of tetraphenylcyclopentadienone. In a 50 ml round bottom flask dissolve 1 g of Benzil and 1 gram of 1,3diphenyl acetone in 30 ml of Ethanol (abs). A little heat may be necessary to help dissolution.
2.
Slowly add 20 ml of 1.25 % KOH/Ethanol to the reaction mixture. Add a few boiling chips, attach a reflux condenser to the flask, start the cooling water, and heat the mixture at reflux for 15 min. The mixture should change color to
a dark purple (might be dark brown). After 15 minutes stop the reflux, and allow the reaction flask to cool to room temperature, and then cool down in an ice bath. 3. 4. Set aside 50 mL of ethanol and put it in an ice batch, this will be used for washing the product. After reaction mixture is cold, filtrate it using vacuum and a Hirsh funnel. Wash the crystals using ice cold ethanol. Keep washing until the filtrate is transparent or light pink. Keep sucking air over the crystals in the filter to dry them. Crystals are very dark purple with a slightly metallic sheen. There is not need to recrystallize as the product is quite pure. 5. 6. Weight the tetraphenylcyclopentadienone obtained and calculate your yield. Obtain a UV spectrum for your product. For the UV dissolve a few crystals in hexane (a very light pink solution) and scan from 650 nm down to 200 nm. The FTIR of the product will be provided.
Part 2 1.
Synthesis of 1,2,3,4-tetraphenylnaphthalene. In a 50ml RB flask dissolve 0.5g of the tetraphenylcyclopentadienone obtained in the first part and 0.23g of anthranilic acid in 10mL of 1,2 dimethoxy ethane (DME). Warning DME is toxic, it should be measured in the fumehood, transported in a stoppered flask and uncapped only under the elephant trunks located over your lab bench. Attach the flask containing the reaction mixture to a reflux condenser and heat up to reflux.
2.
Add 4 ml of DME to a screw cap vial and place the vial in an ice bath. After the DME is cold and right before the next step add 0.5ml of isopentyl nitrite to the vial and reseal it. IMPORTANT - if mixture is not ice cold and/or is exposed to air for long time the nitrite will decompose and no reaction will occur.
3.
Once reflux is established carefully add the DME solution containing the isopentyl nitrite through the top of the condenser. The solution should be
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added slowly (over a period of 2 minutes) If the addition is too fast foaming might occur and the reaction mixture can boil over. 4. Keep the reaction mixture at reflux for 15 more minutes; the reaction mixture should change to an orange-yellow color. If color change is not observed prepare a new mixture of isopentyl nitrite in DME with a higher concentration and add it slowly to the reaction mixture following the same procedure. 5. 6. Set aside 50 ml of ethanol, mixed with 10 ml of water , in a ice bath. Cool the reaction mixture to room temperature. In a 250 ml beaker mix of 25 ml of water and 10 ml of ethanol. Add the reaction mixture to the beaker slowly using a dropper. A precipitate should form. 7. 8. Use a Hirsh vacuum filter to separate the solid 1,2,3,4 tetraphenylnaphthalene. Wash the solid with the cold ethanol/water mixture. Recrystallize your crude product from 2-propanol. If not all the solid is dissolved at the boiling point of the solvent the mixture might need to be filtrated hot to remove insoluble impurities. 9. 10. 11. Needle like crystals should be obtained Measure the melting point and obtain the IR spectra. Compare it to the spectrum obtained for tetraphenylcyclopentadienone. Obtain the UV spectra using 2-propanol as solvent. Compare it with the spectrum obtained for tetraphenylcyclopentadienone.
PRE-LAB QUESTIONS There are not prelab questions, on this session all questions will be asked orally and will heavily influence the mark assigned to the lab. .
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APPENDIX: RECRYSTALLIZATION, MELTING POINT DETERMINATION, AND EXTRACTION A. RECRYSTALLIZATION 1. Theory (a) General Methods of Recrystallization Chemical transformations lead invariably to mixtures of products, and therefore various techniques of separation or purification must be employed to isolate individual components in pure form, from the crude reaction mixtures. In the case of solid substances the most commonly employed technique, at least until the advent of chromatographic methods, was that of recrystallization (or more simply "crystallization"). As commonly practiced, purification by recrystallization depends upon the fact that most solids are more soluble in hot than in cold solvents. The solid to be purified is dissolved in the solvent at its boiling point, the hot mixture is filtered to remove all insoluble impurities, and then crystallization is allowed to proceed as the solution cools. In the ideal case, all of the desired substance separates nicely in crystalline form and all the soluble impurities remain dissolved in the mother liquor. Finally, the crystals are collected on a filter, washed and dried. If a single recrystallization operation does not yield a pure substance, the process may be repeated with the same or another solvent. (b) Nature of Suitable Solvents The single most important factor contributing to a successful recrystallization is the proper choice of solvent. In general, the most "suitable" solvent for recrystallization purposes is one in which the compound to be purified is only very slightly soluble at low temperatures but very soluble at higher temperatures (e.g. at the boiling point of
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the solvent). Most compounds exhibit positive temperature coefficients of solubility. Ideally of course, the impurities to be removed should be readily soluble in the cold solvent in which they will remain after the crystallization process or almost completely insoluble even at elevated temperatures. It should be realized that the solvent selected must be inert and not enter into chemical reaction with the sample. In addition, it is desirable that the solvent be reasonably volatile (low boiling point) so that it can be fairly easily removed from the crystals by evaporation. Where two or more solvents are comparable with respect to the properties already cited, factors such as inflammability, toxicity and cost are to be considered. The lower the solubility of the compound to be purified in the cold solvent, the greater will be the recovery of purified material from the crude mixture. The fact that the solubility of the impurities may be comparable to that of the desired compound does not preclude the use of a particular solvent, since most impurities are present in relatively small amounts. As an example, consider the recrystallization of a mixture of solids consisting of 10 g of A and 1 g of B from a solvent in which the solubility of each is 1.5 g per 100 ml at room temperature and 10 g per 100 ml at the boiling point. One hundred milliliters of hot solvent would be required to dissolve the mixture, and upon cooling the solution would precipitate 8.5 g of A (i.e. 85% recovery) and no B because the solubility of B had not been exceeded. Only if there were more than 1.5 g of B and 10 g of A would any B crystallize, and even then a second recrystallization would complete the separation of up to 2.5 g of B. (c) Choosing a Suitable Solvent If no information concerning the solubility characteristics of the substance to be recrystallized is available, the choice of solvent becomes an experimental problem. It is necessary to test various solvents for their suitability according to the criteria outlined above. As a rule, solvents of decreasing polarity are tried in succession and the solubility behavior in each case observed. To do this, small-scale trial recrystallizations are carried out rapidly in micro (10 X 75 mm) test tubes. A few
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drops of various common solvents (see table below) are added to small portions of the crude, finely divided solid mixture and the crystals are stirred and crushed under the cold solvent with a stirring rod. If solution occurs at room temperature the solvent is obviously unsuitable. If solution does not occur, the test tube is heated gently on a steam bath or over a small flame with stirring or shaking. A few more drops of solvent are added if only partial solution has occurred. (Transfer of solvent is most conveniently done with small clean dropping tubes drawn out at the end like pipettes). If a homogenous solution is obtained it is cooled, and the inside walls of the test tubes are scratched if crystallization does not occur readily. If no crystals can be obtained or if solution does not occur on warming, the solvent is unsuitable and another should be tried. To avoid misleading observations, some care and judgment must be exercised in choosing the relative amounts of solid and solvent to be used in these solubility tests. Choosing a Suitable Solvent The ultimate proof of the suitability of a particular solvent is in achieving a separation of the desired component from the unwanted impurities. This can be established by collecting the crystals which precipitate from the solvent being tested and determining their melting point. In many cases it is difficult to predict a suitable solvent. In general, it is said that "like dissolves like" -that is, a substance will dissolve in a solvent containing similar groups -or better, that polar solvents will dissolve polar molecules and nonpolar solvents will dissolve nonpolar molecules; but a good recrystallization solvent cannot be too like the compound being purified. The accompanying table lists, in order of decreasing polarity, some of the common solvents used for recrystallization.
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2. DETAILED DESCRIPTION OF EXPERIMENTAL STEPS AND APPARATUS (a) Preparation of Hot Solution At this stage the key words are saturated and minimum. Since the compound to be purified will invariably be soluble in cold solvent to some extent, however small, the recovery of pure material will be a maximum only by employing no more solvent than is absolutely essential to obtain a complete solution at the elevated temperature. By working at or near the boiling point of the solvent, full advantage is taken of the temperature coefficient of solubility for that particular solute/solvent combination. Quantitative solubility data are not essential, and the following general approach may be applied to any solute/solvent combination. The solid is placed in a flask of suitable size and just covered with a small quantity of solvent (use a volume comparable to that of the solid phase, but certainly less than will be required ultimately). The flask and contents are heated gently on a steam bath, shaking or swirling, to a temperature just below the solvent's boiling point. Heating may then be interrupted, an additional small quantity of solvent added, and heating resumed. This procedure is repeated until the last bit of solid just dissolves or until no further decrease in the amount of undissolved material is apparent. In many instances it will not be possible to obtain complete solution because of the presence of insoluable impurities in the mixture. For this and all subsequent operations in the recrystallization sequence, it is convenient to use the conically shaped Erlenmeyer flask, but never beakers. This particular design offers many practical advantages. It minimizes both solvent loss (the upper walls acting as a condenser) and the distribution of crystals on the vessel walls out of reach of the solvent phase. It is also particularly convenient for handling in the transfer operations or for corking or fitting with a condenser. In this way, hot, ascending solvent vapor does not escape but is condensed and continuously returned to the solution flask. This is particularly important with solvents such as ethyl ether, benzene, and petroleum ether, but in practice it is advantageous with
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any solvent because loss of solvent over the period of time taken by the subsequent filtration step will cause the solution to become supersaturated prematurely. In fact, it is often desirable to have the solution slightly below saturation at this point to minimize difficulties in the hot filtration (see below). This is especially true for highly volatile solvents (e.g., b.p.<65 C). (b) The Use of Decolorizing Charcoal Frequently, the crude product of a reaction mixture is colored by the presence of certain impurities which may have arisen through some oxidation, charring, or polymerization process accompanying the main transformation. Such impurities are usually highly polar and, even though very soluble in the recrystallization solvent, tend to be adsorbed or occluded by the growing crystals of the solute. In these instances, a series of wasteful and repetitive recrystallizations can be avoided by the addition of a small quantity of animal charcoal ("Norite", Darco", "Nuchar", etc.) to the hot solution. This addition permits selective adsorption of the colored impurities by the active carbon prior to the crystallization process. It is important that the solution not be super-heated when the active carbon is to be added, or excessive frothing and "boiling over" of the flask contents may occur. Usually the flask is removed from the heat, and after a moment the carbon is added. The contents of the flask are kept hot and shaken briefly to ensure wetting of the carbon surface. Adsorption occurs very rapidly, and no advantage is gained by boiling the suspensions for several minutes. Charcoal is actually less effective at elevated temperatures, and the only reason for operating at the boiling point is to keep the substance to be crystallized in solution. The effectiveness of the charcoal in adsorbing the colored impurities is directly proportional to the solvent polarity and is best in an aqueous solution. The smallest amount of decolorizing agent that will do the job should be used because the desired solute may also be adsorbed (thus reducing the yield of product recovered) if the surface of the adsorbent is not saturated by the coloring matter. For this reason (and since the color may also be due to the desired compound) the decolorization step is seldom repeated whatever
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the results of the single trial. In practice, one seldom uses more than 20 mg of charcoal per gram of dry compound. (c) Hot Filtration The hot solution must be filtered to achieve separation from any insoluble impurities or other undissolved materials. If charcoal is used for decolorization the necessity for filtration is obvious. If no undissolved material is evident (which is very seldom) this step may be omitted. The chief difficulty encountered in this operation is that of keeping the solution hot enough to avoid premature crystallization in the filter. This means that the filtration must be done as rapidly as possible with minimal cooling of the solution. Rapid filtration of small quantities of solution is best done by gravity through a fluted filter paper supported in a stemless glass funnel. Fluting of the filter paper (the technique of folding will be demonstrated in the laboratory) increases the rate of filtration by presenting a much larger surface area to the solution. If a regular funnel with a stem is used, there is a good possibility of filtrate cooling in the stem, with crystallization resulting. The relatively narrow stem thus becomes clogged and filtration is impeded. It is often advantageous to preheat the glass funnel simply by briefly heating it in a flame or by pouring a quantity of hot solvent through it immediately prior to filtration. If water is used as the solvent, the filter funnel may be warmed conveniently on a steam bath. When working with particularly volatile solvents or with solids having very large temperature coefficients of solubility, it is particularly difficult to avoid premature crystallization. In these cases it is usually better to prepare the hot solution with excess solvent (i.e. the solution is not saturated at the boiling point). After the hot solution has been filtered the excess solvent must, of course, be removed by evaporation before inducing crystallization. It should be emphasized that the hot filtration is done by gravity (at least in an elementary laboratory) and not by suction filtration as described below for the
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collection of the crystallized product. The use of suction for filtering a hot, nearly saturated solution is nearly always highly unsatisfactory, because the reduced pressure in the filter flask causes rapid evaporation of the hot solvent; consequently, the solution is not only more concentrated but it is cooled by the heat of vaporization and becomes supersaturated. Crystallization in the funnel is then almost inevitable and the funnel may become completely plugged by the deposited crystals. In carrying out the actual filtration, the fluted paper is inserted into the stemless funnel so that the lower tip of the paper projects into the opening at the bottom of the funnel. The hot solution is decanted quickly but carefully into the paper, keeping the level of solvent well below the top of the paper. When all of the solution cannot be put into the funnel at once, the remainder is kept warm on the steam bath or hotplate until it can be transferred to the funnel. After the solution has run through the paper, a crust of crystals often remains around the tip of the funnel and ill-formed crystals often form in the body of the cooling filtrate. It is common practice to rinse the original flask with a little hot solvent and to filter this through the filter paper to redissolve the crystals adhering thereto. The filtrate which has been collected in an Erlenmeyer flask should be reheated to redissolve any material that has crystallized and, if significantly diluted below the saturation point, should be concentrated to its original optimal volume prior to cooling and crystallization. If the various precautions outlined above fail to prevent excessive crystallization of the solute in the filter paper, the simplest expedient is to return the complete filter paper and its contents to the original flask, add additional solvent, boil briefly to ensure complete solution, and begin a new filtration. (d) Cooling/Crystallization
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Crystallization is accomplished by allowing the hot filtrate to cool slowly, undisturbed, to room temperature (or at least until crystallization has begun) and then chilling the mixture in ice or cold water to complete the precipitation. The objective is, of course, that the desired substance be deposited as pure crystals while any "insoluble" impurities remain dissolved in the "mother liquor". The lower the temperature to which the solution is cooled, the more the desired substance will crystallize; however, at some point the impurities may also begin to separate from solution. The size of the crystals which separate will vary with the rate of cooling and the degree of agitation of the solution. Rapid cooling with stirring tends to produce small crystals, while slow cooling of an undisturbed solution tends to give larger crystals. In general, either very large or very small crystals are undesirable. There are problems associated with the collection of very fine crystals because of clogging of the pores in the filter paper and of adhesion of the small particles to the walls of the crystallization flask. Moreover, if the solubility of the impurities is comparable to that of the desired compound, sudden chilling may result in the co-deposition of the impurities; whereas, with slow, undisturbed cooling these tend to remain in supersaturated solution and more complete separation is effected. On the other hand, with very large crystals there is a tendency for the mother liquors to be occluded within the crystals. In the subsequent drying operations, evaporation of the solvent will leave a deposit of impurities on the crystals. Yet another problem associated with too rapid chilling of the solution, especially in the case of low melting solids, is the tendency for the solute to separate first from the solution as an "oil" which subsequently solidifies to a crystalline cake. If this happens, it is possible for impurities to be distributed between the solvent layer and the "oily" layer (see discussion of principles of extraction). The impurities will then be entrapped when the oil solidifies. For this reason it is often desirable to choose a solvent for recrystallization whose boiling point is lower than the melting point of the solid being purified. (e) Collection of Crystals -Cold Filtration
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The important objective in the collection of a purified product is complete separation of the crystals from the "mother liquor" containing the dissolved impurities. This is achieved most effectively by employing suction filtration. The necessary apparatus consists of a Buchner funnel attached to a heavy-walled filter flask which is connected through a "trap" bottle to the source of suction (water aspirator or vacuum pump) -see accompanying illustration. The Buchner funnel is prepared for filtration by attaching it to the filter-flask by means of a cork or rubber adapter, inserting a piece of filter paper whose diameter is just sufficient to cover the holes in the filter plate (the paper must not fold up against the sides of the funnel), wetting the paper with a-small quantity of the solvent being used, then smoothing the paper snugly against the filter plate by the application of gentle suction. The cold contents of the crystallization flask are stirred to break up any lumps and swirled to obtain suspension of crystals. The suspension is decanted quickly into the funnel in such a way that a layer of uniform thickness is obtained across the whole surface of the filter bed. This is essential for obtaining complete separation of the mother liquor. It is important, particularly in the early stages, to use only sufficient suction to obtain a steady flow of filtrate. Very strong suction at this stage will draw the finer particles into the pores of the paper, clogging them, and slowing the rate of filtration unnecessarily. The bulk of the crystals remaining in the flask may be transferred to the funnel with the aid of a metal spatula. Any crystals still remaining are most efficiently transferred to the funnel by rinsing the flask with a portion of the filtrate (which is already saturated with solute) rather than using fresh solvent. When the bulk of the mother liquor has drained through, the cake of crystals is pressed down quickly with a spatula or glass stopper and the suction is interrupted by removing the rubber tubing from the filter flask. It is particularly important at this stage not to draw air through the crystal cake, because this will cause evaporation of the mother liquor and the impurities that were dissolved therein will be deposited on
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the surface of the crystals. If it is intended to use the mother liquor to obtain a second "crop" of crystals after concentration to a suitable volume, it should be transferred at this point to a separate vessel (or the Buchner funnel attached to a clean filter flask). (f) Washing the Crystals To complete the separation of the mother liquor, the crystalline cake must be washed with small quantities of fresh, clean solvent. This is done conveniently by covering the filter cake completely with a thin layer of solvent, with the suction disconnected. If possible the crystalline cake should be loosened with a spatula to ensure complete wetting by the wash solvent, but care must be exercised not to disturb the filter paper. The suction is reapplied and the wash solvent drawn down through the crystals, which are then pressed down firmly as before to remove the wash liquid as completely as possible. For complete removal of the mother liquor from the crystals two or three such washes are recommended; however, to minimize loss of product, the wash portions should be small in volume and the solvent should be cold. After the last wash, full suction is applied to draw air through the filter cake to suck it as dry as possible. (g) Drying the Crystals The final operation in the recrystallization of a product, is the drying of the solid. If the solvent employed in the recrystallization is rather volatile, it is possible that it will have evaporated completely during the last stages of the suction filtration. Otherwise, further drying is necessary. As used here the term "drying" refers to the complete removal of solvent, be it organic or aqueous. The cake of crystals is transferred, with the aid of a spatula, to a sheet of glazed paper, a watch glass, or any suitable container having a relatively large surface area. The solid sample should be spread out and permitted to stand in air with periodic stirring with a spatula. In many instances, however, simple "air-drying" as just described will be inadequate or much too slow. The last traces of solvent (and/or
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atmospheric moisture) are removed most conveniently by using a drying oven, a dessicator, or by evaporation under vacuum. A dessicator is simply a closed vessel with a lower compartment containing an anhydrous salt such as phosphorus pentoxide which can remove water vapor by forming a hydrated salt. When using either an oven or a dessicator the rate of drying can be enhanced even further by reducing the pressure in the system. The temperature at which the crystalline solid is dried in an oven should, of course, be significantly lower than the melting point.
B. MELTING POINT DETERMINATION 1. Use of Melting Points for Analysis Most crystalline organic compounds have characteristic melting points that are sufficiently low (50 300 C) to be conveniently determined with simple equipment. Organic chemists routinely use melting points to a) get an indication of the purity of crystalline compounds and b) help identify such compounds. Pure crystalline compounds usually have a sharp melting point. That is, the meltingpoint range or the difference between the temperature at which the sample begins to melt and the temperature at which the sample is completely melted, is relatively small (narrow). Impurities, even when present in small amounts, usually depress the melting point and broaden the melting point range. A wide melting-point range (more than 5 C) usually indicates that the substance is impure, while a narrow melting point range of about 0.5 2 C usually indicates that the substance is fairly pure. However, there are some exceptions to both of these generalizations. Small differences in melting point (on the order of 2 3 C) may also result from variations in technique, thermometer accuracy, and in the amount of experience possessed by the person doing the melting-point determination.
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Melting points can be used in the following way to help identify a compound. Suppose a sharp-melting, unknown substance X is suspected of being identical to some unknown substance A. If the two are identical, they should have the same melting point. Thus, if A is reported in the chemical literature to have a melting point significantly different from that observed for X, we can be quite certain that X does not have the same structure as A. On the other hand, if A is reported to have a melting point within a few degrees of that observed for X, the two substances may be identical (the small difference being due to variations in technique or purity). To be certain that X and A are identical, a mixture melting point can be determined, i.e. the melting point of a mixture of X and A. If X and A are identical, the mixture should have the same melting point as X or A has alone. On the other hand, if X and A are not the same substance, even though they separately have the same melting point, then a mixture of the two usually have a lower melting point and a broader range than either substance alone. This is because each substance acts as an impurity in the other. To summarize, if a crystalline substance is pure, its melting point is likely to be narrow. If two samples have identical structures, their mixture melting point is not depressed and the melting point range is not broadened. 2. General Technique for Melting Point Determination To determine the melting point, introduce a small amount of the finely powdered material into a thin-walled capillary tube that is sealed at one end. The capillary tube is inserted into a melting point apparatus and heated. Your lab demonstrator will instruct you on its use. Two temperatures are recorded: the temperature at which the substance begins to liquefy and the temperature at which it becomes completely liquefied. The observed melting-point range is the interval between these two temperatures.
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The observed melting point range can be influenced not only by the purity of the material but also be the size of the crystals, the amount of material, how densely it is packed in the tube, and the rate of heating. A finite time is required to transfer heat from the metal block through the walls of the capillary tube and throughout the mass of the sample. When a block is heated too quickly, its temperature rises several degrees during the time required for melting to occur. This can result in an observed range that is higher than the true one. When the temperature of the block approaches the melting point of the sample, it is essential for good results to raise the temperature slowly and at a uniform rate, usually about 2 C per minute. The sample should be small, finely powdered, and packed tightly with a consistent density in a thin-walled capillary tube of small diameter. The column of solid in the capillary tube should be just high enough to be seen clearly during the melting (about 1-2 mm). It is a good idea to carry out the packing process by dropping each sample melting point tube the same number of times, e.g. three times. The behaviour of a material upon melting should be observed and recorded carefully. Record the range of the melting, such as 89.0 89.5 C, as well as any observations (decomposition, colour change, etc.).
C. LIQUID-LIQUID EXTRACTIONS 1. Solvent partitioning in liquid-liquid extractions The physical process that governs liquid-liquid extractions is solvent-solvent partitioning. This is the distribution of solutes between a pair of solvents. In organic chemistry, most commonly one of the solvents is water and the other is an organic solvent that is immiscible with water, such that two layers are formed with the upper
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layer containing the less dense solvent. There are many organic solvents such as diethyl ether, dichloromethane, toluene, and ethyl acetate, which have very limited solubility in water and thus form a two-layer system. Each layer is saturated with the other solvent. Inorganic compounds can usually be easily separated from organic compounds by extraction. The former dissolve in the aqueous phase and the latter in the organic solvent. In such cases, a single extraction may be sufficient to effect a satisfactory extraction. Many organic compounds, such as aldehydes, alcohols, esters, and amines, which can form hydrogen bonds, are partially soluble in water. They distribute themselves between the aqueous phase and the organic phase. For example, if we add solute A to a mixture of water and chloroform, shake the system vigorously to reach equilibrium, then allow the system to settle, solute A will be present in both layers, but with a higher concentration in solvent for which it has higher affinity. The distribution of A between the two solvents is dictated by the partition coefficient of A between the solvents. The partition coefficient is the equilibrium constant for the distribution of a solute between two immiscible layers. For example, for solute A distributed between chloroform (C) and water (W), the partition coefficient K is defined as follows: KC/W = [A] in chloroform/[A] in water To a first approximation, the partition coefficient can be estimated as the ratio of the solubility of the compound in each solvent. For example, the solubility of caffeine in chloroform is approximately 18 g/100 mL, while its solubility in water is approximately 1.8 g/100 mL. Therefore, we expect a partition coefficient KC/W 10 and most of the caffeine will be in the chloroform layer. To illustrate how the partition coefficient can be used, consider performing an extraction of 1.0 g of caffeine using 60 mL of chloroform and 100 mL of water. If we let x be the number of grams of caffeine in the chloroform layer, then (1.0 x) will be the number of grams in the water. The equation for K will therefore be:
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KC/W = [caffeine]chloroform/[caffeine]water 10 = (x/60)/((1.0-x)/100) Solving for x we find that 0.86 g of caffeine will be in the chloroform layer and 0.14 g will remain in the aqueous layer. We could then recover the caffeine by evaporating the chloroform and we should get 0.86 g, which would be an 86 % recovery. In general, the efficiency of a liquid-liquid extraction will depend on the partition coefficient, the volume of solvent used, and the number of extractions. In general, it is desirable to have the highest possible Korg/water. Increasing the volume of the organic phase will also increase the % recovery, as will performing several consecutive extractions. 2. Choice of solvent The selection of an appropriate extraction solvent is critical to the success of this technique. There are several important criteria to consider: The chosen solvent must not react chemically in an irreversible manner with any component of the mixture The chosen solvent must be immiscible or nearly immiscible with the original solution The chosen solvent must be favoured by the distribution coefficient for the component being extracted The chosen solvent must be easily separated from the desired component following the extraction. This generally means it should be low boiling and thus easily removed by distillation or evaporation 3. General Technique for Extraction In this discussion, assume that one of the solvents is water. Place the solution to be extracted in a separatory funnel supported on an iron ring with the stopcock closed (see figure below). The volume of the funnel should be at least twice that of the volume of the solution. Add the extraction solvent and then tightly stopper the flask. As a guideline, the volume of the extracting solvent should be between 25 50 % of the volume of the solution being extracted. Next, grasp the funnel with the palm of
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the right hand around the body and the thumb and first two index fingers around the stopper. Vigorously shake the funnel to mix the phases well. Never point the stem towards your face or anyone nearby. With the funnel inverted, carefully open the stopcock to release the built-up pressure. Close the funnel, shake it again, and carefully vent it again. Repeat this process until the pressure subsides. Approximately 1-2 minutes of shaking should be adequate to reach equilibrium. After the shaking, return the funnel to the ring and remove the stopper. Allow the layers to separate and then collect the lower layer in an Erlenmeyer flask by opening the stopcock. Swirling the funnel may help if the interface between the two layers is unclear. Always try to predict which phase is your desired phase based on the known densities of the solvent, but be aware that the densities of liquids can change depending on what is dissolved in them. To be sure that you do not discard the wrong phase, always save all phases until the end of the experiment. If you are in doubt as to which phase is the aqueous, you can add a small amount of water to the top of the funnel and observe which layer it is miscible with.
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The University of Western Ontario

Faculty of Engineering Science DEPARTMENT OF CHEMICAL AND BIOCHEMICAL ENGINEERING

INDUSTRIAL ORGANIC CHEMISTRY II

CBE2207 LABORATORY MANUAL

Prepared by P. Charpentier, E. R. Gillies and J. Herrera 8th Edition

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

Energy (includes work)

Force Heat capacity (includes entropy) Length

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

Volume (includes capacity)

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

1.2 COMMON ITEMS OF GLASSWARE AND APPARATUS

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

The PASTEUR or DROPPING PIPETTE is for transferring a few drops.

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

A NOTE TO THE STUDENT

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

GENERAL HOUSEKEEPING AND LABORATORY WORK

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

GUIDELINES FOR PREPARATION OF LABORATORY REPORTS

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

State the significance of the results in relation to the objective.

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014

5mL 6N NaOH Hot Plate/ Magnetic stirrer FT-IR Spectrophotometer

CBE2207 Laboratory Manual

Edited by J. Herrera, 2014