Identification and Characterization of Nonflammable Azeotropic Mixtures (Appendix A-C)

APPENDIX A FRACTIONAL DISTILLATION SCOPE This procedure outlines fractional distillation setup as well as instructions for the distillation process. PURPOSE This procedure provides instructions for performing a fractional distillation. SAFETY REQUIREMENTS 1. Before beginning this procedure, read all of the Safety Data Sheets for the chemicals at hand. 2. Contact your supervisor for information regarding the proper personal protection equipment (PPE) to be used in this procedure. 3. Personnel engaged in the handling of chemicals that could present a hazard due to splashing are required to wear safety eyewear with side-shields, or work in a hood, or wear a safety face shield. NOTE Nitrile or equivalent gloves are used for incidental contact only. 4. Wear nitrile or equivalent gloves when handling chemicals. In case of an incidental spill, wear nitrile gloves during cleanup. Do not use latex gloves for organic solvent work. GENERAL INSTRUCTIONS 1. The sequence of operations in this procedure is not mandatory. 2. Waste Disposal NOTE Segregation of halogenated and non-halogenated waste streams is vital to the management of waste disposal costs. Likewise, recycling of solvent is a priority. Do not mix solvents if you do not have to! 2.1. Dispose of halogenated solvents in a properly labeled halogenated solvent waste container. 2.2. Dispose of non-halogenated solvents in a properly labeled non-halogenated solvent waste container. 2.3. Dispose of aqueous waste containing heavy metal waste in a properly labeled heavy metal aqueous waste container. 2.4. Dispose of contaminated PPE and laboratory expendables into the laboratory regulated solid waste container. 2.5. Dispose of uncontaminated PPE and laboratory consumables in the laboratory nonregulated solid waste container. OPERATIONS FOR PERFORMING A FRACTIONAL DISTILLATION 1. Setting up the distillation apparatus. 1.1. Choose an appropriately sized boiling flask and heating mantle for the distillation that needs to be performed. 1.1.1. The flask should be large enough so that the liquid that needs to be distilled does not fill the boiling flask more than 75 percent of its maximum capacity. 1.1.2. The flask should be small enough so that the liquid that needs to be distilled does not fill the boiling flask less than 50 percent of its maximum capacity. 1.1.3. The heating mantle should be the appropriate size for the heating flask that you have chosen. 1.1.4. The heating mantle should cover the lower 50 percent of the flask with good contact between the inside of the heating mantle and the boiling flask. 1.2. Pour the liquid that needs to be distilled into the boiling flask. 1.3. Add some boiling chips to the flask. 1.4. Place the flask into the heating mantle inside of the fume hood. 1.5. Attach a fractionating column to the boiling flask. 1.5.1. Remember to either use stopcock grease or a Teflon sleeve on this connection because it will get very hot. 1.5.2. Remember to clamp the fractionating column to a ring stand to hold it up right during the distillation. 1.6. Attach a three way distilling head to the top of the fractionating column. 1.6.1. Remember to either use stopcock grease or a Teflon sleeve on this connection because it will get very hot. 1.7. Attach a thermometer adaptor to the top of the distilling head. 1.8. Place a thermometer in the thermometer adaptor. 1.9. Lower the thermometer until the end of the thermometer is just below the fork in the distilling head. 1.10. Attach a condenser to the distilling head. 1.10.1. Remember to secure the condenser to the distilling head using a clamp on the connection, a tightly wrapped rubber band from the water outlet on the condenser to the distilling head, or by clamping the condenser to another ring stand. 1.10.2. The water outlet is the one closest to the distilling head. 1.10.3. The water inlet is the one farthest from the distilling head. 1.11. Attach a vacuum adaptor to the end of the condenser. 1.11.1. Remember to secure the vacuum adaptor to the condenser using a clamp on the connection, or a tightly wrapped rubber band from the water inlet on the condenser to the vacuum adaptor. 1.12. Attach an appropriately sized receiving flask to the vacuum adaptor. 1.12.1. Remember to secure the receiving flask by clamping it to another ring stand. 1.13. Run a rubber tube from the water tap to the water inlet on the condenser. 1.14. Run a rubber tube from the water outlet on the condenser to the drain. 1.15. Plug the heating mantle into a power regulator. 1.16. Plug the power regulator into an electrical outlet. 2. Performing a distillation. 2.1. Turn on the water tap so that the pressure is sufficient to rid the condenser water jacket of air. 2.1.1. The water can usually be turned down some after the air has been forced out. 2.2. Power on the power regulator and set it to about 50 percent of its maximum. 2.2.1. The regulator may need to be set to a lower setting for liquids with low boiling points, or a higher setting for liquids with high boiling points. 2.2.2. When the setting is correct, the liquid will be at a gentle rolling boil after it has had time to heat. 2.2.3. If the liquid doesn’t boil or barely boils after giving it time to heat, the setting on the power regulator can be increased. 2.2.4. If the liquid boils up into the column after giving it time to heat, the setting on the power regulator should be decreased. 2.3. Never leave the distillation unsupervised for more than a few minutes. 2.4. The distillation should be checked about every five minutes after the liquid starts to boil to ensure that the liquid is boiling at the proper rate, and to ensure that the process is proceeding safely. 2.4.1. In small distillations, it may need to be constantly observed or checked more often. 2.5. After the first drop of distillate is captured in the receiving flask, record the temperature reading on the thermometer. 2.6. From this point forward, check the temperature every time that the distillation is observed. 2.7. In some cases, low boiling azeotropic mixtures are formed. If the temperature reading is lower than the boiling temperature of any of the components in the original mixture, then this has probably occurred. If this has occurred: 2.7.1. If the purpose of the distillation was to create a low boiling azeotropic mixture, then continue the distillation until the temperature starts to increase to the boiling temperature of one the components. 2.7.2. If the purpose of the distillation was to separate the components of the original mixture, then stop the distillation and report that the mixture cannot be separated by distillation. 2.8. If the temperature reading is close to the literature boiling point of one of the components of the mixture, then continue the distillation. 2.8.1. If the purpose of the distillation was to create a low boiling azeotropic mixture, then it is still possible that an azeotropic or near-azeotropic mixture was formed. 2.8.2. If the purpose of the distillation was to separate the components of the original mixture, then the distillation is on track to fulfill its purpose. 2.9. If separation is the goal, then the receiving flask needs to be changed each time the temperature starts to increase to the boiling temperature of the next lowest boiling component. 2.9.1. If the component that needs to be purified is the lowest boiling component of the mixture, then the distillation can be stopped the first time that the temperature starts to increase to the next lowest boiling temperature. 2.9.2. If several components need to be purified, then change the receiving flask each time the temperature starts to increase to the next lowest boiling temperature. 2.9.2.1. Label each flask with the small temperature range at which it was collected. 2.10. Always stop the distillation before the boiling flask is dry. 3. Stopping the distillation. 3.1. Power off the power regulator. 3.2. Allow the boiling flask to cool until it can be handled comfortably. 3.3. Turn off the water tap. 3.4. Remove the flask from the heating mantle. 3.5. Allow the flask to continue to cool until it reaches room temperature. 3.6. Pour the remaining liquid from the flask into a waste bottle. 3.7. Label the waste bottle with the names of the remaining components of the distilled mixture, the words “Still Bottoms”, and the date. APPENDIX B RAMAN SPECTROSCOPIC AND CHEMOMETRIC ANALYSIS SCOPE This procedure outlines sample preparation, Raman spectrophotometric data collection, and chemometric analysis for determining the volume percent composition of liquid solvent mixtures. PURPOSE This procedure provides instructions for performing Raman spectrophotometric data collection, and chemometric analysis using Microsoft Excel’s Solver Tool. SAFETY REQUIREMENTS 1. Before beginning this procedure, read all of the Safety Data Sheets for the chemicals at hand. 2. Contact your supervisor for information regarding the proper personal protection equipment (PPE) to be used in this procedure. 3. Personnel engaged in the handling of chemicals that could present a hazard due to splashing are required to wear safety eyewear with side-shields, or work in a hood, or wear a safety face shield. NOTE Nitrile or equivalent gloves are used for incidental contact only. 4. Wear nitrile or equivalent gloves when handling chemicals. In case of an incidental spill, wear nitrile gloves during cleanup. Do not use latex gloves for organic solvent work. 5. The Raman instrument contains a 785 nm laser that is not visible. Do not aim the laser probe at any part of your body, especially the eye. GENERAL INSTRUCTIONS 1. The sequence of operations in this procedure is not mandatory. 2. Waste Disposal NOTE Segregation of halogenated and non-halogenated waste streams is vital to the management of waste disposal costs. Likewise, recycling of solvent is a priority. Do not mix solvents if you do not have to! 2.1. Dispose of halogenated solvents in a properly labeled halogenated solvent waste container. 2.2. Dispose of non-halogenated solvents in a properly labeled non-halogenated solvent waste container. 2.3. Dispose of aqueous waste containing heavy metal waste in a properly labeled heavy metal aqueous waste container. 2.4. Dispose of contaminated PPE and laboratory expendables into the laboratory regulated solid waste container. 2.5. Dispose of uncontaminated PPE and laboratory consumables in the laboratory nonregulated solid waste container. OPERATIONS FOR RAMAN SPECTRAL DATA COLLECTION ON CLEAR SOLUTIONS 1. Prepare instrument. 1.1. Check the Raman probe to see if the liquid standoff cap is in place. (This positions the beam so the focus will be inside the wall of a standard glass vial.) 1.1.1. Screw the standoff cap stamped “L” onto the Raman probe, if necessary. 1.1.2. Store the solids standoff cap “S” near the spectrometer with the verification cap “V” that contains a teflon insert. 2. Start instrument and computer. 2.1. Turn on instrument and computer. 2.1.1. Flip the rocker switch to on “1” on the Raman Systems RS-3000 Raman spectrometer. 2.1.2. Turn the key to turn the laser on. 2.1.3. Turn on the PC near the Raman spectrometer. 2.1.4. Ensure that a USB cable connects the PC to the spectrometer. 2.1.5. Start the Raman Desktop software 2.2. Record any error messages, and discuss with your supervisor. NOTE Instrument validation only needs to be performed at the beginning of a series of tests. 3. Validate instrument performance. 3.1. Install the verification cap “V” on the Raman probe OR place a vial of solvent that will exhibit a familiar Raman spectrum into the black aluminum sample chamber. 3.2. Insert the probe into the sample chamber till it is gently pressing against the vial. 3.3. Place the aluminum sample cover over the sample chamber. 3.4. Open the data collection toolbox in the Raman Desktop Software. 3.5. Set the integration mode to “Integration Mode Standard”. 3.6. Set the integration time to 10 s. 3.6.1. Adjust the integration time if necessary to produce peaks in the range of 1000 counts. 3.7. Set the dark spectrum mode to “Automatic Dark Subtract”. 3.8. Set the measurement mode to “Single Measurement”. 3.9. Set the maximum frame time to 10 s. 3.10. Set the total frames to 1. 3.11. Collect a sample spectrum. 3.12. Inspect it to see if the instrument is performing correctly. NOTE The instrument is now validated to be in good working order unless errors occurred. Discuss any errors with your supervisor. OPERATIONS FOR ANALYSIS OF LIQUIDS AND SOLUTIONS 1. Collect data for solvent blend composition analysis. 1.1. Place pure components into separate vials. 1.2. Collect Raman spectra of pure components 1.2.1. Data format = Raman Shift in Wavenumber 1.2.1.1. Insert the following calibration equation to make the software convert pixels (P) to wavenumbers Raman shift (cm-1). All of the decimal places from excel were kept here to ensure that the conversion is as precise as possible. 0.000393424633127776 2.17982010968675 98.6447924612422 1.2.1.2. Set the integration mode to “Integration Mode Standard”. 1.2.1.3. Set the dark and sample integration times to 10 s. 1.2.1.4. Set the dark spectrum mode to “Automatic Dark Subtract”. 1.2.1.5. Set the measurement mode to “Single Measurement”. 1.2.1.6. Set the maximum frame time to 10 s. 1.2.1.7. Set the total frames to 1. 1.2.2. Integration Time = 10 s 1.2.2.1. Modify the integration time to produce a maximum peak height near 1000 counts for the components with the strongest Raman signal. 1.2.2.2. Use this SAME INTEGRATION TIME for both components AND the mixture. 1.3. Place the blended solvent into a vial. 1.4. Collect a Raman spectrum of the blended solvent. 2. Export data as an Excel-compatible (csv) file. OPERATIONS FOR DATA ANALYSIS OF LIQUIDS AND SOLUTIONS 1. Chemometric Analysis of solvent blend spectrum. The following steps provide information on making a Microsoft Excel spreadsheet to perform the data analysis. 1.1. Create a sheet and name it “Raman Data”, and label a column for the wavenumber data, each component and the mixture using the top row. 1.2. Insert the wavenumber data and the counts data from the Raman spectral data starting in row 2 of each of the corresponding columns. 1.3. Create a new sheet and name it “Analysis”, and in the first row type the labels of each of the components and the mixture. These will be referred to as the label cells. 1.3.1. In the second row, type a number between 1 and 0 below each component as a “guess” of what the composition of the mixture is in respect to each component. The number that is typed in these cells are not important. However it is important that the sum does not exceed 1. These will be referred to as the composition cells. 1.3.2. For the last component, insert an equation that subtracts the compositions in respect to the other components from 1. 1.3.3. In a lower row, create columns that perform horizontal look ups to obtain the mixture data and the counts data for all of the components using the labels in the top row. 1.3.4. Create a separate column that calculates a spectrum using the weighted average of the component spectra. 1.3.5. Create a column that calculates the difference in each data point between the mixture spectrum and the calculated spectrum. These are the residuals. 1.3.6. Create a column that squares the residuals. 1.3.7. Create a cell that takes the square root of the sum of the squared residuals. 2. The following steps provide information on performing the data analysis. 2.1. Type the label of the mixture and each component of the mixture that is to be analyzed in the label cells. If the mixture only contains two components, leave the other label cells blank. This automatically updates the component data on this sheet. 2.2. Select “Solver” under the “Data” tab of Excel. 2.3. For a two component mixture, enter the following parameters into the “Solver Parameters” window: 2.3.1. “Set Objective” = [the Sum of the Squares of the Residuals] (ex: “$H$2”) 2.3.2. “To:” = “Min” 2.3.3. “By Changing Variable Cells:” = [composition cells] (ex: “$D$2”) 2.3.4. “Subject to the Constraints:” = [composition cells] <= 1 and >= 0 (ex: “$D$2:$F$2 <= 1”; “$D$2:$F$2 >= 0”) Volume fractions should always be less than or equal to one, and they cannot be negative by definition. 2.3.5. “Select a Solving Method:” = “GRG Nonlinear” 2.4. For a three component mixture, enter the following parameters into the “Solver Parameters” window: 2.4.1. “Set Objective” = [the Sum of the Squares of the Residuals] (ex: “$H$2”) 2.4.2. “To:” = “Min” 2.4.3. “By Changing Variable Cells:” = [composition cells] (ex: “$D$2:$E$2”) 2.4.4. “Subject to the Constraints:” = [composition cells] <= 1 and >= 0 (ex: “$D$2:$F$2 <= 1”; “$D$2:$F$2 >= 0”) Volume fractions should always be less than or equal to one, and they cannot be negative by definition. 2.4.5. “Select a Solving Method:” = “GRG Nonlinear” 2.5. Click “Solve”. The percentage of each component in the mixture will appear in the cell below the label of the corresponding component. 2.6. This method can be extrapolated to mixtures with more components. APPENDIX C CLOSED CUP FLASH POINT DETERMINATION SCOPE This procedure outlines all of the steps for determining the flash point of a liquid sample with a kinematic viscosity of less than 9.5 cSt at 25 degrees Celsius, using a closed cup flash point tester. PURPOSE This procedure provides instructions for determining the flash point of a liquid sample using a closed cup flash point tester. SAFETY REQUIREMENTS 1. Before beginning this procedure, read all of the Safety Data Sheets for the chemicals at hand. 2. Contact your supervisor for information regarding the proper personal protection equipment (PPE) to be used in this procedure. 3. Personnel engaged in the handling of chemicals that could present a hazard due to splashing are required to wear safety eyewear with side-shields, or work in a hood, or wear a safety face shield. NOTE Nitrile or equivalent gloves are used for incidental contact only. 4. Wear nitrile or equivalent gloves when handling chemicals. In case of an incidental spill, wear nitrile gloves during cleanup. Do not use latex gloves for organic solvent work. GENERAL INSTRUCTIONS 1. The sequence of operations in this procedure is not mandatory. 2. Waste Disposal NOTE Segregation of halogenated and non-halogenated waste streams is vital to the management of waste disposal costs. Likewise, recycling of solvent is a priority. Do not mix solvents if you do not have to! 2.1. Dispose of halogenated solvents in a properly labeled halogenated solvent waste container. 2.2. Dispose of non-halogenated solvents in a properly labeled non-halogenated solvent waste container. 2.3. Dispose of aqueous waste containing heavy metal waste in a properly labeled heavy metal aqueous waste container. 2.4. Dispose of contaminated PPE and laboratory expendables into the laboratory regulated solid waste container. 2.5. Dispose of uncontaminated PPE and laboratory consumables in the laboratory nonregulated solid waste container. OPERATIONS FOR DETERMINING THE FLASH POINT OF A LIQUID USING A CLOSED CUP FLASH POINT TESTER. 1. Prepare the flash point tester. 1.1. Fill the bath of the flash point tester. 1.1.1. Fill the bath with ethylene glycol, because the flash point of the sample is not known. The top pipe is the in pipe (for connection to a water tap when water is used), and the bottom pipe is the out pipe. 1.1.2. The bath is full when ethylene glycol is expelled from the out pipe on the back of the flash point tester into the waste container. 1.2. Connect the tester to a natural gas outlet using a rubber hose. 1.3. Wipe out the test cup with a lint-free wipe. 1.4. Place the test cup into the tester slowly allowing for any excess ethylene glycol to be expelled into a waste container through the overflow path built into the tester, and allowing the bath to remain completely full. 1.5. Measure 50 mL of the sample in a graduated cylinder. 1.6. Pour the sample into the cup without getting the cup wet above the liquid level. 1.7. Pop any bubbles in the liquid. 1.8. Place the lid on the tester. 2. Performing the flash point determination. 2.1. Perform the test with a fresh sample each time. 2.2. Perform the test under dim lighting. 2.3. Perform the test with a draft shield 18 inches long on each side, 24 inches high, and open in front. 2.4. Turn on the natural gas. 2.5. Barely turn the natural gas adjustment knob on the tester to allow the gas to reach the flame tip. 2.6. Light the natural gas coming from the flame tip to obtain the test flame. 2.7. Compare the size of the test flame to the flame size bead on the tester lid. 2.7.1. If the test flame is smaller than the bead, adjust the natural gas adjustment knob to make the flame the same size as the bead. 2.7.2. If the test flame is bigger than the bead, completely close the adjustment knob. Once the flame has gone out, try to open the adjustment knob less than it was opened previously. Light the gas to see the size of the flame. Repeat this process if necessary. 2.8. Start recording the test with a video camera. 2.9. At the beginning of the recording state the name of the sample along with the boiling point if it is known. 2.10. Before each application of the test flame to the sample, state the temperature reading from the thermometer of the test cup. 2.11. Apply the flame to the sample. 2.11.1. Turn the knob connected to the flame tip counter clockwise. This will pull open a sliding door and apply the flame to the hole closest to the flame tip. 2.11.2. Apply the flame to the sample for approximately one second. 2.12. Watch the hole farthest from the flame tip during application of the flame. 2.12.1. If the flame can be seen instantaneously propagating itself across the entire surface of the liquid, then the sample has flashed. The lowest temperature at which this occurs is the flash point. 2.12.2. An increase of the size, or a change in color of the test flame is not considered a flash. 2.13. If the sample flashes at this starting temperature, then the test needs to be performed at lower temperatures. In cases of extreme cooling being needed it is acceptable to report the flash point as being less than a certain temperature instead of trying to obtain the actual flashpoint. 2.13.1. To obtain temperatures lower than the ambient temperature, the tester along with the ethylene glycol bath can be placed in a chemical only laboratory refrigerator. Also, place a closed container of the sample in the refrigerator. 2.13.2. Lower temperatures can also be obtained by using an ice water bath instead of ethylene glycol. This bath can only cool down to zero degrees Celsius. 2.14. The starting temperature of the test should always be at least ten degrees Celsius below the flashpoint. 2.14.1. If the sample flashes less than ten degrees above the starting temperature, the test should be performed again with a lower starting temperature. 2.15. If the sample does not flash at the starting temperature, then power on the heater by flipping the switch on the side of the tester base. 2.16. Adjust the control knob to attempt to make the temperature raise by one degree Celsius per minute. 2.16.1. The control knob may need to be adjusted during the test to maintain the temperature rise of one degree Celsius per minute. 2.16.2. During the test, periodically check the temperature and time the rise of the temperature to ensure that the rate of temperature rise is correct. 2.17. Apply the flame to the sample after every one degree of temperature rise. 2.18. If the boiling point of the sample is reached and the sample has yet to flash, then the sample is said to have no flash point.