Identification and Characterization of Nonflammable Azeotropic Mixtures (Appendix D-F)

APPENDIX D SOLVENT COMPARISON FOR CLEANING GREASE SCOPE This procedure outlines the method used for comparing the ability of different solvents to remove grease. PURPOSE This procedure provides instructions for performing a test to compare the ability of various solvents to remove grease. 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 heavy metal waste into the laboratory regulated solid waste container. 2.5. Dispose of contaminated PPE and laboratory expendables into the laboratory regulated solid waste container. 2.6. Dispose of uncontaminated PPE and laboratory consumables in the laboratory nonregulated solid waste container. OPERATIONS FOR COMPARISON OF THE ABILITY OF SOLVENTS TO REMOVE GREASE 1. Producing grease contamination. 1.1. Number enough clean, empty vials to have five replicate vials as blanks, and five replicate vials for each test solvent. 1.1.1. Blanks are empty vials. 1.1.2. Make sure that the caps are also numbered. 1.2. Weigh all of the vials with the caps on. 1.3. Add a small amount of grease to the bottom of every vial, except for the five blank vials, using a syringe. 1.3.1. Take note of which numbers correspond to the blank vials. 1.3.2. Do not to get grease on the top half of the vial! 1.4. Weigh all of the vials again with the caps on. 2. Cleaning the grease from the vials. 2.1. Remove the caps of all of the vials except for the blank vials. 2.2. Fill each vial that contains grease three quarters full with a test solvent. Five vials per solvent. 2.2.1. Take note of which numbered vials contain which solvent. 2.2.2. Do not add solvent to the blank vials. 2.3. Place the caps back on the vials as they are filled. 2.4. Weigh all of the vials again. 2.5. Shake all of the vials for one hour at a high setting on a shaker. 2.6. Number 5 clean aluminum weigh pans for each test solvent for use as transfer pans. 2.6.1. Make sure the numbers correspond to the numbers that are on the vials on the shaker. 2.7. Weigh all of the transfer pans. 2.8. When the shaking period is over, pour the solvent from the vials on the shaker into the corresponding transfer pans. 2.9. Place the vials that were transferred from (without the caps), and the pans that were transferred to, in the GC oven at 100 °C to evaporate the solvent. 2.10. Take vials out of the oven as they get dry. 2.10.1. Do not allow the residue to get cooked to the vials or pans! 2.11. Allow the vials and pans to cool to room temperature. 2.12. Place the caps back onto the vials. 2.13. Weigh the dry transfer pans. 3. Qualitative data collection of the extracted grease contamination. 3.1. Take pictures of the resulting residue in the bottom of the vials that were transferred from, and the pans that were transferred to. 3.2. Examine the vials and pans and make note of any interesting observations. GRAVIMETRIC DATA ANALYSIS 1. Analysis of the grease contamination data. 1.1. Calculating the percent of the grease removed from the vials. 1.1.1. Subtract the mass of the empty vials from the mass of the vials with grease to obtain the mass of grease added to each vial. 1.1.2. Subtract the mass of the transfer pan from the mass of the pan with the transferred residue to obtain the mass of the grease residue that was transferred. 1.1.3. Divide the mass of the grease residue that was transferred by the mass of grease added to each vial to obtain the fraction of grease that was transferred by the solvent. 1.1.4. Multiply the fraction of grease that was transferred by the solvent by 100 to obtain the percentage of grease that was transferred by the solvent. APPENDIX E LIQUID DENSITY AND SURFACE TENSION MEASUREMENT AND DATA ANALYSIS SCOPE This procedure outlines tensiometer preparation, density and surface tension data collection, and data analysis for determining the density and surface tension of liquid samples using a DuNuoy ring tensiometer. PURPOSE This procedure provides instructions for performing density and surface tension measurements, data collection, and data analysis using Microsoft Excel. 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 DENSITY AND SURFACE TENSION MEASUREMENT 1. Construction of the apparatus. 1.1. Find a flat material, such as ply wood, for an upper platform that is big and sturdy enough for a digital laboratory balance to be supported by it. 1.2. Cut a hole in the upper platform where the under-hook of a balance sitting on top of the material could be accessed from the underside of the material. 1.3. Find a raising and lowering platform, such as a hydraulic jack, that is capable of lowering at a very slow rate. 1.4. Mount the upper platform with the hole over the raising and lowering platform in a way that would allow it to support the weight of a laboratory balance with minimal vibration. 1.5. Place a digital laboratory balance on the upper platform so that the under-hook of the balance is over the hole. 1.6. Hang a small bead chain from the under-hook of the balance. 1.7. Bend or cut a small hook connector so that the open side of the hook is lower than the other side. 1.8. Attach the hook connector to the bead chain hanging from the under-hook of the balance. 1.9. Connect the balance to a computer with data collection software such as Hyperterminal. 1.10. Make the balance level. 2. Measure density. 2.1. Tare the balance. 2.2. Obtain a small Pyrex sinker with a volume of 10 cm3. 2.3. Place the sinker on the hook connector. 2.4. Allow the mass reading to stabilize. 2.5. Record the stable mass as the dry mass (md). 2.6. Obtain a container of the sample liquid large enough so that the sinker can be submerged in the liquid without touching the bottom of the container. 2.7. Place the sample container under the hanging sinker. 2.8. Raise the platform so that the sinker enters the liquid sample. 2.9. Keep raising the platform until the sinker is completely submerged and only one side of the hook connector is breaking the surface of the liquid. 2.10. Allow the mass reading to stabilize. 2.11. Record the stable mass reading as the wet mass (mw). 2.12. Lower the platform to remove the sinker from the sample. 2.13. Remove the sinker from the hook connector. 2.14. Measure the temperature of the sample with a thermocouple. 2.15. Repeat to obtain a duplicate measurement. 3. Measure surface tension. 3.1. Obtain a platinum iridium tensiometer ring with a ring radius of 0.9537 cm, and a wire thickness of 0.01779 cm. 3.2. Make sure that the ring is perfectly circular and flat, and that the part that the ring hangs from is perfectly perpendicular to the ring. 3.3. Clean the ring by applying fire to it until it glows red. 3.3.1. Always remove the ring from the fire immediately when it starts glowing red. 3.4. Hang the ring from the hook connector hanging from the under-hook of the balance. 3.5. Obtain a container of your sample. The liquid does not have to be very deep in the container. However, the container should have a large enough diameter for the meniscus in the container to not affect the liquid’s surface in the center of the container. 3.5.1. A 400 or 600 mL beaker has a good diameter for this purpose. 3.6. Place the sample container on the platform directly below the ring. 3.7. Raise the platform until the ring is just below the surface of the sample. 3.8. Make sure that the ring is in the center of the container. 3.9. Bend a thermocouple over the wall of the sample container in a way that allows the thermocouple to be submerged in the sample but close enough to the wall of the container to not interfere with the surface tension measurement. This allows constant measurement of the temperature. 3.10. Tare the balance. 3.11. Begin capturing data with the data collection program on the computer. 3.12. Make the platform begin lowering at a slow and steady rate. 3.13. The ring should begin slowly rising through the surface of the sample. 3.14. The ring will pull the surface of the liquid upward with it. 3.15. The mass lifted should increase, and just before the ring disconnects from the liquid’s surface, the mass lifted should begin decreasing. 3.15.1. If the mass lifted doesn’t start to decrease before the ring disconnects from the surface of the liquid, then the platform was probably lowering too fast. If this happens, restart the measurement. 3.16. When the ring disconnects from the liquid’s surface, the measurement is complete. The temperature should be recorded at the time this occurs. 3.17. Stop the data collection. 3.18. Save the data. 3.19. Obtain at least two measurements. 3.20. Always refresh the surface of the sample by removing the surface with a disposable pipet between measurements. DENSITY AND SURFACE TENSION DATA ANALYSIS 1. Analysis of density data. 1.1. The following equation can be used to calculate the hydrostatic density. Where, dry mass is represented by md, the density of the sinker is represented by ρ1 (this is calculated by dividing the dry mass in grams by the volume of the sinker in mL), the liquid density is represented by ρ2, the wet mass is represented by mw, and the density of the air is represented as ρ3 (this value is kept constant at 0.00118 g/mL in all calculations, because the changes in this value are insignificant). 1.2. This density value can be interpolated to 25 °C. 1.2.1. Take a density measurement at a temperature lower than 25 °C that is also lower than the temperature of the density measurement that needs to be interpolated. 1.2.2. Take a density measurement at a temperature higher than 25 °C that is also higher than the temperature of the density measurement that needs to be interpolated. 1.2.3. The span of these two temperatures should be about 10 to 20 °C. 1.2.4. Convert the high and low temperature density measurements and the two ambient temperature density measurements to Kg/m3. 1.2.5. Use the following equation and the four density measurements to do a regression to obtain the volumetric temperature expansion coefficient (β). 1 In this equation, ρL is the density at the lowest temperature in Kg/m3, ρH is the density at a higher temperature in Kg/m3, TL is the lowest temperature in °C, and TH is the higher temperature in °C. 1.2.5.1. Create a column in excel that calculates the left side of the equation for all four measurements where the low temperature density stays constant at the lowest temperature value for each calculation. These are the y-values for the regression. Keeping the low temperature value constant creates a zero intercept. 1.2.5.2. Create a column in excel that subtracts the lowest temperature from each temperature. These are the x-values for the regression. 1.2.5.3. 1.2.6. The slope obtained from the regression analysis is β. The low temperature density and β can be used to determine the density at 25 °C with the use of the equation from the previous step. 1.2.6.1. The constant β is unique to every liquid. If a different sample is used, then a new β will need to be calculated. 1.2.7. Use the information in the regression output to obtain an uncertainty value for the interpolated density value. 2. Analysis of surface tension data. 2.1. In an Excel workbook, plot all of the mass lifted versus time data. This will be referred to as a force curve. 2.2. Towards the end of the force curve, the mass lifted should reach a maximum and decrease for a small amount of time to create a rounded curve downward before the meniscus breaks and the mass lifted drops almost vertically to zero. 2.2.1. If the mass lifted drops sharply to zero without first decreasing in small increments to create a curve downward, then the data is bad and the procedure needs to be performed again. 2.3. Find the maximum mass lifted (m) in grams for each set of data by using the maximum function in Excel. 2.4. The maximum mass lifted (m) is used to calculate the maximum liquid volume lifted (V). 2.5. The maximum mass lifted can also be used to calculate the maximum equilibrium force of detachment (F). 2.6. In this equation, g is the gravitational acceleration (g = 980.665 cm/s2). This force and the radius of the ring (R) can be used to calculate a first approximation of the surface tension (γ) 4 2.7. Two consecutive corrections are applied to this approximation. The sources of these corrections are discussed further in the Williams paper. The first correction term is for the interface between phase 2 and phase 3, the liquid and the air. This correction (ƒ23) is a function of R3/V and R/a where a is the wire radius of the ring. This correction term is applied as seen in the following equation. 4 ƒ 2.8. The second correction term is calculated using the shape of the interface between phases 2 and 3. The corrected surface tension from the previous equation is used to calculate a scaling factor (C23) for R and V as seen in the following equation. 2.9. This scaling factor is applied to the radius of the ring as seen in the following equation. 2.10. The scaling factor is applied to the volume lifted as seen in the following equation. / 2.11. R’ and V’ are used to calculate the second correction to the surface tension (ƒ’) as seen in the following equation ƒ 4 ′ ′ 2.12. The final surface tension value is calculated using the following equation. 4 ƒ′ 2.13. Use a density value that has been corrected to the temperature of the surface tension measurement when performing these calculations. 2.13.1. Correct the density value using the method given in the density data analysis section replacing 25 °C with the temperature of the surface tension measurement. 2.14. The surface tension value can be interpolated to 25 °C. 2.14.1. Take a surface tension measurement at a temperature lower than 25 °C that is also lower than the temperature of the surface tension measurement that needs to be interpolated. 2.14.2. Take a surface tension measurement at a temperature higher than 25 °C that is also higher than the temperature of the surface tension measurement that needs to be interpolated. 2.14.3. The span of these two temperatures should be about 10 to 20 °C. 2.14.4. A plot of the hot, cold and ambient measurements should reveal a strong linear relationship between temperature and surface tension. The surface tension should decrease as temperature increases. 2.14.5. Perform a regression on the data to decide if the coefficients in the linear equation given are statistically significant. 2.14.6. If the coefficients are statistically significant (p-value < 0.05), use the equation to interpolate the surface tension measurement to 25 °C. 2.14.7. Calculate an uncertainty value for the surface tension using the standard error values from the regression output. APPENDIX F FALLING BALL VISCOSITY MEASUREMENT AND DATA ANALYSIS SCOPE This procedure outlines viscometer preparation, viscosity data collection, and viscosity data analysis for determining the viscosity of liquid samples using a falling ball viscometer. PURPOSE This procedure provides instructions for performing falling ball viscosity measurements, data collection, and data analysis using Microsoft Excel. 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 FALLING BALL VISCOMETER PREPARATION AND VISCOSITY DATA COLLECTION ON LIQUID SAMPLES 1. Prepare viscometer. 1.1. Clean viscometer. 1.1.1. Rinse, all viscometer parts that come in contact with the sample, twice with HPLC or spectrophotometry grade methanol. This includes the tube, top, cap, and ball. 1.1.2. Rinse, all viscometer parts that come in contact with the sample, twice with the sample liquid. This includes the tube, top, cap, and ball. 1.2. Fill viscometer. Always test fresh type I deionized water before any series of measurements, so that the viscometer constant can be calculated later. 1.2.1. Fill the tube with the sample liquid until the liquid level is about ¼ of an inch from the top of the tube. 1.2.2. Add the steel ball to the tube. 1.2.3. Fill the tube to the top with the sample liquid. 1.2.4. Attach the top to the tube using the Teflon screw. The liquid will fill the capillary vent in the top and some of the sample liquid will be expelled from the capillary vent. 1.2.5. Close the tube by screwing the cap onto the capillary vent in the top. 1.2.6. Dry the outside out the tube and top using a paper towel if needed. 1.2.7. Invert the tube a few times, allowing the ball to fall from one end to the other. 1.2.8. Check the tube for air bubbles during 1.2.7. 1.2.9. If air bubbles are observed, empty the tube and repeat all steps from 1.2. 1.2.10. If air bubbles are not observed and the steel ball passes through the timing zone in less than one second, empty the tube and repeat all steps from 1.2 using a glass ball. 1.3. Insert viscometer into the rotating viscometer holder on the viscosity apparatus. 1.4. Wait about 20 minutes for the viscometer and liquid to reach thermal equilibrium with the room. 2. Use of the viscosity apparatus for data collection. 2.1. Prepare the video camera attached to the apparatus. 2.1.1. Power on the video camera. 2.1.2. Ensure that the video camera is aligned with the starting timing lines to avoid parallax errors. 2.2. Measuring the temperature. 2.2.1. Unscrew the cap from the capillary vent. 2.2.2. Insert the end of a thermocouple into the capillary vent just far enough to be submerged in the liquid. 2.2.3. After the temperature reading has stabilized, record the temperature. 2.2.4. Replace the capillary vent cap. 2.3. Taking a viscosity measurement. 2.3.1. Rotate the viscometer up using the rotating viscometer holder until the ball is at rest in the top of the viscometer. 2.3.2. Start recording with the video camera 2.3.3. State the name of the sample, the trial number, and the temperature aloud for the recording. 2.3.4. Rotate the viscometer down so that it rests vertically in front of the camera. 2.3.5. After the ball passes through the first set of timing lines, shine a light behind the second set of timing lines on the viscometer. This will cause the camera to focus on the second set of timing lines. 2.3.6. After the ball passes through the second set of timing lines, stop the recording. 2.3.7. Repeat all steps from 2.2. and 2.3. until a sufficient number of measurements have been performed. FALLING BALL VISCOSITY DATA ANALYSIS 1. Obtain the starting and finishing times for each measurement. These times will be in seconds and fractions of seconds. The fractions depend on how many frames per second are achieved by the video camera. 1.1. Open the viscosity videos in Adobe Premiere Pro or other video software that allows frame-by-frame control. 1.2. Watch the video of each measurement frame by frame to obtain the correct time stamps. 1.3. The starting time is obtained by watching as the ball passes through the first set of timing lines. When the ball is exactly between the two lines, record the time stamp for that frame. 1.4. The finishing time is obtained by watching as the ball passes through the second set of timing lines. When the ball is exactly between the two lines, record the time stamp for that frame. 2. Analysis of the viscosity measurement data. 2.1. Use the following regression equations from the NIST data on water to calculate the density (ρ) and viscosity (η) of water at the temperature (T) of each water measurement. 0.00000500 2 0.0000056 7 1.000271 9 0.000430 2 0.042 1 1.668(1) 2.2. Use the time (t) of the ball drop, the density of the ball (ρb) (steel = 8.020 g/mL and glass = 2.530 g/mL), the viscosity of water, and the density of the sample (ρs) (water in this case) to calculate the viscometer constant (K) at each water measurement temperature. 2.3. Perform a regression analysis on the viscometer constant versus temperature data for water to produce a temperature-dependent viscometer constant equation. 2.4. Interpolate the density values to the temperature of each sample measurement according to the method given in the density and surface tension SOP. 2.5. Use the temperature-dependent viscometer constant equation to calculate the viscometer constant at the temperature of each sample measurement. 2.6. Use the viscosity equation and the time of the ball drop to calculate the viscosity for each measurement of each sample. 3. The viscosity can be interpolated to 25 °C. 3.1. Perform a regression of the temperature versus viscosity data for each sample to obtain an equation that can be used to interpolate the viscosity to 25 °C.