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Understanding Intermolecular Forces Using a Gas Chromatograph: Enthalpy of Vaporization

One well-known application of gas chromatography is its analytical capabilities used to obtain purely physiochemical data such as activity coefficients of solutes in various solvents, heats of solution, and enthalpies of vaporization of volatile compounds. It can also be used to demonstrate colligative properties. Here, we introduce the determination of the enthalpy of vaporization using retention times measured with a gas chromatograph (GC). The enthalpy of vaporization, Hvap, is typically calculated by employing the Clausius-Clapeyron equation with measurements of the vapor pressure of the liquid at various temperatures. The enthalpy of vaporization provides information about the size and nature of intermolecular forces in liquids. Typically, the stronger these forces are, the larger the enthalpy of vaporization. Gas chromatography is based on a solute in a mixture partitioning itself between the mobile phase and the stationary phase. With the Vernier Mini GC, the mobile phase is air and the stationary phase is a nonpolar phase capillary column. The amount of time a given chemical spends in the stationary phase relative to the amount of time it spends in the mobile phase is a very important quantity in elution chromatography; it is called the capacity factor, k, and is given by: k'= tR tM tM

where tR is the retention time of the compound; that is, the amount of time the chemical spends in the column from the point of injection to the point of detection. The time it takes for the mobile phase to pass through the column is referred to as tM; it is typically the retention time of a non retained species. In this experiment, the non retained compound you will be using is acetone and it functions as a very important standard to help normalize the amount of time it takes a species to run though the column, enabling calculation of k. As part of this calculation, we are assuming that the retention time of the non-retained species (acetone) is independent of temperature. To relate the capacity factor to the enthalpy of vaporization, the following equation is used1: k ' H vap 1 ln = +C R T T where Hvap is the standard enthalpy (heat) of vaporization of the compound. This value is assumed to be independent of temperature. T is the temperature in Kelvin, R is the gas constant in appropriate units, and C is a constant. The equation is written in the slopeintercept form where the value of Hvap is determined by plotting ln(k/T) vs. 1/T.

Ellison, H.R., Enthalpy of Vaporization by Gas Chromatography. A Physical Chemistry Experiment. Journal of Chemical Education, 2005. 82(7): p. 1086-1088.

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OBJECTIVES
In this experiment, you will Collect and analyze GC data from various samples. Calculate the enthalpy of vaporization of various compounds from GC temperature dependent data. Identify an unknown sample based on its enthalpy of vaporization using values calculated from known standards.

MATERIALS
LabQuest or computer LabQuest App or Logger Pro Vernier Mini GC 1 L glass syringe Kimwipes or paper towel acetone ethyl acetate 2-butanone 4-methyl-2-pentanone an unknown solution containing acetone and one of the following: 2-butanone, butyl acetate, propyl acetate

PROCEDURE
1. Obtain and wear goggles. Protect your arms and hands by wearing a long-sleeve lab coat and gloves. Conduct this reaction in a fume hood. 2. Prepare or obtain three known solutions, each using acetone as the standard that will pass quickly through the column. Prepare each solution to a total volume of 1 mL in a 1:1 (v/v) mixture. Also obtain a solution of acetone for syringe cleaning. a. Solution 1 contains acetone and ethyl acetate. b. Solution 2 contains acetone and 2-butanone. c. Solution 3 contains acetone and 4-methyl-2-pentanone. 3. Prepare the Vernier Mini GC for data collection. a. Turn on the Mini GC and connect it to the USB port on your computer or LabQuest. b. Start the data-collection program, then choose New from the File menu. c. To bring up the Temperature-Pressure profile, tap on LabQuest or click Collect in Logger Pro. d. Set the Temperature-Pressure values to:
Run 1 Start temperature Hold time Ramp rate Final temperature Hold time Total length Pressure 110C 10.0 min 0C/min 110C 0 min 10.0 min 4.0 kPa

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Understanding Intermolecular Forces with GC e. Select Done to initiate the Mini GC warm up. When the Mini GC is ready for injection in Step 7, the message will read, Inject and click Collect simultaneously, and the LED will turn to green. Continue with Step 4 during warm up. 4. Follow the steps below to clean and flush the syringe with acetone. Important: The glass syringe is fragile. Be careful not to bend the needle or bend the plunger. Never pull the plunger back more than 50% of its total volume. Be careful not to bend the plunger as you press it down. a. Depress the plunger fully. b. Submerge the tip of the syringe needle into the vial of acetone. c. Pull back the plunger to fill the barrel about 1/3 full of acetone. Examine the barrel of the syringe and estimate the amount of acetone in the barrel. d. Expel the liquid onto a Kimwipe or a paper towel. e. Repeat Steps ad at least two times, until you are comfortable pulling up a liquid into the syringe and measuring the volume in the syringe barrel. Use a Kimwipe or a paper towel to carefully pat around the tip of the syringe needle. 5. Follow the process in Step 4 to clean and flush the syringe with Solution 1. 6. Collect a volume of Solution 1 for injection. a. Submerge the needle into the vial of Solution 1 one last time. b. Draw up approximately 0.1 L of liquid. c. After collecting your sample, use a Kimwipe to gently wipe the needle from barrel to tip. 7. Prepare for injection and the start of data collection. Figure 1 a. The Mini GC should now have reached the correct start temperature and pressure and the LED turned to green. b. To insert the needle of the syringe into the injection port of the Mini GC, hold the syringe with one hand and steady the needle with your other hand, as shown in Figure 1. Insert the needle into the injection port until the needle is fully seated. If the needle sticks, rotate it slightly while inserting. Do not move the plunger yet. c. Simultaneously, depress the syringe plunger and select Collect to begin data collection. Pull the needle out of the injection port immediately. 8. While the data collection proceeds, repeat Step 4 to thoroughly clean the syringe and needle. It may take more than three flushes to feel the syringe plunger move smoothly again, which is your indicator that the syringe and needle are both suitably clean. 9. Data collection will end after ten minutes or you can choose to end it early if you are satisfied that your species has eluted completely. 10. Analyze your chromatogram. a. Choose Peak Integration from the Analyze menu. b. Select and integrate the left-most peak. To do this, drag from a little before the peak to a point far enough to the right that includes all of the peak. Then choose Add. c. Record the retention time in your data table. d. Enter the name of the compound, if known.

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e. To analyze another peak on the same graph, repeat Steps b and c. f. When you are finished with all of the peaks, select OK. 11. (optional) You can choose to save this chromatogram and peak analysis for later use, with a unique file name, by choosing Save from the File menu. 12. Select another sample. a. Click Collect in Logger Pro, or tap in LabQuest. This profile will be the same as for your previous run. Change the temperature profile for the next run. Continue to do isothermal runs in decreasing increments of 10C until you reach 80C (see Data Table). Then select Done. b. While the Mini GC adjusts to its Temperature-Pressure profile, repeat Steps 56 with the next sample of the same solution. c. After the Mini GC is ready, repeat Steps 711 using your new sample. 13. Repeat Step 12 until you have completed all four temperature runs for all three solutions. 14. Obtain an unknown sample from your instructor and repeat Steps 511 with your unknown. 15. When you have completed your final data collection run, turn off the Mini GC.

DATA TABLES
Solution 1: Acetone and ethyl acetate (1:1) Temperature (C) 110 100 90 80 Solution 2: Acetone and 2-butanone (1:1) Temperature (C) 110 100 90 80 Retention time for standard compound (min) Retention time for test compound (min) Retention time for standard compound (min) Retention time for test compound (min)

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Understanding Intermolecular Forces with GC


Solution 3: Acetone and 4-methyl-2-pentanone (1:1) Temperature (C) 110 100 90 80 Unknown Solution Temperature (C) 110 100 90 80 Retention time for standard compound (min) Retention time for test compound (min) Retention time for standard compound (min) Retention time for test compound (min)

DATA ANALYSIS
1. Enter your raw data (Temp (C), tM (min), tR (min)) into Logger Pro software or LabQuest App: a. With no sensor connected, choose New from the File menu. b. In LabQuest App, tap the Table tab to display the data table. In Logger Pro, the data table is displayed to the left of the graph. c. In addition to the default X and Y columns, you will need to insert a third (Manual) column. To do this, choose New Manual Column from the Data menu of Logger Pro, or from the Table menu in LabQuest App. d. In the data table, double-click (in Logger Pro) or tap (in LabQuest App) the X column heading. Name the column Temperature, with units of C. In the same manner, assign the Y column heading as Time M (min), and the manual column as Time R (min). Time M and Time R represent tM and tR, respectively. e. Now enter your data. Select the first cell in the Temperature (C) column. Type in the temperature value, then press or tap Enter. f. The cursor will now be in the Time M (min) column. Enter the corresponding Time M value. In the same way, enter the Time R value in the third column. g. Continue in this manner to enter all of your data rows. h. Do not worry about the graph that is automatically generated until you finish making all of the calculated columns in Step 2.

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2. Using the experimental data you collected, calculate the following variables: Temp (K), k, 1/T (1/K), ln(k/T). Here is a brief summary of how to create new calculated columns using the example of converting Temperature (C) into units of Kelvin. a. From the Data Menu, Choose New Calculated Column. b. In Logger Pro: Enter Temperature K as the Name, Temp K as the Short Name, and K as the Unit. Enter the correct formula for the column (Temperature+273) into the Equation edit box. To do this, select Temperature from the Variables list, then type in +273. In the Equation edit box, you should now see displayed: Temperature+273. c. In LabQuest App: Enter the Name (Temp K) and the Units (K). Select the equation, X+A. Use Temperature(C) as the Column for X. Enter 273 as the value for A. Tap OK. d. Repeat Steps ac to create calculated columns for the remaining variables (k, 1/T (1/K), ln(k/T)) using the appropriate formulas found in the introduction. 3. Plot ln(k/T) vs. 1/T (1/K). From the slope, the enthalpy of vaporization can be calculated using the equation in the introduction. 4. Find a literature value for Hvap for each pure compound. Calculate the percent difference between your experimental value and the literature value. 5. Identify your unknown compound based on your calculations of the Hvap for the possible unknowns. Calculate the percent error between your experimental value and the literature value. 6. Discuss the compound structures and the trend with regards to their enthalpy of vaporization. Be sure to include discussion of the types of intermolecular interactions experienced between the standard and test compound and how that affects their enthalpy values.

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Understanding Intermolecular Forces with GC

INSTRUCTOR INFORMATION
1. We recommend having vials of each compound available to the student, with back-up vials retained by the instructor. If a student contaminates a vial by mistake or spills a compound, the back-up vials can be used as replacements. 2. We strongly recommend using reagent grade compounds for the best, most reliable results. 3. Vials must be kept tightly sealed when not in use. These compounds are highly volatile and will evaporate quickly. 4. Be familiar with the MSDS information for each compound and follow safe handling practices. 5. All unknown compounds should be prepared in a 1:1 (v/v) ratio. If you wish to have students confirm their prediction, you can provide the stock compounds for them and have them add a small amount of whichever one they think it is. If the student is correct, the peak size will increase. If they are incorrect, their chromatogram will have three peaks. 6. An alternative standard compound suitable to act as the unretained compound is methanol. 7. Students will calculate their percent differences using values they look up, or you can provide the following:
Compound 4-methyl-2-pentanone propyl acetate 2-butanone ethyl acetate butyl acetate Hvap (kJ/moL) 40.65 33.92 34.92 31.94 43.60

8. As a result of the derivation, the equation given is only valid over short ranges of temperature. Extending the temperature range further than 40C will result in larger percent difference values. 9. Expect data collection (not including data analysis) to take about 1.5 hours. 10. To fit sections of this experiment into a smaller time period, the samples can be divided between the class where 23 pairs prepare and investigate one known and one unknown and the other pairs investigate another, etc. Toward the end of the class, students can share their data on the known samples. 11. Expect for this lab to have fairly large percent errors. Slight deviation on the retention time peak affects the slope.

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HAZARD ALERTS
Acetone: Fire hazard (flash point: 17.0C). Store in dedicated flammables cabinet. Moderately toxic by inhalation or ingestion. Moderately toxic by ingestion. Vapor causes weakness, fatigue, nausea and headache. Skin and eye irritant. HMIS Classification: Health hazard 2, Flammability Physical hazard 3, 0. Ethyl Acetate: Serious fire hazard (flash point: 3.0C). Irritating to body tissues. Severe eye irritant. Avoid all body tissue contact. Slightly toxic by ingestion. Vapor causes weakness, fatigue, nausea and headache. Skin contact causes dermatitis. HMIS Classification: Health hazard Flammability Physical hazard 2, 3, 1. Methanol: Fire hazard (flash point: 11.0C). Store in dedicated flammables cabinet. Moderately toxic by inhalation or ingestion. Moderately toxic by ingestion. Vapor causes weakness, fatigue, nausea and headache. Skin and eye irritant. HMIS Classification: Health hazard 2, Flammability Physical hazard 3, 0. 2 Butanone (Methyl Ethyl Ketone): Fire hazard. Store in dedicated flammables cabinet. Moderately toxic by inhalation or ingestion. Moderately toxic by ingestion. Vapor causes weakness, fatigue, nausea and headache. Skin and eye irritant. HMIS Classification: Health hazard Flammability Physical hazard 2, 3, 0. 4 Methyl pentanone: Fire hazard. Store in dedicated flammables cabinet. Highly flammable 2 liquid and vapor. May be harmful if swallowed. Causes mild skin irritation. Fatal if inhaled. May cause damage to organs. HMIS Classification: Health hazard Flammability Physical 4, 3, hazard 0. Butyl acetate: Fire hazard. Store in dedicated flammables cabinet. Flammable liquid and vapor. Causes skin irritation. Causes serious eye irritation. Toxic if inhaled. May cause damage to organs. Harmful to aquatic life. HMIS Classification: Health hazard Flammability Physical 2, 3, hazard 0. Propyl acetate: Fire hazard. Store in dedicated flammables cabinet. May be harmful if inhaled, absorbed through skin, or swallowed. Causes respiratory tract irritation. Vapors may causedrowsiness and dizziness. Causes eye irritation. HMIS Classification: Health hazard 2, Flammability Physical hazard 3, 0. The hazard information reference is Sigma-Aldrich Co., 1-800-325-3010, www.sigmaaldrich.com/safety-center/msds-search.html.

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Understanding Intermolecular Forces with GC

SAMPLE RESULTS
Gas chromatograms of 4-methyl-2-pentanone in acetone at varying temperatures

Graphical analysis to determine the Hvap of 4-methyl-2-pentanone in acetone

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