Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

TEMPERATURES RELATIONSHIP TO GAS & VAPOR PRESSURE

Adapted from "Chemistry with Computers" Vernier Software, Portland OR, 1997

OBJECTIVES Data will be collected to determine the relationship between gas pressure and temperature and to find absolute zero. Using the same experimental setup the relationship between vapor pressure and temperature will be determined. Furthermore, a plot of the natural log of vapor pressure versus inverse Kelvin will permit the calculation of the heat of vaporization (Hvap) from the Clausius Clapeyron equation: ln P = (Hvap / R) (1/T) + C.

SAFETY Students must wear safety goggles and lab aprons at all times in the lab. Be careful when handling heated glassware. Use paper towels, toweling, or tongs to avoid burns. Ethanol is flammable; make sure there are no sparks or flames in lab. Ethanol fumes can irritate eyes and lungs; avoid contact with fumes.

INTRODUCTION Molecules in the gas phase are in constant motion. Gas pressure is a measurement of the number of collisions of molecules with the walls of the container. The velocity and the number of collisions of these molecules changes when the temperature of the gas increases or decreases. In this experiment, the relationship between the temperature of a gas sample and the pressure it exerts will be investigated. Using the apparatus shown in Figure 1, an Erlenmeyer flask containing an air sample will be placed in water baths of varying temperature.

Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

Figure 1

Pressure will be monitored with a pressure sensor and temperature will be monitored using a temperature probe. The volume of the gas sample and the number of molecules it contains must be kept constant. Pressure and temperature data pairs will be collected during the experiment and then analyzed. From the data and graph, you will determine what kind of mathematical relationship exists between the pressure and absolute temperature of a confined gas. Finally, the value for absolute zero will be determined.

In the next part of this experiment you will investigate the relationship between vapor pressure and temperature and find the heat of vaporization (Hvap) of ethanol. When a liquid is added by syringe to the same sealed Erlenmeyer flask used for the first part of the experiment (Figure 2), it will begin to evaporate into the air above in the flask.

Figure 2

Evaporation will continue until equilibrium is established between the rate of evaporation and the rate of condensation. At this point, the vapor pressure of the liquid is equal to the partial pressure of its vapor in the flask. The pressure sensor will be used to measure changes in the total pressure in the flask (the pressure resulting from air and gaseous ethanol molecules together). 2

Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

First, the pressure in the flask will be measured at room temperature and then the flask will be placed in a water bath so the temperature of the bath can be increased by small increments to determine the effect of temperature on vapor pressure. By plotting the natural log of the vapor pressure (ln P) versus inverse Kelvin temperature (1/T), the heat of vaporization (Hvap) can be determined from the slope of the best fit line using the Clausius Clapeyron equation:

(1) ln P = (Hvap / R) (1/T) + C

(where R = gas constant, 8.3145 J/mol-K and C is a constant.)

A flow chart should be prepared in your duplicate lab notebook and turned in at the beginning of the laboratory period. On the next available page, the experiment title and source(s) (the lab manual website should be listed as well as any other texts or websites used to complete the experimental write-up). Procedures should not be word-for-word from the lab manual. It is not necessary to provide detailed steps for computer program navigation. In other words, give important experimental steps that any student would use, regardless of type (or even presence) of a computer interface. All data and results should be reported in tables followed by calculations and answers to discussion questions.

PROCEDURE Part A. Temperature & Gas Pressure Work in pairs. Wear safety goggles and lab apron in lab at all times. 1. Prepare 4 water baths containing approx 800-mL of water in 1-L beakers. Place a stir bar in each beaker and place the beaker on a stir plate. Stir on the stirrer (not the heat) to make sure that the temperature throughout each bath is even. Boiling-water bath. Use hot tap water; heat to boiling on a hot plate. Hot water bath. Use hot tap water. Room temperature bath. Use tap water and let stand at RT. Ice-water bath. Use cold tap water and ice mixture.

Temperatures Relationship to Gas & Vapor Pressure 2. Prepare the glassware setup for the experiment.

Revised 12/15/10

Obtain a rubber-stopper assembly with a piece of heavy-wall plastic tubing connected to one of its two valves (Figure 3).

Figure 3

Insert the rubber-stopper assembly into a 125-mL Erlenmeyer flask. Important: Twist the stopper into the neck of the flask to insure a tight fit. Attach the connector at the free end of the plastic tubing to the gas pressure sensor valve with a clockwise turn. Wrap parafilm around the stopper and top of the flask to provide extra insurance against gas leaks. (Parafilm should be stretched when doing this or it will not provide a good seal.)

Close the 2-way valve above the rubber stopper as shown in Figure 4. Do this by turning the white valve handle so it is perpendicular with the valve step itself.
open closed

Figure 4

3. Prepare the computer for data collection. (Note: This program is user friendly and typically there is more than one way to change a setting the instructions below are just one example.) If any probes are connected to the teal blue Logger Pro interface box, disconnect them. Open the Logger Pro program. Only one Data Set and one Graph need to be open, close all others. (If the program is already open, close and reopen to avoid any computer issues.) Make the following adjustments: Click on the Experiment menu and choose Set Up Sensor. The Sensor Properties window should appear. In the Sensor Setup tab click on the CH 1 icon in the Lab Pro grouping. Choose Temperature-Stainless in the Sensor field. Choose SS Temperature Deg C in the Calibration field. Plug the temperature probe into CH 1 of the teal blue Logger Pro interface box.

Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

In the Sensor Setup tab click on the CH 2 icon in the Lab Pro grouping. Choose Pressure-Gas in the Sensor field. Choose atm_gps in the Calibration field. (If the atm_gps selection is not automatically visible, click on the up/down arrows of the pull down window.) Plug the pressure sensor into CH 2 of the teal blue Logger Pro interface box.

Go to the Options menu or right click in the middle of the displayed graph. Under the Graph Options tab, enter a concise, descriptive title in the Title field. Click Done. Right click in the middle of the displayed graph and choose the Column Options. Select Data Set | x. Within the Column Definition tab: Enter the correct variable (temperature or pressure) into the Name field. Fill in either T or P into the Short Name field. Enter the correct units in the Units field. The Data Type should be Numeric. Within the Options tab: Under Displayed Precision choose 2 in the pull down window and then circle next to Decimal Places should be darkened. Click Done. Repeat this step for the data set to be plotted on the y-axis.

Click on Experiment and choose Data Collection, go to the Collection tab, and in the Mode field choose Selected Events. Click on Done.

4. All data should be recorded in a table in your duplicate lab notebook (regardless of whether the computer is also collecting it).

5. Click

Collect

to begin data collection of pressure vs. temperature data for the gas sample:

Place temperature probe into the ice-water bath (Figure 1). Clamp the flask so that most of it is immersed. (The water level should be just below the parafilm used to seal in the stopper.)

When the pressure and temperature readings displayed in the Meter window stabilize, click
Keep

. The first pressure-temperature data pair has now been saved.

6. Repeat Step 5 three more times using a room-temperature bath, a hot-water bath, and a boiling water bath. For the boiling water bath place the temperature probe in first. Once the temperature has stabilized use tongs to hold the flask in the boiling water bath. Clamp up tubing and probe wires to prevent melting from the hotplate. Repeat the Step 5 procedure.

Temperatures Relationship to Gas & Vapor Pressure After you have clicked
Keep

Revised 12/15/10

. CAUTION: Do not burn yourself or the probe wires on

the hot glassware or on the hot plate.

7. Click

Stop

when you have finished collecting data. Turn off the hot plate.

8. Print copies of the graph of pressure (atm) vs. temperature (C) for you and your partner. Change the printing orientation to landscape to make sure both the graph and table windows are completely displayed on the print out.

Part B. Temperature & Vapor Pressure Note: Calculate air and vapor pressure as you collect each pressure, temperature data pair (see Part A Calculations #1) many students get erroneous results for this experiment, so calculating as you go will enable you to repeat measurements. Do not inhale fumes and wash hands thoroughly before leaving lab. Ethanol is very flammable, extinguish any open flames in lab. 1. You will need the boiling water and room temperature water baths from part A. Make sure the room temperature bath is truly room temperature. (This is important, if the water is colder than room temperature, it will cause erroneous results for the first few pressure measurements.)

2. Use the experimental set up from Part A. Make sure the 2-way valve shown in Figure 3 is closed. (Leave this valve closed until Step 6.) 3. Obtain 2-3 mL ethanol (EtOH) container and the syringe. (Note: 1 cc = 1 mL). With the two-way valve still closed, screw the syringe onto the two-way valve as shown in Figure 2, but do not place the flask into the water bath until Step 8. 4. Repeat the set up of the Logger Pro program (Part A, step 3) with one exception set the units of pressure to mmHg.

Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

5. Take a reading of the pressure of air trapped in the Erlenmeyer flask. Read the air pressure in mm Hg from the live display below the graph. The pressure reading of air in the flask should be the same as atmospheric pressure (which is around 760 mm Hg on a mild sunny day). Suspend the temp probe in the air (away from the hot plate!) and read the room air temperature in C from the live display below the graph. All data should be recorded in a table in your duplicate lab notebook.

6. Inject the ethanol into the flask: Open the 2-way valve above the rubber stopper: turn the white valve handle so it is aligned with the valve stem itself as shown in Figure 4. Squirt the EtOH into the flask by pushing in the plunger of the syringe. Quickly close the 2-way valve by turning the white valve handle so it is perpendicular with the valve stem. Remove the syringe from the 2-way valve with a counter-clockwise turn taking care not to loosen the stopper assembly from the flask. Leaks are disastrous to this experiment! 7. To monitor and collect pressure and temperature data: Click
Collect

After a few moments equilibrium will be established between EtOH liquid and vapor at a given temperature. (This is indicated when the P and T readings displayed on the computer monitor stabilize.) Once this happens, click
Keep

. The first P-T data

measurement (at room temperature) is now stored. (The T measurement should be the same as the initial T reading in step 5.) Calculate the vapor pressure at room temperature.

8. Place the sealed flask in the water bath with the entire flask covered as shown in Figure 2. Place the temperature probe in the water bath. Next, without disturbing the flask, increase the temperature of the water bath about 3C by adding a small amount of the boiling water prepared on the hot plate. (Use a pipet to measure out hot water or pour the hot water from the beaker protecting your hands with paper towels.) Stir the water bath with the temperature probe. Make sure the flask is still covered with water, wait until P and T readings on the

Temperatures Relationship to Gas & Vapor Pressure computer monitor stabilize and then click
Keep

Revised 12/15/10

. Your second PT data pair is now stored.

Calculate the air and vapor pressure at this temperature. 9. Next, without disturbing the flask, increase the temperature of the water bath about 3C by adding a small amount of the boiling water prepared on the hot plate. (You may need to remove water from the flask first. Use a dipper to measure out hot water or toweling to protect your hands while you pour hot water from the beaker.) Stir the water bath with the temperature probe. Make sure the flask is still covered with water, wait until P and T readings on the computer monitor stabilize and then click
Keep

. Your third PT data pair is

now stored. Calculate the air and vapor pressure at this temperature. 10. Repeat Step 9 by adding small increments of very hot water and collecting PT data. Calculate the air and vapor pressure at each temperature. (Because the capacity of the beaker is only one liter, you may have to pour off some water from the water bath before adding more hot water.) Obtain about 5 measurements between room temperature and 40 C. (EtOH boils at 78 C and above 40 C the stopper begins to pop out of the flask. We also don't want to increase the temperature too much for safety reasons.) 11. When you have completed your five measurements for EtOH, open the 2-way valve above the rubber stopper to release the pressure inside the flask. Remove the stopper assembly and fill the flask to the top with water and pour the solution in the sink. (If an aqueous solution is 40% or less ethanol it poses no environmental threat and can be poured down the drain.) 12. Print copies of the graph of pressure (mm Hg) vs. temperature (C) for you and your partner. Change the printing orientation to landscape to make sure both the graph and table windows are completely displayed on the print out.

Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

CALCULATIONS & DISCUSSION Part B. Temperature & Gas Pressure 1. For this experiment, what variable is (are) a. constant? b. independent? c. dependent?

2.

Is the relationship between pressure and temperature is either direct (P = kT) or inverse (P = k/T)? Calculate the average numerical value of k from this experiment. (Note: Kelvin units must be used.) In terms of the ideal gas law, what variables are represented by k?

3.

Using Excel, create a plot of temperature (K) versus pressure (atm).

(Note: You need to

put the independent variable on y-axis for the following plots. This is against convention the independent variable should go on the x-axis.) All work below should be shown on the plot printout. a. Graphically determine absolute zero using this plot (Hint: Changing the minimums for the axes may be helpful i.e., the experimental data line, for once, does not have to fill the plot area). b. Mathematically determine absolute zero using this plot (Hint: Equations generated by Excel should always be on plots generated for general chemistry lab.) 4. Using Excel, create a plot of temperature (C) versus pressure (atm). Repeat the procedure given in #3. 5. Calculate the percent error for the value you found in #4. (Look up the true value in your textbook.) These calculations and values should be shown on the plot.

Temperatures Relationship to Gas & Vapor Pressure

Revised 12/15/10

Part C. Temperature & Vapor Pressure (1) Find the vapor pressure at each temperature. The total pressure in the flask at temperature, T, is equal to sum of the pressure of air in the flask and the vapor pressure of the ethanol: (P total)T = (P air)T + (VP ethanol)T. Show one sample calculation and then report all values in a Results Table. Remember, for trials at temperatures other than room temperature, even if no ethanol was present, the air pressure would increase due to a higher temperature, or decrease due to a lower temperature (remember those pesky gas laws?). Therefore, the air pressure at room temperature must be corrected to the air pressure at the temperature of the water bath. Use the gas-law equation: P2 / T2 = P1 / T1 (T should have Kelvin units). (2) Construct a Clausius-Clapeyron plot: (Make sure you follow convention and put the independent variable on the x-axis for these plots.) a) In Excel, construct a graph of vapor pressure of EtOH vs. Celsius temperature. What is the general relationship between vapor pressure and temperature? b) Convert vapor pressure of ethanol to ln VP and Celsius temperature to inverse Kelvin temperature (1/T). Construct a graph of ln VP vs. 1/T. Calculate Hvap from the slope. c) The true value for Hvap of ethanol is 42.3 kJ/mol. Calculate your percent error: % error = [(true expt)/ true] x 100 d) In the prelab WebWorks for this experiment you calculated the enthalpy of formation (Hf) of the hydrogen bond between two ethanol molecules. Compare that value with the enthalpy of vaporization (Hvap) you found experimentally for ethanol. The magnitudes of the two values should be close, but the sign is opposite. Why? What are the values and how are the values related?

10