Vapor Pressure, Enthalpy of Vaporization, and Intermolecular Forces Dr.

Mike Perona, California State University, Stanislaus Procedure modified by Dr. Scott Russell 8/30/2007

Purpose: Measure the equilibrium vapor pressure of several liquids at room temperature and explain the results in terms of intermolecular forces. By measuring the equilibrium vapor pressure of a liquid at two temperatures, it will be possible to calculate the molar enthalpy of vaporization for that liquid. Introduction You have probably observed that if water is left in an open container at room temperature it will eventually evaporate completely, even though its temperature is never raised to the boiling point. The explanation for this behavior is that some of the molecules in the liquid have enough kinetic energy to overcome the intermolecular forces, which hold the molecules of the liquid together, and are able to escape into the vapor phase. The molecules in the vapor phase then diffuse away, and a net loss of liquid occurs. The evaporative process results in a momentary loss of the most energetic molecules from the liquid sample. Heat energy is continuously absorbed from the surroundings and so the supply of energetic molecules is maintained. This continues until all of the liquid has evaporated. If the liquid water is placed in a closed container at constant temperature, however, the amount of liquid water will at first decrease and then remain

constant. It will appear as if evaporation has stopped. In fact, evaporation does not stop. What happens is that since the vapor phase molecules cannot escape, their number initially increases. This results in an increase in the frequency of their collisions with each other and with the liquid surface. Collisions with the liquid surface lead to condensation. Ultimately the rate of condensation becomes equal to the rate of evaporation, and the relative amounts of water in the two phases remains constant. This corresponds to a condition of dynamic equilibrium. The word "dynamic" emphasizes the fact that both evaporation and condensation are still occurring, but they are occurring at the same rate. The water molecules in the vapor phase exert a pressure on the container walls. This pressure is referred to as the equilibrium vapor pressure of water or just the vapor pressure. The vapor pressure of a liquid depends upon the molecular structure of the liquid and upon the temperature. Increasing the temperature increases the average kinetic energy of the liquid molecules, and hence the fraction of molecules with sufficient energy to escape from the liquid phase. Thus, the vapor pressure increases with temperature. The variation of the vapor pressure, P, with the absolute or Kelvin temperature, T, is given by

where Hvap is the molar enthalpy of vaporization in units of J/mol and R is the gas constant, also in units of J/mol*K. (R = 8.314 J/mol*K). This equation can be solved for Hvap:

Thus, by measuring the vapor pressure at two different temperatures, the molar enthalpy of vaporization can be determined. As you might expect, Hvap increases with the strength of the intermolecular force. The structure of the molecules in the liquid determines the strength of the intermolecular forces holding the molecules together. If the intermolecular force is strong, the fraction of molecules that have enough energy to escape into the vapor is small and the vapor pressure will be small. On the other hand, if the intermolecular force is relatively weak, a large fraction of the molecules will be able to escape into the vapor and the vapor pressure will be large. By comparing the vapor pressures of various liquids at constant temperature, we can determine the relative strengths of the intermolecular forces in the liquids. Intermolecular Forces: The weakest intermolecular force is the induced dipole-induced dipole or London force. It arises from the fact that the shape of the electronic cloud in a molecule fluctuates with time. This fluctuation results in an instantaneous dipole moment in the molecule, which induces momentary dipole moments in neighboring molecules. The attraction between these momentary dipoles results in the London force. This force exists between all types of molecules whether polar or nonpolar since all molecules contain electrons. It is the primary force responsible for holding together the molecules in nonpolar liquids and solids. The strength of the London force increases with the number of electrons in the molecule. Since the number of electrons increases with molar mass, we generally find the strength of the London force increases with molar mass. In the case of polar substances, London forces exist, but in addition, the presence of a permanent dipole moment in the molecules results in a much stronger dipole-dipole intermolecular force. Thus, polar substances will generally have lower vapor pressures than nonpolar substances with the same molar

mass. For example, consider the substances butane, C4H10, and acetone, C3H6O, both of which have a molar mass of 58, and hence equally strong London forces. The vapor pressures of butane and acetone at 25C, respectively are: 1735 mm Hg and 200. mm Hg. Why is the vapor pressure of butane so much higher than that of acetone? The answer is that in butane, which contains only hydrogen and carbon, the bonds are nonpolar since hydrogen and carbon have nearly equal electronegativities. Hence the molecule as a whole is nonpolar, and the only significant intermolecular force is the London type. On the other hand, acetone is a polar molecule as shown below. Acetone molecules experience both the London Force and the much stronger dipole-dipole force. This explanation is supported by the fact that the molar enthalpy of vaporization of acetone is greater than that of butane (32.0 kJ/mole vs. 24.3 kJ/mole). That is, more energy is required to vaporize one mole of acetone than one mole of butane. An especially strong dipole-dipole intermolecular force, called a hydrogen bond, results when a molecule contains a hydrogen atom attached to either of the highly electronegative atoms O, N or F. This results in highly polar covalent bonds. For example, in water the O-H bond is highly polar due to the large electronegativity difference between the O and H atoms. This H atom bears a large positive partial charge and the O atom bears a large negative partial charge. The attraction between the charged ends of the water molecules results in hydrogen bond formation. A class of compounds in which hydrogen bonding is important are alcohols. These are compounds containing the group -O-H. For example, ethyl alcohol has the structure shown above.

In this experiment you will measure the vapor pressure of the compounds heptane (C7H16), hexane (C6H14 ), and ethyl alcohol (C2H6O), at room temperature. You will also measure the vapor pressure of heptane at 0C. Procedure: To measure the vapor pressure of a liquid at room temperature set up your apparatus as shown in Figure 1. With the pinch clamp closed, the flask is connected through a trap to a vacuum line. The vacuum line pumps air out of the flask. The vacuum line does not remove all of the air in the flask, and a certain pressure of air, (Pair)rt will remain in the flask. The subscript "rt" stands for "room temperature." The value of (Pair)rt is measured with the microlabs pressure sensor. Before the vacuum is pulled on the flask, the pressure should read ~760 Torr. Once the vacuum is open the pressure should drop rapidly to a range of 80-100 Torr. Once (Pair)rt is measured, the liquid whose vapor pressure is to be measured is placed in the funnel, the screw clamp is closed, and some of the liquid is admitted to the flask by opening the pinch clamp. The pressure now rises due to the pressure exerted by the liquid's vapor pressure, (Pvap)rt. The total pressure in the flask at room temperature, (PTOT)rt according to Dalton's Law of Partial Pressures, is equal to the sum of the partial pressures exerted by the remaining air and by the liquid's vapor. That is, (PTOT)rt = (Pair)rt + (Pvap)rt (1) (PTOT)rt is measured by the pressure sensor after introducing the liquid into the flask. The vapor pressure of the liquid is obtained by solving Eq.(1) for (Pvap)rt (Pvap)rt = (PTOT)rt - (Pair)rt (2)

In measuring the vapor pressure of a liquid near 00C the flask is placed in an ice water bath. The pressure in the system with no liquid present, (Pair)iw, and the pressure with the liquid present (PTOT)iw, must both be measured at the temperature of the ice water bath. The subscript "iw" stands for "ice water." The vapor pressure at the ice water temperature given by (Pvap)iw = (PTOT)iw - (Pair)iw (3)

Funnel Pinch clamp To microlabs pressure sensor Screw clamp To lab vacuum line Trap
Figure 1.

Eye protection must be worn when performing this experiment. Part 1a. Measurement of (Pair)rt: Turn on the microlabs FS-522 interface (green button on the front). Start the microlabs software by double clicking on the Microlab.exe icon on the desktop. A window will open; double click on Microlab experiment. This opens the

microlabs interface where you can design your own methods. A method for this lab has already been created. To access it, click file, then open, then double click on the file named Vapor Pressure in the Saved Experiments folder. This experiment will allow you to monitor pressure (Torr) versus time (sec). The data will be displayed as a graph and a spreadsheet. Make sure that all of the connections in the apparatus, shown in Figure 1, are tight and no moisture is present between stopper and flask. Clamp the flask in the room temperature water bath so that it is covered by water as much as possible. Close the screw clamp that connects the flask to the vacuum trap. Insert the medicine dropper from the vacuum trap tubing into the thin-walled tubing. Close the rubber tubing below the funnel with the pinch clamp. Click start in the microlabs software, the pressure should initially read ~760 Torr. Now open the lab vacuum line fully, and slowly loosen the screw clamp to evacuate the flask. The pressure reading on the microlabs display will drop rapidly. Continue evacuating with the vacuum line until pressure readings at oneminute intervals are within 3 Torr. Close the screw clamp and disconnect the flask from the trap. You now have an isolated system. Note the pressure readings on the computer. If there is no leak, the pressure should be stable over a period of several minutes, and you are ready to proceed. If there is a leak, it must be stopped. Normally checking and tightening the seals at the rubber stopper, the screw clamp, and the pinch clamp can fix any leaks. When you are certain that there are no leaks, record your measured (Pair)rt in your notebook and proceed to part 1b. Part 1b: Vapor pressure of hexane: At this point you should have the screw clamp and pinch clamp closed and the pressure should be stable (i.e. no leaks, see Part 1a). To obtain (PTOT)rt of hexane and air, pour 2 mL of hexane into the funnel. Do not inhale the vapor. Slowly open the pinch clamp and admit some of the liquid into the flask. The

liquid enters the flask very rapidly; make sure you close the pinch clamp while there is still about 0.5 mL of liquid remaining in the funnel. If any air enters the flask at this point you must start over. Monitor the pressure at one-minute intervals until consecutive readings agree within 3 Torr. Record the final pressure (PTOT)rt in your notebook. Loosen the screw clamp slowly, and allow the contents of the flask to return to atmospheric pressure. Open the pinch clamp and drain the remaining liquid into the flask. Remove the rubber stopper from the flask, and pour the liquid into the solvent waste container. No water should be used to clean the flasks, but the flask should be dried between trials. This is accomplished by blowing compressed air (fume hood) into the flask to evaporate any remaining liquid. Part 1c: Vapor pressure of heptane and ethanol: Repeat the procedure in Part 1b., with heptane and then with ethanol at room temperature. Part 2 Vapor pressure of heptane near OC Thoroughly dry the flask with compressed air. Reassemble the apparatus, and place the flask in the ice-water bath. Follow the procedure in Part 1a, to measure (Pair)iw, the pressure in the flask with no liquid present. Again, with the flask in the ice-water bath, repeat the procedure in Part 1b for heptane, to obtain (PTOT)iw, the pressure with liquid present. Upon completion of the experiment, return the apparatus to atmospheric pressure by slowly opening the screw clamp, thereby admitting air into the flask. You must repeat each measurement twice. That is, measure the vapor pressure of ethanol, hexane and heptane at room temperature twice and measure the vapor pressure of heptane near 0C twice.

Reporting Your Results 1. Results section Arrange your data in tabular form. A sample data sheet, which you may want to use, is shown below. Calculate values Pvap for each experiment and enter the values in your data sheet. Show all calculations. 2. Conclusions section The conclusion section should contain sentences that answer the following questions. a) What are your measured values of the vapor pressures of heptane, hexane, and ethanol at each temperature? b) Based on your vapor pressure measurements at room temperature, arrange the three compounds in order of increasing strength of the intermolecular forces. Explain your reasoning in terms of types of forces present. c) How does the vapor pressure vary with molar mass? What conclusions can you draw from this behavior about the kinds of intermolecular forces that are predominant in each of the compounds, C7H16, C6H14 and C2H6O? d) Using your values for the vapor pressure of heptane obtained at two different temperatures; calculate the molar enthalpy of vaporization of heptane.
Sample Spreadsheet for Vapor Pressure Experiment Trial 1: hexane at room temp. Temperature = Pressure (Torr) Empty flask (Pair)rt Flask with hexane (PTOT)rt Pvap = (PTOT)rt - (Pair)rt