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Objectives:
(1) Observe and measure the change in the vapor pressure (dependent variable) as a
function of temperature (independent variable).
(2) Analyze the experimental data to determine the normal boiling point and the heat of
vaporization, Hvap, using the Clausius-Clapeyron equation.
This laboratory covers material presented in section 11.8 of the 9th Ed. of the Chang text.
Introduction:
The quantity of vapor above a liquid in a closed system increases with the temperature of the
system. The quantity of vapor can be measured as the vapor pressure of the system. This
relationship is pictorially shown in Figure 1.
Figure 2. The plot shows the kinetic energy distribution for molecules at a low
temperature (blue trace) and at a higher temperature (red trace). As
temperature increases, a greater fraction of the molecules have enough
energy to escape the molecular attractions of the liquid.
For liquids the vapor pressure as a function of temperature has an exponential behavior as shown
in Figure 3.
The author of your text indicates a relationship between pressure and temperature that does not
contain an exponential term.
To remove an exponent from an expression the log function (log or ln) can be used. Taking the
natural log (ln) of both sides of equation (1) gives:
Hvap
(2)
RT
This can be made to look like a straight-line equation similar to textbook equation 11.2 by
rearranging terms.
ln(P) = ln(A)
ln(P) =
y =
H vap 1
+ ln( A)
R T
+ b
The textbook also nicely points out that this is the equation of a straight line if you plot ln(P), y,
vs. 1/T, x, and the slope, m, is equivalent to Hvap/R. This equation is the Clausius-Clapeyron
equation named after the German physicist Rudolf Clausius (1822 - 1888) and the French
engineer Emil Clapeyron (1799 - 1864).
This week in lab you will fit a set of vapor pressure vs. temperature data to the ClausiusClapeyron equation to determine the heat of vaporization of an unknown liquid, shown in Figure
4.
Figure 4. The linear relationship between ln(P) vs 1/T comes from the ClausiusClapeyron equation.
Experimental Procedure:
In measuring vapor pressure vs. temperature you will take advantage of the definition of boiling.
Recall that boiling is defined as the temperature of liquid at which the vapor pressure is equal to
the atmospheric pressure. You will reduce the pressure above a liquid using the vacuum system
in the hood. By recording the temperature and pressure at which the liquid boils for several
different external pressures, the plot in Figure 4 will be created for your unknown liquid.
You must have on safety glasses for this experiment. Glass under vacuum is potentially
hazardous. A small crack in a glass vessel can result in an implosion of the vessel,
dispersing small pieces of glass over a large area.
Become familiar with the apparatus shown in Figure 5 and assembled in the hood. The fist thing
to do is check the apparatus for air leaks. Fixing these leaks can be tedious.
allow the system to warm until the liquid begins boiling. Record your second temperature and
the vapor pressure. The system may leak a little during this time. A few in Hg wont matter and
you can always pump the system back down to the desired pressure. If the system leaks
substantially (> 5 in Hg) while the sample is heating, you should stop the experiment and do
some further leak tests.
After recording your second temperature and vapor pressure data point, bleed air into the system
to again raise the pressure by 3 or 4 in Hg. Again, boiling will stop and you should wait to
measure the new boiling temperature. Repeat the pressure increases and sample warming until a
final gauge pressure of 3 or 4 in Hg is reached in the system. This should give you six or seven
temperature and. vapor pressure data points.
After collecting the last data point, disconnect the tubing from the sidearm of the collection flask.
Continue to heat the solution so that a boiling point at the current atmospheric pressure can be
measured. Todays atmospheric pressure can be read from a barometer or be obtained from your
TA. The boiling point at atmospheric pressure constitutes your final data point.
Place the liquid studied into the appropriate waste beaker. Be sure to pour the extra liquid from
the collection beaker into the waste beaker as well.
Data Analysis:
A plot of ln(vapor pressure) vs. 1/T must be made to determine the heat of vaporization of your
liquid. To make this plot in Excel, create the table shown in Figure 7. You should use the
formula feature in Excel to perform calculations. A formula in Excel is entered by using an =
sign at the beginning of the expression. The formulas needed are shown in row 2 of the example
spreadsheet in Figure 7.
Figure 7. Example spreadsheet used to make the plot of ln(P) vs. 1/T.
A formula can be made to fill a column by clicking and dragging the cell from the lower right
hand corner down the row. The lower arrow in Figure 8 shows where to click and drag in the
formula cell.
Figure 8. This figure shows how to fill a column with a repeated formula.
In Figure 7 column (E) is the vapor pressure of the liquid in the familiar units of mmHg. This
formula is a little unusual. The vacuum gauge reads as if it were the height of a mercury column
in a manometerthe reading tells how much less the pressure inside the system is than the
atmospheric pressure. Therefore, the conversion in cell E2 (=740-B2*25.4) is required. In your
formula, use todays atmospheric pressure (in mmHg) in place of the value 740 in the formula.
Once your spreadsheet has a similar appearance to the sheet in Figure 7, make a plot of ln(VP)
vs 1/T in the following way. To plot the data, click and drag over the 1/T column to highlight the
column and then with the Ctrl button pressed drag on the ln(VP) column. Each column should be
highlighted as in Figure 7.
To plot this data click on the Chart Wizard Icon,
open.
Figure 9. A screen capture of the Excel spreadsheet showing the Chart Wizard
dialogue box.
In the Chart Wizard select XY (Scatter) and points only. Complete the wizard by completing the
appropriate items. Then click Finish. The resulting plot should look similar to the following,
Figure 10.
Clausius Clapyeron Plot
6.8
ln(vap. pres.)
6.6
y = -4869.9x + 21.281
6.4
6.2
6
5.8
5.6
5.4
0.003
0.00305
0.0031
0.00315
0.0032
0.00325
1/Temp (1/K)
The linear fit to the data is done in Excel by selecting Add Trendline. In the trendline dialog
box select the type as Linear and then click on the Options tab. In the Options box, click the
Display Equation on Chart feature. The best-fit line will be given to you in slope-intercept
form. Expect a slope similar to the slope given in Figure 10. Save this Plot to your network
drive. You will need it for your lab assignment.
From the slope, determine the heat of vaporization (Hvap) in kJ/mol. After making the final
calculations in your notebook turn in your duplicate notebook pages.