BCHEM 154 Enthalpy of Vaporization

IMPORTANT: This is a dry lab. Instead of working on chemical techniques you will
create and use a spreadsheet to analyze data. This is a more complex analysis with
multiple calculation steps and graphical analysis. Ask questions early because
tracking down mistakes in a spreadsheet can take time.

Before coming to lab

There is no pre-lab notebook work. The background information in this exercise will
explain the experiment used to collect the data and the equations used in the analysis. After
the background you will find the data you need.

The scientific question

The lowly refrigerator- great holder of moldy leftovers and half-frozen eggs- is a
world-changing application of enthalpy of vaporization (ΔHvap). A liquid called a refrigerant
absorbs thermal energy (heat) from the interior and evaporates. The amount of energy it
takes to evaporate the refrigerant is the enthalpy of vaporization. The gas is then
condensed back to a liquid, which releases the absorbed energy into the air outside the
refrigerator. That's why the bottom, near the compressor, is so hot.
You can use this same process of evaporation and condensation as a measurement
tool to answer the question "What is the enthalpy of vaporization for water measured using
a trapped bubble?"

Enthalpy of vaporization
Enthalpy is the amount of thermal energy (heat) involved in a chemical process.
Chemists discuss enthalpy in many contexts- the heat exchanged in a reaction is the
enthalpy of reaction, the heat needed to melt a solid is the enthalpy of fusion, and the heat
produced by burning something is the enthalpy of combustion. You will measure the
enthalpy of vaporization (ΔHvap) for water, the amount of heat energy needed to convert
liquid water to water vapor. Enthalpy is typically given in units of kJ mol-1.
The value of ΔHvap for a liquid is directly related to the intermolecular forces within
the liquid. These forces exist between individual liquid molecules. Molecules with stronger
intermolecular forces have more attraction to each other. The stronger forces lead to a
larger ΔHvap because it takes more energy to overcome these attractions. Remember- to
evaporate a molecule all of the attractive forces must be overcome.
ΔHvap is extremely difficult to measure directly. Instead, it is much easier to measure
gas properties (temperature, volume, or pressure) and then apply the Clausius-Clapeyron
equation to calculate ΔHvap.

Finding ΔHvap with the Clausius-Clapeyron equation

There is a mathematical relationship between the vapor pressure of a gas and the
temperature of the gas. As temperature increases, vapor pressure increases because higher
temperatures mean more liquid molecules have enough energy to overcome their attraction
to neighboring liquid molecules and enter the gas phase. At any temperature where a liquid
is in equilibrium with its vapor, the vapor pressure is given by the Clausius‐Clapeyron
equation:

ln (Pvap) = (-ΔHvap/R)(1/T) + C Equation 1

y = m * x +b

The Clausius-Clapeyron equation is very similar to the general equation for a straight
line: y=mx+b (shown beneath Equation 1). 'y' represents the natural logarithm of vapor

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pressure (ln(Pvap)) and 'x' represents reciprocal temperature (1/T). A plot of ln(Pvap) on the
y-axis and 1/T on the x-axis will create a straight line. The slope of the line represents (-
ΔHvap/R). In other words, m=-ΔHvap/R. An algebraic rearrangement allows you to calculate
ΔHvap:

ΔHvap = -m*R Equation 2

You are dealing with energy units, so the constant R = 8.314 J mol-1 K-1.
You can use the Clausius-Clapeyron equation to calculate ΔHvap for water. If you
measure the vapor pressure of water at different temperatures, you can create a plot of
ln(Pvap) vs. 1/T, use the plot to find the slope 'm', and then use the slope and the constant R
to calculate ΔHvap.

Measuring Pvap and T by trapping a bubble

Figure 1 illustrates the relationship between vapor pressure and temperature for a
liquid being heated. You are familiar with this affect as boiling. A small air bubble is trapped
in the liquid (Figure 1, left). As temperature increases, the bubble volume increases
(Figure 1, center and right) because more water molecules enter the gas phase
(evaporate) and add volume to the bubble. The opposite is also true- cooling the bubble
causes some water vapor to condense to liquid and the bubble volume decreases.
The temperature of the bubble is the
same as the temperature of the water (they are
in thermal equilibrium). This makes measuring
the bubble temperature easy because you can
measure the water temperature.
Calculating the vapor pressure of water
in the bubble is more challenging and requires
using two gas laws- the ideal gas law and the
law of partial pressure.
When you initially trap the bubble it
contains the same molecules as the air you breathe
(N2, O2, Ar, etc). The total pressure of the bubble Figure 1: The effect of vapor
(Pbubble) you trap is equal to the atmospheric pressure pressure on bubble volume.
of the air in the lab. This value does not change and is
easily measured with a barometer.
The pressure in the bubble is caused by two components- the pressure of the air
molecules (Pair) and the pressure of the water vapor (Pvap). Mathematically the various
pressures are related by the law of partial pressures:

Pbubble = Pair + Pvap Equation 3

There is a problem with this equation though. The partial pressure (Pvap) of water
vapor (the pressure due only to the water vapor molecules) varies as the temperature
changes because water molecules enter and leave the bubble as they evaporate or
condense. The partial pressure of air (Pair) also varies because it depends on temperature
and volume. It appears that Equation 3 has two unknowns, so how can you solve this? The
solution lies in the ideal gas law:

PV = nRT Equation 4

When you trap the bubble, the moles of air (nair) is constant for the rest of the
experiment. This means you can calculate the air pressure (P air) at any point as long as you
know the bubble volume and temperature:

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nair RTbubble
Pair = Equation 5
Vbubble
Now that you can calculate Pair at any volume and temperature combination and you
know Pbubble (remember...this is constant), you can solve Equation 3 for Pvap at any volume
and temperature.
There is one final problem- how do you know how many moles of air you initially
trapped in your bubble? Cold air cannot hold very much water vapor. In fact, for
temperatures very close to 0 oC, you can assume the amount of water vapor in the bubble
is negligible. If you measure the volume of a bubble near 0 oC, you can use the ideal gas
law (Equation 4) to calculate the moles of air (nair) you trapped.

Summary of the measurement and calculations

The challenge in this case is not the measurement, but the analysis itself. Analyzing
the data requires several calculation steps as well as graphical analysis. The process can be
summarized as:
1. Measure the volume of the trapped bubble at different temperatures.
2. Calculate nair using the bubble volume and pressure at 0 oC (Equation 4)
3. Calculate Pair at each temperature (Equation 5)
4. Calculate Pvap at each temperature (Equation 3)
5. Create a plot of ln(Pvap) vs. 1/T
6. Use a linear regression of the ln(Pvap) vs. 1/T plot to find the slope, m.
7. Calculate ΔHvap (Equation 2)

Goals and outcomes

After completing this laboratory you should be able to do the following:
• Explain the relationships between gas variables (P, V, T, and moles)
• Use the ideal gas law and law of partial pressure
• Explain the Clausius-Clapeyron equation and apply it to calculate
thermodynamic quantities
• Apply graphical analysis to obtain chemical information

Data and directions for the report begin on the next page

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 BCHEM 154 Enthalpy of Vaporization
Data
Table 1 provides the raw data that you need for your analysis. It was collected by
carrying out the experiment described above- measuring the volume of a trapped air bubble
at different temperatures.

Table 1: Temperature and volume data for a bubble trapped in a graduated cylinder. The
room pressure and room temperature are given below the table.

Water Temp (°C) Bubble volume (mL)

79.9 5.4
75.2 5.1
70.1 4.9
65.1 4.6
60.0 4.3
50.2 3.9
30.2 3.4
0.1 3.0
Barometric Pressure in the room = 775.5 mmHg
Temperature in the room = 21.4 oC
Lab Report
Your analysis is due in four days. Submit your work electronically to Canvas using
the appropriate drop box. There is no template for this lab. You must create the
spreadsheet yourself. You can answer the short answer question directly in the spreadsheet
below your tables and calculations.
Note: The expectation is that you use Excel to do the calculations (i.e. use formulas
and cell references). If you do not use proper formulas and cell references or you do things
on calculators and type values into Excel you will get very little credit for the report. We are
evaluating your ability to use spreadsheets for analysis, not just do math.

Analysis
1. In Excel, create the following data table:

A B C D E F G H I
1 Bubble Bubble Bubble Corrected Corrected Pair Pvap ln(Pvap) 1/T
Temp Temp volume bubble bubble (atm) (atm) (K-1)
(oC) (K) (mL) volume (mL) volume (L)
2
3
4
5
6
7
8
9
10 n(air):

2. Type the measured data (given in Table 1) into the labeled columns (Column A for
bubble temperature and Column C for bubble volume).
3. Convert the bubble temperature in oC (in Column A) to temperature in Kelvin (in
Column B).

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4. You must account for the meniscus effect when measuring gas volume. Calculate the
corrected bubble volume (in Column D) by subtracting 0.2 mL from the measured
bubble volume (in Column C).
5. In Column E, convert the corrected bubble volume to liters.
6. Calculate the moles of air (nair) for the bubble volume at the zero point using
Equation 4. You will use this value often, so do the calculation in Excel (cell H10)
and you can refer to this cell whenever you need this value.
7. Calculate Pair at each temperature (Column F) using Equation 5. nair is the value
you calculated in Step (6), volume is the corrected volume (in L), and temperature is
the bubble temperature in K.
Note: For the 0 oC measurement, Pair = Pbubble because you are assuming Pvap
= 0 and there is no water vapor at this point. You can type in this value (provided
below Table 1) but make sure the value you type is in correct units!
8. Calculate the vapor pressure, Pvap, in Column G using Equation 3. Pbubble is always
the lab pressure. Pair is the pressure you calculated in Step (7).
Note: Pvap = 0 for the 0 oC measurement.
9. Calculate ln(Pvap) (the natural log of Pvap) in Column H. The Excel command is =LN(X)
where 'X' is the value or cell you want to use.
Note: You cannot do this calculation for the 0 oC point because you are
assuming Pvap = 0 and the natural log of zero is undefined. Leave this cell blank in
your spreadsheet.
10. Calculate 1/T (that's T in Kelvin!) in Column I.
11. Create a graph of ln(Pvap) (y-axis) vs. 1/T (x-axis). Make sure this graph is complete-
labels, title, appropriate units, etc.
12. Use Excel to fit a regression line on your graph. Include the regression equation and
R2 value on the graph.
Check your accuracy: The slope should be approximately -5,172. If the
slope is not within 2% of this value then there is a mistake in your analysis or your
graph that you need to find and correct.
13. Below your table or graph in Excel, calculate the value of ΔHvap (in kJ mol-1) using
Equation 2.
14. Below your table or graph in Excel, calculate the % error between your ΔHvap value
and the true ΔHvap value of 40.7 kJ mol-1.
Check your accuracy: If you did all of your calculations and graphing
correctly, your % error should be very close to 5.6%. If your % error is very
different from this, it means there is a mistake you need to find and correct.

Short answer questions

Type your answers directly into your spreadsheet below all of your analysis. You are
encouraged to discuss answers with others but the final typed answer must be your own
independent wording.

1. In chemical kinetics there is an equation similar to the Clausius-Clapeyron

equation: ln(k)=(Ea/R)(1/T) + ln(A). Ea is very difficult to measure. Instead, you measure
temperature (T) and the rate constant (k) and use graphical analysis to calculate Ea.
Comparing this new equation a straight line (y=mx+b):
a. Which variable in this equation would you plot on the y-axis?
b. Which variable in this equation would you plot on the x-axis?
c. What does the slope, m, of the straight line represent in this equation?
d. Show how you would calculate Ea using the slope of the line (in equation
form...you do not need to calculate an actual value).

Submit your spreadsheet in xls or xlsx format. Do not submit a PDF of the
spreadsheet because it will not have the information we need.

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