Chemistry 化学

Vapor Pressure Measurement Discussion Examples | How to Interpret a Clausius–Clapeyron Plot

Vapor pressure measurement is a physical chemistry experiment used to investigate the tendency of a liquid to become a gas from the relationship between temperature and pressure.
The vapor pressure of a liquid increases as the temperature rises, and by analyzing this temperature dependence, the enthalpy of vaporization can be determined.
A Clausius-Clapeyron plot is commonly used for this analysis.

In a discussion of vapor pressure measurement, it is not sufficient simply to write that “the vapor pressure increased as the temperature rose” or “the Clausius-Clapeyron plot became linear.”
It is necessary to explain why vapor pressure increases with increasing temperature, why a graph of lnP versus 1/T becomes linear, what the slope of the fitted line represents, and how temperature measurement, pressure measurement, and insufficient attainment of equilibrium affect the results.

This article clearly explains the basics of vapor pressure measurement, how to interpret a Clausius-Clapeyron plot, how to determine the enthalpy of vaporization from the slope, sources of error, points for improvement, and discussion examples that can be used in reports.

Note:
This article is a reference intended to assist with discussions of vapor pressure measurement results obtained in physical chemistry experiments at universities and similar institutions.
For the actual measuring apparatus, temperature control, pressure gauge, vacuum system, sample handling, safety precautions, and specified calculation equations, always follow the instructions in your university’s laboratory manual and those given by your instructor or TA.

  1. What Is Vapor Pressure?
  2. Main Items to Include in the Results
    1. Main Items to Include in the Results
  3. Reference Experimental Values for Vapor Pressure Measurement and an Example of Clausius-Clapeyron Plot Analysis
    1. Reference Experimental Conditions
    2. Form of the Clausius-Clapeyron Equation
    3. Example Measurements of Temperature and Vapor Pressure
    4. Converted Data for the Clausius-Clapeyron Plot
    5. Example of Determining the Enthalpy of Vaporization From the Plot Slope
    6. Simple Example of Determining the Slope From Two Points
    7. Example of Boiling-Point Estimation
    8. Differences in Vapor Pressure Among Liquids
    9. Effect of Temperature-Measurement Error
    10. Change in Vapor Pressure With Equilibrium Time
    11. Deviation in Pressure Measurement Caused by Air Contamination
    12. Sources of Error in Vapor Pressure Measurement
    13. Example When an Outlier Is Present
    14. Precautions When Changing Pressure Units
    15. Example of How to Write the Results
    16. Points for Connecting the Results to the Discussion
    17. Example Discussion
    18. Summary
  4. Why Vapor Pressure Increases as Temperature Rises
  5. What Is the Clausius-Clapeyron Equation?
  6. How to Create a Clausius-Clapeyron Plot
    1. Basic Procedure
  7. Meaning of the Plot Slope
  8. Meaning of the Intercept
  9. How to Interpret R2
  10. What Is the Enthalpy of Vaporization?
  11. Relationship Between Vapor Pressure and Intermolecular Interactions
  12. Relationship With Boiling Point
  13. Error Caused by Temperature Measurement
  14. Error Caused by Pressure Measurement
  15. Error Caused by Insufficient Attainment of Equilibrium
  16. Error Caused by Air Contamination
  17. Error Caused by Impurities in the Sample
  18. Discussion When Deviations Occur on the Low- or High-Temperature Side
  19. When the Clausius-Clapeyron Plot Is Not Linear
  20. When the Enthalpy of Vaporization Is Larger Than the Literature Value
  21. When the Enthalpy of Vaporization Is Smaller Than the Literature Value
  22. Handling of Units
  23. Calculation of Error Rate
  24. When the Results Can Be Considered Good
  25. Example Discussion When the Experiment Did Not Go Well
  26. How to Write Points for Improvement
    1. Improvements to Temperature Control
    2. Improvements to Pressure Measurement
    3. Improvements to the Apparatus and Sample
    4. Improvements to Data Analysis
  27. Difference Between a Superficial Discussion and a Good Discussion
  28. Examples of Expressions That Can Be Used in Reports
  29. Points to Check When Discussing Vapor Pressure Measurement
  30. Summary

What Is Vapor Pressure?

Vapor pressure is the pressure exerted by a vapor when a liquid and its vapor are in equilibrium.
When a liquid is placed in a sealed container, molecules evaporate from the liquid surface and move into the gas phase.
At the same time, some molecules in the gas phase return to the liquid surface.
When the rate of evaporation becomes equal to the rate of condensation, the pressure in the gas phase becomes constant, and this pressure is the vapor pressure.

Vapor pressure becomes larger when liquid molecules can move into the gas phase more easily.
Liquids with weak intermolecular interactions or high volatility tend to have high vapor pressures.
In contrast, liquids with strong intermolecular interactions tend to have lower vapor pressures because the molecules are more strongly retained in the liquid.

Example Discussion:
Vapor pressure is the pressure of the gas phase when a liquid and its vapor are in equilibrium.
When the number of molecules evaporating from the liquid surface becomes equal to the number of molecules returning from the gas phase to the liquid, the vapor pressure becomes constant.
Therefore, in vapor pressure measurements, it is important that the liquid and vapor have sufficiently reached equilibrium.

Main Items to Include in the Results

In the results of vapor pressure measurement, organize the vapor pressure at each temperature, conversion of temperature to absolute temperature, 1/T, lnP, the Clausius-Clapeyron plot, the equation of the fitted line, the slope, and the enthalpy of vaporization.
Because calculations will be incorrect if temperature is handled in °C, it must always be converted to K before analysis.

Main Items to Include in the Results

  • Name of the liquid measured
  • Measured temperature
  • Absolute temperature T
  • Vapor pressure P
  • 1/T
  • lnP
  • Clausius-Clapeyron plot
  • Equation of the fitted line
  • Coefficient of determination R2
  • Slope of the fitted line
  • Enthalpy of vaporization
  • Comparison with literature values
  • Error rate
  • Temperature- and pressure-measurement errors

Example of How to Write the Results:
The vapor pressure at each temperature was measured, and the temperature was converted to K.
Furthermore, 1/T and lnP were calculated and plotted, giving an approximately linear relationship.
According to the Clausius-Clapeyron equation, the slope of this fitted line corresponds to −ΔHvap/R, so the enthalpy of vaporization was calculated from the slope.

Reference Experimental Values for Vapor Pressure Measurement and an Example of Clausius-Clapeyron Plot Analysis

Here, reference experimental values are organized for measuring the vapor pressure of a liquid at different temperatures and determining the enthalpy of vaporization from a Clausius-Clapeyron plot.
Temperature, vapor pressure, lnP, 1/T, plot slope, boiling-point estimation, and measurement errors are presented in a form that is easy to discuss in a report.

The vapor pressure of a liquid increases as the temperature rises.
This is because an increase in temperature increases the kinetic energy of liquid molecules and increases the number of molecules that move into the gas phase.
The relationship between vapor pressure and temperature can be analyzed in relation to the enthalpy of vaporization using the Clausius-Clapeyron equation.

Reference Experimental Conditions

Item Details
Substances measured Volatile liquids such as ethanol, acetone, and water
Measurement temperature range 20–60°C
Measured quantities Temperature, vapor pressure, external pressure, equilibrium time
Analysis items lnP, 1/T, Clausius-Clapeyron plot, enthalpy of vaporization, boiling-point estimation
Temperature unit K is used for analysis
Pressure unit kPa or Pa is used. However, the units must be consistent when calculating lnP.

Form of the Clausius-Clapeyron Equation

If the enthalpy of vaporization can be regarded as approximately constant over the measured temperature range, the relationship between vapor pressure P and absolute temperature T can be expressed as follows.

lnP = −ΔHvap / R × 1/T + C

Here, ΔHvap is the enthalpy of vaporization, R is the gas constant, T is the absolute temperature, and C is a constant.
Therefore, when lnP is plotted on the vertical axis and 1/T on the horizontal axis, the slope is −ΔHvap/R.

ΔHvap = −Slope × R

Using the gas constant R = 8.314 J/(mol·K), the enthalpy of vaporization can be determined from the slope of the plot.

Example Measurements of Temperature and Vapor Pressure

Reference data for measuring vapor pressure at different temperatures are shown below using ethanol as an example.

Temperature Absolute Temperature T Vapor Pressure P Observation Direction of Discussion
20°C 293.15 K 5.9 kPa Low vapor pressure Few molecules move into the gas phase
30°C 303.15 K 10.5 kPa Increase Higher temperature makes evaporation easier
40°C 313.15 K 18.0 kPa Large increase Molecular motion increases
50°C 323.15 K 29.5 kPa Further increase Strong temperature dependence of vapor pressure
60°C 333.15 K 47.0 kPa High vapor pressure Approaching the boiling point

Vapor pressure increases rapidly as the temperature rises.
Because the relationship between vapor pressure and temperature is not linear but increases exponentially, it is analyzed by converting the data to lnP and 1/T.

Converted Data for the Clausius-Clapeyron Plot

The following is an example of converting the measured temperature and vapor pressure to 1/T and lnP.
Here, P is used in kPa.

Temperature T 1/T P lnP
20°C 293.15 K 0.003411 K−1 5.9 kPa 1.775
30°C 303.15 K 0.003299 K−1 10.5 kPa 2.351
40°C 313.15 K 0.003193 K−1 18.0 kPa 2.890
50°C 323.15 K 0.003095 K−1 29.5 kPa 3.384
60°C 333.15 K 0.003002 K−1 47.0 kPa 3.850

As 1/T becomes smaller, in other words as temperature becomes higher, lnP becomes larger.
When lnP is plotted on the vertical axis and 1/T on the horizontal axis, a relationship close to a downward-sloping straight line is obtained.

Example of Determining the Enthalpy of Vaporization From the Plot Slope

Suppose linear fitting of the Clausius-Clapeyron plot gives the following equation.

lnP = −5100 × 1/T + 19.17

In this case, the slope is −5100 K.
According to the Clausius-Clapeyron equation, slope = −ΔHvap/R, so

ΔHvap = −Slope × R

ΔHvap = −(−5100) × 8.314 = 42400 J/mol = 42.4 kJ/mol

In this reference example, the enthalpy of vaporization is determined to be 42.4 kJ/mol.

Simple Example of Determining the Slope From Two Points

The slope can also be roughly estimated using the two points at 20°C and 60°C.

Point 1/T lnP
20°C 0.003411 1.775
60°C 0.003002 3.850

Slope = (3.850 − 1.775) ÷ (0.003002 − 0.003411)

Slope = 2.075 ÷ (−0.000409) = −5073 K

ΔHvap = 5073 × 8.314 = 42170 J/mol = 42.2 kJ/mol

The value determined from two points is also close to the value determined from linear fitting.
However, to reduce the effect of experimental error, linear fitting using multiple points is preferable.

Example of Boiling-Point Estimation

The boiling point is the temperature at which the vapor pressure of a liquid becomes equal to the external pressure.
If atmospheric pressure is 101.3 kPa, lnP is as follows.

ln(101.3) = 4.618

Substitute this into the linear equation lnP = −5100 × 1/T + 19.17.

4.618 = −5100 × 1/T + 19.17

−5100 × 1/T = 4.618 − 19.17 = −14.552

1/T = 14.552 ÷ 5100 = 0.002853

T = 350.5 K = 77.4°C

From this calculation, the boiling point is estimated to be approximately 77°C.
This value is close to the boiling point of ethanol, suggesting that the measurement and analysis were generally reasonable.

Differences in Vapor Pressure Among Liquids

Even at the same temperature, vapor pressure differs depending on the type of liquid.
Liquids with weaker intermolecular forces evaporate more readily and have higher vapor pressures.

Liquid Vapor Pressure at 30°C Vapor Pressure at 50°C Approximate Boiling Point Direction of Discussion
Acetone Approximately 37 kPa Approximately 81 kPa Approximately 56°C High vapor pressure and highly volatile
Ethanol Approximately 10 kPa Approximately 30 kPa Approximately 78°C Intermediate
Water Approximately 4 kPa Approximately 12 kPa 100°C Low vapor pressure because of hydrogen bonding

Water has stronger hydrogen bonding, so at the same temperature its vapor pressure is lower than that of ethanol or acetone.
In contrast, acetone has relatively weak intermolecular forces and is highly volatile because of its high vapor pressure.

Effect of Temperature-Measurement Error

Because 1/T is used in the Clausius-Clapeyron plot, errors in temperature measurement affect the analysis results.

Actual Temperature Recorded Temperature Deviation in 1/T Effect on Enthalpy of Vaporization
40.0°C 40.0°C Reference Correct
40.0°C 39.0°C 1/T is slightly larger The slope changes
40.0°C 41.0°C 1/T is slightly smaller The slope changes
Measured before equilibrium Temperature display is constant Differs from the internal liquid temperature Vapor pressure becomes inaccurate

Temperature is converted to K rather than used in °C for calculations.
In addition, it is important not only that the thermometer display be constant but also that the liquid and gas phase have sufficiently reached thermal equilibrium.

Change in Vapor Pressure With Equilibrium Time

Immediately after changing the temperature, the liquid and gas phase may not yet have reached equilibrium, and the vapor pressure may not be stable.

Time After Reaching 50°C Measured Vapor Pressure State How to Interpret the Result
0 min 24.0 kPa Immediately after temperature change Before equilibrium
2 min 27.5 kPa Still increasing Still unstable
5 min 29.1 kPa Almost stable Close to equilibrium
8 min 29.5 kPa Stable Suitable for measurement
10 min 29.5 kPa Stable Equilibrium vapor pressure

Using values measured before equilibrium may cause vapor pressure to be underestimated.
It is important to wait until the measured value becomes constant before recording it.

Deviation in Pressure Measurement Caused by Air Contamination

When vapor pressure is measured with a pressure gauge, if air remains in the container, the measured pressure includes not only the vapor pressure of the liquid but also the partial pressure of air.

Condition Measured Pressure Actual Vapor Pressure Direction of Discussion
Air sufficiently removed 29.5 kPa 29.5 kPa Standard
Small amount of air contamination 34.0 kPa Approximately 29.5 kPa Air partial pressure is added
Insufficient air removal 45.0 kPa Unclear Vapor pressure is overestimated

If total pressure is treated directly as vapor pressure, air contamination may cause vapor pressure to be overestimated.
The effect of air must be checked according to the structure of the experimental apparatus and the measurement principle.

Sources of Error in Vapor Pressure Measurement

Source of Error Effect on Measured Value Trend in the Result Improvement
Temperature is not stable Vapor pressure fluctuates Large variation Measure after equilibrium is reached
Air contamination Pressure appears high Vapor pressure is overestimated Check removal of air
Error in reading the thermometer 1/T shifts Affects the slope Calibrate and read the scale correctly
Zero-point shift of the pressure gauge All values are too high or too low Affects the intercept and boiling-point estimation Check the zero point before measurement
Impurities in the sample Vapor pressure changes Deviates from the pure-substance value Use a high-purity sample
Mixed pressure units lnP shifts The intercept changes Use consistent units

In theory, the enthalpy of vaporization determined from the slope does not change even if the pressure unit is changed from kPa to Pa.
However, if units are mixed within the same data set, lnP shifts unnaturally and the data cannot be analyzed correctly.

Example When an Outlier Is Present

If vapor pressure at one temperature deviates greatly from the linear trend, insufficient equilibrium, reading errors, or air contamination may be possible causes.

Temperature Measured Vapor Pressure Expected Trend Judgment Possible Cause
20°C 5.9 kPa Low Good
30°C 10.5 kPa Increase Good
40°C 27.0 kPa Approximately 18 kPa Possible outlier Air contamination, reading error
50°C 29.5 kPa Further increase Good
60°C 47.0 kPa High Good

If only the value at 40°C is too high, the cause should not simply be attributed to the properties of the liquid; the measurement operation and condition of the apparatus should be checked.
If an outlier is excluded, the reason for exclusion must be clearly stated.

Precautions When Changing Pressure Units

When calculating lnP, the value of lnP changes depending on whether P is expressed in kPa or Pa.
However, if the same unit is used for all data points, the slope of the plot does not change and the enthalpy of vaporization is also unchanged.

P lnP Calculated in kPa lnP Calculated in Pa Difference
5.9 kPa = 5900 Pa 1.775 8.683 Shifted by approximately 6.908
10.5 kPa = 10500 Pa 2.351 9.259 Shifted by approximately 6.908
47.0 kPa = 47000 Pa 3.850 10.758 Shifted by approximately 6.908

Converting from kPa to Pa increases lnP by a constant amount.
The intercept changes, but because the slope does not change, ΔHvap is unaffected.
However, if units are mixed partway through the data, the correct linear relationship cannot be obtained.

Example of How to Write the Results

When the vapor pressure of ethanol was measured over the range of 20–60°C, the vapor pressure increased from 5.9 kPa to 47.0 kPa as the temperature rose.
This is considered to have occurred because the kinetic energy of the molecules increased with increasing temperature, increasing the number of molecules moving from the liquid phase to the gas phase.
The increase in vapor pressure was not linear but showed a tendency to increase strongly as the temperature rose.

Based on the Clausius-Clapeyron equation, 1/T was plotted on the horizontal axis and lnP on the vertical axis.
As a result, an approximately linear relationship was obtained, and the fitted equation was lnP = −5100 × 1/T + 19.17.
Because this slope corresponds to −ΔHvap/R, the enthalpy of vaporization was calculated as −(−5100) × 8.314 = 42400 J/mol, or 42.4 kJ/mol.

Furthermore, when the temperature at which the vapor pressure became 101.3 kPa was determined from the fitted equation, T = 350.5 K, or approximately 77.4°C, was obtained.
This is close to the boiling point of ethanol, suggesting that the measured values and analysis using the Clausius-Clapeyron plot were generally reasonable.

Points for Connecting the Results to the Discussion

In a discussion of vapor pressure measurement, it is important to explain not only the relationship between temperature and vapor pressure but also the linearity of lnP and 1/T, the enthalpy of vaporization determined from the slope, boiling-point estimation, and sources of error in relation to one another.

  • Can you explain why vapor pressure increases with increasing temperature in relation to molecular motion?
  • Have you converted °C to K and calculated 1/T correctly?
  • Have you calculated lnP from vapor pressure P and prepared a Clausius-Clapeyron plot?
  • Can you explain that the slope of the plot corresponds to −ΔHvap/R?
  • Can you calculate the enthalpy of vaporization from the slope?
  • Can you estimate the boiling point as the temperature at which vapor pressure equals the external pressure?
  • Can you discuss differences in vapor pressure among liquids in relation to intermolecular forces?
  • Can you explain measurement before equilibrium, air contamination, temperature-measurement error, and pressure-gauge deviation as sources of error?
  • Do you understand the need to use consistent pressure units?
  • If an outlier is present, can you discuss its cause from the measurement operation or the condition of the apparatus?

Example Discussion

In this experiment, the vapor pressure of a liquid was measured at different temperatures, and the enthalpy of vaporization was determined from a Clausius-Clapeyron plot.
The measured vapor pressure was 5.9 kPa at 20°C and 47.0 kPa at 60°C, showing a large increase in vapor pressure as the temperature rose.
This is because as the temperature increases, the kinetic energy of liquid molecules increases and more molecules can overcome intermolecular forces and move into the gas phase.

To analyze the relationship between vapor pressure and temperature, the temperature was converted to absolute temperature K, and 1/T and lnP were calculated.
When lnP was plotted on the vertical axis and 1/T on the horizontal axis, an approximately linear relationship was obtained.
According to the Clausius-Clapeyron equation, the slope of this line corresponds to −ΔHvap/R.
Because the slope in this experiment was −5100 K, the enthalpy of vaporization was determined to be 42.4 kJ/mol.

The enthalpy of vaporization is an indicator of the energy required for liquid molecules to become gas.
The stronger the intermolecular forces in a liquid, the more energy is required for molecules to move from the liquid to the gas phase, and the larger the enthalpy of vaporization becomes.
In addition, when compared at the same temperature, liquids with stronger intermolecular forces tend to have lower vapor pressures.
Water has a lower vapor pressure than ethanol or acetone because hydrogen bonding acts strongly between water molecules.

Possible sources of error include reading the vapor pressure before the temperature had sufficiently stabilized, residual air in the container, pressure-gauge reading errors, and calibration errors of the thermometer.
In particular, if air is present, the measured pressure includes not only the vapor pressure of the liquid but also the partial pressure of the air, so the vapor pressure may be overestimated.
In addition, if measurement is performed before equilibrium is reached, the vapor pressure may be underestimated.

In the analysis, temperature must be handled in K rather than °C, and the pressure unit must be consistent throughout all data.
If kPa and Pa are mixed, the lnP values shift unnaturally and the correct linear relationship cannot be obtained.
However, if all data are handled using the same pressure unit, the difference in pressure units mainly affects the intercept and has little effect on the enthalpy of vaporization determined from the slope.

Summary

Vapor pressure increases as temperature rises, and the relationship between lnP and 1/T can be analyzed using a Clausius-Clapeyron plot.
The enthalpy of vaporization can be determined from the slope of the plot, and the boiling point can also be estimated from the temperature at which the vapor pressure equals the external pressure.

This reference example covered vapor pressure at different temperatures, calculation of 1/T and lnP, the Clausius-Clapeyron plot, enthalpy of vaporization, boiling-point estimation, differences among liquids, temperature errors, equilibrium attainment, air contamination, pressure units, and outliers.
In a report, it is useful to organize the measured values in a table and discuss the relationship between the slope of the line, intermolecular forces, and the enthalpy of vaporization.

Why Vapor Pressure Increases as Temperature Rises

As the temperature rises, the thermal motion of liquid molecules becomes more active.
More molecules are able to overcome the intermolecular interactions in the liquid and move into the gas phase, making evaporation easier.
As a result, the number of molecules in the gas phase inside a sealed container increases, and the vapor pressure becomes larger.

The increase in vapor pressure with temperature is generally not linear and tends to become more rapid as the temperature rises.
Therefore, plotting vapor pressure P directly against temperature may produce a curve.
The Clausius-Clapeyron plot linearizes this relationship for analysis.

Example Discussion:
Vapor pressure increased as the temperature rose.
This is because higher temperature increased the thermal motion of the liquid molecules and increased the number of molecules able to overcome intermolecular interactions and move into the gas phase.
As a result, the number of molecules in the gas phase increased and the vapor pressure became larger.

What Is the Clausius-Clapeyron Equation?

The Clausius-Clapeyron equation expresses the temperature dependence of vapor pressure.
If the enthalpy of vaporization can be regarded as approximately constant within the temperature range, it can be expressed in the following form.

lnP = −ΔHvap / R × 1/T + C

Here, P is vapor pressure, T is absolute temperature, ΔHvap is the enthalpy of vaporization, R is the gas constant, and C is a constant.
This equation corresponds to the straight-line equation y = ax + b.
When lnP is plotted on the vertical axis and 1/T on the horizontal axis, the slope is −ΔHvap/R.

Example Discussion:
According to the Clausius-Clapeyron equation, a linear relationship exists between lnP and 1/T.
In this experiment, lnP and 1/T were calculated from the vapor pressures measured at each temperature and plotted.
Because the obtained graph was close to a straight line, the enthalpy of vaporization is considered to have been approximately constant over the measured temperature range.

How to Create a Clausius-Clapeyron Plot

To create a Clausius-Clapeyron plot, first convert the measured temperature to absolute temperature T.
Next, calculate 1/T for each temperature and determine the natural logarithm lnP of the vapor pressure P.
Create a scatter plot with 1/T on the horizontal axis and lnP on the vertical axis, and draw a fitted straight line.

Basic Procedure

  1. Measure the vapor pressure P at each temperature
  2. Convert the temperature from °C to K
  3. Calculate 1/T
  4. Calculate lnP
  5. Plot 1/T on the horizontal axis and lnP on the vertical axis
  6. Draw a fitted straight line
  7. Determine the enthalpy of vaporization from the slope

Point:
T must always be expressed as absolute temperature in K.
If 1/T is calculated using °C, it will not correspond to the Clausius-Clapeyron equation and the calculation of the enthalpy of vaporization will be incorrect.

Example Discussion:
The measured temperatures were converted to absolute temperature, and 1/T and lnP were calculated to create a Clausius-Clapeyron plot.
The measured points lay approximately on a straight line, indicating that the temperature dependence of vapor pressure followed the Clausius-Clapeyron equation.
The enthalpy of vaporization can be determined from the slope of the fitted line.

Meaning of the Plot Slope

In a Clausius-Clapeyron plot, 1/T is placed on the horizontal axis and lnP on the vertical axis.
The slope of the fitted line corresponds to −ΔHvap/R.
Because the enthalpy of vaporization ΔHvap is positive, the slope is negative.

Slope = −ΔHvap / R

ΔHvap = −Slope × R

The larger the absolute value of the slope, the more strongly vapor pressure changes with temperature.
This is related to the large amount of energy required to transfer molecules from the liquid to the gas phase.

Example Discussion:
The slope of the Clausius-Clapeyron plot was negative.
Because this slope corresponds to −ΔHvap/R, the enthalpy of vaporization was determined by multiplying the slope by −R.
The slope becomes negative because as the temperature rises, 1/T becomes smaller while the natural logarithm of the vapor pressure, lnP, becomes larger.

Meaning of the Intercept

The intercept of the Clausius-Clapeyron plot corresponds to the constant C in the equation.
This constant is related to the entropy of vaporization, the standard state, and approximation conditions, but in student experiments it is often treated mainly as a value that determines the form of the fitted line.
When determining the enthalpy of vaporization, the slope is used primarily.

However, if the intercept is greatly shifted or the fitted line does not agree well with the measured points, there may have been problems with pressure measurement, temperature measurement, or insufficient attainment of equilibrium.

Example Discussion:
The intercept of the Clausius-Clapeyron plot corresponds to the constant term in the equation.
In this experiment, the slope of the fitted line was mainly used because the objective was to determine the enthalpy of vaporization.
However, if the intercept or linearity is unnatural, the data may contain systematic error, so the temperature- and pressure-measurement conditions must be checked.

How to Interpret R2

The coefficient of determination R2 of a Clausius-Clapeyron plot indicates how well the measured points fit the fitted line.
The closer R2 is to 1, the better the linear relationship between lnP and 1/T is considered to be.

However, a high R2 does not necessarily mean that there are no measurement errors.
If there are systematic errors in the thermometer or pressure gauge, the measured points may still lie on a straight line while the slope differs from the literature value.
Therefore, comparison of the enthalpy of vaporization with literature values is also important in addition to R2.

Example Discussion:
The R2 of the Clausius-Clapeyron plot was close to 1, and the measured points fit the fitted line well.
This suggests that the linear relationship between lnP and 1/T was generally valid within the measured range.
However, even if R2 is high, systematic errors in temperature or pressure may cause the enthalpy of vaporization to differ from the literature value.

What Is the Enthalpy of Vaporization?

The enthalpy of vaporization is the energy required to convert 1 mol of liquid into gas.
For liquid molecules to become gas, they must overcome the intermolecular interactions acting within the liquid.
Therefore, liquids with stronger intermolecular interactions tend to have larger enthalpies of vaporization.

For example, in liquids that form hydrogen bonds, the attractive forces between molecules are strong, so a large amount of energy may be required for vaporization.
In contrast, highly volatile liquids with weak intermolecular interactions tend to have smaller enthalpies of vaporization and higher vapor pressures.

Example Discussion:
The enthalpy of vaporization is the energy required to transfer liquid molecules into the gas phase.
In liquids with strong intermolecular interactions, a large amount of energy is required to separate the molecules from the liquid.
Therefore, the magnitude of the enthalpy of vaporization is considered to reflect the strength of intermolecular interactions in the liquid.

Relationship Between Vapor Pressure and Intermolecular Interactions

Vapor pressure becomes larger when liquid molecules can escape into the gas phase more easily.
In liquids with weak intermolecular interactions, molecules are not strongly bound in the liquid, so they evaporate more readily and the vapor pressure becomes high.
Conversely, in liquids with strong intermolecular interactions, molecules are more strongly retained in the liquid and the vapor pressure becomes low.

In other words, liquids with higher vapor pressure tend to be more volatile and have lower boiling points.
Liquids with lower vapor pressure tend to be less volatile and have higher boiling points.

Example Discussion:
Because the vapor pressure was relatively high, the sample liquid is considered to have a tendency to move easily into the gas phase.
This may be because intermolecular interactions in the liquid are relatively weak and molecules can escape from the liquid phase more easily.
In contrast, liquids with strong intermolecular interactions tend to have lower vapor pressures and larger enthalpies of vaporization.

Relationship With Boiling Point

The boiling point of a liquid is the temperature at which its vapor pressure becomes equal to the external pressure.
When the external pressure is 1 atm, the temperature at which the vapor pressure reaches 1 atm is the normal boiling point.
A liquid with high vapor pressure reaches the external pressure at a lower temperature and therefore has a lower boiling point.
A liquid with low vapor pressure must be heated to a higher temperature before reaching the external pressure, so its boiling point is higher.

Example Discussion:
A liquid boils when its vapor pressure becomes equal to the external pressure.
Liquids with higher vapor pressure reach the external pressure at lower temperatures and therefore have lower boiling points.
Therefore, vapor pressure measurements provide information for discussing differences in volatility and boiling point among liquids.

Error Caused by Temperature Measurement

Because the horizontal axis of a Clausius-Clapeyron plot is 1/T, errors in temperature measurement strongly affect the results.
If temperature is used in °C or conversion to K is incorrect, the graph slope cannot be determined correctly.
Errors in reading the thermometer or failure of the entire sample to reach the set temperature also become sources of error.

Vapor pressure is particularly sensitive to temperature, so even a small temperature difference may cause a large change in pressure.
Therefore, it is important to keep the temperature constant and measure only after sufficient thermal equilibrium has been reached.

Example Discussion:
One possible reason the enthalpy of vaporization differed from the literature value is temperature-measurement error.
Because 1/T is used in the Clausius-Clapeyron plot, even a slight temperature error affects both the horizontal-axis value and the slope of the fitted line.
In addition, if the pressure was read before the sample had sufficiently reached the set temperature, the correct vapor pressure may not have been measured.

Error Caused by Pressure Measurement

In vapor pressure measurement, pressure is measured using a pressure gauge, manometer, or similar device.
Calibration errors of the pressure gauge, reading errors, parallax in reading scales, air contamination in the apparatus, and errors in reading the height of a liquid column affect the measured vapor pressure.
Errors in pressure values shift lnP and therefore affect both the slope and intercept of the Clausius-Clapeyron plot.

Example Discussion:
Pressure-measurement error directly affects lnP, which is the vertical axis of the Clausius-Clapeyron plot.
If the pressure gauge was insufficiently calibrated or the liquid-column height could not be read accurately, the vapor pressure would be overestimated or underestimated.
As a result, the slope of the fitted line may have changed and an error may have occurred in the calculated enthalpy of vaporization.

Error Caused by Insufficient Attainment of Equilibrium

Vapor pressure is the pressure when a liquid and its vapor have reached equilibrium.
If pressure is read immediately after changing the temperature or while the sample has not yet stabilized sufficiently, the measured value may not reflect the true equilibrium vapor pressure.
Before equilibrium is reached, evaporation and condensation are still progressing and the pressure may be changing.

If the measured value changes with time, it is necessary to wait until the pressure stabilizes before reading it.
Insufficient attainment of equilibrium can cause variation and outliers in a Clausius-Clapeyron plot.

Example Discussion:
One possible reason a measured point deviated from the fitted line is that the pressure was read before the liquid and vapor had sufficiently reached equilibrium.
Because vapor pressure is the pressure in an equilibrium state, the correct value cannot be obtained if the pressure is still changing after the temperature has been altered.
As a result, the lnP value shifted and the linearity of the Clausius-Clapeyron plot is considered to have decreased.

Error Caused by Air Contamination

In vapor pressure measurement, if noncondensable gases such as air remain in the apparatus, the measured pressure includes pressure from substances other than the vapor.
In this case, the measured value may become larger than the vapor pressure of the pure liquid.
Therefore, when handling vacuum systems or sealed systems, it is important to avoid air contamination.

Example Discussion:
One possible reason the measured vapor pressure was higher than the literature value is that air remained in the apparatus.
If a noncondensable gas such as air remains, the measured pressure includes the partial pressure of the air in addition to the pressure of the sample vapor.
As a result, the vapor pressure may have been overestimated and the lnP values in the Clausius-Clapeyron plot may have become larger.

Error Caused by Impurities in the Sample

If impurities are present in the sample, the vapor pressure may deviate from the value for the pure substance.
If a low-volatility impurity is present, the vapor pressure of the liquid may decrease.
Conversely, if a highly volatile impurity is mixed in, the measured pressure may increase.

If water or another solvent is mixed into the sample, the measured vapor pressure may represent that of the mixture rather than that of the target liquid alone.
Therefore, sample purity is an important point for discussion.

Example Discussion:
One possible reason the vapor pressure differed from the literature value is the presence of impurities in the sample.
If low-volatility impurities are present, the vapor pressure may decrease compared with that of the pure liquid.
On the other hand, if a highly volatile impurity is present, the measured pressure may increase and the vapor pressure may be overestimated.

Discussion When Deviations Occur on the Low- or High-Temperature Side

In a Clausius-Clapeyron plot, measured points only on the low- or high-temperature side may deviate from the fitted line.
On the low-temperature side, vapor pressure is small, so the relative error of pressure measurement tends to become large.
On the high-temperature side, temperature control may become more difficult, or bubbles, boiling, and large pressure changes in the apparatus may occur.

Checking which temperature range contains the deviating points makes it possible to discuss the source of error more specifically.

Example Discussion:
One possible reason the low-temperature measurements deviated from the fitted line is that vapor pressure was small and the relative error of pressure measurement became large.
On the other hand, on the high-temperature side, temperature control may have been difficult and the sample temperature may have deviated from the set value.
Therefore, examining how the Clausius-Clapeyron plot deviates in each temperature range makes it possible to discuss the sources of error more specifically.

When the Clausius-Clapeyron Plot Is Not Linear

If the Clausius-Clapeyron plot is not linear, possible causes include measurement error, a wide temperature range, limitations of the approximation that assumes constant enthalpy of vaporization, impurities in the sample, and insufficient attainment of equilibrium.
Incorrect pressure or temperature units may also greatly reduce linearity.

In a report, do not simply write that “the plot was not linear.”
Check which points deviate, whether the temperature conversion and pressure units are correct, and whether the measurement conditions were stable.

Example Discussion:
The Clausius-Clapeyron plot did not show sufficient linearity.
Possible causes include temperature- or pressure-measurement errors, insufficient attainment of equilibrium, and impurities in the sample.
In addition, if the measured temperature range is wide, the approximation that the enthalpy of vaporization remains constant may become less valid, causing deviation from a straight line.

When the Enthalpy of Vaporization Is Larger Than the Literature Value

If the experimentally determined enthalpy of vaporization is larger than the literature value, this means that the absolute value of the slope of the Clausius-Clapeyron plot was estimated too large.
Possible causes include reading the low-temperature pressure too low, reading the high-temperature pressure too high, or having a systematic error in temperature measurement.

Example Discussion:
One possible reason the determined enthalpy of vaporization was larger than the literature value is that the absolute value of the slope of the Clausius-Clapeyron plot was overestimated.
If the vapor pressure on the low-temperature side is measured too low and the vapor pressure on the high-temperature side is measured too high, the slope becomes steeper and ΔHvap is overestimated.
Therefore, systematic error in pressure measurement may have affected the result.

When the Enthalpy of Vaporization Is Smaller Than the Literature Value

If the experimentally determined enthalpy of vaporization is smaller than the literature value, this means that the absolute value of the slope of the Clausius-Clapeyron plot was estimated too small.
If the pressure change over the temperature range is measured as too small, or if air contamination causes the low-temperature pressure to be overestimated, the slope tends to become less steep.

Example Discussion:
One possible reason the determined enthalpy of vaporization was smaller than the literature value is that the absolute value of the slope of the fitted line was underestimated.
If air remained in the apparatus and the pressure on the low-temperature side was measured too high, the change in lnP would become smaller and the slope would become less steep.
As a result, ΔHvap is considered to have been underestimated.

Handling of Units

In a Clausius-Clapeyron plot, temperature is handled in K and pressure is handled using a consistent unit.
When calculating lnP, mixing different pressure units partway through causes the values to become inconsistent.
However, if the same pressure unit is used throughout, differences in pressure units mainly affect the intercept and may have little effect on the slope.

When determining the enthalpy of vaporization, attention must also be paid to the units of the gas constant R.
If R = 8.314 J mol−1 K−1 is used, ΔHvap is obtained in J/mol.
To convert to kJ/mol, divide by 1000.

Example Discussion:
In calculating the enthalpy of vaporization, the temperature must be converted to K and the units must correspond to those of the gas constant R.
When R = 8.314 J mol−1 K−1 is used, the unit of ΔHvap determined from the slope is J/mol.
Because errors in unit conversion cause large deviations when comparing with literature values, careful handling of K, J, and kJ is necessary.

Calculation of Error Rate

When comparing the experimentally determined enthalpy of vaporization with a literature value, the error rate can be calculated to express the difference quantitatively.
The error rate is obtained by dividing the difference between the experimental and literature values by the literature value and expressing it as a percentage.

Error rate (%) = |Experimental value − Literature value| ÷ Literature value × 100

Simply showing the error rate is not sufficient as a discussion.
Explain how temperature measurement, pressure measurement, insufficient attainment of equilibrium, air contamination, sample impurities, and unit conversion shifted the value and in which direction.

Example Discussion:
When the experimentally determined enthalpy of vaporization was compared with the literature value, the error rate was ○○%.
Possible causes of this difference include temperature-measurement error, pressure-gauge reading error, insufficient attainment of equilibrium, and air contamination in the apparatus.
In particular, because errors in both temperature and pressure affect the slope of the Clausius-Clapeyron plot, they are considered to have directly affected the enthalpy of vaporization.

When the Results Can Be Considered Good

Vapor pressure measurement results can be considered good when vapor pressure consistently increases with increasing temperature, the Clausius-Clapeyron plot is close to linear, R2 is high, and the determined enthalpy of vaporization does not greatly contradict the literature value.
It is also important that temperature and pressure be sufficiently stable before measurement.

Example Discussion:
Vapor pressure increased as the temperature rose, and the Clausius-Clapeyron plot also showed good linearity.
The enthalpy of vaporization determined from the slope of the fitted line did not greatly contradict the literature value.
From these results, the temperature dependence of vapor pressure is considered to have been measured generally correctly in this experiment.

Example Discussion When the Experiment Did Not Go Well

If vapor pressure measurement does not go well, the causes are considered from results such as vapor pressure not increasing monotonically with temperature, the Clausius-Clapeyron plot not becoming linear, the enthalpy of vaporization differing greatly from the literature value, or large variation among measured points.
Organizing the causes separately into temperature measurement, pressure measurement, attainment of equilibrium, air contamination, sample purity, and unit conversion makes the discussion easier.

Example Discussion:
In this experiment, the measured points in the Clausius-Clapeyron plot were widely scattered from the fitted line.
Possible causes include reading the pressure before the temperature had sufficiently stabilized, air contamination in the apparatus, and pressure-gauge reading errors.
In addition, errors in converting temperature to K and inconsistent handling of pressure units may also have affected the linearity of the graph and the calculated enthalpy of vaporization.

How to Write Points for Improvement

In a discussion of vapor pressure measurement, including points for improvement in addition to sources of error makes the report easier to organize.
Improvements are easier to write when divided into temperature control, pressure measurement, attainment of equilibrium, sample and apparatus management, and data analysis.

Improvements to Temperature Control

  • Keep the temperature constant using a thermostatic bath or similar equipment
  • Measure only after the entire sample has reached the set temperature
  • Calibrate the thermometer
  • Convert temperature from °C to K for analysis
  • Record temperature fluctuations during measurement

Improvements to Pressure Measurement

  • Calibrate the pressure gauge
  • Read the pressure only after it becomes stable
  • Read the liquid-column height or scale accurately
  • Use consistent pressure units
  • Confirm measured values multiple times

Improvements to the Apparatus and Sample

  • Remove as much air as possible from the apparatus
  • Check for leaks
  • Confirm sample purity
  • Avoid contamination by water or volatile impurities
  • Allow sufficient equilibration time after changing the temperature

Improvements to Data Analysis

  • Calculate 1/T and lnP correctly
  • Check the equation of the fitted line and R2
  • Check the cause of outliers
  • Determine ΔHvap from the slope
  • Match the units of R and ΔHvap
  • Check whether the temperature range is the same as that used for the literature value

Example of How to Write Points for Improvement:
To improve the accuracy of vapor pressure measurement, the pressure must be read only after the sample and vapor have sufficiently reached equilibrium at each temperature.
In addition, because vapor pressure is sensitive to temperature, it is important to keep the temperature constant using a thermostatic bath or similar equipment.
Furthermore, preventing air contamination and leaks in the apparatus and correctly calibrating the pressure gauge can reduce the variation in the Clausius-Clapeyron plot.

Difference Between a Superficial Discussion and a Good Discussion

In a discussion of vapor pressure measurement, simply writing that “vapor pressure increased as temperature rose” or “the graph became linear” results in a superficial discussion.
Relating temperature, molecular motion, intermolecular interactions, the Clausius-Clapeyron equation, the slope, the enthalpy of vaporization, and sources of error produces a more persuasive discussion.

Superficial Discussion Good Discussion
Vapor pressure increased as the temperature rose. As the temperature rose, the thermal motion of liquid molecules became more active and more molecules were able to overcome intermolecular interactions and move into the gas phase, so the vapor pressure increased.
The Clausius-Clapeyron plot became linear. According to the Clausius-Clapeyron equation, a linear relationship exists between lnP and 1/T. Because the measured points were close to a straight line, the enthalpy of vaporization is considered to have been approximately constant within the measured temperature range.
There was an error. Possible reasons the enthalpy of vaporization differed from the literature value include temperature-measurement error, pressure-gauge reading error, insufficient attainment of equilibrium, air contamination in the apparatus, and impurities in the sample.

Examples of Expressions That Can Be Used in Reports

The following expressions can be used when writing the results and discussion of vapor pressure measurement.
Adjust the necessary parts according to your own experimental results.

  • Vapor pressure is the pressure of the gas phase when a liquid and its vapor are in equilibrium.
  • As the temperature rose, the thermal motion of the liquid molecules became more active and the vapor pressure increased.
  • According to the Clausius-Clapeyron equation, a linear relationship exists between lnP and 1/T.
  • The slope of the fitted line corresponds to −ΔHvap/R.
  • The enthalpy of vaporization can be determined by multiplying the slope by −R.
  • The enthalpy of vaporization is the energy required to convert 1 mol of liquid into gas.
  • Liquids with stronger intermolecular interactions tend to have larger enthalpies of vaporization.
  • Temperature-measurement error affects the value of 1/T and the slope of the fitted line.
  • Pressure-measurement error directly affects lnP and shifts the calculated enthalpy of vaporization.
  • If measurement is performed before equilibrium is reached, the true equilibrium vapor pressure cannot be reflected.

Points to Check When Discussing Vapor Pressure Measurement

Checking the following points before writing the report makes the discussion easier to write.

  • Have you converted the measured temperature to K?
  • Have you used consistent pressure units?
  • Have you calculated 1/T and lnP correctly?
  • Have you created a Clausius-Clapeyron plot?
  • Have you explained the meaning of the slope of the fitted line?
  • Have you determined the enthalpy of vaporization from the slope?
  • Have you matched the units of R and ΔHvap?
  • Have you explained why vapor pressure increases as temperature rises?
  • Have you related intermolecular interactions to the enthalpy of vaporization?
  • Have you discussed insufficient attainment of equilibrium?
  • Have you considered air contamination and sample impurities as sources of error?
  • Do the points for improvement correspond to the sources of error?

Summary

Vapor pressure is the pressure of the gas phase when a liquid and its vapor are in equilibrium.
As the temperature rises, the thermal motion of liquid molecules becomes more active and more molecules can move from the liquid into the gas phase, so the vapor pressure increases.
Liquids with higher vapor pressure are more volatile and generally tend to have lower boiling points.

In a Clausius-Clapeyron plot, 1/T is placed on the horizontal axis and lnP on the vertical axis.
If the enthalpy of vaporization can be regarded as approximately constant within the measured range, the graph becomes linear and the slope of the fitted line corresponds to −ΔHvap/R.
Therefore, the enthalpy of vaporization can be determined from the slope.

In a report, do not simply write that “the plot became linear.”
Discuss the relationship between temperature and vapor pressure, the meaning of the slope, the enthalpy of vaporization, intermolecular interactions, and sources of error in relation to one another.
Temperature measurement, pressure measurement, insufficient attainment of equilibrium, air contamination, sample impurities, and unit conversion greatly affect both the linearity of the Clausius-Clapeyron plot and the value of the enthalpy of vaporization.