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Thermodynamic study of
the dissociation of a propionic acid dimer

Objectives

 To learn how the thermodynamic parameters of the gaseous chemical reaction of

the type A ⇌ 2B are experimentally determined by measuring the related pressure
vs temperature dependence.

 To determine the equilibrium constant for the dissociation of propionic acid dimer
as a function of temperature.

 To learn how to calculate the enthalpy and entropy of dissociation from the
ln(Kp) = f(1/T) plot.

 To relate the experimental enthalpy of dissociation to the strength of hydrogen

bonds between the carboxylic groups of propionic acid molecules.

Introduction

When low molecular weight carboxylic acids vaporize, they exist in the gaseous
phase as a mixture of dimers and monomers. The dimers form as a consequence of
hydrogen bonding and have a structure roughly similar to that shown in Figure 1.

H H H H H H H
O H O O
H C C C C C C H 2x H C C C
O H O O
H H H H H H
Figure 1. The dissociation of dimers of propionic acid vapor

In this experiment the gas pressure of a fixed amount of vaporized propionic acid
R
is measured as its temperature is raised. From these data, the equilibrium constant for the
dissociation of acid vapor dimers into monomers is determined. From the slope of the
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best-fit line in a plot of the natural log of the equilibrium constant against the reciprocal
temperature, the enthalpy change (Ho) for the dissociation process is determined. The
Ho obtained is related to the strength of the hydrogen bonding between the carboxylic
groups since this is the dominant force that keeps the monomers together. The entropy
(So) and free energy (Go) of the acid dissociation can be calculated from the calculated
Ho.

Theoretical Background
By measuring the total pressure (at a known temperature and volume) of a known
mass of a volatile carboxylic acid, the equilibrium constant for the gas phase dissociation
of the acid dimers into monomers can be obtained. If the entire vapor were in its
monomer form, the total pressure would be twice of what it would be if the entire vapor
were in its dimer form. If some propionic acid vapor were in the form of the monomer,
and some were in the form of the dimer, the total pressure would be somewhere in
between. A measurement of the pressure can be converted to relative amounts of dimer
and monomer. From this the equilibrium constant can be determined. Any homogeneous
gas phase dissociation equilibrium can be written as in Eq. (1).
D  2M (1)

Under low pressure conditions where all species behave ideally, the equilibrium constant,
Kp, can be expressed in terms of pressures by:

 PM 
2 (2)
 o
Kp  
P 
 PD 
 o
P 
where PM and PD are the partial pressures of the monomer and dimer and Po is the
pressure of the standard state. Po = 1.0 atm (see physical chemistry textbook for a
discussion of the choice of units and standard states).

Allowing  (a number between 0 and 1) to represent the degree of dissociation

of the dimer, PM can be expressed as:
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 2  (
PM   P
1  (3)
 2 
where   represents the mole fraction of monomers, since two monomers (2) are
1 
produced from each dimer dissociation. As each dimer dissociates, there is a net increase
of one particle which results in the total number of particles present in the system being
(1+). P is the total pressure of the gas mixture. Similarly, PD can be expressed as:
 1  (
PD   P
1  (4)
 1 
where,   represents the mole fraction of dimers, since (1-) indicates that one
1 
dimer is lost for each dissociation and there is a net increase of one particle (1+) for the
total number of particles in the system, as each dissociation occurs. By substituting Eqs.
(3) and (4) into Eq. (2) the following for Kp expression is obtained:

 4 2  (
K p   P
2 
 1    (5)

At equilibrium, because number of moles of dimer (nD), bulb volume (V), temperature
(T), and pressure (P) are known, the total number of moles of gas molecules, nD(1+) is
given by

n D 1    
PV (
RT (6)
Stated in slightly different terms, this relationship is:
P (7)
1 
Pi
where, Pi is the pressure that would be observed if there were no dissociation. Pi can be
calculated using the following equation:
nD RT  gR  (8)
Pi    T
V  MW )V 
where, g is the mass of the carboxylic acid vaporized and MW is the molecular mass of
the carboxylic acid dimer. By substituting Eq. (7) into Eq. (5) and Eq. (9), Kp for the
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dissociation of carboxylic acid dimers is obtained from the experimental pressures at the
measured temperatures, volume and mass of vapor.

4P  Pi 
2
(9)
Kp 
2 Pi  P
All quantities on the right-hand side of the equation are determined from the
experimental data. The value of Kp depends on the pressure units. (Express the pressure
units in atm.)
Based on Kp and its temperature dependence, standard thermodynamic quantities
can be readily obtained using the following thermodynamic relationships.

G o  RT (ln K p ) (10)

H o  d (ln K p ) (11)

R d (1 / T )

S o 
H o
 G o  (12)
T

where, Go, Ho and So are the standard free energy, enthalpy, and entropy for the
dissociation of the carboxylic acid dimers. Kp is a function of temperature. Note that the
right-hand side of Eq. (11) is the negative slope of a plot of ln Kp versus 1/T.
The experimental value of entropy, So, can be compared to the value of entropy
calculated using the Sackur-Tetrode equation. In this approach only the translational
part of entropy is calculated.
S 0 SackurTetrode  2 S M  S D (13)

where, SM is the entropy of the monomer and SD is the entropy of the dimer.
S  5 3  (14)
 2.303 log P  log T  log( M )  0.5053
R  2 2 
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In Eq. (14), P is in atm, T is in K, and M is the molecular mass of the species (monomer
or dimer) in g mol-1. When calculating So, pressure is in 1 atm and temperature is 25.0 °C
(see your physical chemistry textbook for a discussion of the Sackur-Tetrode equation
and for further explanation of its derivation and usage).

Laboratory Procedure

In this experiment, a known amount of propionic acid will be transferred into a

known volume of an evacuated glass bulb. The bulb is attached to a capacitance
manometer and enclosed in an oven to measure the pressure change while raising the
temperature in increments of 3-5oC from approximately 20oC to 70oC. The temperature
will be measured using a digital thermometer. The capacitance manometer measures the
pressure; it has a transducer in the oven and a digital readout outside the oven. Figures 2
and 3 show the experimental setup.
Before filling the bulb with the propionic acid vapor, all the gaseous molecules
from the system must be removed under vacuum. Figure 2 shows a series of valves and
glass lines that are used to carry out the evacuation of the system and for the introduction
of the acid vapor into the bulb.

Figure 2. Vacuum line of the acid dissociation apparatus.

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CAUTION: The vacuum system is made of glass and is fragile. If not properly
handled, it could implode or explode and send glass flying throughout the laboratory.
GOGGLES MUST BE WORN AT ALL TIMES DURING THE EXPERIMENT!!
Please become familiar with the valves and the fragile components of the vacuum line in
order to work efficiently and safely. When turning valves and stopcocks, use two hands
to avoid applying torsion on the glass tubing. Do not overly tighten the stopcocks
that are hard to close or unscrew them very far to open. Ask a TA or instructor to show
you how the o-ring seals operate. The o-rings have to be replaced quite often due to the
corrosive nature of the acid vapor in the system.

Figure 3. Oven part of the acid dissociation apparatus.

1. Fill a large dewar flask with liquid nitrogen. This flask will be fit around the
vacuum trap at step #7.

CAUTION: Do NOT put your hands into the liquid nitrogen. Liquid nitrogen boils
at 77K; and can freeze tissue quickly and painfully. Ask for help from your TA or
instructor to get this for you.
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2. Check the acid sample container; it should be at least half full and all o-rings
should be in good condition. Have a TA or instructor demonstrate the proper
method for the turning off the valves.

3. Close valve A that vents to the room. If valve A is left open for approximately 20
minutes after liquid nitrogen is placed around the trap, air will begin to liquefy in
the trap which could lead to a potentially dangerous situation when the vacuum
pump is turned on and the liquefied air is vaporized. Another reason for having
valve A closed is to prevent sample distribution into the air in the room. Also close
valve D.

4. Carefully place the large Dewar of liquid nitrogen around the vacuum trap and
firmly clamp the Dewar into position. Wear the blue cryo gloves when doing this
or have the TA do it for you.

5. Start the vacuum pump by pushing on the toggle switch on the cord.

6. Open valves B, C, and E, if they are not already open. Notice an almost immediate
drop of pressure. If there is no sudden drop in the pressure, check if valve A is
completely closed. Allow the system to fully evacuate for 5-10 min. While waiting
for the full evacuation move to step #10. Later on, this step will be called the
residual pressure step and the pressure value will be recorded.

7. While waiting for the evacuation to take place, cool the sample by carefully placing
the small Dewar containing the ice-water bath prepared in step #4 around the
sample container. Clamp the Dewar securely into place. This step is to cool down
the sample to avoid pumping away too much vapor during outgassing.

8. When the pressure reading is between 0.60 and 0.40 torr, close valve E (***do
not over tighten metal valve E doing so will damage the valve and cause a leak in
the vacuum system). This pressure reading will be recorded and called the initial
residual pressure.
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9. When the sample is cold, open valve D and pump on the sample for approximately
1 to 1.5 min to completely outgas the sample. Outgassing purifies the sample from
any air dissolved in the acid or in the sample container environment.

10. Close valve D and remove the ice-water bath. Place the ice water dewar on the lab
bench and place the thermocouple reference wire into it, as you will soon be
recording temperatures.

11. Close valve C and with a kimwipe, remove the acid container from the vacuum
line. Kimwipes prevent fingerprints on the sample container, as fingerprints will
affect the mass. Set the container on the lab bench in a manner so that the acid
inside does not touch the valve. Refer to Figure 4 and let sample container warm
to room temperature. Once room temperature is reached, place a small square
piece of plywood on the balance and weigh it, then place the acid container on the
plywood and record the weight. Since accurate mass determinations are crucial to
the success of this experiment, be consistent in weighing measurements.

Figure 4. Proper placement of an acid container on a plastic weight tray as it warms up

to room temperature to be weighed.

15. The thermocouple reference wires are already in the small dewar containing ice-
water mixture and connected the leads to the voltmeter. Compare the reading on the
voltmeter and the thermometer, which is on the top of the oven. Voltmeter and
thermometer readings should be in close agreement, if not seek the assistance of a
TA or the instructor.
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16. Reattach the sample container to the vacuum line. The volume between valves C
and D must be evacuated before the sample can be admitted into the system.
Therefore, open valve C and pump for 1-2 min. Do not open valve D at this time.

17. Check the pressure reading, it may have slightly increased. Record this pressure as
the current residual pressure. If the pressure is above 0.40 torr, open valve E
and allow the bulb to pump down to a pressure between 0.40 and 0.20 torr.
Record this as the final residual pressure.

18. Open valve E (if it hasn’t been opened in step #17).

19. You are now ready to expand the sample into the bulb in the oven (volume of the
bulb is 3.4 L  0.1 L). Close valve B and open valve D and allow the pressure to
reach 2.85 to 3.35 torr, such that the subtraction of the residual pressure gives a net
pressure of at least 2.25 to 2.75 torr. Do not fill the bulb to greater than 3.35 torr.

Pressure change should start almost immediately; if not, inform a TA. It will take
approximately 10 minutes to fill the bulb to the prescribed pressure. Do not fill the bulb
for any longer than 15-20 min even if you have not reached a net pressure of 2.25 torr. If
time needed to reach pressure is too short inform TA, you may have leak in the system.

20. Once the desired pressure is achieved, isolate the sample (which is propionic acid
vapor) in the bulb by closing valve E.

21. Since only the mass of the gas in the sample bulb is of interest, the remaining
vapor must be condensed back into the sample container. Therefore, place a
small Dewar containing liquid nitrogen (filled by the TA) around the acid sample
container and allow the vapor in the line to condense back into the sample container
for 2 to 5min.

22. Close valves C and D. Remove the liquid nitrogen and allow the acid container to
return to room temperature (since this procedure takes several minutes, continue
onto the next step and come back to this step when room temperature is reached).
Once room temperature is attained, re-weigh the sample container and record the
weight. The difference between this and the initial weight gives the mass of the
propionic acid in the sample bulb.
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NOTE: An accurate measurement of the weight difference is crucial to the success of

this experiment. A weight difference in the range of 0.060 – 0.091 g must be otherwise
consult with your TA BEFORE continuing.
23. Begin taking readings while waiting for the acid sample to warm up. Record the
temperature and corresponding pressure readings at this time. This will be the
initial set of data points.

24. Now, close the oven door. Set the left-hand dial (gross adjust oven temperature
knob) to low by turning it counter-clockwise. This will turn on a red light. Turn the
right-hand dial (fine adjust oven temperature knob) clockwise, until the lower
orange light just comes on. This should cause the temperature to rise at a slow
enough rate that accurate readings can be taken. When the orange light goes off, the
right-hand dial should be turned just far enough to bring the orange light back on
again. Because of the slow equilibrium of the system, make sure that the heating
rate is not faster than ~0.5 K/min. Using this method of heating, temperature
readings should be taken at approximately every 3 oC with the corresponding
pressure readings. It is suggested that one person read the pressure and
temperature readings while the other records them. In this way, the most accurate
data sets will be obtained.

The uncertainty of the pressure reading is P = 0.20%.

A sample data/results table may look like this:
Time, s T, oC P, mm Hg P, atm Pi, atm Kp

Determine 1) P in atm., 2) Pi, and 3) Kp to answer one of the in-lab questions.

BEFORE leaving lab:

The conversion between the P in mm Hg or torr to P in atm. is:
PmmHg (
P(atm) 
760 (15)
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Refer to the introduction to obtain the equations needed to calculate Pi and Kp. Use an
Excel spreadsheet to do these calculations; though you should do one set by hand so that
you are sure you have the formulas put into the spreadsheet correctly.

25. Continue taking readings at 3oC increments up to approximately 70oC. This

process will take approximately one hour.

26. While waiting for the temperature to change during the experiment, calculate the Kp
values for the previous set of readings. (You may do this on a spare computer using
an Excel spreadsheet.) The Kp values should be 0  Kp  1 and should increase or
decrease in a regular pattern.

NOTE: Have the second mass of your sample before calculating Kp.
You may find that some values of Kp are negative (due to the denominator in Eq. (9)
being negative). If this happens with only one or two of the high temperature points and
the others seem reasonable you may ignore this. If it happens with any of your first few
points, stop and get help.

27. Once you have collected 7-10 good data points (the more, the better), shut off the
oven at the dials and open the oven door. In order to get a good idea of the quality
of the data points, plot a graph of ln Kp versus 1/T, K-1. Generally the slope of the
best-fit line should be –7000 to –15000 with a fairly high R2 value.

28. Pump the propionic acid from the bulb by opening valves B and E. (Be careful!
Valve E may be HOT! )

29. Leave the liquid nitrogen in the dewars for the next lab group, unless you are the
last lab group for the day. Pour the ice water down the drain and dry out this Dewar
for the next lab group that will use it.

30. Turn in your in lab questions BEFORE leaving the lab. Also be sure your lab area
is neat and clean before leaving the lab.
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In Lab Questions

1. Explain why the total pressure of a given sample of propionic acid completely in its
dimer form would be half the total pressure if the same sample were completely in its
monomer form.

2. Explain why it is important to let the propionic acid sample warm up to room
temperature before weighing it. You should be as thorough as possible in answering
this question.
3. Think about what is going on at the molecular level as the propionic acid dimers
dissociate. What sign do you expect Ho to have? Do you expect the magnitude of
Ho to be relatively large or small compared to Ho for the combustion of propionic
acid? What sign do you expect So to have? Give reasons for all your answers.

4. Prepare a table for collecting the data and tabulating your results similar to that shown
in Step 24 of the procedure. Be prepared to hand in a table of your calculated
values of Kp BEFORE leaving the lab.

4. Data Analysis

1. Carry out the calculations needed to complete the table shown in Step 24 of the
procedure. Calculate the corresponding uncertainties for each result as you proceed
through the calculations and report these uncertainties along with the tabulated
calculated results. It is best to put the uncertainties in their own columns in a
spreadsheet for ease of calculations. You may find it easiest to break down the error
propagation of Kp into parts and put these intermediate values and their uncertainties
into their own columns on the Excel spreadsheet.
2. Plot ln Kp versus 1/T, where the temperature is in reciprocal of Kelvin.

3. Determine the best-fit line for this data and display the equation of the line and its R2
value on the graph. Also carry out the least squares fit for this line using the
regression analysis program on Excel used for your error analysis problem set.
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Determine the standard error of the slope, Sm, and the standard error of the y-
intercept, Sb, from the regression analysis printout. Report the uncertainty in the
slope as the Sm value and the uncertainty in the y-intercept as the Sb value.
4. Calculate the Kp and its uncertainty at 25.0oC. In the uncertainty calculation, use the
Sm and Sb values, respectively, from the linear regression analysis. Simplification
rules #1 and #4 given in this manual can be found helpful in the uncertainty analysis.
5. Calculate the value of Ho using the slope (-Ho/R ) of lnKp vs 1/T graph. Use the
uncertainty in the slope to determine the uncertainty in Ho.
6. Calculate Go. (Keep in mind that o
means at 298.15 K and 1 atm.) Then calculate
So from the calculated value of Go and the value of Ho determined in step #5.
Once again remember to calculate the corresponding uncertainties in each.

7. Use Reference 2 to find the literature values for Ho, Go and So at the conditions
closest to your experimental conditions (MacDougall’s values) in Table 1 and Table 2
(a copy of this reference exists in the lab on the bulletin board and also in the Chem
457 binder on reserve). Find the literature values for only Ho and So. From these
values, calculate Go and use its value as the literature value for Go.
8. Calculate the SoSackur-Tetrode value corresponding to the changes in translational
entropy as the dimers are dissociated into their monomer form. Use standard
thermodynamic values for the temperature (298.15 K) and pressure (1 atm) in the
Sackur-Tetrode equation.
9. Compare the values of the experimental So and the SoSackur-Tetrode. Calculate the
difference for these two values and comment on their differences. This means you
should suggest possible reasons for these differences. The comments should appear
in your summary.
10. Finally compare the value of the experimental Ho to the Ho of a hydrogen
bond3. Discuss this comparison in the report questions.

Reminders:

Carry out the error analysis on each of the values calculated and report them as the
calculated value  propagated error reported to a value between 3 and 30, such as 25.02
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 0.30 g, but not 25.02  0.50 g. The latter should be reported as 25.0  0.5 g. Present
your data in a table.

Show detailed sample calculations for each different kind of calculation and a detailed
error analysis for each sample calculation shown. If unsure of what is expected here,
refer to your introductory course material or ask one of the TAs or the instructor.

5. Report Questions

1. Based on your results, what happens to the dimer-monomer equilibrium as the

temperature increases? Does the reaction shift to more dimer or more monomer at
higher temperatures? Does this agree with what you would predict from Le
Chatelier’s principle? Give reasons for each of your answers to the above questions.
2. Do both Ho and So contribute to Go in the same way? Explain.

3. Discuss how the experimental Ho compares with typical hydrogen bond energies.

References:

1. Barton, D.; Ralph, R.; Kane, K. J. Chem. Educ. 1968, 45, 440.

2. Allen, G.; Caldin, E. F. Quarterly Reviews 1953, 7, 255.

3. Pauling, L. The Chemical Bond; Cornell University Press, 221 (1967).

Additional references used but not cited in the experiment:

Clagnue, A. D. H.; Bernstein, H. J. Spectrochimica Acta 1969, 25A, 593.

Joesten, M. D.; Schaad, L. J. Hydrogen Bonding, 2 (1974).