In the Laboratory

Understanding the ClausiusClapeyron Equation

by Employing an Easily Adaptable Pressure Cooker
Monica Galleano,* Alberto Boveris, and Susana Puntarulo
Physical Chemistry, School of Pharmacy and Biochemistry, University of Buenos Aires, Junn 956, C1113AAD,
Buenos Aires, Argentina; *mgallean@ffyb.uba.ar

Designing a physical chemistry laboratory that employs
systems of interest to life sciences students is a challenge for an
instructor. Experiments for biochemistry and pharmacy majors
are numerous and diverse in kinetics. However, thermodynamic
laboratory practices are poorly connected with everyday life
or professional activity. This situation does not encourage the
learning of this area of physical chemistry.
In this article we present a quantitative analysis of the dis-
placement of phase equilibrium by modifying external pressure.
Liquidvapor phase transition pressure and temperature for
water are measured to verify the ClausiusClapeyron equation.
Students analyze the principles governing a pressure cooker
and how the pressure cooker can be adapted to function as an
autoclave (1) for sterilizing purposes.

A valve valve lid Time Requirement

thermometer pressure The experiment can be carried out in approximately 3
gauge
hours, divided as follows:
safety valve
lid Measurement of pressure and temperatures of equilibrium
chamber phase under different experimental conditions (1:30
water hours)
container
Sterilization cycle (1 hour)
Report (30 minutes)
B C 20 mm
inner diameter
Equipment
18 mm
metallic
washer The following equipment and materials are needed: pres-
30 mm

sure cooker, pressure gauge, thermometer, timer, distilled water,

valve 46 mm heat source (hot plate or Bunsen burner), metallic washers,
lid outer diameter thermal gloves, glasses, and material to be sterilized.
25 mm 3 mm
thickness
A pressure gauge (a regular oil model with a double scale,
02 bars and 030 psi) and a bimetal thermometer (model
Figure 1. Schematic representation of the pressure cooker: (A) detailed BDTH Badotherm, 0150 C) were fitted to the lid of a pres-
components, including the pressure gauge and the thermometer added
sure cooker (10.5 liter capacity; Marmicoc Argentina SACIFA),
to the lid; (B) the valve lid and the metallic washers used to increase its
mass; and (C) as an example, the 35 g washer is represented.
to read the pressure and the temperature within the chamber
(Figure 1A). Holes were drilled in the lid to insert the pressure
gauge and the thermometer and both holes were fitted with a
brass locknut and synthetic rubber washers on each side of the
Table 1. Internal Pressure and Equilibrium Temperature lid. The pressure indicated by the pressure gauge is the value above
as a Function of the Valve Lid Mass atmospheric pressure; to obtain the real chamber pressure it is
Internal necessary to add the atmospheric pressure to the gauge value.
Mass/ Temperature
Description Pressurea/ Commercially available metallic washers were selected to
g kPa C K
fit in the middle portion of the valve lid. Figure 1B shows how
None -- 101b 100 373 the metallic washers are placed, only resting on the valve lid.
Original valve lid 76 156 114 387 The inner diameter of the washer must be 19 to 24 mm for this
particular pressure cooker model. When the inner diameter was
+ 15 g washerc 91 170 118 391 larger, a smaller washer was added to support it in the correct
+ 15 g + 20 g washerd 111 183 121 394 position. Dimensions and masses of the washers used in this
+ 35 g washerse x2 146 209 124 397
experiment are listed in Table 1.
+ 91.5 g washerf 167.5 225 126.5 399.5
Hazards
aInternal pressure was calculated as the sum of the atmospheric
pressure and the pressure measured by the pressure gauge in each Pressure cookers are usually equipped with a safety valve
condition. bThis value can be assumed as 101 kPa or measured with the that is made from an alloy breakable at 202 kPa of overpressure
appropriate manometer. cWasher dimensions are 19 mm x 40 mm x 1.5
mm (i.d., o.d., and thickness, respectively). dWasher dimensions are 19
(approximately 303 kPa of total pressure), which guaranties the
mm x 40 mm x 2 mm. eWasher dimensions are 20 mm x 46 mm x 3 mm. safety of the process within the pressure range proposed here.
fA 56.5 g washer (27 mm x 60 mm x 3 mm) and a 35 g washer.
Any changes or modifications to the pressure cooker should be

276 Journal of Chemical Education Vol. 85 No. 2 February 2008 www.JCE.DivCHED.org Division of Chemical Education
 In the Laboratory

tested to make sure that they do not compromise the integrity barometric pressure
of the instrument. 101 kPa
The manipulation of the pressure cooker must be made
with appropriate protection and any component of the equip-
ment should not be manipulated until its temperature reaches A B
room temperature. Students should wear aprons or lab coats
and goggles (or any eye protection) and should be advised to Pext  Pbar  101 kPa Pext  Pbar
avoid direct contact with overheated water vapor because of Pext  101 kPa
the risk of burning.
Pvap  Pext  101 kPa Pvap  101 kPa
Experimental Procedure
internal pressure in restricted volume
How Does a Pressure Cooker Work? the chamber
A liquid boils when the vapor pressure of the gas escaping constant (101 kPa)
from the liquid is equal to the pressure exerted on the liquid
by its surroundings (Pvap = Pext). As a consequence, the boiling
point can be manipulated by increasing the external pressure. In C D
a regular cooker, water is exposed to normal external pressure
(normal barometric pressure = 101 kPa) and boils at 100 C
Pext  Pbar
(373 K). When the lid is not in its position or the valve is uncov- Pext  101 kPa
ered (Figure 2A), the pressure cooker works as a regular cooker.
However, if the valve is covered there will be a change in the
Pvap  Pext  101 kPa
inner pressure of the chamber and the liquidvapor equilibrium
point will be displaced (Figure 2B). When the valve is covered, restricted volume vapor escaping to
the condition of the system changes because the vapor phase is maintain pressure
now restricted to the chamber. As a consequence of the added
mass (the valve lid), the pressure raises and the equilibrium internal pressure in the chamber
between phases is displaced to a higher temperature, resulting constant ( 101 kPa)
in a new boiling point (Figure 2C). The mass of the valve lid de-
Figure 2. Schematic interpretation of water molecules behavior during
termines the pressure inside the chamber because the hole of the
vaporization process in the pressure cooker. Circles represent water
valve lets gas escape when the pressure exceeds some fixed value. molecules. Pbar indicates barometric pressure (normal = 101 kPa);
Excess pressure is eliminated through small quantities of vapor Pvap indicates the vapor pressure of the liquid; and Pext indicates
escaping through the valve (Figure 2D) establishing a situation pressure exerted on the liquid by its surroundings. Conditions C and
of intermittent constant volume (Figure 2C and 2D). D will be in equilibrium during the phase change until water converts
completely in vapor.
How To Verify the ClausiusClapeyron Equation?
Water is heated in the pressure cooker under different
5.6
pressures by adding varying washers to the valve lid. First, water
heating starts with the valve uncovered. Prior to covering the 5.4
valve the chamber must be purged or cleansed to ensure the
absence of air. When water boils, vapor will displace the air and 5.2
ln(P / kPa)

after a few minutes the vapor escaping through the hole of the
valve becomes continuous, indicating that only water is in the 5.0

chamber. At this point, the valve lid is placed on the valve and
4.8
the new pressure and temperature of the transition process are
measured. After reaching this new equilibrium, the heat source 4.6
is removed for five minutes, a washer is placed on the valve lid,
and the heating is re-started until the next equilibrium point is 4.4
2.45 2.50 2.55 2.60 2.65 2.70
reached. At the end of 4 or 5 additions or exchanges of differ-
ent washers students have a correlation between the mass of the 3 1
(1/T ) / (10 K )
modified valve lid and the measured pressure and temperature,
Figure 3. Natural logarithm of total pressure in the chamber (P) as a
as shown in Table 1.
function of the reciprocal of the equilibrium temperature (1/T ).
According to the ClausiusClapeyron equation,
% vap H 1
ln P    c (1) may be taken as constant over a small temperature range, as is
R T
the case in this experiment). Under our experimental conditions
where P is the measured pressure (gauge value and atmosphere), (Figure 3), the relationship was verified and vap H was estimated
T is the measured temperature, R is the gas constant, and c is a as 37 1 kJmol. The uncertainty in the slope is calculated ac-
variable, a plot of ln P versus (1T) results in a straight line with cording to ref 2. The experimental value compares favorably with
a slope of vap HR ( vap H is the enthalpy of vaporization that the value from tables (40.4 kJmol).

Division of Chemical Education www.JCE.DivCHED.org Vol. 85 No. 2 February 2008 Journal of Chemical Education 277
 In the Laboratory

Sterilization Cycle 220 400

The second activity is to reproduce a standard sterilization 200 396

cycle (15 min at 121 C) (3). The pressure cooker is prepared

Temperature / K
392

Pressure / kPa
with 1 L of water. Items to be sterilized (empty plastic vials, 180

partially-filled plastic vials, glass vials or tubes; syringes, etc.) are 160
388

wrapped in a medical quality paper envelope and are placed into 384
the chamber inside the inner recipient. The lid is adjusted and 140
380
heating is started. After purging the pressure cooker, additional
120
mass is placed on the valve lid to reach a temperature of 121 C. 376

Pressure is monitored until reaching approximately 101 kPa of 100 372

overpressure (corresponding to 202 kPa of inner chamber pres-
0 10 20 30 40 50 60
sure). At this point the sterilization period begins. After 15 min-
utes, the heat source is removed and the decrease in pressure and Time / min
temperature is monitored. A typical sterilization cycle is obtained Figure 4. Total pressure in the chamber () and equilibrium temperature
with the pressure (and temperature) data taken as a function of () versus time during a sterilization cycle in the pressure cooker.
time (Figure 4). Once the system reaches room temperature, the
pressure cooker can be opened and the items retrieved. A careful
observation of the objects could lead to a discussion about the basis in many fields, an appropriate distinction in the use of these
resistance of the materials under high temperature and the limita- units would be highly advised for students. Finally, this activity
tion of wet heat as a sterilization method (4). provides the students an opportunity to manipulate, determine,
and identify the system conditions: constant volume, constant
Discussion pressure, or constant temperature. Taken as a whole, this labo-
The effect of pressure on phase equilibrium is usually given ratory exercise provides a useful tool to enrich a core concept,
in a classroom lecture without any related experimental exercise; usually discussed in a lecture, directly connected with everyday
however, a few laboratory practices are presented in the literature equipment and biomedical applications.
(5, 6). The main objective of the reported activities is to calculate
the enthalpy of vaporization of different liquids. Driscoll (5) Literature Cited
reported an experiment that requires a liquid with a vapor pres-
1. Franco, M. A. Papel del Farmacutico en el Control de la Con-
sure about 40 mm of Hg at room temperature, restricting the
taminacin Microbiana. In Programa de Educacin y Actualizacin
reagent to toluene, methylcyclohexane, and piperidine. Since all
Farmacutica (PROEF) Tercer Ciclo, Mdulo 2, Editorial Mdica
of these compounds are toxic agents, they are not good choices
Panamericana; Buenos Aires, Argentina, 2001; p 67.
for students manipulation. Other experiments (6) use water, but
2. Colby Chemistry. http://www.colby.edu/chemistry/PChem/notes/
since a temperature of approximately 250 C is needed, it can be
linest.pdf (accessed Nov 2007).
quite dangerous for students handling. Additionally, both of the
3. Russell, A. D. Sterilization and Disinfection by Heat Methods. In
activities require equipment especially designed for the practice.
Principles and Practices of Disinfection, Preservation and Steriliza-
The experiment described in this article requires inexpensive
tion, 3rd ed.; Russell, A. D., Hugo, W. B., Ayliffe, G. A. J., Eds.;
equipment that is easy to obtain and adapt and it is considered
Blackwell Science Ltd.: Oxford, 1999; p 629.
safe even for the temperature range of work (100 C130 C)
4. Alwood, M. C. Medical Applications of Thermal Processes. In
as the liquid is used in the chamber.
Principles and Practices of Disinfection, Preservation and Steriliza-
This exercise was originally developed for a postgraduate
tion, 3rd ed.; Russell, A. D., Hugo, W. B., Ayliffe, G. A. J., Eds.;
course of applied physical chemistry included in the curricula
Blackwell Science Ltd.: Oxford, 1999; p 657.
for obtaining the degree of Specialists in Sterilization at this
5. Driscoll, J. A. J. Chem. Educ. 1980, 57, 667.
university. In this context, the exercise was successful in dem-
6. PHYWE series of publications, Laboratory Experiments, Physics,
onstrating the physicochemical basis of the autoclave function.
PHYWE SYSTEME, 37070 Gttingen, Germany. http://www.
The activity can also be an opportunity for integrating previously
nikhef.nl (accessed Nov 2007).
acquired knowledge, for example, the analysis of the purging
7. Zielinsky, T. J.; Schwenz, R. W. Chem. Educator 2004, 9 (2),
step. Daltons law should be discussed to understand that all
108121. DOI: 10.1333/s00897040771a. http://chemeducator.
components contribute to the pressure inside the chamber
org/bibs/0009002/920108tz.htm (accessed Nov 2007).
and that the ClausiusClapeyron equation is valid only if the
8. Atkins, P. W; de Paula, Julio. Atkins Physical Chemistry, 7th ed.;
pressure detected corresponds to a pure component (water),
Oxford University Press: Oxford, 2004.
explaining the strict requirement for air elimination.
The abstract physical chemistry concepts are partially
Supporting JCE Online Material
responsible for the difficulties some students have incorporat-
http://www.jce.divched.org/Journal/Issues/2008/Feb/abs276.html
ing basic knowledge. Recently, the discipline has become more
interested in the molecular basis of the processes (7) as it is Abstract and keywords
reflected in modern textbooks (8). Thus, a pedagogic approach
Full text (PDF) with links to cited URLs and JCE articles
such as the one presented here (Figure 2) could be useful for
Figure 2 in color
comprehension.
In addition, instructors can discuss exercises where pressure Supplement
values should be expressed in different units (atm, mm of Hg, Student handouts and instructor notes
bars, kPa, psi, etc.). Since pressure is often expressed in different Information about pressure units

278 Journal of Chemical Education Vol. 85 No. 2 February 2008 www.JCE.DivCHED.org Division of Chemical Education