Article

pubs.acs.org/jchemeduc

A Simple Mercury-Free Laboratory Apparatus To Study the

Relationship between Pressure, Volume, and Temperature in a Gas
Donna McGregor,* William V. Sweeney, and Pamela Mills
Department of Chemistry, Hunter College of the City University of New York, New York, New York 10065, United States

ABSTRACT: A simple and inexpensive mercury-free apparatus to measure the

change in volume of a gas as a function of pressure at different temperatures is
described. The apparatus is simpler than many found in the literature and can be
used to study variations in pressure, volume, and temperature.

KEYWORDS: First-Year Undergraduate/General, High School/Introductory Chemistry, Laboratory Instruction, Physical Chemistry,
Hands-On Learning/Manipulatives, Gases, Laboratory Equipment/Apparatus

P reviously we described an integrated, inquiry-based, class-

room and laboratory unit that focused on the physical
behavior of gases and the “discovery” of the ideal gas law.1 The
unit (called the “Gas Module”) was designed for first-year
students and requires an apparatus that can collect both Boyle’s
law data and the temperature dependence of the PV data. The
original apparatus used a capillary tube that is sealed at one
end and contains a fixed volume of air that is trapped beneath
a small plug of mercury (Figure 1).1,2
Figure 1. Schematic diagram of the experimental apparatus used in the
original model to measure the volume of a gas as a function of
pressure. A thick-walled capillary tube, sealed at one end, contained a
small volume of mercury over a trapped volume of air. The capillary
tube is attached to a half-meter stick with millimeter markings.
The force that the mercury plug applies on the trapped
air column can be changed as the angle of tilt of the capillary
tube is varied.1−4 Now, however, the use of mercury in student
© 2012 American Chemical Society and
Division of Chemical Education, Inc.
laboratories is generally considered a safety hazard; as of
September 2004 (according to the Environmental Conserva-
tion law, Article 27, Title 21), the use of elemental mercury is
no longer allowed in New York City schools.5,6 Thus it became
necessary to seek an alternate experimental apparatus.
The Gas Module unit places particular demands on the
apparatus. An apparatus was required that can collect Boyle’s
law (PV) data at a series of different fixed temperatures. The
resultant PV plots must be sufficiently accurate to observe the
curvature in a plot of pressure versus volume. The device must
be amenable to student-designed protocols used to collect PV
data at temperatures above and below room temperature.
An appropriate mercury-free experimental approach from
the literature was not found that satisfied the criteria. How-
ever, numerous experimental methods for the measurement
of changes in volumes as a function of pressure (to determine
Boyle's law at a fixed temperature) were found; data were
collected using cylinders with moving pistons7,8 and syringe
pump type devices.9−12 A range of approaches were found for
measuring pressure (fixed volume) or volume (fixed pressure)
as a function of temperature, including a U-tube apparatus,12
an experimental design consisting of a graduated cylinder in-
verted in a beaker of water,13 and a commercial device from
Vernier.14 None of these designs could be readily adapted to
this experiment.
■ DISCUSSION
The redesigned apparatus is composed of two standard 50 mL
glass burets whose tips are connected using a 7 foot length
of 3/8 in. diameter clear plastic vacuum tubing (Figure 2).
Published: January 27, 2012
509 dx.doi.org/10.1021/ed200605v | J. Chem. Educ. 2012, 89, 509−512
Journal of Chemical Education Article

Figure 2. Schematic representation of the experimental apparatus used

to measure the volume of a gas as a function of pressure: two standard Figure 3. Schematic representation of the apparatus when there is a
50 mL glass burets connected by a fixed length of clear vacuum tubing. positive pressure being applied to the gas in the trapped air column; V
A predetermined volume of water is poured into one of the burets and represents the volume of the air column, h represents the vertical
the system allowed to come to equilibrium. The buret on the left is height difference between the water levels in each buret and Y1 and Y2
then sealed with a stopper and the buret on the right is allowed to represent the vertical heights of each water level relative to a pre-
remain open. In this representation the water in the system is at determined zero point.
equilibrium and the applied pressure on the air column is due only to
the force exerted by the atmospheric pressure. where ρHg and ρH2O are the densities of mercury and water,
respectively.
To create the trapped air column the burets are attached to a The pressure on the trapped air is altered by raising or
ring stand and placed at equal heights on the laboratory bench. lowering one of the burets in relation to the other. This causes
Water, 200 mL, is poured into the top of one of the burets, is a change in h and thus the hydrostatic pressure. In the labo-
allowed to flow through the tubing into the second buret, and ratory students record the volume of the trapped air column
is permitted to reach a state of equilibrium between the two
(V), as well as the vertical heights (Y1 and Y2) of the water
vessels. Once the water in the apparatus has stopped moving,
levels in each buret relative to a predetermined (and arbitrary)
a rubber stopper is secured in the top of one of the burets
zero point such as the floor or the top of the lab bench
thereby trapping a fixed volume of air in its headspace, while
(Figure 3). The values for V are read directly from the buret
leaving the water in the other buret exposed to the atmosphere
and added to the already measured fixed volume of the buret
(Figure 2). At this point the pressure of the trapped air column
that is above its graduations. The vertical height difference (h,
is equal to the atmospheric pressure. The pressure of the trap-
ped volume of air can be varied by creating a height differential where h = Y1 − Y2) between the water levels in each buret
between the two water levels. reflects the hydrostatic force on the trapped air column due to
With a confined incompressible liquid with unequal levels the water column. This force is related to the total pressure of
(Figure 3), Pascal’s principle states that the resulting hydro- the trapped gas column by eq 3.
static pressure is given by To obtain a large enough range of data a maximum h value of
approximately 130 cm must be reached in both the positive
PH = ρg Δh (1) and negative pressure directions. To achieve this, the vacuum
where PH is the hydrostatic pressure, ρ is the density of the tubing must be at least 7 feet long.15 A representative set of
liquid, g the acceleration of gravity, and Δh the difference data, collected at room temperature, can be seen in Table 1.
in height of the two liquid surfaces. When the water is not
moving, the pressure exerted on the trapped air, Ptrappedair, Table 1. Representative Set of Height and Volume Data and
by the water must be equal to the sum of the atmospheric the Calculated Pressure
pressure, Patm, and the hydrostatic pressure, PH: Y1/cma Y2/cma h/cma V/mLa Ptrappedgas /(cmH2O)b
Ptrappedair = Patm + PH (2) 172.2 43.6 128.6 28.1 1168.3
136.9 71.1 65.8 29.6 1105.5
An important consideration is the units of pressure. When PH 0.1 0.0 0.1 31.7 1039.8
is expressed in cm of water, its magnitude is then equal simply 2.1 63.1 −61.0 33.9 978.7
to h. To convert atmospheric pressure in cm mercury to units 44.3 169.4 −125.1 36.5 914.6
of cm water, the relative densities of mercury and water can a
Data collected at room temperature. bData calculated using eq 3.
easily be used,
The plot of pressure versus volume using the data from
Ptrappedair(cmH2O) Table 1 produces a slight, but observable, downward curve
(Figure 4). One useful learning objective for students is to
= Patm(cmHg)(ρHg /ρH2O) + h(cmH2O) (3) understand the functional relationship between variables in a
510 dx.doi.org/10.1021/ed200605v | J. Chem. Educ. 2012, 89, 509−512
Journal of Chemical Education
Figure 4. Representative data correlating the volume (V) of the gas in the
air column with the total applied pressure (Ptrappedgas) at room temperature.
linearized plot of data, including the ability to discern the dif-
ference between a graph with a slight curvature and one that is
linear. Using the above apparatus students are able to observe
both the curvature in the PV data and the linearity in the
P versus 1/V plot (Figure 5).
Figure 5. Representative data demonstrating the linearity of 1/volume
(1/V) of the gas in the air column versus the total applied pressure
(Ptrappedgas) at room temperature. The solid line represents the best
linear fit.
■
TEMPERATURE DEPENDENT MEASUREMENTS
From the above data it is clear that the new apparatus satisfies
the Boyle’s law criterion, but the apparatus must also be able
to acquire useful PV data at a range of temperatures. It is im-
portant to realize that the trapped air contains both dry air and
water vapor,
Ptrappedair = Pdryair + PH20 (4)
where PH2O is the vapor pressure of water and Pdryair is the
pressure of the dry air in the trapped air column. Because
the pressure of the water vapor is temperature dependent, it is
important that the pressure of only the dry air be used when
comparing PV plots over a range of temperatures. Combining
eq 4 with eq 2 gives
Pdryair = Patm + h − PH2O (5)
511
Article
The PH2O values at a various temperatures can be obtained
from tabulated values found in a range of sources, such as the
CRC Handbook of Chemistry and Physics.16
It became clear after the first implementation of the ap-
paratus in the laboratory that students with weak laboratory
skills are not always careful enough in their technique (with
variable temperature data collection) to ensure that the water
near the water−gas interface and the trapped gas are both at
the same temperature.17 For groups of students of this type, a
separate estimation of the water temperature near the interface
is required. This is successfully accomplished by providing the
students with an inexpensive digital infrared thermometer
(Thermapen IR-Mini), with the understanding that students
need to take care to hold the device near the desired point of
measurement.
A diverse number of student-designed protocols have been
used to collect PV data at various temperatures, among them
the use of cold or hot packs attached to the portion of the buret
that houses the trapped air column, ice baths for low tem-
perature data, and hair dryers for high temperature data. In the
representative data shown here (Figure 6), a plastic zipper
Figure 6. Representative data demonstrating the linearity of 1/volume
(1/V) of the gas in the air column versus the total applied pressure
(Pdryair) at 3 temperature values (5, 26, and 57 °C). The solid lines
represent the best linear fits.
storage bag filled with ice and water (attached to the portion of
the buret that contained the air column) was used to collect
cold temperature data (5 °C) and a hairdryer (set on medium
heat), positioned to blow hot air into a large plastic bag
that covered the entire sealed buret, was used to collect hot
temperature data.
Because the apparatus is “self-assembled” and pressure is
dependent on the number of moles of gas in the air column,
any variations in the assembly of the experimental apparatus
will result in inconsistent pressure values for the temperature
trials. The apparatus thus needs to be reconstructed by the
students at the beginning of each lab period to re-collect
the room temperature data.18 This is important to ensure that
all the temperature dependent data can be accurately compared
when combined on a single plot.
To determine the functional relationship between pressure,
volume, and temperature in kelvins (constant number of moles
of trapped gas), students must collapse all their data into a
single line by plotting pressure versus temperature/volume.
dx.doi.org/10.1021/ed200605v | J. Chem. Educ. 2012, 89, 509−512
Journal of Chemical Education Article

A representative graph of the “hybrid variable” (T/V) using the
Kelvin temperature scale is shown in Figure 7. Clearly, the
Figure 7. Representative linear data correlating the volume of the gas
in the air column with the total applied pressure at 3 temperature
values and plotted using the “hybrid variable” temperature/volume.
The solid line represents the best linear fit. The values for slope and R2
are those reported by Microsoft Excell.
temperature-dependent data coalesce. A single slope value can
be obtained with a coefficient of determination (R2) value close
to one. This compares very nicely with data collected using the
original apparatus.1
(7) Practical Physics. http://www.practicalphysics.org/go/
Experiment_380.html
(8) University of Maryland Lab Experiments. http://www.physics.
umd.edu/lecdem/services/demos/demosi3/i3-41.htm (accessed
Dec 2011).
(9) Science Kit. http://sciencekit.com/low-cost-boyleandrsquo%3Bs-
law-apparatus/p/IG0023590/ (accessed Dec 2011).
(10) Lewis, D. L. J. Chem. Educ. 1997, 74, 209.
(11) Deal, W. J. J. Chem. Educ. 1975, 52, 405.
(12) Ivanov, D. T. Phys. Educ. 2007, 42 (2), 193.
(13) Kim, M.-H.; Kim, M. S.; Ly, S.-Y. J. Chem. Educ. 2001, 78, 238.
(14) Bopegedera, A. M. R. P. J. Chem. Educ. 2007, 84, 465.
(15) In order to collect a broad enough range of pressure values and
to ensure that students can clearly see the curvature in a pressure
versus volume plot, 7 feet of clear plastic vacuum tubing is recom-
mended. The same effect can be achieved with as little as 5 feet of
tubing, but the curvature in the pressure versus volume plot becomes
difficult to discern when the range of pressure values is limited in this
way.
(16) CRC Handbook of Chemistry and Physics, 81st ed.; Lide, D. R.,
Ed.; CRC Press: Boca Raton, FL, 2000.
(17) In this module students determine their own experimental
methods to collect variable temperature data. One of the most com-
mon weaknesses observed among students is a failure to obtain a
uniform temperature over the entire length of the air column. In
addition, it is important that the temperature remains constant while
students are collecting their V, Y1 and Y2 measurements. These
problems are obviously not observed for room temperature data.
(18) Two of the more frequent errors observed are (i) students trap
an air column that it too large to accurately collect temperature
dependent data (with a column that is larger than about 15 cm it
becomes difficult to maintain a fixed and uniform temperature, above

■
or below room temperature, over the entire length of the column) and
(ii) students tend to uncork the trapped gas between temperature
CONCLUSION dependent data sets.
As can be seen from the representative data here, this new
experimental apparatus allows the successful collection of pres-
sure and volume data (at various temperatures) using a simple
and safe (mercury free) experimental setup that yields remark-
ably good results. The apparatus is of general utility and can be
used for many types of gas law experiments. The need for a
single, mercury-free apparatus that can be used to collect high
quality P, V, and T data places an extra demand on the quality
of the apparatusone that was met by this device.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: dmcgreg@hunter.cuny.edu.

■ ACKNOWLEDGMENTS
Thank you to Benjamin P. Burton-Pye for his assistance in the
first round of data collection and preparation of figures and to
the Hunter College head CLT, Nicole Popa, for being so
accommodating in the lab.

■ REFERENCES
(1) Mills, P. A.; Sweeney, W. V.; Marino, R.; Clarkson, S. J. Chem.
Educ. 2000, 77, 1161.
(2) Domin, D. J. Chem. Educ. 1999, 76, 543−547.
(3) Breck, W. G.; Holmes, F. W. J. Chem. Educ. 1967, 44, 293.
(4) Hermens, R. A. J. Chem. Educ. 1983, 60, 764.
(5) NYS Dept. of Environmental Conservation. http://www.dec.ny.
gov/chemical/285.html (accessed Dec 2011).
(6) Justia US Law Mercury. http://law.justia.com/newyork/codes/
environmental-conservation/env027-2107_27-2107.html (accessed
Dec 2011).

512 dx.doi.org/10.1021/ed200605v | J. Chem. Educ. 2012, 89, 509−512