Lab 3

Pressure, Volume, and Temperature

Objectives:
Investigate the relationship between the pressure and volume of a gas when the temperature is held
constant. This relationship is known as Boyles law.
Use the ideal gas law to determine the number of air molecules in the tube of the apparatus.
Determine the amount of work done during an isothermal process.
Investigate the relationship between the pressure and temperature of a gas when the volume is held
constant. This relationship is known as Amontons law.
Determine the value of absolute zero by extrapolating the curve to an absolute pressure of zero.

Equipment:

Boyles law apparatus, low pressure type

Absolute zero apparatus
Vernier caliper
Thermometer to measure room temperature, 1 per class
Thermometers with range of approximately -100 C to 150 C, 3 for the three baths
Barometer, 1 per class
Large container(s) with several gallons of room-temperature water; used to fill the large cylinders of the
Boyles law apparatus three-fourths full
Styrofoam cooler with ice/water mixture, 1 or more per class
Electric heating element, pan, boiling water, 1 or more per class
Styrofoam cooler with dry-ice/acetone mixture, 1 or more per class (optional)
Cartesian graph paper, 30 cm ruler

27

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LAB 3. PRESSURE, VOLUME, AND TEMPERATURE

Safety:
Use caution around the electric burner and pan of boiling water.
Use caution around the dry-ice/acetone mixture. Its cold temperature can cause rapid freezing of human
tissue and lead to frostbite.
Use caution around any mercury filled thermometers or barometers. In the event of a spill, notify your
lab instructor who will immediately clean up the spill with a Mercury Spill Kit from the chemistry
stockroom.
Care of the Equipment:
Handle the Boyles law apparatus with care. The long glass tubes can easily be broken.
Handle the absolute zero apparatus with care to prevent percussive damage. Do not allow the stainless
steel bulb to become dented. Do not drop the apparatus or handle it roughly.
Never pressurize the absolute zero apparatus beyond the maximum rating of the pressure gauge. Pressurizing the gauge beyond the 30-psi (20 bar) mark risks destroying the inner parts of the gauge. Overpressurizing the gauge (also referred to as clocking the gauge), will void any warranty and will cause
irreversible damage to the gauge.
Never unscrew the gauge while the system is pressurized.

3.1

Introduction

Boyles law describes the relationship between changes in pressure and volume for an ideal gas. You will experimentally determine this relationship and in the process study a technique for linearizing and interpreting data. You
will also have an opportunity to explore the power of the ideal gas law as you take measurements of macroscopic
quantities such as pressure and volume and temperature and report information about microscopic quantities such
as the number of molecules and the average kinetic energy of an individual molecule. Finally you will see that
work can be defined not only for objects that exert forces through a distance, but also for ideal gases that are
pressurized or depressurized while being expanded or compressed.

3.2
3.2.1

Theory
The Ideal Gas Law

Many scientists contributed to the development of atomic theory and kinetic molecular theory. From John Daltons
work, beginning around 1800, the idea of the chemical atom - that indivisible constituent of all matter that forms
molecules and then compounds - emerged. Experimental work done by Robert Boyle (around 1660), Jacques
Charles and Joseph Louis Gay-Lussac (around 1800), and Guillame Amontons (around 1700) established the
following relationships among the variables of pressure, volume, and temperature in an ideal gas.

3.2. THEORY

29

(3.1)

P V = constant
V
= constant
T
P
= constant
T

(3.2)
(3.3)

These three relationships are combined in what is known as the ideal gas law, which can be expressed in
terms of the number of moles n, or the number of molecules N . The constants are the universal gas constant
R = 8.31446 J/(mol K) and Boltzmanns constant k = 1.381 10 23 J/K.
(3.4)
(3.5)

P V = nRT
P V = N kT

Although any gas will eventually liquify when its temperature is sufficiently lowered, the data from a volume
versus temperature experiment can be extrapolated to the point where the volume of the gas would become zero;
or the data from a pressure versus temperature experiment to the point where the pressure would become zero.
This temperature is 273.15 C or 0 K. The letter K was chosen in honor of William Thomson, Lord Kelvin,
who showed that this value for absolute zero was consistent with the second law of thermodynamics.
Amadeo Avogadro presented a model of gases in an 1811 publication. He stated that at equal temperatures and
pressures equal volumes of all gases, whether elements or compounds, or even mixtures, contain equal numbers
of molecules. This statement is known as Avogadros hypothesis or Avogadros law.
The relative masses of these equal-pressure, -volume, -temperature samples of gases is 2.016 for hydrogen,
28.01 for nitrogen, and about 32.00 for oxygen. This information, taken along with Avogadros law, allows us to
connect volumes of gases to numbers of molecules and masses of elements. The idea of a gram-molecular mass
of 2 g for the diatomic hydrogen molecule or a gram-molecular mass of 28 g for N2 , or of 32 g for O2 , emerges.
A gram-molecular mass, then, of any gaseous element (as well as any element) contains an equal number of
particles. This number of particles is known as Avodgadros number, NA , and defines the quantity, one mole.
NA = 6.022 1023 mol

(3.6)

At standard temperature and pressure, STP, of 273K and 1.01325 105 Pa, the particular volume that all
gases occupy is 22.4 liters or 0.0224 m3 .
In all of the equations thus far, the temperature T must be expressed in kelvins, where T = 273.15 + TCelsius .
Taking the ideas of atomic theory and working with the model of gases that are of sufficiently low density to
obey the laws of Boyle, Charles, and Amontons, scientists from around 1850 to 1900, developed what is known
as the kinetic-molecular theory of gases. Some of the major players in this work were Rudolph Clausius, John
Herapath, Joule, Daniel Bernoulli, James Clerk Maxwell, J. Willard Gibbs, Ludwig Boltzmann, J.D. van der
Waals. The idea that we will make use of in this experiment is that the average kinetic energy of an individual
molecule in an ideal gas is given by
KEavg =

3
kT
2

(3.7)

This expression allows us to use the measurement of a macroscopic property, namely the absolute temperature
of an aggregate sample, to gather information about individual entities at a microscopic level, namely the average
kinetic energy of an individual molecule. Using this result along with an estimate of the number of molecules in
the air column, we can estimate the total kinetic energy of the sample in the air column.

30

LAB 3. PRESSURE, VOLUME, AND TEMPERATURE

Figure 3.1: This is a low-pressure type of a Boyles law apparatus. The pressure exerted on the column of air is taken to be the
pressure at the depth of the water in the outer cylinder where it meets the air column in the inner tube.

3.2.2

Description of the apparatus.

The first of the two experiments to be performed uses a Boyles law apparatus, low pressure type, shown in Fig.
3.1. A fixed mass of air is confined in a slender glass tube which is kept at room temperature and subjected to
small pressure increases as the tube is lowered into a larger cylinder full of water. The changes in volume can be
measured by observing the changes in the height of the air column. The pressure changes are measured by using
the pressure-depth relationship
P1 = P0 + gh

(3.8)

in which P1 is the absolute pressure at a depth h in the water, and P0 is atmospheric pressure at the top of the
water. Water rises slightly into the tube, exerting pressure P1 on the air column.
The second experiment uses an absolute zero apparatus, shown in Fig. 3.2, that consists of a stainless steel
bulb with a valve and an absolute pressure gauge. The valve on the bulb is opened to allow its internal pressure to
equilibrate to atmospheric pressure. Then the bulb is immersed in baths of various temperatures and the pressure
is recorded. The graph of pressure versus temperature is extrapolated to the point of zero pressure.

3.3

Procedure

1. Measure the inside diameter d of the slender glass tube using a Vernier caliper. Measure the length L of the
slender tube using a meter stick. Measure the temperature T of the room, and the barometric pressure P0 in
the room. If a barometer is unavailable, use the internet to access data from a local weather station. Record
these measurements in SI units on the data sheet.
2. Fill the large cylinder about three-fourths full of room-temperature water.

3.3. PROCEDURE

31

Figure 3.2: This absolute zero apparatus is used to investigate Amontons law. The stainless steel bulb must be handled
carefully so as to avoid dents, damage, and pressure leaks.

3. Invert the slender tube, keep it in a vertical alignment, and slowly insert it into the water in the large cylinder.
The plan is gradually lower the slender tube into the water and record about ten pairs of D and H data, as
illustrated in Fig. 3.3. Enter these values in Table 3.1. By lowering the tube slowly, the temperature should
remain constant (isothermal process) and the relationship between pressure and volume can be studied.
4. Continue with Table 3.1 by calculating the pressure P1 acting on the air column for each position, by using
the pressure-depth relationship in which the usual h is replaced by D H.
P1 = P+ g(D

H)

(3.9)

5. For each position of the tube, calculate the volume V of the air in the air column by using the inside diameter
d and
V =

2
d
(L
2

H)

(3.10)

6. Complete the data table by calculating values for the remaining columns. Plot P vs V on Cartesian graph
paper. Is the plot linear or hyperbolic? Is the relationship between the variables a direct relationship or some
kind of an inverse relationship. If it appears to be hyperbolic, it will be necessary to do further analysis to
determine whether the relationship between the variables is in fact inverse, inverse square, inverse cubed,
etc. One method to we can use is to attempt to find a variable transformation that will linearize the data.
7. Lets start with the possibility that the relationship is inverse. Plot P vs V 1 , the reciprocal volume.
By using reciprocal volume rather than actual volume, we have performed a variable transformation; the
variable in the equation is now V 1 rather than V . Does this graph appear linear? If so, P and V 1 are
directly proportional and then have the equation of a straight line, which implies that P and the original
variable V are inversely proportional.
8. Assuming that the last plot is linear, draw the best-fitting straight line through the linearized data. Determine
the slope and the y-intercept of this line. You may do this by hand by using two distant points on the bestfitting straight line and calculating slope as the rise over the run, or by using Logger Pro or a spreadsheet
on a computer to do a linear fit to your data (see Appendix D.5). Note that your slope should be similar to
your P V values in Table 3.1.

32

LAB 3. PRESSURE, VOLUME, AND TEMPERATURE

air
air

LH

P0

P1
D
water

water

Figure 3.3: This figure illustrates the quantities that will be measured in the Boyles law experiment. The inverted, slender
tube is slowly lowered into the water. At about ten different positions, the depth of the slender tube in the water D is recorded
along with a corresponding height H of the water into the tube.

3.3. PROCEDURE

33

9. The second experiment is begun by opening the valve on the absolute zero apparatus and allowing the
pressure to equilibrate with atmospheric pressure. You have already recorded atmospheric pressure and
room temperature. Check the pressure reading on the gauge of the apparatus. If it is different from the
value you have recorded for atmospheric pressure, make a note of this offset.
10. Record the gauge reading and the room temperature in Table 3.2. Close the valve and leave it closed for
the remainder of the experiment. This will maintain a constant volume of air and a constant number of air
molecules.
11. Visit the lab stations with various temperature baths - boiling water, ice/water mixture, dry-ice/acetone
mixture. Immerse the bulb in the baths, allow the pressure to reach equilibrium, and record the temperature
and pressure readings.

Figure 3.4: Immerse the bulb of the absolute zero apparatus into a bath, allow the pressure to reach equilibrium, and record
the temperature and pressure readings. The valve remains closed to keep the volume of the gas constant.

12. Plan a graph of pressure versus temperature with absolute pressure on the vertical axis (the ordinate) and
temperature on the horizontal axis (the abscissa). Plot the four pairs of data.
13. Extrapolate the best-fitting straight line to the point where pressure would be zero. The corresponding
temperature at this point is your approximation of absolute zero.
Density of water: water = 1.000 103 kg/m3
Inside diameter of the slender tube: d =
Length of the slender tube: L =
Temperature of the room: T =
Atmospheric pressure in the room: P0 =
Slope of the line of best fit to the graph of P vs V

y-intercept of the line of best fit to the graph of P vs V

Equation of the line of best fit to the graph of P vs V

1
1

34

LAB 3. PRESSURE, VOLUME, AND TEMPERATURE

Table 3.1: Boyles Law Data and Calculations

D (m)

H (m)

H (m)

H (m)

P1 (Pa)

V (m3 )

(m

Table 3.2: Amontons Law Data and Calculations

Type of Bath

T ( C)

P (psi)

P (bar)

P (Pa)

P1 V (J)

3.4. ANALYSIS AND DISCUSSION

3.4

35

Analysis and Discussion

1. Are your P V values constant to within your experimental error? Estimate the maximum error in P V by
using error propagation rules (see Appendix A.5), and determine whether all of your values fall within this
range.
2. Using Boyles law and the value of the slope of the linearized relation P vs V 1 , show how one may
calculate the number of molecules in the air column. How many molecules were in the air column of your
apparatus?
3. Is your y-intercept equal to zero? Were the pressure values you recorded gauge pressures or absolute
pressures? What effect would the use of gauge pressures have on the value of the y-intercept?
4. Using Eq. 3.7, calculate the average kinetic energy of one of the molecules in the air column. What is the
total kinetic energy of all of the molecules in the air column?
5. The general formula for work done by a gas as it expands from an initial volume Vi to a final volume Vf is,
W =

Vf

P dV

(3.11)

Vi

Using the ideal gas law, Eq. 3.5, to make a substitution for P , evaluate this integral to show that the work
done by the gas as it expands isothermally is given by the formula

Vf
W = N kT ln
(3.12)
Vi
Then, assuming that the air column behaves as an ideal gas, evaluate this formula for the initial and final
volume from your data, using the number of molecules you just calculated, and find the work done by the
air column as it expands isothermally.
6. Does the data provided by your four data points using the absolute zero apparatus support Amontons law?
Describe the pattern of your data points and the extent to which a straight line fits the data.
7. How well does extrapolating your pressure-temperature data to the point of zero pressure lead you to the
accepted value for absolute zero of -273.15 C ? What is your percent error?
8. A possible bath is one containing liquid nitrogen which boils at 77K. Would using this bath provide a good
data point from which to extrapolate the behavior of an ideal gas? Explain.

3.5

Conclusions

1. Based on your error analysis, does Boyles Law appear to hold true? Comment on sources of error in this
lab.

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LAB 3. PRESSURE, VOLUME, AND TEMPERATURE

Figure 3.5: A plot of pressure versus volume.

3.5. CONCLUSIONS

37

Figure 3.6: A plot of pressure versus volume

38

LAB 3. PRESSURE, VOLUME, AND TEMPERATURE

Figure 3.7: A plot of pressure versus temperature.