Foundation Year 2019/20

Experiment EP 2:
CONSTANT-VOLUME GAS LAW

Matias Figueiras – Student ID 31237266

Date: 11/12/2019
Date of Experiment: 11/11/2019
Lab Partner: Steven Gore

"I am aware of the requirements of good academic practice

and the potential penalties for any breaches".

Abstract
In this experiment we set out to determine the relationship between
pressure and temperature for a fixed volume of air. This relationship is later
used to calculate an experimental value for absolute zero. The experiment was
carried out with a special apparatus that let us register the pressure at different
temperatures. The results show the existence of a direct proportion between
these two macroscopic properties of air if the volume is kept constant, and the
estimated value obtained for absolute zero was -272.34 °C with a percent error
of 0.29%.
Table of Contents

1. Introduction..................................................................... 2

2. Theory ............................................................................ 3

3. Method ........................................................................... 5

4. Results ........................................................................... 7

5. Discussion ...................................................................... 9

6. Conclusion.................................................................... 10

7. References ................................................................... 10

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 1. Introduction
This experiment focuses on the relationship between two of the main
properties that define a gas. A gas is a sample of matter that presents special
physical characteristics, such as not having a fixed size nor shape but instead
adopting the shape of a container in which it is held. If not confined to a
container, gaseous matter will disperse into space; however, gases are also
highly compressible (Rouse, 2005).
All the characteristic properties of gases arise because there is a large
distance between molecules. “In any given volume of air, for example, the
molecules take up only about 0.1% of the total volume with the rest being empty
space. Thus, each molecule behaves largely as though the others were not
present” (Brown, et al., 2015). Consequently, even though different gases are
made up of different molecules, their behaviour is mostly quite similar.
In order to study the behaviour of gases, four variables that define the
physical condition are needed: pressure, temperature, volume and the amount
of gas, usually expressed as the number of moles1. The relationships between
these bulk properties are expressed under the ‘Gas Laws’ (Mason, 2019).
The majority of gases obey the expected behaviour expressed by these
laws quite well, however, they do not entirely agree with them. This discrepancy
with the laws is caused when specific conditions occur, that violate the
assumptions made to define the Gas Laws. To evade this problem, the concept
of an ideal or perfect gas has been created. This involves a gas that indeed
accords with the laws under all conditions and its behaviour is explained by the
“Equation of State”. As a consequence, ideal gases are much easier to
manipulate and study mathematically, and calculations come to a good
approximation of a real gas under most conditions.
The main objective of this lab was to explore the relationship between
the temperature and pressure of air while being kept in a closed container (fixed
volume). Because the range of measurements was neither at high pressure nor
really low temperatures, air was treated as an ideal gas to facilitate the
calculations. The purpose of the experiment is to check the theory behind the
ideal gas law and to determine the value of absolute zero experimentally.

1 “One mole is the amount of matter that contains as many objects (atoms, molecules, or
whatever other objects we are considering) as the number of atoms in exactly 12 g of
isotopically pure 12C. From experiments, scientists have determined this number to be
6.02214129 x 1023, which is usually rounded to 6.02 x 1023. This value is also called Avogadro’s
number” (Brown, et al., 2015).

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 2. Theory
The aforementioned “Equation of State” or “Ideal-Gas Law” is an
expression that describes the behaviour of a hypothetical gas that resembles
'real' gases under different conditions. It is given by the following equation:
= (1)

Where P is the pressure of the gas, V is the volume taken up by the gas, T is
the temperature of the gas, R is the universal molar gas constant, and n is the
number of moles of the gas.
As Equation 1 shows, this law also describes the relationship between
variables that define a gas state. If two of the bulk properties are maintained,
the third one can be easily calculated; hence predictions can be made about
what will occur if one of these is changed (Brown, et al., 2015). The different
variations lead to three different Gas Laws.
In this experiment, the gas is kept in the same container, so the volume
is not changed. Therefore, Equation 1 can be rearranged:

= = (2)

This is the definition of the Constant-Volume Gas Law, which states

that “for a fixed mass of gas at constant volume, the absolute pressure divided
by absolute temperature is a constant” (University of Southampton, n.d.). In
other words, pressure is directly proportional to temperature:

∝  = (3)

The equation for an ideal gas and the Constant-Volume Law show how
gases behave; however, they do not explain why they do it in that manner. To
understand why a rise in temperature also involves a rise in pressure at
constant volume, the “Kinetic-Molecular Theory of Gases” is needed.
The kinetic-molecular theory describes both pressure and temperature
at the molecular level. In summary, it explains that the molecules of a gas are
responsible for its pressure, because of the continuous collisions with the walls
of the container. The magnitude of pressure is determined by the frequency
and intensity of the collisions by unit area. Moreover, the model states that the
absolute temperature of a gas is related to the average kinetic energy of its
molecules. Therefore, if the molecules of two gases have the same kinetic
energy, it can be concluded that they are at the same temperature.
This model is based on a series of assumptions in order to be possible
to approach it mathematically: “1. Gases are formed by a large number of
molecules that are in continuous, random motion and behave like perfectly

3
elastic spheres. 2. The combined volume of all the molecules is negligible
compared to the total volume the gas occupies. 3. Attractive and repulsive
forces between gas molecules are negligible. 4. Energy can be transferred
between molecules during collisions but, as long as temperature remains
constant, the average kinetic energy of the molecules does not change with
time. 5. The average kinetic energy of the molecules is proportional to the
absolute temperature. At any given temperature, the molecules of all gases
have the same average kinetic energy” (Brown, et al., 2015).
By applying the kinetic theory of gases, Equation 1 can also be
expressed as follows:

= = (4)

Where N is the number of molecules in the gas, m is the mass of each molecule
and is their mean square speed.
Equation 4 shows that when a gas is heated, the mean square velocity of
the molecules increases proportionally to temperature. If the container has a
constant volume, the molecules will strike the walls of the container more
frequently. This will proportionally increase the force per unit area on the
container’s walls, thus increasing the pressure.
The above-mentioned relationship that Equation 4 expresses is of
extreme importance as it helps understand the concept of absolute zero.
Because molecules’ translational speed decreases in relation to temperature, if
the latter is reduced to zero, the molecules’ kinetic energy will become null. In
the Kelvin scale, a temperature value of zero represents this condition where a
thermodynamic system has the lowest energy minimal thermal energy. It
corresponds to −273.15 °C on the Celsius temperature scale.
Experiments show that reaching absolute zero is impossible because
when values for the bulk properties are either large or very small, the
assumptions behind the kinetic theory of gases no longer hold. For instance, at
high pressures, the total volume of the gas molecules is not negligible relative to
the container volume, and intermolecular forces come into play. Because of
these attractive forces, the collisions with the container walls are lessened, and
the resultant pressure is smaller than the expected value. Furthermore, as a
gas cools, the average speed the molecules decreases. This loss of kinetic
energy means the molecules do not have the energy needed to overcome
intermolecular attraction, and they are likely to stay together rather than
bouncing off each other.
Due to these impediments, any real gas condenses to a liquid or
solidifies before reaching absolute zero (The Editors of Encyclopaedia
Britannica, 2019).

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 3. Method
The following materials were utilised to carry out the experiment (Univeristy of
Southampton, 2019):
 Beaker (1 Litre capacity)  Pressure Meter (Philip Harris
 Universal Clamp SensorMeter)
 Glass “Jolly Bulb” or Absolute  Protective Gloves
Zero Demonstrator  Water at different temperatures
 Thermometer (Fisherbrand™  Electric kettle
Traceable™ Digital  Ice
Thermometer Product Code.  Stirrer
11749715)

Figure 1. Diagram of the apparatus used to carry out the experiment.

The apparatus was set up according to Figure 1. The Jolly Bulb was
clamped, and the pressure meter (also clamped) was connected to the glass
bulb checking that there was a proper seal and therefore a fixed volume of air
inside the bulb. After waiting for the apparatus to adopt ambient temperature,
the pressure sensor was zeroed. This was done to ensure that all pressure
measurements taken were relative to atmospheric pressure only.
The beaker was then half-filled with ice and the “Jolly Bulb” was lowered
and clamped again, cold water was added until the totality of the glass sphere
was covered, and the thermometer was inserted. After stirring and waiting for
the temperature to stabilise near 0°C, pressure and temperature were
registered in a table. The bulb was raised back, and the ice and half the water
of the beaker were removed.

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 On the second water bath, the beaker was topped up with only cold
water. The bulb was lowered, and the water was stirred again. Measurements
of pressure and temperature were registered after a few minutes.
For the following baths, only one-third of the water was removed, and it
was replaced by hot water from a kettle while wearing protective gloves.
Temperature and pressure were noted after stabilising. This step was repeated
several times until the temperature readings were between 70°C and 80 °C,
summing up to a total of ten measurements.
Lastly, one further bath was done using only boiling water, however, the
pressure sensor switched off by itself before the temperature had equilibrated.
Therefore, the last reading was not included in the data set.
After all the data was collected, two graphs of relative and absolute
pressure against temperature were plotted.

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 4. Results
The reference point for all the measurements was at an ambient
temperature of 22.7 °C and a relative pressure inside the Jolly Bulb of 0 kPa.
These were measured by a thermometer with an error of ± 0.05 °C and a
Pressure Meter with an error of ± 0.5 kPa.
Figure 2. The table shows the temperature and its corresponding relative and
absolute pressure values for each water bath.
T (± 0.05 °C) Relative p (± 0.5 kPa) Absolute p (± 0.5 kPa)
2.30 -8.0 92.0
18.10 -2.0 98.0
39.40 5.0 105.0
55.50 11.0 111.0
67.50 15.0 115.0
73.50 16.0 116.0
78.10 18.0 118.0
78.50 18.0 118.0
84.20 20.0 120.0
88.10 21.0 121.0

Figure 2 contains the values of two of the bulk properties of air that were
measured. In order to represent absolute pressure, 100 kPa (atmospheric
pressure) were added to each value of relative pressure obtained.

Relative Pressure of air against Temperature

25.0

20.0
Relative Pressure (kPa)

15.0
y = 0.3367x - 8.3016
10.0 R² = 0.9985

5.0

0.0
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00
-5.0

-10.0
Temperature (°C)

Figure 3. The graph shows the relationship between temperature and relative
pressure for air in a fixed volume container.

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 Absolute Pressure of air against Temperature
140.0

Absolute Pressure (kPa) 120.0

100.0
y = 0.3367x + 91.698
80.0 R² = 0.9985
60.0

40.0

20.0

0.0
-350.00 -300.00 -250.00 -200.00 -150.00 -100.00 -50.00 0.00 50.00 100.00 150.00
-20.0
Temperature (°C)

Figure 4. The graph shows the relationship between temperature and absolute
pressure for air in a fixed volume container.
After considering the atmospheric pressure acting on the Jolly Bulb,
Figure 4 shows a relationship with a trend line that has the following equation:
= 0.3367 ! 91.698 (5)

Equation 5 can be used to obtain an experimental value for absolute

zero. Theoretically, when this temperature is reached, pressure becomes null.
In other words, the value of Figure 4 becomes 0. Therefore, solving for :

0 = 0.3367 ! 91.698
91.698
=%
0.3367
≅ %272.34 °+

A relative percentage error for the experimental value obtained for

absolute zero can be calculated as follows:
|1 ,2. , - / -4, % 5%273.157|
,- ./, % 122 2 = ∗ 100
273.15

| % 272.34 % 5%273.157|
,- ./, % 122 2 = ∗ 100
273.15

,- ./, % 122 2 = 0.297%

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 5. Discussion
Although air is not an ideal gas, the results of this experiment show that it
behaves like one for the range of temperature and pressures measured.
This claim is strongly backed up by Figure 3, which shows that the
correlation factor for the trend line is 0.9985. This means that the relationship
between the temperature of the sample of air and its relative pressure inside the
Jolly Bulb is close to being perfectly linear; considering that a factor of 1
represents a direct relationship. Therefore, it can be said that the result
supports the relationships proposed by the Ideal Gas Law and the Kinetic-
Molecular Theory of Gases. In this experiment, the pressure of the fixed volume
of air increased proportionally to the change in temperature. Because the
volume remained constant, the increase in pressure is related to the gain in
kinetic energy of the gas molecules.
Figure 4 shows the same direct proportionality but considering the
atmospheric pressure. By extrapolating the trend line to the point where there is
no more pressure inside the glass container, an experimental value for absolute
zero of -272.34 °C was obtained. According to the theory, it could be said that
at this temperature the air molecules would not have any translational motion.
Even though our approximation is really close to the theoretical value for
absolute zero, it still presents a per cent error of 0.297%. Various reasons could
have caused this difference with the theoretical value. Firstly, it could be a
consequence of the measuring error of the thermometer (± 0.05 °C) and (or) the
Pressure Meter (± 0.5 kPa). Another important source of error can be the
approach used to measure the temperatures. It was assumed that the
temperature of the air was the same as the temperature of the water. However,
it could have possibly taken longer for the temperature to stabilise than the time
given for each measurement. A possible solution could be to allow more time
between submerging the container and measuring the temperature.
Furthermore, the volume inside the glass bulb was assumed to be
constant throughout the experiment. However, it is a possibility that when
raising and lowering back the bulb, the seal between the neck of the container
and the pressure meter was affected. If this was the case, there could have
been a slight change in volume, that ended up modifying the final absolute zero
approximation. This problem can be lessened by reducing the movement of the
apparatus to the least possible.

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 6. Conclusion
In this experiment, we showed that the relationship between the pressure
and temperature of air at constant volume is entirely linear. This was achieved
by measuring the bulk properties of the gas with a special apparatus, and the
results were found to be completely consistent with the Gas Laws and the
Kinetic Theory of Gases. Consequently, we then utilised this relationship to
arrive at an experimental value for absolute zero of -272.34 °C with a per cent
error of 0.29%. Because of the strong agreement with the theory, air can be
considered an ideal gas under normal conditions.

7. References

Brown, T. L. et al., 2015. Gases. In: Pearson, ed. Chemistry The Central
Science. s.l.:Pearson Education, pp. 398-432.
Constantino, D. & McCullough, J., 2012. Lab2 - Air: An Ideal Gas?, s.l.: s.n.
Mason, E. A., 2019. Encyclopædia Britannica: Gas. [Online]
Available at: https://www.britannica.com/science/gas-state-of-matter
[Accessed 08 12 2019].
Rouse, M., 2005. Gas Definition. [Online]
Available at: https://whatis.techtarget.com/definition/gas
[Accessed 08 12 2019].
The Editors of Encyclopaedia Britannica, 2019. Encyclopædia Britannica.
[Online]
Available at: https://www.britannica.com/science/absolute-zero
[Accessed 08 12 2019].
Univeristy of Southampton, 2019. Foundation Year Laboratory Notes. 2019/20
ed. Southampton: s.n.
University of Southampton, n.d. The Kinetic Theory of Gases. In: GENG0005
Engineering Principles Lecture Notes. Southampton: s.n., pp. 1-3.

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