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Physics Department

Thermodynamics Laboratory

EQUATION OF STATE

AND CRITICAL POINT

1. Aim

Obtain two isotherms on a P-V diagram for a gas.

Obtain the vaporization curve of the gas.

Determine the critical point.

2. Overview

The state of a gas (in a closed system) is determined by three variables: pressure, volume

and temperature. But only two of them can be independent. The other variable will be

determined by these two, according to the equation of state.

The simplest equation of state for gases is the well-known PV=nRT, which is met by all

gases when they are rarefied enough. To deduce it, ignore the size of the gas molecules and

the interactions among them. This way the equation cannot predict the phase transitions

that occur in all substances.

The simplest equation that takes into account the size of the particles

and their interaction is Van der Waals' equation:

( ) nRT = nb V

V

a n

+ P −

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

2

2

[1]

where n is the mole number, b is the size of a molecule, and a is a parameter of attractive

interaction among particles. This equation predicts the liquid-gas phase transition, and it

also predicts some of its main features:

-Some isotherms in the P-V diagram have two regions: High compressibility region

(gas) and low compressibility region (liquid).

-Only below a given temperature (critical temperature T

c

) it is possible to produce the

gas-liquid phase transition at a constant temperature by increasing the pressure on

the system.

- If T

c

is the value of the critical temperature and P

c

and V

c

are the values of pressure

and volume at the critical isotherm's inflexion point, then:

T

c

=

8a

27Rb

[2]

2

V

c

=3b n

[3]

P

c

=

a

27Rb

2 [4]

Also, using the principles of thermodynamics we can deduce that the phase transition (at a

constant temperature) happens at constant pressure: as we reduce the volume of the

system, liquid and gas phases coexist in vapor form without changing pressure by

decreasing the volume of gas and increasing the amount of liquid (which takes up less

volume, see Figure 1).

Figure 1: P-V Diagram

There is also a relationship between the value of pressure where liquid and gas coexist (v

apor pressure) and the absolute temperature. This relationship, Clapeyron's equation, can be

simplified and yields:

P=P

0

e

l /RT

[5]

where P

0

is a constant, R the gas constant, and l the latent heat of vaporization: the heat

necessary to cause the phase transition.

3

3. Learn more...

• On the I nternet

4. Equipment

1. Manometer and thermometer.

2. Graduated gas tube.

3. Water bath.

5. Experimental Procedure

5.1 Measuring equipment

The gas under study will be inside a gas tube immersed in a water bath, the temperature

of which will be controlled by a thermostat. Also, the gas volume can be decreased by

pushing mercury up inside the tube. As a consequence, the pressure inside the tube will rise.

5.2 Measurements

Pressure and volume will be measured for two isotherms, one below the critical

temperature and one approximately at critical temperature.

The values of vapor pressure will be measured for several temperatures (always below the

critical temperature) in order to obtain the value of the latent heat of vaporization.

5.2.1 Isotherm below critical temperature

Set the bath thermostat at minimum temperature and start the circulation of water,

making sure that water does not go over the top of the gas tube.

Write down the value of the temperature of the tube thermometer. Starting at a 4

cm

3

volume, start writing down the values of pressure and volume, in 0.2 cm

3

steps,

at constant temperature.

Do not increase pressure beyond 50x10

5

Pa.

When a condensate starts to appear, continue with the procedure more slowly.

Draw these data on the isotherm graph.

5.2.2 Measurements at a constant volume

Keep a constant volume of approximately 0.5 cm

3

.

Leave the mercury column in this position and start increasing the temperature of the

water bath in steps of one Celsius degree.

Write down the values of pressure for each temperature. For this, wait for about one

minute for the temperature to reach a stable value on each increment.

When the liquid dissapears completely, increase pressure slightly and wait for it to

become stable. If the condensate reappears, then resume the measurement

procedure.

If no condensate appears, then the temperature of the gas is approximately equal to

the critical temperature.

Do NOT increase the temperature any further.

Calculate ln P and 1/T. Draw a graph representing these experimental data.

Perform a least-squares line fit of these data.

From equation [5], discuss the meaning of the parameters of this least-squares fit,

4

and obtain the latent heat of vaporization of the gas, l.

5.2.3 Isotherm near critical temperature

Keep the water bath thermostat at the temperature reached in the previous

experiment.

Write down the value of the temperature of the tube thermometer. Starting at a 4

cm

3

volume, start writing down the values of pressure and volume, in 0.2 cm

3

steps,

at constant temperature.

Do not increase pressure beyond 50x10

5

Pa.

When a condensate starts to appear, continue with the procedure more slowly.

Draw these data on the isotherm graph.

5.2.4 Questions

Estimate the number of moles and the values of the a and b constants in the Van der

Waals equation. Apply equations [2], [3] and [4].

The gas in the column can either be ethane or sulfur hexafluoride. Deduct which one

of them it is.

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