Experiment 1

EQUATION OF STATE AND CRITICAL POINT

I. Objective:
Measure a number of P-V isotherms of SF6.
Determine the critical point and critical quantities of SF6.
Calculate the constants of the van der Waals equation, the Boyle temperature.
Determine vaporization enthalpy of SF6.

II. Theory:

1. Equation of state of an ideal gas and real gas:

The equation of state of an ideal gas is given by
=

=

Where: P is pressure
Vm is the molar volume Vm = n/V
T is the temperature in K and R is the gas constant
For the description of real behavior , the volumes of the molecules must be taken
into account.
= + () + () +
= +
+
In practice, the P is modified as the equation below:

=

Observed pressure Pobs smaller than it would be if the gas particles did not
interact:

= ( ) = ( )


= ( )


= ( )

Rearrangement Van der Waalss equation:

[ + ( ) ] ( ) = (*)

The values of the weighting factors, a and b, are determined for a given gas by
fitting experimental behavior.
 2. Experimental determination of van der Waals constants:

An isotherm slightly below Tc behaves as we have already described: at a certain

pressure, a liquid condenses from the gas and is distinguishable from it by the
presence of a visible surface. If, however, the compression takes place at Tc itself,
then a force separating two phases does not appear and the volumes at each end of
the horizontal part of the isotherm have merged to a single point, the critical point
of the gas. The T, P, and molar V at the critical point are respectively denoted as Tc,
Pc, and Vc of the substance
o The first section: van der Waals equation (*)
o The second section: T= Tc, the isotherm curve has a flat inflexion
Based on the properties of curves, we known that an inflexion occurs when the first
and second derivatives are zero. Hence, we can find the critical constants by
calculating these derivatives and setting them equal to zero:

= + =
( )

= =
( )
at the critical point. The solutions of these two equations are:

=


=


=

3. Boyle temperature:
The term in parentheses of the virial equation of state can be identified with the
compression factor Z. Because thee viral coefficients depend on the temperature,
there may be a temperature at which Z -> 1, with zero slope at low pressure or high
molar volume. At this temperature, which is called the Boyle temperature, TB, the
properties of the real gas do coincide with those of a perfect gas P -> 0. We have a
relation:

() =


=

4. Heat of vaporization:
In the liquefaction process, pressure is unchanged and be considered as the vapor
pressure of SF6 gas which is in equilibrium with liquids phase. The vapor pressure
 depends on the temperature. We can calculate the heat of vaporization based on the
acquired data and the Clapeyron-Clausisus equation:

( ) = ( )

III. Experience procedure:

1. Stage 1
Establish a certain temperature and maintain it during the experiment.
Calculate the heat of vaporization based on the acquired data and the Clapeyron-
Clausisus equation below:

( ) = ( )

Carry out the experiment at six different temperatures, 300C, 350C, 400C, 450C, 470C,
500C and note them, each temperature must be kept unchanged during the courses
of all three stages. To satisfy this requirement, follow the instructions below:
o Step 1: Fill up the bath with water for thermostat
o Step 2: Turn on the accessory set for thermostat and set up the required
temperature
o Step 3: Follow the thermometer 4 until it reaches the needed temperature then wait
for 5 minutes before carrying out the experiment. This is to ensure that the system
reaches the necessary temperature for experiment. Write down the temperature of
the system indicated on thermometer 4

2. Stage 2:
Adjust the volume and observe the pressure change
Turn the pressure regulating wheel clockwise to increase the pressure in the
capillary tube.
Carefully increase the pressure until the pressure gauge indicate a pressure. Observe
a column of mercury rising in the capillary tube at some time after you begin to
increase the pressure on the sample.
The sample we are examining is entirely enclosed in the capillary tube above the
column of mercury. You will also note that some of the sample eventually becomes a
liquid as you increase the pressure, and the pressure will not change much in the
region where the liquid and gas coexist.
IV. Data and processing data:

T(K) T1 = T2 = T3 = T4 = T5 = T6 =
V (ml) P1 (MPa) P2 (MPa) P3 (MPa) P4 (MPa) P5 (MPa) P6 (MPa)
3.50
3.25
3.00
2.75
2.50
2.25
2.00
1.75
1.50
1.45
1.40
1.35
1.30
1.25
1.20
1.15
1.10
1.05
1.00
0.95
0.90
0.85
0.80
0.75
0.70
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
 The dependence of pressure on volume at isotherm
conditions
60

50

T=29.3 oC
40

T=35 oC

T=40 oC
Pressure (MPa)

30
T=45 oC

T=47 oC

T=50 oC
20

10

0
0 0.5 1 1.5 2 2.5 3 3.5 4
Volume (ml)
As can be seen from the graph that the curves of pressure volume at various temperature
are agree with the theory.
- In case of T < TC : The graph shows a plateau at a certain pressure such that gas
and liquid coexists in an equilibrium, followed by a remarkable increase because
the sample has converted absolutely into liquid phase going along with a
decrease in volume.
- In case of T = TC : When T is approximately equal TC , the horizontal segment
shorten and is no longer exist at critical temperature. Hence, the graph shows an
increase in temperature to TC value and when T is exactly equal TC, the behavior
of isotherm curve shows a flat inflexion.
- In case of T > TC : The graph shows a rocket in pressure because the gas are not
able to maintain it liquid phase and convert frankly into gaseous phase. Hence,
we observe a small changes in volume when the temperature is greater than
critical point.

By the way, from the graph. We determine the critical point by adding a coexistence
curve by connecting all the ending points of horizontal segments. Thanks to that, It
is easily to determine the critical temperature is approximately 450C.
On the other hand, the graph also reveals the critical pressure of SF6 is 37.5 Mpa.
By exploiting the equation
3
=
8
we are able to determine the value of critical volume for the following expression.
Where: R=0.0831 MPa.L.K-1.mol-1
Tc = 319 K, Pc = 37.5 MPa.
3
=
8
3 0.0831 1 . 1 318
=
8 37.5
= 0.2643 L.mol-1

Van der Waals constant:

9
=
8
9
= 0.0831 . . 1 . 1 318 0.2643 L. mol1
8
= . . .
And
1 1
= = 0.2643 . 1 = . .
3 3
 Boyle temperature:
We can determine the value of boyles temperature for the following expressions.

=

7.8561 . 2 . 2
=
0.0881 . 1 0.0831 . . 1 . 1
= .

Heat of vaporization
To determine the heat of vaporization. Lets consider a pair of temperature value:
T1=400C and T2=450C such that in which points vapor pressure of SF6 gas is in
equilibrium with its liquid phase
- For T1 = 400C, we observe the pressure still increase slightly in the horizontal
segment due to errors in the experiment. Therefore, we take the average value
for calculation : P1 = 34.65 MPa
- For T2 = 450C , we obtain the value. P2 = 37.5 MPa
Apply these data to the Clapeyron-Clausius equation:
2 1 1
( ) = ( )
1 1 2

( 2 )
1
=
1 1
( )
1 2
37.5
( ) 0.0831 . . 1 . 1
= 34.65
1 1
( )
313 318

= .

V. Discussion :

We do not have the exact value of critical temperature so that the value of critical
temperature and pressure on each experiment are on the prediction, approximation. Thus,
the following constants values hardly are accurate totally to reality. By the way, the
pressure in the stable segments do not keep unchanged totally as the theory.

Because during the experiment, there are some contributors resulting in some errors:
1. The temperature of system is hardly stable during experiment. This affects the value of
pressure corresponding to a certain volume. Thus, the pressure values are not stable so
that hardly can we obtain the exact pressure.
2. Because of restrict of ability of humans sight, we inevitably cannot see and record the
exact value of pressure.
3. There may be some impurities in the SF6 gases. This certainly causes errors in the
experiments
4. Systematic errors.