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Experiment 1

Chem 116 Laboratory- Physical Chemistry Laboratory


Section 2
Department of Chemistry
University of the Philippines

THE VAN DER WAALS EQUATION OF STATE, THE LAW OF


CORRESPONDING STATES, AND THE COMPRESSION FACTOR

Laboratory Report
DINA L. LACSON
BS in Chemistry III
September 5, 2016

ARNOLD C. GAJE
Laboratory Instructor

Abstract
________________________________________________________
Equations of state attempt to describe the relationship between temperature (T),
pressure (P), and molar volume (v) for a standard circumstances. The ideal gas law is the
1

simplest form of an equation of state that can be considered as a large quantity of small
molecules that have no friction and no attractive or repulsive forces. The ideal gas law is a
reasonable approximation at low pressures and high temperatures, but not at higher pressures
and lower temperatures. Van der Waals equation is a model of state equation for real gas
expressed in terms of two parameters, one corresponding to molecular attraction and the other
to molecular repulsions. It captured the general features of the behavior of real gases
including their critical behavior. The properties of real gases are then coordinated by
expressing their equations of state in terms of reduced variables. The use of reduced variables
in comparison to the actual variables was performed to verify the law of corresponding of
states. Microsoft Excel spreadsheet was the software-program employed to compute for
necessary values as well as in creating graphs, curves, trend lines, scattered points and etc.
Two substances (Carbon monoxide and n-pentane) were studied in this experiment. Each of
this substance were examined critically for the behaviors and deviations using the
compression factor Z.

Introduction
________________________________________________________

The perfect gas equation of state is the approximate equation of state of any gas that
becomes increasingly exact as the pressure of the gas approaches zero and the simplest
equation that describes a relationship between the pressure p, molar volume v and the

temperature T of a gas is the so-called ideal gas law:

pv RT

. As we compare the predictions

of this equation of state with the experimental data, it was found that it is only valid in a very
limited range of pressures and volumes so for a more accurate description of the
thermodynamic properties of gases, an improved equation of state is required.
In this laboratory experiment, we study about the van der waals equation of state, the
law of corresponding states, and the compression factor. The van der Waals equation is a
model equation of state for a real gas expressed in terms of two parameters, one
corresponding to molecular attractions and the other to molecular repulsions. It captures the
general features of the behaviour of real gases, including their critical behaviour and also the
properties of real gases are coordinated by expressing their equations of state in terms of
reduced variables.
This lab activity aims to establish the difference between the ideal gas equation of
state and the van der waals equation of state, and the compression factor principle that
determines the extent of deviations from a perfect behavior, and the law of corresponding
states. These concepts about real gases are important especially on learning further on the
isotherms of a real gas that introduces the concept of vapor pressure and critical behavior.
Real gases do not obey the perfect gas law exactly except in the limit of p approaching to 0,
thus the scope of this experiment is only limited on the equations of state for real gases.
After performing this experiment, one should be able to answer whether the law of
corresponding states is coherent with the van der Waals equation of states and what is the
relationship between critical pressure, temperature and volume.

Materials and Method


___________________________________________________________________________
Through the help of a digital personal computer, an excel spreadsheet program was
used in analyzing data, constructing tables, generating graphs and solving mathematical
calculations specifically those related to van der waals equation of state, law of corresponding
states and the compression factor. First, we chose two different substances mentioned in table
1 of the sheet tables in a designated spreadsheet document, then the names of the assigned
substances (C5H12 and CO) for our group were copied into the sheet pvT-calc. Using excel
software, we calculated the van der Waals parameters a and b for these gases by copying their
critical temperature Tc, critical pressure pc and critical molar volume vc into the sheet pvTcalc. Throughout this spreadsheet, there is a blue colour code for input variables which can
be changed and red for the result of a calculation which cannot be changed.
Next, we calculated how the pressure depends on the molar volume for the assigned
two substances using sheet pvT-calc. We did this for a few temperatures for each gas
considering temperatures that are above, slightly above, and slightly below the critical
temperature, we then compared the results we have obtained for the ideal gas equation of
state and the Van der Waals equation of state. We were able to calculate the gas-liquid
coexistence curve using the so-called Maxwell construction (At the equilibrium pressure the
areas that are enclosed by the line van der Waals loop and the line representing the
equilibrium pressure are equal in size) illustrated below:

Figure 1: Gas-liquid coexistence curve using Maxwell construction


4

After comparing the results obtained for the ideal gas equation of state and the Van
der Waals equation of state, we performed the Maxwell construction for the two substances
using the sheet Maxwell. For a given temperature the liquid phase is equilibrium with the
vapour phase when Area 1=Area 2. We then calculated for four temperatures below Tc, the
pressure p and the molar volumes v (i.e., v1 and v3) at which the liquid phase is in equilibrium
with the gas phase for each of the two substances assigned to us (C 5H12 and CO). We adjusted
the Ptrial to have an area difference that is less than 2% and jot down the temperatures at
which we have performed these calculations, also adding the critical temperature, critical
pressure and critical volume calculated in the first step. All data were tabulated in
worksheet_Q3. Using these data, we constructed a p-v phase diagram in the same worksheet.
This phase diagram has several names: the gas-liquid coexistence curve or the binodal curve
or the equilibrium curve. By choosing the insert pane in the customize access toolbar of
excel, we generated the scatter chart of the data, tracing a smooth line through the points to
complete the binodal curve and labelling the curve.
We have also generated the p-V phase diagrams for each of the five temperatures (Tc
and below Tc) in worksheet_Q3 using the p-V data from the Maxwell construction and the
pvT-calc worksheet. The diagrams for each temperature were then superimposed in one
graph and the binodal curve was located in the series of isotherms. A schematic sketch of the
p-T phase diagram of a realistic substance that either can exist in the solid phase, liquid phase
and the gas phase was shown in the figure below.
p
solid
liquid
gas
T

Figure 2: The pressure temperature phase diagram of a real substance.

Using the five temperatures (Tc and below Tc) and the corresponding P trial and % Area
difference for each temperature obtained in the previous calculations, we were able to derive
the liquid-gas coexistence curve (in a p-T diagram). We then plotted this curve in sheet
worksheet_Q4 for both substances (C5H12 and CO).
Next, we constructed a pr-Vr diagram using the reduced pressure pr as a function of
the reduced molar volume r at the same reduced temperature Tr for the two substances
assigned to us in a single graph in the sheet worksheet_Q5,. We then took the critical
constants as calculated by the program in sheet pvT-calc. We then plotted in the same
worksheet the reduced pressure pr as a function of the reduced molar volume Vr for the
pressures and volumes of the coexistence curve for the two substances assigned to us.
We have considered the law of corresponding states only theoretically using the Van
der Waals equation of state in the previous steps. For the next step, we investigated how this
law works for real gases using the experimental data for argon and ethane. The experimental
critical constants were obtained from the given data in Table 1 of the sheet tables. First, we
compared the experimental data with the predictions of the van der Waals equations by
plotting p as a function of 1/v in sheet worksheet_Q8 and calculated the p for each of the
experimental volumes using the van der Waals equation of state. We then plotted p vs. 1/V
diagrams for the Argon and ethane using the experimental data in a chart. We also plotted the
p vs. 1/V diagrams for the gases using the van der Waals predictions in another chart and
made a comparison between the two. We tested as well in sheet worksheet_Q8 whether the
experimental data given in table 2 of the sheet tables obey the law of corresponding states by
plotting pr as a function of 1/vr. By rewriting the van der Waals equation of state in terms of
reduced pressure, reduced volume and reduced temperature, we proved mathematically the
law of corresponding states.
6

The compression factor Z = PVm/RT is a convenient measure of the deviation from


ideal gas behavior. For ideal gases, Z=1 under all conditions; deviation of Z from unity is a
measure of deviations from the ideal behavior. The extent and significance of this deviation in
describing the behavior of real gases can be understood by studying how Z varies with
pressure and temperature.
The variation of Z with pressure and temperature was explained more effectively
using the so-called Boyle temperature (TB) as reference. For a van der Waals gas, TB = a/bR.
The values of a and b was calculated based from the critical constants of the gas. The
following methods were performed in another spreadsheet document saved as Z_Calc- CO.

Firstly, the file Z-calc.xls was opened.


Secondly, the van der Waals constants and the TB for the assigned substance which is
the CO gas were calculated in the Z-calc sheet.
Thirdly, two other temperatures: T > TB and T < TB were selected.

Fourthly, the p from given molar volumes for specified temperature (T = T B, T > TB,
and T < TB.) were generated in the Z-calc sheet.
Next, the p and Vm from Z-calc sheet was copied in sheet worksheet.

Then, p was expressed in atm to calculate Z values and for each temperature, a Z vs.
p/atm diagram was prepared.
Lastly, the trends on how Z varies with p at each temperature region (T < TB, T=TB,
and T > TB), and how it reveals information about intermolecular interactions in real
gases was described in a concise statement.

Results
________________________________________________________

The following data presents the results obtained from the experiment on the van der
waals equation of state, the law of corresponding states, and the compression factor. The
variables and the corresponding values were entered on a spreadsheet document in forms of
tables and the graphs were automatically generated by the excel program.
The van der waals equation of state predicts that the relationship between the pressure
p, molar volume v and temperature T is given by:

a
v b RT
v2

Here R is the gas constant and a and b are numerical constants that can be obtained by
analysing the experimental data on the pressure, volume and temperature. One of the
properties of the van der Waals equation is that it is capable in predicting a gas-liquid
transition.
The gas-liquid coexistence curve can be calculated using the so-called Maxwell
construction wherein the critical point is characterized by the critical temperature Tc, the
critical pressure pc and the critical molar volume vc. The van der Waals constants can be
calculated from these critical properties following these parameters:

27 R 2Tc2
a
64 pc

b
,

RT c
8 pc

The critical properties (e.g., pressure, temperature, and volume) of the two substances
(carbon monoxide and n-pentane) assigned to us are given in the table below:

Substance p(cr)/[Pa] T(cr)/[K] v(cr)/[m3.mol-1]


Carbonmonoxide 3495695
132.9
9.31E-05
n-Pentane 3370000
469.6
3.04E-04
Table 1: Critical properties of carbon monoxide and n-pentane

The following graphs show the comparison of ideal gas and van der waals equations
of state and the relationship of molar volume with pressure.
a. The results obtained for the ideal gas equation of state and van der waals equation of
state of carbon monoxide are plotted comparatively for few temperatures that are

van der Waals

87
71
04
4.
10

0.
63

18
62

28

ideal gas

42
02
06
15

83
38
77
9

above, slightly above, and slightly below the critical temperature.


160
140
120
100
80
60
40
20
0
Pressure (100000Pa)

Molar volume (0.0001m3/mol)

Figure 3: Temperature at T=160 K>>Tc, for carbon monoxide

160
140
120
100
80
60
40
20
0
-20

05
32
65
4.
22

55
79

22
8
86
0.
63
1

58

van der Waals

83
38
7

ideal gas

28

79

Pressure (100000Pa)

Molar volume (0.0001m3/mol)

Figure 4: Temperature at T= 145 K>Tc, for carbon monoxide

10

160
140
120
100
80
60
40
20
0

3.
98

0.
63
1

86
30

86

69

22
8

51
38

54

van der Waals

83
38

ideal gas

06

77
9

Pressure (100000Pa)

Molar volume (0.0001m3/mol)

77
9

Pressure (100000Pa)

van der Waals

02
11
7

13
93
3.
94
9

0.
63
1

86

22
8

83
38

ideal gas

36
69

160
140
120
100
80
60
40
20
0

Molar volume (0.0001m3/mol)


Figure 5: Temperature
at T=132.9 K =Tc, for carbon monoxide

11

Figure 6: Temperature at T= 129 K<Tc, for carbon monoxide

71
62
0

13
.6
0

2.
31
5

21
66

van der Waals

95
01

ideal gas

17

48
36
79
53

Pressure (100000Pa)

54

200
150
100
50
0

Molar volume (0.0001m3/mol)

Figure 7: Temperature at T= 120 K<Tc, for carbon monoxide

12

van der Waals

26
59
6
4.
14
6

0.
63

18
62
28
83
38

ideal gas

77
9

Pressure (100000Pa)

72
23
23
53

160
140
120
100
80
60
40
20
0

Molar volume (0.0001m3/mol)


b.

The

results

obtained for the ideal gas equation of state and van der waals equation of state of npentane are plotted comparatively for different temperatures.

48
36
79
53

Pressure (100000Pa)

84
46
8

14
.4
7

2.
31
5

27
29
9

van der Waals

95
01

ideal gas

73
9

200
150
100
50
0

Molar volume (0.0001m3/mol)


Figure 8: Temperature
at T= 495 K>>Tc, for n-pentane

13

Figure 9: Temperature at T= 480 K>Tc, for n-pentane

95
3

Pressure (100000Pa)

15
.0
5

59
5
2.
31

36
75
96
43
9

van der Waals

01
48
36
7

ideal gas

17
29

200
150
100
50
0

Molar volume (0.0001m3/mol)

Figure 10: Temperature at T= 469.6 K= Tc, for n-pentane

14

01
48
36
7

95
3

Pressure (100000Pa)

2.
31

15
.0
5

36
75
96
43
9

van der Waals

59
5

ideal gas

17
29

180
160
140
120
100
80
60
40
20
0

Molar volume (0.0001m3/mol)

Figure 11: Temperature at T= 450 K< Tc, for n-pentane

11
57

35
3
94
14
.6
1

59
50
14
83
67

van der Waals

2.
31

ideal gas

95
3

Pressure (100000Pa)

27
37

200
150
100
50
0

Molar volume (0.0001m3/mol)

15

Figure 12: Temperature at T= 430 K<< Tc, for n-pentane

As observed, the gas behaved ideally at higher temperatures. The graph of the gases
in the Van der Waals draws near the graph of ideal gas. At lower temperatures, loops are
observed. This is an indication showing the product of the mathematical artefact. In
correcting this loops, the experimenters use the Maxwell construction where A1 = A2.

The table below presents the five temperatures (Tc and below Tc) of carbon monoxide
with their respective volumes (V1,V2,V3), Ptrial, and % Area Difference.
T(K)

V/ m^3/mol

Ptrial / Pa

% Area Difference

3495695.25

Cannot be determined

V1= 8.49E-05
V2= 1.22E-04
V3= 1.87E-04
V1= 7.19E-05
V2= 1.29E-04
V3= 2.74E-04

3001860

1.39

2290450

1.21

V1= 6.72E-05
V2= 1.33E-04
V3= 3.41E-04
V1 = 6.41E-05
V2 = 1.38E-04
V3 = 4.06E-04

1904260

1.08

1620589

0.84

132.9
128

120

115

110.9

Table 2: Five temperatures (Tc and below Tc) of carbon monoxide


16

Using the data given in the tables above, the graphs of the p-V diagrams of Carbon
monoxide for five temperatures were compressed into one as constructed below.

Figure 13: Compressed p-V diagrams of Carbon monoxide for five temperatures
Using excel, a scatter chart of the data was generated. The binodal curve of carbon
monoxide with respect to the pressure and volume is shown below.

17

Binodal Curve

4
3.5
3
2.5
p/10^5 Pa
2

V/m^3/mol

1.5
1
0.5
0
0.00E+00
5.00E-05
1.00E-04
1.50E-04
2.00E-04
2.50E-04
3.00E-04
3.50E-04
4.00E-04
4.50E-04

Figure 14: Binodal curve of Carbon monoxide with respect to v and p


The table below presents the five temperatures (Tc and below Tc) of n-pentane with
their respective volumes (V1,V2,V3), Ptrial, and % Area Difference.
T/K

V/ m^3/mol

Ptrial / Pa

% Area Difference
18

469.6
460

455

440

435

Cannot be determined

3370000
3100760

V1 = 3.36E-04
V2 = 4.41E-04
V3 = 6.00E-04
V1 = 3.19E-04
V2 = 4.45E-04
V3 = 6.56E-04
V1 = 2.86E-04
V2 = 4.57E-04
V3 = 8.18E-04
V1 = 2.78E-04
V2 = 4.61E-04
V3 = 8.74E-04

1.44

2965500

1.84

2581500

1.69

2461100

1.33

Table 3: Five temperatures (Tc and below Tc) of n-pentane


Using the data given in the tables above, the graphs of the p-V diagrams of Carbon
monoxide for five temperatures were compressed into one as constructed below.

p-V Diagrams
100
90
80

p/100000 Pa

70

Tc

60

T=435 K

50

T=440 K

40

T=455 K

30

T=460 K

20
10
0

Vm/m^3 mol-1

Figure 15: Compressed p-V diagrams of n-pentane for five temperatures

19

Binodal Curve
40
35
30
25

Psat/10^5

20
15
10
5
0
2.00E-04

4.00E-04

6.00E-04

8.00E-04

1.00E-03

V/m^3/mol

U
sing excel, a scatter chart of the data was generated. The binodal curve of carbon monoxide
with respect to the pressure and volume is shown below.
Figure 16: Binodal curve of Carbon monoxide with respect to v and p
The following data in the table below was used to plot the liquid-gas coexistence
curve of carbon monoxide in a p-T diagram.
T/K
110.9
115
120
128
132.9

P/(Pa)
1620589
1904260
2290450
3001860
3495695.25

% Area Difference
0.84
1.08
1.21
1.39
Cannot be determined

Table 4: Temperatures of carbon monoxide with their pressures and % area differences

20

CO p-T Diagram
4000000
3500000
3000000
2500000

Psat/105 Pa

2000000
1500000
1000000
500000
0
105 110 115 120 125 130 135

T/ (K)
The liquid-gas
coexistence curve of carbon monoxide was plotted using the previous data for pressure and %
area difference as shown in a p-T diagram below.

Figure 17: Liquid-gas coexistence curve of carbon monoxide plotted in a p-T diagram
The following data in the table below was used to plot the liquid-gas coexistence
curve of n-pentane in a p-T diagram.
T/K
469.6
460
455
440
435

p/Pa
33.7
31.0076
29.655
25.815
24.611

% Area Difference
Cannot be determined
1.44
1.84
1.69
1.33
21

Table 5: Temperatures of n-pentane with their pressures and % area differences

The liquid-gas coexistence curve of n-pentane was plotted using the previous data for
pressure and % area difference as shown in a p-T diagram below.

n-Pentane p-T Diagram


40
35
30
25

Psat/105 Pa

20
15
10
5
0
430 435 440 445 450 455 460 465 470 475

T/ (K)

Figure 18: Liquid-gas coexistence curve of n-pentane plotted in a p-T diagram

Reduced units of a liquid or gas are units that are scaled by their critical constants, i.e.
pr= p/pc, , r= /c and Tr= T/Tc. The chart showing pressure as a function of molar volume
was plotted in a graph of the p-Vm diagram of carbon dioxide and n-pentane.

22

p - Vm Diagram
600
500
400

Pressure

CO

300

n-Pentane

200
100
0
0.00E+00

5.00E-04

1.00E-03

1.50E-03

2.00E-03

Molar Volume

Figure 19: p-Vm diagram of carbon monoxide and n-pentane

The graph below shows the reduced pressure pr as a function of the reduced molar
volume Vr for the pressures and volumes of the coexistence curve.

pr - Vr Diagram
16
14
12
10

Reduced Pressure

CO

n-Pentane

6
4
2
0

Reduced Volume

Figure 20: pr-Vr diagram of carbon monoxide and n-pentane


The graph below shows the reduced pressure pr as a function of the reduced molar
volume Vr for the pressures and volumes of the coexistence curve.

23

Coexistence Curve
Vr - Pr Diagram
1.5

Reduced Pressure
pasat/10^5Pa

0.15

0.1

0.5
0
0.00E+00

0.05
2.00E+00

4.00E+00

n-Pentane
CO

0
6.00E+00

Reduced volume
Vm/m3mol-1

Figure 21: Coexistence curve of Vr-Pr diagram for carbon monoxide and n-pentane
According to the Law of Corresponding States, substances at corresponding states
behave alike at same reduced states. The graph above represents that when V and P of a
substance such as n-pentane and Carbon monoxide are reduced, the behavior of the
substances still corresponds to that of the original V and P.
The experimental critical constants for ethane and argon are given in the table below.
Substance
Ethane

p(cr)/[Pa]
T(cr)/[K]
4883846 305.4

v(cr)/[m3.mol-1]
0.000148

Argon
4863581 150.72
7.53E-05
Table 6: Experimental critical constants for ethane and argon

T(K)
500
247

Tr (K)
1.63719
7
1.6388

* Reduced temperatures at which these data of Ethane and Argon are collected at 1.637197K
and 1.6388K respectively. Derived by dividing T(K) over T(cr in K).

24

p vs 1/V Diagram
Experimental
8.00E+07
6.00E+07
Argon

Pressure/10^5 Pa

4.00E+07

Ethane

2.00E+07
0.00E+00
0.00E+00

1.00E+04

2.00E+04

3.00E+04

1/V

The following graphs show comparison between the experimental data and the predictions of
the van der Waals equations by plotting p as a function of 1/v.

p vs 1/V Diagram
van der Waals
600
500

Pressure/10^5 Pa

400

Argon

300

Ethane

200
100
0
0.00E+00

1.00E+04

2.00E+04

3.00E+04

1/V

Figure 22: Experimental p vs 1/V diagram of argon and ethane


Figure 23: Van der waals p vs 1/V diagram of argon and ethane
As it is observed, the behavior of both the experimental and theoretical graphs agrees
with each other. This means that as the value of 1/V increases the value of pressure also
increases obeying Boyles Law which states that P 1/V.

25

Another graph was constructed to test whether the experimental data given in table 6
obey the law of corresponding states by plotting pr as a function of 1/vr.

pr - 1/Vr Diagram
1.60E+01
1.40E+01
1.20E+01
1.00E+01
Argon

8.00E+00

Pr/Pa

Ethane

6.00E+00
4.00E+00
2.00E+00
0.00E+00
0.00E+00

5.00E-01

1.00E+00

1.50E+00

2.00E+00

1/Vr/m3mol-1

Figure 24: pr as a function of 1/Vr for argon and ethane

To prove the law of corresponding states mathematically, we rewrite the van der
Waals equation of state in terms of reduced pressure, reduced volume and reduced
temperature.
Given:
T
Tr=
Tc

P r=

P
Pc

Pc=

Vc=3 b

V r=

a
27 b 2

V
Vc
Tc=

8a
27 Rb

Solution:
RT
a
P=
2
Vmb Vm
PrPc=

][

R(TrTc)
a

VrVcb
(VrVc)2

][

8a
R Tr (
)
a
27 Rb
a
Pr
=
2
2
Vr ( 3 b )b
27 b
Vr (3 b)2

( )

]
26

][

8a
(
)
a
27 Rb
a
Pr
=
2 2
2
Vr ( 3 b )b
27 b
Vr 9 b

( )

8 aTr
2
27 b
a
27
a
27 b
Pr=

a 27 b2
Vr 3 bb V r 2 9 b 2 a
2

[
[

( )]

[
( )] [

8 aTr
27 b
27(Vr 3 bb) a

Pr=

8 aTr
27 b
27 b(Vr 31) a

Pr=

Pr=

( )]

a
27 b
2
2
a
Vr 9 b

a
27 b
2
2
a
Vr 9 b

( )]
2

8Tr
3
2
3 Vr1 Vr
The variation of Z with pressure and temperature can be explained more effectively

using the so-called Boyle temperature (TB) as reference. For a van der Waals gas, TB = a/bR.
As stated above, the values of a and b can be calculated from the critical constants of the gas.
Using the data for Carbon monoxide, we were able to calculate the van der Waals
constants and the TB, for the substance assigned to us in the Z-calc sheet. For each
temperature, a p vs Z diagram was prepared.

Carbon monoxide (p vs Z Diagram)


2.5
2

T=Tb

1.5

Compression Factor/Z

T>Tb

T<Tb

0.5
0

500

1000

1500

P/atm

27

Figure 25: p vs Z diagram of carbon monoxide for each temperature


As presented by the graph above, the compression factor (Z-calc) varies directly as
the pressure increases. In the T=Tb graph, the Z-calc and p shows a curve in an increasing
trend. Same thing happens with T>Tb and T<Tb graphs. In addition, the above graph
revealed that when temperature is increased the Z-calc and pressure also increases and when
temperature is decreased, the Z-calc and pressure also decreases.

Discussion
________________________________________________________
This laboratory experiment was performed to demonstrate a verified description and
mathematical comparison of how real gases behave differently against ideal gases using the
ideal gas equation and van der Waals equation of state. Based on the graph shown in figure 37 for carbon monoxide and figure 8-12 for n-pentane, it can be observed that the graphs of
van der Waals equation of state was oscillated compared to that of the ideal gas equation
which formed a smooth curve. These oscillations are due to the loops which can be corrected
using Maxwell construction. The loop implies that if pressure increases, the volume also
increases, thus not obeying empirical law: the Boyles Law. Upon the results of the graphs of
molar volume as a function of pressure, found in Figure 13 and 15, an inverse proportionality
was determined for both gases at different temperatures.
The molar volumes V1 and V3 were obtained from the Maxwell construction. As the
loops were corrected, a horizontal line from the isotherms can be seen. Using Maxwell
construction, an assumption that A1 = A2 or the % Area difference not exceeding 2% for the
graph was considered to be good enough. As observed, both gases (carbon monoxide and npentane) behaved ideally at higher temperatures. The graph of the gases in the Van der Waals
draws near the graph of ideal gas (see figure 7 and figure 12 above). At lower temperatures,
28

loops were observed. This is an indication showing the product of the mathematical
innovations. In correcting this loops, the Maxwell construction was utilized with an
assumption that A1 = A2. The region of the curve by which the pressure and volume are
constant is called the critical point which was also observed in Figure 13 and 15.
The binodal curve of gases is the region wherein two phases coexist. In this lab
activity, it is also called the liquid-gas phase. This happens when pressure and temperature in
a region remains unchanged, allowing the compression or expansion of the gases in a certain
point. The bimodal curves of carbon monoxide and n-pentane is shown in figure 14 and 16
respectively.
The p-T diagram also presented a relationship, pressure being the independent
variable and temperature being a dependent variable. The graphs that were generated display
a transition phase where gas and liquid coexist and describes one of the characteristics of a
van der Waals equation of state where attractive and repulsive interactions are in equilibrium,
thus permitting the coexistence of other phases. The branch that is plotted by the gas phase
shown in figure 2 of the materials and method part displays that there is an existing critical
point where solid, liquid and gas phase is possible.
According to the Law of Corresponding States, substances at corresponding states
behave alike at same reduced states. The graph of p-V diagrams in the results show that when
V and P of a substance such as n-pentane and Carbon monoxide are reduced, the behavior of
the substances still corresponds to that of the actual V and P. This is shown in Figure 20 and
figure 21. This also applies whether the reciprocal of the molar volume is reduced since an
identical curve has also formed.
The compression factor Z, the ratio of its measured molar volume Vm= V/n is a
measure of deviation from the perfect behavior of a gas. A value of Z=1 denotes that the gas
29

behaves ideally or perfectly and is assumed to be the basis for a gas to classify as perfect or
not. As presented by the Figure25 above, the compression factor (Z-calc) varies directly as
the pressure increases. In the T=Tb graph, the Z-calc and p shows a curve in an increasing
trend. Similarly, it also happens with T>Tb and T<Tb graphs. In addition, the above graph
revealed that when temperature is increased, the Z-calc and pressure also increases and when
temperature is decreased, the Z-calc and pressure also decreases.

CONCLUSION
________________________________________________________
Generally, at high temperatures, the measure of the behavior of real gas deviation
from perfect gas can be determined when sufficient information is given to generate
isotherms from the van der Waals equation of state. In correcting van der Waals gas curves,
where there is a presence of oscillations produced by loops, the mathematical equation is
used. With the assumption that the areas under the curve are equal that is, A1 = A2, a small
difference not exceeding 2% was also considered. The use of the binodal curves simply
illustrates the regions where gas and liquid coexist. Diagrams of p-T mainly exhibit the
transition phase where the gas and liquid also coexist. The law of corresponding states
generally showed that when the experimental values for a substance, specifically a gaseous
compound were plotted, it generates a curve. Also when the reduced values of the
experimental were plotted, an identical curve was generated showing the same behavior as
that of the experimental values. With the use of the compression factor Z, we were able to
establish and picture out the difference in the behavior of real and ideal gas.

Most

importantly, this experiment showed that real gases actually deviate from ideal gases. In this
30

spreadsheet experiment, it was also determined how real gases behave from ideal ones using
graphical visualizations and calculations. The use of compression factor Z, Law of
corresponding states and van der Waals equation of states accurately illustrated the molecular
interactions predicting the relationship of variables of the state.

References
________________________________________________________
[1]

Atkins, P.., de Paula, J. Physical Chemistry (2010). Chapter 1: The properties of

gases. Physical Chemistry 9th Edition (pp. 19-37). Oxford University Press, 2010
[2]

Reid, R.C., Prausnitz, J.M. , Poling, B.E., The properties of Gases & Liquids, 4th

Edition, McGraw-Hill, 1987


[3]

Reichl, L.E., A modern course in Statistical Physics, Edward Arnold LTD, 1980

[4]

McQuarrie, D.A., Statistical Mechanics, University Science Books, 2000

[5]

Silbey, R.J., Alberty, R.A., Bawendi, M.G. Physical Chemistry, 4th edition, Wiley,

2005
[6]

Garland, C.W., Nibler, J.W., Shoemaker, D.P., Experiments in Physical Chemistry, 9th

edition, McGraw-Hill, 2009

31

[7]

Gaje, A.C., Laboratory Work in University Chemistry, Department of Chemistry-

College of Arts and Sciences, University of the Philippines Visayas


[8]

Coghill, A.M., Garson, L.R., ACS Style Guide: Effective Communication of Scientific

Information, 3rd edition, Oxford University Press, 2006

Acknowledgement
________________________________________________________
I would like to thank the following individuals for the accomplishment of this
laboratory report:
First of all, to my parents who supported me in every aspects of my life, may it be
physically, emotionally and financially and for the guidance and encouragement.
To Haina Jade G. Salvideo and Glaize Ann G. Gamelong for being responsible in
doing their part and in collaborating with the things to be accomplished especially in the
assigned parts of the laboratory work.
Also to my friends, Rammela Ann Camelote, Gwendolyn Delgado, Glydele Mae
Fuene, Trixie Babes Capio, Mary Chrizelle Gonzaga for being there for me not only in good
times but also in bad and difficult times.

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