REAL GASES

Submitted By:
Cesar Ian A. Caermare
Izel Marion Nicole C. Hernando

Date Submitted:
July 21, 2012

Submitted to:
Prof. Sheeva Yahcob-Saddalani
Chem 142 Lab Instructor

ABSTRACT
The study was carried out to graphically evaluate the behavior of real gases at changing
conditions and the ability of selected real gas equations of state to predict P-V-T relationships of
gases.
The pressure exerted by carbon dioxide at 31.1 C and 100 C was plotted against molar
volume and ideal, van der Waals, and experimental isotherm were evaluated. With these, the
absolute accuracy of van der Waals equation isotherm was evaluated by comparing its plot against
ideal isotherm. Redlich Kwong equation of state was validated by attempting to predict the P-V-T
relationship of CO2.
Van der Waals equation of state is best applicable to carbon dioxide at 31.1 C as the
accuracy of the van der Waals isotherm is in unity with the ideal isotherm at a wide range at this
condition. Redlich-Kwong isotherm also best describes CO2 at 100 C since the graph shows that
the deviation of this isotherm is very less to ideal isotherm.
In part two, Redlich-Kwong and Dieterici equations of state were evaluated using the
thermodynamics quantities of selected samples of gases and then plotted to better understand the
equations being evaluated.
The two equations best describe water vapor and ammonia gases as manifested by the plot
produced by these equations. However, the slopes produced by Redlich-Kwong EOS approximate
the gas constant, R value compared to Dieterici EOS. Thus, Redlich-Kwong EOS has better
applicability to water vapor and ammonia. Other equations of state are recommended for validation
using the other gas samples
INTRODUCTION:
Gas is a state of matter that is known to have particles which are very far apart from each
other and that they are in constant random motion. A gas can behave as perfect or real gas.
A Perfect Gas is proposed by the Kinetic Molecular Theory as a very minute particle size
negligible compared to the distance travelled by the molecule and which aside from being very far
apart and in random motion, there is no transfer of energy during collisions. Real Gas system on the
other hand differs from a Perfect Gas system because there is transfer of energy in the collision of
gas molecules, resulting to molecular interactions. However, real gases approximate perfect gas
behavior at very low pressure and significantly high temperature. A real gas deviates increasingly
from ideality as it is compressed and cooled to near the point at which it will condense into liquid.
The deviation from the ideal gas is particularly important at high pressure and low temperature.
The properties of the real gas can be express in terms of isotherm and compression factor
(Z). Because perfect gas has compressibility factor equal to 1 under all conditions, deviation of Z
from 1 is a measure of imperfection. At very low pressure all gases are expected to have Z1 and
are behaving nearly perfectly. At high pressure all gases have Z>1, signifying that they are more
difficult to compress than the perfect gas. At intermediate pressure most of the gases have Z<1,
indicating that attractive forces are dominant and compression is easy.

PART I.
DATA AND CALCULATION
Table 1.1: tabulates real gas equation state relating pressure (P), volume (V) and temperature (T) of
a given quantity of gas.
Real Gas Equations of the State
Van der Waals

P= (RT/Vm-b)-(a/Vm2)
Where a and b are van der Waals constants

P= (RT/Vm-b)-(a/TVm2)
Where a and b are Berthelot constants

Berthelot

Modified Berthelot

P= RT/Vm[1+(9PTc/128PcT)][1-(6Tc2/T2]
Where Pc and Tc are critical state pressure and temperature

Dieterici P= (RTe-a/RTVm/Vm-b)
Where a and b are Dieterici constants
Clausius

[P-(a/T(Vm+c)2)][Vm-b]=RT
Where a, b, and c are Clausius constants

Redlich-Kwong
General Virial

P= (RT/Vm-b)-(a/T 1/2Vm(Vm+b))
Where a and b are Redlich-Kwong constants
PVm=RT[1+(B/Vm)+(C/Vm2)+(D/Vm3)++]
B, C, and D are the second, third, fourthvirial coefficients
Respectively which are functions of temperature

Table 1.2: Tabulates experimental data on the variation of molar volume of carbon dioxide with the
pressure at the critical point, (T=31.1 C) in the table, alpha correspond to volumes to which 17
molar volume of carbon dioxide measured at 0C and 1 atm, would be changed by altering the
pressure to P and temperature to T.
Table 1.3: Tabulates experimental data for T=100C, which is way above the critical temperature.
The data () are volumes equal to Vm/VSTP.
The symbols used are defined as follows:
T= temperature of CO2 sample in degrees Celsius
VSTP= the volume of one mole CO2 at 1 atm and 0 C = 22.264 L
Vm= the molar volume at pressure, P, and temperature, T
Table 1.4: Theoretical P-V-T relationship for carbon dioxide

Pc = 73 atm; Tc = 31.1 C; Vc = 0.0956 L

Van der Waals constants evaluated from Pc and Tc is:
a= 3.60 L2 atm/mole and b= 0.0428 L/mole
T= 31.1 C; RT = 24.98 L atm/mole
Table 1.5: Theoretical P-V-T relationship for CO2; T=100 C; RT = 30.65
L.atm/mole

Tabulation of Data
Table 1.2: Experimental P-V-T relationships for carbon dioxide, T=31.1C
P(atm)
59.77
61.18
62.67
64.27
65.9
67.6
69.39
71.25
73.26
73.83
75.4
77.64
79.92
82.44

alpha
0.202
0.1933
0.1839
0.173
0.1632
0.1542
0.1409
0.1282
0.1122
0.1087
0.0609
0.0513
0.0494
0.0479

Vm
0.264548706
0.253154776
0.240844094
0.226568941
0.2137344
0.201947576
0.184529271
0.167896753
0.1469424
0.142358635
0.079757506
0.067184894
0.064696565
0.062732094

Table 1.3: Experimental P-V-T relationships for carbon dioxide, T=100 C

P(atm)
20.17
22.37
24.85
27.76
31.06
34.57
40.09
45.99
53.81
64.27
80.25
105.69

alpha
0.0654
0.05878
0.05265
0.04684
0.04155
0.03702
0.03153
0.02711
0.02276
0.01855
0.0142
0.00998

Vm
1.456066
1.308678
1.1722
1.042846
0.925069
0.824213
0.701984
0.603577
0.506729
0.412997
0.316149
0.222195

Table 1.4: Theoretical P-V-T relationships for carbon dioxide

Vm

Vm-b

RT/(Vm-b)

Vm2

a/Vm2

P(atm)

RT/Vm

Pexp(atm)

0.08
0.11
0.1
0.12
0.14
0.16
0.18
0.2
0.25
0.3
0.4
0.5

0.0372
0.0672
0.0572
0.0772
0.0972
0.1172
0.1372
0.1572
0.2072
0.2572
0.3572
0.4572

671.5053763
371.7261905
436.7132867
323.5751295
256.9958848
213.1399317
182.0699708
158.9058524
120.5598456
97.12286159
69.93281075
54.63692038

0.0064
0.0121
0.01
0.0144
0.0196
0.0256
0.0324
0.04
0.0625
0.09
0.16
0.25

562.5
297.5207
360
250
183.6735
140.625
111.1111
90
57.6
40
22.5
14.4

109.0053763
74.20552932
76.71328671
73.57512953
73.32241539
72.51493174
70.95885973
68.90585242
62.95984556
57.12286159
47.43281075
40.23692038

312.25
227.0909
249.8
208.1667
178.4286
156.125
138.7778
124.9
99.92
83.26667
62.45
49.96

84.014
80.573
81.72
79.426
77.132
74.838
72.544
70.25
64.515
58.78
47.31
35.84

Table 1.5: Theoretical P-V-T relationships for carbon dioxide at T=100C; RT=30.65
Vm
0.14
0.16
0.2
0.3
0.4
0.5
0.75
1
1.5
2

Vm-b
0.0972
0.1172
0.1572
0.2572
0.3572
0.4572
0.7072
0.9572
1.4572
1.9572

RT/(Vm-b)
315.3292181
261.5187713
194.9745547
119.1679627
85.806271
67.03849519
43.33993213
32.02047639
21.03348888
15.66012671

Vm2
0.0196
0.0256
0.04
0.09
0.16
0.25
0.5625
1
2.25
4

a/Vm2
183.6735
140.625
90
40
22.5
14.4
6.4
3.6
1.6
0.9

P(atm)
131.6557487
120.8937713
104.9745547
79.16796267
63.306271
52.63849519
36.93993213
28.42047639
19.43348888
14.76012671

RT/Vm
218.9286
191.5625
153.25
102.1667
76.625
61.3
40.86667
30.65
20.43333
15.325

Pexp(atm)
96.9822
95.8368
93.546
87.819
82.092
76.365
62.0475
47.73
19.095
-9.54

CALCULATIONS AND EQUATIONS

1. Calculation of experimental volume Vm
Given that VSTP = 22.264 L/mole, the experimental molar volume of CO2 can be computed from
the data as follows:
Alpha = [17 Vm/VSTP]
Vm = [alpha VSTP/17] =1.310(alpha)
(1)
= [Vm/VSTP]
Vm= VSTP = 22.264
(2)
Compute column 3 of tables 2 and 3 by using this equation
2. Calculation of pressure from the van der Waals equation of state.

Tables 4 and 5 has been set up (columns 4-9) so as to compute for the pressure, P, corresponding to
selected values of temperature and molar volume Vm, in accordance with the van der Waals
equation of state.
The van der Waals equation of state is usually written as
[P+ a/Vm2][Vm- b]= RT
Where T is in Kelvin

(3a)

It can be rearranged to solve for the pressure P.

P=[RT/(Vm-b)]-[a/Vm2]

(3b)

For each value of Vm in column 4, compute for the values of the terms in column 5-8 and the van
der Waals pressure in column 9.
3. Calculation of pressure from ideal gas equation of state.
For the selected values Vm and T= 100 C, compute for the corresponding from ideal gas laws.
P= RT/Vm
Tabulate these in column 10 of table 5.

(4)

TREATMENT OF DATA
1. From the data available in Tables 1.2, 1.3, 1.4 and 1.5, plot the different isotherms, P (atm) vs.
Vm (L/mole). Use solid lines for experimental isotherms, dashed lines for van der Waals isotherms,
and a dash and dot line for the ideal isotherms. Combine the plots of these 3 isotherms in a single
graph, one for T=31.1 C and one for T= 100 C.
2. From the experimental isotherm graph, determine the experimental pressure (PEXP) corresponding
to the volume Vm in tables 1.4 and 1.5. You may need to extrapolate from the graph. Use column
11 for these purpose.
3. Comment on the use of van der Waals equation as a description of a real gas with respect to its
absolute accuracy (experimental vs. theoretical) and in comparison with the ideal gas law. You may
do these graphically or you may use tabulated data.
4. Choose another equation of state and evaluate its ability to predict the P-V-T relationship for CO 2
for the same P-V-T range and condition. Consult appropriate references to find the corresponding
constants for the equation chosen.

GRAPHICAL REPRESENTATIONS AND INTERPRETATION

The graphs below plot the Pressure-Volume relationship of Carbon Dioxide at constant
temperature and number of moles using van der Waals isotherm, Ideal Isotherm, and Experimetal
Isotherm. Figure 1.1 plots the Pressure-Volume relationship of CO2 at 31.1C, with pressure as a
function of molar volume.

Fig. 1.1: At 31.1C and below 100 atm, van der Waals isotherm and Experimental Isotherm is
reasonably the same. However, as the molar volume increases indepedently, van der Waals
Isotherm, Experimental Isotherm, and Ideal Isotherm also approaches homogeneity in the sketch,
signifying the behavior of a real gas and perfect gas approaching unity to each other at this
condition.

Fig.1.2 The plot of the experimental isotherm is significantly different from the plot of the van der
Waals Isotherm at 100 C. However, van der Waals isotherm approaches ideality in the condition of
increasing molar volume.

Figures 1.1 and 1.2 shows us that at very low pressure and reasonably high temperature,
gases behavior approaches ideality. In figure 1.1, the temperature is 31.1C compared to figure 1.2
with temperature 100 C. In figure 1.1, ideality is obtained at around 50 atm, while in figure 1.2,
ideality is approximated by the van der Waals isotherm above 50 atm. With increasing molar
volume and decreasing pressure to zero at constant temperature, a gas behaves ideally.
Consequently, a deviation from ideality is significant to high pressure and low molar volume at
constant temperature.
Figures 1.3 and 1.4 Shows the absolute accuracy of the van der Waals equation of state
graphically

Fig.1.3: Experimental and theoretical van der Waals isotherms at 31.1C

Fig. 1.4: Experimental and theoretical van der Waals isotherms at 100C

The curve in figure 1.3 shows that at 31.1C experimental isotherm is accurate with
reference to the theoretical van der Waals isotherm at 0.160Vm0.443 L/mol. Deviation of real
gasfrom a perfect gas is significant at increasing pressure. However, figure 1.4 shows that at 100
C, experimental isotherm attains unity with the theoretical van der Waals isotherm at
approximately 90 atm and 20 atm with molar volumes 0.3 L/mol and 1.5 L/mol, respectively. Thus,
determination of gas is best suitable at a condition of temperature equals 31.1 C as manifested by
figure 1.3
Validation of Redlich-Kwong Equation
Table 1.6: Pressures using Redlich-Kwong EOS at T=31.1C
Vm

RT/Vm

Vm-b

Vm+b

T^1/2*Vm

RT/Vm-b

a/T^1/2*
Vm(Vm+b)

p (atm)

0.08

312.25

0.05031032

0.11

227.0909

0.08031032

0.1

249.8

0.07031032

0.12

208.1667

0.09031032

0.14

178.4286

0.11031032

156.125

0.13031032

0.18

138.7778

0.15031032

0.2

124.9

0.17031032

0.25

99.92

0.22031032

0.3

83.26667

0.27031032

0.4

62.45

0.37031032

0.5

49.96

0.47031032

1.395421
083
1.918703
99
1.744276
354
2.093131
625
2.441986
896
2.790842
167
3.139697
438
3.488552
709
4.360690
886
5.232829
063
6.977105
417
8.721381
771

496.2394
187
310.8686
897
355.0824
964
276.4464
122
226.3248
257
191.5885
4
166.0961
4
146.5910
225
113.3218
088
92.36038
028
67.41903
372
53.08402
323

416.647
8
237.940
2
281.915
8
203.540
9
153.901

0.16

0.109689
68
0.139689
68
0.129689
68
0.149689
68
0.169689
68
0.189689
68
0.209689
68
0.229689
68
0.279689
68
0.329689
68
0.429689
68
0.529689
68

79.591
67
72.928
51
73.166
72
72.905
51
72.423
86
71.123
48
69.229
28
67.001
97
61.033
05
55.394
74
46.146
96
39.279
12

T^1/2*Vm

RT/Vm-B

a/T^1/2*
Vm(Vm+b
)

p (atm)

2.704392
723
3.090734
541
3.863418
176

277.5780
073
234.9753
942
179.7878
062

138.96
8
108.77
64
71.866
57

138.61

120.465
1
96.8668
6
79.5890
5
52.2887
6
36.9656
4
21.2720
8
13.8049

Table 1.7: Pressures using Redlich-Kwong EOS at 100C

Vm

RT/Vm

Vm-b

0.14

218.92
86
191.56
25
153.25

0.11031032

0.16
0.2

Vm+b

0.169689
68
0.13031032 0.189689
68
0.17031032 0.229689
68

126.199
107.921
2

0.27031032

0.4

102.16
67
76.625

0.5

61.3

0.47031032

0.75

40.866
67
30.65

0.72031032

20.433
33
15.325

1.47031032

0.3

1
1.5
2

0.37031032

0.97031032

1.97031032

0.329689
68
0.429689
68
0.529689
68
0.779689
68
1.029689
68
1.529689
68
2.029689
68

5.795127
263
7.726836
351
9.658545
439
14.48781
816
19.31709
088
28.97563
632
38.63418
176

113.2761
739
82.68664
727
65.10535
174
42.50906
583
31.55662
491
20.82534
441
15.54055
648

33.378
88
19.208
06
12.465
42
5.6456
68
3.2062
1
1.4388
11
0.8132
77

79.8972
9
63.4785
9
52.6399
3
36.8634
28.3504
1
19.3865
3
14.7272
8

Data in tables 1.6 and 1.7 regarding the validation of Redlich-Kwong equation can be better
understood using figures 1.5 and 1.6.

Fig. 1.5: Comparison of modified Berthelot isotherm and ideal isotherm at 31.1C

Fig. 1.6: Comparison of modified Berthelot isotherm and ideal isotherm at 100C
Figures 1.5 and 1.6 illustrates the P-V-T relationship of an perfect gas and ideal gas using
Redlich-Kwong equation of state. At 31.1 C, the Redlich-Kwong isotherm behaves ideally at 50
atm while at 100 C, Redlich-Kwong behaves almost perfectly as ideal isotherm below 150 atm and
shows less deviation from ideality for carbon dioxide compared to the condition of carbon dioxide
being treated at 31.1 C. Thus, Redlich-Kwong equation of state best describes the thermodynamic
relationship of P-V-T for carbon dioxide at 100 C.

PART II
Data and Calculations
The following data for nitrogen, methane water and ammonia are taken from the
thermodynamic table. The data are given in terms of volume per kilogram and pressure is in terms
of Mpa or kPa. These data will be used to test real gas equation of state and to calculate the
compressibility factor at each temperature.
Tables 2.1, 2.2, 2.3 and 2.4 describes the behavior of gases in terms of compressibility
factor at increasing temperature.
Table 2.1 shows that nitrogen behaves ideally at 80 K. However, the compressibility factor
decreases as temperature and pressure were raised from 80 K to 125 K.
Table 2.1: Thermodynamic table of nitrogen
T(K)
80
85
90
95
100
105
110
115
120
125

P(Mpa)
0.13699
0.22903
0.36066
0.54082
0.77881
1.08423
1.46717
1.93875
2.51248
3.20886

V(m3/kg)
0.163744
0.101503
0.066146
0.044792
0.031216
0.022195
0.015952
0.011445
0.007998
0.004883

P(atm)
1.351986
2.26035
3.559437
5.337478
7.686257
10.70052
14.47984
19.13397
24.79625
31.66899

V(L/mol)
4.584832
2.842084
1.852088
1.254176
0.874048
0.62146
0.446656
0.32046
0.223944
0.136724

PVm
6.19863
6.424106
6.592391
6.694137
6.718158
6.649944
6.467508
6.131674
5.552971
4.32991

Z
0.944222
0.921006
0.892625
0.858696
0.818688
0.771786
0.716494
0.649755
0.563914
0.422121

Table 2.2 shows the behavior of methane. At 115 K, compression factor of methane is
approximating ideal compression factor. Compression factor for methane continuously decrease
when temperature is raised up to 155 K. At 160 K however, the compression factor for methane
drastically increased from 0.787 to stunning 1.799.
Table 2.2: Thermodynamic table for methane
T(K)

P(Mpa)

V(m3/kg)

P(atm)

V(L/mol)

PVm

115

0.13232

0.43048

1.305897

6.88768

8.9946

120

0.19158

0.30615

1.890748

4.8984

9.261638

125

0.26896

0.22359

2.654429

3.57744

9.49606

130

0.3676

0.16702

3.62793

2.67232

9.69499

135

0.49072

0.12717

4.84303

2.03472

9.85421

140

0.64165

0.09839

6.332593

1.57424

9.969021

145
150

0.82379
1.04065

0.07716
0.06117

8.130175
10.27042

1.23456
0.97872

10.03719
10.05186

0.9531
61
0.9405
65
0.9257
97
0.9088
38
0.8895
5
0.8677
74
0.8435
8
0.8166

155

1.2958

0.04892

12.78855

0.78272

10.00986

160

1.59296

0.03935

15.72129

1.5024

23.61967

53
0.7870
07
1.7990
2

Table 2.3 shows the behavior of water vapor as a function of temperature.378.15K, the
temperature at which the gas behaves more likely as an ideal gas
Table 2.3: Thermodynamic table of water vapor
T(K)
378.15
383.15
388.15
393.15
398.15
403.15
408.15
413.15
418.15
423.15

P(Mpa)
0.12082
0.14328
0.16906
0.19853
0.2321
0.2701
0.313
0.3163
0.4154
0.4759

V(m3/kg)
1.4194
1.2102
1.0366
0.8919
0.77059
0.6685
0.58217
0.50885
0.44632
0.39278

P(atm)
1.192401
1.414064
1.668492
1.959339
2.290649
2.66568
3.08907
3.121638
4.099679
4.696768

V(L/mol)
25.5492
21.7836
18.6588
16.0542
13.87062
12.033
10.47906
9.1593
8.03376
7.07004

PVm
30.46488
30.8034
31.13207
31.45562
31.77272
32.07612
32.37055
28.59202
32.93584
33.20634

Z
0.981757
0.979712
0.97741
0.975009
0.97247
0.96958
0.966493
0.843346
0.959854
0.956302

Table 2.4 shows that at 223.15K, the ammonia gas behaves almost the same with that of the
ideal gas. As the temperature and pressure increases, ammonia gas deviates from ideality to
imperfection as manifested by compression factor, Z, decreasing at increasing temperature and
pressure.
Table 2.4: Thermodynamic table of ammonia
T(K)
223.15
225.15
227.15
229.15
231.15
233.15
235.15
237.15
239.15

P(kPa)
40.86
45.94
51.52
57.66
64.38
71.72
79.74
88.48
97.98

Vm3/kg)
2.62667
2.3544
2.11503
1.90406
1.71769
1.55269
1.40627
1.27607
1.16004

P(atm)
0.403257
0.453393
0.508463
0.56906
0.635381
0.707821
0.786973
0.87323
0.966987

V(L/mol)
44.65339
40.0248
35.95551
32.36902
29.20073
26.39573
23.90659
21.69319
19.72068

PVm
18.00679
18.14695
18.28204
18.41991
18.55359
18.68346
18.81383
18.94314
19.06965

Z
0.983349
0.9822
0.9808
0.979572
0.978144
0.976541
0.974991
0.973413
0.971719

The data in tables 2.1-2.4 were plotted in figure 2.1-2.4 to better understand the data
obtained from calculations.
Relating compressibility factor to pressure, theoretically, the gas are expected to be more
compressible at moderate pressure because in this case forces are helping to draw the molecules
together. At high pressure, the gas can be expected to be less compressible due to the force that help

to drive molecules apart and at low pressure intermolecular forces play no significant role and thus,
gas behaves perfectly. Since, ideal gas has a Z equal to 1 at all conditions; the deviation of the
compressibility factor from 1 is the measure of imperfection.

B. Treatment of Data
1. Calculate the compressibility factor at each temperature for all gases. Consult appropriate
references for the equations and critical constants. Evaluate your results. What do your calculations
indicate regarding the behavior of the gases with increasing temperature?
2. Evaluate the validity of the ideal gas law by testing the linearity of the graph of PVm vs
T. the slope should be equal to R if the ideal gas law is valid.
3. Choose two real gas equation of state and evaluate their applicability to the four gases.
Which equation of state best describes each gas?
GRAPHIAL REPRESENTATION PART II:

Fig. 2.1: Nitrogen gas

Fig.
2.2: Methane gas

Fig. 2.3: Water vapor

Fig. 2.4: Ammonia gas

Figures 2.1-2.4 illustrates the validity of the ideal gas law with the argument stating that ideal
gas is true for the sketch with slope, m equals to R value or 0.0820574. Among the figures, only
figure 2.4 accounting for ammonia has slope nearest to 0.0820574, while others have significantly
far value for m with reference to the R value which is a gas constant. With these, ideal gas law is
appropriate only to ammonia gas.

Validation of Redlich-Kwong equation of state

Table 2.5: Thermodynamic table of nitrogen
T(K)
80
85
90
95
100
105
110
115
120
125

RT
6.5648
6.9751
7.3854
7.7957
8.206
8.6163
9.0266
9.4369
9.8472
10.2575

Vm(L/mol)
4.584832
2.842084
1.852088
1.254176
0.874048
0.62146
0.446656
0.32046
0.223944
0.136724

Vm-b
4.555032
2.812284
1.822288
1.224376
0.844248
0.59166
0.416856
0.29066
0.194144
0.106924

Vm(Vm+b)
21.15731
8.162136
3.485422
1.610332
0.790007
0.404732
0.212812
0.112244
0.056824
0.022768

a/T1/2
Vm(vm+b)
0.04761
0.11972
0.27247
0.57402
1.140446
2.17241
4.03657
7.48500
14.47370
35.39394

P (atm)
1.39360
2.36049
3.78034
5.79305
8.57944
12.39050
17.61742
24.98213
36.24741
60.53868

PVm
6.389464
6.708736
7.001524
7.265515
7.498848
7.700205
7.868928
8.005775
8.11739
8.277091

Z
0.973291
0.961812
0.948022
0.93199
0.913825
0.893679
0.871749
0.848348
0.824335
0.806931

PVm
9.300655
9.664395
10.01897
10.36406
10.69951
11.02537
11.34212
11.65036
11.95149
12.73022

Z
0.985563
0.981436
0.976746
0.971527
0.965825
0.959696
0.953223
0.946491
0.939634
0.969582

PVm
30.98019
31.38264
31.78419
32.18479
32.58438
32.9829
33.38028
33.77647
34.17142
34.56506

Z
0.998363
0.998135
0.997884
0.99761
0.997312
0.99699
0.996641
0.996265
0.995863
0.995432

Table 2.6: Thermodynamic table for methane

T(K)
115
120
125
130
135
140
145
150
155
160

RT
9.4369
9.8472
10.2575
10.6678
11.0781
11.4884
11.8987
12.309
12.7193
13.1296

Vm
(L/mol)
6.88768
4.8984
3.57744
2.67232
2.03472
1.57424
1.23456
0.97872
0.78272
1.5024

Vm-b
6.85468
4.8654
3.54444
2.63932
2.00172
1.54124
1.20156
0.94572
0.74972
1.4694

Vm(Vm+b)
47.66743
24.15597
12.91613
7.229481
4.207231
2.530181
1.564879
0.990191
0.63848
2.306785

a/T1/2
Vm(Vm+b)
0.02637
0.05095
0.09337
0.16357
0.27582
0.45038
0.71553
1.11181
1.69622
0.46209

P (atm)
1.35033
1.97296
2.80059
3.87829
5.25846
7.00361
9.18717
11.90366
15.26917
8.47325

Table 2.7: Thermodynamic table for water vapor

T(K)
378.15
383.15
388.15
393.15
398.15
403.15
408.15
413.15
418.15
423.15

RT
31.03099
31.44129
31.85159
32.26189
32.67219
33.08249
33.49279
33.90309
34.31339
34.72369

VM
(L/mol)
25.5492
21.7836
18.6588
16.0542
13.87062
12.033
10.47906
9.1593
8.03376
7.07004

Vm-b
25.5305
21.7649
18.6401
16.0355
13.85192
12.0143
10.46036
9.1406
8.01506
7.05134

Vm(Vm+b)
653.2394
474.9326
348.4997
258.0376
192.6535
145.0181
110.0067
84.06406
64.69153
50.11768

a/T1/2Vm(V
m+b)
0.00287
0.00393
0.00532
0.00714
0.00951
0.01255
0.01645
0.02139
0.02763
0.03546

P(atm)
1.21256
1.44065
1.70344
2.00475
2.34916
2.74103
3.18542
3.68766
4.25347
4.88894

Table 2.8: Thermodynamic table for ammonia

T(K)
223.15
225.15
227.15
229.15
231.15
233.15
235.15
237.15
239.15

RT
18.31169
18.47581
18.63993
18.80405
18.96817
19.13229
19.29641
19.46053
19.62465

Vm
(L/mol)
44.65339
40.0248
35.95551
32.36902
29.20073
26.39573
23.90659
21.69319
19.72068

Vm-b
44.62919
40.0006
35.93131
32.34482
29.17653
26.37153
23.88239
21.66899
19.69648

Vm(Vm+b)
1993.925
1601.984
1292.798
1047.753
852.682
696.734
571.5245
470.5939
388.9046

a/T1/2Vm(V
m+b)
0.00081
0.00100
0.00124
0.00152
0.00187
0.00228
0.00276
0.00334
0.00403

P(atm)
0.40949
0.46087
0.51752
0.57983
0.64824
0.72321
0.80520
0.89473
0.99231

Data in tables 2.5-2.8 can be better understood using Figures 2.5-2.8.

Fig. 2.5: Nitrogen

PVm
18.28525
18.4466
18.60772
18.76861
18.92927
19.08966
19.2498
19.40965
19.56922

Z
0.998556
0.998419
0.998272
0.998116
0.997949
0.997772
0.997584
0.997386
0.997176

Fig. 2.6: Methane

Fig. 2.7: Water vapor

Fig. 2.8: Ammonia

The graphs from figures 2.5 through 2.8 illustrate the validity of Redlich-Kwong Real Gas
Equation of State. Theoretically, the equation of state must have a slope, m equal to the gas
constant, R. Ammonia gas and Water Vapors slopes show only a very small deviation from R
value with mwater vapor = 0.079 and mammonia = 0.80. With these, Redlich-Kwong equation of state
describes the behavior of Water Vapor and Ammonia more accurately with reference to the
deviation of the slope to the R value obtained by plotting the pVm of gas samples as a function of
their temperature in Kelvins (K).
Validation of Dieterici equation of state
Table 2.9 Thermodynamic Table for Nitorgen
T(K)
80

Vm (L/mol)
RT
4.584832 6.564592

Vm-b
4.543013439

85

2.842084

6.974879

2.800265439

90

1.852088

7.385166

1.810269439

95

1.254176

7.795453

1.212357439

100

0.874048

8.20574

0.832229439

105

0.62146

8.616027

0.579641439

(-a/RT*Vm)

0.057599
53
0.087453
37
0.126744
25
0.177316
98
0.241711
40
-

p (atm)
1.364107371

pVm

6.2542
03

0.9527
18

2.282217116

6.4862
53

0.9299
45

3.593955619

6.6563
22

0.9013
1

5.385213042

6.7540
05

0.8664
03

7.742848278

6.7676
21

0.8247
42

10.75321324

6.6826

0.7756

110

0.446656

9.026314

0.404837439

115

0.32046

9.436601

0.278641439

120

0.223944

9.846888

0.182125439

125

0.136724

10.257175

0.094905439

0.323765
03
0.429998
12
0.573272
03
0.786161
45
1.236168
44

92

12

14.50387186

6.4782
41

0.7177
06

19.08978374

6.1175
12

0.6482
75

24.63217752

5.5162
28

0.5602

31.39608727

4.2925
99

0.4184
97

Table 2.10 Thermodynamic Table for Methane

T(K)
115

V(L/mol)
6.88768

RT
9.436601

Vm-b
6.841261955

120

4.8984

9.846888

4.851981955

125

3.57744

10.257175

3.531021955

130

2.67232

10.667462

2.625901955

135

2.03472

11.077749

1.988301955

140

1.57424

11.488036

1.527821955

145

1.23456

11.898323

1.188141955

150

0.97872

12.30861

0.932301955

155

0.78272

12.718897

0.736301955

160

1.5024

13.129184

1.455981955

(-a/RT*Vm)

0.044678
53
0.060205
23
0.079138
41
0.101868
03
0.128834
24
0.160572
34
0.197692
19
0.241057
14
0.291696
75
0.147219
10

p (atm)
1.319093958

pVm

9.0854
97

0.9627
93

1.910878267

9.3602
46

0.9505
79

2.683848332

9.6013
06

0.9360
58

3.668950681

9.8046
1

0.9191
14

4.897981954

9.9660
22

0.8996
43

6.403794071

10.081
11

0.8775
31

8.217898876

10.145
49

0.8526
82

10.3743914

10.153
62

0.8249
2

12.9036093

10.099
91

0.7940
87

7.782968945

11.693
13

0.8906
21

pVm

Table 2.11 Thermodynamic Table for Water Vapor

T(K)
378.15

V(L/mol)
25.5492

RT
31.03000581

Vm-b
25.51626575

383.15

21.7836

31.44029281

21.75066575

388.15

18.6588

31.85057981

18.62586575

393.15

16.0542

32.26086681

16.02126575

398.15

13.87062

32.67115381

13.83768575

(-a/RT*Vm)

0.008827
52
0.010218
37
0.011775
98
0.013512
43
-

p (atm)
1.205399465

30.796
99

0.9924
91

1.430791141

31.167
78

0.9913
32

1.689999711

31.533
37

0.9900
41

1.986601841

31.893
3

0.9886
07

2.324845537

32.247

0.9870

403.15

12.033

33.08144081

12.00006575

408.15

10.47906

33.49172781

10.44612575

413.15

9.1593

33.90201481

9.126365752

418.15

8.03376

34.31230181

8.000825752

423.15

7.07004

34.72258881

7.037105752

0.015443
21
0.017580
84
0.019940
60
0.022537
74
0.025388
05
0.028507
83

05

19

2.708728796

32.594
13

0.9852
69

3.142839546

32.934

0.9833
47

3.631948007

33.266
1

0.9812
43

4.181086454

33.589
85

0.9789
45

4.795536766

33.904
64

0.9764
43

Table 2.12 Thermodynamic Table for Ammonia

T(K)
223.15

V(L/mol)
44.65339

RT
18.31110881

Vm-b
44.61293013

225.15

40.0248

18.47522361

39.98434013

227.15

35.95551

18.63933841

35.91505013

229.15

32.36902

18.80345321

32.32856013

231.15

29.20073

18.96756801

29.16027013

233.15

26.39573

19.13168281

26.35527013

235.15

23.90659

19.29579761

23.86613013

237.15

21.69319

19.45991241

21.65273013

239.15

19.72068

19.62402721

19.68022013

(-a/RT*Vm)

0.006586
03
0.007282
39
0.008035
20
0.008847
60
0.009722
71
0.010663
65
0.011673
81
0.012756
41
0.013914
99

p (atm)
0.407749669

pVm

18.207
4

0.9943
37

0.458708794

18.359
73

0.9937
49

0.514830621

18.511

0.9931
15

0.576512574

18.661
15

0.9924
32

0.644165682

18.810
11

0.9916
98

0.7182151

18.957
81

0.9909
12

0.7991179

19.104
18

0.9900
7

0.887336151

19.249
15

0.9891
69

0.983365528

19.392
64

0.9882
09

The tables above relates the thermodynamic quantities of selected gas samples using
Dieterici equation of states. Figures 2.9-2.12 plots pVm as a function temperature in Kelvin.

Fig 2.9 Nitrogen Gas

Fig 2.10 Methane Gas

Fig. 2.11 Water Vapor

Fig. 2.12 Ammonia gaa

The graphs from figures 2.9 through 2.12 illustrate the validity of Dieterici Real Gas
Equation of State. The plot of water vapor and ammonia gas are linear compared to the plots
produced by methane and nitrogen gas. However, the slopes of water vapor and ammonia are 0.069
and 0.074, respectively. These slopes deviate significantly from the condition to which an equation
must be valid, that is, when the slope approximates or equals the real gas constant, R, having the
value 0.08206. Thus, Dieterici equation of state has poor applicability to nitrogen gas, methane gas,
water vapor, and ammonia. However, the equation may be better applicable to other gas sample(s).
With these, ammonia and water vapor are the gases best described by the two equations of
state. However, between the two equations, Redlich-Kwong equation has better applicability to the
given gas samples compared to Dieterici equation.

CONCLUSION:
The objectives of this experiment is to evaluate the P-V-T relationship of carbon dioxide
using van der Waals and other equation of state as well as the applicability of two other equations
of state to other given gas samples.
With the calculated and plotted thermodynamics data for carbon dioxide and other gases,
this paper illustrates that real gases approximate ideality at very low pressures and significantly
high temperature as illustrated by the z compression factors of gas samples. Van der Waals
isotherm approximates ideal isotherm at pressure approaching zero and very high temperatures.
Redlich-Kwong and Dieterici equation of state were tested for their applicability with
nitrogen gas, methane, water vapor, and ammonia. With the plots produced by these equations,
Redlich-Kwong equation of state has better applicability to water vapor and ammonia compared to
Dieterici equstion of state. Other equations are recommended for testing their applicability to other
gases.