King Fahad University of Petroleum and Minerals

College Of Engineering
Department of Chemical Engineering
CHE 422

Section 01
Submission Date 21 April
Term Project (182)
Student ID Contribution%
Faisal Alghamdi 201451670 33.3
Bader Alghamdi 201447640 33.3
Saleh Almulhem 201369670 33.3

Abstract:
The aim of this project is choosing a binary system consists of acetaldehyde and
ethanol to find three main parameters which include physical properties by using
Joback method and comparing with the parameters that is in appendix A. Second task
is to find a relationship by making a diagram for P-T, PV, and H-T. Then comparing
with experimental one. Final task is to make a diagram for P-xy and T-xy, then
comparing with the experimental diagrams. The percentage difference between the
physical properties was 0.1% to 12% for acetaldehyde, and 0.1% to 13% for ethanol.
Also, the diagrams for P-V, P-T, and H-T was close to each other as well as the P-xy,
and T-xy diagrams.

Introduction:

In order to study the nature of fluids we need first to study the physical properties of
it. Properties of fluids can be either constant for pure components such as critical
properties, acentric factor, normal boiling and freezing temperature, heat of
evaporation and melting at normal conditions or variable properties for pure
components i.e. M = M(T,P) or mixtures i.e. M=M(T,P,x). Furthermore, properties
of fluids can be classified to volumetric properties such as Z, V, isothermal
compressibility and thermal expansivity.Thermal properties such as heat capacities,
H, S and heat of combustion. Transport properties such as viscosity, thermal,
momentum, and mass diffusivity and surface tension. The methods of estimation of
these properties can be either experimental that are measured in the lab or scientific
that are measured with equations and correlations. The Joback method (often
named Joback/Reid method) predicts eleven important and commonly used pure
component thermodynamic properties from molecular structure only, these properties
are:

1- Normal boiling point

2- Critical temperature
3- Critical pressure
4- Critical volume
5- Heat of formation
6- Gibbs energy of formation
7- Heat capacity
8- Heat of vaporization at normal point
9- Heat of fusion
10- Liquid dynamic viscosity
11- Melting point

The method uses the group contribution from molecular structure only to calculate the
property of interest, For example Acetone is the simplest ketone and is separated into
three groups in the Joback method: two methyl groups (-CH3) and one ketone group
(C=O). Since the methyl group is present twice, its contributions have to be added twice.
Thermodynamic diagrams are diagrams used to represent the thermodynamic states of
a material (typically fluid) and the consequences of manipulating this material.
The vapor–liquid equilibrium (VLE) describes the distribution of a chemical
species between the vapor phase and a liquid phase. The simplest phase diagrams are
pressure–temperature diagrams of a single simple substance, such as water.
The axes correspond to the pressure and temperature. The phase diagram shows, in
pressure–temperature space, the lines of equilibrium or phase boundaries between the
three phases of solid, liquid, and gas.

A PV diagram plots the change in pressure P with respect to volume V for

some process or processes. Typically in thermodynamics, the set of processes forms
a cycle, so that upon completion of the cycle there has been no net change in state of
the system; i.e. the device returns to the starting pressure and volume.
Problem statement:

In this project, we were asked to select any binary non-ideal-system and compute the
following:
1) All the constant properties of the pure components using the group
contribution method.
2) The P-T, the P-V and the H-T diagrams for each pure component.
3) The T-x-y, P-x-y and x-y diagrams using one of the activity-coefficient
models.

Results & Discussion:

The system chosen was the binary system that consisted of acetaldehyde
and ethanol

Steps of calculation:

1. For physical properties:

Founding the physical properties for each component from by using

Joback method and comparing the results for each component with the
results from appendix. A by taking the percentage difference between
each component

From Joback method:

 Properties Acetaldehyde Ethanol
T nb 293.82 337.34
T nf 153.8 172.62
Tc 465.29 499.11
Pc 56.03 57.57
Vc 164.50 166.50
Zc 0.2382 0.2310
Mw 44.05256 46.06844
ω 0.2637 0.5561

From Appendix A:

Properties Acetaldehyde Ethanol

T nb 294 351.4
T nf 150.2 159.1
Tc 461 513.9
Pc 55.7 61.4
Vc 154 167.1
Zc 0.22 0.24
Mw 44.054 46.069
ω 0.303 0.644

Percentage difference:

Properties Acetaldehyde Ethanol

T nb 0.061% 4.001%
T nf %2.397 8.498%
Tc 0.931% 2.878%
Pc 0.585% 6.242%
Vc 6.818% 0.359%
Zc 8.286% 3.763%
Mw 0.003% 0.001%
ω 12.983% 13.652%

The equations used:

 3 Ꝋ
ω= log Pc −1 (2-3.3)
7 1−Ꝋ

2. For P-T diagram:

Varying the temperature from triple point to critical point helps to

determine the vapor pressure from appendix A for each component

And here the tables and figures for acetaldehyde and ethanol for theoretic
part and experiment part:

Acetaldehyde theoretic P vs T
6.00E+01

5.00E+01

4.00E+01
P (bar)

3.00E+01

2.00E+01

1.00E+01

0.00E+00
280 300 320 340 360 380 400 420 440 460 480
T (K)

Acetaldehyde experiment P vs T
60
50
40
P (bar)

30
20
10
0
280 300 320 340 360 380 400 420 440 460 480
T (K)
 Ethanol (theoretic) P vs T
6.00E+01

5.00E+01

4.00E+01
P (bar)

3.00E+01

2.00E+01

1.00E+01

0.00E+00
250 300 350 400 450 500 550
T (K)

Ethanol (experiment) P vs T
60

50

40
P (bar)

30

20

10

0
250 300 350 400 450 500 550
T (K)

For acetaldehyde:

Pvp theo
T (K) (bar) Pvp exp (bar) Error%
1.20766150
298.15 1.21E+00 5 2.15E-01
309.505 1.64038365
3 1.64E+00 1 1.88E-01
320.860 2.18935266
5 2.19E+00 9 1.47E-01
332.215 2.87548153
8 2.88E+00 3 1.05E-01
343.571 3.72E+00 3.72147799 6.96E-02
 1 5
354.926
3 4.75E+00 4.75177179 4.55E-02
366.281 5.99243644
6 5.99E+00 7 3.48E-02
377.636 7.47111105
8 7.47E+00 9 3.72E-02
388.992 9.21692695
1 9.22E+00 8 5.10E-02
400.347 11.2604433
4 1.13E+01 3 7.32E-02
411.702 13.6335949
6 1.36E+01 9 1.00E-01
423.057 16.3696557
9 1.64E+01 2 1.28E-01
434.413 19.5032183
2 1.95E+01 4 1.51E-01
445.768
4 2.31E+01 23.0701936 1.67E-01
457.123 27.1078294
7 2.72E+01 1 1.70E-01
468.478 31.6547496
9 3.17E+01 9 1.56E-01
479.834
2 3.68E+01 36.7510145 1.23E-01
491.189 42.4382009
5 4.25E+01 6 6.79E-02
502.544 48.7595047
7 4.88E+01 8 1.06E-02
55.7598625
513.9 5.57E+01 7 1.07E-01

For ethanol:

Pvp theo
T (K) (bar) Pvp exp (bar) Error%
0.07796825 1.18E+0
298.15 7.89E-02 2 0
309.505 0.14741026 4.18E-
3 1.48E-01 5 01
320.860 0.26414893 1.59E-
5 2.64E-01 8 02
332.215 0.45137805 1.63E-
8 4.51E-01 1 01
343.571 7.38E-01 0.73942977 2.21E-
 1 8 01
354.926 1.16E+0 1.16656197 2.31E-
3 0 6 01
366.281 1.78E+0 2.43E-
6 0 1.77953222 01
377.636 2.63E+0 2.63394456 2.89E-
8 0 9 01
388.992 3.78E+0 3.79438135 3.89E-
1 0 4 01
400.347 5.30E+0 5.33435453 5.51E-
4 0 6 01
411.702 7.28E+0 7.33612593 7.76E-
6 0 5 01
423.057 9.79E+0 1.06E+0
9 0 9.89045532 0
434.413 1.29E+0 1.39E+0
2 1 13.0963375 0
445.768 1.68E+0 17.0607871 1.75E+0
4 1 4 0
457.123 2.14E+0 21.8987248 2.14E+0
7 1 9 0
468.478 2.70E+0 27.7330095 2.53E+0
9 1 1 0
479.834 3.37E+0 34.6946538 2.91E+0
2 1 1 0
491.189 4.15E+0 42.9232526 3.25E+0
5 1 3 0
502.544 5.07E+0 52.5676463 3.54E+0
7 1 5 0
6.14E+0 63.7869120 3.74E+0
513.9 1 2 0

3. For P-V diagram:

Varying the temperature helps to determine the vapor pressure, and to

evaluate the coefficient of C.E.O.S. using RK, and to calculate Z v , Zl , v v , v l
from:
And here the tables and figures for acetaldehyde and ethanol for theoretic
part and experiment part:

Acetaldehyde theoretic P vs V

6.00E+01

5.00E+01

4.00E+01

3.00E+01
a
P(br)

2.00E+01

1.00E+01

0.00E+00
0.00E+005.00E+021.00E+031.50E+032.00E+032.50E+033.00E+033.50E+034.00E+034.50E+035.00E+03
V (cm3/mol)
 Acetaldehyde experiment P vs V

60

50

40

30
a
P(br)

20

10

0
0.00E+00 5.00E+02 1.00E+03 1.50E+03 2.00E+03 2.50E+03 3.00E+03 3.50E+03 4.00E+03 4.50E+03 5.00E+03
V (cm3/mol)

Ethanol theoretical P vs V

6.00E+01

5.00E+01

4.00E+01

3.00E+01
P(bar)

2.00E+01

1.00E+01

0.00E+00
0.00E+00 5.00E+02 1.00E+03 1.50E+03 2.00E+03 2.50E+03 3.00E+03 3.50E+03 4.00E+03 4.50E+03 5.00E+03
V (cm3/mol)
 Ethanol experiment P vs V

60

50

40

30
P(bar)

20

10

0
0.00E+00 5.00E+02 1.00E+03 1.50E+03 2.00E+03 2.50E+03 3.00E+03 3.50E+03 4.00E+03 4.50E+03 5.00E+03
V (cm3/mol)

For acetaldehyde:
T (K) Pvp theo (bar) Pvp exp (bar) V(v) theo (cm 3/mol) V(v) exp (cm 3/mol) Error% V(L) theo (cm 3/mol) V(L) exp (cm 3/mol) Error%
298.15 1.21E+00 1.207661505 2.00E+04 2.05E+04 2.71E+00 7.89E+01 5.75E+01 3.71E+01
309.5053 1.64E+00 1.640383651 1.50E+04 1.55E+04 3.39E+00 8.01E+01 5.84E+01 3.71E+01
320.8605 2.19E+00 2.189352669 1.15E+04 1.20E+04 4.15E+00 8.18E+01 5.93E+01 3.80E+01
332.2158 2.88E+00 2.875481533 8.90E+03 9.36E+03 5.00E+00 8.33E+01 6.03E+01 3.82E+01
343.5711 3.72E+00 3.721477995 6.98E+03 7.43E+03 6.07E+00 8.53E+01 6.13E+01 3.92E+01
354.9263 4.75E+00 4.75177179 5.55E+03 5.97E+03 7.05E+00 8.71E+01 6.24E+01 3.96E+01
366.2816 5.99E+00 5.992436447 4.44E+03 4.85E+03 8.54E+00 8.92E+01 6.36E+01 4.04E+01
377.6368 7.47E+00 7.471111059 3.58E+03 3.99E+03 1.01E+01 9.16E+01 6.48E+01 4.14E+01
388.9921 9.22E+00 9.216926958 2.92E+03 3.31E+03 1.18E+01 9.42E+01 6.62E+01 4.24E+01
400.3474 1.13E+01 11.26044333 2.39E+03 2.77E+03 1.39E+01 9.64E+01 6.77E+01 4.24E+01
411.7026 1.36E+01 13.63359499 1.97E+03 2.34E+03 1.60E+01 1.01E+02 6.93E+01 4.58E+01
423.0579 1.64E+01 16.36965572 1.62E+03 1.99E+03 1.85E+01 1.05E+02 7.11E+01 4.70E+01
434.4132 1.95E+01 19.50321834 1.35E+03 1.71E+03 2.12E+01 1.09E+02 7.31E+01 4.89E+01
445.7684 2.31E+01 23.0701936 1.12E+03 1.48E+03 2.43E+01 1.14E+02 7.55E+01 5.09E+01
457.1237 2.72E+01 27.10782941 9.27E+02 1.28E+03 2.77E+01 1.21E+02 7.82E+01 5.43E+01
468.4789 3.17E+01 31.65474969 7.65E+02 1.12E+03 3.17E+01 1.27E+02 8.14E+01 5.58E+01
479.8342 3.68E+01 36.7510145 6.27E+02 9.85E+02 3.63E+01 1.37E+02 8.55E+01 5.98E+01
491.1895 4.25E+01 42.43820096 5.07E+02 8.70E+02 4.16E+01 1.52E+02 9.11E+01 6.69E+01
502.5447 4.88E+01 48.75950478 3.95E+02 7.71E+02 4.88E+01 1.74E+02 9.99E+01 7.46E+01
513.9 5.57E+01 55.75986257 2.60E+02 6.87E+02 6.22E+01 2.60E+02 6.87E+02 6.22E+01
For ethanol:
T (K) Pvp theo (bar) Pvp exp (bar) V(v) theo (cm 3/mol) V(v) exp (cm 3/mol) Error% V(L) theo (cm 3/mol) V(L) exp (cm 3/mol) Error%
298.15 7.89E-02 0.077968252 3.14E+05 3.18E+05 1.37E+00 7.55E+01 5.85E+01 2.91E+01
309.5053 1.48E-01 0.147410265 1.73E+05 1.75E+05 7.48E-01 7.70E+01 5.93E+01 2.98E+01
320.8605 2.64E-01 0.264148938 1.00E+05 1.01E+05 5.60E-01 7.85E+01 6.01E+01 3.05E+01
332.2158 4.51E-01 0.451378051 6.08E+04 6.12E+04 6.82E-01 7.98E+01 6.10E+01 3.08E+01
343.5711 7.38E-01 0.739429778 3.82E+04 3.86E+04 1.05E+00 8.15E+01 6.20E+01 3.16E+01
354.9263 1.16E+00 1.166561976 2.49E+04 2.53E+04 1.62E+00 8.31E+01 6.30E+01 3.19E+01
366.2816 1.78E+00 1.77953222 1.67E+04 1.71E+04 2.37E+00 8.51E+01 6.40E+01 3.29E+01
377.6368 2.63E+00 2.633944569 1.15E+04 1.19E+04 3.27E+00 8.77E+01 6.52E+01 3.46E+01
388.9921 3.78E+00 3.794381354 8.15E+03 8.52E+03 4.43E+00 9.03E+01 6.65E+01 3.58E+01
400.3474 5.30E+00 5.334354536 5.89E+03 6.24E+03 5.68E+00 9.35E+01 6.79E+01 3.78E+01
411.7026 7.28E+00 7.336125935 4.32E+03 4.67E+03 7.32E+00 9.64E+01 6.94E+01 3.89E+01
423.0579 9.79E+00 9.89045532 3.23E+03 3.56E+03 9.24E+00 1.00E+02 7.11E+01 4.14E+01
434.4132 1.29E+01 13.0963375 2.44E+03 2.76E+03 1.16E+01 1.04E+02 7.30E+01 4.29E+01
445.7684 1.68E+01 17.06078714 1.86E+03 2.17E+03 1.44E+01 1.09E+02 7.52E+01 4.49E+01
457.1237 2.14E+01 21.89872489 1.43E+03 1.74E+03 1.76E+01 1.16E+02 7.78E+01 4.94E+01
468.4789 2.70E+01 27.73300951 1.10E+03 1.40E+03 2.18E+01 1.24E+02 8.08E+01 5.33E+01
479.8342 3.37E+01 34.69465381 8.43E+02 1.15E+03 2.67E+01 1.37E+02 8.47E+01 6.23E+01
491.1895 4.15E+01 42.92325263 6.36E+02 9.51E+02 3.31E+01 1.50E+02 8.98E+01 6.76E+01
502.5447 5.07E+01 52.56764635 4.62E+02 7.95E+02 4.18E+01 1.72E+02 9.78E+01 7.58E+01
513.9 6.14E+01 63.78691202 2.63E+02 6.70E+02 6.07E+01 2.63E+02 6.70E+02 6.07E+01

4. For H-T diagram:

Made a sequence at varying temperature, starting by saturated liquid goes

to saturated vapor, then to ideal, back to saturated vapor, end to saturated
liquid
At each step, calculate the enthalpy to find H v ∧H l for each component

H v =0+∆ H 1 +∆ H 2 +∆ H 3 + ∆ H 4
H l=0+∆ H 1 +∆ H 2 +∆ H 3 + ∆ H 4 +∆ H 5

For ∆ H 1:

Equal to ∆ H v at normal boiling point under some conditions: (T bn, 1atm,

sat v) using Riedell method

For ∆ H 2: equal to zero due to the low pressure

Ti

For ∆ H 3: equal to ∫ Cp dT at 1atm, and ideal gas

T nb

For ∆ H 4: equal to H R at 2 atm and ideal gas

For ∆ H 5: equal to ∆ H v that used from Watson relation

And here the tables and figures for acetaldehyde and ethanol for theoretic
part and experiment part:
For acetaldehyde:

T(K) H(V)theo H(L)theo H(V) H(L) %Error %Error

KJ/mol KJ/mol exp exp H(V) H(L)
KJ/mol KJ/mol

298.15 -164400 -191437 -164700 -191737 0.18215 0.156465

306.7211 -164120 -190490 -164320 -190790 0.121714 0.157241

315.2921 -163647 -189437 -163947 -189837 0.182986 0.210707

323.8632 -163283 -188475 -163583 -188875 0.183393 0.21178

332.4342 -163031 -187605 -163231 -187905 0.122526 0.159655

341.0053 -162592 -186625 -162892 -186925 0.184171 0.160492

349.5763 -162370 -185634 -162570 -185934 0.123024 0.161348

358.1474 -162068 -184630 -162268 -184930 0.123253 0.162224

366.7184 -161689 -183611 -161989 -183911 0.185198 0.163122

375.2895 -161436 -182576 -161736 -182876 0.185487 0.164046

383.8605 -161216 -181520 -161516 -181820 0.18574 0.164998

392.4316 -161135 -180341 -161335 -180741 0.123966 0.221311

401.0026 -161000 -179334 -161200 -179634 0.124069 0.167006

409.5737 -160901 -178191 -161124 -178491 0.138403 0.168075

418.1447 -159850 -177004 -161121 -177304 0.788846 0.169201

426.7158 -158589 -175998 -161219 -176056 1.631322 0.032944

435.2868 -158381 -174421 -161460 -174721 1.906974 0.171702

443.8579 -158112 -173045 -161935 -173245 2.360831 0.115443

452.4289 -157851 -171273 -162905 -171473 3.102428 0.116637

461 -156987 -167555 -167860 -167855 6.477412 0.178726

For ethanol:
T(K) H(V)theo H(L)theo H(V) H(L) %Error %Error
KJ/mol KJ/mol exp exp H(V) H(L)
KJ/mol KJ/mol

298.15 -234868 -278518 -235028 -278818 30.05086 31.33997

306.7211 -234100 -276876 -234300 -277004 29.9533 31.2319

315.2921 -233266 -274871 -233566 -275181 29.93548 31.15908

323.8632 -232528 -273149 -232828 -273349 29.86983 31.04951

332.4342 -231898 -271209 -232094 -271509 29.75659 30.90278

341.0053 -231168 -269360 -231368 -269660 29.72579 30.79255

349.5763 -230358 -267502 -230658 -267802 29.6057 30.68237

358.1474 -229672 -265631 -229972 -265931 29.52696 30.57236

366.7184 -229116 -263880 -229316 -264046 29.49103 30.46255

375.2895 -228402 -261950 -228702 -262144 29.41197 30.35298

383.8605 -227940 -260020 -228140 -260220 29.3345 30.24363

392.4316 -227344 -258070 -227644 -258270 29.21612 30.17322

401.0026 -227029 -256085 -227229 -256285 29.14626 30.02561

409.5737 -226619 -254058 -226919 -254258 29.0933 29.91703

418.1447 -226445 -251951 -226745 -252175 29.50211 29.80903

426.7158 -226458 -249874 -226758 -250016 30.06237 29.6054

435.2868 -226874 -247451 -227047 -247751 30.2432 29.59809

443.8579 -227521 -245116 -227821 -245316 30.59846 29.46021

452.4289 -229682 -242240 -229982 -242540 31.36395 29.38386

461 -238336 -238336 -238636 -238636 34.21479 29.78655

 H vs T acetaldehyde
-250000

-200000
H (KJ/mol)

-150000

-100000

-50000

280 300 320 340 360 380 400 420 440 460 480
0
T(K)

H vs T ethanol
-300000

-250000

-200000
H(KJ/mol)

-150000

-100000

-50000
280 300 320 340 360 380 400 420 440 460 480
0
T(K)
5. finding a relationship between P-xy, and T-xy and compare it with the
experimental one

And here the tables and figures for acetaldehyde and ethanol for theoretic
part and experiment part:

P-x-y
1400.00

1200.00

1000.00

800.00

600.00

400.00

200.00

0.00
0.00 0.20 0.40 0.60 0.80 1.00 1.20

T-x-y
1400

1200

1000

800

600

400

200

0
0.00 0.20 0.40 0.60 0.80 1.00 1.20
Conclusion:
In this project, choosing a binary system to find some tasks. The binary system
consisted of acetaldehyde and ethanol. This project aimed to find some physical
properties using Joback method to compare it with the values of appendix A. the
difference was from 0.1% to 12% for acetaldehyde, and 0.1% to 13% for ethanol.
Diagrams were made to get a relationship between the theoretical and experimental of
P-V diagrams, P-T diagrams, and H-T diagrams for acetaldehyde and ethanol. P-xy
and T-xy were also made for acetaldehyde and ethanol.

References:
1- Molecular Thermodynamics of fluid-phase equilibria (Third edition)
2- Perry's book