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ECE 106 17
Q1
Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel
School of Engineering, Tel-Aviv University, Tel-Aviv 69978, Israel
a r t i c l e
i n f o
a b s t r a c t
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Article history:
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ammonia from its elements is presented. In the exercise, the students are required to calcu-
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late the equilibrium conversion to ammonia using three mathematical models: a regression
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September 2015
model which is based on experimental equilibrium data obtained by Haber and le Rossignol
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over a hundred years ago; a model based on the Gibbs energy and ideal gas conditions; and
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the Gibbs energy model with gas phase non-ideality included. The use of state-of-the-art
problem-solving tools, including mathematical software packages and process simulation
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programs, combined with reliable physical property databases for the equilibrium compu-
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Keywords:
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Ammonia synthesis
tations, is emphasized. On one hand, the exercise gives students an opportunity to become
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familiar with and to appreciate the precision of the experimental work and the manual
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Chemical equilibrium
calculations that were carried out more than a hundred years ago, and on the other hand,
Process simulation
it gives them an opportunity to practice the use of the modern numerical problem-solving
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tools. It also helps them master the complex issues involved in phase and chemical equilibrium in reacting systems.
2015 Published by Elsevier B.V. on behalf of The Institution of Chemical Engineers.
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Introduction
Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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2.
Problem background equilibrium
composition in the ammonia synthesis reaction
X(2 X)
[(1 X)/2]
1/2
[3(1 X)/2]
3/2
(Ptot /P0 )
P NH3
1/2
3/2
P N P H
2
2
= 2.10+
1
4.571
9591
T
0.00046T+0.85 106 T 2
4.98
log 10 T
1.985
Ka (T) = exp
Gr (T)
RT
92
93
(1)
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97
Ka =
94
95
(6)
aNH3
1/2 3/2
aN aH
2
98
99
100
101
102
103
P NH3
NH3
(2)
P NH3
1/2 3/2
P N P H
2
(3)
(7)
The enthalpy of the reaction is a sum of the enthalpy of formation of the various species at standard state (T0 = 298.15 K,
P0 = 1 bar) and a sum of the heat required to bring the reactants
and the products to the temperature of the reaction
0
i Hf,i
+
i S0f,i +
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i Cpi dT
(8)
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T0
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Hr (T) =
105
(5)
(4)
104
Cp
i
T0
dT
(9)
1
In the original publication (Haber, 1920) one of the parameters
is misprinted (498 instead of 4.98).
Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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(a) Calculate the percent equilibrium concentration of ammonia for nine temperatures (t = 473, 573, . . ., 1273 K) and four
pressures (P = 1, 30, 100 and 200 atm). Use the HR correlation (Eq. (5)) to calculate Ka and solve the nonlinear
equation (Eq. (4)) for the extent of the reaction (X). Summarize the results for percent of conversion to ammonia
in a tabular form and compare with the values in the table
provided by Haber (1920).
(b) Redo (a) but this time calculating Ka using the Gibbs energy
of the reaction (Eq. (6)). Retrieve the required thermodynamic property data and correlations from the NIST
database (Linstrom and Mallard, 2015). Summarize the
percent conversion to ammonia results in tabular form,
and plot the % conversion obtained in (a) and (b) on the
same graph. Calculate and compare the percent difference
in the equilibrium ammonia concentrations obtained as
results in (a) and (b) for the corresponding temperature
and pressure values.
(c) Calculate the percent of equilibrium concentration of
ammonia at the nine temperatures and three pressures
(P = 30, 100 and 200 atm) using the Gibbs reactor
module of the ChemCAD (www.chemstations.com/),
or a similar process simulation program with the
SoaveRedlichKwong (SRK) thermophysical property
package. (A property package available in ChemCAD, as in
most of the simulation programs.) Summarize the results
of percent conversion to ammonia in a tabular form and
plot the % conversion obtained in (a) and (c) on the same
graph. Calculate and compare the percent difference in
the equilibrium ammonia concentrations obtained in (a)
and (c) for the corresponding temperature and pressure
values.
(d) Discuss the signicance of the differences between the
ammonia conversion results obtained using the various
methods.
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Problem statement
Problem solution
4.1.
Calculation of the equilibrium concentrations
using the HR correlation
The solution of Eq. (4) for the extent of the reaction, X, requires
the use of a mathematical software package that can solve
implicit nonlinear algebraic equations. We have used the
POLYMATH and MATLAB packages. The POLYMATH program
for calculating the mole fractions of N2 , H2 and NH3 at equilibrium at specied temperature and pressure values is shown in
Table 1. Note that a text starting with the # sign and ending
with the end of the line is interpreted as a comment. The line
Equation/# comment
# Calculation of ammonia synthesis equilibrium
composition
# by Haberle Rossignol correlation
T = 573 # Reaction temperature (K)
P0 = 1 # Reference pressure (atm)
Ptot = 200 # Reaction pressure (atm)
Ka = 10(mLogK
a ) # Chemical equilibrium coefcient in terms
of partial pressures
numbers shown in this table are not part of the program; they
were added as references for the explanations that follow.
Most of the program in Table 1 is self-explanatory. In lines 6
and 7 Ka is calculated using Eq. (5). In line 7, Eq. (4) is rewritten
in the form of f (X) = 0. Lower and upper bounds on X should
be provided in order to solve this nonlinear algebraic equation (NLE) by POLYMATH. These bounds are specied in lines
9 and 10, respectively. In lines 1113 the equilibrium mole
fractions of N2 , H2 and NH3 are calculated. The results for
the case shown (T = 573 K, Ptot = 200 atm, results rounded to
four signicant digits) are: Ka = 0.07007; X = 0.7718; N2 (mole
fraction) = 0.0929; H2 = 0.2787; and NH3 = 0.6284. In the table
presented by Haber the value shown for Ka is 0.070 and the
mole percent of NH3 is 62.8. Thus, the results match (up to the
signicant gures) with those shown by Haber (1920).
The use of MATLAB can be preferable in order to carry
out repetitive calculations for a large number of temperature
and pressure values. The MATLAB function for calculating
Ka and the equilibrium compositions can be automatically
generated by POLYMATH, as demonstrated, for example, by
Cutlip et al. (2009). The library function fzero.m is used to
solve the NLE f(X) = 0. The complete MATLAB program for
this part of the assignment is available for download at:
ftp://ftp.bgu.ac.il/shacham/AmmoniaSynthesis.
The complete set of the calculated values of Ka and percentage of NH3 at equilibrium is shown in Table 2. Comparing
these results with the numbers shown in Habers (1920) table
shows that all the numbers match (up to the signicant gures) with those shown by Haber. The accuracy of the results
obtained by Haber and le Rossignol can be praised, considering
that at that time all the calculations were carried out manually and the calculation of the extent of the reaction involves
solving a NLE.
4.2.
Calculation of the equilibrium concentrations
using Ka values obtained from the Gibbs free energy
The POLYMATH program for calculating Ka from the Gibbs
free energy (Eq. (6)) and the mole fractions of N2 , H2 and NH3
at equilibrium for specied temperature and pressure conditions is shown in Table 3. The coefcients of the equations
for calculating Hr (T), Eq. (8), and Sr (T), Eq. (9), are from
the NIST database. They are shown in lines 7 through 15 in
Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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T (K)
Ka
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3
4
5
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9
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473
573
673
773
873
973
1073
1173
1273
0.65958
0.070068
0.01378
0.0039977
0.0015096
0.0006886
0.0003617
0.000212
0.0001355
15.349
2.1775
0.44356
0.12949
0.048979
0.022352
0.011745
0.0068831
0.0044012
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67.573
31.775
10.705
3.6181
1.4291
0.66202
0.34996
0.20567
0.1317
P = 100 atm
P = 200 atm
80.602
52.134
25.104
10.419
4.4738
2.1415
1.1479
0.67909
0.43633
85.844
62.841
36.308
17.621
8.2536
4.1122
2.2451
1.3402
0.86515
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Equation/# comment
# Ammonia synthesis Gibbs energy
P0 = 0.9869233 # Reference pressure (atm, 1 bar)
Ptot = 30 # Reaction pressure (atm)
T = 573 # Reaction temperature (K)
T0 = 298.15 # Reference temperature
R = 8.314 # Gas constant J/mol*K
# Enthalpy and entropy equation coefcients from the NIST
database
# Common validity range: 5001000 K
A = 19.99563 19.50583/2 3*33.066178/2
B = 49.77119 19.88705/2 + 3*11.363417/2
C = 15.37599 + 8.598535/2 3*11.432816/2
D = 1.921168 1.369784/2 + 3*2.772874/2
E = 0.189174 0.527601/2 + 3*0.158558/2
F = 53.30667 + 4.935202/2 + 3*9.980797/2
G = 203.8591 212.39/2 3*172.707974/2
t = T/1000
+ C*t3/3
+ D*t4/4
E/t + F)*1000 #Enthalpy of
dHr = (A*t + B*t2/2
the reaction J/mol
+ D*t3/3
E/(2*t2)
+ G # Entropy of the
dSr = A*ln(t) + B*t + C*t2/2
reaction J/mol*
DelG = dHr T*dSr # Reaction Gibbs energy, J/mol
Ka = exp(DelG/(R*T)) # Reaction equilibrium coefcient
1
2
3
4
5
6
7
P = 30 atm
4.3.
Calculation of the equilibrium concentrations
using the ChemCAD program
We have used the Gibbs reactor module of ChemCAD
with the SRK thermophysical property package to calculate the
Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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Table 4 Results of calculation of Ka and percentage of NH3 using the Gibbs free energy and NIST data.
No.
T (K)
Ka
1
2
3
4
5
6
7
8
9
286
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288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
473
573
673
773
873
973
1073
1173
1273
0.62287
0.067223
0.013429
0.0039584
0.0015174
0.0007009
0.0003715
0.0002185
0.0001394
14.858
2.1193
0.43804
0.12992
0.049882
0.023054
0.012221
0.0071901
0.0045878
P = 30 atm
66.992
31.311
10.596
3.6292
1.4547
0.68252
0.36405
0.21481
0.13727
P = 100 atm
P = 200 atm
80.217
51.67
24.914
10.446
4.5492
2.2058
1.1934
0.70895
0.45466
85.553
62.434
36.094
17.662
8.3823
4.2308
2.3321
1.3983
0.90118
4.4.
The signicance of the differences between the
results obtained by the different methods
In part (a) of the assignment the results shown in the table
presented by Haber (1920) are compared with the percentage
Fig. 2 ChemCAD owsheet for computation of equilibrium ammonia concentration at T = 500 C and P = 100 atm.
Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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8
T (K)
473
573
673
773
873
973
1073
1173
1273
P = 100 atm
P = 200 atm
67.27
31.66
10.74
3.66
1.46
0.68
0.36
0.21
0.14
80.43
52.07
25.21
10.55
4.57
2.21
1.19
0.71
0.45
85.71
62.79
36.42
17.81
8.42
4.24
2.33
1.40
0.90
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References
Cutlip, M.B., Brauner, N., Shacham, M., 2009. Biokinetic modeling
of imperfect mixing in a chemostat an example of
multiscale modeling. Chem. Eng. Ed. 43 (3), 243248.
Haber, F., 1920. The Synthesis of Ammonia from its Elements.
The Nobel Foundation, Stockholm, Available at: http://www.
nobelprize.org/nobel prizes/chemistry/laureates/1918/haberlecture.pdf (accessed 02.06.20).
Klemola, K.T., 2014. Chemical reaction equilibrium task for ChE
undergraduates simulating Fritz Habers ammonia synthesis
with thermodynamic software. Chem. Eng. Ed. 48 (2), 115120.
Linstrom P.J., W.G. Mallard, Eds., NIST Standard Reference
Database Number 69, National Institute of Standards and
Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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Please cite this article in press as: Shacham, M., Brauner, N., A hundred years of chemical equilibrium calculations The case of ammonia
ECE 106 17
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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