A Hundred Years of Chemical Equilibrium Calculations The Case of Ammonia Synthesis

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ECE 106 17
education for chemical engineers x x x ( 2 0 1 5 ) xxxxxx
Contents lists available at ScienceDirect
Education for Chemical Engineers

journal homepage: www.elsevier.com/locate/ece
A hundred years of chemical equilibrium

calculations The case of ammonia synthesis
Q1
Mordechai Shacham a, , Neima Brauner b
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:
An exercise that involves a process of great historical importance that of synthesizing
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Received 9 June 2015
ammonia from its elements is presented. In the exercise, the students are required to calcu-
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Received in revised form 12
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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Accepted 12 September 2015
over a hundred years ago; a model based on the Gibbs energy and ideal gas conditions; and
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Available online xxx
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
15
programs, combined with reliable physical property databases for the equilibrium compu-
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Keywords:
17
Ammonia synthesis
tations, is emphasized. On one hand, the exercise gives students an opportunity to become
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Numerical problem solving
familiar with and to appreciate the precision of the experimental work and the manual
19
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
20
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
The introduction of the personal computer in the early

nineteen-eighties, and the emergence of commercial Internet providers a few years later, leads to revolutionary changes
in chemical engineering problem-solving. As a result of
these changes, numerical calculations are carried out nowadays mostly by mathematical software packages such as
Excel , MAPLETM , MATHCAD , MATLAB , Mathematica and
POLYMATHTM (Shacham and Cutlip, 1999; Mahecha-Botero
et al., 2011). More complex calculations are carried out by computational uid dynamics (CFD) packages (Morscheidt et al.,
2013) and process simulation programs (such as Aspen, ChemCAD and UniSim; see, for example, Shacham et al., 2009).
Physical and thermodynamic property data needed for the
computation are routinely retrieved from property databases,
such as DIPPR or NIST. It is very important for chemical
engineering students to learn, and practice the use of, these

modern computational tools. In this paper we present an exercise where the use of these tools can be practiced together with
the modeling of chemical equilibrium at various levels of rigor
with respect to the ammonia synthesis process.
The industrial synthesis of ammonia from its elements is
considered by many as the most important technical invention of the twentieth century (Smil, 2001). This is because
large scale production of ammonia enabled production of fertilizers that leads to huge increase in crop yields, which in
turn enabled the expansion of the worlds population from
1.6 billion people in 1900 to 6 billion at the end of the century. The breakthrough in ammonia synthesis was brought
about by Fritz Haber (Haber, 1920) and coworkers, who carried
out many experiments to determine the equilibrium constant
of the ammonia synthesis reaction at various temperatures
and pressures. The objective was to prove that under certain
Corresponding author. Tel.: +972 8 6461481; fax: +972 8 6472916.

E-mail address: shacham@exchange.bgu.ac.il (M. Shacham).
http://dx.doi.org/10.1016/j.ece.2015.09.001
1749-7728/ 2015 Published by Elsevier B.V. on behalf of The Institution of Chemical Engineers.
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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conditions, high enough conversion of the elements H2 and

N2 to ammonia can be reached, which would justify development of a commercially viable large scale process. Haber and
le Rossignol (see p. 277 in Smil, 2001) carried out experiments
at atmospheric and at 30 atm pressures at various temperatures in 1907. The results of the equilibrium constants at
various conditions were reported by Haber (who received the
Nobel Prize in Chemistry in 1918 for proving the feasibility
of this process) in his Nobel lecture (Haber, 1920). Haber and
le Rossignol (HR) used the experimental data they collected
to develop a correlation for the equilibrium constant of the
ammonia synthesis reaction as a function of temperature and
pressure. At that time the physical and thermodynamic data
were less accurate than today, and the calculations were carried out manually, usually with two or at most three decimal
digits accuracy. For example, the heat capacity correlation for
gaseous ammonia used by HR contains three constants with
two or three decimal digits, while the same correlation provided by the NIST database contains ve constants with seven
decimal digits. Prior to the introduction of mathematical software packages, it was necessary to neglect the impact of some
of the less inuential factors (such as gas phase non-ideality)
on the equilibrium conversion, because of the long time and
the great effort involved in the calculations.
The exercises included here can be best given as homework assignments in thermodynamics, reaction engineering
and process simulation courses. Solution of the exercises
requires the use of physical and thermodynamic databases,
such as DIPPR (dippr.byu.edu) or NIST (webbook.nist.gov),
where up-to-date, evaluated (thus more reliable) property data are available. The use of mathematical software
packages (e.g., POLYMATH (www.polymath-software.com),
MATLAB (www.mathworks.com)) and process simuprograms
(e.g.,
Aspen
(www.aspentech.com),
lation
(www.honeywellprocess.com)
ChemCAD
UniSim
(www.chemstations.com)) is also essential. Useful references for the ammonia synthesis equilibrium can be found
in the textbook of Sandler (1999) and in the recent journal
articles of Nasri and Binous (2009) and Klemola (2014).
2.
Problem background equilibrium
composition in the ammonia synthesis reaction
Using Eq. (3) for a specied value of Ka , the molar extent

of the reaction (X) and the mole fractions and the partial
pressures of the various components at equilibrium conditions can be calculated using the initial mole numbers. With
inlet mole number of 1/2 for N2 and 3/2 for H2 , the outlet mole
fractions are the following: X/(2 X) for NH3 , (1 X)/[2 (2 X)]
for N2 , and 3 (1 X)/[2 (2 X)] for H2 (where X is number of
NH3 moles produced). Substituting these expressions and the
total pressure (Ptot ) into Eq. (3) yields:
Ka =
X(2 X)
[(1 X)/2]
1/2
[3(1 X)/2]
3/2
(Ptot /P0 )
Haber and le Rossignol (see p. 277 in Smil, 2001) carried

out ammonia synthesis experiments at atmospheric and at
30 atm. pressures at various temperatures in 1907. Based on
these experiments they developed the following correlation
(the HR correlation) for the equilibrium constant1 :
log 10
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
where T is the temperature in K. Using this correlation implies

that ideal gas phase is assumed as all i values are set to 1 (as
in Eq. (3)).
Using this equation, Haber and Rossignol calculated the
percentage of ammonia at equilibrium for nine temperatures
(T = 473, 573, . . ., 1273 K) and four pressures (P = 1, 30, 100 and
200 atm, P0 = 1 atm, units of atm are used for pressure to be
consistent with the published version of the HR correlation).
Based on thermodynamic considerations, the equilibrium
constant and its temperature dependence can be expressed as
function of the Gibbs energy of the reaction, Gr (T).

Ka (T) = exp
Gr (T)
RT
92
93
Nitrogen and hydrogen react in an exothermic, equilibrium

reaction to form ammonia,
3
1
N2 + H2 NH3
2
2
(1)
96
The reaction is carried in the gas phase in the presence of

a solid catalyst. The chemical equilibrium coefcient for the
reaction can be expressed as:
97
Ka =
94
95
(6)
aNH3
1/2 3/2
aN aH
2
98
99
100
101
102
103
P NH3
NH3
1/2 3/2 1/2 3/2

P N P H N H
2
(2)
where ai is the activity of species i, P i is the dimensionless

partial pressure, P i = Pi /P0 , Pi is the partial pressure, P0 is a
reference (standard state) pressure and i is the fugacity coefcient of species i in the mixture. Assuming ideal gas phase
(low pressure) all i = 1 and Eq. (2) is reduced to
Ka =
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
where i is the stoichiometric coefcient (positive for prod0

ucts, negative for reactants), Hf,i
is the heat of formation at
standard state and Cpi is the ideal gas heat capacity (at constant pressure) of species i. The entropy of the reaction is given
by
Sr (T) =
106
The Gibbs energy of the reaction (at temperature T) can be

calculated from the enthalpy (Hr ) and the entropy (Sr ) of
the reaction at the same temperature.
Hr (T) =
105
(5)
Gr (T) = Hr (T) TSr (T)

91
(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).
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where S0f,i is the entropy of formation at standard state of

species i.
The exercise involves calculation the equilibrium concentration of ammonia at various temperatures and pressures
using: (1) the HR correlation, (2) the Gibbs free energy with
the ideal gas assumption and (3) the Gibbs free energy with
gas phase non-ideality included. The use of a mathematical
software package for the rst two parts of the assignment
is recommended, while the third part is best solved using a
process simulation program.
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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
Table 1 POLYMATH program for calculation of the

equilibrium composition of H2 , N2 and NH3 using the HR
(Haber, 1920) correlation.
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
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)
mLogKa = 2.1 + (1/4.571)*(9591/T 0.00046*T + 0.85*1e6*T2)

4.98 *log(T)/1.985
Ka = 10(mLogK
a ) # Chemical equilibrium coefcient in terms
of partial pressures
f(X) = Ka *((1 X)/2)(1/2)*(3*(1

X)/2)(3/2)*(Ptot /P0 ) X*(2 X) #
Molar extent of the reaction
X(min) = 0.01 # Lower bound for the extent of the reaction
X(max) = 0.99 # Upper bound for the extent of the reaction
N2 = (1 X)/(2*(2 X)) # Mole fraction N2
H2 = 3*(1 X)/(2*(2 X)) # Mole fraction H2
NH3 = X/(2 X) # Mole fraction NH3
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.
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
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Table 2 Results of calculation of Ka and % NH3 at equilibrium with the HR correlation.

No.
T (K)
Ka
Percentage of NH3 at equilibrium

P = 1 atm
1
2
3
4
5
6
7
8
9
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
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
Table 3. Observe that the common validity range of these

coefcients is from 500 K to 1000 K. For temperatures below
500 K, a different set of parameter values needs to be used
for nitrogen; for temperature values above 2000 K, the parameters for hydrogen should be modied. The use of the NIST
parameters requires setting the reference pressure at 1 bar
(line 2). The value of Gr (T) (Eq. (7)) is calculated in line 19
and the corresponding Ka value (Eq. (6)), in line 20. The calculations of the extent of the reaction and the equilibrium
mole fractions of N2 , H2 and NH3 are done in the same way
as explained in the previous section. The results for the case
shown (T = 573 K, Ptot = 200 atm) are: Ka = 0.06722; X = 0.7687; N2
(mole fraction) = 0.09391; H2 = 0.2817; and NH3 = 0.6243. Comparing these values with the values of the HR correlation
shows 4.06% difference in the Ka value and 0.96% difference
in the NH3 mole fraction value. Thus, there is adequate match
Table 3 POLYMATH program for calculation of the

equilibrium composition of H2 , N2 and NH3 using the
Gibbs free energy and NIST data.
No.
21
22
23
24
25
26
Extent of the reaction

X(min) = 0.01 # Lower bound for the extent of the reaction
X(max) = 0.99 # Upper bound for the extent of the reaction
N2 = (1 X)/(2*(2 X)) # mole fraction N2
H2 = 3*(1 X)/(2*(2 X)) # mole fraction H2
NH3 = X/(2 X) # mole fraction NH3
8
9
10
11
12
13
14
15
16
17
18
19
20
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
between the Haberle Rossignol and the Gibbs energy models

for the value of Ka .
To carry out the calculations for the complete set of temperature and pressure values, a MATLAB program is used. In
the MATLAB program, different parameter value sets are used
according to the validity ranges specied in the NIST database.
The complete set of the calculated values of Ka and the percentage of NH3 at equilibrium is shown in Table 4. A plot of
the equilibrium NH3 mole percent values obtained by the HR
correlation and Gibbs free energy calculated from NIST property data vs. temperature is shown in Fig. 1. Observe that the
results obtained by the two methods are essentially indistinguishable. Examining the differences between the equilibrium
NH3 mole percent values obtained by the HR correlation and
by the Gibbs free energy shows that the differences follow the
general trend of the equilibrium ammonia concentration (%
mole) at the various temperatures and pressures. In terms
of percent deviations they are distributed between +3.19% (at
T = 473 K and P = 1 atm) and 4.46% (at T = 1173 and P = 1 atm).
Such differences are very reasonable considering the four
orders of magnitude differences between the numbers shown
in Tables 2 and 4.
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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
f(X) = X*(2 X) Ka *((1 X)/2)(1/2)*(3*(1

X)/2)(3/2)*(P
tot /P0 ) #
1
2
3
4
5
6
7
P = 30 atm
4.3.
using the ChemCAD program
We have used the Gibbs reactor module of ChemCAD
with the SRK thermophysical property package to calculate the
Fig. 1 Comparison of the equilibrium NH3 % mole values

obtained by the HR correlation (p *H) and Gibbs free energy
calculated from NIST property data (p *N).
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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

P = 1 atm
1
2
3
4
5
6
7
8
9
286
287
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
equilibrium ammonia concentration at the various temperatures and pressures.

Part of the ChemCAD ow diagram and worksheet for computation of equilibrium ammonia concentration at T = 500 C
and P = 100 atm is shown in Fig. 2. Feed ow rate of 2 kg mole/h
(0.5 kg mole/h of N2 , 1.5 kg mole/h H2 ) enters the Gibbs reactor
(No. 1), which is kept at a constant temperature of T = 500 C
and a constant pressure of 100 atm. Only the gas phase product exits the reactor with the following mole fraction values:
N2 = 0.223655, H2 = 0.670966 and NH3 = 0.105379. Thus, the percent conversion to ammonia at these conditions is 10.53%.
The complete set of the percentage of NH3 values at equilibrium, as calculated by the equilibrium reactor module
of ChemCAD, is shown in Table 5. The results obtained are
plotted in Fig. 3 and compared to the equilibrium NH3 mole
percent values obtained by the Gibbs free energy with NIST
property data. On this scale the results obtained by the two
methods are essentially indistinguishable. Examining the plot
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
of the differences between the equilibrium NH3 mole percent

values obtained by the Gibbs free energy and ChemCAD shows
that there are noticeable differences in the lower temperature region (473 K through 873 K), while at higher temperatures
the differences are essentially zero. Considering the gas phase
non-ideality increases the mole fraction of ammonia at equilibrium, the largest increase is by 1.32% at T = 573 K and
P = 30 atm. While the ChemCAD results imply a relatively small
inuence of the gas phase non-ideality, other computational
studies (see for example, pp 655 and 656 in Sandler, 1999)
have shown up to 10% increase in the extent of the ammonia
synthesis reaction as result of the gas phase non-ideality.
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.
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Table 5 Percentage of NH3 at equilibrium as provided

by the CHEMCAD program.
No.
0
1
2
3
4
5
6
7
8
T (K)
473
573
673
773
873
973
1073
1173
1273

P = 30 atm
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
simulated with MATLAB. One of the objectives of the course

is to enable the students to utilize up-to-date physical property databases for retrieving property data and equations to
be included in the unit modules. The prerequisites of this
course include all the usual set of required undergraduate
chemical engineering courses (mass and energy balances,
thermodynamics, transport phenomena, reaction engineering
and separation processes), and a basic course of mathematical
modeling and numerical methods. In regards to thermodynamics, prociency is essential in non-ideal phase and
chemical equilibrium models.
Considering the course prerequisites and the above stated
objective, this exercise is very appropriate for this course.
The students nd the exercise challenging, but they point out
that the exercise helps them better understand some of the
more difcult thermodynamic concepts, and appreciate the
importance of the use of up-to-date, reliable data sources. The
chance to carry out an investigation associated with a Nobel
Prize winning process greatly increases the students interest
in the subject matter of the simulation course.
6.
Fig. 3 Comparison of the equilibrium NH3 % mole values

obtained by the HR correlation (p *H) and the CHEMCAD
equilibrium reactor module (p *CC).
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of NH3 at equilibrium calculated using Eq. (5). These results

match up to the signicant gures shown by Haber. Thus, the
difference in the numerical results can be explained by the
limitation on the number of digits of the computational tools
that were available in the nineteen-twenties.
In part (b) the equilibrium concentrations using Ka values obtained from Gibbs free energy are compared with those
obtained by the HR correlation. Here the percent deviations
of the NH3 equilibrium concentration are distributed between
+3.19% (at T = 473 K and P = 1 atm) and 4.46% (at T = 1173 and
P = 1 atm). The most probable source of the differences in this
case is the experimental error, as the uncertainty of the physical property data used for the Gibbs energy computation is
considered to be below 1%.
The source of the differences in the NH3 mole fractions
between parts (c) and (b) is the use of realistic fugacity
coefcients for calculation of Ka . These differences are limited
to the lower temperature range (<873 K) and their highest
value is 1.32%.
5.
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Using the exercise in the classroom
The exercise presented here has been given as a homework

assignment in the Process Simulation elective course to
4th year undergraduate chemical engineering students at the
Ben-Gurion University of the Negev. This course is described
in detail by Shacham (2011). The students are expected to
prepare process models that, in most cases, are ultimately
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Conclusions
The example presented here provides an opportunity to

practice the use of several state-of-the-art problem-solving
tools for calculating the equilibrium conversion of ammonia
when it is synthesized from its elements. The computational
tools used here include the mathematical software packages
Polymath and MATLAB and the ChemCAD process simulation program. The use of a state-of-the-art, reliable physical
property database (NIST) is also practiced.
The mathematical models employed for the equilibrium
computation include a regression model, based on experimental equilibrium data obtained by Haber and le Rossignol over a
hundred years ago (see Smil, 2001); a model based on the Gibbs
free energy assuming ideal gas conditions; and a model based
on the Gibbs energy with gas phase non-ideality included.
Carrying out this exercise gives the students an opportunity to become familiar and to appreciate the precision of the
experimental work and the manual calculations that were carried out more than a hundred years ago. The exercise also
helps them to master the complex issues involved in phase
and chemical equilibrium in reacting systems.
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Appendix A. Supplementary material

The POLYMATH and MATLAB programs used in this
study are available at the site: ftp://ftp.bgu.ac.il/
shacham/AmmoniaSynthesis
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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
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Technology, Gaithersburg MD, 20899, http://webbook.nist.gov

(retrieved 15.07.15).
Mahecha-Botero, A., Reaume, S., Grace, J.R., Ellis, N., 2011.
Independent research as a teaching tool in graduate chemical
reaction engineering. Case study: modelling isomerization of
unsaturated fatty acids with catalyst deactivation. Educ.
Chem. Eng. 6 (1), e1e9.
Morscheidt, W., Cavadias, S., Rousseau, F., Da Silva, B., 2013.
Pollution of the Rhine River: an introduction to numerical
modelling. Educ. Chem. Eng. 8, e119e129.
Nasri, Z., Binous, H., 2009. Applications of the PengRobinson
equation of state using MATLAB. Chem. Eng. Ed. 43 (2),
110.
Sabdler, S.I., 1999. Chemical and Engineering Thermodynamics,
3rd ed. Wiley, New York.
Shacham, M., Cutlip, M.B., 1999. Selecting the appropriate

numerical software for a chemical engineering course. Comp.
Chem. Eng. 23 (Suppl.), S645.
Shacham, M., Cutlip, M.B., Brauner, N., 2009. From numerical
problem solving to model based experimentation
incorporationg computer based tools of various scales into
the ChE curriculum. Chem. Eng. Ed. 43 (4), 315321.
Shacham, M., 2011. Use of advanced educational technologies in
a process simulation course. In: Pistikopoulos, E.N.,
Georgiadis, M.C., Kokossis, A.C. (Eds.), Computer-Aided
Chemical Engineering, 29. Elsevier Science, Amsterdam, pp.
11351139.
Smil, V., 2001. Enriching the Earth: Fritz Haber, Carl Bosch, and
the Transformation of the World Food Production. MIT Press,
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