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7 a r t i c l e i n f o a b s t r a c t
8
9 Article history: An exercise that involves a process of great historical importance – that of synthesizing
10 Received 9 June 2015 ammonia from its elements – is presented. In the exercise, the students are required to calcu-
11 Received in revised form 12 late the equilibrium conversion to ammonia using three mathematical models: a regression
12 September 2015 model which is based on experimental equilibrium data obtained by Haber and le Rossignol
13 Accepted 12 September 2015 over a hundred years ago; a model based on the Gibbs energy and ideal gas conditions; and
14 Available online xxx the Gibbs energy model with gas phase non-ideality included. The use of state-of-the-art
15 problem-solving tools, including mathematical software packages and process simulation
16 Keywords: programs, combined with reliable physical property databases for the equilibrium compu-
17 Ammonia synthesis tations, is emphasized. On one hand, the exercise gives students an opportunity to become
18 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,
20 Process simulation it gives them an opportunity to practice the use of the modern numerical problem-solving
tools. It also helps them master the complex issues involved in phase and chemical equi-
librium in reacting systems.
© 2015 Published by Elsevier B.V. on behalf of The Institution of Chemical Engineers.
1. Introduction engineering students to learn, and practice the use of, these 36
21Q2 The introduction of the personal computer in the early cise where the use of these tools can be practiced together with 38
22 nineteen-eighties, and the emergence of commercial Inter- the modeling of chemical equilibrium at various levels of rigor 39
23 net providers a few years later, leads to revolutionary changes with respect to the ammonia synthesis process. 40
24 in chemical engineering problem-solving. As a result of The industrial synthesis of ammonia from its elements is 41
25 these changes, numerical calculations are carried out nowa- considered by many as the most important technical inven- 42
26 days mostly by mathematical software packages such as tion of the twentieth century (Smil, 2001). This is because 43
27 Excel® , MAPLETM , MATHCAD® , MATLAB® , Mathematica® and large scale production of ammonia enabled production of fer- 44
28 POLYMATHTM (Shacham and Cutlip, 1999; Mahecha-Botero tilizers that leads to huge increase in crop yields, which in 45
29 et al., 2011). More complex calculations are carried out by com- turn enabled the expansion of the world’s population from 46
30 putational fluid dynamics (CFD) packages (Morscheidt et al., 1.6 billion people in 1900 to 6 billion at the end of the cen- 47
31 2013) and process simulation programs (such as Aspen, Chem- tury. The breakthrough in ammonia synthesis was brought 48
32 CAD and UniSim; see, for example, Shacham et al., 2009). about by Fritz Haber (Haber, 1920) and coworkers, who carried 49
33 Physical and thermodynamic property data needed for the out many experiments to determine the equilibrium constant 50
34 computation are routinely retrieved from property databases, of the ammonia synthesis reaction at various temperatures 51
35 such as DIPPR or NIST. It is very important for chemical 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 1–7
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
ECE 106 1–7
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52 conditions, high enough conversion of the elements H2 and Using Eq. (3) for a specified value of Ka , the molar extent 104
53 N2 to ammonia can be reached, which would justify develop- of the reaction (X) and the mole fractions and the partial 105
54 ment of a commercially viable large scale process. Haber and pressures of the various components at equilibrium condi- 106
55 le Rossignol (see p. 277 in Smil, 2001) carried out experiments tions can be calculated using the initial mole numbers. With 107
56 at atmospheric and at 30 atm pressures at various temper- inlet mole number of 1/2 for N2 and 3/2 for H2 , the outlet mole 108
57 atures in 1907. The results of the equilibrium constants at fractions are the following: X/(2 − X) for NH3 , (1 − X)/[2 × (2 − X)] 109
58 various conditions were reported by Haber (who received the for N2 , and 3 × (1 − X)/[2 × (2 − X)] for H2 (where X is number of 110
59 Nobel Prize in Chemistry in 1918 for proving the feasibility NH3 moles produced). Substituting these expressions and the 111
60 of this process) in his Nobel lecture (Haber, 1920). Haber and total pressure (Ptot ) into Eq. (3) yields: 112
calculated from the enthalpy (Hr ) and the entropy (Sr ) of 134
2. Problem background – equilibrium
the reaction at the same temperature. 135
composition in the ammonia synthesis reaction
Gr (T) = Hr (T) − TSr (T) (7) 136
aNH3 P̃NH3 ¯ NH3 where i is the stoichiometric coefficient (positive for prod- 142
97 Ka = = (2) 0
1/2 3/2
aN aH
1/2 3/2 1/2 3/2
P̃N P̃H ¯ N ¯ H ucts, negative for reactants), Hf,i is the heat of formation at 143
2 2 2 2 2 2
standard state and Cpi is the ideal gas heat capacity (at con- 144
P̃NH3
103 Ka = 1/2 3/2
(3) 1
In the original publication (Haber, 1920) one of the parameters
P̃N P̃H
2 2 is misprinted (498 instead of 4.98).
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ECE 106 1–7
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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148 where S0f,i is the entropy of formation at standard state of Table 1 – POLYMATH program for calculation of the
149 species i. equilibrium composition of H2 , N2 and NH3 using the HR
150 The exercise involves calculation the equilibrium concen- (Haber, 1920) correlation.
151 tration of ammonia at various temperatures and pressures No. Equation/# comment
152 using: (1) the HR correlation, (2) the Gibbs free energy with
153 the ideal gas assumption and (3) the Gibbs free energy with 1 # Calculation of ammonia synthesis equilibrium
composition
154 gas phase non-ideality included. The use of a mathematical
2 # by Haber–le Rossignol correlation
155 software package for the first two parts of the assignment
3 T = 573 # Reaction temperature (K)
156 is recommended, while the third part is best solved using a 4 P0 = 1 # Reference pressure (atm)
157 process simulation program. 5 Ptot = 200 # Reaction pressure (atm)
6 mLogKa = 2.1 + (1/4.571)*(9591/T − 0.00046*T + 0.85*1e−6*T2̂)
− 4.98 *log(T)/1.985
7 ˆ
Ka = 10(mLogK a ) # Chemical equilibrium coefficient in terms
3. Problem statement
of partial pressures
8 ˆ
f(X) = Ka *((1 − X)/2)(1/2)*(3*(1 − X)/2)ˆ(3/2)*(Ptot /P0 ) − X*(2 − X) #
158 (a) Calculate the percent equilibrium concentration of ammo-
Molar extent of the reaction
159 nia for nine temperatures (t = 473, 573, . . ., 1273 K) and four 9 X(min) = 0.01 # Lower bound for the extent of the reaction
160 pressures (P = 1, 30, 100 and 200 atm). Use the HR corre- 10 X(max) = 0.99 # Upper bound for the extent of the reaction
161 lation (Eq. (5)) to calculate Ka and solve the nonlinear 11 N2 = (1 − X)/(2*(2 − X)) # Mole fraction N2
162 equation (Eq. (4)) for the extent of the reaction (X). Sum- 12 H2 = 3*(1 − X)/(2*(2 − X)) # Mole fraction H2
163 marize the results for percent of conversion to ammonia 13 NH3 = X/(2 − X) # Mole fraction NH3
164 in a tabular form and compare with the values in the table
165 provided by Haber (1920). numbers shown in this table are not part of the program; they 203
166 (b) Redo (a) but this time calculating Ka using the Gibbs energy were added as references for the explanations that follow. 204
167 of the reaction (Eq. (6)). Retrieve the required thermo- Most of the program in Table 1 is self-explanatory. In lines 6 205
168 dynamic property data and correlations from the NIST and 7 Ka is calculated using Eq. (5). In line 7, Eq. (4) is rewritten 206
169 database (Linstrom and Mallard, 2015). Summarize the in the form of f (X) = 0. Lower and upper bounds on X should 207
170 percent conversion to ammonia results in tabular form, be provided in order to solve this nonlinear algebraic equa- 208
171 and plot the % conversion obtained in (a) and (b) on the tion (NLE) by POLYMATH. These bounds are specified in lines 209
172 same graph. Calculate and compare the percent difference 9 and 10, respectively. In lines 11–13 the equilibrium mole 210
173 in the equilibrium ammonia concentrations obtained as fractions of N2 , H2 and NH3 are calculated. The results for 211
174 results in (a) and (b) for the corresponding temperature the case shown (T = 573 K, Ptot = 200 atm, results rounded to 212
175 and pressure values. four significant digits) are: Ka = 0.07007; X = 0.7718; N2 (mole 213
176 (c) Calculate the percent of equilibrium concentration of fraction) = 0.0929; H2 = 0.2787; and NH3 = 0.6284. In the table 214
177 ammonia at the nine temperatures and three pressures presented by Haber the value shown for Ka is 0.070 and the 215
178 (P = 30, 100 and 200 atm) using the “Gibbs reactor” mole percent of NH3 is 62.8. Thus, the results match (up to the 216
179 module of the ChemCAD (www.chemstations.com/), significant figures) with those shown by Haber (1920). 217
180 or a similar process simulation program with the The use of MATLAB can be preferable in order to carry 218
181 Soave–Redlich–Kwong (SRK) thermophysical property out repetitive calculations for a large number of temperature 219
182 package. (A property package available in ChemCAD, as in and pressure values. The MATLAB function for calculating 220
183 most of the simulation programs.) Summarize the results Ka and the equilibrium compositions can be automatically 221
184 of percent conversion to ammonia in a tabular form and generated by POLYMATH, as demonstrated, for example, by 222
185 plot the % conversion obtained in (a) and (c) on the same Cutlip et al. (2009). The library function fzero.m is used to 223
186 graph. Calculate and compare the percent difference in solve the NLE f(X) = 0. The complete MATLAB program for 224
187 the equilibrium ammonia concentrations obtained in (a) this part of the assignment is available for download at: 225
188 and (c) for the corresponding temperature and pressure ftp://ftp.bgu.ac.il/shacham/AmmoniaSynthesis. 226
189 values. The complete set of the calculated values of Ka and per- 227
190 (d) Discuss the significance of the differences between the centage of NH3 at equilibrium is shown in Table 2. Comparing 228
191 ammonia conversion results obtained using the various these results with the numbers shown in Haber’s (1920) table 229
192 methods. shows that all the numbers match (up to the significant fig- 230
ures) with those shown by Haber. The accuracy of the results 231
4. Problem solution that at that time all the calculations were carried out manu- 233
ally and the calculation of the extent of the reaction involves 234
195 The solution of Eq. (4) for the extent of the reaction, X, requires using Ka values obtained from the Gibbs free energy 237
198 POLYMATH and MATLAB packages. The POLYMATH program free energy (Eq. (6)) and the mole fractions of N2 , H2 and NH3 239
199 for calculating the mole fractions of N2 , H2 and NH3 at equilib- at equilibrium for specified temperature and pressure condi- 240
200 rium at specified temperature and pressure values is shown in tions is shown in Table 3. The coefficients of the equations 241
201 Table 1. Note that a text starting with the “#” sign and ending for calculating Hr (T), Eq. (8), and Sr (T), Eq. (9), are from 242
202 with the end of the line is interpreted as a comment. The line the NIST database. They are shown in lines 7 through 15 in 243
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ECE 106 1–7
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
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244 Table 3. Observe that the common validity range of these between the Haber–le Rossignol and the Gibbs energy models 260
245 coefficients is from 500 K to 1000 K. For temperatures below for the value of Ka . 261
246 500 K, a different set of parameter values needs to be used To carry out the calculations for the complete set of tem- 262
247 for nitrogen; for temperature values above 2000 K, the param- perature and pressure values, a MATLAB program is used. In 263
248 eters for hydrogen should be modified. The use of the NIST the MATLAB program, different parameter value sets are used 264
249 parameters requires setting the reference pressure at 1 bar according to the validity ranges specified in the NIST database. 265
250 (line 2). The value of Gr (T) (Eq. (7)) is calculated in line 19 The complete set of the calculated values of Ka and the per- 266
251 and the corresponding Ka value (Eq. (6)), in line 20. The cal- centage of NH3 at equilibrium is shown in Table 4. A plot of 267
252 culations of the extent of the reaction and the equilibrium the equilibrium NH3 mole percent values obtained by the HR 268
253 mole fractions of N2 , H2 and NH3 are done in the same way correlation and Gibbs free energy calculated from NIST prop- 269
254 as explained in the previous section. The results for the case erty data vs. temperature is shown in Fig. 1. Observe that the 270
255 shown (T = 573 K, Ptot = 200 atm) are: Ka = 0.06722; X = 0.7687; N2 results obtained by the two methods are essentially indistin- 271
256 (mole fraction) = 0.09391; H2 = 0.2817; and NH3 = 0.6243. Com- guishable. Examining the differences between the equilibrium 272
257 paring these values with the values of the HR correlation NH3 mole percent values obtained by the HR correlation and 273
258 shows 4.06% difference in the Ka value and 0.96% difference by the Gibbs free energy shows that the differences follow the 274
259 in the NH3 mole fraction value. Thus, there is adequate match general trend of the equilibrium ammonia concentration (% 275
T = 473 K and P = 1 atm) and −4.46% (at T = 1173 and P = 1 atm). 278
Table 3 – POLYMATH program for calculation of the Such differences are very reasonable considering the four 279
equilibrium composition of H2 , N2 and NH3 using the orders of magnitude differences between the numbers shown 280
Gibbs free energy and NIST data.
in Tables 2 and 4. 281
No. Equation/# comment
1 # Ammonia synthesis − Gibbs energy 4.3. Calculation of the equilibrium concentrations 282
2 P0 = 0.9869233 # Reference pressure (atm, 1 bar) using the ChemCAD program 283
3 Ptot = 30 # Reaction pressure (atm)
4 T = 573 # Reaction temperature (K)
We have used the “Gibbs reactor” module of ChemCAD 284
5 T0 = 298.15 # Reference temperature
with the SRK thermophysical property package to calculate the 285
6 R = 8.314 # Gas constant J/mol*K
7 # Enthalpy and entropy equation coefficients from the NIST
database
8 # Common validity range: 500–1000 K
9 A = 19.99563 − 19.50583/2 − 3*33.066178/2
10 B = 49.77119 − 19.88705/2 + 3*11.363417/2
11 C = −15.37599 + 8.598535/2 − 3*11.432816/2
12 D = 1.921168 − 1.369784/2 + 3*2.772874/2
13 E = 0.189174 − 0.527601/2 + 3*0.158558/2
14 F = −53.30667 + 4.935202/2 + 3*9.980797/2
15 G = 203.8591 − 212.39/2 − 3*172.707974/2
16 t = T/1000
17 dHr = (A*t + B*t2̂/2 + C*t3̂/3 + D*t4̂/4 − E/t + F)*1000 #Enthalpy of
the reaction J/mol
18 dSr = A*ln(t) + B*t + C*t2̂/2 + D*t3̂/3 − E/(2*t2̂) + G # Entropy of the
reaction J/mol*
19 DelG = dHr − T*dSr # Reaction Gibbs energy, J/mol
20 Ka = exp(−DelG/(R*T)) # Reaction equilibrium coefficient
21 ˆ
f(X) = X*(2 − X) − Ka *((1 − X)/2)(1/2)*(3*(1 ˆ
− X)/2)(3/2)*(P tot /P0 ) #
Extent of the reaction
22 X(min) = 0.01 # Lower bound for the extent of the reaction
23 X(max) = 0.99 # Upper bound for the extent of the reaction
24 N2 = (1 − X)/(2*(2 − X)) # mole fraction N2 Fig. 1 – Comparison of the equilibrium NH3 % mole values
25 H2 = 3*(1 − X)/(2*(2 − X)) # mole fraction H2
obtained by the HR correlation (p *H) and Gibbs free energy
26 NH3 = X/(2 − X) # mole fraction NH3
calculated from NIST property data (p *N).
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ECE 106 1–7
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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 Percentage of NH3 at equilibrium
286 equilibrium ammonia concentration at the various tempera- of the differences between the equilibrium NH3 mole percent 304
287 tures and pressures. values obtained by the Gibbs free energy and ChemCAD shows 305
288 Part of the ChemCAD flow diagram and worksheet for com- that there are noticeable differences in the lower tempera- 306
289 putation of equilibrium ammonia concentration at T = 500 ◦ C ture region (473 K through 873 K), while at higher temperatures 307
290 and P = 100 atm is shown in Fig. 2. Feed flow rate of 2 kg mole/h the differences are essentially zero. Considering the gas phase 308
291 (0.5 kg mole/h of N2 , 1.5 kg mole/h H2 ) enters the Gibbs reactor non-ideality increases the mole fraction of ammonia at equi- 309
292 (No. 1), which is kept at a constant temperature of T = 500 ◦ C librium, the largest increase is by 1.32% at T = 573 K and 310
293 and a constant pressure of 100 atm. Only the gas phase prod- P = 30 atm. While the ChemCAD results imply a relatively small 311
294 uct exits the reactor with the following mole fraction values: influence of the gas phase non-ideality, other computational 312
295 N2 = 0.223655, H2 = 0.670966 and NH3 = 0.105379. Thus, the per- studies (see for example, pp 655 and 656 in Sandler, 1999) 313
296 cent conversion to ammonia at these conditions is 10.53%. have shown up to 10% increase in the extent of the ammonia 314
297 The complete set of the percentage of NH3 values at equi- synthesis reaction as result of the gas phase non-ideality. 315
300 plotted in Fig. 3 and compared to the equilibrium NH3 mole results obtained by the different methods 317
301 percent values obtained by the Gibbs free energy with NIST
302 property data. On this scale the results obtained by the two In part (a) of the assignment the results shown in the table 318
303 methods are essentially indistinguishable. Examining the plot presented by Haber (1920) are compared with the percentage 319
Fig. 2 – ChemCAD flowsheet for computation of equilibrium ammonia concentration at T = 500 ◦ C and P = 100 atm.
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ECE 106 1–7
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
ECE 106 1–7
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P = 30 atm P = 100 atm P = 200 atm course include all the usual set of required undergraduate 349
4 873 1.46 4.57 8.42 dynamics, proficiency is essential in non-ideal phase and 354
that the exercise helps them better understand some of the 359
6. Conclusions
Fig. 3 – Comparison of the equilibrium NH3 % mole values The mathematical models employed for the equilibrium 373
obtained by the HR correlation (p *H) and the CHEMCAD computation include a regression model, based on experimen- 374
equilibrium reactor module (p *CC). tal equilibrium data obtained by Haber and le Rossignol over a 375
hundred years ago (see Smil, 2001); a model based on the Gibbs 376
free energy assuming ideal gas conditions; and a model based 377
320 of NH3 at equilibrium calculated using Eq. (5). These results
on the Gibbs energy with gas phase non-ideality included. 378
321 match up to the significant figures shown by Haber. Thus, the
Carrying out this exercise gives the students an opportu- 379
322 difference in the numerical results can be explained by the
nity to become familiar and to appreciate the precision of the 380
323 limitation on the number of digits of the computational tools
experimental work and the manual calculations that were car- 381
324 that were available in the nineteen-twenties.
ried out more than a hundred years ago. The exercise also 382
325 In part (b) the equilibrium concentrations using Ka val-
helps them to master the complex issues involved in phase 383
326 ues obtained from Gibbs free energy are compared with those
and chemical equilibrium in reacting systems. 384
327 obtained by the HR correlation. Here the percent deviations
328 of the NH3 equilibrium concentration are distributed between
329 +3.19% (at T = 473 K and P = 1 atm) and −4.46% (at T = 1173 and Appendix A. Supplementary material
330 P = 1 atm). The most probable source of the differences in this
331 case is the experimental error, as the uncertainty of the phys- The POLYMATH and MATLAB programs used in this 385
332 ical property data used for the Gibbs energy computation is study are available at the site: ftp://ftp.bgu.ac.il/ 386
333 considered to be below 1%. shacham/AmmoniaSynthesis 387
334 The source of the differences in the NH3 mole fractions
335 between parts (c) and (b) is the use of realistic fugacity
336 coefficients for calculation of Ka . These differences are limited
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ECE 106 1–7
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001
ECE 106 1–7
ARTICLE IN PRESS
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ECE 106 1–7
synthesis. Education for Chemical Engineers (2015), http://dx.doi.org/10.1016/j.ece.2015.09.001