HUDPHi EQUILIBRIA

ELSEVIER Fluid Phase Equilibria 104 (1995) 261-275

Vapor-liquid-solid equilibria in the system NH3-CO2-H20 from around 310 to 470 K: New experimental data and modeling
F. Kurz, B. Rumpf and G. Maurer
Lehrstuhl fiir Technische Thermodynamik, Univevsitfft Kaiserslautern, D-67653 Kaiserslautern (Germany)
Keywords: experiments, data, gas solubility, weak electrolytes, ammonia, carbon dioxide, water, correlation Received 12 January 1994;accepted in final form 29 August 1994

ABSTRACT
As part of an ongoing project dealing with experimental and theoretical work on the solubility of weak electrolyte gases like ammonia, carbon dioxide, sulfur dioxide, hydrogen sulfide or hydrogen cyanide in aqueous phases, the simultaneous solubility of ammonia and carbon dioxide in water was measured in the temperature range from 313 K to 353 K at total pressures up to about 0.7 MPa. The model proposed by Edwards et al. (1978) is used to correlate the new as well as literature data (G6ppert and Maurer (1988), Miiller et al. (1988)). Experimental and calculated results are reported and compared.

INTRODUCTION
The solubility of weak electrolyte gases like ammonia, carbon dioxide, sulfur dioxide or hydrogen cyanide in aqueous phases must be known for process design in many technical applications. Typical examples are applications in the chemical and oil related industries, the production of fertilizers or applications in the field of environmental protection. Correlating and predicting the simultaneous solubility of ammonia and sour gases in aqueous phases is an extremely difficult task, partially caused by chemical reactions in the liquid phase but also due to the possible formation of solid phases. Continuing earlier work on the simultaneous solubility of ammonia and sour gases in aqueous phases (GSppert and Maurer (1988), Mfiller et al. (1988), Bieling et al. (1989)), this contribution reports on new experimental results for the simultaneous solubility of ammonia and carbon dioxide in water in the temperature range from 313 to 353 K, ammonia and carbon dioxide molalities up to about 12 and 10 mol/kg and total pressures up to about 0.7 MPa. From the new data and those published earlier (GSppert and Maurer (1988), Mfiller et al. (1988)), interaction parameters for a modification of Pitzer's model were determined. The correlation describes the underlying experimental data nearly within the experimental uncertainty.

67653

1Correspondence to: G. Maurer, Lehrstuhl fiir Technisehe Thermodynamik, Universit~t Kaiserslautern, D Kaiserslautern, Germany

0378-3812/95/$09.50 1995 - Elsevier Science B.V. All rights reserved SSD10378-3812 (94) 02653-X

262

F. Kur= et al. /Fluid Phase Equilibria 104 (1995) 261-275

EXPERIMENTAL
The apparatus and procedure are basically the same used in a previous investigation (G6ppert and Maurer (1988)), therefore only some essentials are repeated here. A thermostated, evacuated cell is filled with a known amount of water. After adding a known amount of ammonia, the cell is filled stepwise with carbon dioxide. After each addition, the mixture is equilibrated and thereafter temperature, pressure and the gas phase volume are measured. Furthermore, a small amount of the gas phase is withdrawn from the cell and analyzed by gas chromatography. From the results for the composition of the vapor phase, the volume of the vapor phase and the total amounts of each substance charged into the cell, the overall amounts of ammonia and carbon dioxide dissolved in the (liquid + solid) phase are calculated. The temperature is measured by a calibrated resistance thermometer with a maximum uncertainty of -4- 0.1 K. The pressure is determined by a pressure transducer mounted on bottom of the cell with an uncertainty of -4- 0.5 kPa. The composition of the vapor phase was determined by using a gas chromatograph with a column of Hayesep P and a thermal conductivity cell. Before and after each series of measurements, the gas chromatograph was calibrated.

SUBSTANCES
Ammonia (> 99.999 moles percent) and carbon dioxide (> 99.995 moles percent) were purchased from Messer-Griesheim, Ludwigshafen and used without further purification. Water was deionized and further purified by vacuum distillation.

RESULTS
The experimental results for the solubility of ammonia and carbon dioxide in water at temperatures from 313 to 353 K are given in tables 1 to 3. Two overall molalities of ammonia (fftNH3 ~ 6 and 12 mol/kg) were investigated at total pressures up to about 0.7 MPa corresponding to overall amounts of carbon dioxide up to about 10 mol/kg. For some of the solutions investigated, the appearance of a solid phase of NH4HC03 was observed, therefore the number of phases is also given in tables 1 to 3. But the numbers given in tables 1 to 3 for the molality of ammonia and carbon dioxide were not corrected for the precipitated salt. Tables 1 to 3 also contain the estimated maximum uncertainties of the total and partial pressures which were calculated considering the propagation of all experimental uncertainties. In Fig. 1 the results for the total pressure at 333 K are plotted vs. the overall molality of carbon dioxide. Adding carbon dioxide to an ammoniacal solution at first results in a decrease in the total pressure as both ammonia and carbon dioxide are converted into ionic, nonvolatile form. After passing a minimum, a steep increase in the total pressure is observed. Increasing the overall amount of ammonia shifts the minimum to higher overall amounts of carbon dioxide. For the 12 molal ammoniacal solution and a carbon dioxide molality of about 8 mol/kg, a slight change of slope in the total pressure curve is observed, thus indicating the formation of a solid

F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

263

Table h Exp. results for the solubility of ammonia and carbon dioxide in water at 313 K

K 313.12 313.16 313.16 313.15 313.17 313.15 313.16 313.15 313.13 313.17 313.11 313.10 313.10 313.09 313.10 313.09 313.12 313.11 313.12 313.11

mol/kg 6.318 6.320 6.324 6.328 6.331 6.333 6.333 6.333 6.333 6.334 11.823 11.825 11.828 11.831 11.834 11.838 11.841 11.842 11.842 11.843 +0.009 4.0.009 4.0.009 4.0.009 4-0.009 4-0.009 4-0.009 4-0.009 4-0.009 4-0.009 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01

mol/kg 0 0.722 1.542 2.353 3.156 3.954 4.646 5.202 5.760 6.039 0 0.965 2.024 3.080 4.224 5.379 6.526 7.667 8.764 9.707 +0.003 4.0.006 4.0.006 4-0.006 4-0.007 4-0.009 4-0.010 4-0.012 4-0.016 4-0.003 4-0.005 4-0.005 4-0.006 4-0.006 4-0.007 4-0.007 4-0.008 4-0.008 24.9 21.0 15.1 9.2 4.6 1.6 0.5 0.2 0.0 0.0 53.0 47.4 39.5 31.7 22.6 12.6 4.9 2.7 1.6 0.9

kPa +1.0 4-1.1 4.1.1 4-0.9 4-0.7 4-0.4 4-0.4 4-0.2 0 0.1 0.3 1.1 5.2 25.4 92.3 143.4 287.1 504.4 4-1.5 4-1.7 4-1.6 4-1.6 4-1.5 4-1.3 4-0.9 4-0.8 4-0.7 4-0.7 0 0.1 0.3 0.4 0.9 3.5 15.8 29.1 41.0 62.5

kPa 4-0.1 4-0.2 4-0.3 4-0.7 4-1.9 4-4.0 4-7.5 4-20.1 4-44.8 4-0.1 4-0.3 4-0.4 4-0.4 4-0.7 4-1.5 4-1.9 4-2.4 4-3.3

kPa 31.5 27.4 22.3 17.5 16.5 33.5 99.6 150.2 293.7 511.3 59.5 52.7 45.4 37.3 28.8 21.4 25.6 36.8 48.0 69.0 +0.7 4-0.7 4-0.7 4-0.7 4-0.6 4-1.3 4-3.2 4-6.6 4-19.3 4-44.2 4-0.8 4-0.8 4-0.8 4-0.8 4-0.7 4-0.7 4-0.8 4-1.0 4-1.3 4-2.1 2 2 2 2 2 2 3 3 3 2 2 2 2 2 2 2 3 3 3

phase of N H , H C O 3 in the cell. This was also confirmed by analyzing the solid phase withdrawn from the cell after the completion of a series of measurements. In Figs. 2 and 3, the partial pressures of ammonia and carbon dioxide are shown for the same series of measurements. W h e n fftco2/fftNH3 is less than about 0.5, carbon dioxide is dissolved nearly completely chemically, therefore the partial pressure of carbon dioxide is very small. In the region where nearly all a m m o n i a is spent by chemical reactions, a steep increase in Pco2 is observed. T h e p a r t i a l pressure of ammonia decreases with increasing overall amount of carbon dioxide whereas the partial pressure of water does not change significantly. The same behaviour is observed at the other t e m p e r a t u r e s investigated. At 313 K, the formation of solid NH4HCO3 was observed for b o t h series of measurements, i.e. a 6 and 12 molal ammoniacal solution, whereas at 353 K the formation of a solid phase could not be detected from the total pressure curve.

MODELING
Fig. 4 shows a scheme of the model applied to correlate the data. The model is an extension and modification of the t h e r m o d y n a m i c framework developed by Edwards et al. (1978). Due to chemical reactions in the liquid phase, ammonia and carbon dioxide are not only present in neutral, b u t also in ionic form. To calculate the true molalities in the liquid phase, the

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F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

Table 2: Exp. results for the solubility of a m m o n i a and carbon dioxide in water at 333 K

T K
333.22 333.17 333.14 333.12 333.14 333.15 333.15 333.14 333.15 333.18 333.14 333.10 333.10 333.08 333.14 333.11 333.15 333.12 333.14 333.14 333.12

~nNtG[AmNH3 fgtC02]ATT~CO2
mol/kg 6.027 6.030 6.036 6.042 6.048 6.053 6.057 6.060 6.061 6.061 11.910 11.918 11.926 11.937 11.947 11.957 11.964 11.968 11.969 11.970 11.970 +0.011 +0.011 +0.011 +0.010 +0.010 4-0.010 +0.010 +0.010 4-0.010 4-0.010 4-0.013 +0.013 +0.012 +0.012 +0.012 4-0.012 4-0.011 +0.011 4-0.011 4-0.011 4-0.011 0 0.517 1.120 1.720 2.329 2.927 3.526 4.161 4.683 4.957 +0.003 +0.003 +0.003 4-0.003 +0.003 4-0.003 4-0.003 4-0.003 4-0.003 mol/kg

PNHa ]ApNHa kPa

50.4 45.4 37.3 28.0 19.7 12.3 6.8 3.2 1.7 1.1 112.6 98.2 82.8 63.8 44.9 27.0 13.9 6.5 5.7 4.2 2.6 +1.6 +1.6 +1.5 +1.3 4-1.1 +0.9 4-0.7 4-0.5 +0.5 4-0.4 4-2.0 4-2.0 4-1.9 4-1.8 4-1.6 4-1.3 4-0.9 4-0.6 4-0.6 4-0.5 4-0.5

Pco2 [Apc02 kPa

0 0.2 0.9 2.5 7.0 19.9 55.1 169.9 410.5 648.0 0 0.3 0.8 2.2 5.7 18.2 65.6 225.1 274.1 340.6 488.2 +0.2 +0.3 +0.3 4-0.6 +1.4 4-3.3 4-7.8 4-18.5 4-32.2 4-0.2 +0.2 4-0.3 4-0.5 +1.2 4-3.1 4-6.6 4-6.2 4-8.1

p
68.3 62.3 55.0 48.3 44.6 49.8 80.1

] Ap kPa
+0.9 +0.9 +0.9 +0.9 +0.8 4-1.0 4-2.4 4-6.5 4-17.2 4-30.9 4-1.1 4-1.1 4-1.1 +1.0 4-1.0 4-0.9 4-2.1 4-5.3 4-5.0 +6.8 4-11.9

7[

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3

190.8 429.6 667.0 129.5 114.9 98.7 81.9 66.8 61.3 95.0 247.4 295.8 360.7

0 1 . 0 8 1 4-0.003 2.179 3.321 4.444 5.565 6.645 7.705 8.066 8.814 9.693 4-0.003 4-0.003 4-0.003 4-0.003 +0.003 4-0.003 4-0.003 4-0.003 4-0.003

4-13.1 506.9

condition for chemical equilibrium for each reaction R is applied:

g n ( T ) = H a 7 ',R

(1)

When a solid phase of pure NH4HCOa is present, the following equation for equilibrium between the solid and the liquid phase holds:

KNH4HCO3(T) = aNH+ . aHCO[ .

(2)

The balance equations for the number of moles of ammonia, carbon dioxide and water yield:

fiNHa = nlVHa + nlVH+ + nNH2CO0- + nNH,tlCOa(s) no02 = rico2 + nHCO~ -l- riCO ~- + nNH2CO0- -l- nNH4HCOa(s) nil20 = nil20 + nOH- + nHCO ~ + nco~- + nNH, HCOa(,)
Together with the charge balance

(3) (4) (5)

nNH+ + nil+ = nHCO~ + 2 n c o ~- + nNH2CO0- + nOH-

(6)

F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-2 75

8.
"s Q.

265

ffi 6.o5

7.
6.

tl.95 5.

\,,

4.

3.

/
-

2~

1 .t
O"
0 2 4

10

Figure I: Total pressure in the system NHs-CO2-H20 &t 333 K. o, C]: exp. results, this work. : calc. results, this work. - ...... : calc. solubility limit for the precipitation NH4HCO 3. this set of equations can be solved in an iterative procedure to yield the true number of moles of each species present in the liquid phase and the number of moles of solid NH4HCO3. The condition of solid-liquid equilibrium is only taken into account when in a preliminary calculation - where the formation of a solid phase was neglected - the right hand side of eq. (2) proved to be larger than the left hand side. The total pressure and the composition of the vapor phase were calculated from p. y~- ~ ' = p~. ~ "
,,,

exp( v~"-~-. (P y p~) ). aw

, . exp(V

(7)
)'mi"7i
.

p.yi .~

= H~.,o (T,p~,)

(m)

"R'-~T"

i=NS3, CO2.

(8)

The calculation requires the knowledge of the temperature dependent equilibrium constants K~-Ks, the solubility constant KNH, HC03, the activity coefficients of all species present in the liquid phase, Henry's constants --,,~ l-l!') for ammonia and carbon dioxide in pure water, the vapor pressure, molar volume and dielectric constant of water as well as information on the vapor phase nonideality and the partial molar volumes of the dissolved gases. The equilibrium constants KI to Ks were taken from Bieling et al. (1989). Henry's constants for ammonia and carbon dioxide were obtained from Bieling et al. (1989) and Rumpf and Maurer (1993a), respectively. To a first approximation, the solubility constant KNH4nco3 was estimated from the numbers for the standard entropies and enthalpies of formation for NH +, HCO 3 and NH4HCO3 given by Wagman et al. (1982). The dielectric constant of pure water was taken from Bradley and Pitzer (1979). The vapor pressure and the molar volume of water were taken from Saul

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F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

~,/(n~/~) =6.o5
7 O.

5,
4' 3" 2"
1"

/
0

0';

10

Figure 2: Partial pressure of carbon dioxide in the system NH3-CO2-H20 at 333 K. o, 1:3: exp. results, this work. : calc. results, this work. - ...... :calc. solubility limit for the precipitation NH4HCO3. and Wagner (1987). A truncated virial equation of state was used to calculate the fugacity coefficients. Pure component second virial coefficients Bi,; were calculated from a correlation based on data recommended by Dymond and Smith (1980). Mixed second virial coefficients Bid were taken from Hayden and O'Connell (1975). The partial molar volumes of the dissolved gases were calculated as recommended by Brelvi and O'Connell (1972). There exist few reliable methods to calculate activity coefficients of both neutral and ionic species in concentrated electrolyte solutions. A well established method is the Pitzer (1973) equation for the excess Gibbs energy of an aqueous electrolyte mixture:

R.T.nw.M,o

=fl(I)+

E mi.mj. (id)#~

(~)+/~!~).f2(I) ) +

E mi.mj.mk.ri,j,k. (id,k)#~,

(9)

where fl and f2 are functions of ionic strength I and/~!0) /~9) and rl,/,k are binary and ternary rliJ ' r $1J interaction parameters. The resulting expressions for the activity of a dissolved species and of water are given elsewhere (Rumpf and Maurer, (1993a,b)). As 8 dissolved species are considered to be present in the liquid phase, that equation in principle requires 72 binary and 120 ternary parameters. But this prohibitively large number of unknowns can be reduced by the following ~(0) approximations: The binary parameter ~'NX3,NH3 Was obtained from the binary subsystem ammonia-water (cf. Rumpf and Maurer (1993b)). As the amount of neutral carbon dioxide in g(o) the liquid phase remains small even at high pressures, the binary parameter ~'co2,co2 was set

F. Kurz et al, / Fluid Phase Equilibria 104 (1995) 261 275

267

itz~--N/(
mdl~)
1 0.8

0.6" 0.4.1~
0.2. 6"05" ~-

O"

r/Cmn/kg)

I0

Figure 3: Partial pressure of ammonia in the system NH3-CO2-H20 at 333 K: o, Q: exp. results, this work. - - : calc. results, this work. - ...... : calc. solubility limit for the precipitation NH4HCO3. vapor NH3 C02 H20

NH3

C02

H20
(1'

NHa + H20 ~ NH + + O H -

CO2 + n20 ~ HCO~ + H+ (2', HCO~ = CO~- + H+ (3' NH3 + HCO3 = NH2COO- + H20 (4',
H20 = H+ + O H (5'

NH4HCO3

solid '

Figure 4: VLE, SLE and chemical reactions in the ammonia-carbon dioxide-water system to zero. The concentration of H + and O H - is rather small in comparison to other species, thus all interaction parameters between those and other solute species were set to zero. The ionic strength dependence of the second virial coefficient in eq. 9 is questionable for interactions

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F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

Table 3: Exp. results for the solubility of a m m o n i a and carbon dioxide in water at 353 K

T
K 353.23 353.23 353.23 353.22 353.22 353.23 353.23 353.23 353.23 353.22 353.23 353.16 353.18 353.14 353.13 353.17 353.12 353.17 353.11 353.12 353.18 353.19

mNH3 ]A~tNH3
mol/kg 6.831 6.838 6.846 6.852 6.858 6.864 6.870 6.876 6.881 6.883 6.884 11.977 11.986 11.998 12.011 12.024 12.038 12.052 12.063 12.073 12.077 12.078 4-0.012 4-0.011 4-0.011 4-0.011 4-0.011 4-0.011 4-0.010 4-0.010 +0.010 4-0.010 4-0.010 4-0.015 4-0.015 4-0.014 4-0.014 4-0.014 4-0.013 4-0.013 4-0.013 4-0.012 4-0.012 4-0.012

r=llC02]AITIC02
mol/kg 0 0.609 1.228 1.686 2.140 2.595 3.043 3.575 4.116 4.458 4.698 0 0.850 1.705 2.579 3.430 4.304 5.179 6.003 6.847 7.348 7.602 4-0.003 4-0.006 +0.006 4-0.007 4-0.007 4-0.009 4-0.010 4-0.013 4-0.016 4-0.018 +0.003 4-0.006 -t-0.006 4-0.006 +0.007 4-0.008 4-0.009 4-0.012 4-0.015 4-0.008

PNH3 ]ApNHs
kPa 114.1 100.2 84.2 72.4 60.5 48.5 37.4 25.9 16.7 12.1 9.9 210.5 192.8 171.1 146.3 121.6 95.3 69.6 47.7 30.3 22.8 20.0 +3.3 4-3.8 4-3.6 4-3.5 4-3.2 4-3.0 4-2.8 +2.3 4-1.9 +1.7 4-1.6 +3.7 +3.5 4-3.4 4-3.3 4-3.1 4-3.1 4-2.8 4-2.3 4-1.7 4-1.3 4-1.1

PC02 [APe02
kPa 0 1.2 4.3 8.8 16.7 31.3 58.7 124.7 271.5 440.7 619.6 0 0.8 2.5 5.8 11.7 23.9 52.7 117.0 4-0.3 4-0.3 4-0.5 4-0.7 4-1.4 4-3.0 4-5.8 4-11.1 4-17.1 4-21.6 4-0.8 4-1.0 4-1.2 4-1.6 4-2.6 4-4.3 4-7.1 4-12.8 4-19.5 4-27.5

P
154.8 141.7 129.5 122.3 118.5 121.2 137.3 191.5 329.1 492.9 670.2 252.5 232.6 211.6 190.2 171.0 157.1 160.7 203.3 345.5 526.6 658.9

I Ap
kPa 4-1.2 4-1.2 4-1.2 4-1.2 4-1.1 4-1.2 4-1.8 4-3.8 4-8.8 4-15.4 4-23.4 4-1.6 4-1.6 4-1.6 4-1.5 -t-1.5 4-1.4 4-1.6 4-3.5 4-8.4 4-14.3 4-18.8

lr
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

277.1
465.9 600.6

between a neutral and a charged component, therefore all parameters fl~,~) for interactions between a neutral and a charged component were set to zero. To further reduce the number of parameters, all parameters for interactions between two or more species with the same sign of charge were neglected. A m m o n i a and carbon dioxide are ra(o) r NHa,NHa,C02 rely simultaneously present in significant amounts, therefore, parameters ~NHa,C02' and rNH3,Co2,co2 were set to zero. It furthermore seems to be reasonable to neglect all t e r n a r y p a r a m e t e r s involving one neutral and two ionic species with the same sign of charge. W i t h these assumptions, the remaining number of parameters is 37 (14 binary and 23 ternary). The binary p a r a m e t e r s g(0) /..i,NH+, ;q(o) r.i,HCO~ , g(0) t.,i,CO ~_ and ~(0) ~'i,NHICO0- (i=NHa or CO2) describe the effect of the dissolved ions on the solubility of a m m o n i a and carbon dioxide. T h e determination of the b i n a r y p a r a m e t e r s for interactions between a m m o n i a and the dissolved ions was done as follows: W i t h the above assumptions and considering only binary parameters, the activity coefficient of a m m o n i a is:
l" 7;qH3 ---- 2" (raN. 3
~(o) /~(]~)H3,NH3 "1- TrtN" 2 " t"NH 3,N"+ +

[nHCO~

. R(o)

r-NH3,.CO ~

F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

269 (10)

~(o)
~ - m c o ~ - " ~"NH~,CO~- -~ m N H ~ C O 0 -

" ~'NH~,NH~CO0- :

:~(o)

Neglecting the concentrations of H + and OH-, the charge balance yields

mNlf4+ ~ m H C O 7 + 2 . m o o ~- + m N m c O O

(11)

From eq. (10) it follows

= 2. . + m.oo " :fifo) , N.3,N.: +

/~(o)

+mco~- . : :~(o)
-~mNH2 cO0" ~" N H 3 , N H +

r ~Nn3,CO~- J
:~(o)
-~ ~ ' N m , N H ~ C O 0 )) "

(12)

With the definition (cf. Rumpf and Maurer (1993a)) B G,MX () = u+ " :~(o) IJG,M + I/_ /3(o) G,X that equation yields
lrtTNH3
---

(13)

2" (mNH3

" 1.4(0) ~'NH3,NH3 -~ m H C O [

. B(o) NH3,NH4HC03

-~-mco]- " /:~(0) ~NH3,(NH4)2C03 "~ mNH~ c O 0 - " B(0) N H3,N H2COO N If4 % /

(14)

which is a similar equation we find for the solubility of a nonreacting gas in an aqueous mixture containing strong electrolytes (for details see Rumpf and Maurer (1993a)). For the present :~(o) case, we can therefore arbitrarily set ~Nn3,NH+ ' to zero. Parameters :~(o) ~(o) r"NH3,1ICO[' ~'NII3,CO~and
~(N)s,NH2CO0 _ were then determined from fits to the new experimental results for the partial pressure of ammonia as well as to the results reported by GSppert and Maurer (1988) and Mfiller et al. (1988). The temperature dependence of the binary parameters was approximated by
~N(O)
H3,1 = aNH3,i ~-

(T/K) "

bN H3,____..~

(15)

Parameters aNH3, i and bNH3,i were then simultaneously determined in the temperature range from 313.15 to 473.15 K from fits to the partial pressure of ammonia. The results are given in table 4. Attempts to include ternary parameters did not yield a significant improvement, therefore all ternary parameters for interactions between ammonia and NH4 +, H C O ~ or CO~- were finally set to zero. In the next step, parameters describing interactions between carbon dioxide and the dissolved ions were determined. Following the argument given above, there are three remaining binary parameters x {~(o) ~(o) R(o) COa,HCO~I ~'CO~,CO~-' ~'CO~,NH2CO0-/

and seven ternary parameters (TCO2,GO2,NH~ , TCO~,CO,,HCO[ , TC02,CO,,CO~_ , TCO2,CO2,NHaCO0_ , rCO2,NH,+,"col' TCO2,NH,+,co]- ' TCO~,N~ +,,NH~CO0- )" Parameters describing interactions between two carbon dioxide molecules and a charged species were neglected as the molality of carbon dioxide remains small. The remaining parameters were then fitted to the experimental results for the partial pressure of carbon dioxide. During this step, all SLV-data were excluded from the data base. Finally, only parameters " c o a , ~ c o [ and "rcoa,NH+HCO H () ~ w e r e found to be ~(o) ~(0) significant. Furthermore, interaction parameters ~,NH+,HCO[ , e,NH+,CO~_ , TNH+,NH+,HCO ~ and

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F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

Table 4: Interaction parameters to describe VLE and SLE in the ammonia-carbon dioxide-water system (313.15<T/K<473.15) Parameter a~,j 0.2857

bi,j
-99.466 151.28 25.263 -16.148 -45.679

Parameter 3(o

N. t,co~-

-0.146 -1.1264.10 -3

NH3,CO~8( C02,HCO~
fl(o)

-0.3391

rCO=,N.,+,HCO~
T + ,CO ~NH~+ ,NH~ 3

~(~)H3,NH2CO0- -0.03933
0.0843 0.1134

TNH4+,NH4+,HCO~ 5.0715"10 -4

1"4007"10-2

NIt:,.co~

rNtI,+,NH+,,CO~- were included in the final fits. The results are given in table 4. Using that

set of parameters, a comparison between calculated and experimental results showed a good agreement for all VLE data points. However, systematic deviations between experimental and calculated total and partial pressures above solutions where a solid phase was present were observed, the deviations increasing with temperature. As no reliable information on the temperature dependence of KNH~HC03 was available, these deviations were expected. Therefore, numbers for the solubility constant at 313 and 333 K were determined from the new data whereas the value at 298.15 K as taken from Wagman et al. (1982) was retained. The temperature dependence of the solubility constant was approximated by
in KNH, HC03 = 8.3413

2465.32 (T/K) "

(16)

In table 5, the results for the average deviations in the total pressure and the partial pressures of ammonia and carbon dioxide are summarized. The model gives a good representation in both the total and the partial pressures up to extremely concentrated solutions. The relative deviations in the total pressures in most cases amount to a few percent, the largest deviations beeing observed when the total pressure increases rapidly with increasing carbon dioxide molality. For the partial pressures of ammonia and water, somewhat larger deviations are observed. Especially for the data reported by Mfiller et al. (1988), systematic deviations in the partial pressure of ammonia are obtained. However, it should be noted that due to the experimental difficulties at these high temperatures these data are more uncertain. Note that some of the data reported by G6ppert and Maurer (1988) as VLE-data are now found to be SLV-data. In Figs. 5 and 6, the new results for the total pressure and the partial pressure of ammonia at 313 K are compared to calculated results. Furthermore, the calculated solubility limit for the precipitation of NH4HCOa is shown. In Fig. 7 , some total pressures at 373.15 K as reported by Mfiller et al. (1988) are compared to calculated results. The model correlates these data with an average relative deviation in the total pressure of 3.6%, the average relative deviation in the partial pressure of ammonia is 4.9%. In Fig. 8, experimental data for the solubility limit of NH4HCO3 in the NH3-CO2-H20system as taken from Jhnecke (1929) are compared to model calculations. A good agreement

F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

271

Table 5: Comparison between calculated and experimental results (data points with p_<50 kPa and Pl <50 kPa omitted) Source T K This work G6ppert and Manrer (1988) Mfiller et al. (1988) 313.15 333.15 353.15 333.15 353.15 360.15 373.15 393.15 373.15 393.15 413.15 433.15 453.15 473.15
mNH3,rnaz mco~,maz

No. of data points

Av. deviation

mol/kg 11.8 12.0 12.1 11.8 12.2 16.0 14.3 12.0 26.0 25.9 25.2 24.6 12.6 10.6

mol/kg
P PNH3 PC02 Pw P PNH3

%
PC02 P~

9.7 9.7 7.6 12.2 11.4 13.5 10.4 7.4 13.3 12.7 8.5 9.8 3.8 2.1

7 18 22 85 93 183 127 74 61 42 72 40 23 16

1 5 12 1 35 48 33 48 35 55 36 22 16

5 9 10 85 91 156 99 63 32 34 69 40 23 16 140 127 74 61 42 72 40 23 16 -

21 3.2 2.7 7.0 3.2 5.6 5.5 4.4 3.6 4.4 4.7 4.9 4.3 12

2 2 2.2 10 8.1 13 20 4.9 10 13 12 14 23

29 4.7 6.1 8.3 3.5 6.9 8.1 11 8.8 6.3 6.3 5.9 8.5 16 11 15 22 4.6 5.8 12 18 8.7 2.2

between experimental and calculated results is observed. However, only few data limited to a small range of temperature and composition are available.

C O N C L U S I O N S
The total and partial pressures above aqueous solutions containing ammonia and carbon dioxide were measured in the temperature range from 313 to 353 K at overall molalities of ammonia of about 6 and 12 mol/kg and carbon dioxide molalities up to about 10 mol/kg. From these data and those reported earlier (GSppert and Manrer (1988), Mfiller et al. (1988)) interaction parameters for an adapted Pitzer model were determined. The model is capable to describe reliably vapor-liquid and vapor-liquid-solid equilibria in this extremely complex system in the temperature range from 313 to 473 K up to concentrated solutions.

272

F. Kurz et al. / F l u i d Phase Equilibria 104 (1995) 2 6 1 - 2 7 5 8 7 6,

Q.. C)

, , . , / ( , ~ / ~ ffi 6 . 3 3
5'

4,

3~

lJ

2'
1'

X
0 2

O"

10

Figure 5: Total pressure in the system NHa-CO2-H20 at 313 K. o, n: exp. results, this work. --: c.alc, results, this work. - ...... : talc. solubility limit for the precipittLtion NH4HCO3.

0.5

~
\

/~-

ass

0.2

0.1

h.f

OoO i

10

Figure 6: Partial pressure of ammonia in the system NH3-CO~-H20 at 313 K. o, D: exp. results, this work. NH4HCOa. : calc. results, this work. - ...... :calc. solubility limit for the precipitation

F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

273

I],

w\

L /
$

4 "',4,~ j

O,
0 3

12

15

~'~:x)t/(rv'wnl/kg)

Figure 7: Total pressure in the system Ntt3-CO2-H20 at 373 K. o: exp. results, Mfiller et al. (1988). - - : calc. results, this work.

le.

12.

8"

4.

4 ~.

6 / ~ ~

Figure 8: Solubility limits for the precipitation of NH4HCOs in the NHrCO2-H20-system. O: exp. results at 293.15 K, JS~necke (1929). [::1: exp. results at 313.15 K, J~necke (1929). - - : calc. results, this work.

274

F. Kurz et al. / Fluid Phase Equilibria 104 (1995) 261-275

ACKNOWLEDGEMENT
Financial support of this investigation by the government of the Federal Republic of Germany (BMFT Grant No. 0326558 C), BASF AG, Ludwigshafen, Bayer AG, Leverkusen, Degussa AG, Hanau, Hoechst AG, Frankfurt, Linde KCA, Dresden and Lurgi AG, Frankfurt is gratefully acknowledged.

LIST OF SYMBOLS
a~ a~,j,bld B (o)
G,MX

B~,~
fi, f2 GE

H!.~) I
KR
KNH4HG03

M,~
r=t.ti rrti

Aml
ni

P
Pi

Ap Ap~ R T Y Greek letters ~(o),/~0) ~o 7*

~'i,R

activity of component i coefficients for the temperature dependence of interaction parameters "observable" combination of binary interaction parameters second virial coefficient for interactions between species i and j functions in Pitzer's equation excess Gibbs energy Henry's constant for the solubility of gas i in water (on molality scale) ionic strength on molality scale equilibrium constant for chemical reaction R (on molality scale) solubility constant for the formation of NH4HCO3 (on molality scale) molar mass of water (kg/mol) overall molality of component i true molality of component i estimated maximum absolute uncertainty in the overall molality of component i overall number of moles of component i true number of moles of component i total pressure partial pressure of component i estimated maximum absolute uncertainty in the total pressure estimated maximum absolute uncertainty in the partial pressure of component i universal gas constant temperature partial molar volume mole fraction in vapor binary interaction parameters in Pitzer's equation fugacity coefficient activity coefficient normalized to infinite dilution (on molality scale) stoichiometric coefficient of component i in reaction R number of cations and anions in salt MX number of phases ternary interaction parameter in Pitzer's equation

v+,u_

F. Kurz et al. / F l u i d Phase Equilibria 104 (1995) 261-275

275

Subscripts G i, j, k MX max R w gas G component i, j, k salt MX maximum reaction R water

Superscripts s c t tt
ttt

saturation normalized to infinite dilution infinite dilution solid phase liquid phase gas phase

REFERENCES
Bieling, V., R u m p f , B., Strepp, F. and M a u r e r , G., 1989. An evolutionary optimization method for modeling the solubility of ammonia and carbon dioxide in aqueous solutions. Fluid Phase Equilibria, 53: 251-259. Bradley, D. J. and P i t z e r , K. S., 1979. Thermodynamics of electrolytes. 12. Dielectric properties of water and Debye-Hiickel parameters to 350C and I kbar. J. Phys. Chem., 83: 1599-1603. Brelvi, S. W . a n d O ' C o n n e l l , J. P., 1972. Corresponding states correlations for liquid compressibility and partial molal volumes of gases at infinite dilution in liquids. AIChE J., 18: 1239-1243. D y m o n d , J. H. a n d Smith, E. B., 1980. The virial coefficients of pure gases and mixtures. Oxford University Press, Oxford. E d w a r d s , T. J., M a u r e r , G., N e w m a n , J. and Prausnitz, J. M., 1978. Vapor-liquid equilibria in multicomponent aqueous solutions of volatile weak electrolytes. AIChE J., 24: 966-976. G 6 p p e r t , U. and M a u r e r , G., 1988. Vapor-liquid equilibria in aqueous solutions of ammonia and carbon dioxide at temperatures between 333 and 393 K and pressures up to 7 MPa; Fluid Phase Equilibria, 41: 153-185. H a y d e n , J. G. a n d O ' C o n n e l l , J. P., 1975. A generalized method for predicting second virial coefficients. Ind. Eng. Chem. Proc. Des. Dev., 14: 209-216. Jilnecke, E. 1929. Z. Elektrochem., 35: 716-727. Miiller, G., B e n d e r , E. and M a u r e r , G., 1988. Das Dampf-Fliissigkeitsgleichgewicht des ternren Systems Ammoniak-Kohlendioxid-Wasser bei hohen Wassergehalten im Bereich zwischen 373 und 473 Kelvin; Ber. Bunsenges. Phys. Chem., 92: 148-160. Pitzer, K. S., 1973. Thermodynamics of electrolytes. 1. Theoretical basis and general equations. J. Phys. Chem., 77: 268-277. R u m p f , B. a n d M a u r e r , G., 1993a. An experimental and theoretical investigation on the solubility of carbon dioxide in aqueous solutions of strong electrolytes. Ber. Bunsenges. Phys. Chem., 97: 85-97. R u m p f , B. a n d M a u r e r , G., 1993b. Solubility of ammonia in aqueous solutions of sodium sulfate and ammonium sulfate at temperatures from 333.15 K to 433.15 K and pressures up to 3 MPa, Ind. Eng. Chem. Res. 32: 1780-1789. Saul, A. a n d W a g n e r , W . , 1987. International equations for the saturation properties of ordinary water substance. J. Phys. Chem. Ref. Data, 16: 893-901. W a g m a n , D. D., Evans, W. H., Parker, V. B., Schumm, R. H.. Halow, I., Bailey, S. M., Churney, K. L. and Nutall, R. L., 1982. The NBS tables of chemical thermodynamic properties, J. Phys. Chem. Ref. Data, Vol. 11.