54 Hydrogen Sulfide in Aqueous Solvents COHPONENTS: 1. Hydrogen sulfide; H2S; [7783-06-4] 2. Ammonia; NH 3; [7664-4-17] 3. Water; H 2 0; [7732-18-5] EVALUATOR: Peter G.T. Fogg, Department of Applied Chemistry and Life Sciences, Polytechnic of North London, Holloway, London N7 8DB, U.K. February 1987 CRITICAL EVALUATION: The original measurements on this system were published by van Krevelen, Hoftijzer, and Huntjens (1). Other work has since been published (2-7) and data cover temperatures from 293.15 K to 373.15 K and a wide range of concentrations of ammonia and of hydrogen sulfide. Direct comparison of different sets of data is only possible to a limited extent because of differing ranges of conditions studied by different authors but the general pattern of behaviour is the same. The concentration of hydrogen sulfide in solution increases with partial pressure of the gas and with concentration of ammonia in solution and decreases as the temperature is raised. One apparent discrepancy between two sets of data has been found by the evaluator: Authors T/K Wt.% in liquid wt.% in gas H 2 S NH3 H 2 S NH3 Oratovskii et a1. (2 ) 353.2 3.0 5.45 33.9 33.6 Ginzburg et a1. (3 ) 353.8 3.20 5.04 26.02 36.02 Models for the behaviour of the system have been published by van Krevelen et a1. (1), by Edwards et a1. (8) and by Beutier & Renon (7). These can only be partially correlated with experimental data. Van Krevelen et a1. (1) investigated the systems H2S-NH3-NH4Cl-H20 and H2S-NH3-{NH4)2S04 and showed that data are consistent with those for the H2S-NH3-H20 system. The system H2S-NH3-C02-H20 was investigated by Badger and Silver (9), by Dryden (10), by van Krevelen et a1.(1) and by Wilson, Gillespie and Owens (11). Data span a range of concentrations of components and temperatures from 298.2 K to 533.2 K. There appear to be no serious discrepancies between the sets of data but detailed comparison is not possible because of the differences in conditions investigated by the different groups. Van Krevelen et a1. have shown that experimental data can be partially correlated with a simple model for the system. Correlation models have also been published by Wilson et a1. Golutvin et a1. have studied the system H2S-NH3-C02-H20-phenol (4). References 1. van Krevelen, D.W.; Hoftijzer, P.J.; Huntjens, F.J. Reel. Trav. Chim. Pays-Bas 1949, 68, 191-216. 2. Oratovskii, V.I.; Gamol'skii, A.M.; Klimenko, N.N. Zhur. Prik. Khim. 1964, 37, 2392-8.; J. App1. Chem. USSR 1964, 37, 2363-7. 3. Ginzburg, D.M.; Pikulina, N.S.; Litvin, V.P. Zhur. Prik1. Khim. 1965, 38, 2117-3.; J. App1. Chem. USSR 1965, 38, 2071-3. 4. Golutvin, YU.M.; Malysheva, T.V.; Skorobogatova, V.I. Izvest. Sibir. Otde1. Akad. Nauk. S.S.S.R. 1958, No.8, 83-87. 5. Leyko, J. Bull. Acad. Po1on. Sci. Ser. sci. chim. 1959, 7, 675-679.
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54 Hydrogen Sulfide in Aqueous Solvents
COHPONENTS:
1. Hydrogen sulfide; H2S; [7783-06-4]
2. Ammonia; NH 3; [7664-4-17]
3. Water; H20; [7732-18-5]
EVALUATOR:
Peter G.T. Fogg,Department of Applied Chemistryand Life Sciences,Polytechnic of North London,Holloway, London N7 8DB, U.K.
February 1987
CRITICAL EVALUATION:
The original measurements on this system were published by van Krevelen,Hoftijzer, and Huntjens (1). Other work has since been published (2-7) and datacover temperatures from 293.15 K to 373.15 K and a wide range of concentrationsof ammonia and of hydrogen sulfide. Direct comparison of different sets of datais only possible to a limited extent because of differing ranges of conditionsstudied by different authors but the general pattern of behaviour is the same.The concentration of hydrogen sulfide in solution increases with partialpressure of the gas and with concentration of ammonia in solution and decreasesas the temperature is raised.
One apparent discrepancy between two sets of data has been found by theevaluator:
Authors T/K Wt.% in liquid wt.% in gasH2S NH3 H2S NH3
Oratovskii et a1. (2 ) 353.2 3.0 5.45 33.9 33.6
Ginzburg et a1. (3 ) 353.8 3.20 5.04 26.02 36.02
Models for the behaviour of the system have been published by van Krevelenet a1. (1), by Edwards et a1. (8) and by Beutier & Renon (7). These canonly be partially correlated with experimental data.
Van Krevelen et a1. (1) investigated the systems H2S-NH3-NH4Cl-H20 andH2S-NH3-{NH4)2S04 and showed that data are consistent with those for theH2S-NH3-H20 system.
The system H2S-NH3-C02-H20 was investigated by Badger and Silver (9),by Dryden (10), by van Krevelen et a1.(1) and by Wilson, Gillespie and Owens(11). Data span a range of concentrations of components and temperatures from298.2 K to 533.2 K. There appear to be no serious discrepancies between thesets of data but detailed comparison is not possible because of the differencesin conditions investigated by the different groups. Van Krevelen et a1. haveshown that experimental data can be partially correlated with a simple model forthe system. Correlation models have also been published by Wilson et a1.
Golutvin et a1. have studied the system H2S-NH3-C02-H20-phenol (4).
11. Wilson, G.M.; Gillespie, P.C.; Owens, J.L.Proc. 64th Ann. Cony. Gas Processors Association, 1955, 282-288.
56
COMPONENTS:
Hydrogen Sulfide in Aqueous Solvents
ORIGINAL MEASUREMENTS:
1. Hydrogen sulfide; H2S;[7783-06-4)
2. Ammonia; NH 3; [7664-41-7)
3. Water; H20; [7732-18-5)
VARIABLES:
Temperature, concentration ofliquid phase.
van Krevelen, D.W.; Hoftijzer, P.J.Huntjens, F.J.
Reel. Trav. Chim. Pays-Bas1949, 68, 191-216.
PREPARED BY:
P.G.T. Fogg
Partial pressures of H2S / mmHgEXPERIMENTAL VALUES:
Cone. of H2S
*in liquid/mol dm- 3
0.007
0.060
0.110
0.120
0.140
0.145
0.185
0.220
0.220
0.285
0.290
0.355
0.375
Cone. of NH3*in liquid
/mol dm- 3
0.280
0.280
0.280
0.585
0.295
0.575
0.300
1.060
0.580
0.585
1 .150
1.720
0.595
293.2 K
0.3
0.8
0.3
0.6
4.2
0.9
1 .7
3.0
1 .1
1 .1
8.2
313.2 K
1 .3
3.7
1 .5
13.3
2.6
6.9
12.7
4.6
4.0
26.9
333.2 K
2.6
11.8
4.9
15.6
8.7
39.6
9.4
20.5
35.5
14.5
12.9
* total H2S & NH3 including that equivalent to ionic species.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:
Solutions were prepared by passingH2S, NH 3 and steam through waterwith exclusion of air. Samples ofvapor in equilibrium with thesolution under test were absorbedby solutions of cadmium acetatein acetic acid which were thenanalysed. These analysestogether with P-V-T data were usedto calculate partial pressures ofNH3 & H2S. Another methodconsisted of passing a measuredvolume of N2 at a measured totalpressure through a series ofvessels containing solution. H2Sin the effluent gas was determinediodimetrically. The two methodsgave similar results.
SOURCE AND PURITY OF MATERIALS:
No information
ESTIMATED ERROR:
REFERENCES:
COMPONENTS:
Hydrogen Sulfide in Aqueous Solvents
I ORIGINAL MEASUREMENTS:
57
1. Hydrogen sulfide; H2S;[ 7783-06-4]
2. Ammonia; NH s ; [7664-41-7]
3. Water; H20; [7732-18-5]
EXPERIMENTAL VALUES:
van Krevelen, D.W.; Hoftijzer, P.J.Huntjens, F.J.
Reel. Trav. Chim. Pays-Bas1949, 68, 191-216.
Partial pressures of H2S / mmHgCone. of H2S*in liquid
/mol dm- s
0.398
0.420
0.435
0.440
0.455
0.550
0.580
0.585
0.590
0.690
0.730
0.860
0.875
1.110
1 .150
1.165
1 .440
1 .540
1 .890
*
Cone. of NHs
*in liquid/mol dm- s
0.795
1 .637
1 .730
2.270
1.175
2.870
1 .190
2.310
3.460
1 .780
2.920
1 .780
2.260
2.860
2.400
1 .790
2.930
2.350
2.920
293.2 K
4.4
1 .7
1 .6
1 .4
3.4
1.6
6.7
2.3
1 .3
4.9
2.8
9.4
6.0
6.7
12.2
18.4
15.8
27.1
38.5
313.2 K
6.4
5.0
12.5
5.9
23.6
8.1
4.7
18.0
10.0
32 .6
22.3
31.4
43.2
54.4
125.4
333.2 K
19.4
16.0
38.6
18.5
66.9
26.0
17.6
54.7
31.8
98.6
68.0
94.2
135.9
182.3
151. 9
310.5
total H2S & NH s including that equivalent to ionic species.
HSDS-CO
58
COMPONENTS:
Hydrogen Sulfide in Aqueous Solvents
ORIGINAL MEASUREMENTS:
1. Hydrogen sulfide; H2S;[ 7783-06-4]
2. Ammonia; NH a ; [7664-41-7]
3. Water; H20; [7732-18-5]
VARIABLES:
Concentration of ammonia
EXPERIMENTAL VALUES:
Golutvin, Yu. M.; Malysheva, T.V.;Skorobogatova, V.I.
Concentrations of NH a and of H2S include all ionic species derived fromthese compounds.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:
Hydrogen sulfide from a Kipp'sapparatus was bubbled throughaqueous solutions of ammonia ofvarious concentrations for sixhours. The total ammonia in theresulting solution was analysedby titration with hydrochloricacid and the total hydrogensulfide by iodimetry.
SOURCE AND PURITY OF MATERIALS:
1. from a Kipp's apparatus.
ESTIMATED ERROR:
oT/K = ± 0.1
REFERENCeS:
COMPONENTS:
Hydrogen Sulfide in Aqueous Solvents
ORIGINAL MEASUREMENTS:
59
1. Hydrogen sulfide; H2S;[7783-06-4 ]
2. Ammonia; NH a ; [7664-41-7]
3. Water; H20; [7732-18-5]
VARIABLES:
Temperature, concentration ofH2S and NHa in the liquid phase.
* total H2S and NH3 including that equivalent to ionic species
AUXILIARY INFORHATION
METHOD/APPARATUS/PROCEDURE:
Solutions of gases were prepared bypassing H2S, NH3 and steam throughwater with exclusion of air.Samples of vapor in equilibriumwith the solution under test, towhich the salt had been added, wereabsorbed by solutions of cadmiumacetate in acetic acid which werethen analysed. These analysestogether with P-V-T data were usedto calculate partial pressures ofNH3 & H2S. Another methodconsisted of passing a measuredvolume of N2 at a measured totalpressure through a series ofvessels containing solution. H2Sin the effluent gas was determinediodimetrically. The two methodsgave similar results.
* total H2S and NH 3 including that equivalent to ionic species
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:
Solutions of gases were prepared bypassing H2S, NH3 and steam throughwater with exclusion of air.Samples of vapor in equilibriumwith the solution under test, towhich the salt had been added, wereabsorbed by solutions of cadmiumacetate in acetic acid which werethen analysed. These analysestogether with P-V-T data were usedto calculate partial pressures ofNH3 & H2S. Another methodconsisted of passing a measuredvolume of N2 at a measured totalpressure through a series ofvessels containing solution. H2Sin the effluent gas was determinediodimetrically. The two methodsgave similar results.
The concentration term [NHs] includes the concentration of NH4+ and anyother species derived from NHs which is present in solution. In the sameway [CO2] and [H2S] include all species such as HCOs- and HS- derived fromCO 2 and H2S respectively.
Solutions under test were prepared by passing an appropriate amount ofH2S into a mixture of ammonium carbonate (1.5 mol dm- 3 ) and ammonia(1.5 mol dm- 3 )
NH3 concn.
in liquid*
Imol dm- 3
in liquid*
Imol dm- 3
R CO 2 concn.
in liquid*t
Imol dm- 3
0.47
0.47
0.48
0.49
0.49
0.49
0.49
0.49
0.51
0.955
0.98
0.98
0.98
0.98
1.00
1 .00
1.01
1.02
1.02
1.02
1.02
1.03
1.04
1.04
1.05
1.05
1 .10
1.10
1.10
1.11
0.20
0.20
0.20
0.205
0.2075
0.195
0.21
0.195
0.205
0.20
0.195
0.21
0.2175
0.20
0.2075
0.2075
0.05
0.06
0.185
0.05
0.20
0.05
0.2075
0.05
0.0525
0.055
0.105
0.105
0.10
0.0525
0.37
1 .33
0.75
1.10
1.47
0.885
0.19
0.37
0.53
1 .165
1.00
1 .50
0.765
0.295
0.85
1.57
1.28
1.07
0.70
0.83
0.55
1.07
1 .35
0.41
0.61
0.21
0.58
0.795
1 .24
1.50
965
210
640
363
148
475
985
1005
720
342
535
124
1045
2420
750
132
310
655
1120
1075
1480
650
202
3120
1810
6000
1830
1055
335
150
0.050
0.180
0.105
0.157
0.208
0.131
0.027
0.055
0.081
0.439
0.392
0.577
0.292
0.115
0.337
0.622
0.614
0.514
0.292
0.403
0.226
0.524
0.562
0.203
0.304
0.104
0.289
0.396
0.620
0.793
3.74
17.20
5.64
10.20
25.32
7.413
3.850
3.504
5.141
10.560
6.582
30.581
3.758
1 .492
4.996
28.385
2.912
1 .654
2.983
0.840
2.440
1.389
18.549
0.289
0.524
0.166
1 .036
1 .797
5.390
6.320
0.004989
0.022927
0.007523
0.013596
0.033753
0.009883
0.005133
0.004672
0.006854
0.014079
0.008775
0.040771
0.005010
0.001989
0.006661
0.037843
0.003882
0.002205
0.003977
0.001120
0.003253
0.001852
0.024730
0.000385
0.000699
0.000221
0.001381
0.002396
0.007186
0.008426
T/K = 293.2 Total pressure = 760 mmHg = 1.01325 bar
Solutions under test were prepared by passing an appropriate amount ofH2S into a mixture of ammonium carbonate (1.5 mol dm- 3 ) and ammonia(1.5 mol dm- 3 )
NH 3 concn.
in liquid*
/mol dm- 3in liquid*
/mol dm- 3
R CO 2 concn.
in liquid*t
/mol dm- 3
1.12
1 .13
1 .1 4
1.16
1 .1 8
1 .18
1.18
1 .20
1.20
1 .21
1. 46
1.47
1.48
1.48
1 .48
1 .48
1.48
1 .52
0.105
0.115
0.105
0.205
0.205
0.21
0.19
0.19
0.21
0.195
0.2075
0.185
0.215
0.2075
0.205
0.19
0.2075
0.17
0.205
1 .59
1.01
0.64
0.85
1 .29
1 .48
1 .06
0.20
0.40
0.44
0.63
0.89
0.235
1 .005
1 .54
1.32
0.84
5400
124
575
1180
680
239
152
424
2700
2180
2440
1560
720
3750
525
117
208
970
0.104
0.807
0.523
0.306
0.414
0.626
0.733
0.535
0.099
0.203
0.276
0.405
0.563
0.150
0.641
0.993
0.840
0.567
0.351
16.747
3.297
3.137
5.444
15.866
22.571
8.092
1 .404
1 .615
1 .536
2.141
5.392
0.999
7.051
29.324
18.014
3.165
0.000468
0.022327
0.004396
0.004182
0.007258
0.021153
0.030092
0.010788
0.001872
0.002153
0.002048
0.002854
0.007189
0.001332
0.009400
0.039095
0.024016
0.004220
T/K = 293.2
R =
Total pressure = 760 mmHg = 1.01325 bar
conc. of C02
conc. of NH 3 - conc. of H2S
All concentrations in this expression refer to the liquid phase and aremeasured in mol dm- 3 • They include ionic and other species derivedfrom the gases.
k 20 = total conc. of H2S in the liquid phase / conc. in the gas phase
* total H2S, NH3 and C02 including that equivalent to ionicand other species derived from the gases.
t calculated by the compiler.
72
COMPONENTS:
Hydrogen Sulfide in Aqueous Solvents
ORIGINAL MEASUREMENTS:
1. Hydrogen sulfide; H2S;[7783-06-4]
2. Ammonia; NH 3 ; [7664-41-7]
3. Carbon dioxide; CO 2 ; [124-38-9]
4. Water; H20; [7732-18-5]
van Krevelen, D.W.; Hoftijzer, P.J.Huntjens, F.J.
Reel. Trav. Chim. Pays-Bas1949, 68, 191-216.
VARIABLES: PREPARED BY:
Temperature, concentration ofcomponents in liquid phase.
* species.total H2S, NH 3 and CO 2 including that equivalent to ionic
** calculated by the compiler.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE
Samples of vapor in equilibriumwith the solution under test, wereanalysed by chemical methods. Theseanalyses together with P-V-T datawere used to calculate the partialpressure of H2S. Another methodconsisted of passing a measuredvolume of N2 at a measured totalpressure through a series ofvessels containing solution. H2Sin the effluent gas was determinediodimetrically. The two methodsgave similar results.
Rocked static equilibrium cellswere used for measurements. Thesewere electrically heated andinsulated with fibreglass.Pressures were measured with a3-D Instruments precision pressuregauge. Platinum resistancethermometers were used tomeasure and control temperature.The vapor phase was analysed eitherby gas chromatography or byabsorbing and weighing thecomponents with NH3 absorbed by ®HC1, H2S by CdS0 4 , H20 by Drieriteand C02 by Ascarite®. Samples ofliquid phase were allowed to cometo ambient temperature and pressureand the components estimated.Further details in refs. 1 & 2.
SOURCE AND PURITY OF MATERIALS:
No information
ESTIMATED ERROR:
REFERENCES:
1. Owens, J.L.; Cunningham, J.R.;Wilson, G.M. Research ReportRR-65, Gas Processors Association,Tulsa, Oklahoma 1983.
2. Wilson, G.M.; Owens, J.L.;Cunningham, J.R. Research ReportRR-52, Gas Processors Association,Tulsa, Oklahoma 1982.
Rocked static equilibrium cellswere used for measurements. Thesewere electrically heated andinsulated with fibreglass.Pressures were measured with a3-D Instruments precision pressuregauge. Platinum resistancethermometers were used tomeasure and control temperature.The vapor phase was analysed eitherby gas chromatography or byabsorbing and weighing thecomponents with NH g absorbed byHCl, H2S by CdS0 4 , H20 by Drierite~
and CO 2 by Ascarite~. Samples ofliquid phase were allowed to cometo ambient temperature and pressureand the components estimated.Further details in refs. 1 & 2.
SOURCE AND PURITY OF MATERIALS:
No information
ESTIMATED ERROR:
REFERENCES:
1. Owens, J.L.; Cunningham, J.R.;Wilson, G.M. Research Report
RR-65, Gas Processors Association.Tulsa. Oklahoma, 1983
2. Wilson, G.M.; Owens, J.L.iCunningham, J.R. Research Report
RR-52. Gas Processors Association.Tulsa. Oklahoma, 1982.
Concentrations of H2S, C02 & NH3 include all ionic species derived fromthese compounds.
AUXILIARY INFORMATION
METHOD/APPARATUS/PROCEDURE:
Premixed hydrogen sulfide andcarbon dioxide were bubbledthrough an aqueous solution ofammonia and phenol in a thermostattedsaturator for 4.5 to 5 hrs. Thegas and liquid phases were analysedby chemical methods.