J. Chem. Eng.

Data 1987, 32, 183-191 183

Vapor-Liquid Equilibria in the Ammonia-Water System

Syed S. H. Rlzvl and Robert A. Heldemann‘

Department of Chemical and Petroleum Engineering, Universiw of Calgary, Calgary, Alberta, Canada T2N IN4

vs. equilibrium pressure under constant composition. Wucherer

Isothermal vapor-llquld equilibrium data were obtained for
prepared these tables by smoothing his experimental data
the ammonia-water system at temperatures from 306 to
graphically. The actual experimental measurements were
618 K and at pressures up to 22 MPa. The equlllbrlum
never reported. However, his data are considered the most
temperatures, pressures, and the compositions of both
reliable obtained in the first half of the 20th century.
liquid and vapor phases were measured slmuitaneously.
Kracek (20)and Wucherer (18)both criticized Wilson’s data
The data were extended Into the critlcal reglons of the
(17),stating that his data did not compare well with the data
seven-phase envelopes at temperatures between the
of other researchers. The ammonia-water tables in Perry’s
critlcai points of ammonia and water.
Handbook (21)were obtained by smoothing and extrapolating
Wilson’s measurements, reportedly (22) with the introduction
Introduction of significant errors.
Mixtures of ammonia and water occur in a variety of indus- Scatchard et ai. (23) claimed that the smoothed Wucherer
tries. Coal, shale oil, and other low-grade hydrocarbon feed PTy data on the ammonia-water system were not precise
stocks include Significant amounts of nitrogen. The nitrogen is enough to apply the second law of thermodynamics and to
often produced in the form of aqueous ammonia solutions caculate the entropies and free energies for refrigeration pur-
during the processing of such feed stocks. Since the economic poses. Therefore, they smoothed Wucherer’s bubble-point data
production capacities of refineries and other fuel processing and applied the Gibbs-Duhem equation to calculate the va-
installations based on these feed stocks are always large, even por-phase composition.
a small percentage of nitrogen in the feed stock would produce Pierre (24)measured P-Tdata at constant composition from
huge aqueous streams containing ammonia and other water- 1.2 MPa to 4.0 MPa, with up to 40 wt YO ammonia in the liquid.
soluble polar gases. The design of industrial equipment for the These data compare well with Wucherer’s data.
processing of these streams requires vapor-liquid equilibrium I n order to check the Wucherer (18) experimental data and
data on the ammonia-water system covering wide ranges of the Scatchard et ai. (23) calculated PTy data, Macriss et al.
temperature and pressure. (25)conducted a dew point study. They measured a few dew
Further, accurate extensive vapor-liquid equilibrium data for point pressures and temperatures from 1.531 to 3.591 MPa and
the ammonia-water system could be useful for thermodynamic from 338.87 to 389.59 K, at 0.47%, 0.93%, 1.76%, and
model testing. Equation of state models that correlate other 3.59% water in ammonia by weight. Their measured vapor-
systems very well often fail to correlate polar and water-con- phase concentrations of water were less than in the data of
taining systems. Wucherer ( 18) and higher than the calculated concentrations
The earliest work on the ammonia-water system in the 19th of Scatchard et ai. (23). Macriss et ai. (25)reported that the
century was done in connection with absorption of polar gases lack of precision in early ammonia-water data led to serious
in water within the application range of Henry’s law. Carius (7), errors in the design of commercial refrigeration units.
Roscoe and Dittmar ( 2 ) ,Sims ( 3 ) ,Watts ( 4 ) ,Raoult ( 5 ) ,and There have been several significant sets of ammonia-water
Mallet ( 6 ) were the pioneers who worked on the ammonia- data published since the Macriss et al. (25)compilation. Tsiklis
water system. et ai. (26)published a phase diagram for the ammonia-water
The eutectic region and the three-phase line in the ammo- system from 370.15 to 623.15 K. The figure is very difficult to
nia-water system were studied by Pickerlng ( 7 ) ,Rupert (8, 9 ) , read. Two types of points are shown on the isotherms, ex-
Smits and Postma ( IO), Postma ( 1 I), Elliott ( 12),and Mironov perimental and correlated, but apparently most of the points are
(13). The existence of two solid hydrates of ammonia, NHH ., O
, correlated.
and 2NH,-H,O, was experimentally observed, questioned, and Polak and Lu (27)measured vapor-liquid equilibria in dilute
then confirmed. I t was Mendeleev who first identified the ex- solutions of ammonia in water. Pawlikowsky, Newman, and
istence of the compound NH,OH through his analysis of the Prausnitz (28)have also reported isothermal measurements at
behavior of aqueous ammonia solutions (Mironov, ref 13). 373.15 and 423.15 K, covering a pressure range from 0.4 to
Mendeleev anticipated that NH,OH could be obtained in the solid 2.44 MPa.
form, possibly with intense cooling. Recently, Giilespie et ai. (22) have measured vapor-liquid
Later, the main thrust of experimental investigation on the equilibria in the ammonia-water system from 313 to 589 K.
system was to obtain data which were suitable for the design The data cover a pressure range up to 20 MPa. While most
of refrigerationequipment. The researchers who investigated of the data are of the PTx type, some PTxy measurements are
the ammonia-water system in the first half of the 20th century also reported.
are Perman ( 74, 15),Mollii ( 76), Wilson ( 17),Wucherer ( 18), Guillevic et ai. (29)have measured vapor-liquid equilibria in
and Clifford and Hunter (19). Kracek (20) correlated the ex- the ammonia-water system at 403.1, 453.1, and 503.1 K up
perimental data on total vapor pressure of ammonia-water to 7.0 MPa.
solutions available prior to 1930, using the Ramsay-Young rule. The literature on the ammonia-water system shows that the
Wucherer (18) reported his measurements in three tables up greatest difficulty was encountered in measuring the vapor-
to 1.961 MPa. Entries in the tables are bubble-point tempera- phase composition, when these measurements were attempted
tures, dew-point temperatures, and vapor-phase compositions at all. The uncertainty in the amount of water present in the
vapor phase became an issue and some of the data were
judged to be inconsistent by Edwards et ai. (30).
Author to whom correspondence should be addressed. Address until July
1, 1987: Instituttet for Kemlteknlk, Danmarks Teknlske Hojskole, Bygnlng Most of the vapor-phase equilibrium compositions that have
229, 2800 Lyngby, Denmark. been reported were measured by passing the ammonia and

0021-9568/87/1732-0183$01.50/0 0 1987 American Chemical Society

184 Journal of Chemical and Engineering Data, Vol. 32, No. 2, 7987

water vapors thorugh a preweighed acid which was contained of the liquid sampling loop, outside the oven. Care was taken
in an absorption apparatus. The mass of ammonia was de- to keep the fluid inside the transducer cavity at room temper-
termined by titrating the excess acid and that of the water was ature by providing cooling. The pressure transducer was cal-
calculated by difference. In this type of analysis, the total mass ibrated with a dead-weight tester that was accurate to better
of vapor absorbed in the acid is small compared to the mass than 0.18% full scale.
of the absorption apparatus. The mass of water vapors de- Pressure uncertainties in the data are mainly due to variations
termined by difference could fall into the range of uncertainty observed while establishing a given data point, not to calibration
in the mass balance. There is also a very high cooling effect uncertainties. These variations are given for each data point
whenever mixed ammonia and water vapors are passed by Rizvi (37).
through the small opening of a valve. With the temperature To check the calibration of temperature and pressure in-
decrease, condensation can occur in the valve body, affecting struments, the vapor pressure of pure water was always
the analysis of the vapor phase. measured at each new oven temperature.
The most likely consequence of these and similar experi- .
Satnping and CmnposiibnDetetminatlon Compositions of
mental difficulties is that vapor analyses would tend to show less equilibrium fluids were measured with a Hewlett Packard Modei
water than is present in the equilibrium vapors. 5840a chromatograph. The compositions of both phases were
Errors in the liquid-phase composition might be due to in- determined at most of the points reported.
sufficient mixing. Also, partial vaporization of the liquid sample A technique was employed in which the equilibrium phases
in sampling lines and valves could lead to the measurement of were withdrawn from the liquid or vapor regions of the equi-
high concentrations of the least volatile component in the liquid librium cell, circulated through a sampling valve of the chro-
phase. This difficutty could occur even if the liquid sample was matograph, then returned to the cell. A bellows pump was
drawn from the system at the equilibrium temperature. I t is developed for this purpose. The pump was driven by high-
therefore advantageous to keep the liquid sampling system pressure nitrogen and was operated simply by opening and
supercooled. closing vaives on either side of the pump and varying the ni-
trogen pressure to compress or expand the bellows.
Present Study The hold-up in exterior tubing was kept very small. The
detailed design of the pump and sample circulating system is
Materials Used. Electronic grade ammonia from Matheson discussed by Rizvi (37).
Gas with 99.999% purity was used for all experiments.
The bellows pumps could be used to circulate liquid to the
Deionized water with a resistivity of 18 MQ was further distilled
top of the cell and vapor to the bottom, thus providing a
and was stored in a stainless steel reservoir for use. After the
mechanism for enhancing mixing and reducing equilibration
water was charged in the equilibrium cell it was degassed by
times.
connecting the equilibrium cell to a vacuum system.
Vapor lines and the vapor sampling valve in the chromato-
EquMbrhvn Celki. Two different static cells were employed
graph were all held at temperatures above the equilibrium cell
in the study. At temperatures up to 180 OC a visual cell with
a volume of approximately 208 cm3 was used. At tempera- temperature. The liquid lines, in contrast, were cooled below
the cell temperature. These steps prevented unwanted con-
tures above 180 O C it was necessary to employ a blind cell
densation or vaporization and assisted in ensuring accurate
because of diffficukies encountered in sealing windows. The
analyses.
blind cell has a volume of approximately 174 cm3.
Both cells were machined from 316 stainless steel. Ports At higher temperatures it became impossible to circulate
were drilled through the cell bodies to permit insertion of tem- through the chromatograph vapor sampling valves because
perature probes and to permit withdrawal and injection of fluids those valves failed at the temperatures necessary to prevent
in both the liquid and vapor portions of the cells. condensation. Two alternative sampling procedures were de-
veloped. Both involved expanding a small volume of vapor into
The cells were mounted in a rocker assembly inside an
electric oven. When the visual cell was used, observations a larger volume so that the pressure was sharply decreased
were made with the aid of mirrors because of concern for and condensation could be avoided. More detail is given by
Rizvi ( 3 1 ) .
safety.
Temperature and Pressure Measurement. A platinum re- The packing material used in the chromatograph column was
sistance probe (6.25 mm 0.d. and 25 ohms) was inserted into Poropak T. This material permitted essentially complete sep-
the liquid phase in the cells. Temperatures up to 325 OC were aration of ammonia and water in a reasonable time, and without
measured with this probe. Above this temperature, E-type excessive tailing of the water peak.
thermocouples were used. A high-precision digital multimeter The ratio of chromatograph areas was used as the indicator
(Fluke Model 8502A) indicated resistance or emf as needed. of composition. This ratio was calibrated against the ratio of
The resistance probe was calibrated against a standard probe moles over the whole composition range. The "response
to an accuracy of f0.01 K. At the higher temperatures, sev- factor" was found to vary with the ammonia/water molar ratio
eral E-type thermocouples mounted in and on the equilibrium in both dilute regions.
cell were used together to determine temperatures. Some of the chromatographic composition results were
The oven temperature was regulated only through the regu- verified by titrating samples withdrawn from the cell.
lation system provided by the manufacturer (the oven is Blue The uncertainties in mole fractions reported in Tables I - X V I
M, Model POM-256B-1.) I t was impossible to set the oven are based on the expected accuracy in the calibration and on
temperature precisely. Also, some long-term temperature variation in composition in replicate samples. In most cases,
variations occurred because of changing ambient conditions. the mole fraction variations were less than f0.005.
Because of difficulty in replicating the oven setting, each point The accuracy of measurements was established by the
is reported at its own temperature. following procedures.
The temperatures reported are the averages of several 1. Measurement of each datum was repeated 3-5 times.
readings made during the course of a given equilibrium deter- 2. Whole phase envelopes were replicated. This was
mination. Variations in the measured temperatures were var- achieved by taking measurements between points previously
iable, but in most instances were less than 0.1 K. measured. Phase envelope determinations at 376, 382, 412,
Pressure was measured with a strain gauge transducer Vi- 483, and 526 K were all repeated, with a time interval as long
tran, Model 304). The transducer was mounted in the tubing as a few months between sets of measurements.
 Journal of Chemical and Engineering Data, Vol. 32, No. 2, 1987 185

Table I. Ammonia-Water Equilibrium Data, Average Table 111. Ammonia-Water Equilibrium Data, Average
Temperature 305.6 K Temoerature 359.7 K
no. T,K P,MPa XNH~ YNH~ KNHs KH~O no. T,K P,MPa XNY- YNU- KNU- Kw-n
1 305.64 0.005 0.0000 O.OOO0 1 359.66 0.061 0.0000 0.0000
2 304.08 0.023 0.0342 2 359.49 0.116 0.0368 0.2025 5.503 0.8280
3 303.24 0.036 0.1122 0.7660 6.827 0.2636 3 359.68 0.121 0.0428 0.2352 5.495 0.7990
4 304.32 0.038 0.1157 0.8039 6.948 0.2218 4 359.70 0.153 0.0777 0.4114 5.295 0.6382
5 303.69 0.066 0.1263 0.8632 6.835 0.1566 5 359.56 0.192 0.1064 0.5534 5.201 0.4998
6 304.32 0.052 0.1883 0.8862 4.706 0.1402 6 359.60 0.253 0.1399 0.6826 4.879 0.3690
7 304.87 0.176 0.2648 0.9633 3.638 0.0499 7 359.61 0.386 0.2054 0.8150 3.968 0.2328
8 305.40 0.239 0.3740 0.9832 2.629 0.0268 8 359.64 0.623 0.2837 0.8948 3.154 0.1469
9 305.94 0.331 0.4017 0.9891 2.462 0.0182 9 359.74 0.644 0.2935 0.9053 3.084 0.1340
10 306.90 0.520 0.5046 0.9935 1.969 0.0131 10 359.73 0.767 0.3261 0.9154 2.807 0.1255
11 306.93 0.507 0.5645 0.9930 1.759 0.0161 11 359.75 1.189 0.4173 0.9517 2.281 0.0829
12 306.10 0.567 0.6051 0.9953 1.645 0.0119 12 359.72 1.510 0.4724 0.9635 2.040 0.0692
13 306.89 0.725 0.6710 0.9960 1.484 0.0122 13 359.75 1.516 0.4805 0.9655 2.009 0.0664
14 307.19 0.942 0.7670 0.9976 1.301 0.0103 14 359.76 1.917 0.5442 0.9750 1.792 0.0548
15 309.03 1.232 0.9085 0.9989 1.100 0.0120 15 359.75 2.415 0.6162 0.9831 1.595 0.0440
16 305.64 1.254 1.0000 1.0000 16 359.67 3.093 0.7257 0.9890 1.363 0.0401
17 359.66 3.147 0.7337 0.9898 1.349 0.0383
18 359.61 3.523 0.7997 0.9918 1.240 0.0409
Table 11. Ammonia-Water Equilibrium Data, Average
19 359.57 4.062 0.8934 0.9957 1.115 0.0403
TemDerature 341.8 K
20 359.64 4.524 0.9711 0.9980 1.028 0.0692
no. T,K p , MPa xNHs YNH3 KNH3 KH20 21 359.66 4.743 1.0000 1.0000
1 341.81 0.029 0.0000 0.0000
2 343.51 0.089 0.0621 0.3825 6.159 0.6584 Table IV. Ammonia-Water Equilibrium Data, Average
3 339.66 0.086 0.0666 Temperature 376.3 K
4 340.87 0.132 0.0985 0.6254 6.349 0.4155
no. T , K P,MPa XNH" YNH, KNH, K H , ~
5 340.87 0.136 0.1029 0.6336 6.157 0.4084
6 340.96 0.118 0.1030 0.6184 6.004 0.4254 1 376.28 0.113 0.0000 0.000
7 340.97 0.130 0.1143 0.6597 5.772 0.3842 2 376.11 0.158 0.0192 0.1752 9.125 0.8409
8 341.18 0.154 0.1491 0.7371 4.944 0.3090 3 376.09 0.171 0.0275 0.2508 9.120 0.7704
9 341.03 0.169 0.1497 0.7357 4.914 0.3108 4 376.91 0.177 0.0318
10 343.95 0.202 0.1688 0.8633 5.114 0.1645 5 376.06 0.192 0.0424 0.3557 8.389 0.6728
11 344.84 0.267 0.2214 0.8930 4.033 0.1374 6 377.15 0.191 0.0426
12 340.96 0.273 0.2416 0.8691 3.597 0.1726 7 376.03 0.228 0.0629 0.4812 7.650 0.5536
13 341.23 0.405 0.3102 0.9235 2.977 0.1109 8 376.08 0.294 0.0965 0.6121 6.343 0.4293
14 344.84 0.534 0.3322 0.9550 2.875 0.0674 9 377.02 0.329 0.1050
15 341.49 0.561 0.3603 0.9542 2.648 0.0716 10 377.00 0.327 0.1188
16 343.78 0.719 0.3900 0.9744 2.498 0.0420 11 375.85 0.382 0.1350 0.7057 5.227 0.3402
17 341.26 0.722 0.4188 0.9693 2.314 0.0528 12 375.94 0.401 0.1404 0.7261 5.172 0.3186
18 340.79 0.900 0.4702 0.9778 2.080 0.0419 13 376.34 0.533 0.1861 0.7960 4.277 0.2506
19 344.95 0.915 0.9770 14 375.94 0.740 0.2442 0.8603 3.523 0.1848
20 344.81 1.125 0.9832 15 376.37 0.885 0.2640 0.8839 3.348 0.1577
21 340.60 1.142 0.5160 0.9879 1.915 0.0250 16 375.99 1.224 0.3418 0.9203 2.693 0.1211
22 340.80 1.436 0.5815 0.9895 1.702 0.0251 17 376.17 1.468 0.3759 0.9344 2.486 0.1051
23 340.69 1.467 0.5909 0.9906 1.676 0.0230 18 376.12 1.936 0.4452 0.9522 2.139 0.0862
24 340.81 1.749 0.6369 0.9937 1.560 0.0174 19 376.20 2.117 0.4556 0.9566 2.100 0.0797
25 340.89 2.175 0.7414 0.9960 1.343 0.0155 20 376.18 2.376 0.5008 0.9626 1.922 0.0749
26 339.51 2.884 0.9560 0.9970 1.043 0.0682 21 376.21 2.781 0.5468 0.9686 1.771 0.0693
27 341.81 3.212 1.0000 1.oooo 22 376.30 3.024 0.5575 0.9685 1.737 0.0712
23 376.27 3.493 0.6402 0.9756 1.524 0.0678
24 376.33 3.909 0.6570 0.9691 1.475 0.0901
3. Temperature, pressure, and composition calibrations were 25 376.10 3.948 0.6842 0.9777 1.429 0.0706
repeated over the period of the experiment. 26 376.36 4.630 0.7388 0.9709 1.314 0.1114
The data along the three lowest temperature nominal iso- 27 376.27 5.239 0.7662 0.9777 1.276 0.0954
therms include some additional uncertainties for several rea- 28 376.28 6.626 1.0000 1.0000
sons. Temperature variations and pressure fluctuations during
operation of the sampling loop were more significant. Also, After a set of measurements of phase compositions, tem-
there were difficulties in operating below atmospheric pressure, perature, and pressure, additional ammonia or water or both
which was necessary for at least some compositions at tem- were charged to the cell. By controlling the relative amounts
peratures below the normal boiling point of water. added it was possible to cover the full pressure range for an
Experlmental Procedures. A schematic diagram of the isotherm.
apparatus is presented in Figure 1. The figure shows the For some isotherms, the equilibrium cell was first charged
windowed cell with ports for the temperature sensor and liquid with enough ammonia and water to establish equilibrium near
and vapor injection and removal. the critical point. I n other cases, the initial charge was nearly
Receivers for ammonia and water were brought to pressure pure ammonia. Ammonia-rich vapor was then purged from the
with the aid of a Ruska pump. Also, nitrogen for operating cell to decrease cell pressure in small steps, with equilibrium
bellows pumps was compressed with mercury using the same compositions measured at each pressure, until the vapor
Ruska pump. pressure of water was approached. This method was espe-
The figure shows the main valves for charging materials to cially useful in obtaining equilibrium conditions in the dilute re-
the equilibrium cell and connections to the sampling loops. gions of the phase envelopes.
The cell was evacuated at oven temperature. Then mea- Results
sured amounts of ammonia and water were charged. I t was
usual to vent some vapor to vacuum in order to remove the last The results of the measurements are presented in Tables
remnants of air from the cell. I - X V I and Figures Figures 2-5. The data in each table are at
186 Journal of Chemical and Engineering Data, Vol. 32, No. 2, 7987

Table V, Ammonia-Water Equilibrium Data, Average Table VIII. Ammonia-Water Equilibrium Data, Average
Temperature 381.9 K Temperature 411.9 K
no. T,K P, MPa XNH, YNH, KNH, K H ~ O no. T,K P, MPa X N H ~ YNH, KNH, K H ~ O
1 381.93 0.137 0.0000 0.0000 1 411.85 0.348 o.oo00 0.0000
2 381.72 0.184 0.0165 0.0729 4.418 0.9427 2 411.71 0.430 0.0231 0.1485 6.429 0.8716
3 382.03 0.188 0.0175 0.0980 5.600 0.9181 3 411.43 0.544 0.0495 0.2814 5.685 0.7560
4 381.60 0.256 0.0553 0.3390 6.130 0.6997 4 411.56 0.552 0.0512 0.2944 5.750 0.7437
5 381.66 0.318 0.0829 0.4755 5.736 0.5719 5 412.01 0.830 0.1128 0.5131 4.549 0.5488
6 381.70 0.381 0.1078 0.5699 5.287 0.4821 6 411.78 1.179 0.1500 0.6117 4.078 0.4568
7 381.68 0.470 0.1375 0.6593 4.795 0.3950 7 411.91 1.496 0.2252 0.7427 3.298 0.3321
8 382.12 0.463 0.1415 0.7273 5.140 0.3176 8 411.78 1.902 0.2406 0.8167 3.394 0.2414
9 382.09 0.535 0.1529 0.7071 4.625 0.3458 9 412.24 2.512 0.3487 0.8496 2.436 0.2309
10 381.94 0.679 0.1981 0.8203 4.141 0.2241 10 411.75 2.996 0.3540 0.8991 2.540 0.1562
11 381.52 0.818 0.2358 0.8454 3.585 0.2023 11 411.24 3.268 0.4158 0.9182 2.208 0.1400
12 382.20 0.919 0.2546 0.8734 3.430 0.1698 12 411.74 4.055 0.4463 0.9147 2.050 0.1541
13 381.54 1.128 0.2989 0.8940 2.991 0.1512 13 412.27 3.447 0.4470 0.8951 2.002 0.1897
14 382.10 1.333 0.3244 0.9218 2.842 0.1157 14 411.65 4.575 0.5074 0.9317 1.836 0.1387
15 381.89 1.525 0.3570 0.9334 2.615 0.1036 15 412.24 5.091 0.5581 0.9299 1.666 0.1586
16 381.62 1.589 0.3688 0.9339 2.532 0.1047 16 411.65 6.049 0.5798 0.9349 1.612 0.1549
17 382.05 2.031 0.4267 0.9473 2.220 0.0919 17 412.16 6.614 0.6672 0.9470 1.419 0.1593
18 382.13 2.598 0.5000 0.9593 1.919 0.0814 18 412.02 7.632 0.7320 0.9547 1.304 0.1690
19 382.28 3.105 0.5531 0.9663 1.747 0.0754 19 412.05 8.690 0.8077 0.9601 1.189 0.2075
20 381.78 3.563 0.5964 0.9746 1.634 0.0629 20 411.97 9.778 0.8808 0.9690 1.100 0.2601
21 382.24 3.615 0.6048 0.9714 1.606 0.0724
22 381.87 4.176 0.6635 0.9785 1.475 0.0639 Table IX. Ammonia-Water Equilibrium Data, Average
23 382.07 4.176 0.6762 0.9758 1.443 0.0747 Temperature 422.5 K
24 382.12 4.516 0.7080 0.9778 1.381 0.0760
25 382.20 4.735 0.7320 0.9785 1.337 0.0802 no. T,K p , MPa XNH, YNH~ KNH~ KH~O
26 381.76 5.073 0.7621 0.9847 1.292 0.0643 1 422.53 0.468 0.0000 0.0000
27 381.93 5.908 0.8064 0.9863 1.223 0.0708 2 422.41 0.563 0.0192 0.1303 6.786 0.8867
28 382.01 5.919 0.8542 0.9893 1.158 0.0734 3 422.44 0.625 0.0348 0.2240 6.437 0.8040
29 382.03 6.470 0.8853 0.9918 1.120 0.0715 4 422.48 0.642 0.0374 0.2429 6.495 0.7865
30 382.00 6.603 0.9181 0.9937 1.082 0.0769 5 422.46 0.708 0.0512 0.3216 6.281 0.7150
31 381.96 6.752 0.9457 0.9943 1.051 0.1050 6 422.42 0.881 0.0848 0.4727 5.574 0.5762
32 381.93 7.363 1.0000 1.0000 7 422.54 1.105 0.1297 0.5913 4.559 0.4696
8 422.70 1.832 0.2220 0.7620 3.432 0.3059
Table VI. Ammonia-Water Equilibrium Data, Average 9 422.53 2.669 0.3078 0.8279 2.690 0.2486
TemDerature 399.1 K 10 422.56 3.671 0.3934 0.8701 2.212 0.2141
11 422.73 4.989 0.4876 0.8951 1.836 0.2047
12 422.70 7.010 0.6098 0.9140 1.499 0.2204
1 399.14 0.239 O.oo00 O.oo00 13 422.80 8.223 0.6780 0.9169 1.352 0.2581
2 399.46 0.366 0.0460 0.3445 7.489 0.6871 14 422.78 10.214 0.7852 0.9163 1.167 0.3897
3 399.84 0.618 0.1206 0.6281 5.208 0.4229 15 421.74 11.396 0.8588 0.9429 1.098 0.4044
4 399.59 0.874 0.1750 0.7415 4.237 0.3133 16 422.45 11.473 0.8714 0.9140 1.049 0.6687
5 399.32 1.233 0.2419 0.8199 3.389 0.2376 17 422.77 11.763 0.8740 0.9153 1.047 0.6722
6 399.28 1.653 0.3042 0.8671 2.850 0.1910
7 399.13 1.955 0.3420 0.8884 2.598 0.1696
8 399.38 2.487 0.4006 0.9120 2.277 0.1468 Table X. Ammonia-Water Equilibrium Data, Average
9 399.45 3.637 0.5006 0.9362 1.870 0.1278 Temperature 451.5 K
10 398.92 4.762 0.9535 no. T,K P, MPa X N H ~ YNHs KNH3 KHzO
11 399.27 4.863 0.5751 0.9516 1.655 0.1139 1 451.52 0.966 0.0000 0.0000
12 399.19 5.365 0.6306 0.9540 1.513 0.1245 2 451.51 1.106 0.0174 0.1302 7.483 0.8852
13 398.99 6.763 0.6997 0.9623 1.375 0.1255 3 451.38 1.194 0.0352 0.2518 7.153 0.7755
14 399.15 8.321 0.8896 0.9682 1.088 0.2880 4 451.46 1.416 0.0571 0.3695 6.471 0.6687
15 396.96 9.458 0.9930 5 451.55 1.709 0.0859 0.4659 5.424 0.5843
16 399.14 10.125 1.0000 1.0000 6 451.84 2.364 0.1720 0.6829 3.970 0.3830
7 451.90 3.353 0.2391 0.7524 3.147 0.3254
Table VII. Ammonia-Water Equilibrium Data, Average 8 452.14 5.172 0.3354 0.8326 2.482 0.2519
Temperature 405.5 K 9 452.03 7.072 0.4668 0.8834 1.892 0.2187
10 451.90 8.851 0.5480 0.9013 1.645 0.2184
11 451.94 10.045 0.5857 0.8995 1.536 0.2426
2 405.21 0.358 0.0111 0.1111 10.009 0.8989 12 451.87 11.677 0.6817 0.9023 1.324 0.3069
3 405.52 0.452 0.0350 0.3077 8.791 0.7174 13 452.00 13.057 0.7335 0.8927 1.217 0.4026
4 405.55 0.665 0.0942 0.5691 6.041 0.4757 14 452.03 13.939 0.7764 0.8879 1.144 0.5013
5 405.76 1.158 0.1848 0.7839 4.242 0.2651 15 452.01 14.723 0.8167 0.8863 1.085 0.6203
6 405.48 2.085 0.3085 0.8780 2.846 0.1764 16 451.40 15.164 0.8602 0.8695 1.011 0.9335
7 405.54 3.128 0.4113 0.9169 2.229 0.1412 17 451.02 15.114 0.8717 0.8854 1.016 0.8932
8 405.53 4.226 0.5063 0.9348 1.846 0.1321 18 449.07 15.458 0.8779
9 405.48 5.066 0.5790 0.9557 1.651 0.1052 19 450.31 15.026 0.8831
10 405.31 5.909 0.6375 0.9680 1.518 0.0883
11 405.39 6.259 0.9637 Figures 2 and 3 contain f x y diagrams for the 15 isotherms.
12 405.67 7.686 0.9743 Figure 2 shows isotherms up to the critical temperature of
13 405.75 8.465 0.7919 ammonia. The higher temperature results are contained in
14 405.30 10.066 0.9318 0.9897 1.062 0.1510 Figure 3. Figures 4 and 5 contain equilibrium ratio
15 405.71 11.193 0.9931 0.9932 1.000 0.9855
16 405.51 11.301 1.0000 1.0000 K = y/x (1)
roughly the same temperature, with the mean temperature in- corresponding to the f x y isotherms of Figures 2 and 3, re-
dicated at the top of the table. spectively.
 Journal of Chemical and Engineering Data, Vol. 32, No. 2, 1987 187

MK!ffi SYSTEM

'
LIQUID SAMPLE
1 ##';
v19
\,!,,lo SAMPLING LOW OWEN /
Figure 1. Experimental apparatus.

Table XI. Ammonia-Water Equilibrium Data, Average Table XII. Ammonia-Water Equilibrium Data, Average
Temperature 483.3 K Temperature 526.2 K
no. T,K P, MPa X N H ~ YNH, KNH~ K H ~ O no* T, p~ MPa xNH~ YNH3 KNH3 KH20
1 483.28 1.913 0.0000 0.0000 1 526.16 4.185 0.0000 0.0000
2 480.83 2.035 0.0139 0.0724 5.209 0.9407 2 523.88 4.246 0.0160
3 482.75 2.231 0.0205 3 526.18 4.675 0.0240 0.0885 3.688 0.9339
4 480.68 2.161 0.0266 0.1300 4.887 0.8938 4 526.04 4.736 0.0301 0.1064 3.535 0.9213
5 481.25 2.342 0.0371 0.1760 4.744 0.8557 5 525.58 5.611 0.0733 0.2242 3.059 0.8372
6 483.22 2.440 0.0407 0.1855 4.558 0.8491 6 525.26 6.321 0.1031 0.3166 3.071 0.7620
7 482.59 2.727 0.0665 0.2334 3.510 0.8212 7 526.05 6.802 0.1050
8 482.98 2.909 0.0746 0.3124 4.188 0.7430 8 525.73 6.830 0.1153
9 483.30 2.867 0.0785 9 526.07 7.203 0.1371 0.3755 2.739 0.7237
10 482.64 3.288 0.1049 0.4103 3.911 0.6588 10 526.09 7.193 0.1473 0.4034 2.739 0.6997
11 484.47 3.919 0.1195 11 525.97 8.487 0.1901 0.4859 2.556 0.6348
12 483.65 3.950 0.1273 0.4839 3.801 0.5914 12 525.54 9.215 0.2142 0.5015 2.341 0.6344
13 483.31 4.063 0.1315 13 525.80 9.231 0.2191 0.4964 2.266 0.6449
14 482.71 4.009 0.1510 0.5240 3.470 0.5607 14 525.71 9.975 0.2400 0.5410 2.254 0.6039
15 483.99 4.907 0.1818 15 525.78 11.617 0.2944 0.5969 2.028 0.5713
16 484.01 5.186 0.2036 0.6504 3.194 0.4390 16 525.86 12.423 0.3081 0.6160 1.999 0.5550
17 482.90 5.149 0.2156 0.6268 2.907 0.4758 17 526.05 12.636 0.3090 0.5960 1.929 0.5847
18 483.74 5.586 0.2276 0.6229 2.737 0.4882 18 525.81 13.535 0.3681 0.6477 1.760 0.5575
19 483.25 6.000 0.2471 0.6854 2.774 0.4179 19 526.00 14.857 0.3941 0.6721 1.705 0.5412
20 482.89 6.764 0.2972 0.7046 2.371 0.4203 20 526.36 15.956 0.4227 0.6591 1.559 0.5905
21 482.88 6.989 0.2991 0.7056 2.359 0.4200 21 525.89 16.992 0.4647 0.6856 1.475 0.5873
22 484.21 8.075 0.3448 0.7444 2.159 0.3901 22 525.81 17.033 0.4702 0.6752 1.436 0.6131
23 484.47 8.890 0.3622 0.7465 2.061 0.3975 23 526.98 18.099 0.4800
24 483.65 9.974 0.3732 0.7810 2.093 0.3494 24 526.62 18.042 0.4833 0.6638 1.373 0.6507
25 484.31 9.555 0.4063 25 526.44 17.804 0.4863 0.6753 1.389 0.6321
26 484.31 9.678 0.4073 26 527.19 18.334 0.6630
27 483.72 9.931 0.4139 0.7891 1.906 0.3598 27 526.13 19.142 0.4956 0.6784 1.369 0.6376
28 484.39 11.682 0.4350 0.8068 1.855 0.3419 28 527.10 18.416 0.5132 0.6527 1.272 0.7134
29 484.69 12.028 0.4724 0.7921 1.677 0.3940 29 526.66 19.647 0.5229 0.6506 1.244 0.7323
30 483.76 12.712 0.5078 0.8052 1.586 0.3958 30 526.68 19.248 0.5239 0.6669 1.273 0.6996
31 483.77 13.077 0.5164 0.7838 1.518 0.4471 31 526.94 20.344 0.5352 0.6572 1.228 0.7375
32 484.23 13.527 0.5409 0.8088 1.495 0.4165 32 526.96 20.683 0.5422 0.6398 1.180 0.7868
33 479.98 14.527 0.8507 33 526.97 20.929 0.5448 0.5946 1.091 0.8906
34 483.77 14.565 0.5743 0.8325 1.450 0.3935 34 527.13 20.989 0.5449 0.5547 1.018 0.9785
35 484.12 15.084 0.5839 0.8153 1.396 0.4439
36 484.16 15.294 0.5909 0.8195 1.387 0.4412
37 483.71 14.974 0.5952 0.8190 1.376 0.4471 The lines drawn in Figures 2-5 were obtained by curve fitting
38 483.34 15.192 0.5992 0.8232 1.374 0.4411 the data. The equatlons are not presented here but are given
39 483.72 15.620 0.6134 0.8205 1.338 0.4643 by Rizvi (37 ).
40 482.64 16.688 0.6317 Critical Points. Some of the measurements made were
41 482.93 17.803 0.6543 0.8012 1.225 0.5751
apparently very close to the critical composition at the tem-
42 483.34 17.131 0.6564 0.8359 1.273 0.4776
43 482.99 17.974 0.6720 perature of the cell. In particular, at 451.5 K critical opales-
44 483.34 18.243 0.6787 0.8153 1.201 0.5749 cence was observed in the form of a reddish brown cloud at
45 482.79 18.566 0.6936 0.7946 1.146 0.6704 the interface that became dispersed as a continuous trans-
188 Journal of Chemical and Engineering Data, Vol. 32, No. 2, 1987

Table XIII. Ammonia-Water Equilibrium Data, Average Table XVI. Ammonia-Water Equilibrium Data, Extra
Temperature 579.7 IC Points
no. T,K P,MPa ~ N H ~Y N H ~ K N H ~ KH@ no. T,K P,MPa zm3 yNH3 KNH3 KH20
1 579.71 9.415 0.0000 0.0000 1 373.10 0.118 0.0138
2 578.36 9.895 0.0166 2 373.63 0.126 0.0195 0.2146 11.005 0.8010
3 577.91 9.826 0.0170 0.0379 2.229 0.9787 3 373.03 0.146 0.0282 0.2768 9.816 0.7442
4 577.94 9.831 0.0186 0.0414 2.226 0.9768 4 372.78 0.147 0.0320
5 577.86 9.822 0.0204 0.0385 1.887 0.9815 5 372.88 0.172 0.0450 0.2919 6.487 0.7415
6 577.80 10.947 0.0467 0.1076 2.304 0.9361 6 374.91 0.208 0.0538 0.4410 8.197 0.5908
7 577.80 10.914 0.0475 0.1025 2.158 0.9423 7 372.21 0.280 0.1116 0.7171 6.426 0.3184
8 578.32 11.994 0.0768 0.1625 2.116 0.9072 8 374.58 0.332 0.1135 0.6641 5.851 0.3789
9 578.48 12.040 0.0814 0.1780 2.187 0.8948 9 446.08 1.159 0.0405 0.2602 6.425 0.7710
10 578.37 13.343 0.1147 0.2194 1.913 0.8817 10 446.18 2.064 0.1268 0.6154 4.853 0.4404
11 578.54 13.370 0.1199 0.2476 2.065 0.8549
12 578.92 15.005 0.1668 0.3336 2.000 0.7998
13 578.14 15.698 0.1861 0.3213 1.726 0.8339 Table XVII. Ammonia-Water Critical Points
14 578.71 15.833 0.1920 0.3373 1.757 0.8202 mole fracn NH, temo, K . . MPa
Dress..
15 578.53 16.017 0.1951
0.116 618.1 22.37
16 580.14 17.745 0.2339 0.4044 1.729 0.7774
17 0.4072 0.244 610.2 22.52
580.64 19.480 0.2842 1.433 0.8282
0.387 579.7 22.39
18 581.81 19.769 0.2893 0.4311 1.490 0.8005
0.570 526.2 21.42
19 581.55 20.842 0.4301
0.748 483.3 19.00
20 581.65 21.637 0.3238 0.4096 1.265 0.8731
0.870 451.5 16.05
21 582.58 21.515 0.3337 0.4319 1.294 0.8526
0.936 422.5 13.85
22 582.71 21.636 0.3518 0.4232 1.203 0.8898
0.3691 0.3947 0.972 411.9 12.47
23 583.80 22.101 1.069 0.9594
1.000 405.5 11.15
24 582.85 21.854 0.3698 0.4082 1.104 0.9391

Table XIV. Ammonia-Water Equilibrium Data, Average

Temperature 610.2 K
no. T,K P,MPa XNH~ YNH, K N H ~ KH*
1 610.23 14.080 0.0000 0.0000
2 611.94 14.821 0.0076
3 611.86 14.318 0.0087 0.0158 1.816 0.9928
4 612.06 14.889 0.0157
5 611.33 15.117 0.0157 0.0279 1.777 0.9876
6 612.26 14.948 0.0234 0.0403 1.722 0.9827
7 607.77 15.060 0.0261 0.0452 1.732 0.9804
8 608.64 15.300 0.0808
9 608.84 15.566 0.0440 0.0759 1.725 0.9666
10 608.49 15.808 0.0498 0.0841 1.689 0.9639 0
11 608.37 15.892 0.0513 a
2
12 609.01 16.144 0.0531 0.0939 1.768 0.9569
13 610.37 16.626 0.0599 0.1156 1.930 0.9408 LLi
LY
14 610.10 16.827 0.0703 0.1229 1.748 0.9434 3
15 610.20 17.229 0.0775 0.1375 1.774 0.9350 0
m
16 610.40 18.003 0.0930 0.1537 1.653 0.9331 W
LY
17 612.00 18.537 0.1167 a
18 612.30 19.159 0.1311
19 609.89 20.321 0.1370 0.2034 1.485 0.9231
20 608.91 20.653 0.1546 0.2225 1.439 0.9197
21 609.19 21.422 0.1623 0.2548 1.570 0.8896
22 610.01 21.887 0.1751 0.2485 1.419 0.9110
23 610.10 21.869 0.1803 0.2522 1.399 0.9123
24 611.42 21.917 0.1884
25 613.22 21.691 0.1904
26 609.44 22.406 0.2251 0.2529 1.124 0.9641
27 607.90 22.468 0.2282 0.2551 1.118 0.9651

Table XV. Ammonia-Water Equilibrium Data, Average

Temwrature 618.1 K 0 0 2 0'. 4 0.6 0' 8 1
MOLE FRACTION OF AMMONIA
Figure 2. Phase diagram for ammonia-water up to the critical point
2 617.68 16.273 0.0160 of ammonia.
3 617.48 16.371 0.0211 0.0345 1.635 0.9863
4 617.94 16.705 0.0260 0.0463 1.781 0.9792
5 617.74 17.654 0.0340 0.0585 1.721 0.9746 Other criticar points were estimated by extrapolating. Esti-
6 618.64 17.629 0.0357 0.0495 1.387 0.9857 mated critical points are presented in the table.
7 618.77 17.919 0.0486 Comparison wtth Other Work. Figures 6-10 present some
8 617.76 18.643 0.0570 0.0714 1.253 0.9847
9 618.66
of the current results in comparison with selected data of
19.263 0.0796
10 618.15 20.436 0.0741 Wucherer, GTllespie et al., and Guillevic et al. The lines in these
figures are those fitted to the present data and plotted in Figures
parent reddish phase over the whole visible area of the window. 2 and 3.
This phase and the two bright phases which resulted when Data from Wucherer (78) are compared with three of our
some water was added were analyzed and are reported in isotherms in Figure 6. I t has been necessary to interpolate
Table X V I I . points from Wucherer's tables of smoothed data in order to
 Journal of Chemical and Engineering Data, Vol. 32, No. 2, 1987 189

26

24

22

20

18
0
a
I 16

W'
Ly: 14
3
v,
v,
W 12
Ly:
a
10

0 U.J 1 1u
0 0'. 2 0.4 0'. 6 0'. 8 1 PRESSURE, MPa
MOLE FRACTION OF AMMONIA
Flgure 5. Egulilbrlum ratios for ammonia-water from the critical point
Flgure 3. Phase diagram for ammonia-water from the crltical point ofammonia.to the criticai point of water.
of ammonia to the critical point of water.

381 9 K 381 9 K
405.5 K ..... 495.5 K
2

0
CL
2
W-
Ir
6
m
W
(r
a '

0
0'. 2 0'. 4 0'. 6 O'. 0
MOLE FRACTION OF AMMONIA
Flgwe 4. Equllibrium ratios for ammonia-water up to the crltical polnt Figure 6. Comparison with data of Wucherer (1932).
of ammonia.
general, however, the agreement is reasonable when viewed
prepare this figure. I n general, Wucherer's vapor and liquid on Pxyaxes.
phases are somewhat richer in ammonia at a given tempera- We have chosen to compare the Pxy measurements of
ture and pressure than is indicated by our measurements. I n Gillespie et ai. (22) for two isotherms close to isotherms we
 190 Journal of Chemical and Engheering Data, Vol. 32, No. 2, 1987

I 1 I I I I I I I
20 --
GILLESPIE ET AL. THIS WORK
- GILLESPIE ET AL. THIS WORK
0 405.9 K - 405.5 K
449.8 K 451.5 K

0
a
5
J
LT
3
v)
u)
W
LT
a

V I 1 1 1
1 3
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 6.6 0.8 1
MOLE FRACTION OF AMMONIA
MOLE FRAC TlON OF AMMONIA IN LIQUID
Fisue 7. Comparison with P7ky data of Gnlespie, wikling, and wilson. Flgure 9. Comparison with relative volatilii data of Gillespie, Wilding,
and Wilson.

0 405 9 K 405 5 K GULLIEVIC ET AL. THIS WORK

0 449 8 K 451 5 K 405.5 K
8
453.1 451.5 K

0
a
2
W-
r
y
3
v)
m 4
W
LT
a

03 1 10
PRESSURE, MPa 0 -r-- r 1

Flpwe 8. Comparison with equilibrium ratio data of Gillespie, Wilding, 0 2 0 4 0 6 o a 1

and Wilson. MOLE FRACTION OF AMMONIA
Flgure 10. Comparison with data of Guillevlc, Richon, and Renon.
measured. The comparisons are made in Figures 7, 8, and 9,
(Gilkpie et al. (22) report many more PTx measuements than at 405.5 K included some points (two points on the P-x curve
, PTxy measurements.) and one point on the P-y curve) that we have since decided
Gulespie et al. (22) had access to our data in an early form were faulty, due to unexplained errors. The elimination of these
when preparing their report. I n this early form, the isotherm points permits the conclusion that our data and those of Gil-
 J. Chem. Eng. Data 1987, 32, 191-193 191

lespie et al. are in quite reasonable correspondence, as viewed (15) Perman, E. P. J . Chem. Soc. (London) 1903, 8 3 , 1168.
(16) Moller, H. Z . Ver. Dtsch Ing. 1908, 52. 1315.
even on relative volatility axes which exaggerate any scatter. (17) Wilson, T. A. The Total and Part&/ Vapor Pressures of Aqueous Am-
Figure 10 shows data of Guillevic et at. (297 at two tem- mon& ; Bulletin 146; Englneering Experimental Section, University of
peratures along with isotherms from our data at temperatures Illinois, Champaign, 1925.
(18) Wucherer. J. J . Gesamt. Kalte-Ind. 1932, 39, 97.
near their values. The temperature differences leave room for (19) Clifford, I.L.; Hunter, E. J . Phys. Chem. 1933, 37, 101.
question, but there seem to be differences between their data (20) Kracek. F. C. J . Phys. Chem. 1930, 34, 499.
(21) Perry, R. H.; Green, D. W.; Maloney, J. 0. Perry's Chemical Engi-
and ours, particularly along the dew-point curve at 453.1 K. neers' Handbook, 6th ed.; McGraw-Hill: New York, 1984.
The difference in relative volatiltty may be around 25 % at some (22) Gillesple, P. C.; Wilding, W. V.; Wilson, G. M. Vapor-LiquM Equilibrium
compositions. Measurements on the Ammonia - Water System from 3 73 K to 589 K ;
Research Report RR-90; Gas Processors Associatlon: Tulsa. OK,
Correletlon of Data. The data have been fitted with a num- 1985.
ber of equationof-state models, as reported elsewhere by Rizvi (23) Scatchard, G.; Epstein, L. F.; Warburton. J. Jr.; Cody, P. J. Refrig.
Eng. 1947, 53, 413.
( 3 1 ) and Heldemann and Rizvi (32). (24) Pierre, 6. Kyltek. Tidskr. 1959, 18, (Sheet 14), 89.
RwIStry NO. NH, 7664-41-7. (25) Macriss, R. A.; Eakin, 6. E.; Elilngton, R. T.; Huebler, J. Physical and
-
Thermodynamic Properties of Ammonia Water Mlxtures ; Bulletin 34;
Institute of Gas Technology: Chicago, IL. 1984.
Literature Clted (26) Tsiklis, D. S.; Linshits, L. R.; Goryunova, N. P. J. Phys. Chem. USSR
1965, 39, 1590.
(1) Carius, V. L. Ann. Chem. Phann. 1858, 99, 129. (27) Polak, J.; Lu, 6. C.-Y. J . Chem. Eng. Data 1975, 24, 182.
(2) Roscoe. H. E.; Mttmar. W. Ann. Chem. phenn. 1859, 772, 326. (28) Pawllkowski, E. M.; Newman, J.; Prausnitz, J. M. Ind. Eng. Chem.
(3) Slms, Th. H. Ann. Chem. pherm. 1861. 178, 333. Process Des. Dev. 1982, 27, 764.
(4) Watts, W. M. Ann. Chem. Phann. 1864, Suppl. 3, 227. (29) Guillevlc, J.-L.; Richon, D.; Renon, H. J. Chem. Eng. Data 1985, 30,
(5) Reouit, M. F.-M. Ann. Chem. Phys. 1874, 1 , 262. 332.
(6) Maiiett, J. W. Am. Chem. J . 1897, 19, 604. (30) Edwards, J.; Newman, J.; Prausnttz, J. M. Ind. Eng. Chem. Fundam.
(7) Pickering, S. U. J. Chem. SOC.(London) 1893, 63, 181. 1978. 77, 45.
(8) Rupert, F. F. J . Am. Chem. Soc. 1909, 31, 866. (31) Rizvi, S. S. H. Ph.D. Dissertation, University of Calgary, Calgary, Al-
(9) Rupert, F. F. J . Am. Chem. SOC. 1910, 32, 748. berta, Canada, 1985.
(10) Smlts. A.; Postma, S. Roc. Sect. Sci. K . ned. Akad. Wet. 1914, (32) Heldemann, R. A.; Rizvi, S. S. H. Fluid Phase Equilibr., 1986, 29, 439.
17, 182.
(11) Postma, S. Red. Trav. Chlm. 1920, 3 9 , 515.
(12) Elliott, L. D. J . Phys. Chem. 1924, 28, 887. Received for review March 28, 1986. Accepted September 17, 1986. This
(13) Mironov, K. E. J. Gen. Chem. USSR(Eng1. Trans/.) 1955, 25, 1039. research was supported by a grant from the Natural Sciences and Englneer-
(14) Perman, E. P. J. Chem. SOC.(London) 1901, 79, 718. lng Research Councll of Canada.

Binary Gaseous Diffusion Coefficients. 5. Cyclooctane and

trans-1,2-Dimethylcyclohexane with Helium, Argon, Methane, and
Sulfur Hexafluoride at 1 atm and 313-343 K

Tracy Park, Timothy R. Rettich,? and Rubln Battino"

Chemistry Department, Wright State University, Dayton, Ohio 45435

Emmerich Wiiheim
Znstitut fur Physikalische Chemie, Universitat Wien, A- 1090 Wien, Austria

systems invoking spherical molecules of a wide range of sizes

The blnary gaseous diffusion coefficients for cyciooctane
(He, Ar, CH, SF,) with two isomeric alicyclic C8 compounds of
and trans-1,2-dimethyicyciohexane diffusing into helium, different ring size, viz., cyclooctane (C8HI8) and trans-l,2di-
argon, methane, and sulfur hexafluoride were measured at
methylcyciohexane (trans-1,2-(CH3)2C6H,0). I n particular, we
about 313.15, 328.15, and 343.15 K and atmospheric wished to determine whether there were any discemible effects
pressure by the capillary tube method of Stefan. The associated with differences in ring size of otherwise quite similar
experimental results are compared wlth diffusion alicyclic isomers.
coefflcients calculated vla the first-order
Chapman-Enskog approximation. For the gases, eff ectlve Experimental Sectlon
LennardJones (6, 12) pair potential parameters were
taken from recent literature; for the iiqulds they were The experimental procedures were identical with those de-
obtained from an extended correspondlng-states scribed in detail in our earlier papers (1-4). Thus, only a brief
correlation suggested by l e e , Gotoh, and Stewart. summary will be presented. The Stefan capillary tube method
(5)was used, running each solvent/gas pair in duplicate at
about 313.15, 328.15, and 343.15 K and approximately at-
Introduction
mospheric pressure. Temperature was controlled to better than
This study continues our earlier investigations ( 1-4) into fO.O1 K in a 80-L water bath over the periods of the mea-
binary gaseous diffusion coefficients. We now report on eight surements, which ranged from 2 to 10 days. Temperatures
were measured with a calibrated platinum resistance ther-
mometer on IPTS-68. The total pressure of about 1 atm
Department of Chemistry, Illinois Wesleyan University, Bioomington, IL
61702. (=101.325 kPa) was controlled with a mercury-filled Cartesian
Visiting Associate Professor at Wright State University. manostat to better than f0.9 kPa for all runs except for helium

002 1-95681871 1732-01 9 180 1.5010 0 1987 American Chemical Society