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    Survey and Assessment of Availablle Measurements On Thermodynmic Properties of The Mixture

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    kangsungjin

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    © All Rights Reserved
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    Survey and Assessment of Available Measurements on Thermodynamic Properties of the Mixture {Water+ Ammonia} Reiner Tillner-Roth”” and Daniel G. Friend (National inatisute of Standards and Tectoology, Physical and Chemical Properties Division, 325 Broadway, Boulder, Colorado 80303 Rooevea Mare 4, 1997; final manuscaptrceved October 30,1997 Mixtures of water and ammonia play an important role in absorption refrigeration cycles and have received attention as working fluids in modem power generation cycles. For design and simulations during the development of any application, the thermody. namic properties have to be known accurately. Measurements of available thermody- namic data are compiled and summarized. The data sets are compared, using a Helmholtz fee energy formulation. Recommendations are given for which data sets are suited to serve as a basis for an equation of state formulation of the thermodynamic properties of {water-+ammonia}. Gaps the database are shown to give experimenters orientation for Future reach. © 1008 Amorican Intute of Physics aoa Aina vane Chenivul Siriety. [s0047-2689(98)00301-8] ey words: ammonia-water, dats survey, iste, themodynsmne properties. Contents. Introdvetion. .... cee 46 2. Survey of Experimental Dai, .--s esses 46 2.1. Vapor—Liquid Equilibrium... 247 2.2. Single-Phase Properties. . 48 29, Sla-Ligs-vapor Boundary and Catal Locus. cee 49 3. Data Comparisons. reopens 2) 3.1. The Teiplo Point Lino. ves vs rv 49 3.2. Fluid Properties.....0.... 49 3.2.1. VLE Data, 50 3.22. Saturated Liquid Densities. . 37 3.23. (p,¥.T,x) Data, pete 324, Clore Proper...» cee 4. Conclusion... : ar) 5. Acknowledgements, cy 6. Appendix, — : 0 7. References... conan ea List of Tables L. Summary of experimental data for {water‘+ammonia}....,. a 2 Summary of experimental data forthe tiple eit line of {water-+ammonia}......... 31 ‘3 Comected VLE data of Wucherer..... 55 1998 by the U.S. Secretary of Commerce oa behal ofthe United Sates. ‘All sigs reserved. This coptigh is tesgned othe Ameen Taste of Pris aod the Amarcan Chemis Sock. Reprints aaa from ACS; se Reps List at back of iste, “Author whom conespoence shold beads: Permanent es \Usverit Hanover, lsat ie Thermodynamik, Caisse 36, 30167 Hanoover, Gentay. Ooe7-2snaran7nasi7i612.00 List of Figures 1. Distribution of measured (p,7,x) data (4 (p.Tx,y) data 00), and (Tex,y) data (0) ina T,x diagram, .. 50 2. Distribution of measured (p,T,y) data ( (pst x,3) data (), and (T.x,y) data (0) ina T.y diagram... .. 50 3. Distribution of measured om V.T,x) data in'a PoP diagram. . oe 50 4. istibuton of liquid caloie data in 7.x dliggram. sl 5. Taple point temperatures of {water rammonia. ‘Triple-point temperatures Ta. in (b) are calculated from Eq. (I)... 2... ae 6. @)=(0) Revintione hotwaen maaenred liquid ‘mole fractions x and values calculated from Eq, (2) at tabulated values of pressure p and temperature 7... - 2 7. (a)=(G) Deviations between measured vapor ‘mole fractions y and values caleulated from Eq, (2) at tabulated values of pressure p and temperature 1... 33 8. Relative deviations of vapor mole fractions y from values calculated from Eq, (2) at tabulated values of temperature T and vapor mole fraction y...... 4 9. Deviations between measured saturated liquid” densities and values caleulated from Fa. 2). 5 10. Deviations between measured compressed liquid dnsities and values calculated from Eq, (2). 58 11 Deviations between measured vapor densities and values calculated from Eq. (2)...0.2s0+0+. 58 12, Deviations between liquid enthalpies and values 4. Phys. Chem. Ret. Ota, Vol 27, No 1, 1998 46 R. TILLNER-ROTH AND D. G. FRIEND calculated from Bg, (2). 9 13. Isobaric heat capacity inthe liquid. C, of NH and HO was calculated from pure fluid ‘equations. Calculated C, at x=0.3, x=0.5, and 2 =U./ 8 aerived trom énthalpies of Zannet. ow 14, Deviations of saturation temperatures for water (@) and ammonia (4) of Wucheres’s original {ablation from valuee ealowlated from tho pure fluid equations of state. . 15, Deviations of liguid mole fractions x measured by Wucherer from values calculated from Ea, (2) at tabulated values of pressure p and temperature Tee... eses.5 9 39 Nomenclature molar Helmholtz free energy molar isobaric heat capacity molar enthalpy uotat uipy OF nating ‘number of tabulated data pressure universal gas constant temperature ‘molar volume liquid mole fraction of ammonia vapor mole fraction of ammonia reduced Helmholtz free energy; A7R,.7 inverse reduced volume or reduced density; oF inverse reduced temperature; 7,/T OY k GBS BEN oy g Subscripts e critical cae calculated ow experinenal n reducing propery © triple, sold-tiquid-yapor boundary om ‘ire component 1 (wer) 2 pure component 2 (ammonia) Superseripts ° ideal gas residual, secured guia 1. Introduction ‘The mixture {water-ammonia} is of special interest as a working fluid in absorption cycles, reftigeration, and heat recovery. Recently, such mixtures have been proposed for use in the Kalina cycle for increased efficiency in power generation." Water and ammonia are natural Nuids which do ‘J. Phys, Chom, Ref, Data, Vol 27, No. 1, 1998 not harm the environment. Therefore. they are also consi eed as alternative refrigerants to replace chlorofluorocarbons n some refrigeration applications. From the thermodynamic point of view, water and ammo- ia are strongly polar substances. ‘Their ctitcal points are considerably different: critical temperatures differ by more than 240 K (7.40540 K for ammonia and T,=647.096 K foc water). “Aloo the critial prosoure of watce (p.=22.064 MPa) is about twice as large as the critical pres- ssure of ammonia (p.=11.339 MPa). ‘The normal beiling point of water (373.13 K) is about 135 K higher than the normal boiling point of ammonia (239.81 K). The mixture {water+ammonia) covers a very wide temperature range from below 200 K to 647.096 K. Compositional differences between the coexisting liguid and vapor phases are consid ctable. Mixing effects in liquid are particularly large. The liquid volume of mixing is in the order of ~10% to ~ 20% and the enthalpy of mixing is up to —4 1 mol”) ‘The thermodynamic properties of the system {oater++ammonia} have been measured by numerous re- searchers during the last 150 years. The vapor—liquid equi librium (VLE) has been of primary interest due to the re- quirements of the absorption cycle, Further measurements ‘dal with caloric or thermal behavior in the liquid and vapor phases. ‘Several data compilations have been published during the last 80 years”""” However, none of them gives a complete ‘overview and detailed comparisons of avilable experimental data necessary to establish an accurate equation of state ‘To fill this gap, available measurements of the thermody- namic properties of {water+ammonia} mixtures have been ‘compiled. Comparisons were conducted with an equation of state which was developed simultaneously with the data as- sessment by Tillner Roth and Friend."! Based on this analy- si, the most reliable measurements fr the thetnicaynaniic properties of {water+ammonia} are identified. 2. Survey of Experimental Data Extensive experimental work hat heen carried out on the system {water+ammonia}. Available sources published through the end of 1995 are summarized in Table 1. Most references report vapor-Liquid equilibrium (VLE) properties. Information on single-phase properties is more limited than available VLE data, ‘A significant effort has been made to survey and update ‘ld experimental da, Temperature conversion OF measure ‘ments dated before 1927 into the current temperature scale {(1TS-90) is not definitive because the first internationally ac- cepted temperanire srale suas releaced that year. Por older sonrees, temperatures were, therefore, assumed to be given according to IPTS-27. Although additional uncertainty oc- curs because ofthis assumption it isnot regarded as a serious source of error, since the uncertainties of most older data are higher than those associated with any differences between the temperature scales, ‘SURVEY OF THERMODYNAMIC PROPERTY DATA OF THE MIXTURE {WATER+AMMONIA} 47 A further difficulty arises when authors give their results in the form of smoothed tables or values rather than listing, ‘heir original experimental data points. Furthermore. some of| these smoothed sets of data are additionally based on mea- surements of other authors. Such sources are of limited value. Errors due to smoothing are already incorporated in the tabulated numbers. By including other experimental data during the smoothing procedure, the original experimental information is further obscured. Therefore, most of these results?®3-5 were not further Cousidered in the data com= parisons. Exceptions were made for the VLE data of Wucherer.” the saturated liquid enthalpies reported by Zinner*, and the (p,T 2) data reported by Pierre! Their tabulated values are based exclusively on their unreported measurements. The data of Zinner and of Pierre were only converted to ITS-90, and those of Wucherer were adjusted inthis study. Wucherer reports vapor pressures for the pure components in addition to measurements for the mixtures. With these vapor pres- sures, sauration wemperauures were calculated from te pure fluid equations of state."-%® These temperatures form 2 tem- perature scale for Wucherer's data and are used to correct the reported temperatures for the mixture measurements. The conversion process is described in the Appendix. 2.4. Vapor—Liquid Equilibrium The distribution of VLE data is illustrated in a (T,x) dia- gram (Fig. 1) for the saturated liquid and in a (7,y) diagram, (Fig. 2) for the saturated vapor. Due to the large number of sources, only different types of VLE data are distinguished by different symbols, ic. (P.T.x), (p.To¥)s (P.Tex¥)y and (Paxy) data. For the liquid side, a very large quantity of experimental data is available. The data extend to the critical ine and reach down tothe feazing Tine. However, rwo regions in the liquid become apparent where comparatively few data are available, The first region is observed between 250 K and 350 K for high ammonia concentrations. The second is the temperature range above $00 K at low and intermediate am- ‘monia concentrations. Some data lying above the critical line ‘drawn in Fig. 1 indicate experimental disagreement in the vieinity of the critical locus. (On the vapor side, the majority of measurements is found at hich ammonia mole fractions. This is not surorising. be- ‘cause the vapor phase consists of almost pure ammonia over 2 large range of pressure and temperature, At lower ammonia concentrations, the number of experimental data becomes smaller. Jn addition to data which are concemed with the (p,T,x,y) behavior, saturated liquid densities were reported for temperatures below 520 K. Additionally, the enthalpy of the saturated Tiquid has been reported by Zinner"* up t0 453 K. These data are discussed in the next section, together with caloric data in the single-phase region. For higher tem- ‘peratures, no densities or calorie properties have been mea~ sured at saturated states. Most important, no information on saturated vapor densities or saturated vapor enthalpies could be found. ‘TaBLe 1, Summary of experinentl data foe [ater Fanmonis) Source Year " TK PIMP AN) (7.2) dia babble print meaninet caas® 1156 6 "13-298 a 025-039 Foote 121 0 233-03 005-02 029-053 Giese oa 19851987 ry 313-588 01-208 mns-099 Guilvi ral 1985 B 403-505, 134 907-027 Seen" 1965 n 231-190 005-37 010-079 Minas eat 1925 si 01-09 021-052 Mote 1998 3s 01-09 012-052 Berman? rat n 0900-028 908-034 Piene™™ 1959 an) pore) 05-01 Postma 1920 2m 001-178 orz-10 ipl and Hebemaa 1087 36 on2-219 0007-088 Roscoe and Dumas" 1859 u 0.002-026 007-069 Susan etal 1990, um 13-215 185-08 Sime 1361 6 mmm (0002-028 006-052 (0.7) data (dew goat messuereis? Gate wa 1985 21 ‘a-503 08-67 oss-o974 Macs a 1968 6 535-390 1536 > 0966 Neahausen and Pate” iat 8 25-313 44-055, Dog Postma 10 ” 433-508 10-16 074-0932 Rio ant Hejtemana® oR 4 3S-ol8 09-193 008-0985, Sassen tal 1990 13 31453 o1-97 02-05 41 Phys. Cham. Raf. Data, Vol. 27, No. 1. 1998 48 R. TILLNER-ROTH AND D. G. FRIEND ‘Tame 1, Sommay of experimental fr (nse nmi Conti Range of da Source Your ” 7 ht ny ars tor a Hee 1 a 333-420 om7-16 0016-026 Gite ra 1381087 4 Bisse ois ‘ias-a38 Guile ea 1935 s ans "4457 18-088 ar Water” 1995 «6 ‘8-373 026-182 ‘308-09 bio ea 197s 2 20-303 ‘101s oms-asrs tar 98s “a sss Sete 7-089 Kia? 1996 135, 313-303 alot Mere at i988 wo m3 foros ‘Neus and Dak? var a” map 038 O46 Perma” 1903 2 23-383 ‘aon2-08 s-025 otk a La 1975 a 3-00 O1-0at ‘aoor-n04 ies and Hes 1987 2s 503-618 003-225 01-099 Woo 1925 a mas ots ‘6-088 Woeneree 1932 3) aa ‘001-2 ‘0ns-03 (Tang) da Dora and Boat” 1963 is 3015 5003, 9<03 Tne ae Drewes 1 Fi ae : eto Sones 1963 is 20-600 s<0001 Pai presses Hoopes” 192s ° 21-300 ao1-a1s Sur td dst ite cr a * 1989 14 313-518 or-on Manne Watt! 1995 a 25-413 01-09) essing 196s 7 27-490 91-079 iste 1936 % m8 oal-os Wacko? 1 2 2S nao p07 data Bena ‘9st 32 ms 000-83 ame Wstrebers (igi) 1995 08 28-413 as. 01-09 Harms Wazcobere™ (yee) 1995 26 33-408 om-as 435-075 ‘Netgeen and Pic wat 31 mas aos 035-087 Sou 193 its 25-403 0 a1-n9 ‘Sette tigid ext ine wu (46) 2-483 oras Enthapy of mise ‘Stud toe 2 oars oa ote-098 ntapy iterences sci tal 1968 ‘a soo-a97 14-52 05-039 (crn a8 Ginsu 1966 1 133-258 on 038, ikea ad Gigue 1953 o 197-290 ot 05-067 rewaky and Kaigrost?™ 1 2 208-334 a aor-040 ‘Social di indicat wh partes Sate ron in column 6 are vapor re eae apr moe fasion me cleaued. ‘an ae repre, ba only tt composton wes messi, “nit fn saan ae oe Ac "arpa | Available sources of single-phase measurements are also listed in Table 1. (p, ¥,T.x) data are plotted in a (p,T) dis- ram in Fig. 3. The extensive set of liquid densities of ‘Harms-Watzenberg” covers temperatures between 243 K and 413 K up to 38 MPa for five diferent compositions. ‘Additional (p, 7,7.) measurements for the liquid density 44 Phys. Chem, Ref, Data, Vol. 27, No.1, 1998 su sept ty Stank! en Fe wae Uf a by Neuhausen and atick” and by Cass.” Thore are n0 single-phase quid densies available above 413 K and be- ow 28 K “Two sources? report densities in the vapor phase reach- ing from 323 K to 523 K. They cover almost the entre concentration range. The maximum densities, however, do not exceed I'S moldm? and donot extend othe sation SURVEY OF THERMODYNAMIC PROPERTY DATA OF THE MIXTURE {WATER+AMMONIA} 49 boundary. No vapor densities are available for higher and supereriical temperatures “Measurements of ealoric properties were found only for the liquid phase. Their distribution is shown in Fig. 4 in a (7.x) diagram. Enthalpies of mixing were measured by Staudt” in the lguid phase between 298 K and 373 K for pressures up to 12 MPa and also by Baud and Gay” at 285 K. Band and Gay do not report pressupes; therefore, tmogphene peste coniions are asume/ bee. Macs er al® report experimental cutlialpy differcuces in the liquid at starting temperatures up to 500 K and pressures up to 5 MPa, Measurements ofthe isobaric heat capacity are avil- able from three sources®™5? herween 24 K and the freezing line. No pressures were given for these cy values. It is as- sumed that these measurements were also catied out at at- rmospheric pressure conditions. 'No calorie measurements could be found forthe vapor oF in the supercritical region. 2.2. Colld_ Liquid Vapor Boundary and Crit Locus ‘Temperatures ofthe solidliquid-vapor loews are reported by hive sources (able 2). All sources are more than 70 years old. In addition, Postma’? measured the triple-point pressure as a function of temperature. Measurements cover the entire concentration range from pure water to pure arsmonia. Com positions and temperatures of the three eutectic points were only given by Postma and by Rupert * ‘A few values for temperature. pressure and composition of, the critical line are reported by Rizvi and Heidemann.” Sas- sen eta, and by Postma.” The critical region and critical locus willbe the topic of a separate paper by Rainwater and Tillner Roth.” 3. Data Comparisons 32, Ine Inpie-Point Line ‘The wipl-point line is shown in a (Tx) diagram [Fg Stall. Thee eutectic points are observed near x=0334, 701584, and x=0.815. Two temperature maxima occur at {he compositions of the solid compounds NH H0 (x=0.5) and 2NH,-H,0 (2=23). The temperature of the soid- Tiguid-vapor boundary has been correlated by the following four equations: Tals) 0s r<033367 urbe ber” o3n267

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