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DOI: http://dx.doi.org/10.20534/AJT-16-9.10-83-90
Soliev Lutfullo,
Department of General and Inorganic Chemistry, Faculty of Chemistry, Tajik State Pedagogical University,
Dushanbe, Tajikistan Jumaev Maruf,
Department of General and Inorganic Chemistry, Faculty of Chemistry, Tajik State Pedagogical University,
Dushanbe, Tajikistan Tursunbadalov Sherali, Department of Chemistry, Faculty of Natural and Applied Sciences, Nigerian Turkish Nile University, Plot 681, Cadastral Zone C-OO, Research & Institution Area,
Abuja, Nigeria, E-mail: sheerchem@gmail.com Usmonov Mahmadsalim, Department of General and Inorganic
Chemistry, Faculty of Chemistry, Tajik State Pedagogical University, Dushanbe, Tajikistan Avloev Shohiddin, Department of General and Inorganic Chemistry, Faculty of Chemistry, Tajik State Pedagogical University,
Dushanbe, Tajikistan
Structure of solubility diagram of the quaternary Na, Са//So4, ta3-H2O water-salt system at 25oC
Abstract: The results of the solubility investigation in the quaternary Na, Ca//SO4, CO3-H2O water salt system along with its solubility diagram at 25oC are considered in this work. There are 4 invariant points, 8 monovariant curves and 6 divariant fields which are saturated with 3, 2 and 1 solid phases and their relevant equilibrium liquid phases respectively. The crystallization field of the calcite CaCO3 covers most of the part of solubility diagram of investigated quaternary water-salt Na, Ca//SO4, CO3-H2O system at 25oC, which signifies the low solubility of the latter salt in the given conditions.
Keyword: solubility, quaternary system, equilibrium, XRD.
The considered quaternary water-salt Na, HCO3, F-H2O system and its constituent five — and
Ca//SO4, CO3-H2O system is a part of more complex six-component Na, Ca//SO4, CO3, HCO3, F-H2O system whose phase equilibria knowledge determine the conditions of exploitation of liquid wastes released from the aluminum production. Wastewater outlets of regeneration of cryolite in aluminum smelters contain fluorides, carbonates, bicarbonates and sulfates of sodium and calcium [1-4]. The crystallization and dissolution processes of salts in aqueous solutions of these wastes are determined by the laws of phase equilibria in the six-component Na, Ca//SO4, CO3,
four-component subsystems.
In the present work; the results of investigation of quaternary Na, Ca//SO4, CO3-H2O system at 25oC by means of solubility method are deliberated with the purpose of establishing the concentration parameters at the geometrical figures of the system along with determining the ratio of the individual equilibrium crystallization fields of existing solid phases in the system.
Literature review shows that; the title quaternary system has not been investigated on the overall composition that is with the involvement of all its four components
simultaneously at 25oC. There are data on some more complex [5-10] systems at 25oC each of which also includes the quaternary Na, Ca//SO4, CO3-H2O system as a subsystem. But those data are unlikely employable on the system under our consideration; as the phase equilibria and a closed phase equilibria diagram is required in order to fully exploit the system ingredients.
The mineral solubilities to high ionic strengths in the multicomponent Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system which also involves the Na, Ca//SO4, CO3-H2O quaternary system as well have been predicted by Charles E. Harvie et al at 25 °C [9]. Unfortunately, neither the phase equilibria diagram has been deliberated thereby nor has the solubility diagram in the considered quaternary Na, Ca//SO4, CO3-H2O system at 25° been presented by the authors.
A chemical equilibrium model of solution behavior and solubility in the H-Na-K-Ca-OH-Cl- HSO4-SO4-H2O system to high concentration and temperatures are published by Christomir Christov and Nancy Moller [10]. Although the three; Na+, Ca 2+ and SO42-components of our considered quaternary system exist in the this multicomponent H-Na-K-Ca-OH-Cl-HSO4-SO4-H2O system and as the third C032-component is missing; it is already insufficient data for the determination of the phase equilibria in the quaternary water-salt Na, Ca//SO4, CO3-H2O system and do not enable one to construct its solubility diagram at 25oC.
As it is evident; the title quaternary Na, Ca//SO4, CO3-H2O system has not been tackled as an independent system in the latter two literature data [9,10]; they are far from enabling one the construction of the closed phase equilibria diagram of the system at 25oC and presenting the complete phase equilibria data at the geometrical figures of the diagram.
The two available data on the entire quaternary system where all its four Na+, Ca2+, SO42-and CO32-com-ponents are dealt as a single set were published in J. Phys. Chem., 11, 415, (1907) and Z. Anorg. Chem., 71, 206, (1911) by F. K. Cameron et al. [11, 13] and W. Herz respectively [12, 13]. The unfortunate case of these works is that; the authors have characterized the system with the presence of the just CaCO3 as the single solid phase which crystallizes in the system at 25oC. As it is dictated by the third basic principle of physicochemical analysis [14] along with the translation method [15; 16]; the geometrical figures of the n-component subsystems are transformed into a unit higher versions; that is the points to curves, the curves to fields and the fields to volumes etc. of the global sys-
tem and translated to the (n+1) - component overall composition. Hence the title quaternary system cannot be characterized with the presence of the only one solid phase when its entire composition is considered. Briefly, according to the founder of third fundamental "compatibility principle" of the physicochemical analysis — Goroshenko Ya. G.; all the solid phases which participate in the composition of the one component less subsystems are expected to take part in the structure of the global system which involves them. This criterion of the physicochemical analysis thus reveals the incompleteness of the latter [11; 12] works better.
The need for recourse on the ternary subsystems of the title quaternary system hence emerges hereby. Earlier the phase equilibria in the title system were investigated [17] by our team members and its schematic closed phase diagram was constructed by means of the translation method [15, 16]. The considered quaternary water-salt Na, Ca//SO4, CO3-H2O system is composed of the following four; Na2SO4-CaSO4-H2O, Na2 C03-CaC03-H2O, Na2SO4-Na2 C03-H2 O, and CaSO4-CaC03-H2O ternary subsystems. The data on the latter ternary subsystems [18-22] of the considered quaternary system were used in order to fully predict the phase equilibria and construct schematic phase equilibria diagram for the considered quaternary watersalt Na, Ca//SO4, CO3 — H2O system [17].
The system at 25oC has been characterized to involve 4 invariant points, 8 monovariant curves and 6 divariant fields which are saturated with 3, 2 and 1 equilibrium solid phases and relevant liquid phases respectively in latter work [17].
As we intend to determine the solubility at the previously predicted geometrical figures [17] and construct the comprehensive solubility diagram of the system in the present study; the experimental procedures have proceeded according to the solution saturation method [23] as follow below:
Initially, the composition of the saturated solutions at the ternary invariant points in; Na2SO4-CaSO4-H2O, Na2 C03-CaC03-H2O, Na2SO4-Na2 C03-H2 O and CaSO4-CaC03-H2O subsystems at 25 0 C of the investigated quaternary Na, Ca//SO4, C03-H2O system were prepared on the basis of the solubility data in literature [18-22]. There are the following six equilibrium solid phases: Na2SO4-10H2O — mirabillite (Mb); CaSO4-2H2O — gyp sum (Gp); Na2SO4-CaSO4 — glauberite (Gb); Na2CO3-CaCO3-5H2O — geylussite (Gl); CaC03 — calcite (Cl) and Na2CO3-10H2O — C-10 which crystallize in the quaternary Na, Ca//SO4,
C03-H2O system at 25oC. The following chemical reagents were used in the experiments: Na2SO4-10H2O (chemically pure); CaSO4-2H2O (chemically pure); Na2 C03 (pure) CaC03 (pure).
Next, the simulated mixtures of the quaternary invariant points which generate according to the translation schemes [17] of the relevant ternary invariant points to the quaternary composition were stirred until the equilibrium states have been reached. The temperature was controlled in G-8 type ultratermostate. The mixtures were stirred by a magnetic stirrer PD — 09 during 50 -100 hours. The temperature was maintained within ± 0,10 oC using contact thermometer. The crystallization of the solid phases was observed through
the "POLAM P-311" microscope. The equilibrium solid phases were photographed with a digital camera «SONY-DSC-S500». The equilibrium achievements were followed on the immutability of the phase compositions of precipitates. Separation of the liquid phase from the solid phases was carried out by a vacuum pump through ashless (blue ribbon) filter paper on a Buchner funnel. The precipitates which are obtained by the filtration were washed with 96% ethanol and dried at 120oC. The chemical analysis of the product was carried out by the known methods [24-26].
The obtained results from the crystal optical analyses [27] of the equilibrium solid phases (photomicrographs) are shown in Figure 1.
Figurel.The photomicrographs of the equilibrium solid phases in the quaternary Na, Ca//SO4, CO3-H2O system at 25oC.
The results of the chemical analysis of the saturated solutions are shown in Table 1. Table 1. - Solubility at knot (invariant) points of the quaternary Na, Ca//SO4, CO3-H2O system at 25oC
Point No Composition of the liquid phase, W.% Phase composition of precipitates
Na2SO4 CaSO4 4 Na2 ^3 СаСО3 H2O
ei 21.9 - - - 78.1 Mb
e2 — 0.209 - - 99.791 Gp
e3 — — 22.95 - 77.05 C-10
— — - 0.0048 99.9952 Cl
E3 21.75 0.197 - - 78.05 Mb + Gp
E2 25.78 0.188 - - 74.032 Gp + Gb
E3 16.40 - 18.40 - 65.30 Mb + C-10
E4 - - 5.649 0.00349 94.347 C-10 + Gl
E5 - - 4.5 0.0024 95.497 Gl + Cl
E6 - 0.213 - 0.0048 99.782 Gp + Cl
E4 14.2 0.273 19.6 - 65.927 Mb + C-10 + Gb
E2 - 0.408 18.55 0.00547 80.987 Gp + Gb + Cl
E4 12.52 - 19.45 0.00521 64.977 C-10 + Gl + Gb
E4 - 0.328 20.7 0.00431 78.928 Cl + Gb + Gl
The solubility diagrams of the quaternary Na, Figure 2 are obtained based on the obtained data. Ca//SO4, CO3-H2O system at 25oC, which are shown in
Figure 2 (a). Solubility diagram of the quaternary Na, Ca//SO4, CO3-H2O system at 25 oC
The locations of the ternary (E 3) and quaternary (E4) invariant points in the diagrams where the "n" denotes the serial number of the relevant point are set by means of the centroid method [14].
Figure 2 (a) and Figure 2 (b) show the "comprehensive" and the "dry-salt" parts of the solubility diagram ofthe quaternary Na, Ca//SO4, CO3-H2O system respectively, where the reciprocal locations ofthe invariant points and the mon-ovariant curves along with the relative areas of the crystallization fields of equilibrium solid phases are reflected.
Figure 2 (b). Dry-salt part of solubility diagram of quaternary Na, Ca//SO4, CO3-H2O system at 25oC As is it shown in the Figure 2; the crystallization field of the calcite CaCO3 covers the significant part of the diagram which signifies the low solubility of the latter salt in the given conditions. The compositions of the geometrical figures (fields, curves, points) of the diagram in Figure 2 are described in Table 2.
Table 2. — Composition of geometric figures in Figure 2
Notation of geometrical figures Composition
1 2
ei Solubility of Na2SO4 phase in water
e2 Solubility of CaSO4 phase in water
e3 Solubility of Na2CO3 phase in water
e4 Solubility of CaCO3 phase in water
E The common crystallization point ofNa2SO4-10H2O and Na2SO4-CaSO4 phases in the ternary Na2SO4-CaSO4-H2O system
E2 The common crystallization point of Na2SO4-CaSO4 and CaSO4-2H2O phases in the ternary Na2SOrCaSO4-H2O system
E3 The common crystallization point of Na2SO4-10H2O and Na2CO3-10H2O phases in the ternary Na2SO4- Na2 C03-H2O system
E4 The common crystallization point of Na2CO3-10H2O and Na2CO3-CaCO3-5H2O phases in the ternary Na2 C03-CaC03-H2O system
E5 The common crystallization point of Na2CO3-CaCO3-5H2O and CaC03 phases in the ternary Na2 C03-CaC03-H2O system
E6 The common crystallization point of CaSO4-2H2O and CaC03 phases in the ternary CaSO4-CaC03 -H2O system
1 2
EÎ The common crystallization point ofNa2SO4-10H2O, Na2CO3-10H2O and Na2SO^CaSO4 phases in the quaternary Na, Ca//SO4, C03-H2O system
E2 The common crystallization point of CaC03 CaSO4^2H2O and Na2SO4-CaSO4 phases in the quaternary Na, Ca//SO4, C03-H2O system
E4 The common crystallization point ofNa2SO4-CaSO4, Na2CO3^10H2O and Na2CO^CaCO^5H2O phases in quaternary Na, Ca//SO4, C03-H2O system
E4 The common crystallization point of Na2SO4-CaSO4 CaC03 and Na2CO3^CaCO3^5H2O phases in quaternary Na, Ca//SO4, C03-H2O system
E3 E The common crystallization curve of Na2SO4-10H2O and Na2SO^CaSO4 phases in the ternary Na2SO4-CaSO-H2O system
E2 E24 The common crystallization curve of Na2SO4-CaSO4 and CaSO4^2H2O phases in the ternary Na2SO4-CaSO-H2O system
E3 E The common crystallization curve of Na2CO3T0H2O and Na2SO4-10H2O phases in the ternary Na2SO4-CaC03-H2O system
E4 E 34 The common crystallization curve of Na2CO3-10H2O and Na2CO3-CaCO3-5H2O in the ternary Na2 C03-CaC03-H2O system
E 3 E4 The common crystallization curve of CaC03 and Na2CO3^CaCO3^5H2O phases in the ternary Na2 C03-CaC03-H2O system
E 3 E24 The common crystallization curve of CaC03 and CaSO4^2H2O phases in the CaSO4-CaC03-H2O system
K Na2SO4 E ^Ej'Ej3 Crystallization field of the Na2SO4-10H2O phase
E 33 Na2 C03 E43E 34i214E 33 Crystallization field of the Na2CO3-10H2O phase
E3e *E4E 3E 43 4 3 4 5 4 Crystallization field of the Na2CO3-CaCO3-5H2O phase
EfE^E 34E44E24EE Crystallization field of the Na2SO4-CaSO4 phase
E 53 CaC03 E ¡E24E\E 3 Crystallization field of CaC03
E\E24E 3 CaSO4 E2 Crystallization field of CaSO4-2H2O
XRD analysis of the solid phased were performed on 0.1 degrees. The interplanar distance (dhkl), correspond-
DRON-3 (filtered CuKaa radiation Ni - filter) diffrac- ing to the reflection angles (0), were found in reference
tometer. The shooting speed of diffractogram was kept at tables [28]. The obtained results are shown in Table 3. 30 ang.s/min. Diffractogramms have been prescribed by
Table 3. - The results of XRD patterns of solid phases in quaternary Na,Ca//SO4,CO3-H2O system at 25oC
q 0, rpag 0, rpag 0, rpag
i 2 3 4 5 6 7 8
10.2 4.3532 12.04 3.6956 15.06 2.9669 14.03 3.1798
10.04 4.4219 11.31 3.9308 14.12 3.1600 13.09 3.4038
8.21 5.3983 10.28 4.3197 12.04 3.6956 11.40 3.9001
8.13 5.4511 9.35 4.7450 11.29 3.9376 11.31 3.9308
7.11 6.2282 7.38 6.0015 10.29 4.3156 10.30 4.3114
1 2 3 4 5 6 7 8
6.33 6.992 7.16 6.1849 9.34 4.7500 9.33 4.7500
- - 7.05 6.2803 8.37 5.2958 8.41 5.2708
- - 5.39 8.207 7.11 6.2282 7.33 6.0422
- - - - - - 7.17 6.1763
The presence of the corresponding solid phases in [28, 29] in diffractogramms. The diffractograms of
precipitates is determined by the existence of the the individual equilibrium solid phases along with their
diffraction patterns of the following; Mb, Gp, C.10, Cs, mixtures at the; divariant fields, monovariant curves
Gl and Gb most characteristic diffraction reflections and invariant points are shown in Figure 3.
Figure 3.Schemes of the X-ray diffraction at equilibrium solid phases in quaternary Na, Ca//SO4, CO3-H2O system at 25oC:
a) Mb + Gb + C.10 (point E 4 ); b) Gp + Gb + Cl (point E 4 ); c) C.10 + Gb + Gl (point E 3 ); d) Cl + Gb + Gl (point E 4 );
1 - Mb, 2 - Gp, 3 - C10, 4 - Cl, 5 - Gl, 6 - Gb
References:
1. Ermatov A. G., Mirsaidov U. M., Safiyev H. S., Azizov B. Recycling of wastes of aluminum smelters. Dushanbe, -2006.
2. Mirsaidov U. M., Ismatdinov M. E., Safiyev H. S. Environmental issues and complex processing of raw materials and wastes of manufacturing. Dushanbe. Donish, - 1999.
3. Morozova V. A., Rzhechitsky E. P. Russian Journal ofApplied Chemistry, - V. 49. - № 5. - 1976. - P. 1152.
4. Morozova V. A., Rzhechitsky E. P. Russian Journal of Inorganic Chemistry, - V.22, - № 3, - 1977, - P. 873.
5. Cameron F., Seidell A., Phys J. Chem., - 5, 653, - 1901.
6. Cameron F., Seidell A., Phys J. Chem., - 6, 53, - 1902.
7. Cameron F. K., Bell J. M., Robinson W. O., Phys J. Chem., - 11. - 416, - 1907.
8. Cameron F. K., Bell J. M., Robinson W. O., Phys J. Chem., - 11. 417, - 1907.
9. Harvie C. E., Moller N.and Weare J. H., Geochimica Cosmochimica Acta, - 48, - P. 723-751, - 1984.
10. Christomir Christov and Nancy Moller, Geochimica Cosmochimica Acta, - 68, - No.18, - 3717-3739, - 2004.
11. Cameron F. K., Bell J. M., Robinson W. O., Phys J. Chem., - 11. - 415, - 1907.
12. Herz W., Z.anorg. Chem., - 71, - 206, - 1911.
13. Handbook of experimental data on solubility of multicomponent water - salt systems. - Vol. II., Book 1&2. Saint Petersburg, Khimizdat, - 2004, - 1247 p.
14. Goroshchenko, Ya. G., The centroid method for imaging multicomponent systems. Naukova Dumka, - Kiev, - 1982.
15. Soliev L. Available from VINITI, - No. 8990-V87, - 1987.
16. Soliev L. Prediction ofMarine-Type Multicomponent Systems' Phase Equilibria by Means of Translation Method. Dushanbe, Book 1 [in Russian], - 2000.
17. Soliev L., Usmonov M. Phase equilibria in the quaternary Na, Ca//SO4, CO3-H2O system at 25oC. Proceedings of Tajik Branch of International Academy of Higher Education - TB IHEAS, - 2010, - № 1, - P. 77-81.
18. Caspari W. A., Chem J. Soc., - 125, - 2383-2385, - 1924.
19. Strakhov N. M., Zarubickaya A. N., Trudi Ins. Geo. Nauk AS USSR, - Vol 124, Geo. Series (№ 45), - 20, - 1951.
20. Hill A. E., Wills J. H., J. Am. Chem. Soc., - 60, - 1650-1653, - 1938.
21. Bury C., Redd R., Chem.Soc. J., - 1161, - 1933.
22. Handbook of experimental data on solubility of multicomponent water - salt systems. - Vol. 1, Book 1&2. Saint Petersburg, Khimizdat, - 2003, - 1151 p.
23. Goroshchenko Y. G., Soliev L., Gornikova Y. I. Ukrainian Journal of Chemistry. - 1987, - Vol. 53, - № 6, - P. 568.
24. Kreshkov A. P. Fundamentals of Analytical Chemistry, Saint Petersburg, Chemistry, - 1970, - Vol. 2, - 456 p.
25. Analysis of the mineral raw materials (under the general editorship of Knipovich Yu. N., Morachevsky Yu. V.). Goskhimizdat, Saint Petersburg, - 1959, -947 p.
26. Reznikov A. A., Mulikovskaya E. P., Sokolov I.Yu. Analytical methods of natural waters. Nedra, - Moscow, -1970, - 488 p.
27. Tatarskiy V. B., Crystal optical and immersion methods of analyzing of substances. Saint Petersburg, Saint Petersburg State University. - 1948, - 268 p.
28. Giller Ya. L. Interplanar spacing tables. - Vol.2. Nedra, - 1966.
29. Mikheev V. I., Roentgenometric determinant of minerals. - Moscow, Gosgeoltekhizdat, - 1975, - 478 p.
DOI: http://dx.doi.org/10.20534/AJT-16-90-95
Nazirova Raxnamo Muxtarovna, Junior researcher scientist, Institute of General and Inorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan
Tashkent, Uzbekistan Tadjiev Sayfuddin Mukhtarovich, PhD in chemistry science, chief of "Complex fertilizer" laboratory, Institute of General and Inorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan
Tashkent, Uzbekistan E-mail: raxnamoxon@mail.ru Tukhtayev Saydiaxral, Doctor of Science, academician, Institute of General and Inorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan
Tashkent, Uzbekistan
Phosphorus-potassium and nitrogen-phosphorus-potassium fertilizer based on washed and dried concentrate from central Kyzylkum phosphorite
Abstract: In this article the findings on the production of complex phosphorus-potassium and nitrogen-phosphorus-potassium fertilizer by decomposition of washed and dried phosphoconcentrate from Central
