CC BY
3DOI: 10.24412/2181-144X-2024-3-21 -27
Umirov F.E., Majidov H.B., Oliqulov F.J.
IDENTIFICATION OF THE 3-COMPONENT SYSTEM CALCIUM CHLORIDE - SODIUM HYPOCHLORITE -
WATER
Umirov F.E.1, Majidov h.B.2[0009-0007-8186-9937], Oliqulov f.J.3[0009-0006-1417-1937]
1Navoi State University of Mining and Technologies, Professor, DSc in technical sciences, 2Navoi State University of Mining and Technologies, assistant, 3Navoi State University of Mining and Technologies, PhD in technical sciences
Abstract.The theoretical basis for the solubility of the sodium hypochlorite (NaClO) - calcium chloride (CaCh) - water system has never been studied before. Using binary and experimental data from eight internal experiments, we have created a solubility chart for the NaClO-CaCh-H2O (sodium chloride, calcium chloride, and water) system in a temperature range between - 55.6 degrees Celsius and 60.8 degrees Celsius. This chart aims to create conditions for the synthesis of a novel compound with high biological activity by utilizing the initial materials in the system. The experiment was divided into four sections: I-IV was conducted on the NaClO side of the system, while V-VIII was conducted on the opposite side (CaC2). Based on these binary systems and their respective sections, we created a polythermal chart that shows the solubility in the calcium chloride and sodium hypochlorite systems. This diagram illustrates the fields of ice crystallization and various hydrates for calcium chloride, sodium chloride, and sodium chlorate. It also identifies new compounds that have not previously been reported in this system, including calcium chlorate and sodium chloride. Key words: calcium chlorate, sodium chloride, calcium and sodium hypochlorite, polythermal diagram, NaClO-CaCl2-H2O, crystallization, hydrates.
Аннотация.Теоретическая основа растворимости системы гипохлорит натрия (NaClO)-хлорид кальция (CaCl2)-вода никогда ранее не изучалась. Используя бинарные и экспериментальные данные восьми внутренних экспериментов, мы создали диаграмму растворимости для системы NaClO-CaCl2-H2O (хлорид натрия, хлорид кальция и вода) в диапазоне температур от -55,6 градусов Цельсия до 60,8 градусов Цельсия. Целью этой диаграммы является создание условий для синтеза нового соединения с высокой биологической активностью путем использования исходных материалов в системе. Эксперимент был разделен на четыре части: I-IV проводились на стороне NaClO системы, в то время как V-VIII проводились на противоположной стороне (CaC2). На основе этих бинарных систем и их соответствующих частей мы создали политермическую диаграмму, которая показывает растворимость в системах хлорида кальция и гипохлорита натрия. Эта диаграмма иллюстрирует поля кристаллизации льда и различные гидраты для хлорида кальция, хлорида натрия и хлората натрия. В нем также идентифицированы новые соединения, которые ранее не были зарегистрированы в этой системе, включая хлорат кальция и хлорид натрия. Ключевые слова: хлорат кальция, хлорид натрия, кальция и гипохлорита натрия, политермическую диаграмму, NaClO-CaC2-H2O, кристаллизации, гидраты.
Introduction
In the world of agriculture, a wide variety of mineral fertilizers and chemical plant protection products are used. These practices, along with an increase in crop yields, have a negative impact on the environment and soil health. Therefore, the development of new technologies for producing harmless and less toxic substances enriched with physiological active compounds that have a complex action with a unique composition of defoliants is necessary. This includes the following areas of research: the development of resource-efficient and energy-saving methods for producing complex and effective defoliators based on sodium hypochloride [1-4]. It becomes relevant to introduce calcium chloride into sodium hypochlorate and obtain calcium chlorate, as well as to synthesize complex-acting defoliators from chemical waste and local calcium sources. [5-9] Defoliation of cotton is an agricultural practice intended to prepare the plant for timely harvesting of its accumulated
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yields of raw cotton. This involves the artificial removal of leaves, typically using chemical substances which cause processes in the plant that mimic those that occur during natural leaf shedding and aging. The efficiency of the chemical preparations used for defoliation depends on several factors, such as the cotton variety, its biological maturity, plant growth vigor, soil moisture, and ambient temperature. Currently, in Uzbekistan and other countries, sodium chlorate, magnesium chlorate, calcium chlorate, and sodium tricarbamide chlorate are commonly used as defoliating agents. Therefore, producing these chemicals from locally sourced raw materials or byproducts of the chemical industry is an important goal as defined in the strategy for the economic development of the Republic of Uzbekistan.
As is known, magnesium chlorate is produced through the exchange reaction between sodium chlorate and bischofite at the joint stock company "Ferganaazot" Sodium chlorate is made through electrolysis, with the current price being about 5 million Uzbekistani som per ton. Bischofite, on the other hand, is imported from Turkmenistan and China, at a price of approximately $1,000 per ton. The process of producing magnesium chlorate using these two substances is inefficient and not economical. Therefore, efforts are being made to find more cost-effective alternatives, such as calcium chlorate-based defoliants. It is known that calcium chlorate can be produced from sodium chlorate and calcium chloride, which are both available in the Republic. In particular, sodium hypochlorite, which is a by-product of the production of caustic soda at the joint stock company "Navoiyazot", and calcium chloride produced at the joint stock company "Kunguradsoda" are currently not fully utilized. By processing them into calcium chlorate, two issues can be addressed simultaneously: the environmental issue, and the production of inexpensive products from soda production waste. Therefore, this article examines the interaction between calcium hloride and sodium hypochloride, and the resulting production of calcium chlorate [10-15].
As is known, magnesium chlorate is produced through the exchange reaction between sodium chlorate and bischofite at the joint stock company "Ferganaazot". Sodium chlorate is made through electrolysis, with the current price being about 5 million Uzbekistani som per ton. Bischofite, on the other hand, is imported from Turkmenistan and China, at a price of approximately $1,000 per ton. The process of producing magnesium chlorate using these two substances is inefficient and not economical. Therefore, efforts are being made to find more cost-effective alternatives, such as calcium chlorate-based defoliants. It is known that calcium chlorate can be produced from sodium chlorate and calcium chloride, which are both available in the Republic. In particular, sodium hypochlorite, which is a by-product of the production of caustic soda at the joint stock company "Navoiyazot", and calcium chloride produced at the joint stock company "Kunguradsoda" are currently not fully utilized. By processing them into calcium chlorate, two issues can be addressed simultaneously: the environmental issue, and the production of inexpensive products from soda production waste. Therefore, this article examines the interaction between calcium hloride and sodium hypochloride, and the resulting production of calcium chlorate [16-19].
Materials and Methods
This study investigates the solubility of sodium hypochlorite in the system of sodium chloride and water, using the visual polythermal method over a wide range of concentrations and temperatures. Infrared spectroscopic analysis was performed on an Irtrace 100 Spectrometer from Shimadzu, in the frequency range of 400-4000 cm-1. Samples were prepared using KBr pellets, and mass spectroscopic analyses were conducted on SRM-20 and S-115 instruments as well as ICP-MS and XRPD analysis were conducted. The sodium content of the samples was determined using flame photometry. The volume method, or Mohr's method, for determining chloride salt concentration relies on precipitation of chloride ions using silver nitrate and potassium chromate. The analysis of chlorate ion concentrations
was performed using a potentiometric technique that relies on their interaction with reducing agents.
To investigate the interaction between calcium chloride and sodium hypochlorite, and to understand the process of producing effective defoliants using these compounds, the solubility of these substances in aqueous solutions was studied over a wide range of temperatures. For the first time, the solubility of the CaCl2-NaClO-H2O mixture was visually investigated using the polythermal technique over a temperature range of -55.6°C to +60.8°C. The solubility diagram for the binary system of calcium chloride and water, which makes up the investigated mixture, shows the lines of liquid ice, CaCl2-6H2O, CaCl2-4H2O, and CaCl2-2H2O. The point where the mixture freezes corresponds to 29.9% calcium chloride and 77.4% water, at a temperature of -49.8 °C. The results obtained are in full agreement with literature data [20].
In the polythermal solubility plot of the NaClO-H2O system, we have identified various branches, including ice crystallization, NaClO5H2O, NaClO2.5H2O and anhydrous NaClO. These branches intersect at the eutectic point, which is located within the 19.2% NaClO concentration range at a temperature of -16.5 °C. The system of calcium chloride - sodium hypochlorite - water was studied in the range from -55.6 °C to +60.8 °C using eight different internal sections. Sections I-IV were conducted on the NaClO-H2O side, while Sections V-VIII were performed on the CaCl2-H2O side. Based on the polythermic binary systems and their internal sections, we constructed a polythermic solubility diagram for the calcium chloride-sodium hypochlorite-water system, which delineates the fields of ice crystallization, calcium chloride hydrates (CaCl2-6H2O and CaCl2-4H2O), sodium chloride oxide hydrates (NaClO5H2O and NaClO2.5H2O), anhydrous sodium chloride oxide, as well as two new compounds for this system: Ca(CI03)2 and sodium chloride (Figure 1).
CaC!2 %
The mentioned fields converge at seven triple points of coexistence between three different solid phases. At these points, the compositions of the equilibrium solution and corresponding crystallization temperatures have been determined (Table 1). Solubility isopleths have been plotted on the polythermal diagram every 10 degrees Celsius. The projection of the solubility curve onto the side of the water phase has been constructed. Table 1 presents the nodal points for the calcium chloride-sodium hypochlorite-water system, where there are seven triple and ten double points. The crystallization fields for
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calcium chlorate and sodium chloride, which are formed through the interaction between the initial components, take up a significant portion of the diagram. Based on the areas of crystalization, it can be concluded that calcium chlorate and sodium chloride are sparingly solubles relative to other compounds in this system.
Table 1.
Binary and Ternary Critical Points of the Calcium Chloride-Sodium Hypochlorite-
Water System.
№ Composition of the liquid phase., % Temperature of crystallization, °C Solid phase
NaCIO CaCl2 H2O
1. 19,2 - 80,8 -16,5 Ice+ NaCIO5H2O
2. 17,8 8,2 74,0 -19,2 Ice + NaCIO5H2O
3. 17,2 14,8 68,0 -22,0 Ice + NaCIO-5H2O+Ca(ClOs)2
4. 13,8 18,8 67,4 -8,0 NaCIO-5H2O+Ca(ClOs)2
5. 9,3 27,5 63,2 6,2 NaCIO-5H2O+Ca(ClOs)2
6. 7,8 36,8 55,4 13,6 NaCIO-5H2O+Ca(ClOs)2
7. 8,2 43,7 48,1 16,0 NaCIO5H2O+ NaCIO-2,5H2O+Ca(CIOs)2
8. 4,0 44,00 52,0 18,5 NaCIO5H2O+ NaCIO2,5H2O
9. - 45,5 54,5 24,5 NaCIO5H2O+ NaCIO2,5H2O
10. 8,3 47,4 44,3 22,8 NaCIO-2,5H2O+Ca(ClOs)2
11. 9,7 57,2 33,1 37,1 NaCIO-2,5H2O+Ca(ClOs)2
12. 12,0 60,0 28,0 44,9 NaCIO2,5H2O+ NaCIO+Ca(ClOs)2
13. 8,0 60,9 31,1 47,6 NaCIO2,5H2O+ NaCIO
14. 3,9 61,5 34,6 50,8 NaCIO2,5H2O+ NaCIO
15. - 62,3 37,7 57,5 NaCIO2,5H2O+ NaCIO
16. 10,5 66,7 22,8 53,6 NaCIO+Ca(ClOs)2
17. 11,3 72,4 16,3 60,8 NaCIO+Ca(ClOs)2
18. 17,3 15,1 67,6 -36,8 Ice +Ca(ClOs)2
19. 23,5 11,9 64,6 -48,0 Ice +NaCl+Ca(ClOs)2
20. 22,8 16,3 60,9 1,2 NaCl+Ca(ClOs)2
21. 20,7 23,8 55,5 19,0 NaCl+Ca(ClOs)2
22. 20,8 28,7 50,5 32,0 NaCl+Ca(ClOs)2
23. 21,1 34,5 44,4 36,5 NaCl+Ca(ClOs)2
24. 21,5 40,9 37,6 44,0 NaCl+Ca(ClOs)2
25. 22,0 44,5 33,5 48,6 NaCl+Ca(ClOs)2
26. 25,9 10,1 64,0 -55,6 Ice +NaCl+CaCl2-6H2O
27. 30,8 - 69,2 -49,8 Ice +CaCl2-6H2O
28. 23,6 9,9 66,5 -48,0 CaCl2-6H2O+NaCl
29. 36,4 8,3 55,3 -22,0 CaCl2-6H2O NaCl
30. 46,2 6,8 47,0 26,4 CaCl2-6H2O+ CaCl2-4H2O+NaCl
31. 50,1 - 49,9 29,8 CaCl2-6H2O+ CaCl2-4H2O
32. 53,3 5,9 40,8 40,8 CaCl2-4H2O+NaCl
33. 56,5 - 43,5 45,3 CaCl2-4H2O+ CaCl2-2H2O
Thus, based on the polymorphism of the solubility of the calcium chloride-sodium hypochlorite-water system, it studied for the first time in the range of -55.6 to +60.8°C using eight internal cuts. Based on the polymorphism of the lateral binary systems and internal
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cuts, a polymorphic solubility diagram of the calcium chloride-sodium hypochlorite-water system was constructed, on which the fields of crystallization of ice, CaCl2*6H2O, CaCl2*4H2O, CaCl2*2H2O (calcium chloride hydrates), NaClO«5H2O, NaClO«2.5H2O (hydrate of anhydrous NaClO), as well as new compounds for this system, Ca(ClO3)2 and NaCl, are distinguished.
Thus, the results of the study on the heterogeneous equilibrium in the CaCl2 - NaClO - H2O system allowed us to determine the concentration limits and the temperature for the formation of compounds Ca(ClO3)2 and NaCl. These were identified through chemical, infrared spectroscopic, X-ray diffraction, and mass spectrometric analyses, as well as physicochemical analysis methods. As demonstrated in Figures 2 and 2a, these analyses indicate that the chemical composition of the solid phases separated from the crystallization areas assumed to be Ca(ClO3)2 and NaCl are as follows: Found, wt%: Ca2+ 19.34% ClO3" 80.67% Na+ 39.33% Cl" 60.68% H2O 3.22% For Ca(ClO3)2 and NaCl, the calculated chemical compositions are as follows, wt%: Ca2+ 17.15% ClO3" 75.78% Na+ 28.60% Cl" 59.47% H2O 3.0%To elucidate the types of chemical bonds and coordination sites of the initial molecules, as well as the coordination methods and studied compounds of NaClO and CaCl2, IR spectra of Ca(ClO3)2 and NaCl and their components have been examined.
In the infrared spectra of calcium chloride, absorption bands between 3000 and 3600 cm-1 are observed. These bands belong to the -O-H group of the crystallized water molecules. Broad absorption bands in these spectra indicate that symmetric valence and deformation vibration bands of chlorides typically appear between 3200 and 2800 cm-1, as is the case with CaCl2 in our study. Deformation vibrations of the N-O-N group appear at 1600-1660 cm-1. In the spectra of sodium hypochlorite, there are broad bands in the range of 3600-3000 cm-1 that are attributed to crystallization water. The same group of deformation vibrations appears at 1633 cm-1.
Bands at 1400 cm-1 can be attributed to antisymmetric valence vibrations of sodium chloride. The spectrum also shows intense bands at 935-950 cm-1, which correspond to symmetric valence vibrations of [ClO3] - ions, with their deformation vibrations at 489 and 681 cm-1. Characteristic bands for NaClO can be observed at 3630 cm-1, corresponding to the symmetric valence vibrations of ClO - ions, and their antisymmetric valence vibrations are at 671-700 cm -1.
Based on the data from infrared spectroscopic studies, it can be concluded that the [ClO]- ion, under the influence of external factors, transforms into the [ClO3] - ion and Cl-(NaCl) ion. In the infrared spectra of the [ClO3], absorption bands related to crystalline water
are observed. The infrared spectrum in the region of 3200-3500 cmA-1 and the Raman spectrum belong both to bands associated with symmetric valence vibrations of CaCl2. The vibration of the water molecule deformation appears at 1632 cmA-1. Weak, intense bands at 1400-1385 cmA-1 are attributed to Na+and Cl-. Intensified bands at 1002 cmA-1 can also be attributed to the [ClO3]A-, while at 973 cmA-1 and 942 cmA-1 they are characteristic of Ca(ClO3)_2. Absorption bands in the range of 621 cmA-1 correspond to antisymmetric valence oscillations of calcium chlorate.
Table 2.
The results of mass spectrometric analyses of the initial raw materials (sodium hypochlorite and calcium chloride), as Well as calcium chlorate, are presented.
№ Ions Measuremen t range Amount of substance, g/ton
NaCIO CaCl2 Ca(CIO3)2
1. Na * 0,004 >550000 0 400 120000
2. Ca * 0,004 21950 >15000000 7400000
3. Al * 0,002 3280 1180 1000
4. P 1,0 1500 4500 470
5. K * 0,008 800 555000 4700
6. Mg * 0,005 19500 272500 1500
7. Sc 0,10 37,5 32,5 1,90
8. Ti * 0,0006 70 50 53,0
9. Cr 1,0 1400 2500 22,0
10. Mn 0,002 402,5 392,5 14,0
11. Fe * 0,006 1250 490 530
12. B * 0,10 40,0 4250 20,0
*- the number of elements whose characteristic values exceed the measurement range of the device.
Conclusion
The resulting new system of solutions, consisting of a mixture of the secondary product of the Kungrad soda industry and the secondary product from the Navoiazot AO workshop, was first studied visually using the polythermal technique, in which fields of ice crystallization were delimited by CaCl2*4H2O, CaCl2, CaCl26H2O, and Ca(ClO3)2, as well as by the compound NaCl.
It was established that new compounds, NaCl and Ca(ClO3)2 were formed in this system, involving NaCl and CaCl2 aqueous solutions. These compounds ray diffraction, mass spectrometry, and infrared spectroscopy methods of chemical and physicochemical analysis. The study of samples through physicochemical analysis revealed the formation of NaCl and Ca(ClO3)2 in the measurement range of this system.
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