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DOI - 10.32743/UniTech.2021.91.10.12410
POLYTHERMAL SOLUBILITY OF THE NACLO3-CO(NH2)2-H2SO4’NH2C2H4OH-H2O SYSTEM
Abdulaziz Sidikov
Basic doctoral student, Institute of General and Inorganic Chemistry of the AS RUz,
Uzbekistan, Tashkent E-mail: [email protected]
Sanzhar Tuychiev
Junior researcher,
Institute of General and Inorganic Chemistry of the AS RUz,
Uzbekistan, Tashkent
Akhat Togasharov
Doctor of Science in Technics, Institute of General and Inorganic Chemistry of the AS RUz,
Uzbekistan, Tashkent
Saidahral Tukhtaev
Doctor of Science, academician, Institute of General and Inorganic Chemistry of the Academy of Sciences of the Republic of Uzbekistan,
Uzbekistan, Tashkent
ПОЛИТЕРМИЧЕСКАЯ РАСТВОРИМОСТЬ СИСТЕМЫ NACLO3*CO(NH2)2-H2SO4*NH2C2H4OH-H2O
Сидиков Абдулазиз Абдуманоп угли
базовый докторант, Институт общей и неорганической химии АН РУз, Республика Узбекистан, г. Ташкент
Туйчиев Санжар Абдусодикович
мл. науч. сотрудник, Институт общей и неорганической химии АН РУз, Республика Узбекистан, г. Ташкент
Тогашаров Ахат Салимович
д-р техн. наук,
Институт общей и неорганической химии АН РУз,
гл. науч. сотр., Республика Узбекистан, г. Ташкент
Тухтаев Сайдахрт
д-р хим. наук, академик, заведующий лабораторией, Институт общей и неорганической химии АН РУз, Республика Узбекистан, г. Ташкент
ABSTRACT
The system NaClO3-CO(NH2)2-H2SO4-NH2C2H4OH-H2O was studied by the polythermal method of solubility in the temperature range from -65.2 to 60 °C. On the basis of the solubility polytherms of binary systems and internal sections, a polythermal diagram of the solubility of this system is constructed. The fields of ice crystallization, NaClO3-CO(NH2)2, CO(NH2)2, H2SO4-NH2C2H4OH and compounds of the composition Na2SO4-NH2C2H4OH are delimited. Chemical and physicochemical analyzes were performed to identify the newly formed compound.
Библиографическое описание: POLYTHERMAL SOLUBILITY OF THE NaaO3-CO(NH2)2-H2SO4-NH2C2H4OH-H2O SYSTEM // Universum: технические науки : электрон. научн. журн. Sidikov A.A. [и др.]. 2021. 10(91). URL: https://7universum.com/ru/tech/archive/item/12410
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АННОТАЦИЯ
Политермическим методом растворимости изучена система NaClO3-CO(NH2)2-H2SO4-NH2C2H4OH-H2O в интервале температур от -65.2 до 60 °С. На основе политерм растворимости бинарных систем и внутренних разрезов построена политермическая диаграмма растворимости данной системы. Разграничены поля кристаллизации льда, NaClO3-CO(NH2)2, CO(NH2)2, H2SO4-NH2C2H4OH и соединения состава Na2SO4-NH2C2H4OH. Химический и физико-химический анализы были выполнены для идентификации новообразованного соединения.
Keywords: solubility, system, diagram, concentration, defoliants, crystallization temperatures, IR spectrum.
Ключевые слова: растворимость, система, диаграмма, концентрация, дефолианты, температуры кристаллизации, ИК-спектр.
Introduction. The unfavorable arrival of autumn weather can negatively affect the yield and quality of crops. Agrochemical measures, such as defoliation are applied to a range of crops to prevent yields from declining as a result of such natural factors.
Defoliants and desiccants are classified as harvest aids because they are commonly used to facilitate mechanical harvesting [1-3].
Appropriate and safe harvesting aids will shorten the time and make cotton picking easier [4].
The effectiveness of the harvest aid depends on the environmental conditions before, during and after application [5, 6]. Therefore, it is important to use the drugs on time, that is before the onset of cold weather.
Existing chlorate-containing preparations do not meet modern requirements due to some properties, i.e. they have a “hard” effect on the plant and completely destroy it and its immature boxes, which in turn leads to a decrease in potential profitability. Currently, it is necessary to offer effective multifunctional “soft” acting drugs by adding physiologically active substances to chlorate-containing defoliants [7]. Therefore, the synthesis of valuable drugs containing physiologically active substances has become one of the priority and necessary directions for the development of modern innovative technologies [8].
Methodology and materials. Sodium monocarbami-dochlorate was used for the study, which had synthesized by dissolving urea together sodium chlorate in a 1: 1 mol ratio. After the formation of a homogeneous solution of the initial components, it was cooled, after which crystals of the compound NaClO3CO(NH2)2 were obtained. Based on the neutralization of monoethanolamine with 94% sulfuric acid (in 1:0.60 molar ratio), sulfate mo-noethanolamine was synthesized.
The solubility polytherm of the NaClO3-CO(NH2)2-H2SO4-NH2C2H4OH-H2O system was investigated by
the visual polythermal method [9]. Liquid nitrogen was used as a freezing reagent in the study of solution solubility.
Chemical and physico-chemical analysis methods were used to identify the obtained new compound. In the quantitative chemical analysis of liquid and solid phases, the content of the chlorate ion was determined by the volumetric permanganatometric method. [10], so-dium-by flame photometry [11], elemental analysis for carbon, nitrogen, hydrogen was carried out according to the method [12]. The MIRacle10 IR spectrometer was used to identify the source material and the new compound [13,14].
Results and discussion. The binary system NaClO3 • CO(NH2)2-H2O was studied by the author [15], this system is part of the system that we are studying and our data are in good agreement with the literature.
The solubility of the NaClO3-CO(NH2)2-
H2SO4-NH2C2H4OH-H2O system was studied using seven internal incisions. Based on the results of the study of binary systems and internal incisions, the complete polythermal diagram of this system was constructed in the temperature range from -65.2 to 60 °C. On the phase diagram of the solubility of the NaClO3-CO(NH2)2-H2SO4-NH2C2H4OH-H2O system, the crystallization fields are distinguished: ice, urea, sodium monocarbami-dochlorate, monoethanolammonium nitrate and compounds of the composition NaClO3CO(NH2)2. The indicated fields converge at two triple nodal points of the system, for which the compositions of the equilibrium solution and the corresponding crystallization temperatures are determined, which are shown in Fig. 1.
The projections of the polythermal curves on the corresponding lateral water sides of the system wera constructed. The solubility diagram (Fig. 1) shows that a new compound of the composition NaClO3CO(NH2)2 is formed in the studied system.
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Figure 1. Polythermal solubility diagram of the NaClO3-CO(NH2)2-H2SOrNH2C2H4OH-H2O system.
On the polythermal diagram, the fields of the formed corresponding compositions of the equilibrium solution
crystals of the system are highlighted with bold lines, and the crystallization temperatures are determined
and these fields are named accordingly. These fields occur (Table l).
at four triple nodal points of the system, for which the
Table 1.
Double and triple points of the system NaClO3CO(NH2)2-H2SO4NH2C2H4OH-H2O
Composition of the liquid phase (%) Tc (°С) Solid phase
NaClO3- CO(NH2)2 HNO3- NH2C2H4OH H2O
61.2 - 38.8 -33.0 Ice + CO(NH2)2
59.8 0.3 39.9 -32.0
39.4 2.4 58.2 -16.2
18.4 6.6 75.0 -5.6
12.7 17.5 69.8 -5.4
5.8 36.6 57.6 -15.2
3.6 49.8 46.6 -22.4 Ice + CO(NH2)2 + Na2SO4- NH2C2H4OH + H2SO4-NH2C2H4OH
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Composition of the liquid phase (%) Тс (°С) Solid phase
NaClOs- CO(NH2)2 HNOs- NH2C2H4OH H2O
- 52.0 48.0 -19.2 Ice + H2SO4-NH2C2H4OH
2.7 58.6 38.7 -37.4 Na2SO4-NH2C2H4OH + H2SO4^NH2CiH4OH
2.5 79.6 18.2 -53.0
2.0 90.2 7.5 -58.6
1.9 95.0 2.9 -61.4
1.6 98.4 - -65.2
11.0 45.3 43.7 -9.8 CO(NH2)2 + Na2SO4-NH2C2H4OH
31.1 32.8 36.1 10.6
33.5 26.3 40.2 18.4 NaClO3-CO(NH2)2 + CO(NH2)2 + Na2SO4- NH2C2H4OH
52.0 9.7 38.3 31.2 NaClO3-CO(NH2)2 + CO(NH2)2
12.2 14.2 73.6 32.0
67.5 - 32.5 37.2
23.2 42.4 34.4 2.6 NaClO3-CO(NH2)2 + Na2SO4- NH2C2H4OH
20.3 48.0 31.7 -3.8
11.4 71.0 17.6 -30.2
10.3 75.5 14.2 -36.4
8.4 86.2 5.6 -50.6
8.2 92.0 - -56.2
The compound Na2SO4^NH2C2H4OH was isolated in the crystalline state and identified by chemical methods and infrared spectroscopy methods.
Chemical analysis of the solid phase of the separated compound Na2SO4-NH2C2H4OH from the assumed crystallization region gave the following results:
Found (wt %): Na+, 22.59; SO42-, 45.5; N, 6.85; C, 11.78; OH-, 8.34.
Anal. calcd. (wt %): Na+, 22.66; SO42-, 45.8; N, 6.89; C, 11.82; OH-, 8.37.
It is well soluble in water. At -10 and 0°С it respectively dissolves 57.1 and 69.8%. In organic solvents - in ethyl alcohol it is completely soluble, insoluble in toluene and chloroform, and when acetone is used as a solvent, excess monoethanolamine is washed out from the compound, and it remains in a pure white crystalline form. This means that acetone can be as a detergent in obtaining crystals of the compound in its pure form.
To clarify the connections in the composition of the isolated new compound, the IR spectra of monoethano-lammonium sulfate and the new compound were studied (Fig.2).
In the IR spectra of monoethanolammonium sulfate, several valence vibrations frequencies are observed in the
ranges of NH and OH bond. The maximum frequency of triethanolammonium sulfate with hydrogen bonds is 137 cm-1, the difference between the Oh group vibrations in methanolamine and elongated vibrations in monoethanolamine is 134 cm-1, and the highest frequency of elongated NH bond vibrations is 1049758 cm-1. The lines 3078-2966 cm-1 are connected by valence vibrations of the CH2 bond. Lines 613 and 432 cm-1 correspond to SO4 vibrations (Fig. 2. A).
In the IR spectra of the compound, ethanolamine sulfate is formed due to the loss of the OH group in monoethanolamine. Elongated vibrations in the range of 3081-2968 cm-1, corresponding to the NH2 group, were observed in the new compound. The difference between these values (Av) is used as a criterion of the structure of the molecule. Vibrations in a field of2483-2268 cm-1 are symmetric and asymmetric stretching vibrations of the CH2 bond, and the vibration bands at 768 [vas SO4] and 416 cm-1 [vs SO4] are asymmetric and symmetric stretching vibrations of the SO4 group. The value of Av equal to 352 cm-1 points to a significant asymmetry of the SO4 group. Thus, there is a loss of valence vibrations of OH-lines in the region of the IR spectra of the compound (Fig. 2. B).
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Figure 2. IR spectra: A-monoethanolammonium sulfate; B - compound: monoethylchloratamine sodium sulfate
The difference between monoethanolammonium sulfate and the resulting new compound was also evident with the peaks representing the functional groups on their IR spectral diagrams.
Conclusions. Thus, from the study of the solubility diagram of the NaClO3^CO(NH2)2-H2SO4^NH2C2H4OH-H2O system, we established the formation of a new
chemical compound Na2SO4-NH2C2H4OH, which was identified and confirmed by chemical and physicochemical analysis methods.
The results of this work will be used to develop a technology for the production of a new mildly acting and effective defoliant by adding physiological active substances to chlorate-containing (monocarbomide chloratanatry) defoliants.
References:
1. Li S., Liu R., Wang, X. et al. Involvement of Hydrogen Peroxide in Cotton Leaf Abscission Induced by Thidiazuron.
J. Plant Growth Regul. (2020). https://doi.org/10.1007/s00344-020-10218-w
2. Pedersen MK, Burton JD, Coble HD (2006) Effect of cyclanilide, ethephon, auxin transport inhibitors, and temperature on whole plant defoliation. Crop. Sci. 46(4):1666-1672. https://doi.org/10.2135/cropsci2005.07-0189
3. Wang Xiaojing, Li Sijia, Liu Ruixian, Zhang Guowei, Yang Changqin, Ni Wanchao. Effect of Defoliants Application on Physiological Characters of Cotton Leaf without Defoliants[J]. Cotton Science, 2019, 31(1): 64-71. doi: 10.11963/1002-7807.wxjlrx.20181228
4. DU, M., REN, X., TIAN, X., DUAN, L., ZHANG, M., TAN, W., & LI, Z. (2013). Evaluation of Harvest Aid Chemicals for the Cotton-Winter Wheat Double Cropping System. Journal of Integrative Agriculture, 12(2), 273-282. doi:10.1016/s2095-3119(13)60226-9
5. Karademir Emine & Karademir Cetin & Basbag Sema. (2007). Determination the effect of defoliation timing on cotton yield and quality. Journal of Central European Agriculture ([email protected]); Vol.8 No.3. 8.
6. Faircloth J.C., Edmisten K.L. Wells R. and Stewart A.M., The Influence of Defoliation Timing on Yields and Quality of Two Cotton Cultivars. Crop Science. (2004), (44) 165-172
7. Component Solubilities in the Acetic Acid-Monoethanolamine-Water System Shukurov Z.S., Khusanov E.S., Mukhitdinova M.S., Togasharov A.S. Russian Journal of Inorganic Chemistrythis link is disabled, 2021, 66(6), стр. 902-908
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8. Sidikov A.A. [and etc.] Solubility in systems including sodium monocarbamidochlorate, monoethanolamine nitrate and triethanolamine nitrate, Univer.: tech. sc.: elec. sc. j. 2020.12 (81). https://7universum.com/ru/tech/archive/item/n138
9. Trunin A.S., Petrova D.G., Visual-polythermal method, Kuib. Poly. Univ., 1977, 94 p.
10. GOST 12257-77. Sodium chlorate. Technical conditions. - M.: Publishing house of standards, 1987, 19.
11. Poluektov N.S. Methods of analysis by flame photometry. - M.: Chemistry. 1967. - 307 s.
12. Schwarzenbach G., Flashka G. Complexometric titration. - M.: Chemistry, 1970, 360.
13. Nakamoto K. IR-spectra and raman spectra of inorganic and coordination compounds. - M.: Mir, 1991 - - 536 p.
14. IR spectroscopy in inorganic technology, Zinyuk R.Yu., Balykov A.G., Gavrilenko I.B., Shevyakov A.M. Chemistry, 1983, 160. https://patents.google.com/patent/WO2008019063A2/en
15. J.S. Shukurov, M.K. Askarova, and S. Tukhtaev, East Eu. Sc.J. Ws. Cz.N. 3, 60 (2016).
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