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Section 4. Technical science
Abdullaeva Marguba,
Narkhodjaev Ä. H,
Institute of General and Inorganic Chemistry, Uzbek Academy of Sciencess E-mail: margubaa@list.ru
INVESTIGATION OF AQUEOUS SYSTEM FROM METHYL ACETATE, MONOETHANOLAMINE, UREA AND AMMONIUM NITRATE
Abstract: Physicochemical justification of liquid fertilizer process based on urea-ammoniac saltpetre by introduction in its composition of physiologically active substance.
Keywords: methyl acetate, mono ethanol amine, N - acetylethanolamine, urea, ammonium nitrate, solubility chart, "composition-property" graph.
Introduction
At JSC "Navoiazot" in the production of synthetic food acetic acid, as a by-product a volatile fraction with composition (mass.%): acetic acid 26.0-27.0; formic acid 4.0-8.0; methyl acetate 1.0-2.0; the rest is water is formed [1]. In the production ofone ton of acetic acid, 0.87-0.90 kg of such waste is generated. At JSC "Navoiazot" acetic acid of the order of 8.0-10.0 thousand tonnes is produced in a year. Thus, the enterprise generates 7.0-7.2 tons ofvolatile fraction per year. The volatile fraction contains monocarboxylic acids, which can be used to prepare physiologically active substances by treating it with monoethanol-amine. The resulting physiologically active substances are modified complex preparations possessing highly effective stimulating properties that promote agricultural crops growth and evolution.
The work [2] is devoted to the study of the interaction of monoethanolamine with inorganic acids and their salts while the results of studies using concentrated solutions of acetic acid, formic acid and
monoethanolamine at 20 °C in [3] and in aqueous solutions are given in [4, 5]. However, the interaction of monoethanolamine with methyl acetate in aqueous solutions has not been studied yet. The system "methyl acetate-monoethanolamine-water" [6] was studied to establish the mechanism of their interaction process.
Materials and methods
In this article visual and polythermic, isomo-lecular, IR spectrum, analytical and NMR methods were used. Measurement of solution viscosity was conducted by capillary viscometer VPJ-2, refractive index by refractometer RF 454 BM, relative density by picnometre, pH medium by pH-metre METLER TOLEDO FE20(FQLl).
Results and discussion
The isotherms of the refractive index, density, viscosity and pH of the medium are characterized by inflection points corresponding to 20 and 50% concentrations of the monoethanolamine solution
(Fig. 1).
Analysis of the isotherms allows us to con- was synthesized on the basis of concentrated mono-
clude that the reaction in an aqueous solution of ethanolamine and methyl acetate. Elemental analy-
monoethanolamine with methyl acetate the com- sis for the content of carbon, hydrogen and nitrogen
pound N - acetyl ethanolamine is formed, which is carried out for the synthesized compound.
Figure 1. System of methyl acetate-monoethanolamine-water (1) - pH of the medium; (2) - is the viscosity; (3) - is the density; (4) - is the refractive index
Table 1. - According to the chemical analysis for CH3CONHC2H4OH
It was found, mass.%:
C O N H
40.10 40.05 11.18 7.09
It was calculated, mass.%:
C O N H
40.30 40.30 11.80 7.60
To determine the identity and phase structure of the N - acetyl-ethanolamine compound, we studied its IR spectrum (Fig. 2). A comparative analysis of the IR spectrum of the compound CH3CON-HC2H4OH and the starting materials monoethanol-amine and methyl acetate shows that the formation of the N - acetyl ethanolamine compound results
in a change in the above-mentioned IR fusion of the compound.
The IR spectrum of the resulting compound showed the following absorption bands: j (OH) = = 3354 cm-1; y(NH) = 3354 cm-1; y (cH2) = = 2878 cm-1; j(C = O) = 1639 cm1; S (NH) = = 1564 cm-1; S(CH3, CH2) = 1376 cm-1 and
1306 cm-1; y(C-N) = 1308 cm-1;Y(C-O) = 1308 cm-1; formation of the amide fragment observed in the
/(C-O) = 1669 cm-1; Short-wavelength mixing resulting compound. That is, the resulting com-
of the y(C = O) and &(NH) absorption bands of pound N - acetyl ethanolamine is an individual
the starting materials and the lack of absorption substance with the chemical formula CH3CON-
bands in the product is characteristic of the ester HC2H4OH (Fig. 2).
Figure 2. IR spectra of the components of the methyl acetate-monoethanolamine-water system and N-acetyl-ethanolamine compounds. 1 - methyl acetate: 2 - monoethanolamine: 3 - N - acetyl ethanolamine
The indices of H1 and C13 NMR spectroscopy of N-acetyl ethanolamine were studied by means of nuclear magnetic resonance spectroscopy (NMR). The NMR spectrum of the resulting compound in dimethyl sulfoxide (DMSO-d) was obtained a spectrum (1.76 ppm) as a singlet, which is due to the presence of the group (C = O); and these allocated signals are inherent in the nature of the action of the methyl-proton group. On the spectrum of 3.05 and 3.35 ppm two methylene groups (CH2) are linked together and their protons similarly formed a quartet (J = 6.0 Hz) and a triplet (J = 6.0 Hz), which form resonance of signals. On the part of the weak field in the center at 7.94 ppm the limit of the signals of the NH group was formed (Fig. 3).
To determine and establish the sequence ofgroups, we used the method of secondary resonance. In it, as in the primary substance-methyl acetate, the C = O group is linked to the CH3 - group with the formation ofthe corresponding signal (1.76 ppm), when interacting with the secondary frequency resonance on the monoethanolamine NH2 group bound to the CH2 group a resonance of the signals is also formed (Fig. 4).
Based on the analysis it was established that the connection between the groups on the NMR spectrum of the synthesized compound on a part of the strong field is 22.66; 41.77 and 60.03 ppm, there are signals of 3 (three) carbon nuclei. Whereas on the spectrum of the weak field region, 169.92 ppm the formation of a carbonyl group corresponding to carbon was established (Fig. 4).
Figure 3. 1H NMR spectra of N - acetyl ethanolamine
Figure 4. 13C NMR spectra of N - acetyl ethanolamine
Figure 5. N - acetylethanolamine spectra of secondary resonance
When comparing the obtained results on the NMR spectrum, the resulting compound has four carbon (Fig. 5). On the basis of the "Disstortion-less Enhancement by Polarization Transfer" experiment, it has been found that one carbon includes a CH3 group, a two - CH2- group, and the balance
d, g/cnr t\, mm" /s pH
1,060
1 «D55
1f050
is a quaternary carbon of N- acetyl-ethanolamine. On the basis of the conducted studies it was established that the substance has the chemical formula CH3-CO-NH-CH2-CH2-OH and is called N- acet-ylethanolamine.
crefractive index 1,356
1,356
cocnh2)2
1,354
10 20 30 40 SO GO TO SO 90 CH3COWHC2H4OH 90 SO TO ©o so 40 30 20 10 J ^ ^
Figure 6. The carbamide-N-acetyl-ethanolamine-water system; (1) - pH of the medium; (2) - is the refractive index; (3) - is the viscosity; (4) - is the density
When studying the character of the interaction in the "carbamide-N- acetylethanolamine-water" system, the isotherms of the refractive index, density, viscosity and pH of the medium were characterized by inflection points corresponding to a content of 50.0 mol.% of carbamide (Fig. 6), that is molar ratio of carbamide: N- acetyl ethanolamine, equal to 1: 1. Thus, the formed inflection points in the system studied confirm the appearance of one new compound - carbamide N- acetylethanolamine, with a molar ratio of the original components of 1: 1.
The following physicochemical properties the crystallization temperature -60.0 °C, the refractive index is n20 = 1.5440; d20 = 1.3023 g/cm3; n20 = = 32.34 mm2/s; the pH ofthe medium-11.0 are typical for the CO(NH2)2CH3CONHC2H4OH compound.
To determine the individuality and phase structure of the compound CO(NH2)2CH3CON-HC2H4OH, we studied its IR spectra.
Comparative analysis of the IR spectrum of the compound CO(NH2)2CH3CONHC2H4OH and urea precursors, N- acetylethanolamine shows that when forming the compound CO(NH2)2CH3CON-HC2H4OH, changes the above compound are took placed in the IR spectrum. For example, the amide band at 1681cm-1 is shifted to the low-frequency re-
gion by 20 cm 1 (1661cm 1). The absorption band of CH3CONHC2H4OH-H2O at 1639 cm-1 is shifted to the high-frequency region, only by ~ 3 cm-1. Hence, the above mentioned, we can assume that there is an intermolecular and hydrogen bond between > C = O carbamide and OH- group of monoethanolamine. The IR spectra of the -OH group are in the region of intense stretching vibrations of the amine groups of the carbamide.
The polytherm of solubility of the ammonium nitrate-N- acetylethanolamine-water system was studied by means of eight internal sections using a visual-polythermal method. Sections I-IV are drawn from the side of N- acetylethanolamine - water to the top of ammonium nitrate, V-VIII - from the side of ammonium nitrate - water to the top of N- acety-lethanolamine.
The binary system N- acetylethanolamine-water was studied for the first time and has a eutectic point of 38.0 °C with a content of 17.4% water and 82.6% N- acetylethanolamine.
On the basis of polythermal sections and data of binary systems of polythermal sides, a diagram of the solubility ofthe system ofammonium nitrate-N- acety-lethanolamine-water from the temperature ofcomplete freezing -47.8 °C to 60 °C was constructed (Fig. 7).
Figure 8. The solubility polytherm of the
In the studied range of temperatures and concentrations, crystallization fields of ice, N- acetyletha-nolamine and a, ft, - modifications of ammonium nitrate have been identified. The system is characterized by one triple nodal point corresponding to 11.6% ammonium nitrate and 77.8% N- acetyletha-nolamine at a temperature of -47.8 °C.
According to the polythermic diagram of solubility, the formation of new chemical compounds has not been established. This system studied belongs to a simple eutonic type (Fig. 8).
Earlier we studied systems: CO(NH2)2-CH3CONHC2H4OH-H2O and NH4NO^ CH3CONHC2H4OH-H2O. To substantiate the process of obtaining a new liquid fertilizer on the basis of carbamide ammonium nitrate (CAN) containing physiologically active substance (PAS)-N- acetylethanolamine, we studied the
NH4NO3-CH3CONHC2H4OH-H2O system mutual influence of the components in the N-acetylethanolamine - [45% CO(NH2)2 + 55% NH4NO3] - water system by the isomolar method. The isotherms of the refractive index, density, and pH of the medium of the system studied show that the inflection points correspond to 50.0 and 72.0 mole% of the sum of salts [45% CO(NH2)2 + 55% NH4NO3] (Fig. 9) i.e. molar ratio of carbamide: N-acetylethanolamine, equal to 1: 1.
Thus, the formed inflection points confirm the appearance of one new compound - N- acetylethanolamine with carbamide at a molar ratio of 1: 1. On the isotherms of the pH medium, the refractive index of the medium and the viscosity, these characteristic bending points appear less clearly.
A complex salt-carbamido N- acetylethanol-amine with a molar ratio of 1: 1 was also isolated from the liquid phase.
Figure 9. System N - acetylethanolamine - [45% carbamide + 55% ammonium nitrate] - water.
(1) - pH of the medium; (2) - is the refractive index; (3) - is the viscosity; (4) - is the density
Conclusion selection of the synthesis conditions of the process,
To concluded, by studying the above system, it sufficiently justify the possibility of obtaining a new
has been established that the results obtained for liquid fertilizer using carbamide ammonium nitrate
rheological properties and solubility, based on the and N- acetyl ethanolamine.
References:
1. TC6.1-00203849-08: 2004 Amendment - No. 1 Synthetic food acetic acid.
2. Khasanova V. M., Saibova M. T., Ismatlova G. Kh. Studies of the interaction of monoethanolamine with sulfuric acid. Inorgan. chem.- Moscow,- 1983.- V. 28.- No. 1.- P. 228-331
3. Narkhodzhaev A. H., Tukhtaev S., Adilova M. Sh., Pogosyan A. G. Investigation of the physicochemical and rheological properties of solutions in the acetic acid-monoethanolamine system at 20 °C. Reporter ofAcadem. Sciences of the Republic of Uzbekistan. Tashkent,- 2007.- No. 6.- P. 52-55.
4. Abdullaeva M. T. Interaction of monoethanolamine with acetic acid. Uzbek Chemical Journal.-Tashkent,- 2008.- No 3.- P. 5-7.
5. Narkhodzhaev A. Kh., Abdullaeva M. T., Adilova M. Sh. The study of the interaction of monoethanolamine with formic acid. Chemistry and chemical technology.- Tashkent, - 2009.- No. 1.- P. 34-36.
6. Abdullaeva M. T. Interaction of between the monoethanolamine and methyl acetate. Proceedings of the Republican scientific and technical conference "Development of effective technology for the production of new fertilizers and agrochemicals of new generation and their application in practice".- Tashkent,-2010.- 142 p.
