Trimetiloltiomochevina mis asetat – suvni 25 va 50°c haroratli sistemada eruvchanligi

Materials and methods.
The isothermal method [4] was used to study the solubility in the trimethylolthiourea–copper acetate–water system at 25 and 50°C. Chemical analysis of liquid and solid phases was carried out by known methods of analytical chemistry [5–7]. The data obtained were used to determine the compositions of solid phases according to Skreinemakereu [8] and plot solubility diagrams at 25 and 50°C.
Results and discussion. Solubility in the HOH₂CNCSN(CH₂OH)₂• •Cu(CH₃COO)₂ • H₂O system has not been previously studied. Therefore, in order to characterize the behavior of the initial components in their joint presence, we first studied this system by the isothermal method at 25 and 50°C.
The data on the solubility of the ternary system trimethylolthiourea - copper acetate - water are presented in tables 1 and 2, from which it follows that in the studied system the formation of a complex compound of the composition HOH₂CNCSN(CH₂OH)₂ • Cu(CH₃COO)₂ • 2H₂O takes place.
At 25⁰C, in the concentration range of solutions of 13.10-14.20% of trimethyloltiourea and 0.-3.70% of copper acetate, trimethylolthiourea crystallizes in the system.
At a concentration range of 3.90-14.20% of trimethyloltiourea and 3.70-11.98% of copper acetate, compounds HOH₂CNCSN(CH₂OH)₂•Cu(CH₃COO)₂• •2H₂O are released from the solution into this phase, and at 0.-3 .90% trimethylolthiourea and 7.30-11.98% copper acetate - copper acetate crystallizes. With an increase in temperature from 25 to 50°C, the concentration limits of crystallization from solutions of the initial components and a new compound, formed on their basis, slightly expand. At a concentration range of 24.92–26.82% HOH₂CNCSN(CH₂OH)₂ and 0.0–3.40% Cu(CH₃COO)₂, HOH₂CNCSN(CH₂OH)₂ is released into this phase.
Between a concentration of 4.22-26.82% HOH₂CNCSN(CH₂OH)₂ and 3.40-17.92% Cu(CH₃COO)₂, the compounds HOH₂CNCSN(CH₂OH)₂• •Cu(CH₃COO)₂ • 2H₂O are formed. The area of ​​crystallization of copper acetate corresponds to a solution of 0-4.22% HOH₂CNCSN(CH₂OH)₂ and 10.32-17.92% Cu(CH₃COO)₂. (Figures 1 and 2)
Table 1
Solubility data in the TMUT - copper acetate - water system at 25⁰C

№ Points composition	Liquid phase composition,%			The composition of the solid residue,%				Solid phase
	ТМUт	Сu (СН3СОО)2	H2O		ТМUт	Сu (СН3СОО)2	H2O
1.	13,10	-	86,90		84,28	-	15,72		ТМUт
2.	13,41	1,87	84,72		82,80	0,50	16,70		“ “
3.	14,20	3,70	82,10		84,30	0,89	14,81		ТМUт +ТМUт•Сu(СН3СОО)2•2H2O
4.	14,21	3,72	82,07		39,98	41,45	18,57		ТМUт•Сu(СН3СОО)2•2H2O
5.	11,42	3,56	85,02		37,96	41,24	20,80		“ “
6.	9,22	4,12	86,66		37,97	41,28	20,75		“ “
7.	7,05	5,98	89,97		36,43	39,75	2,82		“ “
8.	5,96	6,23	87,81		35,12	39,18	25,70		“ “
9.	5,86	9,87	84,27		36,26	40,35	23,39		“ “
10.	3,90	11,98	84,12		35,12	40,01	24,87		ТМUт•Сu(СН3СОО)2•2H2O+ Сu(СН3СОО)2 + Сu(СН3СОО)2
11	3,91	12,00	84,09		1,23	75,89	23,09		Сu(СН3СОО)2
12	2,28	9,32	88,40		1,02	76,98	22,00		“ “
13	-	7,30	92,30		-	80,24	19,76		“ “

Table 2
Solubility data in the TMUT - copper acetate - water system at 50°C

№ Points composition	Liquid phase composition,%			The composition of the solid residue,%				Solid phase
	ТМUт	Сu (СН3СОО)2	H2O		ТМUт	Сu (СН3СОО)2	H2O
1.	24,92	-	75,08		90,28	-	9,72		ТМUт
2.	25,12	1,24	73,64		82,88	0,58	16,54		“ “
3.	26,82	3,40	69,78		83,58	1,28	15,14		ТМUт +ТМUт•Сu(СН3СОО)2•2H2O
4.	26,83	3,41	69,76		41,28	39,34	19,38		ТМUт•Сu(СН3СОО)2•2H2O
5.	23,97	2,88	73,15		40,66	39,56	19,78		“ “
6.	22,01	2,83	75,16		40,45	39,51	20,04		“ “
7.	20,06	2,67	77,27		39,39	39,22	21,39		“ “
8.	17,84	2,96	79,2		39,89	39,78	20,33		“ “
9.	15,96	3,86	80,18		39,12	40,08	20,80		“ “
10.	13,68	4,97	81,35		38,06	36,22	25,72		“ “
11	11,45	6,58	81,97		38,40	40,97	20,63		“ “
12	9,05	8,66	82,29		38,02	40,82	21,16		“ “
13	7,21	11,09	81,70		37,88	41,02	21,10		“ “
14	5,89	13,56	80.55		37,96	41,89	20.15		“ “
15	5,08	15,87	79.05		37,86	41.96	20.18		“ “
16	4,22	17,92	77.86		38,49	44,00	17.51		ТМUт•Сu(СН3СОО)2•2H2O+ Сu(СН3СОО)2 + Сu(СН3СОО)2
17	4,23	17,93	77.84		1,28	83,42	15.30		Сu(СН3СОО)2
18	2,44	13,49	84.07		0,89	83,96	15.69		“ “
19	-	10,82	89.18		-	88,89	11,11		“ “

Figure 1. Solubility diagram of the TMUT - copper acetate - water system at 25⁰C

Figure 2. Solubility diagram of the system ТМUт – copper acetate – water at 50°С
The compounds formed in the studied system were identified by chemical and various methods of physicochemical and various methods of physicochemical analysis. Chemical analysis of the solid phase,
HOH₂CNCSN(CH₂OH)₂•Cu(CH₃COO)₂•2H₂O compound isolated from the supposed region of crystallization gave the following results.
Found,%: Cu - 17.38; CH₃COO - 16.98; H₂O -4.78.
For HOH₂CNCSN(CH₂OH)₂•Cu(CH₃COO)₂•2H₂O calculated, %:
Cu - 17.42; CH₃COO - 16.73; H₂O -4.93.
IR absorption spectra were used to determine the individuality of the synthesized allocated complexes using a two-beam infrared spectrophotometer of the Zeiss IR-20 in the 400-4000 cm^-1 region .Samples were prepared in the form of tablets compressed with KBr.
Some vibrational frequencies (cm^-1) in IR absorption spectra of trimethylolthiourea (L) and its complexes with copper acetate are shown in Table 3.
Comparison of the IR spectra of free trimethylolthiourea and the investigated complex compounds of copper show that the frequencies of valence vibrations of OH bonds are mixed into the low-frequency region by 65 cm^-1. While the assumed C = S bond band at 1250 cm^-1 in the case of copper decreases 14 cm^-1 is reported for copper. However, the low-frequency band at 579 cm^-1 attributed to the deformation vibration of the bond in all cases decreases by 17 cm^-1. These changes indicate that in coordination both the oxygen atoms of the alcohol groups and the sulfur atom of the thioamide group participate.


Table 3
Some vibrational frequencies (cm^-1) in the IR absorption spectra of trimethylolthiourea and its complexes.

Trimethylolthio- urea (L)	Cu(CH3COO)2· L·H2O	Absorption
1	3	5
		(OH)H2O
3359	3294	(OH)alcohol
	3243	(NH)+2 (NH)
3044	3143,3097
2955	2972	(CH)
2897	2843
	1654	(NH), (OH)
1621	1634
	1557	as(COO)
1542	1550
1521	1540
1457	1464	s(COO)
	1399	s(N-C-N)
1423		(C-N)
1364	1350	S(CH3)
1300	1303
1250	1264	(C=S)amide n
1157	1179	(NH)
1064		(CN)
1026		(COH)
988		(CH2)+ (C-C)ац
	923
939	853	(C-С)+ (CH2)
913	737	(CH2)
676	679	(COO)
626
579	562	(N-C=S), (NH)

The thermal analysis was recorded on the derivatograph of the Paulik-Erdei system [9-10] at a rate of 10 deg / min. and samples - 0.10 g with the sensitivity of galvanometers T-900, TG-100 DTA-1/10, DTG-1/10. The recording was carried out under atmospheric conditions with a constant removal of the gaseous medium by means of a water jet pump. The holder was a platinum crucible with a diameter of 7 mm without a cover. Al₂O₃ was used as a reference.

Derivatographic data of thermolysis of trimethylolthiourea and its complexes are given in Table 3. The temperature intervals, the peak of thermal effects, the loss of mass of each effect, the nature of thermal effects and the resulting compounds after each process were determined. It is shown that the thermal behavior of complexes depends on the nature of the metal and the composition of the compounds.
Conclusion. The solubility in the system HOH₂CNCSN(CH₂OH)₂-Cu(CH₃COO)₂-H₂O at temperatures of 25 and 50°C was studied by the isothermal method. An isothermal solubility diagram at 25 and 50°C was constructed, on which the crystallization fields of HOH₂CNCSN(CH₂OH)₂, Cu(CH₃COO)₂ of the new compound and the compound of the composition HOH₂CNCSN(CH₂OH)₂•Cu(CH₃COO)₂•2H₂O are demarcated. The compound was isolated from the expected region of crystallization and identified by chemical and physicochemical analysis methods.

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