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CHEMICAL PROBLEMS 2023 no. 3 (21) ISSN 2221-8688 221
UDC 543.4:54.412:541.49
EXTRACTION OF NICKEL (II) PICRATE FROM SOLID PHASE WITH ORGANIC REAGENTS
L.M. Maharramova, N.E. Jabbarova, M.Y. Abdullayeva
Azerbaijan State University of Oil and Industry, Azadlig 20, Baku, AZ-1010, Azerbaijan e-mail: mayaabdullayeva@hotmail.com
Received 04.05.2023 Accepted 25.07.2023
Abstract: The present work is dedicated to the very important area of analytical chemistry—extraction-photometric determination of ions from a solid phase. We carried out studies on the extraction of nickel picrate (NiPik2) from the solid phase using solutions of tetrahalobicyclic reagents of the acetylene series with a dicarbonyl bridge in the side chain (L1, L2, L3, L4) of chloroform. New organic ligands were synthesized and their physicochemical properties - melting point, molecular weights, as well as their optical density studied. A new technique for the extraction-photometric determination of the nickel ion from the solid phase was developed. It found that new organic reagents (L1-L4) exhibit high extraction ability (0.11-0.64 mg/l) of Ni ions from the solid phase. When comparing the extraction activity of the studied reagents, it was revealed that the ability to extract organic ligands of tetrahalobicyclic reagents (L1-L4) changes in the following order: L4> L3> L1> L2. Magnetic field increased nickel extraction by 3-4%. Keywords: extraction, nickel (II) picrate, organic reagents, equilibrium, optical density, equilibrium, a magnetic field.
DOI: 10.32737/2221-8688-2023-3-221-228
Introduction
One of the simplest and most accessible, but at the same time, effective methods of separation and concentration, in particular, metal ions, is extraction. Extraction is the process of extracting appropriate substances from various objects with solvents. The objects from which the respective compounds are extracted can be solids and liquids. Therefore, extraction processes are divided into extraction in the solid-liquid system and extraction in liquid-liquid system (liquid extraction), in other words, depending on the state of aggregation of the contacting phases, several extraction options are distinguished.
Extraction from the solid phase is a widely used method of separation and preconcentration in analytical chemistry due to rapidity, high efficiency, and the possibility of combination with various physicochemical and
chemical methods for determination of analytes of various nature [1-4].
According to the type of interaction with the substance to be extracted, extractants are divided into neutral and ion-exchange. Neutral extractants are organic substances whose molecules are capable of forming coordination bonds (donor-acceptor type) with the extracted ion, stronger than the bonds of water molecules, that is, the solvation energy of the extractant molecules exceeds the hydration energy. Ionexchange extractants include organic acids and their salts or organic bases and their salts, capable, upon contact with an aqueous solution, of exchanging an inorganic cation or anion, which is part of the extractant, for an inorganic cation or anion, which is in solution. In this case, the condition for the extraction to proceed is higher hydration energy of the ions passing
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CHEMICAL PROBLEMS 2023 no. 3 (21)
from the organic phase to the aqueous one, as compared to the ions extracted from the aqueous solution. The extractants of this group are called liquid ion exchangers and are divided into cation-exchange and anion-exchange depending on the type of exchanged ions [5-11].
Solid phase extraction (SPE) is a fast sample preparation method that uses a sorbent (solid stationary phase) to concentrate and separate the target component or components, followed by elution (washout) with a suitable solvent.
For many years, liquid extraction, precipitation, centrifugation, column and thin layer chromatography have been the main methods for isolating, purifying, and concentrating analytes. Such preparation of samples is a lengthy and multi-stage process that requires the consumption of a large amount of extra pure (does not introduce impurities!) solvents and reagents, additional equipment and labor costs.
An excellent alternative to liquid-liquid extraction is solid phase extraction. Large volume samples can be processed using relatively small amounts of solids, which, in turn, require a small volume of solvents for the subsequent desorption of concentrated compounds, therefore, there is no need for additional evaporation and the risk of sample contamination is significantly reduced. SPE is characterized by wider possibilities for varying the nature and strength of sample interactions with the sorbent and eluent than for liquid-liquid extraction, as a result of which more selective and quantitative isolation or finer purification of the components of interest is carried out. Due to specific interactions, each of
the analyte compounds can be selectively concentrated and recovered or separated from interfering components. Advantages of TFE:
• high degree of extraction of target compounds (> 80%)
• excellent reproducibility and selectivity
• significant reduction in sample preparation time compared to liquid-liquid extraction
• possibility of process optimization
• ease of use
• saving of expensive solvents
Various methods are used for the analytical control of nickel (II) content in various environmental objects. Among them, the most widely used are photometric methods, which are characterized by high sensitivity, accuracy, and simplicity of the equipment used [12-16].
Analytical studies of transition metals in this direction have not yet been studied in detail, and there is not enough information about this in the world scientific literature. Therefore, studies on the extraction of ions from the solid phase with the help of organic ligands are very topical. From an analytical point of view, the separation of ions from the solid phase is of great importance for the development of technology to obtain pure, chemically pure, pure for analysis, and ultrapure metal salts [17- 19].
In this regard, chloroform solutions of new synthesized organic reagents (L1, L2, L3, L4), which are tetrahalogen-containing hydrophobic organic compounds of the bicycloquinone type with an acetylene fragment, were used to extract Ni (II) from the solid phase, and an appropriate method was proposed for the quantitative extraction of photometric determination of Ni (II) from the solid phase.
Experimental part
1. Determination of the degree of extraction - Nickel A-ion from the solid phase by organic ligands L1-L4. Preparation of solutions: organic ligands shown in table 1. L1=71.2 mg; L2=59.6 mg; L3=106.2 mg; L4=109.6 mg was dissolved in 200 ml of chloroform (CHCl3) and a 10-3 molar solution was prepared. Chemically pure nickel picrate (NiPik2) was used for extraction.
2. Determination of the optical density of
organic ligands L1-L4.
Dried at 110-1150C salt of nickel picrate in the form of a powder weighing 100-200 mg was poured into a conical flask and 25 ml of chloroform solutions of organic ligands -L1-L4 with a concentration of W0"3 - 2^10"3 M were added. The solution was stirred with a magnetic stirrer for 3 hours at a temperature of 18 - 200 C. Then after 15 min. samples were taken from the organic phase in a volume of 2 ml and the optical density was determined - A on a Spekol device (l=1.0 cm, X=375 nm). Using an
anhydrous solution (CHCh: CHCN = 1:1) of picric acid, the nickel ion content in the solid phase was determined by extraction with organic ligands LrL4.
3. Extermination of the period of establishment of chemical equilibrium in the process of nickel ion extraction by organic ligands.
The greenish-yellow organic phase was studied spectrophotometrically at the maximum wavelength Xmax=375 nm. For this to happen, we took 100-200 mg of dried nickel picrate salt (NiPik2) and used solutions of Li, L2, L3, L4 in chloroform at room temperature (18-20°C) and determined the period of establishment of
chemical equilibrium between the phases (t).
100-200 mg of nickel (II) picrate salt powder was poured into a 100 ml conical flask, and 25.0 ml of 10-3 M chloroform solution Li was added to it. After inserting a magnetic stirrer into the flask, the neck of the flask was closed with a polished stopper. Stirring was carried out for 5 hours. Every 30 min. the concentration of the organic phase (A) was measured on a Spekol-10 spectrophotometer (l=5.0 cm, X=375 nm). The above procedures were carried out by mixing 1*10"3 M chloroform solutions of L1-L4 organic ligands in a vessel for various time intervals and investigated the time of chemical equilibrium (t) between the phases.
Results and its discussion
Some physicochemical characteristics of organic reagents of the bicycloquinone type with tetra halogen, acetylene fragments are shown in Table 1.
It can be seen from the obtained experimental data (Table 2) that nickel picrate (NiPik2) is extracted from the solid phase into
the organic phase by the ligand L1-R=76%, L2-up to 70.60%, L3- up to 89.11%, L4 up to 95.35%. The amount of Ni ion from 0.49 mg to 0.65 mg was determined by the extraction-photometric method, and it can be concluded that the ability to extract organic ligands (L1-L4) is arranged in a row as follows L4> L3> L1> L2.
Table I. Physicochemical properties of Li-L4 organic ligands
Formula and name of organic ligands (L1-L4) Temperature of Melting, 0C Infrared spectra, cm-1 Yield, %
C13H10Cl4O2- 1,2,3,4-tetrachloro-7,8-quinone-5-(3-methyl-oxy-1- butyl)bicyclo[2,2,2] octene-2 (L1) 141 3400 =O-H 2225 -C=C-1760 =C=C 1600 >C=C 760 =C-Cl 86.2
C13H10Cl4O2- 1,2,3,4-tetrachloro-7,8-quinone-5-ethynyl-bicyclo [2,2,2]octene-2 (L2) 89 3320 =C-2125 -C=C-1760 =C=O 1545 >C=C< 760 =C-Cl 81.0
C13H10Br4O3- 1,2,3,4-tetrabromo-7,8-quinone-5-(4-methyl-4-oxy- 2-pentenyl) bicycle [2,2,2]octene-2 (L3) 170 3420 =C-H 2235 -C=C-1765 >C=O 1605 >C=C< 680 =C-Br 62.7
C14HnBr4O3- 1,2,3,4-tetrabromo-7,8-quinone-5-(4-methyl-oxy-2-pentenyl)bicyclo[2,2,2] octene-2 (L4) 150 3410 =C-H 2240 -C=C-1765 >C=O 1610 >C=C< 675 =C-Br 52.0
Table 2. Maximum extraction of nickel picrate by chloroform solutions L1 -L4 from the solid phase,
t=2.5 h, Xmax=375 nm, l=5.0 cm
Organic ligands Optical density, A Ni, Mg/l Extraction, R, %
Li 0.29 0.49 76.01
L2 0.27 0.46 70.62
L3 0.34 0.57 89.11
L4 0.34 0.65 95.35
The study of the chemical equilibrium of the nickel ion extraction process with organic ligands showed that in the case of the Li, L2 ligand, complete chemical equilibrium between the phases is established after 3 hours, and in
the case of L3, L4 - after 2.5 hours. The resulting chemical equilibrium is not even disturbed by magnetic stirring for 5 hours and remains unchanged (figurei).
Fig.1. Change of optical density (A) over time for organic ligands - L1, L2, L3, L
It is of interest to study the change of optical density (A) over time for organic ligands - L1, L2, L3, L4 extraction of the nickel ion by the photometric method with chloroform solutions of organic ligands - L1-L4 concentration 0.25* 10 - 2.10 M in a strong magnetic field. The equilibrium between the phases is established after 90 minutes, and the extraction of nickel into the organic phase increases by 3-4%. The results obtained are presented in Table 3.
Table 3 shows that nickel picrate salts are extracted from the solid phase into the organic phase in the amount of 0.13-0.64 mg/l, forming macromolecular associates with ligands.
The process of transition from the solid
1, L2, L3, L4
phase to internal complexation with metal ions by extraction of ligands - members that form the internal complex, or the dissolution of metal salts is mainly controlled by the following factors in stages: - for example, depending on the structure of organic ligands containing halogen atoms, the acetylene fragment ( -C=C-), functional groups = N, =NH, -NH2, - OH, =C=O, -S-, =NOH, etc., internal complex compounds are formed and, since the center creates a coordination bond with the transition metal- ion, these organic ligands diffuse to the pores of the metal salt in the solid phase. After a certain time, chemical equilibrium occurs between the phases.
Table 3. Physical and chemical characteristics of organic ligands and degree of nickel ion _extraction in a magnetic field_
Organic ligands, Ln Concentration, C'10"3 M Optical density, A Quantity Ni2+, Mg/l Extraction, R, %
0.25 0.07 0.13 19.75
0.50 0.15 0.24 38.72
C13H10Cl4O2 0.75 0.22 0.36 57.62
1.00 0.27 0.49 78.00
L1 1.25 0.27 0.49 78.00
1.50 0.27 0.49 78.00
0.25 0.11 0.12 194
0.50 0.13 0.22 36.8
C13H10CUO2 0.75 0.21 0.34 56.2
1.00 0.25 0.45 73.6
L2 1.25 0.25 0.45 73.6
1.50 0.25 0.45 73.6
0.25 0.08 0.14 26.01
C13H10Br4O3 0.50 0.75 0.17 0.20 0.28 0.43 48.02 69.03
L3 1.00 0.33 0.56 91.05
1.25 0.33 0.56 91.05
1.50 0.33 0.56 91.05
0.25 0.09 0.16 26.81
0.50 0.19 0.32 50.62
C14H12Br4O3 0.75 0.28 0.48 94.43
1.00 0.36 0.64 98.25
L4 1.25 0.36 0.64 98.25
1.50 0.36 0.64 98.25
Fig. 2. Scheme of nickel ion extraction from the solid phase by organic ligands
At this time, the metal salt dissolves and is extracted into the organic phase. The chemical equilibrium between the liquid organic ligand and the solid phase depends on many factors, such as temperature, surface of the metal salt, which is the solid phase, i.e. on the micron size of the particles, the phase structure of the crystal, the variety of salt-forming anions with metal ions, the ionic radius of the metal.
Aside from this, it also depends on the time of phase contact, the amount of acetylene fragment (-C=C-) and functional groups in tetrahaloorganic ligands, and the energy of formation of metal salts.
Finally, there is a transition from the solid phase to the liquid (anhydrous) phase with tetrahalogenbenzoquinone organic ligands (L1, L2 L3 L4), i.e., transition metal salt ions interact
with molecules of organic ligands, forming macromolecular ions - associates and are extracted into a liquid organic phase due to diffusion. Due to the acetylene (-C=C-) fragment contained in hydrophobic organic ligands, the dissolution of the nickel picric salt
(NiPik2) and its extraction into the organic phase can be considered as the formation of a macromolecular ion, an associate. The scheme of formation of such an associate is shown in the diagram (Figure. 2).
Conclusions
Thus, based on the results of the studies carried out, a new procedure for the extraction of transition metal salts with organic ligands of tetrahalobicyclic reagents L1, L2, L3, L4 into the organic phase has been developed.
The physicochemical characteristics of organic ligands were studied. The optical density of organic ligands and the degree of extraction of nickel ions from the solid phase were determined, which is more than 95%. It found that the magnetic field has a positive effect on the degree of nickel ion extraction
from the solid phase by organic ligands.
On the basis of the results obtained, a flow diagram of the extraction process with organic ligands was proposed.
The proposed technique makes it possible to obtain ultrachemically pure salts of nickel and other metals, as well as the synthesis of some organic substances by interfacial catalysis. In addition, the developed technique opens up opportunities for studying the mechanism of the extraction process from the solid phase.
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ЭКСТРАКЦИЯ ПИКРАТА НИКЕЛЯ(П) ИЗ ТВЕРДОЙ ФАЗЫ ОРГАНИЧЕСКИМИ
РЕАГЕНТАМИ
Л.М. Магеррамова, Н.Э. Джаббарова, М.Я. Абдуллаева
Азербайджанский Государственный Университет Нефти и Промышленности, Азадлыг 20, Баку, AZ-1010, Азербайджан e-mail: mayaabdullayeva@hotmail. com
Аннотация: Настоящая работа посвящена весьма важной области аналитической химии -экстракционно-фотометрическому определению ионов из твердой фазы. Проведены исследования по экстракции пикрата никеля (NiPik2) из твердой фазы с использованием растворов тетрагалогенбициклических реагентов ацетиленового ряда с дикарбонильным мостиком в боковой цепи (Li, L2, L3, L4) в хлороформе. Разработана новая методика экстракционно-фотометрического определения иона никеля из твердой фазы. Определено, что новые органические реагенты (L1-L4) проявляют высокую экстракционную способность
(0.11-0.64 мг/л) ионов № из твердой фазы. При сравнении экстракционной активности изучаемых реагентов установлено, что способность к экстракции органических лигандов тетрагалогенбициклических реагентов (Ь1- Ь4) изменяется в ряду следующим образом L4> Ь3 > Ь1> Ь2.. Магнитное поле увеличивает экстракцию никеля на 3-4%.
Ключевые слова: экстракционная способность, пикрат никеля (II), органические реагенты, твердая фаза, равновесие, магнитное поле.
NiKEL(II) PiKRATIN B9RK FAZADAN ÜZVi REAKTiVL9RL9 EKSTRAKSiYASI L.M. Maharramova, N.E. Cabbarova, M.Y. Abdullayeva
Azdrbaycan Dövldt Neft vd Sdnaye Universiteti, Azadliq 20, Baki, AZ-1010, Azdrbaycan e-mail: mayaabdullayeva@hotmail.com
Xülasa: Taqdim olunan i§ analitik kimyanin 90X mühüm sahasina - ionlarin bark fazadan ekstrasion-fotometrik üsulla tayin edilmasina hasr edilmi§dir. Yan zancirinda dikarbonil körpüsü olan asetilen fraqmentli üzvi liqandlarin (Li, L2, L3, L4) xloroformlu mahlullarindan istifada etmakla nikel (II) pikratin (NiPik2) bark fazadan ekstraksiyasi tadqiq edilmi§dir. Bu maqsadla yeni üzvi liqandlar sintez edilmi§ va onlarin fiziki-kimyavi xassalari - arima temperaturlari, molekul kütlalari, ham^nin optiki sixliqlari tadqiq edilmi§dir. Nikelin (II) pikratin bark fazadan yeni ekstrasion-fotometrik tayini metodikasi i§lanib hazirlanmi§dir. Müayyan edilmi§dir ki, yeni üzvi tetpahalogenbitsiklik reagentlar (L- L4) nikel (II) ionlarini bark fazadan yüksak ekstraksiya etmak qabiliyyatlarina (0.11-0.64 mg/l) malikdirlar. Tadqiq edilan reagentlarin ekstraksiya etmak qabiliyyatlarini müqayisa etdikda müayyan edilmi§dir ki, sintez edilmi§ üzvi liqandlarinin (L1- L4) ekstraksiya qabiliyyatlari a§agidaki kimi dayi§ir L4>L3>L1 >L2. Nikelin ekstraksiyasini maqnit sahasi 3-4 % artirir.
Acar sözlar: ekstraksiya qabiliyyati, nikel (II) pikrat, üzvi reagentlar, bark faza, tarazliq, maqnit sahasi.
