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AZ9RBAYCAN KIMYA JURNALI № 1 2018
65
UDC 543.542.61.546
PRODUCTION AND STUDY OF MIXED LIGAND COMPOUNDS OF METAL IONS WITH fos-AZOCOMPOUNDS AND DEVELOPMENT OF NEW METHODS OF DETERMINING METALS
A.M.Pashaj anov
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
aydin.pashajanov@gmail.com Received 25.12.2017
Mixed ligand complexes of germanium(IV), gallium(III) and titanium(IV) were produced with stilbazo using surfactants, as well as ion-associates of acid complexes of chlorides of tellurium, antimony and iron with azoderivatives of ethoxyacridine. Optimum conditions were established for the formation of complexes and their physico-chemical and analytical characteristics were determined. According to the researches of the complexes a new method was developed to determine metals in different objects.
Keywords: extraction, stilbazo, associate, cetylpyridinium chloride.
Experimental part
Obtaining complexes of metal ions with bis-azocompound sandion-associates with basic dyes, their study and development on this basis of new photometric, extraction-photometric and extraction-atomic-absorption determination of metals is of current importance. For this purpose the following scientific-research works have been carried out.
Homoligand complexes of germanium(IV), gallium(III) and titanium(IV) with stilbazo, as well as mixed ligand complexes by surfactants [cetylpyridinium chloride (CPCh), cetylpyridini-um bromide] were produced. Optimum conditions were established for the formation of these complexes. Optimum pH values for the formation of the complexes of germanium(IV), gallium(III) and titanium(IV) with stilbazo are equal to 6.0, 6.1, and 6.0, correspondingly. Optimum pH values for the formation of mixed ligand complexes of germanium(IV), gallium(III) and titanium(IV) with stilbazo and cetylpyridinium chloride are equal to 3.0, 4.5 and 2.0, correspondingly. Spectra of homo- and mixed ligand complexes in the range of 350-600 nm were taken. Light absorption peaks of the complexes of germanium(IV), gallium(III) and titanium(IV) with stilbazo are: for homoligand complexes at 400, 415 and 408 nm, correspondingly; for mixed ligands - at 490, 510 and 588 nm, correspondingly.
Considerable bathochromic shifts are observed in absorption spectra in the complexation of cetylpyridinium halides. Molar ratio of compo-
nents in the composition of complexes was defined using different spectrophotometric methods. Molar ratios of components in the complexes established by the methods of isomolar series are equal to: Ge(IV):stilbazo:CPCh= 1:2:4; Ga(III):stilbazo:CPCh=1:2:4; Ti(IV):stil-bazo:CPCh=1:2:4. Physico-chemical and analytical characteristics of mixed ligand complexes of germanium(IV), gallium(III) and titanium(IV) were calculated. Molar coefficients of flight absorption of germanium(IV), gallium(III) and ti-tanium(IV) are equal to 39706, 48834 and 62000 correspondingly. Stability constants of the complexes are equal to 3.8-108, 6.8-102, 8.6-108 correspondingly. According to calibration curves it was established that the obedience of Beer-Lambert-Bouguer law is observed at the range of Ge(IV) - 0.05-15 mkg/25 ml, Ga(III) - 0.0810 mkg/25 ml, Ti(IV) - 0.2-12 mkg/25 ml.
The influence of external ions on the determination of germanium(IV), galli-um(III) and titanium(IV). Alkali, alkali-earth metals, Cu(II), Te(III), Bi(III), tartrate-ion, EDTA, citric and tartaric acids and others do not prevent determination of germanium. They prevent complexation of: germanium(IV), F-, Zr(IV), Sb(III), Fe(III). Alkali, alkali-earth metals, Cu, Zn, Cd, Al, Ge ions do not prevent com-plexation of gallium. Fe , Sb , F- ions prevent complexation of gallium. Zr(IV), Fe(III), Cd(III), Mo(VI), Al(III) prevent determination of titanium in a solution. Ascorbic acid, thiocarbamide and Trilon-B are used as masking agents.
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PRODUCTION AND STUDY OF MIXED LIGAND COMPOUNDS
Basing on scientific-research works new photometric and atomic-absorption determination methods of germanium, gallium and titanium in different objects were developed. Accuracy of these methods was tested by determining of germanium(IV), gallium(III) and titanium(IV) in standard samples and by standard addition technique (Table 1).
Table 1. Determination of Ge, Ga and Ti in different objects_
Determined elements Sample By specification % Found, %
Ge oil coke - 0.0014±0.0005 0.002
drilling fluid - 0.00198±0.00005 0.0018
Ga aluminate solution - 0.0051±0.0002 0.0015
Ti AC12M2 0.22 0.21±0,01 0.0020
Alunite waste 0.00279 0.00276±0.00003 0.0022
(red sludge)
Ion-associates of acid complexes of azo-derivatives of ethoxyacridine with tellurium chloride were produced. The effect of a number of factors (acidity, concentration of a dye, ratio of aqueous and organic phases) on production of ion-associates was studied. The best extraction of ion-associates is observed in 3-5 N HCl with the mixture chloroform-aceton (3:2). Optimum capacities of aqueous and organic phases are similar and equal to 5 ml. Light absorption spectra of reagents and ion-associates were taken. Maximum light absorption of reagents occurs at the range of 365-435 nm, for ion-associates - at 516, 520 and 505 nm, correspondingly.
Table 2. Physical and chemical characteristics of ion-associates
£ -
Ion-associates f ic £ в 4- о w 1Л О ca 0х eR ompos tion
<C О
AEADA+[HTeCl6]- 5 520 6.2 4.7 98.64 1:6:1
EADEA+[SbCl6]- 3 516 6.0 5.5 98.0 1:6:1
EADEA+[FeCl4]- 4 505 5.5 6.0 98.3 1:4:1
It was established by different spectropho-tometric methods (Asmus, equilibrium shift) that in ion-associates the ratio between metal and dye is 1:1. Physical and chemical and analytical characteristics of ion-associates were determined. Calibration curves were built to determine metals. Beer-Lambert-Bouguer law is obeyed with metal
content within 0.5-15.0 mkg/ml.
Effect of external ions on the determination of Te, Sb and Fe. The following ions prevent the determination: Te(IV) - Fe(III), Sb(V), Te(III), In(III), Au(III), Ga3+, ascorbic acid; Sb(V) - Fe(III), Te(IV), Tl(III), In(III), Au(III), Hg(II), Ga3+; Fe(III) - Au(iII), Tl(m), Sb(V), In(III), Ga3+, Bi(III), thiocarbamide. Their preventing effect is eliminated by masking agents.
Basing on the research works new methods were developed to determine tellurium, antimony and iron in different objects (Table 3). Developed methods were applied for determination of these metals in alunite and copper alloys and compared with known methods.
Table 3. Determination of tellurium, antimony and iron
in different samples
Element Sample By specification, % Found, %
Tellurium M-94-15(947x) 0.00024 0.00022
Antimony Brof8-3M147x 0.0021 0.0020
Iron Alunite 0.40 0.43
6 new compounds relating to the class of ketoximes and azocompounds were synthesized: 2-hydroxy-5-methylacetophenonoxime, 2-hydroxy-5-methylbenzophenonoxime, 2-hydr-oxy-5-fluoracetophenonoxime, 2-(1-azo-2-hydr-oxynaphthaline)naphthol-1, 4-(picramineazo)-2-hydroxybenzoicacid, 1 -(picramineazo)-2-hydr-oxy-3-naphthoic acid.
The composition and structure of the secompounds were determined by the methods of IR spectroscopy and spectrophotometry, light absorption spectra in different solutions were taken. Complexation of synthesized compounds with some heavy metals (Fe3+, Cu2+, Co2+, Ni2+) was established qualitatively.
Antimicrobial effect of 2-hydroxy-5-fluor-acetophenonoxime to some bacteria and fungus was found out.
Results
Mixed ligand complexes of germani-um(IV), gallium(III) and titanium(IV) with stilba-zo and surfactants - cetylpyridinium chloride, as well as ion-associates of acidcomplexes of chloride of tellurium, antimony and iron with azode-rivatives of ethoxyacridine were produced. New
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 1 2018
A.M.PASHAJANOV
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photometric and extraction-atomic-absorption methods of determining metals (Ge, Ga, Ti, Te, Sb and Fe) in different samples were developed.
6 new compounds relating to the class of ketoximes and azocompounds were synthesized: 2-hydroxy-5-methyl-acetophenonoxime, 2-hydroxy-5-methyl benzophenonoxime, 2-hydr-oxy-5-fluor-acetophenonoxime, 2-( 1 -azo-2-hydr-oxy-naphthaline)-naphthol-1, 4-(picramineazo)-2-hydroxybenzoic acid, 1-(picramineazo)-2-hydr-oxy-3-naphthoic acid.
References
1. Pashajanov A.M. Extraction and Atomic Absorption Determination of Zirconium(IV) with Azo-Deriva-tive Para-Tret-Butylphenol // United Kingdom, Chemistry J. 2015. V. 5. No 4. P. 76-79.
2. Pashajanov A.M. Extraction and Atomic Absorption Determination of Palladium on the basis of the complexation reaction with 2-Hydroxy-5-T-Butylphenol-4'-Methoxy-Azobenzene // India. J. Advances in Chemistry. 2015. V. 11. No 9. P. 3779-3783.
3. Pashajanov A.M. Extraction-Atomic-Absorption Determination of Germanium with 2-Hydroxy-5-T-Butylphenol-4-Methoxy-Azobenzene // J. Advances in Chemistry (JAC). India. 2016. V. 12. No 6. P. 4112-4116.
4. Ismayilov N.i., Pa§acanov A.M // Azo-Substitute of Ethoxy Acridine - A New Reagent for Extraxtion-
Photometric Determionation of Tellurium(IV) // J. Advances in Chemistry (JAC). India. 2016. V. 12. No 11. P. 4476-4479.
5. Pashacanov A.M. Extraction concentrating of tungsten(VI) in complex form with 2-hydroxy-5-tretbutylphenol-4-methyl-azobenzene and its determination by atomic-absorption spectrometry // Int. J. Chem. Studies. India. 2016. V. 4. No 5. P. 49-51.
6. Pashajanov A.M. Extraction and Atomic-Absorption Determination of Scandium(III) with 2-Hydroxy-5-T-Butylphenol-4-Nitroazobenzene // Int. J. Innovative Sci. Engineering and Technology. 2017. V. 4 . Issue 2. P. 11-14.
7. Pashajanov A.M., Agamaliyeva M.M.,.Mugalova G.R, Yusifova N.V. and Piralisoy A.S. Extraction-atomic-absorption determination of titanium(IV) with azoderivate para-tret-butylphenol //Int. J. Current Engineering and Technology. 2017. V. 7. No 4. P. 1457-1460.
8. Ismailov N.I., Osmanova A.KH., Iusifova N.V., Mamedova M.V., Osmanova S.N. Assotciaty khlortellurita s azozameshchennymi etoksiak-ridina v ekstraktcionno-fotometricheskom analize // Butlerovskie soobshcheniia. 2017. T. 50. No 6. C. 137-140.
9. Pashadzhanov A.M. Ekstraktcionno-atomno-absorb-tcionnoe opredelenie nekotorykh d-elementov s azoproizvodnymi para-tret-butilfenola // Krasnodar. 2015. II Vserossiiskaia konf. s mezhdunarodnym uchastiem po analiticheskoi spektroskopii. C. 120.
METAL ÍONLARININ Ais-AZOBiRLa^MOLORLO MÜXTOLÍFLÍQANDLI KOMPLEKSLORiNiN ALINMASI VO TODQiQi VO METALLARIN TOYiNiNiN YENi ÜSULLARININ i§LONiLMOSi
A.M.Pa$acanov
Germanium(IV), Qallium(III) va Titan(IV)-ün stilbazo ila müxtalifliqandli komplekslari, etoksiakridinin tellur-xlorid, stibium-xlorid, damir-xloridasidokomplekslari ila ion assosiatlan ahnmi§dn\ Komplekslarin amala galmasinin optimal §araiti oyranilmi§, fiziki-kimyavi analitik xarakteristikalari tayin edilmi§dir. Alinmi§ komplekslardan istifada edarak gostarilan metallarin müxtalif obyektlarda tayinlari ügün yeni metodikalar i§lanmi§dir.
Agar sozlar: ekstraksiya, stilbazo, assosiat, setilpiridin xlorid.
ПОЛУЧЕНИЕ И ИССЛЕДОВАНИЕ РАЗНОЛИГАНДНЫХ КОМПЛЕКСОВ ИОНОВ МЕТАЛЛОВ С бис-АЗОСОЕДИНЕНИЯМИ И РАЗРАБОТКА НОВЫХ МЕТОДОВ
ОПРЕДЕЛЕНИЯ МЕТАЛЛОВ
А.М.Паш аджанов
Получены разнолигандные комплексы repMaHna(IV), галлия(Ш) и mraHa(IV) со стильбазо при участии ПАВ, а также ионные ассоциаты ацидокомплексов хлоридов теллура, сурьмы и железа с азопроизводными этоксиакри-дина. Установлены оптимальные условия образования комплексов и определены их физико-химические и аналитические характеристики. Разработаны новые методики определения указанных металлов в различных объектах.
Ключевые слова: экстракция, стильбазо, ассоциат, хлорид цетилпиридиния.
