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CHEMICAL PROBLEMS 2019 no. 2 (17) ISSN 2221-8688
UDC 543.42:546.74:54.412. 2 STUDY INTO COMPLEX FORMATION OF NICKEL (II) WITH 1-PHENYL- 2- (2 -HYDROXY -4-NITROPHENYLHYDROSO) BUTANEDIONE-1,3 IN THE PRESENCE
OF THIRD COMPONENTS
1V.I. Mardanova, 2Sh.A. Tahirli, 1A.Q. Babaev, 1F.M.Chiragov
1Baku State University Z. Xalilov str., 23, AZ 1148 Baku Azerbaijan Republic; e-mail:[email protected]
2Lankaran State University 50, H. Aslanov ave., Lankaran, Azerbaijan Republic
Received 13.02.2019
Abstract.The effect of the third components a, a'-dipyridyl (a, a'-dip), ethylene diamine (Ed) and phenontroline (Phen) on the complexation of nickel (II) with 1-phenyl-2-(2-hydroxy-4-nitrophenylhydrozo)butanedione-1,3 was studied. NiR and mixed ligand (NiRa, a'-dip, NiREd and NiRPhen) complex compounds are formed at pH 6, 5, 4.5 and 5, respectively.The ratio of the reacting components in the composition of homogeneous and mixed ligand complexes was established and the interval of subordination to the Beer's law determined.The developed methodology was applied to specify nickel (II) in the river water.
Keywords: nickel (II), mixed ligand complex, a,a'-dipyridyl, ethylene diamine andphenantroline DOI: 10.32737/2221-8688-2019-2-316-322
Introduction
Enhanced content of compounds of heavy metals has a negative effect on human health. Note that nickel is perttaining to metals of the above-mentioned sort, so it is essential to monitor the nickel concentration in the samples of natural and waste waters.
There are different reagents for spectrophotometric determination of nickel (II), including P-diketones and oximes [1-11]. Atomic absorption spectrometry of a flame and graphite furnace and spectrophotometric
methods provide an accurate and rapid determination of nickel in natural and waste waters.
In the present work, the complexation of nickel (II) with 1-phenyl - 2- (2 - hydroxy - 4-nitrophenylhydrozo) butanedione-1,3(R) in the presence of a,a'-dipyridyl (a,a'-dip), ethylenediamine (Ed.) and phenantroline (Phen) was explored through the use of the photometric method.
Materials and methods
Solutions and reagents: The reagent determined by the methods of elemental was synthesized according to the procedure analysis and IR spectroscopy. [12, 13], its composition and structure were
C6H5
I6 5 ho
c=o \
ch n= n—'
c=o
Ch„
^ //
no
Calculated: % C - 58.72; H-3.98; N-12.84, N-8.14, O-24.46 Found: %C - 58.85; H-4.09; N-12.99, N-8.44, O-24.77.
In this work, 1*10-3 M ethanol solution of the reagent and water - ethanol solutions (3:7) of the third components were used and prepared by dissolving their exact weights. A solution of nickel (II) ion was prepared from NiSO4*7H2O by dissolving an exact sample in water. To create the required acidity, ammonium acetate buffer solutions were used. All reagents used are qualified not lower than
analytic reagent grade.
Instrumentation: The optical density of the solutions was measured on a Lambda 40 spectrophotometer (Perkin Elmer) and a KFK-2 photocolorimeter in a cuvette with a layer 1 cm thick. The acidity of the buffer solutions was measured on a PHS-25 ionomer adjusted with standard buffer solutions.
Results and its discussion
We found that R (in ethyl alcohol) at pH 6 has an absorption band with a maximum (X = 425 nm). Under these conditions, it forms a complex with nickel (II) (absorption maximum at 452 nm). The study of the complexes obtained in the presence of a, a'-dipyridyl, ethylenediamine and phenanthroline in a wide pH range showed that under the influence of the third component mixed ligand complexes are formed: Ni (II) -Ra, a'-dip (X =
482 nm ), Ni (II) Red (X = 478 nm) and Ni (II) Rphene (X = 481 nm).) The color of the reagent and complexes depends on pH of the medium, therefore, the absorption spectra during complexation were studied in terms of control experiment R-a, a'-dip, R-Ed and R-Phen. Under the influence of the third components, the bathochromic effect is observed in all the resulting mixed-ligand complexes (Fig. 1).
A
0,6
0,5
0,4
0,3
0,2
0,1
1
200 250 300 350 400 450 500 550 600 650
À,nm
Fig. 1. Absorption spectra of solutions of complexes with nickel (II) 1 -NiR, 2-NiRa,a'-dip. 3- NiRPhen, 4- NiREd CN = 4 • 10-5M ; CR = 1 -10-4M
2
The study into dependence of optical density on the pH of the solution showed that when interacting with a, a'-dipyridyl, ethylene diamine and phenantroline, the optimal conditions for complexation shift to acidic pH 5, 4.5 and 5, respectively (Fig. 2). To select the optimal conditions, the effect of the concentration of reacting substances, the temperature and the effect of time on the
formation of the binary and mixed-ligand complexes were studied.
The output of the NiR complex is maximum at a concentration of 8*10-5M R, NiR-a,a'-dip at 8»10"5M R and 8»10"4 M a, a'-dip, NiRPhen at 8-10"5 M R and 8-10"4 M Phen, NiREd at 8-10"5 M R and 8*10"4 M Ed. All complexes are formed immediately after
Fig. 2. Dependence of the optical density of nickel solution (II) complexes on pH in the presence/absence of third components at A,opt. in terms of control experience: 1 -NiR, 2-NiRa,a'-dip. 3- NiRPhen, 4- NiREd
The stability constants and the ratios of the components in the composition of the resulting complexes were established through methods of isomolar series, the relative yield of the Starik-Barbanel and the equilibrium shift [14].
The Starik-Barbanel method provides an accurate estimate of the stoichiometric coefficients and can be applied to any
A/Cr-103 l/mol
stoichiometric reaction, regardless of the stability of the concentration of interacting substances.
To determine the composition of the complex using this method, prepare a series of solutions: changing the concentration of the reagent CMe = const. Then the dependence is
plotted in A/Cr - A/Amax coordinates.
0,2
0,4
0,6
0,8
A/Am
Fig. 3. Determination of the composition of the NiR complex by the method of the StarikBarbanel
0
0
If the reaction equation is Me + nR ^ MeRn, then n is calculated in accordance with the following expression: 1
n =
1 -
A
A/Cr = max
A
Fig. 3 shows the composition of the fraction of NiR complex components revealed by the Starik-Barbanel method.
The ratio of components in the NiR complex is 1: 2.
The study showed that the ratio of components in mixed-ligand complexes is 1: 2: 1 (NiRa, a'-dip, NiREd) and1: 2: 2 NiRPhen.
The molar absorption coefficients, the linearity range of the calibration curve for the determination of nickel(II), and other analytical characteristics of the reagents are given in Table 1.
Table 1. Spectrophotometric characteristics of the complexes
Complex pH Xmax,nm AX, nm s-10-4, l/mol-sm Me:R Subordinatio n ro the Beer,s law, mkg/ml lgK
NiR 6 452 27 0.875±0.04 1:2 0.46-2.78 8.24±0.04
NiRa,a'-dip 5 482 30 1.31±0.03 1:2:1 0.13 - 2.32 9.19 ±0.06
NiREd 4.5 478 26 1.128±0.02 1:2:1 0.11 - 2.32 9.23±0.06
NiROPhen 5 481 29 1.205±0.03 1:2:2 0.11 - 2.32 9.31±0.04
To establish the influence of the stability of associates and their complexes on the detection limit of nickel (II), the
coefficients of the calibration curve equation were determined by the least squares method [15].
IA = aI C + nb I AC = aZ C2 + bI C
Here A is optical density of complex, C is a concentration of nickel (mkq/ml), n is a number of experiments. Calculation of results show that linear relationship of A= f (C) for the reaction of complex formation. Nickel with reagent can be expressed by the following equations:
A=(0.20±0.02)c+(2.95±0.12)10-2 NiR A=(0.50±0.0l)c+(l.41±0.10)l0-2 NiRa,a'-dip
A= (0.45±0.01)c+(1.32±0.12)10-2 NiRPhen A= (0.35±0.0l)c+(l.74±0.12)l0-2 NiREd
As can be seen, with an increase in the slope angle (a) of linear equations, the molar
absorption coefficients of the complexes increase.
The effect of foreign ions on the complexation of nickel (II) with R in the absence and in the presence of third components was studied. It found that in the presence of third components the selectivity of complex formation reactions significantly increases (Table 2). These reagents are more selective for the spectrophotometric determination of nickel (II) compared to reagents known from the literature [11]. The developed methodology has been applied to determine nickel (II) from the water of the rivers.
Table 2. Admissible ratios of foreign ions to nickel (II) when it is determined in the form of homogeneous and mixed ligand complexes (5% error)
Foreign ions R R-a,a'-dip R-Eg R-PheH 2 - [(2-mercaptophenyl imino) methyl] phenol [11]
Na(I) * * * * 300
K(I) * * * * 300
Mg(II) 166 248 496 579 250
Ca(II) 413 689 827 965 250
Ba(II) 236 236 472 944
Zn(II) 112 224 448 672 300
Cd(II) 113 270 215 386 50
Co(II) 20 30 61 81 20
Cu(II) ** 22 44 110 20
Mn(II) 94 189 293 569 200
Al(III) 93 279 456 665 250
Fe(III) 2 19 96 135 20
Cr(III) 179 258 358 537 20
Pb(II) 21 35 71 142
V(V) 87 123 175 263
W(VI) 197 952 1268 1903
Mo(VI) 248 248 372 620
F- 319 6379 1276 6379
C2O42" 22 43 217 434
HPO42" 123 617 1234 2468 300
Citric acid 116 231 462 462
Tartaric acid 517 1551 1551 2586
Thiourea 26 131 262 786
Note: * does not interfere, ** interferes
Determination of nickel in rivers
water.
For the analysis, 1 liter of water from a river bank was taken provided that non-boiling evaporated water obtains a precipitate. The resulting precipitate was dissolved in 5 ml of HNO3 and transferred to a 50 ml flask and
diluted to the mark with distilled water. When determining nickel (II) by the photometric method, an aliquot part of the obtained solution is placed in a 25 ml flask, 2 ml of M0"3MRand 2 ml of 1-10"2Ma, a'-dipyridyl are diluted to the mark with pH 5.
Table 3. Results of nickel determination (II) in river waters (n=5, P=0,95)
Water sample Revealed by photometric method, Ni, mg/l Revealed Ni, mg/l (ICP-OES thermo ICAP 7400 Duo)
I sample river water 0.160±0.005 0.170±0.004
IIsample river water 0.175±0.004 0.190±0.003
The optical density of the solutions is measured at X = 490 nm in a cuvette with l= 1 cm on KFK-2 relative to the test solution.
The correctness of the procedure was checked using the "ICP-OESthermoICAP 7400 Duo" instrument. The results are
presented in table. 3
These methods can be applied for determination of nickel (II) in different natural and artificial objects. Elaborated methods can be used for nickel determination (II) in various natural and artificial water facilities.
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NiKELiN(II) 1-FENiL-2-(2-HiDROKSMmOFENiLHiDRAZO) BUTADiON-1,3 -REAGENTi iL3 ÛÇÛNCÛKOMPONENTLdR i§TiRAKINDA KOMPLEKSdMdLdGdTiRMdSiMN
TBDQiQi
1V.i. Mardanova, 2§.Ä. Tahirli, 1B.Q. Babayev,1 F.M. Çiraqov
1Baki Dövlst Universiteti AZ1148 Baki, Z.Xslilov kûç., 23; e-mail: [email protected] 2Lsnksran Dövlst Universiteti
Nikelin(II) 1-fenil-2-(2-hidroksinitrofenilhidrazo)butadion-1,3 reagenti ils ûçûncû komponentlsr a,a'-dipiridil (a,a'-dip), etilendiamin (Ed) vs fenontrolin (Fen) içtirakinda komplekssmslsgstirmssi öyrsnilmi^dir. Birli (NiR) vs qariçiqliqandli (Ni(II)-Ra,a'-dip, Ni(II)-REd vs Ni(II)-RFen) komplekslsr uygun olaraq рН 6, 5, 4.5 vs 5 smsls gslir. Qarçiliqli tssirds olan komponentlsrin tsrkibi binar vs qariçiqliqandli komplekslsrds tsyin edilmiçdir. Ber qanununa tabeçilik intervali tsyin edilmiçdir. Nikelin çay sularinda tsyin edilmssi ûçûn metodika i§lsnib hazirlanmiçdir.
Âçar sözlar: nikel(II), qariçiqliqandli komplekslsr, a,a'-dipiridil, etilendiamin, fenontrolin.
ИЗУЧЕНИЕКОМПЛЕКСООБРАЗОВАНИЯНИКЕЛЯ(11) С 1-ФЕНИЛ-2-(2-ГИДРОКСИ-4-НИТРОФЕНИЛГИДРОЗО)БУТАДИОНОМ-1,3 В ПРИСУТСТВИИ ТРЕТЬИХ
КОМПОНЕНТОВ
1В.И.. Марданова, 2Ш.А. Тахирли ,1А.Г.. Бабаев, 1Ф.М. Чырагов
1 Бакинский Государственный Университет А21148 Баку, ул. З.Халилова, 23; в-таИ: [email protected] 2Ленкоранский Государственный Университет Азербайджан, г. Ленкорань, пр.А.Асланова,50
Изучено влияние третьих компонентов а,а'-дипиридила (а,а'-дип), этилендиамина (Ед). и фенантролина (Фен) на комплексообразование никеля(11) с 1-фенил-2-(2-гидрокси-4-нитрофенилгидрозо)бутадионом-1,3. Однородно- (№Я) и смешанолигандные ^(Щ-^а,а'-дип, М(П)-Кед, Ж(П)-КФен) комплексные соединения образуются при рН 6, 5, 4.5 и 5, соответственно. Установлено соотношение реагирующих компонентов в составе однородно- и смешанолигандных комплексов. Определен интервал подчинения закону Бера. Разработанная методика применена для определения никеля(11) в речной воде.
Ключевые слова: никель(И), разнолигандный комплекс, а,а'-дипиридил, этилендиамин и фенантролин
