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1

Struktura i właściwości fizykochemiczne polimerów koordynacyjnych oraz materiałów typu MOF kadmu(II) i cynku(II)

Pobłocki Kacper, Drzeżdżon Joanna, Jacewicz Dagmara

Wiadomości Chemiczne

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2021

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[Z] 75, 7-8

1041--1073

EN

In 1964, J.C. Bailat Jr. was one of the first scientists who use coordination polymers in his research. He established the rules of structure and the composition of compounds containing metal ions and organic ligands connected by coordination bonds to form layered or chain structures. He compared inorganic compounds belonging to polymeric species with organic polymers. The term Metal Organic Frameworks (MOF) was first used in the publication by О. M. Yaghia. Crystalline, microporous structures contain rigid organic ligands (used interchangeably: organic building blocks) that bind metal ions. This is called reticular synthesis. MOF surface area values usually range from 1000 to 10000 m2/g-1, thus exceeding the area values of traditional porous materials such as zeolites and carbons. Metal Organic Frameworks create porous three-dimensional structures, unlike coordination polymers. Inorganic minerals from the aluminosilicate group are used in the widespread heterogeneous catalysis and processes such as: adsorption and ion exchange, while compared to Metal Organic Frameworks, shows a lower potential than zeolites, moreover, the design of structures is less precise and rational due to the lack of shape, size and control functionalization of pores. To date, MOF are the most diverse and most numerous class of porous materials. All aspects have made them ideal structures for storing fuels such as hydrogen and methane. They are perfect for catalytic reactions and are good materials for capturing pollutants, e.g. CO2. The number of publications on coordination polymers (CP), Metal Organic Frameworks (MOF) or a group of hybrid compounds (organic-inorganic) increased tenfold at the turn of 2005, which proves the growing interest in this field by scientists around the world. MOF diversity in terms of structure, size, geometry, functionality and flexibility of MOF has led to the study of over 20,000 different MOF’s over the past decade. The search for new materials consists of combining molecular building blocks with the desired physicochemical properties. To produce a solid, porous material that can be used in the construction of a "molecular scaffold", rigid organic moieties, which are described in the literature as rods, must be combined with multi-core, inelastic inorganic clusters that act as joints (also called SBU secondary building units). By design, multi-core cluster nodes are able to impart thermodynamic stability through strong covalent bonds and mechanical stability due to coordination bonds that can stabilize the position of metals in the molecule. This property contrasts with those of the unstable single coordination polymers. The size and most importantly the chemical environment of the resulting voids are determined by the length and functions of the organic unit. Therefore, adjusting the appropriate properties of the material is made by appropriate selection of the starting materials. The isoretical method made it possible to use MOF structures with large pores (98 Á and low densities (0.13 g/cm3). This method involves changing the size and nature of Metal Organic Frameworks without changing the topology of their substrate. Thanks to this, it was possible to include large molecules such as vitamins (e.g. B12) or proteins (e.g. green fluorescence protein) into their structure and use the pores as reaction vessels. The thermal and chemical stability of many MOFs has made them amenable to functionalization by post-synthetic covalent organic complexes with metals. These properties make it possible to significantly improve gas storage in MOF structures and have led to their extensive research into the catalysis of organic reactions, activation of small molecules such as hydrogen, methane and water, gas separation, biomedical imaging and conductivity. Currently, methods of producing nanocrystals and MOF super crystals for their incorporation into specialized devices are being developed. Crystalline structures of MOF’s are formed by creating strong bonds between inorganic and organic units. Careful selection of MOF components produces crystals of giant porosity, high thermal and chemical stability. These features allow the interior of the MOF to be chemically altered to separate and store gases. The uniqueness of MOF materials is that they are the only solids to modify and increase the particle size without changing the substrate topology.

2

Water Purification from Ions of Cadmium (II) Using a Bio-Plateau

Lapan Oksana, Mikhyeyev Oleksandr, Madzhd Svitlana, Dmytrukha Tetyana, Cherniak Larysa, Petrusenko Valentyna

Journal of Ecological Engineering

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2019

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Vol. 20, nr 11

29--34

EN

The study was conducted with the purpose of experimentally developing the method of water purification from ions of cadmium (II) using a new design of a bio-plateau, which is based on the use of terrestrial plants. In order to construct the bio–plateau, the following chemically inert floating materials were used as the substrate: perlite, expanded clay, granular foam, vermiculite, cork, on top of which the seeds of higher terrestrial plants were placed. The experimental data showed that foam was the best of the tested substrates, and of plants – barley, oats, corn and rye. The constructed bio-plateau was placed into tanks with a solution of cadmium on the 9th day of incubation to study the cleaning efficiency of terrestrial plants on the aquatic environment. Determination of the residual concentration of cadmium was performed with the method of AAC at λ=228.8. As a result, it was found that rye showed the best sorption properties of the tested plants. The influence of additional aeration and pH of the medium on the degree of water purification was established. The highest treatment efficiency was observed in the variant of a bio-plateau with aeration and at a pH of 8-9. The study shows the possibility of using terrestrial plants for the phytoremediation of water bodies.

3

Extraction properties of tetraheptylresorcin[4]arenes in relation to Cr(III) ions

Konczyk J., Miroshnychenko S., Kozlowski C.

Physicochemical Problems of Mineral Processing

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2016

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Vol. 52, iss. 2

835--844

EN

Resorcin[4]arene-based ligand bearing four heptyl chains at the lower rim of the molecule was prepared and modified by four tetradietoxyphosphoryl groups in the upper rim. The compounds obtained were characterized by NMR spectroscopy and their extractability toward chromium(III) ions was studied. The influence of process parameters such as the pH of aqueous phase, agitation time and also extractant’s structure and concentration on efficiency of Cr(III) ions solvent extraction is presented. The highest yield of Cr(III) solvent extraction was obtained for two-hour agitation time of 5.010−4 M metal solution of pH 5.0 and 5.010−3 M chloroform solution of the tetradietoxyphosphorylated derivative of heptyl-resorcin[4]arene. Under optimal conditions, competitive solvent extraction of Cr(III), Zn(II), and Cd(II) ions was performed and separation factor values were established as 77.0 and 24.9 for Cr(III)/Cd(II) and Cr(III)/Zn(II) ions pairs, respectively. The stoichiometry of formed metal-ligand complexes 1:1 was found by classical slope analysis method.

4

Wydzielanie cynku(II) z roztworów odpadowych powstających w przemyśle metalurgicznym

Gajda B., Skrzypczak A., Bogacki M. B.

Rudy i Metale Nieżelazne Recykling

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2015

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R. 60, nr 1

23--29

PL

Celem pracy było zbadanie możliwości selektywnego wydzielenia jonów cynku(II) z polimetalicznych odpadowych roztworów chlorkowych zawierających kationy takich metali, jak: niklu(II), kobaltu(II), kadmu(II) z zastosowaniem polimerowych membran inkluzyjnych. Jako przenośnik jonów w membranie zaproponowany został 1-decyloimidazol. Uzyskane wyniki pozwoliły zauważyć znaczący wpływ stężenia anionów chlorkowych na proces separacji jonów metali. Stwierdzono również, że jony cynku(II) najefektywniej wydzielić można z roztworu o stężeniu 1M anionów chlorkowych. Z roztworu takiego odzyskuje się ok. 88-90 % Zn(II). Zdolność do wydzielenia pozostałych jonów kształtuje się w szeregu: Cd(II) ≥ Co(II) > Ni(II).

EN

The aim of the work was investigation of possibility of selective releasing of zinc(II) ions from polymetalic discarded chloride solutions containing metal cations like: nickel(II), cobalt(II) and cadmium(II) by applying polymer inclusion membranes. As a carrier of metal ions in membrane, the 1-decylimidazole was used. Based on obtained results, significant influence of chloride anions on separation process was observed. It was found that zinc(II) ions were transported fastest from solution containing 1M of chloride anions. In this case, it was possible to release about 88-90 % of Zn(II). The membrane ability to releasing rest of ions change in series: Cd(II) ≥ Co(II) > Ni(II).

5

The use of the steric effect of the carrier molecule in the polymer inclusion membranes for the separation of cobalt(II), nickel(II), copper(II), and zinc(II) ions

Radzyminska-Lenarcik E., Ulewicz M.

Polish Journal of Chemical Technology

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2015

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Vol. 17, nr 2

51--56

EN

In this study, palladium-modified nickel foam substrate was applied to examine ethanol oxidation reaction (EOR) in 0.1 The transport of cobalt(II), nickel(II), copper(II), and zinc(II) ions from chloride solutions across polymer inclusion membranes (PIMs), which 1-heptylimidazole (1̲) or 1-heptyl-2-methylimidazole (2̲) or 1-heptyl-4-methylimidazole (3̲) as the ion carrier was reported. The steric effect for carriers 2̲&enspand 3̲&enspdecreases the transport of all ions except Cu(II). The initial fluxes of metal ions transport across PIMs with the 1̲- 2̲&enspdecrease in the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II), whereas for 3 they were Cu(II) > Zn(II) > Ni(II) > Co(II). The highest recovery values were obtained for Cu(II), this being 99 and 85% for carrier 1̲&enspand 2̲, respectively. In both membranes the degree of deposition of the Zn(II) ions was comparable. Zn(II), Co(II) and Cd(II) ions, which form complexes with coordination numbers 4 and 6, are more easily recovered with the use of carriers 2̲&enspand 3̲. Ni(II) ions, which form complexes with coordination number 6 only, practically remain in the feeding phase. PIMs with alkylimidazoles were characterized by non-contact atomic force microscopy.

6

Separation Of Cadmium(II), Cobalt(II) And Nickel(II) By Transport Through Polymer Inclusion Membranes With Phosphonium Ionic Liquid As Ion Carrier

Pospiech B.

Archives of Metallurgy and Materials

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2015

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Vol. 60, iss. 4

2933--2938

EN

This paper presents study on the facilitated transport of cadmium(II), cobalt(II) and nickel(II) ions from aqueous chloride solutions through polymer inclusion membranes (PIMs) with phosphonium ionic liquid. Cyphos IL 101 (trihexyl(tetradecyl) phosphonium chloride) was used as a selective carrier for synthesis of cellulose triacetate membranes containing o-nitrophenyl pentyl ether (ONPPE) as a plasticizer. Effect of different parameters such as hydrochloric acid concentration in the source phase as well as ion carrier concentration in the polymer membrane on metal ions transport has been investigated. Cd(II) was transported preferably from hydrochloric acid solutions containing Co(II) and Ni(II) through PIM containing 18.8 wt.% CTA and 26.0 wt.% Cyphos 101 and 55.1 wt.% ONPPE into 0.5 M HNO3 as the receiving phase. The obtained results suggest that there is a possibility of application of this membrane with Cyphos IL 101 as ion carrier for separation of Cd(II) over Co(II) and Ni(II) from hydrochloric acid solutions.

PL

Przeprowadzono badania transportu jonów Cd(II), Ni(II) i Co(II) z wodnych roztworów kwasu solnego przez polimerowe membrany inkluzyjne (PIMs) zawierające fosfoniową ciecz jonową – Cyphos IL 101 (chlorek triheksylo(tetradecylo) fosfoniowy) w roli selektywnego przenośnika jonowego. Rolę polimerowej matrycy w membranie pełnił trioctan celulozy (CTA). Jako plastyfikatora użyto eteru nitrofenylopentylowego (ONPPE). W wyniku badań określono wpływ różnych czynników, takich jak stężenie kwasu solnego w fazie zasilającej, jak również stężenie przenośnika w polimerowej membranie na selektywność i efektywność transportu badanych jonów metali. Jony kadmu(II) były selektywnie transportowane z roztworów kwasu solnego zawierającego jony niklu(II) i kobaltu(II) do 0,5 M roztworu kwasu azotowego(V). Uzyskane wyniki wskazują, że istnieje możliwość zastosowania procesów transportu przez polimerowe membrany inkluzyjne z cieczą jonową w roli selektywnego przenośnika do rozdzielania jonów Cd(II) od Ni(II) i Co(II) z roztworów kwasu solnego.

7

Lead(II) removal from aqueous solutions by solvent extraction with tetracarboxylresorcin[4]arene

Konczyk J., Kozlowski C., Walkowiak W.

Physicochemical Problems of Mineral Processing

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2013

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Vol. 49, iss. 1

213--222

EN

A novel tetracarboxylresorcin[4]arene was synthesized and its selective complexing ability towards Pb(II) ions was examined. The influence of several parameters such as pH of aqueous phase, agitation time, extractant and modifier concentrations on solvent extraction of Pb(II) ions from the aque-ous nitrate phase into chloroform organic phase was studied. The stoichiometry of the formed metal-ligand complexes was established by slope analysis. Pb(II) ions were quantitatively extracted in the form of 2:1 Pb(II)-resorcin[4]arene complex from aqueous solutions of pH 5.5 to the solution of ligand in chloroform. Competitive solvent extraction experiments in the presence of Zn(II) and Cd(II) ions were also carried out and high selectivity of the extractant towards Pb(II) over Zn(II) and Cd(II) was found. The selectivity order was: Pb(II) >> Cd(II) > Zn(II).

8

Separation of cobalt(II), nickel(II), zinc(II) and cadmium(II) ions from chloride solution

Gajda B., Skrzypczak A., Bogacki M. B.

Physicochemical Problems of Mineral Processing

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2011

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Vol. 46

289-294

EN

Selective distribution of cobalt(II), nickel(II), zinc(II) and cadmium(II) ions from chloride solutions through polymer inclusion membranes (PIM) has been studied. The carrier was 1-decylimidazole. The effect of chloride ion concentration on the ion permeation was analysed. The results suggest that some of metal ions change for the worse selectivity of separation process. Especially zinc(II) and cadmium(II) ions decreased five-fold selectivity of ion separation process.

PL

W pracy przedstawiono wyniki badań selektywnego rozdziału jonów kobaltu(II), niklu(II), cynku(II) i kadmu(II) z roztworów chlorkowych w procesie selektywnego ich rozdziału w procesie membranowym przez polimerowe membrany inkluzyjne (PIM). Jako przenośnik zastosowano 1-decyloimidazol. Uzyskane wyniki wskazują, że obecność jonów niektórych metali pogarszać może selektywność rozdziału. Szczególne znaczenie mają tutaj jony cynku(II) oraz kadmu(II), które prawie 5-krotnie pogarszają selektywność rozdziału jonów niklu(II) od kobaltu(II).

9

Zastosowanie czynników kompleksujących w procesie usuwania kadmu(ll) z roztworów wodnych

Kołodyńska D., Hubicki Z.

Przemysł Chemiczny

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2008

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T. 87, nr 7

781-785

10

Application of Macrocyclic Compounds to the Transport of Zn(II), Cd(II), and Pb(II) Ions Across the Polymer Inclusion Membrane (PIM)

Ulewicz M.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 6

1237-1244

EN

The applications of macrocyclic ligands for the transport of Zn(II), Cd(II) and Pb(II) ions across PIMs are revisited. As macrocyclic compounds, such chemical substances, as non-ionizable crown ethers, ionizable crown ethers (lar iat ethers), acyclic polyesters, cyclodextrins and calix[4]arenes were used. Literature data, as well as our own recentre search data on the removal and separation of these metal ions are reported. The review has shown that the transport phenomena are dependent on the membrane characteristics, as well as on the physico chemical properties of the source and the receiving aqueous solutions.

11

Selective transport of Pb(II) across polymer inclusion membrane using imidazole azocrown ethers as carriers

Ulewicz M., Sadowska K., Biernat J. F.

Physicochemical Problems of Mineral Processing

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2007

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Vol. 41

133-143

EN

Transport of Pb(II) ions from equimolar aqueous solutions of Zn(II), Cd(II), and Pb(II) as well as from solutions containing only Pb(II) ions source phase (cMe = 0.001 M) through polymer inclusion membranes (PIMs) containing imidazole azocrown ethers as carriers has been investigated. The polymer membranes consisting of cellulose triacetate (support), o-nitrophenyl pentyl ether (plasticizer) and imidazole crown ether derivatives (as ion carriers) were investigated. The influence of lipophilicity of macrocycles on the selectivity and efficiency of Pb(II) transport with azocrown 3 are higher than 1, accordingly with the hydrophile-lipophile balance of imidazole azocrown ethers. The highest transport recovery for Pb(II) ions was observed for 3 (91.6%). The transport selectivity of the polymer inclusion membrane with 3 was: Pb(II) > Zn(II) > Cd(II) and the selectivity coefficient Pb(II)/Cd(II) and Pb(II)/Zn(II) equals 40.1 and 13.4, respectively. The stability of PIM with imidazole azocrown derivatives was confirmed by replicate experiments.

PL

Zbadano selektywność transportu jonów ołowiu(II) z równomolowych roztworów jonów Zn(II), Cd(II) i Pb(II) oraz z roztworów zawierających jony Pb(II) przez polimerowe membrany inkluzyjne (PIM) zawierające imidazolowe etery azokoronowe. Badania prowadzono dla azotanowych roztworów Pb(II) o stężeniu 0,001 M oraz dla roztworów zawierających równomolową mieszaninę jonów Pb(II), Cd(II) i Zn(II) (cMe= 0,001 M każdego). Badane azokorony różniły się miejscem podstawienia imidazolu i rodzajem dołączonej do niego grupy (-H, -CH3, -C6H5). Polimerowe membrany inkluzyjne otrzymywano z trójoctanu celulozy (nośnik), eteru o-nitrofenylopentylowego (pastyfikator) i jednego z eterów koronowych 1 ÷ 3 (przenośnik jonów); stężenie przenośnika jonów w przeliczeniu na objętość plastyfikatora wynosiło 0,05 M. Wykazano, że początkowe wartości strumienia transportu jonów ołowiu(II) maleją ze wzrostem balansu hydrofilowo-hydrofobowego (HLB) eteru koronowego, tj. 3 > 1. Ponadto stwierdzono, że strumienie początkowe transportu jonów przy użyciu eterów 2 i 3 maleją w szeregu: Pb(II) > Zn(II) > Cd(II). Współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) przez PIM przy użyciu eteru 2 z 0,01M roztworu mieszaniny jonów wynosiły 11,3 i 53,6 natomiast z roztworów o stężeniu 0,001 M odpowiednio 16,3 i 46,0. Ponadto wykazano, że polimerowe membrany inkluzyjne z imidazolowymi azokoronami wykazują dużą stabilność, zależną w dużym stopniu od rodzaju jonoforu.

12

Removal of Zn(II), Cd(II) and Pb(II) using polymer inclusion membrane transport with proton ionizable DB-16-C-5 crown ethers

Ulewicz M., Walkowiak W.

Physicochemical Problems of Mineral Processing

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2006

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Vol. 40

185-194

EN

Competitive transport of Zn(II), Cd(II), and Pb(II) ions from aqueous nitrate source phase (Cme = 0.001 M) through polymer inclusion membranes (PIMs) containing cellulose triacetate (as support), o-nitrophenyl pentyl ether (as plasticizer) and proton ionizable lariat ether derivatives (as ion carriers) has been investigated. The influence of varying the lipophilicity of sym(R)(hydroxy)dibenzo-16-crown-5 macrocycles with R groups such as hydrogen (in 1), decyl (in 2) and phenyl (in 3) on the selectivity and efficiency of Zn(II), Cd(II), and Pb(II) transport through polymer inclusion membranes is studied. The influence of HLB (hydrophile-lipophile balance) and Vx (molecular volumes) on the transport selectivity of metal ions was investigated. Relationship between the cation size and initial fluxes transport of metal cation was shown. The selectivity coefficients of Pb(II)/Zn(II) and Cd(II)/Zn(II) decrease with increase of carrier concentration in inclusion membrane.

PL

Zbadano selektywność wydzielania jonów cynku(II), kadmu(II) i ołowiu(II) z wodnych roztworów azotanowych zawierających równomolową mieszaninę metali (cMe= 0,001 M) w procesie transportu przez polimerowe membrany inkluzyjne (PIM) przy użyciu w roli przenośników jonów jonizowalnych eterów koronowych o koronie DB-16-C-5. Badane etery różniły się rodzajem grupy dołączanej do korony ( -H, -C10H21, -C6H5). Polimerowe membrany inkluzyjne syntezowano z trójoctanu celulozy (nośnik), eteru o-nitrofenylopentylowego (pastyfikator) i jednego z eterów koronowych 1 ÷ 3 (przenośnik jonów); stężenie przenośnika jonów w przeliczeniu na plastyfikator zmieniano w granicach 0,3 - 1,0 M. Współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) przez PIM przy użyciu eteru 2 były nieznacznie wyższe niż przy użyciu eteru 3 i 1. Dla badanych eterów o stężeniu 0,5 M w membranie współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) wynosiły odpowiednio 1,4 i 1,8; 1,5 i 3,1 oraz 1,6 i 3,4 dla eterów 1, 2, i 3. Wykazano, że początkowe wartości strumienia transportu badanych jonów rosną ze wzrostem objętości molowej eteru koronowego, natomiast maleją ze wzrostem bilansu hydrofilowo-hydrofobowego (HLB) eteru koronowego. Ponadto stwierdzono, że niezależnie od zastosowanego eteru lariatowego o koronie DB-16-C-5 najlepiej transportowane są kationy o największej średnicy.

13

Studies on removal of Zn(II), Cd(II) and Pb(II) ions in polymer inclusion membrane transport with Calix[4]-crown-6 derivatives

Ulewicz M., Bocheńska M., Lesińska U., Walkowiak W.

Physicochemical Problems of Mineral Processing

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2005

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Vol. 39

107-116

EN

Competitive transport of Zn(II), Cd(II), and Pb(II) ions from aqueous nitrate source phase (CMe = 0.01 M) through polymer inclusion membranes (PIMs) containing cellulose triacetate (support), o-nitrophenyl pentyl ether (plasticizer) and calix[4]crown-6 derivatives (as ion carriers) has been investigated. The influence of the group, i.e. –OH, – OMe attached type to the calix[4]-crown-6 molecule on the selectivity and efficiency of Zn(II), Cd(II), and Pb(II) transport through polymer inclusion membranes is studied. The removal of metal ions by transport through PIM’s from acid nitrate aqueous solutions is presented. The selectivity coefficients of Pb/Zn and Cd/Zn decrease with acid concentration increase in receiving phase. On the other hand, the initial fluxes of investigated ions decrease using the same membrane for the second and third time.

PL

Zbadano selektywność procesu wydzielania jonów cynku(II), kadmu(II) i ołowiu(II) z wodnych roztworów azotanowych zawierających równomolową mieszaninę tych trzech metali (cMe= 0,01 M) w procesie transportu przez polimerowe membrany inkluzyjne (PIM) przy użyciu w roli przenośników jonów pochodnych kaliks[4]-korony-6. Membrany typu PIM syntezowano z trójoctanu celulozy (nośnik), eteru o-nitrofenylopentylowego (pastyfikator) i pochodnych kaliks[4]-korony-6 (przenośnik jonów); stężenie przenośnika jonów w przeliczeniu na plastyfikator wynosiło 0,1 M. Współczynniki separacji Pb/Cd i Pb/Zn przez PIM przy użyciu kalixkorony 2 były nieznacznie wyższe niż przy użyciu kalixarenu 1. Współczynniki separacji Pb(II)/Cd(II) i Pb(II)/Zn(II) wynosiły odpowiednio 2,8;9,9 i 3,1; 12,7 dla 1 i 2, natomiast współczynniki separacji Cd(II)/Zn(II) wynosiły odpowiednio 3,5 i 4,1. Wykazano, że początkowe wartości strumienia transportu badanych jonów maleją ze wzrostem stężenia kwasu azotowego w fazie odbierającej. Maleją również wartości współczynników selektywności Pb(II)/Cd(II) i Pb(II)/Zn(II). Ponadto w pracy zaprezentowano wyniki wydzielania jonów badanych metali przy kilkakrotnym użyciu tej samej membrany. Badania pokazały, że wartości strumienia transportu badanych jonów metali przy dwukrotnym użyciu polimerowej membrany były porównywalne. Natomiast praca membrany przez 192 h i 288 h, powoduje zmniejszenie efektywności transportu jonów przez membranę.

14

Complexes of Cadmium (II) and Mercury(II) with Cytidine 5'-Monophosphate and Diamines in Ternary Systems

Łomozik L., Bregier-Jarzębowska R.

Polish Journal of Chemistry

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2004

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Vol. 78 / nr 4

529-538

EN

Formation of Cd(II) and Hg(II) complexes in ternary systems with cytidine 5_-monophosphate (CMP) and diamines (en, tn, Put) has been studied. In Hg(II)/CMP/diamine systems the formation of heteroligand compounds is accompanied by the occurrence of non-covalent interactions and the formation of molecular complexes. The presence of polyamine in ternary systems does not change the metal-nucleotide mode of coordination. Similarly as in the binary Hg(II)/CMP system, the metallation involves the donor endocyclic nitrogen N(3) atom and CMP phosphate group. On the other hand, in the Cd(II)/CMP system, the introduction of a polyamine changes the coordination mode of the nucleotide. Phosphate group, inactive in binary systems, takes part in the complexation in ternary systems. In systems of cadmium(II) ions, CMP and diamines, only molecular complexes are formed, in which the polyamine is in the outer coordination sphere. In contrast to Cd(CMP)(H2tn) and Cd(CMP)(H2Put) compounds, in Cd(CMP)(H2en) species the phosphate group of nucleotide does not take part in the metallation, i.e. the metal ion coordinates with CMP, through the atom N(3) of the nucleotide, and the phosphate group is involved in non-covalent interactions with en.

15

Removal of zn(II), cd(II) and cu(II) ions by polymer inclusion membrane with side-armed diphosphaza-16-crown-6 ethers

Ulewicz M., Kozłowski C., Walkowiak W.

Physicochemical Problems of Mineral Processing

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2004

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Vol. 38

131-138

EN

Competitive transport of Zn(II), Cd(II), and Cu(II) ions from aqueous chloride source phase (cMe = 0.01 M) through polymer inclusion membranes (PIMs) containing cellulose triacetate (support), o-nitrophenyl pentyl ether (plasticizer) and side-armed lariat ether-type derivative of diphosphaza-16-crown-6 (ion carrier) has been investigated. The influence of the group attached type to the PNP-lariat ether molecule on the selectivity and efficiency of Zn(II), Cd(II), and Cu(II) transport through polymer inclusion membranes is studied. The removal of metal ions by transport through PIM’s from acid aqueous phase into 0.1 M CH3COONH4, NH4OH or EDTA aqueous solution (receiving phase) is presented. The selectivity coefficient of Cd/Zn and Cd/Cu decreases with Cl- concentration increase in source phase for transport with bis-lariat ether, whereas for mono-lariat ether the selectivity coefficients are not changed.

PL

Zbadano selektywność procesu wydzielania jonów cynku(II), kadmu(II) i miedzi(II) z wodnych roztworów chlorkowych zawierających równomolową mieszaninę tych trzech metali (cMe=1,0ź10-2 M) w procesie transportu przez polimerowe membrany inkluzyjne (PIM) przy użyciu w roli przenośników jonów eterów PNP-difosfazakoronowych. Membrany typu PIM zbudowano z trójoctanu celulozy (nośnik), eteru o-nitrofenylopentylowego (pastyfikator) i eteru koronowego (przenośnik jonów); stężenie eteru w przeliczeniu na plastyfikator wynosiło 0,1 M. Współczynniki separacji Cd/Cu i Zn/Cu przez PIM przy użyciu mono-lariat eteru były porównywalne, podczas gdy przy użyciu bis-lariat eteru malały wraz ze wzrostem stężenia jonów Cl- w fazie zasilającej. Współczynniki separacji Cd/Cu wynosiły odpowiednio 8,7; 6,6 i 5,4 dla roztworu 0.1; 0.3 i 0.5 M HCl, natomiast współczynniki separacji Zn/Cu dla tych roztworów wynosiły odpowiednio 7.0; 6.3 i 1.2. Tak więc współczynniki separacji jonów kadmu do miedzi były wyższe niż jonów cynku do miedzi. Separacja jonów Cd/Zn nie zachodzi. W pracy przedstawiono ponadto wyniki transportu badanych jonów przy zastosowaniu różnych faz odbierających, tj., roztworu octanu amonu, wodorotlenku amonu i EDTA. Najwyższy procent wydzielenia jonów badanych metali uzyskano przy zastosowaniu CH3COONH4 (RF ≈ 80 %).

16

Transport of transition metal ions through polymer inclusion membranes with Cyanex 301

Ulewicz M.

Ars Separatoria Acta

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2004

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No. 3

81-88

EN

The selective transport of zinc(II) and cadmium(II) ions from aqueous chloride or sulfate source phase through polymer inclusion membranes (PIM) containing cellulose triacetate (support), o-nitrophenyl pentyl ether (plasticizer) and di(2,4,4-trimethylpentyl)dithiophosphinic acid - Cyanex 301 (ion carrier) is shown. Zn(II) and Cd(II) ions can be effectively removed from dilute chloride and sulfate aqueous solutions into 1.0 M HCl or H2SO4 as the receiving phase. The separation coefficients were practically constant for acid concentrations in the receiving phase ranging from 0.01 to 1.0 M Copper(II), zinc(II), cadmium(II), cobalt(II), and nickel(II) ions removal from aqueous chloride solutions in transport through PIMs is also shown. These metal ions can be effectively removed from dilute aqueous chloride solutions in transport through PIMs with di(2,4,4-trimethylpentyl)dithiophosphinic acid as the ionic carriers into 1.0 M HCl. The selectivity coefficients of Cu(II) over Zn(II), Cd(II), Co(II) and Ni(II) were low and decreased with an increase in the pH of source aqueous phase.

17

A New Substituted Bis(vic-dioxime) of Its Mono and Dinuclear Complexes

Güngör O., Canpolat E., Kaya M.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 4

403-410

EN

9,10-Bis(hydroxyimino)-4,8,11,15-tetra-aza-1,2,17,18-O-di-iso-propylideneoctadecane (H2L) was synthesized by the reaction of 1,2-O-iso-propylidene-4-aza-7-aminoheptane and anti-dichloroglyoxime in ethanol, containing an excess of NaHCO3 as a buffer to neutralize the HCl formed. The mononuclear metal complexes of this ligand have been synthesized with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) salts. H2L forms mononuclear complexes [(HL)2M] with a metal ligand ratio of 1:2 with M = Co(II)_2H2O, Ni(II) and Cu(II). Zn(II) and Cd(II) form with H2L complexes [(H2L)(Cl)2M], which have a metalligand ratio of 1:1 and a dinuclear complex with UO2(VI). H2L forms the dinuclear complex [(HL)2(OH)2M2] with a metal ligand ratio of 1:1 withM=UO2(VI). Structures of the ligand and its metal complexes were identified by elemental analyses, IR, 1H and 13C NMR spectra and thermogravimetric analyses (TGA).

18

Zinc(II) selective removal from other transition metal ions by solvent extraction and transport through polymer inclusion membranes with D2EHPA

Ulewicz M., Walkowiak W., Gęga J., Pośpiech B.

Ars Separatoria Acta

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2003

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No. 2

47-55

EN

An experimental investigation concerns zinc(II), cobalt(II), nickel(II), copper(II) and cadmium(II) ions separation from aqueous chloride solutions by solvent extraction and transport through polymer inclusion membrane (PIM) processes. The selective transport of metal ions from the aqueous chloride source phase through PIM containing cellulose triacetate (support), o-nitrophenyl pentyl ether (plasticizer) and di(2-ethylhexyl)phosphoric acid (ion carrier) is shown. Zn(II) can be effectively removed from dilute aqueous chloride solutions by its transport through PIMs with di(2-ethylhexyl)phosphoric acid as the ionic carriers into 1.0 M HCl as the receiving phase. The transport selectivity of Zn(II) over Co(II), Ni(II), Cu(II) and Cd(II) decreases while the pH of the solution increases in the source phase. Also, by solvent extraction, Zn(II) can be selectively removed from dilute aqueous chloride solutions.

19

Synthesis, Nuclear Magnetic Resonance and Infrared Studies of Zinc(II) and Cadmium(II) Complexes of Thiosemicarbazones Derived from Fluorenone and p-Anisaldehyde

Akinchan N., Drożdżewski P. M., Akinchan R.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 10

1381-1387

EN

Fluorenone (FTSCH) and p-anisaldehyde (ATSCH) thiosemicarbazones react with zinc(II) and cadmium(II) acetates forming M:L 1:2 complexes, characterized by IR, 1H and 13C NMR spectra and elemental analyses. The coordination mode of the ligands is discussed and four-coordinate, pseudo-tetrahedral structures are suggested.

20

Removal of Cr(VI), Zn(II) and Cd(II) ions by transport across polymer inclusion membranes with basic ion carriers

Kozłowski C., Apostoluk W., Walkowiak Wł., Kita A.

Physicochemical Problems of Mineral Processing

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2002

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Vol. 36

115-122

EN

An experimental investigation of chromium(VI), zinc(II), and cadmium(II) ions removal from acidic chloride aqueous solutions by polymer inclusion membrane (PIM) transport with basic ion carriers, i.e. 4-(1'-n-tridecyl)pyridine N-oxide (TDPNO) and tri-n-octylamine (TOA) is presented. The initial fluxes of all metal ions are higher for the less basic carrier, i.e. TDPNO. On the other hand, the more basic carrier, i.e. TOA gives higher Cr(VI)/Cd(II) and Cr(VI)/Zn(II) selectivity coefficients. Also the application of PIM transport process for removal of 99% chromium(VI) from galvanic waste waters is shown.

PL

W pracy przedstawiono wyniki badań transportu jonów chromu(VI), kadmu(II) i cynku(II) przy użyciu polimerowych membran inkluzyjnych z trioctanu celulozy (CTA) zawierających jako przenośniki jonów n-tlenek 4-(1’-n-tridecylo)pirydyny (TDPNO) lub tri-n-oktyloaminę (TOA). W celu określenia najkorzystniejszego składu polimerowych membran inkluzyjnych zbadano wpływ ilości plastyfikatora w membranie na transport jonów chromu(VI). Maksymalną szybkości transportu Cr(VI) osiągnięto używając membrany z TDPNO zawierające więcej plastyfikatora w porównaniu z TOA, ze względu na dobre właściwości plastyfikujące amin. W przypadku transportu jonów Cr(VI), Cd(II) i Zn(II) za pomocą w/w zasadowych przenośników selektywność procesów malała w szeregu: Zn(II) < Cd(II) < Cr(VI). Membrany inkluzyjne z trójoctanu celulozy zawierające TOA zastosowane do wydzielania jonów chromu(VI) z roztworów przemysłowych (ścieki z galwanizerni) pozwoliły na 99 % wydzielenie tego metalu po 30 godzinach procesu transportu.