Amines zinc complexes, extraction

Phenolic antioxidants in rubber extracts were determined indirectly photometrically after reaction with Fe(III) salts which form a red Fe(II)-dipyridyl compound. The method was applicable to Vulkanox BKF and Vulkanox KB [52]. Similarly, aromatic amines (Vulkanox PBN, 4020, DDA, 4010 NA) were determined photometrically after coupling with Echtrotsalz GG (4-nitrobenzdiazonium fluoroborate). For qualitative analysis of vulcanisation accelerators in extracts of rubbers and elastomers colour reactions with dithio-carbamates (for Vulkacit P, ZP, L, LDA, LDB, WL), thiuram derivatives (for Vulkacit I), zinc 2-mercaptobenzthiazol (for Vulkacit ZM, DM, F, AZ, CZ, MOZ, DZ) and hexamethylene tetramine (for Vulkacit H30), were mentioned as well as PC and TLC analyses (according to DIN 53622) followed by IR identification [52]. 8-Hydroquinoline extraction of interference ions and alizarin-La3+ complexation were utilised for the spectrophotometric determination of fluorine in silica used as an antistatic agent in PE [74], Also Polygard (trisnonylphenylphosphite) in styrene-butadienes has been determined by colorimetric methods [75,76], Most procedures are fairly dated for more detailed descriptions see references [25,42,44],... 

Finally, one of the first continuous ion-exchange plants installed used a weak-acid resin to recover copper from rayon-fibre spinning solutions. In the Bemberg or copper(II) ammonium process,357 the spinning takes place in an addic copper sulfate solution, and the fibre is then washed in ammonia solution. The wash water contains as much as 30% of the copper required for the spinning operation and its recovery is important in economic and environmental terms. The copper is extracted as the cationic amine complex by the weak-acid resin, and is then stripped from the resin with the acidic spinning solution. Zinc is recovered in a similar manner from vicrose rayon-spinning operations. 

Extraction of the cadmium-iodide complex from iodide-H2S04 solutions with oxygen-containing solvents (e.g., mesityl oxide, 2-ethyl-1-butanol) is a selective recommended separation method (e.g., from zinc) [1-3]. The iodide complex of cadmium can also be extracted with high molecular weight amines in xylene [4], TBP in benzene [5], and with tetra-n-butylammonium iodide in CHCI3 [6]. 

The selectivity of the method can be increased by prior separation of the zinc, e.g., by its extraction (with benzene or xylene) as the chloride complex in the presence of high molecular-weight amines [44],... 

Amine-extraction equilibria can also be modeled by chemical-reaction equilibrium constants. Figure 8.3-3 indicates that cations such as iron(IIl), zinc, cobelt(ll) and coppeifU) exhibit high distribution coefficients with chloride solutions, wherese nickel. iron(II), and manganese are not extracted to any great extent. The besis for the differences in distribution coefficients lies mainly in the tendency for the former group of cations to fonn chloride complexes. Stability constants for these complexes are available in the literature,11 and they can be used to develop quantitative phase-equilibrium models. 

Adsorption by carbon, which is one of the oldest adsorption methods used, has been reviewed and evaluated for the preconcentration of trace metals (794). Many authors have discussed the preparation of activated charcoal and carbon from a wide variety of usually local sources. The applications to water treatment are far too numerous to mention other than a few. Jo (795) carbonized a resin and a gum and hydrated the residue above 600 C to produce an adsorbant selective for cadmium(II). Kuzin et al, 196) used deashed active carbon and oxidized carbon for the quantitative sorption of copper, lead, zinc, and nickel from nearly neutral solutions containing 1-2 M alkali-metal halide. Pearson and Siviour (797) converted the metal-ion species to amine complexes before adsorbing these onto carbonaceous materials such as brown charcoal char or cellulose. Mercury vapor can be removed from a solution by reduction followed by passage of a nitrogen stream and adsorption by activated charcoal (798). Activated carbon, which had been oxidized with nitric acid, has been used to extract several metals including divalent nickel, cadmium, cobalt, zinc, manganese, and mercury from fresh water, brine, and seawater (799, 200). 

For TIOA with hydrochloric acid the concentration-based equilibrium constant for salt formation" according to reaction (8.2-6) is 1.51 x 10 and the equilibrium constant for amine-hydrochloride salt dimerization" is 8.0 M Combination of these parameters and the ion-complex stability constants with experimental metal-distribution data allows determination of the equilibrium constants for reactions (8.2-5) or (8.2-7). This completes the description of the amine-metal extraction-phase equilibria. For cobalt(II) in acidic sodium chloride solutions the equilibrium constant" for reaction (8.2-7) with TIOA is 2.0 X 10 and that for coppeifll) is 370 The corresponding value for zinc" is 7.5 x 10 Af -In spile of these relative values, the order of selectivity of TIOA for extraction of the metals is Zn > Cu > Co because of the relative extent of chloride complex formation. For the same reason, zinc stripping is difficult in this system, and copper has a tendency to be reduced to cuprous, which also complexes and extracts extensively. 

Activators. Activators are chemicals that increase the rate of vulcanization hy reacting first with the accelerators to form rubber-soluhle complexes. These complexes then react with the sulfur to form sulfurating agents (eqs. 14,15). The most common activators are combinations of zinc oxide and stearic acid. Other fatty acids used include lauric, and oleic, acids. Soluble zinc salts of fatty acid such as zinc 2-ethylhexanoate are also used, and these rubber-soluble activators are effective in natural rubber to produce low set, low creep compoimds used in load-bearing applications. Weak amines and amino alcohols have also been used as activators in combination with the metal oxides. Natural rubber usually contains sufficient levels of naturally occurring fatty acids to solubihze the zinc salt. However, if these fatty acids are first extracted by acetone, the resultant clean natural rubber exhibits a much lower state of cime. Therefore, to ensme consistent cure rate, fatty acids are usually added. Synthetic rubbers, especially the solution polymerized elastomers, do not contain fatty acids and require their addition to the cure system. 

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