Adsorption effects, with ions

These effects can be illustrated more quantitatively. The drop in the magnitude of the potential of mica with increasing salt is illustrated in Fig. V-7 here yp is reduced in the immobile layer by ion adsorption and specific ion effects are evident. In Fig. V-8, the pH is potential determining and alters the electrophoretic mobility. Carbon blacks are industrially important materials having various acid-base surface impurities depending on their source and heat treatment. 

For example, van den Tempel [35] reports the results shown in Fig. XIV-9 on the effect of electrolyte concentration on flocculation rates of an O/W emulsion. Note that d ln)ldt (equal to k in the simple theory) increases rapidly with ionic strength, presumably due to the decrease in double-layer half-thickness and perhaps also due to some Stem layer adsorption of positive ions. The preexponential factor in Eq. XIV-7, ko = (8kr/3 ), should have the value of about 10 " cm, but at low electrolyte concentration, the values in the figure are smaller by tenfold or a hundredfold. This reduction may be qualitatively ascribed to charged repulsion. 

The controhing effect of various ions can be expressed in terms of thermodynamic equhibria [Karger and DeVivo, Sep. Sci., 3, 393 1968)]. Similarities with ion exchange have been noted. The selectivity of counterionic adsorption increases with ionic charge and decreases with hydration number [Jorne and Rubin, Sep. Sci., 4, 313 (1969) and Kato and Nakamori, y. Chem. Eng. Japan, 9, 378 (1976)]. 

In modern practice, inhibitors are rarely used in the form of single compounds — particularly in near-neutral solutions. It is much more usual for formulations made up from two, three or more inhibitors to be employed. Three factors are responsible for this approach. Firstly, because individual inhibitors are effective with only a limited number of metals the protection of multi-metal systems requires the presence of more than one inhibitor. (Toxicity and pollution considerations frequently prevent the use of chromates as universal inhibitors.) Secondly, because of the separate advantages possessed by inhibitors of the anodic and cathodic types it is sometimes of benefit to use a formulation composed of examples from each type. This procedure often results in improved protection above that given by either type alone and makes it possible to use lower inhibitor concentrations. The third factor relates to the use of halide ions to improve the action of organic inhibitors in acid solutions. The halides are not, strictly speaking, acting as inhibitors in this sense, and their function is to assist in the adsorption of the inhibitor on to the metal surface. The second and third of these methods are often referred to as synergised treatments. 

In the case of ions, the repulsive interaction can be altered to an attractive interaction if an ion of opposite charge is simultaneously adsorbed. In a solution containing inhibitive anions and cations the adsorption of both ions may be enhanced and the inhibitive efficiency greatly increased compared to solutions of the individual ions. Thus, synergistic inhibitive effects occur in such mixtures of anionic and cationic inhibitors . These synergistic effects are particularly well defined in solutions containing halide ions, I. Br , Cl", with other inhibitors such as quaternary ammonium cations , alkyl benzene pyridinium cations , and various types of amines . It seems likely that co-ordinate-bond interactions also play some part in these synergistic effects, particularly in the interaction of the halide ions with the metal surfaces and with some amines . 

Precipitation of silver bromide will occur when the concentration of the bromide ion in the solution is 2.0 x 103 times the iodide concentration. The separation is therefore not so complete as in the case of chloride and iodide, but can nevertheless be effected with fair accuracy with the aid of adsorption indicators (Section 10.75(c)). 

Either the Mohr titration or the adsorption indicator method may be used for the determination of chlorides in neutral solution by titration with standard 0.1M silver nitrate. If the solution is acid, neutralisation may be effected with chloride-free calcium carbonate, sodium tetraborate, or sodium hydrogencarbonate. Mineral acid may also be removed by neutralising most ofthe acid with ammonia solution and then adding an excess of ammonium acetate. Titration of the neutral solution, prepared with calcium carbonate, by the adsorption indicator method is rendered easier by the addition of 5 mL of 2 per cent dextrin solution this offsets the coagulating effect of the calcium ion. If the solution is basic, it may be neutralised with chloride-free nitric acid, using phenolphthalein as indicator. 

Figures 6, 7 and 9 show calibration curves using two multi-column combinations and illustrate the degree of "optimization obtained in this system. The mobile phases for Figures 6 and 7 contained 0.025 g polyethylene oxide and ion exclusion and adsorption effects should therefore be largely eliminated. Figure 6 shows that reasonably good resolution can be obtained with a combination of five columns but does exhibit some loss of peak separation at the low cuid high MW ends. In Figure 7 the effect of adding a sixth column of small pore size is illustrated and it is seen that resolution at the low MW end is thereby somewhat improved. This calibration curve is effectively linear with a change of slope at 500,000 MW. It should provide a useful aqueous GPC system for MW and MWD determination of nonionic polyacrylamides.

On the surface of metal electrodes, one also hnds almost always some kind or other of adsorbed oxygen or phase oxide layer produced by interaction with the surrounding air (air-oxidized electrodes). The adsorption of foreign matter on an electrode surface as a rule leads to a lower catalytic activity. In some cases this effect may be very pronounced. For instance, the adsorption of mercury ions, arsenic compounds, or carbon monoxide on platinum electrodes leads to a strong decrease (and sometimes total suppression) of their catalytic activity toward many reactions. These substances then are spoken of as catalyst poisons. The reasons for retardation of a reaction by such poisons most often reside in an adsorptive displacement of the reaction components from the electrode surface by adsorption of the foreign species. 

Figure 2. Representation of the possible site forms in the site-binding model which includes the effect of counter-ion adsorption, combined with a diagram of charges and potentials at the insulator/electrolyte interface. Reproduced with permission from Ref. (14). Copyright 1983, North Holland.

Highly selective ion exchange reactions described here in clay minerals and zeolites are reversible and occur on the constant charge fraction of these minerals. Interactions with a siloxane surface are therefore involved in contrast to the so-called specific adsorption effects occuring on hydroxyl bearing surfaces. 

Effects of Pentavalent Sb Ions on the Adsorption of Divalent Co-57 on Hematite. Benjamin and Bloom reported that arsenate ions enhance the adsorption of cobaltous ions on amorphous iron oxyhydroxide (J 6). Similarly, when divalent Co-57 ions were adsorbed on hematite together with pentavalent Sb ions, an increase of adsorption in the weakly acidic region was observed. For example, when 30 mg of hematite was shaken with 10 cm3 of 0.1 mol/dm3 KC1 solution at pH 5.5 containing carrier-free Co-57 and about 1 mg of pentavalent Sb ions, 95 % of Co-57 and about 30 % of Sb ions were adsorbed. The emission spectra of the divalent Co-57.ions adsorbed under these conditions are shown in Figure 8 together with the results obtained under different conditions. As seen in Figure 8, the spectra of divalent Co-57 co-adsorbed with pentavalent Sb ions are much different from those of Co-57 adsorbed alone (Figure 3). These observations show a marked effect of the.co-adsorbed pentavalent Sb ions on the chemical structure of adsorbed Co-57. 

Effect of initial pH on adsorption of Pb + ions were investigated as follows 0.5 g of the resin was weighed and 100 mL of a heavy metal ion solution was added. The pH of each solution was adjusted to desired values. After stirring 5 h the reaction mixture was filtered through membrane filter to remove particulates and analyzed with an AAS. 

To investigate the effect of ratio of solution volume to mass of solid and adsorption of metal ions 0.5 g resin samples were mixed 25-75 mL of aqueous solution of the constant initial concentration of metal ions (50 ag/mL Pb +). The pH was adjusted to 4 for adsorption of Pb +. The flasks with their contents were stirred for 4 h. 

A fundamental improvement in the facilities for studying electrode processes of reactive intermediates was the purification technique of Parker and Hammerich [8, 9]. They used neutral, highly activated alumina suspended in the solvent-electrolyte system as a scavenger of spurious impurities. Thus, it was possible to generate a large number of dianions of aromatic hydrocarbons in common electrolytic solvents containing tetraalkylammonium ions. It was the first time that such dianions were stable in the timescale of slow-sweep voltammetry. As the presence of alumina in the solvent-electrolyte systems may produce adsorption effects at the electrode, or in some cases chemisorption and decomposition of the electroactive species, Kiesele constructed a new electrochemical cell with an integrated alumina column [29]. 

Sun et al. (1993a) reported the effects HS ion concentration on the adsorption of HS , the amount of extracted sulphur and sulphur-induced flotation of pyrite as shown in Fig. 3.11. The results show that dining sodium sulphide-induced collectorless flotation, it involves the adsorption of HS ion on the mineral and the HS" adsorbed can be oxidized into sulphur to render pyrite and arsenopyrite surface hydrophobic due to the fact that the adsorption density of HS" ion increases with the HS" ion concentration and the amount of extracted sulphur and hence the flotation rate increases with the increase of adsorption density. It suggests that the mechanism of sodium sulphide-induced collectorless flotation of pyrite takes place hy reactions ... 

Similar effects were observed by Stigter e< al. (185) with silica and aluminum chloride. The assumption of hydrolytic adsorption is supported by an observed increase of conductivity upon addition of silica to aluminum chloride solutions. Kautsky and Wesslau (240) observed hydrolytic adsorption of Th + ions. The reaction scheme given above is a simplification since, in reality, solutions of basic iron or aluminum salts contain polynuclear complexes. The size of the aggregates depends on pH and concentration. Chromatographic separation of various metal ions on silica gel columns was first described by Schwab and Jockers (241). The role of hydrolytic adsorption in column chromatography on silica gel was stressed by Umland and Kirchner (242). The use of this technique in analytical separations was investigated in detail by Kohlschiitter and collaborators (243-246). An application to thin-layer chromatography was described by Seiler (247). 

Very few direct measurements of the reaction of surface silanol groups on quartz have been reported. This is apparently caused by the small effects due to the limited surface areas available. Adsorption of sodium ions on quartz was measured by radioactive tracer techniques by Gaudin et al. (293). Saturation was achieved at high pH (>10) and sodium ion concentrations above 0.07 Jlf. The calculated packing density of silanol groups was 4.25/100 A. Goates and Anderson (294) titrated quartz with aqueous sodium hydroxide and alcoholic sodium ethylate. The occurrence of two types of acidic groups was reported. 

Effects of Flooding and Redox Conditions onfs. I know of no published data on this. Bnt it is likely that the natnre of particle surfaces in intermittently flooded soils wonld restrict snrface mobility. For ions to diffuse freely on the surface there must be a continuous pathway of water molecules over the surface and uniform cation adsorption sites. But in intermittently flooded soils the surface typically contains discontinuous coatings of amorphous iron oxides on other clay minerals, and on flooding reduced iron is to a large extent re-precipitated as amorphons hydroxides and carbonates as discussed above, resulting in much microheterogeneity with adsorption sites with disparate cation affinities. 

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