Effects of alkalis

Several studies on the quaternary systems of CaO-SiOj-HiO with NajO or K,0 have been reported (K19,S52,M52). Alkali greatly lowers the concentrations of CaO in the solution and raises those of Si02. The solid phase compositions are difficult to study. Determinations based on changes in concentration on adding CH to alkali silicate solutions are subject to considerable experimental errors, while direct analyses of the solid are difficult to interpret because the alkali cations are easily removed by washing. Suzuki ei al. (S52) considered that they were adsorbed. Macpheeef /. (M52) reported TEM analyses of the C-S-H in washed preparations obtained by reaction ofCjS (lOg) in water or NaOH solutions (250 ml). The C-S-H obtained with water had a mean Ca/Si ratio of 1.77 that obtained with 0.8 M NaOH had a mean Ca/Si ratio of 1.5 and a mean NujO/SiOj ratio of 0.5. These results do not appear to be directly relevant to cement pastes. The pore solutions of the latter may be 0.8 M or even higher in alkali 

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Oil-base (including oil-modified alkyd resin) paint films should not be used in alkaline environments as the paint will deteriorate owing to saponification alkali-resistant coatings are provided by some cellulose ethers, e.g. ethyl cellulose, certain polyurethane, chlorinated rubber, epoxy, p.v.c./ p.v.a. copolymer, or acrylic-resin-based paints. In particular, aluminium and its alloys should be protected by alkali-resistant coatings owing to the detrimental effects of alkali on these metals. 

Figure 2.6. Effect of alkali coverage on (a) the alkali adatom dipole moment and alkali desorption energy (b) for Na, K and Cs adsorbed on Ru (0001) and corresponding effect of work function change AO on the alkali desorption energy (c).26 Reprinted with permission from Elsevier Science.

Most studies of the effect of alkalis on the adsorption of gases on catalyst surfaces refer to CO, NO, C02, 02, H2 and N2, due to the importance of these adsorbates for numerous industrial catalytic processes (e.g. N2 adsorption in NH3 synthesis, NO reduction by CO). Thus emphasis will be given on the interaction of these molecules with alkali-modified surfaces, especially transition metal surfaces, aiming to the identification of common characteristics and general trends. 

Alkali promoters are often used for altering the catalytic activity and selectivity in Fischer-Tropsch synthesis and the water-gas shift reaction, where C02 adsorption plays a significant role. Numerous studies have investigated the effect of alkalis on C02 adsorption and dissociation on Cu, Fe, Rh, Pd, A1 and Ag6,52 As expected, C02 always behaves as an electron acceptor. 

The effect of alkali addition on the adsorption of NO on metal surfaces is of great importance due to the need of development of efficient catalysts for NO reduction in stationary and automotive exhaust systems. Similar to CO, NO always behaves as an electron acceptor in presence of alkalis. 

The effect of alkali presence on the adsorption of oxygen on metal surfaces has been extensively studied in the literature, as alkali promoters are used in catalytic reactions of technological interest where oxygen participates either directly as a reactant (e.g. ethylene epoxidation on silver) or as an intermediate (e.g. NO+CO reaction in automotive exhaust catalytic converters). A large number of model studies has addressed the oxygen interaction with alkali modified single crystal surfaces of Ag, Cu, Pt, Pd, Ni, Ru, Fe, Mo, W and Au.6... 

The interpretation of the beneficial effect of alkali modification on oxygen adsorption has to include both stabilization of the adsorbed oxygen atoms on alkali modified sites, due to direct alkali-oxygen interactions, but also... 

The effect of alkali additives on N2 chemisorption has important implications for ammonia synthesis on iron, where alkali promoters (in the form of K or K20) are used in order to increase the activity of the iron catalyst. 

It is obvious that one can use the basic ideas concerning the effect of alkali promoters on hydrogen and CO chemisorption (section 2.5.1) to explain their effect on the catalytic activity and selectivity of the CO hydrogenation reaction. For typical methanation catalysts, such as Ni, where the selectivity to CH4 can be as high as 95% or higher (at 500 to 550 K), the modification of the catalyst by alkali metals increases the rate of heavier hydrocarbon production and decreases the rate of methane formation.128 Promotion in this way makes the alkali promoted nickel surface to behave like an unpromoted iron surface for this catalytic action. The same behavior has been observed in model studies of the methanation reaction on Ni single crystals.129... 

Oku, N., and MacDonald, R. C. (1983a). Differential effects of alkali metal chlorides on formation of giant liposomes by freezing and thawing and dialysis. Biochemistry. 22. 855-863. 

Pt-Re-alumina catalysts were prepared, using alumina containing potassium to eliminate the support acidity, in order to carry out alkane dehydrocyclization studies that paralleled earlier work with nonacidic Pt-alumina catalysts. The potassium containing Pt-Re catalyst was much less active than a similar Pt catalyst. It was speculated that the alkali metal formed salts of rhenic acid to produce a catalyst that was more difficult to reduce. However, the present ESCA results indicate that the poisoning effect of alkali in Pt-Re catalysts is not primarily due to an alteration in the rhenium reduction characteristics. 

Table 2 Effect of alkali metal hydroxide on activity and selectivity.

Table 10.25 Effect of alkali used with peracetic acid at various pH values on the degree of polymerisation of cotton cellulose [256]...

Kameda, M. Fundamental studies on solution of gold in cyanide solutions. III. Effects of alkalies lead acetate and some impurities contained in foul cyanide solutions. Sci. Repts. Res. Insts. Tohoku Univ. 1949, 1, 435-444. 

The degrading effect of alkali has been known for some time. Schoch, Wilson and Hudson146 concluded, from the fact that methyl /3-maltoside is stable when heated in 0.1 M caustic soda for considerable periods of time, that alkaline degradation of starch occurs only through the reducing end... 

Effect of Alkali Treatment on Maize Amylose Sub-fractions147... 

The effect of alkali treatment on molecular weight (compare with the case of the starch components) has been studied treating a 5% solution of rabbit-liver glycogen in 2 N sodium hydroxide, for 90 minutes at 100°, decreased the sedimentation constant (Sits X 1013) from 86 to 57 (that is, by 34%).237... 

Lemon, H. W. The Effect of Alkali on the Ultraviolet Absorption Spectra of Hydroxyaldehydes, Hydroxyketones and other Phenolic Compounds. J. Amer. chem. Soc. 69, 2998 (1947). 

The readsorption and incorporation of reaction products such as 1-alkenes, alcohols, and aldehydes followed by subsequent chain growth is a remarkable property of Fischer-Tropsch (FT) synthesis. Therefore, a large number of co-feeding experiments are discussed in detail in order to contribute to the elucidation of the reaction mechanism. Great interest was focused on co-feeding CH2N2, which on the catalyst surface dissociates to CH2 and dinitrogen. Furthermore, interest was focused on the selectivity of branched hydrocarbons and on the promoter effect of alkali on product distribution. All these effects are discussed in detail on the basis... 

Alkalization of iron catalysts causes two different effects. The selectivities of 1-alkenes are raised and both the growth probability a2 and the fraction f2 are markedly increased, as already shown in Figure 11.2. Detailed studies on the promoter effect of alkali have revealed the effect on 1-alkene selectivity to saturates at 1 mass% of K2C03, while the effect on f2 already begins at 0.2 mass% of K2C03.1213 This difference points to specific active sites in Fischer-Tropsch syn-... 

Pigos, J.M., Brooks, C.J., Jacobs, G., and Davis, B.H. 2007. Low temperature water-gas shift The effect of alkali doping on the CH bond of formate over Pt/Zr02 catalysts. Appl. Catal. A Gen. 328 14-26. 

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