Rate of reduction

The colour of the precipitate depends upon the size of the cuprous oxide particles, and this in turn upon the rate of reduction, concentration of the solution, etc. 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

Preparation of Dispersion. The reduction process is a two-phase reaction between soluble reducing agent and insoluble dye particles, and therefore the rate of reduction is influenced by the particle size distribution of the dye dispersion. The smaller the particle size the greater the surface area and hence the more rapid the reduction process. However, if the particles are too small, migration will occur in continuous dyeing. It is therefore extremely important to control the size and range of particle size and this is a closely guarded piece of dyestuff manufacturers know-how. 

Electroless plating rates ate affected by the rate of reduction of the dissolved reducing agent and the dissolved metal ion which diffuse to the catalytic surface of the object being plated. When an initial continuous metal film is deposited, the whole surface is at one potential determined by the mixed potential of the system (17). The current density is the same everywhere on the surface as long as flow and diffusion are unrestricted so the metal... 

Table 8.3. Rates of Reduction of Aldehydes and Ketones by Sodium Borohydride...

For a given hydrogen donor S—H, replacement by S—D leads to a decreased rate of reduction, relative to nonproductive decay to the ground state." This decreased rate is consistent with a primary isotope effect in the hydrogen abstraction step,... 

Krapcho and Bothner-By made additional findings that are valuable ii understanding the Birch reduction. The relative rates of reduction o benzene by lithium, sodium and potassium (ethanol as proton donor) wer found to be approximately 180 1 0.5. In addition, they found that ben zene is reduced fourteen times more rapidly when methanol is the protoi donor than when /-butyl alcohol is used. Finally, the relative rates of reduc tion of various simple aromatic compounds by lithium were deteiTnined these data are given in Table 1-2. Taken together, the above data sho that the rate of a given Birch reduction is strikingly controlled by the meta... 

Relative Rates of Reduction of Substituted Benzenes Relative t<... 

The relative rate of reduction by lithium with respect to sodium was misquoted by me ii ref. 29 as 62.5 1. Eastham has criticized the accuracy of the original data and Krapchc and Bothner-By have agreed that their rate constants may have been in error. Thi figures cited above include lough corrections made in accord with Krapcho and Bothner-By estimates of the errors. 

A remarkable feature of the Birch reduction of estradiol 3-methyl ether derivatives, as well as of other metal-ammonia reductions, is the extreme rapidity of reaction. Sodium and -butyl alcohol, a metal-alcohol combination having a comparatively slow rate of reduction, effects the reduction of estradiol 3-methyl ether to the extent of 96% in 5 minutes at —33° lithium also effects complete reduction under the same conditions as is to be expected. Shorter reaction times were not studied. At —70°, reduction with sodium occurs to the extent of 56 % in 5 minutes, although reduction with lithium is virtually complete (96%) in the same time. (The slow rates of reduction of compounds of the 5-methoxytetralin type is exemplified by 5-methoxy-tetralin itself with sodium and f-butyl alcohol reduction occurs to the extent of only 50% in 6 hours vs. 99+% with lithium.) The iron catalyzed reaction of sodium with alcohols must be very fast since it competes so well with the rapid Birch reduction. One cannot compensate for the presence of iron in a Birch reduction mixture containing sodium by adding additional metal to extend the reaction time. The iron catalyzed sodium-alcohol reaction is sufficiently rapid that the aromatic steroid still remains largely unreduced. 

The rho values (2.78 overall, 3.78 for reduction to the cis product and 1.96 for reduction to the trans), determined from a study of the rates of reduction with NaBH4 of a series of 4-substituted cyclohexanones, have been interpreted as supporting a transition state late in the reaction.Other groups have observed positive rho values (2.5 to 3.1) for the reduction with NaBH4 of fluorenones and acetophenones. These results show clearly... 

The relation of rates of reduction with NaBH4 to variations in structure in a wide variety of monocyclic and bridged bicyclic compounds has also been discussed for example, a methyl a to a ketone slows the rate of reduction. Brown ° stated that reactions should not be discussed in terms of axial and equatorial attack, since the rates simply reflect differences in the energies of the possible transition states and not enough is known about the transition state to analyze it. He accepted th concepts of SAC and PDC, but preferred to call them steric strain contrpl and product stability control. ... 

Recently Waters and Witkop observed that irradiation with ultraviolet light of a solution of cholest-4-en-3-one during reduction with NaBH4 in 2-propanol increases the rate of reduction to almost that of cholestan-3-one. The yield of cholest-4-en-3)S-ol is not much decreased by the irradiation, although the mixture of products is more complicated (see page 74). These results may be applicable to problems of selective reduction of a 4-en-3-one system. 

Some generalizations that pertain are (1) Terminal olefins are more rapidly reduced than internal olefins (2) conjugated olefins are not reduced at 1 atmosphere (3) ethylene is not hydrogenated. Rates of reduction compare favorably with those obtained by heterogeneous catalysts such as Raney nickel or platinim oxide. In fact, the hydrogenation of some olefins may be so rapid that the temperature of the solution (benzene) is raised to the boiling point. 

The amount of solvent relative to the amount of total catalyst is usually large, and the amount of solvent relative to the number of active catalyst sites larger still very small amounts of inhibitors or poisons can have, therefore, large adverse influences on the rate of reduction. Solvent purity per se is of little regard in this connection, for gross amounts of innocuous impurities can be present without untoward effect. 

Regardless of detail, the experimental facts are clear process conditions that favor formation of hydrogen-poor catalysts favor migration and isomerization. Table 1 is a convenient summary of this concept. Hydrogen availability refers to hydrogen concentration at the catalyst surface. Additives that retard the rate of reduction increase hydrogen availability and retard isomerization they may also block sites with enhanced activity for migration (53). 

Wide variations in stereoselectivity are possible between the and Z isomers (79). In hydrogenation of several ( )- and (Z)-a-acylaminocinnamic acid derivatives, the Z isomers gave greater enantiomeric excesses at 15-100 times the rate of reduction of the isomer, but in all cases the 5 enantiomer was formed in greater excess (//7). The greater effectiveness of Z-olefins is general If8). 

Solvents have a marked effect on the rate of reduction of carbonyls (J6), in... 

In general, platinum, with or without modifiers, makes the best catalyst for minimizing dehalogenalion, combined with a fast rate of reduction of the nilro function. Excellent results have been obtained by use of supported noble-metal sulfides (4/). These catalysts [manufactured by Engelhard Industries, Newark, New Jersey (5/)] have a high intrinsic selectivity for this type of reduction and have given excellent results under a wide range of conditions. Elevated temperatures and pressures are necessary to achieve reasonable rates (33,34). 

Compounds containing a basic nitrogen, such as 2-chloroaniline. may function as their own hydrogen-halide acceptor (4). The rate of reduction is greatly retarded by added hydrogen chloride. 

Although Table 2.16 shows which metal of a couple will be the anode and will thus corrode more rapidly, little information regarding the corrosion current, and hence the corrosion rate, can be obtained from the e.m.f. of the cell. The kinetics of the corrosion reaction will be determined by the rates of the electrode processes and the corrosion rates of the anode of the couple will depend on the rate of reduction of hydrogen ions or dissolved oxygen at the cathode metal (Section 1.4). 

These considerations have been based entirely on thermodynamics and take no account of the overpotential, which is dependent on the rate of the process and the nature of the surface at which the reaction occurs. For this reason, the rate of reduction of HjO or HjO is usually low, and remains so to potentials from 0-5 to 1-OV below that given in equation 12.1. Even so, the instability of water is an insuperable obstacle to electrodepositing... 

Commercial C.p. chloroplatinic acid varies somewhat in its purity. In this work that from the Mallinckrodt Chemical Works, St. Louis, was used and gave very satisfactory results. Since small amounts of impurities in the catalyst are important factors in the rate of reduction of certain types of compounds, this question of impurities in the chloroplatinic acid must be taken into account (Note 13). In a large proportion of the reductions studied, platinum oxide prepared from the chloroplatinic acid mentioned gave as good results as that from spectroscopically pure chloroplatinic acid made according to the directions of Wichers.1... 

The solvent used is an important factor influencing the rate of reduction 34 and no generalization can be made beyond the one that alcohol, either 95 per cent or absolute has proved to be the best solvent for most of the compounds thus far studied. Ethyl acetate and glacial acetic acid may be used to advantage in some cases. 

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