Solution complexation reactions

The complexation of ions by crown ethers can be detected in solution, but evidence was also obtained by studies in gas and solid phases. Most complexation chemistry is conducted in solution. Complexation reactions can be expressed generally by the equilibrium ... 

The chemical equation for the solution complexation reaction shown in Fig. 5 is... 

Equation (100) is the mass action equation for the solution complexation reaction shown in Fig. 5. For the activity coeiHcients in Eq. (96), the rigorous equation (22) can be substituted so that the activity coefficient can be expressed in terms of valence and electrostatic potentials ... 

The Turing mechanism requires that the diffusion coefficients of the activator and inlribitor be sufficiently different but the diffusion coefficients of small molecules in solution differ very little. The chemical Turing patterns seen in the CIMA reaction used starch as an indicator for iodine. The starch indicator complexes with iodide which is the activator species in the reaction. As a result, the complexing reaction with the immobilized starch molecules must be accounted for in the mechanism and leads to the possibility of Turing pattern fonnation even if the diffusion coefficients of the activator and inlribitor species are the same 62. 

Most reactions involve reactants and products that are dispersed in a solvent. If the amount of solvent is changed, either by diluting or concentrating the solution, the concentrations of ah reactants and products either decrease or increase. The effect of these changes in concentration is not as intuitively obvious as when the concentration of a single reactant or product is changed. As an example, let s consider how dilution affects the equilibrium position for the formation of the aqueous silver-amine complex (reaction 6.28). The equilibrium constant for this reaction is... 

Because of iodine s poor solubility, solutions are prepared by adding an excess of I-. The complexation reaction... 

The concentration of aluminum in serum can be determined by adding 2-hydroxy-1-naphthaldehyde p-methoxybenzoyl-hydrazone and measuring the initial rate of the resulting complexation reaction under pseudo-first-order conditions.The rate of reaction is monitored by the fluorescence of the metal-ligand complex. Initial rates, with units of emission intensity per second, were measured for a set of standard solutions, yielding the following results... 

The Bachmann process, used in the United States and in some European countries, is a simplification of a series of complex reactions. In this process, a solution of one part hexamine in 1.65 parts acetic acid, and a solution of 1.50 parts ammonium nitrate dissolved in 2.0 parts nitric acid and 5.20 parts acetic anhydride are used. The reaction may be summarized as ... 

In the United States, Hquid HLW from the reprocessing of defense program fuels was concentrated, neutralized with NaOH, and stored in underground, mild steel tanks pending soHdification and geologic disposal (see Tanks AND PRESSURE VESSELS). These wastes are a complex and chemically active slurry. Suspended in the supernatant Hquid are dissolver soHds which never went into solution, insoluble reaction products which formed in the tank, and salts which have exceeded their solubiHty limit. The kinetics of many of the reactions taking place are slow (years) so that the results of characterization... 

Silica Polymei Metal Ion Interactions in Solution. The reaction of metal ions with polymeric sihcate species in solution may be viewed as an ion-exchange process. Consequently, it might be expected that sihcate species acting as ligands would exhibit a range of reactivities toward cations in solution (59). Sihca gel forms complexes with multivalent metal ions in a manner that indicates a correlation between the ligand properties of the surface Si-OH groups and metal ion hydrolysis (60,61). For Cu +, Fe +, Cd +, and Pb +,... 

Complex reactions require the solution of simultaneous differential equations, and the Runge-Kutta procedure is applicable to these problems. To illustrate the method, Scheme XIV will be used. The rate equations are, in incremental form. 

Consider now a somewhat different type of complex ion formation, viz. the production of a complex ion with constituents other than the common ion present in the solution. This is exemplified by the solubility of silver chloride in ammonia solution. The reaction is ... 

The processes of complex-ion formation referred to above can be described by the general term complexation. A complexation reaction with a metal ion involves the replacement of one or more of the coordinated solvent molecules by other nucleophilic groups. The groups bound to the central ion are called ligands and in aqueous solution the reaction can be represented by the equation ... 

In the latter function, the reagent behaves as a surfactant and forms a cationic micelle at a concentration above the critical micelle concentration (1 x 10 4M for CTMB). The complexation reactions occurring on the surface of the micelles differ from those in simple aqueous solution and result in the formation of a complex of higher ligand to metal ratio than in the simple aqueous system this effect is usually accompanied by a substantial increase in molar absorptivity of the metal complex. 

A simple example of the application of a complexation reaction to a titration procedure is the titration of cyanides with silver nitrate solution. When a solution of silver nitrate is added to a solution containing cyanide ions (e.g. an alkali cyanide) a white precipitate is formed when the two liquids first come into contact with one another, but on stirring it re-dissolves owing to the formation of a stable complex cyanide, the alkali salt of which is soluble ... 

An analogous cyclization to eventually form five-membered rings has also been observed for l-metalla-l,3,5-hexatrienes with an additional heteroatom within the chain, such as in the complexes 157. These are obtained by Michael additions of imines to alkynylcarbene complexes in good to excellent yields (reaction type F in Scheme 4), and their configurations were determined to be Z (>91%) in all cases. Upon warming in THF solution, complexes 157 underwent cyclization with reductive elimination to furnish 2Ff-pyrroles 158 in up to 97% yield (Scheme 34). With two cyclopropyl substituents at the terminus in... 

In general, corrosion of metal is always accompanied by dissolution of a metal and reduction of an oxidant such as a proton in acidic solution and dissolved oxygen in a neutral solution. That is, metal corrosion is not a single electrode reaction, but a complex reaction composed of the oxidation of metal atoms and the reduction of oxidants. 

The second chapter is by Aogaki and includes a review of nonequilibrium fluctuations in corrosion processes. Aogaki begins by stating that metal corrosion is not a single electrode reaction, but a complex reaction composed of the oxidation of metal atoms and the reduction of oxidants. He provides an example in the dissolution of iron in an acidic solution. He follows this with a discussion of electrochemical theories on corrosion and the different techniques involved in these theories. He proceeds to discuss nonequilibrium fluctuations and concludes that we can again point out that the reactivity in corrosion is determined, not by its distance from the reaction equilibrium but by the growth processes of the nonequilibrium fluctuations. ... 

An important result of the concepts discussed in this section and the preceding one is that precipitation and complexation reactions exert joint control over metal ion solubility and transport. Whereas precipitation can limit the dissolved concentration of a specific species (Me ), complexation reactions can allow the total dissolved concentration of that metal to be much higher. The balance between these two competing processes, taking into account kinetic and equilibrium effects, often determines how much metal is transported in solution between two sites. 

In solution this reaction is rather rapid but in the solid state autoxidation takes place much slower. Nevertheless, commercial sulfides and polysulfides of the alkali and alkali earth metals usually contain thiosulfate (and anions of other sulfur oxoacids) as impurities [6]. For all these reasons the chemistry of polysulfides is rather complex, and some of the earlier studies on polysulfides (prior to ca. 1960) are not very rehable experimentally and/or describe erroneous interpretations of the experimental results. 

Equation (8.9) can be applied to any reaction, even a complex reaction where ctbatch(t) must be determined by the simultaneous solution of many ODEs. The restrictions on Equation (8.9) are isothermal laminar flow in a circular tube with a parabolic velocity profile and negligible diffusion. 

The whole analysis given hitherto has been conditioned by the strict validity of the Arrhenius equation. In fact, this equation is satisfactory for most organic work (191, 230), or for solution reactions in general, the main reason being the limited temperature range available in solution and a relatively low accuracy with complex reactions. What is still more important, the accuracy of the Arrhenius equation is usually completely sufficient when compared with the low... 

The Knoevenagel reaction between o-hydroxyaryl aldehydes and ketones and substituted acetonitriles affords high yields of 3-substituted coumarins in aqueous alkaline media <96H(43)1257>, whilst 4-hydroxycoumarins have been elaborated to pyrano [3,2-c]benzopyran-5-ones by reaction with aromatic aldehydes and malononitiile <96P148>. The imine (10) resulting from the complex reaction of o-hydroxyacetophenone with malononitrile undergoes a 1,5-tautomeric shift in solution <96JCS(P1)1067>. 

Certain quaternary ammonium salts will alkylate [Co (DMG)2py] . The addition of PhCH2NMc3 I to a solution of the complex in methanol gives the PhCH2Co complex in 45% yield. The reaction works more slowly with dimethylpiperidinium iodide to give the CH3—Co complex 15). There is no alkylation with tertiary amines alone 164), but in the presence of equimolar amounts of dimethylacetylenedicarboxylate certain aliphatic tertiary amines can alkylate [Co (DMG)2py] in methanol solution. The reaction also produces the enamine derivative of a maleic ester, and the mechanism appears to involve addition of the amine to the triple bond to form an ammonium salt, which can then attack the Co(I) derivative (75). 

A series of complexes in which the cyanide ligands are modified or replaced arises from the decomposition of methyl and pyridiomethylcobalt(111) pentacyanide derivatives in acid solution. The reactions include protonation of a cyanide ligand, insertion of a cyanide ligand between the organic group and the cobalt atom to produce an imine (see Section VI,D), decomposition of this imine to an acyl product, and replacement of a cyanide ligand by water 100, 101). The products are listed in Table III, 29. 

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