Complexation reaction

The following reaction between the metal ion Cd + and the ligand NH3 is typical of a complexation reaction. 

The product of this reaction is called a metal-ligand complex. In writing the equation for this reaction, we have shown ammonia as NH3 to emphasize the pair of electrons it donates to Cd +. In subsequent reactions we will omit this notation. 

The formation of a metal-ligand complex is described by a formation constant, K. The complexation reaction between Cd + and NH3, for example, has the following equilibrium constant 

The reverse of reaction 6.15 is called a dissociation reaction and is characterized by a dissociation constant, Ka, which is the reciprocal of K.  

Many complexation reactions occur in a stepwise fashion. For example, the reaction between Cd + and NH3 involves four successive reactions 

In this chapter, we will discuss how double layer theory can be incorporated into a geochemical model. We will consider hydrous ferric oxide (FeOOH nH2O), which is one of the most important sorbing minerals at low temperature under oxidizing conditions. Sorption by hydrous ferric oxide has been widely studied and Dzombak and Morel (1990) have compiled an internally consistent database of its complexation reactions. The model we develop, however, is general and can be applied equally well to surface complexation with other metal oxides for which a reaction database is available. 

Surface complexation theory is well described in a number of texts on surface chemistry, including Adamson (1976), Stumm and Morgan (1981), Sposito (1989), Dzombak and Morel (1990), and Stumm (1992) therefore, we merely summarize it in this section. According to the theory, the sorbing surface is composed of metal-hydroxyl sites that can react with ions in solution. 

In Dzombak and Morel s (1990) development, hydrous ferric oxide holds two site types, one weakly and the other strongly binding. In their uncomplexed forms, the sites are labeled (w)FeOH and (s)FeOH the notation represents bonding to the mineral structure, and (w) and (s) signify the weak and strong sites. 

Each site can protonate or deprotonate to form surface species such as (w)FeOH2 and (w)FeO. The corresponding reactions are 

As well, the sites can react with cations and anions from solution to form complexes such as (w)FeOCa+ and (w)FeSOJ 

The stability of liquid water is due in large part to the ability of water molecules to form hydrogen bonds with one another. Such bonds tend to stabilize the molecules in a pattern where the hydrogens of one water molecule are adjacent to oxygens of other water molecules. When chemical species dissolve, they must insert themselves into this matrix, and in the process break some of the bonds that exist between the water molecules. If a substance can form 

The comparisons between pure water and a solution containing dissolved metal ions can be extended by considering the behavior of other 

The exchange of water molecules in the hydration sphere for other dissolved species can be extended to include mixed ligand complexes , i.e. those in which water molecules have been replaced by two or more different types of ligands, and multi-dentate  

Complexation reactions are of crucial importance in the biogeochemical cycling of metals because a large fraction of the total dissolved metal may be complexed. In addition, biological effects can be 

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Mixed parallel and series reactions producing byproducts. In more complex reaction systems, both parallel and series reactions can occur together. Mixed parallel and series reactions are of the type... 

The importance of numerical treatments, however, caimot be overemphasized in this context. Over the decades enonnous progress has been made in the numerical treatment of differential equations of complex gas-phase reactions [8, 70, 71], Complex reaction systems can also be seen in the context of nonlinear and self-organizing reactions, which are separate subjects in this encyclopedia (see chapter A3,14. chapter C3.6). 

Wei J and Prater C D 1962 The structure and analysis of complex reaction systems Advances in Catalysis (New York Academic) pp 203-392... 

Flowever, in order to deliver on its promise and maximize its impact on the broader field of chemistry, the methodology of reaction dynamics must be extended toward more complex reactions involving polyatomic molecules and radicals for which even the primary products may not be known. There certainly have been examples of this notably the crossed molecular beams work by Lee [59] on the reactions of O atoms with a series of hydrocarbons. In such cases the spectroscopy of the products is often too complicated to investigate using laser-based techniques, but the recent marriage of intense syncluotron radiation light sources with state-of-the-art scattering instruments holds considerable promise for the elucidation of the bimolecular and photodissociation dynamics of these more complex species. 

The master equation treatment of energy transfer in even fairly complex reaction systems is now well established and fairly standard [ ]. However, the rate coefficients kjj or the individual energy transfer processes must be established and we shall discuss some aspects of this matter in tire following section. 

In the reaction kinetics context, the tenn nonlinearity refers to the dependence of the (overall) reaction rate on the concentrations of the reacting species. Quite generally, the rate of a (simple or complex) reaction can be defined in temis of the rate of change of concentration of a reactant or product species. The variation of this rate with the extent of reaction then gives a rate-extent plot. Examples are shown in figure A3.14.1. In... 

Figure B2.5.2. Schematic relaxation kinetics in a J-jump experiment, c measures the progress of the reaction, for example the concentration of a reaction product as a fiinction of time t (abscissa with a logaritlnnic time scale). The reaction starts at (q. (a) Simple relaxation kinetics with a single relaxation time, (b) Complex reaction mechanism with several relaxation times x.. The different relaxation times x. are given by the turning points of e as a fiinction of ln((). Adapted from [110].

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. 

With hot water a vigorous but complex reaction occurs, the products including phosphine and phosphoric(V) acid. This disproportionation reaction can be approximately represented as ... 

Den Otter, W.K., Briels, W.J. The reactive flux method applied to complex reactions using the unstable normal mode as a reaction coordinate. J. Chem. Phys. 106 (1997) 1-15. 

Finding snch acids (called snperacids ) turned out to be the key to obtaining stable, long-lived alkyl cations and, in general, carbocations. If any deprotonation were still to take place, the formed alkyl cation (a strong Lewis acid) would immediately react with the formed olefin (a good TT-base), leading to the mentioned complex reactions. 

In a complexation reaction, the reaction unit is an electron pair. For the metal, the number of reaction units is the number of coordination sites available for binding ligands. For the ligand, the number of reaction units is equivalent to the number of electron pairs that can be donated to the metal. One of the most important analytical complexation reactions is that between the ligand ethylenediaminetetracetic acid (EDTA), which can donate 6 electron pairs and 6 coordinate metal ions, such as Cu thus... 

Several types of reactions are commonly used in analytical procedures, either in preparing samples for analysis or during the analysis itself. The most important of these are precipitation reactions, acid-base reactions, complexation reactions, and oxidation-reduction reactions. In this section we review these reactions and their equilibrium constant expressions. 

Equilibrium constants for complexation reactions involving solids are defined by combining appropriate Ksp and K expressions. Eor example, the solubility of AgCl increases in the presence of excess chloride as the result of the following complexation reaction... 

In a complexation reaction, a Lewis base donates a pair of electrons to a Lewis acid. In an oxidation-reduction reaction, also known as a redox reaction, electrons are not shared, but are transferred from one reactant to another. As a result of this electron transfer, some of the elements involved in the reaction undergo a change in oxidation state. Those species experiencing an increase in their oxidation state are oxidized, while those experiencing a decrease in their oxidation state are reduced, for example, in the following redox reaction between fe + and oxalic acid, H2C2O4, iron is reduced since its oxidation state changes from -1-3 to +2. 

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... 

The most important types of reactions are precipitation reactions, acid-base reactions, metal-ligand complexation reactions, and redox reactions. In a precipitation reaction two or more soluble species combine to produce an insoluble product called a precipitate. The equilibrium properties of a precipitation reaction are described by a solubility product. 

Consider the following hypothetical complexation reaction between a metal, M, and a ligand, L... 

A titration in which the reaction between the analyte and titrant is a complexation reaction. 

Quantitative Calculations The stoichiometry of complexation reactions is given by the conservation of electron pairs between the ligand, which is an electron-pair donor, and the metal, which is an electron-pair acceptor (see Section 2C) thus... 

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

Mole-ratio plots used to determine the stoichiometry of a metal-ligand complexation reaction. 

An important assumption in the slope-ratio method is that the complexation reaction continues to completion in the presence of a sufficiently large excess of metal or ligand. The slope-ratio method also is limited to systems that obey Beer s law and in which only a single complex is formed. 

When the potential of an electrode of the first kind responds to the potential of another ion that is in equilibrium with M"+, it is called an electrode of the second kind. Two common electrodes of the second kind are the calomel and silver/silver chloride reference electrodes. Electrodes of the second kind also can be based on complexation reactions. Eor example, an electrode for EDTA is constructed by coupling a Hg +/Hg electrode of the first kind to EDTA by taking advantage of its formation of a stable complex with Hg +. 

A membrane potential develops as the result of a difference in the equilibrium position of the complexation reaction... 

Coupling the mediator s oxidation or reduction to an acid-base, precipitation, or complexation reaction involving the analyte allows for the coulometric titration of analytes that are not easily oxidized or reduced. For example, when using H2O as a mediator, oxidation at the anode produces H3O+... 

Graphical determination of the stoichiometry and formation constant for a 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... 

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