Equilibrium reagents

Solid-phase reactions are heterogeneous and often take up to 10 times as long as their homogeneous counterparts to come to equilibrium. Reagent diffusion into... 

Accordingly, the addition of an alkali monochromate to the equilibrium reagent solution results in an immediate precipitation of nickel dimethyl-glyoxime. Bichromates, which do not consume hydrogen ions, show no action toward this reagent. As little as 2.5 y K2Cr04 can be detected in one drop, after evaporation of the test solution. 

Identification of neodymium oxide with nickel dimethylglyoxime equilibrium reagent ... 

When the oxalates or nitrates of the rare earth elements are heated, they leave a residue of their oxides. With the exception of lanthanum, only neodymium oxide of the rare earth oxides is sufiiciently basic to react with nickel dimethylglyoxime equilibrium reagent to precipitate red nickel dimethylglyoxime. 

A condition of equilibrium is reached (70-90 per cent, of bisulphite compound with equivalent quantities of the reagents in 1 hour), but by using a large excess of bisulphite almost complete conversion into the... 

It is probable that many of the reactions of glucose in solution are due to the small amount of the open chain aldehyde present. If this reacts in a normal manner with a reagent, the equilibrium is disturbed, most of the cyclic form passes into (III) and ultimately the reaction proceeds to completion.-Fructose may be similarly formulated ... 

It has been suggested that SO3 is the actual electrophilic reagent leading to C3HsS03, the anion of CgH5S03H. However, in sulphuric acid, the following equilibrium probably exists ... 

Acetylation with acetic anhydride is comparatively expensive because of the cost of the reagent. The use of the inexpensive glacial acetic acid depends upon the displacement of the reversible equilibrium ... 

Although carbohydrates exist almost entirely as cyclic hemiacetals m aqueous solution they are m rapid equilibrium with their open chain forms and most of the reagents that react with simple aldehydes and ketones react m an analogous way with the carbonyl functional groups of carbohydrates... 

Le Chatelier s principle provides a means for predicting how systems at equilibrium respond to a change in conditions. When a stress is applied to an equilibrium by adding a reactant or product, by adding a reagent that reacts with one of the reactants or products, or by changing the volume, the system responds by moving in the direction that relieves the stress. 

There are many potential advantages to kinetic methods of analysis, perhaps the most important of which is the ability to use chemical reactions that are slow to reach equilibrium. In this chapter we examine three techniques that rely on measurements made while the analytical system is under kinetic rather than thermodynamic control chemical kinetic techniques, in which the rate of a chemical reaction is measured radiochemical techniques, in which a radioactive element s rate of nuclear decay is measured and flow injection analysis, in which the analyte is injected into a continuously flowing carrier stream, where its mixing and reaction with reagents in the stream are controlled by the kinetic processes of convection and diffusion. 

Every chemical reaction occurs at a finite rate and, therefore, can potentially serve as the basis for a chemical kinetic method of analysis. To be effective, however, the chemical reaction must meet three conditions. First, the rate of the chemical reaction must be fast enough that the analysis can be conducted in a reasonable time, but slow enough that the reaction does not approach its equilibrium position while the reagents are mixing. As a practical limit, reactions reaching equilibrium within 1 s are not easily studied without the aid of specialized equipment allowing for the rapid mixing of reactants. 

Dihydropyrroles (2-pyrrolines 231) are in tautomeric equilibrium with the corresponding 1-pyrrolines (232) the latter readily form trimers of type (233). The trimer dissociates in boiling THF to 1-pyrroline (232) trimerization is relatively slow at -78 °C and the monomer can be trapped by reaction with acylating reagents to give (V-acyl-2-pyrrolines (81JOC4791). 

It should be noted that the highest possible absorption rates will occur under conditions in which the hquid-phase resistance is negligible and the equilibrium back pressure of the gas over the solvent is zero. Such situations would exist, for instance, for NH3 absorption into an acid solution, for SO9 absorption into an alkali solution, for vaporization of water into air, and for H9S absorption from a dilute-gas stream into a strong alkali solution, provided there is a large excess of reagent in solution to consume all the dissolved gas. This is known as the gas-phase mass-transfer limited condition, wrien both the hquid-phase resistance and the back pressure of the gas equal zero. Even when the reaction is sufficiently reversible to allow a small back pres-... 

Reaction between an absorbed solute and a reagent reduces the equilibrium partial pressure of the solute, thus increasing the rate of mass transfer. The mass-transfer coefficient hkewise is enhanced, which contributes further to increased absorption rates. Extensive theoretical analyses of these effects have been made, but rather less experimental work and design guidehnes. 

The immobilization of reagents onto sorbents often results in increase of their sensitivity and, in some cases, selectivity, allows to simplify the analysis and to avoid necessity of use of toxic organic solvents. At the same time silicas are characterized by absence of swelling, thenual and chemical stability, rapid achievement of heterogeneous equilibrium. 

In the present work, the technique of XO and MTB immobilization onto silica gel in the form of its complexes with Fe(III) and Bi(III) respectively were found. The acid - base and chemical-analytical characteristics of solid-phase reagents were examined. The optimal conditions of quantitative recovery of Pb(II) and Zn(II) from diluted solutions, such as acidity of aqueous phase, the mass of the sorbents, the volume of solutions and the time of equilibrium reaching, were found. The methods of and F" detenuination were based on a competitive reactions of Zr(IV) with immobilized MTB and or F". Optimal conditions of 0,0 and F" determination in solution using SG, modified ion associates QAS-MTB (pH = 1,5, = 5-10 mol/1). 

Specific acid catalysis is observed when a reaction proceeds through a protonated intermediate that is in equilibrium with its conjugate base. Because the position of this equilibrium is a function of the concentration of solvated protons, only a single acid-dependent term appears in the kinetic expression. For example, in a two-step reaction involving rate-determining reaction of one reagent with the conjugate acid of a second, the kinetic expression will be as follows ... 

Choose which member in each of the following pairs reacts faster or has the more favorable equilibrium constant for reaction with the indicated reagent. Explain your reasoning. 

A further complication arises with Ingold s suggestion" that both the inductive and resonance effects are composed of initial state equilibrium displacements that reveal themselves in equilibrium properties like dipole moments and equilibrium constants and of time-dependent displacements produced during reaction by the approach of an attacking reagent, observed rate effects being resultants of both types of electronic effects. Hammett, however, claims that it is not necessary or possible to make this distinction. 

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