Hydronium ion complex

Buhl, M., Wipff, G. (2002), Hydronium Ion Complex of 18-Crown-6 Where Are the Protons A Density Functional Study of Static and Dynamic Properties, J. Am. Chem. Soc. 124, 4473-4480. 

As an example of the problem of species in solution, consider the case of a solution made by dissolving some potassium chrome alum, KCrfSO s-12H20, in water. On testing, the solution is distinctly acidic. A currently accepted explanation of the observed acidity is based upon the assumption that, in water solution, chromic ion is associated with six H20 molecules in the complex ion, Cr(H20) a. This complex ion can act as a weak acid, dissociating to give a proton (or hydronium ion). Schematically, the dissociation can be represented as the transfer of a proton from one water molecule in the Cr(H20) 3 complex to a neighboring H20 to form a hydronium ion, H30+. Note that removal of a proton from an H20 bound to a Cr+3 leaves an OH- group at that position. The reaction is reversible and comes to equilibrium ... 

The mode of extraction in these oxonium systems may be illustrated by considering the ether extraction of iron(III) from strong hydrochloric acid solution. In the aqueous phase chloride ions replace the water molecules coordinated to the Fe3+ ion, yielding the tetrahedral FeCl ion. It is recognised that the hydrated hydronium ion, H30 + (H20)3 or HgO,, normally pairs with the complex halo-anions, but in the presence of the organic solvent, solvent molecules enter the aqueous phase and compete with water for positions in the solvation shell of the proton. On this basis the primary species extracted into the ether (R20) phase is considered to be [H30(R20)3, FeCl ] although aggregation of this species may occur in solvents of low dielectric constant. 

Although hydrogen ions are always attached to water molecules as hydronium ions, H,0, or more complex species, we write them here as H for simplicity. The (aq) should be taken to imply that the hydrogen ion is actually present as the hydronium ion. 

Acetoin consumes 4 equivalents of V(V) to produce some biacetyl via C-H fission however, this cleavage is not accompanied by a hydronium-ion concentration dependence of the rate thereby differing from a secondary alcohol oxidation. The mechanism of breakdown of the complex is depicted as follows... 

One effect of the electrochemical reactions in an aqueous system is a local pH change around the electrodes. By water electrolysis, hydronium ions (H30+) are generated at the anode, while hydroxyl ions (OH ) are produced at the cathode. These changes have been utilized for controlling the permeability of polyelectrolyte gel membrane or on-off solute release via ion exchange or surface erosion of interpolymer complex gels. 

Of the many reagents, both heterogeneous and homogeneous, that can facilitate chemical reactions, the cycloamyloses stand out. Reactions can be catalyzed with many species such as hydronium ions, hydroxide ions, general acids, general bases, nucleophiles, and electrophiles. More effective catalysis can sometimes be achieved by combinations of catalytic species as in multiple catalysis, intramolecular catalysis, and catalysis by com-plexation. Only the latter catalysis can show the real attributes of an efficient catalytic system, namely speed and selectivity. In analogy to molecular sieves, selectivity can be attained by stereospecific complexation and speed can be likewise attained if the stereochemistry within the complex is correct. The cycloamyloses, of any simple chemical compound, come the closest to these goals. 

Soil pH is perhaps the most critical and common soil measurement where a definite amount of water is added before a measurement is made. Soil pH is a particularly complicated measurement because the proton can and does exist as a hydronium ion in the soil solution, as an exchangeable ion on the cation exchange sites, and bonded to various soil constituents. Because of these complexities, a soil sample is usually brought to a standard moisture content before a pH measurement is made. By bringing different soils to a common moisture content, they can be compared and analytical results from different laboratories will be comparable. Although there is a number of ways to measure soil pH, typically it is carried out using a pH meter and a pH electrode. 

Any substance that stabihzes the concentration of one of its dissociated species, most commonly a proton (or more properly a hydronium ion). The free concentration of a metal ion may also be buffered by use of a metal ion-chelator complex, such as Ca EGTA or KMgEDTA. 

In a previous publication ( ), results were presented on the micellar properties of binary mixtures of surfactant solutions consisting of alkyldimethylamine oxide (C12 to Cig alkyl chains) and sodium dodecyl sulfate. It was reported that upon mixing, striking alteration in physical properties was observed, most notably in the viscosity, surface tension, and bulk pH values. These changes were attributed to 1) formation of elongated structures, 2) protonation of amine oxide molecules, and 3) adsorption of hydronium ions on the mixed micelle surface. In addition, possible solubilisation of a less soluble 1 1 complex, form between the protonated amine oxide and the long chain sulfate was also considered. 

A third, the hydronium ion OH2 + H+ -> OH, will be discussed later. Complex formation is quite a general phenomenon, and even mixed complex ions such as (P03F3) 2 and (P02F2)- can be formed on the other hand, not every coupling of two fluorides or oxides will form a complex, and we will have to investigate what the conditions are for stability of a complex. 

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