Ionic equilibria buffer systems

Under the conditions of temperature and ionic strength prevailing in mammalian body fluids, the equilibrium for this reaction lies far to the left, such that about 500 CO2 molecules are present in solution for every molecule of H2CO3. Because dissolved CO2 and H2CO3 are in equilibrium, the proper expression for H2CO3 availability is [C02(d)] + [H2CO3], the so-called total carbonic acid pool, consisting primarily of C02(d). The overall equilibrium for the bicarbonate buffer system then is... 

A measurement of the ability of a buffer system to limit the change in pH of a solution upon the addition of an increment of strong base. ft is the reciprocal of the slope of the pH-neutralization curve. Consider the simple equilibrium, HA H+ -h A where K = [H+][A ]/ [HA] in which K is a practical dissociation constant determined under conditions of constant ionic strength. In such systems the practical pK is equal to the pH of solution when there are equal concentrations of the two buffer species. Since the total concentration of the two... 

Consider just a few cases of aqueous equilibria. The magnificent formations i n limestone caves and the vast expanses of oceanic coral reefs result from subtle shifts in carbonate solubility equilibria. Carbonates also influence soil pH and prevent acidification of lakes by acid rain. Equilibria involving carbon dioxide and phosphates help organisms maintain cellular pH within narrow limits. Equilibria involving clays in soils control the availability of ionic nutrients for plants. The principles of ionic equilibrium also govern how water is softened, how substances are purified by precipitation of unwanted ions, and even how the weak acids in wine and vinegar influence the delicate taste of a fine French sauce. In this chapter, we explore three aqueous ionic equilibrium systems acid-base buffers, slightly soluble salts, and complex ions. 

As an approximation, the dissolved portion of a slightly soluble salt dissociates completely into ions. In a saturated solution, the ions are in equilibrium with the solid, and the product of the ion concentrations, each raised to the power of its subscript in the compound s formula, has a constant value (Qsp = K p). The value of K p can be obtained from the solubility, and vice versa. Adding a common ion lowers an ionic compound s solubility. Adding HgO" (lowering the pH) increases a compound s solubility if the anion of the compound is that of a weak acid. If Qsp > K p for an ionic compound, a precipitate forms when two solutions, each containing one of the compound s ions, are mixed. Lakes bounded by limestone-rich soils form buffer systems that prevent harmful acidification by acid rain. 

The pKa of the imidazole ring is near 6 (16) so histamine would only exist as an ion in the acidic (pH = 2-3) mobile phase. One would predict no retention on a bonded phase column under this condition however, it does occur. Figure 3 is the simplest way to account for this retention. Here, the mineral acid acts as the counter-ion, as well as the buffer. All of the histamine in the mobile phase is in the ionic form and is in equilibrium with the ion-pair which is only soluble in the stationary phase chemically bonded to silica. Histamine only elutes in the ionic form and is then derivatized for detection. A sharp peak in the chromatogram with good shape and no change in retention time with variation in sample concentration indicates a working system. However, if the paired ion has some solubility in the mobile phase, peak tailing occurs. 

Let us consider ionic systems. In non-equilibrium state, the potential drop across the interface differs from the equilibrium value A tpb (eq). If the adjacent phases a and P chemically buffer the interface on their respective sides, as is normally true considering the large number of particles in the bulk relative to the small number of interface particles, the overall potential drop, Atjb, is only due to the electric potential change 8[Pg.84]

In spite of the partial success in theoretical description, we believe that more realistic models are needed for the theory to have a predicting power. For example, measurements usually take place in the presence of a large excess of simple electrolyte. The electrolyte present is often a buffer, a rather complicated mixture (difficult to model perse) with several ionic species present in the system. Note that many effects in protein solutions are salt specific. Yet, most of the theories subsume all the effect of the electrolyte present into a single parameter, the Debye screening parameter n. In the case of the Donnan equilibrium we measure the subtle difference between the osmotic pressures across a membrane permeable to small ions and water but not to proteins. We believe that an accurate theoretical description of protein solutions can only be built based on the models which take into account hydration effects. 

The solubility measure describes the concentration reached in solution, when a pure phase of the material is allowed to dissolve in the solvent for a defined period of time, at a defined temperature (and pressure). Most often for pharmaceutical purposes, the pure phase is a solid, ideally a crystalline solid, and the liquid is water or a buffered aqueous solution, at a controlled temperature (often 25 or 37 °C) and ambient pressure. The purity of the solid can have a large effect on measured solubility. Solubility can be measured in water or in pH-controlled buffers. In water, the extent of solubility for ionizable compounds will depend upon the p fCa values and the nature of the counterion. In pH-controlled aqueous buffered solution, at equilibrium, the solubility will depend upon the compound s intrinsic solubility, its plQ, and the ionic strength. It may also depend upon the relative solubility of the initial added compound and the solubility of the salt formed by the compound with the buffer salts, with which the solid may equilibrate. In any buffer or solvent system, the measured solubility may depend on the time of sampling, as solubility kinetics... 

The non-equilibrium features can be strongly enhanced by appropriate choices of assembly conditions the interval between consecutive assembly phases can be shortened, and the number of asembly cycles can be increased. Curve 5 of Fig. 6 was obtained at a particularly high protein concentrations in otherwise standard assembly buffer. Assembly becomes very rapid and runs into several damped oscillations before the system reaches a steady state at a lower degree of polymerization. A dramatic increase in oscillatory behavior is achieved by increasing the ionic strength ( oscillation buffer , Fig. 6, curves 6-9). The periodicities are typically in the range of... 

Construct a log R diagram for oxalic acid systems at 0.1 M ionic strength. Estimate the pH of a buffer which is 0.010 M in oxalic acid and 0.100 M in NaHC204. Check your result by looking into the charge and material balance of the equilibrium species. Take the published conditional pK values as 1.13 and 3.85 at 25°. 

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