Dissociation constant, conditional

Chemical reactions were sketched for Brqnsted acid phenomena and for -r.etal adsorption on oxides, but the chief concern was how mass law considerations could be applied to functional groups attached to a solid surface. This. jneem was addressed by appeal to the well-known reactions of polyelectro-r.tes in aqueous solutions. For example, in the simple case of deprotonation reactions, the conditional dissociation constant (Kc)... 

After the equivalence point, EDTA is in excess, and the concentration of Cd + is determined by the dissociation of the CdY complex. Examining the equation for the complex s conditional formation constant (equation 9.15), we see that to calculate Ccd we must first calculate [CdY ] and Cedxa- After adding 30.0 mb of EDTA, these concentrations are... 

An inflection point in a pH-rate profile suggests a change in the nature of the reaction caused by a change in the pH of the medium. The usual reason for this behavior is an acid-base equilibrium of a reactant. Here we consider the simplest such system, in which the substrate is a monobasic acid (or monoacidic base). It is pertinent to consider the mathematical nature of the acid-base equilibrium. Let HS represent a weak acid. (The charge type is irrelevant.) The acid dissociation constant, = [H ][S ]/[HS], is taken to be appropriate to the conditions (temperature, ionic strength, solvent) of the kinetic experiments. The fractions of solute in the conjugate acid and base forms are given by... 

When estimates of k°, k, k", Ky, and K2 have been obtained, a calculated pH-rate curve is developed with Eq. (6-80). If the experimental points follow closely the calculated curve, it may be concluded that the data are consistent with the assumed rate equation. The constants may be considered adjustable parameters that are modified to achieve the best possible fit, and one approach is to use these initial parameter estimates in an iterative nonlinear regression program. The dissociation constants K and K2 derived from kinetic data should be in reasonable agreement with the dissociation constants obtained (under the same experimental conditions) by other means. 

An expression for the ionization of H2CO3 under such conditions (that is, in the presence of dissolved CO2) can be obtained from Kh, the equilibrium constant for the hydration of CO2, and from the first acid dissociation constant for H2CO3 ... 

The affinities of the two states for substrate, S, are characterized by the respective dissociation constants, Kn and Kj- The model supposes that Kj- Kn. That is, the affinity of Rq for S is much greater than the affinity of Tq for S. Let us choose the extreme where Kn/Kj- = 0 (that is, Kj- is infinitely greater than Kjp). In effect, we are picking conditions where S binds only to R. (If Kj-is infinite, T does not bind S.)... 

Attempts have been made to deduce the structure of the predominant form of a potentially tautomeric compound from the shifts which occur in the ultraviolet spectrum of the compound in question on passing from neutral to basic or acidic solutions. The fact that no bathochromic shifts were observed for 2- and 4-hydroxy quinoline and 1-hydroxyisoquinoline under these conditions was taken as evidence that they existed in the oxo form [similar work on substituted quinol-4-ones led to no definite conclusions ]. A knowledge of the dissociation constants is essential to studies of this type, and the conclusions can, in any case, be only very tentative. A further dif-... 

In recent years various attempts have been made to account for the observed differences between the dissociation constants of organic acids, whose molecules differ only slightly from each other. The proposed explanations have naturally been given in each case in terms of the structures of the respective neutral acid molecules.1 In the tentative discussion of HN03 and HI03 that has just been given, the approach has been quite different we focused attention, not on the neutral molecule or on the structure of the anion, but on the condition of the solvent in the vicinity of the anion. 

It is worth mentioning that an attempt was made by Tsao and Willmarth to determine the acid dissociation constant of HO2. The reaction between hydrogen peroxide and peroxydisulphate was used for the generation of the HO2 radical. However, these experiments, like others where the HO2 radical is studied under steady-state conditions, could yield only a value of acidity constant multiplied by a coefficient consisting of a ratio of kinetic parameters. Unfortunately, in this case there are no independent data for the kinetic coefficient, and the value of cannot be evaluated. Considering the kinetic analogue of the titration curve it can be stated only that ionization of HO2 becomes important in the pH range from 4.5-6.5. The value of acidity constant of HO2 obtained by Czapski and Dorfman is (3.5 + 2.0)x 10 mole.l. . ... 

Extensive data are given in the Uterature for the potentiometric titration of polymer acids which may be used to study the behaviour of polyelectrolyte systems under different conditions. For poly(a-D) galacturonic acid there are few data of this kind, especially in connection with the occurrence of a conformational transition induced by pH variations, or with the effect brought about by the addition or the exchange of counterions. Since for a polyacid not exhibiting a conformational transition in the course of titration, pK K denoting the apparent dissociation constant) increases monotonously with degree... 

Equations (2.10) and (2.12) are identical except for the substitution of the equilibrium dissociation constant Ks in Equation (2.10) by the kinetic constant Ku in Equation (2.12). This substitution is necessary because in the steady state treatment, rapid equilibrium assumptions no longer holds. A detailed description of the meaning of Ku, in terms of specific rate constants can be found in the texts by Copeland (2000) and Fersht (1999) and elsewhere. For our purposes it suffices to say that while Ku is not a true equilibrium constant, it can nevertheless be viewed as a measure of the relative affinity of the ES encounter complex under steady state conditions. Thus in all of the equations presented in this chapter we must substitute Ku for Ks when dealing with steady state measurements of enzyme reactions. 

Because for now we are concerned only with equilibrium conditions and not with the rate at which equilibrium is reached, we can combine k and k x to form a new constant, KA = MM which has the unit of concentration. KA is a dissociation equilibrium constant (see Appendix 1.2A [Section 1.2.4.1]), though this is often abbreviated to either equilibrium constant or dissociation constant. Replacing k and k gives ... 

It is also common when building the knowledge base to find that the insertion of one piece of knowledge generates the need for further material. One step in a chemical analysis may require strongly acidic conditions, which are achieved by using a low pH. This implies that the ES needs to know about pH, which in turn demands an understanding of what is meant by the concentration of H+ ion. This may then require that the ES contains some information that relates to acid dissociation constants. 

Here Fmin is the fluorescence intensity without binding and /,max is the intensity when the sensor molecules are totally occupied. Kd is the dissociation constant. The differences in intensities in the numerator and denominator allow compensating for the background signal, and the obtained ratio can be calibrated in target concentration. But since F, Fmin and Fmax are expressed in relative units, they have to be determined in the same test and in exactly the same experimental conditions. This requires proper calibration, which is difficult and often not possible. 

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