Dissociation constant acid-base indicators

The plT at which an acid-base indicator changes color is determined by its acid dissociation constant. For an indicator that is a monoprotic weak acid, ITIn, the following dissociation reaction occurs... 

Discussion. The dissociation of an acid-base indicator is well suited to spectrophotometric study the procedure involved will be illustrated by the determination of the acid dissociation constant of methyl red (MR). The acidic (HMR) and basic (MR-) forms of methyl red are shown below. 

It is a well-known fact that upon covalent immobilization at the surface, the dissociation constant of the acid-base indicator changes by as much as 3 pK units. This shift clearly illustrates the dramatic effect that the interphase has on the ionization equilibria. It is perhaps the most serious problem with optical sensors that the surface concentration of any species is related to its corresponding bulk activity value through an adsorption isotherm which, with the exception of Henry s law, is a highly nonlinear and variable relationship. It is also known (Davies and Rideal, 1963) that the surface pH is different from the bulk value due to the electrostatic repulsion. 

It is important to know the dissociation constant of an indicator in order to use it properly in acid-base titrations. Spectrophotometry can be used to measure the concentration of these intensely colored species in acidic versus basic solutions, and from these data the equilibrium between the acidic and basic forms can be calculated. In one such study on the indicator wj-nitrophenol, a 6.36 X 10 M solution was examined by spectrophotometry at 390 nm and 25°C in the following experiments. In highly acidic solution, where essentially all the indicator was in the form HIn, the absorbance was 0.142. In highly basic solution, where essentially all of the indicator was in the form In , the absorbance was 0.943. In a further series of experiments, the pH was adjusted using a buffer solution of ionic strength I, and absorbance was measured at each pH value. The following results were obtained ... 

Basicity is a measure of how well a compound (a base) shares its lone pair with a proton. The stronger the base, the better it shares its electrons. Basicity is measured by an equilibrium constant (the acid dissociation constant, K ) that indicates the tendency of the conjugate acid of the base to lose a proton (Section 1.17). 

The first part of this table lists some common acid-base indicators in alphabetical order along with the approximate pH range(s) at which a color change occurs. Following this is a table of the same indicators ordered by pH range, which includes the nature of the color change, instructions on preparation of the indicator solution, and the acid dissociation constant p/C, when available. 

Acid-base indicators Amphoteric oxides, hydroxides Common strong acids and bases Dissociation constants (complexions), Ionization constants for weak acids, K, Ionization constants for weak bases, Aj, Names and formulas of common ions Solubility product constants,... 

The importance of the equilibrium law is widespread throughout chemistry. We have seen in Chapter 7 that defining the optimum conditions for certain key industrial gas phase reactions is dependent on a thorough understanding of the factors that determine the proportions of reactants and products in an equilibrium mixture, and we will return to a consideration of the Haber process later in this chapter. However, chemists use the equilibrium law to represent the extent to which a weak acid or base ionizes or dissociates, defining terms such as the dissociation constants and in relation to these effects. The behaviour of acid-base indicators is also explained in terms of the equilibria involved and the application of Le Chatelier s principle. 

The subscript a on indicates that this is an acid dissociation constant (not an association constant Ki, is the dissociation constant for bases). Taking the logarithm of both sides of Equation (22.30) for Ka gives the Henderson-Hasselbalch equation. 

It has been shown that for most acid-base titrations the inflection point, which corresponds to the greatest slope in the titration curve, very nearly coincides with the equivalence point. The inflection point actually precedes the equivalence point, with the error approaching 0.1% for weak acids or weak bases with dissociation constants smaller than 10 , or for very dilute solutions. Equivalence points determined in this fashion are indicated on the titration curves in figure 9.8. 

The initial goal of the kinetic analysis is to express k as a function of [H ], pH-independent rate constants, and appropriate acid-base dissociation constants. Then numerical estimates of these constants are obtained. The theoretical pH-rate profile can now be calculated and compared with the experimental curve. A quantitative agreement indicates that the proposed rate equation is consistent with experiment. It is advisable to use other information (such as independently measured dissociation constants) to support the kinetic analysis. 

Ionic strength adjuster buffer 565, 570 Ionisation constants of indicators, 262, (T) 265 of acids and bases, (T) 832, 833, 834 see also Dissociation constants Ionisation suppressant 793 Iron(II), D. of by cerium(IV) ion, (cm) 546 by cerium(IV) sulphate, (ti) 382 by potassium dichromate, (ti) 376 by potassium permanganate, (ti) 368 see also under Iron... 

The authors studied, as they call it, "acid-base equilibria in glacial acetic acid however, as they worked at various ratios of indicator-base concentration to HX or B concentration, we are in fact concerned with titration data. In this connection one should realize also that in solvents with low e the apparent strength of a Bronsted acid varies with the reference base used, and vice versa. Nevertheless, in HOAc the ionization constant predominates to such an extent that overall the picture of ionization vs. dissociation remains similar irrespective of the choice of reference see the data for I and B (Py) already given, and also those for HX, which the authors obtained at 25° C with I = p-naphthol-benzein (PNB) and /f B < 0.0042, i.e., for hydrochloric acid K C1 = 1.3 102, jjrfflci 3 9. IQ-6 an jjHC1 2.8 10 9 and for p-toluenesulphonic acid Kfm° = 3 7.102( K ms 4 0.10-6) Kmt = 7 3.10-9... 

Three experimental methods that are capable of determining dissociation constants with a precision of the order of tenths of 1% have been most commonly used. Each of these methods—the cell potential method (2), the conductance method (3), and the optical method (4)—provides data that can be treated approximately, assuming that the solutions obey Henry s law, or more exactly on the basis of the methods developed in Chapter 19. We will apply the more exact procedures. As the optical method can be used only if the acid and conjugate base show substantial differences in absorption of visible or ultraviolet light, or differences in raman scattering or with the use of indicators, we shall limit our discussion to the two electrical methods. 

Hammett acidity function chem An expression for the acidity of a medium, defined as ho = Kbh+ BH / B, where Kbh+ is the dissociation constant of the acid form of the Indicator, and BH+ and B are the concentrations of the protonated base and the unprotonated base respectively. ham at a sid ad e. faijk shan ) hand sugar refractometer analy chem Portable device to read refractive Indices of sugar solutions. Also known as protelnometer. hand shCig ar. re.frak tam-3d-3r1... 

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