Acids Henderson-Hasselbalch

This relationship is one form of the Henderson-Hasselbalch equation It is a useful relationship m chemistry and biochemistry One rarely needs to cal culate the pH of a solution—pH is more often mea sured than calculated It is much more common that one needs to know the degree of ionization of an acid at a particular pH and the Henderson-Hasselbalch equation gives that ratio... 

An alternative form of the Henderson-Hasselbalch equation for acetic acid is... 

Hemiketal (Section 17 8) A hemiacetal derived from a ketone Henderson-Hasselbalch equation (Section 19 4) An equa tion that relates degree of dissociation of an acid at a partic ular pH to its... 

As in Example 6.13, the Henderson-Hasselbalch equation provides a simple way to calculate the pH of a buffer and to determine the change in pH upon adding a strong acid or strong base. 

Multiprotic weak acids can be used to prepare buffers at as many different pH s as there are acidic protons. For example, a diprotic weak acid can be used to prepare buffers at two pH s and a triprotic weak acid can be used to prepare three different buffers. The Henderson-Hasselbalch equation applies in each case. Thus, buffers of malonic acid (pKai = 2.85 and = 5.70) can be prepared for which... 

Although this treatment of buffers was based on acid-base chemistry, the idea of a buffer is general and can be extended to equilibria involving complexation or redox reactions. For example, the Nernst equation for a solution containing Fe + and Fe + is similar in form to the Henderson-Hasselbalch equation. 

Suppose you need to prepare a buffer with a pH of 9.36. Using the Henderson-Hasselbalch equation, you calculate the amounts of acetic acid and sodium acetate needed and prepare the buffer. When you measure the pH, however, you find that it is 9.25. If you have been careful in your calculations and measurements, what can account for the difference between the obtained and expected pHs In this section, we will examine an important limitation to our use of equilibrium constants and learn how this limitation can be corrected. 

Any solution containing comparable amounts of a weak acid, HA, and its conjugate weak base, A-, is a buffer. As we learned in Chapter 6, we can calculate the pH of a buffer using the Henderson-Hasselbalch equation. 

This relationship is known as the Henderson-Hasselbalch equation. Thus, the pH of a solution can be calculated, provided and the concentrations of the weak acid HA and its conjugate base A are known. Note particularly that when [HA] = [A ], pH = pAl,. For example, if equal volumes of 0.1 MHAc and 0.1 M sodium acetate are mixed, then... 

The Henderson-Hasselbalch equation provides a general solution to the quantitative treatment of acid-base equilibria in biological systems. Table 2.4 gives the acid dissociation constants and values for some weak electrolytes of biochemical interest. 

If the pfC, value of a given acid and the pH of the medium are knowrn, the percentages of dissociated and undissociated forms can be calculated using what is called the Henderson-Hasselbalch equation. 

As an example of how to use the Henderson-Hasselbalch equation, let s find out what species are present in a 0.0010 M solution of acetic acid at pH = 7.3. According to Table 20.3, the pKa of acetic acid is 4.76. From the Henderson-Hasselbalch equation, we have... 

We saw in Section 20.3 that the extent of dissociation of a carboxylic acid HA in an aqueous solution buffered to a given pH can be calculated with the Henderson-Hasselbalch equation. Furthermore, we concluded that at the physiological... 

Amino Acids, the Henderson-Hasselbalch Equation, and Isoelectric Points... 

To apply the Henderson-Hasselbalch equation to an amino acid, let s find out what species are present in a 1.00 M solution of alanine at pH = 9.00. According to Table 26.1, protonated alanine [ NCHfCH CC H] has p/Cal =2.34, and neutral zwitteTionlc alanine [+ll3NCH(CH3)C02-] has pK52 = 9.69 ... 

Heat of combustion, 113 Heat of hydrogenation, 186 table of, 187 Heat of reaction, 154 Helicase, DNA replication and, 1106 Hell-Volhard-Zelinskii reaction, 849 amino acid synthesis and. 1025 mechanism of, 849 Heme, biosynthesis of, 966 structure of, 946 Hemiacetal, 717 Hemiketal, 717 Hemithioacetal, 1148 Henderson-Hasselbalch equation,... 

Chapter 20, Carboxylic Aciils and Nitriles—A new Section 20.3 discusses biological carboxylic acids and the Henderson-Hasselbalch equation. 

The values of [HA] and [A ] in this expression are the equilibrium concentrations of acid and base in the solution, not the concentrations added initially. However, a weak acid HA typically loses only a tiny fraction of its protons, and so [HA] is negligibly different from the concentration of the acid used to prepare the buffer, [HA]initia. Likewise, only a tiny fraction of the weakly basic anions A- accept protons, and so [A-] is negligibly different from the initial concentration of the base used to prepare the buffer. With the approximations A ] [base]initia and [HA] [acid]initia, we obtain the Henderson-Hasselbalch equation ... 

A note on good practice Keep in mind the approximations required for the use of the Henderson-Hasselbalch equation (that the concentrations of both the weak acid and its conjugate base are much greater than the hydronium ion concentration). Because the equation uses molar concentration instead of activities, it also ignores the interactions between ions. 

In practice, the Henderson-Hasselbalch equation is used to make rapid estimates of the pH of a mixed solution intended to be used as a buffer, and then the pH is adjusted to the precise value required by adding more acid or base and monitoring the solution with a pH meter. 

Step 5 Use an equilibrium table to find the H.O concentration in a weak acid or the OH concentration in a weak base. Alternatively, if the concentrations of conjugate acid and base calculated in step 4 are both large relative to the concentration of hydronium ions, use them in the expression for /<, or the Henderson—Hasselbalch equation to determine the pH. In each case, if the pH is less than 6 or greater than 8, assume that the autoprotolysis of water does not significantly affect the pH. If necessary, convert between Ka and Kh by using Kw = KA X Kb. 

Heisenberg uncertainty principle If the location of a particle is known to within an uncertainty Ax, then the linear momentum parallel to the x-axis can he known only to within an uncertainty Ap, where ApAx > till. Henderson-Hasselbalch equation An approximate equation for estimating the pH of a solution containing a conjugate acid and base. See also Section 11.2. Henry s constant The constant kH that appears in Henry s law. 

The Henderson-Hasselbalch Equation Describes the Behavior of Weak Acids Buffers... 

The Henderson-Hasselbalch equation is derived below. A weak acid, HA, ionizes as follows ... 

Generally it is only the non-dissociated or unionised drug that is lipid-soluble and a drug s degree of ionisation depends on its dissociation constant (pA) and the pH of the environment in which it finds itself. For an acidic drug this is represented by the Henderson Hasselbalch equation as... 

The case of a buffer consisting of a weak base and its acidic form (for example, NH3 and NH4) is treated in an analogous way. Equations of the type of (1.4.26) are sometimes called the Henderson-Hasselbalch equations. 

Fig. 1.9 Dependence of pH on the buffer composition according to the Henderson-Hasselbalch equation (1) acidic buffer (Eq. 1.4.26) (2) basic buffer. Calculation for K A = K B = 10-4, s = 0.1 mol dm-3...

Dissociation of the neutral acid in water necessitates modifications for air-sea exchange in the model, which is based on Henry s law. Other possible pathways, e.g. sea spray, are neglected. Henry s law is restricted to concentrations of physically solved, non dissociated substances. Since only the non-dissociated acid is volatile, it is important to correct the air-water partition coefficient as to reflect the relative proportions of volatile and non-volatile components. The corrected parameter is the effective Henry s law coefficient, which is related to the Henry s law coefficient as a function of pH (modified Henderson-Hasselbalch equation) ... 

There are two ways of dealing with the bicarbonate buffer system. The first uses the Henderson-Hasselbalch equation and an effective pKa of 6.1. If there is more base (HCO 3) than acid (C02), the pH will always be bigger than the pKa. This is usually the case physiologically (pH = 7.4 pKa = 6.1) so that on a molar basis there is always more than 10-fold more HCO 3 than C02. 

For formic acid, pATa = - log(1.8 x 10 4) = 3.74. The Henderson-Hasselbalch equation provides the pH of the original buffer solution ... 

Instead of the algebraic solution, we use the Henderson-Hasselbalch equation, since the final pH falls within one pH unit of the pATa of acetic acid. We let z indicate the increase... 

We use the Henderson-Hasselbalch equation to determine Ki of lactic acid. 

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