Predict the pH region in which each of the following buffers will be effective, assuming equal molarities of the acid and its conjugate base: (a) sodium nitrite and nitrous acid; (b) sodium formate and formic acid; (c) sodium carbonate and sodium hydrogen carbonate; (d) ammonia and ammonium chloride; (c) pyridine and pyridinium chloride.

Short Answer

Expert verified
Effective pH ranges: (a) Sodium nitrite and nitrous acid: pH close to pKa of nitrous acid. (b) Sodium formate and formic acid: pH close to pKa of formic acid. (c) Sodium carbonate and sodium hydrogen carbonate: pH close to second pKa of carbonic acid. (d) Ammonia and ammonium chloride: pH close to converted pKa from pKb of ammonia. (e) Pyridine and pyridinium chloride: pH close to pKa of pyridinium ion.

Step by step solution

01

- Understanding Buffer Systems

A buffer system is most effective when the pH is close to the pKa of the acid component of the buffer. The pH range of a buffer is typically considered to be effective within 1 pH unit above and below its pKa value.
02

- Identifying pKa Values

Identify the pKa values of nitrous acid, formic acid, carbonic acid, and acetic acid. These values are usually found in a chemistry reference or textbook. For ammonia, use the pKb value and convert it to pKa using the relationship pKa + pKb = 14.
03

- Predicting the Effective pH Range of Each Buffer

The effective pH range for each buffer can now be calculated using the respective pKa or converted pKa for ammonia.(a) For sodium nitrite and nitrous acid, use the pKa of nitrous acid.(b) For sodium formate and formic acid, use the pKa of formic acid.(c) For sodium carbonate and sodium hydrogen carbonate, use the pKa of carbonic acid.(d) For ammonia and ammonium chloride, convert the pKb of ammonia to pKa and use that value.(e) For pyridine and pyridinium chloride, use the pKa of the conjugate acid of pyridine.
04

- Considering the Buffering Capacity

Keep in mind that the buffers will have substantial buffering capacity within 1 pH unit above and below the pKa value of the acid component because the concentrations of the acid and its conjugate base are equal in these examples.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

pH Range of Buffers
Understanding the pH range of buffers is critical for effectively managing chemical reactions and biological processes sensitive to pH changes. A buffer system consists of a weak acid and its conjugate base or a weak base and its conjugate acid, capable of neutralizing small amounts of added acid or base. This ability stabilizes the pH of the solution within a specific range, which is typically within approximately one pH unit above and below the acid's pKa value.

When the components of the buffer are present in equal concentrations, the pH of the buffer solution is very close to the pKa of the acid. For a practical perspective, if the pH of a process must be maintained around 4.75, a buffer with a pKa close to this value should be selected. Hence, the knowledge of a buffer's effective range is crucial in both laboratory and industrial settings for maintaining the desired environment for chemical and biochemical operations.
pKa Values
The pKa value is a critical parameter in buffer systems as it represents the acid dissociation constant, revealing the acid strength. Lower pKa values indicate stronger acids, which dissociate more completely in water. To select an appropriate buffer system, one must first consider the pKa values of potential acid components.

In the world of buffers, the pKa provides the pivot around which the buffer functions. For most effective buffering, the pH of the solution should be near this value. When working with weak bases, such as ammonia in the provided example, the pKb value is given instead, which refers to the base dissociation constant. Converting pKb to pKa allows the usage of the same principle, as pKa and pKb are related through the equation \( pKa + pKb = 14 \) in aqueous solutions at 25°C. This relationship ties together the dissociation constants of conjugate acid-base pairs.
Conjugate Acid-Base Pairs
Conjugate acid-base pairs are the heart of buffer systems. They consist of a weak acid and its conjugate base, or vice versa. The 'conjugate' nature of these pairs means that they can rapidly interconvert in response to pH changes: the acid can lose a proton to become its conjugate base, and the conjugate base can accept a proton to become the acid.

This dynamic equilibrium is what allows buffers to resist changes in pH. For instance, when an acid is added to a buffered solution, the conjugate base component will react with the added hydrogen ions, thereby minimizing the pH change. Similarly, when a base is added, the weak acid in the buffer will donate a proton, counteracting the increase in pH. The choice of the conjugate acid-base pairs is pivotal for targeting the desired pH range, ensuring that the buffer performs optimally under specific conditions.
Buffering Capacity
The buffering capacity indicates the amount of acid or base that a buffer solution can absorb without a significant change in pH. It is a measure of the buffer's strength and is most considerable when the pH is close to the pKa of the acid in the buffer. The capacity is directly related to the concentrations of the conjugate acid-base pairs in the solution.

When a buffer has equal concentrations of an acid and its conjugate base, as in the textbook examples, it exhibits substantial buffering capacity. This capacity peaks at the pKa, where the ability to neutralize added acids or bases is the greatest. Thus, when preparing buffers, controlling the molar concentrations of the components is essential to ensure the necessary buffering capacity for the intended application.
Acid-Base Equilibria
Acid-base equilibria are the foundation of buffer systems, governing how conjugate acid-base pairs interact with each other and with added acids or bases. Equilibria refer to the state of balance between the forward and reverse reactions of acid and base dissociation.

In a buffer solution, the dissociation of the weak acid into its conjugate base and the re-association of the conjugate base into the weak acid occur constantly, maintaining a steady pH. Le Chatelier’s principle explains that any change in concentration, temperature, or pressure can shift the equilibrium position, but well-designed buffer systems can withstand these stresses by adjusting the ratio of acid to base. This dynamic chemical balance enables buffers to maintain a steady pH, a condition essential in many chemical, biological, and industrial processes.

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Most popular questions from this chapter

Which indicators could you use for a titration of \(0.20 \mathrm{M}\) ammonia with \(0.20 \mathrm{M} \mathrm{HCl}(\mathrm{aq}):\) (a) bromocresol green; (b) methyl red; (c) phenol red; (d) thymol blue? Fxplain your selections.

(a) What must be the ratio of the concentrations of \(\mathrm{CO}_{3}{ }^{2-}\) and \(\mathrm{HCO}_{3}{ }^{-}\)ions in a buffer solution having a \(\mathrm{pH}\) of \(11 . \mathrm{O}\) ? (b) What mass of \(\mathrm{K}_{2} \mathrm{CO}_{3}\) must be added to \(1.00 \mathrm{~L}\) of \(0.100 \mathrm{M} \mathrm{KHCO}_{3}(\mathrm{aq})\) to prepare a buffer solution with a pH of \(11.0\) ? (c) What mass of \(\mathrm{KHCO}_{3}\) must be added to \(1.00 \mathrm{~L}\) of \(0.100 \mathrm{M} \mathrm{K}_{2} \mathrm{CO}_{3}(\mathrm{aq})\) to prepare a buffer solution with a pH of \(11.0\) ? (d) What volume of \(0.200 \mathrm{M} \mathrm{K}_{2} \mathrm{CO}_{3}(\mathrm{aq})\) must be added to \(100 \mathrm{~mL}\) of \(0.100 \mathrm{M} \mathrm{KHCO}_{3}(\mathrm{aq})\) to prepare a buffer solution with a pH of \(11.0\) ?

Predict the \(\mathrm{pH}\) region in which each of the following buffers will be effective, assuming equal molarities of the acid and its conjugate base: (a) sodium lactate and lactic acid; (b) sodium benzoate and benzoic acid; (c) potassium hydrogen phosphate and potassium phosphate; (d) potassium hydrogen phosphate and potassium dihydrogen phosphate; (e) hydroxylamine and hydroxylammonium chloride.

Sketch reasonably accurately the \(\mathrm{pH}\) curve for the titration of \(20.0 \mathrm{~mL}\) of \(0.10 \mathrm{M} \mathrm{HCl}(\mathrm{aq})\) with \(0.20 \mathrm{M} \mathrm{KOH}(\mathrm{aq})\). Mark on the curve (a) the initial \(\mathrm{pH}\); (b) the pH at the stoichiometric point.

Novocaine, which is used by dentists as a local anesthetic, is a weak base with \(\mathrm{pK}_{\mathrm{b}}=5.05\). Blood has a pH of \(7.4\). What is the ratio of concentrations of Novocaine to its conjugate acid in the bloodstream?

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