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Related Concept Videos

Buffer Effectiveness02:19

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Buffer solutions do not have an unlimited capacity to keep the pH relatively constant . Instead, the ability of a buffer solution to resist changes in pH relies on the presence of appreciable amounts of its conjugate weak acid-base pair. When enough strong acid or base is added to substantially lower the concentration of either member of the buffer pair, the buffering action within the solution is compromised.
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The addition of an inert ionic compound increases the solubility of a sparingly soluble salt. For example, adding potassium nitrate to a saturated solution of calcium sulfate significantly enhances the solubility of calcium sulfate. Le Châtelier's principle cannot predict this shift in the equilibrium. Instead, this could be explained in terms of changes in the effective concentration of the ions in solution in the presence of added inert salt.
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Buffers play a crucial role in stabilizing the pH of a solution by mitigating the effects of small amounts of added acid or base. They consist of a weak acid and its conjugate base or a weak base and its conjugate acid. A solution of acetic acid and sodium acetate is an example of a buffer that consists of a weak acid and its salt: CH3COOH (aq) + CH3COONa (aq). An example of a buffer that consists of a weak base and its salt is a solution of ammonia and ammonium chloride: NH3 (aq) + NH4Cl (aq).
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The effect of an inert salt on the solubility of a sparingly soluble salt is known as the salt effect. The degree of the salt effect varies with the ionic strength of the solution, which in turn depends on the activity of the species in the solution. The activity is expressed as the product of concentration and the activity coefficient of the species.
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Buffer and Salt Effects in Aqueous Host-Guest Systems: Screening, Competitive Binding, or Both?

Jacobs H Jordan1, Henry S Ashbaugh2, Joel T Mague3

  • 1Agricultural Research Service Southern Regional Research Center, U.S. Department of Agriculture, New Orleans, Louisiana 70124, United States.

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|October 27, 2021
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Supramolecular chemistry models often ignore ion screening effects in buffered solutions. This study shows competitive buffer binding is more significant than screening for strong binders, but both matter for weak binders.

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Area of Science:

  • Supramolecular Chemistry
  • Physical Chemistry
  • Biochemistry

Background:

  • Existing mathematical models for supramolecular chemistry do not account for ion screening.
  • Buffers were historically designed without considering their supramolecular properties.
  • Uncertainty exists regarding the magnitude of screening effects versus competitive salt/buffer binding.

Purpose of the Study:

  • To compare halide affinities using screened and unscreened models.
  • To quantify the impact of screening and competitive binding in buffered solutions.
  • To provide guidance for supramolecular chemists studying ions in water.

Main Methods:

  • Utilized a tetra-cation cavitand to study halide affinities.
  • Compared affinity data obtained from a traditional unscreened model and a Debye-Hückel screened model.
  • Developed a competitive mathematical model to assess binding attenuation.

Main Results:

  • A rule of thumb: consider screening if ionic strength changes by over an order of magnitude.
  • Competitive binding by the buffer significantly attenuates host-guest binding.
  • For the studied system, competitive binding effects are approximately twice as large as screening effects.

Conclusions:

  • For strong binders, competitive complexation is more critical than screening.
  • For weaker binders, both screening and competitive complexation must be considered.
  • Findings aid in understanding buffer properties and biomacromolecule studies.