Category: 2. Electrolyte Solutions
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Practice Problems
P18.1. a. Compute the freezing point depression for an aqueous solutions that is 3 wt% NaCl. b. Compute the boiling point elevation for an aqueous solutions that is 3 wt% NaCl. c. Compute the osmotic pressure for an aqueous solutions that is 3 wt% NaCl. 18.27. Homework Problems 18.1. Calcium chloride is used occasionally as an alternative to sodium…
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Supplement 4: Conversion of Equilibrium Constants
Equilibrium constants in electrolyte literature are often presented on the molal scale. For clarity in this section, we will use Ka,m to denote the molality equilibrium constant and Ka to denote the rational (Henry’s law scale) using mole fractions. Recall that the solvent (usually water) is on the Lewis-Randall scale. Using the molality scale for the electrolytes, On the…
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Supplement 3: Standard States
An important principle of the following discussion is that the chemical potential should be a property of the state of the system. All models should result in an identical value for the chemical potential at the same state. The standard state provides a convenient reference condition, but is slightly different from a reference state because…
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Supplement 2: Relation of Apparent Chemical Potential to Species Potentials
To understand the origin of the models for the mean activity coefficient, some discussion of the chemical potentials is necessary. Many of the concepts are extensions of the methods used for reaction engineering. For example, consider the general case of an electrolyte dissociating in solvent. When an electrolyte dissociates, the material balance gives the molality…
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Supplement 1: Interconversion of Concentration Scales
Throughout this chapter, subscript s indicates solvent, and Mw,i represents molecular wt in (g/mol). relation of mole fraction to molality: The relation for molality leads to another commonly used substitution for xs,
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Summary
This chapter began with a review of acid-base behavior to stress the importance of pH on equilibrium. Compounds are in the acid form below the pKa,A and in the base form above. Techniques including Sillèn’s graphical method were provided to determine solution pH values and species distributions at various concentrations. We explained the origin of charges…
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Extending Activity Calculations to High Concentrations
This chapter has served as an introduction to electrolyte models, and the extended Debye-Hückel leaves much to be desired in its limitations to concentrations lower than 0.1 m. However, the model has been used as an introduction, and those who work with electrolytes can find more models in the literature. In the older literature, the…
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Mean Ionic Activity Coefficients
Mean ionic activity coefficients are often used for electrolytes modeling in the literature. The mean ionic activity coefficients provide an alternative method to express the activity of the apparent electrolyte species. This section provides the background to relate those activity coefficients to the ion activity coefficients. The chemical potential of the apparent electrolyte species is…
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Transformed Biological Gibbs Energies and Apparent Equilibrium Constants
The transformed Gibbs energies in Section 18.12 are a convenient method to handle biological reactions but the details were not discussed earlier. The transformation of Gibbs energy to a field of buffered pH is analogous to the other Legendre transforms used previously. To obtain Gibbs energy from internal energy, starting from dU = TdS – PdV, we introduced G = U – TS + PV, resulting in a potential where T and P are the…
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Biological Reactions
Oxidation States and Degree of Reduction Oxidation states, introduced in Section 18.11, provide an important balance condition for any chemical process, but particularly for biochemical reactions and fermentations. Recall that glucose oxidation to CO2 and H2O is an important energy-generating reaction in eurakyrotic cells to permit synthesis reactions. The oxidation of glucose or other foodstuffs provides electrons…