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7: Mixtures and Solutions

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  • Up until this point, we have conserved single-component systems which do not change in composition. By and large, nature consists of much more complicated systems, containing many components and continually undergoing changes in composition through phase changes or chemical reactions or both! In order to expand our thermodynamic toolbox, we will begin by discussing mixtures.

    • 7.1: Thermodynamics of Mixing
      A natural place to begin a discussion of mixtures is to consider a mixture of two gases.
    • 7.2: Partial Molar Volume
      he partial molar volume of compound A in a mixture of A and B can be defined using the total differential of V.
    • 7.3: Chemical Potential
      The chemical potential tells how the Gibbs function will change as the composition of the mixture changes. And since systems tend to seek a minimum aggregate Gibbs function, the chemical potential will point to the direction the system can move in order to reduce the total Gibbs function.
    • 7.4: The Gibbs-Duhem Equation
      The Gibbs-Duhem equation relates how the chemical potential can change for a given composition while the system maintains equilibrium. So for a binary system, consisting of components A and B (the two most often studied compounds in all of chemistry)
    • 7.5: Non-ideality in Gases - Fugacity
      The relationship for chemical potential was derived assuming ideal gas behavior. But for real gases that deviate widely from ideal behavior, the expression has only limited applicability. In order to use the simple expression on real gases, a “fudge” factor is introduced called fugacity. Fugacity is used instead of pressure.
    • 7.6: Colligative Properties
      Colligative properties are important properties of solutions as they describe how the properties of the solvent will change as solute (or solutes) is (are) added.
    • 7.7: Solubility
      The maximum solubility of a solute can be determined using the same methods we have used to describe colligative properties. If this chemical potential is lower than that of a pure solid solute, the solute will dissolve into the liquid solvent (in order to achieve a lower chemical potential!) So the point of saturation is reached when the chemical potential of the solute in the solution is equal to that of the pure solid solute.
    • 7.8: Non-ideality in Solutions - Activity
      The bulk of the discussion in this chapter dealt with ideal solutions. However, real solutions will deviate from this kind of behavior. So much as in the case of gases, where fugacity was introduced to allow us to use the ideal models, activity is used to allow for the deviation of real solutes from limiting ideal behavior.
    • 7.E: Mixtures and Solutions (Exercises)
      Exercises for Chapter 7 "Mixtures and Solutions" in Fleming's Physical Chemistry Textmap.
    • 7.S: Mixtures and Solutions (Summary)
      Summary for Chapter 7 "Mixtures and Solutions" in Fleming's Physical Chemistry Textmap.

    Contributors and Attributions

    • Patrick E. Fleming (Department of Chemistry and Biochemistry; California State University, East Bay)