Enthalpy of mixingIn thermodynamics, the enthalpy of mixing (also heat of mixing and excess enthalpy) is the enthalpy liberated or absorbed from a substance upon mixing. When a substance or compound is combined with any other substance or compound, the enthalpy of mixing is the consequence of the new interactions between the two substances or compounds. This enthalpy, if released exothermically, can in an extreme case cause an explosion. Enthalpy of mixing can often be ignored in calculations for mixtures where other heat terms exist, or in cases where the mixture is ideal.
Determination of equilibrium constantsEquilibrium constants are determined in order to quantify chemical equilibria. When an equilibrium constant K is expressed as a concentration quotient, it is implied that the activity quotient is constant. For this assumption to be valid, equilibrium constants must be determined in a medium of relatively high ionic strength. Where this is not possible, consideration should be given to possible activity variation. The equilibrium expression above is a function of the concentrations [A], [B] etc.
Thermodynamic activityIn chemical thermodynamics, activity (symbol a) is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on concentration for an ideal solution. The term "activity" in this sense was coined by the American chemist Gilbert N. Lewis in 1907. By convention, activity is treated as a dimensionless quantity, although its value depends on customary choices of standard state for the species.
Apparent molar propertyIn thermodynamics, an apparent molar property of a solution component in a mixture or solution is a quantity defined with the purpose of isolating the contribution of each component to the non-ideality of the mixture. It shows the change in the corresponding solution property (for example, volume) per mole of that component added, when all of that component is added to the solution. It is described as apparent because it appears to represent the molar property of that component in solution, provided that the properties of the other solution components are assumed to remain constant during the addition.
Pitzer equationsPitzer equations are important for the understanding of the behaviour of ions dissolved in natural waters such as rivers, lakes and sea-water. They were first described by physical chemist Kenneth Pitzer. The parameters of the Pitzer equations are linear combinations of parameters, of a virial expansion of the excess Gibbs free energy, which characterise interactions amongst ions and solvent. The derivation is thermodynamically rigorous at a given level of expansion.
Equilibrium constantThe equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture.
FugacityIn chemical thermodynamics, the fugacity of a real gas is an effective partial pressure which replaces the mechanical partial pressure in an accurate computation of chemical equilibrium. It is equal to the pressure of an ideal gas which has the same temperature and molar Gibbs free energy as the real gas. Fugacities are determined experimentally or estimated from various models such as a Van der Waals gas that are closer to reality than an ideal gas. The real gas pressure and fugacity are related through the dimensionless fugacity coefficient φ.
Raoult's lawRaoult's law (ˈrɑːuːlz law) is a relation of physical chemistry, with implications in thermodynamics. Proposed by French chemist François-Marie Raoult in 1887, it states that the partial pressure of each component of an ideal mixture of liquids is equal to the vapor pressure of the pure component (liquid or solid) multiplied by its mole fraction in the mixture. In consequence, the relative lowering of vapor pressure of a dilute solution of nonvolatile solute is equal to the mole fraction of solute in the solution.
Ideal solutionIn chemistry, an ideal solution or ideal mixture is a solution that exhibits thermodynamic properties analogous to those of a mixture of ideal gases. The enthalpy of mixing is zero as is the volume change on mixing by definition; the closer to zero the enthalpy of mixing is, the more "ideal" the behavior of the solution becomes. The vapor pressures of the solvent and solute obey Raoult's law and Henry's law, respectively, and the activity coefficient (which measures deviation from ideality) is equal to one for each component.
Colligative propertiesIn chemistry, colligative properties are those properties of solutions that depend on the ratio of the number of solute particles to the number of solvent particles in a solution, and not on the nature of the chemical species present.McQuarrie, Donald, et al. Colligative properties of Solutions" General Chemistry Mill Valley: Library of Congress, 2011. . The number ratio can be related to the various units for concentration of a solution such as molarity, molality, normality (chemistry), etc.
