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The term molality is formed in analogy to molarity which is the molar concentration of a solution. The earliest known use of the intensive property molality and of its adjectival unit, the now-deprecated molal, appears to have been published by G. N. Lewis and M. Randall in the 1923 publication of Thermodynamics and the Free Energies of Chemical Substances. [3]
The relative activity of a species i, denoted a i, is defined [4] [5] as: = where μ i is the (molar) chemical potential of the species i under the conditions of interest, μ o i is the (molar) chemical potential of that species under some defined set of standard conditions, R is the gas constant, T is the thermodynamic temperature and e is the exponential constant.
Molar concentration or molarity is most commonly expressed in units of moles of solute per litre of solution. [1] For use in broader applications, it is defined as amount of substance of solute per unit volume of solution, or per unit volume available to the species, represented by lowercase c {\displaystyle c} : [ 2 ]
In thermodynamics, the ebullioscopic constant K b relates molality b to boiling point elevation. [1] It is the ratio of the latter to the former: = i is the van 't Hoff factor, the number of particles the solute splits into or forms when dissolved. b is the molality of the solution.
By dividing this relation to the molar amount of one component a relation between the apparent molar property of a component and the mixing ratio of components can be obtained. This equation serves as the definition of ~ . The first term is equal to the volume of the same quantity of solvent with no solute, and the second term is the ...
Here K f is the cryoscopic constant (equal to 1.86 °C kg/mol for the freezing point of water), i is the van 't Hoff factor, and m the molality (in mol/kg). This predicts the melting of ice by road salt. In the liquid solution, the solvent is diluted by the addition of a solute, so that fewer molecules are available to freeze.
The van 't Hoff factor i (named after Dutch chemist Jacobus Henricus van 't Hoff) is a measure of the effect of a solute on colligative properties such as osmotic pressure, relative lowering in vapor pressure, boiling-point elevation and freezing-point depression.
For liquid solutions, the osmotic coefficient is often used to calculate the salt activity coefficient from the solvent activity, or vice versa. For example, freezing point depression measurements, or measurements of deviations from ideality for other colligative properties, allows calculation of the salt activity coefficient through the osmotic coefficient.