In 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. The sign convention is the same as for enthalpy of reaction: when the enthalpy of mixing is positive, mixing is endothermic, while negative enthalpy of mixing signifies exothermic mixing. In ideal mixtures, the enthalpy of mixing is null. In non-ideal mixtures, the thermodynamic activity of each component is different from its concentration by multiplying with the activity coefficient.
One approximation for calculating the heat of mixing is Flory–Huggins solution theory for polymer solutions.
For a liquid, enthalpy of mixing can be defined as follows
Where:
H(mixture) is the total enthalpy of the system after mixing
ΔHmix is the enthalpy of mixing
xi is the mole fraction of component i in the system
Hi is the enthalpy of pure i
Enthalpy of mixing can also be defined using Gibbs free energy of mixing
However, Gibbs free energy of mixing and entropy of mixing tend to be more difficult to determine experimentally. As such, enthalpy of mixing tends to be determined experimentally in order to calculate entropy of mixing, rather than the reverse.
Enthalpy of mixing is defined exclusively for the continuum regime, which excludes molecular-scale effects (However, first-principles calculations have been made for some metal-alloy systems such as Al-Co-Cr or β-Ti).
When two substances are mixed the resulting enthalpy is not an addition of the pure component enthalpies, unless the substances form an ideal mixture. The interactions between each set of molecules determines the final change in enthalpy.
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In thermodynamics, an activity coefficient is a factor used to account for deviation of a mixture of chemical substances from ideal behaviour. In an ideal mixture, the microscopic interactions between each pair of chemical species are the same (or macroscopically equivalent, the enthalpy change of solution and volume variation in mixing is zero) and, as a result, properties of the mixtures can be expressed directly in terms of simple concentrations or partial pressures of the substances present e.g. Raoult's law.
En thermodynamique, une grandeur molaire partielle quantifie l'évolution d'une grandeur extensive d'un système thermodynamique en fonction de l'évolution de la quantité de l'un de ses constituants. La grandeur molaire partielle, notée , d'un corps dans un mélange est définie par la dérivée partielle de la grandeur extensive totale du mélange par rapport à la quantité (nombre de moles) du corps , à pression , température et quantités des autres composants du mélange constantes : La grandeur molaire partielle d'un corps dans un mélange représente la contribution du corps à la grandeur totale du mélange : celle-ci est en effet reliée aux grandeurs molaires partielles de tous les constituants du mélange par le théorème d'Euler.
In chemistry, a regular solution is a solution whose entropy of mixing is equal to that of an ideal solution with the same composition, but is non-ideal due to a nonzero enthalpy of mixing. Such a solution is formed by random mixing of components of similar molar volume and without strong specific interactions, and its behavior diverges from that of an ideal solution by showing phase separation at intermediate compositions and temperatures (a miscibility gap).
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