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Van Laar Equation
The Van Laar equation is a thermodynamic activity model, which was developed by Johannes van Laar in 1910-1913, to describe phase equilibria of liquid mixtures. The equation was derived from the Van der Waals equation. The original van der Waals parameters didn't give good description of vapor-liquid equilibria of phases, which forced the user to fit the parameters to experimental results. Because of this, the model lost the connection to molecular properties, and therefore it has to be regarded as an empirical model to correlate experimental results. Equations Van Laar derived the excess enthalpy from the van der Waals equation: : H^= \frac \left( \frac- \frac \right)^2 In here ''a''i and ''b''i are the van der Waals parameters for attraction and excluded volume of component i. He used the conventional quadratic mixing rule for the energy parameter ''a'' and the linear mixing rule for the size parameter ''b.'' Since these parameters didn't lead to good phase equilibrium desc ...
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Thermodynamic Activity
In chemical thermodynamics, activity (symbol ) 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. The activity of pure substances in condensed phases (solid or liquids) is normally taken as unity (the number 1). Activity depends on temperature, pressure and composition of the mixture, among other things. For gases, the activity is the effective partial pressure, and is usually referred to as fugacity. The difference between activity and other measures of concentration arises because the interactions between different types of molecules in non-ideal gas ...
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Johannes Van Laar
Johannes van Laar (10 July 1860 in The Hague – 9 December 1938 in Montreux) was a Dutch chemist who is best known for the equations regarding chemical activity (Van Laar equation). Biography Van Laar lost his parents early, his mother in 1862 and his father 1873. From that point on his uncle N. A. Rost van Tonningen was responsible for him. He finished school in 1876 and joined the Royal Naval Institute at Willemsoord. After several trips on steam ships and reaching the rank of a sub-lieutenant he asked for discharge when he became of age. Van Laar started his studies of physics, chemistry and mathematics at the University of Amsterdam in 1891. Johannes van der Waals, and Jacobus Henricus van 't Hoff both were professors at that University in that time. His education deprived him from obtaining a Ph.D. and therefore a career at a Dutch University was nearly impossible. After being a teacher at a middle school he became unsalaried lecturer at the University of Amsterdam 1898 a ...
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Phase Equilibria
In thermodynamics, the phase rule is a general principle governing "pVT" systems, whose thermodynamic states are completely described by the variables pressure (), volume () and temperature (), in thermodynamic equilibrium. If is the number of degrees of freedom, is the number of components and is the number of phases, then :F = C - P + 2 It was derived by American physicist Josiah Willard Gibbs in his landmark paper titled ''On the Equilibrium of Heterogeneous Substances'', published in parts between 1875 and 1878. The rule assumes the components do not react with each other. The number of degrees of freedom is the number of independent intensive variables, i.e. the largest number of thermodynamic parameters such as temperature or pressure that can be varied simultaneously and arbitrarily without determining one another. An example of one-component system is a system involving one pure chemical, while two-component systems, such as mixtures of water and ethanol, have two che ...
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Van Der Waals Equation
In chemistry and thermodynamics, the Van der Waals equation (or Van der Waals equation of state) is an equation of state which extends the ideal gas law to include the effects of interaction between molecules of a gas, as well as accounting for the finite size of the molecules. The ideal gas law treats gas molecules as point particles that interact with their containers but not each other, meaning they neither take up space nor change kinetic energy during collisions (i.e. all collisions are perfectly elastic). The ideal gas law states that the volume ''V'' occupied by ''n'' moles of any gas has a pressure ''P'' at temperature ''T'' given by the following relationship, where ''R'' is the gas constant: :PV=nRT To account for the volume occupied by real gas molecules, the Van der Waals equation replaces V/n in the ideal gas law with (V_m-b), where ''Vm'' is the molar volume of the gas and ''b'' is the volume occupied by the molecules of one mole: :P(V_m - b)=R T The second m ...
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Enthalpy
Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant pressure, which is conveniently provided by the large ambient atmosphere. The pressure–volume term expresses the work required to establish the system's physical dimensions, i.e. to make room for it by displacing its surroundings. The pressure-volume term is very small for solids and liquids at common conditions, and fairly small for gases. Therefore, enthalpy is a stand-in for energy in chemical systems; bond, lattice, solvation and other "energies" in chemistry are actually enthalpy differences. As a state function, enthalpy depends only on the final configuration of internal energy, pressure, and volume, not on the path taken to achieve it. In the International System of Units (SI), the unit of measurement for enthalpy is the joule. ...
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Vapor–liquid Equilibrium
In thermodynamics and chemical engineering, the vapor–liquid equilibrium (VLE) describes the distribution of a chemical species between the vapor phase and a liquid phase. The concentration of a vapor in contact with its liquid, especially at equilibrium, is often expressed in terms of vapor pressure, which will be a partial pressure (a part of the total gas pressure) if any other gas(es) are present with the vapor. The equilibrium vapor pressure of a liquid is in general strongly dependent on temperature. At vapor–liquid equilibrium, a liquid with individual components in certain concentrations will have an equilibrium vapor in which the concentrations or partial pressures of the vapor components have certain values depending on all of the liquid component concentrations and the temperature. The converse is also true: if a vapor with components at certain concentrations or partial pressures is in vapor–liquid equilibrium with its liquid, then the component concentration ...
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Activity Coefficient
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. Deviations from ideality are accommodated by modifying the concentration by an ''activity coefficient''. Analogously, expressions involving gases can be adjusted for non-ideality by scaling partial pressures by a fugacity coefficient. The concept of activity coefficient is closely linked to that of activity in chemistry. Thermodynamic definition The chemical potential, \mu_\mathrm, of a substance B in an ideal mixture of liquids or an ideal solution is given by :\mu_ ...
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Ideal Mixture
In 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. The concept of an ideal solution is fundamental to chemical thermodynamics and its applications, such as the explanation of colligative properties. Physical origin Ideality of solutions is analogous to ideality for gases, with the important difference that intermolecular interactions in liquids are strong and cannot simply be neglected as they can for ideal gases. Instead we assume that the mean strength of the interactions are the same between all the ...
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