Extensive thermodynamic properties defined

If M represents the molar value of any extensive thermodynamic property, an excess property is defined as the difference between the actual property value of a solution and the value it would have as an ideal solution at the same temperature, pressure, and composition. Thus,... 

This equation defines the partial molar volume of species i in solution. It is simply the volumetric response of the system to the addition at constant T and P of a differential amount of species i A partial molar property may be defined in like fashion for each extensive thermodynamic property. Letting M represent the molar value of such a property, we write the general defining equation for a partial molar property as... 

A curious example is that of the distribution of benzene in water benzene will initially spread on water, then as the water becomes saturated with benzene, it will round up into lenses. Virtually all of the thermodynamics of a system will be affected by the presence of the surface. A system containing a surface may be considered as being made up of three parts two bulk phases and the interface separating them. Any extensive thermodynamic property will be apportioned among these parts. For example, in a two-phase multicomponent system, the extra amount of an i component that can be accom-mondated in the system due to the presence of the interface ( ) may be expressed as Qi Qii where is the total number of molecules of i in the whole system, Vj and Vjj are the volumes of phases I and II, respectively, and Q and Qn are the concentrations of i in phases I and II, respectively. The surface (excess) concentration of i is defined as Fj = A, where A is the surface area. At equilibrium, the chemical potential of any component is the same in each bulk phase and at the surface. The Gibbs adsorption equation, which is one of the most widely used expression in surface and colloid science is shown in Eq. (2) ... 

All extensive thermodynamic properties Z (volume, enthalpy, entropy, Gibbs energy, heat capacity) when defined as functions of the set of the variables p, T, and, ... 

From these equations it may be seen that four independent variables are required to define each extensive thermodynamic property, whereas in normal three-dimensional thermodynamics only three variables are required for a single-component system. The additional variable is of course the total surface area or quantity of adsorbent over which the moles of sorbate are distributed. 

The thermodynamic analysis of solutions is facilitated by the introduction of quantities that measure how the extensive thermodynamic quantities (V, E, H, G,. ..) of the system depend on the state variables T, P, and nj. This leads to the definition of partial molar quantities where, if we let Y be any extensive thermodynamic property, we can define the partial molar value of Y for the ith component as ... 

Before describing these thermodynamic variables, we must talk about their properties. The variables are classified as intensive or extensive. Extensive variables depend upon the amount while intensive variables do not. Density is an example of an intensive variable. The density of an ice crystal in an iceberg is the same as the density of the entire iceberg. Volume, on the other hand, is an extensive variable. The volume of the ocean is very different from the volume of a drop of sea water. When we talk about an extensive thermodynamic variable Z we must be careful to specify the amount. This is usually done in terms of the molar property Zm, defined as... 

Students often ask, What is enthalpy The answer is simple. Enthalpy is a mathematical function defined in terms of fundamental thermodynamic properties as H = U+pV. This combination occurs frequently in thermodynamic equations and it is convenient to write it as a single symbol. We will show later that it does have the useful property that in a constant pressure process in which only pressure-volume work is involved, the change in enthalpy AH is equal to the heat q that flows in or out of a system during a thermodynamic process. This equality is convenient since it provides a way to calculate q. Heat flow is not a state function and is often not easy to calculate. In the next chapter, we will make calculations that demonstrate this path dependence. On the other hand, since H is a function of extensive state variables it must also be an extensive state variable, and dH = 0. As a result, AH is the same regardless of the path or series of steps followed in getting from the initial to final state and... 

The most important new concept to come from thermodynamics is entropy. Like volume, internal energy and mole number it is an extensive property of a system and together with these, and other variables it defines an elegant self-consistent theory. However, there is one important difference entropy is the only one of the extensive thermodynamic functions that has no obvious physical interpretation. It is only through statistical integration of the mechanical behaviour of microsystems that a property of the average macrosystem, that resembles the entropy function, emerges. 

The inequalities of the previous paragraph are extremely important, but they are of little direct use to experimenters because there is no convenient way to hold U and S constant except in isolated systems and adiabatic processes. In both of these inequalities, the independent variables (the properties that are held constant) are all extensive variables. There is just one way to define thermodynamic properties that provide criteria of spontaneous change and equilibrium when intensive variables are held constant, and that is by the use of Legendre transforms. That can be illustrated here with equation 2.2-1, but a more complete discussion of Legendre transforms is given in Section 2.5. Since laboratory experiments are usually carried out at constant pressure, rather than constant volume, a new thermodynamic potential, the enthalpy H, can be defined by... 

Pressure, volume, temperature, and number of moles are thermodynamic properties or thermodynamic variables of a system—in this case, a gas sample. Their values are measured by experimenters using thermometers, pressure gauges, and other instruments located outside the system. The properties are of two types those that increase proportionally with the size of the system, such as n and K called extensive properties, and those defined for each small region in the system, such as P and T, called intensive properties. Terms that are added together or are on opposite sides of an equal sign must contain the same number of... 

All the above three provide extensive data sources and simulators for estimating various thermodynamic properties of pure compounds, well-defined mixtures and petroleum fluids. The respective manuals describe in detail various methods used for estimating the properties and their limitations while at the same time providing the user with choices. The Aspen Physical Property System and SUPBRTRAPP can also be used to estimate thermodynamic profrerties using the pseudo-component characterization of petroleum fluids. The reader is referred to the respective manuals/sim-ulators for details. 

Recent years have seen the extensive application of computer simulation techniques to the study of condensed phases of matter. The two techniques of major importance are the Monte Carlo method and the method of molecular dynamics. Monte Carlo methods are ways of evaluating the partition function of a many-particle system through sampling the multidimensional integral that defines it, and can be used only for the study of equilibrium quantities such as thermodynamic properties and average local structure. Molecular dynamics methods solve Newton s classical equations of motion for a system of particles placed in a box with periodic boundary conditions, and can be used to study both equilibrium and nonequilibrium properties such as time correlation functions. 

Various chemical surface complexation models have been developed to describe potentiometric titration and metal adsorption data at the oxide—mineral solution interface. Surface complexation models provide molecular descriptions of metal adsorption using an equilibrium approach that defines surface species, chemical reactions, mass balances, and charge balances. Thermodynamic properties such as solid-phase activity coefficients and equilibrium constants are calculated mathematically. The major advancement of the chemical surface complexation models is consideration of charge on both the adsorbate metal ion and the adsorbent surface. In addition, these models can provide insight into the stoichiometry and reactivity of adsorbed species. Application of these models to reference oxide minerals has been extensive, but their use in describing ion adsorption by clay minerals, organic materials, and soils has been more limited. 

We could now institute an extensive search of possible thermodynamic functions in the hope of finding a function that is a state variable and also has the property that its rate of internal generation is a positive quantity. Instead, we will just introduce this new thermodynamic property by its definition and then show that the property so defined has the desired characteristics. 

These residual properties are defined only for those thermodynamic properties F that can be made extensive ... 

The set of all the thermodynamic properties of a multiparticle system including its temperature, pressure, volume and internal energy is defined as the thermodynamic state of this system. An important aspect of the relationships between thermod5mamic properties in a large, macroscopic and also known as extensive system is the question of how many different thermodynamic properties of a given system are independently variable. The number of these represents the smallest number of properties, which must be specified in order to completely determine the entire thermodynamic state of the system. 

Phases in thermodynamic systems are then macroscopic homogeneous parts with distinct physical properties. For example, densities of extensive thermodynamical variables, such as particle number N of the fth species, enthalpy U, volume V, entropy S, and possible order parameters, such as the nematic order parameter for a liquid crystalline polymer etc, differ in such coexisting phases. In equilibrium, intensive thermodynamic variables, namely T,p, and the chemical potentials pi have to be the same in all phases. Coexisting phases are separated by well-defined interfaces (the width and internal structure of such interfaces play an important role in the kinetics of the phase transformation (1) and in other... 

This donor number scale is widely referenced in relation to thermodynamic properties, as well as electron-transfer kinetics and photochemical properties. It has been criticized because of the neglect of solvent effects and side reactions that contribute to and because a one-parameter scale can never be entirely adequate. Ambiguities can arise for solvents which have more than one donor site, such as the formamide and sulfoxide derivatives. Recent measurements with BFj as the acid have provided some points of comparison and criticism for the original donor numbers. Recently, Linert et al. have used the solvatochromic shifts of a Cu(II) complex to define donor numbers for anions in dichloromethane. They also have suggested how these values can be converted for use in other solvents through a correlation with the acceptor number of the solvent. Linert et al. have reviewed the area and provided an extensive compilation of donor numbers from calorimetric and solvatochromic shift measurements. Some anion donor numbers in dichloromethane are included in Table 3.4, and the values for anions in water are 21 kcal moH smaller than those given. 

The state of a system represents the condition of the system as defined by the properties. Properties are macroscopic quantities that are perceived by our senses and can be measured by instruments. A quantity is defined as the property if it depends only on the state of fhe system and independent of the process by which it has reached at the state. Some of the common thermodynamic properties are pressure, temperature, mass, volume, and energy. Properties are also classified as infensive and exfensive. Infensive properties are independent of fhe mass of fhe system and a few examples of this include pressure, temperature, specific volume, specific enthalpy, and specific entropy. Extensive properties depend on the mass of the system. All properties of a system at a given state are fixed. For a system that involves only one mode of work, fwo independent properties are essential to define the thermodynamic state of fhe system and the rest of the thermodynamic properties can be determined on the basis of fhe fwo known independent properties and using thermodynamic relations. For example, if pressure and temperature of a system are known, the state of fhe system is then defined. All other properties such as specific volume, enthalpy, internal energy, and entropy can be determined through the equation of state and thermodynamic relations. 

We can express the use of all the different units in evolution in the language of thermodynamics. While the genome is defined by a DNA sequence so that each base has a singular intensive property as in a computer code of symbols, by way of contrast, the protein content of a cell is an extensive property being concentration dependent and therefore varies under circumstances such as temperature and pressure although... 

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