Solid, standard state

The standard state of a substance in a condensed phase is the real liquid or solid at 1 atm and T. 

The values of the thermodynamic properties of the pure substances given in these tables are, for the substances in their standard states, defined as follows For a pure solid or liquid, the standard state is the substance in the condensed phase under a pressure of 1 atm (101 325 Pa). For a gas, the standard state is the hypothetical ideal gas at unit fugacity, in which state the enthalpy is that of the real gas at the same temperature and at zero pressure. 

The first term, AG°, is the change in Gibb s free energy under standard-state conditions defined as a temperature of 298 K, all gases with partial pressures of 1 atm, all solids and liquids pure, and all solutes present with 1 M concentrations. The second term, which includes the reaction quotient, Q, accounts for nonstandard-state pressures or concentrations. Eor reaction 6.1 the reaction quotient is... 

II The increment in the free energy, AF, in the reaction of forming the given substance in its standard state from its elements in their standard states. The standard states are for a gas, fugacity (approximately equal to the pressure) of 1 atm for a pure liquid or solid, the substance at a pressure of 1 atm for a substance in aqueous solution, the hyj)othetical solution of unit molahty, which has all the properties of the infinitely dilute solution except the property of concentration. 

For species present as gases in the actual reac tive system, the standard state is the pure ideal gas at pressure P°. For liquids and solids, it is usually the state of pure real liquid or solid at P°. The standard-state pressure P° is fixed at 100 kPa. Note that the standard states may represent different physical states for different species any or all of the species may be gases, liquids, or solids. 

But that is not all. For dilute solutions, the solvent concentration is high (55 mol kg ) for pure water, and does not vary significantly unless the solute is fairly concentrated. It is therefore common practice and fully justified to use unit mole fraction as the standard state for the solvent. The standard state of a close up pure solid in an electrochemical reaction is similarly treated as unit mole fraction (sometimes referred to as the pure component) this includes metals, solid oxides etc. 

In defining the activity through equations (6.83) and (6.84), we have made no restrictions on the choice of a standard state except to note that specification of temperature is not a part of the standard state condition. We are free to choose standard states in whatever manner we desire.p However, choices are usually made that are convenient and simplify calculations involving activities. The usual choices differ for a gas, pure solid or liquid, and solvent or solute in solution. We will now summarize these choices of standard states and indicate the reasons. Before doing so, we note that activities for a substance with different choices of standard states are proportional to one another. This can be seen as follows With a particular choice of standard state... 

Standard States for Pure Solids and Pure Liquids For condensed phases, the pure solid or liquid under 1 bar (100 kPa) external pressure is usually chosen as the standard state. With this choice, the standard state fugacity is given by... 

Standard State of a Solvent in a Mixture The usual choice of a standard state for a solvent in a solution is the pure solvent at a pressure of 1 bar, the same convention as for a pure solid or liquid. Thus,u... 

We now have the foundation for applying thermodynamics to chemical processes. We have defined the potential that moves mass in a chemical process and have developed the criteria for spontaneity and for equilibrium in terms of this chemical potential. We have defined fugacity and activity in terms of the chemical potential and have derived the equations for determining the effect of pressure and temperature on the fugacity and activity. Finally, we have introduced the concept of a standard state, have described the usual choices of standard states for pure substances (solids, liquids, or gases) and for components in solution, and have seen how these choices of standard states reduce the activity to pressure in gaseous systems in the limits of low pressure, to concentration (mole fraction or molality) in solutions in the limit of low concentration of solute, and to a value near unity for pure solids or pure liquids at pressures near ambient. 

With the choice of a pure substance standard state for the solid, and a strong electrolyte standard state for the dissolved AgCl, we get... 

A note on good practice Recall that the standard state of a pure substance is its pure form at a pressure of 1 bar (Section 6.15). For a solute, the standard state is for a concentration of 1 mol-L 1. Pure solids and liquids may always be regarded as being in their standard states provided the pressure is close to 1 bar. 

In this expression, E° is the standard emf of the cell, the emf measured when all the species taking part are in their standard states. In practice, this condition means that all gases are at 1 bar, all participating solutes are at 1 molT-1, and all liquids and solids are pure. For example, to measure the standard emf of the Daniell cell, we use 1 M CuS04(aq) and a pure copper electrode in one electrode compartment and 1 M ZnS04(aq) and a pure zinc electrode in the other. 

In the reaction shown above, the volume of the reaction products (2 mol CO) is seen to be much greater than that of the reactants (2 mol of solid carbon plus 1 mol of oxygen). The effect of pressure on the free energy of formation of an oxide associated with an increase in the number of gas molecules which is representative of the type of reaction in the present illustration is shown in Figure 4.2 (A). Applying the criterion of volume increase per mole accompanying reaction at standard state to the case of metal oxidation such as... 

Low Resolution Nuclear Magnetic Resonance (LR-NMR) systems are routinely used for food quality assurance in laboratory settings [25]. NMR based techniques are standardized and approved by the American Oil Chemist s Society (AOCS) (AOCSd 16b-93, AOCS AK 4-95), the International Union of Pure and Applied Chemistry (IUPAC) (solid fat content, IUPAC Norm 2.150) and the International Standards Organization (ISO) (oil seeds, ISO Dis/10565, ISO CD 10632). In addition to these standardized tests, low resolution NMR is used to measure moisture content, oil content and the state (solid or liquid) of fats in food. Table 4.7.1 summarizes common food products that are analyzed by low-resolution NMR for component concentration. 

For a heterogeneous reaction, the state of all components is not uniform, for example, a reaction between a gas and a liquid. This requires standard states to be defined for each component. The activity of a solid in the equilibrium constant can be taken to be unity. 

The effect of pressure on AG° and AH0 depends on the choice of standard states employed. When the standard state of each component of the reaction system is taken at 1 atm pressure, whether the species in question is a gas, liquid, or solid, the values of AG° and AH0 refer to a process that starts and ends at 1 atm. For this choice of standard states, the values of AG° and AH0 are independent of the system pressure at which the reaction is actually carried out. It is important to note in this connection that we are calculating the enthalpy change for a hypothetical process, not for the actual process as it occurs in nature. This choice of standard states at 1 atm pressure is the convention that is customarily adopted in the analysis of chemical reaction equilibria. 

The fundamental fact on which the analysis of heterogeneous reactions is based is that when a component is present as a pure liquid or as a pure solid, its activity may be taken as unity, provided the pressure on the system does not differ very much from the chosen standard state pressure. At very high pressures, the effect of pressure on solid or liquid activity may be determined using the Poynting correction factor. 

When the standard states for the solid and liquid species correspond to the pure species at 1 atm pressure or at a low equilibrium vapor pressure of the condensed phase, the activities of the pure species at equilibrium are taken as unity at all moderate pressures. Consequently, the gas phase composition at equilibrium will not be... 

The equilibrium constants are based on a standard state of unit fugacity for the gaseous species and on a standard state corresponding to the pure solid for carbon. 

The thermodynamic standard state of a substance is its most stable state under standard pressure (1 atm) and at some specific temperature (usually 25°C). Thermodynamic refers to the observation, measurement and prediction of energy changes that accompany physical changes or chemical reaction. Standard refers to the set conditions of 1 atm pressure and 25°C. The state of a substance is its phase gas, liquid or solid. Substance is any kind of matter all specimens of which have the same chemical composition and physical properties. 

Figure 3.8 The molar Gibbs energy of mixing of molten Fe-Ni at 1850 K using both the Raoultian (solid line) and Henrian (dashed line) standard states for Ni as defined in Figure 3.7. The Raoultian standard state is used for Fe. Data are taken from reference [3].

Figure 3.12 The integral molar Gibbs energy of liquid Ge-Si at 1500 K with pure liquid Ge and solid Si as standard states. Data are taken from reference [4].

The activity of a solid The activity of a pure solid in its standard state is unity, so the activity of pure copper or of zinc metal electrodes is one. We write this as a(cU) or a,zn, = 1. 

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