Choice of standards

For temperature ranges where no metal transitions are appropriate other materials may be used as reference materials. These may not be certified materials but may be the best available. Use fresh materials of as high purity as possible. 

These materials have a certificate giving values obtained after the material has been tested by a range of certified laboratories. This is not necessarily a certificate of purity but they are regarded as the ultimate in reference materials. They can be obtained from Lab of the Government Chemist [4]. Other materials may, for example, possess a certificate of high purity allowing use of theoretical melting and heat of fusion values. These types of materials are termed reference materials and are also widely accepted. 

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Equilibrium constants for protein-small molecule association usually are easily measured with good accuracy it is normal for standard free energies to be known to within 0.5 kcal/mol. Standard conditions define temperature, pressure and unit concentration of each of the three reacting species. It is to be expected that the standard free energy difference depends on temperature, pressure and solvent composition AA°a also depends on an arbitrary choice of standard unit concentrations. 

The uptake, in column 10, has been converted into a liquid volume at the outset rather than at a later stage as in the original papers. Columns 1-8 are based on Table 3.2. In the original papers the values of p/p° corresponded to actual points on the experimental isotherm, but the work sheet is much simplified by the choice of standard intervals of pjp° (or of r " cf. p. 135). 

The numerical values of AG and A5 depend upon the choice of standard states in solution kinetics the molar concentration scale is usually used. Notice (Eq. 5-43) that in transition state theory the temperature dependence of the rate constant is accounted for principally by the temperature dependence of an equilibrium constant. 

The problem has been recognized by many of the developers concerned, who have consequently themselves adopted the environmental standards of other industrialized nations. In the absence of national controls this is a responsible and laudable approach. However, the piecemeal adoption of standards taken from elsewhere does not take account of local conditions. These conditions may either enhance or limit the ability of the environment to disperse and attenuate or assimilate pollutants (e.g. the occurrence of temperature inversions will limit the dispersion of air pollutants). Similarly, the use to which local resources are put may demand particularly high standards of environmental quality (e.g. the use of sea water or river water as the basis of potable water supply). The choice of standards must also take into account local practices and existing local administration. 

Activity can be thought of as the quantity that corrects the chemical potential at some pressure and/or composition condition" to a standard or reference state. The concept of a standard state is an important one in thermodynamics. The choice of the pressure and composition conditions for the standard state are completely arbitrary, and unusual choices are sometimes made. The common choices are those of convenience. In the next section, we will describe and summarize the usual choices of standard states. But, first, we want to describe the effect of pressure and temperature on a,. 

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... 

Activity is a dimensionless quantity, and / must be expressed in kPa with this choice of standard state. It is inconvenient to carry f° = 100 kPa through calculations involving activity of gases. Choosing the standard state for a gas as we have described above creates a situation where SI units are not convenient. Instead of expressing the standard state as /° = 100 kPa, we often express the pressure and fugacity in bars, since 1 bar = 100 kPa. In this case, /0 — 1 bar, and equation (6.92) becomes4... 

Later, we will make equilibrium calculations that involve activities, and we will see why it is convenient to choose the ideal gas as a part of the standard state condition, even though it is a hypothetical state/ With this choice of standard state, equations (6.94) and (6.95) allow us to use pressures, corrected for non-ideality, for activities as we make equilibrium calculations for real gases.s... 

In summary, the usual choice of standard states and the implications of these choices are shown in Table 6.1. 

For electrolytes where dissociation is extensive, but not complete, the classification is somewhat arbitrary, and the electrolyte can be considered to be either strong or weak. Thermodynamics does not prevent us from treating an electrolyte either way, but we must be careful to designate our assignment because the choice of standard state is different for a strong electrolyte and a weak electrolyte. Assuming that an electrolyte is weak requires that we have some nonthermodynamic procedure for distinguishing clearly between the dissociated and undissociated species. For example, Raman spectroscopy... 

With the choice of standard states used in Table 7.2, Hf = H°. Making this substitution and adding and subtracting n2H°2 gives... 

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 these choices of standard states, our examples become (with r/H o = 1) Kw = aH + a0u- —... 

With our choice of standard states and the low pressure involved, we can write... 

This last example provides a demonstration of the flexibility inherent in the choice of standard states. A strong electrolyte standard state is chosen for NaA(aq) and NaCl(aq) so that... 

Injection (GC) 258 interface (LC/GC) 801 Retention index system (GC) 176 choice of standards 181 isothermal 176... 

The design of an assay is, in large measure, prospective quality assurance. The factors that are likely to affect the results of the assay must be defined and controlled to the greatest extent possible. Once the general outlines of an assay have been established, key features should be examined, including optimization of sample preparation, sample stability, choice of standards, assay range, assay repeatability, optimization of separation, and optimization of detection. 

Certain choices of standard states have found such widespread use that they have achieved... 

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. 

It should be emphasized that the choice of standard states implied by equation 2.2.9 is not that which is conventionally used in the analysis of chemically reacting systems. Furthermore,... 

For cases where the standard states of the reactants and products are chosen as 1 atm, the value of AG° is pressure independent. Consequently, equation 2.4.7 indicates that Ka is also pressure independent for this choice of standard states. For the unconventional choice of standard states discussed in Section 2.2, equations 2.4.7 and 2.2.10 may be combined to give the effect of pressure on Ka. 

This illustrates the statement made earlier that the most convenient choice of standard state may depend on the problem. For gas-phase problems involving A, it is convenient to choose the standard state for A as an ideal gas at 1 atm pressure. But, where the vapor of A is in equilibrium with a solution, it is sometimes convenient to choose the standard state as the pure liquid. Since /a is the same for the pure liquid and the vapor in equilibrium... 

One cannot emphasize too often that the numerical values of I a > °A> ar d Ya depend on the choice of standard state. The usual thermodynamic... 

In Equation 50 the chemical potential of non-electrolyte A depends on the usual choice of standard-state conventions described above, and the chemical potentials of both H2(g) and H+(sod are taken to be zero (this defines e.s.s., the electrolyte standard state). By setting the standard-state free energy of the solvated proton equal to zero, this standard-state convention... 

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