Standard pressure equilibrium constant

For the ideal-gas (a good approximation for real gas mixtures at relatively low pressures) reaction A(g) -I- B(g) AB(g), the standard pressure equilibrium constant K° is... 

The equilibrium constant is governed by a function of temperature and pressure and can be expressed using the standard state equilibrium constant and the change in standard free energy of the reaction ... 

Figure B2.5.7 shows the absorption traces of the methyl radical absorption as a fiinction of tune. At the time resolution considered, the appearance of CFt is practically instantaneous. Subsequently, CFl disappears by recombination (equation B2.5.28). At temperatures below 1500 K, the equilibrium concentration of CFt is negligible compared witli (left-hand trace) the recombination is complete. At temperatures above 1500 K (right-hand trace) the equilibrium concentration of CFt is appreciable, and thus the teclmique allows the detennination of botli the equilibrium constant and the recombination rate [54, M]. This experiment resolved a famous controversy on the temperature dependence of the recombination rate of methyl radicals. Wliile standard RRKM theories [, ] predicted an increase of the high-pressure recombination rate coefficient /r (7) by a factor of 10-30 between 300 K and 1400 K, the statistical-adiabatic-chaunel model predicts a...

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 equilibrium constant can be determined at any temperature from standard state information on reactants and product. Considering the synthesis of NH3, the equilibrium conversion can be determined for a stoichiometric feed of Hj and Nj, at the total pressure. These conversions are determined by the number of moles of each species against conversion X by taking as a basis, 1 mole of N2. 

You may wonder why the equilibrium constant, 11, has no units. The reason is that each term in the reaction quotient represents the ratio of the measured pressure of the gas to the thermodynamic standard state of one atmosphere. Thus the quotient (f3No2)2/f>N2o4 in Experiment 1 becomes... 

The equation just written is generally applicable to any system. The equilibrium constant may be the K referred to in our discussion of gaseous equilibrium (Chapter 12), or any of the solution equilibrium constants (Rw Ra, Rj, K, . . . ) discussed in subsequent chapters. Notice that AG° is the standard free energy change (gases at 1 atm, species in solution at 1M). That is why, in the expression for K, gases enter as their partial pressures in atmospheres and ions or molecules in solution as their molarities. 

Alternative forms of the equilibrium constant can be obtained as we express the relationship between activities, and pressures or concentrations. For example, for a gas phase reaction, the standard state we almost always choose is the ideal gas at a pressure of 1 bar (or 105 Pa). Thus... 

It is important to note that, for any given temperature, the [thermodynamic] equilibrium constant is directly related to the standard change in free energy. Since, at any given temperature, the free energy in the standard state for each reactant and product, G°, is independent of the pressure, it follows that the standard change in free energy for the reaction, AfG°, is independent of the pressure.g Therefore, at constant temperature, the equilibrium constant K. .. is also independent of the pressure. That is,... 

We use a different measure of concentration when writing expressions for the equilibrium constants of reactions that involve species other than gases. Thus, for a species J that forms an ideal solution in a liquid solvent, the partial pressure in the expression for K is replaced by the molarity fjl relative to the standard molarity c° = 1 mol-L 1. Although K should be written in terms of the dimensionless ratio UJ/c°, it is common practice to write K in terms of [J] alone and to interpret each [JJ as the molarity with the units struck out. It has been found empirically, and is justified by thermodynamics, that pure liquids or solids should not appear in K. So, even though CaC03(s) and CaO(s) occur in the equilibrium... 

We will see functions like the one occurring under the logarithm operator quite often. For efficiency, this is generally written as In(Products)/(Reactants), where (Products) and (Reactants) denote the partial pressures of the species relative to the standard state pressure raised to a power that is equal to the stoichiometric coefficients. Kp is the equilibrium constant in terms of pressures. Since all pressures are in the same units, Rp is dimensionless. Note that in some literature there may be a combination of some power of P with Kp to obtain an equilibrium constant with pressure units. In this case. 

Recall that from the perspective of thermodynamics, every concentration is measured relative to a defined standard concentration. For any gas, the defined standard is 1 bar pressure for any solute in aqueous solution, the defined standard is 1 M. We treat the concentration terms in equilibrium constant expressions in this same way. 

The equilibrium constant Ka is independent of pressure for those cases where the standard states are taken as the pure components at 1 atm. This case is the one used as the basis for deriving equation 2.6.9. Tjie effect of pressure changes then appears in the terms KfjP and ps + t+ b c . The influence of pressure on KfjP is quite small. However, for cases where there is no change in the total number of gaseous moles during the reaction, this is the only term by which pressure changes affect the equilibrium yield. For these... 

The stoichiometric coefficient for methanol is +1 because it is a product and — 1 for CO and -2 for H2 because they are reactants. The reaction is not spontaneous under standard conditions of temperature and pressure but at 500 K the equilibrium constant is given by Equation 8.12 ... 

Equilibrium constants do not have units because in the strict thermodynamic definition of the equilibrium constant, the activity of a component is used, not its concentration. The activity of a species in an ideal mixture is the ratio of its concentration or partial pressure to a standard concentration (1 M) or pressure (1 atm). Because activity is a ratio, it is unitless and the equilibrium constant involving activities is also unitless. 

The equilibrium constants can be approximated by ratios of ion currents in some instances otherwise, the currents are converted to partial pressures by comparison with the evaporation of known amounts of a standard material. Various geometric corrections (K) such as the solid angle subtended by the sample at the orifice, the Clausing factor for orifice geometry, molecular cross-section (o-), which control ionization efficiency, and detector efficiency are included in the general relationship... 

Here fif (T) is the Gibbs free energy per mole of an ideal gas at temperature T and standard pressure P°. Thus the condition of equilibrium for a gas phase system subject to a chemical reaction (Equation 4.36), whether at constant T and P or constant T and V, is given by... 

Here AGr° is the Gibbs free energy change in the ideal gas phase reaction system when all the gases are in their respective standard states. The equilibrium constant Kp is given in terms of the partial pressures at equilibrium by... 

The form of the equilibrium constant in Equation (10.21) is different from that presented in introductory courses. It has the advantages that 1) it is explicit that Kp is a dimensionless quantity 2) it is explicit that the numerical value of Kp depends on the choice of standard state but not on the units used to describe the standard state pressure the equilibrium constant has the same value whether P° is expressed as 750.062 Torr, 0.98692 atm, 0.1 MPa, or 1 bar. 

The equilibrium constant depends on the temperature at which a reaction takes place, but at any given temperature, it is independent of pressure. If the standard enthalpies of the reactants and products of a reaction are known, the equilibrium constant for the reaction at a temperature other than that of the standard state may be calculated using the van t Hoff equation, i.e. 

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