Molal activity coefficient

Although one can probably find exceptions, most equilibrium calculations involving flue gas slurries are performed with temperature as a known variable. With temperature known, the numerical values of the appropriate equilibrium constants can be immediately calculated. The remaining unknown variables to be determined are the activities, activity coefficients, molalities, and the gas phase partial pressures. The equations used to determine these variables are formulated from among the equilibrium expressions presented in Table 1, the expressions for the activity coefficients, ionic strength, material balance expressions, and the electroneutrality balance. Although there are occasionally exceptions, the solution sequence generally is an iterative or cyclic sequence. 

Table 4.1. Single ion activity coefficients (molal scale) for uni-univalent chlorides at 25° C derived from hydration theory [11].

Absorptivity for radiation Activity Activity coefficient, molal basis Coefficient of expansion a a T Diffusivity Molecular, volumetric Thermal Emissivity ratio for radiation Dv,8 a ft /(h) (ft) ft2/h a = k/cp, ft2 /h... 

Table VI. Mean Ionic Activity Coefficients (Molality Scale) of HBr in H20/NMA Solvent Mixtures at 25°C...

Molar activity coefficient Molal activity coefficient... 

Activity coefficient (molality scale) of species i Activity coefficient (Raonlt scale) of species i... 

Figure 1.6 Activity coefficient-molality relationship for aqueous sulphuric acid...

The following data (for 25°C) were obtained at the pzc for the Hg-aqueous NaF interface. Estimate and plot it as a function of the mole fraction of salt in solution. In the table,/ is mean activity coefficient such that a = f m , where m is mean molality. 

The activity of an ion is related to its molality through the mean activity coefficient 7+ therefore... 

Table 21.9 Stoichiometric mean molal activity coefficients (7,) for aqueous inorganic...

There are several different scales 011 which the activity of a solute may be defined.1 In thermodynamic expressions for a solute in a non-ideal solution the activity on the molality scale plays the same part that is played by the molality of a solute in an ideal solution. Since the activity is expressed in the same units as the molality, the ratio of the activity to the molality—the activity coefficient—is a pure number whose value is independent of these units it is also indopendont of the particular b.q.s. that has been adopted. Thus the numerical values of all activities and molalities would change in the same ratio, if at any time a new choice were made for the b.q.s. 

In agreement with (98), the left-hand side is just the standard free energy of solution AF°. Here y, as defined by (106), is the usual activity coefficient on the molality scale. In particular, when the solid is in contact with its saturated solution, there is no change in the free energy when additional ions are taken into solution. In this case, if in (108) we write m, t and y,at, the values of m and y in the saturated solution, we may set AF equal to zero. This will be discussed in Sec. 100. 

Finally, as an example of a highly soluble salt, we may take sodium chloride at 25° the concentration of the saturated solution is 6.16 molal. The activity coefficient of NaCl, like that of NaBr plotted in Fig. 72, passes through a minimum at a concentration between 1.0 and 1.5 molal and it has been estimated2 that in the saturated solution the activity coefficient has risen to a value very near unity. Writing y = 1.0, we find that the work required to take a pair of ions from the surface of NaCl into pure water at 25° has the rather small value... 

Lithium Carbonate in Aqueous Solution. As an illustration, we shall evaluate the conventional AF° and AS0 for lithium carbonate in aqueous solution. At 25°C the concentration of the saturated solution is 0.169 molal.1 In this solution the molality of the Li+ ion is of course 0.338. The activity coefficient of the Li2CO.t in the saturated solution is not accurately known, but its value is not far from y,at = 0.59. Substituting in (186) we have then... 

The saturated solution of silver sulfate in water at 25°C has a molality equal to 0.02689, and the activity coefficient y of tho solute in this saturated solution is 0.533. 

The saturated solution of potassium iodate in water at 25°C has a molality equal to 0.43. Taking the activity coefficient y in this saturated solution to be 0.52, find the conventional free energy of solution at 25°C, and calculate in electron-volts per ion pair the value of L for the removal of tho ions K+ and (IOs) into water at 25°C. 

As an example, take the molecule aminoazobenzene, one of the solutes listed in Table 39. When colorimetric measurements were made at room temperature on very dilute aqueous solutions of HC1, containing a trace of this substance, it was found that neutral molecules and (BH)+ ions were present in equal numbers when the concentration of the HCl was 0.0016 molal.1 At this low concentration the activity coefficient of the HCl is very near unity, and we may use (216) to find how far the vacant proton level provided by the aminoazobenzene molecule in aque-... 

The symbol used is dependent upon the method of expressing the concentration of the solution. The recommendations of the IUPAC Commision on Symbols, Terminology and Units (1969) are as follows concentration in moles per litre (molarity), activity coefficient represented by y, concentration in mols per kilogram (molality), activity coefficient represented by y, concentration expressed as mole fraction, activity coefficient represented by f... 

So far we have considered only symmetrical 1 1 electrolytes such as HC1, K.CI, or MgS04. For unsymmetrical electrolytes, the limiting law takes a different form, and different relationships between activity, molality and activity coefficient are obtained. For example, for the 2 1 electrolyte, Na SO,, the dissociation reaction is... 

E6.12 The HC1 pressure in equilibrium with a 1.20 molal solution is 5.15 x 10 8 MPa and the mean ionic activity coefficient is known from emf measurements to be 0.842 at T = 298.15 K. Calculate the mean ionic activity coefficients of HC1 in the following solutions from the given HC1 pressures... 

Rard also employed Pitzer s electrolyte activity coefficient model to correlate the data. It was found that the quality of the fit depended on the range of molalities that were used. In particular, the fit was very good when the molalities were less than 3 mol/kg. 

Estimate Pitzer s electrolyte activity coefficient model by minimizing the objective function given by Equation 15.1 and using the following osmotic coefficient data from Rard (1992) given in Table 15.5. First, use the data for molalities less than 3 mol/kg and then all the data together. Compare your estimated values with those reported by Rard (1992). Use a constant value for in Equation 15.1. 

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