Seawater activity coefficients

Table A6.2 includes historical information on the comparison of ion activity coefficients at the effective ionic strength of seawater. Activity coefficients measured in single salt solutions are compared with those measured in seawater and those calculated from an association model. We have to distinguish between total activity coefficients (cf. equations 3 and 4)...

The approximation is equivalent to saying that the activity coefficient is unity. The approximation fails in a solution of high ionic strength such as seawater. Activity coefficients appropriate for seawater are 0.26 for Ca- and 0.20 for CO -. Now the reaction quotient looks like this ... 

Among the possible analytical methods for alkalinity determination, Gran-type potentiometric titration [2] combined with a curve-fitting algorithm is considered a suitable method in seawaters because it does not require a priori knowledge of thermodynamic parameters such as activity coefficients and dissociation constants, which must be known when other analytical methods for alkalinity determination are applied [3-6],... 

Table 6.4. Calculated molalities (m), activity coefficients (y), and log activities (a) of the most abundant species in seawater...

The resulting species distribution (Table 6.7), as would be expected, differs sharply from that in seawater (Table 6.4). Species approach millimolal instead of molal concentrations and activity coefficients differ less from unity. In the Amazon River water, the most abundant cation and anion are Ca++ and HCOJ in seawater, in contrast, Na+ and Cl- predominate. Seawater, clearly, is not simply concentrated river water. 

In a series of papers, Harvie and Weare (1980), Harvie el al. (1980), and Eugster et al (1980) attacked this problem by presenting a virial method for computing activity coefficients in complex solutions (see Chapter 8) and applying it to construct a reaction model of seawater evaporation. Their calculations provided the first quantitative description of this process that accounted for all of the abundant components in seawater. 

Ionic media are solutions of background electrolytes which are concentrated enough so that the activity coefficients of the electrolytes of interest do not change during processes which are occurring. Typical ionic media are a 1 m HCl0U or NaClOq solution and seawater. 

Calcite mole fraction X, solid state activity coefficients X, and Yp, the solute mole fractions of calcium at equilibrium in seawater. 

Despite the additional complexity, all the equations in Table 5.3 are functionally equivalent. That is, the activity coefficients approach a value of 1 as the ionic strength of the solution is decreased to 0 m. Thus, in dilute solutions, w,. In other words, the effective concentration of an ion decreases with increasing ionic strength. In contrast, the activity coefficients of uncharged solutes can be greater than 1 in solutions of high ionic strength, such as seawater. 

Gas solubility decreases with increasing salinity. This phenomenon is referred to as salting out. It is caused by the electrostatic forces exerted by the salt ions. These forces have to be overcome to create spaces between water molecules to accommodate a gas atom or molecule. So higher salinities lead to less favorable energetics for gas dissolution. The high salt content of seawater also leads to nonspecific interactions that cause gases to have activity coefficients on the order of 1.1 to 1.2 at a salinity of 35%o and temperature of 25°C. 

The individual activity coefficients calculated from (4.12), suitable for calibration of ISEs for chloride ions, the alkali metal and alkaline earth ions, are given in tables 4.1 and 4.2. Ion activity scales have also been proposed for KF [141], choline chloride [98], for mixtures of electrolytes simulating the composition of the serum and other biological fluids (at 37 °C) [106,107], for alkali metal chlorides in solutions of bovine serum albumine [132] and for mixtures of electrolytes analogous to seawater [140]. 

Gordon JE, Thome RL (1967b) Salt effect on the activity coefficient of naphthalene in mixed aqueous electrolyte solutions salts 2. Artificial and natural seawater. Geochim Cosmochim Acta 31 2433-2443... 

In summary, we can conclude that at moderate salt concentrations typical for seawater ( 0.5 M), salinity will affect aqueous solubility (or the aqueous activity coefficient) by a factor of between less than 1.5 (small and/or polar compounds) and about 3 (large, nonpolar compounds, n-alkanals). Hence, in marine environments for many compounds, salting-out will not be a major factor in determining their partitioning behavior. Note, however, that in environments exhibiting much higher salt concentrations [e.g., in the Dead Sea (5 M) or in subsurface brines near oil fields], because of the exponential relationship (Eq. 5-28), salting-out will be substantial (see also Illustrative Example 5.4). 

Estimate the solubility and the activity coefficient of phenanthrene in (a) seawater at 25°C and 30%o salinity, and (b) a salt solution containing 117 g NaCl per liter water. 

Explain in words how environmentally relevant inorganic salts affect the aqueous solubility of a (a) liquid, (b) solid, and (c) gaseous compound. Is it true that the effect is linearly related to the concentration of a given salt What is the magnitude of the effect of salt on the aqueous activity coefficient of organic compounds in typical seawater ... 

P 5.6 Evaluating the Effect of Temperature on the Solubility and/or the Activity Coefficient of a Gaseous Compound (Freon 12) in Freshwater and in Seawater... 

For an assessment of the global distribution of persistent volatile halogenated hydrocarbons, the solubility and activity coefficients of such compounds in natural waters need to be known. Warner and Weiss (1985) have determined the solubilities of dichlorodifluoromethane (Freon 12) at 1 bar partial pressure at various temperatures in freshwater and in seawater (35.8%o salinity) ... 

A colleague of yours who works in oceanography bets you that both the solubility as well as the activity coefficient of naphthalene are larger in seawater (35%o salinity) at 25°C than in distilled water at 5°C. Is this not a contradiction How much money do you bet Estimate C and for naphthalene in seawater at 25°C and in distilled water at 5°C. Discuss the result. Assume that the average enthalpy of solution (A wsHh Fig. 5.1) of naphthalene is about 30 kJmol-1 over the ambient temperature range. All other data can be found in Tables 5.3 and 5.7 and in Appendix C. 

Berner, R. A. Activity coefficients of bicarbonate, carbonate and calcium ions in seawater. Geochim. Cosmochim. Acta 29, 947-965 (1965). 

Table A.2 is model output for seawater freezing at 253.15 K. Beneath the title, the output includes temperature, ionic strength, density of the solution (p), osmotic coefficient amount of unfrozen water, amount of ice, and pressure on the system. Beneath this line are the solution and gaseous species in the system. The seven columns include species identification, initial concentration, final (equilibrium) concentration, activity coefficient, activity, moles in the solution phase, and mass balance. The mass balance column only contains those components for which a mass balance is maintained. The number of these components minus 1 is generally the number of independent components in the system (in this case, 8 — 1 = 7). The mass balances (col. 7) should equal the initial concentrations (col. 2). This mass balance comparison is a good check on the computational accuracy.

In theory, it should be possible to deal with all carbonate geochemistry in seawater simply by knowing what the appropriate activity coefficients are and how salinity, temperature, and pressure affect them. In practice, we are only now beginning to approach the treatment of activity coefficients under this varying set of conditions with sufficient accuracy to be useful for most problems of interest. That is why "apparent" and stoichiometric equilibrium constants, which do not involve the use of activity coefficients, have been in widespread use in the study of marine carbonate chemistry for over 20 years. The stoichiometric constants, usually designated as K. involve only the use of concentrations, whereas expressions for apparent equilibrium constants contain both concentrations and aH+ derived from "apparent pH". These constants are usually designated as K Examples of these different types of constants are ... 

It should be noted that in seawater the molinity concentration scale (moles kg-1 of seawater) is often used, and care must be taken to make certain that stoichiometric and apparent constants are on the same concentration scale as the measured values. The ratios of thermodynamic constants to their apparent or stoichiometric constant are activity coefficients, for example ... 

In this chapter, we introduced the reader to some basic principles of solution chemistry with emphasis on the C02-carbonate acid system. An array of equations necessary for making calculations in this system was developed, which emphasized the relationships between concentrations and activity and the bridging concept of activity coefficients. Because most carbonate sediments and rocks are initially deposited in the marine environment and are bathed by seawater or modified seawater solutions for some or much of their history, the carbonic acid system in seawater was discussed in more detail. An example calculation for seawater saturation state was provided to illustrate how such calculations are made, and to prepare the reader, in particular, for material in Chapter 4. We now investigate the relationships between solutions and sedimentary carbonate minerals in Chapters 2 and 3. 

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