Dissolved ions

Dissolved metals in seawater have various sources, for example the dissolution of redox-sensitive metals from reducing ocean floor and mid-ocean ridge hydrothermal sediments. Hydrothermal sediments, for example, are typically 

The chemistry of dissolved metals in seawater can be grouped into three classes, which describe the behaviour of the metal during chemical cycling. These classes—conservative, nutrient-like and scavenged—have been recognized by the shapes of concentration profiles when plotted against depth in the oceans. 

Total input—dissolved plus particulate. Estimates are based on data available in early 1990s and so include significant amounts of material mobilized by human activity. 

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Particulate interferents can be separated from dissolved analytes by filtration, using a filter whose pore size retains the interferent. This separation technique is important in the analysis of many natural waters, for which the presence of suspended solids may interfere in the analysis. Filtration also can be used to isolate analytes present as solid particulates from dissolved ions in the sample matrix. For example, this is a necessary step in gravimetry, in which the analyte is isolated as a precipitate. A more detailed description of the types of available filters is found in the discussion of precipitation gravimetry and particulate gravimetry in Chapter 8. 

Although there are only three principal sources for the analytical signal—potential, current, and charge—a wide variety of experimental designs are possible too many, in fact, to cover adequately in an introductory textbook. The simplest division is between bulk methods, which measure properties of the whole solution, and interfacial methods, in which the signal is a function of phenomena occurring at the interface between an electrode and the solution in contact with the electrode. The measurement of a solution s conductivity, which is proportional to the total concentration of dissolved ions, is one example of a bulk electrochemical method. A determination of pH using a pH electrode is one example of an interfacial electrochemical method. Only interfacial electrochemical methods receive further consideration in this text. 

Water Treatment. Flotation in water treatment is used both for the removal of dissolved ions such as Cu ", Cr ", or (PO or surfactants and suspended soHds as in the case of sludge treatment. The final product in this case is purified water rather than a mineral concentrate. Furthermore, water is treated either for drinking purposes (potable water preparation) or safe disposal to the environment. 

N. E. Peters, Evaluation of Environmental Eactors Affecting Yields of Major Dissolved Ions of Streams in the Ended States, U.S. Geological Survey Water-Supply Paper 2228, U.S. Geological Survey, Reston, Va., 1984. 

Electrodialysis. Electro dialysis processes transfer ions of dissolved salts across membranes, leaving purified water behind. Ion movement is induced by direct current electrical fields. A negative electrode (cathode) attracts cations, and a positive electrode (anode) attracts anions. Systems are compartmentalized in stacks by alternating cation and anion transfer membranes. Alternating compartments carry concentrated brine and purified permeate. Typically, 40—60% of dissolved ions are removed or rejected. Further improvement in water quaUty is obtained by staging (operation of stacks in series). ED processes do not remove particulate contaminants or weakly ionized contaminants, such as siUca. 

Attack associated with nonuniformity of the aqueous environments at a surface is called concentration cell corrosion. Corrosion occurs when the environment near the metal surface differs from region to region. These differences create anodes and cathodes (regions differing in electrochemical potential). Local-action corrosion cells are established, and anodic areas lose metal by corrosion. Shielded areas are particularly susceptible to attack, as they often act as anodes (Fig. 2.1). Differences in concentration of dissolved ions such as hydrogen, oxygen, chloride, sulfate, etc. eventually develop between shielded and nearby regions. 

Thus damage locations, although usually widespread, are dependent on many factors. Metallurgy, deposition, design, temperature, pH, water content, dissolved-ion concentration, flow, and other factors all influence attack. 

Erosion-corrosion can be defined as the accelerated degradation of a material resulting from the joint action of erosion and corrosion when the material is exposed to a rapidly moving fluid. Metal can be removed as solid particles of corrosion product or, in the case of severe erosion-corrosion, as dissolved ions. 

In the presence of dissolved ions, the ion charge at the metal surface can be neutralized by the migration of the counter-ions to the reaction site. The following reactions take place ... 

Ultrafiltration membranes are commercially fabricated in sheet, capillary and tubular forms. The liquid to be filtered is forced into the assemblage and dilute permeate passes perpendicularly through the membrane while concentrate passes out the end of the media. This technology is useful for the recovery and recycle of suspended solids and macromolecules. Excellent results have been achieved in textile finishing applications and other situations where neither entrained solids that could clog the filter nor dissolved ions that would pass through are present. Membrane life can be affected by temperature, pH, and fouling. 

Ultrafiltration Solution or colloidal suspension of high molecular weight organics One stream concentrated in high molecular weight organics one containing dissolved ions... 

The presence of dissolved ions facilitates the passage of an ionic current through the solution. 

Thus in the system depicted in Figure 53.1, for any metal which is thermodynamically unstable with respect to its dissolved ions in the solution (and this includes most metals of industrial importance) corrosion will occur. The rate of corrosion is determined by several factors ... 

As with all determinations of thermodynamic stability, we comihehce by defining all stable phases possible, and their standard, chemical, potentials. For inost, metals there are many such phases, including oxides, hydroxides and dissolved ions. For brevity, here, only the minimum number of phases is Considered. The siriiplest system is a metal, ilf, which can oxidise lo form a stable dissolved pro,duct, (qorrpsipn), or to form a stable oxide MO (passivation), lit aqueous environments thfbe equilibria Can thereby be... 

Electrolyte Solution a solution in which the conduction of electric current occurs by the passage of dissolved ions. 

Immunity the state of a metal whose corrosion rate is low or negligible because its potential is below (less positive than) that of equilibrium with a very small concentration (or activity of its dissolved ions. The metal is thus regarded as thermodynamically stable. Pourbaix has suggested that the small metal ion concentration be 10 mol dm (Atlas of Electrochemical Equilibria in Aqueous Solutions, p. 71, Pergamon/ CEBELCOR, Oxford (1966)). 

Reference Electrode an equilibrium (reversible) electrochemical half-cell of reproducible potential against which an unknown electrode potential can be measured. Examples of those commonly used in corrosion are the Pt, H /H (the hydrogen electrode), Hg/Hg Clj/Cl" (the calomel electrode), Cu/CuS04/Cu, Ag/AgCl/Cl", all with fixed activities of the dissolved ions. 

Dissolution of Calculi Model. Dissolved Ions from Ca3(PCf)2. Dissolution of calcium phosphate by macrocyclic polyamines proceeds at pH 7, which is established by measuring the freed cation concentration as well as the freed anion concentration with respect to the control values (Table 7). The molar ratio of [Ca2 + ] to [P04 ]... 

Equation (7) shows that when calcium chloride dissolves, ions are present—Ca+2(aq) and Cl (aq) ions. In this case, each calcium ion has the positive charge of two protons. Therefore it has twice the positive charge held by a sodium ion, Na+(aq). The chloride ion that forms, C (aq), is the same negative ion that is present in the sodium chloride solution, though it comes from the calcium chloride solid instead of the sodium chloride. Because both CaCUfsJ and... 

The dissolving of limestone by ground water is another example of chemical equilibrium. The behavior of this system depends upon the chemical equilibrium between CaC03 and its dissolved ions and the equilibrium between carbonate ion and dissolved C02 in the water. When CaC03 dissolves in water it establishes the equilibrium... 

A complete ionic equation for a precipitation reaction shows all the dissolved ions explicitly. For example, the complete ionic equation for the silver chloride precipitation reaction shown in Fig. 1.5 is... 

STRATEGY First, write and balance the complete ionic equation, showing all the dissolved ions as they actually exist in solution, as separate, charged ions. Insoluble solids are shown as complete compounds. Next, cancel the spectator ions, the ions that remain in solution on both sides of the arrow. 

SOLUTION The complete ionic equation, with all the dissolved ions written as they exist in the solutions before and after mixing, is... 

Up to this point, we have focused on aqueous equilibria involving proton transfer. Now we apply the same principles to the equilibrium that exists between a solid salt and its dissolved ions in a saturated solution. We can use the equilibrium constant for the dissolution of a substance to predict the solubility of a salt and to control precipitate formation. These methods are used in the laboratory to separate and analyze mixtures of salts. They also have important practical applications in municipal wastewater treatment, the extraction of minerals from seawater, the formation and loss of bones and teeth, and the global carbon cycle. 

The equilibrium constant for the solubility equilibrium between an ionic solid and its dissolved ions is called the solubility product, Ksp, of the solute. For example, the solubility product for bismuth sulfide, Bi2S3, is defined as... 

Water is more highly conducting when it has dissolved ions, and the formation of rust is then accelerated. That is one reason why the salt air of coastal cities and salt used for de-icing highways is so damaging to exposed metal. 

Much research focuses on the structures, properties, and uses of the complexes formed between d-metal ions acting as Lewis acids and a variety of Lewis bases, partly because they participate in many biological reactions. Hemoglobin and vitamin B12, for example, are both complexes—the former of iron and the latter of cobalt (Box 16.1). Complexes of the d-metals are often brightly colored and magnetic and are used in chemistry for analysis, to dissolve ions (Section 11.13), in the... 

The material transported by rivers consists of dissolved ions (dissolved load), sediment suspended in the flow (suspended load), and sediment transported along the bed of the river (bedload). The total load and the proportion of the load represented by these phases varies widely among rivers in different environments. In particular, climate, topography, and erosion influence the amount and composition of riverine sediment loads. 

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