Acids and oceans

The overall reaction is exothermic but required the use of an electric arc furnace which, even with relatively cheap hydroelectricity, made the process very expensive. The severe activation energy barrier, though economically regrettable, is in fact essential to life since, in its absence, all the oxygen in the air would be rapidly consumed and the oceans would be a dilute solution of nitric acid and its salts. [Dilution of HN03(1) to HNOafaq) evolves a further 33.3kJmol at 25 C.l... 

The most important type of mixed solution is a buffer, a solution in which the pH resists change when small amounts of strong acids or bases are added. Buffers are used to calibrate pH meters, to culture bacteria, and to control the pH of solutions in which chemical reactions are taking place. They are also administered intravenously to hospital patients. Human blood plasma is buffered to pH = 7.4 the ocean is buffered to about pH = 8.4 by a complex buffering process that depends on the presence of hydrogen carbonates and silicates. A buffer consists of an aqueous solution of a weak acid and its conjugate base supplied as a salt, or a weak base and its conjugate acid supplied as a salt. Examples are a solution of acetic acid and sodium acetate and a solution of ammonia and ammonium chloride. 

Alternatives to fossil fuels, such as hydrogen, are explored in Box 6.2 and Section 14.3. Coal, which is mostly carbon, can be converted into fuels with a lower proportion of carbon. Its conversion into methane, CH4, for instance, would reduce C02 emissions per unit of energy. We can also work with nature by accelerating the uptake of carbon by the natural processes of the carbon cycle. For example, one proposed solution is to pump C02 exhaust deep into the ocean, where it would dissolve to form carbonic acid and bicarbonate ions. Carbon dioxide can also be removed from power plant exhaust gases by passing the exhaust through an aqueous slurry of calcium silicate to produce harmless solid products ... 

Figure 4-13 shows an example from a three-dimensional model simulation of the global atmospheric sulfur balance (Feichter et al, 1996). The model had a grid resolution of about 500 km in the horizontal and on average 1 km in the vertical. The chemical scheme of the model included emissions of dimethyl sulfide (DMS) from the oceans and SO2 from industrial processes and volcanoes. Atmospheric DMS is oxidized by the hydroxyl radical to form SO2, which, in turn, is further oxidized to sulfuric acid and sulfates by reaction with either hydroxyl radical in the gas phase or with hydrogen peroxide or ozone in cloud droplets. Both SO2 and aerosol sulfate are removed from the atmosphere by dry and wet deposition processes. The reasonable agreement between the simulated and observed wet deposition of sulfate indicates that the most important processes affecting the atmospheric sulfur balance have been adequately treated in the model. 

Rainwater and snowmelt water are primary factors determining the very nature of the terrestrial carbon cycle, with photosynthesis acting as the primary exchange mechanism from the atmosphere. Bicarbonate is the most prevalent ion in natural surface waters (rivers and lakes), which are extremely important in the carbon cycle, accoxmting for 90% of the carbon flux between the land surface and oceans (Holmen, Chapter 11). In addition, bicarbonate is a major component of soil water and a contributor to its natural acid-base balance. The carbonate equilibrium controls the pH of most natural waters, and high concentrations of bicarbonate provide a pH buffer in many systems. Other acid-base reactions (discussed in Chapter 16), particularly in the atmosphere, also influence pH (in both natural and polluted systems) but are generally less important than the carbonate system on a global basis. 

Removal to sediments. Removal of surface-reactive trace elements from the oceans readily occurs by adsorption onto settling particles, and this process is most pronounced in the typically high-energy, particle-rich estuarine environment. Particles are supplied by rivers, augmented by additions of organic material generated within the estuary. Also, floes are created in estuaries from such components as humic acids and Fe. The interaction between dissolved and colloidal species is enhanced by the continuous resuspension of sediments in... 

E. L. Shock (1990) provides a different interpretation of these results he criticizes that the redox state of the reaction mixture was not checked in the Miller/Bada experiments. Shock also states that simple thermodynamic calculations show that the Miller/Bada theory does not stand up. To use terms like instability and decomposition is not correct when chemical compounds (here amino acids) are present in aqueous solution under extreme conditions and are aiming at a metastable equilibrium. Shock considers that oxidized and metastable carbon and nitrogen compounds are of greater importance in hydrothermal systems than are reduced compounds. In the interior of the Earth, CO2 and N2 are in stable redox equilibrium with substances such as amino acids and carboxylic acids, while reduced compounds such as CH4 and NH3 are not. The explanation lies in the oxidation state of the lithosphere. Shock considers the two mineral systems FMQ and PPM discussed above as particularly important for the system seawater/basalt rock. The FMQ system acts as a buffer in the oceanic crust. At depths of around 1.3 km, the PPM system probably becomes active, i.e., N2 and CO2 are the dominant species in stable equilibrium conditions at temperatures above 548 K. When the temperature of hydrothermal solutions falls (below about 548 K), they probably pass through a stability field in which CH4 and NII3 predominate. If kinetic factors block the achievement of equilibrium, metastable compounds such as alkanes, carboxylic acids, alkyl benzenes and amino acids are formed between 423 and 293 K. 

Plants were probably the first to have polyester outerwear, as the aerial parts of higher plants are covered with a cuticle whose structural component is a polyester called cutin. Even plants that live under water in the oceans, such as Zoestra marina, are covered with cutin. This lipid-derived polyester covering is unique to plants, as animals use carbohydrate or protein polymers as their outer covering. Cutin, the insoluble cuticular polymer of plants, is composed of inter-esterified hydroxy and hydroxy epoxy fatty acids derived from the common cellular fatty acids and is attached to the outer epidermal layer of cells by a pectinaceous layer (Fig. 1). The insoluble polymer is embedded in a complex mixture of soluble lipids collectively called waxes [1], Electron microscopic examination of the cuticle usually shows an amorphous appearance but in some plants the cuticle has a lamellar appearance (Fig. 2). 

Equation 8.26 predicts a concentration of CO2 in one litre of water at 25°C of 3.32 x 10-2 moll-1 at a pressure of 1 bar. The pH of the oceans is related to the amount of dissolved C02 but also to the equilibria controlling the formation of carbonic acid and the bicarbonate and carbonate ions ... 

The pK of Ca2+aq (204), 12.6 at zero ionic strength, rising to over 13 as ionic strength increases, means that concentrations of CaOH+aq will be negligible in body fluids (lpolluted waters, and under all conditions of biological relevance, from the very low pHs of 0.5 (Thiobacillus thiooxidans) to 1.5 at which bacteria used for oxidative metal extraction operate (205), through acid soils and acid rain (pH 3 to 6), streams, rivers, and oceans (pH 6 to 8), soda lakes (pH 10), up to the pHs of 11 or more in Jamaican Red Mud slurry ponds (206) (cf. Section II.C.l below). 

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