Aqueous Solutions An Introduction

Approximately three-fourths of the earth s surface is covered with water. The body fluids of all plants and animals are mainly water. Thus we can see that many important chemical reactions occur in aqueous (water) solutions or in contact with water. In Chapter 3, we introduced solutions and methods of expressing concentrations of solutions. It is useful to know the kinds of substances that are soluble in water, and the forms in which they exist, before we begin our systematic study of chemical reactions. 

Many substances that interact with water are classified as acids, bases, and salts. An add can be defined as a substance that produces hydrogen ions, H , in aqueous solutions. We usually write the formulas of inorganic acids with hydrogen written first Organic adds can often be recognized by the presence of the COOH group in the formula. Many properties of aqueous solutions of acids are due to H (aq) ions. These are described in Section 10-4. A base is a substance that produces hydroxide ions, OH , in aqueous solutions. Adds and bases are further identified in Subsections 2,3, and 4. A salt is an ionic compound that contains a cation other than and an anion other than hydroxide ion, OH , or oxide ion, (see Table 2-2). As we will see later in this chapter, salts are formed when acids react with bases. 

Unless otheiwise noteiJ, all content on this page Is Cengage Learning. 

Dissodation refers to the process in which a solid ionic compound, such as NaCl, separates into its ions in solution  

Molecular compounds, for example pure HCl, exist as discrete molecules and do not contain ions however, many such compounds form ions in solution. Ionization refers to the process in which a molecular compound separates or reacts with water to form ions in solution  

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The Periodic Table Metals, Nonmetals, and Metalloids 4-2 Aqueous Solutions An Introduction... 

D. Benson, Mechanisms oi Inorganic Reactions in Aqueous Solution An Introduction, McGraw-Hill, London, 1968. 

Thompson M., Pahlavanpour B., Walton S. J. and Kirkbright G. F. (1978) Simultaneous determination of trace concentrations of arsenic, antimony, bismuth, selenium and tellurium in aqueous solution by introduction of the gaseous hydrides into an ICP source for emission spectrometry, Analyst 103 568-579. 

Atomization The most important difference between a spectrophotometer for atomic absorption and one for molecular absorption is the need to convert the analyte into a free atom. The process of converting an analyte in solid, liquid, or solution form to a free gaseous atom is called atomization. In most cases the sample containing the analyte undergoes some form of sample preparation that leaves the analyte in an organic or aqueous solution. For this reason, only the introduction of solution samples is considered in this text. Two general methods of atomization are used flame atomization and electrothermal atomization. A few elements are atomized using other methods. 

The present Section, which provides an outline of selected relevant topics in electrochemistry, is intended primarily as an introduction to aqueous corrosion for those readers whose basic training has not involved a study of electrochemistry. The scope of electrochemistry is enormous and cannot be treated adequately here, but there are now a number of excellent books on the subject, and it is hoped that this outline will serve to stimulate further study. The topics selected are as follows a) the nature of the electrified interface between the metal and the solution, (b) adsorption, (c) transfer of charge across the interface under equilibrium and non-equilibrium conditions, d) overpotential and the rate of an electrode reaction and (e) the hydrogen evolution reaction and hydrogen absorption by ferrous alloys. For reasons of space a number of important topics, such as the electrochemistry of electrolyte solutions, have been omitted. 

Aqueous standard solutions are a source of certain difficulties In electrothermal atomic absorption spectrometry of trace metals In biological fluids The viscosities and surface tensions of aqueous standard solutions are substantially less than the viscosities and surface tensions of serum, blood and other proteln-contalnlng fluids These factors Introduce volumetric disparities In pipetting of standard solutions and body fluids, and also cause differences In penetration of these liquids Into porous graphite tubes or rods Preliminary treatment of porous graphite with xylene may help to minimize the differences of liquid penetration (53,67) A more satisfactory solution of this problem Is preparation of standards In aqueous solutions of metal-free dextran (50-60 g/llter), as first proposed by Pekarek et al ( ) for the standardization of serum chromium analyses This practice has been used successfully by the present author for standardization of analyses of serum nickel The standard solutions which are prepared In aqueous dextran resemble serum In regard to viscosity and surface tension Introduction of dextran-contalnlng standard solutions Is an Important contribution to electrothermal atomic absorption analysis of trace metals In body fluids. 

Most electrode materials are hydrophilic and readily wetted by aqueous solutions. Two methods are used to create and maintain an optimum gas/solution ratio in the electrode. The first method employs a certain excess gas pressure in the gas space. This causes the liquid to be displaced from the wider pores in finer pores the liquid continues to be retained by capillary forces. The second method employs partial wetproofing of tfie electrode by the introduction of hydrophobic materials (e.g., fine PTFE particles). Tfien the electrolyte will penetrate only those pores in the hydrophilic electrode material where the concentration of hydrophobic particles is low. 

Some of the types of equilibria involved in the unit operations separation and concentration are listed in the introduction, Section 9.17.1. Those which depend most on coordination chemistry, and for which details of metal complex formation are best understood, are associated with hydrometallurgy. Once the metal values have been transferred to an aqueous solution, the separation from other metals and concentration can be achieved by one of the following processes.3... 

Relatively little attention has been devoted to the direct electrodeposition of transition metal-aluminum alloys in spite of the fact that isothermal electrodeposition leads to coatings with very uniform composition and structure and that the deposition current gives a direct measure of the deposition rate. Unfortunately, neither aluminum nor its alloys can be electrodeposited from aqueous solutions because hydrogen is evolved before aluminum is plated. Thus, it is necessary to employ nonaqueous solvents (both molecular and ionic) for this purpose. Among the solvents that have been used successfully to electrodeposit aluminum and its transition metal alloys are the chloroaluminate molten salts, which consist of inorganic or organic chloride salts combined with anhydrous aluminum chloride. An introduction to the chemical, electrochemical, and physical properties of the most commonly used chloroaluminate melts is given below. 

Deoxoartemisinin and carboxypropyldeoxoartimisinin have also been shown to have anti-tumour activity and, NMR studies on solution conformations have been reported <00BBR359>. One of the problems with artemisinin use is its poor water solubility characteristics. An attempt to rectify this, and to overcome stability problems associated with sodium artesunate in solution, has involved the introduction of amino group functionality as in 127 (eg. R = 0(CH2)3NR r2 where NR r2 = morpholine). The maleate salt of this compound has reasonable water solubility and aqueous solutions are stable at room temperature for an extended time. However activity against Plasmodium knowlesi in rhesus monkeys after oral administration was poorer compared with artesunic acid <00JMC1635>. 

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