Basic solution examples

The distinction between primary and secondary amines thus depends on the different solubility properties of their benzenesulfonamide derivatives. However, the potassium salts of certain primary sulfonamides are not completely soluble in basic solution. Examples usually involve primary amines of higher molar mass and those having cyclic alkyl groups. To avoid confusion and possible misassignment... 

For chemical processes, some examples are the elimination of aromatics by sulfonation, the elimination of olefins by bromine addition on the double bond (bromine number), the elimination of conjugated diolefins as in the case of the maleic anhydride value (MAV), and the extraction of bases or acids by contact with aqueous acidic or basic solutions. 

In basic solutions a different set of redox equilibria obtain and a different set of reduction potentials must be used. I or example ... 

In the sulfuric acid solvent system, compounds that enhance the concentration of the solvo-cation HSO4- will behave as bases and those that give rise to H3S04 will behave as acids (p. 425). Basic solutions can be formed in several ways of which the following examples are typical ... 

In order to obtain good yields from a Weiss reaction sequence, the H+-concentration has to be adjusted properly in the reaction mixture. The reaction is usually carried out in a buffered, weakly acidic or weakly basic solution. By the Weiss reaction simple starting materials are converted into a complex product of defined stereochemistry. There is no simpler procedure for the synthesis of the l,5-c -disubstituted bicyclo[3.3.0]octane skeleton it has for example found application in the synthesis of polyquinanes. ... 

Strong basic solutions are effective solvents for acid gases. However, these solutions are not normally used for treating large volumes of natural gas because the acid gases form stable salts, which are not easily regenerated. For example, carbon dioxide and hydrogen sulfide react with aqueous sodium hydroxide to yield sodium carbonate and sodium sulfide, respectively. 

When an alkene reacts with BH3 in THF solution, rapid addition to the double bond occurs three times and a tricilkylborcme, R3B, is formed. For example, 1 molar equivalent of BH3 adds to 3 molar equivalents of cyclohexene to yield tricyclohexylborane. When tricvclohexylborane is then treated with aqueous hydrogen peroxide (H2C>2) in basic solution, an oxidation takes place. The three C-B bonds are broken, -OH groups bond to the three carbons, and 3 equivalents of cyclohexanol are produced. The net effect of the... 

You are probably familiar with a variety of aqueous solutions that are either acidic or basic (Figure 4.6). Acidic solutions have a sour taste and affect the color of certain organic dyes known as acid-base indicators. For example, litmus turns from blue to red in acidic solution. Basic solutions have a slippery feeling and change the colors of indicators (e.g., red to blue for litmus). 

Bromopyrogallol red. This metal ion indicator is dibromopyrogallol sulphon-phthalein and is resistant to oxidation it also possesses acid-base indicator properties. The indicator is coloured orange-yellow in strongly acidic solution, claret red in nearly neutral solution, and violet to blue in basic solution. The dyestuff forms coloured complexes with many cations. It is valuable for the determination, for example, of bismuth (pH = 2-3. nitric acid solution endpoint blue to claret red). 

The deoxygeneration of nitroarenes by trivalent phosphorus compounds in the presence of amines is a useful route to 3/f-azepin-2-amines (cf. compounds 32, Section 3.1.1.4.2.2.). Subsequently, it has been shown, by carrying out the reaction in strongly basic solution, that the process can be extended to the synthesis of 1H-. 3H- and 5//-2-benzazepines from nitronaph-thalenes 43 For example, 1-nitronaphthalenes 3 with dimethyl phosphite in the presence of sodium methoxide and a primary or secondary aliphatic amine, yield the dimethyl 5//-2-ben-zazepin-3-yl phosphonates 4 accompanied, in some cases, by the isomeric 3//-2-bcnzazepin-3-yl phosphonates 5. 

Owing to the reactions of the initial primary radiolysis products among themselves, as in Eqs. (11-58)—(11-62), it is usually necessary to add another reagent to remove the unwanted ones. For example, to study reactions of e alone, one must work in neutral or basic solution to avoid its destruction by HsO+ (see Problem 11-12). Also, hydroxyl radicals and hydrogen atoms are removed from the system by prior addition of terf-butyl alcohol to give noninterfering products,... 

There are a limited number of such "steady radiolysis" studies of Pu in neutral or basic solutions that have been reported. Here too, the results are not unambiguous. For example, in a series of studies ( 5) with 20 mM Pu and added 2l+ltCm (1.8 x 10 D/mM/ml) the Pu(III) decreased over periods of days in solutions containing Cl- (i.e., artificial sea water and WIPP Brine) as well as in triply distilled water. The most striking result was the growth and disappearance of Pu(VI) in distilled H2O over some 300 days. 

While there have been only a limited number of reactions of e-(aq) and Pu ions in near neutral or basic solutions, apparently systematic reactivity patterns provide some additional insight. For example, it has been noted that the second order rate parameters (M s-1) for the reactions of... 

All anions that are the conjugate bases of weak acids produce basic solutions. For example, formic acid, HCOOH, the acid in ant venom, is a weak acid, and so the formate ion acts as a base in water ... 

To calculate the pH of a salt solution, we can use the equilibrium table procedure described in Toolboxes 10.1 and 10.2—an acidic cation is treated as a weak acid and a basic anion as a weak base. However, often we must first calculate the Ka or Kh for the acidic or basic ion. Examples 10.10 and 10.11 illustrate the procedure. 

EXAMPLE 12.2 Sample exercise Balancing a redox equation in basic solution... 

The following examples illustrate how to calculate the pH of acidic and basic solutions. 

An aqueous solution of a soluble salt contains cations and anions. These ions often have acid-base properties. Anions that are conjugate bases of weak acids make a solution basic. For example, sodium fluoride dissolves in water to give Na, F, and H2 O as major species. The fluoride anion is the conjugate base of the weak acid HF. This anion establishes a proton transfer equilibrium with water ... 

A second separation technique is leaching, which uses solubility properties to separate the components of an ore. For example, modem gold production depends on the extraction of tiny particles of gold from gold-bearing rock deposits. After the rock is crushed, it is treated with an aerated aqueous basic solution of sodium cyanide. Molecular oxygen oxidizes the metal, which forms a soluble coordination complex with the cyanide anion ... 

For example, Pt/Si02 catalysts are conveniently made by impregnating a silica support vith a basic solution (pH 8-9) of platinum tetraammine ions, Pt(NH3)4 (dissolved as chloride). As the silica surface is negatively charged, the Pt-containing ions attach to the SiO entities and disperse over the surface. The pH should be kept belo v 9 because other vise the silica surface starts to dissolve. 

Aluminas. Aluminas, porous AI2O3, are available in many forms. They constitute the most important carrier material in heterogeneous catalysis. Alumina is amphoteric and, as a con.sequence, soluble in both acidic and basic media. Precipitation can be performed from an acid solution by adding a base or from a basic solution by adding an acid, as schematically represented in Fig. 3.18. If, for example, at a pH of less than about 3 a base is added to an aqueous solution of aluminium sulphate, a precipitate is formed. If this material is filtered, dried and calcined, an amorphous porous AI2O3 is obtained. At other pH values different porous aluminas can be synthesized. 

In practice, promising results have been obtained for several systems. For example, fair to good yields of epoxides are obtained when a two-phase system consisting of alkene and ethyl chloroformate is stirred with a buffered basic solution of hydrogen peroxide. The active oxidant is presumed to be O-ethyl peroxycarbonic acid.85... 

An interesting further example of a homolytic aromatic reaction involves the oxidation of phenols in basic solution with one-electron oxidising agents (e.g. Fe(m), H20 + the enzyme peroxidase) ... 

The activity of many enzymes is pH-dependent because the enzyme may ionize in solution and the biological activity of unionized and ionized forms may be different. In this case, the rate of an enzyme-mediated reaction can be expected to depend on the acidity of the solution. If the enzyme can lose more than one proton as the pH increases (Figure 8.12), the rate of reaction as a function of pH may display a maximum if the forms of the enzyme in strongly acidic or strongly basic solution are inactive, but the intermediate, monoanion, is active. An example of this behavior is provided by fumarase (Figure 8.13). 

Oxides of metals are sometimes called basic anhydrides because they react with water to produce basic solutions. Some examples of this type of reaction are the following ... 

Neither the catalysis by acids nor by bases is conclusive evidence of a non-radical mechanism however. For example, the semiquinone radical is more stable in basic solution where it exists as a negative ion-radical, and the related nitrogen radicals are more stable in acid solution where they exist as positive ion-radicals. In both cases the ion-radicals have symmetrical resonance not possessed by the neutral radical. 

---