Weak acids reaction with strong base

Of the several syntheses available for the phenothiazine ring system, perhaps the simplest is the sulfuration reaction. This consists of treating the corresponding diphenylamine with a mixture of sulfur and iodine to afford directly the desired heterocycle. Since the proton on the nitrogen of the resultant molecule is but weakly acidic, strong bases are required to form the corresponding anion in order to carry out subsequent alkylation reactions. In practice such diverse bases as ethylmagnesium bromide, sodium amide, and sodium hydride have all been used. Alkylation with (chloroethyl)diethylamine affords diethazine (1), a compound that exhibits both antihista-minic and antiParkinsonian activity. Substitution of w-(2-chloroethyl)pyrrolidine in this sequence leads to pyrathiazine (2), an antihistamine of moderate potency. 

A typical weak acid-strong base titration is that of acetic acid with sodium hydroxide. The net ionic equation for the reaction is... 

When an acid in solution is exactly neutralized with a base the resulting solution corresponds to a solution of the salt of the acid-base pair. This is a situation which frequently arises in analytical procedures and the calculation of the exact pH of such a solution may be of considerable importance. The neutralization point or end point in an acid-base titration is a particular example (Chapter 5). Salts may in all cases be regarded as strong electrolytes so that a salt AB derived from acid AH and base B will dissociate completely in solution. If the acid and base are strong, no further reaction is likely and the solution pH remains unaffected by the salt. However if either or both acid and base are weak a more complex situation will develop. It is convenient to consider three separate cases, (a) weak acid-strong base, (b) strong acid-weak base and (c) weak acid-weak base. 

We ve seen on numerous occasions that the neutralization reaction of an acid with a base produces water and a salt. But to what extent does a neutralization reaction go to completion We must answer that question before we can make pH calculations on mixtures of acids and bases. Let s look at four types of neutralization reactions (1) strong acid-strong base, (2) weak acid-strong base, (3) strong acid-weak base, and (4) weak acid-weak base. 

Considering this new H+-transfer acid-base definition, take a look at the type of acid-base reaction in which the acid is weak and the base is strong. An example is the reaction of acetic acid, HC2H3O2, the weak acid present in vinegar, with sodium hydroxide. The equation of the overall reaction is similar to that of a strong acid-strong base reaction. 

Calculating the pH The calculation procedure for the weak acid-strong base titration is different from that for the strong acid-strong base titration because we have to consider the partial dissociation of the weak acid and the reaction of the conjugate base with water. There are four key regions of the titration curve, each of which requires a different type of calculation to find [H30 ] ... 

For a weak acid-strong base titration, the calculation of pH at different stages of the titration requires a different approach than the one used in Example 17-7. Consider, for example, the titration of a solution of CH3COOH with NaOH. Because the equilibrium constant for the neutralization of CH3COOH by NaOH is extremely large, we can justifiably say that the neutralization reaction... 

A base is any material that produces hydroxide ions when it is dissolved in water. The words alkaline, basic, and caustic are often used synonymously. Common bases include sodium hydroxide (lye), potassium hydroxide (potash lye), and calcium hydroxide (slaked lime). The concepts of strong versus weak bases, and concentrated versus dilute bases are exactly analogous to those for acids. Strong bases such as sodium hydroxide dissociate completely while weak bases such as the amines dissociate only partially. As with acids, bases can be either inorganic or organic. Typical reactions of bases include neutralization of acids, reaction with metals, and reaction with salts ... 

Alcohols undergo many reactions and can be converted into many other functional groups. They can be dehydrated to give alkenes by treatment with POCI3 and can be transformed into alkyl halides by treatment with PBr3 or SOCU- Furthermore, alcohols are weakly acidic (p/C, — 16-18) and react with strong bases and with alkali metals to form alkoxide anions, which are used frequently in organic synthesis. 

Because carbonyl compounds are only weakly acidic, a strong base is needed for enolate ion formation. If an alkoxide such as sodium ethoxide is used as base, deprotonation takes place only to the extent of about 0. l% because acetone is a weaker acid than ethanol (pKa - 16). If, however, a more powerful base such as sodium hydride (NaH) or lithium diisopropylamide ILiNO -CjHy ] is used, a carbonyl compound can be completely converted into its enolate ion. Lithium diisopropylamide (LDA), which is easily prepared by reaction of the strong base butyllithium with diisopropylamine, is widely used in the laboratory as a base for preparing enolate ions from carbonyl compounds. 

When we write the net ionic equation for the neutralization of a weak acid or a weak base, we use the molecular form of the weak acid or base, because molecules are the dominant species in solution. For example, we write the net ionic equation for the reaction of the weak acid HCN with the strong base NaOH in water (Fig. J.3) as... 

In a weak acid or base, the backwards reaction (where ions join to form the acid or base) occurs more often than it does in a strong acid or base. Therefore, with a weak acid or base, some hydrogen and hydroxide ions are released, but there are many more molecules of intact acid or base than there would be with a strong acid or base. Most acids and bases are weak. They do not completely break down in water. 

Compound 51 was found to be unstable and difficult to purify, as described in the literature [93—95]. Therefore, 51 was not isolated, but was instead converted to the stable pinacol 1-acetamido-l-hexylboronate derivative 52. However, the acylated derivative 52 could not be purified by column chromatography as it was destroyed on silica gel and partially decomposed on alumina. Fortunately, we found that it dissolves in basic aqueous solution (pH > 11) and can then be extracted into diethyl ether when the pH of the aqueous layer is 5—6. Finally, pure 52 was obtained by repeated washing with weak acids and bases. It should be mentioned here that exposure to a strongly acidic solution, which also dissolves compound 51, results in its decomposition. Compared with other routes, the present two-step method involves mild reaction conditions (THF, ambient temperature) and a simple work-up procedure. It should prove very useful in providing an alternative access to a-aminoboronic esters, an important class of inhibitors of serine proteases. 

You learned about acids and bases in your previous chemistry course. In this chapter, you will extend your knowledge to learn how the structure of a compound determines whether it is an acid or a base. You will use the equilibrium constant of the reaction of an acid or base with water to determine whether the acid or base is strong or weak. You will apply your understanding of dissociation and pH to investigate buffer solutions solutions that resist changes in pH. Finally, you will examine acid-base titrations that involve combinations of strong and weak acids and bases. 

In this section, you examined acid-base titration curves for combinations of strong and weak acids and bases. You may have noticed the absence of a curve for the reaction of a weak acid with a weak base. A weak acid-weak base titration curve is difficult to describe quantitatively, because it has competing equilibria. You may learn about this curve in future chemistry courses. 

However, attempts to make an aqueous solution of the base sodium amide would result in the formation of sodium hydroxide and ammonia. The amide ion is a strong base and abstracts a proton from water, a weak acid. The reverse reaction is not favoured, in that hydroxide is a weaker base than the amide ion, and ammonia is a weaker acid than water. Take care with the terminology amide the amide... 

Pyrroles, indoles, isoindoles and carbazoles having no substituent at the nitrogen atom are weakly acidic and, upon treatment with a strong base, form anions which are capable of subsequent reaction with electrophiles at the nitrogen atom and/or the 1-position of isoindoles, the 2-position of pyrroles and the 3-position of indoles. 1-Substituted pyrroles and indoles also react with butyllithium to give 1-substituted 2-pyrrolyl and 2-indolyl anions (see Section 3.05.1.2.9). 

A salt containing at least one ion which is conjugate to a weak acid or base undergoes a reaction with water of an acid-base nature. Let us look at NaC2H302, a salt produced from a strong base, NaOH, and a weak acid, HC2H3O2. The acetate ion in sodium acetate is conjugate to the acetic acid, a weak acid. The acetate ion is a base and can accept a proton from an acid or from the solvent (water) ... 

Section 19.1 discusses the Brpnsted theory of acids and bases, which extends the concepts of add and base beyond aqueous solutions and also explains the acidic or basic nature of solutions of most salts. Dissociation constants, the equilibrium constants for the reactions of weak acids or bases with water, are introduced in Section 19.2. The concept of the ionization of covalent compounds is extended to water itself in Section 19.3, which also covers pH, a scale of acidity and basicity. Section 19.4 describes buffer solutions, which resist change in their acidity or basicity even when some strong acid or base is added. Both the preparation and the action of buffer solutions are explained. Section 19.5 discusses the equilibria of acids containing more than one ionizable hydrogen atom per molecule. 

A buffer solution can be prepared by adding a weak acid or base plus its conjugate to a solution or by preparing one of these from the other in the solution by reaction with strong acid or base, using the principles of hmiting quantities reactions (Section 10.4). 

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