Determining Acids and Bases

Other acids are made up of more than two elements and often contain polyatomic ions. Polyatomic ions are collections of two or 

The numeral two written in front of the hydrogen ion shows that for every molecule of sulfuric acid, two hydrogen ions and one sulfate ion (again, the one is understood) are released. At least this is the way it works in theory. In reality, hydrogen ions do not really just float in water, but instead pretty quickly attach themselves to a water molecule. The molecule formed, H30+, is called a hydro-nium ion  

The hydronium ion is really the ion that gives an acid its properties. For the sake of simplicity, however, most chemists ignore the hydronium ion in favor of just saying a hydrogen ion (or proton) and writing Ff+ in a chemical equation. 

Nitric acid acts in a similar manner to sulfuric acid when it is dissolved in water  

For every molecule of nitric acid dissolved in water, one hydrogen ion and one nitrate ion are produced. 

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You no doubt noticed that some of the bases in Table 16-1 don t contain a hydroxide ion, which means that the Arrhenius definition of acids and bases can t apply. When chemists realized that several substances behaved like bases but didn t contain a hydroxide ion, they reluctantly acknowledged that another determination method was needed. Independently proposed by Johannes Bronsted and Thomas Lowry in 1923 and therefore named cifter both of them, the Bronsted-Lowry method for determining acids and bases accounts for those pesky non-hydroxide-containing bases. 

B. Factors Determining Acid and Base Sites Generation a. Composition... 

Determination of the dissociation constants of acids and bases from the change of absorption spectra with pH. The spectrochemical method is particularly valuable for very weak bases, such as aromatic hydrocarbons and carbonyl compounds which require high concentrations of strong mineral acid in order to be converted into the conjugate acid to a measurable extent. 

Care must be exercised in determining the number of reaction units associated with the acid and base. The number of reaction units for an acid, for instance, depends not on how many acidic protons are present, but on how many... 

This relationship between and Kb simplifies the tabulation of acid and base dissociation constants. Acid dissociation constants for a variety of weak acids are listed in Appendix 3B. The corresponding values of Kb for their conjugate weak bases are determined using equation 6.14. 

With samples that are difficult to dissolve, the first approach is usually to try digesting the sample with an acid or base. Table 7.2 lists the most commonly used acids and bases and summarizes their use. Digestion is commonly carried out in an open container, such as a beaker, using a hot plate as a source of heat. The chief advantage of this approach is its low cost as it requires no special equipment. Volatile reaction products, however, are lost, leading to a determinate error if analyte is included among the volatile substances. 

Quantitative Calculations In acid-base titrimetry the quantitative relationship between the analyte and the titrant is determined by the stoichiometry of the relevant reactions. As outlined in Section 2C, stoichiometric calculations may be simplified by focusing on appropriate conservation principles. In an acid-base reaction the number of protons transferred between the acid and base is conserved thus... 

Equivalent Weights Acid-base titrations can be used to characterize the chemical and physical properties of matter. One simple example is the determination of the equivalent weighf of acids and bases. In this method, an accurately weighed sample of a pure acid or base is titrated to a well-defined equivalence point using a mono-protic strong acid or strong base. If we assume that the titration involves the transfer of n protons, then the moles of titrant needed to reach the equivalence point is given as... 

When the leaving group is better, breakdown can occur directly from A. This is the case when R"0 is a phenolate anion. The mechanism also depends upon the pH and the presence of general acids and bases because the position of the equilibria among the tetrahedral intermediates and their rates of breakdown are determined by these factors. 

New Chapter 1 has been retitled Structure Determines Properties to better reflect its purpose and has been rewritten to feature a detailed treatment of acids and bases. Rather than a review of what students learned about acids and bases in general chemistry. Sections 1.12-1.17 discuss acids and bases from an organic chemistry perspective. 

As pointed out in Chapter 4, an acid-base indicator is useful in determining the equivalence point of an acid-base titration. This is the point at which reaction is complete equivalent quantities of acid and base have reacted. If the indicator is chosen properly, the point at which it changes color (its end point) coincides with the equivalence point To understand how and why an indicator changes color, we need to understand the equilibrium principle involved. 

The general approach illustrated by Example 18.7 is widely used to determine equilibrium constants for solution reactions. The pH meter in particular can be used to determine acid or base equilibrium constants by measuring the pH of solutions containing known concentrations of weak acids or bases. Specific ion electrodes are readily adapted to the determination of solubility product constants. For example, a chloride ion electrode can be used to find [Cl-] in equilibrium with AgCl(s) and a known [Ag+]. From that information, Ksp of AgCl can be calculated. 

Fluoride ion, and weak acids and bases do not interfere, but nitrate, nitrite, perchlorate, thiocyanate, chromate, chlorate, iodide, and bromide do. Since analysis of almost all boron-containing compounds requires a preliminary treatment which ultimately results in an aqueous boric acid sample, this procedure may be regarded as a gravimetric determination of boron. 

In very dilute solutions of strong acids and bases, the pH is significantly affected by the autoprotolysis of water. The pH is determined by solving three simultaneous equations the charge-balance equation, the material-balance equation, and the expression for Kw. 

Step 5 Use an equilibrium table to find the H.O concentration in a weak acid or the OH concentration in a weak base. Alternatively, if the concentrations of conjugate acid and base calculated in step 4 are both large relative to the concentration of hydronium ions, use them in the expression for /<, or the Henderson—Hasselbalch equation to determine the pH. In each case, if the pH is less than 6 or greater than 8, assume that the autoprotolysis of water does not significantly affect the pH. If necessary, convert between Ka and Kh by using Kw = KA X Kb. 

This is always the case for any two acids, and by measuring the positions of the equilibrium the relative strengths of acids and bases can be determined. Of course, if the two acids involved are close to each other in strength, a measurable reaction will occur from both sides, though the position of equilibrium will still be over to the... 

This quick glance at the acid-base properties of some (poly)azamacro-cycles already suggests which parameters will determine the p a of macrocyclic and related acids and bases. Hydrogen bonds will probably be very important and in polyions Coulomb interactions have to be taken into consideration. But the geometry of the acid-base function has to be defined. In Sections 2, 3 and 4 we shall therefore focus on compounds with intra-annular acid-base functionalities (the 1,3-xylyl trick). 

Most acids and bases are weak. A solution of a weak acid contains the acid and water as major species, and a solution of a weak base contains the base and water as major species. Proton-transfer equilibria determine the concentrations of hydronium ions and hydroxide ions in these solutions. To determine the concentrations at equilibrium, we must apply the general equilibrium strategy to these types of solutions. 

The first four steps of the seven-step strategy are identical to the ones in Example. In this example, addition of a strong acid or base modifies the concentrations that go into the buffer equation. We need to determine the new concentrations (Step 5) and then apply the buffer equation (Step 6). In dealing with changes in amounts of acid and base, it is often convenient to work with moles rather than molarities. The units cancel in the concentration term of the buffer equation, so the ratio of concentrations can be... 

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