Chapter 16

Write the chemical equation and the \(K_{b}\) expression for the reaction of each of the following bases with water: (a) dimethylamine, \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH} ;(\mathbf{b})\) carbonate ion, \(\mathrm{CO}_{3}^{2-} ;(\mathbf{c})\) formate ion, \(\mathrm{CHO}_{2}^{-} .\)

Write the chemical equation and the \(K_{b}\) expression for the reaction of each of the following bases with water: (a) propylamine, \(\mathrm{C}_{3} \mathrm{H}_{7} \mathrm{NH}_{2} ;\) (b) monohydrogen phosphate ion, \(\mathrm{HPO}_{4}^{2-} ;(\mathbf{c})\) benzoate ion, \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CO}_{2}^{-}.\)

Calculate the molar concentration of \(\mathrm{OH}^{-}\) in a 0.075 \(\mathrm{M}\) solution of ethylamine \(\left(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2} ; K_{b}=6.4 \times 10^{-4}\right) .\) Calculate the pH of this solution.

Calculate the molar concentration of \(\mathrm{OH}^{-}\) in a 0.724 \(\mathrm{M}\) solution of hypobromite ion \(\left(\mathrm{BrO}^{-} ; K_{b}=4.0 \times 10^{-6}\right) .\) What is the pH of this solution?

Ephedrine, a central nervous system stimulant, is used in nasal sprays as a decongestant. This compound is a weak organic base: $$\mathrm{C}_{10} \mathrm{H}_{15} \mathrm{ON}(a q)+\mathrm{H}_{2} \mathrm{O}(l) \rightleftharpoons \mathrm{C}_{10} \mathrm{H}_{15} \mathrm{ONH}^{+}(a q)+\mathrm{OH}^{-}(a q)$$ A 0.035\(M\) solution of ephedrine has a pH of 11.33 . (a) What are the equilibrium concentrations of \(\mathrm{C}_{10} \mathrm{H}_{15} \mathrm{ON}, \mathrm{C}_{10} \mathrm{H}_{15} \mathrm{ONH}^{+},\) and \(\mathrm{OH}^{-} ?\) (b) Calculate \(K_{b}\) for ephedrine.

codeine \(\left(\mathrm{C}_{18} \mathrm{H}_{21} \mathrm{NO}_{3}\right)\) is a weak organic base. \(\mathrm{A} 5.0 \times 10^{-3} \mathrm{M}\) solution of codeine has a pH of \(9.95 .\) Calculate the value of \(K_{b}\) for this substance. What is the \(\mathrm{pK}_{b}\) for this base?

Phenol, \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH},\) has a \(K_{a}\) of \(1.3 \times 10^{-10}.\) (a) Write out the \(K_{a}\) reaction for phenol. (b) Calculate \(K_{b}\) for phenol's conjugate base. (c) Is phenol a stronger or weaker acid than water?

(a) Given that \(K_{a}\) for acetic acid is \(1.8 \times 10^{-5}\) and that for hypochlorous acid is \(3.0 \times 10^{-8}\) , which is the stronger acid? (b) Which is the stronger base, the acetate ion or the hypochlorite ion? (c) Calculate \(K_{b}\) values for \(C H_{3} C O O^{-}\) and \(C 1 O^{-}.\)

(a) Given that \(K_{b}\) for ammonia is \(1.8 \times 10^{-5}\) and that for hydroxylamine is \(1.1 \times 10^{-8}\) , which is the stronger base? (b) Which is the stronger acid, the ammonium or the hydroxylammonium ion? (c) Calculate \(K_{a}\) values for \(\mathrm{NH}_{4}^{+}\) and \(\mathrm{H}_{3} \mathrm{NOH}^{+}.\)

Pyridinium bromide \(\left(\mathrm{C}_{5} \mathrm{H}_{5} \mathrm{NHBr}\right)\) is a strong electrolyte that dissociates completely into \(\mathrm{C}_{5} \mathrm{H}_{5} \mathrm{NH}^{+}\) and \(\mathrm{Br}^{-} .\) An aqueous solution of pyridinium bromide has a pH of \(2.95 .\) (a) Write out the reaction that leads to this acidic pH. (b) Using Appendix D, calculate the \(K_{a}\) for pyridinium bromide. (c) A solution of pyridinium bromide has a pH of 2.95 . What is the concentration of the pyridinium cation atequilibrium, in units of molarity?

Predict whether aqueous solutions of the following compounds are acidic, basic, or neutral: \((\mathbf{a})\mathrm{NH}_{4} \mathrm{Br},(\mathbf{b}) \mathrm{FeCl}_{3}\) \((\mathbf{c}) \mathrm{Na}_{2} \mathrm{CO}_{3},(\mathbf{d}) \mathrm{KClO}_{4},(\mathbf{e}) \mathrm{NaHC}_{2} \mathrm{O}_{4}\)

Predict whether aqueous solutions of the following subsstances are acidic, basic, or neutral: \((\mathbf{a})\mathrm{AlCl}_{3},\) \((\mathbf{b})\mathrm{NaBr}\) \((\mathbf{c}) \mathrm{NaClO},(\mathbf{d})\left[\mathrm{CH}_{3} \mathrm{NH}_{3}\right] \mathrm{NO}_{3},(\mathbf{e}) \mathrm{Na}_{2} \mathrm{SO}_{3}\)

An unknown salt is either NaF, NaCl, or NaOCl. When 0.050 mol of the salt is dissolved in water to form 0.500 L of solution, the pH of the solution is 8.08. What is the identity of the salt?

An unknown salt is either \(\mathrm{KBr}, \mathrm{NH}_{4} \mathrm{Cl}, \mathrm{KCN},\) or \(\mathrm{K}_{2} \mathrm{CO}_{3} .\) If a 0.100 \(\mathrm{M}\) solution of the salt is neutral, what is the identity of the salt?

Predict the stronger acid in each pair: (a) HNO \(_{3}\) or HNO \(_{2};\) \((\mathbf{b})\mathrm{H}_{2} \mathrm{S}\) or \(\mathrm{H}_{2} \mathrm{O} ;(\mathbf{c}) \mathrm{H}_{2} \mathrm{SO}_{4}\) or \(\mathrm{H}_{2} \mathrm{SeO}_{4}(\mathbf{d}) \mathrm{CH}_{3} \mathrm{COOH}\) or \(\mathrm{CCl}_{3}\) \(\mathrm{COOH}.\)

Based on their compositions and structures and on conjugate acid-base relationships, select the stronger base in each of the following pairs: (a) \(\mathrm{BrO}^{-}\) or \(\mathrm{ClO}^{-},(\mathbf{b}) \mathrm{BrO}^{-}\) or \(\mathrm{BrO}_{2}^{-}\) (c) \(\mathrm{HPO}_{4}^{2-}\) or \(\mathrm{H}_{2} \mathrm{PO}_{4}^{-}.\)

Based on their compositions and structures and on conjugate acid-base relationships, select the stronger base in each of the following pairs: (a) \(\mathrm{NO}_{3}^{-}\) or \(\mathrm{NO}_{2}^{-},(\mathbf{b}) \mathrm{PO}_{4}^{3-}\) or \(\mathrm{AsO}_{4}^{3-}\) \((\mathbf{c}) \mathrm{HCO}_{3}^{-}\) or \(\mathrm{CO}_{3}^{2-}.\)

Indicate whether each of the following statements is true or false. For each statement that is false, correct the statement to make it true. (a) In general, the acidity of binary acids increases from left to right in a given row of the periodic table. (b) In a series of acids that have the same central atom, acid strength increases with the number of hydrogen atoms bonded to the central atom. (c) Hydrotelluric acid \(\left(\mathrm{H}_{2} \mathrm{Te}\right)\) is a stronger acid than \(\mathrm{H}_{2} \mathrm{S}\) because Te is more electronegative than \(\mathrm{S} .\)

Indicate whether each of the following statements is true or false. For each statement that is false, correct the statement to make it true. (a) Acid strength in a series of \(\mathrm{H}-\) A molecules increases with increasing size of \(\mathrm{A} .\) (b) For acids of the same general structure but differing electronegativities of the central atoms, acid strength decreases with increasing electronegativity of the central atom.(c) The strongest acid known is HF because fluorine is the most electronegative element.

Ammonia, \(\mathrm{NH}_{3},\) acts as an Arrhenius base, a Bronsted-Lowry base, and a Lewis base, in aqueous solution. Write out the reaction \(\mathrm{NH}_{3}\) undergoes with water and explain what properties of ammonia correspond to each of the three definitions of "base."

The fluoride ion reacts with water to produce HF. (a) Write out the chemical equation for this reaction. (b) Will a concentrated solution of NaF in water be acidic, basic, or neutral? (c) Is fluoride acting as a Lewis acid or as a Lewis base when reacting with water?

Identify the Lewis acid and Lewis base among the reactants in each of the following reactions: (a) \(\operatorname{Fe}\left(\mathrm{ClO}_{4}\right)_{3}(s)+6 \mathrm{H}_{2} \mathrm{O}(l) \rightleftharpoons\) \(\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\left[\mathrm{Fe}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}(a q)+3 \mathrm{ClO}_{4}^{-}(a q)\) (b) \(\mathrm{CN}^{-}(a q)+\mathrm{H}_{2} \mathrm{O}(l) \Longrightarrow \mathrm{HCN}(a q)+\mathrm{OH}^{-}(a q)\) (c)\(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{N}(g)+\mathrm{BF}_{3}(g) \rightleftharpoons\left(\mathrm{CH}_{3}\right)_{3} \mathrm{NBF}_{3}(s)\) (d)\(\operatorname{HIO}(l q)+\mathrm{NH}_{2}^{-}(l q) \Longrightarrow \mathrm{NH}_{3}(l q)+\mathrm{IO}^{-}(l q)\) (\(lq\) denotes liquid ammonia as solvent)

Identify the Lewis acid and Lewis base in each of the following reactions: (a) \(\mathrm{HNO}_{2}(a q)+\mathrm{OH}^{-}(a q) \rightleftharpoons \mathrm{NO}_{2}^{-}(a q)+\mathrm{H}_{2} \mathrm{O}(l)\) (b) \(\mathrm{FeBr}_{3}(s)+\mathrm{Br}^{-}(a q) \rightleftharpoons \mathrm{FeBr}_{4}^{-}(a q)\) (c) \(\mathrm{Zn}^{2+}(a q)+4 \mathrm{NH}_{3}(a q) \rightleftharpoons \mathrm{Zn}\left(\mathrm{NH}_{3}\right)_{4}^{2+}(a q)\) (d) \(\mathrm{SO}_{2}(g)+\mathrm{H}_{2} \mathrm{O}(l) \rightleftharpoons \mathrm{H}_{2} \mathrm{O}_{3}(a q)\)

Predict which member of each pair produces the more acidic aqueous solution: (a) \(\mathrm{K}^{+}\) or \(\mathrm{Cu}^{2+},(\mathbf{b}) \mathrm{Fe}^{2+}\) or \(\mathrm{Fe}^{3+}\) , (c) \(\mathrm{Al}^{3+}\) or \(\mathrm{Ga}^{3+}\) .

Indicate whether each of the following statements is correct or incorrect. (a) Every Bronsted-Lowry acid is also a Lewis acid. (b) Every Lewis acid is also a Bronsted-Lowry acid. (c) Conjugate acids of weak bases produce more acidic solutions than conjugate acids of strong bases. (d) \(\mathrm{K}^{+}\) ion is acidic in water because it causes hydrating water molecules to become more acidic. (e) The percent ionization of a weak acid in water increases as the concentration of acid decreases.

A solution is made by adding \(0.300 \mathrm{g} \mathrm{Ca}(\mathrm{OH})_{2}(s), 50.0 \mathrm{mL}\) of \(1.40 \mathrm{MNN}_{3},\) and enough water to make a final volume of 75.0 \(\mathrm{mL}\) . Assuming that all of the solid dissolves, what is the pH of the final solution?

The odor of fish is due primarily to amines, especially methylamine \(\left(\mathrm{CH}_{3} \mathrm{NH}_{2}\right) .\) Fish is often served with a wedge of lemon, which contains citric acid. The amine and the acid react forming a product with no odor, thereby making the less-than-fresh fish more appetizing. Using data from Appendix \(\mathrm{D},\) calculate the equilibrium constant for the reaction of citric acid with methylamine, if only the first proton of the citric acid \(\left(K_{a 1}\right)\) is important in the neutralization reaction.

Which, if any, of the following statements are true? (a) The stronger the base, the smaller the \(\mathrm{pK}_{b}\). (b) The stronger the base, the larger the \(\mathrm{pK}_{b}.\) (c) The stronger the base, the smaller the \(K_{b}\) . (a) The stronger the base, the larger the \(K_{b} .\) (e) The stronger the base, the smaller the \(\mathrm{p} K_{a}\) of its conjugate acid. (f) The stronger the base, the larger the \(\mathrm{p} K_{a}\) of its conjugate acid.

Calculate the \(\mathrm{pH}\) of a solution made by adding 2.50 \(\mathrm{g}\) of lithium oxide \(\left(\mathrm{Li}_{2} \mathrm{O}\right)\) to enough water to make 1.500 \(\mathrm{L}\) of solution.

Benzoic acid \(\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{COOH}\right)\) and aniline \(\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}\right)\) are both derivatives of benzene. Benzoic acid is an acid with \(K_{a}=6.3 \times 10^{-5}\) and aniline is a base with \(K_{a}=4.3 \times 10^{-10} .\) (a) What are the conjugate base of benzoic acid and the conjugate acid of aniline? (b) Anilinium chloride \(\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{3} \mathrm{Cl}\right)\) is a strong electrolyte that dissociates into anilinium ions \(\left(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{3}^{+}\right)\) and chloride ions. Which will be more acidic, a 0.10\(M\) solution of benzoic acid or a 0.10 M solution of anilinium chloride? (c) What is the value of the equilibrium constant for the following equilibrium? $$\begin{array}{c}{\mathrm{C}_{6} \mathrm{H}_{5} \operatorname{COOH}(a q)+\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}(a q) \rightleftharpoons} \\\ \quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad\quad {\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{COO}^{-}(a q)+\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{3}^{+}(a q)}\end{array}$$

What is the \(\mathrm{pH}\) of a solution that is \(2.5 \times 10^{-9} \mathrm{M}\) in \(\mathrm{NaOH}\) ? Does your answer make sense? What assumption do we normally make that is not valid in this case?

Butyric acid is responsible for the foul smell of rancid butter. The \(\mathrm{pK}_{a}\) of butyric acid is 4.84 (a) Calculate the pK \(_{b}\) for the butyrate ion. (b) Calculate the pH of a 0.050 \(M\) solution of butyric acid. (c) Calculate the pH of a 0.050\(M\) solution of sodium butyrate.

Arrange the following 0.10\(M\) solutions in order of increasing acidity: (i) \(\mathrm{NH}_{4} \mathrm{NO}_{3},(\mathrm{ii}) \mathrm{NaNO}_{3},(\mathrm{iii}) \mathrm{CH}_{3} \mathrm{COONH}_{4},(\mathrm{iv})\) \(\mathrm{NaF},(\mathrm{v}) \mathrm{CH}_{3} \mathrm{COONa}.\)

A 0.25 M solution of a salt NaA has \(\mathrm{pH}=9.29 .\) What is the value of \(K_{a}\) for the parent acid HA?

The following observations are made about a diprotic acid \(\mathrm{H}_{2} \mathrm{A} :(\mathrm{i}) \mathrm{A} 0.10 \mathrm{M}\) solution of \(\mathrm{H}_{2} \mathrm{A}\) has \(\mathrm{pH}=3.30 .\) (ii) \(\mathrm{A} 0.10 \mathrm{M}\) solution of the salt NaHA is acidic. Which of the following could be the value of \(\mathrm{p} K_{a 2}\) for \(\mathrm{H}_{2} \mathrm{A} :\) (i) \(3.22,\) (ii) 5.30 , (iii) \(7.47,\) or (iv) 9.82\(?\)

Many moderately large organic molecules containing basic nitrogen atoms are not very soluble in water as neutral molecules, but they are frequently much more soluble as their acid salts. Assuming that pH in the stomach is \(2.5,\) indicate whether each of the following compounds would be present in the stomach as the neutral base or in the protonated form: nicotine, \(K_{b}=7 \times 10^{-7} ;\) caffeine, \(K_{b}=4 \times 10^{-14}\) ; strychnine, \(K_{b}=1 \times 10^{-6} ;\) quinine, \(K_{b}=1.1 \times 10^{-6} .\)

The \(\mathrm{p} K_{\mathrm{b}}\) of water is ______ . (a) 1 (b) 7 (c) 14 (d) not defined (e) none of the above

Calculate the number of \(\mathrm{H}^{+}(a q)\) ions in 1.0 \(\mathrm{mL}\) of pure water at \(25^{\circ} \mathrm{C} .\)

How many milliliters of concentrated hydrochloric acid solution \((36.0 \%\) HCl by mass, density \(=1.18 \mathrm{g} / \mathrm{mL})\) are required to produce 10.0 \(\mathrm{L}\) of a solution that has a pH of 2.05\(?\)

The volume of an adult's stomach ranges from about 50 mL when empty to 1 when full. If the stomach volume is 400 mL and its contents have a pH of \(2,\) how many moles of \(\mathrm{H}^{+}\) does the stomach contain? Assuming that all the \(\mathrm{H}^{+}\) comes from \(\mathrm{HCl}\) , how many grams of sodium hydrogen carbonate will totally neutralize the stomach acid?

Atmospheric CO \(_{2}\) levels have risen by nearly 20\(\%\) over the past 40 years from 320 ppm to 400 ppm. (a) Given that the average \(\mathrm{pH}\) of clean, unpolluted rain today is \(5.4,\) determine the pH of unpolluted rain 40 years ago. Assume that carbonic acid \(\left(\mathrm{H}_{2} \mathrm{CO}_{3}\right)\) formed by the reaction of \(\mathrm{CO}_{2}\) and water is the only factor influencing pH. $$\mathrm{CO}_{2}(g)+\mathrm{H}_{2} \mathrm{O}(l) \rightleftharpoons \mathrm{H}_{2} \mathrm{CO}_{3}(a q)$$ (b) What volume of \(\mathrm{CO}_{2}\) at \(25^{\circ} \mathrm{C}\) and 1.0 \(\mathrm{atm}\) is dissolved in a 20.0 -L bucket of today's rainwater?

At \(50^{\circ} \mathrm{C},\) the ion-product constant for \(\mathrm{H}_{2} \mathrm{O}\) has the value \(K_{w}=5.48 \times 10^{-14}\) . (a) What is the pH of pure water at \(50^{\circ} \mathrm{C} ?\) (b) Based on the change in \(K_{w}\) with temperature, predict whether \(\Delta H\) is positive, negative, or zero for the autoionization reaction of water: $$2 \mathrm{H}_{2} \mathrm{O}(l) \Longrightarrow \mathrm{H}_{3} \mathrm{O}^{+}(a q)+\mathrm{OH}^{-}(a q)$$

In many reactions, the addition of \(\mathrm{AlCl}_{3}\) produces the same effect as the addition of \(\mathrm{H}^{+} .\) (a) Draw a Lewis structure for \(\mathrm{AlCl}_{3}\) in which no atoms carry formal charges, and determine its structure using the VSEPR method. (b) What characteristic is notable about the structure in part (a) that helps us understand the acidic character of AlCl \(_{3} ?\) (c) Predict the result of the reaction between \(\mathrm{AlCl}_{3}\) and \(\mathrm{NH}_{3}\) in a solvent that does not participate as a reactant. (d) Which acid-base theory is most suitable for discussing the similarities between \(\mathrm{AlCl}_{3}\) and \(\mathrm{H}^{+}\) ?

What is the boiling point of a 0.10\(M\) solution of \(\mathrm{NaHSO}_{4}\) if the solution has a density of 1.002 \(\mathrm{g} / \mathrm{mL} ?\)

The iodate ion is reduced by sulfite according to the following reaction: $$\mathrm{IO}_{3}^{-}(a q)+3 \mathrm{SO}_{3}^{2-}(a q) \longrightarrow \mathrm{I}^{-}(a q)+3 \mathrm{SO}_{4}^{2-}(a q)$$ The rate of this reaction is found to be first order in \(\mathrm{IO}_{3}^{-}\) , first order in \(\mathrm{SO}_{3}^{2-}\) , and first order in \(\mathrm{H}^{+}\) . (a) Write the rate law for the reaction. (b) By what factor will the rate of the reaction change if the pH is lowered from 5.00 to 3.50\(?\) Does the reaction proceed more quickly or more slowly at the lower pH? (c) By using the concepts discussed in Section 14.6, ex-plain how the reaction can be pH-dependent even though H' does not appear in the overall reaction.

(a) Using dissociation constants from Appendix D, determine the value for the equilibrium constant for each of the following reactions. \((\mathrm{i}) \mathrm{HCO}_{3}^{-}(a q)+\mathrm{OH}^{-}(a q) \rightleftharpoons \mathrm{co}_{3^{-}(a q)}+\mathrm{H}_{2} \mathrm{O}(l)\) (ii) \(\mathrm{NH}_{4}^{+}(a q)+\mathrm{CO}_{3}^{2-}(a q) \rightleftharpoons \mathrm{NH}_{3}(a q)+\mathrm{HCO}_{3}^{-}(a q)\) (b) We usually use single arrows for reactions when the for- ward reaction is appreciable \((K\) much greater than 1\()\) equilibrium is never established. If we follow this convention, which of these equilibria might be written with a single arrow?