Chapter 17

Benzenesulfonic acid is a monoprotic acid with \(\mathrm{p} K_{a}=2.25\). Calculate the \(\mathrm{pH}\) of a buffer composed of \(0.150 \mathrm{M}\) benzenesulfonic acid and \(0.125 M\) sodium benzenesulfonate.

The acid-base indicator bromcresol green is a weak acid. The yellow acid and blue base forms of the indicator are present in equal concentrations in a solution when the \(\mathrm{pH}\) is \(4.68 .\) What is the \(\mathrm{p} K_{a}\) for bromcresol green?

Equal quantities of \(0.010 \mathrm{M}\) solutions of an acid \(\mathrm{HA}\) and a base \(\mathrm{B}\) are mixed. The \(\mathrm{pH}\) of the resulting solution is \(9.2 .(\mathrm{a})\) Write the equilibrium equation and equilibrium-constant expression for the reaction between \(\mathrm{HA}\) and \(\mathrm{B}\). (b) If \(K_{a}\) for HA is \(8.0 \times 10^{-5}\), what is the value of the equilibrium constant for the reaction between HA and \(B\) ? (c) What is the value of \(K_{b}\) for B?

Two buffers are prepared by adding an equal number of moles of formic acid (HCOOH) and sodium formate (HCOONa) to enough water to make \(1.00 \mathrm{~L}\) of solution. Buffer \(\mathrm{A}\) is prepared using \(1.00 \mathrm{~mol}\) each of formic acid and sodium formate. Buffer B is prepared by using \(0.010 \mathrm{~mol}\) of each. (a) Calculate the \(\mathrm{pH}\) of each buffer, and explain why they are equal. (b) Which buffer will have the greater buffer capacity? Explain. (c) Calculate the change in \(\mathrm{pH}\) for each buffer upon the addition of \(1.0 \mathrm{~mL}\) of \(1.00 \mathrm{M} \mathrm{HCl}\). (d) Calculate the change in \(\mathrm{pH}\) for each buffer upon the addition of \(10 \mathrm{~mL}\) of \(1.00 \mathrm{M} \mathrm{HCl}\). (e) Discuss your answers for parts (c) and (d) in light of your response to part (b).

A biochemist needs \(750 \mathrm{~mL}\) of an acetic acid-sodium acetate buffer with \(\mathrm{pH}\) 4.50. Solid sodium acetate \(\left(\mathrm{CH}_{3} \mathrm{COONa}\right)\) and glacial acetic acid \(\left(\mathrm{CH}_{3} \mathrm{COOH}\right)\) are available. Glacial acetic acid is \(99 \% \mathrm{CH}_{3} \mathrm{COOH}\) by mass and has a density of \(1.05 \mathrm{~g} / \mathrm{mL}\). If the buffer is to be \(0.15 \mathrm{M}\) in \(\mathrm{CH}_{3} \mathrm{COOH}\), how many grams of \(\mathrm{CH}_{3} \mathrm{COONa}\) and how many milliliters of glacial acetic acid must be used?

A sample of \(0.2140 \mathrm{~g}\) of an unknown monoprotic acid was dissolved in \(25.0 \mathrm{~mL}\) of water and titrated with \(0.0950 \mathrm{M} \mathrm{NaOH}\). The acid required \(27.4 \mathrm{~mL}\) of base to reach the equivalence point. (a) What is the molar mass of the acid? (b) After \(15.0 \mathrm{~mL}\) of base had been added in the titration, the \(\mathrm{pH}\) was found to be 6.50 . What is the \(K_{a}\) for the unknown acid?

A sample of \(0.1687 \mathrm{~g}\) of an unknown monoprotic acid was dissolved in \(25.0 \mathrm{~mL}\) of water and titrated with \(0.1150 \mathrm{M} \mathrm{NaOH}\). The acid required \(15.5 \mathrm{~mL}\) of base to reach the equivalence point. (a) What is the molecular weight of the acid? (b) After \(7.25 \mathrm{~mL}\) of base had been added in the titration, the \(\mathrm{pH}\) was found to be 2.85 . What is the \(K_{a}\) for the unknown acid?

Show that the \(\mathrm{pH}\) at the halfway point of a titration of a weak acid with a strong base (where the volume of added base is half of that needed to reach the equivalence point) is equal to \(\mathrm{p} K_{a}\) for the acid.

A hypothetical weak acid, HA, was combined with \(\mathrm{NaOH}\) in the following proportions: \(0.20 \mathrm{~mol}\) of \(\mathrm{HA}, 0.080 \mathrm{~mol}\) of \(\mathrm{NaOH}\). The mixture was diluted to a total volume of \(1.0 \mathrm{~L}\) and the pH measured. (a) If \(\mathrm{pH}=4.80\), what is the \(\mathrm{p} K_{a}\) of the acid? (b) How many additional moles of \(\mathrm{NaOH}\) should be added to the solution to increase the \(\mathrm{pH}\) to \(5.00 ?\)

What is the \(\mathrm{pH}\) of a solution made by mixing \(0.30 \mathrm{~mol}\) \(\mathrm{NaOH}, 0.25 \mathrm{~mol} \mathrm{Na}_{2} \mathrm{HPO}_{4},\) and \(0.20 \mathrm{~mol} \mathrm{H}_{3} \mathrm{PO}_{4}\) with water and diluting to \(1.00 \mathrm{~L} ?\)

Suppose you want to do a physiological experiment that calls for a pH 6.50 buffer. You find that the organism with which you are working is not sensitive to the weak acid \(\mathrm{H}_{2} \mathrm{X}\) \(\left(K_{a 1}=2 \times 10^{-2} ; K_{a 2}=5.0 \times 10^{-7}\right)\) or its sodium salts. You have available a \(1.0 \mathrm{M}\) solution of this acid and a \(1.0 \mathrm{M}\) solution of \(\mathrm{NaOH}\). How much of the \(\mathrm{NaOH}\) solution should be added to \(1.0 \mathrm{~L}\) of the acid to give a buffer at \(\mathrm{pH} 6.50 ?\) (Ignore any volume change.)

How many microliters of \(1.000 \mathrm{M} \mathrm{NaOH}\) solution must be added to \(25.00 \mathrm{~mL}\) of a \(0.1000 \mathrm{M}\) solution of lactic acid \(\left[\mathrm{CH}_{3} \mathrm{CH}(\mathrm{OH}) \mathrm{COOH}\right.\) or \(\left.\mathrm{HC}_{3} \mathrm{H}_{5} \mathrm{O}_{3}\right]\) to produce a buffer with \(\mathrm{pH}=3.75 ?\)

The solubility of \(\mathrm{CaCO}_{3}\) is pH dependent. (a) Calculate the molar solubility of \(\mathrm{CaCO}_{3}\left(K_{s p}=4.5 \times 10^{-9}\right)\) neglecting the acid-base character of the carbonate ion. (b) Use the \(K_{b}\) expression for the \(\mathrm{CO}_{3}^{2-}\) ion to determine the equilibrium constant for the reaction \(\mathrm{CaCO}_{3}(s)+\mathrm{H}_{2} \mathrm{O}(l) \rightleftharpoons \mathrm{Ca}^{2+}(a q)+\mathrm{HCO}_{3}^{-}(a q)+\mathrm{OH}^{-}(a q)\) (c) If we assume that the only sources of \(\mathrm{Ca}^{2+}, \mathrm{HCO}_{3}^{-},\) and \(\mathrm{OH}^{-}\) ions are from the dissolution of \(\mathrm{CaCO}_{3},\) what is the molar solubility of \(\mathrm{CaCO}_{3}\) using the preceding expression? What is the \(\mathrm{pH} ?\) (d) If the \(\mathrm{pH}\) is buffered at 8.2 (as is historically typical for the ocean), what is the molar solubility of \(\mathrm{CaCO}_{3} ?\) (e) If the \(\mathrm{pH}\) is buffered at \(7.5,\) what is the molar solubility of \(\mathrm{CaCO}_{3} ?\) How much does this drop in \(\mathrm{pH}\) increase solubility? solution remains \(0.50 \mathrm{~L},\) calculate the \(\mathrm{pH}\) of the resulting solution.

Tooth enamel is composed of hydroxyapatite, whose simplest formula is \(\mathrm{Ca}_{5}\left(\mathrm{PO}_{4}\right)_{3} \mathrm{OH},\) and whose corresponding \(K_{s p}=6.8 \times 10^{-27} .\) As discussed in the "Chemistry and Life" box on page 730 , fluoride in fluorinated water or in toothpaste reacts with hydroxyapatite to form fluoroapatite, \(\mathrm{Ca}_{5}\left(\mathrm{PO}_{4}\right)_{3} \mathrm{~F},\) whose \(K_{s p}=1.0 \times 10^{-60} \cdot(\mathrm{a})\) Write the expres- sion for the solubility-constant for hydroxyapatite and for fluoroapatite. (b) Calculate the molar solubility of each of these compounds.

Calculate the solubility of \(\mathrm{Mg}(\mathrm{OH})_{2}\) in \(0.50 \mathrm{M} \mathrm{NH}_{4} \mathrm{Cl}\).

The solubility-product constant for barium permanganate, \(\mathrm{Ba}\left(\mathrm{MnO}_{4}\right)_{2}\), is \(2.5 \times 10^{-10}\). Assume that solid \(\mathrm{Ba}\left(\mathrm{MnO}_{4}\right)_{2}\) is in equilibrium with a solution of \(\mathrm{KMnO}_{4}\). What concentration of \(\mathrm{KMnO}_{4}\) is required to establish a concentration of \(2.0 \times 10^{-8} \mathrm{M}\) for the \(\mathrm{Ba}^{2+}\) ion in solution?

Calculate the ratio of \(\left[\mathrm{Ca}^{2+}\right]\) to \(\left[\mathrm{Fe}^{2+}\right]\) in a lake in which the water is in equilibrium with deposits of both \(\mathrm{CaCO}_{3}\) and \(\mathrm{FeCO}_{3}\). Assume that the water is slightly basic and that the hydrolysis of the carbonate ion can therefore be ignored.

The value of \(K_{s p}\) for \(\mathrm{Mg}_{3}\left(\mathrm{AsO}_{4}\right)_{2}\) is \(2.1 \times 10^{-20} .\) The \(\mathrm{AsO}_{4}{\underline{\phantom{xx}}}^{3-}\) ion is derived from the weak acid \(\mathrm{H}_{3} \mathrm{AsO}_{4}\left(\mathrm{p} K_{a 1}=2.22\right.\); \(\left.\mathrm{p} K_{a 2}=6.98 ; \mathrm{p} K_{a 3}=11.50\right) .\) When asked to calculate the molar solubility of \(\mathrm{Mg}_{3}\left(\mathrm{AsO}_{4}\right)_{2}\) in water, a student used the \(K_{s p}\) expression and assumed that \(\left[\mathrm{Mg}^{2+}\right]=1.5\left[\mathrm{AsO}_{4}^{3-}\right]\) Why was this a mistake?

The solubility product for \(\mathrm{Zn}(\mathrm{OH})_{2}\) is \(3.0 \times 10^{-16} .\) The formation constant for the hydroxo complex, \(\mathrm{Zn}(\mathrm{OH})_{4}^{2-},\) is \(4.6 \times 10^{17}\). What concentration of \(\mathrm{OH}^{-}\) is required to dissolve 0.015 mol of \(\mathrm{Zn}(\mathrm{OH})_{2}\) in a liter of solution?

The value of \(K_{s p}\) for \(\mathrm{Cd}(\mathrm{OH})_{2}\) is \(2.5 \times 10^{-14}\) (a) What is the molar solubility of \(\mathrm{Cd}(\mathrm{OH})_{2} ?(\mathbf{b})\) The solubility of \(\mathrm{Cd}(\mathrm{OH})_{2}\) can be increased through formation of the complex ion \(\mathrm{CdBr}_{4}^{2-}\left(K_{f}=5 \times 10^{3}\right) .\) If solid \(\mathrm{Cd}(\mathrm{OH})_{2}\) is added to a NaBr solution, what would the initial concentration of \(\mathrm{NaBr}\) need to be in order to increase the molar solubility of \(\mathrm{Cd}(\mathrm{OH})_{2}\) to \(1.0 \times 10^{-3}\) moles per liter?

(a) Write the net ionic equation for the reaction that occurs when a solution of hydrochloric acid (HCl) is mixed with a solution of sodium formate \(\left(\mathrm{NaCHO}_{2}\right) .\) (b) Calculate the equilibrium constant for this reaction. (c) Calculate the equilibrium concentrations of \(\mathrm{Na}^{+}, \mathrm{Cl}^{-}, \mathrm{H}^{+}, \mathrm{CHO}_{2}^{-},\) and \(\mathrm{HCHO}_{2}\) when \(50.0 \mathrm{~mL}\) of \(0.15 \mathrm{M} \mathrm{HCl}\) is mixed with \(50.0 \mathrm{~mL}\) of \(0.15 \mathrm{M} \mathrm{NaCHO}_{2}\)

(a) A 0.1044 -g sample of an unknown monoprotic acid requires \(22.10 \mathrm{~mL}\) of \(0.0500 \mathrm{M} \mathrm{NaOH}\) to reach the end point. What is the molecular weight of the unknown? (b) As the acid is titrated, the \(\mathrm{pH}\) of the solution after the addition of \(11.05 \mathrm{~mL}\) of the base is \(4.89 .\) What is the \(K_{a}\) for the acid? (c) Using Appendix D, suggest the identity of the acid. Do both the molecular weight and \(K_{a}\) value agree with your choice?

A sample of \(7.5 \mathrm{~L}\) of \(\mathrm{NH}_{3}\) gas at \(22{ }^{\circ} \mathrm{C}\) and 735 torr is bubbled into a 0.50 - \(\mathrm{L}\) solution of \(0.40 \mathrm{M} \mathrm{HCl}\). Assuming that all the \(\mathrm{NH}_{3}\) dissolves and that the volume of the solution remains \(0.50 \mathrm{~L},\) calculate the \(\mathrm{pH}\) of the resulting solution.

Aspirin has the structural formula At body temperature \(\left(37^{\circ} \mathrm{C}\right), K_{a}\) for aspirin equals \(3 \times 10^{-5}\). If two aspirin tablets, each having a mass of \(325 \mathrm{mg},\) are dissolved in a full stomach whose volume is \(1 \mathrm{~L}\) and whose \(\mathrm{pH}\) is \(2,\) what percent of the aspirin is in the form of neutral molecules?

What is the \(\mathrm{pH}\) at \(25^{\circ} \mathrm{C}\) of water saturated with \(\mathrm{CO}_{2}\) at a partial pressure of \(1.10 \mathrm{~atm} ?\) The Henry's law constant for \(\mathrm{CO}_{2}\) at \(25^{\circ} \mathrm{C}\) is \(3.1 \times 10^{-2} \mathrm{~mol} / \mathrm{L}\) -atm. The \(\mathrm{CO}_{2}\) is an acidic oxide, reacting with \(\mathrm{H}_{2} \mathrm{O}\) to form \(\mathrm{H}_{2} \mathrm{CO}_{3}\).

The osmotic pressure of a saturated solution of strontium sulfate at \(25^{\circ} \mathrm{C}\) is 21 torr. What is the solubility product of this salt at \(25^{\circ} \mathrm{C} ?\)

A concentration of \(10-100\) parts per billion (by mass) of \(\mathrm{Ag}^{+}\) is an effective disinfectant in swimming pools. However, if the concentration exceeds this range, the \(\mathrm{Ag}^{+}\) can cause adverse health effects. One way to maintain an appropriate concentration of \(\mathrm{Ag}^{+}\) is to add a slightly soluble salt to the pool. Using \(K_{s p}\) values from Appendix \(D\), calculate the equilibrium concentration of \(\mathrm{Ag}^{+}\) in parts per billion that would exist in equilibrium with (a) \(\mathrm{AgCl},(\mathbf{b})\) \(\mathrm{AgBr},(\mathrm{c}) \mathrm{AgI}\)