Learning objectives
By the end of this section, you will be able to:
- Describe examples of systems involving two (or more) coupled chemical equilibria
- Calculate reactant and product concentrations for coupled equilibrium systems
As discussed in preceding chapters on equilibrium, coupled equilibria involve two or more separate chemical reactions that share one or more reactants or products. This section of this chapter will address solubility equilibria coupled with acid-base and complex-formation reactions.
An environmentally relevant example illustrating the coupling of solubility and acid-base equilibria is the impact of ocean acidification on the health of the ocean’s coral reefs. These reefs are built upon skeletons of sparingly soluble calcium carbonate excreted by colonies of corals (small marine invertebrates). The relevant dissolution equilibrium is
Rising concentrations of atmospheric carbon dioxide contribute to an increased acidity of ocean waters due to the dissolution, hydrolysis, and acid ionization of carbon dioxide:
Inspection of these equilibria shows the carbonate ion is involved in the calcium carbonate dissolution and the acid hydrolysis of bicarbonate ion. Combining the dissolution equation with the reverse of the acid hydrolysis equation yields
The equilibrium constant for this net reaction is much greater than the Ksp for calcium carbonate, indicating its solubility is markedly increased in acidic solutions. As rising carbon dioxide levels in the atmosphere increase the acidity of ocean waters, the calcium carbonate skeletons of coral reefs become more prone to dissolution and subsequently less healthy (CNX_Chem_15_03_CoralReef).
View original figure (external; image not reproduced in this text edition)
Original figure description: This figure contains two photographs of coral reefs. In a, a colorful reef that includes hues of purple and pink corals is shown in blue green water with fish swimming in the background. In b, grey-green mossy looking coral is shown in a blue aquatic environment. This photo does not have the colorful appearance or fish that were shown in figure a.
The dramatic increase in solubility with increasing acidity described above for calcium carbonate is typical of salts containing basic anions (e.g., carbonate, fluoride, hydroxide, sulfide). Another familiar example is the formation of dental cavities in tooth enamel. The major mineral component of enamel is calcium hydroxyapatite (CNX_Chem_15_03_Apatite), a sparingly soluble ionic compound whose dissolution equilibrium is
View original figure (external; image not reproduced in this text edition)
Original figure description: This figure includes an image of two large light blue apatite crystals in a mineral conglomerate that includes white, grey, and tan crystals. The blue apatite crystals have a dull, dusty, or powdered appearance.
This compound dissolved to yield two different basic ions: triprotic phosphate ions
and monoprotic hydroxide ions:
Of the two basic productions, the hydroxide is, of course, by far the stronger base (it’s the strongest base that can exist in aqueous solution), and so it is the dominant factor providing the compound an acid-dependent solubility. Dental cavities form when the acid waste of bacteria growing on the surface of teeth hastens the dissolution of tooth enamel by reacting completely with the strong base hydroxide, shifting the hydroxyapatite solubility equilibrium to the right. Some toothpastes and mouth rinses contain added NaF or SnF2 that make enamel more acid resistant by replacing the strong base hydroxide with the weak base fluoride:
The weak base fluoride ion reacts only partially with the bacterial acid waste, resulting in a less extensive shift in the solubility equilibrium and an increased resistance to acid dissolution. See the Chemistry in Everyday Life feature on the role of fluoride in preventing tooth decay for more information.
The solubility of ionic compounds may also be increased when dissolution is coupled to the formation of a complex ion. For example, aluminum hydroxide dissolves in a solution of sodium hydroxide or another strong base because of the formation of the complex ion
View original figure (external; image not reproduced in this text edition)
Original figure description: An H atom is bonded to an O atom. The O atom has 2 dots above it and 2 dots below it. The O atom is bonded to an A l atom, which has three additional O atoms bonded to it as well. Each of these additional O atoms has 4 dots arranged around it, and is bonded to an H atom. This entire molecule is contained in brackets, to the right of which is a superscripted negative sign.
The equations for the dissolution of aluminum hydroxide, the formation of the complex ion, and the combined (net) equation are shown below. As indicated by the relatively large value of K for the net reaction, coupling complex formation with dissolution drastically increases the solubility of Al(OH)3.
Increased Solubility in Acidic Solutions
Compute and compare the molar solublities for aluminum hydroxide, Al(OH)3, dissolved in (a) pure water and (b) a buffer containing 0.100 M acetic acid and 0.100 M sodium acetate.Solution
(a) The molar solubility of aluminum hydroxide in water is computed considering the dissolution equilibrium only as demonstrated in several previous examples:(b) The concentration of hydroxide ion of the buffered solution is conveniently calculated by the Henderson-Hasselbalch equation:
At this pH, the concentration of hydroxide ion is
The solubility of Al(OH)3 in this buffer is then calculated from its solubility product expressions:
Compared to pure water, the solubility of aluminum hydroxide in this mildly acidic buffer is approximately ten million times greater (though still relatively low).
Check Your Learning
What is the solubility of aluminum hydroxide in a buffer comprised of 0.100 M formic acid and 0.100 M sodium formate?
Multiple Equilibria
Unexposed silver halides are removed from photographic film when they react with sodium thiosulfate (Na2S2O3, called hypo) to form the complex ion (Kf = 4.7 1013).View original figure (external; image not reproduced in this text edition)
Original figure description: A chemical reaction is shown using structural formulas. On the left, A g superscript plus is followed by a plus sign, the number 2, and a structure in brackets. The structure is composed of a central S atom which has O atoms single bonded above, right, and below. A second S atom is single bonded to the left. Each of these bonded atoms has 6 dots around it. Outside the brackets is a superscript 2 negative. Following a bidirectional arrow is a structure in brackets with a central A g atom. To the left and right, S atoms are single bonded to the A g atom. Each of these S atoms has four dots around it, and an S atom connected with a single bond moving out from the central A g atom, forming the ends of the structure. Each of these atoms has three O atoms attached with single bonds above, below, and at the end of the structure. Each O atom has six dots around it. Outside the brackets is a superscript 3 negative.
What mass of Na2S2O3 is required to prepare 1.00 L of a solution that will dissolve 1.00 g of AgBr by the formation of
Solution
Two equilibria are involved when silver bromide dissolves in an aqueous thiosulfate solution containing the ion:dissolution:
complexation:
Combining these two equilibrium equations yields
The concentration of bromide resulting from dissolution of 1.00 g of AgBr in 1.00 L of solution is
The stoichiometry of the dissolution equilibrium indicates the same concentration of aqueous silver ion will result, 0.00532 M, and the very large value of ensures that essentially all the dissolved silver ion will be complexed by thiosulfate ion:
Rearranging the K expression for the combined equilibrium equations and solving for the concentration of thiosulfate ion yields
Finally, the total mass of required to provide enough thiosulfate to yield the concentrations cited above can be calculated.
Mass of required to yield 0.00532 M
Mass of required to yield 0.00110 M
The mass of required to dissolve 1.00 g of AgBr in 1.00 L of water is thus 1.68 g + 0.17 g = 1.85 g
Check Your Learning
AgCl(s), silver chloride, has a very low solubility: Ksp = 1.6 10–10. Adding ammonia significantly increases the solubility of AgCl because a complex ion is formed: Kf = 1.7 107. What mass of NH3 is required to prepare 1.00 L of solution that will dissolve 2.00 g of AgCl by formation ofKey Concepts and Summary
Systems involving two or more chemical equilibria that share one or more reactant or product are called coupled equilibria. Common examples of coupled equilibria include the increased solubility of some compounds in acidic solutions (coupled dissolution and neutralization equilibria) and in solutions containing ligands (coupled dissolution and complex formation). The equilibrium tools from other chapters may be applied to describe and perform calculations on these systems.
Chemistry End of Chapter Exercises
A saturated solution of a slightly soluble electrolyte in contact with some of the solid electrolyte is said to be a system in equilibrium. Explain. Why is such a system called a heterogeneous equilibrium?
Calculate the equilibrium concentration of Ni2+ in a 1.0-M solution [Ni(NH3)6](NO3)2.
0.014 M
Calculate the equilibrium concentration of Zn2+ in a 0.30-M solution of
Calculate the equilibrium concentration of Cu2+ in a solution initially with 0.050 M Cu2+ and 1.00 M NH3.
7.2 10–15 M
Calculate the equilibrium concentration of Zn2+ in a solution initially with 0.150 M Zn2+ and 2.50 M CN–.
Calculate the Fe3+ equilibrium concentration when 0.0888 mole of K3[Fe(CN)6] is added to a solution with 0.00010 M CN–.
4.4 10−22 M
Calculate the Co2+ equilibrium concentration when 0.010 mole of [Co(NH3)6](NO3)2 is added to a solution with 0.25 M NH3. Assume the volume is 1.00 L.
Calculate the molar solubility of Sn(OH)2 in a buffer solution containing equal concentrations of NH3 and
Calculate the molar solubility of Al(OH)3 in a buffer solution with 0.100 M NH3 and 0.400 M
[OH−] = 4.5 10−6; [Al3+] = 2 10–16 (molar solubility)
What is the molar solubility of CaF2 in a 0.100-M solution of HF? Ka for HF = 6.4 10–4.
What is the molar solubility of BaSO4 in a 0.250-M solution of NaHSO4? Ka for = 1.2 10–2.
; (molar solubility)
What is the molar solubility of Tl(OH)3 in a 0.10-M solution of NH3?
What is the molar solubility of Pb(OH)2 in a 0.138-M solution of CH3NH2?
[OH–] = 7.6 10−3 M; [Pb2+] = 2.1 10–11 (molar solubility)
A solution of 0.075 M CoBr2 is saturated with H2S ([H2S] = 0.10 M). What is the minimum pH at which CoS begins to precipitate?
A 0.125-M solution of Mn(NO3)2 is saturated with H2S ([H2S] = 0.10 M). At what pH does MnS begin to precipitate?
7.66
Both AgCl and AgI dissolve in NH3.
(a) What mass of AgI dissolves in 1.0 L of 1.0 M NH3?
(b) What mass of AgCl dissolves in 1.0 L of 1.0 M NH3?
The following question is taken from a Chemistry Advanced Placement Examination and is used with the permission of the Educational Testing Service.
Solve the following problem:
In a saturated solution of MgF2 at 18 °C, the concentration of Mg2+ is 1.21 10–3 M. The equilibrium is represented by the preceding equation.
(a) Write the expression for the solubility-product constant, Ksp, and calculate its value at 18 °C.
(b) Calculate the equilibrium concentration of Mg2+ in 1.000 L of saturated MgF2 solution at 18 °C to which 0.100 mol of solid KF has been added. The KF dissolves completely. Assume the volume change is negligible.
(c) Predict whether a precipitate of MgF2 will form when 100.0 mL of a 3.00 10–3-M solution of Mg(NO3)2 is mixed with 200.0 mL of a 2.00 10–3-M solution of NaF at 18 °C. Show the calculations to support your prediction.
(d) At 27 °C the concentration of Mg2+ in a saturated solution of MgF2 is 1.17 10–3 M. Is the dissolving of MgF2 in water an endothermic or an exothermic process? Give an explanation to support your conclusion.
(a) Ksp = [Mg2+][F–]2 = (1.21 10–3)(2 1.21 10–3)2 = 7.09 10–9
(b) 7.09 10–7 M
(c) Determine the concentration of Mg2+ and F– that will be present in the final volume. Compare the value of the ion product [Mg2+][F–]2 with Ksp. If this value is larger than Ksp, precipitation will occur.
0.1000 L 3.00 10–3 M Mg(NO3)2 = 0.3000 L M Mg(NO3)2
M Mg(NO3)2 = 1.00 10–3 M
0.2000 L 2.00 10–3 M NaF = 0.3000 L M NaF
M NaF = 1.33 10–3 M
ion product = (1.00 10–3)(1.33 10–3)2 = 1.77 10–9
This value is smaller than Ksp, so no precipitation will occur.
(d) MgF2 is less soluble at 27 °C than at 18 °C. Because added heat acts like an added reagent, when it appears on the product side, the Le Châtelier’s principle states that the equilibrium will shift to the reactants’ side to counter the stress. Consequently, less reagent will dissolve. This situation is found in our case. Therefore, the reaction is exothermic.
Which of the following compounds, when dissolved in a 0.01-M solution of HClO4, has a solubility greater than in pure water: CuCl, CaCO3, MnS, PbBr2, CaF2? Explain your answer.
Which of the following compounds, when dissolved in a 0.01-M solution of HClO4, has a solubility greater than in pure water: AgBr, BaF2, Ca3(PO4)2, ZnS, PbI2? Explain your answer.
BaF2, Ca3(PO4)2, ZnS; each is a salt of a weak acid, and the from perchloric acid reduces the equilibrium concentration of the anion, thereby increasing the concentration of the cations
What is the effect on the amount of solid Mg(OH)2 that dissolves and the concentrations of Mg2+ and OH– when each of the following are added to a mixture of solid Mg(OH)2 and water at equilibrium?
(a) MgCl2
(b) KOH
(c) HClO4
(d) NaNO3
(e) Mg(OH)2
What is the effect on the amount of CaHPO4 that dissolves and the concentrations of Ca2+ and when each of the following are added to a mixture of solid CaHPO4 and water at equilibrium?
(a) CaCl2
(b) HCl
(c) KClO4
(d) NaOH
(e) CaHPO4
Effect on amount of solid CaHPO4, [Ca2+], [OH–]: (a) increase, increase, decrease; (b) decrease, increase, decrease; (c) no effect, no effect, no effect; (d) decrease, increase, decrease; (e) increase, no effect, no effect
Identify all chemical species present in an aqueous solution of Ca3(PO4)2 and list these species in decreasing order of their concentrations. (Hint: Remember that the ion is a weak base.)
Glossary
- coupled equilibria
- system characterized the simultaneous establishment of two or more equilibrium reactions sharing one or more reactant or product