What mass of Ca(NO3)2 must be added to 1.0 L of a 1.0 M HF

Which of the following will affect the total amount of solute that can dissolve in a given amount of solvent? a. The solution is stirred. b. The solute is ground to fine particles before dissolving. c. The temperature changes

Devise as many ways as you can to experimentally determine the Ksp value of a solid. Explain why each of these would work.

You are browsing through the Handbook of Hypothetical Chemistry when you come across a solid that is reported to have a Ksp value of zero in water at 25C. What does this mean?

A friend tells you: The constant Ksp of a salt is called the solubility product constant and is calculated from the concentrations of ions in the solution. Thus, if salt A dissolves to a greater extent than salt B, salt A must have a higher Ksp than salt B. Do you agree with your friend? Explain.

Explain the following phenomenon: You have a test tube with about 20 mL silver nitrate solution. Upon adding a few drops of sodium chromate solution, you notice a red solid forming in a relatively clear solution. Upon adding a few drops of a sodium chloride solution to the same test tube, you notice a white solid and a pale yellow solution. Use the Ksp values in the book to support your explanation, and include the balanced equations

What happens to the Ksp value of a solid as the temperature of the solution changes? Consider both increasing and decreasing temperatures, and explain your answer.

Which is more likely to dissolve in an acidic solution, silver sulfide or silver chloride? Why?

You have two salts, AgX and AgY, with very similar Ksp values. You know that HX is a strong acid and HY is a weak acid. Which salt is more soluble in an acidic solution? Explain.

Ag2S(s) has a larger molar solubility than CuS even though Ag2S has the smaller Ksp value. Explain how this is possible

Solubility is an equilibrium position, whereas Ksp is an equilibrium constant. Explain the difference.

The salts in Table 16.1, with the possible exception of the hydroxide salts, have one of the following mathematical relationships between the Ksp value and the molar solubility s. i. Ksp  s 2 iii. Ksp  27s 4 ii. Ksp  4s 3 iv. Ksp  108s 5 For each mathematical relationship, give an example of a salt in Table 16.1 that exhibits that relationship

When Na3PO4(aq) is added to a solution containing a metal ion and a precipitate forms, the precipitate generally could be one of two possibilities. What are the two possibilities?

The common ion effect for ionic solids (salts) is to significantly decrease the solubility of the ionic compound in water. Explain the common ion effect

Sulfide precipitates are generally grouped as sulfides insoluble in acidic solution and sulfides insoluble in basic solution. Explain why there is a difference between the two groups of sul- fide precipitates.

List some ways one can increase the solubility of a salt in water

The stepwise formation constants for a complex ion are all generally values much greater than 1. What is the significance of this?

Silver chloride dissolves readily in 2 M NH3 but is quite insoluble in 2 M NH4NO3. Explain.

If a solution contains either Pb2(aq) or Ag(aq), how can temperature be manipulated to help identify the ion in solution?

Write balanced equations for the dissolution reactions and the corresponding solubility product expressions for each of the following solids. a. AgC2H3O2 b. Al(OH)3 c. Ca3(PO4)2

Write balanced equations for the dissolution reactions and the corresponding solubility product expressions for each of the following solids. a. Ag2CO3 b. Ce(IO3)3 c. BaF2

Use the following data to calculate the Ksp value for each solid. a. The solubility of CaC2O4 is 4.8  105 mol/L. b. The solubility of BiI3 is 1.32  105 mol/L.

Use the following data to calculate the Ksp value for each solid. a. The solubility of Pb3(PO4)2 is 6.2  1012 mol/L. b. The solubility of Li2CO3 is 7.4  102 mol/L.

Approximately 0.14 g nickel(II) hydroxide, Ni(OH)2(s), dissolves per liter of water at 20C. Calculate Ksp for Ni(OH)2(s) at this temperature

The solubility of the ionic compound M2X3, having a molar mass of 288 g/mol, is 3.60  107 g/L. Calculate the Ksp of the compound.

The concentration of Pb2 in a solution saturated with PbBr2(s) is 2.14  102 M. Calculate Ksp for PbBr2.

The concentration of Ag in a solution saturated with Ag2C2O4(s) is 2.2  104 M. Calculate Ksp for Ag2C2O4.

Calculate the solubility of each of the following compounds in moles per liter. Ignore any acidbase properties. a. Ag3PO4, Ksp  1.8  1018 b. CaCO3, Ksp  8.7  109 c. Hg2Cl2, Ksp  1.1  1018 (Hg2 2 is the cation in solution.) 10

Calculate the solubility of each of the following compounds in moles per liter. Ignore any acidbase properties. a. PbI2, Ksp  1.4  108 b. CdCO3, Ksp  5.2  1012 c. Sr3(PO4)2, Ksp  1  1031 2

Calculate the molar solubility of Mg(OH)2, Ksp  8.9  1012.

Calculate the molar solubility of Cd(OH)2, Ksp  5.9  1011.

Calculate the molar solubility of Al(OH)3, Ksp  2  1032.

Calculate the molar solubility of Co(OH)3, Ksp  2.5  1043.

For each of the following pairs of solids, determine which solid has the smallest molar solubility. a. CaF2(s), Ksp  4.0  1011, or BaF2(s), Ksp  2.4  105 b. Ca3(PO4)2(s), Ksp  1.3  1032, or FePO4(s), Ksp  1.0  1022 34

For each of the following pairs of solids, determine which solid has the smallest molar solubility. a. FeC2O4, Ksp  2.1  107 , or Cu(IO4)2, Ksp  1.4  107 b. Ag2CO3, Ksp  8.1  1012, or Mn(OH)2, Ksp  2  1013 35

Calculate the solubility (in moles per liter) of Fe(OH)3 (Ksp  4  1038) in each of the following. a. water b. a solution buffered at pH  5.0 c. a solution buffered at pH  11.0

Calculate the solubility of Co(OH)2(s) (Ksp  2.5  1016) in a buffered solution with a pH of 11.00.

The Ksp for silver sulfate (Ag2SO4) is 1.2  105 . Calculate the solubility of silver sulfate in each of the following. a. water b. 0.10 M AgNO3 c. 0.20 M K2SO4

The Ksp for lead iodide (PbI2) is 1.4  108 . Calculate the solubility of lead iodide in each of the following. a. water b. 0.10 M Pb(NO3)2 c. 0.010 M NaI

Calculate the solubility of solid Ca3(PO4)2 (Ksp  1.3  1032) in a 0.20 M Na3PO4 solution.

Calculate the solubility of solid Pb3(PO4)2 (Ksp  1  1054) in a 0.10 M Pb(NO3)2 solution.

The solubility of Ce(IO3)3 in a 0.20 M KIO3 solution is 4.4  108 mol/L. Calculate Ksp for Ce(IO3)3.

The solubility of Pb(IO3)2(s) in a 0.10 M KIO3 solution is 2.6  1011 mol/L. Calculate Ksp for Pb(IO3)2(s).

Which of the substances in Exercises 27 and 28 show increased solubility as the pH of the solution becomes more acidic? Write equations for the reactions that occur to increase the solubility.

For which salt in each of the following groups will the solubility depend on pH? a. AgF, AgCl, AgBr c. Sr(NO3)2, Sr(NO2)2 b. Pb(OH)2, PbCl2 d. Ni(NO3)2, Ni(CN)2

What mass of ZnS (Ksp  2.5  1022) will dissolve in 300.0 mL of 0.050 M Zn(NO3)2? Ignore the basic properties of S2.

The concentration of Mg2 in seawater is 0.052 M. At what pH will 99% of the Mg2 be precipitated as the hydroxide salt? [Ksp for Mg(OH)2  8.9  1012.] 4

Will a precipitate form when 100.0 mL of 4.0  104 M Mg(NO3)2 is added to 100.0 mL of 2.0  104 M NaOH?

A solution contains 1.0  105 M Ag and 2.0  106 M CN. Will AgCN(s) precipitate? (Ksp for AgCN(s) is 2.2  1012.) 49.

A solution is prepared by mixing 100.0 mL of 1.0  102 M Pb(NO3)2 and 100.0 mL of 1.0  103 M NaF. Will PbF2(s) (Ksp  4  108 ) precipitate? 5

A solution contains 2.0  103 M Ce3 and 1.0  102 M IO3 3. Will Ce(IO3)3(s) precipitate? [Ksp for Ce(IO3)3 is 3.2  1010.] 51.

Calculate the final concentrations of K(aq), C2O4 2(aq), Ba2(aq), and Br(aq) in a solution prepared by adding 0.100 L of 0.200 M K2C2O4 to 0.150 L of 0.250 M BaBr2. (For BaC2O4, Ksp  2.3  108 .) 52.

A solution is prepared by mixing 75.0 mL of 0.020 M BaCl2 and 125 mL of 0.040 M K2SO4. What are the concentrations of barium and sulfate ions in this solution? Assume only SO4 2 ions (no HSO4 ) are present.

A 50.0-mL sample of 0.00200 M AgNO3 is added to 50.0 mL of 0.0100 M NaIO3. What is the equilibrium concentration of Ag in solution? (Ksp for AgIO3 is 3.0  108 .)

A solution is prepared by mixing 50.0 mL of 0.10 M Pb(NO3)2 with 50.0 mL of 1.0 M KCl. Calculate the concentrations of Pb2 and Cl at equilibrium. [Ksp for PbCl2(s) is 1.6  105 .] 5

A solution contains 1.0  105 M Na3PO4. What is the minimum concentration of AgNO3 that would cause precipitation of solid Ag3PO4 (Ksp  1.8  1018)?

The Ksp of Al(OH)3 is 2  1032. At what pH will a 0.2 M Al3 solution begin to show precipitation of Al(OH)3?

A solution is 1  104 M in NaF, Na2S, and Na3PO4. What would be the order of precipitation as a source of Pb2 is added gradually to the solution? The relevant Ksp values are Ksp(PbF2)  4  108 , Ksp(PbS)  7  1029, and Ksp[Pb3(PO4)2]  1  1054. 5

A solution contains 0.25 M Ni(NO3)2 and 0.25 M Cu(NO3)2. Can the metal ions be separated by slowly adding Na2CO3? Assume that for successful separation 99% of the metal ion must be precipitated before the other metal ion begins to precipitate, and assume no volume change on addition of Na2CO3.

Write equations for the stepwise formation of each of the following complex ions. a. Ni(CN)4 2 b. V(C2O4)3 3 6

Write equations for the stepwise formation of each of the following complex ions. a. CoF6 3 b. Zn(NH3)4 2

In the presence of CN, Fe3 forms the complex ion Fe(CN)6 3. The equilibrium concentrations of Fe3 and Fe(CN)6 3 are 104 8.5  1040 M and 1.5  103 M, respectively, in a 0.11 M KCN solution. Calculate the value for the overall formation constant of Fe(CN)6 3.

In the presence of NH3, Cu2 forms the complex ion Cu(NH3)4 2. If the equilibrium concentrations of Cu2 and Cu(NH3)4 2 are 1.8  1017 M and 1.0  103 M, respectively, in a 1.5 M NH3 solution, calculate the value for the overall formation constant of Cu(NH3)4 2. 63. W

When aqueous KI is added gradually to mercury(II) nitrate, an orange precipitate forms. Continued addition of KI causes the precipitate to dissolve. Write balanced equations to explain these observations. (Hint: Hg2 reacts with I to form HgI4 2.) 6

As sodium chloride solution is added to a solution of silver nitrate, a white precipitate forms. Ammonia is added to the mixture and the precipitate dissolves. When potassium bromide solution is then added, a pale yellow precipitate appears. When a solution of sodium thiosulfate is added, the yellow precipitate dissolves. Finally, potassium iodide is added to the solution and a yellow precipitate forms. Write equations for all the changes mentioned above. What conclusions can you draw concerning the sizes of the Ksp values for AgCl, AgBr, and AgI?

The overall formation constant for HgI4 2 is 1.0  1030. That is, What is the concentration of Hg2 in 500.0 mL of a solution that was originally 0.010 M Hg2 and 0.78 M I ? The reaction is 66

A solution is prepared by adding 0.10 mol Ni(NH3)6Cl2 to 0.50 L of 3.0 M NH3. Calculate [Ni(NH3)6 2] and [Ni2] in this solution. Koverall for Ni(NH3)6 2 is 5.5  108 . That is, for the overall reaction 6

A solution is formed by mixing 50.0 mL of 10.0 M NaX with 50.0 mL of 2.0  103 M CuNO3. Assume that Cu(I) forms complex ions with X as follows: with an overall reaction Calculate the following concentrations at equilibrium.

A solution is prepared by mixing 100.0 mL of 1.0  104 M Be(NO3)2 and 100.0 mL of 8.0 M NaF. Calculate the equilibrium concentrations of F, Be2, BeF, BeF2, BeF3 , and BeF4 2 in this solution. 69.

a. Calculate the molar solubility of AgI in pure water. Ksp for AgI is 1.5  1016.

b. Calculate the molar solubility of AgI in 3.0 M NH3. The overall formation constant for Ag(NH3)2 is 1.7  107 .

c. Compare the calculated solubilities from parts a and b. Explain any differences.

Solutions of sodium thiosulfate are used to dissolve unexposed AgBr (Ksp  5.0  1013) in the developing process for blackand-white film. What mass of AgBr can dissolve in 1.00 L of 0.500 M Na2S2O3? Ag reacts with S2O3 2 to form a complex ion: 7

Kf for the complex ion Ag(NH3)2 is 1.7  107 . Ksp for AgCl is 1.6  1010. Calculate the molar solubility of AgCl in 1.0 M NH3.

The copper(I) ion forms a chloride salt that has Ksp  1.2  106 . Copper(I) also forms a complex ion with Cl: a. Calculate the solubility of copper(I) chloride in pure water. (Ignore CuCl2 formation for part a.) b. Calculate the solubility of copper(I) chloride in 0.10 M NaCl. 7

A series of chemicals were added to some AgNO3(aq). NaCl(aq) was added first to the silver nitrate solution with the end result shown below in test tube 1, NH3(aq) was then added with the end result shown in test tube 2, and HNO3(aq) was added last with the end result shown in test tube 3. Explain the results shown in each test tube. Include a balanced equation for the reaction(s) taking place.

The solubility of copper(II) hydroxide in water can be increased by adding either the base NH3 or the acid HNO3. Explain. Would added NH3 or HNO3 have the same effect on the solubility of silver acetate or silver chloride? Explain.

The Ksp of hydroxyapatite, Ca5(PO4)3OH, is 6.8  1037. Calculate the solubility of hydroxyapatite in pure water in moles per liter. How is the solubility of hydroxyapatite affected by adding acid? When hydroxyapatite is treated with fluoride, the mineral fluorapatite, Ca5(PO4)3F, forms. The Ksp of this substance is 1  1060. Calculate the solubility of fluorapatite in water. How do these calculations provide a rationale for the fluoridation of drinking water?

The U.S. Public Health Service recommends the fluoridation of water as a means for preventing tooth decay. The recommended concentration is 1 mg F per liter. The presence of calcium ions in hard water can precipitate the added fluoride. What is the maximum molarity of calcium ions in hard water if the fluoride concentration is at the USPHS recommended level? (Ksp for CaF2  4.0  1011)

Cream of tartar, a common ingredient in cooking, is the common name for potassium bitartrate (abbreviated KBT, 188.2 g/mol). Historically, KBT was a crystalline solid that formed on the casks of wine barrels during the fermentation process. Calculate the maximum mass of KBT that can dissolve in 250.0 mL of solution to make a saturated solution. The Ksp value for KBT is 3.8  104

Barium sulfate is a contrast agent for X-ray scans that are most often associated with the gastrointestinal tract. Calculate the mass of BaSO4 that can dissolve in 100.0 mL of solution. The Ksp value for BaSO4 is 1.5  109 .

There are many different three-dimensional shapes that proteins adopt to perform important functions in the body. A common characteristic found in many transcription factors and regulatory proteins is zinc fingers, where a zinc atom plays an important role in the structure and function of the protein. For this reason, different forms of zinc are often found in commercial vitamin supplements, including zinc sulfate. If the solubility of ZnSO4 is 54.0 g per 100.0 mL of solution, calculate the Ksp value.

Mg(OH)2 is the main ingredient in the antacid TUMS and has a Ksp value of 8.9  1012. If a 10.0-g sample of Mg(OH)2 is placed in 500.0 mL of solution, calculate the moles of OH ions present. Because the Ksp value for Mg(OH)2 is small, not a lot of solid dissolves in solution. Explain how Mg(OH)2 works to neutralize large amounts of stomach acids.

Nanotechnology has become an important field, with applications ranging from high-density data storage to the design of nano machines. One common building block of nanostructured architectures is manganese oxide nanoparticles. The particles can be formed from manganese oxalate nanorods, the formation of which can be described as follows: Calculate the value for the overall formation constant for Mn(C2O4)2 2: K  3Mn1C2O422 2 4 3Mn2 4 3C2O4 2 4 2 K2

The equilibrium constant for the following reaction is 1.0  1023: EDTA4  EDTA is used as a complexing agent in chemical analysis. Solutions of EDTA, usually containing the disodium salt Na2H2EDTA, are used to treat heavy metal poisoning. Calculate [Cr3] at equilibrium in a solution originally 0.0010 M in Cr3 and 0.050 M in H2EDTA2 and buffered at pH  6.00. 8

Calculate the concentration of Pb2 in each of the following. a. a saturated solution of Pb(OH)2, Ksp  1.2  1015 b. a saturated solution of Pb(OH)2 buffered at pH  13.00 c. Ethylenediaminetetraacetate (EDTA4) is used as a complexing agent in chemical analysis and has the following structure: Solutions of EDTA4 are used to treat heavy metal poisoning by removing the heavy metal in the form of a soluble complex ion. The reaction of EDTA4 with Pb2 is Consider a solution with 0.010 mol Pb(NO3)2 added to 1.0 L of an aqueous solution buffered at pH  13.00 and containing 0.050 M Na4EDTA. Does Pb(OH)2 precipitate from this solution? 84.

The active ingredient of Pepto-Bismol is the compound bismuth subsalicylate, which undergoes the following dissociation when added to water: If the maximum amount of bismuth subsalicylate that reacts by this reaction is 3.2  1019 mol/L, calculate the equilibrium constant for the preceding reaction.

A solution contains 0.018 mol each of I, Br, and Cl. When the solution is mixed with 200. mL of 0.24 M AgNO3, what mass of AgCl(s) precipitates out, and what is [Ag]? Assume no volume change. 86

You have two salts, AgX and AgY, with very similar Ksp values. You know that Ka for HX is much greater than Ka for HY. Which salt is more soluble in acidic solution? Explain.

What mass of Ca(NO3)2 must be added to 1.0 L of a 1.0 M HF solution to begin precipitation of CaF2(s)? For CaF2, Ksp  4.0  1011 and Ka for HF  7.2  104 . Assume no volume change on addition of Ca(NO3)2(s).

Calculate the mass of manganese hydroxide present in 1300 mL of a saturated manganese hydroxide solution. For Mn(OH)2, Ksp  2.0  1013.

On a hot day, a 200.0-mL sample of a saturated solution of PbI2 was allowed to evaporate until dry. If 240 mg of solid PbI2 was collected after evaporation was complete, calculate the Ksp value for PbI2 on this hot day

Will a precipitate of Cd(OH)2 form if 1.0 mL of 1.0 M Cd(NO3)2 is added to 1.0 L of 5.0 M NH3?

a. Using the Ksp value for Cu(OH)2 (1.6  1019) and the overall formation constant for Cu(NH3)4 2 (1.0  1013), calculate the value for the equilibrium constant for the following reaction:

b. Use the value of the equilibrium constant you calculated in part a to calculate the solubility (in mol/L) of Cu(OH)2 in 5.0 M NH3. In 5.0 M NH3 the concentration of OH is 0.0095 M.

Describe how you could separate the ions in each of the following groups by selective precipitation. a. Ag, Mg2, Cu2 c. Pb2, Bi3 b. Pb2, Ca2, Fe2 93. Th

The solubility rules outlined in Chapter 4 say that Ba(OH)2, Sr(OH)2, and Ca(OH)2 are marginally soluble hydroxides. Calculate the pH of a saturated solution of each of these marginally soluble hydroxides

In the chapter discussion of precipitate formation, we ran the precipitation reaction to completion and then let some of the precipitate redissolve to get back to equilibrium. To see why, redo Example 16.6, where

The copper(I) ion forms a complex ion with CN according to the following equation: a. Calculate the solubility of CuBr(s) (Ksp  1.0  105 ) in 1.0 L of 1.0 M NaCN. b. Calculate the concentration of Br at equilibrium. c. Calculate the concentration of CN at equilibrium.

Consider a solution made by mixing 500.0 mL of 4.0 M NH3 and 500.0 mL of 0.40 M AgNO3. Ag reacts with NH3 to form AgNH3 and Ag(NH3)2 : D

a. Calculate the molar solubility of AgBr in pure water. Ksp for AgBr is 5.0  1013.

b. Calculate the molar solubility of AgBr in 3.0 M NH3. The overall formation constant for Ag(NH3)2 is 1.7  107 , that is,

c. Compare the calculated solubilities from parts a and b. Explain any differences

d. What mass of AgBr will dissolve in 250.0 mL of 3.0 M NH3?

e. What effect does adding HNO3 have on the solubilities calculated in parts a and b?

Calculate the equilibrium concentrations of NH3, Cu2, Cu(NH3) 2, Cu(NH3)2 2, Cu(NH3)3 2, and Cu(NH3)4 2 in a solution prepared by mixing 500.0 mL of 3.00 M NH3 with 500.0 mL of 2.00  103 M Cu(NO3)2. The stepwise equilibria are 99.

Calculate the solubility of AgCN(s) (Ksp  2.2  1012) in a solution containing 1.0 M H. (Ka for HCN is 6.2  1010.) 1

Calcium oxalate (CaC2O4) is relatively insoluble in water (Ksp  2  109 ). However, calcium oxalate is more soluble in acidic solution. How much more soluble is calcium oxalate in 0.10 M H than in pure water? In pure water, ignore the basic properties of C2O4 2. 1

What is the maximum possible concentration of Ni2 ion in water at 25C that is saturated with 0.10 M H2S and maintained at pH 3.0 with HCl?

A mixture contains 1.0  103 M Cu2 and 1.0  103 M Mn2 and is saturated with 0.10 M H2S. Determine a pH where CuS precipitates but MnS does not precipitate. Ksp for CuS  8.5  1045 and Ksp for MnS  2.3  1013. 103

Sodium tripolyphosphate (Na5P3O10) is used in many synthetic detergents. Its major effect is to soften the water by complexing Mg2 and Ca2 ions. It also increases the efficiency of surfactants, or wetting agents that lower a liquids surface tension. The K value for the formation of MgP3O103 is 4.0  108 . The reaction is . Calculate the concentration of Mg2 in a solution that was originally 50. ppm Mg2 (50. mg/L of solution) after 40. g Na5P3O10 is added to 1.0 L of the solution. M

You add an excess of solid MX in 250 g water. You measure the freezing point and find it to be 0.028C. What is the Ksp of the solid? Assume the density of the solution is 1.0 g/cm3

a. Calculate the molar solubility of SrF2 in water, ignoring the basic properties of F. (For SrF2, Ksp  7.9  1010.)

b. Would the measured molar solubility of SrF2 be greater than or less than the value calculated in part a? Explain

c. Calculate the molar solubility of SrF2 in a solution buffered at pH  2.00. (Ka for HF is 7.2  104 .)

A solution saturated with a salt of the type M3X2 has an osmotic pressure of 2.64  102 atm at 25C. Calculate the Ksp value for the salt, assuming ideal behavior.

Consider 1.0 L of an aqueous solution that contains 0.10 M sulfuric acid to which 0.30 mol barium nitrate is added. Assuming no change in volume of the solution, determine the pH, the concentration of barium ions in the final solution, and the mass of solid formed

The Ksp for Q, a slightly soluble ionic compound composed of M2 2 and X ions, is 4.5  1029. The electron configuration of M is [Xe]6s 1 4f 145d10. The X anion has 54 electrons. What is the molar solubility of Q in a solution of NaX prepared by dissolving 1.98 g NaX in 150. mL solution? *

Aluminum ions react with the hydroxide ion to form the precipitate Al(OH)3(s), but can also react to form the soluble complex ion Al(OH)4 . In terms of solubility, Al(OH)3(s) will be more soluble in very acidic solutions as well as more soluble in very basic solutions. a. Write equations for the reactions that occur to increase the solubility of Al(OH)3(s) in very acidic solutions and in very basic solutions. b. Lets study the pH dependence of the solubility of Al(OH)3(s) in more detail. Show that the solubility of Al(OH)3, as a function of [H], obeys the equation where S  solubility  [Al3]  [Al(OH)4 ] and K is the equilibrium constant for c. The value of K is 40.0 and Ksp for Al(OH)3 is 2  1032. Plot the solubility of Al(OH)3 in the pH range 412. A