If acetate ion is added to the solution, Le Chtelier says the equilibrium will shift to the left.
Bellwork
Bellwork
Bellwork
Bellwork
a) [NH4+] = 0.10 M [Cl] = 0.10 M [NH3] = 0.12 M b) Cl c)NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
Buffers:
Buffers:
Solutions of a weak conjugate acid-base pair.
Buffers:
Solutions of a weak conjugate acid-base pair. They are particularly resistant to pH changes, even when strong acid or base is added.
HNO3 and NO3 will not work as a buffer because NO3 is a spectator ion.
Buffers
If a small amount of hydroxide is added to an equimolar solution of HF in NaF, for example, the HF reacts with the OH to make F and water.
Buffers
Buffer Calculations
Consider the equilibrium constant expression for the dissociation of a generic acid, HA: HA + H2O H3O+ + A
Buffer Calculations
Consider the equilibrium constant expression for the dissociation of a generic acid, HA: HA + H2O
Ka =
H3O+ + A
[H3O+] [A] [HA]
Buffer Calculations
Rearranging slightly, this becomes
Ka = [H3O+] [A] [HA]
Buffer Calculations
Rearranging slightly, this becomes
Ka = [H3O+] [A] [HA]
Buffer Calculations
Rearranging slightly, this becomes
Ka = [H3O+] [A] [HA]
[A] [HA]
base
acid
Buffer Calculations
So [base] pKa = pH log [acid]
Buffer Calculations
So [base] pKa = pH log [acid] [base] pH = pKa + log [acid]
Buffer Calculations
So [base] pKa = pH log [acid] [base] pH = pKa + log [acid] This is the HendersonHasselbalch equation.
HendersonHasselbalch Equation
What is the pH of a buffer that is 0.12 M in lactic acid, HC3H5O3, and 0.10 M in sodium lactate? Ka for lactic acid is 1.4 104.
HendersonHasselbalch Equation
[base] pH = pKa + log [acid] pH = log (1.4 104) (0.10) + log (0.12)
PRACTICE EXERCISE
Calculate the pH of a buffer composed of 0.12 M benzoic acid and 0.20 M sodium benzoate. (Refer to Appendix D.)
PRACTICE EXERCISE
Calculate the pH of a buffer composed of 0.12 M benzoic acid and 0.20 M sodium benzoate. (Refer to Appendix D.)
Answer: 4.42
How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer whose pH is 9.00? (Assume that the addition of NH4Cl does not change the volume)
How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer whose pH is 9.00? (Assume that the addition of NH4Cl does not change the volume)
The major species in the solution will be NH4+, Cl, and NH3. Of these, the Cl ion is a spectator (it is the conjugate base of a strong acid).
How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer whose pH is 9.00? (Assume that the addition of NH4Cl does not change the volume)
The major species in the solution will be NH4+, Cl, and NH3. Of these, the Cl ion is a spectator (it is the conjugate base of a strong acid).
and so
How many moles of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer whose pH is 9.00? (Assume that the addition of NH4Cl does not change the volume)
The major species in the solution will be NH4+, Cl, and NH3. Of these, the Cl ion is a spectator (it is the conjugate base of a strong acid).
and so
Because Kb is small and the common ion NH4+ is present, the equilibrium concentration of NH3 will essentially equal its initial concentration:
Comment: Because NH4+ and NH3 are a conjugate acidbase pair, we could use the HendersonHasselbalch equation to solve this problem. To do so requires first using Equation 16.41 to calculate pKa for NH4+ from the value of pKb for NH3. Try this approach to convince yourself that you can use the HendersonHasselbalch equation for buffers for which you are given Kb for the conjugate base rather than Ka for the conjugate acid.
PRACTICE EXERCISE
Calculate the concentration of sodium benzoate that must be present in a 0.20 M solution of benzoic acid (HC7H5O2) to produce a pH of 4.00.
PRACTICE EXERCISE
Calculate the concentration of sodium benzoate that must be present in a 0.20 M solution of benzoic acid (HC7H5O2) to produce a pH of 4.00.
Answer: 0.13 M
pH Range
The pH range is the range of pH values over which a buffer system works effectively.
pH Range
The pH range is the range of pH values over which a buffer system works effectively. It is best to choose an acid with a pKa close to the desired pH.
PRACTICE EXERCISE
Determine (a) the pH of the original buffer described in Sample Exercise 17.5 after the addition of 0.020 mol HCl, and (b) the pH of the solution that would result from the addition of 0.020 mol HCl to 1.00 L of pure water.
PRACTICE EXERCISE
Determine (a) the pH of the original buffer described in Sample Exercise 17.5 after the addition of 0.020 mol HCl, and (b) the pH of the solution that would result from the addition of 0.020 mol HCl to 1.00 L of pure water.
Answers: (a) 4.68, (b) 1.70
Titration
A known concentration of base (or acid) is slowly added to a solution of acid (or base).
Titration
A pH meter or indicators are used to determine when the solution has reached the equivalence point, at which the stoichiometric amount of acid equals that of base.
Calculate the pH when the following quantities of 0.100 M NaOH have been added to 50.0 mL of 0.100 M HCl: (a) 49.0 mL, (b) 51.0 mL.
Calculate the pH when the following quantities of 0.100 M NaOH have been added to 50.0 mL of 0.100 M HCl: (a) 49.0 mL, (b) 51.0 mL.
Solve: The number of moles of H+ in the original HCl solution is given by the product of the volume of the solution (50.0 mL = 0.0500 L) and its molarity (0.100 M):
Calculate the pH when the following quantities of 0.100 M NaOH have been added to 50.0 mL of 0.100 M HCl: (a) 49.0 mL, (b) 51.0 mL.
Solve: The number of moles of H+ in the original HCl solution is given by the product of the volume of the solution (50.0 mL = 0.0500 L) and its molarity (0.100 M):
There are more moles of H+ present than OH. Each mole of OH will react with one mole of H+.
There are more moles of H+ present than OH. Each mole of OH will react with one mole of H+.
The volume of the reaction mixture increases as the NaOH solution is added to the HCl solution. At this point in the titration, the solution has a volume of 50.0 mL + 49.0 mL = 99.0 mL. Thus, the concentration of H+(aq) is
There are more moles of H+ present than OH. Each mole of OH will react with one mole of H+.
The volume of the reaction mixture increases as the NaOH solution is added to the HCl solution. At this point in the titration, the solution has a volume of 50.0 mL + 49.0 mL = 99.0 mL. Thus, the concentration of H+(aq) is
Calculate the pH when the following quantities of 0.100 M NaOH have been added to 50.0 mL of 0.100 M HCl: (a) 49.0 mL, (b) 51.0 mL.
Plan: We are now past the equivalence point and have more OH in the solution than H+. The initial number of moles of each reactant is determined from their volumes and concentrations. The reactant present in smaller stoichiometric amount (the limiting reactant) is consumed completely, leaving an excess this time of hydroxide ion.
In this case the total volume of the solution is Hence, the concentration of OH(aq) in the solution is
In this case the total volume of the solution is Hence, the concentration of OH(aq) in the solution is
In this case the total volume of the solution is Hence, the concentration of OH(aq) in the solution is
when the following quantities of 0.100 M HNO3 have been added to 25.0 mL of 0.100 M KOH: (a) 24.9 mL, (b) 25.1 mL.
when the following quantities of 0.100 M HNO3 have been added to 25.0 mL of 0.100 M KOH: (a) 24.9 mL, (b) 25.1 mL.
Answers: (a) 10.30, (b) 3.70
At each point below the equivalence point, the pH of the solution during titration is determined from the amounts of the acid and its conjugate base present at that particular time.
The nearly vertical equivalence point portion of the titration curve is smaller for a weak acid-strong base titration, and fewer indicators undergo their color change within this narrow range.
Calculate the pH of the solution formed when 45.0 mL of 0.100 M NaOH is added to 50.0 mL of 0.100 M HC2H3O2 (Ka = 1.8 105).
Calculate the pH of the solution formed when 45.0 mL of 0.100 M NaOH is added to 50.0 mL of 0.100 M HC2H3O2 (Ka = 1.8 105).
Plan: We first must determine the number of moles of weak acid and strong base that have been combined. This will tell us how much of the weak acids conjugate base has been produced, and we can solve for pH using the equilibrium-constant expression.
Calculate the pH of the solution formed when 45.0 mL of 0.100 M NaOH is added to 50.0 mL of 0.100 M HC2H3O2 (Ka = 1.8 105).
Plan: We first must determine the number of moles of weak acid and strong base that have been combined. This will tell us how much of the weak acids conjugate base has been produced, and we can solve for pH using the equilibrium-constant expression.
The 4.5 103 mol of NaOH consumes 4.5 103 mol of HC2H3O2:
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore Equilibrium Calculation: The equilibrium between HC2H3O2 and C2H3O2 must obey the equilibrium-constant expression for HC2H3O2:
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore Equilibrium Calculation: The equilibrium between HC2H3O2 and C2H3O2 must obey the equilibrium-constant expression for HC2H3O2: Solving for [H+] gives
The resulting molarities of HC2H3O2 and C2H3O2 after the reaction are therefore Equilibrium Calculation: The equilibrium between HC2H3O2 and C2H3O2 must obey the equilibrium-constant expression for HC2H3O2: Solving for [H+] gives
PRACTICE EXERCISE
(a) Calculate the pH in the solution formed by adding 10.0 mL of 0.050 M NaOH to 40.0 mL of 0.0250 M benzoic acid (HC7H5O2, Ka = 6.3 105). (b) Calculate the pH in the solution formed by adding 10.0 mL of 0.100 M HCl to 20.0 mL of 0.100 M NH3.
PRACTICE EXERCISE
(a) Calculate the pH in the solution formed by adding 10.0 mL of 0.050 M NaOH to 40.0 mL of 0.0250 M benzoic acid (HC7H5O2, Ka = 6.3 105). (b) Calculate the pH in the solution formed by adding 10.0 mL of 0.100 M HCl to 20.0 mL of 0.100 M NH3.
Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH.
Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH.
Analyze: Because the neutralization of a weak acid produces its anion, which is a weak base, we expect the pH at the equivalence point to be greater than 7. Plan: Determine how many moles of acetic acid there are initially. This will tell us how many moles of acetate ion there will be at the equivalence point. Determine the volume of the solution at the equivalence point and the resultant concentration of acetate ion. Because the acetate ion is a weak base, we can calculate the pH using Kb and the concentration of acetate .
Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH.
Analyze: Because the neutralization of a weak acid produces its anion, which is a weak base, we expect the pH at the equivalence point to be greater than 7. Plan: Determine how many moles of acetic acid there are initially. This will tell us how many moles of acetate ion there will be at the equivalence point. Determine the volume of the solution at the equivalence point and the resultant concentration of acetate ion. Because the acetate ion is a weak base, we can calculate the pH using Kb and the concentration of acetate .
Solve:
Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH.
Analyze: Because the neutralization of a weak acid produces its anion, which is a weak base, we expect the pH at the equivalence point to be greater than 7. Plan: Determine how many moles of acetic acid there are initially. This will tell us how many moles of acetate ion there will be at the equivalence point. Determine the volume of the solution at the equivalence point and the resultant concentration of acetate ion. Because the acetate ion is a weak base, we can calculate the pH using Kb and the concentration of acetate .
Solve: Hence 5.00 103 mol of C2H3O2 is formed. It will take 50.0 mL of NaOH to reach the equivalence point . 50 mL + 50 mL = 100mL = 0.1000 L.
Calculate the pH at the equivalence point in the titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH.
Analyze: Because the neutralization of a weak acid produces its anion, which is a weak base, we expect the pH at the equivalence point to be greater than 7. Plan: Determine how many moles of acetic acid there are initially. This will tell us how many moles of acetate ion there will be at the equivalence point. Determine the volume of the solution at the equivalence point and the resultant concentration of acetate ion. Because the acetate ion is a weak base, we can calculate the pH using Kb and the concentration of acetate .
Solve: Hence 5.00 103 mol of C2H3O2 is formed. It will take 50.0 mL of NaOH to reach the equivalence point . 50 mL + 50 mL = 100mL = 0.1000 L. The C2H3O2 ion is a weak base.
The Kb for C2H3O2 can be calculated from the Ka value of its conjugate acid, Kb = Kw/Ka = (1.0 1014)/(1.8 105) = 5.6 1010.
The Kb for C2H3O2 can be calculated from the Ka value of its conjugate acid, Kb = Kw/Ka = (1.0 1014)/(1.8 105) = 5.6 1010.
The Kb for C2H3O2 can be calculated from the Ka value of its conjugate acid, Kb = Kw/Ka = (1.0 1014)/(1.8 105) = 5.6 1010.
Approximating that and then solving for x, we have x = [OH] = 5.3 106 M, which gives pOH = 5.28 and pH = 8.72. Check: The pH is above 7, as expected for the salt of a weak acid and strong base.
PRACTICE EXERCISE
Calculate the pH at the equivalence point when (a) 40.0 mL of 0.025 M benzoic acid (HC7H5O2, Ka = 6.3 105) is titrated with 0.050 M NaOH; (b) 40.0 mL of 0.100 M NH3 is titrated with 0.100 M HCl.
PRACTICE EXERCISE
Calculate the pH at the equivalence point when (a) 40.0 mL of 0.025 M benzoic acid (HC7H5O2, Ka = 6.3 105) is titrated with 0.050 M NaOH; (b) 40.0 mL of 0.100 M NH3 is titrated with 0.100 M HCl.
How much can be in solution before a solid is formed or the maximum solute that can be dissolved in a given amount of solvent.
Solubility Products
Consider the equilibrium that exists in a saturated solution of BaSO4 in water:
BaSO4(s)
Ba2+(aq) + SO42(aq)
Solubility Products
The equilibrium constant expression for this equilibrium is Ksp = [Ba2+] [SO42] where the equilibrium constant, Ksp, is called the solubility product.
Write the expression for the solubility-product constant for CaF2, and look up the Ksp value in Appendix D.
Write the expression for the solubility-product constant for CaF2, and look up the Ksp value in Appendix D.
Write the expression for the solubility-product constant for CaF2, and look up the Ksp value in Appendix D.
Write the expression for the solubility-product constant for CaF2, and look up the Ksp value in Appendix D.
PRACTICE EXERCISE
Give the solubility-product-constant expressions and the values of the solubilityproduct constants (from Appendix D) for the following compounds: (a) barium carbonate, (b) silver sulfate.
(a) Ksp = [Ba2+][CO32] = 5.0 109; (b) Ksp = [Ag+]2[SO42] = 1.5 105
PRACTICE EXERCISE
Give the solubility-product-constant expressions and the values of the solubilityproduct constants (from Appendix D) for the following compounds: (a) barium carbonate, (b) silver sulfate.
(a) Ksp = [Ba2+][CO32] = 5.0 109; (b) Ksp = [Ag+]2[SO42] = 1.5 105
Solubility Products
Solubility Products
Ksp is not the same as solubility.
Solubility Products
Ksp is not the same as solubility. Solubility is generally expressed as the mass of solute dissolved in 1 L (g/L) or 100 mL (g/mL) of solution, or in mol/L (M).
Solid silver chromate is added to pure water at 25C. Some of the solid remains undissolved at the bottom of the flask. The mixture is stirred for several days to ensure that equilibrium is achieved.
Analysis of the equilibrated solution shows that its Ag+ concentration is 1.3 104 M.
Assuming that Ag2CrO4 dissociates completely in water and that there are no other important equilibria involving the Ag+ or CrO42 ions in the solution, calculate Ksp
Analysis of the equilibrated solution shows that its Ag+ concentration is 1.3 104 M,
Analysis of the equilibrated solution shows that its Ag+ concentration is 1.3 104 M,
Analysis of the equilibrated solution shows that its Ag+ concentration is 1.3 104 M,
PRACTICE EXERCISE A saturated solution of Mg(OH)2 in contact with undissolved solid is prepared at 25C. The pH of the solution is found to be 10.17. Assuming that Mg(OH)2 dissociates completely in water and that there are no other simultaneous equilibria involving the Mg2+ or OH ions in the solution, calculate Ksp for this compound.
PRACTICE EXERCISE A saturated solution of Mg(OH)2 in contact with undissolved solid is prepared at 25C. The pH of the solution is found to be 10.17. Assuming that Mg(OH)2 dissociates completely in water and that there are no other simultaneous equilibria involving the Mg2+ or OH ions in the solution, calculate Ksp for this compound.
Answer: 1.6 1012
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
(Remember that to calculate the cube root of a number, you can use the yx function on your calculator, with )
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
Solubilities are measured per mole or gram of formula unit (ionic formula). The solubility is x.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
Solubilities are measured per mole or gram of formula unit (ionic formula). The solubility is x. [F-] = 4.2 x 10-4mol/L [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
Solubilities are measured per mole or gram of formula unit (ionic formula). The solubility is x. [F-] = 4.2 x 10-4mol/L [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Check: We expect a small number for the solubility of a slightly soluble salt.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Check: We expect a small number for the solubility of a slightly soluble salt.
If we reverse the calculation, we should be able to recalculate Ksp: Ksp = (2.1 104)(4.2 104)2 = 3.7 1011, close to the Ksp, 3.9 1011 .
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Check: We expect a small number for the solubility of a slightly soluble salt.
If we reverse the calculation, we should be able to recalculate Ksp: Ksp = (2.1 104)(4.2 104)2 = 3.7 1011, close to the Ksp, 3.9 1011 .
Comment: Because
F is the anion of a weak acid, you might expect that the hydrolysis of the ion would affect the solubility of CaF2.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Check: We expect a small number for the solubility of a slightly soluble salt.
If we reverse the calculation, we should be able to recalculate Ksp: Ksp = (2.1 104)(4.2 104)2 = 3.7 1011, close to the Ksp, 3.9 1011 .
Comment: Because
F is the anion of a weak acid, you might expect that the hydrolysis of the ion would affect the solubility of CaF2. The basicity of F is so small (Kb = 1.5 1011), however, that the hydrolysis occurs to only a slight extent and does not significantly influence the solubility.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
The Ksp for CaF2 is 3.9 1011 at 25C. Calculate the solubility of CaF2 in grams per liter.
[F-] = 4.2 x 10-4mol [Ca2+] = 2.1 x 10-4mol/L The molar solubility of CaF2 is 2.1 104 mol/L.
Check: We expect a small number for the solubility of a slightly soluble salt.
If we reverse the calculation, we should be able to recalculate Ksp: Ksp = (2.1 104)(4.2 104)2 = 3.7 1011, close to the Ksp, 3.9 1011 .
Comment: Because
F is the anion of a weak acid, you might expect that the hydrolysis of the ion would affect the solubility of CaF2. The basicity of F is so small (Kb = 1.5 1011), however, that the hydrolysis occurs to only a slight extent and does not significantly influence the solubility. The reported solubility is 0.017 g/L at 25C.
PRACTICE EXERCISE The Ksp for LaF3 is 2 1019 . What is the solubility of LaF3 in water in moles per liter? Answer: 9.28 106 mol/L
PRACTICE EXERCISE The Ksp for LaF3 is 2 1019 . What is the solubility of LaF3 in water in moles per liter? Answer: 9.28 106 mol/L
If one of the ions in a solution equilibrium is already dissolved in the solution, the equilibrium will shift to the left and the solubility of the salt will decrease.
BaSO4(s) Ba2+(aq) + SO42(aq)
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
In (a) the common ion is Ca2+ and NO3 is a spectator ion. In (b) the common ion is F and Na+ is a spectator ion.
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
In (a) the common ion is Ca2+ and NO3 is a spectator ion. In (b) the common ion is F and Na+ is a spectator ion.
Because the slightly soluble compound is CaF2, we need to use the Ksp for this compound, which is available in Appendix D:
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
In (a) the common ion is Ca2+ and NO3 is a spectator ion. In (b) the common ion is F and Na+ is a spectator ion.
Because the slightly soluble compound is CaF2, we need to use the Ksp for this compound, which is available in Appendix D:
The value of Ksp is unchanged by the presence of additional solutes, but the solubility of the salt will decrease in the presence of common ions.
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF. Solve: (a) The initial concentration of Ca2+ is 0.010 M
because of the dissolved Ca(NO3)2:
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF. Solve: (a) The initial concentration of Ca2+ is 0.010 M
because of the dissolved Ca(NO3)2:
Even without the common-ion effect, the solubility of CaF2 is very small. Assume
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
Substituting into the solubility-product expression gives
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
Substituting into the solubility-product expression gives
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
Substituting into the solubility-product expression gives
The very small value for x validates the simplifying assumption we have made. Our calculation indicates that 3.1 105 mol of solid CaF2 dissolves per liter of the 0.010 M Ca(NO3)2 solution.
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
(b) In this case the common ion is F, and at equilibrium we have
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
(b) In this case the common ion is F, and at equilibrium we have
Assuming that
Thus, 3.9 107 mol of solid CaF2 should dissolve per liter of 0.010 M NaF solution.
Calculate the molar solubility of CaF2 at 25C in a solution that is (a) 0.010 M in Ca(NO3)2, (b) 0.010 M in NaF.
the molar solubility of CaF2 in pure water 2.1 104 M in 0.010 M Ca2+ 3.1 105 M in 0.010 M F 3.9 107 M.
More effect because [F-] is squared
PRACTICE EXERCISE
The value for Ksp for manganese(II) hydroxide, Mn(OH)2 , is 1.6 1013. Calculate the molar solubility of Mn(OH)2 in a solution that contains 0.020 M NaOH.
PRACTICE EXERCISE
The value for Ksp for manganese(II) hydroxide, Mn(OH)2 , is 1.6 1013. Calculate the molar solubility of Mn(OH)2 in a solution that contains 0.020 M NaOH.
Which of the following substances will be more soluble in acidic solution than in basic solution:
(a) Ni(OH)2(s), (c) BaF2(s), (b) CaCO3(s), (d) AgCl(s)?
Ionic compounds that dissociate to produce a basic anion will be more soluble in acid solution.
Which of the following substances will be more soluble in acidic solution than in basic solution:
(a) Ni(OH)2(s), (c) BaF2(s), (b) CaCO3(s), (d) AgCl(s)?
(a) Ni(OH)2(s) will be more soluble in acidic solution because of the basicity of OH ; the H+ ion reacts with the OH ion, forming water.
Which of the following substances will be more soluble in acidic solution than in basic solution:
(a) Ni(OH)2(s), (c) BaF2(s), (b) CaCO3(s), (d) AgCl(s)?
(b) Similarly, CaCO3(s) dissolves in acid solutions because CO32 is a basic anion.
The reaction between CO32 and H+ occurs in a stepwise fashion, first forming HCO3. H2CO3 forms in appreciable amounts only when the concentration of H+ is sufficiently high.
Which of the following substances will be more soluble in acidic solution than in basic solution:
(a) Ni(OH)2(s), (c) BaF2(s), (b) CaCO3(s), (d) AgCl(s)?
(c) The solubility of BaF2 is also enhanced by lowering the pH, because F is a basic anion.
Which of the following substances will be more soluble in acidic solution than in basic solution:
(a) Ni(OH)2(s), (c) BaF2(s), (b) CaCO3(s), (d) AgCl(s)?
(d) The solubility of AgCl is unaffected by changes in pH because Cl is the anion of a strong acid and therefore has negligible basicity.
PRACTICE EXERCISE
Write the net ionic equation for the reaction of the following compounds with acid: (a) CuS, (b) Cu(N3)2.
PRACTICE EXERCISE
Write the net ionic equation for the reaction of the following compounds with acid: (a) CuS, (b) Cu(N3)2.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
When NH3(aq) is added to Ag+(aq) a reaction occurs forming Ag(NH3)2+. Because Kf for the formation of Ag(NH3)2+ is quite large, we assume that essentially all the Ag+ is converted to Ag(NH3)2+ and approach the problem as though we are concerned with the dissociation of Ag(NH3)2+ rather than its formation.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
When NH3(aq) is added to Ag+(aq) a reaction occurs forming Ag(NH3)2+. Because Kf for the formation of Ag(NH3)2+ is quite large, we assume that essentially all the Ag+ is converted to Ag(NH3)2+ and approach the problem as though we are concerned with the dissociation of Ag(NH3)2+ rather than its formation. We need to reverse the formation equation to represent the formation of Ag+ and NH3 from Ag(NH3)2+ and also make the corresponding change to the equilibrium constant.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
If [Ag+] is 0.010 M initially, then [Ag(NH3)2+] will be 0.010 M following addition of the NH3.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
If [Ag+] is 0.010 M initially, then [Ag(NH3)2+] will be 0.010 M following addition of the NH3. Note that the NH3 concentration given in the problem is an equilibrium concentration rather than an initial concentration.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
If [Ag+] is 0.010 M initially, then [Ag(NH3)2+] will be 0.010 M following addition of the NH3. Note that the NH3 concentration given in the problem is an equilibrium concentration rather than an initial concentration.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
Calculate the concentration of Ag+ present in solution at equilibrium when concentrated NH3 is added to 0.010M AgNO3 to give an equilibrium concentration of [NH3] = 0.20M.
Neglect the small volume change that occurs when NH3 is added.
Solving for x, we obtain x = 1.5 108 M = [Ag+]. Formation of the Ag(NH3)2+ complex drastically reduces the concentration of free Ag+ ion in solution.
PRACTICE EXERCISE Calculate [Cr3+] in equilibrium with Cr(OH)4 when 0.010 mol of Cr(NO3)3 is dissolved in a liter of solution buffered at pH 10.0.
PRACTICE EXERCISE Calculate [Cr3+] in equilibrium with Cr(OH)4 when 0.010 mol of Cr(NO3)3 is dissolved in a liter of solution buffered at pH 10.0.
Answer: 1 1016 M
They are insoluble in water but dissolve readily in the presence of an acid or base.
They are insoluble in water but dissolve readily in the presence of an acid or base.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product. The possible metathesis products are PbSO4 and NaNO3.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product. The possible metathesis products are PbSO4 and NaNO3. Sodium salts are quite soluble;
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Plan: Determine the concentrations of all ions immediately upon mixing of the solutions and compare the value of the reaction quotient, Q, to the solubility-product constant, Ksp, for any potentially insoluble product. The possible metathesis products are PbSO4 and NaNO3. Sodium salts are quite soluble; PbSO4 has a Ksp of 6.3 107 (Appendix D), however, and will precipitate if the Pb2+ and SO42 ion concentrations are high enough for Q to exceed Ksp for the salt.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L. The number of moles of Pb2+ is
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L. The number of moles of Pb2+ is
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
When the two solutions are mixed, the total volume is 0.10 L + 0.40 L = 0.50 L.
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
Will a precipitate form when 0.10 L of 8.0 103 M Pb(NO3)2 is added to 0.40 L of 5.0 103 M Na2SO4?
PRACTICE EXERCISE
Will a precipitate form when 0.050 L of 2.0 102 M NaF is mixed with 0.010 L of 1.0 102 M Ca(NO3)2?
PRACTICE EXERCISE
Will a precipitate form when 0.050 L of 2.0 102 M NaF is mixed with 0.010 L of 1.0 102 M Ca(NO3)2?
yes, CaF2 precipitates because Q = 4.6 108 is larger than Ksp = 3.9 1011
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
Plan: We can calculate what concentration of Cl ion would be necessary to begin precipitation of each. The salt requiring the lower Cl ion concentration will precipitate first.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
[Ag+] = 1.0 102 M
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
[Ag+] = 1.0 102 M
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Any Cl in excess of 1.8 x 10-10 Which salt precipitates first? will cause AgCl to precipitate.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Any Cl in excess of 1.8 x 10-10 Which salt precipitates first? will cause AgCl to precipitate.
[Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
[Cl] in excess of 1.8 x 10-10 will cause AgCl to precipitate. [Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
[Cl] in excess of 1.8 x 10-10 will cause AgCl to precipitate. [Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate. AgCl will precipitate first because it requires a much smaller concentration of Cl.
A solution contains 1.0 102 M Ag+ and 2.0 102M Pb2+. When Cl is added to the solution, both AgCl (Ksp = 1.8 1010) and PbCl2 (Ksp = 1.7 105) precipitate from the solution. What concentration of Cl is necessary to begin the precipitation of each salt? Which salt precipitates first?
[Cl] in excess of 1.8 x 10-10 will cause AgCl to precipitate. [Cl] in excess of 2.9 102 M will cause PbCl2 to precipitate. AgCl will precipitate first because it requires a much smaller concentration of Cl.
Ag+ can be separated from Pb2+ by slowly adding Cl so [Cl] is between 1.8 108 M and 2.9 102 M.
PRACTICE EXERCISE
A solution consists of 0.050 M Mg2+ and 0.020 M Cu2+. Which ion will precipitate first as OH is added to the solution? What concentration of OH is necessary to begin the precipitation of each cation? Ksp = 1.8 1011 for Mg(OH)2 Ksp = 2.2 1020 for Cu(OH)2.
PRACTICE EXERCISE
A solution consists of 0.050 M Mg2+ and 0.020 M Cu2+. Which ion will precipitate first as OH is added to the solution? What concentration of OH is necessary to begin the precipitation of each cation? Ksp = 1.8 1011 for Mg(OH)2 Ksp = 2.2 1020 for Cu(OH)2.
Answer: Cu(OH)2 precipitates first. Cu(OH)2 begins to precipitate when [OH] exceeds 1.0 109 M; Mg(OH)2 begins to precipitate when [OH] exceeds 1.9 105 M.
A high concentration of H2S and a low concentration of H+ (high pH) will reduce [Cu2+].
The solution must contain one of the following cations: Ag+, Pb2+ or Hg22+.