Solubility Products Slide 2 / 57 Solubility Products Consider the - - PDF document

Solubility Products

Aqueous equilibria II Slide 1 / 57

Solubility Products

Consider the equilibrium that exists in a saturated solution of BaSO4 in water: BaSO4(s) ↔ Ba2+(aq) + SO4

2-(aq)

Slide 2 / 57

Solubility Products

The equilibrium constant expression for this equilibrium is Ksp = [Ba2+] [SO4

2−]

where the equilibrium constant, Ksp, is called the solubility product. There is never any denominator in Ksp expressions because pure solids are not included in any equilibrium expressions.

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1 Which Ksp expression is correct for AgCl?

A

[Ag+]/[Cl-]

B

[Ag+][Cl-]

C

[Ag2+]2[Cl2-]2

D

[Ag+]2[Cl-]2

E

None of the above.

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2 Given the reaction at equilibrium: Zn(OH)2 (s) <--> Zn2+ (aq) + 2OH- (aq) what is the expression for the solubility product constant, Ksp, for this reaction?

A

Ksp= [Zn2+][OH-]2 / [Zn(OH)2]

B

Ksp= [Zn(OH)2] / [Zn2+][2OH-]

C

Ksp= [Zn2+][2OH-]

D

Ksp= [Zn2+][OH-]2

Slide 5 / 57

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).

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The term "solubility" represents the maximum amount

• f solute that can be dissolved in a certain volume

before any precipitate is observed. The solubility of a substance can be given in terms of grams per liter g/L

• r in terms of

moles per liter mol/L The latter is sometimes referred to as "molar solubility."

Solubility

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Example #1 Consider the slightly soluble compound barium oxalate, BaC2O4. The solubility of BaC2O4 is 1.3 x 10-3 mol/L. The ratio of cations to anions is 1:1. · This means that 1.3 x 10-3 moles of Ba2+ can dissolve in one liter. · Also, 1.3 x 10-3 moles of C2O4

2- can dissolve in one

liter. · What is the maximum amount (in grams) of BaC2O4 that could dissolve in 2.5 L (before a solid precipitate

• r solid settlement occurs)?

Solubility

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What is the maximum amount (in grams) of BaC2O4 that could dissolve in 2.5 L (before a precipitate occurs)? 2.5 L 1

x 1 L x 1 mol BaC2O4 225.3 g BaC2O4

This is the maximum amount that could dissolve in 2.5 L before a precipitate occurs.

Solubility

1.3 x 10-3 mol BaC2O4

1 mol BaC2O4 225.3g

• ------------------- = -----------

1.3 x 10-3 mol BaC2O4 x g = 0.293g BaC2O4 x 2.5L = 0.73g 1L The solubility of BaC2O4 is 1.3 x 10-3 mol/L. BaC2O4 --> Ba2+ + C2O4

2-

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Example #2 Consider the slightly soluble compound lead (II) chloride, PbCl2. The solubility of PbCl2 is 0.016 mol/L. The ratio of cations to anions is 1:2. · This means that 0.016 moles of Pb2+ can dissolve in

• ne liter. Molar solubility always refers to the ion

with the lower molar ratio. · Twice as much, or 2(0.016) = 0.032 moles of Cl- can dissolve in one liter.

Solubility

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Example #3 Consider the slightly soluble compound silver sulfate, Ag2SO4. The solubility of Ag2SO4 is 0.015 mol/L. The ratio of cations to anions is 2:1. · This means that 0.015 moles of SO4

2- can dissolve

in one liter. · Twice as much, or 2(0.015) = 0.030 moles of Ag+ can dissolve in one liter.

Solubility

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Remember that molar solubility refers to the ion with the lower mole ratio. It does not always refer to the cation, although in most cases it does.

Solubility

Compound Molar Solubility of Compound [Cation] [Anion]

BaC2O4

1.3 x 10-3 mol 1.3 x 10-3 mol 1.3 x 10-3 mol

PbCl2

0.016 mol/L 0.016 mol/L 0.032 mol/L

Ag2SO4

0.015 mol/L 0.030 mol/L 0.015 mol/L

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3 If the solubility of barium carbonate, BaCO3 is 7.1 x 10-5 M, this means that a maximum of _______barium ions, Ba2+ ions can be dissolved per liter of solution. A

7.1 x 10-5 moles

B

half of that

C

twice as much

D

• ne-third as much

E

• ne-fourth as much

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4 If the solubility of barium carbonate, BaCO3 is 7.1 x 10-5 M, this means that a maximum of _______carbonate ions, CO3

2- ions can be dissolved per liter of solution.

A

7.1 x 10 -5 moles

B

half of that

C

twice as much

D

• ne-third as much

E

• ne-fourth as much

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5 If the solubility of Ag2CrO4 is 6.5 x 10-5 M, this means that a maximum of _______chromate ions, CrO4

2-, can

be dissolved per liter of solution. A

6.5 x 10-5 moles

B

twice 6.5 x 10-5 moles

C

half 6.5 x 10-5 moles

D

• ne-fourth 6.5 x 10-5 moles

E

four times 6.5 x 10-5 moles

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6 If the solubility of Ag2CrO4 is 6.5 x 10-5 M, this means that a maximum of _______ Ag+ ions can be dissolved per liter of solution. A

6.5 x 10-5 moles

B

twice 6.5 x 10-5 moles

C

half 6.5 x 10-5 moles

D

• ne-fourth 6.5 x 10-5 moles

E

four times 6.5 x 10-5 moles

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Sample Problem The molar solubility of lead (II) bromide, PbBr2 is 1.0 x 10-2 at 25oC. Calculate the solubility product, Ksp, for this compound.

Calculating Ksp from the Solubility

[Pb2+] = 1.0 x 10-2 mol/L [Br-] = 2.0 x 10-2 mol/L

Substitute the molar concentrations into the Ksp expression and solve.

Ksp = [Pb2+][Br-]2 = (1.0 x 10-2)(2.0 x 10-2)2 = 4.0 x 10-6

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7 For the slightly soluble compound, AB, the molar solubility is 3 x 10-8 moles per liter. Calculate the Ksp for this compound. No calculator. AB <--> A + + B-

A 3 x 10-8 B

1/2 (3 x 10-8)

C

(3 x 10-8)^1/2

D

2 (3 x 10-8)

E

(3 x 10-8)^2

AgCl < - - > Ag+ + Cl-

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8 For the slightly soluble compound, XY, the molar solubility is 5 x 10-5 M. Calculate the Ksp for this

• compound. No calculator.

XY <--> X + + Y-

A 5 x 10-5 B

10 x 10-5

C

25 x 10-5

D

5 x 10-10

E

25 x 10-10

BaCO3 < - - > Ba2+ + CO3

2-

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9 For the slightly soluble compound, MN, the molar solubility is 4 x 10-6 M. Calculate the Ksp for this

• compound. No calculator.

MN <--> M+ + N-

A 4 x 10-6 B

16 x 10-6

C

16 x 10-12

D

16 x 10-36

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10 For the slightly soluble compound, AB2, the molar solubility is 3 x 10-4 M. Calculate the solubility- product constant for this compound. No calculator. AB2 <--> A2+ + 2B-

A 9 x 10-4 B

9 x 10-8

C

18 x 10-8

D

36 x 10-8

E

108 x 10-12

PbCl2 < - - > Pb2+ + 2Cl-

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11 For the slightly soluble compound, X3Y, the molar solubility is 1 x 10-4 M. Calculate the solubility product for this compound. No calculator. X3Y <-> 3X+ + Y3-

A 3 x 10-4 B

3 x 10-8

C

27 x 10-12

D

27 x 10-16

Fe(OH)3 < - - > Fe3+ + 3(OH)- Na3P <--> 3Na+ + P3-

Slide 22 / 57

Calculating Solubility from the Ksp

Sample Problem Calculate the solubility of CaF2 in grams per liter in a) pure water b) a 0.15 M KF solution c) a 0.080 M Ca(NO3)2 solution

The solubility product for calcium fluoride, CaF2 is 3.9 x 10-11

Slide 23 / 57

Ksp = [Ca2+] [F-]2 = (x)(2x)2 Ksp = 3.9 x 10-11 = 4x3 So x = 2.13 x 10-4 mol/L x (78 g/mol CaF2) Solubility is 0.0167 g/L

Calculating Solubility from the Ksp

a) pure water CaF2 < - - > Ca2+ + 2F- If we assume x as the dissociation then, Ca2+ ions = x and [F-] = 2x

2.13 x10-4 Ca 2+ mol/L x 1mol/L CaF2 78g/L

• -------------------- x -------------

1mol/L Ca2+ ions 1 mol CaF2

Slide 24 / 57

b) a 0.15 M KF solution remember KF is a strong electrolyte, is completely ionized. the major source of F- ions, then [F-] =0.15M The solubility product for calcium fluoride, CaF2 is 3.9 x 10-11 [ F-] = 0.15M Ksp = [Ca2+] [F-]2 = (x)(0.15)2 Ksp = 3.9 x 10-11 = 0.0225x So x = ______ mol/L Solubility is = ______ x (78 g/mol CaF2) = ______ g/L

Calculating Solubility from the Ksp

1.73 x10-9 Ca 2+ mol/L x 1mol/L CaF2 78g/L

• -------------------- x -------------

1mol/L Ca2+ ions 1 mol CaF2

Slide 25 / 57

Calculating Solubility from the Ksp

Calculate the solubility of CaF2 in grams per liter in c) a 0.080 M Ca(NO3)2 solution [Ca2+ ] = 0.08M The solubility product for calcium fluoride,CaF2 is 3.9 x 10-11 Ksp = [Ca2+] [F-]2 = (0.080)(x)2 Ksp = 3.9 x 10-11 = 0.080x2 So x = 2.2 x 10-5 mol/L * (78 g/mol CaF2)/ 2 Solubility is 0.000858 g/L CaF2 (s) <---> Ca2+

(aq)

+ 2 F-

(aq)

Slide 26 / 57

Calculating Solubility from the Ksp

Recall from the Common-Ion Effect that adding a strong electrolyte to a weakly soluble solution with a common ion will decrease the solubility of the weak electrolyte. Compare the solubilities from the previous Sample Problem CaF2 (s) <---> Ca2+

(aq)

+ 2 F-

(aq)

CaF2 dissolved with:

Solubility of CaF2

pure water 0.016 g/L 0.015 M KF 0.080 M Ca(NO3)2 0.0017 g/L These results support Le Chatelier's Principle that increasing a product concentration will shift equilibrium to the left.

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12 Calculate the concentration of silver ion when the solubility product constant of AgI is 10-16.

A

0.5 (1 x 10-16)

B

2 (1 x 10-16)

C

(1 x 10-16)2

D

(1 x 10-16)

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13 The Ksp of a compound of formula AB3 is 1.8 x 10-18. The molar solubility of the compound is ----

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14 The Ksp of a compound of formula AB3 is 1.8 x 10-18. The solubility of the compound is ---- The molar mass is 210g/mol

Slide 30 / 57

15 The concentration of hydroxide ions in a saturated solution of Al(OH)3 is 1.58 x10-15. The concentration of Al 3+ is -------

Slide 31 / 57

16 The concentration of hydroxide ions in a saturated solution of Al(OH)3 is 1.58 x10-15. The ksp of Al (OH)3 is-----

Slide 32 / 57

Factors Affecting Solubility

· Recall The Common-Ion Effect · 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) + SO4

2-(aq)

· So adding any soluble salt containing either Ba2+ or SO4

2- ions will decrease the solubility

• f barium sulfate.

Slide 33 / 57

Factors Affecting Solubility

· The Common-Ion Effect applies when a basic anion is involved, such as conjugate base of a weak acid. · Consider the dissociation of the salt calcium fluoride: CaF2 <--> ______ + ______ What do you expect will happen to equilibrium point if the pH of this system is lowered by adding a strong acid?

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Write the dissociation equation for magnesium hydroxide: Suppose you have a saturated solution of magnesium hydroxide in a flask. What will happen if you add a small amount of strong acid to it? (Think Le Châtelier’s Principle.)

Factors Affecting Solubility

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Factors Affecting Solubility

Main idea: Adding an acid, or otherwise lowering the pH of a solution will _______________________ the solubility of a salt containing a ___________________________________.

Slide 36 / 57

Factors Affecting Solubility

· pH · If a substance has a basic anion, it will be more soluble in an acidic solution. · Substances with acidic cations are more soluble in basic solutions.

Slide 37 / 57

17 Given the system at equilibrium AgCl (s) <--> Ag+ (aq) + Cl- (aq) When 0.01M HCl is added to the sytem, the point of equilibrium will shift to the ________.

A

right and the concentration of Ag+ will decrese

B

right and the concentration of Ag+ will increase

C

left and the concentration of Ag+ will decrease

D

left and the concentration of Ag+ will increase

Slide 38 / 57

Factors Affecting Solubility

· Complex Ions · Metal ions can act as Lewis acids and form complex ions with Lewis bases in the solvent.

Slide 39 / 57

Factors Affecting Solubility

· Complex Ions · The formation of these complex ions increases the solubility of these salts.

Slide 40 / 57

Factors Affecting Solubility

· Amphoterism · Amphoteric metal oxides and hydroxides are soluble in strong acid or base, because they can act either as acids or bases. · Examples of such cations are Al3+, Zn2+, and Sn2+.

Slide 41 / 57

Solubility rules to memmorize by this time. Will help you to identify which will precipitate as you mix two solutions. · Any salt made with a Group I metal is soluble. · All salts containing nitrate ion are soluble. · All salts containing ammonium ion are soluble.

Precipitation Problems

Slide 42 / 57

18 What is the name of the solid precipitate that is formed when a solution of sodium chloride is mixed with a solution of silver nitrate?

A

sodium silver

B

sodium nitrate

C

chloride nitrate

D

silver chloride

E

Not enough information

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19 What is the name of the solid precipitate that is formed when a solution of potassium carbonate is mixed with a solution of calcium bromide?

A

potassium bromide

B

calcium carbonate

C

potassium calcium

D

carbonate bromide

E

Not enough information

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20 What is the name of the solid precipitate that is formed when a solution of lead (IV) nitrate is mixed with a solution of magnesium sulfate?

A

PbSO4

B

Pb(SO4)2

C

Pb2SO4

D

Mg(NO3)2

E

Not enough information

Slide 45 / 57

Most of the problems in this section ask you whether a precipitate will form after mixing certain solutions together. General Problem-Solving Strategy Step 1 - Determine which of the products is the precipitate. Write the Ksp expression for this compound. Step 2 - Calculate the cation concentration of this slightly soluble compound. Step 3 - Calculate the anion concentration of this slightly soluble compound. Step 4 - Substitute the values into the reaction quotient (Q)

• expression. Recall that this is the same expression as K.

Step 5 - Compare Q to K to determine whether a precipitate will form.

Precipitation Problems

Slide 46 / 57

If Q = Ksp If Q > Ksp If Q < Ksp then you have an exactly perfect saturated solution with not one speck of undissolved solid. then YES you will

• bserve a precipitate;

the number of cations and anions exceeds the solubility then NO precipitate will form; there are so few cations and anions that they all remain dissolved

Precipitation Problems

Analyzing quantitative results: In a solution, · If Q = Ksp, the system is at equilibrium and the solution is saturated. · If Q > Ksp, the salt will precipitate until Q = Ksp. · If Q < Ksp, more solid can dissolve until Q = Ksp.

Slide 47 / 57

21 The Ksp for Zn(OH)2 is 5.0 x10-17. Will a precipitate form in a solution whose solubility is 8.0x10-2 mol/L Zn(OH)2?

A

yes, because Qsp < Ksp

B

yes, because Qsp > Ksp

C

no, because Qsp = Ksp

D

no, because Qsp < Ksp

E

no, because Qsp > Ksp

Slide 48 / 57

Sample Problem Will a precipitate form if you mix 50.0 mL of 0.20 M barium chloride, BaCl2, and 50.0 mL of 0.30 M sodium sulfate, Na2SO4? · Qualitatively, you know that ____________ will be the solid that would theoretically form. · Quantitatively, however, the question is, are there enough _________________ ions and ____________________ ions to produce a solid precipitate, or will there be so few of them that they will all dissolve?

Precipitation Problems

Slide 49 / 57

Sample Problem - Answers Will a precipitate form if you mix 50.0 mL of 0.20 M barium chloride, BaCl2, and 50.0 mL of 0.30 M sodium sulfate, Na2SO4?

Step 1 - Determine which of the products is the precipitate. Write the Ksp expression for this compound.

BaSO4 (s) <--> Ba2+ (aq) + SO4

2- (aq)

Step 2 - Calculate the cation concentration of this slightly soluble compound.

M1V1 =M2V2 M2 = (M1V1) / V2 M2= (0.20M*50.0mL) / 100 mL M2 = 0.10 M BaCl2 [Ba2+] = 0.10 M

Step 3 - Calculate the anion concentration of this slightly soluble compound.

M1V1 =M2V2 M2 = (M1V1) / V2 M2= (0.30M*50.0mL) / 100 mL M2 = 0.15 M Na2SO4 [SO4

2-] = 0.15 M

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22 The Ksp for zinc carbonate is 1 x 10-10. If equivalent amounts of 0.1M sodium carbonate and 0.1M zinc nitrate are mixed, what happens?

A

A zinc carbonate precipitate forms, since Q>K.

B

A zinc carbonate precipitate forms, since Q<K.

C

A sodium nitrate precipitate forms, since Q>K.

D

No precipitate forms, since Q=K.

Slide 51 / 57

Sample Problem - Answers (con't) Will a precipitate form if you mix 50.0 mL of 0.20 M barium chloride, BaCl2, and 50.0 mL of 0.30 M sodium sulfate, Na2SO4? Step 4 - Substitute the values into the reaction quotient (Q)

• expression. Recall that this is the same expression as K.

Ksp = [Ba2+] [SO4

2-] = (0.10) (0.15) = 0.015

Step 5 - Compare Q to K to determine whether a precipitate will form. The Ksp for barium sulfate is 1 x 10-10. Therefore, since Q > K, there will be a precipitate formed when you mix equal amounts of 0.20 M BaCl2, and 0.30 M Na2SO4.

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23 Which of the following factors affect solubility?

A

pH

B

Concentration

C

Common-Ion Effect

D

A and C

E

A, B, and C

Slide 53 / 57

Selective Precipitation of Ions

One can use differences in solubilities of salts to separate ions in a mixture.

Slide 54 / 57

HW question

Slide 55 / 57

http://www.ktf-split.hr/periodni/en/abc/kpt.html

To a solution containing 2.0 x 10-5 M Barium ions and 1.8 x 10-4 M lead ions, Na2CrO4 is added. Which would precipitate first from this solution?

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