Chapter 17b Solubility

CH160 General Chemistry II Lecture Presentation Solubility Equilibria
Chapter 17
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Chapter 17
Why Study Solubility Equilibria?

Many natural processes involve precipitation or dissolution of salts. A few examples: Dissolving of underground limestone deposits (CaCO3) forms caves
Note: Limestone is water insoluble (How can this be?)
Precipitation of limestone (CaCO3) forms stalactites and stalagmites in underground caverns Precipitation of insoluble Ca3(PO4)2 and/or CaC2O4 in the kidneys forms kidney stones Dissolving of tooth enamel, Ca5(PO4)3OH, leads to tooth decay (ouch!) Precipitation of sodium urate, Na2C5H2N4O2, in joints results in gouty arthritis.
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Many chemical and industrial processes involve precipitation or dissolution of salts. A few examples:
Production/synthesis of many inorganic compounds involves their precipitation reactions from aqueous solution Separation of metals from their ores often involves dissolution Qualitative analysis, i.e. identification of chemical species in solution, involves characteristic precipitation and dissolution reactions of salts Water treatment/purification often involves precipitation of metals as insoluble inorganic salts
Toxic Pb2+, Hg2+, Cd2+ removed as their insoluble sulfide (S2-) salts PO43- removed as insoluble calcium salts Precipitation of gelatinous insoluble Al(OH)3 removes suspended matter in water
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To understand precipitation/dissolution processes in nature, and how to exploit precipitation/dissolution processes for useful purposes, we need to look at the quantitative aspects of solubility and solubility equilibria.
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Solubility of Ionic Compounds

Solubility Rules
general rules for predicting the solubility of ionic compounds strictly qualitative
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Solubility Rule Examples
All alkali metal compounds are soluble Most hydroxide compounds are insoluble. The exceptions are the alkali metals, Ba2+, and Ca2+ Most compounds containing chloride are soluble. The exceptions are those with Ag+, Pb2+, and Hg22+ All chromates are insoluble, except those of the alkali metals and the NH4+ ion
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large excess added
NaOH
Fe(OH)3 Cr(OH)3 Fe3+ Cr3+

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Precipitation of both Cr3+ and Fe3+ occurs

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small excess added slowly +
NaOH
Cr3+ Fe(OH)3 Fe3+ Cr3+

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less soluble salt precipitates only

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Solubility Rules
general rules for predicting the solubility of ionic compounds strictly qualitative
Do not tell how soluble Not quantitative
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Solubility Equilibrium
saturated solution solid
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My+ Ax-
xMy+
yAx-
My+ Ax-
Chapter 17
MxAy
10

Solubility Equilibrium
MxAy(s) <=> xMy+(aq) + yAx-(aq)
The equilibrium constant for this reaction is the solubility product, Ksp:
Ksp = [My+]x[Ax-]y
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Solubility Product, Ksp

Ksp is related to molar solubility
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qualitative comparisons
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Ksp used to compare relative solubilities
smaller Ksp = less soluble larger Ksp= more soluble
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qualitative comparisons quantitative calculations
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Calculations with Ksp

Basic steps for solving solubility equilibrium problems
Write the balanced chemical equation for the solubility equilibrium and the expression for Ksp Derive the mathematical relationship between Ksp and molar solubility (x)
Make an ICE table Substitute equilibrium concentrations of ions into Ksp expression
Using Ksp, solve for x or visa versa, depending on what is wanted and the information provided
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Example 1
(1 on Example Problems Handout)
Calculate the Ksp for MgF2 if the molar solubility of this salt is 2.7 x 10-3 M.
(ans.: 7.9 x 10-8)
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Example 2
Calculate the Ksp for Ca3(PO4)2 (FW = 310.2) if the solubility of this salt is 8.1 x 10-4 g/L.
(ans.: 1.3 x 10-26)
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Example 3
The Ksp for CaF2 (FW = 78 g/mol) is 4.0 x 10-11. What is the molar solubility of CaF2 in water? What is the solubility of CaF2 in water in g/L?
(ans.: 2.2 x 10-4 M, 0.017 g/L)
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Precipitation
Precipitation reaction
exchange reaction
one product is insoluble
Example
Overall: CaCl2(aq) + Na2CO3(aq) --> CaCO3(s) + 2NaCl(aq)
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Precipitation
exchange reaction
Example
Overall: CaCl2(aq) + Na2CO3(aq) --> CaCO3(s) + 2NaCl(aq)
Na+ and Ca2+ exchange anions
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Precipitation
exchange reaction
Example
Overall: CaCl2(aq) + Na2CO3(aq) --> CaCO3(s) + 2NaCl(aq) Net Ionic: Ca2+(aq) + CO32-(aq) <=> CaCO3(s)
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Precipitation
Compare precipitation to solubility equilibrium
Ca2+(aq) + CO32-(aq) <=> CaCO3(s) prec.
sol. Equil.
vs
CaCO3(s) <=> Ca2+(aq) + CO32-(aq)
saturated solution
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Precipitation
Compare precipitation to solubility equilibrium:
Ca2+(aq) + CO32-(aq) <=> CaCO3(s)
vs
CaCO3(s) <=> Ca2+(aq) + CO32-(aq)
saturated solution
Precipitation occurs until solubility equilibrium is established.
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Precipitation
Ca2+(aq) + CO32-(aq) <=> CaCO3(s) vs CaCO3(s) <=> Ca2+(aq) + CO32-(aq)
saturated solution
Key to forming ionic precipitates: Mix ions so concentrations exceed those in saturated solution (supersaturated solution)
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Predicting Precipitation
To determine if solution is supersaturated: Compare ion product (Q or IP) to Ksp
For MxAy(s) <=> xMy+(aq) + yAx-(aq)
= [My+]x[Ax-]y Q calculated for initial conditions
Q
Q > Ksp supersaturated solution, precipitation occurs, solubility equilibrium established (Q = Ksp)
= Ksp saturated solution, no precipitation Q < Ksp unsaturated solution, no precipitation
Q
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Predicting Precipitation
Basic Steps for Predicting Precipitation
Consult solubility rules (if necessary) to determine what ionic compound might precipitate Write the solubility equilibrium for this substance
Pay close attention to the stoichiometry
Calculate the moles of each ion involved before mixing

moles = M x L or moles = mass/FW
Calculate the concentration of each ion involved after mixing assuming no reaction Calculate Q and compare to Ksp
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Example 4
(7 and 8 on Example Problems Handout)
Will a precipitate form if (a) 500.0 mL of 0.0030 M lead nitrate, Pb(NO3)2, and 800.0 mL of 0.0040 M sodium fluoride, NaF, are mixed, and (b) 500.0 mL of 0.0030 M Pb(NO3)2 and 800.0 mL of 0.040 M NaF are mixed?
(ans.: (a) No, Q = 7.5 x 10-9; (b) Yes, Q = 7.5 x 10-7)
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Solubility of Ionic Compounds Solubility Rules

All alkali metal compounds are soluble The nitrates of all metals are soluble in water. Most compounds containing chloride are soluble. The exceptions are those with Ag+, Pb2+, and Hg22+ Most compounds containing fluoride are soluble. The exceptions are those with Mg2+, Ca2+, Sr2+, Ba2+, and Pb2+
Ex. 4: Possible precipitate = PbF2 (Ksp = 4.1 x 10-8)
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Example 5
(10 on Example Problem Handout)
A student carefully adds solid silver nitrate, AgNO3, to a 0.0030 M solution of sodium sulfate, Na2SO4. What [Ag+] in the solution is needed to just initiate precipitation of silver sulfate, Ag2SO4 (Ksp = 1.4 x 10-5)?
(ans.: 0.068 M)
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Factors that Affect Solubility

Common Ion Effect pH Complex-Ion Formation
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Factors that Affect Solubility

Common Ion Effect pH Complex-Ion Formation
These sure sound familiar. Where have I seen them before?
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Common Ion Effect and Solubility

Consider the solubility equilibrium of AgCl. AgCl(s) <=> Ag+(aq) + Cl-(aq) How does adding excess NaCl affect the solubility equilibrium? NaCl(s) Na+(aq) + Cl-(aq)
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Consider the solubility equilibrium of AgCl. AgCl(s) <=> Ag+(aq) + Cl-(aq) How does adding excess NaCl affect the solubility equilibrium? NaCl(s) Na+(aq) + Cl-(aq)
2 sources of ClCl- is common ion
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Example 6
(11 on Example Problem Handout)
What is the molar solubility of AgCl (Ksp = 1.8 x 10-10) in a 0.020 M NaCl solution? What is the molar solubility of AgCl in pure water?
(ans.: 8.5 x 10-9, 1.3 x 10-5)
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How does adding excess NaCl affect the solubility equilibrium of AgCl?
AgCl in H2O
Molar solubility
1.3 x 10-5 M
Molar solubility
+ 0.020 M NaCl
AgCl in 0.020 M NaCl

8.5 x 10-9 M
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Why does the molar solubility of AgCl decrease after adding NaCl?
Understood in terms of LeChateliers principle: NaCl(s) --> Na+ + Cl-
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Understood in terms of LeChateliers principle: NaCl(s) --> Na+ + ClAgCl(s) <=> Ag+ + Cl-
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Understood in terms of LeChateliers principle: NaCl(s) --> Na+ + ClAgCl(s) <=> Ag+ + ClCommon-Ion Effect
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pH and Solubility
How can pH influence solubility?
Solubility of insoluble salts will be affected by pH changes if the anion of the salt is at least moderately basic
Solubility increases as pH decreases Solubility decreases as pH increases
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pH and Solubility
Salts contain either basic or neutral anions:
basic anions
Strong bases: OH-, O2Weak bases (conjugate bases of weak molecular acids): F-, S2-, CH3COO-, CO32-, PO43-, C2O42-, CrO42-, etc. Solubility affected by pH changes
neutral anions (conjugate bases of strong monoprotic acids)

Cl-, Br-, I-, NO3-, ClO4Solubility not affected by pH changes
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pH and Solubility
Example:
Fe(OH)2
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq)
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pH and Solubility
Example:
Fe(OH)2-Add acid
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq)
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pH and Solubility
Example:
Fe(OH)2-Add acid
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq) 2H3O+(aq) + 2OH-(aq) 4H2O
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pH and Solubility
Example:
Fe(OH)2-Add acid
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq) 2H3O+(aq) + 2OH-(aq) 4H2O
Which way does this reaction shift the solubility equilibrium? Why? Understood in terms of LeChatliers principle
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pH and Solubility
Example:
Fe(OH)2-Add acid
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq)
More Fe(OH)2 dissolves in response Decrease = stress
Solubility increases
Stress relief = increase [OH-]
2H3O+(aq) + 2OH-(aq) 4H2O
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pH and Solubility
Example:
Fe(OH)2
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq) 2H3O+(aq) + 2OH-(aq) 4H2O(l) overall Fe(OH)2(s) + 2H3O+(aq) <=> Fe2+(aq) + 4H2O(l)
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pH and Solubility
Example:
Fe(OH)2
Fe(OH)2(s) <=> Fe2+(aq) + 2OH-(aq) 2H3O+(aq) + 2OH-(aq) 4H2O(l) overall Fe(OH)2(s) + 2H3O+(aq) <=> Fe2+(aq) + 4H2O(l)
decrease pH
solubility increases
increase pH
solubility decreases
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pH, Solubility, and Tooth Decay

Enamel (hydroxyapatite) = Ca10(PO4)6(OH)2 (insoluble ionic compound)
Ca10(PO4)6(OH)2 10Ca2+(aq) + 6PO43-(aq) + 2OH-(aq)

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Enamel (hydroxyapatite) = Ca10(PO4)6(OH)2 (insoluble ionic compound)
weak base
strong base
Ca10(PO4)6(OH)2 10Ca2+(aq) + 6PO43-(aq) + 2OH-(aq)

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+ food
(Yummy)
metabolism
organic acids
(H3O+)
bacteria in mouth
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Ca10(PO4)6(OH)2(s) 10Ca2+(aq) + 6PO43-(aq) + 2OH-(aq)
OH-(aq) + H3O+(aq) 2H2O(l)

PO43-(aq) + H3O+(aq) HPO43-(aq) + H2O(l)
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Ca10(PO4)6(OH)2(s) 10Ca2+(aq) + 6PO43-(aq) + 2OH-(aq)
Decrease = stress
More Ca10(PO4)6(OH)2 dissolves in response Solubility increases Leads to tooth decay Decrease = stress
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OH-(aq) + H3O+(aq) 2H2O(l) PO43-(aq) + H3O+(aq) HPO43-(aq) + H2O(l)
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Tooth Decay
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Why fluoridation?
F- replaces OH- in enamel
Ca10(PO4)6(F)2(s) 10Ca2+(aq) + 6PO43-(aq) + 2F-(aq)
fluorapatite
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Why fluoridation?
Less soluble (has lower Ksp) than Ca10(PO4)6(OH)2
weaker base than OHmore resistant to acid attack
Factors together fight tooth decay!

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Why fluoridation?
F- added to drinking water as NaF or Na2SiF6

1 ppm = 1 mg/L
F- added to toothpastes as SnF2, NaF, or Na2PO3F

0.1 - 0.15 % w/w
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Complex Ion Formation and Solubility

Metals act as Lewis acids (see Chapter 15)
Example Fe3+(aq) + 6H2O(l) Fe(H2O)63+(aq)
Lewis acid Lewis base
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Complex ion Complex ion/complex contains central metal ion bonded to one or more molecules or anions called ligands Lewis acid = metal Lewis base = ligand
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Complex ion Complex ions are often water soluble Ligands often bond strongly with metals Kf >> 1: Equilibrium lies very far to right.
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Other Lewis bases react with metals also
Examples
Fe3+(aq) + 6CN-(aq) Fe(CN)63-(aq)

Lewis acid Lewis base Complex ion
Ni2+(aq) + 6NH3(aq) Ni(NH3)62+(aq)

Lewis acid Lewis base Complex ion
Ag+(aq) + 2S2O32-(aq) Ag(S2O3)23-(aq)

Lewis acid
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Lewis base
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Complex ion
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Complex-Ion Formation and Solubility

How does complex ion formation influence solubility?
Solubility of insoluble salts increases with addition of Lewis bases if the metal ion forms a complex with the base.
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Example
AgCl
AgCl(s) Ag+(aq) + Cl-(aq)
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Example
AgCl-Add NH3
AgCl(s) Ag+(aq) + Cl-(aq) Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)
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Example
AgCl-Add NH3
AgCl(s) Ag+(aq) + Cl-(aq) Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)
Which way does this reaction shift the solubility equilibrium? Why?
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Example
AgCl-Add NH3
AgCl(s) Ag+(aq) + Cl-(aq)
More AgCl dissolves in response Solubility increases Decrease = stress
Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)
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Example
AgCl
AgCl(s) Ag+(aq) + Cl-(aq) Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq) AgCl(s) + 2NH3(aq) Ag(NH3)2+(aq) + Cl-(aq)
overall
Addition of ligand solubility increases
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Summary: Factors that Influence Solubility

Common Ion Effect
Decreases solubility
pH
pH decreases
Increases solubility
pH increases
Decreases solubility
Salt must have basic anion
Complex-Ion Formation
Increases solubility
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End of Presentation
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Chapter 17b Solubility

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Chapter 17b Solubility

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CH160 General Chemistry II Lecture Presentation Solubility Equilibria

Why Study Solubility Equilibria?

Why Study Solubility Equilibria?

Why Study Solubility Equilibria?

Solubility of Ionic Compounds

Solubility of Ionic Compounds

Solubility of Ionic Compounds

Fe(OH)3 Cr(OH)3 Fe3+ Cr3+

Precipitation of both Cr3+ and Fe3+ occurs

Solubility of Ionic Compounds

Cr3+ Fe(OH)3 Fe3+ Cr3+

less soluble salt precipitates only

Solubility of Ionic Compounds

Solubility of Ionic Compounds

Solubility Product, Ksp

Solubility Product, Ksp

Solubility Product, Ksp

Solubility Product, Ksp

Calculations with Ksp

Na+ and Ca2+ exchange anions

Calculate the moles of each ion involved before mixing

Solubility of Ionic Compounds Solubility Rules

Factors that Affect Solubility

Factors that Affect Solubility

These sure sound familiar. Where have I seen them before?

Common Ion Effect and Solubility

Common Ion Effect and Solubility

Common Ion Effect and Solubility

AgCl in 0.020 M NaCl

Common Ion Effect and Solubility

Common Ion Effect and Solubility

Common Ion Effect and Solubility

neutral anions (conjugate bases of strong monoprotic acids)

Stress relief = increase [OH-]

2H3O+(aq) + 2OH-(aq) 4H2O

pH, Solubility, and Tooth Decay

Ca10(PO4)6(OH)2 10Ca2+(aq) + 6PO43-(aq) + 2OH-(aq)

pH, Solubility, and Tooth Decay

Ca10(PO4)6(OH)2 10Ca2+(aq) + 6PO43-(aq) + 2OH-(aq)

pH, Solubility, and Tooth Decay

pH, Solubility, and Tooth Decay

OH-(aq) + H3O+(aq) 2H2O(l)

pH, Solubility, and Tooth Decay

OH-(aq) + H3O+(aq) 2H2O(l) PO43-(aq) + H3O+(aq) HPO43-(aq) + H2O(l)

pH, Solubility, and Tooth Decay

pH, Solubility, and Tooth Decay

Less soluble (has lower Ksp) than Ca10(PO4)6(OH)2

weaker base than OHmore resistant to acid attack

Factors together fight tooth decay!

pH, Solubility, and Tooth Decay

F- added to drinking water as NaF or Na2SiF6

F- added to toothpastes as SnF2, NaF, or Na2PO3F

Complex Ion Formation and Solubility

Complex Ion Formation and Solubility

Complex Ion Formation and Solubility

Complex Ion Formation and Solubility

Fe3+(aq) + 6CN-(aq) Fe(CN)63-(aq)

Ni2+(aq) + 6NH3(aq) Ni(NH3)62+(aq)

Ag+(aq) + 2S2O32-(aq) Ag(S2O3)23-(aq)

Complex-Ion Formation and Solubility

Complex-Ion Formation and Solubility

Complex-Ion Formation and Solubility

Complex-Ion Formation and Solubility