Aqueous Solubility of Ionic Compounds

John W. Moore • Not all compounds dissolve in water.

Conrad L. Stanitski
Peter C. Jurs • Solubility varies from compound to compound.

http://academic.cengage.com/chemistry/moore

Chapter 5
Chemical Reactions
Soluble ionic
compounds
Molecular compounds
dissociate. Ions are usually stay associated.
Stephen C. Foster • Mississippi State University solvated

Soluble Ionic Compounds (Table 5.1) Insoluble Ionic Compounds (Table 5.1)
ALL ALL
• ammonium and group 1A (Na+, K+… and NH4+ salts) • phosphates (PO43-)
• nitrates (NO3-)
• carbonates (CO32-)
• acetates (CH3COO-)
• oxalates (C2O42-)
• chlorates (ClO3-)
• oxides (O2-) Except grp 1A, NH4+
• perchlorates (ClO4-)
• sulfides (S2-)
MOST
 MgS, CaS & BaS are slightly soluble.
• chlorides, bromides and iodides
• hydroxides (OH-)
 (not: AgX, Hg2X2, and PbX2 ; X = Cl-, Br-, I-).
 Sr, Ba & Ca are slightly soluble
• sulfates (SO42-)
 (not: CaSO4, SrSO4, BaSO4, and PbSO4)

Aqueous Solubility of Ionic Compounds Exchange Reactions: Precipitation

Three types of exchange reactions:
(a) Nitrates (b) Hydroxides
(soluble) (insoluble) • Form a precipitate
 an insoluble ionic compound
 AgNO3(aq) + KCl(aq) → KNO3(aq) + AgCl
AgCl(s)
AgNO3 Cu(NO3)2 Cu(OH)2 AgOH • Form a molecular compound
 Often water

(c) Sulfides
 HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(ℓ)

• Form a molecular gas

CdS Sb2S3 PbS (NH4)2S
 2 HCl(aq) + Na2S(aq) → 2 NaCl(aq) + H2S(g)
soluble
insoluble

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Precipitation Reactions Precipitation Reactions
When ionic solutions mix, a precipitate may form: Na2SO4(aq) and Ba(NO3)2(aq) are
mixed. Will they react?
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)
Products? Na+ SO42-
KNO3(aq) + NaCl(aq) No reaction Ba2+ NO3-

NaNO3 and BaSO4 . Insoluble?

A reaction occurs if a product is insoluble.

The solubility rules help predict reactions. Yes.

Yes BaSO4 – A reaction occurs:

Na2SO4(aq) + Ba(NO3)2(aq) → BaSO4(s) + 2 NaNO3(aq)

Net Ionic Equations Net Ionic Equations

Soluble ionic compounds fully dissociate:
General rules:
AgNO3(aq) Ag+(aq) + NO3-(aq)
KCl(aq) K (aq) + Cl-(aq)
+ 1. Write a balanced equation.
On mixing:
2. Solubility?
Ag+(aq) + NO3-(aq) + K+(aq) + Cl-(aq) →
AgCl(s) + K+(aq) + NO3-(aq) 3. Dissociate soluble compounds.

K+ and NO3- appear on both sides 4. Write the complete ionic equation.
 NO3- and K+ are spectator ions. 5. Cancel ions appearing on both sides (spectators).
 They are not directly involved in the reaction.
6. Check the charges are balanced.
Net ionic equation: Ag+(aq) + Cl-(aq) → AgCl(s)

Net Ionic Equations Net Ionic Equations

Aqueous solutions of (NH4)2S and Hg(NO3)2 react to (NH4)2S(aq) + Hg(NO3)2(aq) → HgS + 2 NH4NO3
give HgS and NH4NO3.
Product Solubility
(a) Write the overall balanced equation HgS – insoluble
(b) Name each compound (All sulfides – except group 1A, 2A and NH4+ salts)
(c) Write the net ionic equation
(d) What type of reaction is this? NH4NO3 – soluble
(All ammonium salts; all nitrates)
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS + NH4NO3
not balanced (b) name each compound

ammonium sulfide mercury(II) sulfide

(NH4)2S(aq) + Hg(NO3)2(aq) → HgS + 2 NH4NO3
mercury(II) nitrate ammonium nitrate
balanced

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Net Ionic Equations Acids
Increase the concentration of H+ ions in water.
(c) Write a net ionic equation
(NH4)2S(aq) + Hg(NO3)2(aq) → HgS(s) + 2 NH4NO3(aq) • Protons (H+) always combine with
water to form H3O+ (hydronium
hydronium ion).
ion
2 NH4+(aq) + S2-(aq) + Hg2+(aq) + 2 NO3-(aq) • Sour tasting.
→ HgS(s) + 2 NH4+(aq) + 2 NO3-(aq) • Change the color of pigments (indicators)
§ Litmus, phenolphthalein…
S2-(aq) + Hg2+(aq) → HgS(s)
Strong acids dissociate (>99%) in water (strong
(d) Type of reaction? electrolytes).
Exchange reaction
Precipitation reaction Weak acids partially dissociate (weak electrolytes).

Acids Bases
Hydrochloric acid (HCl) ≈ 100% dissociated in H2O Increase the concentration of OH- (hydroxide ion) in
• Very few HCl molecules exist in solution. water. Bases:
HCl(aq) + H2O(ℓ) H3O+(aq) + Cl-(aq) • Counteract an acid (neutralize an acid).
• HCl is a strong acid. • Change an indicator’s color (phenolphthalein…).
• Have a bitter taste.
Acetic acid (CH3COOH) is 5% dissociated in H2O. • Feel slippery.
• 95% intact.
Bases can be “strong” or “weak”.
CH3COOH(aq) + H2O(ℓ) H3O+(aq) + CH3COO-(aq) H2O
NaOH(s) Na+(aq) + OH-(aq) strong
• Acetic acid is a weak acid.
NH3(aq) + H2O(ℓ) NH4 +(aq) + OH-(aq) weak

Common Acids and Bases Neutralization Reactions

Strong Acid Strong Base acid + base  salt + water.
HCl Hydrochloric acid LiOH Lithium hydroxide
HBr Hydrobromic acid NaOH Sodium hydroxide
HI Hydroiodic acid
salt = ionic compound made from an acid anion and
KOH Potassium hydroxide
HNO3 Nitric acid Ca(OH)2 Calcium hydroxide base cation.
H2SO4 Sulfuric acid Ba(OH)2 Barium hydroxide
HClO4 Perchloric acid Sr(OH)2 Strontium hydroxide
HX(aq) + MOH(aq) MX
MX(aq) + H2O(ℓ)
Weak Acid Weak Base
HF Hydrofluoric acid NH3 Ammonia HBr(aq) + KOH(aq) KBr(aq) + H2O(ℓ)
KBr
H3PO4 Phosphoric acid CH3NH2 Methylamine
CH3COOH Acetic acid
H2CO3 Carbonic acid H3PO4(aq) + 3 NaOH(aq) Na3PO4(aq) + 3 H2O(ℓ)
HCN Hydrocyanic acid
HCOOH Formic acid
C6H5COOH Benzoic acid Neutralizations are exchange reactions.

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Net Ionic Equations for Acid-Base Reactions Net Ionic Equations for Acid-Base Reactions
Strong Acid + Strong Base Weak Acid + Strong Base
Overall: HX + MOH → MX + H2O Similar: HA + MOH → MA + H2O

but the weak-acid remains undissociated:

Full ionic:
ionic
H+(aq) + X-(aq) + M+(aq) + OH-(aq) →
Full ionic
M+(aq) + X-(aq) + H2O(ℓ)
HA(aq) + M+(aq) + OH-(aq) →
M+(aq) + A-(aq) + H2O(ℓ)
net ionic: H+(aq) + OH-(aq) → H2O(ℓ)

Net ionic: HA(aq) + OH-(aq) → A-(aq) + H2O(ℓ)

Gas-Forming Exchange Reactions Gas-Forming Exchange Reactions

Metal carbonate/acid exchange Carbonic acid Metal hydrogen carbonate/acid exchange
(unstable)
Overall: Overall:
CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + H2CO3(aq) NaHCO3(aq) + HCl(aq)→ NaCl(aq) + H2O(ℓ) + CO2(g)

Tums®
H2CO3(aq) → H2O(ℓ) + CO2(g)
Alka-Seltzer ®

often written:
CaCO3(s) + 2 HCl(aq) → CaCl2(aq) + H2O(ℓ) + CO2(g)
Net ionic
HCO3-(aq) + H+(aq) → H2O(ℓ) + CO2(g)
Net ionic:
ionic
CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2O(ℓ) + CO2(g)

Gas-Forming Exchange Reactions Gas-Forming Exchange Reactions

Metal sulfite/acid exchange Sulfurous acid
(unstable)
Similar. Overall: Metal sulfide/acid exchange
Na2SO3(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2SO3(aq) Overall:
Na2S(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2S(g)
H2SO3(aq) → H2O(ℓ) + SO2(g)
or
Na2SO3(aq) + 2 HCl(aq) →
net ionic: S2-(aq) + 2 H+(aq) → H2S(g)
2 NaCl(aq) + H2O(ℓ) +SO2(g)

net ionic: SO32-(aq) + 2 H+(aq) → H2O(ℓ) + SO2(g)

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Oxidation-Reduction Reactions Oxidation-Reduction Reactions
Oxidation In all cases:
Originally: add oxygen. • If something is oxidized, something must be reduced.
2 Cu(s) + O2(g) 2 CuO(s) • Ox
Oxidation-red
reduction = redox.
redox
2 CO(g) + O2(g) 2 CO2(g) • Redox reactions move e-.
Cu and CO are oxidized. O2 is the oxidizing agent for both. +2 e-
2 Ag+(aq) + Cu(s) 2 Ag(s) + Cu2+(aq)
Reduction -2 e-
Originally: reduce ore to metal; reverse of oxidation.
Here:
CuO(s) + H2(g) Cu(s) + H2O
• Cu changes to Cu2+.
SnO2(s) + 2 C(s) Sn(s) + 2 CO(g)
• Cu loses 2 e-; each Ag+ gains one e-
CuO and SnO2 are reduced. H2 and C are the reducing agents
• Ag+ is reduced (ore turned to metal)
(note: H2 is oxidized, so CuO is an oxidizing agent) • Gain of e- = reduction (so, loss of e- = oxidation)

Redox Reactions and Electron Transfer Redox Reactions and Electron Transfer

Loss of electrons is oxidation

e-
Gain of electrons is reduction

Leo says ger

M X
M loses electron(s) X gains electron(s)

Oxidation is loss M is oxidized X is reduced

Reduction is gain M is a reducing agent X is an oxidizing agent
Oil rig

Common Oxidizing and Reducing Agents Oxidation Numbers & Redox Reactions
Oxidizing Agent Reaction Product Oxidation number
O2 (oxygen) O2- (oxide ion) Compares the charge of an uncombined atom with its
H2O2 (hydrogen peroxide) H2O(ℓ)
actual or relative charge in a compound.
F2, Cl2, Br2, I2 (halogen) F-, Cl-, Br-, I- (halide ion)
HNO3 (nitric acid) nitrogen oxides (NO, NO2..) General rules:
Cr2O7- (dichromate ion) Cr3+ (chromium(III) ion)
 Pure element = 0.
MnO4- (permanganate ion) Mn2+ (manganese(II) ion)
 Monatomic ion = charge of ion.
Reducing Agent Reaction Product
H2 (hydrogen) H+ or H2O  Some elements have the same oxidation
C CO and CO2
number in almost all their compounds…
M (metal: Na, K, Fe…..) Mn+ (Na+, K+, Fe3+…..)  The sum of the oxidation numbers of all atoms in
any species = the charge of the species.

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Oxidation Numbers & Redox Reactions Oxidation Numbers & Redox Reactions
Find the oxidation number for all elements in SO32-
Element Ox# Exceptions
O = -2 ( not a peroxide, not bonded to halogen)
F −1 None

O −2 Metal peroxides (MO2) = -1 Sulfur?

Halogen oxides (OXn) (varies) Sum of the oxidation numbers = charge = -2
(ox. no. for S) + 3(ox. no. for O) = -2
Cl, Br, I −1 Interhalogens (strongest = -1)
(ox. no. for S) + 3(-2) = -2
H +1 Metal hydrides (e.g. NaH) = -1 (ox. no. for S) – 6 = -2
Sulfur = +4

Oxidation Numbers & Redox Reactions Oxidation Numbers & Redox Reactions
Compound Known Unknown Ox. numbers always change during redox reactions
SO2 O = -2 S = +4 Increase ox. number = Oxidation
SO42- O = -2 S = +6 Decrease ox. number = Reduction
NH4+ H = +1 N = -3
NO2- O = -2 N = +3 If an element reacts to form a compound, it is a redox
NO3- O = -2 N = +5 reaction.
OF2 F = -1 O = +2 Oxidation and reduction must both occur.
ClF5 F = -1 Cl = +5
S8(s) + 8 O2(g) 8 SO2(g)
KMnO4 K = +1 O = -2 Mn = +7
S : 0 → +4 (oxidized: added O; lost e-; increased ox. no.)
H2O2 H = +1 O = -1 O : 0 → -2 (reduced: lost O; gained e-; decreased ox. no.)

Oxidation Numbers & Redox Reactions Oxidation Numbers & Redox Reactions
A more complex example:
Exchange reactions are not redox
0 +1 +5 −2 – no change in oxidation state occurs.
Cu(s) + 4 H+(aq) + 2 NO3-(aq)
Cu2+ (aq) + 2 NO2 (g) + 2 H2O(ℓ)
+2 +4 −2 +1 −2 e.g.
+1 +1 −1 +1 +1 −1
Cu is oxidized (ox. no. ↑; loss of e-). AgNO3(aq) + KCl(aq)  KNO3(aq) + AgCl (s)

H is unchanged.
NO3-: N is in a +5, and O is in a -2 ox. state.
O is unchanged.
N is reduced (ox. no. ↓; gain of e-).

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Displacement Reactions Activity Series of Metals Li
K
Ba
+ + Displace H2 from H2O (ℓ), Sr
steam or acid Ca
Na
A XZ AZ X
Mg
Redox: Displace H2 from steam or Al
Mn
Fe(s) + CuSO4(aq) FeSO4(aq) + Cu(s) acid Zn
Cr
0 +2 +2 0 Ease of
Fe
Cu(s) + 2 AgNO3(aq) Cu(NO3)2(aq) + 2 Ag(s) Ni
oxidation
Displace H2 from acid increases
Sn
0 +1 +2 0 Pb

Not all metals can displace another from its salts: H

Sb
Cu(s) + ZnSO4(aq) no reaction Cu
Hg
No reaction with H2O, Ag
An activity series was developed… steam or acid Pd
Pt
Au

Displacement Reactions Li
K
Displacement Reactions
Ba
Powerful reducing agents at the top. Sr
Ca
Na
Mg
Higher elements displace lower ones: Al
Mn
Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s) Zn
Cr
Mg(s) + 2 HCl(aq)  MgCl2(aq) + H2(g) Fe
Ni
Sn
Pb
H
Metals at the bottom are unreactive.
Sb
• Coinage metals Cu
Hg
• Their ions are powerful oxidizing agents. Ag
Pd
Pt
Au

Displacement Reactions Solution Concentration

Potassium + water
Relative amounts of solute and solvent.

 solute – substance dissolved.

2 K(s) + 2 H2O(ℓ)   solvent – substance doing the dissolving.
2 KOH(aq) + H2(g)

There are several concentration units.

Most important to chemists: Molarity

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Molarity Molarity
Calculate the molarity of sodium sulfate in a solution
Molarity = moles solute = mol that contains 36.0 g of Na2SO4 in 750.0 mL of
liters of solution L solution.
36.0 g = 0.2534 mol
• V of solution not solvent. nNa2SO4 =
142.0 g/mol

• Shorthand: [NaOH] =1.00 M 0.2534 mol

[Na2SO4 ] = Unit change!
0.7500 L (mL to L)
Brackets [ ] represent
“molarity of ”
[Na2SO4 ] = 0.338 mol/L = 0.338 M

Molarity Molarity
6.37 g of Al(NO3)3 in a 250. mL aqueous solution. Calculate (a) the molarity of the
6.37 g of Al(NO3)3 are dissolved to make a 250. mL Al(NO3)3 , (b) the molar concentration of Al3+ and NO3- ions in solution.
aqueous solution. Calculate (a) [Al(NO3)3] (b) [Al3+]
and [NO3-]. (b) Molarity of Al3+ , NO3-?
Al(NO3)3(aq) → Al3+(aq) + 3 NO3-(aq)
(a) Al(NO3)3 FM = 26.98 + 3(14.00) + 9(16.00)
= 213.0 g 1 Al(NO3)3 ≡ 1 Al3+ 1 Al(NO3)3 ≡ 3 NO3-
mol
6.37 g 1 Al3+
nAl(NO3)3 = = 2.991 x 10-2 mol [Al3+] = 0.120 M Al(NO3)3 = 0.120 M Al3+
213.0 g/mol 1 Al(NO3)3

-2 3 NO3- = 0.360 M NO -
[Al(NO3)3] = 2.991 x 10 mol = 0.120 M [NO3-] = 0.120 M Al(NO3)3 3
0.250 L 1 Al(NO3)3

Solution Preparation Solution Preparation by Dilution

Solutions are prepared either by:
1. Diluting a more concentrated solution.
or…
MconcVconc = MdilVdil
Example
Commercial concentrated sulfuric acid is 17.8 M. If
75.0 mL of this acid is diluted to 1.00 L, what is the
final concentration of the acid?

Mconc = 17.8 M Vconc = 75.0 mL

2. Dissolving a measured amount of solute and Mdil = ? Vdil = 1000. mL
diluting to a fixed volume.
Mdil = MconcVconc = 17.8 M x 75.0 mL = 1.34 M
Vdil 1000. mL

8
Solution Preparation from Pure Solute Solution Preparation from Pure Solute
Prepare a 0.5000 M solution of potassium • Weigh exactly 19.75 g of pure KMnO4
permanganate in a 250.0 mL volumetric flask.
• Transfer it to a volumetric flask.

Mass of KMnO4 required

nKMnO4 = [KMnO4] x V
• Rinse all the solid from the weighing
= 0.5000 M x 0.2500 L (M ≡ mol/L) dish into the flask.
= 0.1250 mol KMnO4 • Fill the flask ≈ ⅓ full.
• Swirl to dissolve the solid.
Mass of KMnO4 = 0.1250 mol x 158.03 g/mol
= 19.75 g • Fill the flask to the mark on the neck.
• Shake to thoroughly mix.

Molarity and Reactions in Aqueous Solution Molarity and Reactions in Aqueous Solution
What volume, in mL, of 0.0875 M H2SO4 is required
Grams of Grams of to neutralize 25.0 mL of 0.234 M NaOH?
A Use molar B
Use molar mass of B
mass of A
H2SO4(aq) + 2 NaOH(aq) → Na2SO4(aq) + 2 H2O(ℓ)
Moles of Moles of
A B
Use mole ratio
0.234 mol
Use solution nNaOH = 0.0250 L = 5.850 x 10-3 mol
molarity of A
Use solution
molarity of B
L
Liters of
Liters of B solution
A solution 2 NaOH ≡ 1 H2SO4
nA = [ A ] x V 1 H2SO4
nH2SO4 = 5.850 x 10-3 mol NaOH
2 NaOH
[product] = nproduct / (total volume).
= 2.925 x 10-3 mol

Molarity and Reactions in Aqueous Solution Molarity and Reactions in Aqueous Solution
H2SO4(aq) + 2 NaOH(aq) → Na2SO4(aq) + 2 H2O(ℓ) A 4.554 g mixture of oxalic acid, H2C2O4 and NaCl
0.002925 mol 0.00585 mol
V? 25.0 mL
was neutralized by 29.58 mL of 0.550M NaOH. What
was the weight % of oxalic acid in the mixture?
Vacid needed: H2C2O4(aq) + 2 NaOH(aq) → Na2C2O4(aq) + 2 H2O(ℓ)

nNaOH = 0.02958 L x 0.550 mol/L = 0.01627 mol

mol H2SO4 1L
V = = 2.925 x 10-3 mol
[H2SO4] 0.0875 mol 1 H2C2O4 ≡ 2 NaOH

Oxalic acid reacted =

= 0.0334 L = 33.4 mL 1 H2C2O4
0.01627 mol NaOH = 8.135 x10-3 mol
2 NaOH

9
Molarity and Reactions in Aqueous Solution
A 4.554 g H2C2O4 / NaCl mixture … Wt % of oxalic acid in the mixture?
Mass of acid consumed, macid
= 8.135 x10-3 mol x (90.04 g/mol acid)
= 0.7324 g
Molarity and Reactions in Aqueous Solution
25.0 mL of 0.234 M FeCl3 and 50.0 mL of 0.453 M
NaOH are mixed. Which reactant is limiting? How
many moles of Fe(OH)3 will form?
FeCl3(aq) + 3 NaOH(aq) → 3 NaCl (aq) + Fe(OH)3(s)

macid
Weight % = sample mass x 100% nFeCl3 = 0.0250 L x 0.234 mol/L = 0.005850 mol

0.7324 g
Weight % = x 100% = 16.08%
4.554 g nNaOH = 0.0500 L x 0.453 mol/L = 0.02265 mol

Molarity and Reactions in Aqueous Solution Aqueous Solution Titrations

FeCl3(aq) + 3 NaOH(aq) → 3 NaCl (aq) + Fe(OH)3(s) Titration = volume-based method used to determine
0.005850 mol 0.01925 mol nFe(OH)3 ? an unknown concentration.

1 Fe(OH)3 A standard solution (known concentration) is added

0.00585 mol FeCl3 = 0.00585 mol Fe(OH)3 to a solution of unknown concentration.
1 FeCl3
 Monitor the volume added.

 Add until equivalence is reached – stoichiometrically

1 Fe(OH)3 equal moles of reactants added.
0.02265 mol NaOH = 0.00755 mol Fe(OH)3
3 NaOH  An indicator monitors the end point.

FeCl3 is limiting; 0.00585 mol Fe(OH)3 produced. Often used to determine acid or base concentrations.

Aqueous Solution Titrations

Titrant: Base Buret = volumetric glassware used for
of known titrations.
concentration

Slowly add standard solution.

End point: indicator changes

color.

Determine Vtitrant added.

Unknown acid + phenolphthalein

(colorless in acid)… …turns pink
in base

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