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Lecture Unit 4
Reactions in Aqueous Solutions
1
Scope
1. Types of Reactions in Aqueous Solutions
Precipitation reactions, Acid-Base, Redox
Net Ionic Equation
Dilution of Solution
2. Theories of Acids and Bases
3. Strengths of Acids
4. Acid- Base Reaction/ Titration
5. Redox reactions
2
A Review on Classification of Solute
C6 H12O6 (s)
C6 H12O6 (aq)
The water molecules are not shown explicitly,
although their presence is indicated by the “(aq)”
on the product side.
A Review on Classification of Solute
Soluble ionic
compounds
dissociate. Most molecular
Ions are
compounds stay
solvated
associated in water.
Types of Reaction in Aqueous Solutions
Precipitation Reactions
Acid –Base
Reduction –Oxidation (Redox)
Precipitation Reaction
Precipitates are called insoluble – they do
not dissolve in solution
Precipitation of an insoluble solid
Mix a solution of nickel(II) chloride with one of
sodium hydroxide
A solid forms: Ni(OH)2 (s)
Precipitation Reaction
Precipitation Reaction
Soluble species
All ammonium and group 1A (Na+, K+,…. and NH4+ salts)
All nitrates (NO3-)
Most chlorides, bromides and iodides
(exceptions: AgX, Hg2X2, and PbX2 ; X = Cl-, Br-, I-).
Most sulfates (SO42-)
(exceptions: CaSO4, SrSO4, BaSO4, Ag2SO4, PbSO4, and Hg2SO4)
All chlorates (ClO3-)
All perchlorates (ClO4-)
All acetates (CH3COO-)
Precipitation Reaction
(a) Nitrates (b) Hydroxides
(soluble) (insoluble)
(c) Sulfides
precipitate
an insoluble ionic compound
AgNO3(aq) + KCl(aq) → KNO3(aq) + AgCl(s)
Precipitation Reaction
When ionic solutions mix, a precipitate may
form:
AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)
H (aq) + NH 3 (g)
+
NH (aq)
+
4
c) net ionic
Acid- Base Reactions
Neutralization Reactions
acid + base salt + water.
salt = ionic compound made from an acid anion and
base cation.
HX(aq) + MOH(aq) MX(aq) + H2O(l)
Full ionic:
H+(aq) + X-(aq) + M+(aq) + OH-(aq) →
M+(aq) + X-(aq) + H2O(l)
Net ionic:
CaCO3(s) + 2 H+(aq) → Ca2+(aq) + H2O(l) + CO2(g)
Acid- Base Reactions
Metal hydrogen carbonate/acid exchange
Overall:
NaHCO3(aq) + HCl(aq)→ NaCl(aq) + H2O(l) + CO2(g)
Alka-Seltzer ®
Net ionic
HCO3-(aq) + H+(aq) →
H2O(l) + CO2(g)
Acid- Base Reactions
Metal sulfite/acid exchange Sulfurous acid
(unstable)
Similar. Overall:
Na2SO3(aq) + 2 HCl(aq) → 2 NaCl(aq) + H2SO3(aq)
H2SO3(aq) → H2O(l) + SO2(g)
or
Na2SO3(aq) + 2 HCl(aq) →
2 NaCl(aq) + H2O(l) +SO2(g)
a) molecular
b) total ionic
c) net ionic
THEORIES OF ACIDS AND BASES
Arrhenius Theory
Brønsted-Lowry Concept
Lewis Theory
Arrhenius Definition
Arrhenius: any substance which ionizes in
water to produce:
• Protons is an Acid
• Hydroxide ions is a Base
HCO3- + H+ H2CO3
Base: Conjugate
H+ acceptor Acid
H2SO3 HSO3-
HSO4- SO42-
H3PO4 H2PO4-
HF F-
CH3COOH CH3COO-
H2S HS-
H2PO4- HPO42-
NH4+ NH3
HCO3- CO32-
H2O OH-
OH- O2-
H2 extremely H- strong base
CH4 weak acids CH3 -
Autoionization of Water
Two water molecules can react to form ions.
Autoionization occurs:
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Base Acid Acid Base
10 0.29 x 10-14
15 0.45 x 10-14
20 0.68 x 10-14
25 1.01 x 10-14
30 1.47 x 10-14
50 5.48 x 10-14
Autoionization of Water
H3O+ and OH- are present in all aqueous
solutions.
Neutral solution.
Pure water (@ 25°C): [H3O+] = 10-7 M = [OH-]
• [ H3O+ ] is increased, disturbing the equilibrium:
2 H2O H3O+ + OH-
Acidic solution
If acid is added to water:
• LeChatelier: equilibrium shifts to remove [H3O+] (and [OH-])
• Equilibrium is reestablished: [ H3O+ ] > 10-7 M > [OH-]
H+ is harder to remove
Ka decreasing
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4- (aq)
Ka = 7.5 x 10-3
Ka = 6.2 x 10-8
Ka = 3.6 x 10-13
Molecular Structure and Acid Strength
What makes a strong acid?
A weak H–A bond, so H+ can be easily removed!
Consider the binary acids HF, HCl, HBr, HI.
A + A B
..
B
Coordinate covalent bond: a shared e- pair, with both e- donated by the same atom.
Lewis Acids and Bases
H H
Examples:
H + O H O H
Lewis acid Lewis base H
H+ + H2O H3O+
F H F H
F B + N H F B N H
F H F H
Lewis acid Lewis base
Positive Metal Ions as Lewis Acids
Metal ions can act as Lewis acids. They have:
Missing e-
Empty valence orbitals
Metal atom + Lewis base → complex ion
Ag+ (aq) + 2 :NH3 (aq) [H3N:Ag:NH3]+ (aq)
:
:O–H
Can easily donate an e- pair to a bond
:
Positive Metal Ions as Lewis Acids
Many metal hydroxides are amphoteric – they react
with acids and bases.
or as a Brønsted-Lowry base:
Al(OH)3(s) + 3 H3O+(aq) Al3+(aq) + 6 H2O(l)
Lewis Acids and Bases
Predict if the following are Lewis acids or Lewis bases.
PH3 BCl3 Cr3+ CO
base acid acid base
H Cl
P H Cl B
C O
H Cl
Acid-Base Titrations
Commonly used to determine the
concentration of a dissolved species or its
percentage in a mixture
Titration
Measuring the volume of a standard solution
(known concentration) needed to react with a
measured quantity of a sample
Titrations
Titrant (in the buret)
Know concentration
Know volume
Analyte (in the Erlenmeyer flask)
Know volume or mass
Determine concentration or mass percent by
reacting with the titrant
Analyzing for Acetic Acid
HC2H3O2 (aq) + OH- (aq) ⇌ C2H3O2- (aq) + H2O
The objective is to determine when the reaction is
complete
When the number of moles of acid equals the
number of moles of OH-, the equivalence point has
been reached
Equivalence point is where the number of moles of
acid equals the number of moles of base
The endpoint is indicated by a color change in the
acid-base indicator
An Acid- Base Titration
An Acid- Base Titration
Titrant: Base
of known
concentration
Buret = volumetric glassware used for
titrations.
Slowly add standard solution.
M V = M V
write the following equation, where the subscripts
denote initiali and final
i values.
f f
Dilution of Solution
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
Mdil = ? Vdil = 1000. mL
Mdil = MconcVconc = 17.8 M x 75.0 mL = 1.34 M
Vdil 1000. mL
Dilution of Solution
A chemist requires 1.5 M hydrochloric acid,
HCl, for a series of reactions. The only
solution available is 6.0 M HCl. What
volume of 6.0 M HCl must be diluted to
obtain 5.0 L of 1.5 M HCl?
Solution Preparation from Pure Solute
nA = [ A ] x V
75
Calculations Involving Molarity
77
Calculations Involving Molarity
Example 11-2: If 130.0 mL of 1.00 M KOH
and 100.0 mL of 0.500 M H2SO4 solutions
are mixed, what will be the concentration of
KOH and K2SO4 in the resulting solution?
What is the balanced reaction?
78
Calculations Involving Molarity
2 KOH + H 2SO 4 K 2SO 4 + 2 H 2 O
Reaction
Ratio: 2 mmol 1 mmol 1 mmol 2 mmol
Before
Reaction: 130 mmol 50 mmol 0 mmol 0 mmol
After
Reaction: 30 mmol 0 mmol 50 mmol 100 mmol
79
Calculations Involving Molarity
What is the total volume of solution?
130.0 mL + 100.0 mL = 230.0 mL
What are the potassium hydroxide and
potassium sulfate amounts?
30.0 mmol & 50.0 mmol
What is the molarity of the solution?
M = 30.0 mmol/230.0 mL = 0.130 M KOH
M = 50.0 mmol/230.0 mL = 0.217 M K2SO4
80
Calculations Involving Molarity
Example 11-3: What volume of 0.750 M
NaOH solution would be required to
completely neutralize 100 mL of 0.250 M
H3PO4?
You do it!
81
Calculations Involving Molarity
82
Oxidation-Reduction Reactions
Oxidation
Originally: add oxygen.
2 Cu(s) + O2(g) 2 CuO(s)
2 CO(g) + O2(g) 2 CO2(g)
Cu and CO are oxidized. O2 is the oxidizing agent for both.
Reduction
Originally: reduce ore to metal; reverse of oxidation.
CuO(s) + H2(g) Cu(s) + H2O
SnO2(s) + 2 C(s) Sn(s) + 2 CO(g)
CuO and SnO2 are reduced. H2 and C are the reducing agents
• Oxidation-reduction = redox.
• Redox reactions move e-.
+2 e-
2 Ag+(aq) + Cu(s) 2 Ag(s) + Cu2+(aq)
-2 e-
Here:
• Cu changes to Cu2+.
• Cu loses 2 e-; each Ag+ gains one e-
• Ag+ is reduced (ore turned to metal)
• Gain of e- = reduction (so, loss of e- = oxidation)
Redox Reactions and Electron Transfer
Loss of electrons is oxidation
Gain of electrons is reduction
Leo says ger
Oxidation is loss
Reduction is gain
Oil rig
Redox Reactions and Electron Transfer
e-
M X
M loses electron(s) X gains electron(s)
M is oxidized X is reduced
M is a reducing agent X is an oxidizing agent
Common Oxidizing and Reducing Agents
Oxidizing Agent Reaction Product
O2 (oxygen) O2- (oxide ion)
H2O2 (hydrogen peroxide) H2O(l)
F2, Cl2, Br2, I2 (halogen) F-, Cl-, Br-, I- (halide ion)
HNO3 (nitric acid) nitrogen oxides (NO, NO2..)
Cr2O7- (dichromate ion) Cr3+ (chromium(III) ion)
MnO4- (permanganate ion) Mn2+ (manganese(II) ion)
Reducing Agent Reaction Product
H2 (hydrogen) H+ or H2O
C CO and CO2
M (metal: Na, K, Fe…..) Mn+ (Na+, K+, Fe3+…..)
Oxidation Numbers & Redox Reactions
Oxidation number
Compares the charge of an uncombined atom
with its actual or relative charge in a
compound.
General rules:
Pure element = 0.
F −1 None
Cl, Br, I −1 Interhalogens (various values)
H +1 Metal hydrides = -1
(e.g. NaH, MgH2)
O −2 Metal peroxides = -1
(MO2)
Halogen oxides (various values)
(OXn)
Oxidation Numbers & Redox Reactions
91
Oxidation Numbers
K2Sn(OH)6
K = +1
O = -2
H = +1
Sn = +5
Calculate
2(+1) + 6(-2) + 6(+1) + x = 0
x = +5
92
Oxidation Numbers
H3PO4
You do it!
H = +1
O = -2
P = +5
93
Oxidation Numbers
HCO3-
O = -2
H = +1
C = +4
Calculate
+1 + 3(-2) + x = -1
x = +4
94
Oxidation Numbers
Cr2O72-
You do it!
O = -2
Cr = +6
95
Oxidation Numbers & Redox Reactions
Compound Known Unknown
SO2 O = -2 S = +4
SO42- O = -2 S = +6
NH4+ H = +1 N = -3
NO2- O = -2 N = +3
NO3- O = -2 N = +5
OF2 F = -1 O = +2
ClF5 F = -1 Cl = +5
KMnO4 K = +1 O = -2 Mn = +7
H2O2 H = +1 O = -1
Oxidation Numbers & Redox Reactions
Ox. numbers always change during redox
reactions
Increase ox. number = Oxidation
Decrease ox. number = Reduction
If an element reacts to form a compound, it is a redox
reaction.
H is unchanged.
O is unchanged.
N is reduced (ox. no. ↓; gain of e-).
Oxidation Numbers & Redox Reactions
2
2 H 2SO 3aq O2g 4 H (aq) 2 SO 4(aq)100
Oxidation-Reduction Reactions
Net ionic equation
You do it!
2
2 H 2SO 3aq O2g 4 H (aq) 2 SO 4(aq)
101
Oxidation-Reduction Reactions
H2SO3 is oxidized.
The oxidation state of S in H2SO3 is +4.
In SO42-, S has an oxidation state of +6.
O2 is reduced.
Oxidation state of O in O2 is 0
In SO42-, O has an oxidation state of –2.
H2SO3 is reducing agent.
O2 is oxidizing agent.
102
Redox Titrations
Redox reactions can be used to analyze an unknown in
the same way as is done with acid-base reactions
Stoichiometry of Redox Reactions
Just as we have done stoichiometry
with acid-base reactions, it can also
be done with redox reactions.
Example : What volume of 0.200 M
KMnO4 is required to oxidize 35.0
mL of 0.150 M HCl? The balanced
reaction is:
2 KMnO 4 16 HCl 2 KCl + 2 MnCl 2 5 Cl2 8 H2O
You do it!
104
Stoichiometry of Redox Reactions
35 mL HCl0150
. M HCl 5.25 mmol HCl
2 mmol KMnO 4
5.25 mmol HCl 0.656 mmol KMnO 4
16 mmol HCl
1 mL
0.656 mmol KMnO 4 3.28 mL
0.200 mmol KMnO 4
105
Stoichiometry of Redox Reactions
Example : A volume of 40.0 mL of iron
(II) sulfate is oxidized to iron (III) by
20.0 mL of 0.100 M potassium
dichromate solution. What is the
concentration of the iron (II) sulfate
solution? The balanced equation is:
2
6 Fe Cr2O7 14 H + 6 Fe3+ 2 Cr3+ 7 H2O
2+
You do it!
106
Stoichiometry of Redox Reactions
2+
6 mmol Fe
2.00 mmol Cr2 O 7
2
2
12.0 mmol Fe 2+
1 mmol Cr2 O 7
12.0 mmol Fe2+
0.300 M Fe 2+
40.0 mL
107
End of Lecture Unit 4
Many medicines are
deliberately made as
conjugate acids or
bases so that they
become active
ingredients after
passage through the
stomach.
108
Scope
1. Types of Reactions in Aqueous Solutions
Precipitation reactions, Acid-Base, Redox
Net Ionic Equation
Dilution of Solution
2. Theories of Acids and Bases
3. Strengths of Acids
4. Acid- Base Reaction/ Titration
5. Redox reactions
109
CHM12-3
Lecture Unit 4
Reactions in Aqueous Solutions
110