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Chapter 4

Reactions in Aqueous Solutions


Precipitatation Reactions
Acid/Base Reactions
Oxidation/Reduction Reactions
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Solutions
A solution is a mixture of 2 or more
pure substances. We will be
studying homogeneous solutions
all components are in the same
phase (can be solid, liquid, or gas)

Solutions contain one solvent and


one or more solutes
Stoichiometry of Solutions: A Solvent

retains its phase (if different from the


solute)
is present
in greater amount (if the
same phase as the solute)
Stoichiometry of Solutions: A Solute
dissolves in solvent (aqueous means
solvent is water, H2O)

changes phase (if different from the


solvent)

ispresent in lesser amount (if the


same phase as the solvent)
Working with Solutions
Molar Concentration
Molar concentration, or molarity (M), is
defined as the moles of solute dissolved in
one liter (cubic decimeter) of solution.
moles of solute
Molarity (M)
liters of solution
Volume of solution = solvent + solute
Sample Problem Calculating the Molarity of a Solution

PROBLEM: Glycine (H2NCH2COOH) is the simplest amino acid.


What is the molarity of an aqueous solution that
contains 0.715 mol of glycine in 495 mL?
PLAN: Molarity is the number of moles of solute per liter of
solution.
SOLUTION:
mol of glycine
1000mL
divide by volume 0.715 mol glycine x
495 mL soln 1 L soln
concentration(mol/mL)
glycine = 1.44 M glycine

103mL = 1L
molarity(mol/L) glycine
Working with Solutions
From the equation moles of solute = Molarity
Liters of solution

Moles = M or, rearranging: L x M = moles


L
How many moles of NaCl are in 25.0 mL of 0.100 M
NaCl solution?
First, convert mL to L: 25.0 mL x 10-3 L/mL = 0.0250 L
0.0250 L soln x (0.100 moles NaCl/L soln) = 0.00250 moles
NaCl
Sample Problem Calculating Mass of Solute in a Given Volume of
Solution
PROBLEM: A buffered solution maintains acidity as a reaction occurs. In
living cells phosphate ions play a key buffering role, so
biochemistry often study reactions in such solutions. How
many grams of solute are in 1.75 L of 0.460 M sodium
hydrogen phosphate?
PLAN: Molarity is the number of moles of solute per liter of solution.
Using the molarity and volume allows us to find the # moles
and then the # of grams of solute. The formula for the solute
is Na2HPO4.
volume of soln M = moles/L and L x M = moles
SOLUTION:
multiply by M 1.75 L x 0.460 moles = 0.805 mol Na2HPO4
moles of solute 1L
0.805 mol Na2HPO4 x 141.96 g Na2HPO4
multiply by Mm mol Na2HPO4
grams of solute = 114 g Na2HPO4
MASS (g)
Summary of of compound
mass-mole-number- in solution
volume relationships in
Mm (g/mol)
solution.
AMOUNT (mol)
of compound moles/M = L
in solution

Avogadros number
M, molarity, moles/L
(molecules/mol)

MOLECULES VOLUME (L)


(or formula units) of solution
of compound
in solution
L x M = moles
What is the molarity of a solution which
contains 2 moles of NaCl in 0.500 L of
solution? M = moles/L
85%

A. 0.500 M
B. 1.00 M
C. 2.00 M
D. 3.00 M
E. 4.00 M 11%
0% 1% 3%
0M

M
00

00

00

00
50

1.

2.

3.

4.
0.
Solution Terminology

Stock - routinely used solutions prepared in


concentrated form.

Concentrated - relatively large ratio of solute to


solvent. (5.0 M NaCl)

Dilute - relatively small ratio of solute to


solvent. (0.01 M NaCl)
Aqueous solution with water as the solvent
(aq) phase label
Converting a concentrated solution to a dilute solution.

Molarity =

moles
liter
Working with Solutions
Diluting Solutions
The molarity of a solution and its volume are
inversely proportional. Therefore, adding
water makes the solution less concentrated.
This inverse relationship takes the form of:
Moles = Moles
M i Vi M f V f
So, as water is added, increasing the final volume,
Vf, the final molarity, Mf, decreases.
How many liters of 0.100 M HCl will be needed
to prepare 0.500 L of 0.0750 M HCl?

Use MiVi = MfVf


We want to solve for Vi
Mi = 0.100 M HCl
Mf = 0.0750 M HCl
Vf = 0.500 L HCl

Solving the equation for Vi


Vi = (MfVf)/ Mi = (0.0750 M x 0.500 L)/(0.100 M) =
0.375 L
(a) A measuring pipet
is graduated
and can be used to
measure various
volumes of liquid
accurately.

(b) a volumetric
(transfer) pipet
is designed to
measure one volume
accurately.
Dilution Procedure
a) About 100 mL of water is added to a 500 mL flask.
(b) A measuring pipet is then used to transfer 375 of 0.100 M HCl
solution to a volumetric flask.
(c) Water is added to the flask to the calibration mark.
(d) The resulting solution is 0.0750 M HCl.

Always add
acids to water
to prevent
violent boiling!
Sample Problem Preparing a Dilute Solution from a Concentrated Solution
Isotonic saline is a 0.15 M aqueous solution of NaCl that
PROBLEM: simulates the total concentration of ions found in many
cellular fluids. Its uses range from a cleaning rinse for contact
lenses to a washing medium for red blood cells. How would
you prepare 0.80 L of isotonic saline from a 6.0 M stock
solution?
PLAN: It is important to realize the number of moles of solute does
not change during the dilution but the volume does. The new
volume will be the sum of the two volumes, that is, the total
final volume. MdilxVdil = #mol solute = MconcxVconc
volume of dilute soln
Vconc = (MdilVdil/Mconc)
multiply by M of dilute solution SOLUTION:
moles of NaCl in dilute soln = mol NaCl 0.80 L soln x 0.15 mol NaCl = 0.12 mol NaCl
in concentrated soln L soln
divide by M of concentrated soln 0.12 mol NaCl x L solnconc = 0.020 L soln
L of concentrated soln 6 mol
NaCl
Dilute 0.020 L stock solution to 0.800 L with deionized water!
How many L of 0.100 M HCl are
needed to prepare 1.00 L of 0.005 M
HCL? MiVi = MfVf
84%
A. 0.020 L
B. 0.050 L
C. 0.100 L
D. 0.500 L

9%
0L 4% 3%

0L

0L

0L
02

05

10

50
0.

0.

0.

0.
Stoichiometry Steps for Reactions in
Solution.
Sample Problem Calculating Amounts of Reactants and Products for a
Reaction in Solution

PROBLEM: Specialized cells in the stomach release HCl to aid digestion. If they
release too much, the excess can be neutralized with antacids. A
common antacid contains magnesium hydroxide, which reacts with
the acid to form water and magnesium chloride solution. As a
government chemist testing commercial antacids, you use 0.10M HCl
to simulate the acid concentration in the stomach. How many liters
of stomach acid react with a tablet containing 0.10g of magnesium
hydroxide?
Write a balanced equation for the reaction; find the grams of
PLAN:
Mg(OH)2; determine the mol ratio of reactants and products;
use mols to convert to molarity.
mass Mg(OH)2 L HCl
divide by divide by
Mm Molarity
mol Mg(OH)2 mol HCl

mol ratio Mg(OH)2 (s)+ 2 HCl(aq)


2H2O(l) + MgCl2(aq)
Sample Problem Calculating Amounts of Reactants and Products for a
Reaction in Solution
continued

SOLUTION: Mg(OH)2(s) + 2HCl(aq) MgCl2(aq) + 2 H2O(l)

mol Mg(OH)2
0.10g Mg(OH)2 = 1.714 x10-3 mol Mg(OH)2
58.33g Mg(OH)2

2 mol HCl
1.714 x10-3 mol Mg(OH)2 = 3.429 x10-3 mol HCl
1 mol Mg(OH)2
1L
3.429 x10-3 mol HCl = 3.4 x10-2 L HCl
0.10mol HCl
Electron distribution in molecules of H2 and H2O.
Some Properties of Water

Water is bent or V-shaped.

The O-H bonds are covalent.

Water is a polar molecule.

Hydration occurs when salts dissolve


in water.
(a) The ethanol molecule contains a polar OH bond
similar to those in the water molecule. (b) The polar
water molecule interacts strongly with the polar OH
bond in ethanol. This is a case of "like dissolving like."

+ -

Water interacts with other polar molecules


What happens when an ionic solute dissolves?
There are attractive forces between the solute particles
holding them together (positive and negative ions).
There are also attractive forces between the solvent
molecules (positive end of H2O and negative end of H2O).
When we mix the solute with the solvent, there are
attractive forces between the solute particles and the
solvent molecules.
If the attractions between solute and solvent are strong
enough, the solute will dissolve.

26
Table Salt Dissolving in Water
Each ion is attracted to
the surrounding water
molecules and pulled
off and away from the
crystal.
When it enters the
solution, the ion is
surrounded by water
molecules, insulating it
from other ions.
The result is a solution
with free-moving
charged particles able to
conduct electricity.
27
Ionic Theory of Solutions
Substances that dissolve in water are either
electrolytes or nonelectrolytes.
Nonelectrolytes form nonconducting solutions
because they dissolve as molecules (see slide
with interaction between ethanol & water).

Electrolytes form conducting solutions because


they dissolve as ions
Electrolytes can be strong or weak.
Almost all ionic substances that dissolve are strong
electrolytes.

Molecular substances that dissolve are either


nonelectrolytes or weak electrolytes.
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strong weak nonelectrolyte

Electrical
conductivity
of aqueous
solutions.
PracticeWrite the equation for the process
that occurs when the following strong
electrolytes dissolve in water.

H2O
CaCl2 CaCl2(s) Ca2+(aq) + 2 Cl(aq)

H2O
HNO3 HNO3(s) H+(aq) + NO3(aq)
H2O
(NH4)2CO3 (NH4)2CO3(s) 2 NH4+(aq) + CO32(aq)

Note that polyatomic ions stay together as single charged unit!

31
Sample Problem Determining Moles of Ions in Aqueous Ionic
Solutions
PROBLEM: How many moles of each ion are in the following solutions?
(a) 5.0 mol of ammonium sulfate dissolved in water
(b) 78.5 g of cesium bromide dissolved in water
(c) 7.42x1022 formula units of copper(II) nitrate dissolved in water
(d) 35 mL of 0.84 M zinc chloride

PLAN: We have to relate the information given and the number of moles
of ions present when the substance dissolves in water.
H2O
SOLUTION: (a) (NH4)2SO4(s) 2NH4+(aq) + SO42-(aq)
2 mol NH4+
5.0 mol (NH4)2SO4 = 10. mol NH4+
1 mol (NH4)2SO4

1 mol SO42-
5.0 mol (NH4)2SO4 = 5.0 mol SO42-
1 mol (NH4)2SO4
Sample Problem Determining Moles of Ions in Aqueous Ionic
Solutions
continued

(b) CsBr(s) H2O Cs+(aq) + Br-(aq)


= 0.369 mol Cs+
mol CsBr
78.5 g CsBr = 0.369 mol CsBr
212.8 g CsBr
= 0.369 mol Br-
H2O
(c) Cu(NO3)2(s) Cu2+(aq) + 2NO3-(aq) = 0.123 mol Cu2+
7.42x1022 formula mol Cu(NO3)2 = 0.123 mol Cu(NO3)2
-
units Cu(NO3)2 6.022x1023 formula units 2 mol NO3 = 0.246 mol NO -
3
1 mol Cu(NO3)2
HO
(d) ZnCl2(aq) 2 Zn2+(aq) + 2Cl-(aq)
L x M = moles
1L 0.84 mol ZnCl2
35 mL ZnCl2 3 = 2.9x10-2 mol ZnCl2
10 mL L
2 mol Cl- -2 mol Cl-
= 5.8x10
= 2.9x10-2 mol Zn2+ 1 mol ZnCl2
Writing Equations for Aqueous Ionic Reactions

The molecular equation

shows all of the reactants and products as intact, undissociated


compounds.
The total ionic equation

shows all of the soluble ionic substances dissociated into ions.

The net ionic equation

eliminates the spectator ions and shows the actual


chemical change taking place.
Ions in Aqueous Solution
Molecular and Ionic Equations
Complete and net ionic equations
Write an equation showing the reaction between aqueous calcium
A complete ionic equation is a chemical
nitrate and potassium carbonate to form the precipitate, calcium
equation
carbonate, in which
and aqueous strongnitrate.
potassium electrolytes (such as
Complete soluble
molecular ionic
compounds) are written as
Ca( NO 3separate
)2 (aq ) ions in solution.
K 2CO 3 (aq ) CaCO 3 (s ) 2KNO 3 (aq )
(strong) (strong)
(insoluble) (strong)
Complete ionic
2 2
Ca (aq ) 2NO 3 (aq ) 2K (aq ) CO 3 (aq )

CaCO 3 (s ) 2K (aq ) 2NO 3 (aq )
Ions in Aqueous Solution
Molecular and Ionic Equations
Complete and net ionic equations.
A net ionic equation is a complete ionic
equation from which the spectator ions have
been removed.
A spectator ion is an ion in a complete ionic
equation that does not take part in the
reaction.
2
Ca 2 (aq ) 2NO 3 (aq ) 2K (aq ) CO 3 (aq )

CaCO 3 (s ) 2K (aq ) 2NO 3 (aq )

Ca2+ (aq) + CO32- (aq) CaCO3 (s)


A precipitation
reaction and its
equation.
What is the complete ionic equation for the
reaction between zinc hydroxide and HCl acid?
Zn(OH)2 (s) + 2HCl (aq) ZnCl2(aq) + 2 H2O (l)

A. Zn(OH)2 (s) + 2HCl (aq) 93%

ZnCl2(aq) + 2 H2O (l)


B. Zn(OH)2 (s) + 2H+ (aq) + 2 Cl- (aq)
Zn2+ Cl22-(aq) + 2 H2O (l)
C. Zn(OH)2 (s) + 2H+ (aq) + 2 Cl- (aq)4% 2% 2%
Zn2+ + 2 Cl-(aq) + 2 H2O (l)

..

..

e
2.

2.
...

es
)+

)+
)

th
aq
D. None of these

aq

aq
l(

of
(

(
HC

H+

H+

ne
+2

No
+2

+2
(s)

(s)

(s)

D.
2

2
H)

H)

H)
(O

(O

(O
Zn

Zn

Zn
What is the net ionic equation for the complete ionic
equation shown below?
Zn(OH)2 (s) + 2H+ (aq) + 2 Cl- (aq) Zn2+ (aq)+ 2 Cl-(aq)
+ 2 H2O (l)
A. Zn(OH)2 (s) + 2H+ (aq) Zn2+ (aq)
+ 2 H2O (l)
B. Zn(OH)2 (s) + 2H+ (aq) + 2 Cl- (aq)
Zn2+ (aq)+ 2 Cl-(aq) + 2 H2O (l)
C. Zn2+ (s) + 2H+ (aq) + 2 Cl- (aq)
Zn2+(s)+ 2 H2O (l)
D. None of these
2 KI(aq) + Pb(NO3)2(aq) PbI2(s) + 2 KNO3(aq)

If40 you are not part of the solution, youre the precipitate!
The reaction of Pb(NO3)2 and KI.

KI(aq) + Pb(NO3)2 (aq)


PbI2(s) + KNO3(aq)

2KI(aq) + Pb(NO3)2 (aq)


PbI2(s) + 2KNO3(aq)

2K+(aq) + 2I-(aq) + Pb2+(aq) + 2NO3-(aq)


PbI2(s) + 2K+(aq) + 2NO3-(aq)

2 I- (aq) + Pb2+ (aq) PbI2 (s)


Predicting Whether a Precipitate Will Form

1. Note the ions present in the reactants.

2. Consider the possible cation-anion combinations.

3. Decide whether any of the ion combinations is


insoluble.
See the table on the next slide for
solubility rules.
4. If the species for the possible products are identical to
the reactant species and present in the same amount, then
there is NO REACTION.
Solubility Guidelines For Ionic Compounds in Water
Soluble Ionic Compounds
1. All common compounds of Group 1A(1) ions (Li+, Na+, K+, etc.) and
ammonium ion (NH4+) are soluble.
2. All common nitrates (NO3-), acetates (CH3COO- or C2H3O2-) and most
perchlorates (ClO4-) are soluble.
3. All common chlorides (Cl-), bromides (Br-) and iodides (I-) are soluble,
except those of Ag+, Pb2+, Cu+, and Hg22+.
4. All common sulfates (SO42-) are soluble except those of Ca2+, Sr2+,
Ba2+, Ag+, Pb2+.
Insoluble Ionic Compounds
1. All common metal hydroxides and sulfides are insoluble, except those of
Group 1A(1) and the larger members of Group 2A(2)(beginning with Ca2+).
2. All common carbonates (CO32-) , phosphates (PO43-), chromates (CrO42-),
oxalates (C2O42-), and oxides are insoluble, except those of Group 1A(1)
and NH4+ and and chromates of containing Mg2+ and Ca2+.
3. All common fluorides are insoluble except those of Group 1A(1) and
NH4+.
Sample Problem Predicting Whether a Precipitation Reaction Occurs; Writing
Ionic Equations
PROBLEM: Predict whether a reaction occurs when each of the following pairs
of solutions are mixed. If a reaction does occur, write balanced
molecular, total ionic, and net ionic equations, and identify the
spectator ions.
(a) lithium sulfate(aq) + barium nitrate(aq)
(b) ammonium perchlorate(aq) + sodium bromide(aq)
SOLUTION:
PLAN:
(a) Li2SO4(aq) + Ba(NO3)2 (aq) 2 LiNO3(aq) + BaSO4(s)
write ions
2Li+(aq) +SO42-(aq)+ Ba2+(aq)+2NO3-(aq)
combine anions & cations 2Li+(aq) +2NO3-(aq)+ BaSO4(s)

check for insolubility SO42-(aq)+ Ba2+(aq) BaSO4(s)


using solubility (b) NH4ClO4(aq) + NaBr (aq) NH4Br (aq) + NaClO4(aq)
guidelines NH4+ (aq) + ClO4- (aq) + Na+ (aq) + Br- (aq)
eliminate spectator ions NH 4
+ (aq) + ClO - (aq) + Na+ (aq) + Br- (aq)
4

for net ionic equation All reactants and products are soluble so no reaction
occurs.
Which is the precipitation reaction?
1. 211%NaCl (aq) + MgBr2 (aq) MgCl2(aq) + 2 NaBr (aq)
84%
2. Pb(NO 3)2 (aq) + 2 NaCl (aq) PbCl2 (s) + 2 NaNO3 (aq)
5%
3. 2H 2 (g) + O2(g) 2 H2O (l)
Sample Problem Solving Limiting-Reactant Problems for Reactions in
Solution
Mercury and its compounds have many uses, from fillings for
PROBLEM:
teeth (as an alloy with silver, copper, and tin) to the industrial
production of chlorine. Because of their toxicity, however,
soluble mercury compounds, such mercury(II) nitrate, must be
removed from industrial wastewater. One removal method
reacts the wastewater with sodium sulfide solution to
produce solid mercury(II) sulfide and sodium nitrate solution.
In a laboratory simulation, 0.050L of 0.010M mercury(II)
nitrate reacts with 0.020L of 0.10M sodium sulfide. How
many grams of mercury(II) sulfide form? What is the
concentration of excess reactant still in solution?
PLAN: As usual, write a balanced chemical reaction. Since this is a problem
concerning a limiting reactant, we proceed as we would for a
limiting reactant problem. Find the amount of product which would
be made from each reactant. Then choose the reactant that gives
the lesser amount of product.
Mercury(II) nitrate (aq) + sodium sulfide (aq) mercury(II) sulfide (s) + sodium
nitrate(aq)
Hg(NO3)2 (aq) + Na2S (aq) HgS (s) + 2 NaNO3 (aq)
0.050 L of 0.010 M 0.020 L of 0.10 M
Hg(NO3)2 Na2S
How many grams of mercury(II) sulfide form?
Determine the limiting reagent: calculate moles of each reactant and determine
which is in short supply. Since L x M = moles
Moles Hg(NO3)2 = 0.050 L x 0.010 M = 0.00050 moles of Hg(NO3)2 and
0.00050 mole Hg(NO3)2 x (1 mole HgS/1 mole Hg(NO3)2 )= 0.00050 mole HgS

Moles Na2S = 0.020 L of 0.10 M = 0.0020 moles of Na2S and


0.002 moles NasS x (1 mole HgS /1 mole Na2S ) = 0.0020 mole HgS

0.00050 moles Hg(NO3)2 x 1 mole HgS x 232.67 g = 0.116 g or 0.12 g


1 mole Hg(NO3)2 mole HgS
What is the concentration of excess reactant still in solution?
Plan: Na2S was the excess reactant. Determine the moles of
Na2S that have reacted and subtract from the initial
number of moles. Finally, divide the remaining moles of
excess reactant by the volume of the solution in L.
Initial moles of Na2S: 0.00200 mol Na2S
Hg2+ (aq) + S2- (aq) HgS (s)
Moles of Na2S reacted:
0.000500 mol Hg2+ x (1 mol S2-) = 0.00050 mol S2- reacted
(1 mol Hg2+)
Excess S2- = 0.00200 mol 0.00050 mol = 0.00150 mole S2-
Total volume of reaction solution: 0.020 L + 0.050 L = 0.070 L
[S2-] = 0.00150 mol S2-/0.070 L = 0.0214 M
Types of Chemical Reactions
Acid-Base Reactions
The Brnsted-Lowry Concept

A. Involves the transfer of a proton (H+) from the


acid to the base.

B. Defines an acid as the species (molecule or ion)


that donates a proton (H+) to another species in
a proton-transfer reaction.

C. A base is defined as the species (molecule or ion)


that accepts the proton (H+) in a proton-transfer
reaction.
Types of Chemical Reactions
Acid-Base Reactions
The Brnsted-Lowry Concept
HCl reacts immediately with water to form
H3O+(aq).

HCl (aq) + H2O (l) H3O+(aq) + Cl- (aq)

The product formed is called the hydronium ion.

H+ = H3O+
Types of Chemical Reactions
Acid-Base Reactions
The Brnsted-Lowry Concept
In the reaction of ammonia with water,


NH 3 (aq ) H 2O(l ) NH 4 (aq ) OH (aq )

H+
the H2O molecule is the acid because it donates a
proton. The NH3 molecule is a base, because it accepts
a proton.
A flowchart for naming acids. An acid is best
considered as one or more H+ ions weakly
bonded to an anion.
Acids
Strong acids - react completely to produce H+ in
solution molecular compounds with very polar
bonds between H and second bonding atom
(halogen, oxygen)
hydrochloric and sulfuric acid
HCl H2SO4

Weak acids react to a slight extent to give H+ in


solution
acetic and formic acid
HC2H3O2 HCO2H
HCl(aq) is
completely ionized.

HCl (g) + H2O (l) H3O+ (aq) + Cl- (aq)

HCl is a molecular substance with a


strongly polar H-Cl bond. The proton
is transferred from the HCl molecule to
the H2O molecule leaving a Cl- in solution!
Acetic acid (HC2H3O2)
exists in water mostly as
unreacted molecules. Only
a small percentage of the
molecules react to form
ionic species.

HC2H3O2 (aq) + H2O (l) H3O+ (aq) + C2H3O2- (aq)


Acetic acid is an oxyacid (contains
O-H in structure) with a fairly strong
O-H bond it doesnt react strongly to
donate a proton to the water molecule!

CH3COOH or HC2H3O2
An aqueous
solution of sodium
hydroxide.

NaOH Na+ (aq) + OH- (aq)

The metal-oxygen bond is weaker than


the O-H bond in the NaOH structure,
so the ionic compound dissociates
into ions (ionic compounds = metal + anion
or 2 polyatomic ions)
The reaction of
NH3 in water.

NH3 (aq) + H2O NH4+ (aq) + OH- (aq)

Ammonia and water are molecular com-


pounds. The water donates a proton to the
ammonia because the O-H bond is more
polar (weaker) than the N-H bond.
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Selected Acids and Bases Know these strong acids and bases

Acids Bases
Strong Strong

hydrochloric acid, HCl Lithium hydroxide, LiOH


sodium hydroxide, NaOH
hydrobromic acid, HBr
potassium hydroxide, KOH
hydroiodic acid, HI
rubidium hydroxide, RbOH
nitric acid, HNO3 cesium hydroxide, CsOH
sulfuric acid, H2SO4 calcium hydroxide, Ca(OH)2
perchloric acid, HClO4 strontium hydroxide, Sr(OH)2
chloric acid, HClO3
barium hydroxide, Ba(OH)2
Weak
hydrofluoric acid, HF Weak
phosphoric acid, H3PO4 ammonia, NH3
acetic acid, CH3COOH (or
HC2H3O2)
Types of Chemical Reactions
Acid-Base Reactions

Neutralization Reactions
One of the chemical properties of acids and bases
is that they neutralize one another.
A neutralization reaction is a reaction of an acid
and a base that results in an ionic compound and
water.
The ionic compound that is the product of a
neutralization reaction is called a salt.
HCN(aq ) KOH(aq ) KCN(aq ) H 2O(l )
acid base salt
HCN (aq) + OH- (aq) H2O (l) + CN- (aq)
In ionic equations, we will write strong acids as completely
reacted (as separate ions) and weak acids as unreacted.
Soluble salts are dissociated in aqueous solution.

Strong acid + Strong base


HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l) Complete molecular
Complete
H+ (aq) + Cl- (aq) + Na+ (aq) + OH- (aq) Na+ (aq) + Cl- (aq) + H2O (l)
ionic
H+ (aq) + OH- (aq) H2O (l) Net ionic
Actually: H+ (aq) + H2O (l) H3O+ ()
We will use H+ (aq) = H3O+ (aq)
Weak acid + strong base

HC2H3O2 (aq) + NaOH (aq) NaC2H3O2 (aq) + H2O(l) Complete molecular

HC2H3O2 (aq) + Na+ (aq) + OH-(aq) Na+ (aq) + C2H3O2- (aq) + H2O(l) Complete
ionic
HC2H3O2 (aq) + OH- (aq) C2H3O2- (aq) + H2O(l) Net ionic
Polyprotic Acids and Polybasic Bases
Polyprotic Acids have more than 1 acidic hydrogen. The acids may be strong or
weak depending on the strength of the bond between the acid hydrogen and its
bonding partner.
1st ionization: H2SO4 (aq) H+(aq) + HSO4- (aq)
strong
2nd ionization: HSO4- (aq) H+ (aq) + SO42-(aq)
weak
Polybasic bases have more than one OH- or accept more than 1 proton. The bases can
be strong or weak depending on the ability of the base to accept a proton.

1st ionization: C2H4(NH2)2 (aq) + H2O (l) C2H4(NH2)(NH3)+ (aq) + OH-(aq)


weak
2nd ionization: C2H4(NH2)(NH3)+ (aq) + H2O (l) C2H4(NH3)22+ (aq) + OH- (aq)
weak
Sample Problem Writing Ionic Equations for Acid-Base Reactions

PROBLEM: Write balanced molecular, total ionic, and net ionic equations for
each of the following acid-base reactions and identify the
spectator ions.
(a) Barium hydroxide(aq) + perchloric acid(aq)
(b) strontium hydroxide(aq) + sulfuric acid(aq)
PLAN: SOLUTION:

reactants are strong acids and (a) Ba(OH)2(aq)+2HClO4(aq) 2H2O(l)+Ba(ClO4)2(aq)


bases and therefore
completely ionized in water Ba2+(aq) + 2OH-(aq)+ 2H+(aq)+ 2ClO4-(aq)
2H2O(l)+Ba2+(aq)+2ClO4-(aq)
products are
2OH-(aq)+ 2H+(aq) 2H2O(l)
water (b) Sr(OH)2(aq) + H2SO4(aq) 2H2O(l) + SrSO4(s)
spectator ions Sr2+(aq) + 2OH-(aq)+ H+(aq)+ HSO4-(aq)
or precipitate
2 H2O (l) + SrSO4 (s)
2OH-(aq)+ H+(aq) + Sr2+ (aq) + HSO4- (aq) 2H2O(l) + SrSO4 (s)
Sample Problem Determining the Molarity of H+ Ions in Aqueous Solutions of
Acids
PROBLEM: Nitric acid is a major chemical in the fertilizer and explosives
industries. In aqueous solution, each molecule dissociates and the
H becomes a solvated H+ ion. What is the molarity of H+(aq) in
1.4M nitric acid?
PLAN: Use the formula to find the molarity of H+.

SOLUTION: One mole of H+(aq) is released per mole of nitric acid (HNO3)
H2O
HNO3(aq) H+(aq) + NO3-(aq)

1.4M HNO3(aq) should have 1.4M H+(aq).

Actually: H+ (aq) + H2O (l) H3O+ (aq)


We will use H+ (aq) = H3O+ (aq)
An acid-base titration.

Start of titration Point of Slight excess of


Excess of acid neutralization base

At the equivalence pt moles of acid (H+) = moles of base (OH-)


Acid Base Reactions -
Stoichiometry
Consider the reaction of sulfuric acid, H2SO4,
with sodium hydroxide, NaOH:

H 2SO 4 (aq ) 2NaOH(aq ) 2H 2O(l ) Na 2SO 4 (aq )

Suppose a beaker contains 35.0 mL of 0.175 M


H2SO4. How many milliliters of 0.250 M NaOH
must be added to completely react with the
sulfuric acid?
Stoichiometry of acid-base reactions, contd
After balancing the equation, we must convert
the 0.0350 L (35.0 mL) to moles of H2SO4 (using the
molarity of the H2SO4).
Then, convert to moles of NaOH (from the
balanced chemical equation).
Finally, convert to volume of NaOH solution (using
the molarity of NaOH).

0.175 mole H 2SO 4 2 mol NaOH 1 L NaOH soln.


(0.0350L )
1 L H 2SO 4 solution 1 mol H 2SO 4 0.250 mol NaOH
0.0490 L NaOH solution (or 49.0 mL of NaOH solution)
Sample Problem Finding the Concentration of Acid from
an Acid-Base Titration
PROBLEM: You perform an acid-base titration to standardize an HCl solution
by placing 50.00 mL of HCl in a flask with a few drops of indicator
solution. You put 0.1524 M NaOH into the buret, and the initial
reading is 0.55 mL. At the end point, the buret reading is 33.87
mL. What is the concentration of the HCl solution?
PLAN:
SOLUTION:
volume(L) of base
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
multiply by M of base
(33.87-0.55) mL x 1L = 0.03332 L
mol of base
103 mL
molar ratio
0.03332 L X 0.1524 M = 5.0780x10-3 mol NaOH
mol of acid
Molar ratio is 1:1 5.0780x10-3 mol NaOH x 1mol HCl
divide by L of acid
5.0780x10-3 mol HCl 1 mol NaOH
M of acid = 0.1016 M HCl
0.05000 L
50.00 mL x 1 L/1000 mL
If 20.0 mL of X M HCl is completely
neutralized by 20.0 mL of 0.1000 M
NaOH, what is its molarity?
6% 1. 0.0500 M
23% 2. 0.1000 M
67% 3. 0.0200 M
4% 4. 0.2000 M
Acid-Base Reactions

bisulfides HCl (aq) + KHS (aq) H2S(g) + KCl (aq)

HCl(aq) + KHCO3(aq) H2O(l) + CO2 (g)+ KCl (aq)

HCl (aq) + KHSO3(aq) H2O(l) + SO2 (g) + KCl (aq)


Oxidation Reduction Reactions

Reaction of
iron with Cu2+
(aq).
Photo courtesy of
American Color.

Fe (s) + Cu2+ (aq) Cu (s) + Fe2+ (aq)


Types of Chemical Reactions
Oxidation-Reduction Reactions

Oxidation-Reduction Reactions

The net ionic equation shows the reaction of


iron metal with Cu2+(aq) to produce iron(II) ion
and copper metal.
Loss of 2 e-1 oxidation

2 2
Fe(s ) Cu (aq ) Fe (aq ) Cu(s )
Gain of 2 e-1 reduction
Types of Chemical Reactions
Oxidation-Reduction Reactions

Oxidation-Reduction Reactions

Oxidation-reduction reactions involve the


transfer of electrons from one species to
another.
Oxidation is defined as the loss of electrons.
Reduction is defined as the gain of electrons.
Oxidation and reduction always occur
simultaneously.
The redox process in compound formation.

Oxidation number is 1+

Oxidation number is -1
Types of Chemical Reactions
Oxidation-Reduction Reactions

Oxidation Numbers

The concept of oxidation numbers is a simple


way of keeping track of electrons in a reaction.
The oxidation number (or oxidation state) of
an atom in a substance is the actual charge of
the atom if it exists as a monatomic ion.
Alternatively, it is hypothetical charge assigned
to the atom in the substance by simple rules.
Types of Chemical Reactions
Oxidation-Reduction Reactions

Oxidation Number Rules know these rules!


Rule Applies to Statement

1 Elements The oxidation number of an atom in an element is zero. This


includes molecular elements.
H2
2 Monatomic ions The oxidation number of an atom in a monatomic ion
equals the charge of the ion. Group 1A elements always
are assigned a 1+, Group 2A are 2+ Na+
3 Oxygen The oxidation number of oxygen is 2 in most of its
compounds. (An exception is O in H2O2 and other
peroxides, where the oxidation number is 1.)

Na2O2 sodium peroxide


Types of Chemical Reactions
Oxidation-Reduction Reactions

Oxidation Number Rules


Rule Applies to Statement

4 Hydrogen The oxidation number of hydrogen is +1 in its covalent


compounds. When combined with metals or boron, it is -1.
BH3
5 Halogens Fluorine is 1 in all its compounds. The other halogens are
1 unless the other element is another halogen or oxygen.
ICl3

6 Compounds and The sum of the oxidation numbers of the atoms in a


ions compound is zero. The sum in a polyatomic ion equals the
charge on the ion.
Highest and lowest
oxidation numbers of He
reactive main-group
Ne
elements.
Ar
Nonmetals in groups 4A
7A have positive (+) oxidation Kr
Numbers when combined with
O or F (and O has a + oxidation Xe
Number when combined with
Rn
F F2O should be OF2)
Sample Problem Determining the Oxidation Number of an Element

PROBLEM: Determine the oxidation number (O.N.) of each element in these


compounds:
(a) cesium chloride (b) nitrogen dioxide (c) nitric acid

PLAN: Write the formula for the compound. The O.N.s of the ions in a polyatomic
ion add up to the charge of the ion and the O.N.s of the ions in the
compound add up to zero.
Sum of + oxidation number + sum of oxidation number =
SOLUTION:
0 (neutral compound) or charge on ion

(a) CsCl. The O.N. for cesium is +1 and that for chloride is -1.

(b) NO2. Each oxygen is an oxide with an O.N. of -2. Therefore the O.N. of
nitrogen must be +4.

(c) HNO3. H has an O.N. of +1 and each oxygen is -2. Therefore the N
must have an O.N. of +5.
NO3- X 6 = -1
Let X = o.n. of N, then
X + (total charges on O) = charge on ion where X is the O.N. of N
What is the oxidation number of the Cl
in ClO4- ion?
A. 1-
86%
B. 3+
C. 5+
D. 7+
E. 8-

6% 5%
2% 1%
3+

5+

7+
1-

8-
Oxidation and Reduction
Another Definition

Oxidation occurs when an atoms oxidation state


increases during a reaction.
Reduction occurs when an atoms oxidation
state decreases during a reaction.
CH4 + 2 O2 CO2 + 2 H2O
4 +1 0 +4 2 +1 2
Oxidation
Loss of 8 e- Reduction
Gain 8 e-
82
ExampleAssign oxidation states, determine the
elements oxidized and reduced, and determine the
oxidizing agent and reducing agent in the following
reaction.

Reducing Oxidizing
Agent Agent
Fe + MnO4 + 4 H+ Fe3+ + MnO2 + 2 H2O
0 +7 2 +1 +3 +4 2 +1 2

Reduction Gain 3 e-
Oxidation
Lose 3 e-

83
ExampleAssign oxidation states, determine the elements
oxidized and reduced, and determine the oxidizing agent and
reducing agent in the following reaction.

Sn4+(aq) + Ca (s) Sn2+ (aq) + Ca2+ (aq)


+4 0 +2 +2
Ca is oxidized, Sn4+ is reduced.
Ca is the reducing agent, Sn4+ is the oxidizing agent.

16 F2 (g) + S8(s) 8 SF4 (l)


0 0 +4 1
S is oxidized, F is reduced.
S is the reducing agent, F2 is the oxidizing agent.
84
Sample Problem Recognizing Oxidizing and Reducing Agents

PROBLEM: Identify the oxidizing agent and reducing agent in each of the following:

(a) 2Al(s) + 3H2SO4(aq) Al2(SO4)3(aq) + 3H2(g)


(b) PbO(s) + CO(g) Pb(s) + CO2(g)
(c) 2H2(g) + O2(g) 2H2O(g)
PLAN: Assign an O.N. for each atom and see which atom gained and which atom
lost electrons in going from reactants to products.
An increase in O.N. means the species was oxidized (and is the reducing
agent) and a decrease in O.N. means the species was reduced (is the
oxidizing agent).
SOLUTION: 0 +1 +6 -2 +3 +6 -2 0

(a) 2Al(s) + 3H2SO4(aq) Al2(SO4)3(aq) + 3H2(g)


The O.N. of Al increases; it is oxidized; it is the reducing agent.
The O.N. of H decreases; it is reduced; H2SO4 is the oxidizing agent.
Sample Problem Recognizing Oxidizing and Reducing Agents

continued +2 -2 +2 -2 0 +4 -2

(b) PbO(s) + CO(g) Pb(s) + CO2(g)

The O.N. of C increases; it is oxidized; CO is the reducing agent.


The O.N. of Pb decreases; it is reduced; PbO is the oxidizing agent.

0 0 +1 -2

(c) 2H2(g) + O2(g) 2H2O(g)

The O.N. of H increases; it is oxidized; it is the reducing agent.


The O.N. of O decreases; it is reduced; it is the oxidizing agent.
For the reaction:
2 Al (s) + 3 Fe2+ (aq) 2 Al3+ (aq) + 3 Fe (s)
The react Al undergoes :

4% 1. An oxidation reaction
30% 2. A reduction reaction
67% 3. Neither an oxidation nor a reduction reaction
The Activity Series of the Elements
Cu(s) + 2Ag+(g) Cu2+(aq) + 2Ag(s)

Which one of these reactions will occur?

2Ag(s) + Cu2+(g) 2Ag+(aq) + Cu(s)

Copyright 2010 Pearson


Chapter 7/88
Prentice Hall, Inc.
Redox Stoichiometry
Titration: A procedure for determining the
concentration of a solution by allowing a carefully
measured volume to react with a solution of another
substance (the standard solution) whose
concentration is known.

5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)

10CO2(g) + 2Mn2+(aq) + 8H2O(l)

Copyright 2010 Pearson


Chapter 7/91
Prentice Hall, Inc.
Chapter 7/92
Redox Stoichiometry

A solution is prepared with 0.2585 g of oxalic acid,


H2C2O4. 22.35 mL of an unknown solution of potassium
permanganate are needed to titrate the solution. What is
the concentration of the potassium permanganate
solution?
5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)
10CO2(g) + 2Mn2+(aq) + 8H2O(l)
Mass of Moles of Moles of Molarity of
H2C2O4 H2C2O4 KMnO4 KMnO4

Molar Mass Mole Ratio Molarity of


of H2C2O4 KMnO4
Copyright 2010 Pearson Prentice Hall, Inc. Chapter 7/93
Redox Stoichiometry

5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)


10CO2(g) + 2Mn2+(aq) + 8H2O(l)

Moles of H2C2O4 available:


0.2585 g H2C2O4 1 mol
x = 0.002871 mol H2C2O4
90.04 g

Moles of KMnO4 reacted:


0.002871 mol H2C2O4 2 mol KMnO4
x = 0.001148 mol KMnO4
5 mol H2C2O4

Copyright 2010 Pearson Prentice Hall, Inc. Chapter 7/94


Redox Stoichiometry

5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)


10CO2(g) + 2Mn2+(aq) + 8H2O(l)

Concentration of KMnO4 solution:


0.001148 mol KMnO4 1000 mL
x = 0.05136 M KMnO4
22.35 mL 1L

Copyright 2010 Pearson Prentice Hall, Inc. Chapter 7/95


Key Points About Redox Reactions

GER
LEO
Oxidation (electron loss) always accompanies reduction
(electron gain).

The oxidizing agent is reduced, and the reducing agent is


oxidized.

In the balanced equation, the number of electrons gained by


the oxidizing agent always equals the number lost by the
reducing agent.
A summary of redox terminology.

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)


OXIDATION
One reactant loses electrons. Zn loses electrons.
Reducing agent is oxidized. Zn is the reducing agent
and becomes oxidized.

Oxidation number increases. The oxidation number of


Zn increases from x to +2.

REDUCTION
Other reactant gains electrons. Hydrogen ion gains
electrons.
Oxidizing agent is reduced. Hydrogen ion is the oxidizing agent and
becomes reduced.
Oxidation number decreases. The oxidation number of H decreases
from +1 to 0.