Chapter 4:

Aqueous Reactions and

Solution Stoichiometry
Solution Composition
Molarity
Dilution
Properties of Solutes
Ionic Compounds
Molecular Compounds
Electrolytes--strong/weak
Acids/Bases/Salts/Neutralization Reactions
Ionic Equations
Metathesis Reactions
Precipitation Reactions
Solubility
Products & Prediction
Oxidation-Reduction Reactions
Activity Series
Solution Stoichiometry
Titration
Solution Composition
Solutions are composed of a solute and a
solvent
solute--present in smallest quantity
solvent--present in largest quantity
Molarity
concentration gives ratio of solute :
solvent/solution
molarity, M = moles solute
1 L solution
Practice Ex. 4.1:
Calculate the molarity of a solution made by
dissolving 5.00 g of glucose, C
6
H
12
O
6
, in
sufficient water to form 100 mL of solution.

5.00 g C
6
H
12
O
6
x 1 mol = 0.0278 mol = 0.278 M
180 g 0.100 L
Practice Ex. 4.2:
How many grams of Na
2
SO
4
are there in 15
mL of 0.50 M Na
2
SO
4
? How many mL of 0.50
M Na
2
SO
4
solution are required to supply 0.038
mol of salt?

15 mL x 1 L x 0.50 mol Na
2
SO
4
x 142 g = 1.1 g
10
3
mL 1 L mol Na
2
SO
4



0.038 mol Na
2
SO
4
x 1 L x 10
3
mL = 76 mL
0.50 mol 1 L Na
2
SO
4

Dilution
Stock solutions are generally concentrated
solutions that are diluted before use
General format for diluting a concentrated
solution:

M
initial
V
initial
= M
final
V
final


or

M
conc
V
conc
= M
dil
V
dil

Practice Ex. 4.3:
How many mL of 5.0 M K
2
Cr
2
O
7
solution
must be diluted in order to prepare 250 mL
of 0.10 M solution?
M
conc
= 5.0 M K
2
Cr
2
O
7
M
dil
= 0.10 M
K
2
Cr
2
O
7

V
conc
= ? V
dil
= 250 mL

M
conc
V
conc
= M
dil
V
dil


0.10 mol x 0.250 L x 1 L = 0.0050 L or
L 5.0 mol 5.0 mL
M
dil
x V
dil
x 1 = V
conc

M
conc

Properties of Solutes
Electrolytes
conduct electricity
form ions in solution stoichiometrically
Nonelectrolytes
do not conduct electricity
do not form ions in solution
Weak Electrolytes
slightly conduct electricity
form less than stoichiometric amounts of ions
Ionic Compounds
dissociate into constituent ions when dissolved
hence, they are electrolytes if they are soluble
H
Na
+
O O
O
H
H
H
H
H
O
H
H
O
H
H
d-
d+
d+
Cl
-
O
H
H
O
H
H
O
H
H
d-
d+
d+
NaCl Na
(aq)
+
+ Cl
(aq)
-

ions dissociate stoichiometrically

Na
2
SO
4
2Na
+
(aq)
+ SO
4(aq)
2-


(NH
4
)
2
SO
4
2NH
4(aq)
+
+ SO
4(aq)
2-


Ca(NO
3
)
2(aq)
Ca
2+
(aq)
+ 2NO
3(aq)
-

Practice Ex. 4.4
How many moles of K
+
ions are present in
0.25 L of 0.015 M K
2
CO
3
solution?

K
2
CO
3
2K
(aq)
+
+ CO
3(aq)
2-



0.25 L x 0.015 mol x 2 mol K
+
= 0.0075
1 L 1 mol K
2
CO
3
mol
K
+

Molecular Compounds
structure of the molecules remains intact
do not separate into ions !
molecules themselves are separated on the
molecular level
generally not electrolytes
CH
3
OH CH
3
OH CH
3
OH
vs
CH
3
OH H
2
O CH
3
OH H
2
O CH
3
OH
Strong and Weak Electrolytes
All soluble ionic compounds are strong
electrolytes
ions are produced stoichiometrically--exist
completely or nearly completely as ions in solutions
Some molecular compounds are weak
electrolytes--produce small concentrations of
ions when dissolved
Since molecular compounds do not contain ions,
they must produce ions through a reaction with
water, eg.
NH
3(aq)
+ H
2
O NH
4(aq)
+
+ OH
(aq)
-


HC
2
H
3
O
2(aq)
+ H
2
O H
3
O
(aq)
+
+ C
2
H
3
O
2(aq)
-

Some molecular compounds are strong
electrolytes
HCl
(aq)
+ H
2
O H
3
O
(aq)
+
+ Cl
(aq)
-

Note the difference in arrows used for chemical
equations for weak vs strong electrolytes
Acids/Bases/Salts
Acids
have an ionizable hydrogen, H
+
eg. HCl
(aq)
or
HC
2
H
3
O
2(aq)

can be strong or weak electrolytes
HCl
(aq)
+ H
2
O H
3
O
(aq)
+
+ Cl
(aq)
-

HC
2
H
3
O
2(aq)
+ H
2
O H
3
O
(aq)
+
+ C
2
H
3
O
2(aq)
-
strong acids are more reactive than weak acids
can be monoprotic
HCl
(aq)
+ H
2
O H
3
O
(aq)
+
+ Cl
(aq)
-
or diprotic
H
2
SO
4(aq)
+ 2H
2
O 2H
3
O
(aq)
+
+ SO
4(aq)
2-

Strong Acids--know these!
HCl, HBr, HI, HNO
3
, H
2
SO
4
, HClO
4


Bases
substances that react with acids
produce hydroxide ions, OH
-
, in solution
can be strong or weak electrolytes
NaOH
(aq)
Na
(aq)
+
+ OH
(aq)
-


NH
3(aq)
+ H
2
O NH
4(aq)
+
+ OH
(aq)
-


Strong Bases--know these!
Group IA metal hydroxides (LiOH, NaOH, KOH,
RbOH, CsOH)
Heavy group IIA metal hydroxides [Ca(OH)
2
,
Sr(OH)
2
, Ba(OH)
2
]

Neutralization Reactions
occur between acids and metal hydroxide bases
produce water and a salt (any ionic compound)
HCl
(aq)
+ NaOH
(aq)
H
2
O
(l)
+ NaCl
(aq)

Water Soluble
ionic?
YES NO
acid?
YES NO
NH
3
or other
molecular
base?
NO YES
strong acid?
NO YES
Strong
Electrolyte
Weak
Electrolyte
Weak
Electrolyte
Non-
Electrolyte
Strong
Electrolyte
Ionic Equations
Three ways to express ionic equations
molecular equation--all species expressed in
molecular form
HCl
(aq)
+ NaOH
(aq)
H
2
O
(l)
+ NaCl
(aq)

HCl
(aq)
is really H
+
(aq)
and Cl
-
(aq)
complete ionic equation--all species expressed in
ionic form
H
+
(aq)
+ Cl
-
(aq)
+ Na
+
(aq)
+ OH
-
(aq)
H
2
O
(l)
+ Na
+
(aq)
+ Cl
-
(aq)


note that spectator ions undergo no change
net ionic equation--incl. only species that
change
H
+
(aq)
+ OH
-
(aq)
H
2
O
(l)

only soluble, strong electrolytes are written in
ionic form

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


2H
+
(aq)
+ SO
4
2-
(aq)
+ 2Na
+
(aq)
+ 2OH
-
(aq)

2H
2
O
(l)
+ 2Na
+
(aq)
+ SO
4
2-
(aq)


net ionic equation--incl. only species that
change
H
+
(aq)
+ OH
-
(aq)
H
2
O
(l)

only soluble, strong electrolytes are written in
ionic form

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


2H
+
(aq)
+ SO
4
2-
(aq)
+ 2Na
+
(aq)
+ 2OH
-
(aq)

2H
2
O
(l)
+ 2Na
+
(aq)
+ SO
4
2-
(aq)


net ionic equation--incl. only species that
change
H
+
(aq)
+ OH
-
(aq)
H
2
O
(l)

only soluble, strong electrolytes are written in
ionic form

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


2H
+
(aq)
+ + 2OH
-
(aq)
2H
2
O
(l)

Metathesis Reactions
General Form
ion partner exchange
AX + BY AY + BX
Pb(NO
3
)
2(aq)
+ 2KCl
(aq)
PbCl
2(s)
+ 2KNO
3(aq)


Driving Forces
formation of an insoluble solid
formation of a weak or non-electrolyte
formation of a gas
Solubility guidelines
Soluble Compounds Exceptions
Cmpds. NO
3
-
None
containing NH
4
+
None
C
2
H
3
O
2
-
None
Grp IA None
Cl
-
, Br
-
Salts of Ag
+
, Hg
2
2+
, Pb
2+

SO
4
2-
Salts of Ca
2+
, Sr
2+
, Ba
2+
,
Hg
2
2+
, Pb
2+


Solubility guidelines
Insoluble Compounds Exceptions
Cmpds. S
2-
Salts of NH
4
+
, Gp I, Ca
2+
,
containing Sr
2+
, Ba
2+

CO
3
2-
Salts of NH
4
+
, Gp I
PO
4
3-
Salts of NH
4
+
, Gp I
OH
-
Cmpds. of Gp I, Ca
2+
,
Sr
2+
, Ba
2+



Precipitation Reaction
formation of an insoluble solid
know the solubility guidelines!!
examples:
NaCl
(aq)
+ KNO
3(aq)
NR



AgNO
3(aq)
+ KCl
(aq)


AgCl + KNO
3
Na
+
+ Cl
-
+ K
+
+ NO
3
-

Na
+
+ Cl
-
+ K
+
+ NO
3
-

aq
solid
Ag
+
+ NO
3
-
+ K
+
+ Cl
-
AgCl
(s)
+ K
+
+ Cl
-
Ag
+
(aq)
+ Cl
-
(aq)
AgCl
(s)

Precipitation Reaction
formation of an insoluble solid
know the solubility guidelines!!
examples:
NaCl
(aq)
+ KNO
3(aq)
NR



AgNO
3(aq)
+ KCl
(aq)


AgCl + KNO
3
Na
+
+ Cl
-
+ K
+
+ NO
3
-

NR
aq
solid
Ag
+
+ NO
3
-
+ K
+
+ Cl
-
AgCl
(s)
+ K
+
+ Cl
-
Ag
+
(aq)
+ Cl
-
(aq)
AgCl
(s)

Formation of a weak or non-electrolyte
common example is an acid/base reaction--H
2
O
forms
know/recognize electrolyte vs non-electrolyte
examples:

HCl
(aq)
+ NaOH
(aq)
H
2
O
(l)
+ NaCl
(aq)




NiO
(s)
+ 2HNO
3(aq)
Ni(NO
3
)
2(aq)
+ H
2
O
(l)

H
+
+ Cl
-
+ Na
+
+ OH
-
H
2
O + Cl
-
+ Na
+

NiO
(s)
+ 2H
+
+ 2NO
3
-
Ni
2+
+ 2NO
3
-
+ H
2
O
Formation of a gas
gases exit the reacting solution driving the
reaction
examples:

2HCl
(aq)
+ Na
2
CO
3(aq)
2NaCl
(aq)
+ H
2
O
(l)
+ CO
2(g)






2HCl
(aq)
+ Na
2
S
(aq
2NaCl
(aq)
+ H
2
S
(g)

2H
+
+ 2Cl
-
+ 2Na
+
+ CO
3
2-
2Na
+
+ 2Cl
-
+ H
2
CO
3

H
2
O + CO
2

Oxidation-Reduction Reactions
the loss of electrons by a substance
Ca
(s)
Ca
2+
+ 2e
-

the gain of electrons by a substance
Cl
2(g)
+ 2e
-
2Cl
-

Oxidation and Reduction always occur together
Ca
(s)
+ Cl
2(g)
CaCl
2(s)

Ca
(s)
+ O
2(g)
CaO
(s)

2Na
(s)
+ Cl
2(g)
2NaCl
(s)

Oxidation of Metals by Acids & Salts
metal + acid salt + hydrogen
(metal)
Mg
(s)
+ HCl
(aq)
MgCl
2(aq)
+ H
2(g)


2Al
(s)
+ 6HCl
(aq)
2AlCl
3(aq)
+ 3H
2(g)


Mg
(s)
+ Zn(NO
3
)
2(aq)
Mg(NO
3
)
2(aq)
+
Zn
(s)


Activity Series
metals arranged relative to the ease of their
oxidation
most active metals are the easiest to oxidize
least active metals are the least easy to oxidize
Examples:
does a reaction occur between Co
(s)
and
Cu(NO
3
)
2(aq)
?
which is the more active metal?
the more active metal prefers the oxidized state

Co
(s)
+ Cu(NO
3
)
2(aq)



what about Ag
(s)
and Pb(NO
3
)
2(aq)
?

2Ag
(s)
+ Pb(NO
3
)
2(aq)

more active less active
Co(NO
3
)
2(aq)
+ Cu
(s)

less active more active
2Ag
(s)
+ Pb(NO
3
)
2(aq)

Examples:
does a reaction occur between Co
(s)
and
Cu(NO
3
)
2(aq)
?
which is the more active metal?
the more active metal prefers the oxidized state

Co
(s)
+ Cu(NO
3
)
2(aq)



what about Ag
(s)
and Pb(NO
3
)
2(aq)
?

2Ag
(s)
+ Pb(NO
3
)
2(aq)

Co(NO
3
)
2(aq)
+ Cu
(s)

more active less active
NR
less active more active
Solution Stoichiometry
Chemical Analysis of Solutions
All discussions of stoichiometry apply to
solutions as well as solid reactants and products
use the same format for stoichiometric problems
as in chapter 3
determine the moles of reactant, convert to
moles of product
a solution volume and concentration can give
you solute moles
General Sequence of Conversion:
vol or M
of A
moles of
A
M or vol. of
A
moles of
B
mole
ratio
molarity of
B
volume of
B
note: the central theme is
conversion of moles
react
to moles
prod

Practice Ex. 4.12:
What volume of 0.500 M HCl
(aq)
is required to react
completely with 0.100 mol of Pb(NO
3
)
2(aq)
, forming
a precipitate of PbCl
2(s)
?

write a correct equation:
2HCl
(aq)
+ Pb(NO
3
)
2(aq)
PbCl
2(s)
+ 2HNO
3(aq)


determine amt. HCl to react w/ Pb(NO
3
)
2
:
0.100 mol Pb(NO
3
)
2
x 2 mol HCl = 0.200 mol HCl
1mol Pb(NO
3
)
2


convert mol HCl to vol. HCl solution:
0.200 mol HCl x 1 L soln = 0.400 L or
0.500 mol HCl 400 mL HCl
Practice Ex. 4.13:
What is the molarity of an NaOH solution if 48.0
mL is needed to neutralize 35.0 mL of 0.144 M
H
2
SO
4
? H

write the equation for the reaction:
H
2
SO
4(aq)
+ 2NaOH
(aq)
H
2
O + Na
2
SO
4(aq)

0.144 M ? M
0.0350 L 0.0480 L


determine mol of H
2
SO
4(aq)
:
0.0350 L H
2
SO
4
x 0.144 mol H
2
SO
4
= 0.00504 mol
1 L soln H
2
SO
4


Practice Ex. 4.13:
What is the molarity of an NaOH solution if 48.0
mL is needed to neutralize 35.0 mL of 0.144 M
H
2
SO
4
? H

write the equation for the reaction:
H
2
SO
4(aq)
+ 2NaOH
(aq)
2H
2
O + Na
2
SO
4(aq)





determine mol of H
2
SO
4(aq)
:
0.0350 L H
2
SO
4
x 0.144 mol H
2
SO
4
= 0.00504 mol
1 L soln H
2
SO
4
0.144 M ? M
0.0350 L 0.0480 L
determine mol of NaOH:
0.00504 mol H
2
SO
4
x 2 mol NaOH = 0.0101 mol
1 mol H
2
SO
4
NaOH

determine Molarity of NaOH:
0.0101 mol NaOH = 0.210 M NaOH
0.0480 L soln
H
2
SO
4(aq)
+ 2NaOH
(aq
2H
2
O + Na
2
SO
4(aq)
Titrations
Used commonly, but not exclusively, in
neutralization reactions
the first reactant is titrated with the second
reactant until stoichiometric equivalence is
reached
the first reactant is added slowly, in small aliquots

this is used to determine:
the concentration of the first reactant or
the molarity of the second reactant
Practice Ex. 4.14:
What mass of chloride ion is present in a sample of
water if 15.7 mL of 0.108 M AgNO
3
is required to
titrate the sample?

AgNO
3(aq)
+ Cl
-
(aq)
AgCl
(s)
+ NO
3
-
(aq)

0.0157 L ? g
0.108 M

General Sequence of Conversion:
vol or M
of A
moles of
A
M or vol. of
A
moles of
B
mole
ratio
amount of
B
volume of
B
Practice Ex. 4.14:
What mass of chloride ion is present in a sample of
water if 15.7 mL of 0.108 M AgNO
3
is required to
titrate the sample?

AgNO
3(aq)
+ Cl
-
(aq)
AgCl
(s)
+ NO
3
-
(aq)

0.0157 L ? g
0.108 M
0.0157 L x 0.108 mol AgNO
3
= 0.00170 mol AgNO
3

1 L soln

0.00170 mol AgNO
3
x 1mol Cl
-
= 0.00170 mol Cl
-

1 mol AgNO
3


0.00170 mol Cl
-
x 35.5 g Cl-

= 0.0602 g Cl
-



1 mol