1

Chapter 5: Reactions Between

Ions in Aqueous Solutions
Solution
A solution is a homogeneous mixture in
which the two or more components mix p
freely
The solvent is taken as the component
present in the largest amount
A solute is any substance dissolved in the
solvent
Formation of a solution of
iodine molecules in ethyl
alcohol. Ethyl alcohol is the
solvent and iodine the
solute.
Solutionshavevariable Solutions have variable
composition. They may be
characterized using a solute-
to-solvent ratio called the
concentration.
For example, the percentage concentration
is the number of grams of solute per 100 g
of solution
The relative amounts of solute and solvent
are often given without specifying the
actual quantities actual quantities
The dilute solution on the left
has less solute per unit volume
than the (more) concentrated
solution on the right.
Concentrated and dilute are
relative terms.
2
There is usually a limit to the amount of
solute that can dissolve in a given amount
of solvent
For example, 36.0 g NaCl is able to dissolve in
100 g of water at 20C
A solution is said to be saturated when no
l b di l d h more solute can be dissolved at the current
temperature
The solubility of a solute is the number of
grams of solute that can dissolve in 100
grams of solvent at a given temperature
Solubilities of some common substances
Substance Formula
Solubility
(g/100 g water)
Sodiumchloride NaCl 35.7 at 0C
39.1 at 100C
Sodiumhydroxide NaOH 42 at 0C
347 at 100C
Calciumcarbonate CaCO
3
0.0015 at 25C
A solution containing less solute is called unsaturated
because it is able to dissolve more solute.
Solubility usually increases with
temperature
Supersaturated solutions contain more
solute than required for saturation at a given
temperature
They can be formed, for example, by
careful cooling of saturated solutions
Supersaturated solutions are unstable and
often result in the formation of a
precipitate
3
A precipitate is the solid substance that
separates from solution
Precipitates can also form from reactions
Reactions that produce a precipitate are
called precipitation reactions
Many ionic compounds dissolve in water
Solutes that produce ions in solution are
called electrolytes because their solutions
can conduct electricity
An ionic compounds dissociates as it
dissolves in water
Ions separate fromthe solid
and become hydrated or
surrounded by water
molecules.
The ions move freely and the
solution is able to conduct
electricity.
Ionic compounds that dissolve completely are
strong electrolytes
Most solutions of molecular compounds do
not conduct electricity and are called
nonelectrolytes
The molecules of a
nonelectrolyte separate
but stay intact. The
solutionisnonconducting solution is nonconducting
because no ions are
generated.
Some ionic compounds have low solubilities in
water but are still strong electrolytes because what
does dissolve is 100% dissociated.
4
The dissociation of ionic compounds may
be described with chemical equations
The hydrated ions, with the symbol (aq),
) ( SO ) ( Na 2 ) ( SO Na
- 2
4 4 2
aq aq s +
+
have been written separately
Since physical states are often omitted, you
might encounter the equation as:
- 2
4 4 2
SO Na 2 SO Na +
+
Ionic compounds often react when their
aqueous solutions combine
When a
solution of
Pb(NO
3
)
2
is
mixed with
a solution of
KI the
yellow
precipitate
PbI
2
rapidly
forms.
This reaction may be represented with a
molecular, ionic, or net ionic equation:
Molecular:
Ionic:
) ( 2KNO ) ( PbI ) 2KI( ) ( ) Pb(NO
3 2 2 3
aq s aq aq + +
) ( 2NO ) ( 2K ) PbI2(
) ( 2I ) ( 2K ) ( 2NO ) ( Pb
-
3
- -
3
2
aq aq s
aq aq aq aq
+ +
+ + +
+
+ +
2
Net Ionic:
The most compact notation is the net ionic
equation which eliminates all the non-
reacting spectator ions from the equation
) ( PbI ) ( 2I ) ( Pb
2
2
s aq aq +
+
5
Criteria for balanced ionic and net ionic
equations:
1) Material balance the same number of each
type of atomon each side of the arrow
2) Electrical balance the net electrical charge
on the left side of the arrow must equal the on the left side of the arrow must equal the
net electrical charge on the right side of the
arrow
Remember that the charge on an ion must be included
when it is not in a compound. Adding the charges on all
the ions on one side of the arrow gives the net electrical
charge.
In the reaction of Pb(NO
3
)
2
with KI the
cations and anions changed partners
This is an example of a metathesis or
double replacement reaction
Solubility rules allows the prediction of
h i i i i ill when a precipitation reaction will occur
For many ionic compounds the solubility
rules correctly predict whether the ionic
compound is soluble or insoluble
Solubility rules for ionic compounds in water:
Soluble Compounds
soluble. are
O H C and , ClO , ClO , NO , NH containing salts All 2)
soluble. are IA) (Group metals alkali the of compounds All 1)
-
2 3 2
-
3
-
4
-
3 4
+
. Ba and , Hg
, Sr , Ca , Pb of those soluble are sulfates All 4)
. Hg and , Pb , Ag with combined
when soluble are I or , Br , Cl containing salts All 3)
2 2
2
2 2 2
2
2
2
- - -
+ +
+ + +
+ + +
except
except
6
Insoluble compounds
insoluble, are S and , SO , CO , PO contain that salts All 6)
in water. exist not does , O ion, oxide The . hydroxides
form water to react with they dissolve, do oxides
metal When . Ba and , Sr , Ca of and IA Group of
those insoluble are oxides and hydroxides metal All 5)
- 2 - 2
3
- 2
3
- 3
4
- 2
2 2 2 + + +
except
A knowledge of these rules will allow you to
predict a large number of precipitation reactions
. NH and IA Group of those
insoluble, are S and , SO , CO , PO contain that salts All 6)
4
3 3 4
+
except
Acids and bases
Acids and bases are another important class of
compounds
Acids and bases affect the color of certain natural
dye substances
Theyarecalledacid base indicators becausethey They are called acid-base indicators because they
indicate the presence of acids or bases with their
color
The first comprehensive theory of acids, bases,
and electrical conductivity appeared in 1884 in the
Ph.D. thesis of Savante Arrhenius
He proposed that acids form hydrogen ions
and bases released hydroxide ions in
solution
The characteristic reaction between acids
and bases is neutralization
HCl(aq) +NaOH(aq) NaCl(aq) +H O(l) HCl(aq) +NaOH(aq) NaCl(aq) +H
2
O(l)
In general, the reaction of an acid and a
base produces water and a salt
We can state the Arrhenius definition of
acids and bases in updated form
7
Ingeneral, acidsaremolecular compounds
in water. ion hydroxide produces that substance a is A
. O H ion, hydronium the
produce r to with wate reacts that substance a is An
Bases and Acids of Definition Arrhenius
3
base
acid
+
In general, acids are molecular compounds
that react with water to produce ions
This is called ionization:
) ( Cl ) ( O H O H ) HCl(
-
3 2
aq aq g + +
+
It is common to encounter the hydrogen ion
(H
+
) instead of the hydronium ion
The previous ionization is also written as
Monoprotic acids are capable of furnishing
) ( Cl ) ( H ) HCl(
- O H
2
aq aq g +
+
only one hydrogen ion per molecule
Acids that can furnish more than one
hydrogen ion per molecule are called
polyprotic acids
) ( PO ) ( O H O H ) ( HPO
) ( HPO ) ( O H O H ) ( PO H
) ( PO H ) ( O H O H ) ( PO H : Triprotic
) ( CO ) ( O H O H ) ( HCO
) ( HCO ) ( O H O H ) ( CO H : Diprotic
) ( Cl ) ( O H O H ) HCl( : Monoprotic
- 3
4 3 2
- 2
4
- 2
4 3 2
-
4 2
-
4 2 3 2 4 3
- 2
3 3 2
-
3
-
3 3 2 3 2
-
3 2
aq aq aq
aq aq aq
aq aq aq
aq aq aq
aq aq aq
aq aq aq
+ +
+ +
+ +
+ +
+ +
+ +
+
+
+
+
+
+
Some nonmetal oxides react with water to
produce acids
They are called acidic anhydrides
(anhydride means without water)
) ( ) ( ) (
4 3 2 4
q q q
8
Soluble metal oxides are base anhydrides
Examples include:
acid nitric ) ( 2HNO O H ) ( O N
acid sulfuric ) ( SO H O H ) ( SO
: Oxides Nonmetal
3 2 5 2
4 2 2 3
aq g
aq g
+
+
hydroxide sodium ) 2NaOH( O H ) O( Na
hydroxide calcium ) ( Ca(OH) O H ) CaO(
: Oxides Metal
acid carbonic ) ( CO H O H ) ( CO
2 2
2 2
3 2 2 2
aq s
aq s
aq g
+
+
+
Ammonia gas ionizes in water producing
hydroxide ions
It is an example of a molecular base
Many molecules that contain nitrogen can
act as a base
) ( OH ) ( NH O H ) ( NH
-
4 2 3
aq aq aq
+
+ +
) ( OH ) ( HB O H ) ( B
: B base general For the
2
aq aq aq
+
+ +
Binary compounds of many nonmetals and
hydrogen are acidic
In water solution these are referred to as binary
acids
Naming Acids and Bases
They are named by adding the prefix hydro-
and the suffix ic to the stem of the
nonmetal name, followed by the word acid
Acid Binary Compound Molecular
ic acid hydro aq g
ic acid hydro aq g
sulfur ) S( H sulfide hydrogen ) S( H
chlor ) HCl( chloride hydrogen ) HCl(
Acid Binary Compound Molecular
2 2
9
Acids that contain hydrogen, oxygen, plus
another element are called oxoacids
They are named according to the number of
oxygen atoms in the molecule and do not
take the prefix hydro-
Wh h id h i h When there are two oxoacids, the one with
the larger number of oxygens takes the
suffix ic and the one with the fewer
oxygen atoms takes the suffix ous
The halogen can occur with up to four
different oxoacids
The oxoacid with the most oxygens has the
ous acid ous acid
ic acid ic acid
nitr HNO sulfur SO H
nitr HNO suflur SO H
2 3 2
3 4 2
prefix per- the one with the least has the
prefix hypo-
ic acid per ous acid
ic acid ous acid hypo
chlor HClO chlor HClO
chlor HClO chlor HClO
4 2
3
Anions are produced when oxoacids are
neutralized
There is a simple relationship between the
name of the polyatomic ion and the parent
acid
1) i id i t i 1) ic acids give ate ions
2) -ous acids give ite ions
In naming polyatomic anions, the prefixes
per- and hypo- carry over from the parent
acid
10
Polyprotic acids can be neutralized
An acidic salt contains an anion that is
capable of furnishing additional hydrogen
ions
The number of hydrogens that can still be
li di l i di d neutralized is also indicated
phosphate dihydrogen sodium PO NaH
phosphate hydrogen sodium HPO Na
sulfate hydrogen sodium NaHSO
4 2
4 2
4
Naming bases is much less complicated
Ionic compounds containing metal ions are
named like any other ionic compound
Molecular bases are specified by giving the
name of the molecule
Acids and bases can be classified as strong
or weak and so as strong or weak
electrolytes
Strong acids are strong electrolytes
The most common strong acids are:
acid hydroiodic ) HI(
acid c hydrobromi ) HBr(
acid ic hydrochlor ) HCl(
acid perchloric ) ( HClO
4
aq
aq
aq
aq
Strong bases are the soluble metal
hydroxides
acid sulfuric ) ( SO H
acid nitric ) ( HNO
4 2
3
aq
aq
11
These include:
hydroxide strontium Sr(OH) hydroxide rubidium RbOH
hydroxide calcium Ca(OH) hydroxide potassium KOH
hydroxide sodium NaOH
hydroxide lithium LiOH
IIA Group IA Group
2
2
Most acids are not completely ionized in
water
They are classified as weak electrolytes
hydroxide barium Ba(OH) hydroxide cesium CsOH
y ( ) y
2
2
The brightness
of light is
experimental
verification of
the
classification
as a strong or
weak
electrolyte.
Weak acids and bases are weak electrolytes
because less than 100% of the molecules ionize.
Weak acids and bases are in dynamic
equilibrium in solution
Consider the case of acetic acid:
Two opposing reactions
occur in solution: the
ionizationof theacid, ionization of the acid,
called the forward
reaction, and the
recombination of ions into
molecules, called the
reverse reaction.
Chemical or dynamic equilibriumresults when the rate of the
forward and reverse reaction are equal.
12
Neutralization of a strong acid with strong
base gives a salt and water:
O H ) ( OH ) ( H : ionic Net
) ( Cl ) ( K O H ) ( OH ) ( K ) ( Cl ) ( H : Ionic
O H ) KCl( ) KOH( ) HCl( : Molecular
2
-
-
2
- -
2
+
+ + + + +
+ +
+
+ + +
aq aq
aq aq aq aq aq aq
aq aq aq
This net ionic equation applies only to
strong acids and bases
The neutralization of a weak acid with a
strong base involves a strong and weak
electrolyte
Consider the neutralization of acetic acid
with NaOH:
O H ) ( O H C ) ( OH ) ( O H HC : ionic Net
O H ) ( O H C ) ( Na
) ( OH ) ( Na ) ( O H HC : Ionic
O H ) ( O H NaC ) NaOH( ) ( O H HC : Molecular
2
-
2 3 2
-
2 3 2
2
-
2 3 2
-
2 3 2
2 2 3 2 2 3 2
+ +
+ +
+ +
+ +
+
+
aq aq aq
aq aq
aq aq aq
aq aq aq
Note that in ionic equations the formulas of
weak electrolytes are written in molecular
form
O H ) ( O H C ) ( OH ) ( O H HC : ionic Net
2 2 3 2 2 3 2
+ + aq aq aq
The situation is similar when a strong acid
reacts with a strong base
For ammonia and HCl the net ionic
equation is:
) ( NH ) ( H ) ( NH
4 3
+
+ +
aq aq aq
Note that water only appears as a product if
the hydronium ion is used
O H ) ( NH ) ( O H ) ( NH
or
2 4 3 3
+ +
+ +
aq aq aq
13
Both strong and weak acids react with
insoluble hydroxides and oxides
The driving force is the formation of water
Magnesium hydroxide has a low solubility
in water, but reacts with strong acid
The net ionic equation is:
Magnesium hydroxide is written as a solid
because it is insoluble
O H 2 ) ( Mg ) ( H 2 ) ( Mg(OH)
2
2
2
+ +
+ +
aq aq s
A number of metal oxides also dissolve in
acids
For example, iron(III) oxide reacts with
hydrochloric acid:
O 3H ) ( 2Fe ) ( 6H ) ( O Fe : ionic Net
O 3H ) ( 2FeCl ) 6HCl( ) ( O Fe : Molecular
2
3
3 2
2 3 3 2
+ +
+ +
+ +
aq aq s
aq aq s
Some reactions with acids or bases produce
a gas
The reactions are driven to completion
because the gas escapes and is unavailable
for back reaction
) ( ) ( ) (
2 3 2
q q
O H SO SO 2H S lfit SO
O H CO HCO H Carbonates Hydrogen
O H CO CO 2H Carbonates CO
HCN CN H Cyanides HCN
S H S 2H Sulfides S H
Equation Ionic Net Compounds Gas
- 2
2 2
-
3
2 2
- 2
3 2
-
2
- 2
2
+ +
+ +
+
+
+
+
+
+
+
(CO
2
and SO
2
are produced by the decomposition
of H
2
CO
3
and H
2
SO
3
, respectfully)
O H NH OH NH Salts Ammonium NH
O H SO HSO H Sulfites Hydrogen
O H SO SO 2H Sulfites SO
2 3
-
4 3
2 2
- 2
3
2 2
2
3 2
+ +
+ +
+ +
+
+
+
14
Stoichiometry of chemical reaction in solution
Solutions are characterized by their
concentration
The molar concentration or molarity (M) is
defined as
The molarity of a solution gives an equivalence
relation between the moles of solute and volume
of solution
solution of liters
solute of moles
(M) molarity =
Solutions provide a convenient way to
combine reactants in many chemical
reactions
Example: How many grams of AgNO
3
are
needed to prepare 250 mL of 0.0125 M AgNO
3
solution?
ANALYSIS: Find moles, then mass of solute.
SOLUTION:
3
AgNO mol
AgNO g 169.9
sol AgNO L 1.00
AgNO mol 0.0125
3
AgNO g 531 . 0
sol AgNO L 0.250
3
3
3
3
=

Density, percentage mass and
Molarity
Reagen pekat Densitas % massa Molaritas
HCl 1,18 36 12
H
3
PO
4
1,7 85 15
HNO
3
1,42 70 16
CH
3
COOH 1,05 100 17,5
NH
3
0,90 28 15
15
Solutions of high concentration can be
diluted to make solutions of lower
concentration
Conservation of solute mass requires:
h d l l b l h dil d d d h
concd concd dil dil
M V M V =
Where dil labels the diluted and concd the
concentrated solution
Stoichiometry problems often require
working with volumes and molarity
Example: How many mL of 0.124 M NaOH are
required to react completely with 15.4 mL of
0.108 M H
2
SO
4
?
2 NaOH +H
2
SO
4
Na
2
SO
4
+2H
2
O
ANALYSIS: Use the mole-to-mole ratio to
convert.
SOLUTION:
sol NaOH mL 8 . 26
sol SO H L 0.0154
L 1
mL 1000
NaOH mol 0.124
sol NaOH L 1.00
SO H mol 1
NaOH mol 2
sol SO H L 1.00
SO H mol 0.108
4 2
4 2 4 2
4 2
=

Limiting reagent problems are also common
Example: How many moles of BaSO
4
will form
if 20.0 mL of 0.600 M BaCl
2
is mixed with
30.0 mL of 0.500 M MgSO
4
?
BaCl
2
+MgSO
4
BaSO
4
+MgCl
2
ANALYSIS: Thisisalimitingreagent problem. ANALYSIS: This is a limiting reagent problem.
SOLUTION:
formed BaSO mol 0.0120
BaSO mol 0150 . 0 sol MgSO L 0300 . 0
BaSO mol 0120 . 0 sol BaCl L 0.0200
4
4 MgSO mol 1
BaSO mol 1
sol MgSO L 1.00
MgSO mol 0.500
4
4 BaCl mol 1
BaSO mol 1
sol BaCl L 1.00
BaCl mol 0.600
2
4
4
4
4
2
4
2
2

=
=
16
Titration is a technique used to make
quantitative measurements of the amounts
of solutions
The end-point is often determined visually
The long tube is g
called theburet. The
valve at the bottomof
the buret is called the
stopcock. The
titration is complete
when the indicator
changes color.
Paths for working stoichiometry problems
may be summarized with a flowchart: