Chapter 4

Aqueous Reactions and

Solution Stoichiometry

Chemistry of solutions in which H2O is

the dissolving medium (solvent).

AQUEOUS SOLUTIONS
Understanding aqueous chemistry is vital as it:
 is the chemistry of life.

 rationalizes the chemistry of chemical

reactions occurring in the environment.

Definitions:

 A solution is a homogeneous
mixture of substances.

 The solvent is the substance

present in the greatest quantity.
 Properties of Aqueous Solutions
Electrolytic Properties
• Aqueous solutions have the potential to conduct
electricity.
• The ability of the solution to conduct depends on the
number of ions in solution.

No ions few ions many ions

Transport of ions through solution causes flow of current.
 Distribution of charge on the water molecule
The ability of water to dissolve substances
is related to the structure of the water
molecule. δ+ Attracted by anions
and groups with a δ-
H charge

O H δ+
δ-
Attracted by cations and
groups with a δ+ charge

The water molecule is polar. The hydrogens have partial

positive charges, while the oxygen has a partial negative
charge.
Each anion is surrounded by partial positive
charges of water molecules, and each cation is
surrounded by partial negative charges of water.

δ+ δ+

δ-
anion cation
δ+ δ+
δ-

δ+ δ+
δ- δ-
δ+ δ+
δ+ δ+
δ- δ-
δ+
δ- δ+
 Ionic Compounds
Ionic compounds when dissolved in water tend to
dissociate/ionise completely: Strong Electrolytes
water
molecules
The water molecules
overcome the attraction
between the oppositely
charged ions and
separates them.

Ions in solution
transport electric
charge.

Na+ cation Cl- anion

NaCl(s) → Na+(aq) + Cl-(aq)

 Molecular Compounds
Most molecular compounds do not dissociate when they dissolve
in water: Non-Electrolytes
Methanol molecule not ionized

water

+ H2O

Methanol
(molecular compound)

methanol dissolved in water

As there are no ions in solution, there is nothing to transport
electric charge. These solutions do not conduct electricity.
Molecular Compounds that ionize in water.
Some molecular compounds dissociate (ionize)
in water (mainly acids)
Strong acids, such as hydrochloric acid,
dissociate completely (single arrow shows
equilibrium lies well to the right):
HCl(aq) → H+(aq) + Cl-(aq)

Weak acids, such as acetic acid, dissociate only

partially (the ionised and unionised forms exist
in equilibrium with each other):

HC2H3O2(aq) ⇌ H+(aq) + C2H3O2-(aq)

acetic acid acetate anion
 Strong and Weak electrolytes

Strong electrolytes are completely ionized in water.

A single arrow is used to indicate complete ionization of

strong electrolytes, e.g. NaOH:

NaOH(aq) → Na+ (aq) + OH- (aq)

Weak electrolyes only partially ionize in water.

An example of a weak electrolyte is acetic acid. It only
ionizes to a small extent as indicated by a double arrow:

HC2H3O2(aq) ⇌ H+(aq) + C2H3O2-(aq)

NB: Do not confuse solubility (extent to which
electrolyte dissolves) with electrolyte strength

Many ionic compounds are only sparingly soluble in H2O

eg: BaSO4
KClO4
Ca(OH)2

but, whatever dissolves is still completely ionised

eg: sparingly soluble
KClO4 K+(aq) + ClO4-(aq)

Such compounds are therefore still strong electrolytes

Three types of solute: Strong electrolytes, Weak
electrolytes, Non-electrolytes
The diagrams represent aqueous solutions of three
substances (solvent molecules are omitted).
Classify AX, AY and AZ as strong, weak or non-electrolytes
No ions Partially ionised. Totally ionised.
Molecular Weak acid/base. Strong acid/base
Molecular Ionic Compound

Strong
Weak
Non
Which of these best represents a solution of Li2SO4?
 Precipitation Reactions
When two solutions are mixed and a solid is formed,
the solid is called a precipitate.

yellow precipitate
Mixing clear
of silver iodide
solutions of AgNO3
AgI
and NaI produces
a precipitate of AgI(s)
Remaining solution
containing sodium
nitrate
NaNO3

A precipitation reaction is an example of an exchange or metathesis

reaction, and involves the swapping of ions in solution.

AX + BY  AY + BX
Whether a precipitate is formed or not will depend on
whether the potential products are soluble in water or
not.
AB(s) + H2O  A+(aq) + B-(aq)

CD(s) + H2O  C+(aq) + D-(aq)

Mixing a solution of AB(aq) and CD(aq) gives us a solution

with the ions A+(aq), B-(aq), C+(aq) and D-(aq) in solution.

We know that AB(s) and CD(s) are soluble.

A precipitate will form if AD(s) is insoluble and/or CB(s) is

insoluble.
 Guide to solubility of Ionic compounds

The following are soluble:

Compounds Exceptions
containing
NO3- none
C2H3O2- none
Cl- Ag+, Hg22+, Pb2+
Br- Ag+, Hg22+, Pb2+
I- Ag+, Hg22+, Pb2+
SO42- Sr2+, Ba2+, Hg22+, Pb2+

Guidelines for predicting solubility of Ionic compounds derived

from experimental observation.
 Guide to solubility of Ionic compounds

The following are insoluble:

Compounds Exceptions
Containing
S2- alkali metal cations, NH4+, Ca2+, Sr2+, Ba2+
OH- alkali metal cations, NH4+, Ca2+, Sr2+, Ba2+
CO32- alkali metal cations, NH4+
PO43- alkali metal cations, NH4+

See Table in text book

Examples
Which of the following compounds are insoluble in water?
BaSO4 K2SO4 PbCl2 (NH4)2CO3
Additional Example (Q 4.27)
A bottle contains a white substance that is either
AgNO3, CaCl2, or Al2(SO4)3
The substance dissolves in water.
You are told to test a portion of this solution with a few
drops of firstly Ba(NO3)2 solution and then with NaCl
solution. How will this identify the unknown substance?

Compound Ba(NO3)2(aq) result NaCl(aq) result

AgNO3(aq) No ppt AgCl(s)

CaCl2(aq) No ppt No ppt
Al2(SO4)3(aq) BaSO4(s) No ppt
Example (Q 4.26)
Portions of the solution of an ionic compound are tested
separately with a few drops of solutions of

(i) AgNO3
(ii) Pb(NO3)2
(iii) BaCl2

A precipitate occurs in each case.

Which of the following could be the anion of the ionic

compound?

Br – CO32- NO3–
 Ionic Equations
A precipitation reaction may be written as:

• A complete ionic equation in which all species are listed

H+(aq) + Cl-(aq) + Ag+(aq) + NO3-(aq)  H+(aq) + NO3–(aq) +

AgCl(s)
Electrolytes shown as ions.
Some ions do not participate in the reaction. They are spectator ions.

If we leave out the spectator ions we get the net ionic

equation which lists only unique ions:
Ag+(aq) + Cl-(aq)  AgCl(s)
Example
Consider the precipitation reaction between Pb(NO3)2 and
KI.

Molecular equation: (shows chemical formulae)

Pb(NO3)2 + 2 KI → PbI2(s) + 2 KNO3

Complete Ionic equation (show all ions):

Pb2+ + 2 NO3- + 2 K+ + 2 I- → PbI2(s) + 2 K+ + 2 NO3-

Net ionic equation (omit spectator ions, NO3- and K+):

Pb2+(aq) + 2 I-(aq) → PbI2(s)
Example
Consider the precipitation reaction between Ca(NO3)2 and
NaC2H3O2.

Molecular equation: (shows chemical formulae)

Ca(NO3)2 + 2 NaC2H3O2 → Ca(C2H3O2)2 + 2 NaNO3

Complete Ionic equation (show all ions):

Ca2+ + 2 NO3- + 2 Na+ + 2 C2H3O2- → Ca2+ + 2 C2H3O2-
+ 2 NO3- + 2 Na+
Net ionic equation (omit spectator ions)
All spectator ions! No precipitation reaction occurs.
 Acids and Bases
 Acids ionise in solution to produce hydronium ions (H+)aq.

 Acids often called proton donors.

The hydronium ion is aquated/solvated and is

often written as H3O+(aq).
Acids with one acidic proton are called monoprotic.
They ionise to give only one proton per acid molecule.

HCl hydrochloric
HBr hydrobromic
HNO3 nitric
HNO2 nitrous
HClO4 perchloric
HClO3 chloric
HClO2 chlorous
HClO hypochlorous

HNO3(aq)  H+(aq) + NO3-(aq)

• Acids with two acidic protons are called diprotic

H2SO4 sulphuric
H2SO3 sulphurous

H2SO4(aq) → 2H+(aq) + SO42-(aq)

Ionisation occurs in two steps:
H2SO4(aq) → H+(aq) + HSO4-(aq)
HSO4-(aq) ⇌ H+(aq) + SO42-(aq)

• Acids with many acidic protons are called polyprotic

H3PO4 phosphoric
 Bases
 Bases are substances that accept protons (H+ ions).
 Bases produce hydroxide ions (OH-) when dissolved in water.

Water here is acting as an acid (a proton donor) towards NH3.

NH3 is the proton acceptor.

Bronsted-Lowry definition: an acid is a proton

donor and a base is a proton acceptor.
Ammonia – a weak base
Many bases do not contain OH-, such as NH3 (ammonia).

NH3(aq) + H3O+(aq) ⇌ NH4+(aq) + H2O

or NH3(aq) + H2O
ammonia
↽
⇀ NH4+(aq) + OH-(aq)
ammonium
bigger arrow shows equilibrium
lies to the left

The latter equilibrium lies well to the left, so NH3 is a weak base.
A solution of NH3 in water contains only a small fraction as NH4+
ions (< 1%).
The difference between ammonia and
ammonium:
To remember the difference between ammonia and
ammonium, remember that ammonium is a cation
like sodium or potassium.

H
+
N N
H + H+ H
H H
H H

ammonia ammonium
NH3 (neutral molecule) NH4+ (a cation)
 Strong and Weak Acids and Bases
Strong acids and bases are strong electrolytes.
– They are completely ionised in solution.
Acids:
HCl, HBr, HI, HClO3, HClO4, HNO3, H2SO4.
Bases:
Group 1. LiOH, NaOH, KOH, RbOH, CsOH
Heavy group 2: Ca(OH)2, Sr(OH)2, Ba(OH)2.
Weak acids and bases are weak electrolytes.
– They are partially ionised in solution.
Weak acids:
HF, H3PO4, H2SO3, HC2H3O2,
(hydrofluoric, phosphoric, sulfurous, acetic acids)
Weak bases:
NH3 (ammonia)
 p. 133

Classify each of he following substances as a strong, weak or non

electrolyte: CaCl2, C2H5OH (ethanol), HCHO2 (formic acid)

CaCl2 – Ionic compound. Ionises completely when dissolved.

Therefore a strong electrolyte.

C2H5OH – Molecular compound. Is neither an acid or base.

Therefore a nonelectrolyte.
HCHO2 – Molecular compound. Weak acid partially ionising in water.
Therefore a weak electrolyte.
Neutralisation Reactions
Neutralisation occurs when a solution of an acid and a base
are mixed:
HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq)
Notice we form a salt (NaCl) and water.
Neutralisation between acid and metal hydroxide produces
water and a salt.
Salt = ionic compound whose cation comes from a base
and anion from an acid. ∴Neutralisation reactions are
Metathesis reactions.
complete ionic equation :
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) → H2O(l) + Na+(aq) + Cl-
(aq)
net ionic equation :
H+(aq) + OH-(aq) → H2O(l)
 Balancing Acid-Base Reactions
NB: to balance acid-base equations, ensure OH- and
H+ balance out.
2 HCl(aq) + Ca(OH)2(aq) → CaCl2(aq) + 2 H2O

Two protons needed for two hydroxides

Complete Ionic equation :
2 H+ + 2 Cl- + Ca2+ + 2 OH- → Ca2+ + 2 Cl- + 2H2O
Net ionic equation (omit spectator ions)
2 H+(aq) + 2 OH-(aq) → 2 H2O(l)
H+(aq) + OH-(aq) → H2O(l)
 Acid-Base Reactions with Gas Formation

Sulphides, carbonates and bicarbonates (hydrogen

carbonates) react with H+ and also neutralise acids. A gas
is evolved in these reactions.

2HCl(aq) + Na2S(aq) → H2S(g) + 2NaCl(aq)

2HNO3(aq) + K2CO3(aq)  H2O(l) + CO2(g) + 2KNO3(aq)
HClO4(aq) + NaHCO3(aq)  H2O(l) + CO2(g) + NaClO4(aq)
 Concentration of Solutions

Concentration of a solution or Molarity (M):

Moles of solute per liter of solution

moles of solute
Concentration (molarity) 
volume of solution in liters

n
Conc =
V

Units: mol L-1 (or mol l-1)

mol dm-3
M
A 1.00 molar (written 1.00 M) solution has one mol
of substance dissolved in every liter of solution:

fill the
flask to
line on the 1 liter
neck of mark with
flask shows water
1 liter mark
Dissolve the
1 mole of
CuSO4 in
the flask

1 liter flask 1 mole 1.00 M

(empty) CuSO4 (159.5 g) CuSO4
Examples:
What strength solution do we obtain if we
dissolve:

1) 0.25 mol CuSO4 in a 250 ml flask:

 What molarity solution do we obtain if we
dissolve:

2) 4.82 g CuSO4 in a 200 ml flask:

Expressing the Concentration of an Electrolyte

A 1.00 M solution of NaOH is also 1.00 M in Na+ ions

and OH- ions.

NaOH(aq)  Na+(aq) + OH-(aq)

1 mol 1 mol 1 mol

A 1.00 M solution of H2SO4 is 1.00 M in SO42-, but 2.00

M in H+ . (for two step ionisation)

H2SO4(aq)  2 H+(aq) + SO42-(aq)

1 mol 2 mol 1 mol
NB: Coefficients of the balanced equation

A 1.00 M solution of Na3PO4 is 1.00 M in PO43-,but

3.00 M in Na+. What about a 0.1 M solution?

Na3PO4(aq)  3 Na+(aq) + PO43-(aq)

1 3 1
1M 3M 1M
0.1 M 0.3 M 0.1 M

Notice the importance of the balanced

chemical equation. You can multiply all the
coefficients by 1.0 M or 0.1 M.
 Interconverting Molarity, Moles, and Volume

If we know any two of the above, we can calculate the third quantity.

Example
Calculate no. of moles HNO3 in 2.0 L of 0.200 M HNO3.
Example

How many grams of Na2SO4 are required to

make 0.35 L of 0.500 M Na2SO4?
 Dilution

When we dilute a solution, we take a volume

of the solution and by adding water to it in a
larger container dilute the solution!

transfer make up
solution to mark
1M 0.5 M
to larger with
CuSO4 CuSO4
flask water
solution solution

1 L flask 2 L flask 2 L of dilute solution

 Dilution (p. 148).

Molarity = moles
liter
∴ moles = molarity x liter

In diluting a solution, the number of moles of

dissolved substance stays the same.

∴ Moles before dilution = moles after dilution

before dilution after dilution

M(conc) x V(conc) = M(dil) x V(dil)
Exercise 4.14
How many milliliters of 3.0 M H2SO4 are needed to
make 450 ml of 0.10 M H2SO4?
M(conc) × V(conc) = M(dil) × V(dil)

3.0 M x V(conc) = 0.10 M x 450 ml

V(conc) = 0.10 M x 450 ml

3.0 M

= 15 ml

NB:
Units of volume must be the same on both sides.
liters and liters, or ml and ml.
Example
What volume of 2.50 M Pb(NO3)2 contains
0.0500 mol of Pb?
M = moles / volume
∴ volume = moles / M
= 0.0500 mol / 2.50 M
= 0.0500 mol x 1 liter
2.50 mol
= 0.0200 L or 20.0 ml
 Solution Stoichiometry
Problems require that grams be converted to moles.
M = moles / volume
Using the expression above then convert from moles to
molarity.

79.8 g x 1 mole 0.5 mol x 1 liter

159.5 g 1 liter

0.500 mol

79.8 g of CuSO4 1 liter of 0.5 M CuSO4

Example
How many grams of Ca(OH)2 are needed to
neutralize 25.0 ml of 0.100 M HCl?

Balanced equation:

2HCl + Ca(OH)2 → CaCl2 + 2 H2O

2 moles 1 mol 2 mol 2 mol

1 mole calcium hydroxide needed to neutralize

2 moles HCl.
 Solution Stoichiometry and Chemical Analysis

What volume of a 0.30 M HCl solution is

needed to completely react 3.5 g of Ca(OH)2 ?
2 HCl (aq) + Ca(OH)2 (aq) → 2 H2O (aq) + CaCl2 (aq)

 How many moles of Ca(OH)2 do we have?

 Determine how many moles of HCl will react with it?
From the balanced equation we see that we need 2
mol of HCl for each mol Ca(OH)2:
What is the concentration of a solution that is
made by adding 0.3L of water to 15mL of a
0.65M solution?

M conc × V conc = M dil × V dil

Mconc= 0.65M Vconc = 15mL = 0.015L

Vdil = 0.3L + 15mL

rearrange = 0.3L + 0.015L = 0.315L

M conc  Vconc
M dil 
Vdil
0.65M  0.015L
M dil   0.031 M
0.315L
 End of Chapter 4:
Aqueous Reactions and
Solution Stoichiometry