Lecture 2: Reactions in Aqueous Solution

Objectives:
• Determine whether a reaction results to the formation of precipitates.
• Identify the oxidation number of any given element.
• Balance chemical equations that involve oxidation and reduction.
• Determine the products of the different reactions

Lecture Notes:
A solution is a homogeneous mixture of two or more substances. The substance present in a smaller amount is
called the solute, whereas the substance present in a larger amount is called the solvent. A solution may be
gaseous (such as air), solid (such as an alloy), or liquid (seawater, for example). In this module we will discuss only
aqueous solutions, in which the solute initially is a liquid or a solid and the solvent is water. Aqueous solution’s
general properties are as follows:
1. All solutes that dissolve in water fit into one of two categories: electrolytes and nonelectrolytes. An
electrolyte is a substance that, when dissolved in water, results in a solution that can conduct electricity. A
nonelectrolyte does not conduct electricity when dissolved in water. Solid NaCl, an ionic compound,
undergo dissociation (breaking up of the compound into cations and anions) and forms into Na+ and Cl-
ions when dissolved in water.
H2 O
NaCl(s) → Na+ (aq) + Cl- (aq)
2. Water is a very effective solvent for ionic compounds. When dissolved in water, the three-dimensional
network of the solute is destroyed and the ions are separated from each other. The process in which an ion
is surrounded by water molecules arranged in a specific manner is called hydration. This happens when
water molecules orients their negative ends toward the cation while their positive ends are oriented toward
the anion.
3. Electrolytes can be classified as either weak or strong. Certain acids and bases including most molecules
can undergo ionization (breaking up of acids and bases into positive and negative ions). Strong electrolytes
are those solutes that exist in solution completely or nearly completely as ions. Weak electrolytes are those
solutes that exist in solution mostly in the form of neutral molecules with only a small fraction in the form of
ions. When acetic acid (CH3COOH), which is found in vinegar, is ionized in water, the molecules break up
to yield CH3COO- and H+ ions. As time goes on, some of the CH3COO- and H+ ions recombine to form
CH3COOH molecules.
CH3 COOH (aq)⇌ CH3 COO- (aq)+H+ (aq)
Eventually, a state is reached in which the acid molecules break up as fast as the ions recombine. Such a
chemical state, in which no net change can be observed (although continuous activity is taking place on the
molecular level), is called chemical equilibrium.
Strong Electrolyte Weak Electrolyte Nonelectrolyte
HCl CH3COOH (NH2)2CO (urea)
HNO3 HF CH3OH (methanol)
HClO4 HNO2 C2H5OH (ethanol)
H2SO4 NH3 C6H12O6 (glucose)
NaOH H2O C12H22O11 (sucrose)
Ba(OH)2
Ionic compounds

One common type of reaction that occurs in aqueous solution is the precipitation reaction, which results in the
formation of an insoluble product, or precipitate. A precipitate is an insoluble solid that separates from the solution.
Precipitation reactions usually involve ionic compounds. Mixing lead (II) nitrate and potassium iodide forms:
Pb(NO3 )2 (aq)+ 2 KI(aq)→ PbI2 (s)+ 2 KNO3 (aq)

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The precipitate is lead iodide (PbI2 ), a compound that has a very low solubility in water. Note that potassium nitrate
(KNO3 ) remains in solution but undergoes dissociation. Here are the general solubility guidelines for common ionic
compounds in water
Soluble Ionic Compounds Important Exceptions
Compounds containing NO3- None
CH3COO- None
Cl- Compounds of Ag+, Hg22+, and Pb2+
Br- Compounds of Ag+, Hg22+, and Pb2+
I- Compounds of Ag+, Hg22+, and Pb2+
SO42- Compounds of Sr2+, Ba2+, Hg22+, and Pb2+
Insoluble Ionic Compounds Important Exceptions
Compounds containing S2- Compounds of NH4+, the alkali metal cations, Ca2+, Sr2+, and Ba2+
CO32- Compounds of NH4+ and the alkali metal cations
PO43- Compounds of NH4+ and the alkali metal cations
OH- Compounds of NH4+, the alkali metal cations, Ca2+, Sr2+, and Ba2+
To predict whether a precipitate forms when we mix aqueous solutions of two strong electrolytes, we must:
1. note the ions present in the reactants
2. consider the possible cation–anion combinations, and
3. use the table above to determine if any of these combinations is insoluble.
→ Worked Examples:
• Will a precipitate form when solutions of Mg(NO3)2 and NaOH are mixed?
Solution: (1) Note the ions present in the reactants. You can do this by separating a reactant into two. Make sure
that the ions did exist by looking them up at your periodic table. We have: Mg2+, NO3-, Na+, and OH- ions.
(2) Consider the possible cation–anion combinations. Mix each ions to form an anion-cation combination: Mg(OH)2
and NaNO3.
(3) Use the table above to determine if any of these combinations is insoluble. Knowing from table above that
Mg(NO3)2 and NaOH are both soluble in water, our only possibilities are Mg2+ with OH- and Na+ with NO3-. From the
table, we see that hydroxides are generally insoluble. Because Mg2+ is not an exception, Mg(OH)2 is insoluble and
thus forms a precipitate. NaNO3, however, is soluble, so Na+ and NO3- remain in solution. The balanced equation
for the precipitation reaction is:
Mg(NO3 )2 (aq) + 2 NaOH(aq) → Mg(OH)2 (s) + 2 NaNO3 (aq)
→ Exercises:
• Classify these ionic compounds as soluble or insoluble in water: (a) sodium carbonate, Na2CO3, (b) lead
sulfate, PbSO4.
Precipitation reactions are called either exchange reactions or metathesis reactions, cations and anions appear to
exchange partners conform to the general equation:
AX+BY →AY+BX
Example: AgNO3 (aq) + KCl (aq) → AgCl (s) + KNO3 (aq)
To complete and balance the equation for a metathesis reaction, we follow these steps:
1. Use the chemical formulas of the reactants to determine which ions are present.
2. Write the chemical formulas of the products by combining the cation from one reactant with the anion of the
other, using the ionic charges to determine the subscripts in the chemical formulas.
3. Check the water solubilities of the products. For a precipitation reaction to occur, at least one product must
be insoluble in water.
4. Balance the equation.
As pointed out earlier, when ionic compounds dissolve in water, they break apart into their component cations and
anions. To be more realistic, the equations should show the dissociation of dissolved ionic compounds into ions.
Therefore, returning to the reaction between potassium iodide and lead nitrate, we would write:
Pb2+ (aq)+2NO3 - (aq)+ 2K+ (aq)+ 2I- (aq)→ PbI2 (s)+ 2K+ (aq)+2NO3 - (aq)
The preceding equation is an example of an ionic equation, which shows dissolved species as free ions. To see
whether a precipitate might form from this solution, we first combine the cation and anion from different compounds.
The dissolved KNO3 remains in solution as separate K+ and NO2- ions, which are called spectator ions, or ions that
are not involved in the overall reaction. Because spectator ions appear on both sides of an equation, they can be
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eliminated from the ionic equation ending up with the net ionic equation, which shows only the species that
actually take part in the reaction.
Pb2+ (aq) + 2I- (aq)→ PbI2 (s)
If every ion in a complete ionic equation is a spectator, no reaction occurs.
Procedure for writing net ionic equations:
1. Write a balanced molecular equation for the reaction.
2. Rewrite the equation to show the ions that form in solution when each soluble strong electrolyte dissociates
into its ions. Only strong electrolytes dissolved in aqueous solution are written in ionic form.
3. Identify and cancel spectator ions.

→ Worked Examples:
• Predict what happens when a potassium phosphate (K3PO4) solution is mixed with a calcium nitrate
[Ca(NO3)2] solution. Write a net ionic equation for the reaction.
Solution: In solution, K3PO4 dissociates into K+ and PO43- ions and Ca(NO3)2 dissociates into Ca2+ and NO2- ions.
According to table, calcium ions (Ca2+) and phosphate ions (PO43-) will form an insoluble compound, calcium
phosphate [Ca3(PO4)2], while the other product, KNO3, is soluble and remains in solution. Therefore, this is a
precipitation reaction. We follow the stepwise procedure just outlined.
(1) Write a balanced molecular equation for the reaction.
2K3PO4 (aq) + 3Ca(NO3)2 (aq) → Ca3(PO4)2 (s) + 6KNO3 (aq)
(2) Rewrite the equation to show the ions that form in solution when each soluble strong electrolyte dissociates into
its ions.
6K+ (aq) + 2PO43- (aq) + 3Ca2+ (aq) + 6NO3- (aq) → 6K+ (aq) + 6NO3- (aq) + Ca3(PO4)2(s)
(3) Canceling the spectator ions (K+ and NO3-) on each side of the equation, we obtain the net ionic equation:
2PO43- (aq) + 3Ca2+ (aq) → Ca3(PO4)2(s)
Note that because we balanced the molecular equation first, the net ionic equation is balanced as to the number of
atoms on each side and the number of positive (+6) and negative (-6) charges on the left-hand side is the same.
→ Exercises:
• Predict the precipitate produced by mixing an Al(NO3)3 solution with a NaOH solution. Write the net ionic
equation for the reaction.

Acids are substances that ionize in water to produce H+ ions and bases are substances that ionize in water to
produce OH- ions. These definition were formulated in the late nineteenth century by the Swedish chemist Svante
Arrhenius to classify substances whose properties in aqueous solutions were well known.
Acids
• Acids have a sour taste; for example, vinegar owes its sourness to acetic acid, and lemons and other citrus
fruits contain citric acid.
• Acids cause color changes in plant dyes; for example, they change the color of litmus from blue to red.
• Acids react with certain metals, such as zinc, magnesium, and iron, to produce hydrogen gas. A typical
reaction is that between hydrochloric acid and magnesium: 2HCl(aq) + Mg(s) → MgCl2(aq) + H2(g)
• Acids react with carbonates and bicarbonates, such as Na2CO3, CaCO3, and NaHCO3, to produce carbon
dioxide gas.
• Aqueous acid solutions conduct electricity.
Bases
• Bases have a bitter taste.
• Bases feel slippery; for example, soaps, which contain bases, exhibit this property.
• Bases cause color changes in plant dyes; for example, they change the color of litmus from red to blue.
• Aqueous base solutions conduct electricity.

Acids and bases that are strong electrolytes (completely ionized in solution) are strong acids and strong bases.
Those that are weak electrolytes (partly ionized) are weak acids and weak bases. When reactivity depends only
on H+ (aq) concentration, strong acids are more reactive than weak acids.
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 Strong Acids Strong Bases
Hydrochloric acid, HCl Group 1A metal hydroxides [LiOH, NaOH, KOH, RbOH, CsOH]
Hydrobromic acid, HBr Heavy group 2A metal hydroxides [Ca(OH)2, Sr(OH)2, Ba(OH)2]
Hydroiodic acid, HI
Chloric acid, HClO3
Perchloric acid, HClO4
Nitric acid, HNO3
Sulfuric acid (first proton), H2SO4

When a solution of an acid and a solution of a base are mixed, a neutralization reaction occurs. This produces
water and salt [ionic compound whose cation comes from a base (for example, Na+ from NaOH) and whose anion
comes from an acid (for example, Cl from HCl)].
HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq)
acid base water salt r

In neutralization reactions, protons are transferred from one reactant to another. A kind of reaction in which
electrons are transferred from one reactant to another is called either oxidation-reduction reactions or redox
reactions.

When an atom, ion, or molecule becomes more positively charged (that is, when it loses electrons), we say that it
has been oxidized. Loss of electrons by a substance is called oxidation. When an atom, ion, or molecule becomes
more negatively charged (gains electrons), we say that it is reduced. The gain of electrons by a substance is called
reduction.
Example: 2 Ca(s) + O2(g) → 2 CaO(s)
In this reaction Ca is oxidized to Ca2+ and neutral O2 is transformed to O2- ions. When an atom, ion, or molecule
becomes more negatively charged (gains electrons), we say that it is reduced. The gain of electrons by a substance
is called reduction. When one reactant loses electrons (that is, when it is oxidized), another reactant must gain
them. In other words, oxidation of one substance must be accompanied by reduction of some other substance. The
oxidation involves transfer of electrons from the calcium metal to the O2, leading to formation of CaO.
The concept of oxidation numbers (also called oxidation states) was devised as a way of doing this. Each atom in a
neutral substance or ion is assigned an oxidation number. For monatomic ions the oxidation number is the same
as the charge. For neutral molecules and polyatomic ions, the oxidation number of a given atom is a hypothetical
charge. This charge is assigned by artificially dividing up the electrons among the atoms in the molecule or ion. We
use the following rules for assigning oxidation numbers:
1. For an atom in its elemental form, the oxidation number is always zero. Thus, each H atom in the H2
molecule has an oxidation number of 0 and each P atom in the P4 molecule has an oxidation number of 0.
2. For any monatomic ion the oxidation number equals the ionic charge. Thus, K+ has an oxidation number
of +1, S2- has an oxidation number of -2, and so forth.
In ionic compounds the alkali metal ions (group 1A) always have a +1 charge and therefore an oxidation
number of +1. The alkaline earth metals (group 2A) are always +2, and aluminum (group 3A) is always +3
in ionic compounds. (In writing oxidation numbers we will write the sign before the number to distinguish
them from the actual electronic charges, which we write with the number first.)
3. Nonmetals usually have negative oxidation numbers, although they can sometimes be positive:
a. The oxidation number of oxygen is usually -2 in both ionic and molecular compounds. The major
exception is in compounds called peroxides, which contain the O22- ion, giving each oxygen an
oxidation number of -1.
b. The oxidation number of hydrogen is usually +1 when bonded to nonmetals and -1 when bonded
to metals. For example, metal hydrides such as sodium hydride, NaH.
c. The oxidation number of fluorine is -1 in all compounds. The other halogens have an oxidation
number of -1 in most binary compounds. When combined with oxygen, as in oxyanions, however,
they have positive oxidation states.

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 4. The sum of the oxidation numbers of all atoms in a neutral compound is zero. The sum of the oxidation
numbers in a polyatomic ion equals the charge of the ion. For example, in the hydronium ion H3O+, which is
a more accurate description of H+(aq), the oxidation number of each hydrogen is +1 and that of oxygen is -
2. Thus, the sum of the oxidation numbers is 3(+1) + (-2) = +1, which equals the net charge of the ion. This
rule is useful in obtaining the oxidation number of one atom in a compound or ion if you know the oxidation
numbers of the other atoms.
→ Worked Examples:
• Determine the oxidation number of sulfur in (a) H2S, (b) S8, (c) SCl2, (d) Na2SO3, (e) SO42-.
Solution: In each species the sum of oxidation numbers of all the atoms must equal the charge on the species. We
will use the rules outlined previously to assign oxidation numbers.
(a) When bonded to a nonmetal, hydrogen has an oxidation number of +1. Because the H2S molecule is neutral,
the sum of the oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have 2(+1) + x =
0. Thus, S has an oxidation number of -2.
(b) Because S8 is an elemental form of sulfur, the oxidation number of S is 0.
(c) Because SCl2 is a binary compound, we expect chlorine to have an oxidation number of -1. The sum of the
oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have x + 2(-1) = 0.
Consequently, the oxidation number of S must be +2.
(d) Sodium, an alkali metal, always has an oxidation number of +1 in its compounds. Oxygen commonly has an
oxidation state of -2. Letting x equal the oxidation number of S, we have 2(+1) + x + 3(-2) = 0. Therefore, the
oxidation number of S in this compound (Na2SO3) is +4.
(e) The oxidation state of O is -2. The sum of the oxidation numbers equals -2, the net charge of the SO42- ion.
Thus, we have x + 4(-2) = -2. From this relation we conclude that the oxidation number of S in this ion is +6.
→ Exercises:
• Identify the oxidation numbers:
• P4 • O in H2O • Cl in ClO3-
• H2 • O in CO2 • H3O+
• H in H2 • O in H2O2 • NaCl
• K + • H in HCl • N in AlN
• S-2 • H in NaH • N in HNO3
• Alkali metal ions • CH4 • S in H2S
• Alkaline earth metal ions • F in LiF • S in S8
• Group 3A • Br in CaBr2 • S in SCl2

A reduction-oxidation (redox) reaction is a displacement reaction (ion in solution is displaced (replaced) through
oxidation of an element). For example:

The oxidation number of Mg changes from 0 to +2, an increase that indicates the atom has lost electrons and has
therefore been oxidized. The oxidation number of H+ in the acid decreases from +1 to 0, indicating that this ion has
gained electrons and has therefore been reduced. Chlorine has an oxidation number of -1 both before and after the
reaction, indicating that it is neither oxidized nor reduced. In fact the Cl- ions are spectator ions, dropping out of the
net ionic equation: Mg(s) + 2 H+(aq) → Mg2+(aq) + H2(g).
→ Exercises:
• Identify the reducing and the oxidizing agent:
• Mn (s) + Pb(NO3)2 (aq) → Mn(NO3)2 (aq) + Pb (s)
• Mg (s) + 2 HCl (aq) → MgCl2 (aq) + H2 (g)
• Fe(s) + Ni(NO3)2(aq) → Fe(NO3)2(aq) + Ni(s)
• ZnCl2(aq) + NaOH(aq) → Zn(OH)2(s) + NaCl(aq)

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Different metals vary in the ease
with which they are oxidized. A list
of metals arranged in order of
decreasing ease of oxidation is
called an activity series. The metals
at the top of the table, such as the alkali
metals and the alkaline earth metals,
are most easily oxidized; that is, they
react most readily to form compounds.
It follows the two most important rules:
▪ Any metal on the list can be
oxidized by the ions of
elements below it.
▪ Only metals above
hydrogen in the activity
series are able to react with
acids to form H2.
→ Some Thoughts:
Does a reaction occur (a) when an
aqueous solution of NiCl2(aq) is
added to a testtube containing
strips of metallic zinc, and (b)
when NiCl2(aq) is added to a test
tube containing Zn(NO3)2(aq)?

Scientists use the term concentration to designate the amount of solute dissolved in a given quantity of solvent or quantity of
solution. The greater the amount of solute dissolved in a certain amount of solvent, the more concentrated the resulting
solution. In chemistry we often need to express the concentrations of solutions quantitatively.
Molarity (symbol M) expresses the concentration of a solution as the number of moles of solute in a liter of solution (soln)
moles solute
Molarity =
volume of solution in liters
→ Worked Examples:
• Calculate the molarity of a solution made by dissolving 23.4 g of sodium sulfate (Na2SO4) in enough water
to form 125 mL of solution.
Solution: Calculate the number of moles of Na2SO4:
1 mol Na SO
Moles Na2SO4:= (23.4 g Na2SO4) (142.1 g Na2 SO4 ) = 0.165 mol Na2SO4
2 4
Convert the volume of the solution to liters:
1L
Liters soln = (125 mL)(1000 mL) = 0.125 L
Thus, the molarity is:
0.165 mol Na2 SO4
Molarity = =1..32 M
0.125 L
→ Exercises:
• Which is more concentrated, a solution prepared by dissolving 21.0 g of NaF (0.500 mol) in enough water
to make 500 mL of solution or a solution prepared by dissolving 10.5 g (0.250 mol) of NaF in enough water
to make 100 mL of solution?
• How many grams of Na2SO4 are required to make 0.350 L of 0.500 M Na2SO4?

Solutions of lower concentrations can then be obtained by adding water, a process called dilution. In laboratory
situations, calculations of this sort are often made with an equation derived by remembering that the number of
moles of solute is the same in both the concentrated and dilute solutions and that moles = (molarity) (liters):
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 Moles solute in conc soln = moles solute in dilute soln
Mconc × Vconc = Mdil × Vdil

Molality (m), is a concentration unit that relates the number of moles of solute per kilogram of solvent.
moles solute
Molality =
kilograms of solvent
Note: Molarity depends on the volume of solution, whereas molality depends on the mass of solvent.

Common Stoichiometric Expressions for Solutions:

mass/mass percent concentration, (m / m)% Concentration expressed as the number of grams of solute per 100 grams of
solution
mass of solute (g)
(m⁄m)% concentration= ×100%
mass of solution (g)
volume/volume percent concentration, (v/v)% Concentration expressed as the number of milliliters of solute dissolved in 100
mL of solution.
volume of solute (mL)
(v⁄v)% concentration= ×100%
volume of solution (mL)
mass/volume percent concentration, (m / v)% Concentration expressed as the number of grams of solute per 100 mL of
solution.
mass of solute (g)
(m⁄v)% concentration= ×100%
volume of solution (mL)
Parts per million (ppm) - Number of parts per one million (106) parts.
mass of solute (g) volume of solute (mL)
ppm= ×106 or ppm= ×106
mass of solution (g) volume of solution (mL)
Parts per billion (ppb) - Number of parts per one billion (109) parts.
mass of solute (g) volume of solute (mL)
ppb= ×109 or ppb= ×109
mass of solution (g) volume of solution (mL)

Colligative property refers to the property of a solution that depends only on the number of dissolved particles, not on their
chemical identity. It includes:
• Vapor pressure is lower for a solution than for a pure solvent.
• Boiling point is higher for a solution than for a pure solvent.
• Freezing point is lower for a solution than for a pure solvent.
• Osmosis occurs when a solution is separated from a pure solvent by a semipermeable membrane.

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