LECTURE 12

Topic 4: Aqueous Reactions

A solution is a homogeneous mixture of two substances in which one (the solvent) forms
the medium in which the other (solute) is uniformly distributed. We generally say that the
solute is dissolved in the solvent.

The most common solvent is water, and for this course it is the solvent that we will me
concerned about. A solution in which the solvent is water is called an aqueous solution.

An electrolyte is solute that produces ions in solution, such as Na+ and Cl-. Electrolytic
solutions have high electrical conductivity.

Non-electrolytes are solutes that dissolve without dissociating in aqueous solution. They
exist in molecular form in solution. An example is sucrose (common sugar), C12H22O11.

The dissolution processes for an electrolyte and a non-electrolyte as exemplified by NaCl

NaCl (s) + H2O (l)  Na+ (aq) + Cl- (aq)

C12H22O11(s) + H2O (aq)  C12H22O11 (aq)

A strong electrolyte: This is an electrolyte that ionizes 100% in aqueous solution e.g. HCl,

HCl (aq)  H+(aq) + Cl-(aq)

Initially: 100 molecules 0 cations 0 anions

After ionization: 0 molecules 100 cations 100 anions

So, a strong electrolyte ionizes (or, in the case of an ionic compound dissociates)
completely.

A weak electrolyte: An electrolyte that only partially ionizes. Only a small fraction of the
molecules ionize before equilibrium . Example, CH3COOH (aq)

CH3COOH (aq) CH3COO- (aq) + H+(aq)

Initially: 100 molecules 0 ions 0 ions

Number of ions formed in electrolyte solutions

The total number of ions formed upon dissolution of a strong electrolyte depends on the
stoichiometry of the salt. In this discussion, we are assuming 100% dissociation.

Examples:

NiSO4  Ni2+(aq) + SO42- (aq) , 2 ions formed per formula unit. This also means 2
moles of ions are formed per mole of formula unit (I mole of nickel ions and 1 mole of
sulfate ions).

Ca(NO3)2  Ca2+ (aq) + 2NO3-(aq), 3 ions formed per formula unit. This also means that 3
moles of ions are formed per mole of formula unit of calcium nitrate (1 mole of calcium ions
and 2 moles of nitrate ions).

Na3PO4  3Na+(aq) + PO43-(aq), 4 ions are formed per formula unit OR 4 moles of ions
formed per mole of formula unit ( 3 moles of sodium ions and 1 mole of phosphate ions).

Al2(SO4)3(aq)  2Al3+(aq) + 3SO42-(aq) , 5 ions are formed per formula unit, OR 5 moles of
ions are formed per mole of formula unit (2 moles of aluminium ions and 3 moles of sulfate
ions).

Precipitation Reactions

Some salts are classified as soluble in water (to form an aqueous solution), because they
completely dissociate

Others are classified as sparingly soluble or insoluble because they do not dissociate
completely, some or most of the formula units remain undissociated.

When two solutions A and B are mixed together and there is an anion, X2- in solution A that
forms an insoluble salt with a cation M2+ in solution B, when solutions A and B are mixed a
precipitate of salt MX(s) will be formed. A precipitate is a solid that forms out of a solution.

Example: The salt PbI2 is insoluble, whereas both Pb(NO3)2 and KI are soluble
in water. So when a solution of Pb(NO3)2 is mixed with a solution of KI, we
would expect a precipitate of PbI(s) to be formed according to the equation;
 Pb(NO3)2(aq) + 2KI (aq)  PbI2(s) + 2KNO3(aq)

But how does one know which salt is soluble and which is not? This is information that has
been gathered from experimental observation (experience) and is documented. You will
need to simply learn the solubility rules. They can be found on page 62 of your prescribed
textbook, third edition.

Remember the last example of a precipitation reaction?

Example: The salt PbI2 is insoluble, whereas both Pb(NO3)2 and KI are soluble
in water. So when a solution of Pb(NO3)2 is mixed with a solution of KI, we
would expect a precipitate of PbI(s) to be formed according to the equation;

Pb(NO3)2(aq) + 2KI (aq)  PbI2(s) + 2KNO3(aq)………1

With the knowledge of solubility rules, it is easy to correctly write the states in which the
products will be formed.

Writing ionic equations

The equation shown above is given as a full formula-unit equation. In terms of the effective
reaction that has taken place, it is more informative to write the equation in ionic form, ie
the ionic equation. The ionic equation shows us clearly which salts exist in ionic form (are
soluble) in water and which do not. If there are any insoluble salts or stable molecules
formed, the ionic equation will also reveal that. Equation 1 above can be written in its ionic
form as follows;

Pb2+(aq) + 2NO3 (aq) + 2K+(aq) + 2I- (aq)  PbI2(s) + 2K+(aq) + NO3-(aq) ………2

If you consider the above equation closely, you will notice that there are species that are the
same both in identity and in state on the reactant as well as on the product side. These are
colour coded. These are called spectator ions because they do not participate in the
reaction but are just present in solution at the beginning of the reaction and at the end, in
the same state.

The net ionic equation simply shows only those ions that actually react (combine) to form
the precipitate, in this case;

Pb2+(aq) + 2I- (aq)  PbI2(s)

Acid-Base Reactions

In our context at this point, an acid is defined as a chemical species that produces H+ or H3O+
ions in water.

An acid is a chemical species that produces OH- ions in water

Examples:

HCl (aq)  H+(aq) + Cl-(aq).

So HCl ionizes in water to produce H+ and therefore it is an acid. Because HCl is a strong
acid, it ionizes completely, meaning that 100% of the molecules ionize as indicated in the
equation, and none remain in their molecular state in solution.

Note: In water, H+(aq) never exists in isolation. It combines with a water molecule by sharing
one of the loan electron pairs on the oxygen atom of the water molecule. The resulting
polyatomic ion is called the hydronium ion, H3O+. An illustration of the formation of the
hydronium ion is shown below.

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coordinate-bond-with-an-example-How-does-it-differ-from-covalent-bond/Chemical-
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So, the ionization of HCl can be illustrated in two steps; the separation of the H+ and the Cl-
ions, followed by attachment of H+ to a H2O molecule. The overall reaction is therefore the
sum of the two steps.

Step 1: Ionization of HCl in water; HCl (aq)  H+(aq) + Cl-(aq)

Step 2: Attachment of H+ to a water molecule; H+(aq) + H2O  H3O+(aq)

A weak acid

A weak acid is one that only partially dissociates in water. Unlike the strong acid, not all the
molecules of a weak acid will ionize when it is put in water. In the case of acetic acid (a weak
acid, for example) only 1 in every 100 molecules will ionize according to the equilibrium
reaction below, as exemplified by HF(aq);

HF(aq) H+(aq) + F-(aq)

In the same way as for a strong acid, the ionization of a weak acid can be regarded as a two-
step process involving loss of a proton by the acid molecule, followed by the proton
attacking a water molecule. The overall equation can be shown by addition of the two steps
as shown below;

Step 1: Partial ionization of HF in water; HF(aq) H+(aq) + F-(aq)

Step 2: Attachment of H+ to a water molecule; H+(aq) + H2O  H3O+(aq)

Overall: The net reaction; HF(aq) + H2O(l) H3O+(aq) + F-(aq)

Strong bases

These are bases that dissociate/ionize completely in water. An example of a strong base is
NaOH (aq) , which completely dissociates in water to produce Na+(aq) ions and OH- ions.

NaOH (aq)  Na+(aq) + OH-(aq)

Weak bases

These produce OH- ions by partial ionization in the same way as weak acids. An example is
NH3(aq). In water, NH3(aq) produces OH- according to the reaction below (the two dots are
lone pairs of electrons);
Source:
http://highered.mheducation.com/sites/0073402621/student_view0/chapter8/self_quiz_1.
html

The ammonia molecule accepts a proton directly from a water molecule and is thus
converted to an ammonium ion, while the water molecule is converted to a hydroxide ion.

Note that the reaction is shown as an equilibrium because ammonia is a weak base. That
means that when a small percentage of NH3 molecules have accepted a proton from water,
the rate of the forward reaction (to form NH4+ and OH-) becomes equal to the rate of the
backward reaction (forming back NH3 and H2O). At that point, there is no net change in the
number of molecules of water and ammonia or the NH4+ and OH- ions.

Neutralization Reactions

A. Strong acids and strong base

e.g. HCl (aq) + NaOH(aq)  NaCl (aq) + H2O(l)

Full Ionic Equation: H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq)  Na+(aq) + Cl-(aq) + H2O(l)

Net ionic equation: H+(aq) + OH-(aq)  H2O(l)

B. Weak acid and strong base

e.g. CH3COOH (aq) + NaOH (aq)  CH3COONa(aq) + H2O(l)

Full Ionic Equation: CH3COOH(aq) + Na+(aq) + OH- (aq)  CH3COO-(aq) + Na+(aq) + H2O(l)

Net ionic equation: CH3COOH(aq) + OH- (aq)  CH3COO-(aq) + H2O(l)

C. Weak base and strong acid

e.g. NH3(aq) + HCl(aq)  NH4Cl(aq) + H2O(l)

Net Ionic Equation: NH3(aq) + H+(aq)  NH4+(aq) + H2O(l)

D. Weak acid and weak base

e.g. NH3(aq) + H2O(aq)  NH4+(aq) + OH- (aq)

B A CA CB

This is already a full ionic equation as well as a net ionic equation. B and A denote “acid” and
“base”, respectively. CA and CB denote “conjugate acid” and “conjugate base”, respectively.
So NH4+ is the conjugate acid of NH3 and OH- is the conjugate base of H2O. The difference
between an acid or base and its conjugate is an H+ which must be gained or lost in order to
convert it to the other species.