TOPICS TO BE COVERED IN MY SECTION

1. Electrolytes – acids, bases, and salts

2. Ionization of acids, bases and salts
3. Buffers
4. Elementary electrochemistry
5. Elementary Chemical Kinetics

ELECTROLYTES
These are substances which in solution or molten state can conduct electricity and are decomposed in the
process. Examples of electrolytes includes; Na2SO4 = 2Na+ + SO42-; CuSO4 = Cu2+ + SO42- ; NaCl = Na+ +
Cl- etc. Most conventional acids and bases are electrolytes.

Acids and Bases

Arrhenius Concept of Acids

Arrhenius acid is any substance which dissociates in aqueous solution to produce H+. Note that, strong acids
completely dissociate unlike weak acids.

Advantages of Arrhenius concept of acids

(i) It recognizes role of water as solvent in the dissociation of acids.

(ii) It explains why substances such as hydrogen chloride and ethanoic acid can only show their
usual acidic properties in the presence of water.

Pure dry ethanoic acid and solution of hydrogen chloride or ethanoic acid in organic solvents such as
toluene do not contain H+ ions. Thus, they are non-electrolytes.

Arrhenius Concept of Bases: An Arrhenius base is any substance which reacts with H+ ions to form water.
For instances:
Meanwhile, alkalis (i.e. soluble bases) are regarded as substances, which dissociate in water to produce OH-

Assignment

1. Write chemical equations to show how each of the following substances behave as an Arrhenius acid
or base: HBr, KOH, Cl3CCOOH, and Zn (OH)2.
2. Explain why pure dry benzoic acid does not affect a litmus paper.

Bronsted – Lowry Concept of Acids and Bases

Arrhenius shortcomings:

(i) It can be applied to only aqueous solutions.

(ii) It is restricted to a base which reacts with H+.

Thus, B – L concept approach include non-aqueous systems and wide range of bases.

Bronsted – Lowry acid (B –L acid): B-L acid is a proton donor.

B-L base: B-L base is a proton acceptor.

Furthermore, an acid- base conjugate pair are any two substances which differ in chemical composition by a
proton.

According to the B- L theory, an acid salt such as KHSO4 and NH4+ are recognized as acids alongside HCl
and CH3COOH. The definition of base includes the following; H2O, NH3 and OH- etc.

Relative strength of Acids and Bases

The dissociation of an acid HB in water is given by the following equilibrium;

HB + H2O → B- + H3O+
Strong acids donate all their H+ to water molecules. In which case, if an acid is weak, its conjugate base is
strong since it must have strong affinity for H+. For instance, CH3COOH is a weak acid, but CH3COO- ion is
a strong base.

Assignment

1. Give a list of relative strength of acids and bases

Any substance which has ability to accept or donate proton is called amphiprotic. e.g. water.

Lewis Concept of Acids and Bases

An acid is an electron pair acceptor. While a base is an electron pair donor. The Lewis theory is a more general
concept. It satisfies the requirements of the Arrhenius and B- L concepts. This involves other substances not
covered by the previous concepts. e.g. AlCl3 = Lewis acid, why HCl = Arrhenius acid, Bronsted-Lowry acid
as well as Lewis acid.

(i) Cu2+ + 2e- → Cu. Cu2+ is electron acceptor, hence it is Lewis acid
(ii) SnCl4 + 2Cl- → SnCl62-. SnCl4 is Lewis acid because it accepts 2 electron pair from Cl- ions; Cl- =
Lewis base.
(iii) 2Cl- → Cl2 + 2e-. Cl- it is a Lewis base because it has donated electron
(iv) Hg2+ + 4CN- →Hg (CN)42-. Hg2+= Lewis acid and CN- = Lewis base.

Ionization of water

Note that water is amphiprotic, therefore;

Therefore, the equilibrium constant for the reaction is;

Hence; Kc [H2O]2 = [H3O+] [OH-]. Small fraction of water ionizes at equilibrium; thus, the concentration of
water molecules remains virtually unchanged.

Kw = Kc [H2O]2 = [H3O+] [OH-]. For pure water at 25 OC, [H+] = [OH-] = 1.00 x 10-7 M. Hence, Kw = (1.00 x
10-7)2 M = 1.00 x 10-14 M

Example: Concentration of OH- ions in a certain household ammonia cleaning solution is 0.005 M. Calculate
the concentration of H+ ions.

Note; Kw = [H3O+] [OH-]. Hence;

Note; M = molL-1 = moldm-3

Furthermore, pH = -log[H+]; similarly, pOH = -log [OH-]

[H+] [OH-] = 1.0 X 10-14 M; Take –ve log of each side;

= -log [H+] – log [OH-] = -log (1) – log (10-14) = pH + pOH = 0 + 14; Hence, pH + pOH = 14.

Example: Calculate the pH and pOH of a 0.01 M H2SO4.

Solution:

pH = -log [0.02] = 1.70; Therefore, pOH = 14 – pH = 14-1.70 = 12.30.

Ionization of weak monobasic acid, HA

Calculation of pH of a weak acid by approximation

Let C and α be the initial concentration and the degree of dissociation of the acid respectively. Therefore,

Therefore,

Note that if the acid is very weak, α << 1, so that 1- α approx. 1

However, in aqueous solution, [H+] = [H3O+]. Therefore, [H+] = Cα. Hence,

Example: Calculate (a) [H+] (b) [CH3COO-] (c) [CH3COOH] (d) α and (e) pH (f) pOH of 0.07 M acetic
acid solution (Note Ka = 1.85 x 10-5 M).

C
Because Ka > 1000, the approximation equation can be used

SALTS

Salts are products of the neutralization reaction between an acid and a base. These salts could come from
strong acids and strong bases; or from weak acids and weak bases. Hence there are several categories of salts,
i.e. we could have salt of (i) strong acid and strong base (ii) strong acid and weak base (iii) strong base and
weak acid (iv) weak acid and weak base.

Salts can completely ionize in aqueous solutions and hence their behavior in aqueous solution will be
determined by the nature of the constituent ions in water. Dissolution of a salt in water may change the pH of
the solution. The extent of the change in pH will depend on the nature of the salt. See Table 1 below.
 Table 1: Type of salts

Type of salt pH of the aqueous solution

Strong acid- strong base (e.g. NaCl) 7
Weak acid- strong base (e.g. CH3COOK) >7
Strong acid- Weak base (e.g. HONH3Cl) <7
Weak acid- Weak base (e.g. NH4NO2) Depend on the salt

Assignment: Write 5 examples each of strong & weak acids; strong & weak bases.

This shows that ions of salts react with water to produce either excess H3O+ (H+) or OH- which causes the
solution to be either acidic or basic. Hence, we can say that the ions do undergo solvolysis, i.e. the reaction of
ion and solvent. When water is the solvent the reaction is referred to as hydrolysis.

CH3COONa + H2O → Na+ + CH3COO-; also, H2O → H+ + OH-

CH3COO- + H+ → CH3COOH (it’s a weak acid; it incompletely ionizes). This leads to excess of OH- ion in
the solution and the solution will therefore be basic (pH > 7), due to the reaction;

Na+ + CH3COO- + H2O → Na+ + CH3COOH + OH-

This represent the hydrolysis reaction of the acetate ion. Ignore Na+ on both side of the equation. The
equilibrium constant is called hydrolysis constant, Kh and is expressed as;

Therefore; Kh = 1/Ka x [OH-][H3O+] = 1/Ka x Kw. Hence the extent to which a species can undergo hydrolysis
may be determined from the ionic product of water (Kw) and the ionization constant of that species.

Assignment:

Predict whether the aqueous solutions of the following salts will be acidic, basic or neutral. (i) NaCl (ii) KF
(iii) HONH3Cl (hydroxylamine chloride).
Example: What is the pH of 0.15 M CH3COONa solution? Ka = 1.74 x 10-5.

The change in the pH will result from the hydrolysis reaction. If we assume that the amount of OH- formed is
X m. The equilibrium concentrations arising from the reaction will be;

BUFFER SOLUTIONS

It has been observed that addition of small quantities of acid or base to pure water changes the pH of the
solution immensely because of the repression of the ionization of water.

Example: Consider the change in pH when 1 mL of 0.1 M HCl is added to 1 L of pure water. Pure water at
25 ℃ has a pH of 7.0.

Total concentration of H+ = (1.00 x 10-4 + 1.00 x 10-7) M = 1.0 x 10-4 M. pH = -log (1.0 x 10-4) = 4.0

Hence, the pH change of 3.0 units in 1 L of pure water following the addition of this acid is significant.
Similarly, addition of 1 mL of 0.1 M NaOH will cause change of 3.0 pH units in 1 L of pure water.
However, there are solutions which do not show profound change in pH when an acid or base is added. Let’s
consider addition of 0.1 M CH3COONa and 0.1 M CH3COOH. Their net equilibrium would be;
Now if we add 1.0 mL of 0.1 M HCl to 1 L of this solution of weak acid and its salt.

CH3COO- + H3O+ → CH3COOH + H2O. It is logical that; [H3O+] = [CH3COOH] = [CH3COO-]

At equilibrium [CH3COOH] = 0.1 M + 1.0 x 10-4 = 0.1001 M

[CH3COO-] = 0.1 M - 1.0 x 10-4 = 0.099 M. Therefore,

This shows that there is hardly any change in the pH of solution of a weak acid and its salt when a small
amount of acid is added. In same vein, addition of 1 mL of 0.1 M NaOH would not cause any change in the
pH of the solution. Hence, we can say that, solution of weak acid and its salt resists change in pH when small
amount of acid and base is added. Such solutions that show resistance to changes in pH when small amount
of acids and bases are added are called buffer solutions.

Henderson Hassel-Balch Equation

HA + OH- → H2O + A-. If an acid is added to this system, the acid reacts with the conjugate base to form acid.
H+ + A- → HA. The pH associated with this addition of acid may be calculated from the equation that defines
the acid dissociation constant of the weak acid.
[A-] = anion = conjugate base. Note: Concentration of anion is approximately equal to the concentration of
the salt (salt dissociates completely, while the ionization of weak acid is only to a small extent). We can finally
write this Henderson Hassel-Balch Equation as;

Some typical examples of buffer solutions; NH3 & NH4Cl; CH3COOH & CH3COONa; HCOOH &
HCOONa etc.

Example: A buffer comprises 6.0 g CH3COONa and 250 mL of 0.21 M acetic acid. What is the pH of the
buffer?
Take the pKa = 4.76

Rates of Reactions
Reaction Rate: The change in the concentration of a reactant or a product with time (M/s). The rate of a
reaction tells as to what speed the reaction occurs. Let us consider a simple reaction below.
A→B
The concentration of the reactant A decreases and that of the product B increases as time passes. The rate of
reactions is defined as the change in concentration of any of reactant or products per unit time. For the
given reaction the rate of reaction may be equal to the rate of disappearance of A which is equal to the rate of
appearance of B.

[ ] represents the concentration in moles per liter, and d represents infinitesimally small change in
concentration. Negative sign shows the concentration of the reactant A decreases whereas the positive sign
indicates the increase in concentration of the product B.
The results are also shown graphically in below;

Figure 1: Graph of CO concentrations versus time

The rate is equal to the slope of the curve. The rates for the first 10 and the last 10 seconds are shown.
In the time interval between 30 and 40 seconds.

TYPES OF RATE
Average Rate: Average rate is measured as change in concentration of reactant or product during the whole
period of the progression of the chemical reaction.
∆ [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡] ∆ [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
Average = - or
∆𝑡𝑖𝑚𝑒 ∆𝑡𝑖𝑚𝑒
Instantaneous Rate: Is measured as change in concentration of reactant or product during a known short
period. An instantaneous rate is also known as differential rate as represented below.

𝑑 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡] 𝑑 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
Rate = - Rate =
𝑑 𝑡𝑖𝑚𝑒 𝑑 𝑡𝑖𝑚𝑒

Initial Rate: Is the instantaneous rate at the start of the reaction when time

Factors affecting rate of reaction

1. Temperature: Increasing the temperature causes the particles (atoms or molecules) of the reactants
to move more quickly so that they collide with each other more frequently and with more energy.
Thus, the higher the temperature, the greater the rate of reaction. If you decrease the temperature, the
opposite effect occurs. The particles move more slowly, colliding less frequently and with less energy.
In this case, the rate of reaction decreases.

2. Concentration refers to how much solute is dissolved in a solution. If a greater concentration of

reactant atoms and molecules is present, there is a greater chance that collisions will occur among
them. More collisions mean a higher reaction rate. Thus, increasing the concentration of the reactants
usually results in a higher reaction rate. At lower concentrations, there is less chance for collisions
between particles. This means that decreasing the concentrations of the reactants results in a lower
reaction rate.

3. Surface area is the measure of how much area of an object is exposed. For the same mass, many small
particles have a greater total surface area than one large particle. For example, steel wool has a larger
surface area than a block of steel of the same mass. This allows oxygen molecules to collide with many
more iron atoms per unit of time. The more surface contact between reactants, the higher the rate of
reaction. The less surface contact, the lower the reaction rate. Surface area can also be important if a
reaction occurs between two liquids that do not mix. In this case, the reaction occurs only at the
boundary where the two liquids meet. It is also important to note that not all reactions depend on
surface area. If both reactants are gases or liquids that mix together, then there is no surface, and
surface area is not a factor.
4. A catalyst is a substance that speeds up the rate of a chemical reaction without being used up in the
reaction itself. Catalysts reduce the amount of energy required to break and form bonds during a
chemical reaction. When catalysts are used, a reaction can proceed although less energy is added
during the reaction. For example, enzymes are catalysts that allow chemical reactions to occur at
relatively low temperatures within the body.

5. As the pressure on a GAS increases, the reaction rate increases. As the volume of a GAS container
decreases, the reaction rate increases. Pressure/volume does not affect solids or liquids. For Gas,
particles are very far apart, so they can be compressed if there is an outside pressure; when the particles
are more compressed, they are closer together and collide more frequently.
Electrochemistry
Electrochemistry deals with the interconversion of electrical energy and chemical reactions in a chemical cell.
Electrical current in the cell is transferred with the aid of the component, electrodes. It is worth stressing that;
electrochemical reactions are carried out in in a special device called cell. Two types of cells are known.

1. Electrolytic cells - In these cells, electrical energy causes a non-spontaneous chemical change to occur.
2. Voltaic or galvanic cells - Here, the spontaneous chemical reactions produce electricity which is
supplied to the external circuit.

In general, electrochemistry is concerned with reduction-oxidation (redox) reactions. Note, oxidation is loss
of electrons; while reduction is gain of electron. Suppose we have; Na + Cl → Na+ Cl-. The oxidization process
is; Na = Na+ + e-; whereas the reduction process is; Cl + e- = Cl-. Each of these processes (the oxidation or
reduction) is called half reaction. The two processes combine is known as redox reaction.

Balancing Redox Equations

Redox reactions can become quite complicated and the equations describing them may become difficult to
balance. We shall discuss oxidation number method for balancing redox equations. However, other methods
for balancing redox reactions include; half reaction method, algebraic method, redox reactions in alkaline
solutions method and so on.
Oxidation Number Method of Balancing Redox Reactions

When an element undergoes oxidation, the oxidation number increases, while an element undergoing
reduction shows decrease in in the oxidation number. If a reaction occurs in which no atom undergoes a
change in its oxidation states, the reaction will not be considered as redox reaction. For example, consider this
equation 3 below; it’s a non-redox process because no atom has undergone change in the oxidation state.
However, in the equation 4, the species had undergone change in the oxidation states as depicted. Hence,
equation 4 is qualified to be called redox process.

Importantly, consider that; I2 + HNO3 → HIO3 + H2O + NO. In order to balance this equation, we must
remember that, the total increase in oxidation number be equal to the total decrease in the oxidation number.

Step 1. Determine the oxidation number of the atoms and identify the atoms undergoing oxidation and
reduction. I = oxidized species (there is increased in the oxidation with respect to iodine atom) and the N =
reduced species (there is decreased in the oxidation number for the nitrogen atom).

Step 2. Use of coefficients to ensure that the total increase in oxidation number is equal to total decrease in
oxidation number.

Total increase in oxidation number = 3 * 5 = 15; and Total decrease in oxidation number = 5 * 5 – 5 * 2 =
15.

In effect, this is same as taking the difference in oxidation number for the oxidised species as the coefficients
for the reduced species (HNO3 and NO) and vice versa. From equation five above, the difference in oxidation
number of the oxidised species is 5 and the difference in the oxidation number for the reduced species is 3.
Therefore, in going forward for the balancing we have;

3I2 + 5HNO3 → 3HIO3 + H2O + 5NO ………………………………. (6)

Step 3. Balance the rest of the equation by inspection

Take 3I2 as reference. Then multiply all other terms with 2 except the reference.

3I2 + 10HNO3 → 6HIO3 + 2H2O + 10NO …………………..………. (7)

Assignment: Balance the following redox reactions using the oxidation method

(i) Cu(s) + H+(aq) + NO3-(aq) ↔ Cu2+(aq) + NO(g) + H2O(l)

(ii) As2S3(s) + H+(aq) + NO3-(aq) + H2O(l) ↔ H3AsO4 + NO(g) + S(s)

Electrode Potential and Electromotive Force

Consider a metal electrode immerse in a solution containing its ions below;

An equilibrium established between metal and its ions is; M(s) = Mn+ + ne-. At the equilibrium, the electrode
acquires electrical charge opposite to the solution because of the difference in number of electrons on the
electrode before and after the equilibrium. That is, there is electrical potential between the electrode and its
solution. The magnitude of the electrical potential depends on;

(i) Ability of electrode to form ions;

(ii) Concentration of the solution; and
(iii) Tendency of the metal ions to be reduced to metal neutral.

Two half-cell can be combined together to further demonstrate this electrical potential. Such combination will
result into formation of electrical circuit. Thus, it is an electrochemical cell as shown below.

The half cells have different electrical potentials; therefore, electrons will flow from region of high electrical
potential to the region of low electrical potential. The spontaneous reactions in the electrochemical cell are:
Zn(s) → Zn2+(aq) + 2e- (oxidation process); and Cu2+(aq) + 2e- → Cu(s) (reduction process). Hence, the net redox
reaction in this electrochemical cell is; Zn(s) + Cu2+(aq) ↔ Zn2+(aq) + Cu(s)In addition, another representation for
this equation is;
More so, the single vertical line symbolizes the interphase between the electrode and its ions, whereas the
double vertical line shows the salt bridge. As the reaction starts, Zn2+ is gradually built, while, Cu2+ gets
deposited on the cathode and SO42- is left in the solution (overall charge is –ve). Also, continuous building of
Zn2+ could prevent additional Zn2+ ions from entering the solution (overall charge is +ve). This is electrical
imbalance and the electron flow will cease. However, the above scenario can be avoided by linking the 2 half
cells together with salt bridge (a tube filled with electrolyte such as KNO 3 and KCl in gelatin). The driving
force for the flow of electrons is called electromotive force (emf), cell potential or cell voltage. The unit is
volt. Note the emf of a cell is given as follows; ECell = EOx + ERed.

Reduction Potential

Consider these two equations; Zn2+(aq) + 2e- → Zn(s); and Cu2+(aq) + 2e- → Cu(s). Each of these reactions has its
reduction potential. Now when the half cells combine, there will be competition for reduction. Eventually the
species with greater reduction potential will win. Then the other will be forced to oxidize and supply the
electrons. That is to say, EMF is also, the difference between the reduction potential of the half reactions.
However, the reduction potential of individual half-cell is not directly measured. The standard reduction
potentials of half cells are determined experimentally from the emf i.e. when hydrogen electrode is used. The
reaction for standard reduction potential of hydrogen is as follows; 2H+(1 M) + 2e- = H2 (1 atm); EORed = 0.
Standard Hydrogen Electrode is described below;
For instance, if we have a net reaction from a cell between Zn and H+ as follows; Zn(s) + 2H+ (1 M) ↔ Zn2+
(1 M) + H2 (g, 1 atm); EoCell = 0.763 V. What will be the EoOx for zinc?

Remember, EoCell = EoOx + EoRed. Take EoRed = 0; i.e. the electrode potential of the Standard Hydrogen
Electrode;

0.763 V = EoOx + 0. Hence, EoOx = 0.763 V = the cell potential for the oxidation reaction. i.e. Zn(s) → Zn2+(aq)
= 2e-; EoOx = 0.763 V.

The half-cell potential for any oxidation is equal in magnitude but opposite in sign to that of the reverse
reduction. Thus; Zn2+(aq) + 2e- = Zn(s); EoRed = -0.763 V.

By convention, standard (std) electrode potentials are listed as std reduction potentials or merely as electrode
potentials. Furthermore, any electrode at which the reduction half reaction shows a greater tendency to occur
than does the reduction potential of H+ will have a positive electrode potential; otherwise, the electrode
potential will be –ve.

Assignment:

1. Consider this electrochemical cell comprising;

(i) Sn2+(aq) + 2e- → Sn(s); Eo = -0.136 V (reduction potential)
(ii) Zn2+(aq) + 2e- → Zn(s); Eo = -0.760 V (reduction potential); write the overall cell equation and
hence determine the cell EMF.