ELECTROCHEMISTRY

Electrochemistry is a branch of chemistry that studies the interchange between

chemical and electrical energy. Many technological breakthroughs have been achieved
from various researches and developments in electrochemistry. Recall that a redox
reaction is composed of oxidation and reduction half-reactions. In performing an
electrochemical experiment, an electrochemical cell is used, which is made up of two
metallic conductors called electrodes. The two electrodes are where the oxidation and
reduction take place. Oxidation occurs in the anode, and the reduction occurs in the
cathode. The electrodes are interconnected through a supporting electrolyte, a medium
that is electrically conducting. When a solution containing electro active components
comes in contact with the electrode, it releases electrons at the anode. The electrons
then travel through the electrochemical cell through the salt bridge going to the other
cathode, where another electro active component is reduced. In an electrochemical cell,
the following events take place:
 Electrons flow from the anode to the cathode.
 Oxidation occurs at the anode, with the anions traveling to the direction of the
anode.
 Reduction takes place at the cathode, with the cations flowing toward the
cathode.
There are two types of electrochemical cells: (1) galvanic cells and (2) electrolytic
cells. A galvanic cell is an electrochemical cell that produces electricity from
spontaneous chemical reaction. On the other hand, an electrolytic cell uses electricity
to produce a chemical reaction.
Galvanic Cells specifically called as Daniell Cell. It was named after a British chemist
John Frederic Daniell (1790-1845), who invented it in 1836. A galvanic cell is made up
of two electrodes: a zinc (Zn) anode and a copper (Cu) cathode. The electrode are
made up of metals, but other materials such as graphite can also be used. Each vessel
contains an aqueous solution of ions, a molten salt, or a solid such as Zinc (II) nitrate
and copper (II) nitrate, which are electro active in nature.
For example- Daniell cell is a galvanic cell in which zinc and copper are used for a
redox reaction to take place.
Zn(s) + Cu+2(aq) → Zn+2 + Cu(s)
At anode (oxidation half)
Zn(s) →Zn+2 + 2e–
At cathode( reduction half)
Cu+2(aq) + 2e– → Cu(s)
Salt bridge: Salt bridge is a U-shaped tube that contains a concentrated aqueous salt
solution or a molten solid, such as potassium chloride or potassium nitrate, contain in
gels. The salt bridge keeps the flow of the electrons going throughout the Daniell Cell,
such as the net charge for each compartment is zero. The electrochemical setup is
attached to an electronic volumeter the charge in potential
Notation for the electrode can be written as
Anode: Zn(s) / Zn^2+ (aq)
Cathode: Cu^2+ / Cu (s)
Notation for overall redox equation: Zn(s) // Zn^2+ (aq) / Cu (s)
The notation, which describes the arrangement of electrodes in galvanic cell, is called
cell diagram. Notice that the notation includes vertical line; this indicates the boundary
between the metal electrode and the electrolyte solution. Typically, if it is used in the
anode, the metal is written first; if it is used as a cathode in the cell, it is written last.
Double vertical lines indicate the salt bridge. Also, if the electro active components (both
oxidized and reduce) exists in the same phase (e.g., Ce^4+ (aq), Ce^3+ (aq) / Pt),
wherein both Ce^4+ and Ce^3+ are ions in the solution, then coma separates the two
elements instead of using a single vertical line.
The Cell Potential
The transfer of electrons in a redox process is always accompanied with energy
release. These electrons need to be pulled, such as they flow all the way to the cathode
to produce a reduction reaction. The extent of such drive and pull requires energy, and
its magnitude is measured by its voltage is also called electromotive force, or simply
EMF.
The SI unit for cell potential is volt (V) and is equivalent to the release of one joule (J) of
energy when one coulomb (C) of charge travels between electrodes. Mathematically,
1 V = 1 J/C
For a Daniell Cell, the overall redox equation is Zn(s) + Cu^2+ (aq)  Zn^2+ (aq) +
Cu(s), from which the respective oxidation and reduction half-reactions can be derived:
Zn(s) →Zn+2 + 2e–
 Cu+2(aq) + 2e– → Cu(s)

For each half-reaction, a standard cell potential (Eo) is measured at the standard phase
of each element. If ion concentration in solution is 1mol/L, then the ion in solution is said
to be in its standard state. The standard electrode potential of a cell is obtained from the
sum of the standard potential (cathode) and the standard electrode potential (anode).

Cell potential or emf of a cell: In the galvanic cell there are two half cell, the oxidation
half-cell( anode) and the reduction half -cell( cathode).Due to the difference in the
potentials of these half-cells, the electric current moves from the electrode of higher
potential (cathode) to the electrode of lower potential( anode). The difference between
the electrode potential of the two half cell is called cell potential or emf of a cell.

Eocell= ECathode– Eanode

ECathode= standard reduction potential of the cathode.

Eanode= standard reduction potential of the anode.

If Eocell is positive then the reaction is feasible.

If Eocell is negative then the reaction is not feasible.

The Eo for each redox couple is determined by comparing its potential to a reference
couple.

Spontaneity of Redox Reactions: Thermodynamics Versus Electrochemistry

A galvanic cell gives a positive potential, which implies that the reaction is spontaneous.
This means that the electrons are driven from the anode to the cathode through a salt
bridge. If the Gibbs free energy is large and negative, then a large cell potential (E) is
generated. This indicates that the chemical reaction is spontaneous in releasing
electrons, therefore yielding electric current. If the Gibbs free energy is small and
negative, the cell potential would also be small. This gives to

ΔG ∝ -E

The negative sign indicates that the work is done by the system. Specifically , for n
number of electrons released from the anode to the cathode multiplied by the Faraday’s
constant, which reflects the magnitude of the charge per mole of electrons, the previous
relationship can be written as

ΔG= -nFE

Where F is the Faraday’s constant equal to 9.6485 x 10^4 C/mol e–, E is the cell
potential, and ΔG is the Gibbs free energy. Thus, for a Daniell cell,
 ΔG = - (2 mol e–) (9.6485x10^4 C/mol e–)(1.10 J/C)

ΔG = -2.12 x 20^5 J = -212 J

The Nerst Equation: Effect of Concentration on Electrode Potential

The cell potential depends on concentration and pressure. The Nerst equation is named
after German chemist Walther Hermann Nerst (1864-1941).

E = Eo – (RT/nF) In Q

Alternatively, at 298K (25 o)

E = Eo –(0.0591/n) In Q

Determining the Equilibrium Constant

The equilibrium constant of any reaction can also be determined using the standard
reduction potential.

-nFE o = -RT In K

Which can be rearrange to form

In K = nFE o / RT
Elements reduction reaction
 BUFFER AND SOLUBILITY EQUILIBRIA

A buffer is an aqueous solution containing a weak acid and its conjugate base or a
weak base and its conjugate acid. A buffer’s pH changes very little when a small
amount of strong acid or base is added to it. It is used to prevent any change in the pH
of a solution, regardless of solute. Buffer solutions are used as a means of keeping pH
at a nearly constant value in a wide variety of chemical applications. For example, blood
in the human body is a buffer solution.

Buffer solutions are necessary in a wide range of applications. In biology, they are
necessary for keeping the correct pH for proteins to work; if the pH moves outside of a
narrow range, the proteins stop working and can fall apart. A buffer of carbonic acid
(H2CO3) and bicarbonate (HCO3−) is needed in blood plasma to maintain a pH between
7.35 and 7.45. Industrially, buffer solutions are used in fermentation processes and in
setting the correct conditions for dyes used in colouring fabrics.

Example:

Suppose you plan on preparing a solution that is buffered to a pH level of 5 using acetic
acid (Ka = 1.8 x 10^-5) and the sodium acetate buffer system. What mass of sodium
acetate must be dissolved to 250 mL of 0.250 M acetic acid?

Solution:

The equilibrium reactions are

NaC2H2O2  Na^+ (aq) + C2H202^- (aq)

HC2H2O2  H3O^+ (aq) + C2H203^- (aq)

Acetic acid is a weak acid; therefore, it partially dissociates to give H30^+ and
C2H2O3^- , whereas sodium acetate is completely dissociated into Na^+ (aq) and
C2H2o3^- (aq)

At equilibrium

NaC2H2O2  Na^+ (aq) + C2H202^- (aq)

x x x

At start, 0.250 M - -

At equilibrium

0.250 – x x x
Because the pH level of the solution is 5, then the (H3O^+) concentration is equal to
1.00 x 10^-5 M. As shown previously, the acetate ion has two sources; therefore, its
concentration can be represented as 2x. The equilibrium equation can be written as

Ka = (H3O+)(C2H3O2-) / (HC2H3O2)

Substituting the equation, you have

Ka = (1.00 x 10-5 M)(2x) / (0.250 M – x )

x = 0.225 M

2x = 0.450 M = (C2H2O2-)

The mass of sodium acetate that must be dissolved is

g = (M) formula mass (NaC2H2O2) (volume of solution)

= (0.450 mol/L)(82 g/mol)(0.250 L)

g = 9.2 g

CALCULATING THE CHANGE IN pH when OH ION IS ADDED TO A BUFFER

SOLUTION

Example Problem:

The 100- ml buffers are 0.15 M HC 2H2O2 (aq) and 0.15 M NaC2H2O2 (aq). The Ka for
HC2H2O2 (aq) is 1.8 x 10^-5. Suppose 10.0 mL of 0.80 M NaOH (aq) was added to the
acetic acid-buffer solution. What is the resulting pH level of the solution and the level of
pH change from the said solution?

Solution:

The equilibrium reaction is

OH-(aq) + HC2H3O2 (aq)  C2H2O2-(aq) + H2O

The molarity of the OH- ion is 0.0073 M. The initial concentrations of HC 2H2O2 (aq) and
C2H2O2-(aq) are

(0.15 mol/L)(0.100 L) / 0.110 L = 0.14 M

Because this amount reacted with HC 2H3O2 (aq) 0.073 M must also be deducted from the
initial amount of HC2H3O2 (aq) to yield 0.063 M. The reaction produces C 2H2O2-(aq) ;
therefore, the equilibrium concentration of C 2H2O2-(aq) is obtained by adding 0.073 M to
its initial concentration of 0.14 M, which gives 0.21 M.
 pH = 4.74 + log (0.21/0.063)

= 4.74 + 0.52

pH = 5.26

ΔpH = 0.52

Predicting the Solubility of Salts: The Solubility Equilibria

The solubility of salts refers to the maximum amount of salt that can be dissolved in a
given solvent.

The solubility product constant is an equilibrium constant; therefore, it has only one
value for a particular solid at a given temperature.

Example:

Supposed Ka of ferrous hydroxide is 1.6 x 10 -14 mol/L. What is its molar solubility? What
is the mass of the salt that can dissolve in 500 Ml of water at 298 K (25* C)?

Solution:

The Equilibrium reaction is

Fe(OH)2  Fe2+(aq) + 2OH-(aq)

FeCl2(aq)  Fe2+(aq) + 2Cl-(aq)

Fe2+ is present in both the solid and the solution; hence, it is a common ion.

Concentration table of Fe2+ and OH-

CONCENTRATION Fe2+ OH-

Initial Concentration - -

Change in concentration x 2x

Equilibrium concentration x 2x

1.6 x 10-14 = (x)(2x)

x = 1.6 x 10-5 M
Now calculate the mass of Fe(OH)2 in grams.

Mass of Fe(OH)2 = (1.6 x 10-5 M Fe(OH)2 ) (89.95 g/mol Fe(OH)2)(0.50L)

= 7.2 x 10-4 grams or 0.72 milligrams

The Solubility of a Solid as Influenced by the Common Ion Effect

A precipitate is usually formed if the ion product, Q, is greater than K sp. In the case of
precipitation of Fe(OH)2, Q can be expressed as Q = (Fe2+)(OH-)2.

This equilibrium expression could change due to the factors such as the presence of a
common ion in the solution further reduces the solubility of the solid.

Example:

Suppose that ferrous hydroxide (Fe(OH)2 ) is prepared in a 1.04 x 10 -4 M ferrous

chloride (FeCl2) solution. What is its molar solubility?

Fe(OH)2  Fe2+(aq) + 2OH-(aq)

FeCl2(aq)  Fe2+(aq) + 2Cl-(aq)

Fe2+ is present in both the solid and the solution; hence, it is a common ion.

Concentration table of Fe2+ and OH-

CONCENTRATION Fe2+ OH-

Initial Concentration - -

Change in concentration x 2x

Equilibrium concentration 1 x 10-4 M + x 2x

1.6 x 10-14 = (1 x 10-4 M + x)( 2x)2

To simplify the equation, x may be dropped from (1 x 10 -4 M + x) because the initial

concentration of the salt would be larger than the increase in the ion concentration when
Fe(OH)2 dissolves. The resulting molar solubility of Fe(OH) 2 when dissolved in FeCl2
solution is 6.3 x 10-6 M when salt was dissolved in water.

Selective Separation of Ions via Precipitation

To bring about a successful precipitation reaction, higher concentration of the individual
solutions containing the cation and the anion of the slightly soluble salt are used.
Consider the reaction that occurs between potassium chromate and aqueous silver
chromate. The overall precipitation reaction is

K2CrO4(s) + 2AgNO3  Ag2Cro4(aq) + 2KNO3(aq)

While the net ionic reaction is

Ag2Cro4(aq)  2Ag+(aq) + CrO4-(s) (Ksp = 9.0 x 10-12 M)

Therefore, the equilibrium expression is

Ksp = (Ag+)2(CrO4-)

Ksp is a useful parameter in designing a selective precipitation scheme for performing

qualitative analysis on mixture of metal ions. For qualitative purposes, the solubility
quotient Q for each solid equilibrium is determined based on the K sp of the solid. For
example, for silver chromate,

Solubility quotient, Q = (Ag+)2(CrO4-)

As previously discussed, Q allows us to predict whether a precipitate is formed, a solid

is dissolved, or If the and its ions are in equilibrium. The following are the criteria in
deciding whether the precipitation reaction will proceed or not:

Criteria for determining if precipitation will occur

Condition Meaning

Q < Ksp The equilibrium shifts to the right; product formation is formed; no
precipitation occurs.

Q > Ksp The equilibrium shifts to the left; reverse reaction is favoured toward
reactants; precipitation is successful.

Q = Ksp The system is at equilibrium; therefore, there is no shift in the

direction of the equilibrium position. The solution is saturated.
Quantitative Analysis employs the concept of selective precipitation in isolating, one
by one, the cations or anions present in the mixture. The ions are classified into five
major groups based on their solubility in a given medium:

 Group 1 is composed of insoluble chlorides containing Silver, Lead, and Mercury.

For precipitation to occur, a dilute aqueous hydrochloric acid is added to yield
AgCl, PlCl2, Hg2Cl2.

 Group 2 is composed of the most insoluble sulfides, containing bismuth, tin,

cadmium, copper, and Hg2+. In this group, a very low concentration of sulphide is
present due to the presence of H+ ions.

 Group 3 members are mainly sulfides containing cobalt, zinc, manganese, nickel,
chromium, and aluminium, which only soluble in basic solutions. Aqueous
sodium hydroxide and more hydroxide sulphide are added for precipitation to
occur. However, Cr3+ and Al3+ ions are precipitated in the form of insoluble
hydroxides.

 Group 4 is composed of barium, calcium, and magnesium, which form insoluble

carbonates upon the addition of dilute aqueous sodium carbonate.

 Group 5 refers to alkali metals (such as Na + and potassium and ammonium) ions;
they form soluble salts and thus remain in the solution.
 TRANSFER OF LEARNING FOR ELECTROCHEMISTRY

Example Solved Problem.

In an electrolysis experiment, a current was passed for 5 hours through two cells
connected in series. The first cell contains a solution gold salt and the second cell
contains copper sulphate solution. 9.85 g of gold was deposited in the first cell. If the
oxidation number of gold is +3, find the amount of copper deposited on the cathode in
the second cell. Also calculate 
the magnitude of the current in ampere. 

Solution:

We know that 
(Mass of Au deposited)/(Mass f Cu deposited)=(Eq.mass of Au)/(Eq.Mass of Cu) 
Eq. mass of Au = 197/3;
Eq. mass of Cu 63.5/2 
Mass of copper deposited   = 9.85 × 63.5/2 x 3/197 g = 4.7625 g 
Let Z be the electrochemical equivalent of Cu. 
E = Z × 96500 
or Z =E/96500=63.5/(2×96500) 
Applying W = Z × I × t 
T = 5 hour = 5 × 3600 second 
4.7625 = 63.5/(2×96500) × I × 5 × 3600 
or I = (4.7625 × 2 × 96500)/(63.5 × 5 × 3600)=0.0804 ampere 
 TRANSFER OF LEARNING FOR BUFFER AND SOLUBILITY EQUILIBRIA

Example Solved Problem.

 What [CrO42–] must be present in 0.00105 M AgNO 3(aq) to just cause Ag 2CrO4(s) to
precipitate?

Solution:

AgNO3(s)→Ag+(aq)+NO3–(aq)

Ag2CrO4(s)→ ←2 Ag+(aq)+CrO42–(aq)

Ksp = [Ag+]e2[CrO42–]e = 1.1×10–12

Initial0.001050

Change+0+x

Equilibrium0.00105x

(Note: the silver ion only arises from the silver nitrate; none comes from silver chromate
because no silver chromate was introduced by the experiment.)

1.1×10–12 = [0.00105]2[x]

x = 1.0×10–6 M = the concentration of chromate required to just start precipitation.