ELECTROCHEMICAL EQUILIBRIUM

Electrochemical is a chemistry that studies electrical energy and chemical reactions, namely:
 chemical reactions caused by electrical energy
 chemical reactions that produce electrical energy
 Electrochemical cells are a device that can make the interaction of chemical energy
with electrical energy.

The various electrochemical cells are as follows:

 Two electrodes or metal conductors in contact with electrolytes
 Electrolytes or ionic conductors (solutions or liquids)

Electrodes and electrolytes are transformed by forming electrode compartments. Both

electrodes can use the same compartment. If the electrolyte is different, the two
compartments can be connected via a salt bridge which is a U-shaped tube containing
concentrated electrolyte solution such as potassium chloride in jelly so that it completes a
series of electrical devices and that allows the cell to perform its function.

There are 2 types of electrochemical cells, namely:

1. Galvanic cells:
An electrochemical cell that can produce electric current as a result of spontaneous
reactions that occur in it. Or from the technical understanding that changes in chemical
energy into electricity.
2. Electrolytic cells:
An electrochemical cell where a reaction that is not spontaneous is carried out by an
external electric current. Or from the technical understanding is from electrical energy to
chemical energy.

( Source : Petrucci,et
al, 2007 )
Figure 1. Electrochemical Cells. A galvanic cell (left) transforms the energy released by a
spontaneous redox reaction into electrical energy that can be used to perform work. The
oxidative and reductive half-reactions usually occur in separate compartments that are
connected by an external electrical circuit; in addition, a second connection that allows
ions to flow between the compartments (shown here as a vertical dashed line to
represent a porous barrier) is necessary to maintain electrical neutrality. The potential
difference between the electrodes (voltage) causes electrons to flow from the reductant
to the oxidant through the external circuit, generating an electric current. In an
electrolytic cell (right), an external source of electrical energy is used to generate a
potential difference between the electrodes that forces electrons to flow, driving a
nonspontaneous redox reaction; only a single compartment is employed in most
applications. In both kinds of electrochemical cells, the anode is the electrode at which
the oxidation half-reaction occurs, and the cathode is the electrode at which the
reduction half-reaction occurs.

Electrochemical Cells

(source:http://www.libretextchemistry/electrochemicalcell
-voltaic-cell)
Figure 2. A voltaic cell.

A device that uses a chemical reaction to produce or use electricity is

an electrochemical cell, also known as a voltaic cell. Because the liquid state allows reactions
to occur more readily than in either solids or gases, most electrochemical cells are built using
a liquid called an electrolyte, a solution that contains ions and conducts electricity. This word
has previously been mentioned with regard to ionic dissociation. Pure, distilled water is a
very poor conductor of electricity, but a high concentration of dissolved ions leads to high
conductivity. That is why acids, bases, and salts that ionize to a high degree are referred to as
strong electrolytes, while those that ionize only slightly are referred to as weak electrolytes.

A simple electrochemical cell can be made from two test tubes connected with a third
tube (the crossbar of the “H”), as shown in Figure 2. The hollow apparatus is filled by
simultaneously pouring different solutions into the two test tubes, an aqueous solution of zinc
sulfate into the left tube and a copper (II) sulfate solution into the one on the right. Then a
strip of zinc metal is dipped into the ZnSO4 solution; a piece of copper is inserted into the
CuSO4 solution; and the two ends of the metal strips are connected by wires to a voltmeter.
The lateral connecting tube allows ionic migration necessary for a closed electrical circuit.
The voltmeter will show the electrical potential of 1.10 volts, which leads to the movement of
electrons in the wire from the zinc electrode toward the copper electrode.
 The electric current is caused by a pair of redox reactions. At the zinc electrode, the
metallic zinc is slowly being ionized by an oxidation reaction:

Zn (s) Zn2+ (aq) + 2e-

Metal Ion electron

An electrode at which oxidation occurs is called an anode; it strongly attracts negative ions
in the solution, and such ions are consequently called anions.

Simultaneously, a reduction reaction at the copper cathode causes Cu 2+ cations to be

deposited onto the electrode as copper metal:

Cu2+ (aq) + 2e- Cu (s)

Ion electron Metal

Because negatively charged electrons are flowing from the anode to the cathode, the anode
becomes the positive electrode. The cathode is, therefore, the negative electrode.

Adding the reactions at the two electrodes gives

Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)

which is the overall redox reaction in the zinc‐copper cell.

Faraday’s Laws

Chemists throughout the nineteenth century discovered new elements from the
electrolytic decomposition of many compounds.

The quantitative laws of electrochemistry were discovered by Michael Faraday of

England. His 1834 paper on electrolysis introduced many of the terms that you have seen
throughout this book, including ion, cation, anion, electrode, cathode, anode, and electrolyte.
He found that the mass of a substance produced by a redox reaction at an electrode is
proportional to the quantity of electrical charge that has passed through the electrochemical
cell. For elements with different oxidation numbers, the same quantity of electricity produces
fewer moles of the element with the higher oxidation number.

The basic unit of electrical charge used by chemists is appropriately called a faraday,
which is defined as the charge on one mole of electrons (6 × 10 23 electrons). Incidentally,
note that chemists have extended the original definition of the mole as a unit of mass to a
corresponding number (Avogadro's number) of particles. Use the electrolysis of molten
sodium chloride to see the relationship between faradays of electricity and moles of
decomposition products.
Faraday first law stated that “the mass of the substance produced at an electrode
during electrolysis (G) is directly proportional to the amount of electric charge used (Q)”
Mathematically first law of Faraday can written as G ~ Q
As the amount of electric charge (Q) is equal to the product of the electric current (i) with the
time interval (t),
Q=i×t
G~i×t
the mass of the substance produced during electrolysis (G) is also directly proportional to the
current strength (i) and time interval (t). Electric charge (Q) used in electrolysis is directly
proportional to the number of moles of electrons involved in redox (ne) reactions.
Experimentally it was found that 1 mole of electrons has an electric charge of 96,500
coulombs. The value of the electron's electric charge is specified as the Faraday constant (F).
So, this relationship can be formulated as follows.
Q = ne × F
Faraday second law stated that "The mass of the substance produced at an electrode
during electrolysis (G) is directly proportional to the equivalent mass of the substance
(Meq)."
Mathematically second law of Faraday can written as G ~ Meq
The equivalent mass of a substance is the mass of a substance with an equivalent number of
moles stoichiometry with 1 mole of electrons. The equivalent mass of an element is equal to
the relative atomic mass (Ar) of the element divided by the change in oxidation number
(oxidation) experienced in an electrolysis reaction.
the above equation will be obtained which is a combination of the two Faraday laws, where:

Based on basic stoichiometry concept regarding the relationship of mass (m), number of
moles (n) and molar mass (}) as follows :
m=nx}
G = ne x Mel
G= Q/F x Meq

The combination of both law will obtain :

G ~ i x t x Meq , where
G = mass of substance produced (gram)
Q = electric charge (coulomb)
i = strong electric current (ampere)
t = time (second)
Meq = equivalent mass of substance (gram / mole)
F = Faraday constant (96,500 coulomb / mole)
Therefore, if given the same amount of electric charge, the mass ratio of the
substances produced will be the same as the equivalent mass ratio of each.
 GA : GB = MeqA : MeqB
Systematically, the relationship between the amount of electricity supplied with the mass of
substance produced in electrolysis can bee seen in the following scheme :

The electrochemical cell with zinc and copper electrodes had an overall potential
difference that was positive (+1.10 volts), so the spontaneous chemical reactions produced an
electric current. Such a cell is called a voltaic cell. In contrast, electrolytic cells use an
externally generated electrical current to produce a chemical reaction that would not
otherwise take place.
An instance of such electrolysis is the decomposition of water to elemental hydrogen and
oxygen. The pertinent half‐reactions are given in Table 1.

The overall reaction for the electrolysis of water is given by adding the two half‐reactions to
obtain 2H2O (l) 2H2 (g) + O2 (g)

with an overall potential of –1.23 volts. With a negative potential, it requires an externally
imposed electrical current to decompose water by the reaction shown. Figure 3 shows two
platinum electrodes in water containing a little salt or acid so that the solution can conduct
electricity.
 (source:http://www.libretextchemistry/electrochem
icalcell-electrolysis-of-water)
Figure 3.The electrolys of water

The reduction at the cathode yields H2 gas, and the oxidation at the anode yields
O2 gas. Notice that the figure shows that the volume of hydrogen is twice the volume of
oxygen—look at the bubbles. The molar coefficients in the decomposition reaction imply 2
volumes of H2 gas for each 1 volume of O2 gas.

Electrolysis is used to decompose many compounds into their constituent elements. You have
seen this process with water. Another example is the electrolysis of molten sodium chloride to
yield molten sodium metal and chlorine gas: 2NaCl (l) 2Na (l) + Cl2 (g)

The reduction half‐reaction is

Na+ (l) + e- Na (l)

so to produce 1 mole of sodium metal requires 1 mole of electrons, so 1 faraday of charge

must pass through the cell.

The oxidation half‐reaction is

2Cl- (l) Cl2 (g) + 2e-

and to produce 1 mole of chlorine gas, 2 faradays of electric charge must pass through the
apparatus. Notice how the number of electrons in redox reactions determines the quantity of
electricity needed for the reaction.

These half‐reactions sum to the overall reaction in the electrolytic cell:

2Na+ (l) + 2Cl- (l) 2Na (l) + Cl2 (g)

The passage of 2 faradays of charge yields 2 moles of sodium metal and 1 mole of chlorine
gas.

The first of Faraday's laws states that the mass of substance produced is proportional to the
quantity of electricity. To apply this law to the NaCl example, where 1 mole of Cl 2 was
produced by 2 faradays, means that to produce 10 moles of Cl 2 requires the passage of 20
faradays through the apparatus.
The second of Faraday's laws states that a given quantity of electricity produces fewer moles
of substances with higher oxidation numbers. Compare the reduction of sodium and calcium
ions:

Na+ + e- Na (1 mole of electron)

Ca2+ + 2e- Ca (2 mole of electron)

It requires twice as much electricity to produce 1 mole of calcium metal as 1 mole of sodium
metal.

The electrolytic decomposition of sodium chloride and calcium oxide appear similar:

2NaCl (l) 2Na (l) + Cl2 (g)

2CaO (l) 2Ca (l) + O2 (g)

but the NaCl decomposition requires the transfer of only half as many electrons as does the
CaO decomposition. For the NaCl electrolysis, it was previously calculated that the passage
of 20 faradays of electric charge produced 20 moles of sodium metal and 10 moles of
chlorine gas. The same amount of electric charge passing through the CaO cell yields only 10
moles of calcium metal and 5 moles of oxygen gas.

The reduction half‐reaction with balanced coefficients:

Ca2+ + 2e- Ca (l)
The oxidation half‐reaction with balanced coefficients:
2O2- (l) O2 (g) + 2e-

Example :
1. How many gram of calcium that could produced from electrolysis of melted CaCl2
with graphite electrode in an hour if the elecricity flow that we used is 10 A ? (Ar Ca
= 40)
Answer :
Mass of Ca that produced can calculated by formula :

Known that i = 10 A and 1 hour = 3600 s, the half reaction of calcium reduction in
electrolysis : Ca2+ + 2e- Ca, so :

So we got that :