Electrochemical cell

Electrochemical cell is a device that converts chemical energy into electrical energy when a
chemical reaction is occurring in the cell or vice versa. Based on the activity taking place in
them, these devices are classified into two categories

1. Electrolytic cells

2. Galvanic (Voltaic cells) These are further divided into

 Chemical cells
 Concentration cells
Electrolytic cell is an electrochemical cell that converts electrical energy into chemical energy.
The chemical reactions do not occur spontaneously at the electrodes when they are connected
through an external circuit. The reaction must be forced by applying an external electric
current. It is used to decompose or produce (synthesize) new chemicals by the application of
electrical power. This process is called electrolysis, e.g., water can be decomposed into
hydrogen gas and oxygen gas.
A DC electrical power source is connected to two electrodes, or two plates
(typically made from an inert metal such as platinum or iridium) which are
placed in the water.
Hydrogen will appear at the cathode (where electrons enter the water), and
oxygen will appear at the anode.
The amount of hydrogen generated is twice the amount of oxygen, and both
are proportional to the total electrical charge conducted by the solution.

Overall reaction: 2 H2O(l) → 2 H2(g) + O2(g)

Galvanic cells: Such cells capable of generating an electric current from the chemical reactions
occurring in them are called Galvanic cells or Voltaic cells.

Galvanic cell consists of two electrodes or two half-cells, combined in such a way that when
they are connected externally by a wire, an electric current flows through the wire.

Each electrode or half-cell consists of an electronic conductor (metals) in contact with an

electrolytic conductor (electrolytic solutions). At the point of contact of the two conductors, a
potential difference arises and this is known as the electrode potential or half-cell potential.
When the two electrodes are connected externally, a spontaneous reaction takes place at each of
the two electrodes.
Oxidation reaction occurs at one of the electrodes.
Hence, electrons are released at this electrode and it
becomes the negative terminal of the cell.
Reduction reaction occurs at the other electrode. Hence,
electrons are used up and there is a deficiency at this
electrode. This electrode becomes the positive terminal.
Now, if these two electrodes are connected externally,
there will be a flow of electrons from the electron
excess point towards the deficient point. Hence, electric
current will flow in the opposite direction.

It is to be noted that both oxidation and reduction processes must occur simultaneously. for a
continuous flow of electric current. The net reaction is a redox reaction.

Redox reactions
DIRECT REDOX REACTIONS: The chemical reaction where oxidation as well as reduction takes place
simultaneously in a same container is called direct redox.

INDIRECT REDOX REACTIONS: The redox reaction in which oxidation and reduction takes place in two
separate containers are called indirect redox reaction.
Electrode Potential
Standard electrode potential is defined as the measures the individual potential of reversible
electrode at standard state with ions at an effective concentration of 1mol dm-3 at the pressure of
1 atm.

Standard Electrode Potential Definition

Under standard conditions, the standard electrode potential occurs in an electrochemical cell say the temperature =
298K, pressure = 1atm, concentration = 1M. The symbol ‘Eocell’ represents the standard electrode potential of a cell.

Standard Electrode Potential Example

The calculation of the standard electrode potential of a zinc electrode with the help of the standard hydrogen
electrode is illustrated below.
It can be noted that this potential is measured under standard conditions where the temperature is 298K, the
pressure is 1 atm, and the concentration of the electrolytes is 1M.

Electrochemical Cells (in details)

 Oxidation-reduction or redox reactions take place in electrochemical cells.

 There are two types of electrochemical cells (Galvanic and Electrolytic Cells)

 In both galvanic and electrolytic cells, oxidation takes place at the anode and electrons
flow from the anode to the cathode.

 The anode of an electrolytic cell is positive (cathode is negative).

However, the anode of a galvanic cell is negatively charged.

Electrolytic Cells
The redox reaction in an electrolytic cell is nonspontaneous. Electrical energy is required to
induce the electrolysis reaction. An example of an electrolytic cell is shown below, in which
molten NaCl is electrolyzed to form liquid sodium and chlorine gas. The sodium ions migrate
toward the cathode, where they are reduced to sodium metal. Similarly, chloride ions migrate to
the anode and are oxidized to form chlorine gas. This type of cell is used to produce sodium and
chlorine. The chlorine gas can be collected surrounding the cell. The sodium metal is less dense
than the molten salt and is removed as it floats to the top of the reaction container.
Galvanic or Voltaic Cells
The redox reaction in a galvanic cell is a spontaneous reaction. For this reason, galvanic cells
are commonly used as batteries. Galvanic cell reactions supply energy which is used to perform
work. A galvanic cell consists of two electrodes immersed in solution of their respective salts.
When the two electrodes are connected externally, a redox reaction occurs in which one of the
electrodes undergo oxidation while other undergoes reduction.
A common galvanic cell is the Daniell cell, shown below.

Construction and working of Daniel cell

By definition:
The anode is the electrode where oxidation (loss of electrons) takes place; in a galvanic
cell, it is the negative electrode, as when oxidation occurs, electrons are left behind on the
electrode. These electrons then migrate to the cathode (positive electrode).
Salt Bridge
If the electrodes in a galvanic cell are not connected internally, initially the cell generates
electrical energy, the electrodes get polarized with the passage of time and the cell stops
working. For continuous generation of electrical energy, the electrodes need to be internally
connected. A salt bridge is usually used to connect the electrodes of a galvanic cell. It consists
of a gel drawn into a clean U-tube. The gel is formed by adding agar-agar into boiling water
containing a suitable electrolyte like KCl. Generally KCl is preferred because the ionic
conductance of K+ and Cl- are almost same. The gel holds the electrolyte in the tube as shown in
the figure below. As the reaction proceeds in the galvanic cell, there will be accumulation of
particular ions around the electrodes. This results in slowdown of the electrode reactions. From
the electrolyte of the salt bridge, say KCl , the K+ and Cl – ions migrates towards the end of the
salt bridge. K+ ions would migrate towards the reduction electrode (cathode) while Cl- would
migrate towards the oxidation electrode (anode).
At the oxidation electrode (anode, ions would polarize (attract) some of the oppositely charged
ions towards themselves. Simultaneously, the K+ ions would move the reduction electrode
(cathode) and polarize the negatively charged ions surrounding the metal. Thus, the cell works
as usual.

Faraday constant
The Faraday constant represents the amount of electric charge carried by one mole, or
Avogadro's number, of electrons.

It is commonly symbolized by the italic uppercase letter F.

It is expressed in coulombs per mole (C/mol).

Faraday's constant can be derived by dividing the Avogadro constant, or the number of
electrons per mole, by the number of electrons per coulomb. The former is equal to
approximately 6.02 x 10 23, and the latter is approximately 6.24 x 10 18.

Therefore:
number of electrons per mole
F=
number of electrons per coulomb

F = (6.02 x 10 23 ) / (6.24 x 10 18 )

= 9.65 x 10 4 C/mol = 96500 C/mol ( coulombs per mole)

Electrochemical Cells: Notations and Sign Convention

An electrochemical cell may be prepared by combining any two half-cells. Such cells and half-cells are
conveniently described by an abbreviated notation together with appropriate conventions so that the convention
will correspond to the chemical reaction taking place in the cell. Moreover, the conventions used for the cells
must be compatible with other thermodynamic conventions. The following notations are used by convention for
describing cells and half-cells:

(1) The half-cells written in the sequence electrode│electrolyte represents oxidation and if the sequence is
electrolyte│electrode, it means reduction. Examples are:

Note that gas electrodes or oxidation-reduction electrodes have an inert metal (platinum) as the electron
carrying medium.

(2) A complete cell is written such that the left hand side represents the oxidation reaction half-cell (anode) and
the right hand side represents the reduction half-reaction half-cell (cathode) cell as shown below:

Zn (s)│ZnSO4 (aq)│CuSO4 (aq)│Cu (s)

The vertical line in the middle means that the two solutions are in direct contact. If, however, contact between
the two solutions is made through a salt bridge two vertical lines are placed between the two electrolytes as
shown below:

Zn (s)│ZnSO4 (aq)││CuSO4 (aq)│Cu (s)

These are also written simply as-

Zn (s)│Zn2+ (aq)││Cu2+ (aq)│Cu (s)

(3) Oxidation and reduction potential values of an electrode are numerically the same, with opposite signs.

(4) The electrode where electron is released, i.e., oxidation takes place is written on the left side and is the
anode and the cathode is written on the right side. An e.m.f. will be called positive if there is a tendency for
electrons to be driven through the external circuit from left to right. If the cell is written such that reduction is
taking place at the left hand electrode, the e.m.f. of the cell will be negative.

(5) For calculating the cell potential always reduction potential is used along with the relation.

(6) If the e.m.f of the cell has a positive value the cell reaction is spontaneous, i.e., if the cell works in such a
way that electron is released at the left electrode and is driven through the external circuit from left to right the
cell reaction will be spontaneous.

(7) Emf of a cell is represented as

Ecell = ER -EL

Where ER and EL are the reduction potentials of RHS and LHS electrodes respectively.

Nernst Equation
The relation between the actual cell potential E and the standard potential E° is developed in the
following way. We begin with the equation which relates the standard free energy change (for
the complete conversion of products into reactants) to the standard potential

ΔG ° = –nFE°

By analogy we can write the more general equation

ΔG = –nFE

which expresses the change in free energy for any extent of reaction— that is, for any value of
the reaction quotient Q. We now substitute these into the expression that relates ΔG and ΔG°
which you will recall from the chapter on chemical equilibrium:

ΔG = ΔG° + RT ln Q

𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑎
Q= 𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑜𝑟 Q= 𝑎 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

In dilute solution, activities are replaced by molar concentration terms.

which gives

–nFE = –nFE° + RT ln Q

which can be rearranged to

 (1)

This is the very important Nernst equation which relates the cell potential to the standard potential and to the
activities of the electroactive species. Notice that the cell potential will be the same as E° only if Q is unity. The
Nernst equation is more commonly written in base-10 log form and for 25°C:

(2)

Nerst equation can be applied to any cell reaction such as

aA + bB  cC + dD

0.0591 [𝐶]𝑐 [𝐷]𝑑

Ecell = E ocell - log
𝑛 [𝐴]𝑎 [𝐵]𝑏

The Nernst Equation is especially used in electrochemistry to determine the equilibrium reduction potential
for the half cell reaction in electrochemical cell.

The voltage and concentration of an electrochemical cell is also determined by the Nernst Equation.

The Nernst Equation is represented as

Ecell = E0cell - (RT/nF) lnQ

Where

 Ecell = potential of cell in nonstandard conditions in volt,

 E0cell = potential of cell in standard conditions,
 R is the gas constant which is equal to 8.31 (volt-coulomb)/ (mol-K),
 T is the temperature in Kelvin, n stands for number of moles of electrons which get exchanged in the
electrochemical reaction,
 F is Faraday's constant which equals to 96500 coulombs/mol, and Q is the reaction quotient which stands for
equilibrium expression.

The Nernst equation can also be expressed in the different form which is show below.

Ecell = E0cell - (2.303 x RT/nF) logQ