Galvanic Cells

Galvanic Cells

Shivani PooniaUpdated on 02 Jul 2025, 06:18 PM IST

The galvanic cell, also known as the Voltaic pile, consists of alternating layers of zinc and copper discs separated by pieces of paper soaked in saltwater. And it converts free energy into a chemical cell into an electrical cell. Volta’s discovery was driven by his interest in understanding the nature of electricity. Volta's galvanic cell was the first device capable of providing a steady electrical current.

This Story also Contains

  1. Galvanic Cells
  2. Some Solved Examples
  3. Summary
Galvanic Cells
Galvanic Cells

Galvanic Cells

It is the device in which the decrease of free energy during the indirect redox reaction is made to convert chemical energy into electrical energy. Luigi Galvani and Alessandro Volta developed such devices therefore these cells are also known as Galvanic cells Voltaic cells or Redox cells.

Species having a greater tendency to get oxidized (greater oxidation potential value ) is selected as the anode while species having a greater tendency of getting reduced (greater reduction potential value) is selected as a cathode.

FeatureCathodeAnode
SignPositive due to
consumption of
electrons

Negative due
to release of
electrons

ReactionReductionOxidation
Movement of electronsInto the cellOut of cell


Galvanic Cell

image-3

  • The Daniel cell is a typical galvanic cell. It is designed to make use of the spontaneous redox reaction between zinc and cupric ions to produce an electric current.
  • The Daniel cell can be conventionally represented as $\underset{\text { Saltbridge }}{\mathrm{Zn}(\mathrm{s})\left|\mathrm{ZnSO}_4(\mathrm{aq})\right|\left|\mathrm{CuSO}_4(\mathrm{aq})\right| \mathrm{Cu}(\mathrm{s})}$ Zn(s)|ZnSO4(aq)||CuSO4(aq)|Cu(s) Saltbridge
  • The Daniel cell reaction is represented as: $\mathrm{Zn}(\mathrm{s})+\mathrm{Cu}^{2+}(\mathrm{aq}) \rightarrow \mathrm{Zn}^{2+}(\mathrm{aq})+\mathrm{Cu}(\mathrm{s})$ Zn(s)+Cu2+(aq)→Zn2+(aq)+Cu(s)
  • In Daniel's cell, electrons flow from the zinc electrode to the copper electrode through the external circuit while metal ions flow from one-half cell to the other through a salt bridge.
  • Here current flows from the copper electrode to the zinc electrode that is, cathode to anode in an external circuit.
  • Daniel cell is a reversible cell while a voltaic cell may be reversible or irreversible depending upon the e.g. if one of the products is gaseous and escapes, then the cell is not reversible.
Electrochemical CellElectrolytic Cell

It is a combination of two half cells, containing the same or different electrodes in the same or different electrolytes.

It is a single cell containing the same electrodes present in the same electrolyte.

The anode is negative, the cathode is positive

The anode is positive, the cathode is negative

Electrons move from anode to cathode in the external circuit.

Electrons enter through cathode and leave through the anode.

It converts chemical energy into electrical energy, produced as a result of a redox reaction.

It converts electrical energy into chemical energy. Energy is supplied to the electrolytic solution to bring about the redox reaction.

The cell reaction is spontaneous.

Cell reaction is non-spontaneous.

Salt bridge is required.

No salt bridge is required.

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Some Solved Examples

Example.1

1. Which of the following reactions is possible at the anode?

1) (correct)$2 \mathrm{Cr}^{3+}+7 \mathrm{H}_2 \mathrm{O} \rightarrow \mathrm{Cr}_2 \mathrm{O}_7^{2-}+14 \mathrm{H}^{+}$

2)$\mathrm{F}_2 \rightarrow 2 \mathrm{~F}^{-}$

3)$\frac{1}{2} \mathrm{O}_2+2 \mathrm{H}^{+} \rightarrow \mathrm{H}_2 \mathrm{O}$

4)none of these

Solution

Let's look at the oxidation states of the reactants and the products both

$2 \mathrm{Cr}^{3+}+7 \mathrm{H}_2 \mathrm{O} \rightarrow \stackrel{6}{\mathrm{Cr}_2} \mathrm{O}_7^{2-}+14 \mathrm{H}^{+}$

Here Cr goes from +3 OS to +6 OS, this oxidation reaction is possible at the anode.

$\stackrel{0}{F}_2 \rightarrow 2 \mathrm{~F}^{-}$

This is a reduction reaction where the O.S of F changes from 0 to -1. Reduction reactions are not possible in an anode.

$\frac{1}{2} \mathrm{O}_2+2 \mathrm{H}^{+} \rightarrow \mathrm{H}_2 \mathrm{O}$

This is also a reduction reaction where the OS of oxygen changes from 0 to -2. Reduction reactions are not possible at the anode.

Hence, the answer is the option (1).

Example.2

2. Two half cells have potential -0.36 and 0.82 Volts respectively. These two are coupled to make a galvanic cell. Which of the following will be true?

1) (correct)The electrode of half cell potential -0.36 V will act as an anode

2)The electrode of half cell potential -0.36 V will act as a cathode

3)The electrode of half-cell potential 0.82 V will act as an anode

4)The electrode of half-cell potential -0.36 V will act as the positive terminal

Solution

Electrode potentials are conventionally Reduction potentials which denote the ability of a species to get reduced. The greater the reduction potential, the greater the ability to get reduced.

Correspondingly, an electrode with a negative reduction potential has a greater tendency to get oxidized and would act as an anode.

Since the electrode with potential -0.36 is more negative than the electrode with potential 0.82, therefore it will act as an anode and oxidation will occur there.

Hence, the answer is the option (1).

Example.3 Which of the following statements is correct about the Galvanic cell?

1) (correct)The anode is negatively charged

2)The cathode is negatively charged

3)Oxidation occurs at the cathode

4)Reduction occurs at the anode

Solution

The anode is negatively charged due to the release of electrons. Oxidation occurs at the anode always.

Hence, the answer is the option (1).

Example.4

4.17284417759981728441773351

$\mathrm{E}_{\mathrm{Cu}^2+\mid \mathrm{Cu}}^0=+0.34 \mathrm{~V}$

$\mathrm{E}_{\mathrm{Zn}^2+\mid \mathrm{Zn}}^o=-0.76 \mathrm{~V}$

Identify the incorrect statement from the options below for the above cell:

1)If Eext > 1.1 V, e- flows from Cu to Zn

2) (correct)If Eext > 1.1 V, Zn dissolves at Zn electrode, and Cu deposits at the Cu electrode

3)If Eext < 1.1 V Zn dissolves at the anode and Cu deposits at the cathode

4)If Eext = 1.1 V, no flow of e- or current occurs

Solution

We know,

$\begin{aligned} & \mathrm{E}_{\text {cell }}^o=\mathrm{E}_{\text {right }}^{\mathrm{o}}-\mathrm{E}_{\text {left }}^o \\ & \mathrm{E}_{\text {cell }}^{\mathrm{o}}=0.34-(-0.76) \\ & \mathrm{E}_{\text {cell }}^o=1.10 \mathrm{volt}\end{aligned}$


17284417766151728441773391

Incorrect statement - If Eext > 1.1 V, Zn dissolves at Zn electrode, and Cu deposits at the Cu electrode

Therefore, the correct option is (2).

Example.5 Which of the following can be classified as a chemical cell?

1)Electrolytic cell

2)Galvanic cell

3)Daniel Cell

4) (correct)2 & 3

Solution

Chemical Cells - The cells in which electrical energy is produced from the energy change accompanying a chemical reaction or a physical process are known as chemical cells.

The Electrolytic cell is a device in which electrolysis is carried out by using electricity or in which the conversion of electrical energy into chemical energy is done.

The Galvanic cell is a device in which the redox reactions lead to the conversion of chemical energy into electrical energy.

A Daniell cell is a galvanic cell that converts chemical energy into electrical energy by using the spontaneous redox reaction between zinc and cupric ions.

Hence, the answer is the option (4).

Summary

Alessandro Volta's work was so influential that the unit of electric potential, the volt, was named in his honor. His invention revolutionized the way electricity was understood and utilized, paving the way for future innovations in science and technology. Galvaniv call has various significance in such a way that the Electrochemical Principle as Volta’s cell was the first to provide a stable and continuous electrical current.

Frequently Asked Questions (FAQs)

Q: What is the significance of the Cottrell equation in understanding transient processes in galvanic cells?
A:
The Cottrell equation describes how the current in an electrochemical system changes with time following a sudden change in potential. In galvanic cells, it's particularly relevant for understanding mass transport effects and the behavior of the cell immediately after it starts operating or experiences a change in load. This equation is
Q: How does the concept of limiting reactant apply to galvanic cells?
A:
In a galvanic cell, the limiting reactant determines the maximum amount of electrical energy that can be produced. Once the limiting reactant is consumed, the cell reaction stops, and no more current is generated. Understanding which reactant is limiting is crucial for predicting the cell's capacity and lifetime, especially in battery design and usage.
Q: What is meant by the term "electrochemical window" in the context of galvanic cells?
A:
The electrochemical window refers to the range of potentials within which an electrolyte is neither oxidized nor reduced. Outside this window, the electrolyte itself may undergo redox reactions, leading to its decomposition. In galvanic cells, choosing an electrolyte with an appropriate electrochemical window is crucial to ensure stable operation and prevent unwanted side reactions that could degrade cell performance.
Q: How do corrosion processes relate to the principles of galvanic cells?
A:
Corrosion processes, such as the rusting of iron, can be understood as naturally occurring galvanic cells. In these processes, different parts of a metal surface or different metals in contact act as anodes and cathodes. The principles of electron flow from areas of lower to higher reduction potential, the role of electrolytes, and the importance of completing the circuit all apply in corrosion as they do in intentionally designed galvanic cells.
Q: What is the significance of the Butler-Volmer equation in understanding galvanic cell kinetics?
A:
The Butler-Volmer equation describes the relationship between electrical current and electrode potential in electrochemical systems, including galvanic cells. It's crucial for understanding the kinetics of electrode reactions, particularly how the rate of electron transfer depends on the overpotential. This equation helps explain why actual cell performance often deviates from thermodynamic predictions and is essential for optimizing real-world electrochemical devices.
Q: How does the concept of charge transfer coefficient relate to galvanic cell performance?
A:
The charge transfer coefficient, typically denoted as α, is a measure of the symmetry of the energy barrier for an electrochemical reaction. It affects the relationship between overpotential and current in a galvanic cell. Understanding this coefficient is crucial for analyzing the kinetics of electrode reactions and for optimizing cell design to achieve desired performance characteristics, such as high power output or long-term stability.
Q: What is the importance of the exchange current density in galvanic cells?
A:
The exchange current density is a measure of the background level of oxidation and reduction occurring at an electrode when the net current is zero. It's an indicator of how easily an electrode reaction occurs. In galvanic cells, a higher exchange current density generally means faster kinetics and lower overpotentials, leading to better cell performance. Understanding this parameter is crucial for electrode material selection and cell design optimization.
Q: How does the concept of activity coefficients affect calculations involving galvanic cells?
A:
Activity coefficients account for the non-ideal behavior of electrolyte solutions in galvanic cells. They modify the concentration terms in the Nernst equation to reflect the effective concentration (activity) of species. In concentrated or complex electrolyte solutions, using activities instead of concentrations can significantly improve the accuracy of cell potential calculations and predictions of cell behavior.
Q: What is the role of a reference electrode in studying galvanic cells?
A:
A reference electrode provides a stable and reproducible potential against which other electrode potentials can be measured. In galvanic cell studies, it allows for the individual measurement of anode and cathode potentials, rather than just the overall cell potential. This is crucial for understanding the behavior of each half-cell, diagnosing performance issues, and optimizing cell design.
Q: How does the concept of Tafel plots relate to the analysis of galvanic cell performance?
A:
Tafel plots are graphical representations of the relationship between electrode overpotential and the logarithm of current density. In galvanic cell analysis, these plots help in understanding the kinetics of electrode reactions, determining exchange current densities, and identifying rate-limiting steps. They are particularly useful for optimizing electrode materials and predicting how a cell will perform under different operating conditions.