CV - Cyclic Voltammetry

Cyclic voltammetry (CV) is an electrochemical technique used to study the redox properties of a chemical species. It provides information about the electron transfer processes that occur during oxidation and reduction reactions. Cyclic voltammetry is widely employed in various fields, including analytical chemistry, materials science, and electrochemistry.

Cyclic voltammetry is a versatile technique that can be used for qualitative and quantitative analysis, as well as mechanistic investigations. It provides insights into the kinetics and thermodynamics of electron transfer processes and is widely employed in the development and characterization of electrochemical systems and materials.

Technique Overview Fundamental Equations Obtaining Info Analyzing CV

Technique Overview

Here's an overview of the cyclic voltammetry technique:

Principle: Cyclic voltammetry involves applying a potential waveform to an electrochemical cell and measuring the resulting current. The potential is swept linearly with time, starting from an initial value, called the initial potential (Ei), to a final potential (Ef), and then back to the initial potential. The current response is recorded as a function of the applied potential.
Electrochemical Cell: The electrochemical cell typically consists of a working electrode, a reference electrode, and a counter electrode. The working electrode is the surface where the redox reaction of interest occurs. The reference electrode provides a stable reference potential against which the potential of the working electrode is measured. The counter electrode completes the electrical circuit and allows the flow of current.
Experimental Setup: The electrochemical cell is placed in an electrolyte solution, which contains the chemical species of interest. The choice of electrolyte depends on the specific system being studied. The cell is connected to a potentiostat, which controls the applied potential and measures the resulting current.
Potential Sweep: In cyclic voltammetry, the potential is swept between the initial and final potentials at a constant scan rate (typically expressed in volts per second). The direction of the potential sweep can be either forward (from Ei to Ef) or reverse (from Ef to Ei). The potential is usually swept linearly, but other waveform shapes, such as square wave and staircase voltammetry, can also be employed.
Current Measurement: As the potential is swept, the redox reactions occurring at the working electrode result in a flow of current. The potentiostat measures this current and plots it as a function of the applied potential. The resulting graph is called a voltammogram or cyclic voltammogram.
Interpretation: The voltammogram provides valuable information about the electrochemical behavior of the system. Key features include peak currents, peak potentials, and peak shapes. These parameters can be used to determine various electrochemical properties, such as the formal potential, diffusion coefficient, and rate constants of the redox reactions.
Analysis: Cyclic voltammetry data can be analyzed using various mathematical models and theoretical frameworks, such as the Randles-Sevcik equation, which relates the current response to the electrochemical parameters. The data can also be compared to standard reference systems or simulated using computational methods.

Fundamental Equations

Cyclic Voltammetry Fundamental Equations

Cyclic voltammetry (CV) is based on several fundamental equations that describe the electrochemical processes occurring during the potential sweep. Here are some of the key equations used in cyclic voltammetry:

Nernst Equation: The Nernst equation relates the electrode potential (E) to the concentration (C) of the species undergoing a redox reaction:

E = E° + (RT/nF) * ln(C_red/C_ox)

where E° is the standard electrode potential, R is the gas constant, T is the temperature, n is the number of electrons involved in the redox reaction, F is Faraday's constant, C_red is the concentration of the reduced species, and C_ox is the concentration of the oxidized species. The Nernst equation provides a quantitative relationship between the potential and the concentration of the electroactive species.

Try Gamry's online Nernst Equation Calculator. Here you are able to input E°, T, n, and Q (as O/R) and see the resulting Ecell.

Butler-Volmer Equation: The Butler-Volmer equation describes the relationship between the current density (i) and the electrode potential (E) during an electrochemical reaction. It considers the kinetics of the redox process and incorporates the exchange current density (i0) and the transfer coefficient (α):

i = i0 * [exp(α * n * F * (E - E0)/RT) - exp(-(1 - α) * n * F * (E - E0)/RT)]

where E0 is the formal potential. The Butler-Volmer equation accounts for the forward and backward reaction rates and provides insights into the reaction kinetics.

Randles-Sevcik Equation: The Randles-Sevcik equation relates the peak current (ip) in a cyclic voltammogram to the concentration (C) and diffusion coefficient (D) of the electroactive species:

ip = (2.69 * 10^5) * n^3/2 * A * D^(1/2) * C * ν^(1/2)

where n is the number of electrons involved in the redox reaction, A is the electrode area, ν is the scan rate, and ip is usually reported in amperes. The Randles-Sevcik equation provides a quantitative relationship between the peak current and the electrochemical parameters, allowing for the determination of diffusion coefficients and concentration values.

These equations form the basis for analyzing cyclic voltammetry data and extracting valuable information about the electrochemical system under investigation. It's important to note that additional factors, such as electrode kinetics, mass transport, and double-layer capacitance, may also need to be considered in more complex systems or under specific experimental conditions.

Obtaining Info

What information can I obtain with Cyclic Voltammetry?

Cyclic voltammetry (CV) provides valuable information about the electrochemical system under investigation. Here are some key insights and information that can be obtained through cyclic voltammetry:

Redox Behavior: Cyclic voltammetry helps identify the redox behavior of the electroactive species in the system. It provides information about the oxidation and reduction potentials, as well as the reversibility or irreversibility of the redox processes. This knowledge is crucial for understanding the redox properties and reactivity of the species.
Electrochemical Kinetics: By analyzing the shape, position, and magnitude of the peaks in the cyclic voltammogram, information about the kinetics of the electrochemical reactions can be obtained. Parameters such as peak currents, peak potentials, and peak shapes can be used to determine rate constants, electron transfer coefficients, and reaction mechanisms. This information aids in the understanding of reaction kinetics and the study of reaction mechanisms.
Diffusion Coefficient: The Randles-Sevcik equation, derived from cyclic voltammetry data, allows the determination of the diffusion coefficient of the electroactive species. By examining the relationship between the peak current and the scan rate, information about the species' diffusion behavior in the electrolyte can be obtained. Diffusion coefficients provide insights into the mobility and transport of species within the electrochemical system.
Concentration Analysis: Cyclic voltammetry can be used for qualitative and quantitative analysis of chemical species in a solution. By comparing the obtained voltammogram with those of known standards or performing calibration experiments, the concentration of the electroactive species can be determined. This is particularly useful in analytical chemistry applications where concentration measurements are required.
Electrode Surface Properties: Cyclic voltammetry can provide information about the electrochemical behavior of the working electrode surface. By examining the voltammogram, characteristics such as the double-layer capacitance, surface area, and adsorption processes can be inferred. This information is crucial for the characterization and understanding of electrode surfaces and their interactions with the electrolyte.
Stability and Reactivity: Cyclic voltammetry can help assess the stability and reactivity of the electroactive species. By observing changes in the voltammogram over multiple cycles, information about the stability of the species can be obtained. Additionally, the peak currents and potential shifts can provide insights into the reactivity and electrochemical reactivity of the species.

Overall, cyclic voltammetry is a powerful technique that provides a wealth of information about the electrochemical properties, kinetics, concentration, and surface characteristics of chemical species. It is widely used in various fields, including analytical chemistry, materials science, and electrochemistry, for both fundamental research and practical applications.

Electrochemistry Applications