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Define the term overvoltage. How does overvoltage affect electrolytic processes?

Short Answer

Expert verified
Overvoltage is the extra voltage required in electrochemical reactions, increasing energy consumption in electrolytic processes.

Step by step solution

01

Understanding Overvoltage

Overvoltage refers to the extra voltage required beyond the theoretical potential needed to drive an electrochemical reaction. This term is critical in electrochemistry, especially in electrolytic processes.
02

Components of Overvoltage

The total overvoltage is composed of several parts: activation overvoltage, ohmic overvoltage, and concentration overvoltage. Each component adds to the difficulty of driving the reaction.
03

Impact of Overvoltage on Electrolytic Processes

In electrolytic processes, overvoltage can lead to increased energy consumption, as more voltage than theoretically required must be applied. It affects the efficiency and costs of these processes, making them more expensive and less energetically efficient.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Electrochemistry
Electrochemistry is a branch of chemistry that studies the relationship between electricity and chemical reactions. It involves chemical processes that cause electrons to move, creating an electric current. Electrochemical reactions are essential in various applications, including batteries, electrolysis, and fuel cells.
  • Batteries: Store energy through electrochemical reactions.
  • Fuel cells: Convert chemical energy into electrical energy.
  • Electrolysis: Uses electricity to drive non-spontaneous chemical reactions.
Understanding electrochemistry is crucial for optimizing processes like electrolytic refining and electroplating. These processes rely on controlled exchanges of electrons to achieve desired chemical transformations. To simplify, whenever you think of electrochemistry, picture how we harvest energy from chemical reactions or use electrical energy to effect chemical changes.
Electrolytic processes
Electrolytic processes are techniques that employ electricity to drive non-spontaneous chemical reactions. These reactions would not occur naturally without an external supply of energy. The process happens in a device called an electrolytic cell where the external current source provides the necessary energy. In electrolytic processes, energy input is crucial, and efficiency is often challenged by factors like overvoltage. These methods are widely used for purposes such as:
  • Electrolysis of water: Breaks down water into hydrogen and oxygen gases.
  • Electroplating: Deposits a layer of metal onto a surface for protection or decoration.
  • Electrorefining: Purifies metals by dissolving impure metal at the anode and plating pure metal at the cathode.
Although electrolytic processes have diverse applications, it's critical to manage the involved energy consumption to ensure cost-effectiveness and environmental friendliness.
Activation overvoltage
Activation overvoltage is the extra voltage needed to overcome the energy barrier of initiating a chemical reaction at the electrode surface. It is a significant component of total overvoltage and is caused by the inertia of the initial chemical step that requires a boost to get started. This type of overvoltage is dependent on the reaction kinetics, which describes how quickly a reaction proceeds. Factors that affect activation overvoltage include:
  • Nature of the electrode surface: Surface roughness and materials can significantly influence overvoltage.
  • Temperature: Higher temperatures generally lower activation overvoltage because they provide more energy to the reacting species.
  • Catalysts: Catalytic materials can reduce the activation energy needed, thereby lowering the activation overvoltage.
By understanding and managing activation overvoltage, we improve the efficiency of electrochemical processes, ultimately leading to savings in energy and costs.
Ohmic overvoltage
Ohmic overvoltage arises from the resistance encountered as current passes through an electrolytic system. This resistance can come from the electrolyte, the electrodes, and any other component in the circuit that opposes electron flow. The amount of ohmic overvoltage follows Ohm's Law, where voltage drop across a circuit component is proportional to the current and resistance (\[V = IR\]). Reducing this overvoltage involves:
  • Improving conductivity: Use of electrolytes with higher ionic conductivity.
  • Optimizing electrode size and placement: Reducing resistance by minimizing distance and resistance between electrodes.
  • Temperature management: Higher temperatures can reduce ionic resistance but need to be managed against other factors like energy cost.
Effective management of ohmic overvoltage leads to more energy-efficient electrochemical processes, vital for cost-effective industrial applications.
Concentration overvoltage
Concentration overvoltage is linked to the concentration gradient of reactants and products near the electrode surface. This occurs when there is a difference between concentrations in the bulk solution and at the electrode interface. During an electrochemical reaction, reactants are consumed and products are formed at the electrode surface, creating a concentration gradient that can slow down the reaction. This gradient results in concentration overvoltage, requiring extra voltage to maintain reaction rates. Strategies to minimize concentration overvoltage include:
  • Stirring or agitation: Enhances mixing of solutions, reducing concentration gradients.
  • Optimizing flow rates: Ensures that fresh reactants are continuously supplied and products removed.
  • Electrode design modifications: Increase surface area or structure to facilitate mass transport.
Taking steps to manage concentration overvoltage can lead to improved performance and efficiency of electrochemical systems, contributing to reduced energy consumption in electrolytic processes.

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Most popular questions from this chapter

An acidified solution was electrolyzed using copper electrodes. A constant current of 1.18 A caused the anode to lose \(0.584 \mathrm{~g}\) after \(1.52 \times 10^{3} \mathrm{~s}\). (a) What is the gas produced at the cathode, and what is its volume at STP? (b) Given that the charge of an electron is \(1.6022 \times 10^{-19} \mathrm{C},\) calculate Avogadro's number. Assume that copper is oxidized to \(\mathrm{Cu}^{2+}\) ions.

Given that: $$ \begin{array}{ll} 2 \mathrm{Hg}^{2+}(a q)+2 e^{-} \longrightarrow \mathrm{Hg}_{2}^{2+}(a q) & E^{\circ}=0.92 \mathrm{~V} \\\ \mathrm{Hg}_{2}^{2+}(a q)+2 e^{-} \longrightarrow 2 \mathrm{Hg}(l) & E^{\circ}=0.85 \mathrm{~V} \end{array} $$ calculate \(\Delta G^{\circ}\) and \(K\) for the following process at \(25^{\circ} \mathrm{C}:\) $$\mathrm{Hg}_{2}^{2+}(a q) \longrightarrow \mathrm{Hg}^{2+}(a q)+\mathrm{Hg}(l)$$ (The preceding reaction is an example of a disproportionation reaction in which an element in one oxidation state is both oxidized and reduced.)

A piece of magnesium ribbon and a copper wire are partially immersed in a \(0.1 M \mathrm{HCl}\) solution in a beaker. The metals are joined externally by another piece of metal wire. Bubbles are seen to evolve at both the \(\mathrm{Mg}\) and Cu surfaces. (a) Write equations representing the reactions occurring at the metals. (b) What visual evidence would you seek to show that Cu is not oxidized to \(\mathrm{Cu}^{2+} ?(\mathrm{c})\) At some stage, \(\mathrm{NaOH}\) solution is added to the beaker to neutralize the HCl acid. Upon further addition of \(\mathrm{NaOH},\) a white precipitate forms. What is it?

A \(9.00 \times 10^{2} \mathrm{~mL}\) amount of \(0.200 \mathrm{M} \mathrm{MgI}_{2}\) solution was electrolyzed. As a result, hydrogen gas was generated at the cathode and iodine was formed at the anode. The volume of hydrogen collected at \(26^{\circ} \mathrm{C}\) and \(779 \mathrm{mmHg}\) was \(1.22 \times 10^{3} \mathrm{~mL}\). (a) Calculate the charge in coulombs consumed in the process. (b) How long (in min) did the electrolysis last if a current of 7.55 A was used? (c) A white precipitate was formed in the process. What was it, and what was its mass in grams? Assume the volume of the solution was constant.

The magnitudes (but not the signs) of the standard reduction potentials of two metals \(\mathrm{X}\) and \(\mathrm{Y}\) are: $$ \begin{aligned} \mathrm{Y}^{2+}+2 e^{-} \longrightarrow & \mathrm{Y} & &\left|E^{\circ}\right|=0.34 \mathrm{~V} \\\ \mathrm{X}^{2+}+2 e^{-} \longrightarrow & \mathrm{X} & &\left|E^{\circ}\right|=0.25 \mathrm{~V} \end{aligned}$$ where the \(\|\) notation denotes that only the magnitude (but not the sign) of the \(E^{\circ}\) value is shown. When the half-cells of \(X\) and \(Y\) are connected, electrons flow from \(X\) to \(Y\). When \(X\) is connected to a SHE, electrons flow from \(\mathrm{X}\) to SHE. (a) Are the \(E^{\circ}\) values of the halfreactions positive or negative? (b) What is the standard emf of a cell made up of \(X\) and \(Y ?\)

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