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Chapter 18 - Electrochemistry

18.1 - Redox Reactions

  • The discipline of chemistry that deals with the interconversion of electrical and chemical energy are known as electrochemistry.

  • During oxidation, the electron loss through an element is marked by an increased oxidation number of the element.

  • The oxidation number is reduced as a result of the electrode gain by an element.

  • The Mg metal was oxidized and H+ ions were reduced in the preceding reaction; the Cl− ions were spectator ions.

18.2 - Galvanic Cells

  • The experimental method for generating electricity through a spontaneous reaction is known as a galvanic cell or voltaic cell.

    • After the Italian scientists Luigi Galvani and Alessandro Volta who built early versions of the technology.

  • The Daniell cell is a specific configuration of electrodes (Zn and Cu) and solutions (ZnSO4 and CuSO4).

  • The anode of a galvanic cell is the electrode where oxidation takes place, whereas the cathode is the electrode where reduction takes place.

    • The cell voltage, or cell potential, is the voltage across the electrodes of a galvanic cell.

    • The electromotive force, or emf (E), is another term for cell voltage that, despite its name, is a measure of voltage rather than force.

18.3 - Standard Reduction Potentials

  • E° is the standard reduction potential, or the voltage associated with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm, and the superscript “°” denotes standard-state conditions.

  • The surface of the reduction is provided by the Pt electrode.

  • When all reactants (H2 in 1 atm, H+ and Zn2+ in 1 M) in their standard states, the cell emf is 0.76 V in 25°C.

  • A cell with a copper electrode and a SHE [Figure 18.4(b)] can be used to achieve the standard electrode potential for copper similarly.

    • Here, the copper electrode is the cathode, since its mass increases while the cell operates, as the decrease reaction is consistent: Cu2+(aq) + 2e− ⟶ Cu(s)

18.4 - Thermodynamics of Redox Reactions

  • The Faraday constant (F) is the charge of one mole of electrons, named after the English chemist and scientist Michael Faraday.

  • The total charge can now be expressed as nF, in the total redox process equation n is the number of moles of electrons exchanged between the oxidizing agent and the reduction agent

  • The emf (Ecell) measured is the cell's maximum voltage.

  • The electrical labor performed, wele, the maximum work possible (wmax), is therefore given by the overall charge product and cell emf: wmax = wele = −nFEcell

18.5 - The Effect of Concentration on Cell Emf

  • Under nonstandard-state conditions, there is a mathematical relationship between the emf of a galvanic cell and the concentration of reactants and products in a redox reaction.

  • The electrons flow to the cathode during the operation of a galvanic cells, which leads to the formation of products and a decline in the amount of reactants.

    • Therefore, Q is increasing, meaning E is decreasing.

    • The cell eventually strikes a balance.

  • At balance, there is no net electron transfer, so E = 0 and Q = K where K is a constant balance.

  • A dilute hydrochloric acid solution contains a silver wire covered with silver chloride.

  • The possibilities between both ends of the membrane can be monitored by means of the reference electrode when the electrode is placed in a solution with a pH different from that of the inner solution.

  • A voltmetre, measured in pH units, measures the emff of the cell made up of the glass electrode and the reference electrode.

18.6 - Batteries and Fuel Cells

  • A battery is a galvanic cell or a group of galvanic cells, that can be utilized as a constant-voltage source of direct electric current.

  • A fuel cell is a galvanic cell that requires a constant supply of reactants to function.

  • The battery of mercury is widely used in medicine and in electronics and is costlier than the common dry cell.

  • The Mercury battery is made up of a zinc anode (mercury amalgamated) that comes with a strongly alkaline electrolyte containing zinc oxide and mercury(II) oxide.

18.7 - Corrosion

  • Corrosion is the term used to describe the electrochemical process that causes metals to corrode.

  • Cathodic protection is a corrosion-prevention technique in which the metal to be protected becomes the cathode in a galvanic cell.

  • The iron is not limited to metallic corrosion. Take aluminum, a metal for many helpful items, including aircraft and drink cans.

    • Aluminum has a much greater tendency to oxidize than iron does.

  • A number of methods for protecting metals from corrosion have been developed.

  • The aim of most of these methods is to prevent the formation of rust.

    • The clearest approach is to paint the metal surface.

  • But if the color is scraped, punched or dentated, even the smallest part of bare metal is exposed, rust forms under the layer of paint.

  • A process called passivation can make the surface of iron metal inactive.

    • When a strong oxidizing agent such as concentrated nitric acid treats the metal, a thin oxide layer forms.

    • In the refrigeration systems and radiators a sodium chromate solution is often added to prevent the formation of rust.

  • A layer of other metal like tin or zinc can cover the iron container.

  • The application of a thin layer of tin over iron can produce a "tin."

  • The formation of rust is avoided while the tin layer remains unbroken.

    • But once the surface is scratched, rusting happens quickly

18.8 - Electrolysis

  • Electrolysis is a process in which electrical energy is utilized to cause a non-spontaneous chemical reaction to occur, as opposed to spontaneous redox reactions

    • which result in the transfer of chemical energy into electrical energy.

    • An electrolytic cell is a device that performs electrolysis.

  • The discrepancy between the electrode potential and the actual voltage necessary to initiate electrolysis is known as minimumovervoltage.

  • The battery is used as a "electron pump" which leads to the cathode where there is a reduction and removes electrons from the anode where oxidation takes place.

Chapter 18 - Electrochemistry

18.1 - Redox Reactions

  • The discipline of chemistry that deals with the interconversion of electrical and chemical energy are known as electrochemistry.

  • During oxidation, the electron loss through an element is marked by an increased oxidation number of the element.

  • The oxidation number is reduced as a result of the electrode gain by an element.

  • The Mg metal was oxidized and H+ ions were reduced in the preceding reaction; the Cl− ions were spectator ions.

18.2 - Galvanic Cells

  • The experimental method for generating electricity through a spontaneous reaction is known as a galvanic cell or voltaic cell.

    • After the Italian scientists Luigi Galvani and Alessandro Volta who built early versions of the technology.

  • The Daniell cell is a specific configuration of electrodes (Zn and Cu) and solutions (ZnSO4 and CuSO4).

  • The anode of a galvanic cell is the electrode where oxidation takes place, whereas the cathode is the electrode where reduction takes place.

    • The cell voltage, or cell potential, is the voltage across the electrodes of a galvanic cell.

    • The electromotive force, or emf (E), is another term for cell voltage that, despite its name, is a measure of voltage rather than force.

18.3 - Standard Reduction Potentials

  • E° is the standard reduction potential, or the voltage associated with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm, and the superscript “°” denotes standard-state conditions.

  • The surface of the reduction is provided by the Pt electrode.

  • When all reactants (H2 in 1 atm, H+ and Zn2+ in 1 M) in their standard states, the cell emf is 0.76 V in 25°C.

  • A cell with a copper electrode and a SHE [Figure 18.4(b)] can be used to achieve the standard electrode potential for copper similarly.

    • Here, the copper electrode is the cathode, since its mass increases while the cell operates, as the decrease reaction is consistent: Cu2+(aq) + 2e− ⟶ Cu(s)

18.4 - Thermodynamics of Redox Reactions

  • The Faraday constant (F) is the charge of one mole of electrons, named after the English chemist and scientist Michael Faraday.

  • The total charge can now be expressed as nF, in the total redox process equation n is the number of moles of electrons exchanged between the oxidizing agent and the reduction agent

  • The emf (Ecell) measured is the cell's maximum voltage.

  • The electrical labor performed, wele, the maximum work possible (wmax), is therefore given by the overall charge product and cell emf: wmax = wele = −nFEcell

18.5 - The Effect of Concentration on Cell Emf

  • Under nonstandard-state conditions, there is a mathematical relationship between the emf of a galvanic cell and the concentration of reactants and products in a redox reaction.

  • The electrons flow to the cathode during the operation of a galvanic cells, which leads to the formation of products and a decline in the amount of reactants.

    • Therefore, Q is increasing, meaning E is decreasing.

    • The cell eventually strikes a balance.

  • At balance, there is no net electron transfer, so E = 0 and Q = K where K is a constant balance.

  • A dilute hydrochloric acid solution contains a silver wire covered with silver chloride.

  • The possibilities between both ends of the membrane can be monitored by means of the reference electrode when the electrode is placed in a solution with a pH different from that of the inner solution.

  • A voltmetre, measured in pH units, measures the emff of the cell made up of the glass electrode and the reference electrode.

18.6 - Batteries and Fuel Cells

  • A battery is a galvanic cell or a group of galvanic cells, that can be utilized as a constant-voltage source of direct electric current.

  • A fuel cell is a galvanic cell that requires a constant supply of reactants to function.

  • The battery of mercury is widely used in medicine and in electronics and is costlier than the common dry cell.

  • The Mercury battery is made up of a zinc anode (mercury amalgamated) that comes with a strongly alkaline electrolyte containing zinc oxide and mercury(II) oxide.

18.7 - Corrosion

  • Corrosion is the term used to describe the electrochemical process that causes metals to corrode.

  • Cathodic protection is a corrosion-prevention technique in which the metal to be protected becomes the cathode in a galvanic cell.

  • The iron is not limited to metallic corrosion. Take aluminum, a metal for many helpful items, including aircraft and drink cans.

    • Aluminum has a much greater tendency to oxidize than iron does.

  • A number of methods for protecting metals from corrosion have been developed.

  • The aim of most of these methods is to prevent the formation of rust.

    • The clearest approach is to paint the metal surface.

  • But if the color is scraped, punched or dentated, even the smallest part of bare metal is exposed, rust forms under the layer of paint.

  • A process called passivation can make the surface of iron metal inactive.

    • When a strong oxidizing agent such as concentrated nitric acid treats the metal, a thin oxide layer forms.

    • In the refrigeration systems and radiators a sodium chromate solution is often added to prevent the formation of rust.

  • A layer of other metal like tin or zinc can cover the iron container.

  • The application of a thin layer of tin over iron can produce a "tin."

  • The formation of rust is avoided while the tin layer remains unbroken.

    • But once the surface is scratched, rusting happens quickly

18.8 - Electrolysis

  • Electrolysis is a process in which electrical energy is utilized to cause a non-spontaneous chemical reaction to occur, as opposed to spontaneous redox reactions

    • which result in the transfer of chemical energy into electrical energy.

    • An electrolytic cell is a device that performs electrolysis.

  • The discrepancy between the electrode potential and the actual voltage necessary to initiate electrolysis is known as minimumovervoltage.

  • The battery is used as a "electron pump" which leads to the cathode where there is a reduction and removes electrons from the anode where oxidation takes place.