Electrochemical processes

Сентябрь 8, 2022

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Electrochemical processes

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2. Today’s objectives: Define electrode, anode, cathode, anion, cation, salt bridge/porous cup, electrolyte, and voltaic cell Predict
3. REMINDER: “Redox” Chemistry: Reduction and Oxidation reactions are all reactions that involve the change of an
4. Electrochemistry is the branch of science which deals with the relationship between chemical reaction and electricity.
5. Electrochemical Reaction: Redox (oxidation-reduction) reactions in which electrons are transferred from a donor (reducing agent) to
6. Relating electricity and chemical reactions Transfer of electrons Galvanic Cell In put: Chemical energy Out put:
7. In pure solid metal ion - atom located in the sites of the crystal lattice, and
8. Metal surface Water
9. (-) Ме ANODE (+) Ме CATHODE Ме - - - - - + + + +
10. An electrode in an electrochemical cell is referred to as either an anode or a cathode
11. The layer of positive / negative ions formed on the metal is called Helmholtz Electrical Double
12. Standard electrode potential (SEP) is a measure of the tendency of the metallic electrode to loose
13. Measurement of SEP SEP cannot be measured directly. The electrode is coupled with a reference electrodes:
14. Type of electrode: Gas electrode (Primary Reference Electrode) Components: Electrode component: Pt – H2 Electrolyte component:
15. STANDARD HYDROGEN ELECTRODE (SHE) is compared the potentials of any metal electrodes If SHE is an
16. Cathode: Cu2+ +2e = Cu° Anode: H2° – 2e = 2H+ Н2 Voltmeter: ΔE=+0.34V
18. Saturated Calomel Electrode (SCE) Type/class: Metal-metal insoluble salt electrode (Secondary Reference Electrode) Components: Electrode component: Pt
20. In electrochemistry, for calculating electrode potential of half-cell used the Nernst equation. This equation is relates
21. At any specific temperature, the Nernst equation derived above can be reduced into a simple form.
22. Problem: Calculate the electrode potential of zinc if it was dipped in 0,01M ZnSO4 solution Using
23. We know that reduction (gaining electrons) can’t happen without an oxidation to provide the electrons. When
24. An electrochemical cell is a device capable of either generating electrical energy from chemical reactions or
25. An electrichemical cell converts chemical energy into electrical energy Alessandro Volta invented the first electric cell
26. Alessandro Volta’s invention was an immediate technological success because it produced electric current more simply and
27. A galvanic cell, or voltaic cell, named after Luigi Galvani, or Alessandro Volta respectively, is an
28. Galvanic cell composed of two half-cells; which each consist of a metal rod or strip immersed
29. The driving force which makes the electrons to flow from a region of higher potential to
30. If the ΔE>0, it is positive, the reaction occurring is spontaneous. If the ΔE THE ELECTROMOTIVE
32. Representation of a galvanic cell Galvanic cell consists of two electrodes, anode and cathode The anode
33. Many natural phenomena are based on electrochemical processes, such as the corrosion of metals, the ability
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Today’s objectives:
Define electrode, anode, cathode, anion, cation, salt bridge/porous cup,

electrolyte, and voltaic cell
Predict and write the half-reaction equation that occurs at each electrode in an electrochemical cell

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REMINDER:
“Redox” Chemistry: Reduction and Oxidation reactions are all reactions that involve

the change of an oxidation number, and transfer of electrons among the reacting substances.
Oxidation: Loss of electrons (increase in oxidation number): Zn° – 2e → Zn2+
Reduction: Gain of electrons (a reduction in oxidation number): Cu2+ + 2e → Cu°
Electrons are transferred from the reducing agent (the species being oxidized) to the oxidizing agent (the species being reduced).

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Electrochemistry is the branch of science which deals with the relationship

between chemical reaction and electricity.
An electrochemical process is a chemical reaction that either causes or is caused by the movement of electrical current. These processes are a type of oxidation-reduction reaction in which one atom or molecule loses an electron to another atom or molecule.
In electrochemical reactions, the atoms or molecules in the reaction are relatively far apart from each other compared to other reactions, forcing the electrons being transferred to travel a greater distance and thereby produce an electrical current.

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Electrochemical Reaction:
Redox (oxidation-reduction) reactions in which electrons are transferred from a

donor (reducing agent) to an acceptor (oxidant).
Redox reactions takes place by movement of electrons or ions across the interface of metal electrode.
Each of the reaction is known as half-reaction and system of an electrode with electrolyte is called half-cell.
A half-cell is a structure that contains a conductive electrode and a surrounding conductive electrolyte separated by a naturally occurring Helmholtz electrical double layer.
Both half-reactions must always go side by side to sustain the electrochemical reaction.

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Relating electricity and chemical reactions
Transfer of electrons
Galvanic Cell
In put: Chemical energy
Out

put: Electrical energy
Echem → Eelec

Electrolytic Cell
In put: Electrical Energy
Out put: Chemical reaction /energy
Eelec → Echem

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In pure solid metal ion - atom located in the sites

of the crystal lattice, and are in equilibrium with free electrons:
Ме+n • ē → Ме+n + nē

When a metal is immersed in the water in the system is established redox equilibrium:

Ме° + mH2O → Me (H2O)m + nē

electrode solution electrode

Ме°

WHAT IS A ELECTRODE?

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Metal surface
Water

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(-) Ме ANODE
(+) Ме CATHODE
Ме
-
-
-
-
-
+
+
+
+
If metal is oxidized in solution (dissolved

in water), it is anode

When a metal is placed in its own salt solution it may under go oxidation or reduction according to its tendency to loose or gain electrons.

If metal is reduced in solution (insoluble in water), it is cathode

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An electrode in an electrochemical cell is referred to as either an anode or a cathode (words

that were coined by William Whewell at Faraday's request).
Electrodes: are usually metal strips/wires connected by an electrically conducting wire.
Anode: is the electrode where oxidation takes place, it is the negative (-) electrode (example, active metals are soluble in water).
Cathode: is the electrode where reduction takes place, it is the positive (+) electrode (example, passive metals are insoluble in water).

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The layer of positive / negative ions formed on the metal

is called Helmholtz Electrical Double Layer. A difference of potential is set up between the metal ions and the solution.
At equilibrium, the potential difference becomes a constant value and is called as electrode potential of the metal.

Ме+n

– H2O +

An-m

1st layer

2nd layer

M
E
T
A
L

dipol

anion

cation

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Standard electrode potential (SEP) is a measure of the tendency of

the metallic electrode to loose or gain electrons when it (metal electrode) is dipped in its own salt solution of unit concentration (1M), at 25°C and atmospheric pressure (1 atm = 101,325kPa).

Herman von Helmholtz
1821 – 1894

An EDL can be formed on the surface of an electrode by adsorption of ions from an electrolyte solution

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Measurement of SEP
SEP cannot be measured directly. The electrode is coupled

with a reference electrodes:
Standard Hydrogen electrode (SHE)
Saturated Calomel Electrode (SCE)
Reference electrode is an electrode which has a stable electrode potential and with which we can compare the potentials of other electrodes.

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Type of electrode: Gas electrode (Primary Reference Electrode)
Components:
Electrode component: Pt

– H2
Electrolyte component: H2SO4 (1M)
Electrode representation:
Pt, H2 (1atm) / 2H+ (1M)

Construction: Hydrogen electrode consists of a Platinum foil connected to a platinum wire sealed in a glass tube. The electrode is in contact with 1M H2SO4 and hydrogen gas (1 atmosphere) is constantly bubbled.
Limitations
• It requires pure hydrogen gas and is difficult to set up and to transport
• It requires large volume of test solution
• The potential of the electrode is dependent on atmospheric pressure

STANDARD HYDROGEN ELECTRODE (SHE)

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STANDARD HYDROGEN ELECTRODE (SHE) is compared the potentials of any metal

electrodes

If SHE is an anode:

If SHE is a cathode:

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Cathode:
Cu2+ +2e = Cu°
Anode:
H2° – 2e = 2H+
Н2
Voltmeter:
ΔE=+0.34V

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Saturated Calomel Electrode (SCE)
Type/class: Metal-metal insoluble salt electrode (Secondary Reference
Electrode)
Components:
Electrode component:

Pt – Hg
Electrolyte component: Hg2Cl2(s) / KCl
Electrode representation:
Hg, Hg2Cl2(s) - KCl (sat. solution)

Construction: Calomel electrode consists of a glass tube containing mercury at the bottom over which mercurous chloride paste (calomel) is placed. The tube is filled with saturated KCl solution. A platinum wire is fused into the layer of mercury to provide electrical contact. The electrode potential differs with the concentration of KCl.

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In electrochemistry, for calculating electrode potential of half-cell used the Nernst

equation. This equation is relates the electrode potential of a half-cell at any point in time to the standard electrode potential, temperature, activity, and reaction quotient of the underlying reactions and species:

EMe is the half-cell metal electrode potential at the temperature of interest
EoMe is the standard half-cell electrode potential
R is the universal gas constant: R = 8.314 472(15) J *K−1 *mol−1
T is the absolute temperature
a is the chemical activity for the relevant species, activities in the Nernst equation are frequently replaced by simple concentrations.)
F is the Faraday constant: F = 9.648 533 99(24)×104 C mol−1
z is the number of moles of electrons transferred in the cell reaction or half-reaction

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At any specific temperature, the Nernst equation derived above can be

reduced into a simple form. For example, at room temperature (25 °C), RT/F may be treated like a constant and replaced by 25.693 mV for cells. The Nernst equation is frequently expressed in terms of base 10 logarithms (i.e., common logarithms) rather than natural logarithms, in which case it is written, for a cell at 25 °C:

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Problem:
Calculate the electrode potential of zinc if it was dipped in

0,01M ZnSO4 solution

Using the Nernst equation:

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We know that reduction (gaining electrons) can’t happen without an oxidation

to provide the electrons.
When two half-cells (metal electrodes) are joined by a salt bridge or some other path (porous membrane) that allows ions to pass between the two sides in order to maintain electro neutrality are obtained electrochemical cell, where oxidation occurs at one half cell while reduction takes place at the other half cell.

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An electrochemical cell is a device capable of either generating electrical

energy from chemical reactions or facilitating chemical reactions through the introduction of electrical energy.

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An electrichemical cell converts chemical energy into electrical energy
Alessandro Volta invented

the first electric cell but got his inspiration from Luigi Galvani. Galvani’s crucial observation was that two different metals could make the muscles of a frog’s legs twitch. Unfortunately, Galvani thought this was due to some mysterious “animal electricity”. It was Volta who recognized this experiment’s potential.
An electric cell produces very little electricity, so Volta came up with a better design:
A battery is defined as two or more electric cells connected in series to produce a steady flow of current
Volta’s first battery consisted of several bowls of brine (NaCl(aq)) connected by metals that dipped from one bowl to another
His revised design, consisted of a sandwich of two metals separated by paper soaked in salt water.

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Alessandro Volta’s invention was an immediate technological success because it produced

electric current more simply and reliably than methods that depended on static electricity.
It also produced a steady electric current –something no other device could do.

Luigi Galvani

Alessandro Volta

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A galvanic cell, or voltaic cell, named after Luigi Galvani, or

Alessandro Volta respectively, is an electrochemical cell that derives electrical energy from spontaneous redox reactions taking place within the cell. It generally consists of two different metals connected by a salt bridge, or individual half-cells separated by a porous membrane.
Galvanic or voltaic cell: Produces energy by a spontaneous reaction which produces electricity as a result of electron transferred. Discharging of battery, corrosion, etc

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Galvanic cell composed of two half-cells; which each consist of a

metal rod or strip immersed in a solution of its own ions or an inert electrolyte.
Electrodes: solid metal conductors connecting the cell to an external circuit.
Anode: electrode where oxidation occurs (-).
Cathode: electrode where reduction occurs (+).
The electrons flow from the anode to the cathode (“a before c”) through an electrical circuit rather than passing directly from one substance to another.

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The driving force which makes the electrons to flow from a

region of higher potential to a region of lower potential is called the electromotive force abbreviated as EMF. It is measured in Volts (V).

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If the ΔE>0, it is positive, the reaction occurring is spontaneous.

If the ΔE<0, it is negative, the reaction occurring is non-spontaneous

THE ELECTROMOTIVE FORCE

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Representation of a galvanic cell
Galvanic cell consists of two electrodes, anode

and cathode
The anode is written on the left hand side while the cathode is written on right side.
The anode is written with the metal first and then the electrolyte .The two are separated by a vertical line or semicolon. Example:
The cathode is written with electrolyte first and then the metal both are separated by vertical line or semicolon. Example:
The two half cells are connected by a salt bridge which is indicated by two parallel lines:

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Many natural phenomena are based on electrochemical processes, such as the corrosion of

metals, the ability of some sea creatures to generate electrical fields, and the workings of the nervous systems of humans and other animals.
They also play an important role in modern technology, most prominently in the storage of electrical power in batteries, and the electrochemical process called electrolysis is important in modern industry.

Electrochemical processes

Содержание

Today’s objectives: Define electrode, anode, cathode, anion, cation, salt bridge/porous cup,

REMINDER:“Redox” Chemistry: Reduction and Oxidation reactions are all reactions that involve