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Electrochemical Cells

Phillip Cook

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Phillip Cook

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Contents www.ck12.org

Contents

1 Galvanic Cells 1

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www.ck12.org Chapter 1. Galvanic Cells

CHAPTER 1 Galvanic CellsLesson Objectives

The student will:

describe the conditions necessary for a cell to be a standard cell.

balance the redox equation, calculate the standard cell potential, and determine the direction of electron flow

in the external circuit given a table of standard reduction potentials and a diagram or description of a Galvanic

cell.

Introduction

Electrochemistry can be defined as the study of the interchange of electrical and chemical energy. Electrochemical

reactions generate an electric current from a spontaneous oxidation-reduction chemical reaction. Recall that in

oxidation, a substance loses one or more electrons, and in reduction, a substance gains one or more electrons. This

gain and loss of electrons always goes hand-in-hand.

Spontaneous Redox Reactions

Spontaneous oxidation-reduction reactions occur because the products contain less potential energy in their bonds

than the reactants do. The energy produced from excess potential energy not only allows the reaction to occur, but

it often gives off energy to the surroundings. Some of these reactions can be physically arranged so that the energy

given off is in the form of an electric current. These are the type of reactions that occur inside batteries. When a

reaction is arranged to produce an electric current as it runs, the arrangement is called an electrochemical cell or a

Galvanic Cell.If a strip of copper is placed in a solution of silver nitrate, the following reaction takes place:

2 Ag+ + Cu! 2 Ag + Cu2+

In this reaction (illustrated below), copper atoms are donating electrons to silver ions so that the silver ions are

reduced to silver atoms and the copper atoms are oxidized to copper(II) ions.

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As the reaction occurs, an observer would see the solution slowly turn blue (Cu 2+ ions are blue in solution), and a

mass of solid silver atoms would build up on the copper strip.

Electrochemical Cells

The reaction 2 Ag+ + Cu ! 2 Ag + Cu2+ is one that could be physically arranged to produce an external electriccurrent. To do this, the two half-reactions must occur in separate compartments, and the separate compartments

must remain in contact through an ionic solution and an external wire.

In the electrochemical cell illustrated above, the copper metal must be separated from the silver ions to avoid a direct

reaction. Each electrode in its solution could be represented by the following half-reactions:

Cu! Cu2+ + 2 e

Ag!Ag+ + e

The external wire will allow electrons to flow between the metal strips. In each half-cell, atoms may be oxidized to

ions, leaving excess electrons on the electrode. It can be determined experimentally that electrons will flow in the

wire from the copper electrode to the silver electrode. The reason for the direction of electron flow can be explained

in several ways. We could say that silver ions have a greater electron affinity than copper ions, so the silver atomspull the electrons through the wire from copper. On the other hand, we could also say that copper atoms are more

active (see the metal activity series) and thus have a greater tendency to give up electrons than silver, so the copper

electrode becomes more negative and will push the electrons through the wire toward the silver electrode. Whichever

way we look at it, the electrons flow from copper to silver in the external wire. The silver electrode, therefore, will

acquire an excess of electrons that causes the silver half-reaction to run in the reverse direction.

Ag+ + e!Ag

As the electrons on the silver electrode are used up in the reduction of silver ions, more copper atoms are oxidized,

and more electrons sent through the wire. The net reaction for the entire cell is:

2 Ag+(aq) + Cu(s) ! 2 Ag(aq) + Cu2+(aq)

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As the cell runs, electrons are transferred from the copper half-cell to the silver half-cell. Unchecked, this reac-

tion would result in the silver half-cell becoming negatively charged and the copper half-cell becoming positively

charged. Once the half-cells became charged in that manner, the reaction could only continue to run if it produced

sufficient energy to take electrons away from a positive charge and push them onto an already negatively charged

half-cell. Chemical reactions, however, do not produce enough energy to push electrons against a charge gradient.

The salt bridge is present to allow negative ions to flow from the silver half-cell to the copper half-cell, and positive

ions to flow from the copper half-cell to the silver half-cell. This migration of ions balances the charge movement

of the electrons. The salt bridge is the upside-down U-shaped tube connecting the two beakers in the image above.This tube is filled with an ionic solution, and the ends are fitted with porous plugs. An ionic solution is chosen such

that neither of its ions will react chemically with any of the other ions in the system. The porous plugs are there to

avoid general mixing but to allow ion migration. If the salt bridge were not present or were removed, the reaction

would immediately stop. As long as the two beakers remain neutral and there are sufficient reactants (Ag+ and Cu)

to continue the reaction, the reaction will continue to run.

We can now see that the silver electrode is the cathode because cations migrate toward it and because reduction

occurs there. The copper electrode is the anode because anions migrate toward it and because oxidation occurs

there. As the cell runs and produces electric current, the mass of the silver electrode increases because when a silver

ion is reduced to a silver atom, it attaches to the silver electrode. The copper electrode will lose mass because as a

copper atom is oxidized to a copper ion, it dissolves in the solution. Eventually, the silver electrode will show a mass

of attached solid silver, and the copper electrode will develop holes and edges as evidence of the reaction wearing

away the strip.

The electrons that pass through the external circuit can do useful work, such as lighting lights, running cell phones,

and so forth. Several cells can be operated together to produce greater current. When we have a series of cells

operating together as one, we call the arrangement a battery. If the light bulb is removed from the circuit with the

electrochemical cell and replaced with a voltmeter (see illustration below), the voltmeter will measure the voltage

(electrical potential energy per unit charge) of the combination of half-cells.

The size of the voltage produced by a cell depends on the temperature, the metals used for electrodes, and the

concentrations of the ions in the solutions. If you increase the concentration of the reactant ion (not the product ion),

the reaction rate will increase and so will the voltage.

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It may seem complicated to construct an electrochemical cell because of all its complexities. Electrochemical cells,

however, are actually easy to make and sometimes even occur accidentally. If you take two coins of different

different metal composition, one copper and one silver for example, and push them part way through the peel of a

whole lemon (as illustrated below), upon connecting the two coins with a wire, a small electric current will flow.

Electrochemical cells occasionally occur accidentally when two water pipes of different material are connected. The

reactions at the joint cause a great deal of corrosion. Plumbing professionals take great care to make sure such

reactions do not occur at pipe joints.

Another common way to construct an electrochemical cell is with the use of a porous cup, as shown in the figure

above. A porous cup is made of a material that is permeable to ions and allows the ions to migrate through the walls.

The cup is not, however, porous enough to allow liquid to flow through. Unfinished clay is one such substance.

The porous cup is soaked in ionic solution to ensure that the pores are filled with ionic solution. One electrode and

its solution are placed in the porous cup, and the other electrode and its corresponding ionic solution is placed in a

beaker. The porous cup with its contents is then set inside the beaker, and a wire is connected between the electrodes.

The walls of the porous cup act as the salt bridge in this cell.

A more unique way to create a battery utilizes a electrolyte dough, which serves as the salt bridge to allow for

charge movement throughout the cell. The video below shows how an electrochemical cell can be constructed using

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aluminum foil, carbon and electrolyte dough. In this cell, aluminum is oxidized, and oxygen from the air is reduced.

The carbon acts as the pathway for the oxygen gas to interact with the other cell components.

MEDIA

Click image to the left for more content.

This animation shows the function of a galvanic cell: http://www.youtube.com/watch?v=A0VUsoeT9aM (1:33).

MEDIA

Click image to the left for more content.

The Standard Hydrogen Half-Cell

When designing cells for specific purposes, it would be very convenient if chemists were able to predict which

half-reaction would gain electrons and which would lose. It would also be useful to predict the voltages that will be

produced by various combinations of half-cells. Recall, however, that both the temperature and the concentrations

of the ion solutions can change the reaction rate and the voltage of a cell. Therefore, the conditions for comparing

half-reactions must be standardized. The conditions chosen to be the standard for half-cells are 25C, 1.0 M for all

solutions, and 1.0 atmosphere pressure.

It would be convenient if a chemist could make 100 standard half-cells, attach them to a voltmeter, and measure

the voltage of each standard half-cell. Unfortunately, as you know, half-cells will not run alone. There must be twohalf-cells connected together; one where oxidation occurs and one where reduction occurs. When you connect two

half-cells together, you can indeed measure the voltage produced, but you do not know how much of the voltage is

due to each of the two standard half-cells. Chemists solved the problem by assigning the standard hydrogen half-cell

a potential of zero. When another standard half-cell was combined with the hydrogen half-cell, the cell voltage could

be measured, and the potential of the cell assigned to the other half-cell.

For example, the standard silver half-cell, Ag+ + e!Ag, could be combined with the standard hydrogen half-cell,2 H+ + 2e! H2, and the resultant voltage of the cell could then be measured. In this cell, the silver ions arereduced and the hydrogen atoms are oxidized. Since both half cells were written in terms of reduction, in order to

write the equation for the cell, the hydrogen half-reaction must be reversed.

2 Ag+ + 2 e ! 2 Ag (reduction)

H2 ! 2 H+ + 2 e (oxidation)2 Ag+ + H2 ! 2 H

+ + 2 Ag (net reaction)

When this cell runs, it produces a voltage of 0.80 volts. This voltage is assigned to the silver half-cell as its voltage

when the silver ions are reduced. The assigned voltages of 0.80 V for the silver half-cell and 0.00 V for the hydrogen

half-cell do not have any meaning in terms of voltages on an absolute scale, but they are perfectly accurate as an

indication of the difference in the abilities of the two half-cells to take electrons. The silver half-cell has a greater

pull on electrons than the hydrogen half-cell, and it is stronger by 0.80 volts.

It was found that some of the standard half-cells are not strong enough to take electrons from the hydrogen half-cell.

In fact, the hydrogen half-cell is the one that takes the electrons and forces the other half-reaction to oxidize. Since

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the hydrogen half-cell was assigned a strength of zero and these half-cells are weaker than hydrogen, their assigned

voltages are negative numbers.

When many half-cells have been combined with the hydrogen half-cell and the voltages measured, we have a list

of half-cells in order of their strength at taking electrons, and we have a numerical value for the difference in their

strength compared to the hydrogen half-cell. Table 1.1 is an expanded list of half-reactions and their assigned

voltages based on comparison to the hydrogen half-cell.

TABLE 1.1: Standard Reduction Potentials

Half-Reactions E (volts)F2(g) + 2 e

! 2 F +2.87

MnO4 + 8 H+ + 5 e ! Mn2+ +

4 H2O

+1.52

Au3+ + 3 e! Au(s) +1.50Cl2(g) + 2 e

! 2 Cl +1.36

Cr2O27 +14 H

+ +6 e! 2 Cr3+ +7 H2O

+1.33

MnO2(s) + 4 H+ + 2 e! Mn2+ +

2 H2

O

+1.28

12

O2(g) + 2 H+ + 2 e!H2O +1.23

Br2(l) + 2 e! 2 Br +1.06

NO3 + 4 H+ + 3 e ! NO(g) +

2 H2O

+0.96

Ag+ + e!Ag +0.80Hg2+ + 2 e! Hg(l) +0.78

NO3 + 2 H+ + e!NO2(g) + H2O +0.78

Fe3+ + e! Fe2+ +0.77I2(s) + 2 e

! 2 I +0.53

Cu2+ + 2 e! Cu(s) +0.34

SO24 + 4 H+ + 2 e ! SO2(g) +

2 H2O

+0.17

Sn4 + +2 e! Sn2+ +0.152 H+ + 2 e!H2(g) 0.00

Pb2+ + 2 e! Pb(s) 0.13Sn2+ + 2 e! Sn(s) 0.14

Ni2+ + 2 e!Ni(s) 0.25Co2+ + 2 e!Co(s) 0.28Fe2+ + 2 e! Fe(s) 0.44Cr3+ + 3 e! Cr(s) 0.74Zn2+ + 2 e! Zn(s) 0.762 H2O + 2 e

! 2 OH+ H2(g) 0.83

Mn2+ + 2 e!Mn(s) 1.

18

Al3+ + 3 e!Al(s) 1.66Mg2+ + 2 e!Mg(s) 2.37

Na+ + e!Na(s) 2.71Ca2+ + 2 e! Ca(s) 2.87Sr2+ + 2 e! Sr(s) 2.89Ba2+ + 2 e! Ba(s) 2.90K+ + e! K(s) 2.92Li+ + e! Li(s) 3.00

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Example:

In a cell formed by the Cu2+ + 2 e! Cu and the Zn2+ + 2 e! Zn standard half-cells, determine which half-cellwill undergo oxidation, which half-cell will undergo reduction, the voltage for the cell, and the balanced equation

for the cell.

Solution:

Simply by looking at the placement of the half-reactions in the standard reduction potential chart, we can determine

that the copper half-cell is closer to the top of the chart than the zinc half-cell, so we know that copper is better atattracting electrons and that half-reaction will run in the reduction direction. The zinc half-cell will be forced to give

up electrons and be oxidized, so that half-reaction will also need to be reversed.

Cu2+ + 2 e ! Cu(s) (reduction)Zn(s) ! Zn

2+ + 2 e (oxidation)

When a half-reaction is reversed in direction, the sign of the E value must be changed. Therefore, the two half-

reactions, along with their E values, become:

Cu2+ + 2 e ! Cu(s) E = +0.34 volts

Zn(s) ! Zn2+ + 2 e E = +0.76 volts

When the two half-reactions are added, we get both the balanced equation and the standard cell voltage.

Cu2+ + 2 e ! Cu(s) E = +0

.

34 volts

Zn(s) ! Zn2+ + 2 e E = +0.76 volts

Zn(s) + Cu2+

! Zn2+ + Cu(s) E

NET = +1.10 volts

Example:

For the standard cell involving the dichromate half cell (Cr2O27 + 14 H

+ + 6 e! 2 Cr3+ + 7 H2O) whose E is

+1.33 volts, and the silver half-cell (Ag+ + e! Ag(s)) whose E is +0.80 volts, determine what will be oxidized

and reduced, name the oxidizing and reducing agents, find the ENET for the cell, and balance the net equation.

Solution:

When we find the two half-reactions in the standard potential chart, the dichromate half-reaction is closer to the top

of the chart, which means that it will run forward (reduction). The silver half-reaction, then, will be forced to reverse

its direction (oxidation). We can write the two half-reactions in the direction they will run with the adjusted E sign

for the silver half-cell.Cr2O

27 + 14 H

+ + 6 e ! 2 Cr3+ + 7 H2O E = +1.33 volts

Ag(s) ! Ag+ + e E =0.80 volts

When we check the number of electrons on the two sides of the equation, we recognize that we must multiply the

silver half-reaction by 6 in order for the electrons to cancel out. This brings up a question when we multiply the

half-reaction by 6, do we multiply the E by 6? In the case of standard half-cells, in order for the half-cell to be

standard, it must be at 25C and the concentration of the ions must be 1.00 M. Hence, when you multiply a half-

reaction in order to balance an equation, you may be doubling an amount of solution, but the molarity must remain

exactly 1.

00 M. Therefore, when you multiply a standard half-cell for balancing purposes, the E

remains exactlythe same. The only instance where the E of a standard half-cell changes is when the sign is changed to reverse the

direction of the reaction. The half-reactions and net reaction for this problem become:

Cr2O27 + 14 H

+ + 6 e ! 2 Cr3+ + 7 H2O E = +1.33 volts

6 Ag(s) ! 6 Ag+ + 6 e E =0.80 volts

6 Ag(s) + Cr2O27 + 14 H

+! 6 Ag+ + 2 Cr3+ + 7 H2O E

NET = +0.53 volts

The chromium in Cr2O27 is being reduced and is therefore the oxidizing agent. It is acceptable to just say the

dichromate ion is the oxidizing agent rather than specifying the chromium in the dichromate ion.

The silver metal is being oxidized and is as a result the reducing agent.

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This may be a convenient place to mention that standard cells last for only some small fraction of second when you

turn them on. When cells begin to run, the ions on the reactant side of the equation are being used up, and the ions

on the product side of the equation are being produced. When a standard cell begins to run, the molarities of the ions

immediately change and are no longer exactly 1.00 M. Consequently, the cell is no longer a standard cell.

Electrochemical Reactions and Metallic Corrosion

The corrosion of metals is usually an electrochemical reaction. The reaction is usually between a metal and the

oxygen and water in the surroundings. Iron is a material that readily rusts (corrodes) in contact with oxygen and

moisture. Since iron is an extremely common metal used for many purposes, such as building construction, doors,

fencing materials, ships hulls, bolts, screws, and nails, considerable effort is spent trying to keep iron from rusting.

There are several common ways of protecting iron from corrosion.

The most common way of protecting iron objects from corrosion is to paint them so that the oxygen and moisture

cannot touch the metal. This system would include storing the iron objects in thick grease to keep possible reactants

away. In certain cases, iron can be alloyed with other metals to make the product more resistant to corrosion.

Stainless steel is an alloy of iron and small amounts of chromium. The addition of the small amount of chromium

makes the steel less susceptible to corrosion. The addition of small amounts of other substances when alloying with

iron also yields other positive properties.Metallic iron may also be coated with a protective layer of a more reactive metal. Iron objects are often electroplated

with chromium or zinc to provide the protective layer. Sometimes iron objects are dipped in molten zinc to produce

a layer of more reactive metal. Covering a metal with a layer of zinc is called galvanizing and is a fairly common

practice with fence wire, nails, buckets, and tubs. To protect ship hulls from corrosion, it is common to place a large

mass of magnesium in electrical contact with the iron hull. The magnesium will corrode more easily than iron, so

the reactants that contact the hull will react with the magnesium first, leaving the hull intact. This system is called

cathodic protection.

Lesson Summary

The redox reaction in an electrochemical cell is a spontaneous reaction.

Ion flow between the chambers of an electrochemical cell keeps the chambers neutral.

Standard potentials for half-cells are determined by measuring the potential of an electrochemical cell in which

the tested cell is paired with the standard hydrogen half-cell.

All standard potentials are measured at standard cell conditions of 25C and 1.00 M solutions of all ions.

The voltage of a standard electrochemical cell is obtained by finding the difference between the reduction

potentials of the two half-cells.

Further Reading / Supplemental Links

The learner.org website allows users to view streaming videos of the Annenberg series of chemistry videos. You arerequired to register before you can watch the videos but there is no charge. The website has one video that relates to

this lesson called The Busy Electron that explains the principles of electrochemical cell design through batteries,

sensors, and a solar-powered car.

http://learner.org/resources/series61.html

The following provides text and animations about electrochemical cells and batteries.

http://www.splung.com/content/sid/3/page/batteries

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Review Questions

1. In a standard cell composed of the zinc and copper half-cells, will the current in the external circuit flow from

Zn to Cu or from Cu to Zn?

2. For a standard cell with the following balanced equation: Sn(s) + 2 Ag+! Sn2+ + 2 Ag(s),

a. what is being oxidized?

b. what is the reducing agent?

c. what is the ENET ?d. after the reaction has reached equilibrium, what will be its voltage?

3. Balance the following equation using the half-reactions from the standard reduction potential chart: Cr2O27 +

Fe2+ + H+ ! Cr3+ + Fe3+ + H2O.

All images, unless otherwise stated, are created by the CK-12 Foundation and are under the Creative Commons

license CC-BY-NC-SA.

electrochemical cell an arrangement of electrodes and ionic solutions in which a spontaneous redox reaction is

used to produce a flow of electrons in an external circuit

salt bridge a U-shaped tube containing an electrolyte that connects two half-cells in an electrochemical cell

voltage the potential difference between two points in an electric circuit

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