Chap 19 Electrochemistry - Bakersfield College B1B Notes Fall_09/Chap_… · Equilibrium Constants from Cell Potentials 7. ... In this chapter we will focus on electron transfer rather

1

Electrochemistry

Half-Reactions

1. Balancing Oxidation–Reduction Reactions in Acidic and Basic Solutions

Voltaic Cells

2. Construction of Voltaic Cells

3. Notation for Voltaic Cells

4. Cell Potential

5. Standard Cell Potentials and Standard Electrode Potentials

6. Equilibrium Constants from Cell Potentials

7. Dependence of Cell Potentials on Concentration

8. Some Commercial Voltaic Cells

Electrolytic Cells

9. Electrolysis of Molten Salts

10. Aqueous Electrolysis

11. Stoichiometry of Electrolysis

2

Electrochemistry

• Balancing Oxidation–Reduction Reactions in Acidic and Basic Solutions

a. Learn the steps for balancing oxidation–reduction reactions using the half-reaction method.

b. Balance equations by the half-reaction method (acidic solutions).

c. Learn the additional steps for balancing oxidation–reduction reactions in basic solution using the half-reaction method.

d. Balance equations using the half-reaction method (basic solution).

Learning Objectives

2. Construction of Voltaic Cells

– Define electrochemical cell, voltaic (galvanic

cell), electrolytic cell, and half-cell.

– Describe the function of the salt bridge in a

voltaic cell.

– State the reaction that occurs at the anode and

the cathode in an electrochemical cell.

– Define cell reaction.

– Sketch and label a voltaic cell.

3. Notation for Voltaic Cells

– Write the cell reaction from the cell notation.

4. Cell Potential

– Define cell potential and volt.

– Calculate the quantity of work from a given

amount of cell reactant.

3

5. Standard Cell Potentials and Standard Electrode Potentials

– Explain how the electrode potential of a cell is an intensive property.

– Define standard cell potential and standard electrode potential.

– Interpret the table of standard reduction potentials.

– Determine the relative strengths of oxidizing and reducing agents.

– Determine the direction of spontaneity from electrode potentials.

– Calculate cell potentials from standard potentials.

6. Equilibrium Constants from Cell Potentials

– Calculate the free-energy change from electrode

potentials.

– Calculate the cell potential from free-energy

change.

– Calculate the equilibrium constant from cell

potential.

7. Dependence of Cell Potential on Concentration

– Calculate the cell potential for nonstandard

conditions.

– Describe how pH can be determined using a

glass electrode.

8. Some Commercial Voltaic Cells

– Describe the construction and reactions of a

zinc–carbon dry cell, a lithium–iodine battery, a

lead storage cell, and a nickel–cadmium cell.

– Explain the operation of a proton-exchange

membrane fuel cell.

– Explain the electrochemical process of the

rusting of iron.

– Define cathodic protection.

9. Electrolysis of Molten Salts

– Define electrolysis.

4

10. Aqueous Electrolysis

– Learn the half-reactions for water undergoing

oxidation and reduction.

– Predict the half-reactions in an aqueous

electrolysis.

11. Stoichiometry of Electrolysis

– Calculate the amount of charge from the amount

of product in an electrolysis.

– Calculate the amount of product from the

amount of charge in an electrolysis.

Our first step in studying electrochemical cell is to

balance its oxidation–reduction reaction.

We will use the half-reaction method from Section 4.6

and extend it to acidic or basic solutions.

In this chapter we will focus on electron transfer rather

than proton transfer so the hydronium ion, H3O+(aq), will

be represented by its simpler notation, H+(aq). Only the

notation, not the chemistry, is different.

Oxidation-Reduction Reactions

• In Chapter 4 we introduced the half-reaction

method for balancing simple oxidation-reduction

reactions.

– Oxidation-reduction reactions always

involve a transfer of electrons from one species to another.

– Recall that the species losing electrons is oxidized, while the species gaining

electrons is reduced.

5


• Describing Oxidation-Reduction Reactions

– An oxidizing agent is a species that oxidizes another species; it is itself reduced.

– A reducing agent is a species that reduces another species; it is itself oxidized.

)()(2

)(2

)( saqaqs CuFeCuFe ++++→→→→++++++++++++

oxidizing agent

reducing agentLoss of 2 e-1 oxidation

Gain of 2 e-1 reduction

What reaction is going

on and what is the

equation?

A voltaic cell employs a spontaneous oxidation–reduction reaction

as a source of energy. It separates the reaction into two half-

reactions, physically separating one half-reaction from the other.

We will be studying more complex situations, so our initial

analysis is key.

First, we need to identify what is being oxidized and what

is being reduced.

Then, we determine if the reaction is in acidic or basic

conditions.

6

Balancing Oxidation-Reduction Equations in Acid Solution

1. Assign oxidation numbers

2. Determine half reactions

3. Complete and balance each half-reaction

a. Balance all atoms except O and H

b. Balance O atoms by adding H2O’s to one side

c. Balance H atoms by adding H+ to one side

d. Balance electric charges by adding e- to the more positive side

4. Combine each half reaction to obtain the final balanced

oxidation reduction equation (Multiply by appropriate

factors and cancel species appearing on both sides of equation

Balancing Oxidation-Reduction Equations in Basic Solution

1. Assign oxidation numbers

2. Determine half reactions

3. Complete and balance each half-reaction

a. Balance all atoms except O and H

b. Balance O atoms by adding H2O’s to one side

c. Balance H atoms by adding H+ to one side

d. Balance electric charges by adding e- to the more positive side

4. Note the number of H+ ions in the equation. Add this number

of OH- ions to both sides of the equation.

6. Combine each half reaction to obtain the final balanced

oxidation reduction equation (Multiply by appropriate

factors and cancel species appearing on both sides of equation

5. Simplify the equation by noting that H+ and OH- react to form

H2O. Cancel waters that occur on both sides of the equation and

reduce the equation to simplest terms.

Balance in acid solution:

Mn+2 + BiO3- → MnO4

- + Bi+3

Balance in Basic solution:

S2- + I2 → SO42- + I-

7

Balance in acid solution:

Mn+2 + BiO3- → MnO4

- + Bi+3

2(Mn+2 + 4 H2O → MnO4- + 8 H+ + 5e- )

5(6 H+ + BiO3- + 2e- → Bi+3 + 3 H2O)

2Mn+2 + 8 H2O → 2MnO4- + 16 H+ + 10e- )

30 H+ + 5 BiO3- + 10e- → 5Bi+3 + 15 H2O)

2Mn2+ + 14 H+ + 5 BiO3- → 2 MnO4

- + 5 Bi3+ + 7 H2O


S2- + I2 → SO42- + I-

8 OH- +4H2O + S2-→ SO4

2- + 8 H+ + 8 OH-+ 8e-

I2 + 2 e-→ 2I-

4 (I2 + 2 e-→ 2I-)

4 I2 + 8 e-→ 8I-

8 OH- + S2- + 4 I2 → SO42- + 8 I- +4 H2O

8 OH- +4H2O + S2-→ SO4

2- + 8 H+ + 8 OH-+ 8e-

8 OH- +4H2O + S2-→ SO4

2- + 8 H+ + 8 OH-+ 8e-

• Dichromate ion in acidic solution is an oxidizing

agent. When it reacts with zinc, the metal is oxidized

to Zn2+, and nitrate is reduced. Assume that

dichromate ion is reduced to Cr3+.

• Write the balanced ionic equation for this reaction

using the half-reaction method.

8

First we determine the oxidation numbers of N and Zn:

+6 +3 0 +2

Cr2O72-(aq) � Cr3+(aq) and Zn(s) � Zn2+(aq)

Cr was reduced from +6 to +3.

Zn was oxidized from 0 to +2.

Now we balance the half-reactions.

Oxidation half-reaction

Zn(s) � Zn2+(aq) + 2e-

Reduction half-reaction

First we balance Cr and O:

Cr2O72-(aq) � 2Cr3+(aq) + 7H2O(l)

Next we balance H:

14H+(aq) + Cr2O72-(aq) � 2Cr3+(aq) + 7H2O(l)

Then we balance e-:

6e- + 14H+(aq) + Cr2O72-(aq) � 2Cr3+(aq) + 7H2O(l)

Now we combine the two half-reactions by multiplying

the oxidation half reaction by 3.

3Zn(s) � 3Zn2+(aq) + 6e-

6e- + 14H+(aq) + Cr2O72-(aq) � 2Cr3+(aq) + 7H2O(l)

3Zn(s) + 14H+(aq) + Cr2O72-(aq) �

3Zn2+(aq) + 2Cr3+(aq) + 7H2O(l)

Check that atoms and charge are balanced.

3Zn; 14H; 2Cr; 7O; charge +12

9

To balance a reaction in basic conditions, first follow

the same procedure as for acidic solution.

• Then

1. Add one OH- to both sides for each H+.

2. When H+ and OH- occur on the same side,

combine them to form H2O.

3. Cancel water molecules that occur on both sides.


S2- + I2 → SO42- + I-

Did This Earlier

• Lead(II) ion, Pb2+, yields the plumbite ion, Pb(OH)3-,

in basic solution. In turn, this ion is oxidized in basic

hypochlorite solution, ClO-, to lead(IV) oxide, PbO2.

• Balance the equation for this reaction using the half-

reaction method. The skeleton equation is

• Pb(OH)3- + ClO- � PbO2 + Cl-

Another example

First we determine the oxidation number of Pb and

Cl in each species.

+2 +1 +4 -1

Pb(OH)3- + ClO- � PbO2 + Cl-

Pb is oxidized from +2 to +4.

Cl is reduced from +1 to -1.

Now we balance the half-reactions.

10

Oxidation half-reaction

First we balance Pb and O:

Pb(OH)3-(aq) � PbO2(s) + H2O(l)

Next we balance H:

Pb(OH)3-(aq) � PbO2(s) + H2O(l) + H+(aq)

Then we balance e-:

Pb(OH)3-(aq) � PbO2(s) + H2O(l) + H+(aq) + 2e-

Reduction half-reaction

First we balance Cl and O:

ClO-(aq) � Cl-(aq) + H2O(l)

Next we balance H:

2H+(aq) + ClO-(aq) � Cl-(aq) + H2O(l)

Finally we balance e-:

2e- + 2H+(aq) + ClO-(aq) � Cl-(aq) + H2O(l)

Now we combine the half-reactions.

Pb(OH)3-(aq) � PbO2(s) + H2O(l) + H+(aq) + 2e-

2e- + 2H+(aq) + ClO-(aq) � Cl-(aq) + H2O(l)

H+(aq) + Pb(OH)3-(aq) + ClO-(aq) �

PbO2(s) + Cl-(aq) + 2H2O(l)

11

H+(aq) + Pb(OH)3-(aq) + ClO-(aq) �

PbO2(s) + Cl-(aq) + 2H2O(l)

To convert to basic solution, we add OH- to each side,

converting H+ to H2O.

H2O(l) + Pb(OH)3-(aq) + ClO-(aq) �

PbO2(s) + Cl-(aq) + 2H2O(l) + OH-(aq)

Finally, we cancel the H2O that is on both sides.

Pb(OH)3-(aq) + ClO-(aq) �

PbO2(s) + Cl-(aq) + H2O(l) + OH-(aq)

Do exercise 19.1 & 2 and see problems 19.35-37

The next several topics describe battery cells or

voltaic cells (galvanic cells).

An electrochemical cell is a system consisting of

electrodes that dip into an electrolyte and in which a

chemical reaction either uses or generates an electric

current.

A voltaic or galvanic cell is an electrochemical cell

in which a spontaneous reaction generates an electric

current.

An electrolytic cell is an electrochemical cell in

which an electric current drives an otherwise

nonspontaneous reaction.


• In this chapter we will show how a cell is

constructed to physically separate an oxidation-reduction reaction into two half-reactions.

– The force with which electrons travel from

the oxidation half-reaction to the reduction half-reaction is measured as voltage.

12

Electrochemistry• An electrochemical cell is a system

consisting of electrodes that dip into an electrolyte in which a chemical reaction either

uses or generates an electric current.

– A voltaic, or galvanic, cell is an electrochemical cell in which a spontaneous reaction generates an electric current.

– An electrolytic cell is an electrochemical cell in which an electric current drives an otherwise nonspontaneous reaction.

– In this chapter we will discuss the basic principles behind these cells and explore some of their commercial uses.

Voltaic Cells

• A voltaic cell consists of two half-cells that are

electrically connected.

– Each half-cell is a portion of the electrochemical cell in which a half-reaction takes place.

– A simple half-cell can be made from a metal strip dipped into a solution of its metal ion.

– For example, the zinc-zinc ion half cell consists consists of a zinc strip dipped into a solution of a zinc salt.

Voltaic Cells

• A voltaic cell consists of two half-cells that are electrically connected.

– Another simple half-cell consists of a copper strip dipped into a solution of a copper salt.

– In a voltaic cell, two half-cells are connected in such a way that electrons flow from one metal electrode to the other through an external circuit.

– Figure 19.2 illustrates an atomic view of a zinc/copper voltaic cell.

13

Figure 19.2: Atomic view of voltaic cell.

x

The zinc metal atom loses two electrons, forming Zn2+

ions.

The Cu2+ ions gain two electrons, forming solid

copper.

The electrons flow through the external circuit from the zinc electrode to the copper electrode.

Ions flow through the salt bridge to maintain charge balance.

Voltaic Cells

• As long as there is an external circuit, electrons

can flow through it from one electrode to the

other.

– Because zinc has a greater tendency to lose electrons than copper, zinc atoms in the zinc electrode lose electrons to form zinc ions.

– The electrons flow through the external circuit to the copper electrode where copper ions gain the electrons to become copper metal.

14

Voltaic Cells

• The two half-cells must also be connected

internally to allow ions to flow between them.

– Without this internal connection, too much positive charge builds up in the zinc half-cell (and too much negative charge in the copper half-cell) causing the reaction to stop.

– Figure 19.3A and 19.3B show the two half-cells of a voltaic cell connected by salt bridge.

Figure 19.3: Two electrodes are connected by an

external circuit.

Voltaic Cells

• A salt bridge is a tube of an electrolyte in a gel

that is connected to the two half-cells of a voltaic

cell.

– The salt bridge allows the flow of ions but prevents the mixing of the different solutions that would allow direct

reaction of the cell reactants.

– Figure 19.3C shows an actual setup of the zinc-copper cell.

15

Voltaic Cells• The two half-cell reactions, as noted earlier, are:

– The first reaction, in which electrons are lost, is the oxidation half-reaction.

– The electrode at which oxidation occurs is the anode.

−−−−++++ ++++→→→→ e2)aq(Zn)s(Zn 2

)s(Cue2)aq(Cu2

→→→→++++−−−−++++

(oxidation half-reaction)

(reduction half-reaction)

– The second reaction, in which electrons are gained, is the reduction half-reaction.

– The electrode at which reduction occurs is the cathode.

Voltaic Cells

• Note that the sum of the two half-reactions

– Note that electrons are given up at the anode and thus flow from it to the cathode where reduction occurs.

)s(Cu)aq(Zn)aq(Cu)s(Zn22

++++→→→→++++++++++++

is the net reaction that occurs in the voltaic cell; it is called the cell reaction

– The anode in a voltaic cell has a negative sign because electrons flow from it. (See Figure 20.4 andAnimation: Anode Reaction)

– The cathode in a voltaic cell has a positive sign (See Animation: Cathode Reaction)

16

Figure 19.4:

Voltaic Cell

Do exercise 19.3

And look at

Problems 19.43-44

Notation for Voltaic Cells

• It is convenient to have a shorthand way of

designating particular voltaic cells.

– The anode (oxidation half-cell) is written on the left. The cathode (reduction half-cell) is written on the right.

– The cell consisting of the zinc-zinc ion half-cell and the copper-copper ion half-cell, is written

)s(Cu|)aq(Cu||)aq(Zn|)s(Zn22 ++++++++

anode cathode

– The cell terminals are at the extreme ends in the cell notation.

)s(Cu|)aq(Cu||)aq(Zn|)s(Zn22 ++++++++

anode cathodesalt bridge

– The cell consisting of the zinc-zinc ion half-cell and the copper-copper ion half-cell, is written

– A single vertical bar indicates a phase boundary, such as between a solid terminal and the electrode solution.

anode cathodesalt bridge

)s(Cu|)aq(Cu||)aq(Zn|)s(Zn22 ++++++++

17

Notation for Voltaic Cells

• When the half-reaction involves a gas, an

inert material such as platinum serves as a

terminal and an electrode surface on which

the reaction occurs.

– Figure 19.5 shows a hydrogen electrode; hydrogen bubbles over a platinum plate immersed in an acidic solution.

– The cathode half-reaction is

)g(He2)aq(H2 2→→→→++++

−−−−++++

– The notation for the hydrogen electrode,

written as a cathode, is

Pt|)g(H|)aq(H 2

++++

– To write such an electrode as an anode, you simply reverse the notation.

)aq(H|)g(H|Pt 2

++++

– In the cell notation, these are written in

parentheses. For example,

Pt|)atm0.1(H|)aq(H||)M0.1(Zn|)s(Zn 22 ++++++++

Figure 19.5:

Hydrogen

Electrode

18

A Problem To Consider

• Give the overall cell reaction for the voltaic cell

Pt|)atm0.1(H|)aq(H||)M0.1(Cd|)s(Cd 22 ++++++++

– The half-cell reactions are

)g(He2)aq(H2 2→→→→++++

−−−−++++

−−−−++++++++→→→→ e2)aq(Cd)s(Cd

2

)g(H)aq(Cd)aq(H2)s(Cd 22

++++→→→→++++++++++++

Do Exercise 19.4 and see problems 19.49-50

Electromotive Force (Cell Potential)

• The movement of electrons is analogous to the

pumping of water from one point to another.

– Water moves from a point of high pressure to a point of lower pressure. Thus, a pressure difference is required.

– The work expended in moving the water through a pipe depends on the volume of water and the pressure difference.

– An electric charge moves from a point of high electrical potential (high electrical pressure) to one of lower electrical potential.

– The work expended in moving the electrical charge through a conductor depends on the amount of charge and the potential difference.

Electromotive Force• Potential difference is the difference in electric

potential (electrical pressure) between two points.

– You measure this quantity in volts.

– The volt, V, is the SI unit of potential

difference equivalent to 1 joule of energy per coulomb of charge.

CJ1volt1 ====

Electrical work = charge x potential difference

Joules = coulombs x volts

19

Electromotive Force

• The Faraday constant, F, is the magnitude of

charge on one mole of electrons; it equals 96,500

coulombs (9.65 x 104 C).

– In moving 1 mol of electrons through a circuit, the numerical value of the work done by a voltaic cellis the product of the Faraday constant (F) times the potential difference between the electrodes.

)coulombvolts(J/)F(coulombswork(J) ××××−−−−====

work done by the system

– In the normal operation of a voltaic cell, the potential difference (voltage) across the electrodes is less than than the maximum possible voltage of the cell.

Electromotive Force

– The actual flow of electrons reduces the electrical pressure.

– Thus, a cell voltage has its maximum value when no current flows.

Electromotive Force

• The maximum potential difference between

the electrodes of a voltaic cell is referred to

as the electromotive force (emf) of the cell,

or Ecell.

– It can be measured by an electronic digital

voltmeter (Figure 19.6), which draws negligible current.

20

Electromotive Force

• We can now write an expression for the

maximum work attainable by a voltaic

cell.

– The maximum work for molar amounts of reactants is

cellmax nFE−−−−====w

– Let n be the number of (mol) electrons transferred in the overall cell reaction.

Work Exercise 19.6 Look at Problems 19.57-60

A Problem To Consider• The emf of the electrochemical cell below is 0.650

V. Calculate the maximum electrical work of this

cell when 0.500 g H2 is consumed.

)aq(H2)l(Hg2)g(H)aq(Hg 2

2

2

++++++++++++++++

– The half-reactions are

)l(Hg2e2)aq(Hg2

2

−−−−++++++++

−−−−++++++++ e2)aq(H2)g(H2

– n = 2, and the maximum work for the reaction is written as


)V650.0()C1065.9(2 4max

××××××××××××−−−−====w

21

)V650.0()C1065.9(2 4max

××××××××××××−−−−====w


J1025.1 5max

××××−−−−====w

• The emf of the electrochemical cell below is 0.650

V. Calculate the maximum electrical work of this

cell when 0.500 g H2 is consumed.

– For 0.500 g H2, the maximum work is

J1009.3Hmol1

J1025.1

Hg02.2

Hmol1Hg500.0

4

2

5

2

22

××××−−−−====××××−−−−

××××××××

)aq(H2)l(Hg2)g(H)aq(Hg 2

2

2

++++++++++++++++

Standard Cell emf’s and Standard Electrode

Potentials

• A cell emf is a measure of the driving force

of the cell reaction.

– The reaction at the anode has a definite oxidation potential, while the reaction at the cathode has a definite reduction potential.

– Thus, the overall cell emf is a combination of these two potentials.

–Ecell = oxidation potential + reduction potential

– A reduction potential is a measure of the tendency to gain electrons in the reduction half-reaction.

– You can look at the oxidation half-reaction as the reverse of a corresponding reduction reaction.

– The oxidation potential for an oxidation half-reaction is the negative of the

reduction potential for the reverse reaction.

22

– Consider the zinc-copper cell described earlier.

)s(Cu|)aq(Cu||)aq(Zn|)s(Zn22 ++++++++

Standard Cell emf’s and Standard Electrode

Potentials

• By convention, the Table of Standard

Electrode Potentials (Table 19.1) are

tabulated as reduction potentials.

−−−−++++++++→→→→ e2)aq(Zn)s(Zn

2

– The two half-reactions are

)s(Cue2)aq(Cu2

→→→→++++−−−−++++

– The zinc half-reaction is an oxidation.

– If you write EZn for the reduction potential of zinc, then –EZn is the oxidation potential of zinc.

)s(Zne2)aq(Zn2

→→→→++++−−−−++++

−−−−++++++++→→→→ e2)aq(Zn)s(Zn

2

(EZn) Reduction

-(EZn)

– The copper half-reaction is a reduction..

(ECu))s(Cue2)aq(Cu2

→→→→++++−−−−++++

– Write ECu for the electrode potential.

– For this cell, the cell emf is the sum of the reduction potential for the copper half-cell and the oxidation potential for the zinc half-cell.

Oxidat.

)E(EE ZnCucell−−−−++++====

ZnCucell EEE −−−−====

– Note that the cell emf is the difference between

the two electrode potentials.

anodecathodecellEEE −−−−====

– In general, Ecell is obtained by subtracting the anode potential from the cathode potential.

– The electrode potential is an intensive property whose value is independent of the amount of species in the reaction.

23

– Thus, the electrode potential for the half-reaction

)s(Cu2e4)aq(Cu22

→→→→++++−−−−++++

is the same as for

)s(Cue2)aq(Cu2

→→→→++++−−−−++++

– Note that individual electrode potentials require that we choose a reference electrode.

Tabulating Standard Electrode Potentials

• The standard emf, E°cell, is the emf of a cell

operating under standard conditions of

concentration (1 M), pressure (1 atm), and

temperature (25°C).

– You arbitrarily assign this reference electrode a potential of zero and obtain the potentials of the

other electrodes by measuring the emf’s.

– By convention, the reference chosen for comparing electrode potentials is the standard hydrogen electrode. (see Figure 19.5)

– Standard electrode potentials (Table 19.1) are measured relative to this hydrogen reference.

24

– For example, when you measure the emf of a

cell composed of a zinc electrode connected to a hydrogen electrode, you obtain 0.76 V.

Tabulating Standard Electrode Potentials

• The standard electrode potential, E°, is the

electrode potential when concentrations of solutes

are 1 M, gas pressures are 1 atm, and the

temperature is 25°C. (Table 19.1)

– Since zinc acts as the anode (oxidation) in this cell, its reduction potential is listed as –0.76 V.

25

Strengths of Oxidizing and Reducing Agents

• Standard electrode potentials are useful in determining the

strengths of oxidizing and reducing agents under

standard-state conditions.

– A reduction half-reaction has the general form

speciesreducednespeciesoxidized →→→→++++−−−−

– The oxidized species acts as an oxidizing agent.

– Consequently, the strongest oxidizing agents in a table of standard electrode potentials are the oxidized speciescorresponding to the half-reactions with the largest (most positive) Eo values. (For example F2(g))

– An oxidation half-reaction has the general form

−−−−++++→→→→ nespeciesoxidizedspeciesreduced

– The reduced species acts as a reducing agent.

– Consequently, the strongest reducing agentsin a table of standard electrode potentials are the reduced species corresponding to the

half-reactions with the smallest (most negative) Eo values. (for example, Li(s))

26

• Which is the stronger reducing agent under

standard conditions: Sn2+ (to Sn4+) or Fe (to

Fe2+)?

• Which is the stronger oxidizing agent under

standard conditions: Cl2 or MnO4-?

The stronger reducing agent will be oxidized and has the more negative electrode potential.

The standard (reduction) potentials areSn2+ to Sn4+ E = 0.15 VFe to Fe2+ E = –0.41 V

The stronger reducing agent is Fe (to Fe2+).

• The stronger oxidizing agent will be reduced.

• The standard (reduction) potentials are

• Cl2 to Cl- E = 1.36 V

• MnO4- to Mn2+ E = 1.49 V

• The stronger oxidizing agent is MnO4-.

Calculating Cell emf’s from Standard Potentials

• The emf of a voltaic cell constructed from standard

electrodes is easily calculated using a table of electrode

potentials.– Consider a cell constructed of the following two half-

reactions.

V0.40E);s(Cde2)aq(Cdo2

−−−−====→→→→++++−−−−++++

V0.80E);s(Age1)aq(Ago

====→→→→++++−−−−++++

– You will need to reverse one of these reactions to obtain the oxidation part of the cell reaction.


−−−−====→→→→++++−−−−++++


====→→→→++++−−−−++++

27

– This will be Cd, because has the more negative electrode potential.


−−−−====→→→→++++−−−−++++


====→→→→++++−−−−++++

– Therefore, you reverse the half-reaction and

change the sign of the half-cell potential.

V0.40E;e2)aq(Cd)s(Cdo2

====++++→→→→−−−−++++


====→→→→++++−−−−++++

– We must double the silver half-reaction so that when the reactions are added, the electrons

cancel.


====++++→→→→−−−−++++


====→→→→++++−−−−++++

– This does not affect the half-cell potentials, which do not depend on the amount of substance.


====++++→→→→−−−−++++


====→→→→++++−−−−++++

– Now we can add the two half-reactions to obtain the overall cell reaction and cell emf.


====++++→→→→−−−−++++

V0.80E);s(Ag2e2)aq(Ag2o

====→→→→++++−−−−++++

– Now we can add the two half-reactions to obtain the overall cell reaction and cell emf.


====++++→→→→−−−−++++

V0.80E);s(Ag2e2)aq(Ag2o

====→→→→++++−−−−++++

V1.20E);s(Ag2)aq(Cd)aq(Ag2)s(Cdocell

2====++++→→→→++++

++++++++

– The corresponding cell notation would be

)s(Ag|)M1(Ag||)M1(Cd|)s(Cd2 ++++++++

Do Exercise 19.7 See Problems 19.61-64

28

– Note that the emf of the cell equals the standard electrode potential of the cathode minus the

standard electrode potential of the anode.

oanode

ocathode

ocell EEE −−−−====

• Calculate the standard emf for the following

voltaic cell at 25°C using standard electrode

potentials. What is the overall reaction?

)s(Fe|)aq(Fe||)aq(Al|)s(Al23 ++++++++

– The reduction half-reactions and standard potentials are

V1.66E);s(Ale3)aq(Alo3

−−−−====→→→→++++−−−−++++

V0.41E);s(Fee2)aq(Feo2

−−−−====→→→→++++−−−−++++

V1.66E;e3)aq(Al)s(Alo3

====++++→→→→−−−−++++

V0.41E);s(Fee2)aq(Feo2

−−−−====→→→→++++−−−−++++

)s(Fe|)aq(Fe||)aq(Al|)s(Al23 ++++++++

– You reverse the first half-reaction and its half-cell potential to obtain

– To obtain the overall reaction we must balance the electrons.

V1.66E;e6)aq(Al2)s(Al2 o3====++++→→→→

−−−−++++

V0.41E);s(Fe3e6)aq(Fe3o2

−−−−====→→→→++++−−−−++++

)s(Fe|)aq(Fe||)aq(Al|)s(Al23 ++++++++

– Now we add the reactions to get the overall cell reaction and cell emf.

V1.66E;e6)aq(Al2)s(Al2o3

====++++→→→→−−−−++++

V0.41E);s(Fe3e6)aq(Fe3o2

−−−−====→→→→++++−−−−++++

V25.1E);s(Fe3)aq(Al2)aq(Fe3)s(Al2o32

====++++→→→→++++++++++++

29

How do you determine the

direction of spontaneity?

Look at example 19.7 and example 19.8

See problems 19.65 and 19.66

∆G

Look at Concept check 19.2

Page 790

Equilibrium Constants from emf’s

• Some of the most important results from

electrochemistry are the relationships among

E°cell, free energy, and equilibrium constant.

– In Chapter 18 we saw that DG equals the maximum

useful work of a reaction.

– For a voltaic cell, work = -nFEo, so when reactants are in their standard states

oonFEG −−−−====∆∆∆∆

– The measurement of cell emf’s gives you yet another way of calculating equilibrium constants.

30

– Combining the previous equation, ∆Go = -nFEocell,

with the equation ∆Go = -RTlnK, we get

KlnRTnFEocell

====

KlognF

RT303.2E

ocell

====

– Or, rearranging, we get

– Substituting values for the constants R and F at 25 oC gives the equation

Klogn

0592.0E

ocell

====

(values in volts at 25 oC)

Look at Examples 19.9 and 19.10

Do Exercises 19.10 and 19.11

Look at problems 19.73 & 74, 81 & 82

Do Exercise 19.9 and see problems 19.69 and 19.70

– Figure 19.7 summarizes the various relationships

among K, ∆Go,and Eo

cell.

31


• The standard emf for the following cell is 1.10 V.

)s(Cu|)aq(Cu||)aq(Zn|)s(Zn22 ++++++++

Calculate the equilibrium constant Kc for the reaction


++++++++++++++++

– Note that n=2. Substituting into the equation relating Eo

cell and K gives

Klog2

0592.0V10.1 ====

KlognF

RT303.2E o

cell====

– Solving for log Kc, you find

37.2Klog ====

– Now take the antilog of both sides:

37c 101.637.2)log(antiK ××××========

– The number of significant figures in the answer equals the number of decimal places in 37.2 (one). Thus

37c 102K ××××====

Dependence of emf on Concentration

• Recall that the free energy change, ∆G, is related

to the standard free energy change, ∆G°, by the

following equation.

– Here Q is the thermodynamic reaction quotient.

QlnRTGGo

++++∆∆∆∆====∆∆∆∆

QlnRTnFEnFEocellcell

++++−−−−====−−−−

– Combining the previous equation, ∆Go = -nFEocell,

with the equation ∆Go = -RTlnK, we get

32


• The result rearranges to give the Nernst equation,

an equation relating the cell emf to its standard

emf and the reaction quotient.

QlognF

RT303.2EE

ocellcell

−−−−====

– Substituting values for R and F at 25 oC, we get

Qlogn

0592.0EE

ocellcell

−−−−====

(values in volts at 25 oC)


• The result rearranges to give the Nernst equation,

an equation relating the cell emf to its standard

emf and the reaction quotient.

– The Nernst equation illustrates why cell emfdecreases as the cell reaction proceeds.

– As reactant concentrations decrease and product concentrations increase, Q increases, thus increasing log Q which in

turn decreases the cell emf.


• What is the emf of the following voltaic cell at 25°C?

)s(Cu|)M100.0(Cu||)M101(Zn|)s(Zn252 ++++−−−−++++

××××

The standard emf of the cell is 1.10 V.

– The cell reaction is


++++++++++++++++

– The number of electrons transferred is 2; hence n = 2. The reaction quotient is

45

2

2

1000.1100.0

1000.1

]Cu[

]Zn[Q

−−−−

−−−−

++++

++++

××××====××××

========

33

– The standard emf is 1.10 V, so the Nernst equation becomes

Qlogn

0592.0EE

ocellcell

−−−−====

)1000.1log(2

0592.0V10.1E

4cell

−−−−××××−−−−====

V22.1)12.0(V10.1Ecell====−−−−−−−−====

– The cell emf is 1.22 V.

Do Exercise 19.13 Look at Problems 19.85 &86

Concept Check 19.3

Page 796

Some Commercial Voltaic Cells

• The Leclanché dry cell, or zinc-carbon dry cell, is

a voltaic cell with a zinc can as the anode and a

graphite rod in the center surrounded by a paste of

manganese dioxide, ammonium and zinc

chlorides, and carbon black, as the cathode.

– The electrode reactions are

−−−−++++++++→→→→ e2)aq(Zn)s(Zn

2

→→→→++++++++−−−−++++

e2)s(MnO2)aq(NH2 24 )aq(NH2)l(OH)s(OMn 3232++++++++

anode

cathode

(see Figure 19.9)

34

Figure 19.9:

Leclanché Dry Cell


• The alkaline dry cell, is similar to the Leclanché

cell, but it has potassium hydroxide in place of

ammonium chloride.

– The electrode reactions are−−−−++++

++++→→→→ e2)aq(Zn)s(Zn2

→→→→++++++++−−−−

e2)l(OH)s(MnO 22 )aq(OH2)s(OMn 32

−−−−++++

anode

cathode

(see Figure 19.10)

Figure 19.10: A Small Alkaline Dry Cell

35


• The lithium-iodine battery is a solid state battery

in which the anode is lithium metal and the

cathode is an I2 complex.

– The solid state electrodes are separated by a thin crystalline layer of lithium iodide.

(see Figure 19.11)

– Although it produces a low current, it is very reliable and is used to power pacemakers.

Figure 19.11:

Solid-State

Lithium-Iodine

Battery


• The lead storage cell (a rechargeable cell)

consists of electrodes of lead alloy grids; one

electrode is packed with a spongy lead to form the

anode, and the other electrode is packed with lead

dioxide to form the cathode.

)l(OH2)s(PbSO 24++++


−−−−++++−−−−++++++++→→→→++++ e2)aq(H)s(PbSO)aq(HSO)s(Pb 44

→→→→++++++++++++−−−−−−−−++++ e2)aq(HSO)aq(H3)s(PbO 42

anode

cathode

(see Figure 20.12)

36

Figure 19.12: Lead Storage Battery


• The nickel-cadmium cell (nicad cell) consists of

an anode of cadmium and a cathode of hydrated

nickel oxide on nickel; the electrolyte is potassium

hydroxide.


−−−−−−−−++++→→→→++++ e2)s()OH(Cd)aq(OH2)s(Cd 2

→→→→++++++++−−−−

e)l(OH)s(NiOOH 2)aq(OH)s()OH(Ni 2

−−−−++++

anode

cathode

(see Figure 19.14)

Figure 19.14: Nicad Storage Batteries

37


• A fuel cell is essentially a battery, but differs by

operating with a continuous supply of energetic

reactants, or fuel.

– For a hydrogen-oxygen fuel cell, the electrode reactions are

−−−−−−−−++++→→→→++++ e4)l(OH)aq(OH4)g(H2 22

)aq(OH4e4)l(OH2)g(O 22

−−−−−−−−→→→→++++++++

anode

cathode

(see Figure 19.15)

Figure 19.15: Hydrogen-Oxygen Fuel Cell

Research

how a fuel

cell works

and what

different

types exist.

To do:

Figure 19.16: The Electrochemical Process

Involved in the Rusting of Iron

38

Figure 19.17:

Cathodic

Protection of

Buried Steel

Pipe

Figure 19.18: A Demonstration of

Cathodic Protection

Unprotected nail

Fe2+ + Ferricyanide →

39

Electrolytic Cells

• An electrolytic cell is an electrochemical cell in

which an electric current drives an otherwise

nonspontaneous reaction. (See Video: Electrolysis

of Water)

– The process of producing a chemical change in an electrolytic cell is called electrolysis.

– Many important substances, such as aluminum metal and chlorine gas are produced commercially by electrolysis.

Figure 19.19: Electrolysis of Molten

Sodium Chloride

Electrolysis of Molten Salts

• A Downs cell is a commercial electrochemical cell

used to obtain sodium metal by electrolysis of

molten NaCl. (see Figure 19.20)

– A number of other reactive metals are obtained by the electrolysis of a molten salt.

– Lithium, magnesium, and calcium metals are all obtained by the electrolysis of the chlorides.

Do Exercise 19.15 See Problems 19.91-92

40

Figure 19.20: Downs Cell for Preparation of

Sodium Metal

Figure 19.22: Chlor-Alkali Membrane Cell

Figure 19.23: Chlor-Alkali Mercury Cell

41

Figure 19.24: Purification of Copper by

Electrolysis

Figure 19.24: Purification of Copper by

Electrolysis (cont’d)

42

Stoichiometry of Electrolysis

• What is new in this type of stoichiometric

problem is the measurement of numbers of

electrons.

– You do not weigh them as you do substances.

– Rather, you measure the quantity of electric chargethat has passed through a circuit.

– To determine this we must know the current and the length of time it has been flowing.

– Electric current is measured in amperes.

– An ampere (A) is the base SI unit of current equivalent to 1 coulomb/second.

– The quantity of electric charge passing through a circuit in a given amount of time is given by

Electric charge(coul) = electric current (coul/sec) ×××× time lapse(sec)


• When an aqueous solution of potassium iodide is

electrolyzed using platinum electrodes, the half-

reactions are

How many grams of iodine are produced when a current of

8.52 mA flows through the cell for 10.0 min?

−−−−−−−−++++→→→→ e2)aq(I)aq(I2 2

)aq(OH2)g(He2)l(OH2 22

−−−−−−−−++++→→→→++++

– When the current flows for 6.00 x 102 s (10.0 min), the amount of charge is

C11.5)s1000.6()A1052.8(23

====××××××××××××−−−−

43

Figure 19.21: Electrolysis of Aqueous

Potassium Iodide


How many grams of iodine are produced when a current of

8.52 mA flows through the cell for 10.0 min?

−−−−−−−−++++→→→→ e2)aq(I)aq(I2 2

)aq(OH2)g(He2)l(OH2 22

−−−−−−−−++++→→→→++++

– Note that two moles of electrons are equivalent to one mole of I2. Hence,

−−−−

−−−−

××××××××

××××

emol2

Imol1

C1065.9

emol1C11.5 2

4 23

2

2 Ig1073.6Imol1

Ig254 −−−−××××====××××

• When an aqueous solution of potassium iodide is

electrolyzed using platinum electrodes, the half-

reactions are

Do Exercise 19.16

See Problems 19.93-94

Do Exercise 19.17

See Problems 19.95-96

Do Exercise 19.18

See problems 19.97-98

44

Operational Skills

• Balancing oxidation-reduction reactions

• Sketching and labeling a voltaic cell

• Writing the cell reaction from the cell notation

• Calculating the quantity of work from a given amount of cell reactant

• Determining the relative strengths of oxidizing and reducing agents

• Determining the direction of spontaneity from electrode potentials

• Calculating the emf from standard potentials

Operational Skills

• Calculating the free-energy change from electrode

potentials

• Calculating the cell emf from free-energy change

• Calculating the equilibrium constant from cell emf

• Calculating the cell emf for nonstandard conditions

• Predicting the half-reactions in an aqueous

electrolysis

• Relating the amounts of product and charge in an

electrolysis

End of Chapter 19

Documents

Chap 19 Electrochemistry - Bakersfield College B1B Notes Fall_09/Chap_… · Equilibrium Constants from Cell Potentials 7. ... In this chapter we will focus on electron transfer rather