Chapter 18 Notes

CHEM 1411 General Chemistry

Chemistry: A Molecular Approach by Nivaldo J. Tro

18

Electrochemistry

Objectives: Understand oxidation-reductions reactions, and be able to balance a redox equation. Understand the operation of galvanic and electrolytic cells. Understand how to calculate the potential of a cell, and how this quantity is related to other thermodynamic quantities. Mr. Kevin A. Boudreaux
Angelo State University
www.angelo.edu/faculty/kboudrea 1

Electrochemistry
Electrochemistry is the study of the relationship between chemical and electrical energy. Galvanic or voltaic cells convert chemical energy into electrical energy (batteries). Electrolytic cells use electrical energy to drive chemical changes. Many essential chemicals and materials are made through electrochemical processes. Electrochemistry is also deeply connected to thermodynamics.

Chapter 18 Notes

A Review of Oxidation and Reduction

Oxidation and Reduction

An oxidation-reduction (redox) reaction is a process in which electrons are transferred from one substance to another. Oxidation is the loss of electron(s). Reduction is the gain of electron(s). Oxidation: Zn Zn2+ + 2eReduction: 2H+ + 2e- H2 Oxidation always accompanies reduction.
oxidation

half-reactions

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

reduction
4

Chapter 18 Notes

Oxidizing and Reducing Agents

The oxidizing agent is the substance that causes oxidation to occur by accepting electrons. The oxidizing agent itself becomes reduced. The reducing agent is the substance that causes reduction to occur by losing electrons. The reducing agent itself becomes oxidized. The number of electrons gained by the oxidizing agent always equals the number lost by the reducing agent. This is important when balancing redox equations.
oxidation

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

reduction
5

Balancing Redox Reactions

Since oxidation and reduction reactions always occur together, balancing a redox reaction also requires balancing the number of electrons which are transferred. A redox reaction may look balanced, but if the charges are not the same on both sides, it isnt: Al(s) + Cu2+(aq) Al3+(aq) + Cu(s) [not balanced] Simple redox reactions can often be balanced by inspection, but more complicated ones require a systematic approach. There are two methods for balancing redox reactions: the oxidation number method the half-reaction method
6

Chapter 18 Notes

The Half-Reaction Method

Step 1. Divide the skeleton reaction into two halfreactions, each of which contains the oxidized and reduced forms of one of the species. Step 2. Balance atoms and charges in each halfreaction. a. Balance atoms other than O and H. b. Balance O atoms by adding H2O. c. Balance H atoms by adding H+ ions. d. Balance charge by adding electrons (e-). Step 3. Multiply each half-reaction by some integer to make the number of e- gained in the reduction equal the number of e- lost in the oxidation.
7

The Half-Reaction Method

Step 4. Add the balanced half-reactions and include states of matter. Step 4a. If the reaction occurs in basic solution, add one OH- to both sides of the equation for every H+ ion present; combine H+ and OHions to form waters, and cancel out those that appear on both sides. Step 5. Double-check that the atoms and charges are balanced.

Chapter 18 Notes

The Oxidation Number Method

Step 1. Assign oxidation numbers to all elements in the reaction. Step 2. Identify the oxidized and reduced species. Step 3. Compute the number of electrons lost in the oxidation and gained in the reduction from the oxidation number changes. Step 4. Multiply one or both of these numbers by appropriate factors to make the electrons lost equal the electrons gained, and use the factors as balancing coefficients. Step 5. Complete the balancing by inspection, adding phase labels.
9

Examples: Balancing Redox Reactions

1. Use the half-reaction method to balance the following redox reactions. (sim. to Ex. 18.1-18.3) a. Cr2O72-(aq) + I-(aq) Cr3+(aq) + I2(s) [acidic solution]

b. Sn(s) + NO3-(aq) SnO2(aq) + NO(g) [acidic solution]

c. MnO4-(aq) + C2O42-(aq) MnO2(s) + CO32-(aq) [basic solution]

Rules
10

Chapter 18 Notes

Galvanic (Voltaic) Cells

11

An Overview of Electrochemical Cells

There are two types of electrochemical cells: A galvanic cell (or voltaic cell) uses a spontaneous reaction (G < 0) to generate electrical energy. The difference in potential energy between higher energy reactants and lower energy products is converted into electrical energy. The reactants do work on the surroundings. An electrolytic cell uses electrical energy to drive a nonspontaneous reaction (G > 0). Lower energy reactants are converted into higher energy products by electrical energy. The surroundings do work on the reactants.
12

Chapter 18 Notes

An Overview of Electrochemical Cells

13

A Zn Bar in a Cu2+ Solution

If a bar of zinc metal is placed in a solution of Cu2+ ions, a spontaneous reaction takes place: Zn(s) Zn2+(aq) + 2eCu2+(aq) + 2e- Cu(s) [oxidation] [reduction]

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) [overall]

When this is done in a beaker (Fig. 18.1), the zinc slowly dissolves as it is oxidized into soluble Zn2+ ions, and the blue color of the solution fades as Cu2+ is reduced to copper metal and deposits on the bar. However, no electrical energy is generated because the oxidizing and reducing agents are in physical contact; the enthalpy of the reaction escapes into the surroundings as heat.

14

Chapter 18 Notes

A Zn Bar in a Cu2+ Solution

Figure 18.1

15

A Zn - Cu2+ Galvanic Cell

If, however, the oxidation and reduction processes are separated from each other in two separate halfcells (Fig. 18.2), electrical energy can be generated: A rod of zinc metal (the anode) is immersed in a Zn2+ solution and connected by a wire to a rod of copper metal (the cathode) in a Cu2+ solution. The zinc is oxidized, releasing electrons which travel through the wire and reduce Cu2+ in the other half-cell, producing and electrical current. A salt bridge between the half-cells maintains electrical neutrality and completes the circuit. The chemical energy in the reactants can then be used to light a bulb or run an electrical device. This type of galvanic cell is called a Daniell cell.
16

Chapter 18 Notes

A Zn - Cu2+ Galvanic Cell

Figure 18.2

MOV: Copper-Zinc Cell movie

17

Fig. 18.2

Galvanic Cells Electrolytes

In a galvanic (voltaic) cell, the components of each half-reaction are placed in separate containers called half-cells, consisting of an electrode dipping into an electrolyte solution; the cells are joined by a wire and a salt bridge. The electrolyte solutions are solutions of ions (usually dissolved in water) that are involved in the reaction or that carry the charge between the electrodes. Unless an inert electrode is being used, the electrolyte is usually a soluble ionic compound containing a cation of the electrode metal. In this example, the zinc half-cell electrolyte could be any soluble zinc compound, such as zinc nitrate, zinc chloride, zinc sulfate, etc.

18

Chapter 18 Notes

Fig. 18.2

Galvanic Cells Electrodes

The electrodes are usually metal rods or sheets that are immersed in the electrolyte solutions of each half-cell; they conduct the electricity between the cell and the surroundings. An electrode is classified by the half-reaction which takes place there: The anode is where the oxidation half-reaction takes place. Electrons are given up by the substance being oxidized (reducing agent) and leave the cell at the anode. The cathode is where the reduction half-reaction takes place. Electrons are taken up by the substance being reduced (oxidizing agent) and enter the cell at the cathode.
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Fig. 18.2

Galvanic Cells Electrodes

In this example, the oxidation half-cell consists of a Zn metal bar acting as the anode, which is immersed in a Zn2+ electrolyte solution [Zn(NO3)2]. The Zn anode will dissolve as it is oxidized into Zn2+, and will conduct e-s out of its half-cell. Zn(s) Zn2+(aq) + 2e In this example, the reduction half-cell consists of a Cu metal bar acting as the cathode, which is immersed in a Cu2+ electrolyte solution [Cu(NO3)2]. The Cu cathode will gain more Cu metal as Cu2+ is reduced, and will conduct e-s into its half-cell. Cu2+(aq) + 2e- Cu(s) By convention, the anode compartment is always drawn on the left.

20

Chapter 18 Notes

Fig. 18.2

Galvanic Cells Electrodes

The relative charges on the electrodes are determined by the source of the electrons and the direction of the electron flow. Electrons are generated at the anode and consumed at the cathode, therefore: In any voltaic cell, the anode is negative and the cathode is positive.

CPR Cathode Positive Reduction

ANO Anode Negative Oxidation

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Fig. 18.2

Galvanic Cells The Salt Bridge

The salt bridge consists of a non-reactive electrolyte suspended in a gel. It completes the circuit between the half-cells by maintaining charge neutrality in the electrolyte solutions. As Zn is oxidized to Zn2+, anions (NO3-) diffuse out of the salt bridge into its electrolyte solution, balancing out the charge. As Cu2+ is reduced to Cu, cations (K+) diffuse out of the salt bridge into its electrolyte solution. As electrons move left to right through the wire, anions move right to left (towards the anode) and cations move left to right (toward the cathode) through the salt bridge. Thus, the overall charge in each solution is maintained, and the circuit is completed.
22

Chapter 18 Notes

Fig. 18.2

Galvanic Cells Summary

23

Active and Inactive Electrodes

In this example, active electrodes are used, which are active participants in the half-reactions. The electrodes are consumed or added to during the course of the reaction. Often, inactive (or inert) electrodes are used, usually made of graphite or platinum: 2I-(aq) I2(s) + 2e[anode]

MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) [cathode] In this case, the species involved cant act as electrodes, and so something else must be used. The electrolyte solutions must contain all of the species involved in the half-reaction. (Fig 21.6)

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Chapter 18 Notes

Active and Inactive Electrodes

Active Electrodes:

anode:

Zn(s) Zn2+(aq) + 2e-

cathode: Cu2+(aq) + 2e- Cu(s) overall: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Inactive Electrodes:

anode:

2I-(aq) I2(s) + 2e-

cathode: MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) overall: 2MnO4-(aq) + 16H+(aq) + 10I-(aq) 2Mn2+(aq) + 5I2(s) + 8H2O(l)

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Active and Inactive Electrodes

This examples uses both an active and an inactive electrode:

anode:

Fe(s) Fe2+(aq) + 2e-

cathode: MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) overall: 5Fe(s) + 2MnO4-(aq) + 16H+(aq) 5Fe2+(s) + 2Mn2+(aq) + 8H2O(l)
Figure 18.4
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Chapter 18 Notes

Cell Notation
Cell notation is a useful shorthand description for the components of a voltaic cell:
Anode Anode Cathode | electrolyte || electrolyte | Cathode
electron flow

The anode components are always written on the left and the cathode components on the right A vertical line | represents a boundary between two phases. Two or more components in the same phase are separated by commas. A double vertical line || represents the salt bridge. The electron flow is left to right in this notation.
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Cell Notation
In the Zn-Cu2+ voltaic cell, the cell notation is: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s) The order in which the cell notation is written suggests the overall reaction: Zn is oxidized to Zn2+, and Cu2+ is reduced to Cu. In the I--MnO4- cell, where inert electrodes are used, and the electrolyte solutions contain all of the reacting species, the cell notation is Graphite(s) |I2(s) | I-(aq) || H+(aq), MnO4-(aq), Mn2+(aq) | Graphite(s)
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Chapter 18 Notes

Examples: Galvanic Cells

2. Diagram, show balanced equations, and write the cell notation for a voltaic cell that consists of one half-cell with a Cr bar in a Cr(NO3)3 solution, another half-cell with an Ag bar in an AgNO3 solution, and a KNO3 salt bridge. Measurement indicates that the Cr electrode is negative relative to the Ag electrode.

29

Examples: Galvanic Cells

3. Design a galvanic cell that uses the redox reaction Fe(s) + 2Fe3+(aq) 3Fe2+(aq) Identify the anode and cathode half-reactions, and sketch the experimental setup. Label the anode and cathode, indicate the direction of electron and ion flow, and identify the sign of each electrode.

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Chapter 18 Notes

Examples: Galvanic Cells

4. Given the following cell notations, write balanced equations for the cell reactions, and give a brief description of the cells. a. Pt(s)|Sn2+(aq),Sn4+(aq)||Ag+(aq)|Ag(s) b. Cu(s)|Cu2+(aq)||Cl2(g)|Cl-(aq)|C(s)

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Examples: Galvanic Cells

5. Write the shorthand notations for galvanic cells that use the reactions shown below. a. Fe(s) + Sn2+(aq) Fe2+(aq) + Sn(s) b. Pb(s) + Br2(l) Pb2+(aq) + 2Br-(aq)

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Chapter 18 Notes

Cell Potentials

33

Cell Potential
The driving force that causes electrons to move from anode to the cathode is the electromotive force (emf), or cell potential (Ecell). This represents the potential energy difference between the materials in the anode and cathode compartments. Electrical units in the SI system: electrical charge: coulomb, C electrical potential: volt, V

1V = 1A =

1J 1C 1C 1s
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electrical current: ampere, A

Chapter 18 Notes

The Standard Hydrogen Electrode (SHE)

Since it is not possible to measure the potential of a half-cell without connecting it to another cell, a standard reference half-cell has been defined to have a potential of 0 V. All other cell potentials are combined with the reference half-cell, and measured relative to that value. The standard hydrogen electrode (SHE) consists of a platinum electrode in a 1 M H+(aq) solution at 25C, through which H2(g) at 1 atm is bubbled: 2H+(aq, 1 M) + 2e- H2(g, 1 atm); E = 0 V H2(g, 1 atm) 2H+(aq, 1 M) + 2e-; E = 0 V
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Figure 18.6

MOV: Zinc-Hydrogen Cell movie

Using the SHE to Obtain a Reduction Potential

If we connect a Zn/Zn2+ half-cell to a SHE half-cell (Fig. 18.7), the cell potential is found to be +0.76 V, with the zinc half-cell acting as the anode: Zn(s) Zn2+(aq) + 2e-; E = ? V
_______________________________________________________________________________________________________

2H+(aq) + 2e- H2(g); E = 0 V

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g); E = +0.76 V

Figure 18.7

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Chapter 18 Notes

Using the SHE to Obtain a Reduction Potential

The cell potential is obtained from the formula: Ecell = Ered + Eox Since Ecell = +0.76 V, and Ered = 0 V (SHE); Eox for the zinc cell is 0.76 V. If the Zn/Zn2+ half-cell instead runs as a reduction, we would write the reaction backwards and reverse the sign on the cell potential. Its standard reduction potential would be -0.76 V: Zn2+(aq) + 2e- Zn(s); E = -0.76 V By convention, tables of half-cell potentials are written as reductions; the reaction for the cell which occurs as an oxidation is reversed.
37

Using the SHE to Obtain a Reduction Potential

If we connect a Cu/Cu2+ half-cell to a SHE half-cell, the overall cell potential is found to be +0.34 V, with the copper half-cell acting as the cathode: H2(g) 2H+(aq) + 2e-; E = 0 V Cu2+(aq) + 2e- Cu(s); E = ? V
_______________________________________________________________________________________________________

H2(g) + Cu2+(aq) 2H+(aq) + Cu(s); E = +0.34 V Since Ecell = +0.34 V, and Eox = 0 V (SHE); Ered for the copper cell is +0.34 V: Cu2+(aq) + 2e- Cu(s); E = +0.34 V
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Chapter 18 Notes

Standard Reduction Potentials

In the following charts, the standard reduction potentials (or standard electrode potentials) for a number of half-cells are listed. In all cases, the halfreactions are written as reductions. In other words, the potential listed is the potential that the half-cell has if the half-cell reactions occurs as a reduction. Oxidizing agents (which get reduced) and electrons are on the left side of each half-reaction; reducing agents (which get oxidized) are on the right. The half-reactions are listed by decreasing standard reduction potential. Thus, the strongest oxidizing agents are located in the upper left (F2, H2O2, MnO4-, etc.) and the strongest reducing agents are found in the lower right (Li, Na, Mg, etc.).
This list is essentially where the activity series for single displacement reactions is derived.
39

Standard Reduction Potentials

40

Chapter 18 Notes

Standard Reduction Potentials

41

Standard Reduction Potentials

more standard reduction potentials are listed in Appendix IID, p. A-15

42

Chapter 18 Notes

Standard Reduction Potentials

Standard Reduction Potentials at 25C Half-Reaction F2(g) + 2e- h 2F-(aq) O3(g) + 2H+(aq) + 2e- h O2(g) + 2H2O(l) Co3+(aq) + e- h Co2+(aq) H2O2(aq) + 2H+(aq) + 2e- h 2H2O(l) PbO2(s) + SO42-(aq) + 4H+(aq) + 2e- h PbSO4(s) + 2H2O(l) 2HOCl(aq) + 2H+(aq) + 2e- h Cl2(g) + 2H2O(l) Ce4+(aq) + e- h Ce3+(aq) MnO4-(aq) + 8H+(aq) + 5e- h Mn2+(aq) + 4H2O(l) Au3+(aq) + 3e- h Au(s) BrO3-(aq) + 6H+(aq) + 6e- h Br-(aq) + 3H2O Cl2(g) + 2e- h 2Cl-(aq) Cr2O72-(aq) + 14H+(aq) + 6e- h 2Cr3+(aq) + 7H2O(l) MnO2(s) + 4H+(aq) + 2e- h Mn2+(aq) + 2H2O(l) O2(g) + 4H+(aq) + 4e- h 2H2O Br2(g) + 2e- h 2Br-(aq) NO3-(aq) + 4H+(aq) + 3e- h NO(g) + 2H2O 2Hg2+(aq) + 2e- h Hg22+(aq) Hg22+(aq) + 2e- h Hg(l) Ag+(aq) + e- h Ag(s) Fe3+(aq) + e- h Fe2+(aq) O2(g) + 2H+(aq) + 2e h H2O2(aq) MnO4-(aq) + 2H2O(l) + 3e- h MnO2(s) + 4OH-(aq) I2(g) + 2e- h 2I-(aq) NiO2(s) + 2H2O + 2e- h Ni(OH)2(s) + 2OH-(aq) O2(g) + 2H2O(l) + 4e- h 4OH-(aq) Cu2+(aq) + 2e- h Cu(s) AgCl(s) + e- h Ag(s) + Cl-(aq) SO42- + 4H+(aq) + 2e- h SO2(g) + 2H2O(l) Cu2+(aq) + e- h Cu+(aq) Sn4+(aq) + 2e- h Sn2+(aq) 2H+(aq) + 2e- h H2(g) E (V) +2.87 +2.07 +1.82 +1.77 +1.69 +1.63 +1.61 +1.51 +1.50 +1.44 +1.36 +1.33 +1.23 +1.23 +1.07 +0.96 +0.92 +0.85 +0.80 +0.77 +0.70 +0.59 +0.53 +0.49 +0.40 +0.34 +0.22 +0.20 +0.15 +0.15 0.00

43

Standard Reduction Potentials

Standard Reduction Potentials at 25C Half-Reaction 2H+(aq) + 2e- h H2(g) Pb2+(aq) + 2e- h Pb(s) Sn2+(aq) + 2e- h Sn(s) N2(g) + 5H+(aq) + 4e- h N2H5+(aq) Ni2+(aq) + 2e- h Ni(s) Co2+(aq) + 2e- h Co(s) PbSO4(s) + 2e- h Pb(s) + SO42-(aq) Cd2+(aq) + 2e- h Cd(s) Fe2+(aq) + 2e- h Fe(s) Cr3+(aq) + 3e- h Cr(s) Zn2+(aq) + 2e- h Zn(s) 2H2O + 2e- h H2(g) + 2OH-(aq) Mn2+(aq) + 2e- h Mn(s) Al3+(aq) + 3e- h Al(s) Mg2+(aq) + 2e- h Mg(s) Na+(aq) + e- h Na(s) Ca2+(aq) + 2e- h Ca(s) Sr2+(aq) + 2e- h Sr(s) Ba2+(aq) + 2e- h Ba(s) K+(aq) + e- h K(s) Li+(aq) + e- h Li(s) E (V) 0.00 -0.13 -0.14 -0.23 -0.25 -0.28 -0.31 -0.40 -0.44 -0.74 -0.76 -0.83 -1.18 -1.66 -2.37 -2.71 -2.87 -2.89 -2.90 -2.93 -3.05

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Chapter 18 Notes

Using Standard Reduction Potentials

An overall redox reaction is the sum of the halfreactions associated with each half-cell process: one occurs as a reduction (at the cathode), written in the forward direction. the other occurs as an oxidation (at the anode), written in the reverse direction. The potential of the cell (Ecell) is the difference between the standard half-cell potentials of the cathode and the anode:

Ecell = Ecathode + (- Eanode) Ecell = Ered + (- Eox)

NOTE: Do NOT multiply Ehalf-cell values by the coefficient; it is an intensive property, since it is the ratio of J/C.
45

Using Standard Reduction Potentials

For example, to calculate the cell potential (Ecell) for the oxidation of Zn(s) by Ag+(aq): 2Ag+(aq) + Zn(s) 2Ag(s) + Zn2+(aq) consider the relevant half-reactions: reduction (cathode): 2 [Ag+(aq) + e- Ag(s)] oxidation (anode): Zn(s) Zn2+(aq) + 2eE = 0.80 V -E = -(-0.76 V)

Ecell = Ecathode + (- Eanode) Ecell = 0.80 V + 0.76 V = 1.56 V

46

Chapter 18 Notes

Relative Strengths of Oxidizing & Reducing Agents

Cu2+(aq) + 2e- Cu(s) 2H+(aq) + 2e- H2(g) Zn2+(aq) + 2e- Zn(s) Ecell = +0.34 V Ecell = 0.00 V Ecell = -0.76 V

The more positive the Ecell value, the more the reaction tends to occur as written. Thus, Cu2+ gains two electrons more easily than H+, and H+ gains electrons more easily than Zn2+. Therefore, Cu2+ is the strongest oxidizing agent, and Zn2+ is the weakest oxidizing agent. Since reversing the reaction reverses the sign of Ecell, Zn is the strongest reducing agent and Cu is the weakest reducing agent.
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Writing and Predicting Spontaneous Reactions

Table 18.1 can be used as a guide to writing spontaneous redox reactions, which is useful when trying to construct electrochemical cells. Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
stronger reducing agent stronger oxidizing agent weaker oxidizing agent weaker reducing agent

The members of a redox couple (such as Zn and Zn2+) differ by one or more electrons. A spontaneous reaction (Ecell > 0) will occur between an oxidizing agent and a reducing agent that lies below it on Table 18.1.
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Chapter 18 Notes

Writing and Predicting Spontaneous Reactions

In other words, if the overall reaction is split into half reactions, the half-reaction with the more positive reduction potential takes place as a reduction, while the other one runs in reverse as an oxidation. To determine whether a given reaction is spontaneous, look at the oxidation (anode) and reduction (cathode) processes, and calculate the cell potential. If the cell potential is positive, the reaction is spontaneous; if negative it is nonspontaneous (or spontaneous in the reverse direction). Ecell = Ecathode + -Eanode Ecell = Ered + -Eox
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Metals Dissolving in Acids

Some metals, such as Zn, dissolve in acidic solutions: Zn2+(aq) + 2e- Zn(s); E = -0.76 V 2H+(aq) + 2e- H2(g); E = 0 V Zn(s) + 2H+(aq) Zn2+(aq) + H2(g); E = +0.76 V Cu, however, does not dissolve in most acids: Cu2+(aq) + 2e- Cu(s); E = +0.34 V Cu(s) + 2H+(aq) Cu2+(aq) + H2(g); E = -0.34 V An important exception is nitric acid, which oxidizes metals through the redox reaction NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l); Ered = 0.96 V
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Chapter 18 Notes

Examples: Using Reduction Potentials

6. Arrange the following oxidizing agents in order of increasing strength under standard-state conditions: Br2(l), Fe3+(aq), Cr2O72-(aq).

51

Examples: Using Reduction Potentials

7. Arrange the following reducing agents in order of increasing strength under standard-state conditions: Al(s), Na(s), Zn(s).

52

Chapter 18 Notes

Examples: Using Reduction Potentials

8. Use the following half-reactions to predict the spontaneous reaction that occurs when Br-, SO42-, H2SO3, and Br2 are mixed in an acidic solution. Br2(aq) + 2e- 2Br-(aq); E = +1.07 V SO42-(aq) + 4H+(aq) + 2e- H2SO3(aq) + H2O E = +0.17 V

53

Examples: Using Reduction Potentials

9. What spontaneous reaction occurs if Cl2 and Br2 are added to a solution that contains both Cl- and Br-?

54

Chapter 18 Notes

Examples: Using Reduction Potentials

10. Predict from Table 18.1 whether Pb2+(aq) can oxidize Al(s) or Cu(s) under standard-state conditions. Calculate E for each reaction at 25C.

55

Examples: Using Reduction Potentials

11. What is the overall cell reaction and the standard cell potential of a galvanic cell employing the following half-reactions? Cr3+(aq) + 3e- h Cr(s); ECr3+ = -0.74 V MnO4-(aq) + 8H+(aq) + 5e- h Mn2+(aq) + 4H2O EMnO4- = +1.51 V

56

Chapter 18 Notes

Examples: Using Reduction Potentials

12. Which of the following reactions occur spontaneously in the forward direction? (sim. to Ex. 18.5)
Br2(aq) + Cl2(g) + 2H2O 2Br-(aq) + 2HOCl(aq) + 2H+(aq)

3Zn(s) + 2Cr3+(aq) 3Zn2+(aq) + 2Cr(s)

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A Shocking Dental Galvanic Cell

Biting on aluminum foil produces pain if you have fillings in your teeth. Al acts as the anode (-1.66 V), saliva as the electrolyte, and the silver/tin/mercury alloy filling as an inert cathode. O2 is reduced to water (1.23 V), and the short circuit between the foil in contact with the filling creates a current that jolts the nerve in the tooth.

58

Chapter 18 Notes

Cell Potentials and Thermodynamics

59

Cell Potential and Free Energy

In the examples weve seen of spontaneous cell reactions, the cell potentials have been positive. There must then be some connection between the cell potential and the free energy change. The cell potential (Ecell) and the free energy change (G) are related by the equation G = - n F Ecell n = the number of moles of electrons transferred in the reaction. F = the faraday, F , the charge on one mole of electrons (named for Michael Faraday): 1 F = 96,485 C / mol e1 F = 96,485 J V-1 mol e-1
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Chapter 18 Notes

Cell Potential and Free Energy

This gives us a connection between cell potential and spontaneity:
G + 0 Ecell Spontaneity + 0 spontaneous nonspontaneous at equilibrium

The more positive the Ecell, the more work the cell can do, and the farther the reaction proceeds to the right as written. If Ecell = 0, the reaction has reached equilibrium, and the cell can do no more work (dead battery).
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Standard Cell Potentials

Since Ecell is affected by concentration, pressure, and temperature, a standard cell potential, Ecell is defined, in which all components are at standard thermodynamic conditions (25C, 1 atm, pure solids for electrodes, ions at 1.00 M). When all components are at standard conditions,

G = - nFEcell

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Chapter 18 Notes

Examples: Cell Potential and Free Energy

13. Calculate the standard free-energy change at 25C for the following reaction. (sim. to Ex. 18.6) Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

63

Examples: Cell Potential and Free Energy

14. Calculate the standard cell potential at 25C for the following reaction, which has a standard freeenergy change of -266.3 kJ. Al(s) + Cr3+(aq) Al3+(aq) + Cr(s)

64

Chapter 18 Notes

The Relationship Between Ecell, G, and K

When all components are in their standard states, G = - nFEcell Using the relationship between K and G, G = - RT ln K - RT ln K = - nFEcell
o Ecell =

RT ln K nF
o nEcell log K = 0.0592 V
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o cell

0.0592 V = log K n

Examples: Calculating K and G from E

15. Lead can displace silver from solution: Pb(s) + 2Ag+(aq) Pb2+(aq) + 2Ag(s) As a consequence, silver is a valuable by-product in the industrial extraction of lead from its ore. Calculate K and G at 25C for this reaction. (sim. to Ex. 18.7)

66

Chapter 18 Notes

The Nernst Equation

Most electrochemical cells do not start out with all of their components in their standard states or at their standard concentrations, and even if they did, would not remain that way for long. In order to obtain Ecell, the cell potential under nonstandard conditions, we start with the expression for G under nonstandard conditions: G = G + RT ln Q -nFEcell = -nFEcell + RT ln Q Solving for Ecell gives the Nernst equation (W. H. Nernst, 1889)
o Ecell = Ecell -

RT ln Q nF

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The Nernst Equation

o Ecell = Ecell -

0.0592 V log Q n

(at 25o C)

If Q < 1 [product] < [reactant] log Q < 0 Ecell > Ecell If Q > 1 [product] > [reactant] log Q > 0 Ecell < Ecell If Q = 1 [product] = [reactant] log Q = 0 Ecell = Ecell Remember when calculating the value of Q, solids (even solid electrodes) do not appear in the massaction expression: Cd(s) + 2Ag+(aq) Cd2+(aq) + 2Ag(s) Q = [Cd2+] / [Ag+]2
68

Chapter 18 Notes

Examples: Using the Nernst Equation

16. Consider a galvanic cell that uses the reaction Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) Calculate Ecell at 25C when [H+] = 1.0 M, [Zn2+] = 0.0010 M, and PH2 = 0.10 atm. (sim. to Ex. 18.8)

69

Examples: Using the Nernst Equation

17. A galvanic cell was constructed by connecting a nickel electrode that was dipped into 1.20 M NiSO4 solution to a chromium electrode that was dipping into a solution containing Cr3+ at an unknown concentration. The potential of the cell was measured to be 0.552 V, with the chromium serving as the anode. The standard cell potential for this system was determined to be 0.487 V. What was the concentration of Cr3+ in the solution of unknown concentration?

70

Chapter 18 Notes

Concentration Cells
Because cell potentials change with concentration, two of the same half-cells at different concentrations can be joined to produce a current: In cell A, two Cu/Cu2+ half-cells are connected, with all of the components at standard conditions. There is no voltage difference, and no current. A B

Figure 18.12

71

Concentration Cells
In cell B, the left half-cell has a concentration 0.010 M and the right half-cell is at 2.0 M. This concentration difference causes electrons to flow from the half-cell with the dilute Cu2+ to the halfcell with the concentrated Cu2+, and produces a voltage of 0.068 V. The flow of electrons increases the concentration of Cu2+ in the dilute cell (as Cu gets oxidized) and decreases the concentration of Cu2+ in the concentrated cell (as Cu2+ is reduced to Cu). Nerve cells use a concentration gradient to cause Na+ and K+ ions to diffuse into or out of a nerve cell, creating a spike in the electrochemical potential across the membrane, which travels down the nerve cell.
72

Chapter 18 Notes

The Nernst Equation and pH

pH meters are electronic devices that are used for measuring pH (duuuh!). They are based on a cell which is similar to the SHE half-cell, which dips into a solution of unknown pH, and a calomel reference electrode: Pt(s) | H2(1 atm) | H+(? M) || Reference cathode The potential for the hydrogen half-reaction is obtained from the Nernst equation: H2(g) 2H+(aq) + 2e-

EH

H+

= E

o H2 H+

[H + ]2 0.0592 V log PH n 2
73

The Nernst Equation and pH

Since E = 0 V, n = 2, and PH2 = 1 atm, this simplifies to:

EH

0.0592 V log [H + ]2 2 0.0592 V = (2) log [H + ] 2 = (0.0592 V)(-log [H + ]) = (0.0592 V)(pH) = -

The overall cell potential is and therefore

Ecell = (0.0592 V)(pH) + Eref

pH = Ecell Eref 0.0592 V

74

Chapter 18 Notes

The pH Meter
In practice, a glass electrode containing a silver wire coated with silver chloride immersed in a solution of HCl is used as the test electrode; the solution in the cell is separated from the test solution by a thin glass membrane (Figure 18.6). The reference electrode is a calomel (Hg2Cl2) electrode in contact with liquid mercury and KCl(aq): Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-(aq); E = +0.28 V A typical pH meter measures the cell potential, and electronically converts the potential to the pH value:

pH =

Ecell 0.28 V 0.0592 V

75

The pH Meter

76

Chapter 18 Notes

Batteries

77

Electrochemical Processes in Batteries

A battery is a self-contained group of voltaic cells arranged in series (plus-to-minus-to-plus) so that their individual voltages are added together. The term is also sometimes used to refer to single voltaic cells. A primary battery cannot be recharged, and must be disposed of when it is dead. A secondary, or rechargeable, battery can be restored to use by supplying electricity to reverse the cell reactions and regenerate the reactants. A fuel cell, or flow battery, is not self-contained; the reactants (usually a combustible fuel and oxygen) enter the cell and the products leave, generating electricity through controlled oxidation of the fuel.

78

Chapter 18 Notes

Dry Cell (Leclanch cell) (primary) A common household battery Anode: Zn(s) Zn2+(aq) + 2eCathode: 2MnO2(s) + 2NH4+(aq) + 2e- Mn2O3(s) + 2NH3(aq) + H2O(l) etc. Ecell = 1.5 V

79

Alkaline Battery (primary) A modified form of the Leclanch cell, using a basic (alkaline) electrolyte; corrodes more slowly, and produces higher power and a more stable current Anode: Zn(s) + 2OH-(aq) ZnO(s) + H2O(l) + 2eCathode: 2MnO2(s) + 2H2O(l) + 2e- 2Mn(OH)2(s) + 2OH-(aq) Ecell = 1.5 V

80

Chapter 18 Notes

Lead-Acid Battery (rechargeable) Six cells in series, each of which delivers about 2 V. The electrolyte solution is ~4.5 M H2SO4. The reactions can be run in reverse, thus recharging the battery, by using current from the alternator. Anode: Pb(s) + HSO4-(aq) PbSO4(s) + H+(aq) + 2eCathode: PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e- PbSO4(s) + 2H2O(l)

81

Mercury and Silver (Button) Batteries (primary) Anode: Zn(s) + 2OH-(aq) ZnO(s) + H2O(l) + 2eCathode (mercury): HgO(s) + H2O(l) + 2e- Hg(l) + 2OH-(aq) Cathode (silver): Ag2O(s) + H2O(l) + 2e- 2Ag(s) + 2OH-(aq) Ecell = 1.3 V (mercury); 1.6 V (silver)

82

Chapter 18 Notes

Nickel-Cadmium (Nicad) Battery (rechargeable) Anode: Cd(s) + 2OH-(aq) Cd(OH)2(s) + 2eCathode: 2NiO(OH)(s) + 2H2O(l) + 2e- 2Ni(OH)2(s) + 2OH-(aq) Ecell = 1.4 V

83

Nickel-Metal-Hydride (NiMH) Battery (rechargeable) Replaces the toxic cadmium anode with a metal matrix impregnated with hydrogen atoms in a strongly basic electrolyte. At the anode, hydrogen atoms are released as water molecules; supplying external current reverses the reactions and recharges the battery. Anode: MH(s) + OH-(aq) M(s) + H2O(l) + eCathode: NiO(OH)(s) + H2O(l) + e- Ni(OH)2(s) + OH-(aq) Ecell = 1.2 V

84

Chapter 18 Notes

Lithium Solid-State Battery (rechargeable) Lightweight batteries which produce high voltages; common in computers, digital camereas, cell phones, etc. Anode: Li(s) Li+(in solid electrolyte) + eCathode: MnO2(s) + Li+ + e- LiMnO2(s) Ecell = 3 V

85

Fuel Cells Differs from an ordinary battery in that the reactants are not contained within the cell, but are continually supplied from outside. In a hydrogen-oxygen fuel cell, the reactants are H2 and O2 gases; there are no pollutants formed, but the electrode materials are expensive and short-lived. Anode: 2H2(g) + 4OH-(aq) 4H2O(l) + 4eCathode: O2(g) + 2H2O(l) + 4e- 4OH-(aq) Overall: 2H2(g) + O2(g) 2H2O(l) Ecell = 1.2 V

86

Chapter 18 Notes

Experimental Systems: Aluminum-Air Battery An aluminum anode is oxidized and oxygen from flowing moist air is reduced at an inactive porous graphite cathode. An aqueous NaOH electrolyte circulates through the cell. Anode: 4[Al(s) + 4OH-(aq) Al(OH)4-(aq) + 3e-] Cathode: 3[O2(g) + 2H2O(l) + 4e- 4OH-(aq) Ecell = 2.7 V

Sodium-Sulfur Battery Molten Na is the anode, and molten S8 is the cathode. Anode: 2Na(l) 2Na+(l) + 2eCathode: n/8S8(l) + 2e- nS2-(l) Ecell = 2.1 V
87

88

Chapter 18 Notes

Corrosion

89

The Corrosion of Iron

Corrosion is the oxidative deterioration of a metal, such as the rusting of iron. Iron does not rust because of a simple reaction between iron metal and oxygen gas: 4Fe + 3O2(g) 2Fe2O3(s) Water must be present for rusting to occur; in oxygen-free water or dry air, iron does not rust. Rusting is accelerated by electrolytes and acids. Rusting also involves pitting of the metal surface, but the rust is deposited at a different location from the pits. Iron is oxidized in one region, and oxygen is reduced in another region.
90

Chapter 18 Notes

The Corrosion of Iron

Figure 18.27

The surface of the iron and the droplet of water form a tiny galvanic cell. Portions of the iron surface act as an anode, where iron is oxidized. Other portions act as cathodes, where oxygen is reduced to water. The water droplet itself acts as an electrolyte.
91

The Corrosion of Iron

anode: 2Fe(s) 2Fe2+(aq) + 4e-; E = 0.45 V cathode: O2(g) + 4H+(aq) + 4e- 2H2O(l); E = 1.23 V When Fe2+ ions migrate away from the pitted anode region, they come in contact with O2 dissolved in the water droplet and are oxidized to Fe3+ ions: 4Fe2+(aq) + O2(g) + 4H+(aq) 4Fe3+(s) + 2H2O The Fe3+ ions form a very insoluble hydrated oxide, which is deposited as red-brown rust: 2Fe3+(aq) + 4H2O(g) 4Fe2O3H2O(s) + 6H+(aq)
ACT: Corrosion Activity
92

Chapter 18 Notes

The Corrosion of Iron

Ionic compounds dissolved in the water accelerate the rusting process by increasing the conductivity of the electrolyte solution; this is a problem in areas where salt is used to melt ice on the roads, and is a big problem in ocean-going vessels. Rusting also occurs faster at lower pH. Many other metals, such as Al, Mg, Cr, Ti, and Zn, form hard, impenetrable metal oxide coatings when they oxidize, which prevent any further corrosion. Iron(III) oxide is too porous to shield the underlying metal from further oxidation.

93

Preventing Corrosion
The corrosion of iron can be prevented or minimized by shielding the metal surface from oxygen and moisture with paint, or by coating the iron with a more durable metal such as Cr, Sn, or Zn. Galvanized iron is produced by dipping iron into molten zinc. When oxidation occurs, Zn is oxidized instead of Fe, since Zn has a lower reduction potential. (Zn also reduces Fe2+ back to Fe.) The zinc oxide does not flake off the metal surface, and forms a protective coating.
Fe2+ + 2e- h Fe(s); E = -0.44 Zn2+ + 2e- h Zn(s); E = -0.76
94

Chapter 18 Notes

Preventing Corrosion
Protecting a metal from corrosion by connecting it to a more easily oxidized metal is called cathodic protection. It is not always necessary to coat the entire metal surface, as long as there is electrical contact with the second metal. Underground iron pipelines or propellers on boats can be protected by placing them in contact with Mg, which is more easily oxidized, and acts as a sacrificial anode.

95

Preventing Corrosion
If iron is in contact with a less active metal, such as copper, the iron anodic action is improved, and will corrode more rapidly (since Fe2+ is lost only at the anode). When iron plumbing is connected directly to copper plumbing with no electrical insulation between them, the iron pipe corrodes rapidly.

Figure 21.16

96

Chapter 18 Notes

Electrolytic Cells

97

Galvanic vs. Electrolytic Cells

Galvanic cells use spontaneous redox reactions (E > 0; G < 0) to generate electricity. Chemical energy is converted to electrical energy as the reaction proceeds toward equilibrium. Electrolytic cells use electric current from an external source to drive a nonspontaneous redox reaction (E < 0; G > 0). Electrical energy in converted to chemical energy as the reaction proceeds away from equilibrium.
Reaction Type Spontaneous Equilibrium

Ecell G Cell Type

+ Galvanic + 0 Electrolytic Dead Battery
98

Nonspontaneous 0

Chapter 18 Notes

Galvanic vs. Electrolytic Cells

Figure 18.22

99

Electrolytic Cells and Electrolysis

The process of using an electric current to bring about chemical change is called electrolysis. Electrolysis can be performed on pure substances (molten salts, water), mixtures of molten salts, or aqueous solutions of salts. In an electrolytic cell, oxidation occurs at the anode, and reduction occurs at the cathode. The cathode is negative and the anode is positive. (Current is supplied to the cathode by the battery, and electrons are pulled out of the anode by the battery). A rechargeable battery functions as a galvanic cell when it is operating (i.e., supplying current), but as an electrolytic cell when it is being recharged.
100

Chapter 18 Notes

Electrolysis of Molten Salts

If a pure molten salt is subjected to electrolysis, the cation will be reduced at the cathode and the anion will be oxidized at the anode. Anode: 2Cl-(l) Cl2(g) + 2eCathode: Na+(l) + e- Na(s) Overall: 2Na+(l) + 2Cl-(l) 2Na(s) + Cl2(g) The electrolyte is the molten salt itself. Na+ is attracted to the negative electrode, and Clis attracted to the positive electrode. The moving charges allow current to flow through the molten salt, completing the circuit.
101

Electrolysis of Molten Salts

Figure 18.23

102

Chapter 18 Notes

Electrolysis of Mixed Molten Salts

When there are two or more molten salts present in an electrolytic cell: the more easily oxidized species (stronger reducing agent) reacts at the anode (oxidation). the more easily reduced species (stronger oxidizing agent) reacts at the cathode (reduction). In determining which potential oxidations and reductions take place, we cannot use the table of reduction potentials, since these are determined for aqueous ions. Instead, we have to rely on our knowledge of periodic atomic trends to predict which species will gain or lose electrons more easily.
103

Examples: Electrolysis of Molten Salts

18. In the electrolysis of molten MgBr2, what products form at the anode and cathode?

104

Chapter 18 Notes

Examples: Electrolysis of Molten Salts

19. A chemical engineer melts a naturally occurring mixture of NaBr and MgCl2 and decomposes it in an electrolytic cell. Predict the substance formed at each electrode, and write balanced half-reactions and the overall cell reaction. (sim. to Ex. 18.9a)

105

Examples: Electrolysis of Molten Salts

20. Metallic potassium was first prepared in 1807 by Humphrey Davy by the electrolysis of molten potassium hydroxide. For this cell, label the anode and cathode, and show the direction of ion flow, and write balanced equations for the anode, cathode, and overall cell reactions.

106

Chapter 18 Notes

Electrolysis of Water
The electrolysis of water is usually carried out in the presence of a nonreacting salt, such as Na2SO4, since pure water does not carry electrical currents well. Anode (oxidation): -E = -0.82 V 2H2O(l) O2(g) + 4H+(aq) + 4eCathode (reduction): 2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.41 V Overall: 2H2O(l) 2H2(g) + O2(g) E = -1.23 V Since the cell is not at standard conditions, the potentials are calculated from the Nernst equation.
107

Electrolysis of Water

Figure 18.20

108

Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

When predicting the electrolysis products of an aqueous ionic solution, it is necessary to consider that water is also present, and may be reduced or oxidized instead of the ionic compound. For example, in an ionic solution of NaI, there are two processes that can potentially take place at the anode and cathode: Anode: Oxidation of I-: 2I-(aq) I2(s) + 2eOxidation of water: 2H2O(l) O2(g) + 4H+(aq) + 4eOxidation of I- takes place. -E = -0.82 V
109

-E = -0.54 V

Electrolysis of Aqueous Salt Solutions

Cathode: Reduction of Na+: Na+(aq) + e- Na(s) Reduction of water: 2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.41 V Reduction of water takes place. Overall Reaction: 2I-(aq) + 2H2O(l) I2(s) + H2(g) + 2OH-(aq)
110

E = -2.71 V

Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

Figure 18.24

111

Electrolysis of Aqueous Salt Solutions

If electrolysis were performed on aqueous KNO3: Anode: Oxidation of NO3-: cant be done Oxidation of water: 2H2O(l) O2(g) + 4H+(aq) + 4e- -E = -0.82 V Oxidation of H2O takes place. Cathode: Reduction of K+: E = -2.93 V K+(aq) + e- K(s) Reduction of water: 2H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.41 V Reduction of water takes place. Overall Reaction: 2H2O(l) 2H2(g) + O2(g)

112

Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

113

Electrolysis of Aqueous Salt Solutions

Sometimes unexpected products are obtained, however. When gases are produced at electrodes, an additional voltage called the overvoltage is required to overcome the kinetic factors (such as high Eact). E.g., in the electrolysis of NaCl, H2 forms at the cathode and Cl2 forms at the anode, even through a comparison of electrode potentials would seem to indicate that O2 should form: Oxidation of water: 2H2O(l) O2(g) + 4H+(aq) + 4e- -E = -0.82 V (~ -1.4 V with overvoltage) Oxidation of Cl-: 2Cl-(aq) Cl2(g) + 2e- -E = -1.36 V
114

Chapter 18 Notes

Electrolysis of Aqueous Salt Solutions

In general, cations of less active metals are reduced to the neutral metal, such as Au, Ag, Cu, Cr, Pt, and Cd. More active metals are not reduced, such as those of Group I, Group II, and Al. Water is reduced to H2 and OH- instead. Anions that are oxidized include the halides (except F-.) Anions that are not oxidized include F-, SO42-, NO3-, and PO43-. Water is oxidized to O2 and H+ instead.

115

Examples: Predicting Electrolysis Products

21. Predict the half-cell reactions that occur when aqueous solutions of the following salts are electrolyzed in a cell with inert electrodes. What is the overall cell reaction in each case? (sim. to Ex. 18.9a) a. KBr b. AgNO3 c. MgSO4 d. CuSO4

116

Chapter 18 Notes

The Stoichiometry of Electrolysis

Faradays law of electrolysis the amount of substance produced at each electrode is directly proportional to the quantity of charge flowing through the cell. (Michael Faraday, 1830s) In order to calculate how much charge is needed to produce a given amount of material: Balance the half-reaction to find the number of moles of electrons needed per mole of product. Use the Faraday constant (F = 9.65 104 C/mol e-) to find the corresponding charge. Use the molar mass the find the charge needed for a given mass of product.
117

The Stoichiometry of Electrolysis

The amount of charge flowing through the cell is determined from the current, measured in amperes (A): 1A = 1C/s Thus, current multiplied by time gives the charge: A s = C/s s = C

118

Chapter 18 Notes

Examples: Stoichiometry and Electrolysis

22. How many minutes will it take for a current of 10.0 A to deposit 3.00 g of gold from a solution of AuCl3?

119

Examples: Stoichiometry and Electrolysis

23. How many grams of copper are deposited on the cathode of an electrolytic cell if an electric current of 2.00 A is run through a solution of CuSO4 for a period of 20.0 min? (sim. to Ex. 18.10)

120

Chapter 18 Notes

Examples: Stoichiometry and Electrolysis

24. What current must be supplied to deposit 3.00 g of gold from a solution of AuCl3 in 20.0 min?

121

122

Chapter 18 Notes

Industrial Applications of Electrolysis

123

Manufacture of Sodium

Sodium metal is produced in a Downs cell from a mixture of sodium chloride and calcium chloride; the cell is designed to keep the sodium metal separate from the chlorine gas, or they will recombine (violently!).

124

Chapter 18 Notes

Manufacture of Chlorine and Sodium Hydroxide

The production of Cl2 gas and NaOH by electrolysis is the basis of the chlor-alkali industry, which generates sales of about $4 billion in the US alone. Saturated NaCl(aq) is oxidized in the anode compartment to produce Cl2; water is reduced in the cathode compartment to OH-; Na+ from the anode compartment moves by osmosis through a cation-permeable membrane to the cathode compartment, maintaining neutrality and thereby producing sodium hydroxide.

125

Manufacture of Aluminum

Aluminum is the third most abundant element in the crust (8.3%), usually in the form of the ore bauxite (Al2O3). Al used to be extremely valuable because of the difficulty in extracting Al metal from the ore. Now, Al is produced using the HallHroult process by dissolving bauxite in molten cryolite (Na3AlF6), and subjecting it to electrolysis. Al3+ is reduced to Al, and the liquid metal is drained off, cooled, and rolled into plates, sheets, or foil. This process made the production of Al much more cost-effective, but still requires large amounts of electricity (n=3: 1 mol e- produces 9.0 g Al).

126

Chapter 18 Notes

Electroplating
In electroplating, a 0.03 to 0.05 mm coating of one metal is deposited on another metal. In this illustration, silver dissolves from a solid Ag bar (the anode) and is deposited as solid silver on a fork (the cathode). Electroplating can be used to provide a variety of protective or decorative metal surfaces, such as chrome (Cr), galvanized metal (Zn), gold, silver, etc.

127

Refining of Copper

Copper can be obtained from ore in 99% purity, but this is not good enough to use in wire. Impure copper is used as the anode, and a sheet of very pure copper is used as the cathode; Cu dissolves at the anode, and plates out as pure copper at the cathode. Other easily oxidized metal ions, such as Zn2+ and Fe2+ remain in solution, and less easily oxidized metals fall to the bottom of the cell as anode mud. The anode mud contains such impurities as silver, gold, and platinum.

128

Chapter 18 Notes

Equation Summary
Cell Potentials: Ecell = Ered + (-Eox) Thermodynamics: G = - nFEcell
o Ecell =

0.0592 V log K n

129

Equation Summary
The Nernst equation:
o Ecell = Ecell -

0.0592 V log Q n

(at 25o C)

Electrolysis: 1A=1C/s 1V=1J/C 1 mol e- = 9.65104 C (F, Faraday constant)

130