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CHEM 1411 General Chemistry
Chemistry: A Molecular Approach by Nivaldo J. Tro
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
• 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.
Zn(s) + 2H+(aq) ⎯⎯→ Zn2+(aq) + H2(g)
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.
Zn(s) + 2H+(aq) ⎯⎯→ Zn2+(aq) + H2(g)
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 isn’t: 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
7 The Half-Reaction Method Step 4. Divide the skeleton reaction into two halfreactions. If the reaction occurs in basic solution. Multiply each half-reaction by some integer to make the number of e. Balance atoms and charges in each halfreaction. Balance O atoms by adding H2O.Chapter 18 Notes The Half-Reaction Method Step 1. and cancel out those that appear on both sides. add one OH.gained in the reduction equal the number of e. Double-check that the atoms and charges are balanced. Step 2. Balance atoms other than O and H. Step 3. Balance H atoms by adding H+ ions.lost in the oxidation. c.to both sides of the equation for every H+ ion present. combine H+ and OHions to form waters. 8 . Balance charge by adding electrons (e-). Step 4a. each of which contains the oxidized and reduced forms of one of the species. a. Step 5. Add the balanced half-reactions and include states of matter. d. b.
(sim. Step 3. and use the factors as balancing coefficients.Chapter 18 Notes The Oxidation Number Method Step 1. 9 Examples: Balancing Redox Reactions 1. Compute the number of electrons lost in the oxidation and gained in the reduction from the oxidation number changes. Assign oxidation numbers to all elements in the reaction. 18.1-18. Step 5. Step 2. adding phase labels. to Ex. Step 4.3) a. Cr2O72-(aq) + I-(aq) → Cr3+(aq) + I2(s) [acidic solution] b. Identify the oxidized and reduced species. Sn(s) + NO3-(aq) → SnO2(aq) + NO(g) [acidic solution] c. Complete the balancing by inspection. Use the half-reaction method to balance the following redox reactions. MnO4-(aq) + C2O42-(aq) → MnO2(s) + CO32-(aq) [basic solution] Rules 10 . Multiply one or both of these numbers by appropriate factors to make the electrons lost equal the electrons gained.
• An electrolytic cell uses electrical energy to drive a nonspontaneous reaction (ΔG° > 0). 12 . – The difference in potential energy between higher energy reactants and lower energy products is converted into electrical energy.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 (ΔG° < 0) to generate electrical energy. – Lower energy reactants are converted into higher energy products by electrical energy. – The surroundings do work on the reactants. – The reactants do work on the surroundings.
• However. 18.1). a spontaneous reaction takes place: Zn(s) → Zn2+(aq) + 2eCu2+(aq) + 2e.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.→ Cu(s) [oxidation] [reduction] —————————————————————————————————— Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) [overall] • When this is done in a beaker (Fig. and the blue color of the solution fades as Cu2+ is reduced to copper metal and deposits on the bar. 14 . the enthalpy of the reaction escapes into the surroundings as heat. the zinc slowly dissolves as it is oxidized into soluble Zn2+ ions. no electrical energy is generated because the oxidizing and reducing agents are in physical contact.
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. 18. – This type of galvanic cell is called a Daniell cell. – The zinc is oxidized.Cu2+ Galvanic Cell • If. however. producing and electrical current.2). – A salt bridge between the half-cells maintains electrical neutrality and completes the circuit.Chapter 18 Notes A Zn Bar in a Cu2+ Solution Figure 18. – The chemical energy in the reactants can then be used to light a bulb or run an electrical device. releasing electrons which travel through the wire and reduce Cu2+ in the other half-cell.1 15 A Zn . the oxidation and reduction processes are separated from each other in two separate halfcells (Fig. 16 .
18.2 Galvanic Cells — Electrolytes • In a galvanic (voltaic) cell. the electrolyte is usually a soluble ionic compound containing a cation of the electrode metal. zinc chloride. the components of each half-reaction are placed in separate containers called half-cells. zinc sulfate.Cu2+ Galvanic Cell Figure 18.Chapter 18 Notes A Zn . the cells are joined by a wire and a salt bridge. etc. the zinc half-cell electrolyte could be any soluble zinc compound. consisting of an electrode dipping into an electrolyte solution. – In this example. 18 . such as zinc nitrate.2 MOV: Copper-Zinc Cell movie 17 Fig. • 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.
→ Cu(s) • By convention. Electrons are taken up by the substance being reduced (oxidizing agent) and enter the cell at the cathode. Electrons are given up by the substance being oxidized (reducing agent) and leave the cell at the anode. 20 . which is immersed in a Cu2+ electrolyte solution [Cu(NO3)2]. – The cathode is where the reduction half-reaction takes place. which is immersed in a Zn2+ electrolyte solution [Zn(NO3)2]. Cu2+(aq) + 2e. the reduction half-cell consists of a Cu metal bar acting as the cathode. the anode compartment is always drawn on the left.Chapter 18 Notes Fig. the oxidation half-cell consists of a Zn metal bar acting as the anode. 19 Fig. and will conduct e-’s into its half-cell. 18.2 Galvanic Cells — Electrodes • The electrodes are usually metal rods or sheets that are immersed in the electrolyte solutions of each half-cell. and will conduct e-’s out of its half-cell. Zn(s) → Zn2+(aq) + 2e• In this example. An electrode is classified by the half-reaction which takes place there: – The anode is where the oxidation half-reaction takes place. – The Cu cathode will gain more Cu metal as Cu2+ is reduced. – The Zn anode will dissolve as it is oxidized into Zn2+.2 Galvanic Cells — Electrodes • In this example. 18. they conduct the electricity between the cell and the surroundings.
22 . CPR Cathode Positive Reduction ANO Anode Negative Oxidation 21 Fig. the overall charge in each solution is maintained. – As Zn is oxidized to Zn2+.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. It completes the circuit between the half-cells by maintaining charge neutrality in the electrolyte solutions. therefore: – In any voltaic cell. – As Cu2+ is reduced to Cu. anions move right to left (towards the anode) and cations move left to right (toward the cathode) through the salt bridge. 18. 18.Chapter 18 Notes Fig. – Thus.2 Galvanic Cells — The Salt Bridge • The salt bridge consists of a non-reactive electrolyte suspended in a gel. anions (NO3-) diffuse out of the salt bridge into its electrolyte solution. cations (K+) diffuse out of the salt bridge into its electrolyte solution. – As electrons move left to right through the wire. and the circuit is completed. balancing out the charge. the anode is negative and the cathode is positive.
which are active participants in the half-reactions. and so something else must be used.→ Mn2+(aq) + 4H2O(l) [cathode] – In this case. usually made of graphite or platinum: 2I-(aq) → I2(s) + 2e[anode] MnO4-(aq) + 8H+(aq) + 5e. 18. The electrodes are consumed or added to during the course of the reaction. the species involved can’t act as electrodes.Chapter 18 Notes Fig.6) 24 . (Fig 21. inactive (or inert) electrodes are used. The electrolyte solutions must contain all of the species involved in the half-reaction. active electrodes are used.2 Galvanic Cells — Summary 23 Active and Inactive Electrodes • In this example. • Often.
→ 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.4 26 .→ Mn2+(aq) + 4H2O(l) overall: 2MnO4-(aq) + 16H+(aq) + 10I-(aq) → 2Mn2+(aq) + 5I2(s) + 8H2O(l) 25 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.Chapter 18 Notes Active and Inactive Electrodes Active Electrodes: anode: Zn(s) → Zn2+(aq) + 2e- cathode: Cu2+(aq) + 2e.→ Mn2+(aq) + 4H2O(l) overall: 5Fe(s) + 2MnO4-(aq) + 16H+(aq) → 5Fe2+(s) + 2Mn2+(aq) + 8H2O(l) Figure 18.
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+. MnO4-(aq). • In the I--MnO4. – The electron flow is left to right in this notation. – A double vertical line || represents the salt bridge. Mn2+(aq) | Graphite(s) 28 . Two or more components in the same phase are separated by commas.cell. the cell notation is Graphite(s) |I2(s) | I-(aq) || H+(aq). where inert electrodes are used. and the electrolyte solutions contain all of the reacting species. and Cu2+ is reduced to Cu. 27 Cell Notation • In the Zn-Cu2+ voltaic cell.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.
and sketch the experimental setup.Chapter 18 Notes Examples: Galvanic Cells 2. show balanced equations. 29 Examples: Galvanic Cells 3. 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. Diagram. Design a galvanic cell that uses the redox reaction Fe(s) + 2Fe3+(aq) → 3Fe2+(aq) Identify the anode and cathode half-reactions. and identify the sign of each electrode. Measurement indicates that the Cr electrode is negative relative to the Ag electrode. another half-cell with an Ag bar in an AgNO3 solution. Label the anode and cathode. 30 . and a KNO3 salt bridge. indicate the direction of electron and ion flow.
Sn4+(aq)||Ag+(aq)|Ag(s) b. write balanced equations for the cell reactions. Pb(s) + Br2(l) → Pb2+(aq) + 2Br-(aq) 32 .Chapter 18 Notes Examples: Galvanic Cells 4. Given the following cell notations. Pt(s)|Sn2+(aq). Cu(s)|Cu2+(aq)||Cl2(g)|Cl-(aq)|C(s) 31 Examples: Galvanic Cells 5. a. a. and give a brief description of the cells. Write the shorthand notations for galvanic cells that use the reactions shown below. Fe(s) + Sn2+(aq) → Fe2+(aq) + Sn(s) b.
V 1V = 1A = 1J 1C 1C 1s 34 – electrical current: ampere. This represents the potential energy difference between the materials in the anode and cathode compartments. or cell potential (Ecell). A .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). C – electrical potential: volt. • Electrical units in the SI system: – electrical charge: coulomb.
E° = ? V _______________________________________________________________________________________________________ 2H+(aq) + 2e. 1 M) + 2e. 1 M) + 2e-. with the zinc half-cell acting as the anode: Zn(s) → Zn2+(aq) + 2e-.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. the cell potential is found to be +0.7 36 . and measured relative to that value. E° = 0 V Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g). 18. through which H2(g) at 1 atm is bubbled: 2H+(aq.7).→ H2(g. E° = 0 V 35 Figure 18. a standard reference half-cell has been defined to have a potential of 0 V.76 V Figure 18. E° = 0 V H2(g. 1 atm) → 2H+(aq. E° = +0.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. All other cell potentials are combined with the reference half-cell. • The standard hydrogen electrode (SHE) consists of a platinum electrode in a 1 M H+(aq) solution at 25°C.→ H2(g). 1 atm).76 V.
→ Zn(s).76 V • By convention. • If the Zn/Zn2+ half-cell instead runs as a reduction. E°ox for the zinc cell is 0.34 V • Since E°cell = +0. E° = -0.34 V.→ Cu(s). E°red for the copper cell is +0.→ Cu(s). the reaction for the cell which occurs as an oxidation is reversed. tables of half-cell potentials are written as reductions. Its standard reduction potential would be -0.34 V. and E°red = 0 V (SHE).34 V: Cu2+(aq) + 2e. the overall cell potential is found to be +0.76 V.34 V 38 . 37 Using the SHE to Obtain a Reduction Potential • If we connect a Cu/Cu2+ half-cell to a SHE half-cell.Chapter 18 Notes Using the SHE to Obtain a Reduction Potential • The cell potential is obtained from the formula: E°cell = E°red + E°ox • Since E°cell = +0. we would write the reaction backwards and reverse the sign on the cell potential.76 V. E° = +0. E° = ? V _______________________________________________________________________________________________________ H2(g) + Cu2+(aq) → 2H+(aq) + Cu(s). E° = +0. with the copper half-cell acting as the cathode: H2(g) → 2H+(aq) + 2e-. and E°ox = 0 V (SHE).76 V: Zn2+(aq) + 2e. E° = 0 V Cu2+(aq) + 2e.
• The half-reactions are listed by decreasing standard reduction potential. MnO4-. – This list is essentially where the activity series for single displacement reactions is derived. etc.) and the strongest reducing agents are found in the lower right (Li.Chapter 18 Notes Standard Reduction Potentials • In the following charts. etc.). the halfreactions are written as reductions. • Oxidizing agents (which get reduced) and electrons are on the left side of each half-reaction. 39 Standard Reduction Potentials 40 . Mg. the strongest oxidizing agents are located in the upper left (F2. Na. the potential listed is the potential that the half-cell has if the half-cell reactions occurs as a reduction. reducing agents (which get oxidized) are on the right. the standard reduction potentials (or standard electrode potentials) for a number of half-cells are listed. H2O2. In all cases. In other words. Thus.
A-15 42 . p.Chapter 18 Notes Standard Reduction Potentials 41 Standard Reduction Potentials more standard reduction potentials are listed in Appendix IID.
85 +0.82 +1.00 43 Standard Reduction Potentials Standard Reduction Potentials at 25°C Half-Reaction 2H+(aq) + 2e.h Mn2+(aq) + 4H2O(l) Au3+(aq) + 3e.87 -2.h SO2(g) + 2H2O(l) Cu2+(aq) + e.h Hg22+(aq) Hg22+(aq) + 2e.h Ni(OH)2(s) + 2OH-(aq) O2(g) + 2H2O(l) + 4e.34 +0.h N2H5+(aq) Ni2+(aq) + 2e.23 +1.49 +0.h Hg(l) Ag+(aq) + e.23 +1.h Pb(s) + SO42-(aq) Cd2+(aq) + 2e.h Cu+(aq) Sn4+(aq) + 2e.h MnO2(s) + 4OH-(aq) I2(g) + 2e.89 -2.h Ag(s) Fe3+(aq) + e.20 +0.87 +2.h Co2+(aq) H2O2(aq) + 2H+(aq) + 2e.40 -0.70 +0.h H2(g) Pb2+(aq) + 2e.h 2H2O Br2(g) + 2e.25 -0.h Mn(s) Al3+(aq) + 3e.22 +0.h 2I-(aq) NiO2(s) + 2H2O + 2e.h 2Br-(aq) NO3-(aq) + 4H+(aq) + 3e.h 2Cr3+(aq) + 7H2O(l) MnO2(s) + 4H+(aq) + 2e.h Br-(aq) + 3H2O Cl2(g) + 2e.+ 4H+(aq) + 2e.40 +0.h Ce3+(aq) MnO4-(aq) + 8H+(aq) + 5e.15 0.76 -0.28 -0.18 -1.h NO(g) + 2H2O 2Hg2+(aq) + 2e.80 +0.h K(s) Li+(aq) + e.90 -2.63 +1.83 -1.00 -0.71 -2.05 44 .h Li(s) E° (V) 0.53 +0.h Sr(s) Ba2+(aq) + 2e.23 -0.96 +0.h Al(s) Mg2+(aq) + 2e.h 2F-(aq) O3(g) + 2H+(aq) + 2e.33 +1.h O2(g) + 2H2O(l) Co3+(aq) + e.h Cu(s) AgCl(s) + e.15 +0.44 +1.59 +0.77 +0.h Ni(s) Co2+(aq) + 2e.07 +0.31 -0.h Ag(s) + Cl-(aq) SO42.h 4OH-(aq) Cu2+(aq) + 2e.51 +1.36 +1.h Cd(s) Fe2+(aq) + 2e.92 +0.13 -0.93 -3.h Au(s) BrO3-(aq) + 6H+(aq) + 6e.37 -2.66 -2.h 2H2O(l) PbO2(s) + SO42-(aq) + 4H+(aq) + 2e.h H2(g) + 2OH-(aq) Mn2+(aq) + 2e.69 +1.07 +1.h Zn(s) 2H2O + 2e.74 -0.h PbSO4(s) + 2H2O(l) 2HOCl(aq) + 2H+(aq) + 2e.h Cr(s) Zn2+(aq) + 2e.h Ca(s) Sr2+(aq) + 2e.h Ba(s) K+(aq) + e.61 +1.h Fe(s) Cr3+(aq) + 3e.h Mn2+(aq) + 2H2O(l) O2(g) + 4H+(aq) + 4e.h Pb(s) Sn2+(aq) + 2e.77 +1.h Mg(s) Na+(aq) + e.h Co(s) PbSO4(s) + 2e.h Fe2+(aq) O2(g) + 2H+(aq) + 2e— h H2O2(aq) MnO4-(aq) + 2H2O(l) + 3e.h Na(s) Ca2+(aq) + 2e.Chapter 18 Notes Standard Reduction Potentials Standard Reduction Potentials at 25°C Half-Reaction F2(g) + 2e.14 -0.h Sn2+(aq) 2H+(aq) + 2e.h H2(g) E° (V) +2.50 +1.h Sn(s) N2(g) + 5H+(aq) + 4e.h 2Cl-(aq) Cr2O72-(aq) + 14H+(aq) + 6e.h Cl2(g) + 2H2O(l) Ce4+(aq) + e.44 -0.
– The potential of the cell (E°cell) is the difference between the standard half-cell potentials of the cathode and the anode: E°cell = E°cathode + (. since it is the ratio of J/C.→ Ag(s)] oxidation (anode): Zn(s) → Zn2+(aq) + 2eE° = 0.76 V = 1.E°anode) E°cell = 0. it is an intensive property.56 V 46 . written in the reverse direction. – the other occurs as an oxidation (at the anode).E°anode) E°cell = E°red + (. 45 Using Standard Reduction Potentials • For example.76 V) E°cell = E°cathode + (.E°ox) • NOTE: Do NOT multiply E°half-cell values by the coefficient.80 V + 0.80 V -E° = -(-0. to calculate the cell potential (E°cell) 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. written in the forward direction.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).
and Zn2+ is the weakest oxidizing agent.→ Zn(s) E°cell = +0. – Since reversing the reaction reverses the sign of E°cell.1.Chapter 18 Notes Relative Strengths of Oxidizing & Reducing Agents Cu2+(aq) + 2e. Zn is the strongest reducing agent and Cu is the weakest reducing agent.→ Cu(s) 2H+(aq) + 2e.34 V E°cell = 0. which is useful when trying to construct electrochemical cells.1 can be used as a guide to writing spontaneous redox reactions. Thus. Cu2+ is the strongest oxidizing agent. – Therefore. the more the reaction tends to occur as written. 48 . Cu2+ gains two electrons more easily than H+.76 V • The more positive the E°cell value. 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.00 V E°cell = -0. 47 Writing and Predicting Spontaneous Reactions • Table 18.→ H2(g) Zn2+(aq) + 2e. • A spontaneous reaction (E°cell > 0) will occur between an oxidizing agent and a reducing agent that lies below it on Table 18. and H+ gains electrons more easily than Zn2+.
E° = -0. does not dissolve in most acids: Cu2+(aq) + 2e. the reaction is spontaneous.→ Zn(s). dissolve in acidic solutions: Zn2+(aq) + 2e.→ H2(g). if negative it is nonspontaneous (or spontaneous in the reverse direction). E° = 0 V Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g).Chapter 18 Notes Writing and Predicting Spontaneous Reactions • In other words. • To determine whether a given reaction is spontaneous.76 V 2H+(aq) + 2e. Ered° = 0. If the cell potential is positive.76 V • Cu. look at the oxidation (anode) and reduction (cathode) processes. E° = +0.→ Cu(s).34 V • An important exception is nitric acid. such as Zn. E°cell = E°cathode + -E°anode E°cell = E°red + -E°ox 49 Metals Dissolving in Acids • Some metals. however.96 V 50 . E° = -0.34 V Cu(s) + 2H+(aq) → Cu2+(aq) + H2(g). E° = +0. the half-reaction with the more positive reduction potential takes place as a reduction.→ NO(g) + 2H2O(l). if the overall reaction is split into half reactions. which oxidizes metals through the redox reaction NO3-(aq) + 4H+(aq) + 3e. while the other one runs in reverse as an oxidation. and calculate the cell potential.
Zn(s). Arrange the following oxidizing agents in order of increasing strength under standard-state conditions: Br2(l).Chapter 18 Notes Examples: Using Reduction Potentials 6. 52 . Na(s). Cr2O72-(aq). Fe3+(aq). 51 Examples: Using Reduction Potentials 7. Arrange the following reducing agents in order of increasing strength under standard-state conditions: Al(s).
Use the following half-reactions to predict the spontaneous reaction that occurs when Br-.→ 2Br-(aq). H2SO3. E° = +1. What spontaneous reaction occurs if Cl2 and Br2 are added to a solution that contains both Cl.→ H2SO3(aq) + H2O E° = +0. Br2(aq) + 2e.07 V SO42-(aq) + 4H+(aq) + 2e.Chapter 18 Notes Examples: Using Reduction Potentials 8.and Br-? 54 . and Br2 are mixed in an acidic solution. SO42-.17 V 53 Examples: Using Reduction Potentials 9.
h Mn2+(aq) + 4H2O E°MnO4.74 V MnO4-(aq) + 8H+(aq) + 5e.= +1. E°Cr3+ = -0.Chapter 18 Notes Examples: Using Reduction Potentials 10.h Cr(s). Predict from Table 18. 55 Examples: Using Reduction Potentials 11.1 whether Pb2+(aq) can oxidize Al(s) or Cu(s) under standard-state conditions. Calculate E° for each reaction at 25°C.51 V 56 . What is the overall cell reaction and the standard cell potential of a galvanic cell employing the following half-reactions? Cr3+(aq) + 3e.
saliva as the electrolyte. 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) 57 A Shocking Dental Galvanic Cell • Biting on aluminum foil produces pain if you have fillings in your teeth. Al acts as the anode (-1. and the short circuit between the foil in contact with the filling creates a current that jolts the nerve in the tooth. 58 .23 V). and the silver/tin/mercury alloy filling as an inert cathode. O2 is reduced to water (1.Chapter 18 Notes Examples: Using Reduction Potentials 12.66 V).
Chapter 18 Notes Cell Potentials and Thermodynamics 59 Cell Potential and Free Energy • In the examples we’ve seen of spontaneous cell reactions. the charge on one mole of electrons (named for Michael Faraday): 1 F = 96.485 C / mol e1 F = 96. • The cell potential (Ecell) and the free energy change (∆G) are related by the equation ∆G = . F = the faraday.n F Ecell n = the number of moles of electrons transferred in the reaction. the cell potentials have been positive.485 J V-1 mol e-1 60 . F . There must then be some connection between the cell potential and the free energy change.
the more work the cell can do. and the farther the reaction proceeds to the right as written. a standard cell potential. E°cell is defined. the reaction has reached equilibrium. and the cell can do no more work (“dead battery”). ions at 1.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. ΔG° = .00 M). pressure. 1 atm.nFE°cell 62 . in which all components are at standard thermodynamic conditions (25°C. and temperature. • When all components are at standard conditions. • If Ecell = 0. 61 Standard Cell Potentials • Since Ecell is affected by concentration. pure solids for electrodes.
Calculate the standard cell potential at 25°C for the following reaction.3 kJ.Chapter 18 Notes Examples: Cell Potential and Free Energy 13. to Ex. 18. Al(s) + Cr3+(aq) → Al3+(aq) + Cr(s) 64 . (sim. which has a standard freeenergy change of -266. Calculate the standard free-energy change at 25°C for the following reaction.6) Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) 63 Examples: Cell Potential and Free Energy 14.
to Ex. (sim.Chapter 18 Notes The Relationship Between E°cell.RT ln K . ΔG° = .nFE°cell o Ecell = RT ln K nF o nEcell log K = 0. Lead can displace silver from solution: Pb(s) + 2Ag+(aq) → Pb2+(aq) + 2Ag(s) As a consequence. and K • When all components are in their standard states.0592 V 65 E o cell 0.7) 66 .RT ln K = . Calculate K and ΔG° at 25°C for this reaction.nFE°cell • Using the relationship between K and ΔG°.0592 V = log K n Examples: Calculating K and ΔG° from E° 15. ΔG°. ΔG° = . silver is a valuable by-product in the industrial extraction of lead from its ore. 18.
and even if they did.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. we start with the expression for ΔG under nonstandard conditions: ∆G = ∆G° + RT ln Q -nFEcell = -nFE°cell + RT ln Q • Solving for Ecell gives the Nernst equation (W. would not remain that way for long. • In order to obtain Ecell. solids (even solid electrodes) do not appear in the massaction expression: Cd(s) + 2Ag+(aq) → Cd2+(aq) + 2Ag(s) Q = [Cd2+] / [Ag+]2 68 .0592 V log Q n (at 25o C) If Q < 1 [product] < [reactant] log Q < 0 Ecell > E°cell If Q > 1 [product] > [reactant] log Q > 0 Ecell < E°cell If Q = 1 [product] = [reactant] log Q = 0 Ecell = E°cell • Remember when calculating the value of Q. Nernst. H. the cell potential under nonstandard conditions. 1889) o Ecell = Ecell - RT ln Q nF 67 The Nernst Equation o Ecell = Ecell - 0.
What was the concentration of Cr3+ in the solution of unknown concentration? 70 . 18.487 V. The standard cell potential for this system was determined to be 0.0 M. Consider a galvanic cell that uses the reaction Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g) Calculate Ecell at 25°C when [H+] = 1. with the chromium serving as the anode.8) 69 Examples: Using the Nernst Equation 17.20 M NiSO4 solution to a chromium electrode that was dipping into a solution containing Cr3+ at an unknown concentration. (sim.10 atm.Chapter 18 Notes Examples: Using the Nernst Equation 16.0010 M. [Zn2+] = 0. and PH2 = 0. The potential of the cell was measured to be 0. to Ex.552 V. A galvanic cell was constructed by connecting a nickel electrode that was dipped into 1.
A B Figure 18. creating a spike in the electrochemical potential across the membrane. and produces a voltage of 0. – Nerve cells use a concentration gradient to cause Na+ and K+ ions to diffuse into or out of a nerve cell. with all of the components at standard conditions. – 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). the left half-cell has a concentration 0. two of the same half-cells at different concentrations can be joined to produce a current: – In cell A. This concentration difference causes electrons to flow from the half-cell with the dilute Cu2+ to the halfcell with the concentrated Cu2+.068 V. There is no voltage difference. two Cu/Cu2+ half-cells are connected. which travels down the nerve cell.0 M.010 M and the right half-cell is at 2.12 71 Concentration Cells – In cell B.Chapter 18 Notes Concentration Cells • Because cell potentials change with concentration. 72 . and no current.
0592 V 74 .0592 V)(pH) = - • The overall cell potential is • and therefore Ecell = (0. They are based on a cell which is similar to the SHE half-cell.0592 V)(pH) + Eref pH = Ecell − Eref 0. this simplifies to: EH 2 →H + 0.0592 V = (2) log [H + ] 2 = (0. 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 2 → H+ = E o H2 → H+ ⎛ [H + ]2 ⎞ 0. and PH2 = 1 atm. n = 2.0592 V ⎟ log ⎜ ⎜ PH ⎟ n 2 ⎠ ⎝ 73 The Nernst Equation and pH • Since E° = 0 V.0592 V)(-log [H + ]) = (0.0592 V log [H + ]2 2 0.Chapter 18 Notes The Nernst Equation and pH • pH meters are electronic devices that are used for measuring pH (duuuh!).
6).Chapter 18 Notes The pH Meter • In practice.0592 V 75 The pH Meter 76 . the solution in the cell is separated from the test solution by a thin glass membrane (Figure 18.28 V • A typical pH meter measures the cell potential. E° = +0. • The reference electrode is a calomel (Hg2Cl2) electrode in contact with liquid mercury and KCl(aq): Hg2Cl2(s) + 2e.28 V 0. and electronically converts the potential to the pH value: pH = Ecell − 0. a glass electrode containing a silver wire coated with silver chloride immersed in a solution of HCl is used as the test electrode.→ 2Hg(l) + 2Cl-(aq).
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. or rechargeable. generating electricity through controlled oxidation of the fuel. – A primary battery cannot be recharged. The term is also sometimes used to refer to single voltaic cells. or flow battery. the reactants (usually a combustible fuel and oxygen) enter the cell and the products leave. – A fuel cell.” – A secondary. 78 . is not self-contained. battery can be restored to use by supplying electricity to reverse the cell reactions and regenerate the reactants. and must be disposed of when it is “dead.
→ 2Mn(OH)2(s) + 2OH-(aq) Ecell = 1.5 V 80 . Ecell = 1.→ Mn2O3(s) + 2NH3(aq) + H2O(l) etc. and produces higher power and a more stable current Anode: Zn(s) + 2OH-(aq) → ZnO(s) + H2O(l) + 2eCathode: 2MnO2(s) + 2H2O(l) + 2e. using a basic (alkaline) electrolyte.Chapter 18 Notes Dry Cell (Leclanché cell) (primary) A common household battery Anode: Zn(s) → Zn2+(aq) + 2eCathode: 2MnO2(s) + 2NH4+(aq) + 2e.5 V 79 Alkaline Battery (primary) A modified form of the Leclanché cell. corrodes more slowly.
thus recharging the battery. The reactions can be run in reverse.→ 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. by using current from the alternator.Chapter 18 Notes Lead-Acid Battery (rechargeable) Six cells in series.→ 2Ag(s) + 2OH-(aq) Ecell = 1.6 V (silver) 82 .5 M H2SO4. Anode: Pb(s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2eCathode: PbO2(s) + 3H+(aq) + HSO4-(aq) + 2e.→ Hg(l) + 2OH-(aq) Cathode (silver): Ag2O(s) + H2O(l) + 2e. 1.3 V (mercury). The electrolyte solution is ~4. each of which delivers about 2 V.
supplying external current reverses the reactions and recharges the battery.→ 2Ni(OH)2(s) + 2OH-(aq) Ecell = 1. hydrogen atoms are released as water molecules.2 V 84 . Anode: MH(s) + OH-(aq) → M(s) + H2O(l) + eCathode: NiO(OH)(s) + H2O(l) + e.Chapter 18 Notes Nickel-Cadmium (Nicad) Battery (rechargeable) Anode: Cd(s) + 2OH-(aq) → Cd(OH)2(s) + 2eCathode: 2NiO(OH)(s) + 2H2O(l) + 2e. At the anode.→ Ni(OH)2(s) + OH-(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.
but the electrode materials are expensive and short-lived.Chapter 18 Notes Lithium Solid-State Battery (rechargeable) Lightweight batteries which produce high voltages.→ LiMnO2(s) Ecell = 3 V 85 Fuel Cells Differs from an ordinary battery in that the reactants are not contained within the cell. Anode: Li(s) → Li+(in solid electrolyte) + eCathode: MnO2(s) + Li+ + e. there are no pollutants formed.→ 4OH-(aq) Overall: 2H2(g) + O2(g) → 2H2O(l) Ecell = 1. common in computers. etc. Anode: 2H2(g) + 4OH-(aq) → 4H2O(l) + 4eCathode: O2(g) + 2H2O(l) + 4e. the reactants are H2 and O2 gases. but are continually supplied from outside. cell phones.2 V 86 . In a hydrogen-oxygen fuel cell. digital camereas.
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.→ nS2-(l) Ecell = 2.1 V 87 88 .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. and molten S8 is the cathode.7 V Sodium-Sulfur Battery Molten Na is the anode. Anode: 2Na(l) → 2Na+(l) + 2eCathode: n/8S8(l) + 2e.→ 4OH-(aq) Ecell = 2.
iron does not rust. – Iron is oxidized in one region. and oxygen is reduced in another region. • 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. – Rusting also involves pitting of the metal surface. – Rusting is accelerated by electrolytes and acids. such as the rusting of iron. but the rust is deposited at a different location from the pits. 90 . in oxygen-free water or dry air.Chapter 18 Notes Corrosion 89 The Corrosion of Iron • Corrosion is the oxidative deterioration of a metal.
Chapter 18 Notes The Corrosion of Iron Figure 18. – The water droplet itself acts as an electrolyte. E° = 1. Other portions act as cathodes.23 V • When Fe2+ ions migrate away from the pitted anode region.→ 2H2O(l). – Portions of the iron surface act as an anode. which is deposited as red-brown rust: 2Fe3+(aq) + 4H2O(g) → 4Fe2O3•H2O(s) + 6H+(aq) ACT: Corrosion Activity 92 . 91 The Corrosion of Iron anode: 2Fe(s) → 2Fe2+(aq) + 4e-. where iron is oxidized. 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.27 • The surface of the iron and the droplet of water form a tiny galvanic cell. where oxygen is reduced to water.45 V cathode: O2(g) + 4H+(aq) + 4e. E° = 0.
• Galvanized iron is produced by dipping iron into molten zinc. which prevent any further corrosion.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.76 94 . or by coating the iron with a more durable metal such as Cr. such as Al. (Zn also reduces Fe2+ back to Fe. E° = -0.) – The zinc oxide does not flake off the metal surface. Cr. form hard. When oxidation occurs. or Zn. 93 Preventing Corrosion • The corrosion of iron can be prevented or minimized by shielding the metal surface from oxygen and moisture with paint. • Many other metals. and forms a protective coating. Mg. E° = -0. impenetrable metal oxide coatings when they oxidize. and is a big problem in ocean-going vessels. Fe2+ + 2e. Ti. and Zn. • Rusting also occurs faster at lower pH.h Zn(s).h Fe(s). Zn is oxidized instead of Fe.44 Zn2+ + 2e. since Zn has a lower reduction potential. this is a problem in areas where salt is used to melt ice on the roads. Sn. Iron(III) oxide is too porous to shield the underlying metal from further oxidation.
which is more easily oxidized. – When iron plumbing is connected directly to copper plumbing with no electrical insulation between them. and will corrode more rapidly (since Fe2+ is lost only at the anode). 95 Preventing Corrosion • If iron is in contact with a less active metal. and acts as a sacrificial anode. the iron pipe corrodes rapidly.Chapter 18 Notes Preventing Corrosion • Protecting a metal from corrosion by connecting it to a more easily oxidized metal is called cathodic protection. such as copper. – It is not always necessary to coat the entire metal surface. the iron anodic action is improved.16 96 . – Underground iron pipelines or propellers on boats can be protected by placing them in contact with Mg. Figure 21. as long as there is electrical contact with the second metal.
Reaction Type Spontaneous Equilibrium Ecell ΔG Cell Type + Galvanic + 0 Electrolytic Dead Battery 98 Nonspontaneous 0 . – Chemical energy is converted to electrical energy as the reaction proceeds toward equilibrium. ΔG < 0) to generate electricity. • Electrolytic cells use electric current from an external source to drive a nonspontaneous redox reaction (E < 0.Chapter 18 Notes Electrolytic Cells 97 Galvanic vs. – Electrical energy in converted to chemical energy as the reaction proceeds away from equilibrium. ΔG > 0). Electrolytic Cells • Galvanic cells use spontaneous redox reactions (E > 0.
Chapter 18 Notes
Galvanic vs. Electrolytic Cells
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.
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.
Electrolysis of Molten Salts
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.
Examples: Electrolysis of Molten Salts
18. In the electrolysis of molten MgBr2, what products form at the anode and cathode?
cathode. A chemical engineer melts a naturally occurring mixture of NaBr and MgCl2 and decomposes it in an electrolytic cell. Metallic potassium was first prepared in 1807 by Humphrey Davy by the electrolysis of molten potassium hydroxide. Predict the substance formed at each electrode.Chapter 18 Notes Examples: Electrolysis of Molten Salts 19. For this cell. and overall cell reactions. 106 . and write balanced half-reactions and the overall cell reaction.9a) 105 Examples: Electrolysis of Molten Salts 20. (sim. to Ex. label the anode and cathode. 18. and write balanced equations for the anode. and show the direction of ion flow.
41 V Overall: 2H2O(l) → 2H2(g) + O2(g) E = -1. since pure water does not carry electrical currents well.82 V 2H2O(l) → O2(g) + 4H+(aq) + 4eCathode (reduction): 2H2O(l) + 2e. such as Na2SO4.20 108 .Chapter 18 Notes Electrolysis of Water • The electrolysis of water is usually carried out in the presence of a nonreacting salt.23 V • Since the cell is not at standard conditions. 107 Electrolysis of Water Figure 18.→ H2(g) + 2OH-(aq) E = -0. the potentials are calculated from the Nernst equation. Anode (oxidation): -E = -0.
-E = -0.Chapter 18 Notes Electrolysis of Aqueous Salt Solutions • When predicting the electrolysis products of an aqueous ionic solution.→ Na(s) Reduction of water: 2H2O(l) + 2e.takes place.→ H2(g) + 2OH-(aq) E = -0. in an ionic solution of NaI.71 V .82 V 109 -E° = -0. 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.41 V Reduction of water takes place. and may be reduced or oxidized instead of the ionic compound. Overall Reaction: 2I-(aq) + 2H2O(l) → I2(s) + H2(g) + 2OH-(aq) 110 E° = -2.54 V Electrolysis of Aqueous Salt Solutions Cathode: Reduction of Na+: Na+(aq) + e. it is necessary to consider that water is also present. • For example.
93 V K+(aq) + e.24 111 Electrolysis of Aqueous Salt Solutions • If electrolysis were performed on aqueous KNO3: Anode: Oxidation of NO3-: can’t be done Oxidation of water: 2H2O(l) → O2(g) + 4H+(aq) + 4e.82 V Oxidation of H2O takes place. Cathode: Reduction of K+: E° = -2.-E = -0.41 V Reduction of water takes place.→ K(s) Reduction of water: 2H2O(l) + 2e.→ H2(g) + 2OH-(aq) E = -0. Overall Reaction: 2H2O(l) → 2H2(g) + O2(g) 112 .Chapter 18 Notes Electrolysis of Aqueous Salt Solutions Figure 18.
– E. 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.. however.82 V (~ -1.Chapter 18 Notes Electrolysis of Aqueous Salt Solutions 113 Electrolysis of Aqueous Salt Solutions • Sometimes unexpected products are obtained. When gases are produced at electrodes.-E° = -1.4 V with overvoltage) Oxidation of Cl-: 2Cl-(aq) → Cl2(g) + 2e. H2 forms at the cathode and Cl2 forms at the anode.g.-E = -0.36 V 114 . in the electrolysis of NaCl. an additional voltage called the overvoltage is required to overcome the kinetic factors (such as high Eact).
SO42-. Group II. Pt. and Cd. • Anions that are oxidized include the halides (except F-. NO3-. MgSO4 d. and Al. What is the overall cell reaction in each case? (sim. such as those of Group I. Water is reduced to H2 and OH. • More active metals are not reduced. Ag. Predict the half-cell reactions that occur when aqueous solutions of the following salts are electrolyzed in a cell with inert electrodes. Water is oxidized to O2 and H+ instead. 115 Examples: Predicting Electrolysis Products 21. 18. Cu. KBr b. AgNO3 c. and PO43-. CuSO4 116 . Cr.) • Anions that are not oxidized include F-. such as Au.9a) a. cations of less active metals are reduced to the neutral metal.instead. to Ex.Chapter 18 Notes Electrolysis of Aqueous Salt Solutions • In general.
(Michael Faraday. current multiplied by time gives the charge: A × s = C/s × s = C 118 . 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.65 × 104 C/mol e-) to find the corresponding charge. measured in amperes (A): 1A = 1C/s • Thus. – 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.Chapter 18 Notes The Stoichiometry of Electrolysis • Faraday’s law of electrolysis — the amount of substance produced at each electrode is directly proportional to the quantity of charge flowing through the cell. – Use the Faraday constant (F = 9.
Chapter 18 Notes Examples: Stoichiometry and Electrolysis 22.10) 120 .0 A to deposit 3.0 min? (sim. How many minutes will it take for a current of 10. 18.00 g of gold from a solution of AuCl3? 119 Examples: Stoichiometry and Electrolysis 23. to Ex.00 A is run through a solution of CuSO4 for a period of 20. How many grams of copper are deposited on the cathode of an electrolytic cell if an electric current of 2.
00 g of gold from a solution of AuCl3 in 20. What current must be supplied to deposit 3.Chapter 18 Notes Examples: Stoichiometry and Electrolysis 24.0 min? 121 122 .
the cell is designed to keep the sodium metal separate from the chlorine gas. or they will recombine (violently!). 124 .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.
0 g Al). and rolled into plates. Al used to be extremely valuable because of the difficulty in extracting Al metal from the ore.produces 9. and subjecting it to electrolysis. sheets. This process made the production of Al much more cost-effective. Na+ from the anode compartment moves by osmosis through a cation-permeable membrane to the cathode compartment. and the liquid metal is drained off. Saturated NaCl(aq) is oxidized in the anode compartment to produce Cl2. which generates sales of about $4 billion in the US alone. 126 .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. water is reduced in the cathode compartment to OH-. maintaining neutrality and thereby producing sodium hydroxide. usually in the form of the ore bauxite (Al2O3). Now. Al3+ is reduced to Al. but still requires large amounts of electricity (n=3: 1 mol e. 125 Manufacture of Aluminum Aluminum is the third most abundant element in the crust (8.3%). Al is produced using the HallHéroult process by dissolving bauxite in molten cryolite (Na3AlF6). cooled. or foil.
galvanized metal (Zn). a 0. such as chrome (Cr). etc. Impure copper is used as the anode.Chapter 18 Notes Electroplating In electroplating.05 mm coating of one metal is deposited on another metal. In this illustration. 127 Refining of Copper Copper can be obtained from ore in 99% purity. silver dissolves from a solid Ag bar (the anode) and is deposited as solid silver on a fork (the cathode). Cu dissolves at the anode. gold. 128 .03 to 0. and platinum. but this is not good enough to use in wire. The anode mud contains such “impurities” as silver. Other easily oxidized metal ions. and less easily oxidized metals fall to the bottom of the cell as anode mud. and plates out as pure copper at the cathode. Electroplating can be used to provide a variety of protective or decorative metal surfaces. silver. gold. and a sheet of very pure copper is used as the cathode. such as Zn2+ and Fe2+ remain in solution.
Chapter 18 Notes Equation Summary • Cell Potentials: E°cell = E°red + (-E°ox) • Thermodynamics: ΔG° = . Faraday constant) 130 .0592 V log Q n (at 25o C) • Electrolysis: 1A=1C/s 1V=1J/C 1 mol e.0592 V log K n 129 Equation Summary • The Nernst equation: o Ecell = Ecell - 0.65×104 C (F.= 9.nFE°cell o Ecell = 0.