Chemistry 1C-Foothill College

Electrochemistry
Objectives:
• • • • Be able to balance net ionic equations for redox reactions: (Half Reaction Method-Covered in Lab). Understand what we mean by standard reduction potential (SRP). Be able to determine cell voltages using SRP. Understand Voltaic cells: The “good”-batteries and fuel cells The “bad”-metal corrosion (rust) and methods used to inhibit corrosion! The Nernst equation and cell voltage under nonstandard conditions Understand electrolytic cells: Electroplating Quantitative calculations Understand the relationship between cell voltage, thermodynamics and equilibria: !G and equilibrium constants, again! Understand terms used for electrical power: My PG&E bill is so high!!! What’s a watt anyway? What’s a kilowatthour?
Electrochemistry

1

Review of Terms: Section 4.4
• Oxidation: the loss or apparent loss of one or more electrons. An increase in oxidation number for the atom. Example: • Reduction: the gain or apparent gain of one or more electrons. A decrease in oxidation number for the atom. Example: • Oxidizing Agent (oxidant): a species that will oxidize (take electrons from) another species. An oxidizing agent is reduced as it oxidizes the other species. Example(s): • Reducing Agent (reductant): a species that will reduce (give electrons to) another species. A reducing agent is oxidized as it reduces the other species. Example(s):

Electrochemistry

2

L.J. Larson-All Rights Reserved

Chemistry 1C-Foothill College

Review of Terms: Section 4.4
• Remember that the oxidation number of an atom does not generally equal the actual charge on the atom, it is a convenient form of “electron bookkeeping” that enables us to decide if a redox reaction has occurred. For covalently bonded atoms, oxidation numbers are assigned as if the electrons in the bond “belong” to the more electronegative element. Under what circumstances is the oxidation number of an atom equal to its actual charge? When is oxidation number not equal to the charge on an atom?

Oxidation and reduction always occur together. The number of electrons lost in oxidation must equal the number of electrons gained in reduction. CHARGE BALANCE MUST BE MAINTAINED.
Electrochemistry

3

Reduction Potential
Let’s begin by doing a simple (and fun!) experiment to rank the reduction potentials of H+, Zn2+, Ag+ and Cu2+. Reduction Potential: The ease with which a substance is reduced. A higher reduction potential means that reduction occurs more readily.

Electrochemistry

4

L.J. Larson-All Rights Reserved

Chemistry 1C-Foothill College

Electromotive Force (emf)
• Water flows spontaneously only one way in a waterfall. Likewise, electrons spontaneously flow only one way in a redox reaction— from higher to lower potential energy. Based upon our experiment to rank reduction potentials, do the valence electrons in Cu or in Zn have the lower potential energy.

Electrochemistry

5

Electromotive Force (emf)
• • There is an electromotive force (“causing electron motion”) or emf that drives the electrons in a spontaneous redox reaction. For a nonspontaneous redox reaction there is an emf that must be applied to force the reaction to occur. What’s the sign of ! G and !Suniverse for spontaneous reactions? For nonspontaneous reactions?

This emf is a difference in potential energy between the two electrodes of a cell. There are no “absolute” emf measurements. We measure this force (emf or potential difference) as a voltage, the difference in potential energy per unit charge (Joule/Coulomb). The emf of a cell, Ecell, is also called the cell potential or cell voltage.

• •

Electrochemistry

6

L.J. Larson-All Rights Reserved

J. One electron has a charge of 1. Anode (-): • • Cathode (+): • • This system can do work! The e– lose 0.Chemistry 1C-Foothill College Understanding the Volt • 1 Volt (V) = 1 Joule(J)/1 Coulomb(C) Voltage => The difference in potential energy (J) between two electrodes per unit charge (C). Which one is at the higher potential energy. the Cu or the Ag electrode? 1M Electrochemistry 8 L. Think about it” Is voltage an intensive or an extensive property? What is the total charge in coulombs of a mole of electrons? Electrochemistry 7 Simple Voltaic Cells: Video-Cu Zn Cell Spontaneous: What’s the sign of !G? • Two half-cells connected with a salt bridge to maintain charge neutrality in each halfcell.46 J/C of potential energy as they move from anode to cathode. A) is a measure of the number of electrons in motion: 1 amp = 1 C/sec Coulombs are used to “count” electrons moving in circuit. Larson-All Rights Reserved . 1 Coulomb is the fundamental unit of charge. Voltage is the force or “push” electrons feel to move.602176 x 10–19 C Current (ampere.

At the cathode. Any conducting electrode can be used and the Ag+ ions will still “plate-out” on the electrode. a negative charge must also accompany them. Migration of Cu2+ ions through the salt bridge can also occur to maintain charge balance. If a load is present (light bulb.). Larson-All Rights Reserved . where electrons are produced is given a negative sign (–) by convention. as each Ag+ ion is consumed in the reduction. switch that carries the electrons and a salt bridge to maintain charge balance between the two cells. a charge imbalance will develop unless a salt bridge is provided. the anode. When the circuit is closed the solid Cu electrode begins to oxidize and produce Cu2+ ions that enter the electrolyte solution.J. useful work can be done by the electrical current generated. Since solid silver is not a reactant a solid silver electrode for the cathode is not needed for the reduction process. These labels do not denote the charges on the electrodes. a Na+ ion diffuses from the salt bridge into the electrolyte solution. and the reduction half-cell. The cathode is given a positive sign (+). As the electrons enter the cathode.Chemistry 1C-Foothill College Voltaic Cells: Sequence of Events The oxidation reduction reaction is separated into two half-cells. When the electrode does not actively participate in the oxidation/reduction it is termed an inactive electrode. Could the Cu electrode be replaced by an inactive electrode for the oxidation process? Why or why not? Electrochemistry 9 Summary: Simple Voltaic Cells Electrochemistry 10 L. the anode. The half-cells are physically connected by a circuit (wire. the cathode. the oxidation half cell. Because electrons are moving from one cell to another. The electrons leave the anode and are carried towards the cathode. etc. Ag+ ions in the electrolyte solution are reduced to form solid Ag that “plates-out” on the Ag electrode. As the Cu2+ ions move into the electrolyte solution during oxidation. the electrode charges are essentially zero. In a voltaic cell. Two NO3– ions from the salt bridge will diffuse into the anode electrolyte solution for each Cu2+ ion produced.

Video: Standard Reduction Potentials Video: Zinc-Hydrogen Cell Electrochemistry 12 L.Chemistry 1C-Foothill College Problem Identify the anode and cathode half-reactions in the following unbalanced reaction: MnO4–(aq) + Fe(s) —> Mn2+(aq) + Fe3+(aq) Electrochemistry 11 Standard Reduction (Half -Cell) Potentials • To determine the emf of a half-cell we use the standard hydrogen electrode) SHE as a reference. Thus. • By convention the SHE half-cell emf is set to 0 V. Gaseous species are 1 atm (1 bar). • Measurements are made under standard conditions for each half-cell: Solid and liquid reactants and products are pure. Solutes are 1 M.J. half-cell emf values are given as standard reduction potentials RELATIVE to the SHE. all measurements are taken relative to the SHE. • By convention. Larson-All Rights Reserved .

The most common inert electrodes used are Pt metal and carbon (graphite). Black probe Red probe Electrochemistry 14 L.J. 2 H+(aq.Chemistry 1C-Foothill College Standard Hydrogen Electrode • The standard hydrogen electrode uses an inert electrode (one that just serves to carry the electrons). 1 atm) E°red= 0 V What is E°oxid for the standard hydrogen electrode? What reaction does it correspond to? Electrochemistry 13 Measuring E°red for the Zn/Zn2+ half-cell (Understanding how voltmeters work) Zn metal is shown reacting with hydrochloric acid. 1M) + 2 e. Larson-All Rights Reserved .—> H2(g.

The sign of the voltage is interpreted as follows: (+) voltage: The red probe has a higher reduction potential (that is a greater tendency to be reduced) than the black probe. The black probe is attached to the anode (where oxidation occurs) and the red probe is attached to the cathode (where reduction occurs). • The electrons are moving from the Zn metal to the H+ ions.76V relative to the SHE. (–) voltage: The black probe has a higher reduction potential than the red probe. This means that the SHE is 0. Electrochemistry 15 Measuring E°red for the Zn/Zn2+ half-cell • With the Zn/Zn2+ half-cell connected to a SHE a voltage of +0. E°red for the Zn/Zn2+ half-cell is -0. • Remember the following!!!! The cathode is always at a lower potential energy than the anode in a voltaic cell.J.76V higher in reduction potential compared to the Zn/Zn2+ half-cell. Larson-All Rights Reserved . The cathode always has a higher reduction potential than the anode in a voltaic cell.Chemistry 1C-Foothill College Understanding How Voltmeters Work: Important for the Voltaic Cell Experiment! • How do we know which half-cell is the cathode and which is the anode? We use the sign of the voltage and the placement of the voltmeter probes. The black probe is attached to the cathode and the red probe is attached to the anode. • Remember: the voltmeter measures a voltage difference between the two probes and by convention measures the reduction potential of the half-cell connected to the red probe relative to the half-cell connected to the black probe. the anode (oxidation) is the Zn half-cell while the cathode (reduction) is the SHE half-cell. We can say that the SHE half-cell has a higher reduction potential and is at a lower potential energy compared to the Zn half-cell. ! Question: If the black probe were to be placed on the SHE half-cell and the red probe on the Zn/Zn2+ half-cell. what voltage would you observe? What does this result give you for E°red of the Zn/Zn2+ half-cell? Electrochemistry 16 L. • Thus.76V was observed with the black probe attached to the Zn half-cell.

Reducing agents are given on the RIGHT side of the table. • Identify: (1) The strongest oxidizing agent in this table. 2. STRONGEST at the top.J. Oxidizing agents are given on the LEFT side of the table. Larson-All Rights Reserved . The more (+) E°red the more favorable is the reduction. 5. When the half-cell reaction is reversed the sign of the voltage changes. Hence a better oxidizing agent. (2) The strongest reducing agent. 3.1: Standard Reduction Potentials • The more positive the value of E°red. the greater the driving force for reduction. WEAKEST at the bottom. All potentials are for the reduction half-reaction. • Locate/Identify the reaction corresponding to: (1) Reduction of water (2) Oxidation of water Electrochemistry 17 Summary-Properties of E°red 1. WEAKEST at the top. STRONGEST at the bottom.Chemistry 1C-Foothill College Text Table 20. Electrochemistry 18 L. 4.

The value of E°cell will always be (+) under these conditions. The greater reduction potential at the cathode compared to the anode can be thought of as driving the anode reaction in “reverse”.J. the reaction at the cathode has a more positive E°red. remember that it is an intensive property. The greater the difference in E°red between the two. Since cell potential is the potential energy per unit of charge. Larson-All Rights Reserved .Chemistry 1C-Foothill College Calculating Standard Voltaic Cell Potentials • The cell potential under standard conditions is denoted E°cell and can be determined using the following equation: E°cell = E°red(cathode) – E°red(anode) or E°cell = E°red+ E°oxid A (+) E°cell indicates: A (–) E°cell indicates : • The individual E°red(cathode) and E°red(anode) half-cell potentials are STANDARD REDUCTION POTENTIALS. as oxidation. Electrochemistry • • • 19 Using the Table of Potentials • A spontaneous redox reaction will occur when: Any substance on the LEFT (oxidizing agent) reacts with any substance on the RIGHT (reducing agent) LOWER in the table. E°oxid is a standard oxidation potential: E°oxid = –E°red(anode) In any voltaic cell. Electrochemistry 20 L. the greater the voltage of the cell.

Assume standard conditions. d) What is the emf (voltage) generated by the cell under standard conditions? Electrochemistry 22 L. The two beakers are connected with a salt bridge. and in the other beaker a platinum electrode is immersed in a 1M NaCl solution. with 1 atm Cl2 gas bubbled around the electrode. 4 Fe3+(aq) + 4 OH–(aq) —> 4 Fe2+(aq) + O2(g) + 2 H2O(l) Electrochemistry 21 Using the Table of Standard Reduction Potentials Text Problem 20. a) b) c) Which electrode serves as the anode.J. and which as the cathode? Does the Pb electrode gain or lose mass as the cell reaction occurs? Write the net-ionic chemical equation for the overall cell reaction. Is the reaction spontaneous as written? 1. Larson-All Rights Reserved .38: A voltaic cell consists of a strip of lead in a solution of 1M Pb(NO3) 2 in one beaker. 2 H+ (aq) + Cu(s) —> Cu2+ (aq) + H2(g) 2.Chemistry 1C-Foothill College Using the Table of Standard Reduction Potentials • Determine E°cell for the following reactions.

Based upon standard reduction potentials. What halogens are stable in water? 4. Rank the halogens in order of their strength as oxidizing agents. we find that permanganate is actually stable in water solution. However. What metals in the table are unstable in water? 5. Electrochemistry 24 L. Fe3+(aq) and Na(s). Copper dissolves in a nitric acid solution with the evolution of NO(g). Larson-All Rights Reserved . 1. Choose the best reducing agent between Fe2+(aq). b) Write the balanced net ionic equation for the reaction that occurs when copper is placed in a nitric acid solution. Choose the best oxidizing agent between Fe2+(aq). 3. a) Explain these observations. 2. Zn2+(aq) and Cu(s). Assuming standard conditions and using the half reactions listed in Table 20.Chemistry 1C-Foothill College Using the Table of Standard Reduction Potentials • A ranking of oxidizing and reducing agents can be made from the table and stability in water can be predicted. it appears as if MnO4– ions should be spontaneously reduced by water. Given: Au3+(aq)+ 3e– —> Au(s) E°red = +1.J. In contrast. copper does not dissolve in a hydrochloric acid solution. Why is this? Electrochemistry 23 Using the Table of Standard Reduction Potentials 1.50 V What halogens can oxidize Au? 3.1 of the text. 2.

Larson-All Rights Reserved . 1M). 1M)|Pt • Write the shorthand notation for the standard Zn/Zn2+. A double vertical line separates the half-cells. A comma is used to separate half-cell components within the same phase that appear in the balanced half reactions. A single vertical line represents phase boundaries. SHE voltaic cell.J. Electrochemistry 25 Shorthand Cell Notation for Voltaic Cells Examples: Cu(s) + 2 Ag+(aq) —> Cu2+(aq) + 2 Ag Cu(s)|Cu2+(aq. Which electrode will decrease in mass? What is E°cell? Write the balanced net-ionic chemical equation for the overall reaction for this cell. 1M)|Ag(s) The anode half-cell is written first (oxidation). unless it is being oxidized or reduced.Chemistry 1C-Foothill College Voltaic Cell Diagrams Consider the following voltaic cell: a) In which direction do electrons flow? b) c) d) Where does oxidation occur? Where are electrons consumed? Which electrode is labeled (–)? Fe Ni 1 M Fe2+ 1 M Ni 2+ e) f) g) h) i) Suggest a solution for the anode electrolyte. Mn2+(aq. Suggest a pair of ions for the salt bridge. 1M)||Ag+ (aq. Electrochemistry 26 L. " H2O is generally omitted. 1 M)|| MnO4– (aq. " " " " MnO4– (aq) + Fe(s) —> Mn2+(aq) + Fe3+(aq) Fe(s)| Fe3+(aq.

d. the redox reaction takes place. Sept. 25. As the cell does work. Aug. The voltaic cell continues to do work until an equilibrium is reached between the reactants and products. The equation is: ! G = -nFE cell where n is the moles of electrons transferred in the reaction. have become common ideas in modern physics. ! G in units of ? (Recall 1 C = 1 J/V) Michael: The English chemist and physicist Michael Faraday. 1867. Larson-All Rights Reserved . such as lines of magnetic force. the absolute value of the amount of charge in 1 mol of electrons. b. 1F = 96. the concentrations of reactants and products change and move towards equilibrium. Several concepts that he derived directly from experiments. Many consider him the greatest experimentalist who ever lived. electrons flow.485 C/mol e– Terminology: When we say 1 Faraday of electrons we mean 1 mole of electrons. 22.J. the cell potential continually decreases. is known for his pioneering experiments in electricity and magnetism.Chemistry 1C-Foothill College Electrochemistry and Thermodynamics • Voltaic cells can do work because !G for the redox reaction is negative. Ecell. F is Faraday’s constant. • At equilibrium the voltaic cell has: Ecell = Q= !G = Are there any electrons flowing? Electrochemistry 27 Electrochemistry and Thermodynamics • From Michael Farady’s1 work on electrochemical cells the difference in free energy (! G) was found to be directly proportional to the electrochemical potential of the cell. Under standard state conditions: ! G˚ = -nFE˚cell 1Faraday. Electrochemistry 28 L. 1791.

nonspontaneous or at equilibrium. we can directly measure ! G˚ and K for the reaction by simply measuring the cell potential under standard conditions! Complete the table given below by: (1) giving the sign of ! G°. of a redox reaction to its equilibrium constant. Eo. • !G˚ K E˚cell Forward reaction at standard state conditions >0 0 <0 Electrochemistry 30 L.J.98: Derive an equation that directly relates the standard emf. Larson-All Rights Reserved .Chemistry 1C-Foothill College Electrochemistry and Thermodynamics Text Problem 20. Electrochemistry 29 Electrochemistry and Thermodynamics • What does this mean? For redox reactions. greater than or equal to 1 and (3) determining if the forward reaction is spontaneous. (2) indicating if K is less than.

Electrochemistry 32 L. calculate Ksp for AgSCN.99: Calculate ! G° and the equilibrium constant for the disproportionation of copper(I) ion at 25°C: 2Cu+(aq) <—> Cu2+(aq) + Cu(s) Electrochemistry 31 Electrochemistry. Equilibria and Thermodynamics Text Problem 20.Chemistry 1C-Foothill College Electrochemistry.J. Larson-All Rights Reserved .116: The standard cell potential for the reduction of AgSCN(s) is +0.0895V. AgSCN(s) + e– —> Ag(s) + SCN–(aq) Using this value and the standard electrode potential for Ag+ (aq). Equilibria and Thermodynamics Text Problem 20.

was awarded the NOBEL PRIZE for chemistry in 1920 for his discovery (1906) of the third law of thermodynamics. Recall from thermodynamics that the free energy change for the system ( !G) when it moves from nonstandardstate conditions to equilibrium is given by: ! G = ! G˚ + RT ln Q where Q is the reaction quotient. 18. Q predicts the direction of chemical change to reach equilibrium. to change.) Since ! G = -nFEcell and ! G˚= -nFE°cell we can derive an equation (The Nernst Equation2) that allows us to calculate the cell potential under nonstandard conditions. June 25. 2Nernst. (Q is defined exactly like K but is evaluated under any condition. Walther: The German physical chemist and inventor Hermann Walther Nernst.J.Chemistry 1C-Foothill College Cell EMF Under Nonstandard Conditions (Nernst Equation) • Changes in concentrations of the electrolytes that comprise the half-cell electrodes will cause the cell potential. d. This change can be understood by looking at how changes in concentrations effect the free energy change of the system. Larson-All Rights Reserved . He introduced the Nernst equation (1889). Nov. which states that entropy approaches zero as temperature approaches absolute zero. b. E cell. 1941. which relates electric potential to various properties of the electric cell. Electrochemistry 33 Derivation of the Nernst2 Equation !G = ! G˚ + RT ln Q !G = -nFEcell and ! G˚= -nFE° cell Electrochemistry 34 L. 1864.

0 M)| Pt a) b) Write the balanced net ionic equation for the reaction.00 M in equilibrium with PbSO4( s) what is the Ksp of PbSO4? Electrochemistry 36 L. P(H2) = 0. Larson-All Rights Reserved .50 atm and the pH in both compartments is 5.220 V. 1. 1.0 atm)|H+ (aq. Without doing ANY calculations.Fe2+(aq.66: A voltaic cell is constructed that is based on the following reaction: Sn2+(aq) + Pb(s) –> Sn(s) + Pb2+(aq) a) If the concentration of Sn2+ in the cathode compartment is 1.00? c) Electrochemistry 35 Using the Nernst Equation Text Problem 20. 1. What is the emf of the cell when [Fe3+] = 1. [Fe2+] = 0. determine if the reaction is spontaneous under the conditions given.Chemistry 1C-Foothill College Using the Nernst Equation • Consider the following cell: Pt|H2(g.J.50 M.0 M)||Fe3+(aq.0 M).00 M and the cell generates an emf of +0.0010 M. 1. what is the concentration of Pb2+ in the anode compartment? b) If the anode compartment contains [SO42"] = 1.

58: A voltaic cell is utilizes the following reaction: 3Ag+(aq) + Al(s) –> 3Ag(s) + Al3+(aq) What is the effect on the cell emf of each of the following changes? a) Water is added to the anode compartment. In a concentration cell the half-reactions at the anode and cathode are identical! Consider the following cell: E˚cell is zero: E˚ cell = E˚ cathode – E˚ anode = +0. if the concentrations of the Ag+ ions are different in the half-cells. Electrochemistry d) 37 A Weird? Consequence of the Nernst Equation: Concentration Cells • An examination of the Nernst equation shows that Ecell can be non zero even if E˚cell is zero! Why? Ecell will be non zero if the concentrations of reactants and products are not equal. However. precipitating some of the Ag+ as AgCl. diluting the solution.80 V – (+0. c) A solution of AgNO3 is added to the cathode compartment. Ag(s) | Ag+(aq) || Ag+(aq) | Ag(s) Electrochemistry 38 L. HCl is added to the AgNO3 solution. b) The size of the aluminum electrode is increased.80 V) = 0. then a cell potential exists and electricity will flow until the Ag+ concentrations in the half-cells are equal. Larson-All Rights Reserved . This allows us to construct a concentration cell. increasing the quantity of Ag+ but not changing its concentration.Chemistry 1C-Foothill College Using the Nernst Equation Text Problem 20.J.00 V.

! S univ and ! G for this process? c) Which electrode corresponds the the anode half-cell? Electrochemistry 39 Concentration Cell Problem Continued c) Write the half reaction for each electrode: A: B: d) e) Add these two equations to get the overall cell reaction: What is Q for this system? f) Using the Nernst equation find Ecell at 298K. ! Ssurr.) b) “Think about it”: What is ! Hsys. ! S sys. Electrochemistry 40 L.50 M.010 M and the concentration of Ag+ ions at electrode B be 0. a) In what direction will electrons flow to equalize the Ag+ ion concentrations between the two cells? (Sketching a drawing of the cell is helpful here. Let the concentration of Ag+ ions at electrode A be 0.Chemistry 1C-Foothill College Concentration Cell Problem • Consider a concentration cell using Ag(s) electrodes and AgNO3(aq) as the electrolyte. Larson-All Rights Reserved .J.

10) and a hydrogen electrode (with 1 atm pressure of H2 gas) dipped into the solution of unknown pH>0. and calculate the standard emf.J. The two half-cells are connected by a salt bridge or porous glass disk. A simple (but impractical) pH meter can be constructed by using two hydrogen electrodes: one standard hydrogen electrode (Figure 20. Larson-All Rights Reserved .293 V at 25°C what is the pH of the unknown solution? c) Electrochemistry 41 Measuring pH: Extra Space for Calculations Electrochemistry 42 L. b) What is the pH of the solution in the half-cell that has the standard hydrogen electrode? If the cell emf is 0. a) Write the half-cell reactions for the cell.Chemistry 1C-Foothill College Measuring pH • A pH meter employs a voltaic cell for which the cell potential is very sensitive to pH.

Following voltaic cell labeling conventions. constant voltage. Batteries are made from a voltaic cell or a series of voltaic cells connected anode to cathode.Chemistry 1C-Foothill College Batteries: Commercial Voltaic Cells • The first known battery. long life. ! Desired qualities: compact. the voltage of the battery is the sum of the individual voltaic cells. Larson-All Rights Reserved . high current. anode to cathode. the electrodes of a battery are labeled (+) for the cathode and (–) for the anode. a Zn/Cu battery was built in 1836 by English chemist John Frederick Daniell. When connected in series.J. low cost Electrochemistry 43 Batteries There are three major types of batteries: 1) Primary: 2) Secondary: 3) Fuel Cell: Electrochemistry 44 L.

Chemistry 1C-Foothill College “Dry Cell” Primary Batteries (Throw away) • About 1.—> 2 NH3(g) + H2(g) Advantage: Low cost Disadvantages: Deteriorate over time (short shelf life).J. • Anode is zinc: Zn(s) —> Zn2+(aq) + 2 e- • Cathode is NH4+: • Gases are trapped by side rxns: 1. Electrochemistry 45 Alkaline Primary Batteries (Throw away) • • • Anode is zinc: Cathode is MnO2: Zn(s) + 2 OH-(aq) —> Zn(OH)2(s) + 2 e- MnO2(s) + 2H2O(l) + 2 e.55 V • Not as common as in the past. Larson-All Rights Reserved . voltage and current drops.—> 2MnO(OH)(s) + 2 OH-(aq) Single cell emf = 1. longer shelf life than dry cell.55 V at room temperature • Advantages: Low cost. 2 MnO2(s) + H2(g) —> Mn2O 3 (s) + H2O(l) NH4 +(aq) + 2 e. Zn2+(aq) + 2 NH3(g) + 2 Cl-(aq) —> Zn(NH3) 2Cl2(s) 2. constant voltage. no gases produced • Disadvantages: ? Electrochemistry 46 L.

Advantage: small.Chemistry 1C-Foothill College Mercury Cell Primary Batteries (Throw away) • Anode is zinc: Zn(s) + 2 OH-(aq) —> ZnO(s) + H2O(l) + 2 e- • Cathode is HgO: HgO(s) + H2O(l) + 2 e. Fails over time due to mechanical dislodging (loss) of the PbSO4 from the electrodes. Electrochemistry 48 L. Pb disposal. Pb and PbSO4 (Why is this?). remains attached to each electrode. high current. Advantages: low cost.J.—> Hg(l) + 2 OH-(aq) • • • These are also “alkaline” batteries. Disadvantages: heavy. Voltage relatively constant since emf not dependent on relative amounts of PbO2. constant voltage Disadvantages: mercury disposal Electrochemistry 47 Lead Storage Battery (rechargeable) • • • Series of six 2 V cells: Total Voltage = ? Plates immersed in H2 SO4(aq) Overall Reaction (Discharge): PbO2 (s) + Pb(s) + 2HSO4–(aq) + 2H+(aq) —> PbSO4(s) + 2 H2O(l) Anode: Cathode: • • • Rechargeable by reversing each half-cell reaction since the product. PbSO4(s). Larson-All Rights Reserved .

b) Given the following reduction potentials. constant voltage • Disadvantages: high cost. disposal of Cd.101 a) Write the overall balanced reactions for the discharge and charge of a nickelcadmium rechargeable battery.—> Ni(OH)2(s) + OH-(aq) E°red = +0. Larson-All Rights Reserved .49 V Electrochemistry 50 L. Electrochemistry 49 Nickel-Cadmium (“ni-cad”) Rechargeable Text Problem 20.Chemistry 1C-Foothill College Nickel-Cadmium (“ni-cad”) Rechargeable • Anode is Cd: Cd(s) + 2 OH-(aq) —> Cd(OH)2(s) + 2 e- • Cathode is NiO(OH): NiO(OH)(s) + H2O(l) + e. short life.30 V • Advantages: light weight.76 V NiO(OH)(s) + H2O(l) + e.—> Ni(OH)2(s) + OH-(aq) • Single Cell Emf = 1. calculate the standard emf of the cell: Cd(OH)2(s) + 2 e-—> Cd(s) + 2 OH-(aq) E°red = –0.J.

Electrochemistry 51 Nickel-Metal-Hydride battery (“NiMH”) Rechargeable • Anode Reaction: • Cathode Reaction H —> H+(aq) + e The H is absorbed by the anode.J. Suggest a reason why is there a difference between this value and the one you calculated in part (b). Electrochemistry 52 L. no Cd to dispose of. a metal alloy such as ZrNi2.101 continued c) A typical nicad voltaic cell generates an emf of +1. NiO(OH)(s) + H2O(l) + e.30 V.—> Ni(OH)2(s) + OH-(aq) • Used in hybrid gas-electric cars.Chemistry 1C-Foothill College Nickel-Cadmium (“ni-cad”) Rechargeable Text Problem 20. d) Calculate the equilibrium constant for the overall ni-cad battery reaction based upon this typical emf value. • Advantages over ni-cad batteries: Longer life (Up to 8 years). Larson-All Rights Reserved .

Fe(s). H2O(l). The structural integrity of the steel is compromised. The corrosion of iron. A combustion reaction separated into two half-cells is used to produce electricity.Chemistry 1C-Foothill College Fuel Cells • Electrochemical cells with an external reservoir of reactants. The fuel does not ‘burn’ in the traditional sense. Several features of the corrosion should be noted: 1) 2) 3) 4) 5) 6) Moisture. • • One type of fuel cell uses H2 & O2 Anode is H2 Under acidic conditions: H2 (g) —> 2 H+(aq) + 2 eCathode is O2 Under acidic conditions: O2 (g) + 4H+(aq) + 4 e. Disadvantages: Not self-contained (source of fuel continually needed).J.—> 2H2 O(l) What’s the net reaction? • • • • Used by NASA as a fuel source for spacecraft. The process can be broken down into three chemical steps. • NOT self contained. Iron rusts faster in ionic solutions and low pH (acidic) solutions The loss of Fe(s) and the deposition of rust (Fe2O 3) can occur at different places Iron rusts faster in the presence of certain inactive metals (Cu for example) Iron rusts slower in the presence of active metals (Zn for example) Electrochemistry • 54 L. Larson-All Rights Reserved . A constant supply of fuel is needed. The iron in steel is spontaneously oxidized to Fe2O 3(s) in the presence of water and dissolved oxygen. must be present O2 must be present in the moisture. electrodes are shortlived and expensive Electrochemistry 53 Corrosion: Rust Formation on Iron Surfaces • The rusting of steel is of major economic concern. is a complex electrochemical process.

J. and 3: 4Fe(s) + 3O2(g) + (2x)H2O(l) ! 2Fe2O3•xH2O(s) • What role does the H+(aq) play in this reaction sequence? • Why can the rust form at a different place than where the Fe(s) is oxidized? • Why do steel bridges form rust at the water line. 2. but not above or below the water line? Electrochemistry 56 L. • Step 2: the reduction of O2 to form H2O(l) at the cathodic region: O2(g) + 4H+ (aq) +4e– ! 2H2O(l) Why are acidic conditions favored? • The sum of steps 1 and 2 do not form the rust! Write the net balanced redox reaction from steps 1 and 2: Electrochemistry 55 Corrosion: Rust Formation on Iron Surfaces • Step 3: Rust formation occurs through a separate redox reaction: 4Fe2+(aq) + O2(g) + 4H2O(l) + (2x)H2O(l) ! 2Fe2O3•xH2O(s) + 8H+(aq) • The overall redox reaction for rust formation is the sum of steps 1. Larson-All Rights Reserved .Chemistry 1C-Foothill College Corrosion: Rust Formation on Iron Surfaces • Step 1: the loss of solid Fe at the anodic region: Fe(s) ! Fe2+(aq) + 2e– Why must water be present? The damage is done at this point. A pit is left where the Fe(s) was oxidized.

Explain why galvanizing is preferable to painting. What happens if a scratch or break is made in the paint? Galvanize: Coat surface with a thin layer of zinc. Objects can be galvanized by electroplating zinc onto the surface or by dipping the object in molten zinc. The overall chemical reaction is changed by the presence of the sacrificial anode. Electrochemistry 57 Cathodic Protection of Iron When a sacrificial anode is used. Electrochemistry 58 L. Why is this?) • • • Painting the surface of a metal provides protection from corrosion. To prevent or slow down the rusting. Explain why the zinc or magnesium is preferentially oxidized instead of the iron.Chemistry 1C-Foothill College Protection from Corrosion • • Wash off road salt from cars! Passivation: Some active metals form oxides on their surfaces that are impermeable to O2 and H2O. Al (NOTE: The tendency of these metals to “passivate” makes them ineffective as electrodes in voltaic cells. Larson-All Rights Reserved .J. The oxide provides a coating that protects the underlying metal from further corrosion. The zinc or magnesium is preferentially oxidized in place of the iron. a sacrificial anode made from an active metal such as zinc or magnesium is often placed in contact with steel. Galvanized Nails: Steel nails coated with zinc. the iron in the steel simply serves as a cathode to conduct electrons to oxygen that is then reduced. Examples: Mg.

• Examples of electrolysis: 1. The breakdown of water into O2 and H2 gases. A copper water pipe should NEVER be directly attached to a steel pipe! An insulating spacer must be used between them. Larson-All Rights Reserved . but not the chemistry. The presence of the Cu(s) affects the kinetics of the reaction. These electrons are used to reduce the O2(g) in step 2. Electrolysis of salts. Electroplating of metals. 2. • Electrolytic Cell: Electrical energy from an external source drives a nonspontaneous reaction. therefore the overall corrosion rate also increases. STEP 2 is the slow or rate limiting step in the reaction sequence. 3. 1) 2) The Cu acts as a conductor for the electrons produced in step 1. Purification of metals.Chemistry 1C-Foothill College Speeding Up Corrosion: Oh No!!!!! • When the Fe(s) is in contact with some inactive metals such as Cu. Electrochemistry 60 L. If step 2 takes place at the surface of Cu(s) the rate of reduction increases. 3) • Which of the following metals would be a good choice to use for a sacrificial anode to protect iron from corrosion? Ag Na Cr Electrochemistry 59 Electrolysis • In electrolysis we use electrical energy to bring about chemical change. 4.J. An otherwise non-spontaneous reaction is “driven” in the forward direction by application of a voltage.

Inert electrodes are used in these cases. What products are formed? What is the overall cell reaction? Oxidation half-reaction: Reduction half-reaction: Overall Reaction: Electrochemistry 62 L.Chemistry 1C-Foothill College Electrolysis of Molten Salts • • Molten salts can be transformed into their elements.J. Larson-All Rights Reserved .—> Na(l) Anode: 2Cl–(l) —> Cl2(g) + 2 e- Overall: 2NaCl(l) —> 2Na(l) + Cl2(g) Electrochemistry 61 Electrolysis of Molten Salts • A sample of MgI2 contaminated with BaI2 is melted and electrolyzed. Cathode: Na+ (l) + e . Conditions are non-standard! Standard Reduction Potentials do not apply.

• • Electrochemistry 63 Electrolysis of Water • • Conditions are nonstandard! Why? In practice. Larson-All Rights Reserved .J. Oxidation takes place at the anode: 2H2 O(l) —> O2 (g) + 4H+(aq) + 4e– • Reduction takes place at the cathode: 2H2 O(l) + 2e– —> H2 (g) + 2OH–(aq) • The anode is connected to the positive terminal of the battery and is labeled (+). the half-reaction voltages required are as follows: Reduction: 2H2O(l) + 2e– —> H2(g) + 2OH–(aq) Oxidation: 2H2O(l) —> O2(g) + 4H+(aq) + 4e– • • E oxid E red " –1 V " –1. 2 H2 O(l) —> 2 H2(g) + O2(g) A 9 V battery is sufficient. The cathode is connected to the negative terminal of the battery and is labeled (–).) What is the overall minimum voltage that must be applied (Ecell) for the electrolysis of water? Electrochemistry 64 L.4 V These are the voltages we will use. even though our text book does not address it! (Many general chemistry books do.Chemistry 1C-Foothill College Electrolysis of Water • Water is decomposed into its elements by application of a DC current. An inert salt must be present to transport charge.

Chemistry 1C-Foothill College Electrolysis of AQUEOUS Salts Under aqueous conditions we must include the possible oxidation or reduction of water instead of the salt ions.—> Na(s) E°red = -2.J.536 V 2 H2 O(l) —> O2 (g) + 2 H+ + 2 eEox " -1. for electrolysis of 1 M SnCl2(aq). For example consider 1 M NaI(aq): Cathode possibilities: Na+ + e. using the minimum voltage needed to produce a reaction.—> H2 (g) + 2 OH– Ered " -1 V (nonstandard) Anode possibilities: 2 I– —> I2 (s) + 2 eE°ox = -0.4 V (nonstandard) Determine the net reaction.71 V 2 H2 O(l) + 2 e. Larson-All Rights Reserved . Cathode: (+) electrode of voltage source (–) electrode of voltage source Anode: Net: Electrochemistry 66 L. What voltage is needed? Electrochemistry 65 Electrolysis of AQUEOUS Salts • Determine the products.

E°cell = 0 V Only a small emf is needed! • • • • Electrochemistry 68 L. Ni atoms are transferred from the nickel anode to the steel cathode. Larson-All Rights Reserved . plating the steel with a thin layer of nickel atoms. Ni2+(aq) is reduced at the cathode. Net Reaction? During electrolysis.Chemistry 1C-Foothill College Electrolysis of AQUEOUS Salts Write a net ionic equation for the expected reaction when the electrolysis of 1 M Cu(NO3) 2(aq) is conducted using: a) A Pt anode and a Pt cathode b) A Cu anode and Cu cathode Electrochemistry 67 Electroplating • Ni(s) is oxidized at the anode.J.

Electrochemistry 69 Counting Electrons (Units) Energy (J): SI unit: 1J =kg•m2/s2 Coulomb (C): fundamental unit of electric charge. Electrochemistry F = 9.485 C = 1 equivalent (eq) • Equivalent mass is defined as grams of a substance per mole of electrons lost or gained (g/mole e– or g/eq).241x1018 e– = 1.J. A) = Coulombs (C)/seconds 1 mole e.602x10-19 C.0364x10-5 mole e– Current (A): the number (counting) of electrons that “flow” per second.Chemistry 1C-Foothill College Counting Electrons (Current) • In electrolysis the extent of reaction depends upon the number of electrons transferred. Current (amps.= 1 Faraday (F) = 96. Voltage (V): the force the electrons “feel”. SI unit: ampere (A) 1 A = C/s Faraday (F): absolute charge of one mole of electrons. SI unit: 1C=A•s One electron has a charge of 1. We usually measure electron flow (number/second) in amperes (amps). 1 C = 6.6485x104 C/mole SI unit(V): m2 kg/(s3 A)=J/(A•s) 1 V = J/C 70 L. Larson-All Rights Reserved .

what mass of Ni is produced if a current of 74 mA is maintained for 3.8 hours? Electrochemistry 71 Counting Electrons (Problem) • What current is needed to electroplate a 3’x3’ total area aluminum sheet with zinc metal to a thickness of 20. Larson-All Rights Reserved .14 g/ml Electrochemistry 72 L.Chemistry 1C-Foothill College Counting Electrons (Problems) • In the electrolysis of NiCl2(aq).0 #m in 20.0 hours? dZn = 7.J.

In order to make the process occur.Chemistry 1C-Foothill College Electrical Work (Energy) • Energy (J): When electrons move through an electrical potential (voltage). the maximum work is: wmax = !G = –nFE (done by the system) Where n is the number of electrons (moles) transferred from anode to cathode. Larson-All Rights Reserved . From thermodynamics the work done on the surroundings is: –wmax = nFE (done on the surroundings) Electrochemistry 73 Electrical Work • For a electrolytic cell an external source of energy is used to bring about a nonspontaneous process. the surroundings are doing work on the system. The product nF is the total electrical charge in coulombs supplied to the system by the external source of electricity. energy is either released or absorbed in the form of work. an external potential (Eext) that is larger in magnitude than Ecell must be applied. F is faraday’s constant (96. Assuming no heat loss (q= 0).J. The work energy is equal to the voltage difference times the amount of charge moved: J = VxC • A voltaic cell can do work due to the spontaneous flow of electrons. When an external potential is applied.485 C/mol) and E is the cell voltage. Electrochemistry 74 L. The minimum amount of work that must be applied to the system is given by w = nFEext (work done by the surroundings increases the energy of the system) • The quantity n is the number of moles of electrons forced to flow in the reaction by the external potential.

the rate of energy expenditure).87: A voltaic cell is based upon the reaction: Sn(s) + I2(s) <–> Sn2+(aq) + 2I–(aq) Under standard conditions. The watt (W) is a unit of electrical power (that is. Larson-All Rights Reserved . in joules. Power (Watt. A 60 W light bulb uses 60 J/s Energy (J): A 60 W light bulb operated for 10 seconds uses 600 J of energy PG&E measures energy usage in kW•hr: kilowatt hours Calculate the amount of energy (J) in one kW•hr. that the cell can accomplish if 75.J.Chemistry 1C-Foothill College Electrical Work Text Problem 20. SI unit: m2kg/s3 = J/s 1 W = J/s = V•A J = W•s = V•A•s.0 g of tin is consumed? Electrochemistry 75 Electrical Work and Power: Units Electrical work can be expressed in units of watts times time. what is the maximum electrical work. W): energy used per unit time. Electrochemistry 76 L.

How long can a fluorescent bulb be operated using a total of 1.J. • A 14 W fluorescent light bulb provides about the same brightness as a 60 W incandescent light bulb.00 V.0 kW•hr? • Are there any special problems associated with fluorescent light bulbs? Electrochemistry 77 Electrical Work • Calculate the number of kilo-watt hours of electricity required to produce 1.0 kW•hr to operate a 60 W incandescent light bulb for about 17 hours.00 kg of Mg from the electrolysis of molten MgCl2 if the applied emf is 5. Assume that the process is 100% efficient.Chemistry 1C-Foothill College Practice with Units of kW•hr • It requires 1. Electrochemistry 78 L. Larson-All Rights Reserved .

Sign up to vote on this title
UsefulNot useful

Master Your Semester with Scribd & The New York Times

Special offer: Get 4 months of Scribd and The New York Times for just $1.87 per week!

Master Your Semester with a Special Offer from Scribd & The New York Times