Chapter 20BLorrosion

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!!! Whats a watt anyway? Whats a kilowatthour?
Electrochemistry
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
L.J. Larson-All Rights Reserved
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
Reduction Potential
Lets 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
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
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. Whats 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
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). Voltage is the force or push electrons feel to move. 1 Coulomb is the fundamental unit of charge. One electron has a charge of 1.602176 x 1019 C Current (ampere, 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. Think about it Is voltage an intensive or an extensive property?
What is the total charge in coulombs of a mole of electrons?
Electrochemistry
Simple Voltaic Cells: Video-Cu Zn Cell Spontaneous: Whats the sign of !G?
Two half-cells connected with a salt bridge to maintain charge neutrality in each halfcell. Anode (-):
Cathode (+):
This system can do work! The e lose 0.46 J/C of potential energy as they move from anode to cathode. Which one is at the higher potential energy, the Cu or the Ag electrode?
1M
Electrochemistry
Voltaic Cells: Sequence of Events

The oxidation reduction reaction is separated into two half-cells, the oxidation half cell, the anode, and the reduction half-cell, the cathode. The half-cells are physically connected by a circuit (wire, switch that carries the electrons and a salt bridge to maintain charge balance between the two cells. When the circuit is closed the solid Cu electrode begins to oxidize and produce Cu2+ ions that enter the electrolyte solution. The electrons leave the anode and are carried towards the cathode. If a load is present (light bulb, etc.), useful work can be done by the electrical current generated. As the electrons enter the cathode, Ag+ ions in the electrolyte solution are reduced to form solid Ag that plates-out on the Ag electrode. Because electrons are moving from one cell to another, a charge imbalance will develop unless a salt bridge is provided. As the Cu2+ ions move into the electrolyte solution during oxidation, a negative charge must also accompany them. Two NO3 ions from the salt bridge will diffuse into the anode electrolyte solution for each Cu2+ ion produced. At the cathode, as each Ag+ ion is consumed in the reduction, a Na+ ion diffuses from the salt bridge into the electrolyte solution. Migration of Cu2+ ions through the salt bridge can also occur to maintain charge balance. In a voltaic cell, the anode, where electrons are produced is given a negative sign () by convention. The cathode is given a positive sign (+). These labels do not denote the charges on the electrodes; the electrode charges are essentially zero. Since solid silver is not a reactant a solid silver electrode for the cathode is not needed for the reduction process. Any conducting electrode can be used and the Ag+ ions will still plate-out on the electrode. 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
Summary: Simple Voltaic Cells
Electrochemistry
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Problem
Identify the anode and cathode half-reactions in the following unbalanced reaction: MnO4(aq) + Fe(s) > Mn2+(aq) + Fe3+(aq)
Electrochemistry
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Standard Reduction (Half -Cell) Potentials

To determine the emf of a half-cell we use the standard hydrogen electrode) SHE as a reference. Thus, all measurements are taken relative to the SHE. By convention the SHE half-cell emf is set to 0 V. Measurements are made under standard conditions for each half-cell:
Solid and liquid reactants and products are pure. Solutes are 1 M. Gaseous species are 1 atm (1 bar).
By convention, half-cell emf values are given as standard reduction potentials RELATIVE to the SHE. Video: Standard Reduction Potentials Video: Zinc-Hydrogen Cell
Electrochemistry
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Standard Hydrogen Electrode

The standard hydrogen electrode uses an inert electrode (one that just serves to carry the electrons). The most common inert electrodes used are Pt metal and carbon (graphite).
2 H+(aq, 1M) + 2 e- > H2(g, 1 atm) Ered= 0 V What is Eoxid for the standard hydrogen electrode? What reaction does it correspond to?
Electrochemistry
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Measuring Ered for the Zn/Zn2+ half-cell

(Understanding how voltmeters work) Zn metal is shown reacting with hydrochloric acid.
Black probe Red probe
Electrochemistry
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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. 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 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). () voltage: The black probe has a higher reduction potential than the red probe. The black probe is attached to the cathode and the red probe is attached to the anode.
Electrochemistry
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Measuring Ered for the Zn/Zn2+ half-cell

With the Zn/Zn2+ half-cell connected to a SHE a voltage of +0.76V was observed with the black probe attached to the Zn half-cell. This means that the SHE is 0.76V higher in reduction potential compared to the Zn/Zn2+ half-cell. Ered for the Zn/Zn2+ half-cell is -0.76V relative to the SHE. Thus, the anode (oxidation) is the Zn half-cell while the cathode (reduction) is the SHE half-cell. The electrons are moving from the Zn metal to the H+ ions. 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. Remember the following!!!! The cathode is always at a lower potential energy than the anode in a voltaic cell. The cathode always has a higher reduction potential than the anode in a voltaic 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 Ered of the Zn/Zn2+ half-cell?
Electrochemistry
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Text Table 20.1: Standard Reduction Potentials

The more positive the value of Ered, the greater the driving force for reduction. Identify: (1) The strongest oxidizing agent in this table. (2) The strongest reducing agent. Locate/Identify the reaction corresponding to: (1) Reduction of water (2) Oxidation of water
Electrochemistry
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Summary-Properties of Ered
1. All potentials are for the reduction half-reaction. 2. The more (+) Ered the more favorable is the reduction. Hence a better oxidizing agent. 3. Oxidizing agents are given on the LEFT side of the table. STRONGEST at the top, WEAKEST at the bottom. 4. Reducing agents are given on the RIGHT side of the table. WEAKEST at the top, STRONGEST at the bottom. 5. When the half-cell reaction is reversed the sign of the voltage changes.
Electrochemistry
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Calculating Standard Voltaic Cell Potentials

The cell potential under standard conditions is denoted Ecell and can be determined using the following equation: Ecell = Ered(cathode) Ered(anode) or Ecell = Ered+ Eoxid A (+) Ecell indicates: A () Ecell indicates : The individual Ered(cathode) and Ered(anode) half-cell potentials are STANDARD REDUCTION POTENTIALS. Eoxid is a standard oxidation potential: Eoxid = Ered(anode) In any voltaic cell, the reaction at the cathode has a more positive Ered. The greater reduction potential at the cathode compared to the anode can be thought of as driving the anode reaction in reverse, as oxidation. Since cell potential is the potential energy per unit of charge, remember that it is an intensive property.
Electrochemistry
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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. The value of Ecell will always be (+) under these conditions. The greater the difference in Ered between the two, the greater the voltage of the cell.
Electrochemistry
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Using the Table of Standard Reduction Potentials

Determine Ecell for the following reactions. Is the reaction spontaneous as written? 1. 2 H+ (aq) + Cu(s) > Cu2+ (aq) + H2(g)
2. 4 Fe3+(aq) + 4 OH(aq) > 4 Fe2+(aq) + O2(g) + 2 H2O(l)
Electrochemistry
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Text Problem 20.38: A voltaic cell consists of a strip of lead in a solution of 1M Pb(NO3) 2 in one beaker, and in the other beaker a platinum electrode is immersed in a 1M NaCl solution, with 1 atm Cl2 gas bubbled around the electrode. The two beakers are connected with a salt bridge. Assume standard conditions. a) b) c) Which electrode serves as the anode, 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.
d)
What is the emf (voltage) generated by the cell under standard conditions?
Electrochemistry
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A ranking of oxidizing and reducing agents can be made from the table and stability in water can be predicted. Assuming standard conditions and using the half reactions listed in Table 20.1 of the text. 1. Rank the halogens in order of their strength as oxidizing agents. 2. Given: Au3+(aq)+ 3e > Au(s) Ered = +1.50 V What halogens can oxidize Au? 3. What halogens are stable in water? 4. What metals in the table are unstable in water? 5. Based upon standard reduction potentials, it appears as if MnO4 ions should be spontaneously reduced by water. However, we find that permanganate is actually stable in water solution. Why is this?
Electrochemistry
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1. Choose the best oxidizing agent between Fe2+(aq), Fe3+(aq) and Na(s). 2. Choose the best reducing agent between Fe2+(aq), Zn2+(aq) and Cu(s). 3. Copper dissolves in a nitric acid solution with the evolution of NO(g). In contrast, copper does not dissolve in a hydrochloric acid solution. a) Explain these observations.
b)
Write the balanced net ionic equation for the reaction that occurs when copper is placed in a nitric acid solution.
Electrochemistry
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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. Suggest a pair of ions for the salt bridge. Which electrode will decrease in mass? What is Ecell? Write the balanced net-ionic chemical equation for the overall reaction for this cell.
Electrochemistry
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Shorthand Cell Notation for Voltaic Cells

Examples: Cu(s) + 2 Ag+(aq) > Cu2+(aq) + 2 Ag Cu(s)|Cu2+(aq, 1M)||Ag+ (aq, 1M)|Ag(s) The anode half-cell is written first (oxidation). A single vertical line represents phase boundaries. 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. " H2O is generally omitted, unless it is being oxidized or reduced. " " " " MnO4 (aq) + Fe(s) > Mn2+(aq) + Fe3+(aq) Fe(s)| Fe3+(aq, 1 M)|| MnO4 (aq, 1M), Mn2+(aq, 1M)|Pt Write the shorthand notation for the standard Zn/Zn2+, SHE voltaic cell.
Electrochemistry
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Electrochemistry and Thermodynamics

Voltaic cells can do work because !G for the redox reaction is negative. The voltaic cell continues to do work until an equilibrium is reached between the reactants and products. As the cell does work, electrons ow, the redox reaction takes place, the concentrations of reactants and products change and move towards equilibrium, the cell potential continually decreases. At equilibrium the voltaic cell has: Ecell = Q= !G = Are there any electrons owing?
Electrochemistry
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From Michael Faradys1 work on electrochemical cells the difference in free energy (! G) was found to be directly proportional to the electrochemical potential of the cell, Ecell. The equation is: ! G = -nFE cell where n is the moles of electrons transferred in the reaction, F is Faradays constant, the absolute value of the amount of charge in 1 mol of electrons, 1F = 96,485 C/mol e Terminology: When we say 1 Faraday of electrons we mean 1 mole of electrons. Under standard state conditions: ! G = -nFEcell
1Faraday,
! G in units of ? (Recall 1 C = 1 J/V)
Michael: The English chemist and physicist Michael Faraday, b. Sept. 22, 1791, d. Aug. 25, 1867, is known for his pioneering experiments in electricity and magnetism. Many consider him the greatest experimentalist who ever lived. Several concepts that he derived directly from experiments, such as lines of magnetic force, have become common ideas in modern physics.
Electrochemistry
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Text Problem 20.98: Derive an equation that directly relates the standard emf, Eo, of a redox reaction to its equilibrium constant.
Electrochemistry
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What does this mean? For redox reactions, 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, (2) indicating if K is less than, greater than or equal to 1 and (3) determining if the forward reaction is spontaneous, nonspontaneous or at equilibrium.
!G
Ecell
Forward reaction at standard state conditions
>0 0 <0
Electrochemistry
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Electrochemistry, Equilibria and Thermodynamics

Text Problem 20.99: Calculate ! G and the equilibrium constant for the disproportionation of copper(I) ion at 25C: 2Cu+(aq) <> Cu2+(aq) + Cu(s)
Electrochemistry
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Electrochemistry, Equilibria and Thermodynamics

Text Problem 20.116: 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), calculate Ksp for AgSCN.
Electrochemistry
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Cell EMF Under Nonstandard Conditions (Nernst Equation)

Changes in concentrations of the electrolytes that comprise the half-cell electrodes will cause the cell potential, E cell, to change. This change can be understood by looking at how changes in concentrations effect the free energy change of the system. 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. (Q is defined exactly like K but is evaluated under any condition. Q predicts the direction of chemical change to reach equilibrium.) Since ! G = -nFEcell and ! G= -nFEcell we can derive an equation (The Nernst Equation2) that allows us to calculate the cell potential under nonstandard conditions.
2Nernst,
Walther: The German physical chemist and inventor Hermann Walther Nernst, b. June 25, 1864, d. Nov. 18, 1941, was awarded the NOBEL PRIZE for chemistry in 1920 for his discovery (1906) of the third law of thermodynamics, which states that entropy approaches zero as temperature approaches absolute zero. He introduced the Nernst equation (1889), which relates electric potential to various properties of the electric cell.
Electrochemistry
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Derivation of the Nernst2 Equation

!G = ! G + RT ln Q !G = -nFEcell and ! G= -nFE cell
Electrochemistry
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Using the Nernst Equation

Consider the following cell: Pt|H2(g, 1.0 atm)|H+ (aq, 1.0 M)||Fe3+(aq, 1.0 M),Fe2+(aq, 1.0 M)| Pt a) b) Write the balanced net ionic equation for the reaction. Without doing ANY calculations, determine if the reaction is spontaneous under the conditions given. What is the emf of the cell when [Fe3+] = 1.50 M, [Fe2+] = 0.0010 M, P(H2) = 0.50 atm and the pH in both compartments is 5.00?
c)
Electrochemistry
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Text Problem 20.66: 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 M and the cell generates an emf of +0.220 V, what is the concentration of Pb2+ in the anode compartment?
b)
If the anode compartment contains [SO42"] = 1.00 M in equilibrium with PbSO4( s) what is the Ksp of PbSO4?
Electrochemistry
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Text Problem 20.58: 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, diluting the solution.
b)
The size of the aluminum electrode is increased.
c)
A solution of AgNO3 is added to the cathode compartment, increasing the quantity of Ag+ but not changing its concentration. HCl is added to the AgNO3 solution, precipitating some of the Ag+ as AgCl.
Electrochemistry
d)
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A Weird? Consequence of the Nernst Equation: Concentration Cells

An examination of the Nernst equation shows that Ecell can be non zero even if Ecell is zero! Why? Ecell will be non zero if the concentrations of reactants and products are not equal. This allows us to construct a concentration cell. In a concentration cell the half-reactions at the anode and cathode are identical! Consider the following cell: Ecell is zero: E cell = E cathode E anode = +0.80 V (+0.80 V) = 0.00 V. However, if the concentrations of the Ag+ ions are different in the half-cells, then a cell potential exists and electricity will flow until the Ag+ concentrations in the half-cells are equal. Ag(s) | Ag+(aq) || Ag+(aq) | Ag(s)
Electrochemistry
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Concentration Cell Problem

Consider a concentration cell using Ag(s) electrodes and AgNO3(aq) as the electrolyte. Let the concentration of Ag+ ions at electrode A be 0.010 M and the concentration of Ag+ ions at electrode B be 0.50 M. 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.)
b)
Think about it: What is ! Hsys, ! S sys, ! Ssurr, ! S univ and ! G for this process?
c)
Which electrode corresponds the the anode half-cell?

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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.
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Measuring pH
A pH meter employs a voltaic cell for which the cell potential is very sensitive to pH. A simple (but impractical) pH meter can be constructed by using two hydrogen electrodes: one standard hydrogen electrode (Figure 20.10) and a hydrogen electrode (with 1 atm pressure of H2 gas) dipped into the solution of unknown pH>0. The two half-cells are connected by a salt bridge or porous glass disk. a) Write the half-cell reactions for the cell, and calculate the standard emf.
b)
What is the pH of the solution in the half-cell that has the standard hydrogen electrode? If the cell emf is 0.293 V at 25C what is the pH of the unknown solution?
c)
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Measuring pH: Extra Space for Calculations
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Batteries: Commercial Voltaic Cells

The first known battery, a Zn/Cu battery was built in 1836 by English chemist John Frederick Daniell. Batteries are made from a voltaic cell or a series of voltaic cells connected anode to cathode. When connected in series, anode to cathode, the voltage of the battery is the sum of the individual voltaic cells. Following voltaic cell labeling conventions, the electrodes of a battery are labeled (+) for the cathode and () for the anode.
! Desired qualities: compact, high current, constant voltage, long life, low cost
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Batteries
There are three major types of batteries:
1) Primary:
2)
Secondary:
3)
Fuel Cell:
Electrochemistry
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Dry Cell Primary Batteries (Throw away)

About 1.55 V Not as common as in the past. Anode is zinc:
Zn(s) > Zn2+(aq) + 2 e-
Cathode is NH4+:
Gases are trapped by side rxns:

1. Zn2+(aq) + 2 NH3(g) + 2 Cl-(aq) > Zn(NH3) 2Cl2(s) 2. 2 MnO2(s) + H2(g) > Mn2O 3 (s) + H2O(l)
NH4 +(aq) + 2 e- > 2 NH3(g) + H2(g)
Advantage: Low cost Disadvantages: Deteriorate over time (short shelf life), voltage and current drops.
Electrochemistry
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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- > 2MnO(OH)(s) + 2 OH-(aq) Single cell emf = 1.55 V at room temperature
Advantages: Low cost, constant voltage, longer shelf life than dry cell, no gases produced Disadvantages: ?
Electrochemistry
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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- > Hg(l) + 2 OH-(aq)
These are also alkaline batteries. Advantage: small, constant voltage Disadvantages: mercury disposal
Electrochemistry
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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), remains attached to each electrode. Advantages: low cost, high current. Voltage relatively constant since emf not dependent on relative amounts of PbO2, Pb and PbSO4 (Why is this?). Disadvantages: heavy, Pb disposal. Fails over time due to mechanical dislodging (loss) of the PbSO4 from the electrodes.
Electrochemistry
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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- > Ni(OH)2(s) + OH-(aq)
Single Cell Emf = 1.30 V Advantages: light weight, constant voltage Disadvantages: high cost, short life, disposal of Cd.
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Text Problem 20.101
a) Write the overall balanced reactions for the discharge and charge of a nickelcadmium rechargeable battery.
b) Given the following reduction potentials, calculate the standard emf of the cell: Cd(OH)2(s) + 2 e-> Cd(s) + 2 OH-(aq) Ered = 0.76 V NiO(OH)(s) + H2O(l) + e- > Ni(OH)2(s) + OH-(aq) Ered = +0.49 V
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Text Problem 20.101 continued
c) A typical nicad voltaic cell generates an emf of +1.30 V. Suggest a reason why is there a difference between this value and the one you calculated in part (b).
d) Calculate the equilibrium constant for the overall ni-cad battery reaction based upon this typical emf value.
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Nickel-Metal-Hydride battery (NiMH) Rechargeable

Anode Reaction: Cathode Reaction
H > H+(aq) + e The H is absorbed by the anode, a metal alloy such as ZrNi2. NiO(OH)(s) + H2O(l) + e- > Ni(OH)2(s) + OH-(aq)
Used in hybrid gas-electric cars. Advantages over ni-cad batteries: Longer life (Up to 8 years), no Cd to dispose of.
Electrochemistry
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Fuel Cells
Electrochemical cells with an external reservoir of reactants. A combustion reaction separated into two half-cells is used to produce electricity. The fuel does not burn in the traditional sense. NOT self contained. A constant supply of fuel is needed.
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- > 2H2 O(l) Whats the net reaction?
Used by NASA as a fuel source for spacecraft. Disadvantages: Not self-contained (source of fuel continually needed), electrodes are shortlived and expensive
Electrochemistry
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Corrosion: Rust Formation on Iron Surfaces

The rusting of steel is of major economic concern. The iron in steel is spontaneously oxidized to Fe2O 3(s) in the presence of water and dissolved oxygen. The structural integrity of the steel is compromised. The corrosion of iron, Fe(s), is a complex electrochemical process. The process can be broken down into three chemical steps. Several features of the corrosion should be noted: 1) 2) 3) 4) 5) 6) Moisture, H2O(l), must be present O2 must be present in the moisture. 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)
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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. 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:
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Step 3: Rust formation occurs through a separate redox reaction: 4Fe2+(aq) + O2(g) + 4H2O(l) + (2x)H2O(l) ! 2Fe2O3xH2O(s) + 8H+(aq) The overall redox reaction for rust formation is the sum of steps 1, 2, and 3: 4Fe(s) + 3O2(g) + (2x)H2O(l) ! 2Fe2O3xH2O(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, but not above or below the water line?
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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. The oxide provides a coating that protects the underlying metal from further corrosion. Examples: Mg, Al (NOTE: The tendency of these metals to passivate makes them ineffective as electrodes in voltaic cells. Why is this?) Painting the surface of a metal provides protection from corrosion. What happens if a scratch or break is made in the paint? Galvanize: Coat surface with a thin layer of zinc. To prevent or slow down the rusting, a sacrificial anode made from an active metal such as zinc or magnesium is often placed in contact with steel. The zinc or magnesium is preferentially oxidized in place of the iron. The overall chemical reaction is changed by the presence of the sacrificial anode. Explain why the zinc or magnesium is preferentially oxidized instead of the iron. Explain why galvanizing is preferable to painting.
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Cathodic Protection of Iron

When a sacrificial anode is used, the iron in the steel simply serves as a cathode to conduct electrons to oxygen that is then reduced.
Galvanized Nails: Steel nails coated with zinc. Objects can be galvanized by electroplating zinc onto the surface or by dipping the object in molten zinc.
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Speeding Up Corrosion: Oh No!!!!!

When the Fe(s) is in contact with some inactive metals such as Cu. The presence of the Cu(s) affects the kinetics of the reaction, but not the chemistry. 1) 2) The Cu acts as a conductor for the electrons produced in step 1. These electrons are used to reduce the O2(g) in step 2. STEP 2 is the slow or rate limiting step in the reaction sequence. If step 2 takes place at the surface of Cu(s) the rate of reduction increases, therefore the overall corrosion rate also increases. A copper water pipe should NEVER be directly attached to a steel pipe! An insulating spacer must be used between them.
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. An otherwise non-spontaneous reaction is driven in the forward direction by application of a voltage. Electrolytic Cell: Electrical energy from an external source drives a nonspontaneous reaction. Examples of electrolysis:
1. 2. 3. 4. Electrolysis of salts. The breakdown of water into O2 and H2 gases. Electroplating of metals. Purification of metals.
Electrochemistry
60
Electrolysis of Molten Salts

Molten salts can be transformed into their elements. Inert electrodes are used in these cases. Conditions are non-standard! Standard Reduction Potentials do not apply.
Cathode: Na+ (l) + e - > 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. What products are formed? What is the overall cell reaction? Oxidation half-reaction:
Reduction half-reaction:
Overall Reaction:
Electrochemistry
62
Electrolysis of Water
Water is decomposed into its elements by application of a DC current. 2 H2 O(l) > 2 H2(g) + O2(g) A 9 V battery is sufficient. An inert salt must be present to transport charge. 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 cathode is connected to the negative terminal of the battery and is labeled ().
Electrochemistry
63
Electrolysis of Water
Conditions are nonstandard! Why? In practice, 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
" 1.4 V
These are the voltages we will use, even though our text book does not address it! (Many general chemistry books do.) What is the overall minimum voltage that must be applied (Ecell) for the electrolysis of water?
Electrochemistry
64
Electrolysis of AQUEOUS Salts

Under aqueous conditions we must include the possible oxidation or reduction of water instead of the salt ions. For example consider 1 M NaI(aq): Cathode possibilities:
Na+ + e- > Na(s) Ered = -2.71 V 2 H2 O(l) + 2 e- > H2 (g) + 2 OH Ered " -1 V (nonstandard)
Anode possibilities:
2 I > I2 (s) + 2 eEox = -0.536 V 2 H2 O(l) > O2 (g) + 2 H+ + 2 eEox " -1.4 V (nonstandard) Determine the net reaction.
What voltage is needed?

Electrochemistry
65

Determine the products, using the minimum voltage needed to produce a reaction, for electrolysis of 1 M SnCl2(aq).
Cathode:
(+) electrode of voltage source () electrode of voltage source
Anode:
Net:
Electrochemistry
66

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. Ni2+(aq) is reduced at the cathode. Net Reaction? During electrolysis, Ni atoms are transferred from the nickel anode to the steel cathode, plating the steel with a thin layer of nickel atoms. Ecell = 0 V Only a small emf is needed!
Electrochemistry
68
Counting Electrons (Current)

In electrolysis the extent of reaction depends upon the number of electrons transferred. We usually measure electron flow (number/second) in amperes (amps). Current (amps, A) = Coulombs (C)/seconds 1 mole e- = 1 Faraday (F) = 96,485 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).
Electrochemistry
69
Counting Electrons (Units)

Energy (J): SI unit: 1J =kgm2/s2
Coulomb (C): fundamental unit of electric charge. SI unit: 1C=As One electron has a charge of 1.602x10-19 C. 1 C = 6.241x1018 e = 1.0364x10-5 mole e
Current (A): the number (counting) of electrons that ow per second. SI unit: ampere (A) 1 A = C/s
Faraday (F): absolute charge of one mole of electrons. Voltage (V): the force the electrons feel.
Electrochemistry
F = 9.6485x104 C/mole SI unit(V): m2 kg/(s3 A)=J/(As) 1 V = J/C

70
Counting Electrons (Problems)

In the electrolysis of NiCl2(aq),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 3x3 total area aluminum sheet with zinc metal to a thickness of 20.0 #m in 20.0 hours? dZn = 7.14 g/ml
Electrochemistry
72
Electrical Work (Energy)

Energy (J): When electrons move through an electrical potential (voltage), energy is either released or absorbed in the form of work. 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. Assuming no heat loss (q= 0), the maximum work is: wmax = !G = nFE (done by the system) Where n is the number of electrons (moles) transferred from anode to cathode, F is faradays constant (96,485 C/mol) and E is the cell voltage. 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. In order to make the process occur, an external potential (Eext) that is larger in magnitude than Ecell must be applied. When an external potential is applied, the surroundings are doing work on the system. 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 product nF is the total electrical charge in coulombs supplied to the system by the external source of electricity.
Electrochemistry
74
Electrical Work
Text Problem 20.87: A voltaic cell is based upon the reaction: Sn(s) + I2(s) <> Sn2+(aq) + 2I(aq) Under standard conditions, what is the maximum electrical work, in joules, that the cell can accomplish if 75.0 g of tin is consumed?
Electrochemistry
75
Electrical Work and Power: Units

Electrical work can be expressed in units of watts times time. The watt (W) is a unit of electrical power (that is, the rate of energy expenditure). Power (Watt, W): energy used per unit time. 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 kWhr: kilowatt hours Calculate the amount of energy (J) in one kWhr. SI unit: m2kg/s3 = J/s 1 W = J/s = VA J = Ws = VAs.
Electrochemistry
76
Practice with Units of kWhr

It requires 1.0 kWhr to operate a 60 W incandescent light bulb for about 17 hours. A 14 W fluorescent light bulb provides about the same brightness as a 60 W incandescent light bulb. How long can a fluorescent bulb be operated using a total of 1.0 kWhr?
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 1.00 kg of Mg from the electrolysis of molten MgCl2 if the applied emf is 5.00 V. Assume that the process is 100% efficient.
Electrochemistry
78

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