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Generating electric current from spontaneous chemical reactions and use of current to produce chemical change Labs #31 The Thermodynamics of the Dissolution of Borax #33 Electrolytic Cells; Avogadros Number Chemical Equations Chapter 12
Redox reaction can be written as two half-reactions (one reduction, one oxidation) To generate current Separate oxidizing agent from reducing agent Electron transfer occurs through wire Electron transfer directed through device to provide useful work Reactants separated by salt bridge/porous partition Each half-reaction has a potential, or voltage, associated with it Given as reduction half-reactions Read in reverse and change sign on voltage to get oxidation potentials
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Electrochemical cells device associated with redox reaction (galvanic cells, electrolytic cells)
Electrochemical process involves electron transfer at interface between electrode and solution
Species undergoing reduction receive electrons from cathode
Species in solution act as oxidizing agent
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http://college.hmco.com/chemistry/shared/media/animations/anodereaction.html
http://college.hmco.com/chemistry/shared/media/animations/cathodereaction.html
Chemical energy electrical energy Harnesses energy of spontaneous redox reactions Physically separate chemicals in 2 half-reactions
Electrons generated by oxidation half-reaction flow through electrical conductor before being used in reduction half-reaction Flow diverted through meters, motors, light bulbs to perform useful work before reaching destination Current (defined by physicists as flow of positive charge) always in opposite direction from flow of electrons (always from anode to cathode)
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http://college.hmco.com/chemistry/shared/media/animations/electrochemicalhalf.html
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Electron Flow
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The ANODE...
The CATHODE...
Supplies electrons to external circuit (wire) Is negative pole of battery Is site of OXIDATION Is written on left- hand side if convention is followed Is half-cell with lowest electrode potential
Accepts electrons from external circuit (wire) Is positive pole of battery Is site of REDUCTION Is written on right-hand side if convention is followed Is half-cell with highest electrode potential
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Under standard conditions, voltage of cell is same as total voltage of redox reaction
Standard emf of standard cell potential (E0cell)
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Under nonstandard conditions, cell voltage computed by using Nernst equation As galvanic cell operates
Redox reaction of cell approaches equilibrium Capacity to deliver useful electrical energy decreases At equilibrium, cell ceases to function (dead battery)
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Measuring Potential
Galvanic cell under standard conditions made using arbitrary standard hydrogen electrode (SHE) and test half-cell w/different half reaction
Assigned standard electrode potential of exactly 0.00 V
Under ideal conditions where ideal behavior is assumed
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Each half-reaction associated w/signed numerical value More positive it is, greater oxidizing power of redox half-reaction More negative it is, greater reducing power of reverse redox halfreaction Larger difference between Ered values, larger Ecell
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(1 atm)
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Line Notation
Vertical bar is boundary between two phases If both substances in same phase, separated by comma, not vertical bar Double line represents salt bridge or porous disk When platinum electrode present, placed at left and/or right end of cell diagram
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Using the table of standard reductions provided write the equation for the reaction between the following two half cells, and determine its voltage Au (s) | Au 3+ (aq) ||Cu 2+ (aq) | Cu (s) Gold is higher on table and written as found on table Au 3+ (aq) + 3 e - Au (s) Eo = + 1.50 V Copper is lower so it's written as oxidation (sign reversed) Cu (s) Cu 2+ (aq) + 2 eEo = -0.34 V Equation balanced for exchange of electrons (each needs 6) 2 Au 3+ (aq) + 6e - 2 Au (s) E = + 1.50 V 3 Cu (s) 3 Cu 2+ (aq) + 6e E = -0.34 V
*** Size of values for Eo of reactions not changed ***
Add two half reactions and E0 values 2 Au 3+ (aq) + 3 Cu (s) 2 Au (s) + 3 Cu 2+ (aq) E = + 1.50 V + ( - 0.34 V ) = 1.16 V
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-0.44
0.954
2.87
0.22
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Homework:
Read 17.1-17.2, pp.827-837 Q pp. 867-869, #14 a/b/c/f/i/k, 16 a/b/d/f, 26a, 28 (a only), 30b, 32 (b only), 34a, 36b
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Electrical energy delivered by galvanic cell equal to quantity of useful work obtained as result of cell operation
Work, w, measured in relation to amount of charge, q, transferred between anode/cathode of cell This quantity, potential difference, E, is defined as E = w/q. SI unit is joule per coulomb or volt (V) Cell potential (always positive for galvanic cell)
Direction of electron flow (direction that yields + potential) Designation of anode/cathode Nature of each electrode/ions present in compartments
Chemically inert conductor (such as Pt) required if only ions are present (no substance in reaction is conducting solid)
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Faraday (F) = charge in coulombs per mole of electrons (96,485 C/mol e-)
Then q = nF and w = -nFE n = number of moles of electrons
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G (Gibbs free energy) is measure of spontaneity of process occurring at constant T/P emf, E, of redox reaction also indicates whether reaction is spontaneous From thermodynamics we know that
G = U TS + (PV) and U = heat + w Therefore, at constant T/P: G = w Therefore: G = -nFE and at standard state: G0 = -nFE0 (relationship between emf/free energy changes )
Go = Standard Gibbs free energy change (kJ/mol or Joules) n = moles of electrons exchanged in reaction (mol) F = Faradays constant, 96,485 coulombs/mole (1 mole of electrons has a charge of 96,485 coulombs) Eo = Standard reaction potential (V or Joules/Coulomb)
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Relationship between reaction potential and free energy for a redox reaction is given by
Emf = potential difference (V) = work (J) charge (C) Driving force (emf) is defined in terms of potential difference (in V) between two points in circuit One coulomb is amount of charge that moves past any given point in circuit when current of 1 ampere (amp) is supplied for one second (1 ampere = 1 coulomb/sec) Faradays law states that during electrolysis, passage of 1 faraday through circuit brings about oxidation of one equivalent weight of substance at one electrode (anode) and reduction of one equivalent weight at other electrode (cathode)
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Relationship to free energy (energy driving reaction due to movement of charged particles giving rise to potential difference)
wmax = EG EG = -qEmax = -nFEmax EG = -qEmax EG0 = -nFE0
When Ecell positive (spontaneous), EG will be negative (spontaneous), so there is agreement
Standard cell potential, Eocell, measured and standard electrode potential of test half-cell determined by using Eocell = Eocathode - Eoanode
Eocathode-standard reduction potential for reaction occurring at cathode, represents tendency to remove es from electrode surface Eoanode-standard reduction potential for reaction occurring at anode and represents its tendency to remove es from anode
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Nernst Equationway to relate E0 at standard conditions and E, potential at any real condition
Standard state impossible to achieve in reality As soon as wire hooked to two half-cells, reaction proceeds and changes concentrations of all reactants and products Heating or cooling makes reaction deviate from standard temperature
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Expressed in terms of base 10 rather than ln (standard conditions of 298K) Can be used to find cell potential at any set of conditions Cells spontaneously discharge until they achieve 37 equilibrium (at equilibrium, cell is dead) 4/7/2014
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0.0592 E E logQ n
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Cell in which current flows due only to difference in concentration of ion in 2 different compartments of cell Le Chteliers principle used to determine effect on potential
Shift to left reduces potential Shift to right increases potential
If concentrations are different, stress is put on system that will be equalized by electron flow to allow reduction and oxidation to occur
Voltages typically small
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Calculate the EMF of the cell Zn(s) | Zn2+ (0.024 M) || Zn2+ (2.4 M) | Zn(s)
Zn2+ (2.4 M) + 2 e = Zn Reduction Zn = Zn2+ (0.024 M) + 2 e Oxidation Zn2+ (2.4 M) = Zn2+ (0.024 M), DE = 0.00 Using Nernst equation:
(0.024) DE = 0.00 - 0.0592/2 log (0.024/(2.4) = (-0.296)(-2.0) = 0.0592 V
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Show that voltage of electric cell is unaffected by multiplying reaction equation by positive number Mg | Mg2+ || Ag+ | Ag Mg + 2 Ag+ = Mg2+ + 2 Ag
DE = DEo 0.0592/2 log [Mg2+]/[Ag+]2
2 Mg + 4 Ag+ = 2 Mg2+ + 4 Ag
DE = DEo 0.0592/4 log [Mg2+]2/[Ag+]4 Simplified to the 1st equation, showing cell potential DE not affected
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The standard reaction potential is related to the equilibrium constant At equilibrium, Ecell = 0 and Q = K
For a cell at concentrations and conditions other than standard, a potential can be calculated using the Nernst equation
If Eo is positive, then K > 1 and forward reaction favored If Eo is negative, then K < 1 and reverse reaction is favored
nE log( K ) at 25 C 0.0592
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The standard cell potential dE for the reaction Fe + Zn2+ = Zn + Fe2+ is -0.353 V. If a piece of iron is placed in a 1 M Zn2+ solution, what is the equilibrium concentration of Fe2+?
Equilibrium constant K may be calculated using K = 10(n DE)/0.0592 = 10-11.93 = 1.2x10-12 = [Fe2+]/[Zn2+]. Since [Zn2+] = 1 M, it is evident that [Fe2+] = 1.2-12 M
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Homework:
Read 17.3-17.4, pp. 837-846 Q pp. 869-871, #38, 40, 46, 48, 54, 60, 66, 70
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Batteries
Portable, self-contained electrochemical power source (DC) consisting of one or more voltaic cells, connected in series Greater voltages achieved by using multiple voltaic cells in single battery (12V) When connected in series, battery produces voltage that is sum of emfs of individual cells Higher emfs achieved by using multiple batteries in series Electrodes marked + (cathode) and (anode)
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Mercury Battery
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Fuel Cells
Galvanic cells where reactants continuously supplied Energy normally lost as heat is captured and used to produce an electric current Redox reaction
Hydrogen oxidized at anode and oxygen reduced at cathode to form water and electricity 2x as effective as gas, oil or coal-powered generators in converting chemical energy into electricity
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Type of Battery
Lead acid
Advantages
Rechargeable Long life 12 V Inexpensive No toxic metals used Lots of power (1.5 V down to 1.2 V) Lightweight Higher capacity (3.6-3.9 V) Rechargeable Longer lasting Less likely to leak/explode
Disadvantages
Heavy Contain acid Weather issues Heavier
Alkaline/Dry cell
Expensive
Fuel cells
high initial cost Fuel not readily available Toxic metals Expensive
Nickel-Cadmium (Ni-Cd)
Mercury
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More expensive
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Corrosion of Iron
Anodic regions Regions of steel alloy where iron is more easily oxidized Fe Fe2+ + 2eCathodic regions Areas resistant to oxidation Electrons flow from anodic regions & react w/oxygen O2 + 2H2O + 4e- 4OHPresence of water essential to iron corrosion Presence of salt accelerates corrosion by increasing electron conduction from anodic to cathodic regions
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Prevention of Corrosion
Coating w/metal that forms oxide coat to protect metal that would not develop protective coat Galvanizing
Place sacrificial of more easily oxidized metal on top of metal to protect
Zinc over iron
Alloying
Addition of metals that change steels reduction potential.
Nickel and chromium alloyed to iron
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Cathodic Protection
Connection of easily oxidized metals (an anode) to less easily oxidized metals keeps less from experiencing corrosion Anode corrodes-must be replaced periodically
Magnesium as anode to iron pipe Titanium as anode to steel ships hull
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Electrolysis
Decomposition of substance by electric current
Galvanic Cell Electrolytic Cell
http://www.infoplease.com/chemistry/simlab/electrolpt3.html
Electrolytic cells
Electrical energy is converted into chemical energy Electrolytic cells are used for electroplating
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(a) Standard galvanic cell based on spontaneous reaction Zn + Cu2+ Zn2+ + Cu (b) Standard electrolytic cell: Power source forces opposite reaction Cu + Zn2+ Cu2+ + Zn
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A 40.0 amp current flowed through molten iron(III) chloride for 10.0 hours (36,000 s). Determine the mass of iron and the volume of chlorine gas (measured at 25oC and 1 atm) that is produced during this time.
Calculate number of moles of electrons Calculate moles of iron/chlorine produced using number of moles of electrons calculated and stoichiometries from balanced half-reactions. (3 moles electrons produce 1 mole of Fe/2 moles of electrons produce 1 mole of chlorine gas)
Calculate mass of iron using molar mass and calculate volume of chlorine gas using ideal gas law (PV = nRT).
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How long must a 20.0 amp current flow through a solution of ZnSO4 in order to produce 25.00 g of Zn metal
Convert mass of Zn produced into moles using molar mass of Zn Write the half-reaction for the production of Zn at the cathode Zn2+(aq) + 2 e- Zn(s) Calculate moles of e- required to produce moles of Zn using stoichiometry of the balanced half-reaction (2 moles of electrons produce 1 mole of zinc) Convert moles of electrons into coulombs of charge using Faraday's constant Calculate time using current and coulombs of charge
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What current is required to produce 400.0 L of hydrogen gas, measured at STP, from the electrolysis of water in 1 hour (3600 s)? Calculate number of moles of H2 Write equation for half-reaction that takes place. Hydrogen produced during reduction of water at cathode. Equation for this half-reaction is 4 e- + 4 H2O(l) 2 H2(g) + 4 OH-(aq) Calculate number of moles of electrons (4 mole of erequired to produce 2 moles of hydrogen gas, or 2 moles of e-'s for every one mole of hydrogen gas) Convert moles of electrons into coulombs of charge Calculate current required
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How many grams of copper can be reduced by applying a 3.00 A current for 16.2 min to a solution containing Cu2+ ions?
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Electrolysis can be used to separate mixture of ions, if reduction potentials are fairly far apart
Remember, metal ion with highest reduction potential is easiest to reduce Predict order of reduction and which of following ions will reduce first at cathode of electrolytic cell: Ag+, Zn2+, IO3-
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Electroplating
Deposit neutral metal atoms on electrode by reducing metal ions in solution
One metal coated with another
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How long must a current of 5.00 A be applied to a solution of Ag+ to produce 10.5 g silver metal?
10.5 g Ag 1 mol Ag 1 mol e- 96,485 C 1 sec 1 min = 107.868 g Ag 1 mol Ag 1 mol e- 5 C 60 sec 31.3 min
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http://college.hmco.com/chemistry/shared/media/animations/electrolysisofwater.html
Electrolysis of Water
Requires soluble salt/dilute acid to serve as electrolyte
Anode
2H2O(l) O2(g) + 4H+(aq) + 4eEoox = -1.23 V
Cathode
2H2O(l) H2(g) + 2OH-(aq) Eored = -0.83 V
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Overall reaction
6H2O(l) 2 H2(g) + O2(g) + 4H+(aq) + 4e- Eocell = -2.06 V If in single container, H+/OHcombine to yield 4 additional water molecules
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What volume of H2(g) and O2(g) is produced by electrolyzing water at a current of 4.00 A for 12.0 minutes (assuming ideal conditions)?
2H2O(l) 2H2(g) + O2(g) Actual ratio is not exactly 2:1 for a variety of reasons including oxygen solubility.
12 min 60 sec 4 C 1 mol e- 1 mol H2 22.4 L = 1 min 1 sec 96,486 C 2 mol e- 1 mol H2 0.334 L H2 0.167 L O2
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NaCl
Good conductor as liquid Melting salt frees ions Makes it electrically conductive
If metal ion is very active metal, water will be reduced (2H2O + 2e- H2 + 2OH-) If metal ion is inactive or active metal, metal ion will be reduced
Oxidation of salts anion or () Oxidation of water (2H2O O2 + 4H+ + 4e-)
At anode
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If anion in one salt is oxidized in aqueous electrolysis, that same anion in any other salt will also be oxidized
If solution of NaBr results in Br- being oxidized to Br2, predict that solutions of KBr, CaBr2, NH4Br and AlBr3 will all produce Br2 at anode
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Since metals are easily oxidized, most found as ores, mixtures of ionic compounds. Au, Ag, and Pt are more difficult to oxidize, so often found as pure metals.
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Hall-Heroult process
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Metal Plating
Electroplating thin layers of decorative metal on less expensive metal (silver and gold onto iron, chromium on to car parts for decoration and resistance to corrosion)
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Electrolysis of concentrated aqueous sodium chloride solutions (brine) produces hydrogen and hydroxide ions at cathode and chlorine gas at anode If electrodes separated by porous membrane, H2, NaOH, and Cl2 produced If solution stirred, chlorine gas reacts with sodium hydroxide to form sodium hypochlorite (NaOCl) solution (bleach) Electrolysis of molten NaCl produces sodium metal and chlorine gas (Downs cell)
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Homework:
Read 17.5-17.8, pp. 846-866 Q pp. 871-872, #74, 76, 78, 80, 84, 88 a (dont forget water) Do 1 additional exercise and 1 challenge problem Submit quizzes by email to me: http://www.cengage.com/chemistry/book_content/05471253 21_zumdahl/ace/launch_ace.html?folder_path=/chemistry /book_content/0547125321_zumdahl/ace&layer=act&src= ch17_ace1.xml http://www.cengage.com/chemistry/book_content/05471253 21_zumdahl/ace/launch_ace.html?folder_path=/chemistry /book_content/0547125321_zumdahl/ace&layer=act&src= ch17_ace2.xml http://www.cengage.com/chemistry/book_content/05471253 21_zumdahl/ace/launch_ace.html?folder_path=/chemistry /book_content/0547125321_zumdahl/ace&layer=act&src= 4/7/2014 90 ch17_ace3.xml