# Galvanic Cells Spontaneous Electrochemistry. Electrolytic Cells Backwards Electrochemistry

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1 Today Galvanic Cells Spontaneous Electrochemistry Electrolytic Cells Backwards Electrochemistry

2 Balancing Redox Reactions There is a method (actually several) Learn one ( ) Practice (worksheet)

3 Electrons have a lower free energy in Zn 2+ (and Cu) than Cu 2+ (and Zn) 2 e - Zn Cu 2+ Zn 2+ Cu Depends on the concentrations!

4 Which has the lower Standard Gibb's free energy? A. Zn 2+ (1M) + Cu B. Zn + Cu 2+ (I M) C. They are exactly equal

5 A moment to think again about Free Energy and Standard Free Energy G Difference in Free Energy between reactants and product under the current conditions (depends on the concentrations of the reactants and products) The concentration will change until G = 0 G Difference in Free Energy between reactants and product under standard conditions standard conditions are 1 M for all aqueous species or 1 atm pressure for all gases

6 Last time, we look at this idea Use a wire to connect the two sides and have e- flow in an external circuit 2e - Zn Cu 2+ Zn 2+ Cu Problem, one side is getting more positive one side is getting more negative. We need to keep each side neutral

7 2e - Zn Zn 2+ SO4 2- Cu Cu 2+ SO4 2- SO4 2- Add a connection that let's a "counter" ion move between the two sides As the reaction proceeds Zn is oxidized into Zn 2+ Cu 2+ is reduced into Cu note I have two solid pieces of metal (electrodes) connected to the wire

8

9 Oxidation Zn -> Zn e - Reduction Cu e - -> Cu

10 Initially we start with 0.5M CuSO4 and ~ 0 M ZnSO4 As the reaction proceeds... A. [Zn 2+ ] is increasing B. [Cu 2+ ] is increasing C. neither is changing

11 Initially we start with 0.5M CuSO4 and ~ 0 M ZnSO4 As the reaction proceeds... A. the voltage is increasing B. the voltage is decreasing C. neither is changing

12 Initially we start with 0.5M CuSO4 and ~ 0 M ZnSO4 When the reaction stops A. the voltage is zero B. the free energy difference is zero C. both are zero

13 Salt Bridge or Porous Disk allow ions to flow back and forth between the two beakers. As e - move from one side to the other, counter anions move the opposite direction

14 Define by the chemistry we want to happen Anode. Oxidation reaction Cathode. Reduction Reaction

15 How will I ever remember? AN OX and RED CAT ANode OXidation REDuction CAThode Cathode Ray Tube Shoots out electrons Alternatively just remember it!

16 In our reaction of Zn goes to Zn 2+ and Cu 2+ goes to Cu What is the cathode? A. The Cu strip B. The Zn strip C. neither

17 Oxidation Zn -> Zn e - Reduction Cu 2+ -> Cu + 2 e -

18 To write this out we develop a short hand symbol for the short hand = salt bridge this divides the cell into to halves = show the different compounds of each 1/2 reaction By convention the anode is always on the left So for the cell we just had

19 We can write this as <Zn Zn 2+ Cu 2+ Cu> if we knew the concentrations of the ions <Zn Zn 2+ (1 M) Cu 2+ (10-3 M) Cu>

20 Other reactions One half is Oxidation (Anode) Ag goes to Ag+ Reduction (Cathode) Fe 3+ goes to Fe 2+ < Ag Ag + Fe 3+ Fe 2+ > but we would like this to represent the actual cell I cannot hook a wire up to Fe 2+. I need an electrode in the solution. Let s say I use a Pt electrode < Ag Ag + Fe 3+ Fe 2+ Pt >

21 Two kinds of electrochemical cells Galvanic (Voltaic) Reaction is spontaneous we can use these to make a battery Electrolytic Reaction is not spontaneous we have to input work to get these reactions to proceed

22 Nomenclature Galvanic Cell Voltaic Cell Battery E>0 volt meter Spontaneous G<0 E > 0 electrons flow to cathode Anode Cathode get the PLUS sign - + Cathode This is spontaneous. It can be used as a power supply

23 First some nomenclature Electrolytic Cell Non-Spontaneous G>0 E < 0 electrons flow to cathode Anode + E<0 volt meter - Cathode Anode get the PLUS sign This reaction must be driven by an external power supply

24 In the following cell, how many electrons flow for each Zinc atom that reacts? Zn(s) Zn 2+ Cu 2+ Cu (s) A. 0.5 B. 1 C. 2 D. 4 E. Zinc doesn t react, Zn 2+ do

25 If I use this battery for a while how much Zn reacts? Charge = Current x Time Coulomb (C) = Amp (C s -1 ) x Second (s) How many electrons are in a Coulomb? What is the charge of 1 mole of electrons? F is the charge of one mole of electrons F = 96,485 C (Faraday's Constant)

26 If I run this cell for 100 s at a current of 30 ma how many moles of electrons flow? Zn(s) Zn 2+ Cu 2+ Cu (s) A. (30 x 10-3 ) x 100 x F B. 30 x 100 x F C. 30 / (100 x F) D. (30 x 10-3 ) / (100 x F) E. [(30 x 10-3 ) x 100] / F

27 If I run this cell for 100 s at a current of 1 ma how many moles of Zn react? Zn(s) Zn 2+ Cu 2+ Cu (s) A. (3/F) B. (3/F) x 2 C. (3/F) / 2

28 How do we know what the voltage is?

29 The voltage depends on the concentrations (we ve all had dead batteries) Mix up standard concentrations 1 M Zn 2+ and 1 M Cu 2+ (note this is very concentrated)

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1 of 13 interesting links: Battery Chemistry Tutorial at http://www.powerstream.com/batteryfaq.html Duracell Procell: Battery Chemistry at http://www.duracell.com/procell/chemistries /default.asp I. Oxidation