1. Chem. 133 – 2/24 Lecture

2. Announcements I Pass Back Graded Assignments –HW1.2 + Q2 Exam 1 –Next Tues. –Format: part multiple choice/short answer, part problems –Typically hardest exam (based on scores) –Will Review Topics on Thursday –Will Cover: All of Electronics + Beginning Electrochem. (what we get through today) –Can have a review session Monday (in place of office hours?)

3. Announcements II Today’s Lecture –Noise – just questions –Electrochemistry intro redox balancing definitions galvanic cells electrolytic cells

4. Noise Questions 1.What type of noise is likely to be present when using thermocouples to measure temperature? 2.Why is modulation normally required to reduce 1/f noise? 3.What is the percent noise on a current producing transducer which generates signal over a 1000 Hz band if the signal is 10 nA? if the signal is 2.0 pA? 4.What specific type of noise is reduced best by shielding electronics? 5.How would use of a low pass filter reduce shot noise? 6.Suggest one method for reducing thermal noise. 7.What type of noise is not effectively reduced by using a low pass filter?

5. Electronics Additional Questions Answer the questions 1-3 from the following plots which were obtained from background measurements (instrument noise): 1.Which plot is most likely shows 1/f noise: ______________________ 2.Which plot when Fourier transformed will produce a plot with a peak at 55 Hz: ______________ 3.If plot c) shows noise from a GC signal in which peaks typically are on the order of 2 s (2000 ms) wide, what can be done to reduce the noise? a) b) c)

6. Electrochemistry Overview Applications –quantitative analysis potential measurement methods (e.g. pH electrode) current based measurements (amperometry) –qualitative analysis (voltammetry) –note: potential normally gives qualitative information and current quantitative measurements –HPLC/IC detectors Why Use? –lower cost –high sensitivity possible (particularly mass sensitivity) –simpler equipment, more useful for field, in-situ type measurements

7. Electrochemistry Redox Reactions Reduction = loss of charge –e.g. Fe 3+ + e - → Fe 2+ Oxidation = gain in charge –e.g. Pb 2+ + 2H 2 O → PbO 2 (s) + 4H + + 2e - (Pb goes from +2 to +4) Balancing reactions –review steps in general chemistry book –example: Fe 2+ + Cr 2 O 7 2- → Fe 3+ + Cr 3+

8. Electrochemistry Fundamental Equations Relationship between charge, energy and current –redox reactions involve the exchange of electrons –when the exchange occurs on an electrode surface, current can be measured –Total charge transfer = q = nF, where n = moles of electrons in reaction and F = Faraday ’ s constant = 96500 C/moles e F = N Avogadro · e (e = elementary charge) –Current Produced = I = dq/dt or q = ∫I · dt (or = I · t under constant current conditions) can be used to determine battery lifetime

9. Electrochemistry Fundamental Equations Relationship between charge, energy and current (continued) –Electrical work = E·q (E = potential in volts) –and ΔG = -E·q = -nFE –under standard conditions (1 M reactant/product conc., 298K, etc.), ΔGº = -nFEº –ΔGº are given in Tables and allows calculation of K values –Eº, standard reduction potential, also given in Tables (see Appendix H), but for “half-reactions”

10. Electrochemistry Fundamental Equations Example problem: A NiCad battery contains 12.0 g of Cd that is oxidized to Cd(OH) 2. How long should the battery last if a motor is drawing 421 mA? Assume 100% efficiency.

11. Electrochemistry Galvanic Cells What are galvanic cells? –Cells that use chemical reactions to generate electrical energy –Batteries are examples of useful galvanic cells –Example reaction –If reactants are placed in a beaker, only products + heat are produced –When half reactions are isolated on electrodes, electrical work can be produced Zn(s) + 2Ag + → Zn 2+ + 2Ag(s) Salt Bridge voltmeter Zn(s) ZnSO 4 (aq) Ag(s) AgNO 3 (aq) GALVANIC CELL

12. Electrochemistry Galvanic Cells Description of how example cell works –Reaction on anode = oxidation –Anode = Zn electrode (as the E º for Zn 2+ is less than for that for Ag + ) –So, reaction on cathode must be reduction and involve Ag –Oxidation produces e -, so anode has ( – ) charge (galvanic cells only); current runs from cathode to anode –Salt bridge allows replenishment of ions as cations migrate to cathode and anions toward anodes Salt Bridge voltmeter Zn(s) ZnSO 4 (aq) Ag(s) AgNO 3 (aq) GALVANIC CELL Zn(s) → Zn 2+ + 2e - Ag + + e - → Ag(s) – +

13. Electrochemistry Galvanic Cells Cell notation –Example Cell: Zn(s)|ZnSO 4 (aq)||AgNO 3 (aq)|Ag(s) Salt Bridge voltmeter Zn(s) ZnSO 4 (aq) Ag(s) AgNO 3 (aq) GALVANIC CELL left side for anode (right side for cathode) “|” means phase boundary “||” means salt bridge

14. Electrochemistry Galvanic Cells Given the following cell, write the cell notation: Salt Bridge voltmeter – reads +0.43 V Pt(s) FeSO 4 (aq), Fe 2 (SO 4 ) 3 (aq) Ag(s) NaCl(aq) GALVANIC CELL AgCl(s) + –

15. Electrochemistry Standard Reduction Potential A half cell or electrode, is half of a galvanic cell A standard electrode is one under standard conditions (e.g. 1 M AgNO 3 (aq)) Standard reduction potential (E º ) is cell potential when reducing electrode is coupled to standard hydrogen electrode (oxidation electrode) Large + E º means easily reduced compounds on electrode Large – E º means easily oxidized compounds on anode Ag(s) AgNO 3 (aq) Pt(s) H + (aq) H 2 (g)

16. Electrochemistry Electrolytic Cells Used in more advanced electrochemical analysis (not covered in detail) Uses voltage to drive (unfavorable) chemical reactions Example: use of voltage to oxidize phenol in an HPLC electrochemical detector (E° of 0 to 0.5 V needed) anode (note: oxidation driven by voltage, but now + charge) cathode (reduction, - charge)