In this dissertation the pros and cons of cyclic voltammetry are discussed

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In this dissertation the pros and cons of cyclic voltammetry are discussed

Attribution Non-Commercial (BY-NC)

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3 -theyre not exceptionally long questions to explain, but writing them on the board takes some time, so lets begin Question 1 Intro In this question were dealing with electrochemical potentials. Its essential to know the potentials of all the electro-active materials in solution, because when monitoring changes in potential or impedance, or whatever youre monitoring in your system, you have to be certain of what youre actually measuring. To put it simply, if you want to observe reaction A, you have to be certain that youre not observing reaction B. And the initial sanity check you should always perform is to take stock of your species, and check their electric potentials. This leads us into our question: Statement of problem 1.1 Consider each of the following electrode-solution interfaces, and write the equation for the electrode reaction that occurs first when the potential is moved in (1) a negative direction and (2) a positive direction from the open-circuit potential. Next to each reaction write the approximate potential for the reaction in V vs. SCE (assuming the reaction is reversible). (a) Pt/Cu2+(0.01 M), Cd2+(0.01 M), H2SO4(1 M) (b) Pt/Sn2+(0.01 M), Sn4+(0.01 M), HC1(1 M) (c) Hg/Cd2+(0.01 M), Zn2+(0.01 M), HC1(1 M) Solve Problem -easy, just talk - list potentials -order the reduction and oxidation reactions separately - the most will be what happens, that will be the first reaction to occur Limitations The largest limiting assumption here is the fact that we cannot use our Nernst equation for two reasons. The first is that we are not given the activity coefficients. The activity coefficients are derived from the thermodynamic relations, and so its not trivial to calculate them. However, to a good approximation, in most situations, we can avoid thermodynamic arguments and the use of the Debye-Huckel equation,

which would yield these activity coefficients, by just using concentrations. Which leads to the other complication. The second complication is that were not given concentrations of both oxidized and reduced forms in solution. Thus, our redox reactions are not well defined, and so we choose to just not use the Nernst equation. Real life Example So, a place where this concept would actually be important in the real world would be electroplating. in electroplating we want to coat our conductive material with a certain other metal however, refining metals to sufficient purities is expensive so, if we know information about which reactions will first, we can do a few things to make the process more successful and less costly if we know that the reduction or oxidation process required to electroplate, lets say Platinum, on our substrate occurs at a much lower potential than that of our impurities, then by applying a sufficiently low potential, we can plate only with platinum, while leaving the impurities behind also, if we know that the potential of the next reaction after platinum is much greater, then we can apply a higher potential to increase the rate of platinum plating, without getting any copper plating finally, if we were to find that the other metal in our refining process does have a similar electrochemical potential, we may choose a different variety of solution, one that perhaps uses a different refining technique which uses some other solutes which are more conductve to this electroplating, that being that their potentials are much higher, so they wont occur at the same potential

QUESTIONS?!?!

Question 2 Intro this question deals with rotating disk electrodes usually this means that we have: an conductive disk, being our electrode, embedded in a nonconductive polymer or resin, which is attached to some electric motor using the motor, we can change the rate of rotation to a great deal of precision and thats important, because as we change the angular the velocity of this spinning electrode, we can think of it as what people like to call centrifugal force, where things on the surface seem to get pushed outwards as the spinning occurs the pushing outwards occurs on the Nernst diffusion layer as the solution is displaced, more solution flows up perpendicularly to replace the boundary later so, overall, we get this laminar, this sheet flow over the electrode, and we get access to more electroactive material and most importantly, by changing the rate of rotation, we can change the rate at which our diffusion layer is displaced, and we can demonstrate mathematically by the equations we are about to use, that this will also change the current we generate This flow can quickly achieve conditions in which the steady-state current is controlled by the solution flow rather than diffusion. This is a contrast to still and unstirred experiments such as cyclic voltammetry where the steady-state current is limited by the diffusion of substrate.

Statement of Problem For a rotating disk electrode, the treatment of steady-state, mass-transfer-controlled electrode reactions applies, where the mass-transfer coefficient is mo = 0.62DQ O)XI2 J>~1/6. Here, Do is the diffusion coefficient (cm2/s), is the angular velocity of the disk (s"1) (a) = 2irf, where/is the frequency of rotation in revolutions per second), and v is the kinematic viscosity (v = r]/d, r\ = viscosity, and d = density; for aqueous solutions v ~ 0.010 cm2/s). A rotating disk electrode of area 0.30 cm2 is used for the reduction of 0.010 M Fe3 + to Fe2 + in 1 M H2SO4. Given Do for Fe3 + at 5.2 X 10~6 cm2/s, calculate the limiting current for the reduction for a disk rotation rate of 10 r/s. Include units on variables during calculation and give units of current in the answer.

Solving Identify that we want the limiting current -> limiting current is when Co (concentration at the electrode) is 0, and the current is maximized. In this circumstance, we will then use the following equations Identify constants/unknowns, set up equations, and solve Complications

This question is fairly straight forward however, some might get mixed up in keeping track of units something to keep in mind are units remember that radians are essentially unitless easy way to see that is by thinking of the definition of a radian the number of radians gone through = length of arc / radius both have units of length cancel out, give solution another limitation, although its not really essential here, but if youre doing more theoretical calculations dealing with these electrodes, and you need to see the picture in a more correct manner, you have to be comfortable with the idea that theres no such thing as a centripetal force if you look at this stuff in the rotating frame of the disk electrode, then you can say theres some force that looks like its pushing outwards, but in our xyz reference frame, its merely frictional forces applied at different points on the disc, which gives this appearance of solution being pushed outwards, whereas its really being pushed linearly

Real life Example linear sweep voltammetry we could have a three electrode system: platinum cathode, platinum anode, and SCE reference then we need to stir the solutions, and would do that by embedding the platinum cathode in an insulator, and allowing it to revolve, thus creating laminar flow across the cathode

Linear sweep voltammetry is a method where the current at a working electrode is measured the potential between the working electrode and a reference electrode is swept linearly in time Oxidation or reduction of species is registered as a peak or trough in the current signal at the potential at which the species begins to be oxidized or reduced. By running linear sweep voltammetry and other experiments at various rotation rates, different electrochemical phenomena can be investigated, including multi-electron transfer, the kinetics of a slow electron transfer, adsorption/desorption steps, and electrochemical reaction mechanisms.

QUESTIONS?!?!?!

Question 3 Intro As I sort of alluded to in problem 1, the Nernst equation shows that activity coefficients will have an effect on the electric potential of certain reactions. These activity coefficients are related to the thermodynamics of our system, and so in this way we can see that the actual thermodynamics of our system will have a key role to play in the electrochemical evolution of our system. One of the key thermodynamic variables discussed in any introductory thermodynamics class is Gibbs free energy. Statement of Problem 2.3 Devise a cell in which the following reaction is the overall cell process (T = 298 K): 2Na+ + 2 -> 2Na(Hg) + Cl2 (aqueous) where Na(Hg) symbolizes the amalgam. Is the reaction spontaneous or not? What is the standard free energy change? Take the standard free energy of formation of Na(Hg) as 85 kJ/mol. From a thermodynamic standpoint, another reaction should occur more readily at the cathode of your cell. What is it? It is observed that the reaction written above takes place with good current efficiency. Why? Could your cell have a commercial value? Solving need delta G use calculation need E get E by using this set up figure out net G this shows that it isnt spontaneous check out other one more readily happens, but our overpotential stops it

Problems The problem that you might have with this question is with keeping track of n between these calculations. Also, Cl2 aqueous could not be found

Real Life Well, simply put, by calculating the thermodynamics of this system, we can what will realistically happen within our system. As in the first question that I tackled today, we could see we need to be acutely aware of all the factors present in our system. When we look at the individual constituents of our system, we can make accurate predictions of how our system is going to behave simply given

thermodynamics and electric potentials. Using these, we can predict what will happen in large scale production, and can say, to some degree of certainty, whether or not our system will be commercially viable in the production of a certain species. QUESTIONS?!?!?

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