Current efficiencies

Current efficiency (CE) was calculated based on both the amount of oxygen generated and the quantity of aluminum produced (Table 1.6.1). 

Description of test CE on oxygen (%, average) Al expected (g) Al produced (g) CE on aluminum (g) 

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This, of course, assumes a 100% current efficiency regarding metal dissolution, i.e. no other competitive electrochemical reactions occur. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

In coulometry, current and time are measured, and equation 11.24 or equation 11.25 is used to calculate Q. Equation 11.23 is then used to determine the moles of analyte. To obtain an accurate value for N, therefore, all the current must result in the analyte s oxidation or reduction. In other words, coulometry requires 100% current efficiency (or an accurately measured current efficiency established using a standard), a factor that must be considered in designing a coulometric method of analysis. 

If the initial concentration of Cu + is 1.00 X 10 M, for example, then the cathode s potential must be more negative than -1-0.105 V versus the SHE (-0.139 V versus the SCE) to achieve a quantitative reduction of Cu + to Cu. Note that at this potential H3O+ is not reduced to H2, maintaining a 100% current efficiency. Many of the published procedures for the controlled-potential coulometric analysis of Cu + call for potentials that are more negative than that shown for the reduction of H3O+ in Figure 11.21. Such potentials can be used, however, because the slow kinetics for reducing H3O+ results in a significant overpotential that shifts the potential of the H3O+/H2 redox couple to more negative potentials. 

Maintaining Current Efficiency To illustrate why changing the working electrode s potential can lead to less than 100% current efficiency, let s consider the coulometric analysis for Fe + based on its oxidation to Fe + at a Pt working electrode in 1 M H2SO4. 

Since the current due to the oxidation of H3O+ does not contribute to the oxidation of Fe +, the current efficiency of the analysis is less than 100%. To maintain a 100% current efficiency the products of any competing oxidation reactions must react both rapidly and quantitatively with the remaining Fe +. This may be accomplished, for example, by adding an excess of Ce + to the analytical solution (Figure 11.24b). When the potential of the working electrode shifts to a more positive potential, the first species to be oxidized is Ce +. 

In this manner, a current efficiency of 100% is maintained. Furthermore, since the concentration of Ce + remains at its initial level, the potential of the working electrode remains constant as long as any Fe + is present. This prevents other oxidation reactions, such as that for liiO, from interfering with the analysis. A species, such as Ce +, which is used to maintain 100% current efficiency, is called a mediator. 

End Point Determination Adding a mediator solves the problem of maintaining 100% current efficiency, but does not solve the problem of determining when the analyte s electrolysis is complete. Using the same example, once all the Fe + has been oxidized current continues to flow as a result of the oxidation of Ce + and, eventually, the oxidation of 1T20. What is needed is a means of indicating when the oxidation of Fe + is complete. In this respect it is convenient to treat a controlled-current coulometric analysis as if electrolysis of the analyte occurs only as a result of its reaction with the mediator. A reaction between an analyte and a mediator, such as that shown in reaction 11.31, is identical to that encountered in a redox titration. Thus, the same end points that are used in redox titrimetry (see Chapter 9), such as visual indicators, and potentiometric and conductometric measurements, may be used to signal the end point of a controlled-current coulometric analysis. For example, ferroin may be used to provide a visual end point for the Ce -mediated coulometric analysis for Fe +. 

Any Fe + lost in this fashion must be replaced by the additional reduction of Fe +, reducing the current efficiency and increasing the time needed to reach the titration s end point. The net result is that the reported concentration of Cr207 is too large. 

Accuracy The accuracy of a controlled-current coulometric method of analysis is determined by the current efficiency, the accuracy with which current and time can be measured, and the accuracy of the end point. With modern instrumentation the maximum measurement error for current is about +0.01%, and that for time is approximately +0.1%. The maximum end point error for a coulometric titration is at least as good as that for conventional titrations and is often better when using small quantities of reagents. Taken together, these measurement errors suggest that accuracies of 0.1-0.3% are feasible. The limiting factor in many analyses, therefore, is current efficiency. Fortunately current efficiencies of greater than 99.5% are obtained routinely and often exceed 99.9%. 

In controlled-potential coulometry, accuracy is determined by current efficiency and the determination of charge. Provided that no interferents are present that are easier to oxidize or reduce than the analyte, current efficiencies of greater than 99.9% are easily obtained. When interferents are present, however, they can often be eliminated by applying a potential such that the exhaustive electrolysis of the interferents is possible without the simultaneous electrolysis of the analyte. Once the interferents have been removed the potential can be switched to a level at... 

The current efficiency of an electrolytic process ( current) ratio of the amount of material produced to the theoreticaUy expected quantities. 

The oxygen contribution from these reactions is dependent on the nature of the anode material and the pH of the medium. The current efficiency for oxygen is generally 1—3% using commercial metal anodes. If graphite anodes are used, another overall reaction leading to inefficiency is the oxidation of... 

Current Efficiency. Current efficiency for caustic production in diaphragm and membrane cells can be estimated from collection of a known amount of caustic over a period of time and from a knowledge of the number of coulombs of electricity passed during that time period. An alternative method involves analysis of the gases evolved during electrolysis and determining the anolyte composition. Material balance considerations (7) show the expression for the caustic efficiency for membrane cells to be... 

Current efficiency values based on the six equation are higher by approximately 1.0% than those from equation 16. 

However, the iadustry s popular terminology is the energy consumption expressed ia terms of kilowatt hours per ton of (Pq[) oi of NaOH An estimate of this value requires a knowledge of cell voltage, current efficiency, and the efficiency of the rectifier used to convert a-c power to d-c. The energy consumption for producing a ton of is... 

Data, for a 32% caustic concentration at 90°C and a current efficiency of 96.0%, obtained in laboratory cells using a DSA anode and an activated cathode, where the membrane is against the anode at a 3-mm gap. 

The ammonia values can be recycled or sold for fertilizer use. The most important consideration ia this process is the efficient elimination of the phosphoms from the product, because as Htfle as 0.01% P2 5 electrolyte causes a 1—1.5% reduction ia current efficiency for aluminum production (28). 

Another use for cryoHte is in the production of pure metal by electrolytic refining. A high density electrolyte capable of floating Hquid aluminum is needed, and compositions are used containing cryoHte with barium fluoride to raise the density, and aluminum fluoride to raise the current efficiency. 

Ethylene glycol can be produced by an electrohydrodimerization of formaldehyde (16). The process has a number of variables necessary for optimum current efficiency including pH, electrolyte, temperature, methanol concentration, electrode materials, and cell design. Other methods include production of valuable oxidized materials at the electrochemical cell s anode simultaneous with formation of glycol at the cathode (17). The compound formed at the anode maybe used for commercial value direcdy, or coupled as an oxidant in a separate process. 

Electrolysis. Electro winning of hafnium, zirconium, and titanium has been proposed as an alternative to the KroU process. Electrolysis of an all chloride hafnium salt system is inefficient because of the stabiHty of lower chlorides in these melts. The presence of fluoride salts in the melt increases the StabiHty of in solution and results in much better current efficiencies. Hafnium is produced by this procedure in Erance (17). 

The temperature in the ceU is 40°C. Most electrolyte ceUs are equipped with 24 anodes spaced approximately 10 cm apart, center to center 25 cathode starting sheets are used, one at each end and others evenly spaced between the anodes. Current density is typicaUy 15 mA/cm of cathode area ceU voltage ranges from 0.30 to 0.70 V, and a current efficiency of 90—95% is usuaUy realized. 

Lithium carbonate addition to HaH-Heroult aluminum ceU electrolyte lowers the melting point of the eutectic electrolyte. The lower operating temperatures decrease the solubiHty of elemental metals in the melt, allowing higher current efficiencies and lower energy consumption (55). The presence of Hthium also decreases the vapor pressure of fluoride salts. 

Many factors other than current influence the rate of machining. These involve electrolyte type, rate of electrolyte flow, and other process conditions. For example, nickel machines at 100% current efficiency, defined as the percentage ratio of the experimental to theoretical rates of metal removal, at low current densities, eg, 25 A/cm. If the current density is increased to 250 A/cm the efficiency is reduced typically to 85—90%, by the onset of other reactions at the anode. Oxygen gas evolution becomes increasingly preferred as the current density is increased. 

If the ECM of titanium is attempted in sodium chloride electrolyte, very low (10—20%) current efficiency is usually obtained. When this solution is replaced by some mixture of fluoride-based electrolytes, to achieve greater efficiencies (> 60%), a higher voltage (ca 60 V) is used. These conditions ate needed to break down the tenacious oxide film that forms on the surface of titanium. It is this film which accounts for the corrosion resistance of titanium, and together with its toughness and lightness, make this metal so useful in the aircraft engine industry. 

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