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Chapter 17: QGE (page 426)

Consider the cyclic voltammogram of the Co3+compoundrole="math" localid="1663646447735" Co(B9C2H11)2- . Suggest a chemical reaction to account for each wave. Are the reactions reversible? How many electrons are involved in each step? Sketch the sampled current and square wave polarograms expected for this compound.

Cyclic voltammogramofrole="math" localid="1663646461802" Co(B9C2H11)2- . [Data from W. E. Geiger, Jr., W. L. Bowden, and N. El Murr, "An Electrochemical Study of the Protonation Site of the Cobaltocene Anion and of Cyclopentadienylcobalt(I) Dicarbollides," Inorg. Chem. 1979,18,2358.]

Short Answer

Expert verified

The chemical process was linked to waves in a cobalt ion cyclic voltammogram. Cobalt ion cyclic polarograms were sketched.

Step by step solution

01

Definition of Cyclic voltammetry

Cyclic voltammetry can be used to determine the redox behaviour of substances as well as the kinetics of electrode reactions. The cathodic wave dominates the upper section of a cyclic voltammogram. Anodic wave dominates the lowest section of the cyclic voltammogram.

02

Chemical reaction relates to waves in cyclic voltammogram of cobalt

Reaction sequence occurred in cyclic voltammetry is given as

CoIIIB9C2H112-鈫�CoIIB9C2H1122-鈫�CoIB9C2H1123-

From EpaandEpcit is obvious that two reduction reactions took place, as depicted above.

The reactions are reversiblebecause the anodic and cathodic peaks are the same. The current sampled is presented as


Figure 1

The polarogram of square wave is drawn as

Figure 2

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Most popular questions from this chapter

(a) Explain the difference between charging current and faradaic current.

(b) What is the purpose of waitingafter a voltage pulse before measuring current in sampled current voltammetry?

(c) Why is square wave voltammetry more sensitive than sampled

current voltammetry?

What cathode potential (versus S.H.E.) is required to reduce 99.99%of cd(II) from a solution containing 0.10Mcd (II) in 1,0M ammonia if there is negligible current? Consider the following reactions and assume that nearly all (II) is in the form Cd(NH3)42+

localid="1663647104121" Cd2++4NH3鈬�Cd(NH3)42+尾4=3.6脳106Cd2++2e-鈬�Cd(s)E掳=-.402V

Ions that react with Ag+can be determined electrogravimetrically by deposition on a silver working anode:

Ag(s)+X-鈫�AgX(s)+e-

(a) What will be the final mass of a silver anode used to electrolyze 75.00 mL of 0.02380 M KSCN if the initial mass of the anode is 12.4638 g?

(b) At what electrolysis voltage (versus S.C.E.) will AgBr(s) be deposited from 0.10M Br? (Consider negligible current flow, so that there is no ohmic potential, concentration polarization, or overpotential.)

(c) Is it theoretically possible to separate 99.99% of0.10M Klfrom0.10MKBr by controlled-potential electrolysis?

Suppose that the diffusion current in a polarogram for reduction of Cd2+at a mercury electrode is14渭础If the solution containsof 25mLof0.50mMCd2+what percentage ofCd2+is reduced in the 3.4 min required to scan from-0.6to-1.2V?

(a) How does the amperometric glucose monitor in Figure 7-12 work? b) Why is a mediator advantageous in the glucose monitor? c) How does the coulometric glucose monitor in Figure 17-14 work? (d) Why does the signal in the amperometric measurement depend on the temperature of the blood sample, whereas the signal in coulometry is independent of temperature? Do you expect the signal to increase or decrease with increasing temperature in amperometry?

(e) Glucose(C6H12O6$,FM180.16)is present in normal human blood at a concentration near 1g/L How many microcoulombs are required for complete oxidation of glucose in 0.300渭L of blood in a home glucose monitor if the concentration is 1.00g/L ?
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