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Tutorial 5
1
Example 1:
Ions that react with Ag+ can be determined electrogravimetrically by deposition on a silver working anode: Ag(s) + X AgX(s) + eWhat will be the final mass of a silver anode used to electrolyze 75.00 mL of 0.0238 M KSCN if the initial mass of the anode is 12.463 g.
Solution
75.00 mL of 0.0238 M KSCN = 1.785 mmol of SCN - which gives 1.785 mmol of AgSCN, CONTAINING 0.1037 g of SCN-.
Example 2:
H2S(aq) can be analyzed by titration with coulometrically generated I2.
H2S I2 S s) 2H 2I (
To 50.0 mL of sample were added 4 g KI. Electrolysis required 812 s at 52.6 mA. Calculate the concentration of H2S (g/mL) in the sample.
Solution:
Faraday's Law The number of grams reduced at the cathode or oxidized at the anode is given by:
mass
Where
It FW F n
I = current in amps t = time in seconds FW = formula weight n = number of electrons transferred per species
Mass of H2S
Example 3:
A 1.00-L electrolysis cell initially containing 0.0250 M Mn2+ and another metal ion, M3+, is fitted with Mn and Pt electrodes. The reactions are:
Mn(s) Mn2+ + 2eM3+ + 3e- M(s) a) Is the Mn electrode the anode or the cathode? b) A constant current of 2.60 A was passed through the cell for 18.0 min, causing 0.504 g of the metal M to plate out on the Pt electrode. What is the atomic mass of M? c) What will the concentration of Mn2+ in the cell be at the end of the experiment?
Solution
a) Sine Mn is oxidized, it is the anode
c) In the electrolysis 0.0291/2 = 0.01455 mol of Mn 2+ were produced. [Mn2+] = 0.0250 + 0.01455 = 0.0396 M
Example 4:
Chlorine has been used for decades to disinfect drinking water. An undesirable side effect of this treatment is the reaction of chlorine with organic impurities to create organochlorine compounds, some of which could be toxic. Monitoring total organic halide is now required for many water providers. A standard procedure is to pass water through activated charcoal that adsorbs organic compounds.
Then charcoal is combusted to liberate hydrogen halide: Organic halide (RX) CO2 + H2O + HX
The HX is absorbed into aqueous solution and measured by automatic coulometric titration with a silver anode: Ag(s) Ag+ + eAg+ AgX(s)
(Ag+ generated anodically) (formed AgX is deposited on anode)
X-(aq) +
When 1.00 L of drinking water was analyzed, a current of 4.23 mA was required for 387 s. A blank prepared by oxidizing charcoal required 6 s at 4.23 mA. Express TOX of the drinking water as mol halogen/L. If all halogen 6 is chlorine, express the TOX as g Cl/L
Solution
The corrected coulometric titration time is 387 6 = 381 s q = It/F = [(4.23 mA)(381 s)] / (96500 C/mol) = 0.0167 mmol e= 16.7 mol e-.
organohalide is 16.7 M.
If all halogen is Cl, this corresponds to 592 g Cl/L (16.7 mol/L x 35.45 g/mol).
Exercise 1
A heated buffer solution containing indium(III), In3+, was treated with an excess of 8-hydroxyquinoline (HOC9H6N) to precipitate quantitatively an insoluble indium(III) compound, according to the following reaction: In3+ + 3HOC9H6N In(OC9H6N)3(s) + 3H+
After the precipitate was separated and washed, it was dissolved in dilute hydrochloric acid solution (which caused the above reaction to proceed in the right-to-left direction). Then an excess of bromide ion (Br) was added, and the solution was transferred to an electrochemical cell equipped with a platinum generator anode and a platinum auxiliary cathode. Elemental bromine (Br2), which was electrogenerated by oxidation of bromide ion, 2Br Br2 + 2e
reacted with the 8-hydroxyquinoline (HOC9H6N) that was released when the indium(III) compound was dissolved: HOC9H6N + 2Br2 HOC9H4NBr2 + 2HBr
An end point was reached after a titration time of 186.6 seconds at a constant current of 125.3 mA. Calculate the mass of In3+ in milligrams in the original sample solution. Faraday constant (F) = 96,500 coulombs/mol e-. Atomic mass of In = 114.8) (Answer: 2.318 mg of In3+)
Try to solve Exercise 17-B and problems 17-1, 17-2, 17-4, 17-8 1711, 17-12, 17-13, 17-19 (Harris text book, p400-403)