Chem 336

Quiz 4 Spring 2012 Name:

1. Determine the stability constant of the silver ammine ion (Ag(NH3)2+ from the cell

Ag | AgNO3(0.025 M), NH3 (1.00 M) || KNO3 || AgNO3 (0.010 M, KNO3 (0.015 M) | Ag which has a measured cell potential of +0.394 V at 25oC. The chemistry that we are working with is the formation of the silver ammine complex

Since the formation constant for these complexes are large, and since the [NH3] is large compared to [Ag+], [Ag(NH3)2+] = 0.025 M This simplifies the above equation to: ( And therefore Kf = 1.9 X 106 ) ( )

2. Describe the principle of ISE. Why is the term ion-specific electrode not used? Explain with an example. The fluoride ISE is routinely used for measuring fluoridated water and the fluoride ion in dental products such as mouthwash. A 50 mL aliquot of water containing sodium fluoride is analyzed using a fluoride ion electrode and the method of standard additions. The pH and ionic strength are adjusted so that all fluoride ion is present as free Fion. The potential of the ISE/reference electrode combination in a 50 mL aliquot of the water was -0.1805 V. Addition of 0.5 mL of 100 mg/L F- ion standard solution to the beaker changed the potential to -0.3490 V. Calculate the concentration of fluoride ion, and sodium fluoride in the water sample. Express in ppm. I expected to see a discussion how an ISE provides a potential, and how that potential can be related to the concentration of the analyte in solution.

The term ion-specific electrode is not used because most of the ISE have other ions besides the analyte that can cause interference. They are called Ion Selective, because they generally provide significant changes in potential as the concentration of an ion is changed. Many examples, not the least of which is the pH electrode. The concentration is related to the potential by the following general relationship (excluding interferences, etc.

To relate the potential to the concentration the electrode has to therefore be calibrated to establish the slope and L. For this problem, the calibration is being done by standard addition. The first potential, for the 50 mL of water is given:

After the addition of the standard solution: [ ]

Where Cx is the unknown concentration and C is the standard added [ ( ) ]

To remove L from the relationship, we can subtract one measurement from the other

Cx = 13.15 gF-/mL = 13.15 ppm

3. You decided to monitor the titration of iron in iron ore (last semester) using sodium dichromate at the titrant. Establish the titration curve for this titration, using the Ag/AgCl reference electrode and a Pt indicating electrode. Determine at least three points before the endpoint, the endpoint potential and two points after the endpoint.

You could select the conditions you wished to use for the titration. Below are the conditions I used: Initial [Fe2+] = 0.100 M Initial [Fe2+] = 10 mL [H+] = 1.00 M Eoref = 0.222 v

Titrant concentration[Cr2O72-] = 0.100 M The two half reactions: Fe3+ + 1 eFe2+ Eo = 0.771 v 2 Cr3+ + 7 H2O

Cr2O72- + 14 H+ + 6 e-

Eo = 1.33 v

Need to recognize there is are 6 mmoles Fe2+oxidized for every 1 mmole of Cr2O72- , and 2 Cr3+ mmole formed. You also need to recognize that without the addition of titrant, there does not exist a redox couple that will establish the potential. For a potential to be measured, you need both oxidized and reduced forms of the couple. Therefore at 0.00 mL titrant added, there is not a stable potential. Before the Equivalence Point: Both Fe2+ and Fe3+ are present, but only Cr3+ , therefore the half reaction that will establish the potential measured will be the Fe2+ /Fe3+ couple. 0.5 mL titrant added: [ titrated Initially we had (10 mL)(0.1 M) = 1 mmol of Fe2+, this leaves 0.0700 mmol Fe2+ and 0.0300 mmol Fe3+ in the solution. ][ ]= 0.0300 mmolFe2+

Using the same relationships for 1.00 mL Ecell = 0.543 and 1.5 mL Ecell = 0.609

After the equivalence point, all of the Fe2+ is gone, therefore the Fe2+/Fe3+ couple can not be used, but we now have both Cr2O72- and Cr3+ so we use that half reaction couple. 2.0 mL titrant added: We have added 0.2000 mmol Cr2O72- , but 0.1667 mmol Cr2O72- was used to titrate the Fe2+. This leaves 0.00333 mmol Cr2O72- . Since we get 2 Cr3+ for each dichromate, we have formed 0.3334 mmol Cr3+.

= 1.088 v And at 3.00 mL titrant added: Ecell = 1.134 v The equivalence point potential is a little more difficult to get at since at the equivalence point the equilibria comes into play. In essence, neither the Fe or Cr2O7 couple are there in amounts that allow you to establish concentrations. For instance, [Fe2+] is very small but the equilibria will allow some to be there, but not at a concentration that can be determined. The same can be said about the Cr2O7. As a result, you need to approach the solution in a different fashion. The equivalence point potential can be measured with either of the half reactions, except for the problem with concentrations. Therefore, you can create two equations:

And

[ [

] ]

If we multiply the bottom equation by 6, we can then add the top and bottom equations together.

[ For every [

] that is unreacted there are 6 Fe2+ therefore at the equivalence point, [Fe2+] = 6[Cr2O72-]

In a similar fashion [Fe3+] = 3[Cr3+]; now substituting these relationships into the combined equation: [ [ ] ]

Now the dichromate ions cancel out of the equation, and one of the Cr3+ cancels out. Since we are at the equivalence point, we know that [Cr3+] is approximately 0.333 mmol since we started with 1 mmol Fe2+ Substituting into the equation:

Eeq = 1.253 Eref = 1.03 v Note that the equivalence point potential is NOT at the inflection point, NOT half way up the titration curve, but is instead closer to the potential of the titrant.
4. Give the schematic of a simple electronic circuit that could be used to measure the potential in either of the above problems.

You will want to measure the difference between the Pt electrode and the reference electrode WITHOUT letting current flow. You will want to use a couple voltage followers and a difference amp.