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Chapter 23
Chapter 23
A.) Introduction:
1.) Potentiometric Methods: based on measurements of the potential of electrochemical
cells in the absence of appreciable currents (i 0)
2.) Basic Components:
a) reference electrode: gives reference for potential measurement
b) indicator electrode: where species of interest is measured
c) potential measuring device
2Hg + 2Cl-
SCE
Ag(s) + Cl-
Vycor plug
Cu (s)
Kf =
aca2+ . aY4aCaY2-
Ca2+ + Y4-
aCaY2ay4- =
Kf . aca2+
Eind = 0.21 (0.0592/1) log aY4-/aHgY2Note: aY4- and Eind now also changes with aCa2+
Ce3+
Si
O-
Glass Surface
in analyte solution)
v. Acid Error
Errors at low pH (Acid error) can give readings that are too high
Exact cause not known
- usually occurs at pH 0.5
Solution
the side of the membrane with the lower aFbecomes positive relative to the other surface:
Eind = c 0.0592 pF
P
R-O
O-R
P
O-Ca-O
O-R
At solution/membrane interfaces:
[(RO)2POO]2Ca 2(RO2)POO- + Ca2+
Solution
Organic
Organic
(membrane) (membrane surface) (aqueous sample)
membrane
pores
internal
solution
internal
solution
2NH3 + 2H
Example 18: The following cell was used for the determination of pCrO4:
SCE||CrO42- (xM), Ag2CrO4 (satd)|Ag
Calculate pCrO4 if the cell potential is -0.386.