CHEM 340: Instrumental Analysis

Tutorial: Potentiometry

Question One

a) State two properties of Corning glass which makes it a suitable membrane material for pH
measurements.

b) Draw a schematic diagram showing how ‘soft’ glass can be used for the direct measurement
of the concentration of H+ ions in solution. Using the diagram and any appropriate
equations, explain clearly how the electrode is designed to directly measure the
concentration H+ ions.

c) Comment on the specificity, sensitivity and linearity of the pH glass ion-selective electrodes.

d) Briefly discuss the major applications of pH glass ion-selective electrodes.

Question Two

A set of pH standards (with [H+] ranging from 10-2 M -10-11 M) was prepared and the potential of
the standards measured using a Corning 015 pH electrode. When the pH values of the standards
were plotted against the measured potentials, the following calibration graph and data were
obtained.

300

200

100
E, mV

-100

-200

-300

2 4 6 8 10 12

pH

Linear Regression for Data1_B:

y=c+m*x
Parameter Value
----------------------------
c 427.4
m -65.46
----------------------------
a) Is the response of the pH glass ion-selective electrode Nernstian? Calculate the absolute
error and relative error in the Nernstian response of the pH glass electrode.
b) The following cell potentials were recorded:

(i) +167 mV (for tomato juice); (ii) -27 mV (for tap water); (iii) +122 mV (for coffee) and
(iv) -276 mV (for a drainage cleaning reagent). Determine the pH of each of the samples.

c) Which of the samples is likely to carry the largest error in the measured pH due to how the
glass ion-selective electrode responds? Explain why.

d) Given that the selectivity coefficient for sodium ions for a Corning 015 glass membrane,
K(Na+/H+) is approximately 10–11, calculate the actual pH for the sample referred in (c)
assuming a Na+ ion concentration of 0.16 M for that solution.

Question Three

The fluoride ion concentration of a certain sample solution was determined by a fluoride ion-
selective electrode. The pF electrode developed a potential of -0.496 V when immersed in 25.00
mL of the sample and -0.412 V after the addition of 2.00 mL of 2.45 x 10-2 M NaF.

a) Calculate the (i) molar concentration and

(ii) the pF of the 25.00 mL solution.

b) Give an advantage of analyzing the analyte by the standard addition method.

The following work-up procedure had been followed to prepare the 25.00 mL solution that was
used for the one-point standard addition described above. A mass of 3.700 g of a bone powder
had been taken for acid digestion, filtered and the pH of the filtrate adjusted to a pH range of
4.5-5.5 before it was diluted to 250 mL using a volumetric flask. A 5.00 mL aliquot of this
solution was pipetted into a 25.00 mL volumetric flask and 5.00 mL of a total ionic strength
adjustment buffer (TISAB) solution added. The solution was diluted to mark with distilled
water.

c) Calculate the percentage fluoride ions in the bone sample.

d) Why was it necessary to adjust the pH of the 250 mL solution to a pH range of 4.5 – 5.5.

A total ionic strength adjustment buffer (TISAB) can be prepared from a mixture of:
(i) 1.0 M NaCl;
(ii) glacial acetic acid /acetate buffer and
(iii) trans-1,2-cyclohexylenedinitrilotraacetic acid (CDTA).

e) Given this composition, discuss the role of the TISAB in the precise and accurate
measurement of fluoride ions.

f) State a disadvantage of standard addition method in the context of potentimetric analysis.

Question Four

Below is a diagram of a pH glass electrode.

a) Briefly explain the functions of each of the parts labeled on the diagram.

b) A boundary potential is created across the glass membrane. Explain concisely, how this
boundary potential is created and how the signal is related to the activity of the hydrogen
ions to which the electrode is immersed.

Question Five

a) Draw a properly labeled diagram of an electrode that can be used to analyze routinely the
concentration of fluoride ions in a solution. How is the electrode designed to measure
accurately the fluoride activity/concentration in aqueous solution to which it is dipped?
b) What would you plot on each axes of the calibration curve?

Question six

The Ca2+ ion concentration of a solution was determined by measurement with a calcium ion
selective electrode. The electrode system developed a potential of 213.3 mV when immersed in
a solution which was 2.17x10-4 M Ca2+, using the SCE as the reference electrode. An unknown
solution of Ca2+ ions developed a potential of 184.6 mV, also using SCE as the reference
electrode.

a) Calculate the calcium ion concentration in the unknown solution.

b) What is the major weakness associated with this approach to analysis.