7

Potentiometric pH
Measurements with a
Glass electrode
Potentiometric pH Measurements with a
Glass electrode

• the most important indicator electrode for hydrogen ion

• convenient to use, subject to few interferences
• available at relatively low cost and come in many shapes
and sizes

combination glass electrode

Potentiometric Titrations

• involves measuring the potential of

a suitable indicator electrode as a
function of titrant volume
con’t. Potentiometric Titrations

Features:
• provide data that are more reliable than data
from titrations that use chemical indicators

• useful with colored or turbid solutions and for

detecting unsuspected species

• can be readily automated

• Disadvantage: more time consuming

Potentiometric titration set-up

888.88 mV

buret

stirring bar

stirring plate

ü Cell potential is taken at regular intervals of added

titrant volume, smaller interval is made at around the
equivalence point
Equivalence Point Detection

Ecell or pH Direct Titration

Curve
Inflection point

Volume titrant, mL

DE/Dvol 1st derivative

maximum

Ave volume titrant, mL

Equivalence Point Detection

x-axis
D2E/Dvol2 intersection 2nd derivative

Ave volume titrant, mL

con’t. Potentiometric Titrations

Types of Titrations

1. Neutralization Titration

• acid-base titration

H+ + OH- = H2O

• indicator electrode: pH glass electrode

• valuable for the analysis of mixtures of acids

or polyprotic acids
con’t. Types of Titrations

2. Precipitation Titration

Mn+ + A- = MA(s)

• indicator electrode: the metal form of the

reacting cation or a membrane electrode
responsive to this cation or the anion

e.g. for the titration:

Ag+ + Cl- = AgCl(s)
titrant analyte

indicator electrode: Ag wire or Cl- selective

electrode
con’t. Types of Titrations

3. Complex Formation Titration

Mn+ + nL- = MLn

• both metallic and membrane electrodes have

been used in titrations involving complex
formation
con’t. Types of Titrations

4. Oxidation/Reduction Titration

Ox1 + Re2 = Re1 + Ox2

• indicator electrode: normally inert electrode

constructed of Pt
8
ISE Applications
Typical ISE Applications

Agriculture

• Animal Feeds -- determinations of bromide, calcium, chloride,

fluoride, iodide, Kjeldahl nitrogen, nitrate, potassium and
sodium

• Fertilizers -- Fluoride in phosphate rock; and Kjeldahl analysis

of nitrogen; nitrate using the NH3 electrode and the Nitrate
Test Kit; potassium in potash

• Plant Tissue -- Calcium, chloride, cyanide, fluoride, iodide,

nitrate, potassium and sodium

• Soils -- Ammonia, bromide, boron, calcium, chloride, fluoride,

nitrate, potassium and sodium
con’t. Typical ISE Applications

Biomedical Research

• Culture Media -- Ammonia, calcium and carbon dioxide

are commonly measured parameters in biological
cultures.
(Not approved for in vitro or in vivo diagnostic use.)

• Tooth Enamel -- Calcium and fluoride determinations

are often of interest in dental research.
(Not approved for in vitro or in vivo diagnostic use.)
con’t. Typical ISE Applications

Education

• Electrodes are an important part of many analytical and

instrumentation courses.

• They have applications to kinetics, equilibria, activity

coefficients, solubility, and ion pairing.

• Research using electrodes is done in the departments of

agriculture, agronomy, biology, chemistry, dentistry,
engineering/environmental science, food technology,
geology, medicine, oceanography, pharmacology and
physics.
con’t. Typical ISE Applications

Food Processing

• Meat and Fish -- Salt, nitrate, and nitrite in processed

meat and fish are common measurements. Fluoride
levels of fish protein are also monitored to check for
elevated levels of this toxin.

• Milk and Dairy Products -- Chloride in cheese, butter,

ice cream, and milk; Fluoride and iodide are monitored
to control levels of these toxins

• Soft Drinks and Juices -- Chloride, fluoride, carbon

dioxide, and residual chlorine
con’t. Typical ISE Applications

con’t. Food Processing

• Spirits, Wine and Beer -- Potassium, sodium, carbon

dioxide, fluoride, bromide, calcium, and residual chlorine

• Vegetables -- Nitrate is routinely measured in canned

vegetables and baby foods. Chlorine levels in wash
waters are also of interest.

The Kjeldahl analysis utilized in scores of food processing

applications is simplified by the use of electrode
techniques.
con’t. Typical ISE Applications

Geology and Mining

• Fluoride and calcium measurements in various types
of rock

Metallurgy and Metal Plating

• Fluoride can be measured in cryolite, aluminum
fluoride, and tungsten.
• Cupric ion, free cyanide, total cyanide, fluoride,
fluoriborate, nitrate, chlorine, and ammonia in
various plating baths can be measured by electrode.
con’t. Typical ISE Applications

Paper and Pulp

• Sodium, chloride, calcium, and sulfide can be determined
by electrode in white, green, and black liquors.

Petroleum Refining Stack Gases

• Ammonia, hydrogen sulfide, hydrogen cyanide, hydrogen
fluoride, and hydrogen chloride gases can be measured
after scrubbing.

• Chloride can be measured at low levels in water used to

desalt crude oil, and mercaptans can be determined in
naphtha and gasoline.
con’t. Typical ISE Applications

Pharmaceuticals
• Fluoride can be measured in vitamins and toothpaste.
Vitamin B1 is determined in various drugs

Sewage Treatment
• Nitrate, ammonia, residual chlorine, nitrite, and Kjeldahl
nitrogen are routinely measured in sewage.

Steam and Power Generation

• Choride levels must be routinely determined in boiler cleaning
solutions, boiler feed water, and other high purity waters.
• Sodium is often used as an indication of contamination.
Residual chlorine measurements are also important.
con’t. Typical ISE Applications

Water

1. Drinking water
• Fluoride is routinely measured in drinking water.
Other parameters frequently measured are total
residual chlorine, nitrite, chloride, and water hardness

2. Natural waters
• Bromide, calcium, chloride, fluoride, nitrate, nitrite,
potassium, silver, sodium, sulfide, and carbonate.

3. Sea water
• Sodium, chloride, fluoride, and nitrate.
 Advantages of Potentiometry

§ Potentiometry has many advantages, the primary one being the range
of concentrations over which it is effective.

For example, pH electrodes generally work best in the pH range

of 2-10. This refers to concentrations between 10-2 and 10-12 M, a
range of 1010!

§ In addition, the method can be used regardless of the color or

turbidity of the solution, is non-destructive and non-contaminating.

§ The method is also very inexpensive, often requiring less than $1000
to obtain all items necessary for measurements.

The on-going expenses are only the calibration standards (which

can be reused) and occasionally replacing an electrode
 Other Exercises

(1) The following cell was found to have a potential

of 0.124 V:
SCE // Cu 2+ (3.25 x 10-3 M) / membrane
electrode for Cu2+
When the solution of known activity was replaced
with unknown solution, the potential was found to be
0.105 V. What is the pCu of this unknown solution?
(pCu = - log [Cu2+] = 3.14)
 Other Exercises
(1) The following cell was found to have a potential of 0.124 V:
SCE // Cu 2+ (3.25 x 10-3 M) / membrane electrode for Cu2+
When the solution of known activity was replaced with unknown solution, the
potential was found to be 0.105 V. What is the pCu of this unknown solution?
(pCu = - log [Cu2+] = 3.14)
SOLN:
0.124 V = K + (0.05916 / 2) log (3.25 x 10-3 M)
0.105 V = K + (0.05916 / 2) log [Cu2+] UNK
, K = 0.105 V - (0.05916 / 2) log [Cu2+]UNK

0.124 V = [0.105 V – (0.05916 / 2) log [Cu2+]UNK ] +

[(0.05916 / 2) log (3.25 x 10-3 M)]

0.124 V – 0.105 V = (0.05916 / 2) pCu + (0.05916 / 2) (-2.488)

 Other Exercises
(1) The following cell was found to have a potential of 0.124 V:
SCE // Cu 2+ (3.25 x 10-3 M) / membrane electrode for Cu2+
When the solution of known activity was replaced with unknown solution, the
potential was found to be 0.105 V. What is the pCu of this unknown solution?
(pCu = - log [Cu2+] = 3.14)
con’t. SOLN:

0.124 V – 0.105 V = (0.05916 / 2) pCu + (0.05916 / 2) (-2.488)

0.019 V = (0.05916 / 2) [pCu - 2.488]

0.6423 V = pCu - 2.488
pCu = 3.1303
 Other Exercises

(2) The following cell was employed for the

determination of pCrO4:
SCE // CrO4 2- (xM) / Ag2CrO4 (s) / Ag (s)
Find the pCrO4 if the cell potential is - 0.402 V
(E0 Ag/Ag2CrO4 = - 0.316 V ; E SCE = 0.241 V)
(pCrO42- = 6.76)
 Other Exercises

(2) The following cell was employed for the determination of pCrO4:
SCE // CrO4 2- (xM) / Ag2CrO4 (s) / Ag (s)
Find the pCrO4 if the cell potential is - 0.402 V
(E0 Ag/Ag2CrO4 = - 0.316 V ; E SCE = 0.241 V) (pCrO42- = 6.76)

SOLN: (pCrO4= 6.76)

(-0.316 V) – 0.241 V = K + (0.05916) log [CrO42-]

-0.557 V = K + (0.05916 ) log [CrO42-]
-0.557 V = K

-0.402 V = (-0.557 V) + (0.05916 ) log [CrO42-]

Other Exercises

(3) A glass / calomel electrode system was found to develop a

potential of - 0.0412 V when used in a buffer of pH 6.00; with an
unknown solution the potential was observed to be - 0.204 V.
Calculate the pH and the [H+] of the unknown.
(pH = 8.69 ; [H+] = 2.05 x 10-9 M
SOLN:
E(pH 6.00) = K - 0.05916 pH6.00

EUNK = K - 0.05916 pHUNK

, K = EUNK - 0.05916 pHUNK

E(pH 6.00) = (EUNK - 0.05916 pHUNK ) – (- 0.05916 pH6.00)

 Other Exercises

con’t. SOLN:

E(pH 6.00) = (EUNK - 0.05916 pHUNK ) – (- 0.05916 pH6.00)

E(pH 6.00) - EUNK = 0.05916 (- pHUNK + pH6.00)

E(pH 6.00) - EUNK = - pHUNK + pH6.00

0.05916

E(pH 6.00) - EUNK

pHUNK = pH6.00 -
0.05916
Other Exercises

con’t. SOLN:

E(pH 6.00) - EUNK

pHUNK = pH6.00 -
0.05916

pHUNK = pH6.00 - [(E(pH 6.00) - EUNK) / 0.05916]

pHUNK = 6.00 - [(-0.0412) - (-0.204 V) / 0.05916]

pHUNK = 6.00 – (2.75)

pHUNK = 4.75
Thank you.