Polarographic Analyzer:

- Also refered to as “polarographic oxygen sensor” or “Clark Cell”

- Both anode (typically silver) and cathode (typically gold) are soaked or immersed in aqueous
electrolyte of potassium chloride.
- Electrodes are separated by a semi – permeable membrane that allows the mechanism to
diffuse oxygen into the sensor.
- Silver anode is typically held at a potential of 0.8V (polarizing voltage) with respect to the
gold cathode.
- Molecular oxygen is consumed electrochemically with an accompanying flow of electrical
current directly proportional to the oxygen concentration based on Faraday’s law.
- The current output generated from the sensor is measured and amplified electronically to
provide a percent oxygen measurement.

Advantages:

- While inoperative, no consumption of electrode occur.

- Indefinite storage times
- Not position sensitive

Disadvantages:

- For gas phase, sensor is only suitable for % level oxygen.

- Has a relatively high sensor replacement frequency.

Coulometer

- Device to determine electric charges.

- The term comes from the unit of charge, the coulomb.
A. Electronic Coulometer:
- Based on the application of the operational amplifier in the "integrator"-type circuit.
- The current passed through the resistor R1 makes a potential drop which is integrated by
operational amplifier on the capacitor plates; the higher current, the larger the potential
drop.
B. Electrochemical coulometers:
 Copper Coulometer
 Consists of two identical copper electrodes immersed in slightly acidic pH-
buffered solution of copper(II) sulfate.
 Passing of current through the element leads to the anodic dissolution of the
metal on anode and simultaneous deposition of copper ions on the cathode.
 These reactions have 100% efficiency over a wide range of current density.
 Mercury Coulometer
 Consists of two reservoirs connected by a thin graduated capillary tube
containing a solution of the mercury(II)-ions.
 Each of the reservoirs has an electrode immersed in a drop of mercury.
Another small drop of mercury is inserted into the capillary.
 When the current is turned on, it initiates dissolution of the metallic mercury
on one side of the drop in the capillary and deposition on the other side of
the same drop. This drop starts to move.
 Because of the high efficiency of the deposition/dissolution of the mercury
under the current influence, the mass or volume of this small drop is
constant and its movement is linearly correlated with the passed charge.
 If the direction of the current is changed, the drop moves in the opposite
direction. The sensitivity of this type of coulometer depends on the diameter
of the capillary.
 Hofmann Voltameter
 Apparatus for electrolyzing water, invented by August Wilhelm von Hofmann
(1818–1892) in 1866. It consists of three joined upright cylinders, usually glass.
 The inner cylinder is open at the top to allow addition of water and an ionic
compound to improve conductivity, such as a small amount of sulfuric acid.
 A platinum electrode is placed inside the bottom of each of the two side
cylinders, connected to the positive and negative terminals of a source of
electricity.
 When current is run through Hofmann's voltameter, gaseous oxygen forms
at the anode and gaseous hydrogen at the cathode. Each gas displaces water
and collects at the top of the two outer tubes.
References:

https://en.wikipedia.org/wiki/Coulometry

https://aoi-corp.com/articles/oxygen-sensor-types/