Section 8 : Measurement of Sulfur in Solid and Liquid Samples (TSX-S MODE)

Section 8 : Measurement of Sulfur in Solid and

Liquid Samples (TSX-S MODE)
This section covers procedures for measuring sulfur in solid and liquid samples.
8-1. Measurement Principles
8-1-1. Combustion
Insert the weighed sample in the Sample Boat slowly into the Pyrolysis Tube through the Sample
Inlet Port in the Argon flow.
The sample is vaporized at high temperature and chlorine is converted into hydrogen chloride.

X (Cl)
Combustion in Oxygen flow

HX (HCl Cl2) S
SO2 > SO3

These product gases are dehydrated and cleaned in the Dehydrating Tube with the Argon / Oxygen
carrier and are introduced into the Titration Cell.

8-1-2. Titration
The electrolysis current in this analyzer, which is controlled to keep a preset electrolytic potential
(End point potential: End Point), flows to the Agar-less Working Electrode - Counter Electrode.
Before sulfur dioxide is introduced into the cell, the electrolytic potential ( E ) is kept automatically
at the end point potential and is equilibrated as shown by Equation 8-1 against the potential shown
by Equation 8-2.

E = E0 + RT / nF ln I3- / I- ( Equation 8-1 )

E0
n
R
F
T

: Standard oxidation-reduction potential

: The number of electrons which contribute to electrode
: Gas Constant
: Faraday Constant
: Absolute Temperature

3I-

I3- + 2e-

( Equation 8-2 )

When sulfur dioxide is introduced into the cell, the reaction shown by Equation 8-3 occurs and the
potential changes according to Equation 8-1.

SO2 + I3- + H2O

SO3 + 3I- + 2H+ ( Equation 8-3 )

8-1

Section 8 : Measurement of Sulfur in Solid and Liquid Samples (TSX-S MODE)

When the potential changes, electrolysis current is applied to the working electrode to generate
triiodide ions ( I3 ) from the Working Electrode and titration is run. (Equation 8-4).

3I-

I3- + 2e-

( Equation 8-4 )

When titration proceeds and the potential returns to the end point potential, the electrolysis current
equilibrates to the blank current and titration is completed.
From the electric energy used for this titration, the quantity of Sulfur (g-S) is digitally indicated
based on Faradays Law.

Quantity of Sulfur (g -S) = (32.06 / 2) (Q / 96487) = 1.661 10-4 Qt

( Equation 8-5 )

8-2

Section 8 : Measurement of Sulfur in Solid and Liquid Samples (TSX-S MODE)

8-3-3. Setting of electrodes

1 Set electrodes to cell cap and connect their terminals to each connector.
* Positive terminal and negative terminal forms are same. Therefore, insert the same color
connector.

2 Set stirrer rotation speed knob (SPEED). Set the scale to 4.

Illustration 8-7. Preparation of the Working Electrode / Counter Electrode