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0 International Labmate Feature

A Rapid, Accurate and Simple


Coulometric Method for C & S
Analysis

Accurate and precise determination of carbon and sulphur, bustion products of the carbon or sulphur content in the
especially when present at high levels in diverse sample sample are then quantitatively absorbed in the electrolyte
matrices, are analytically challenging requirements. of the coulometric titration cell through employment of a
Author Quality control of product materials often requires high high-speed gas dispersion stirrer.
accuracy. Although the coulometric technique finds appli- The detection principle is based upon the change of pH
Jrgen Behr cation with even small amounts of analyte, the accuracy, in the titration cell, which results from the dissolution of
precision and simplicity of coulometry are unrivalled at the CO2 or SO2. In the case of SO2, hydrogen peroxide is
behr Labor-Technik GmbH
high analyte contents. used to oxidise the SO2 to sulphuric acid, which produces
Dsseldorf Coulometry, being an absolute method based on a pronounced pH alteration. A glass electrode with built-in
Faradays Law, does not require calibration with reference reference is used to detect the pH deviation. Response
Germany standards. The ability of modern electronics to accurately time is enhanced, while sensitivity to electronic interfer-
measure and integrate current-time functions permits ence and electromagnetic perturbation is minimised by
coulometry to be applied even with relatively small use of a preamplifier mounted directly on the pH electrode.
amounts of sample material [1,2,3,4,5]. Coulometry finds Since the potential of the pH electrode is temperature
application in micro and trace analysis of elements such as dependent, the temperature of the titration cell is water-
C, H, O, Cl, Br, I and S in organic and inorganic matrices. jacketed for maintenance of temperature constancy. In
Indeed, the coulometric titration of carbon has been addition to the pH electrode, the titration cell is provided
increasingly accepted as the method of choice in numer- with a platinum cathode. The cathodic electrode reactions,
ous applications [6,7,8,9]. Coulometric analysis is excel- which proceed at 100% current efficiency in the elec-
lently suited to the determination of total carbon in the fol- trolytes utilised are:
lowing sample materials:
silicon carbide and tungsten carbide 2H2O + 2e- 2OH- + H2 (1)
ferrous and non-ferrous metals 2H3O+ +e- 2H2O + H2 (1a)
cement
soil for the carbon determination.
ceramic materials
minerals Thus, the cathodic electrode reaction is used to quantita-
coal, etc. tively neutralise the alkalinity shift produced by the disso-
total carbonate and non-carbonate carbon in sedimenta- lution of the carbon dioxide.
ry rock [10]. The platinum anode, at which the oxidation reaction pro-
ceeds, is separated from the titration cell by a ceramic
A typical coulometric system, applicable to determination diaphragm, which prevents intermixing of the electrolytes
of both carbon and sulphur, consists of a high temperature in the two cells.
furnace, a microcoulometric current controller/current-time
integrator, a sensitive indicating electrode as detector and
associated computational and data storage capabilities
(Fig. 1).
It is important that the determination
of carbon and sulphur is accurate and
precise, to meet stringent quality
control demands. Coulometry is a
versatile and simple method of
determination; small amounts of
analyte can be used, but it is also
suited to high analyte contents.
Figure 1: A typical coloumetric system
This article examines the
A furnace for a system designed for both carbon and sul-
coloumetric process and looks at a phur analyses contains two separate combustion tubes for
each analyte, as well as an internal combustion tube for
coulometric method, used for the pre-purification of the oxygen supply. Carbon or sulphur Figure 2: Diagrams showing the process
samples are typically combusted in the respective furnace
analysis of both Carbon and Sulphur. tube at a temperature of 1,350 C in an oxygen stream. At the start of determination, the pH within the titration
Excess oxygen exiting from the sample insertion port pre- cell (Fig. 3) is adjusted automatically to a specified initial
vents the entry of atmospheric CO2 into the furnace. On value. For carbon analysis, a basic pH of approximately 10
exiting the furnace, the combustion gases are passed is employed. This initial pH is exactingly established elec-
through dust traps and reagent tubes, which remove mois- trolytically, and exactingly measured by the pH electrode.
ture and interferants (CO2 would interfere in the sulphur The amount of electricity (in Coulombs, determined as the
Sue Fakes determination and oxides of sulphur would interfere in the integral of titration current over time) required to restore
ILM Features Editor carbon determination). The CO2 or SO2 produced as com- the pH to its initial value, after the deviation resulting from
Feature International Labmate 0

It is thus evident that the carbon or sulphur analytes in be used to optimise the combustion process. Realisation
absorption of the combustion gas, is directly proportional
the samples, which are quantitatively converted to their of these possibilities by means of software programming is
(Faradays Law) to the mass of CO2 or SO2, which has dis-
respective oxides, result in an acidic shift of the pH in the in development at the present time.
solved in the titration cell. A simple stoichiometric compu-
titration cell electrolyte. By means of the electrolysis reac- The software used for operation of the instrument, the
tation then enables calculation of the percentage of carbon
tions (1), the pH can be restored exactly to its initial value. signal processing, data computation and display as stor-
or sulphur in the sample mass.
The amount of carbon or sulphur in the sample is then age of analysis findings development of measuring data
obtained from the coulometric current-time integral. operates under Windows 98 as well as Windows NT
Coulometric analysis conducted under conditions of 4.0. Other commercially available application software
100% current efficiency is an absolute method and as operating under Windows, such as data base or spread-
such requires no calibration. Nonetheless, for quality con- sheet programs, can be used for
trol purposes, the accuracy and precision should be veri- data management and recording,
fied using reference standards. For the carbon determina- statistical analysis.
tion, calcium carbonate is well suited as a standard, while GLP control
for the sulphur determination, silver sulphate is LIMS
recommended.
The coulometric procedure using a ceramic tube furnace The system conveniently allows for the direct communica-
has been successfully applied to the determination of tion of the sample weight from the analytical balance to
sulphur in the computer by means of a serial cable.
oils, greases, petrochemicals Optionally, the high temperature (max. 1,550 C) ceram-
ferrous and non-ferrous metals ic tube furnace can be replaced by an infrared quartz-tube
plastics furnace (max. temp 1,100 C) coupled to a two-zone down-
raw materials and natural products containing sulphur, stream resistance furnace. The IR furnace has rapid heat-
such as wood,etc. ing rates and enables execution of temperature-time pro-
The electronic and control unit of the coulometer consists grams (a sequence of up to five increasing temperature
of gradients and five temperature plateaus are freely pro-
a very precise pH detection system, grammable). The infrared furnace requires no cooling
a digitally controlled current source, water for operation. Rapid cooling by means of heat pipes
a coulometer (for integration of the titration current-time enables the furnace to return to room temperature within
curve), and minutes after completion of a program which ran to maxi-
a combustion-gas pump and gas splitter, the operation mum temperature. The downstream constant temperature
of which is coupled to the pH in the titration cell. resistance furnaces ensure complete oxidation and
removal of interferences in various applications, such as
The potential of a glass pH electrode is used as a signal to the determination of
control the level of titration current and to detect the titra- TC,TIC and TOC in aqueous, sludge and solid samples
tion end point. A preamplifier is mounted directly atop the organic components in dust
glass electrode to enhance response time and minimise Diesel soot and motor emissions in accordance with the
effects of electromagnetic perturbations. The analog out- German standard methods
put of the preamplifier is digitalised in a 20 bit A/D con- Compliance with workplace air safety standards through
verter and then input into the micro-controller. determination of carbon compounds and elemental car-
The titration current is regulated quasi continuously (in bon (particulate) content
256 constant-current steps) and controlled by a PID-con- adsorbable organically bound carbon in exhaust gases.
troller. The PID parameters are user-programmable by
means of system software installed in a conventional PC. General technical characteristics:
Integration of the titration current is performed by means
Figure 3: Graph of pH against Charge (mC)
of a 16 bit processor within the controller module. The Analysis time: typically 2-5 minutes, depending on
same micro-processor also controls A/D converters, the weight and nature of sample
The electrolyte employed for the carbon determination is a Analytical range Carbon: 5 ppm 100%, depending on
current source and the initial processing of raw data. The
barium perchlorate solution. On introduction of the carbon sample weight
completion of the computations and display of the analysis
dioxide into the cathode chamber of the titration cell, the Sulphur: 10 ppm 10%, depending on
parameters and findings in both numerical and graphical
following reaction leads to a decrease in the cell pH: sample weight
form is done by a personal computer.
The following four analytical parameters may be option- Precision better than 0.05%
Ba2+ + CO2 + 2OH BaCO3 + H2O (2)
ally displayed as functions of time on the monitor: (Fig. 4).
Ba2+ + CO2 + 3H2O BaCO3 + 2H3O+ (2a)
References
The electrolyte employed for the sulphur determination is [1] Lingane, J.J., Anal. Chem.26 (1954), 522-626
a sodium sulphate solution containing hydrogen peroxide, [2] Abresch,K., Claasen, J., Die Coulometrische Analyse,
which has been adjusted to an initial pH of approximately Weinheim, 1961
4. On dissolution in the titration cell (cathode chamber), [3] Ehrenberger, F., Quantitative Organische
the sulphur dioxide is converted to sulphuric acid accord- Elementaranalyse. VCH, Weinheim 1991, New York,
ing to the following equation: Basle, Cambridge
[4] Kupka, J.,Luitjens, M.,Grinewitschus, V., Dalsa, K.,
Fresenius Z. Anal. Chem. 347 (1993), 87-91
SO2 + H2O2 H2SO4 (3)
[5] Luitjens, M., Kupka, J., Gherban, D., Baumgarten, E.,
Fresenius Z. Anal. Chem. 357 (1997), 592-592
The corresponding reduction on the cathode electrode pro- [6] Staats, G., Fresenius Z. Anal. Chem. 731 (1984),
ceeds according to equation (1), so that electronically gen- 761-764
erated sodium hydroxide tends to change the pH of the [7] Frank, D., Staats, G., Fresenius Z. Anal. Chem. 327
solution until the initial value is reached. Figure 4: Four analytical parameters displayed as functions of time (1987), 456-460
Within the anode chamber, the complementary reaction [8] Kupka, J., Lottmann, J., Stremming, H., Stahl u. Eisen
to equations (1) and (1a) proceeds at the platinum the pH at the start of the analysis. The value may be 113 (1993) No. 9, 121-124
electrode: specified by the user by entry into the computer pro- [9] Ohnemller, W., Solf, A., Zement-Kalk-Gips 59 (1973),
gram. The value actually achieved will be displayed. 200-202
[10] Herrmann, A. G., Knacke, D., Z. Anal. Chem. 266 (1973)
3H2O 2H3O+ + 1/2O2 + 2e (4) the real-time pH-value in the titration cell
196-201
2OH H2O + 1/2O2 + 2e 4a) the titration current
the mass of analyte, and optionally
for the carbon analysis. Reaction (4) also takes places the temperature of the combustion furnace.
within the anode chamber of the sulphur apparatus.
A solid phase of barium carbonate within the anode A mathematical treatment of the time-dependent rate of
cell is used to neutralise the ions H3O+ arising according analyte mass flow into the titration cell offers the prospect
to eq. (4). Similarly, in the case of sulphur determination of employing the coulometric analyser for online determi-
the acid H2SO4 is precipitated by means of ZnO to ZnSO4 nations [4]. Furthermore, evaluation of the analyte mass
in order to maintain the pH within the cell at a constant flow as a function of time discloses useful information per- International Labmate Ltd
level. taining to the process of sample combustion, which may

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