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Determination of anions in the primary circuits of nuclear or conventional power plants

IC System Setup

For this application the «MIC-6 Advanced» is used: a modular anion system with chemical suppression, sample preconcentration and matrix elimination, extended by matrix neutralization, 800 Dosino, Metrosep I Trap 1 and transfer tubing.

A total of five «MISP» techniques are used:

The composition of the sample corresponds to the water used in the primary circuit, and contains 2.5 g/L boron, added in the form of boric acid. This high concentration makes inline matrix elimination necessary. This is carried out by rinsing the anion preconcentration column with ultrapure water before the sample is injected.

 

Calibration

For anion determinations the calibration values are selected so that the whole of the expected concentration range is covered. The linearity of the inline calibration is excellent. The coefficients of correlation for all anions are
> 0.9999.

 

Anion Measurement

For measurements, a 2000 µL sample is preconcentrated. The preconcentration volume depends on the expected concentrations and the matrix. For measurements in the lower ppt range (singledigit ppt), more than 100 mL sample can be preconcentrated. Particular attention is given to the separation between fluoride and the rapidly eluting anions glycolate, acetate and formate. The
Metrosep A Supp 7 – 250 column is used, which separates these anions from the other standard anions in an isocratic run.

No. Ion Concentration
1 Fluoride 20.21
2 Glycolate 3.36
3 Acetate 9.67
4 Formate 3.10
5 Chloride 25.51
  Carbonate -
6 Nitrite 10.73
7 Bromide 0.20
8 Nitrate 22.32
9 Phosphate 17.79
10 Sulfate 69.65

anions in the primary circiut of a nuclear power plant
Column: Metrosep A Supp 7 - 250
Eluent: Sodium carbonate eluent
Sample: from the primary circiuts of a nuclear power plant
Concentration: ppb - µg/L
Preconcentration volume: 2000 µL

 

Data Security

In accordance with the requirements, methods can be validated and checked. Most statistical methods can be easily implemented and are supported by the Metrodata IC Net software: determining blanks, spiking, reproducibility, recovery rate, variability of the retention times, etc.

To check the present measurements, four different volumes – 500, 1000, 1500 and 2000 µL – were preconcentrated and a three-fold determination carried out on each. The blank value was determined and subtracted. The data was then used to check the linearity and reproducibility of the analysis. Metrohm inline calibration with fixed sample loop, the use of only one standard solution and the extraordinary precision of the 800 Dosino provide excellent results; both under normal laboratory conditions and under the rough conditions prevailing in the power plant turbine room.

Carryover

Samples, standards, regeneration and transfer solutions partly use the same tubing within the IC system. Particular attention has been given to keeping carryover within the system negligible.

Air bubble: As simple as effective: a defined volume of air is aspirated between different liquid portions and transferred through the tubing system. Even this simple step significantly reduces carryover.

Rinsing the sample needle: In order to prevent carryover caused by the sample needle, it is assigned a special position by the sample changer and thoroughly rinsed both inside and out with a freely selectable rinsing solution. If the risk of carryover is insignificant, it is sufficient to rinse the needle at one of the three special positions on the sample rack. Liquid handling during the rinsing process is carried out by the 800 Dosino.

Rinsing the flow path: The 800 Dosino is used to rinse the complete flow path of the system that comes into contact with the sample. This is normally done with ultrapure water, but solvent-water mixtures can also be used as the whole system is solvent-resistant.

The longer the rinsing with ultrapure water, the lower the carryover from sample to sample. Even in normal operation with rinsing times of two minutes, the carryover between two samples is below 0.3%. If ultrapure water is injected a second time then the carryover is less than one part per thousand.

 

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