Procedure for determining the concentration of BARIUM
(Ba++) in WATER
NOTE: The barium electrode is interfered with by several ions which are constituents of the most commonly used ISABs so there is no recommended ISAB for this ion and the best results will be obtained using the Standard Addition method (or Sample Addition for samples with >100 ppm Ba) rather than direct potentiometry. Furthermore, best results are obtained by measuring in still (not stirred) solutions using the following procedure:
1) After removing the electrodes from a previous solution, rinse with a jet of deionised water and dry gently with a paper towel.
2) Immerse the electrodes in pure water for about 30 seconds (or until mV are lower than lowest standard) then remove and dry again before immersing in lowest concentration standard (or next sample) - so all equilibration and "memory" effects are approached from the same direction.
3) After immersion, manually swirl beaker for about 30 seconds - or until mV are stable ± 1mV.
4) Leave to stand still and watch mV fall until stable or until start to rise again - this normally takes less than 2 mins for 10 ppm and above - upto 5 mins for less than 1 ppm.
5) Take mV reading at lowest point
6) Remove electrodes from solution and repeat from 1) with higher concentration standards or next sample.
Apparatus Required:
Ion-Selective Electrode for Barium ion (ELIT 8081 PVC membrane)
Reference electrode: single junction silver chloride (ELIT 001)
Dual electrode head (ELIT 201)
Standard solution: 1000 ppm Ba as BaCl2
ELIT Computer Interface/Ion Analyser, or Ion/pH/mV meter.
100 or 150 ml polypropylene beakers, 100ml volumetric flask, 1, 2, 5, 10ml
pipettes.
Calibration
Before use, the electrodes must be Pre-conditioned by soaking in 1000 ppm Ba for at least 5 mins if the electrodes are in regular use or preferably overnight or even longer on first use or after a prolonged rest. If the sample concentration is completely unknown then an initial calibration must be made by measuring say 1, 10, 100, 1000 ppm standards and finding the slope in the conventional manner. This can then be used to measure a few representative samples by Direct Potentiometry. Once the concentration range expected for the samples is known then a more precise calibration can be made
under the current operating conditions and in the appropriate range by making up a standard with approximately the same concentration as the samples and analysing it by the Standard Addition method, then adjusting the slope and recalculating using the ELIT software until the calculated concentration is correct. If samples have a wide range of concentrations, over several orders of magnitude, then it may be necessary to use different standards for each decade of concentration to ensure the most accurate slope determination.
Standard Selection
Enter the electrode slope and expected sample concentration and volume into the Standard Addition (or Sample Addition) software to calculate an appropriate standard concentration and volume. Make up the calculated standard concentration by serial dilution of the 1000ppm standard.
Sample Measurement
1) Pipette the pre-determined sample volume (usually 50 or 100ml) into a beaker,
immerse the electrodes, manually swirl the solution then leave to stand still and watch as the voltage falls to a stable value or starts to rise again. Record the stable voltage or the lowest value before it starts to rise again.
2) Add the calculated volume of standard and swirl or stirr well until a roughly stable reading indicates that two solutions have completely mixed. Then wait with still solution (switch off stirrer, if used) for a new stable voltage or reversal of drift (when the electrodes have re-equilibrated) and record the second reading.
The software will then calculate the sample concentration and give an estimate of the quality of the determination - if the sample concentration is very different from the expected value then you will be prompted to make a second measurement using a more appropriate volume or concentration of standard.