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  • Title: Accurate calibration of mercury vapour measurements.
    Author: Brown RJ, Brown AS.
    Journal: Analyst; 2008 Nov; 133(11):1611-8. PubMed ID: 18936841.
    Abstract:
    Almost all measurements of mercury vapour, for example those to determine mass concentration in air, are currently ultimately traceable to the vapour pressure of mercury, usually via a bell-jar calibration apparatus. This allows a saturated concentration of mercury vapour in air to develop in a confined space in equilibrium with ambient conditions, from which a known mass of mercury can be removed for calibration purposes. Setting aside the uncertainty in the vapour pressure of mercury at a given temperature, the accuracy of vapour phase mercury determinations depends critically on fully understanding the operation and sensitivities of the mercury bell-jar apparatus. This paper discusses the thermodynamic and kinetic considerations that must be taken into account when using the bell-jar apparatus, provides the theoretical basis for understanding the operation of the bell-jar, and presents experimental data demonstrating the systematic biases which may be obtained if the bell-jar is used incorrectly. These biases depend on the temperature difference between the mercury vapour in the bell-jar and the syringe used to remove the mercury vapour from the bell-jar, but they may be well in excess of 10% under some operating conditions. The results from this study have been used to propose best practice solutions for mercury vapour calibrations using the bell-jar.
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