Arc. Hill et C. Von Holst, A comparison of simple statistical methods for estimating analytical uncertainty, taking into account predicted frequency distributions, ANALYST, 126(11), 2001, pp. 2044-2052
Error in chemical analysis is propagated mainly by multiplication (not addi
tion) of random, systematic and spurious errors. Individual random errors t
end to have symmetrical frequency distributions but their combined error di
stribution has a positive skew. Certain systematic errors (bias) conceivabl
y could have frequency distributions which would enhance or lessen the over
all skew but they are unlikely to produce a truly normal distribution. Each
analytical method, or modification of it, may produce a unique frequency d
istribution of results. Hence an ideal general statistical treatment of res
ults cannot exist and the best practical compromise should be utilised. Thr
ee simple statistical treatments of data produced from various analytical m
odels were compared, to identify the best compromise. Conventional statisti
cs, with no transformation of data, generally treated low results too favou
rably and high results too harshly. Prior transformation of results to loga
rithms tended to do the reverse. Transformation of results to factors, foll
owed by derivation of a robust standard deviation, treated the extremes mor
e equally, if somewhat harshly. Factor statistics for precision have low se
nsitivity to outliers and the assigned true value and they offer a good com
promise for the description of analytical data.