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develop their own.
The snacks are sampled directiy from
the bag or box, and the sodium chloride is
extracted from the samples into an aque-
ous solution. The design of the experiment
is intended to isolate the variance for each
step. The students also compare the results
from two of the measurement techniques
to see whether they differ statistically. Fig-
In the lab
The issue of obtaining a representative sam-
Imagine that you have been assigned the quality of the data can be no better than the ple is significant In heterogeneous materi-
task of determining the concentrations of least precise operation in the method; thus, als, the variance associated witii die sam-
heavy metals in a heterogeneous sample while the precision of the measurement may pling component is expected to be die larg-
such as a railcar-load of coal or incinerator be high, the overall data quality may be est source of uncertainty in an analytical
waste. A powerful, computer-controlled, in- much lower because of imprecise sampling metiiod. The procedures for sampling solid
ductively coupled plasma-optical emission or sample preparation techniques. materials include considerations of the mini-
spectrometer (ICP-OES) is available for the The goal of the current exercise is to mum mass, particle size, and sample split-
measurement. However, obtaining useful identify the weakest or least precise opera- ting (4-7). A possible variation of this sxer-
data also means taking representative sam- tion in an analysis and evaluate ehe magni- cise would be to study the effects of system-
ples and preparing them for measurement tudes of the variance for each of the three
while preserving their integrity (i). operations. Variance, which is the square of
Chemical analysis involves three major the standard deviation (s2), is used because,
operations—sampling, sample preparation, unlike standard deviations, variances are
and measurement This educational exercise additive. Thus, the variance of a method is
is designed to emphasize me importance of die sum of the variances of its component
sampling. Although powerful instrumental operations: Variance (total) = Variance (sam-
techniques such as ICP-OES tend to focus pling) + Variance (sample preparation) +
attention on measurement, the other two Variance (measurement). Once the values of
operations are also critical to die quality of the variances for the component operations
the data obtained from the analysis. The are known, the weakest link can be identi-
fied, and efforts to improve the overall preci-
Frank A. Settle sion of die metiiod can be undertaken.
Michael Pleva Determining the sodium content of
Washington and Lee University salted snack foods provides a relatively sim-
4=2X/2* (2)
equal portions labeled a and b and the component variances will not be equal to
of each of the eight (2k) portions is die variance of the averages in Table l's
obtained with 4 df. This value of sn contains botii the right-hand column.
Each portion is extracted with water, fil- sample preparation and the measurement When die values for s ^ , , s^^^, and
s
tered, and diluted in volumetric flasks of the effects. In fact, meas n a v e Deen determined, students ask
appropriate volume to give samples Vla, Vlb, tiiemselves, "Are these values statistically
V2a, etc. This volume, based on the percent- S
II= S extract+ ' S meas '^' *• ) different?" The answer is found by calculat-
age of sodium stated on the snack food's ingtiieF ratio of any two variances. By con-
label, should give a reasonable concentration The "2" in the denominator of die s^,eas vention, die larger variance is divided by die
of sodium for the measurement and provide term takes into account the facttiiattwo smaller andtiiencompared widi die appro-
the quantity necessary for replicate measure- titration values were used to generate one priate tabular F value. The degrees of free-
ments. The sodium percentages are repre- value for an average of the percent sodium. dom of each variance are used to determine
sented as Ala, Alb, A2a, A2b, Bla, Bib, etc. The differences oftiieseaverages are used die appropriate value from the table. If die
A data set from silver nitrate titrations (Table to determine die variance associated widi calculated F ratio exceeds die tabular F
1) illustrates die procedure for recording sample preparation. value,tiiendie null hypothesis (no differ-
and processing die 16 measurements. The Finally, die variance for level I is deter- between die two variances at die stated
sodium content in a subset of the samples mined by replacing each pair of die eight confidence level) is not valid and wf1 cfin sflv
(Table 2) also determined by flame averages in Table 1 witii four averages. The tiiat die variances sre etatistically different at
emission spectrometrv variances from all component operations— the specified confidence level After checking
sampling, sample preparation, and mea- all differences in this manner the process widi
Determining variances surement—are nested in sf the larsest variance is the least nrecise and
The variance associated with level III (mea- thus is tde weakest link in the anatvsis
surement by titration) is determined first S S S S
I = samp+ ' extract/ *> + ' meas' *' *• )
by using values from the 16 titrations, Ta- And t h e w e a k e s t link is...
ble 1, and with 3 df. The "2" and "4" in the denomina- Table 1 contains the titration data from the
tors of die second and third terms of Equa- experimental design outiined in Figure 1.
tion 4 take into account the number of val- From die statistical procedure described in
ues required to calculate one value in Table the preceding section,
with 2k degrees of freedom (8 df). Column l'sright-handaverage column. Inciden-
d3 in Table 1 contains die differences be- tally, the best estimate of the percentage of s mea s=S]j] = 1.39x 10 (5)
tween the averages of the duplicate titra- sodium in die sample is the average of the
tions of samples Via and Yib. 4 final averages, which corresponds to the ^extract= Sj] -(•S me as/2) = 8.oo x W (6)
When die variance associated with die overall average of die 16 separate titrations
measurement is known, the variance for in level III. Note that the metiiods for calcu- Ssamp"" S I —
^extract' ' -
level II can be determined using lating variances mean that the sum of the (S m e a s/'*) = 3.W X ID (7)