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Education

ple and engaging opportunitytointroduce

the the concept of die weakest link. Options for


die measurement link include gravimetry,
flame emission spectrometry, atomic absorp-
tion spectrometry, volumetric titratton (2))

Weakest and potentiometry. Each method has its as-


sets and liabilities. Students work in teams of
two or three, depending on the level of the
student and the laboratory environment,
and they are either given specific proce-
dures for the determination or asked to

Link
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-

exercise ure 1 shows the overall strategy for this


exercise (3), which is designed for k sam-
ples (for this example, k = 4).

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-

538 A Analytical Chemistry News & Features, August 1, 1999


Figure 1 . Experimental design.

atic versus "grab" sampling by running the


entire experiment twice. The students used
only the grab sample technique.
A three-level nested design based on
duplicates (Figure 1) is used to estimate
the variances caused by sampling, sample
preparation, and measurement (8). Other
sets of variables, such as between labora-
tory, within laboratory, and between ana-
lysts, can be investigated using the same
design. In this experiment, S ^ repre-
sents the four samples (k = 4) taken ran-
domly from a bag of Fritos. After grinding
and crushing, each of the four test sam-
ples are divided into two approximately

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)

Analytical Chemistry News & Features, August 1, 1999 5 3 9 A


Education
Table 1. Titration data.
Sample Mass (g) Titrant % Na d3 Avg d3 (12 Avg tl2
volume (mL)
ferent at the 99% confidence level. This re-
A1a 11.20 13.60 0.324 0.000 0.324
"Alb 11.20 13.60 6.324 0.014 6.317 sult indicates a systematic error in one of
A2a 10.70 12.40 6.309 6.003 6.311 the measurement techniques; however, it
'" A2b 1070 1JL50 6.312 is not possible to determine which tech-
B1a 1l7l'6 18.78 6.451 6.007 6.455 nique from the existing data.
Bib TTJO 19.08 6.458 6.013 6.461 This exercise familiarizes students with
1
B2a I]L20 "§l! 67*37 6.066 6.467 the components of chemical analysis and
B2b 11.26 19.63 6.467
CI a 11.26 17.61 6.419 6.002 6.420 emphasizes the importance of sampling. The
CI b 1120 1770 6.421 6.643 6.442 experimental design and statistical proce-
C2a 1T26 19.69 " 6.469 6.012 6.463 dures allow them to evaluate the impact of
C2b "Tl.26 19.21 6.457 each step on the overall quality of the infor-
Dla lT'26 18.87 6.449 6.664 6.447
mation. The comparison of the different mea-
6Tb 1T26 18.68 6.445 6.071 6.412
D2a 11.20 15.81 6.376 6.001 6.377 surement techniques also reinforces the use
D2b ~~11.20 ~ ~ "15.83 6,377 of statistical methods. Finally, students are
Sin SH Si forced to think about factors that caused unex-
iWxW sJsJW 4M\'W pected results and ways to improve analytical
methods. These experiences are important for
both future analysts and those who will use
Table 2. Comparison of measurement techniques. information from chemical analyses.
Sample Emission ppm Na % Na from % Na from Difference
emission titration
We would like to acknowledge the six students
A1 162.0 4.608 0.411 0.324 0.087 who labored long and hard to make this a mean-
A2 1J8.5" "4T2T8 ' 6.394 6.310 67684 ingful exercise—David Cooper, Nathaniel Dunn,
B1 20276 57357 6.485 67l55 0m0 Marium Holland, Nicole Johnson, Anne McEl-
B2 21176 5.542 6.493 6.467 6.026 haney, and Leonard Rorrer.
ci 18675 57654 6.456 a42o £636
C2 204.0 5.397 6.481 0.463 0.018 Frank A. Settle was a professor at Virginia
D1 19975 57307 6^474 67»47 a027 Military Institute and a program director
D2 17275 4427 6.427 67377 07650 at the National Science Foundatton before
Mean 6.452 67408 6.044" assuming his present position as a professor
Std'dev 0.037 0.063 0.027
at Washington and Lee University. Michael
Pleva is department chair and a professor at
Washington and Lee University. He teaches
with 8,4, and 3 df, respectively. Applying the bution of the salt within the sample, the analytical chemistry and a course on chaos.
Ftest (7) at a 99% confidence level for statis- method of sampling, and the efficiency of Address correspondence to Settle atDept. of
Chemistry, Washington nnd Lee University,
tical differences, ^|lttractA^ieas= 63.9, and the extraction process.
Lexington, VA 24450 (settlef@wlu.edu).
critical F is 8.81 (one tailed 4,8 df). At a 99% Table 2 lists the data for determining
confidence level, there is a difference be- sodium in the eight samples by titration
References
tween the variance associated with measure- and atomic emission. The emission results
(1) Storer, D. A Sample Preparation for Chemi-
ment and sample preparation, or sJ,™ / represent the average of duplicate mea- cal Analysis; Terrifif Science Press, Miami
s
meas= 259.0, and critical F is 9.60 (one tailed surements. The two measurement tech- University Press: Middletown, OH, 1998.
3,8 df). Thus, at a 99% confidence interval, a niques can be compared using the paired (2) Harris, D. Quantitative Chemical Analysis,
5th ed.; W. H. Freeman Co.. New York,
statistical difference exists between the vari- t test (5), in which the null hypothesis says 1998; 165-66.
ances for measurement and sampling. that no difference between the two means (3) Taylor, J. Statistical Techniques for Data
The magnitudes of the variances indicate (i.e., ud = 0) exists. The mean of the differ- Analysis; Lewis Publishers, Inc.: Chelsea,
MI, 1990; 50-56.
that the sampling is the weakest link. If sam- ences (ard) is 0.044, and the standard devia- (4) Schwedt, G. The Essential Guide to Analyti-
pling can be improved, then attention can be tion of the differences (sd) is 0.027. Be- cal Chemistry; John Wiley and Sons: New
devoted to the extraction process. The data cause ud = 0, York, 1997; 18-21.
(5) Dean, J. Analytical Chemistry Handbook;
indicate that percentages reported at 95% McGraw-Hill, Inc.: New York, 1995; ;.1-1.44
confidence limits for sodium (0.408 ± 0.056% t = {x& \ri) /sd (8) (6) Benedeni-Pichler, A. In Physical Methods for
by titration and 0.452 ± 0.033% by flame emis- Chemical Analysis; Berl, W., Ed.; Academic
Press: New York, 1956; Vol. .; 183-217.
sion) were lower than the value on the label From the data, the calculated value for (7) Laitinen, H. A; Harris, W. E. Chemical
of the Fritos bag (0.57%). This is not surpris- t is 4.58. The critical t value at 99% confi- Analysis; ;2d ed.; McGraw-Hilll New York,
ing in view of the large variances associated dence is 3.50 for 7 df. Therefore, the null 1975; Chapter 27.
(8) Miller, J. C; Miller, J. N. Statistics for Ana-
with sampling and extraction. Factors con- hypothesis is rejected, and the results from lytical Chemistry, 2n2nd.e Ellis Horwood:
tributing to these differences are the distri- the two measurements are statistically dif- New York, 1992; Chapter 3.

5 4 0 A Analytical Chemistry News & Features, August 1, 1999

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