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Evaluating Analytical Data

Characterizing Measurements and Results

Mean 𝑿, is the numerical average obtained by dividing

the sum of the individual measurements by the number
of measurements

x1  x2  ...  xn

n

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Characterizing Measurements and Results

Median (𝑋med).
The data from the smallest to the largest value
3.056 3.080 3.094 3.107 3.112 3.174 3.198 the median is
3.107
Range
Range = w = Xlargest – X smallest

Characterizing Measurements and Results

Standard Deviation

Relative standard deviation

SD
% RSD  x100
xmean

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Characterizing Measurements and Results

Example 1: What are the standard deviation, the

relative standard deviation, and the percent relative
standard deviation for the data 3.056 3.080 3.094 3.107
3.112 3.174 3.198

Variance: The square of the standard deviation

Characterizing Experimental Errors

Accuracy
Accuracy is usually expressed as either an absolute error
E = X–µ

Determinate error: can be traced to an identifiable

source.

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Characterizing Experimental Errors

 Sampling error An error introduced during the

process of collecting a sample for analysis.
 Heterogeneous Not uniform in composition.
 Method error An error due to limitations in the
analytical method used to analyze a sample.
 Measurement error An error due to limitations in the
equipment and instruments used to make
measurements
 Tolerance The maximum determinate measurement
error for equipment or instrument as reported by the
manufacturer.

Precision

hight low

low
precision
and
accuracy

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Precision

 Repeatability The precision for an analysis in which

the only source of variability is the analysis of
replicate samples.
 Reproducibility The precision when comparing
results for several samples, for several analysts
or several methods.
 indeterminate error Any random error that causes
some measurements or results to be too high
while others are too low

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Sources of Indeterminate Error

Can be traced to several sources,

- The collection of samples,
- The manipulation of samples during
- The analysis
- The making of measurements

Evaluating Indeterminate Error

Indeterminate errors may be estimated by an appropriate

measure of spread

Uncertainty The range of possible values for a

measurement
Uncertainty When Adding or Subtracting
the equations R = A + B + C or R = A + B – C, or
any other combination of adding and subtracting A, B,
and C, the absolute uncertainty in R is

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Example

The class A 10 mL pipet characterized in Table 4.2 is used

to deliver two successive volumes. Calculate the absolute
and relative uncertainties for the total delivered volume.
SOLUTION
The total delivered volume is obtained by adding the
volumes of each delivery; thus Vtot = 9.992 mL + 9.992
mL = 19.984 mL Using the standard deviation as an
estimate of uncertainty, the uncertainty in the total
delivered volume is

Example

Thus, we report the volume and its absolute uncertainty

as 19.984 ± 0.008 mL.
The relative uncertainty in the total delivered volume is

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Uncertainty When Multiplying or Dividing

The equations R = A × B × C or R = A × B/C, or any other

combination of multiplying and dividing A, B, and C, the
relative uncertaintyin R is

Example
The quantity of charge, Q, in coulombs passing through
an electrical circuit is Q = I × t
where I is the current in amperes and t is the time in
seconds. When a current of 0.15 ± 0.01 A passes
through the circuit for 120 ± 1 s, the total charge is Q =
(0.15 A) × (120 s) = 18 C
Calculate the absolute and relative uncertainties for the
total charge.

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SOLUTION
Since charge is the product of current and time, its
relative uncertainty is

The absolute uncertainty in the charge is

sR = R × 0.0672 = (18) × (±0.0672) = ±1.2
Thus, we report the total charge as 18 C ± 1 C.

Confidence Intervals for Populations

Confidence interval Range of results around a mean value

that could be explained by random error

true mean value

population’s variance,

confidence interval

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Example
 What is the 95% confidence interval for the amount of
aspirin in a single analgesic tablet drawn from a
population where µ is 250 mg and σ2 is 25?
 SOLUTION
The 95% confidence interval for a single member of a
normally distributed population is
Xi = µ ± 1.96σ = 250 mg ± (1.96)(5) = 250 mg ± 10 mg
Thus, we expect that 95% of the tablets in the
population contain between 240 and 260 mg of aspirin.

Confidence Intervals for Populations

 Degrees of Freedom Unlike the population’s

variance, the variance of a sample includes the term
n – 1 in the denominator, where n is the size of the
sample

 Confidence Intervals for Samples

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t-Student
Degrees of 0.1 (90 %) 0,05 (95 %) 0,02 (98%) 0,01 (99%)
freedom
1 6,31 12,71 31,82 63,66
2 2,92 4,30 6,96 9,92
3 2,35 3,18 4,54 5,84
4 2,13 2,78 3,75 4,60
5 2,02 2,57 3,36 4,03
6 1,94 2,45 3,14 3,71
7 1,89 2,36 3,00 3,50
8 1,86 2,26 2,90 3,25
9 1,83 2,23 2,76 3,17
10 1,81 2,18 2,68 3,05

Statistical Methods for Normal Distributions

 Null hypothesis, H0,

Retained if the significance test does not fail (H0).

 Alternative hypothesis
accepted if the significance test shows that null hypothesis
should be rejected (HA)

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Statistical Methods for Normal Distributions

 Comparing X— to µ
The equation for the test (experimental) statistic, t
exp, is derived from the confidence interval for µ

Comparing X— to µ

t-test
Statistical test for comparing
two mean values to see if
their difference is too large
to be explained by
indeterminate error.

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Example
Before determining the amount of Na2CO3 in an unknown
sample, a student decides to check her procedure by analyzing a
sample known to contain 98.76% w/w Na2CO3. Five replicate
determinations of the %w/w Na2CO3 in the standard were made
with the following results 98.71% 98.59% 98.62% 98.44%
98.58%. Is the mean for these five trials significantly different
from the accepted value at the 95% confidence level (α = 0.05)?

Statistical Methods for Normal Distributions

 Comparing s2 to σ2
F-test: Statistical test for comparing two variances to see
if their difference is too large to be explained by
indeterminate error.

 A critical value, F(α, νnum, νden), gives the largest value

of F that can be explained by indeterminate error.

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Example
A manufacturer’s process for analyzing aspirin tablets has
a known variance of 25. A sample of ten aspirin tablets is
selected and analyzed for the amount of aspirin, yielding
the following results:
254; 249; 252; 252; 249; 249; 250; 247; 251; 252
Determine whether there is any evidence that the
measurement process is not under statistical control at α =
0.05.

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Statistical Methods for Normal Distributions

 Comparing Two Sample Variances
The F-test can be extended to the comparison of
variances for two samples, A and B,

 sA2 = 0.00259
 and sB2 = 0.00138
 F (0.05, 6, 4) is 9.197; Fexp is less than F (0.05, 6, 4), the null
hypothesis is retained. There is no evidence at the
chosen significance level to suggest that the difference
in precisions is significant.

Fisher (F-test)
B\A 1 2 3 4 5 6 7 8 9
1 647.8 799.5 864.2 899.6 921.8 937.1 948.2 956.7 963.3
2 38.51 39.0 39.17 39.25 39.30 39.33 39.36 39.377 39.39
3 17.44 16.04 15.44 15.10 14.88 14.73 14.62 14.54 14.47
4 12.22 10.65 9.979 9.605 9.364 9.197 9.074 8.980 8.905
5 10.01 8.434 7.764 7.388 7.146 6.978 6.853 6.757 6.681
6 8.813 7.260 6.599 6.227 5.988 5.820 5.695 5.600 5.523
7 8.073 6.542 5.890 5.523 5.285 5.119 4.995 4.899 4.823
8 7.571 6.059 5.416 5.053 4.817 4.652 4.529 4.433 4.357
9 7.209 5.715 5.078 4.718 4.484 4.320 4.197 4.102 4.026
10 6.937 5.456 4.826 4.468 4.236 4.072 3.950 3.855 3.779

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Comparing Two Sample Means (t-test)

Confidence intervals for

µA and µB

Comparing Two Sample Means (t-test)

Equal varian

t exp is compared with a critical value, t (α, ,), as determined

by the chosen significance level, , the degrees of freedom
for the sample, 

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Comparing Two Sample Means (t-test)

 Unequal varian
 the degrees of freedom is calculated

 The null hypothesis is rejected if t exp is greater than

 t (α, ν), and retained if t exp is less than or equal to t (α, ν).

Example
 The %w/w Na2CO3 in soda ash can be determined
by an acid–base titration. The results obtained by
two analysts are shown here. Determine whether the
difference in their mean values is significant at α =
0.05.


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Comparing Two Sample Means (t-test)

 The null and alternative hypotheses are

 The degrees of freedom are calculated

Outliers : The Q-test compares the difference between

the suspected outlier and its nearest numerical neighbor
to the range of the entire data set

Dixon’s Q-test: Statistical test for deciding if an outlier

can be removed from a set of data.

 the suspected outlier

is the smallest value (X1)

 the suspected outlier is

the largest value (Xn)

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Example
 The following to determine the content KMnO4 :
 3.067; 3.049; 3.039; 2.514; 3.048; 3.079; 3.094
3.109; 3.102 g/L
 Determine if the value of 2.514 g is an outlier at α =
0.05.

Solution
 place the masses in order from smallest to
largest : 2.514; 3.039; 3.048; 3.049; 3.067
3.079; 3.094; 3.102; 3.109
calculate Qexp

 Q (0.05, 9) is 0.493. Since Q exp > Q (0.05, 9) the

value is assumed to be an outlier, and can be
rejected.

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Case study
 Shown in the following rows are results for the
determination of acetaminophen (mg) in 10 separate tablets
224.3; 240.4; 246.3; 239.4; 253.1; 261.7; 229.4, 255.5
235.5; 249.7
(a) Report the mean, median, range, standard deviation, and
variance for these data.
 (b) Assuming that 𝑋 and s2 are good approximations for µ
and σ2, and that the population is normally
distributed, what percentage of tablets are expected to
contain more than the standard amount of 250 mg
acetaminophen per tablet

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Case study
 Alexiev and associates describe an improved photometric
method for the determination of Fe3+ based on its catalytic
effect on the oxidation of sulphanilic acid by KIO4.29

 Determine whether there is a significant difference between

the two methods at α = 0.05

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