Outline
Sample
Example
questions
Chemical
analysis
Subject
Set of instruction
Reliability in accuracy,
reproducibility
Analytical
problem
Method
Procedures
Validate
Based on
purpose and
intended quality
Techniques
Radiochemical
Electrochemical
Thermal
Chromatography
Mass spectrometry
AAS
Gravimetry
spectrometry
HPLC
GC
FTIR
Validation method
Performance
characteristic
of detector
for single
analyte
calibration
standards
Process
repeated for
mixed analyte
calibration
standards
Process
repeated for
analyte
calibration
standard with
possible
interfering
substances
and for
reagent blank
Process
repeated for
analyte
calibration
standard with
anticipated
matrix
component to
evaluate
matrix
interference
Analysis of
spike
simulated
matrix
matrix with
added known
amount of
analyte, to
test
recoveries
Field trials in
routine lab
with more
junior
personnel to
test
ruggedness
Analysis
Representative sample
Coning
grab
Random
pick
2
2
1
3
4
2
1
4
4
- ensure the
operational techniques and
activities in analytical lab
provide result suitable for
intended purpose
QA
- managerial
component/ responsibility of
an analytical lab with all QC
procedures are in place.
Confidence in validity
Cost effective
Determinate errors
Accumulated error
Systematic error lead to bias in the measured value from analyst, equipment or
procedure which require record keeping, training or equipment maintenance.
Indeterminate error
10
Indeterminate error
Gaussian distribution
Random errors follow a Gaussian or normal distribution.
We are 95% certain that the true value falls within 2 (infinite population),
IF there is no systematic error.
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Difference
If
If
the Xm is based on
average of several
measurement the value
is called mean error.
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Relative error
Example 3.6
The
What
Absolute
Relative
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Statistical analysis
Used
statistical model
follow
Average
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R chart was used to present the precision which record the property of interest in a running
sequence. Show centerline or average, standard deviation and warning or control limit
This X chart requires result from known sample composition and used to evaluate accuracy.
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Statistical parameters
Descriptive statistic
Check data for any problematic or non normality data set depart from bell shape or with
outliers, use frequency chart or normal plot
Means,
standard deviation, or S (data <10),
Variance, 2
Skewness and kurtosis for any trend about the data indicating cluster or particular pattern
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Skewness asymmetric with high frequencies on one side and a long tail of low freq on other side
Kurtotic distribution has high peak and long tail on both side
Confidence limit, CL
Data distribution
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Confidence limit
Estimate the range within a given probability which the true value might fall defined by
the experimental mean and standard deviation
The range is called confidence interval and the limit is called confidence limit.
The likelihood that the true value fall within the range is called the probability or
confidence level
Select a confidence level (95% is good) for the number of samples analyzed
=(degrees of freedom +1).
Confidence limit = x ts/N.
It depends on the precision, s, and the confidence level you select.
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Inferential statistic
Researcher
of sample
Types
20
of inferential statistic
Significance test
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F = s12/s22
(Eq. 3.10)
where s12 > s22
F value
F = s12/s22.
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Example 3.16
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127
125
123
130
131
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129
130
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131
129
127
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t-Test
Do the sample follow a normal distribution? If small is sample then the test is
incorrect, moderate sample size of 40-100 to be accurate
the variance for the two groups is about the same. Check homogeneity of variance
assumption, can lead to inaccurate result particularly for small groups with unequal
sample sizes
Statistic calculate the sample means divided by a variance for comparison with the critical value
obtained from a probability table at the selected p value (0.05, 0.01 or 0.001)
if the t statistic is equal or exceed the critical value, then the difference between the two group
means is significant at the chosen level of alpha.
The test can be one-sided or twosided. The former is used when the mean for a particular
group is hypothesized to be higher than the mean for other group, the latter is used when the
mean are expected to be different.
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Example 3.18
A new gravimetric method is developed for iron (III) in which the iron
is precipitated in crystalline form with an organoboron cage
compound. The accuracy of the method is checked by analyzing the
iron in an ore sample and comparing with the results using the
standard precipitation with ammonia and weighing of Fe2O3. The
results, reported as % Fe for each analysis, were as follows:
Find
given
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18.89
19.20
19.00
19.70
19.40
ANOVA
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ANOVA was used to examine the variability of scores within and between
groups.
Subject scores within groups vary due to differences in individual and random
error
ANOVA assume the observation are independent, normal and group variances
are equal
ANOVA test determine if any group mean is significant different from any other
group mean by overall F test.
If no different (i.e. F-test is not significant), then the is no point in comparing any
of the groups retain null hyphothesis.
Q-test
QCalc = outlier difference/range.
If QCalc > QTable, then reject the outlier as due to a systematic error.
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Example of Q-test
Performed
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Sydney
Cherry
Tien
Dick
10.2
10.8
11.6
9.9
9.4
7.8
10.0
9.2
11.3
9.5
10.6
11.6
Correlation
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Regression
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The equation represent a line that best fit through a scatter plot of points
describing the relationship between variable and one or more independent
variables
The beta weight or coefficient of the independent variables in the equation give
info on relationships between the independent and dependent variables
The slope of single line best fit data of the x-y axis, represent the beta weight
and reflect changes in the value of the dependent variable that associated with
each change of one unit in the independent variable.
Regression
Simple
Multiple
R2
31
A least-squares plot gives the best straight line through experimental points.
Excel will do this for you.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
32
This Excel plot gives the same results for slope and intercept as calculated in
the example.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
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References
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