Analytical Chemistry LAB

01/26/2019
Statistical Data Analysis  Precision VS Accuracy
 PRECISION
1. Uncertainties of Measurement  Reproducibility
 Impossible of
The analytical results measurements;
are free of errors or the closeness of
uncertainties results to each
 Possible other
Minimize errors and  Determined by
estimate their size with repeating the
acceptable accuracy measurement
 Measurements are always on replicate
accompanied by uncertainty. samples
The true value always falls  Described
within a range due to using:
uncertainty  SD, V,
 Measurement of uncertainties COV
can never be eliminated;  Sample Standard
measurement data can give only Deviation (s)
estimates of the “true value”  A precision
 Statistical test is performed to estimated based
sharpen scientific judgements on deviations of
concerning the quality of individual data
experimental data from the mean
 Reliability Can Be Assessed
 Standards of known
composition can be
 analyzed, and the results
compared with the  Sample Variance (s²)
known composition  A precision
 Calibrating equipment estimate
enhances the quality of consisting the
data square of the
 Mean and Median standard
 Measure of central deviation;
value; used to report estimation of
what is considered the the population
most representative variance
value for a set of
measurements
 Used advantageously
when a set of data
contains an outlier, a
result that differs
significantly from
others in the set
 Coefficient of Variation  ACCURACY
(CV)  Indicates the
 The percent closeness of the
relative measurement to
standard its true or
deviation accepted value
and is expressed
by the error
 Described in
terms of:
 Standard Error of  Absolu-
Mean (sm) te or
 The deviation relative
of a set of data error
(s) divided by  Absolute Error
the square root  Difference
of the number between the
of data points measured value
(N) in the set and the true
 Indicates how value
the mean varies  The sign of the
with different absolute error
experiments tells you
measuring the whether the
same quantity value in
question is high
or low
E = Xi – Xt
 Relative Standard  Where Xi is the
Deviation (sr) measured value
 Explains how and Xt is the
data is tightly true or
clustered acceptable
around the value
mean  Relative Error
 The lower the  Absolute error
RSD, the higher divided by the
the precision true value
𝒙𝒊 −𝒙𝒕
Er =
𝒙𝒕

 Where Xi is the
measured value
and Xt is the
true or
acceptable
value
  Percentage Error  3 Types of Systematic Error
 Percentage of  Instrumental Errors
error between  Caused by non-
the measured ideal instrument
value against behavior, faulty
the true value calibrations or
 More useful by use under
quantity than inappropriate
the absolute conditions
error  Method Errors
𝒙𝒊 −𝒙𝒕  From non-ideal
Er = x 100%
𝒙𝒕 chemical or
physical
 ACCURACY measures behavior of
agreement between a analytical
result and its true value systems
 PRECISION describes  Personal Errors
the agreement among  Result from
several results that have carelessness,
been obtained in the inattention, or
same way personal
limitations of
2. Experimental Data Errors the
 Random (Indeterminate) experimenter
 Random (or  Gross Error
indeterminate) error  They usually occur only
causes data to be occasionally, are often
scattered more or less large, and may cause a
symmetrically around a result to be either high
mean value or low
 Uncertainties resulting  Gross errors lead to
from the operation of outliers, results that
small uncontrolled appear to differ
variables that are markedly from all other
inevitable data in a set of replicate
 These errors affect measurements
measurement precision  Detection of Gross
 Systematic (Determinate) Error
 Errors that have a  Q Test
known source  Widely used
 Causes the mean of a statistical test
set of data to differ from for deciding
the accepted value whether a
 These errors affect the suspected result
result accuracy should be
retained or
rejected
 Absolute value
of the
difference
 between the one or more explanatory
questionable variables (or
result Xq and its independent variable)
nearest
neighbor Xn is
divided by the
spread w of the
entire set
|𝑿𝒒 − 𝑿𝒏|
𝑸=
𝒘
 The ratio is then
compared with
the critical
values Qcrit. If
Q > Qcrit, the
questionable
result can be
rejected
3. Data Linearity
 Linearity
 Property of a
mathematical
relationship or function
which means that it can
be graphically
represented as a straight
line
 In analytical chemistry,
the quantity of interest
is often estimated from
a calibration line
 A calibration line is
constructed from
generating multiple
responses from multiple
standard samples of
known quantities
 Linearity refers to how
well a plot of the
analytical response
versus the quantity of
interest follows a
straight line
 Linear Regression
 A linear approach to
modelling the
relationship between a
scalar response (or
dependent variable) and