Exercise No. 7: Figures of Merits analytical chemistry.

Figures of Merits in Analytical

Chemistry

In analytical chemistry,
figures of merit are essential
performance characteristics that
help evaluate and compare the
effectiveness of different
analytical methods. Below is a
detailed overview of key figures
of merit, including their
definitions,
measurement methods, formulas,
and significance.

1.Accuracy

Definition:
Accuracy refers to the
degree of closeness between a
measured value and the true or
accepted value. It reflects how
well an analytical method can
provide results that are close to
the actual value of the analyte
being measured.

Measurement:
Accuracy can be assessed
by comparing the results
obtained from an analytical
method to a known standard or
reference value.

Formula:
𝐴𝑐𝑐𝑢𝑟𝑎𝑐𝑦 = (
𝑇𝑟𝑢𝑒 𝑉𝑎𝑙𝑢𝑒 − 𝑀𝑒𝑎𝑠𝑢𝑟𝑒𝑑
𝑇𝑟𝑢𝑒
𝑉𝑎𝑙𝑢𝑒
)×100
𝑉𝑎𝑙𝑢𝑒

Methods:

- Compare experimental
results with certified
reference materials
(CRMs).
- Apply calibration methods
to correct systematic
errors.
- Use recovery studies in
Significance:

High accuracy indicates that

the method produces results that
are very close to the true value,
which is crucial for reliable
analysis.

2. Precision

Definition:

Precision measures the

degree of reproducibility or
consistency of measurements under
unchanged conditions. It indicates
how closely multiple measurements
of the same sample agree with each
other.

Measurement:

Precision is quantified using

statistical measures such as
standard deviation (SD) or relative
standard deviation (RSD).

Formulas:

Standard Deviation and Relative

Standard Deviation:

Methods:

- Repeatability: Measure
precision under identical
conditions within a short time.
- Reproducibility: Measure
precision across different
operators, equipment, or
laboratories.
Significance: 4. Detection Limit (LOD)
A high precision indicates Definition:
that the method yields consistent
results, which is important for The detection limit is the
quality control and method lowest concentration of an
validation. analyte that can be reliably
detected but not necessarily
3. Sensitivity quantified under stated
conditions.
Definition:
Measurement:
Sensitivity refers to the
ability of an analytical method to The DL can be determined
detect small changes in analyte using various methods, including
concentration. It is often defined signal-to-noise ratio assessments.
as the slope of the calibration
curve relating signal response to Formula:

𝐷𝐿 =
concentration.
3.3 σ
�
Measurement: �

Sensitivity can be - where σ is the standard

measured by constructing a deviation of the blank
calibration curve and response and S is the slope
determining how much the signal of the calibration curve.
changes with a change in
concentration. Methods:

Formula: - Signal-to-noise ratio (S/N)

approach, where LOD is
𝑆𝑒𝑛𝑠𝑖𝑡𝑖𝑣𝑖𝑡𝑦 = ∆𝑆 defined at S/N = 3.
∆
𝐶
- Use a calibration curve to
estimate the concentration
- where S is the signal and C corresponding to the
is the concentration. threshold signal.
Methods: Significance:
- Construct a calibration A lower detection limit
curve by plotting response indicates a more sensitive
signals against known method capable of detecting
concentrations. trace amounts of analytes.
- Ensure measurements are
within the linear response
range of the instrument. 5. Selectivity

Significance: Definition:

Higher sensitivity allows Selectivity refers to the

for the detection of lower ability of an analytical method to
concentrations of analytes, which distinguish between the analyte
is particularly important in trace and other components in a
analysis. mixture, minimizing interference
from other substances.
Measurement: Methods:
Selectivity can be evaluated - Analyze samples across a
by analyzing samples containing wide range of
potential interferents and concentrations.
assessing their effect on analyte - Perform regression
measurement. analysis to confirm
linearity.
Formula:
Significance:
The selectivity coefficient
A broader linear range
KA,I can be calculated as: allows for more versatile

𝐾𝐴, 𝐼 =𝑆 𝑆𝐼
applications of an analytical
method across varying
𝐴 concentrations.
- where SI is the signal from
interferents and SA is the 7.Signal-to-Noise Ratio (S/N)
signal from the analyte.
Definition:
Methods:
The signal-to-noise ratio
- Use spiked samples with quantifies how much a signal
known interferents. stands out from background
- Perform matrix- noise, indicating measurement
matching experiments. quality.
Significance: Measurement:
High selectivity ensures The S/N ratio is calculated
that only the target analyte by dividing the mean signal by
contributes to the measurement, the standard deviation of noise
enhancing accuracy and (background).
reliability.
Formula:

𝑆/𝑁
𝑆𝑖𝑔𝑛𝑎𝑙
6. Linear Range

=
𝑁𝑜𝑖𝑠𝑒
Methods:
Definition:
- Measure noise as the
The linear range (or standard deviation of the
dynamic range) is defined as the baseline signal.
range of concentrations over - Use S/N to optimize
which an analytical method instrument settings.
provides a linear response to
changes in analyte concentration. Significance:

Measurement: A higher S/N ratio indicates

better measurement quality,
The linear range is allowing for more reliable
determined by plotting a detection and quantification.
calibration curve and identifying
the range over which it remains
linear.
8. Linearity Exercise No. 8: Calibration
Methods
Definition:

Linearity refers to how well

a method's response correlates Calibration Methods in
with analyte concentration across Analytical Chemistry
its range. It assesses whether
results are proportional to Calibration methods are
concentration levels. essential for accurately
determining the concentration of
Measurement: analytes in various samples. The
choice of calibration technique
Linearity is evaluated can significantly affect the
through regression analysis on reliability and accuracy of
calibration data points to analytical results. Below are
determine correlation coefficients detailed descriptions of four
(R²). common calibration methods:
external standard calibration,
Formula:
single standard addition, multiple
Linearity can be expressed standard addition, and internal
through regression equations: standard addition. Each section

𝑌 = 𝑚𝑋 + 𝑏
includes
definitions,
methodologies, plotting
- where Y is the response, m techniques, and preparation
is slope (sensitivity), X is steps.
concentration, and b is
intercept (ideally zero).

Methods: 1.External Standard

Calibration
- Analyze multiple
concentrations of the Definition:
analyte.
External standard
- Ensure is close to 1 for
calibration involves preparing a
acceptable linearity.
series of standard solutions with
Significance: known concentrations of the
analyte. The instrument response
Good linearity ensures to these standards is used to
reliable quantification across create a calibration curve.
concentrations, enhancing
method validity for quantitative Methodology:
analysis.
Preparation of Standards:
Prepare a series of standard
solutions by diluting a stock
solution of the analyte to known
concentrations.

Measurement:

Analyze each standard

solution using the analytical
instrument to obtain the
corresponding signal (e.g.,
absorbance, peak area).
Plotting: Measure the signal from this
spiked sample.
Plot the instrument
response (y-axis) against the Plotting Technique:
known concentrations (x-axis) to
create a calibration curve. The signal from the original
sample (S1) and from the spiked
Plotting Technique: sample (S2) can be compared.
The relationship can be
The resulting plot should expressed as:
yield a straight line if the
relationship is linear, described S2 = S1 + k (Cstd)
by the equation:
- where k is a proportionality
Y = mX + b constant and Cstd is the
concentration of the added
- where Y is the response, m standard. The
is the slope, X is the concentration of the
concentration, and b is the original analyte can be
intercept. extrapolated from this
relationship by plotting S2
Significance:
against Cstd.
This method is
Significance:
straightforward and effective
when matrix effects are minimal This method is particularly
or absent. useful for complex matrices
where external standards may
2. Single Standard Addition
not adequately represent sample
Definition: behavior.

Single standard addition 3. Multiple Standard Addition

involves adding a known quantity
Definition:
of a standard solution directly to
a sample containing an unknown Multiple standard addition
concentration of analyte. This involves adding varying amounts
method helps account for matrix of a standard solution to multiple
effects. aliquots of a sample. This method
further refines correction for
Methodology:
matrix effects.
Sample Preparation:
Methodology:
Measure a specific volume of the
sample containing the unknown Sample Preparation: Divide a
analyte concentration. single sample into several
aliquots.
Addition of Standard:
Addition of Standards: To each
Add a known volume of a
aliquot, add different known
concentrated standard solution to
volumes or concentrations of a
this sample.
standard solution.
Measurement:
Measurement:
 Analyze each modified
sample to obtain corresponding
signals.
Plotting Technique: Plotting Technique:
Plot the measured signals Calculate the ratio of
against the concentrations of signals (analyte/internal
added standards. The resulting standard) for each sample and
graph should ideally produce a plot this ratio against known
linear relationship: concentrations of analytes:

= 𝑘𝐶𝑎𝑛𝑎𝑙𝑦𝑡𝑒
S = S0 +
𝑆𝑎𝑛𝑎𝑙𝑦𝑡
𝑒
kCstd
𝑆𝑖𝑛𝑡𝑒𝑟𝑛
𝑎𝑙
- where S0 is the signal from
the original sample - where and analyt are
e
without added
Sinternal S
standard. Signal Measurement: Measure
- Extrapolate back to find S0, both the analyte signal and that of
which corresponds to the the internal standard.
concentration of analyte in
the original sample.

Significance:

This method provides

enhanced accuracy in quantifying
analytes in complex samples by
compensating for matrix effects
more effectively than single
addition.

4. Internal Standard Addition

Definition:

Internal standard addition

incorporates a constant amount
of an internal standard (a
compound similar but not
identical to the analyte) into all
samples and standards. This
approach corrects for variations
in measurement conditions.

Methodology:

Preparation: Add a fixed amount

of internal standard to all
samples and standards.

Measurement: Analyze all

samples and standards using the
analytical instrument.
 signals from the analyte
and
internal standard,
respectively.
- The resulting plot should
yield a linear relationship
that allows for
quantification based on
ratios rather than absolute
values.

Significance:

This method is especially

useful when there are significant
variations in sample composition
or instrument response that
could affect accuracy.

Summary

Each calibration method

serves specific purposes
depending on sample complexity
and expected interferences:

External Standard Calibration is

best for simple matrices without
interference.

Single Standard Addition

corrects for matrix effects in
complex samples.

Multiple Standard Addition

provides enhanced accuracy
through multiple corrections.

Internal Standard
Addition
compensates for variability in
measurement conditions
effectively.