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faridsidikStandard addition
The Standard addition method, often used in analytical chemistry, quantifies the analyte present in an
unknown. This method is useful for analyzing complex samples where a matrix effect interferes with the
analyte signal. In comparison to the calibration curve method, the standard addition method has the
advantage of the matrices of the unknown and standards being nearly identical.[1] This minimizes the
potential bias arising from the matrix effect when determining the concentration.
Variations
Standard addition involves adding known amounts of analyte to an unknown sample, a process known as
spiking. By increasing the number of spikes, the analyst can extrapolate for the analyte concentration in
the unknown that has not been spiked.[2] There are multiple approaches to the standard addition. The
following section summarize each approach.
Single standard addition used in polarography
In classic polarography, the standard addition method involves creating two samples – one sample
without any spikes, and another one with spikes. By comparing the current measured from two samples,
the amount of analyte in the unknown is determined.[1] This approach was the first reported use of
standard addition, and was introduced by a German mining chemist, Hans Hohn, in 1937.[3] In his
polarography practical book, titled Chemische Analysen mit dem Polargraphen, Hohn referred this
method as Eizhusatzes, which translates to "calibration addition" in English. Later in the German
literature, this method was called as Standardzugabe, meaning "standard addition" in English.
Modern polarography typically involves using three solutions: the standard solution, the unknown
solution, and a mixture of the standard and unknown solution. By measuring any two of these solutions,
the unknown concentration is calculated.[1]
As polarographic standard addition involves using only one solution with the standard added – the two-
level design, polarographers always refer to the method as singular, standard addition.[4]
Successive addition of standards in constant sample and total volume
Outside the field of polarography, Harvey's book Spectrochemical Procedures was the next earliest
reference book to mention standard addition.[4] Harvey's approach, which involves the successive
addition of standards, closely resembles the most commonly used method of standard addition today.
To apply this method, analysts prepare multiple solutions containing equal amounts of unknown and
spike them with varying concentrations of the analyte. The amount of unknown and the total volume are
the same across the standards and the only difference between the standards is the amount of analyte
spiked. This leads to a linear relationship between the analyte signal and the amount of analyte added,
allowing for the determination of the unknown's concentration by extrapolating the zero analyte signal.
One disadvantage of this approach is that it requires sufficient amount of the unknown.[2] When working
with limiting amount of sample, an analyst might need to make a single addition, but it is generally
considered a best practice to make at least two additions whenever possible.[5]
Note that this is not limited to liquid samples. In atomic absorption spectroscopy, for example, standard
additions are often used with solid as the sample.[6]
In atomic emission spectroscopy, background signal cannot be resolved by standard addition. Thus,
background signal must be subtracted from the unknown and standard intensities prior to extrapolating
for the zero signal.[5]
As this approach involves varying amount of standards added, it is often referred in the plural form as
standard additions.[4]
Example
Suppose an analyst is determining the concentration of silver in samples of waste solution in
photographic film by atomic absorption spectroscopy. Using the calibration curve method, the analyst can
calibrate the spectrometer with a pure silver aqueous solutions, and use the calibration graph to determine
the amount of silver present in the waste samples. This method, however, assumes the pure aqueous
solution of silver and a photographic waste sample have the same matrix and therefore the waste samples
are free of matrix effect.
Matrix effects occur even with methods such
as plasma spectrometry, which have a
reputation for being relatively free from
interferences. As such, analyst would use
standard additions in this case.
For standard additions, equal volumes of the
sample solutions are taken, and all are
separately spiked with varying amounts of
the analyte – 0, 1, 2, 3, 4, 5 mL, where 0 mL
addition is a pure test sample solution. All
solutions are then diluted to the same volume Spreadsheet for standard addition example on determining
of 25 mL, by using the same solvent as the the silver concentration of photographic film waste. Please
refer to the Limitation and Uncertainty of Standard Addition
one used to prepare the spiking solutions.
section for more information on how to calculate for the
Each prepared solution is then analyzed using
Error Analysis portion. The silver concentration in the test
an atomic absorption spectrometer. The sample is the x-intercept of the plot. The dilution factor is
resulting signals and corresponding spiked multiplied by this initial concentration to determine the
silver concentrations are plotted, with original concentration.
concentration on the x-axis and the signal on
the y-axis. A regression line is calculated
through least squares analysis and the x-intercept of the line is determined by the ratio of the y-intercept
and the slope of the regression line. This x-intercept represents the silver concentration of the test sample
where there is no standard solution added.
Error
While the standard addition method is effective in reducing the interference of most matrix effects on the
analyte signal, it cannot correct for the translational matrix effects.[7] These effects are caused by other
substances present in the unknown sample that are often independent of the analyte concentration. They
are commonly referred to as 'background' and can impact the intercept of the regression line without
affecting the slope. This results in bias towards the unknown concentration. In other words, standard
addition will not correct for these backgrounds or other spectral interferences.[5]
Analysts also needs to evaluate the precision of the determined unknown concentration by calculating for
the standard deviation, . Lower indicates greater precision of the measurements. The value of is
given by
where the calculation involves the following variables:
standard deviation of the residuals,
absolute value of the slope of the least-squares line,
y-intercept of the linear curve,
number of standards,
average measurement of the standards,
concentrations of the standards,
average concentration of the standards,
See also
Standard curve
Isotope dilution
Internal standard
References
1. Bader, Morris (1980). "A systematic approach to standard addition methods in instrumental
analysis" (https://pubs.acs.org/doi/abs/10.1021/ed057p703). Journal of Chemical Education.
57 (10): 703. doi:10.1021/ed057p703 (https://doi.org/10.1021%2Fed057p703). ISSN 0021-
9584 (https://search.worldcat.org/issn/0021-9584).
2. Skoog, Douglas A.; Holler, James F.; Crouch, Stanley R. (2016). Principles of Instrumental
Analysis (6th ed.). Boston, MA, USA: Cengage Learning. pp. 13–14. ISBN 978-1-305-
57721-3.
3. Hohn, Hans (1937). Chemische Analysen mit dem Polarographen. Berlin, Germany:
SpringerVerlag. p. 51.
4. Harvey, Charles E. (1950). Spectrochemical Procedures (1st ed.). Glendale: Applied
Research Laboratories.
5. Robinson, James W.; Skelly Frame, Eileen M.; Frame II, George M. (2005). Introduction to
Spectroscopy (6th ed.). New York: Marcel Dekker. pp. 84–87. ISBN 0-203-99730-1.
6. Fan, Xiaoyu; Li, Qing; Lin, Ping; Jin, Zhonggan; Chen, Meizi; Yi, Zu (2022). "A standard
addition method to quantify serum lithium by inductively coupled plasma mass
spectrometry" (https://pubmed.ncbi.nlm.nih.gov/34719967/). Ann Clin Biochem. 59 (3): 166–
170. doi:10.1177/00045632211054745 (https://doi.org/10.1177%2F00045632211054745).
PMID 34719967 (https://pubmed.ncbi.nlm.nih.gov/34719967).
7. Ellison, Stephen L.; Thompson, Michael (2008). "Standard additions: myth and reality" (http
s://pubmed.ncbi.nlm.nih.gov/18645637/). The Analyst. 133 (8): 992–7.
doi:10.1039/b717660k (https://doi.org/10.1039%2Fb717660k). PMID 18645637 (https://pub
med.ncbi.nlm.nih.gov/18645637).
