CHEMICAL ENGINEERING–5EX–5EY–5EZ - INSTRUMENTAL ANALYTICAL CHEMISTRY - 2020

ATOMIC SPECTROMETRY – STANDARD ADDITION METHOD

ANALITO (X)

MATRIX: Other components of the sample

UNKNOWN SAMPLE

What to do when the sample matrix influences the result of the analysis?
Imitate the matrix. This is not always possible.
2) Method of standard addition of the analyte.
How to do it?
How does it work?

In the standard addition, known quantities of the standard are added to the sample.
unknown.
From the increase in signal, it is deduced how much analyte is present in the original sample.
This method requires a linear response for the analyte.
The standard addition is especially appropriate when the composition of the sample is

unknown or complex and affects the analytical signal.

The symbolism employed will be:

X–Analyte to be investigated, contained in the unknown sample under study.

S-Standard, a known contraction solution that contains the element (X) that is in
analysis.
I–Signal Intensity, which can be:
a) Emission Intensity (Iissuance)–when the technique used is Spectrometry of
Atomic Emission, E.E. A.
b) Absorbance (A) - when the technique used is Atomic Absorption Spectrometry,
E.A.A.

There are two approaches to the Standard Addition Method:

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A) Standard Addition Method of Single Point

The signal intensities are measured by EEA or EAA in two analyses, namely:
ANALYSIS 1: Unknown sample - containing the analyte X
The intensity of the signal measured experimentally is Ix.
There is a linear relationship between I and E[X]ipresented in equation (1)

Ix= k . [X]i (eq. 1)

2) ANALYSIS 2: Unknown sample + Standard

+
A solution containing is prepared:
The aliquot (Vi) of the unknown sample with the analyte concentration [X]i
The aliquot (Vi) of a standard solution of known concentration [S]i
final volume (Vf) will be the sum of the applicable rates or the volume of the
balloon used for preparation.

As there has been a dilution of the aliquots, the concentration of the

components in the balloon:

a) Standard:c1.V1= c2.V2you[S]i. VI[S]f. Vf

Therefore:f= [S]I. Vi/ Vf(eq.2)

b)Analito:c1.V1= c2.V2ou[X]i. Vi[X]f. Vf

Therefore:[X]f[X]i. Vi/ Vf(eq.3)

The signal intensity of a sample of the prepared mixture (X+S) is measured.

experimentally under the same conditions as ANALYSIS 1, let the obtained value be Ix+S.
There is a linear relationship between IX+S e([X]f[S]fpresented in equation (4):

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Ix+S = k . ([X]f+ [S]f) (eq. 4)

If equation (1) is divided by equation (4), the slope of the line (k) can be canceled and
the resulting equation is the Standard Point Addition Equation:

__Ix = [X]i____
Ix+S ([X]f+ [S]f)

The signal intensities (Ix and Ix+s) are known experimental values.
The concentrations of the added standard, [X]fe [S]fcan be determined by the equations
(2) and (3), using dilution calculation.
The concentration of the analyte in the sample [X]ioriginal can be determined.

B) Standard Addition Method - graphical (with multiple standard addition points)

Several solutions containing a fixed volume of the unknown sample are prepared,
containing the analyte X and variable volumes of the standard solution.

Description of the standard addition method:

1) Add equal volumes of unknown sample in all flasks. E.g.: 10.00 mL

2) Add increasing volumes of standard for concentrations of ½, 1; 1.5, and 2 times the
concentration of 1o balloon. Ex.: 0, 5, 10, 15, 20 mL.
3) Fill the volume with distilled water.

4) Read the analytical signal with samples from each balloon prepared by EEA or EAA.
5) Calculate the standard concentrations in each balloon.
6) Build the standard addition graph, where the x-axis represents the concentrations and the y-axis represents the response.

signal strength.

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Graph: Standard Addition Curve

The concentration where the signal intensity is zero corresponds to the concentration of the analyte.

searched (cx).
7) Using linear regression with a calculator, determine the linear coefficient (a),
the slope coefficient (b) and the correlation coefficient (r) to check the linearity of the
points.
Write the equation of the line: Y = a + b.X
Where:
Y is I (Signal Intensity, it can be I)issuanceor Absorbance).
X is C (concentration of the standard)

Therefore, the equation of the Standard Addition line is: I = a + b.C

ParaI = 0,a concentraçãoC = Cx(concentração do analito no balão)

Thus:
0 = a + [Link]

Cx= - a/b, therefore the concentration of the analyte in the flask will be: Cx = a/b
8) As the unknown sample is diluted when prepared in each flask, there is a dilution.
to be considered for the final determination of the analyte concentration in the sample
Dilution:C1.V1= C2.V2Where:
C1it is the concentration of the analyte in the original sample.
See the sample rate placed in each balloon.
C2it is the concentration of the analyte in each balloon, obtained from the straight line equation, by regression
linear.
V2it is the volume of the balloon used in the dilutions.

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Examples:

A serum containing Na+ provides a signal of 4.27 mV in an atomic emission analysis.

So, 5.00 mL of a 2.08 mol/L NaCl solution was added to 95.0 mL of serum.
This serum in this sample provides a signal of 7.98 mV. What is the original concentration of
Na+ no syrup?
Resolution:
oAnalito = Na
Standard = NaCl

Analysis (1): Ix = 4.27 mV

Analysis (2): IX+S 7.98 mV

Final volume = Vf= 5.00 + 95.00 = 100.00 mL

Calculation of the concentrations of the sample solution with standard addition:

the standard:

2.08 mol/Lf100.00 mL
[S]f 0.104 mol/L
oAnalito:
[Na]i95.00 mL = [Na]f100.00 mL
[Na]f0.95. [Na]I

2) Calculation of the analyte concentration in the original sample.

Ix = translatedTextI____
Ix+S ([X]ff)

4,27 = [Na]i____
7.98 (0.95 [Na]i+ 0.104

[Na]i0.113 mol/L

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2. Chromium was determined in an aqueous solution by pipetting 10 mL of a solution.
unknown in each of the 5 volumetric flasks of 50.0 mL. Various volumes of
standards containing 12.2 ppm of Cr were added to the flasks, after which in the solutions
were diluted to the final volume.

Sample (mL) Standard (mL) Absorbance

10.0 0,0 0.201
10.0 10.0 0.292
10.0 20.0 0.378
10.0 30.0 0.467
10.0 40.0 0.554

a) Determine the molar concentration of the solutions used.

b) Determine by linear regression, using the calculator: linear coefficient, coefficient
angular and correlation coefficient and write the complete equation of the work line.
c) What is the concentration of Cr in the original sample?

Resolution:
oAnalito = Cr, aliquots of 10.0 mL in 50.0 mL flasks
The standard = Cr at 12.2 ppm, variable aliquots in 50.0 mL flasks

1) Calculation of the standard concentrations in each flask:

Solution (1)
12.2 ppm . 0.0 mL = C150.0 mL C10.00 mol/L

Solution (2)
12.2 ppm . 10.0 mL = C250.0 mL C22.44 mol/L

Solution (3)
12.2 ppm . 20.0 mL = C350.0 mL C34.88 mol/L

Solution (4)
12.2 ppm. 30.0 mL = C450.0 mL C47.32 mol/L

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Solution (5)
12.2 ppm . 40.0 mL = C550.0 mL C59.76 mol/L

2) Data Table:
Concentration (mol/L) Absorbance
0.00 0.201
2.44 0.292
4,88 0.378
7.32 0.467
9.76 0.554

3) Determination of the standard addition line equation by linear regression

using the calculator:
a = linear coefficient =......

b = slope coefficient =.....

r = correlation coefficient = .....

The equation of the Standard Addition Line is: I = ....... + ....C

4) Calculation of the analyte concentration in the diluted solution:

I=0
C = Cx

Cx....................ppm

5) Calculation of the analyte concentration in the original solution of the unknown sample.
C1.V1= C2.V2
Cx, original10.00 mL = Cx, balloon50.00 mL

Cx, original ....................ppm