Analytical Chemistry Laboratory 2

Atomic Absorption Spectroscopy Measurement

Mr. *****

Department of Chemical Engineering and Chemistry, Mapua Institute of Technology

The effects of instrumental parameters on calcium absorption are studied. The calcium
sample in its pure form was determined by comparing the absorbance with that of standards. The
concentration calculated by linear regression was 19.35 ppm for an absorbance of 0.459 for
sample number 3. The calibration curve revealed by the computer was in linear form.

The analyte to be examined is

Objective calcium. The metal is obtained mainly by

The purpose of this experiment is to electrolysis of fused calcium chloride, a

familiarize the principles and operation of
the Atomic Absorption Spectrophotometer
(AAS), and to determine the concentration
of calcium in a sample using AAS.
Discussion
Overview
Atomic Absorption Spectroscopy
uses the absorption of light to measure the
concentration of gas-phase atoms. Since
samples are usually liquids or solids, the
analyte atoms or ions must be vaporized in a
flame or graphite furnace. The atoms absorb
ultraviolet or visible light and make
transitions to higher electronic energy
levels. The analyte concentration is
determined from the amount of absorption.
Applying the Beer-Lambert law directly in
AA spectroscopy is difficult due to
variations in the atomization efficiency from
the sample matrix, and nonuniformity of
concentration and path length of analyte
atoms (in graphite furnace AA).
Concentration measurements are usually
determined from a working curve after
calibrating the instrument with standards of
known concentration.
costly process. Until recently the pure metal
had little use in industry. It is being used to
an increasing extent, however, as a
deoxidizer for copper, nickel, and stainless
steel. Because calcium hardens lead when
alloyed with it, lead-calcium alloys are
excellent for bearings, superior to ordinary
lead antimony for grids in storage batteries,
and more durable as sheathing for lead-
covered cable. Calcium is present in the
chemically combined state in lime (calcium
hydroxide), cement and mortar (as calcium
hydroxide or a variety of silicates of
calcium), teeth and bones (as a calcium
hydroxyphosphate), and in many body fluids
(as complex proteinaceous compounds)
essential to muscle contraction, the
transmission of nerve impulses, and the
clotting of blood.
Methodology
500 mL of 50 ppm stock solution of
Ca2+ primary standard was prepared.
Preparation was made with 50 mL standards
from the stock solution corresponding to 5
ppm, 15 ppm, and 30 ppm concentrations.
The pH of the standards was adjusted to the
pH of the sample. The solution was filtered.
The standards and the sample were aspirated
using the required instrument parameters for
calcium (Ca) of the Perkin Elmer
AAAnalsyt 100 Spectrophotometer. The K
content (concentration) of the sample was
then calculated.
Instrumentation
Schematic of an atomic-absorption experiment:
Light source
The light source is usually a hollow-
cathode lamp of the element that is being
measured. Since lasers are intense enough to
excite atoms to higher energy levels, they
allow AA and atomic fluorescence
measurements in a single instrument.
Atomizer
AA spectroscopy requires that the
analyte atoms be in the gas phase. Ions or
atoms in a sample must undergo desolvation
and vaporization in a high-temperature
source such as a flame or graphite furnace.
Flame AA can only analyze solutions, while
graphite furnace AA can accept solutions,
slurries, or solid samples.
Light separation and detection
AAS use monochromators and
detectors for uv and visible light. The main
purpose of the monochromator is to isolate
the absorption line from background light
due to interferences.
Picture of a flame atomic-absorption spectrometer
Interpretation
The sample solution is aspirated into
a flame and the sample element which is
calcium is converted to atomic vapor. The
flame then contains the calcium atoms.
Some are thermally excited by the flame, but
most remain in the ground state. These
ground-state atoms can absorb radiation of a
particular wavelength that is produced by a
special source made from that element. The
wavelengths of radiation given off by the
source are the same as those absorbed the
atoms in the flame. Here are the absorbance
from the experimental data, including the
unknown sample:
Concentration Absorbance
1 ppm 0.018
5 ppm 0.098
15 ppm 0.333
30 ppm 0.733
Unknown 0.459
The absorbtion follows Beer’s law.
That is, the absorbance is directly
proportional to the pathlength in the flame
and to the concentration of atomic vapor in
the flame. The read-out computer prepared a
calibration curve of concentration in the
solution versus absorbance. From this curve,
as it is a straight line, the unknown sample
#3 computed was 19.35 ppm by linear
regression.
Conclusion
AA specophotometry uses a flame
as the atomizer and follows Beer’s law. The
major disadvantage of making
measurements by atomic absorption is that a
different source is required for each element.
The concentration of the sample was 19.35
ppm according to the read-out.
References
1. Christian, G.D., Analytical Chemistry, 6th
edition, New Jersey, John Wiley, 2004.

2. Skoog, D. A., and Leary, J. J., Principles

of Instrumental Analysis, 4th edition,
Saunders, New York 1992.

3. Harris, D.C., Quantitative Chemical

Analysis, 3rd edition, Freeman, New York,
1991.

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