NAME: NDJIVATERA KANDJOU

STUDENT NUMBER: 202002413

GROUP/DAY: GROUP A TUESDAY

WEEK: 12

DATE: 18/04/2023

TITLE: SOLVENT EXTRACTION OF METALS AND ANALYSIS USING AAS

EXPERIMENT: 2
AIM

The aim of the experiment was to separate copper (Cu), magnesium (Mg) and lead (Pb) from a
sample mixture by liquid-liquid extraction and analysis by AAS.

INTRODUCTION

According to Walsh (1991) Atomic Absorption Spectrometry (AAS) is an analytical technique

Atomic absorption spectrometry (AAS) detects elements in either liquid or solid samples through
the application of characteristic wavelengths of electromagnetic radiation from a light source.
Individual elements will absorb wavelengths differently, and these absorbances are measured
against standards. In effect, AAS takes advantage of the different radiation wavelengths that are
absorbed by different atoms. Hence from this experiment, copper, lead and magnesium are
separated from a mixture by liquid-liquid extraction and analysed using AAS,(Yoshinari et-al,
2002).

In AAS, analytes are first atomized so that their characteristic wavelengths are emitted and
recorded. Then, during excitation, electrons move up one energy level in their respective atoms
(figure 1) when those atoms absorb a specific energy. This energy corresponds to a specific
wavelength that is characteristic of the element. Depending on the light wavelength and its
intensity, specific elements can be detected and their concentrations measured, ( Harvey 2010).

As electrons return to their original energy state, they emit energy in the form of light (figure 2).

Figure 1. Excitation of an atom. Figure 2. Relaxation and photon emission of an atom.

AAS has an unlimited number of applications and is still a popular choice for uncomplicated
trace elemental analysis.
The technique makes use of absorption spectrometry to assess the concentration of an analyte in
a sample. It requires standards with known analyte content to establish the relation between the
measured absorbance and concentration of the analyte hence rely on the Beer-Lambert Law
which states that;
A = έbc
Where; A is the absorbance of the sample
έ is the molar absorptivity coefficient
b is the path length and
c is the concentration

APPARATUS AND REAGENTS

REAGENTS APPARATUS
0.5M Chloroacetate Separating funnel
0.10M Oxine in CHCl3 Pipettes
Cu/Pb/Mg ion mixture 100 ml Erlenmeyer flask
1 M Ammonia solution 100 ml beaker
2 M hydrochloric acid 50 ml and 100 ml volumetric flasks
Distilled water Cotton wool, Teflon stop-cock
Small filter funnel
AAS instrument
PROCEDURE

1.00mL of the Cu/Mg/Pb mixture was pipetted into a 125mL separation funnel containing 10ml
of distilled water. To extract Cu; 10ml of 0.5M chloroacetate was added to the funnel followed
by addition of 0.10M oxine in CHCl 3. The mixture was then shaken for 1 minute and the layers
were then allowed to separate. CHCl3 layer was extracted through a smaller filter funnel with a
small plug of cotton wool (predamped in CHCl3) into a 100ml conical flask. The extraction of
copper was repeated 2 times with two 5ml aliquots of oxine solution and 3 oxine extracts were
combined and labeled flask1. The remaining aqueous solution was then drawn off from the
separation funnel into a 100ml beaker then 3 drops of dilute ammonia solution (1M) were added
to the solution. This solution was then transferred back into the separation funnel with two small
rinses of distilled water. Pb was extracted from the solution with 0.1M oxine in CHCl 3 following
the same procedure as for copper extraction. The extraction of Pb with 2 more 5ml aliquots of
oxine solution was done then the extracts were combined and labeled flask 2. The top aqueous
layer was drawn off into 50 ml volumetric flask and was then rinsed with distilled water and
made up to the mark with distilled water and the flask was labeled flask C. Copper was back
extracted in the first CHCl3/oxine extract in flask 1 three times with 10 ml, 5 ml and 5 ml of 2M
HCl. The aqueous layer was then collected into a 50 ml volumetric flask and made up to the
mark with distilled water and labeled flask A. Lead was back extracted in the same way as
copper with 10 ml, 5 ml and 5 ml of 2 M HCl successively and made up to 50 ml and was
labelled flask B. All the flasks A, B and C were kept in cold room for a week. The 10ppm
standards of Cu, Pb, and Mg were prepared and were used to make a suitable range of standards
to bracket the expected concentration (0.5, 1.0, 1.5, 2.0, and 2.5ppm) in the extracts. Then the
concentrations of Cu in flasks A and B, Pb in flasks A, B, C and Mg in flasks B and C were
determined using appropriate Atomic Absorption conditions.

RESULTS AND ANALYSIS

The concentrations of copper, lead and magnesium in flasks A, B and C were determined by
taking the average of readings under each flask hence the concentrations of Cu and Mg in flasks
were found to be:

Table 1: concentrations of Cu and Mg in flasks

Copper,Cu (mg/L) Magnesium, Mg (mg/L)

The calibration curves of 5 standards that were determined from this experiment for three metals
(copper,magnesium and lead) were used to calculate the concentration of the three metals in
solutions as seen from the attached results. The graphs were straight subsequently complying the
Beer’s law. It is typical in atomic spectroscopy for the sample to be found in one of
two forms solid or liquid. The liquid case would appear to be the least demanding form in which
to handle the sample, with perhaps a prerequisite for filtration being all that
is required. However, the inherent need of sensitivity of numerous spectroscopic techniques and
the need to carry out determinations at lower levels implies that constantly some form of pre-
concentrations is required (Douglas et-al, 2007). The liquid – liquid extraction method was
successfully used in extracting the metals before analysis using the AAS. Though the method is
highly laborious, it is the best method to use for separation and extraction of chemical species
like metals.

From this experiment the expectation was that copper, lead and Magnesium would be detected in
flask A, B, C respectively even though there is a possibility of traces of other metals being
detected in either one flask it wasn’t supposed to be detected. The concentration of copper was
found to be 0.364 mg/L in flask A and 0.145 mg/L in flask B, For magnesium the concentration
were determined to be 0.1779mg/L in flask B and 0.2568mg/L in flask C. Unfortunately the
concentrations of lead flasks could not be analyzed under the AAS due to lack of function of the
lamps hence results were affected.

The possible errors may include; Use of volumetric apparatus for preparing solutions and
standards not meeting the cleanliness requirements, Contamination and losses from reagents,
solvents and water used for sample preparations as according to Welz & Sperling, (2019) losses
are a particularly significant problem in trace analysis. As well as human error; It could also have
happened that not all the metal were extracted from the separation funnel due to failure to run off
all the desired solution containing the metal. FAAS machine was used to analyze the amount of
each metal in each flask, it might have happened that the machine/instrument was not
appropriately set or calibrated hence instrumental error. This has been observed from the
deviations obtained from both the concentration and absorbance values.

To help mitigate the possible sources of errors the followimg measures can be put into place; Use
high purity research grade reagents for sample preparation,. Use clean glassware for preparing
samples and standards as well as inert container material for trace level analysis. Water should be
freshly prepared and used for making solutions and should be double distilled or commercially
prepared by reverse osmosis systems. According to Skoog (1992), the efficiency of liquid-liquid
extraction can also be enhanced by adding one or more extractants to the solvent phase. The
extractants interacts with component to be extracted, increasing the capacity of the solvent.
The main advantages of AAS  include, High sample throughput, Easy to use, High precision and
Inexpensive technique whereas the main disadvantages of AAS  are as follows: only solutions
can be analyzed, less sensitivity compared to graphite furnace, relatively large sample quantities
are required (1-3 ml) and problems with refractory elements.

CONCLUSION

In this experiment liquid-liquid extraction method was used to separate Cu, Mg and Pb metals in
a sample mixture and only Cu and Mg were able to be analyzed using Atomic absorption
spectroscopy (AAS). The concentration of Cu determined in flasks A and B which were found to
be 0.364mg/L and 0.145 mg/L respectively whereas for Mg; 0.1779 mg/L and 0.2568 mg/L were
obtained in flask B and C respectively and as for Pb the concentrations in flask A, B, C could not
be analyzed under the AAS due to faults with the lamps.
REFERENCES

1. a) A. Walsh, Anal. Chem., 63, 933A–941A, 1991

(b) S.R. Koirtyohann, Anal. Chem., 63, 1024A–1031A, 1991

(c) W. Slavin, Anal. Chem., 63, 1033A–1038A, 1991.

2. D. Harvey,  “Modern Analytical Chemistry”, McGraw-Hill Companies Inc., 2010

3. D.A. Skoog, F.J.  Holler, T.A.  Nieman,  “Principles of Instrumental Analysis”.

4. García, R. Belmont, H. Padilla, M. C. Torres and A. Báez. (2009). “Trace metals and
inorganic ions measurements in rain from Mexico City and a nearby rural area”. Rev.
Chemistry and Ecology. 25(2), pp. 71-86.
5. Welz. B and Sperling. M, (2019), Atomic Absorption Spectroscopy, Wiley-VCH,
Weinheim, Germany, p 445 – 476.