3 Atomic Absorption Spectroscopy (AAS)

3.1 Method
3.2 Sample- & Standard preparation
3.3 Results from the AAS
3.3.1 K O
2

3.3.2 ZnO
3.3.3 Pb
3.4 Discussion & Preliminary conclusion
3.5 Reference
https://en.wikipedia.org/wiki/Atomic_absorption_spectroscopy
3.1 Method
Atomic Absorption Spectroscopy is a spectroanalytical procedure for the quantitative
determination of chemical elements using the absorption of optical radiation (light) by
free atoms in the gaseous state. Atomic absorption spectroscopy is based on
absorption of light by free metallic ions.
Atomic absorption spectroscopy was first used as an analytical technique, and the
underlying principles were established in the 1950s by Robert Wilhelm Bunsen.

Fig.1 Atomic absorption spectrophotometer Fig 2. Simple principal

In 1987
Atomic absorption spectrometry has many uses in different areas of chemistry such as
clinical analysis of metals in biological fluids and tissues such as whole blood,
plasma, urine, saliva, brain tissue, liver, hair, muscle tissue, semen, in some
pharmaceutical manufacturing processes, minute quantities of a catalyst that remain in
the final drug product, and analyzing water for its metal content.

As is known to as the relationship between the Energy(E) transition and the

wavelength (λ)
E = hc/λ = hν = hcν, (1)
,
h Planck’s constant, c light velocity, ν frequency, ν wave number

When the atom of sample absorb energy from light, it becomes excited and jump into
higher energy state from ground state. In this cast, this state is not stable so that high
energy atom release energy as a consequence of photon, that is what we called DE-
excitation.

When the frequency of the incident radiation is equal to the energy frequency required
for the electrons in the atom to transition from the ground state to the higher energy
state (generally the first excited state), the outer electrons in the atom will selectively
absorb the characteristic line of same element; hence, the incident light attenuated
The degree of attenuation of the characteristic line due to absorption is called
absorbance A.

Fig 3.Atomic Absorption Process

A = log10 (P0/P) = abc (2)

Beer’s law (Lambert-Beer law) for different amounts of absorbing species
with
A = absorbance a = absorptivity (or absorption coefficient)
P0 = initial light power b = path length within the sample
P = final light power c = analyte concentration (n moles absorbing species)

Fig 4. Idealized and Deviation curve of absorbance and concentration

In general, since the atomic energy level is quantified, in all cases, the atom's
absorption of radiation is selective. Since the atomic structure of each element and the
arrangement of the outer electrons are different, the energy absorbed by the element
from the ground state to the first excited state is different, and thus the resonance
absorption lines of the elements have different characteristics.

3.3 Results from the AAS

Two different elements K and Zn are detected in Analytik jena - vario 6 (Flame
AAS). Moreover, element Pb is detected in Perkin Elmer - AAnalyst60 (Graphite
AAS) which has higher precision.

3.3.1 K O
2

This chart is the summary of K-element data result.From the second row of this chart,
the result of 0.5ppm K-Standard is 0.4947 which is quite near to the real
concentration; hence, this K-standard Calibration curve is usable and reliable. Then ,
from the Calibration curve and the extinction result, the corresponding values of
concentration of K in Phonolite 16 are calculated automatically by multiplying the
dilution factors.

Konz
Name ASVF SD
mg/L

K-Standard _ A:0.4947 0.00141

0.5ppm 1.000 O:0.4947 0.00141

Phonolite 16 _ A:1.127 0.00525

Ⅰ 44247.00 O:49866 262.8

Phonolite 16 _ A:1.089 0.00235

Ⅱ 50000.00 O:54450 104.2

Analysis result
A: Analysis sample O: Original sample

ASVF：dilution factor SD: standard deviation

 Fig 5. K Standard Calibration Curve

According to the equation : wt. % K2O =(Mk*2+Mo)/Mk*2*ppm/10000 (3)

Phonolite 16 Ⅰ：6.0067 ± 0.0316 wt.%

Phonolite 16 Ⅱ ：6.5589 ± 0.0125 wt.%

Finally, compared with data from XRF of wt. % K2O:

Phonolite 16 Ⅰ：6.67 wt.%
Phonolite 16 Ⅱ ：6.67 wt.%

From the comparison, we can infer the difference probably comes from the dilution
factors. As the data chart shows, the results of two analysis sample are 1.127 and
1.089 which are not far from each other; however, the big difference of results appears
when times the dilution factors.Hence, the XRF data of K2O is more reliable.
3.3.2 ZnO

This diagram is the summary of Zn-element data result.From the second row of this
chart, the result of 1ppmZn-Standard is 0.9777 which is approximately similar to the
real concentration; hence, we can infer that this Zn-standard Calibration curve is
usable and reliable. Then , as the same way of K element, from the Calibration curve
and the extinction result, the corresponding values of concentration of Zn in Phonolite
16 are calculated automatically by multiplying the dilution factors.

Konz
Name ASVF SD
mg/L

K-Standard _ A:0.9777 0.00781

1 ppm 1.000 O:0.9777 0.00781

Phonolite 16 _ A:1.065 0.01694

Ⅰ 221.238 O:235.7 3.747

Phonolite 16 _ A:0.9668 0.00596

Ⅱ 250.000 O:214.7 1.492

Analysis result
A: Analysis sample O: Original sample

ASVF：dilution factor SD: standard deviation

 Fig 6.Zn Standard Calibration Curve

According to the equation :wt.% ZnO=(Mz+Mo)/Mz*ppm/10000

Phonolite 16 Ⅰ：0.0293 ±0.0004 wt.% 236 ± 4 ppm

Phonolite 16 Ⅱ ：0.0267 ± 0.0002 wt.% 215 ± 1 ppm

Lastly,compared with data from XRF of ZnO:

Phonolite 16 Ⅰ：231 ppm
Phonolite 16 Ⅱ ：231 ppm

As it demonstrates that the results from AAS and XRF are both reliable, but from our
perspective, we trust AAS result more due to the reason that XRF analysis is faster
time-saving but lower precise,especially under 1000ppm.Therefore, the concentration
of ZnO in Phonolte 16 is above 215ppm~236ppm.
3.3.3 Pb

Different from Flame AAS, Graphite AAS is more precise due to fact that there is no
dilution required and higher order of magnitude (ppb). Because of the lower fraction
of Pb in Phonolite , Graphite AAS is accepted.

Fig 7 Pb Standard Calibration Curve

By using the four special points given in the data result, the concentration of 4
standard solutions are 0.00ppb, 50.00ppb, 100.00ppb, 200.00ppb respectively and
corresponding signals (Extinction energy) are 0.0102, 0.1112, 0.2281, 0.4335.
A linear curve is drawn as illustrated in Fig 7.

Konz
Name SD ppb
mg/kg

Phonolite 16
31.87 0.285 144.1
Ⅰ

Phonolite 16
35.97 0.253 143.9
Ⅱ
According to the equation wt. % PbO =(MPb+Mo)/MPb*ppm/10000

Phonolite 16 Ⅰ： 0.003433 ± 0.000031 wt.% 32 ± 0.3 ppm

Phonolite 16 Ⅱ ：0.003874 ± 0.000027 wt.% 36 ± 0.2 ppm

Eventually, when comparing with XRF of PbO

Phonolite 16 Ⅰ：17 ppm

Phonolite 16 Ⅱ ：15 ppm

As it demonstrates that the result from AAS has higher credibility , as the reason that
XRF analysis is faster time-saving but lower precise, especially under 1000 ppm
.Therefore, the concentration of PbO in Phonolte 16 is above 32ppm~36ppm.

3.4 Discussion & Preliminary conclusion

In conclusion, from AAS analysis, the concentration of K2O, ZnO, PbO are 6.5589
wt.%, 236 ppm, 32ppm separately. When analyze element which order is beyond
1000ppm, AAS and XRF are both good choice.However, when it comes to order of
magnitude below 1000 ppm, AAS is more acceptable and reliable.

3.5 Reference
https://en.wikipedia.org/wiki/Atomic_absorption_spectroscopy
3.2 Sample- & Standard preparation
3.2.1 Sample preparation

Acid needed: HNO3 65%; H2O2 30%; HBF450%

 Sample powder has to be dried ( 2h at 105°C) and cooled down

 Weigh 0.1 g sample into weighing glass, our samples are 0.113 g and 0.101 g respectively.
 Transfer sample into digestion vessel (MPV100) with a bit aqua
 Add 5 ml HNO3 65% + 1 ml H2O2 30% + 2 ml HBF4 50%
 Carefully close digestion vessel and put it into the microwave digestion apparatus(MLS)
 Start digestion program
 After cooling to < 70°C cautiously open the vessels
 Transfer the solution quantitatively into a 25 ml flask

3.2.2 Standard solution preparation

Table XX Standard solution Setting
100 ppm solution Blank Standard 1 Standard 2 Standard 3
K 0.2 0.5 1 ppm
Zn 0.5 1 2 ppm
CsCl 30% 1% 1% 1% 1%

Take K as an example,
 Dilution: use 0.5 ml from previous 25 ml sample solution and dilute it in 100 ml vessel
 According to the Setting table, make standard solution
Use 100 ppm intermediate solution to set different standard solutions
Due to dilution equation :(100 ppm* V= C* 100ml)
0 ppm: Blank
0.2 ppm: 0.2 ml Intermediate solution in 100 ml vessel
0.5 ppm: 0.5 ml Intermediate solution in 100 ml vessel
1.0 ppm: 1.0 ml Intermediate solution in 100 ml vessel
 Add CsCl 30% 1 ml to each blank and standard solution

Do the same to Zn according to setting table, then all the standard solutions are prepared.