SSA

(Spektroskopi Serapan Atom)

 Concern In AAS analysis
• SOLVENT
– Flame emission of solvent
– Surface tension of solvent effect size of droplets
– Solvent also adsorb the light  make a blank
– Organic solvents increase adsorption signal
– FOREIGN ANION AND CATION
• Cation almost give no interference
• Bonding between metal-anion hard to break and give lower absorption
signal
– METAL BONDING
• Metal bonding give lower adsorption signal
– FLAME
• Choose temperature of flame
1

2
 Spectral Interference
• SPECTRAL
Spectral interference is also effected by the radiation of an emission
line of another element or compound, or background radiation from
flame, solvent or sample
Example 1: Vanadium line is 3082.11 A and Aluminum is at 3082.15
A. Choose a different Aluminum line at 3092.7 A.
! Commonly happen in ICP-AES
Example2: Radiation interference in the determination of Na with
Mg present, and in the determination of Fe with Cu or Ni present
•  use alternate wavelength, smaller slit width, or blank
Background Correction
Deutrium Lamp as a corrector will reduce adsorption of background
then detector only show absorption of analyte only

3
 Chemical Interference
• Low volatility
– Eliminated by using higher temperature flame, releasing
agent, protective agents (EDTA, 8 hydroxyquinoline, APDC
ammonium 1-pyrrolidine carbodithioic acid)
– Example
1. when calcium is to be measured in a matrix rich in phosphate
ions then strontium or lanthanum chloride are added to
liberate calcium and to increase the volatility of the medium to
ensure a more efficient during the decomposition step.
2. measuring sodium or potassium it is usual to add a little of
Schinkel’s solution (CsCl/LaCl3 ~releasing agent)

4
 Chemical Interference
– Dissociation Equilibria
• Dissociation occurs when metal oxides and hydroxides dissociate in
flame to release the metal atom
• Alkaline earth metal oxides and hydroxides are stable and will produce
broad band spectra. Very high temperature is required to break them up
• However, Alkali metal oxides and hydroxides are unstable even at low
temperature and will produce line spectra
• Example : Determination of Vanadium in presence of Al and Ti.
– Fuel rich flame – gives higher absorbance for V because the little oxygen
present in flame will be captured by the Al and Ti, and more V atoms
available.
– Lean flame – oxygen is present and V will form the oxide. Addition of extra
Al or Ti will not affect the signal – decreased absorbance

5
 Chemical Interference
– Ionization in Flame
This occurs only in hot flames. The energy of
the flame excite the ground state atoms to
ionic state by loss of electron resulting in a
depletion of ground state atoms, and the
element does not absorb at the correct
wavelength
• Using low temperature flame
• Addition of Ionization Suppressor/
suppressant / buffer
An ionization buffer is a salt of an alkali
metal which ionizes to give a mass of
electrons that shift the ionization
equilibrium of analyte to form atoms.
 Add a 0.1% KCl soln to blank, standard, and
sample

6
 Self Absorption
• When atoms in ‘cooler’ flame area region emit
resonance wavelength
• In the extreme, the main wavelength may
become less intense or disappear, this result is
division of emission maximum into what
appears to be two peaks by self-reversal
• Control the concentration of analyte can be a
solution to prevent this interferens but if it
too low can undergo ionization interference
7
Transmittances (Lambert-Beer Law)
I dI
T   kcdb
I0 I0
I dI b

I0 I
I0 I 0  kc 0 db
I I
 ln( )  kbc  2.303 log( )
I0 I0
I
b   log( )   log T  A  bc
I0
k

2.303
8
 Sample Dissolution For Elemental
Analysis : Preparation
• Dry Ashing – decompose and eliminate the organic
matter of sample with calcination in the furnace
(450℃) then dissolve using appropriate acid
• Oxygen Flask Combustion – combustion in an oxygen-
rich atmosphere,
• Wet Digestion – chemical degradation of sample
matrices in solution, usually with a combination of
acids to increase solubility
• Microwave Digestion – addition the electromagnetic
waves with frequencies in the range of 300-300,000
MHz could increase the efficiency and reduce the
number of sample

9
Beberapa hal yang perlu diperhatikan dlm analisis dgn
AAS antara lain:
• Larutan sampel seencer mungkin kadar unsur yang
dianalisis tidak lebih 5% dalam pelarut yang sesuai.
Larutan yang dianalisis lebih disukai diasamkan atau
kalau dilebur dengan alkali tanah terakhir harus
diasamkan lagi.
• Hindari pemakaian pelarut aromatik atau halogenida.
Pelarut organik yang umum dipakai adalah keton,
ester dan etil asetat. Hendaklah dipakai pelarut-
pelarut untuk analisis (p.a).
• Dilakukan perhitungan atau kalibrasi dengan zat
standar sama seperti pada pelaksanaan
spektrofotometri UV-Vis.
 QUANTITATIVE ANALYSIS
CALIBRATION CURVE

METHODS STANDARD ADDITION

INTERNAL STANDARD

11
 Calibration Curve Methods
• External standard  Prepare standard solutions of
at least three different concentrations, measure
the absorbance of these standard solutions, and
prepare a calibration curve from the values
obtained.
• Then measure the absorbance of the test solution
adjusted in concentration to a measurable range,
and determine the concentration of the element
from the calibration curve.

12
 Preparation
SAMPLE

Abs = 0.321
[sample] =
A set of standard with different concentration
5.602 ppm

Measure the absorbance of

standard
[C] ppm Abs.
0 0
2 0.086
4 0.209
6 0.367
8 0.469
10 0.565 13
 Internal Standard Methods
• Metoda standar internal adalah metoda standar murni (single elemen) yang dapat
digunakan sebagai pembanding. Pada contoh maupun standar ditambahkan unsur
dengan sifat hampir sama dengan unsur yang dianalisis. Hal ini untuk mencegah
terjadinya energi radiasi yang dipancarkan oleh dua unsur dengan panjang
gelombang yang berdekatan.
• An internal standard should be added at the start of the sample analysis work so
that it joins the sample in dissolving, mixing, filtering prior to measurement
• Criteria
– Its concentration samples and standards is always the same
– Its chemical and physical properties are as similar as possible to those of the
element being determined
– The ionization energies of the internal standard and analyte should be similar
to assure that both have the same distributions ratio of atoms in the source

F = relative intensity

14
 Preparation
BLANK

INTERNAL
STANDARD SAMPLE
(KNOWN) STANDARD

SAMPLE

15
 Internal Standard Methods
• Five standard solutions were prepared for measuring the lead
concentration in two solutions, A and B. The two solutions A and B
contain the same concentration of magnesium used as an internal
standard. The following data were obtained
Steps:
Concentration Emission of Signal of Mg (A) 1.Make a calibration curve
(mg/L) Signal Pb (A) ( x = [Pb] , y = APb/AMg)
0.10 13.86 11.88 2.Get an equation y = a x
0.20 23.49 11.76 3.Plot the Aanalyte /AMg to that
equation
0.30 33.81 12.24
0.40 44.50 12.00
0.50 53.63 12.12
Sol A 15.50 11.80
Sol B 42.60 12.40

16
Concentration Emission of Signal of Mg (A) APb/ AMg
(mg/L) Signal Pb (A)
0.10 13.86 11.88 1.167
0.20 23.49 11.76 2.013
0.30 33.81 12.24 2.762
0.40 44.50 12.00 3.708
0.50 53.63 12.12 4.425
Sol A 15.50 11.80 1.314
Sol B 42.60 12.40 3.435

17
 Standard Addition Method
• the standard solution is added so that the analyte contain
stepwise increasing amounts of the element, and add the
solvent to make a definite volume. Measure the
absorbance for each solution
• Pada teknik ini larutan sampel dengan volume yang sama
dimasukkan ke dalam masing-masing labu takar. Kemudian
ditambahkan larutan standar dengan volume yang
berbeda.
• Keunggulan dari metode penambahan standar adalah
dapat mengatasi kesalahan atau gangguan yang disebabkan
oleh interferensi fisika dan interferensi kimia dalam larutan
sampel.

18
 Preparation
STANDARD
(KNOWN)
SAMPLE

Sample Unknown (ml) Standard (ml)

Blank 0.0 0.0
A 10.0 0.0
B 10.0 10.0
C 10.0 20.0
D 10.0 30.0
E 10.0 40.0

19
20
21
 Standard Addition Method
The cobalt in an aqueous sample was determined by pipetting 10,0 ml
of the unknown into each of four 50.0 ml volumetric flasks. Various
volumes of a standard containing 6.23 ppm Co were added to flask
following which the solutions were diluted to volume. Calculate parts
per million of cobalt in the sample from the data that follow.

Sample Unknown (ml) Standard (ml) Absorbance

Blank 0.0 0.0 0.042
A 10.0 0.0 0.201
B 10.0 10.0 0.292
C 10.0 20.0 0.378
D 10.0 30.0 0.467
E 10.0 40.0 0.554

22
 Solution 1
Sample Unknown (ml) Standard (ml) Absorbance Plot
Absorbance
Blank 0.0 0.0 0.042
A 10.0 0.0 0.201 0,159
B 10.0 10.0 0.292 0,250
C 10.0 20.0 0.378 0,336
D 10.0 30.0 0.467 0,425
E 10.0 40.0 0.554 0,512

y = 0,0088x + 0,1602
0 = 0,0088x + 0,1602
x = - 0,1602/0,0088
x = - 18,2045

23
 Solution 2
Sample Unknown (ml) Standard (ml) Absorbance Final Plot
Concentration Absorbance
Blank 0.0 0.0 0.042
A 10.0 0.0 0.201 0,00 0,159
B 10.0 10.0 0.292 1,246 0,250
C 10.0 20.0 0.378 2,492 0,336
D 10.0 30.0 0.467 3,738 0,425
E 10.0 40.0 0.554 4,984 0,512

y = 0,0707x + 0,1602
0 = 0,0707x + 0,1602
x = - 0,1602 / 0,0707
= -2,2659

24
 SOAL
Analysis of Calcium in hard water was using AAS at
422.7 nm with N2O-asetilene flame. Absorbance of
sample was 0,380. If calibration curve from several Ca
standard solution was below, calculate concentration
of Ca in sample (ppm)! Steps:
1.Make a calibration curve
Ca (ppm) Absorbance ( x = [Ca] , y = Aca)
2.Get an equation y = a x
0.0 0.0 3.Plot the Aanalyte to that
1.0 0.090 equation
2.2 0.194
3.10 0.273
3.9 0.340
5.0 0.440
6.0 0.525 25