Ph nguyn t

Atomic Spectrometric Methods

Atomic Spectrometric Methods

S hp thu ca nguyn t
4d
5s
4p
3d
4s

N
M

3p
3s

2p
2s

1s

11Na:

Atomic Spectrometric Methods

1s2 2s2 2p6 3s1

Nguyn tc
- Trng thi
c bn M0
(nhiu)

Ngun
cung cp
nng
lng

Mu

- Trng thi
kch thch
M*(t)
- Trng thi
ion M n+ (rt
t

pht x M* - M0(-h)
+ bc x
(n cathode
lm)

hp thu M0 M* (+h)

Atomic Spectrometric Methods

Quang ph pht x nguyn t

-h

detector

tn hiu o

cng detector
tn hiu o
bc x
gim i
Quang ph hp thu nguyn t
3

Flame Emission Spectrometry (FES)

Atomic Spectrometric Methods

S nguyn t ha (Atomization)

Atomic Spectrometric Methods

Flame atomizers
Fuels and Oxidants Used for Combustion

Atomic Spectrometric Methods

Flame Emission Spectrometry (FES)

Atomic Spectrometric Methods

The Boltzmann Distribution

N e The relative population of
No

N e g e ( E e E o ) / kT

e
No g0

g e and g o

T
E

Atomic Spectrometric Methods

excited-state
The relative population of groundstate
The statistical weights of
the excited and ground
states, respectively

The absolute temperature

The energies of the two states
The Boltzmann constant,
k = 1,381 x 10 16 erg/K

The Boltzmann Distribution

Atomic Spectrometric Methods

Flame Emission Spectrometry (FES)

Ca0, Ca0*, Ca+ : atom in its ground, excited or

ionized states

Atomic Spectrometric Methods

10

Atomic Absorption Spectrophotometry (AAS)

Atomic Spectrometric Methods

11

Hollow cathode lamp

Atomic Spectrometric Methods

12

Electrothermal Atomizer
Graphite furnace
Graphite furnace: 1-3 cm in length and 3-8 mm
in diameter

Diagram of an electrothermal analyzer

Atomic Spectrometric Methods

13

Graphite furnace*
Sample volume (5-10 L)
Atomizer (3 stages):
desolvation (to = 110 0C)
ashing (to = 350 - 1200 0C)
atomization (to = 2000 3000 0C)

Sensitivitive : 1000 folds higher than flame

atomization

Atomic Spectrometric Methods

14

Atomic Absorption Detection Limits for Selected Elements

Atomic Spectrometric Methods

15

Intrumentation
Flame Emission Spectrometry

- Atomizer
- Monochromator
- Detector
Atomic Spectrometric Methods

Flame Absorption Spectrometry

- Hollow-cathode lamp
- Atomizer
- Monochromator
- Detector

16

ICP MS and ICP-OES

ICP-MS: Inductively coupled plasma mass
spectrometry
ICP-OES: Inductively coupled plasma
optical emission spectra
Plasma (to: 6000 10 000 oK)
Nguyn t ha hu ht cc nguyn t
trong bng tun hon nguyn t

Atomic Spectrometric Methods

17

ICP-OES

Atomic Spectrometric Methods

18

ICP-MS

Atomic Spectrometric Methods

19

ng dng*
Qualitative
Quatitative
Selecting the wavelenth and split width
Minimizine spectral interferences
Minimizing chemical interferences

Atomic Spectrometric Methods

20

Selecting the wavelength and slit width*

Characteristic
Concentrations:
nng cht phn
tch ng vi A =
0.00436 (T = 99%)

Atomic Spectrometric Methods

21

Minimizing chemical interferences

Nonvolative compounds containing the analyte
V d: Phn tch Ca2+ :
5 ppm Ca2+ (A= 0.5);
5 ppm Ca2+ + 100 ppm Al3+ (A = 0.14);
5 ppm Ca2+ + 500 ppm PO43- (A = 0.38)

Al-Ca-O oxide
Ca3 (PO4)2

Gia tng nhit ngn la

Thay i t l fuel-to-oxidant ca ngn la
Thm tc nhn phng thch (releasing agent) hay tc
nhn bo v (protecting agent)
Atomic Spectrometric Methods

22

Minimizing chemical interferences

Releasing agent a reagent whose reaction with an
interferant is more favorable than the interferants
reaction with the analyte
V d: Phn tch Ca2+ :
5 ppm Ca2+ (A= 0.5);
5 ppm Ca2+ + 100 ppm Al3+ (A = 0,14)

Al-Ca-O oxide

5 ppm Ca2+ + 100 ppm Al3+ + 2000 ppm SrCl2 (A = 0.48)

5 ppm Ca 2+ + 2000 ppm SrCl2 (A = 0,49)

Atomic Spectrometric Methods

23

Minimizing chemical interferences

Protecting agent a reagent that reacts with the
analyte, preventing it from transforming into a
nonanalyzable form
V d: Phn tch Ca2+ :
5 ppm Ca2+ (A= 0.5);
5 ppm Ca2+ + 500 ppm PO43- (A = 0.38)

Ca3 (PO4)2

5 ppm Ca 2+ + 500 ppm PO43- + 1% EDTA (A = 0,52)

5 ppm Ca 2+ + 1% EDTA (A = 0,55)

Atomic Spectrometric Methods

24

Ionization interferences
M
M e
Ionization suppressor: K or Ce

Atomic Spectrometric Methods

25

Minimizing spectral interference

Samples matrix (wavelength < 300 nm)
Gia tng nhit ngn la
Thay i thnh phn ngn la
Thm chun vo mu

Atomic Spectrometric Methods

26

Sample Preparing*

V d

Atomic Spectrometric Methods

27

Sample Preparing Example*

Determination of Cu and Zn in tissue samples

Atomic Spectrometric Methods

28

Quantitative - Example
Determination of Cu and Zn in tissue samples

Atomic Spectrometric Methods

29

Quantitative
Determination of Cu and Zn in tissue samples

A 0.0002 0.0661 ( ppm Cu )

r 0.9999
1
g Cu / g FFDT 0,35110 5
11,23 10 3
(0.351 g / mL)(5 mL)

156 g Cu / g FFDT
0.01123
3

Atomic Spectrometric Methods

30

Cc yu t nh hng pht x v
hp thu nguyn t ngn la

nh hng ca dung mi
nh hng ca dng anion lin kt
nh hng ca s ion ha
nh hng ca s cng hng
Hin tng t hp thu

Atomic Spectrometric Methods

31

Summary
Sensitivity
Accuracy = 0,5 5%
Precision (A> 0,1, relative standard deviation (% RSD)
= 0,3 1% for flame atomization; = 1 5% for
electrothermal atomization)
Selectivity
Time, cost and equipment

Atomic Spectrometric Methods

32