ATOMIC SPECTROSCOPY

11/22/2012

dcapodaca_CHM115_MAPUA

Atomic Spectroscopy
A principal tool of analytical chemistry:
high sensitivity
simultaneous multi-element analyses are possible
automatic analysis is easy
Measuring analyte concentrations at the ppm and ppb levels
are routine
Precision is typically 1-2%

11/22/2012

dcapodaca_CHM115_MAPUA

Atomic spectra development

1950 Flame emission

1960 Atomic absorption
Mid 1960s Atomic fluorescence
1970 ICP-MS

11/22/2012

dcapodaca_CHM115_MAPUA

11/22/2012

dcapodaca_CHM115_MAPUA

An Overview
A liquid sample is aspirated into a flame whose temperature is
2000-3000 K. Liquid evaporates and the remaining solid is
atomized in the flame. To create the specific frequencies of
light that are absorbed by a particular atom, the hollow
cathode lamp has a cathode made of that particular atom.
When the cathode is bombarded with energetic Ne+ or Ar+
ions, excited atoms vaporize and emit light with the same
frequencies that are absorbed by analyte atoms in the flame

11/22/2012

dcapodaca_CHM115_MAPUA

11/22/2012

dcapodaca_CHM115_MAPUA

11/22/2012

dcapodaca_CHM115_MAPUA

Atomization
The process of converting the analyte into free
atoms to emit or absorb light energy
Types of Atomization
Flame ppm
Flameless - ppb
Graphite furnace AAS (electrothermal)
Hydride vapor generator (HVG)
Mercury vapor unit
11/22/2012

dcapodaca_CHM115_MAPUA

Atomization:

Flames,
and Plasmas

Furnaces,

FLAMES
Premix burner - fuel, oxidant and sample are
mixed before introduction into the flame.
Most common fuel-oxidizer combination is
acetylene and air (2400 - 2700 K)
Acetylene-nitrous oxide ( 2900 - 3100 K) is used
to atomize high-boiling elements
Regions in the flame
11/22/2012

dcapodaca_CHM115_MAPUA

11/22/2012

dcapodaca_CHM115_MAPUA

10

Atomic Spectroscopy based on

Flame Atomization
Digested
sample

Gaseous atoms
elementary ions

Nebulize

Mist

Oxidation

Solvent
evaporates

Flame

11/22/2012

dcapodaca_CHM115_MAPUA

11

Steps in flame atomization

Nebulization
Desolvation of droplets
Vaporization of solids
Dissociation of molecular species
Ionization of analyte atoms

11/22/2012

dcapodaca_CHM115_MAPUA

12

Sources of flame
Type of flame

Temperature (deg C)

determinations

Ar H2

1577

Absorption wavelength at
UV range (As, Se, Zn, Pb, Cd,
Sn)

Air H2

2045

Air C2H2

2300

Most elements

N2O C2H2

2955

Refractory elements (Al, V,

Ti)

11/22/2012

dcapodaca_CHM115_MAPUA

13

Electrothermal Atomization
Furnaces
Graphite Furnace offers greater sensitivity than that
afforded by flames and requires less sample
From 1 to 100 L of a sample are injected into the furnace
through the hole at the center. Light from a hollow
cathode lamp travels through windows at each end of the
38-mm-long tube. To prevent oxidation of the graphite, Ar
gas is passed over the furnace, and the maximum
recommended temperature is 2550oC for not more than 7
s.

11/22/2012

dcapodaca_CHM115_MAPUA

14

11/22/2012

dcapodaca_CHM115_MAPUA

15

The furnace is heated in three or more steps to properly

atomize the sample.
drying
charring/pyrolysis
Atomization

Matrix modifier - a substance added to the sample to reduce

the loss of analyte during the charring by making the matrix
more volatile or the analyte less volatile.

11/22/2012

dcapodaca_CHM115_MAPUA

16

Flame vs Electrothermal
Atomization principle

Atomized through the heat

of the flame

Atomized by the heat

generated when a current
is passed through a
resistance bulb

Atomization efficiency

~10%

> 90%

Amount of sample
required

1 mL

5 to 50 L

Shape of absorption signal

Stationary signal

Peak shaped signal

Sensitivity

ppm

ppb

Reproducibility

< 1.0% RSD

~ 2-5% RSD

Matrix effect

Small

Large

Analysis time

Short
10-30s/sample

Long
1-5 min/sample

11/22/2012

dcapodaca_CHM115_MAPUA

17

Hydride Vapor Generation (HVG)

For volatile elements such as As, Se, Sb, Sn, Bi
and Te
Conversion of elements to metal hydrides by
sodium borohydride under acidic condition
Detection limit improved to ppb level
Suitable for environmental analysis

11/22/2012

dcapodaca_CHM115_MAPUA

18

AAS-VGA with argon or nitrogen gas

11/22/2012

dcapodaca_CHM115_MAPUA

19

 As, Bi, Sb, Se, Sn, Te Gaseous hydride

Flame

Atomization
Electrical heating cell

BH4- + 3H2O + H+ H3BO3 + 4H2

3BH4- + 3H+ + 4H3AsO3 AsH3 + 3H2O + 3H3BO3
11/22/2012

dcapodaca_CHM115_MAPUA

20

 Mercury ion in solutions reduced by SnCl2 to

elemental Hg which vaporizes at room
temperature
Suitable for environmental analysis of Hg in
water
Can detect 0.1 ppb Hg
11/22/2012

dcapodaca_CHM115_MAPUA

21

Plasma Atomization
Inductively Coupled Plasma
reaches a much higher temperature than ordinary
combustion flames.
eliminates interference encountered with
combustion flames.
Simultaneous multi-element analyses are
becoming routine with ICP instruments

11/22/2012

dcapodaca_CHM115_MAPUA

22

11/22/2012

dcapodaca_CHM115_MAPUA

23

Interference
Any effect that changes the signal while analyte concentration
remains unchanged.
Spectral interference - unwanted signals overlapping analyte
signal.
Chemical interference - chemical reactions decreasing the
concentration of analyte atoms

Ionization interference - ionization of analyte atoms decreases the

concentration of neutral atoms

11/22/2012

dcapodaca_CHM115_MAPUA

24

Physical Interference
In flame AAS, spray efficiency fluctuates due
to differences in viscosity and surface tension
between the standard and sample
In GFA
Sample dispersion measurement value
fluctuates due to graphite tube temperature
distribution (samples in organic solvents)
Sample viscosity adherence to sampler tip
causing errors in collection quantity ( blood
extracts)
11/22/2012 samples, or juice
dcapodaca_CHM115_MAPUA

25

Addressing Physical interference

Employ standard addition method
For flame AAS, carry out large dilution or small
dilution with acetone or butanol
For electrothermal AAS, use
pyrolytic/platform graphite tube

11/22/2012

dcapodaca_CHM115_MAPUA

26

Chemical Interferences in flame AAS

Generation of various compounds from
chemical reactions between components in
the sample (phosphate interfers with Ca, Mg
etc analysis)
Ionic interference shift of atom/ion
equilibrium within the flame due to
coexistence of metals with low ionic potentials
(influence of K during Na measurement or Na
during K measurement)
11/22/2012

dcapodaca_CHM115_MAPUA

27

Chemical Interferences in GFA AAS

Generation of low boiling point compounds by coexisting
matrices (influence of chloride ions relative to Cd in
furnace analyses, causing target elements to scatter at
ashing step)
Influence of coexisting matrices (samples with high O2
content such as biological samples)
Metals reacting with graphite tube to form carbides:
Metallic carbide Ti, V, Mo, Cr
Intermetallic carbide Mn, Co, Ni
Heteropolar carbide - Ca, Ba
Diamond type carbide - Si
11/22/2012

dcapodaca_CHM115_MAPUA

28

Addressing Chemical Interferences

Removal of obstructing materials by ion exchange and
solvent extraction
Target element extraction
Use of hotter flame such as N2O/C2H2
Standard addition method
Ionization buffers in flame
Provide an excess of electrons, to increase the free
atom population of elements with low ionization
potential
Cesium chloride, cesium nitrate, lithium chloride,
lithium nitrate, potassium chloride, potassium nitrate
11/22/2012

dcapodaca_CHM115_MAPUA

29

Addressing Chemical Interference

Use of releasing agents (flame AAS)
Minimizes chemical interference by combining
with the interfering anions, liberating the element
to be analyzed
Lanthanum chloride, lanthanum nitrate, strontium
salts

Use of matrix modifier (GFA)

Reduces the volatility of the analyte
Increases the atomization efficiency of the analyte
by changing its chemical composition
11/22/2012

dcapodaca_CHM115_MAPUA

30

 Permits the use of high charring temperatures to

volatile interfering substances and improve
sensitivity
Increases the volatility of the matrix
Magnesium nitrate, palladium nitrate, calcium
nitrate, ammonium phosphate, ammonium
nitrate, nickel nitrate

11/22/2012

dcapodaca_CHM115_MAPUA

31

 NaCl + NH4NO3 NH4Cl + NaNO3

decomposed at 400oC, this makes the chloride
ion easier to sublimate or evaporate due to
lower boiling point
Volatile elements (Cd, Pb) + H3PO4
Cd3(PO4)2 less volatile, higher ashing
temperature can be used
11/22/2012

dcapodaca_CHM115_MAPUA

32

Matrix Modifier
Element

11/22/2012

Matrix Modifiers

As

Ni nitrate or Pd nitrate + Mg nitrate

Cd

Ammonium phosphate + Mg nitrate

Cr

Mg nitrate

Co

Mg nitrate

Cu

Pd nitrate + Mg nitrate or ammonium nitrate

Au

Pd nitrate + Mg nitrate

Pb

Ammonium phosphate + Mg nitrate or ammonium

nitrate

Ni

Mg nitrate or ammonium phosphate

Hg

Pd nitrate + Mg nitrate
dcapodaca_CHM115_MAPUA

33

Spectrophotometric Interference
Molecular absorption caused by
undissociated molecules in the sample path,
the absorption bands from molecules are
usually broad in UV region
Light scattering caused by particles in the
sample path, and also produces a broad band
effect
11/22/2012

dcapodaca_CHM115_MAPUA

34

 Spectral interference caused by overlapping

of the atomic absorption of an analyte and
other free atoms in sample (two spectrals with
close absorption wavelengths)
Self absorbance if lamp current is too high
Absorption and scattering by molecules
Absorption by wings of resonance absorption lines

11/22/2012

dcapodaca_CHM115_MAPUA

35

Target element

Spectral Line (nm)

Target element

Spectral line (nm)

Al

308.215

308.211

Ca

422.673

Ge

422.657

Cd

228.802

As

228.812

Co

252.136

In

252.137

Cu

324.754

Eu

324.753

Fe

271.903

Pt

271.904

Ga

403.298

Mn

403.307

Hg

253.652

Co

253.649

Mn

403.307

Ga

403.298

Sb

217.023

Pb

216.999

Si

250.690

250.690

Zn

213.856

Fe

213.859

11/22/2012

dcapodaca_CHM115_MAPUA

36

Addressing Spectrophotometric
interference
Removal of obstructing materials by solvent
extraction
Background correction by instrument

11/22/2012

dcapodaca_CHM115_MAPUA

37

Background Correction
To distinguish analyte signal from absorption, emission, and
optical scattering of the sample matrix, the flame, plasma or a
white-hot graphite furnace.
Beam chopping or electrical modulation of the hollow
cathode lamp
Deuterium lamp background correction
Smith-Hieftje background correction
Zeeman effect

11/22/2012

dcapodaca_CHM115_MAPUA

38

Background correction
Required when the sample contains other
materials that can absorb light at the element
wavelength
If no correction take places, the absorbance
will be excessively high and the concentration
of the element will be overestimated
Determination of analyte at UV region

11/22/2012

dcapodaca_CHM115_MAPUA

39

Background Correction
Deuterium lamp correction for molecular
absorption interference
Deuterium lamp correction for light scattering
by particles
Spectral correction for spectral interference

11/22/2012

dcapodaca_CHM115_MAPUA

40

Deuterium correction
Most common type of background correction
Effective range is up to 430 nm
Corrects the molecular absorption and light
scattering

11/22/2012

dcapodaca_CHM115_MAPUA

41

Self reversal correction

Step 1
The lamp is first run at a low current (10 mA) and its
light is absorbed by the sample elements and
background
Step 2
Then a very brief pulse of high current (200 mA) is
passed through the lamp causing self-reversal and
background is measured
Emission line becomes broader and the atomic
absorbance from the analyte is greatly reduced hence
it is called self reversal
11/22/2012

dcapodaca_CHM115_MAPUA

42

Zeeman Correction
Intense magnetic field cause atomic spectra
lines to split into 2 or more components which
can only absorb polarized light
A polarizer can be used to separate these
components so that (target element +
background) and (background) can be
measured
11/22/2012

dcapodaca_CHM115_MAPUA

43

Wavelength Range

D2 Lamp

Self Reversal

Zeeman

Wavelength range,
nm

190-430

190-900

190-900

Molecular
absorption
correction

Yes

Yes

Yes

Spectral
interference
correction

No

Yes

Yes

Deterioration of
sensitivity

No

Yes

Yes

Loss of light
intensity

No

No

Yes

Instrumental
requirement

D2 lamp

SR lamp

Polarizer and
magnet

Optical adjustment

Necessary

Not necessary

Not necessary

Atomizing unit
specificity

None (flame and

GFA)

None (flame and

GFA)

Specific (GFA)

11/22/2012

dcapodaca_CHM115_MAPUA

44

Sample preparation

To clean up samples
To remove interfering species
To isolate analyte of interest
To decompose the organic substance by dry
ashing, wet ashing methods, etc
Sample preparation method is dependent on
Nature of element
Sample, potential interference
Analysis method

11/22/2012

dcapodaca_CHM115_MAPUA

45

Sample pretreatment
Dilution method
The sample is diluted using purified water, dilute
acids and organic solvents
Effective only for homogeneous/uniform samples
Food products, pharmaceutical, wastewater,
plating solution, lubricants, biological samples

11/22/2012

dcapodaca_CHM115_MAPUA

46

 Treat inorganic samples in mineral acids, with

heating
Convert organic samples by oxidative
treatment to CO2 and H2O with
Dry ashing
Wet ashing (digestion)
High pressure decomposition (microwave
digestion)
11/22/2012

dcapodaca_CHM115_MAPUA

47

Dry ashing
Drying

Oxidation,
Ashing

Acid dissolution
11/22/2012

dcapodaca_CHM115_MAPUA

48

Wet ashing
Volatile elements = Sample + acid
heated at low temp

Extremely small amount of organic

substances and suspensions = boiling
by using HCl or HNO3
For samples containing OH, oxide,
sulfide and phosphate = HCl or HNO3

Organic substances that are difficult

to oxidize = HCl or HNO3
11/22/2012

dcapodaca_CHM115_MAPUA

49

Wet Ashing
Clean, readily oxidized sample

HNO3

For samples containing OH, oxide,

sulfide and phosphate = HCl or HNO3

HCl - HNO3
H2SO4 - HNO3

Difficult to oxidize organic samples

HClO4 - HNO3
HClO4 HF HNO3

11/22/2012

dcapodaca_CHM115_MAPUA

50

Sample
H2SO4
Digestion and oxidation

H2O2
oxidation

boiling
Remove H2O2
11/22/2012

dcapodaca_CHM115_MAPUA

51

High pressure decomposition or

microwave decomposition
The sample and acid are decomposed in a
closed vessel at high temperature and high
pressure
Short decomposition time
No volatilization during decomposition
Minimal contamination
Optimal for trace elements and samples
Safety features
11/22/2012

dcapodaca_CHM115_MAPUA

52

 Alkaline fusion
Sample is fused with alkaline flux (sodium
carbonate) by heating to a high temperature
For metallic compounds and ceramics, high MW
and complex samples (polymers, sand, etc)
The sample will have high salt concentration
interference and contamination must be
considered

11/22/2012

dcapodaca_CHM115_MAPUA

53

 Solvent extraction method

Extracting element in solvent which does not mix
with water
Chelate extraction system at optimum pH value
Solvents: MIBK, ethyl acetate, isobutyl acetate,
amy acetate, MEK
Chelating agents: DDTC, APDC
MIBK extraction for Au analysis in ore
APDC-MIBK extraction of trace metals in seawater
DDTC extraction
11/22/2012

dcapodaca_CHM115_MAPUA

54

Detection limits (ppb)

Element

Flame AAS

Graphite Furnace
AAS

Mercury Hydride

Antimony

30

0.2

0.1

Arsenic

100

0.2

0.02

Bismuth

20

0.1

0.02

Mercury

200

20

0.008

Selenium

70

0.5

0.02

Tellurium

20

0.1

0.02

Copper

0.02

Calcium

0.05

Lead

10

0.05

11/22/2012

dcapodaca_CHM115_MAPUA

55

Detection Limits
The concentration of an element that gives a signal equal
to three times the peak-to-peak noise level of the
baseline.
Detection limits vary from instrument to instrument.
The detection limit for furnaces is typically lower than that
observed with a flame; detection limits for the ICP are
intermediate between the flame and the furnace.

11/22/2012

dcapodaca_CHM115_MAPUA

56

 Sample Problem:
A series of sequential baseline absorbance measurements are
made in a spectrophotometric

method, using a blank solution. The absorbance readings are

0.002, 0.000, 0.008, 0.006, and 0.003. A standard 1 ppm
analyte solution gives an absorbance reading of 0.051. What is
the detection limit?

Solution:
std. dev. = 0.0032
mean = 0.004
detection limit = 3 x 0.0032 = 0.0096 absorbance reading
net reading for the std. (1 ppm) = 0.051 - 0.004 = 0.047
the detection limit would correspond to 1 ppm
(0.0096/0.047) = 0.2 ppm and would give a total absorbance
reading of 0.0096 + 0.004 = 0.014
11/22/2012

dcapodaca_CHM115_MAPUA

57

Quantification Methods
Calibration curve method
calibration curve shows the response of a chemical analysis to
known quantities (std. solns) of analyte.

Constructing a Calibration Curve

1. Prepare known samples of analyte.
2. Subtract the ave. absorbance of the three blank
samples from each measured absorbance to
obtain corrected absorbance.
3. Make a graph of corrected absorbance versus
quantity of the analyte in the sample. Find the best straight
line through the linear portion of the data.
11/22/2012

dcapodaca_CHM115_MAPUA

58

Internal standard method

a known amount of a compound, different from analyte, that is
added to the unknown. Signal from analyte is compared with
signal from the internal standard to find out how much analyte
is present

Especially useful when:

the quantity of sample analyzed is not very reproducible,
the absolute instrument response varies from run to run for
reasons that are hard to control
controlled sample losses occur during sample preparation

11/22/2012

dcapodaca_CHM115_MAPUA

59

Standard Addition method

a known quantity of analyte is added to an unknown to increase
the concentration of analyte by a known amount.

Frequently used to calibrate the response of an analytical

procedure when matrix effects are important.

11/22/2012

dcapodaca_CHM115_MAPUA

60

Standard Addition Plot

0.6
0.5
0.4
0.3
0.2
0.1
0

Absorbance

Absorbance

Calibration Curve

0.02 0.05

0.1

0.2
-0.2

Concentration, mg/L
11/22/2012

dcapodaca_CHM115_MAPUA

0.2

0.4

0.6

Unknown + Std. Samples

0.8

1
61