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Spring 2017 CHEMISTRY 105

Instrumental Methods in Analytical Chemistry


Lecture: MW 9 AM 10 AM 219 Dwinelle
Labs: MTuWTh 1 5 PM 305 Latimer

Lecture 7. Atomic Emission Spectroscopy

Prof. Ke Xu

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Questions
Q1: For AA, why is it not ideal to use a
white light source + monochromator?

The noise is much greater than the signal

Q2: What light source is commonly used for AA?


How does it work?
Hollow-cathode lamp (HCL)

Q3: Is it correct to assume that because


the emission line from HCL is so narrow,
there is no need to use monochromators in
AA? Choosing the resonance signal

Q4: Different ways to measure and Non-absorbed lines


correct for background in AA? Continuum source-deuterium lamp
Zeeman effect
Source self-reversal
Chemical Interference matrix effects

Formation of compounds -low volatility, and/or no AA


MO & MOH:
MO M + O
MOH M + OH
Others: Calcium + phosphate

Minimized by increasing T (dissociation).


G = H TS (S is positive for dissociation)
Reduce oxidant in flame
Lower the height to use in flame
Releasing agents: competitive binding with interference. E.g.: Strontium binds
stronger than calcium to phosphate
Separation before loading
Standard addition

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Ionization equilibria

M M+ + e- (Spectra of M+ is different from M)

Depends on ionization potential (IP) and T


Prominent for alkali metals: >50% at high T!
Minimized by decreasing T!
Ionization suppressor: more easily ionized elements drives equilibrium
e.g. Adding Cs to release electron to measure Sr.
Toward unionized state

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Ionization suppressor
Adding potassium to measure strontium

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Standard addition Difference in slope: Matrix interference or ionization effect.

Actual concentration

Compensates for many of the interferences by adding known quantities of analyte to the
unknown in its complex matrix
Adding small amount of standards keeps the matrix nearly identical
Background removal is critical
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Atomic emission spectroscopy (AES)

Setup

AE Source Monochromator Detector

Principle

Luminescence PL

Thermal
energy

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Advantages of AES

(Qualitative)

Cs is not in the sample

Detection of multiple elements at the same time


Good for both qualitative and quantitative measurements
Reduced chemical interference (ICP at high T)
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AES for quantification
Signal proportional to number of atoms in
the excited state!

For fixed measuring conditions:


When the concentration is low

I = ac (Ideal; low c)

Taking into account of self-absorption:


When higher concentration, b is slightly smaller than 1
I = acb (Scheibe-Lomakin equation)

Linear on a log-log plot!

log I log a b log c

Slope

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For better reproducibility

Internal-standard!
Add into samples a component that
is not present in the test samples
produces a signal similar to, but
distinguishable from that of the analyte
is added in a constant amount to all
samples and standards
Use ratio of the measured signal of the
analyte to the measured signal of the
internal standard!

Add into samples an element that have non-


overlapping emission lines
Good reproducibility and calibration curves

R I / I 0 log R log I log I 0


Example: added fixed amount of yttrium,
log I log a b log c and used 242.2 nm emission line as
internal standard
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Sources to generate AE
Whats needed:
High T so more atoms are in the excited state
Stable/repeatable
Low background emission from source itself
Whats available
Flame
Rarely used performance not as good as AA
Arc and spark sources old school
OK performance; T ~ 5,000 K
Useful for solid samples
Instability of arc/spark
Poor atomization / matrix effects

Inductor L

~50 V, EDC V G
30 A
R
A
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Plasma sources - Inductively Coupled Plasma (ICP)

Torch of plasma:
Plasma: electrically conductive gaseous mixture
containing cations and electrons
High temperature up to 10,000 K
Energy from the coupling of induction coil:
powered by a radio-frequency generator (10 kW)
Plasma isolated from the quartz by Ar flow

Quartz
tube

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Characteristics of ICP torch

High temperature for AES excitation


Good atomization: Sample passes through ~8,000
K plasma. Reduced chemical interferences
Ionization is suppressed: high density of electrons
in plasma
M M+ + e-
Uniform temperature less self-absorption. Linear
calibration over large dynamic range.
Relatively clean spectroscopic background
Wide dynamic range (106)
Hard to work with solid samples.
High cost

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The many lines in AES

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Spectral overlap is a real problem for AE
AA: Analyzes a single element at one time; one HCL light source only generates a
few very narrow lines use one single, narrow line for AA at a time
AE: Multiple elements in the sample emitting at the same time no way to only excite
only one element at a time.
Use non-overlapping lines
Often need to use multiple lines to confirm the existence of one element
High-resolution monochromator helps

Echelle grating:
High-resolution spectra
in 2D format

Directly recording
with a camera (CCD)
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Single-channel + scanning!

Use slit + scanning to


obtain spectrum!

Rotating the grating selects


the wavelength of light
incident on the exit slit.
Only need one single
element detector (PMT)
low cost
Slow for full spectrum
need to scan

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Multichannel

ICP Source
Grating
Entrance
Slit

Mirror Arc/Spark Source

Photomultipliers
Multiple channels

Fixed positions of slits + multiple PMTs


Useful for quick measurement of a few
preset lines/elements
Computer
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=ppb

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Homework due 2/13 in class

Skoog:
6-7, 6-14, 6-15, 8-5, 9-13, 10-8

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