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    Simon Siu
    This document summarizes a lecture on atomic spectroscopy. It discusses three main topics: 1) definitions of key terms like sensitivity, dynamic range, and selectivity; 2) different methods used in atomic spectroscopy like standard addition and internal standards; and 3) the basic principles of different spectroscopic techniques like absorption, emission, and scattering methods and how they are used to analyze atomic spectra and transitions between energy levels to identify elements. It provides examples of applications like flame tests and describes components of spectrometers like dispersive elements, detectors, and how full spectra are recorded.

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    Note4 PDF

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    Simon Siu
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    This document summarizes a lecture on atomic spectroscopy. It discusses three main topics: 1) definitions of key terms like sensitivity, dynamic range, and selectivity; 2) different methods used in atomic spectroscopy like standard addition and internal standards; and 3) the basic principles of different spectroscopic techniques like absorption, emission, and scattering methods and how they are used to analyze atomic spectra and transitions between energy levels to identify elements. It provides examples of applications like flame tests and describes components of spectrometers like dispersive elements, detectors, and how full spectra are recorded.

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    This document summarizes a lecture on atomic spectroscopy. It discusses three main topics: 1) definitions of key terms like sensitivity, dynamic range, and selectivity; 2) different methods used in atomic spectroscopy like standard addition and internal standards; and 3) the basic principles of different spectroscopic techniques like absorption, emission, and scattering methods and how they are used to analyze atomic spectra and transitions between energy levels to identify elements. It provides examples of applications like flame tests and describes components of spectrometers like dispersive elements, detectors, and how full spectra are recorded.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    57 views24 pages

    Note4 PDF

    Uploaded by

    Simon Siu
    This document summarizes a lecture on atomic spectroscopy. It discusses three main topics: 1) definitions of key terms like sensitivity, dynamic range, and selectivity; 2) different methods used in atomic spectroscopy like standard addition and internal standards; and 3) the basic principles of different spectroscopic techniques like absorption, emission, and scattering methods and how they are used to analyze atomic spectra and transitions between energy levels to identify elements. It provides examples of applications like flame tests and describes components of spectrometers like dispersive elements, detectors, and how full spectra are recorded.

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    of 24

    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 4. Atomic Spectroscopy

    Prof. Ke Xu

    1
    Q&A 2

    Q1. Define:
    Sensitivity
    Dynamic range
    Selectivity

    Q2: What method helps remove matrix effects?

    Standard-Addition

    Q3: What method helps to account for instrument instability?

    Internal-Standard
    The electromagnetic spectrum 3

    core valence
    nuclear molecular nuclear
    electron electron molecular
    transition vibrations spin flip
    transition transition rotations

    micro-
    wave
    How to generate a spectrum: spectrometer/monochromator
    Refocuse in different position

    Dispersion unit: Spread a


    line-shaped light beam
    into a band according to
    wavelength

    Recording the resultant


    spectrum: directly, or slit +
    scan

    4
    Characteristics of monochromators

    Dispersion

    Angular dispersion: DA = d / d

    Linear dispersion: Dl = dl / d = fDA f=Focus length of the lens

    1
    Reciprocal linear dispersion: Dl = d / dl Unit: nm/mm

    Resolving power
    Unitless
    R= Desired: >10,000 to separate Fe lines

    Light-gathering capability

    Output energy
    L=
    Input energy
    5
    Spectra at different spectral resolution 6

    larger band width, lower resolution

    Effect similar to
    averaging/smoothing
    Dispersive element: Prism

    light interaction with te material differenetly dependent on the wavelength. the shorther the wavelenth is, the hight energy is, higher energy interact with te material
    more strongly. the refract index would be higher. e.g. the blue ligh is baned more compare to read light.

    Difference in refraction index n for different wavelengths


    Higher n for shorter wavelength higher energy and stronger interaction: bends
    more

    7
    Dispersive element: Diffraction gratings 8

    n = d sin
    n: order of diffraction
    d: periodicity of grating
    : angle
    Grating, long lof light on lot of line gap, ligh can
    only pass through those gap, the black dot line. the
    light can travel to the screen, and at some spot the
    light would be interference constructively, with
    the form nlambda=dsinetheta, if strateed with
    Denser pattern = wider angle
    dmultiple wavelentgh, there will be different Longer wavelength = wider angle
    angle.
    longer wavelength, father away from the center

    Stronger dispersion and higher resolving power with denser grating


    May be transmitting or reflecting
    CDs as gratings 9

    9
    Detection and recording of spectrum 10

    Take a real photo on photographic film! traditionally, people take the black and white photo

    AgBr/AgI

    Glass

    CCD and other multi-pixel imagers, digital cameras


    Arrays of light sensors
    Single-element detectors for spectrum recording
    moving the slit at the exit site with one detector to meausre the wavelength

    Single-element detector:
    Slit + scanning!

    Rotating the grating selects wavelength at the exit slit.


    Record the full spectrum over time through scanning
    Narrowing entrance and exit slits:
    Resolution
    Transmission 11
    Photomultiplier (PMT) as a common single-element detector
    Photoelectric effect
    when light strike the cathode, the cathode emit the electron and pass through to the anode, and get detected

    Emits electrons for wavelengths shorter than the threshold


    12
    13
    Photomultiplier as a common single-element detector
    Secondary emission
    one electron is hard to get detected, using photomltiplier to amplify the the signal using multiple dynode.

    PMT Film CCD


    Dynamic Range >1000 <100 >10,000
    Detection Speed fastest slow slow
    Quantum Efficiency 5-20% 5-20% 25-95%
    Multi-channel no yes yes
    Real-time yes no yes
    Spectral Sensitivity (nm) 300-900 200-1300 300-1100
    Dark Signal good poor best
    Read Noise good good best
    14
    Absorption methods

    Absorbed energy converted into heat and/or light of other wavelengths and
    directions
    15
    Emission methods

    Bring the energy level of the system to excited state


    Or, other forms of
    energy input: thermal,
    electrical, or chemical

    Examples
    Photoluminescence (fluorescence,
    phosphorescence)
    Atomic emission
    Chemiluminescence
    16
    Scatter methods (e.g., Raman)

    Monochromatic light

    measure the side wavelength instead of the fornt

    Measures the shift in wavelength due to molecular interactions


    17
    Atomic spectra: First noted in the solar spectrum

    Fraunhofer lines: atomic absorption (AA)


    Na! Na absorb particular wavelength of sun light
    Solar spectrum in details

    AA reveals many chemical elements in the solar atmosphere


    Many spectral lines are in the UV-visible range
    Atomic emission (AE) 19

    Na K Li Ba

    Flame test

    Fireworks
    Atomic spectra: transitions between atomic energy levels

    Na
    AE

    AA

    Spectral lines are due to fixed energy levels


    Same positions for AE and AA
    E = h = hc/
    A few eV visible light range

    Spin-orbit
    coupling

    [Ne] 3s1
    Valence angstroms
    electron Sodium lamp Electric Pickle
    20
    Atomic absorption (AA) vs. emission (AE) 21

    Absorption lines: Atomic gas between a light source and the detector. Decrease
    in the intensity of transmitted light at particular wavelengths due to absorption.

    Thermal
    energy

    Emission lines: Detector sees photons emitted directly from a glowing gas
    22
    Energy levels: Na vs. Mg+

    Na Mg+

    Split of p-orbital
    energy due to
    spin-orbital
    interaction

    [Ne] 3s1
    angstroms Valence electron

    One single valence electron: Similar patterns for Na and Mg+


    Actual energy is different by ~two folds
    Energy levels for hydrogen-like atoms
    Magnesium 23

    angstroms

    Two valence electrons: Singlet vs.


    triplet sates
    More complicated transitions
    Take-home messages for atomic spectroscopy: 24

    Not all transitions are allowed selection rules

    Allowed transitions and spectral lines are still numerous.


    Alkali metals: ~200 lines. Transition metals: 1,000+ lines!

    Different spectral lines have different intensities. Population + selection rules

    Resonance lines: transition between the ground state and first excited state.
    Strongest!

    Detection of specific spectral lines


    existence and/or concentration
    of an element

    Flame emission of sodium

    Sodium lamp

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