Applications of UV-Vis Molecular Absorption Spectrometry Chap 14

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NASA's alpha particle X-ray spectrometer (APXS). Image credit: NASA The APXS is designed to study the alpha particles (from radioactive decay) and X-rays emitted by rocks and soils in order to determine their elemental chemistry. Knowing the elemental composition of Martian rocks will provide the scientists with information about the formation of the planet's crust, as well as any weathering that has taken place. Clues as to the nature or weathering on the surface of Mars, will, again raise the issue of whether or not there was surface water.

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Transcript of Applications of UV-Vis Molecular Absorption Spectrometry Chap 14

Page 1: Applications of UV-Vis Molecular  Absorption Spectrometry Chap 14

                                                                                                    

         NASA's alpha particle X-ray spectrometer (APXS).

Image credit: NASA

The APXS is designed to study the alpha particles (from radioactive decay) and X-rays emitted by rocks and soils in order to determine their elemental chemistry. Knowing the elemental composition of Martian rocks will provide the scientists with information about the formation of the planet's crust, as well as any weathering that has taken place. Clues as to the nature or weathering on the surface of Mars, will, again raise the issue of whether or not there was surface water.

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Applications of UV-Vis MolecularApplications of UV-Vis Molecular Absorption SpectrometryAbsorption Spectrometry

Chap 14

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Spectral data may be plotted with ordinate as:

• absorbance (A)

• percent transmittance (%T)

• log absorbance (log10 A)

Abscissa normally:

• wavelength (nm)

• wavenumber (cm-1)

• frequency (GHz)

ordinate

abscissa

Application to Qualitative Analysis

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Table 14.1 Absorption Characteristicsof Some Common Chromophores

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Table 14-4 Absorption Characteristics of Aromatics

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Fig 6-24 (a)

Partial energy leveldiagram for UV-Vis

absorption in an organicmolecule

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Fig 14-1

UV-Vis AbsorptionSpectra for

1,2,4,5 tetrazine

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Fig 14-6

Effect ofsolvent onabsorptionspectrum of

acetaldehyde

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Transparency: Solvents for the UV-Vis

Table 14-3

Cutoff wavelengths

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Solvents: Effect on absorbing system

• Polar solvents tend to “blur” vibrational

features more than nonpolar solvents

• Polar solvents more likely to shift λmax

n → π * blue shiftedblue shifted

• solvation of lone pair lowers energy of n

• ∼ 30 nm when hydrogen-bonding possible

π → π* red shiftedred shifted

• ∼ 5 nm due to attractive polarization

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Solvent effects imply that:

UV-Vis is not reliable for qualitative

but excellent for quantitative analysis

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Develop Calibration Curve

with Standards

Challenge:

Preparing standards in

same matrix as analyte

Quantitative Analysis

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Fig. 14-8Standard Addition Method

Determination of NO2ˉ in water by UV-Vis

M7709.2]NO[ 2

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Case (a) : Significant overlap

• Best treated by using aspreadsheet procedure with data obtained at many λ’s.

Case (b) : Little overlap

• Measure Abs of X at λʹ• Measure Abs of Y at λʺ• Solve simultaneousequations for [X] and [Y]

Analogous to Fig. 14-9

Analysis of a Binary Mixture

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Analysis of a Binary Mixture of Ti and V

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Analysis of a Binary Mixture of Cr2O72- and MnO4

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