In an absorption spectrum an aspect of the molecule is moving from a lower energy level to a higher one, and it does this

by absorbing the missing energy. These energy levels could be for electrons (UV-VIS spectroscopy), for covalent bond vibration (IR spectroscopy) for rotation (microwave spectroscopy) etc.

Energy

Absorbed energy allows the higher level to be populated, if temporarily

Of course when something is excited (yes, that really is the word to use) to a higher level it becomes unstable and will often fall back down again. When it does so it must emit the energy it gained, for example as heat, in the form of light of specific wavelengths.

Heat, or other form of energy, is applied to the sample

Molecules emit exact wavelengths as the excited electrons eventually drop down to a lower energy level

Emission Spectrum detected

Or to put it another way:

Energy

As the energy level falls back, exact wavelength light is emitted.

The ultimate in emission spectra!

3. Infra Red spectroscopy (IR)

The cheap and cheerful method of analytical spectroscopy is infra red spectroscopy. If IR light is shone onto molecules, the energy it carries has the potential to vibrate the covalent bond. Think of the bond as being a spring and the IR being able to initiate the vibration. Real springs vibrate at a frequency which depends on the strength of the spring. Bonds do exactly the same. In an IR spectrometer the light is passed through the sample and the frequency (actually a variation called wavenumber, with units of cm-1) is slowly changed. A detector determines

One last word about chromatography; in all the diagrams above I have shown components that are coloured because it makes the point more easily. In reality they probably wont be so you can either stain them so they become visible or shine UV light on the stationary phase. With some molecules they will then radiate in the visible violet so you can see them (this is called fluorescence and washing powder and toothpaste both do it!).

This marks the (welcome) end of this option for all SL chemists. However not for you HL types, oh no! You have hardly begun; thirsting for more; craving for deeper knowledge and understanding. So hold onto your hats, here we go

8. Visible and ultraviolet spectroscopy (UV-VIS)

We think of visible and UV light as distinct and separate, but it is better to think of the visible spectrum as a small extension to UV, after all they both excite electrons in molecules. For most organic molecules the excitation of electrons absorbs wavelengths from the UV region, so to see this we need UV spectroscopy which well come to in a bit. However if the electron jump can be made particularly small then the absorbance moves into the visible region and we get colour. Organic colour, also, will be covered later on, but to start with we will examine the colour in many transition metal solutions. s, p and d atomic orbitals have strict geometric shapes. It is the d orbital that concerns us here. Most have four lobes and the five orbitals that make up the d subshell sit around the nucleus on differing axes. We take it for granted that all the orbitals within a subshell have the same energy why wouldnt they? For a d subshell that holds good for an isolated gaseous ion, but if we have it in solution then things change, and its all because of those ligands you covered in the core. A ligand is any species that has a lone pair of electrons and can form dative covalent (coordinate) bonds with a vacant d orbital. Three good examples are H2O, NH3 and Cl-, and note that if this were organic chemistry, we would be calling them nucleophiles! Take Cu2+ as an example. In solution, all the water molecules crowd around the ion. Six of them succeed in forming dative bonds and become ligands. This gives us the complex ion 2+ [Cu(H2O)6] which is that familiar blue colour. But why is it blue?
Energy

E The 3d subshell of an isolated, gaseous Cu2+ ion. All the orbitals have the same energy

However, in a complex ion the subshell has split. The ligands approach along certain axes only, repelling some orbitals but not others.

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IB Chemistry Option A Modern Analytical Chemistry Higher and Standard Level Contents Standard Level Principles of spectroscopy Infra red spectroscopy Mass spectroscopy NMR (part one) Atomic absorption spectroscopy Chromatography (part one) Visible / Ultra spectroscopy Higher Level NMR (part two) Chromatography (part two) Test yourself questions Page

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