4.2.4

Colours of Ions (A2 Only)

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d Sub-Shell Splitting

The colour of transition metals ions depends on their ligands and their geometries.

Splitting

Splitting

  • Without ligands, all of the d orbitals have the same energy.
    • In the presence of ligands, the orbitals will split. Some of them gain energy, and some of them lose energy.
    • This is shown in the following diagram.
    • The difference in energy of the upper level and the lower level is given the symbol ΔE.
Light absorption

Light absorption

  • Electrons will occupy the lower energy orbitals first. This is called the ground electronic state of the ion.
    • If an electron absorbs energy equal to the energy gap, it can move to occupy the higher energy orbitals. This is called an excited electronic state.
    • Electrons will absorb frequencies of light that contain enough energy to jump the energy gap.
    • This is shown pictorially on the next slide.
Calculating the energy gap

Calculating the energy gap

  • You can calculate the energy gap from the wavelength of absorbed light by using the following formula:
    • ΔE=hν=hcλ\Delta E = h\nu = \frac{hc}{\lambda}
    • ν is the frequency of light in hertz, h is planck’s constant (which will be given if you need it), c is the speed of light in ms-1 and λ is the wavelength of the light in metres.
  • The energy gap depends on the metal ion, its oxidation state, its ligands, and also its coordination number.

Colours of Transition Metal Ions

The colour of a transition metal ion depends on the colour of the light it absorbs.

Absorption process

Absorption process

  • When a transition metal ion is in light, it will absorb the frequencies which correspond to the d sub-shell energy gap.
    • The rest of the frequencies will be reflected.
    • You only see the reflected light.
Absorption example

Absorption example

  • Suppose you have a metal complex which absorbs red light.
    • The red light is removed from the light you can see.
    • You see the rest of the colours in the spectrum.
    • So the complex appears blue.
  • Metal ions that absorb red light do NOT appear red, because there’s no red light for you to see.
Identifying metal ions

Identifying metal ions

  • Every transition metal ion will be a different colour with different ligands.
    • But we can identify all the hexaaqua ions (the ones with six water ligands), and we also know the colours of some other specific ones.
    • The ones you need to know are on the next slide.
Iron(III) in solution

Iron(III) in solution

  • On the previous slide, we gave you the colours of certain ions. While these colours are true, you might not always observe them.
    • Iron(III) in solution usually appears yellow or orange if its concentrated.
    • This is because hexaaqua iron(III) is quite acidic, and will lose protons to become Fe(H2O)5(OH-) (and this is yellow).
    • If you’re asked what colour hexaaqua iron(III) is, you should say purple. Just be aware that if it's in solution, you’ll have a yellow solution.
    • We’ll talk about the acidic properties in a later module.

Spectroscopy

You can use the colour of ions to find their concentrations. This uses a technique called spectroscopy.

Principles of spectroscopy

Principles of spectroscopy

  • You can shine white light through a coloured filter to remove everything but that colour of light.
    • You can then let this light fall on a sample of a transition metal solution.
    • The more light it absorbs, the higher the concentration of the solution.
    • We can compare the amount of light absorbed to a calibration curve (this is explained on the next slide).
Calibration curves

Calibration curves

  • When doing spectroscopy, we can’t calculate the concentration of a sample without comparing it to known concentrations.
    • We first measure the absorbances of solutions whose concentrations we know. Then we plot these on a graph.
    • This graph is called a calibration curve. An example is on the next slide.
  • We then use the absorbance of the unknown sample to work out from the graph what its concentration is.
Diagram
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Physical Chemistry

1.1

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1.2

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1.3

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1.4

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1.5

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1.6

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1.7

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2

Physical Chemistry 2 (A2 Only)

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4

Inorganic Chemistry 2 (A2 Only)

5

Organic Chemistry 1

6

Organic Chemistry 2 (A2 Only)

6.1

Optical Isomerism (A2 Only)

6.2

Aldehydes & Ketones (A2 Only)

6.3

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6.4

Aromatic Chemistry (A2 Only)

6.5

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6.6

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6.7

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6.8

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6.9

NMR Spectroscopy (A2 Only)

6.10

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6.11

A-A* (AO3/4) - Organic 2

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