Light, Spectroscopy and

Metal complexes
Dr Finn Purcell-Milton
School of Dentistry, TCD
2016
 Outline of lecture

• The Properties of Light

• Atomic and Absorption spectroscopy
• The Bier Lambert Law
 The Nature of Light
• Light is a form of electromagnetic radiation, existing as a wave and particle at the same time ,
termed wave-particle duality
• A particle of light is called a photon
• Photons travel at a speed of 299,792,458 m/s (normally rounded to 3 x 10 8 m/s) in a vacuum
and is termed the speed of light which is a universal constant and given the symbol c
• Photons exist as an oscillating electromagnetic field, which consists of an electric field wave
and a magnetic field perpendicular to each other

• Photons are categorised according to their wavelengths (λ) and frequency (v)
• The wavelength of a photon describes the spatial period of the wave—the distance over
which the wave's shape repeats and is given in meters
• The frequency of a photon describes the number of wave crests passing a point per second
and is given in counts per second called hertz (Hz)
  𝑐
• The frequency and wavelength of light is related by this equation : v=
𝜆
 Electromagnetic Radiation
 • The electromagnetic radiation ranges from the
highest energy waves, termed gamma rays, to High energy Low energy
the lowest energy waves, termed radio waves. photons photons
• Visible light is a very specific segment of the EM
radiation spectrum, ranging from 400 nm to 750
nm in wavelength.
• The energy (E) of a photon is related to its
wavelength and frequency
• Energy is proportional to the frequency (v) of
light and is given by

• Energy is inversely proportional to the

wavelength (λ) of light

• Note: h is Planck’s constant, 6.63 × 10-34Js and c

is the speed of light
Definitions
• Spectroscopy is the study of the interaction
between matter and electromagnetic radiation.
This is used in chemistry as a means of detecting,
identifying and characterising the properties of a
range of chemicals.
 Atomic Spectroscopy
• Atomic spectroscopy is the study of the electromagnetic radiation absorption and emitted
by atoms
• Electrons can only occupy certain energy levels – like steps on a ladder, which coincide
with the possible orbitals of the system
• When all of the electrons in a atom are in their lowest energy level possible, the atom is
said to be in its ground state
• Matter can capture electromagnetic radiation and convert the energy of a photon to
internal energy
• This process is called absorption and given the symbol A and is usually unit less
• If an electron absorbs a photon, it is elevated to a higher energy level – an excited state
• When the electron falls to lower energy state, it gives up this energy in specific quanta,
which can be in the form of light. This process is called emission

excited state
ground state
 UV-Vis Absorption Spectroscopy
• Ultraviolet- visible (UV-Vis) absorption spectroscopy is an analytical technique based upon the
absorption of photons in the visible and ultra violet range of the electromagnetic spectrum
• One of the most common spectrometry techniques and is commonly one of the first
approaches carried on a unknown material
• This absorption occurs due to excitement of the valence electrons of the materials being
analysed
• The spectrometer directs a beam of light of variable wavelength through the sample, and
compares the intensity of the emerging beam (I) relative to the incident beam (I0),
• Transmission is the fraction of incident electromagnetic power that is transmitted through a
sample and is given the symbol T
• It is related to the intensity of the beam by
𝐼
𝑇  =
𝐼0
• The absorption of the material is related to the inverse of the transmittance and is given by

 𝐴=−𝑙𝑜𝑔 10 𝑇
 UV-Vis Absorption Spectroscopy

• The transmission/absorption is determined for a range of

wavelengths of light
• The transmission/absorption is then graphed relative to the
wavelength of light producing a graph
Definitions
• Spectrophotometry is a method to measure how
much a chemical substance absorbs light by
measuring the intensity of light as a beam of light
passes through sample solution. The basic principle
is that each compound absorbs or transmits light
over a certain range of wavelength
 Bier lambert law
 A = Absorbance
I =Intensity of incident light
  𝐼0 I =Intensity of transmitted light
𝐴 =𝑙𝑜𝑔 10 =𝑐𝑙 𝜀
𝐼 = Path length
ε = Absorption coefficient
c = Concentration
• This law relates the linear relationship between the
absorbance and the concentration of an absorbing species.
• This can be used to determine the concentration of molecule
in solution, when the path length and the absorption
coefficient is known
• The path length refers to the amount of solution the beam
passes through
• The absorption coefficient determines how far into a material
light of a particular wavelength can penetrate before it is
absorbed. In a material with a low absorption coefficient, light
is only poorly absorbed, and if the material is thin enough, it
will appear transparent to that wavelength. The absorption
coefficient depends on the material and also on the
wavelength of light which is being absorbed.
 Metal Complexes
• A metal complex consists of a central atom or ion and a surrounding array of
bound molecules or ions which are referred to as ligands.
• Commonly the metal centre consists of a transition metal ion, which will be the
only example of metal complexes covered for this course
• The number of ligands surrounding the central atom are refererred to as the
coordination number
• Depending on the coordination number a different shape will be adopted by the
metal complex
 L
Metal Complexes: Dative bonds and Lewis L L

theory L
M
L

• Dative bonding ( also called coordinate bonds )is the type of bonding found between the ligands
and the metal centre
• Dative bonds are a type of covalent bond in which the shared electron pair is supplied by one
atom ( the ligand ), as opposed to a simple covalent bond in which each atom donates a single
electron
• Lewis acids and bases can form dative bonds
• A lone pair is a pair of electrons in the valence shell which are not participating in a bond with
another atom
• Potential ligands: Possess lone pairs of electrons in the outer energy level
• Metal complexes are formed when metal ions (Lewis acids) react with several ligands (Lewis
bases)

 Remember : Lewis Theory

Definition: An acid accepts a pair of electrons; a base donates a pair of electrons
General formula Acid Base
 Metal Complexes
 • Water forms complexes with most transition metal ions when they dissolve in
it (Water molecules as ligands) e.g. H O
3+
2

H2O OH2
Cr
H2O OH2
H2O

• Aqueous solutions of transition metal ions are simply solutions of their water
complexes
• Many complexes are prepared by mixing a solution of the metal ion water
complex with the desired Lewis base
e.g.
3+
H2O
H2O OH2
Cr
H2O OH2
H2O

• Because the aqueous Cr3+ is actually complexed with water, this is an example
of a substitution reaction, in which one ligand replaces another
• There is a range of Lewis bases / ligands which can be used to produce metal
complexes , some of which may be charged or may have no charge
 Reminders: Chemical Equilibrium
Refers to the extent of the reaction – when no further change occurs in the concentrations of
the product/reactants and is achieved given a certain time
Rateforward

An equilibrium reaction: Reactants Products

Ratebackward

When at equilibrium: the rate of the forward reaction = the rate of the backwards reaction
Rateforward = Ratebackward
Equilibrium constant (K)
This describes the equilibrium point in a reaction, and is a function of reactant and product
concentration at equilibrium
 
   

When: (i) K > 1 , the product is favoured, (ii) K < 1 the reactant is favoured
 Le Chatelier’ s Principle
When a chemical system at equilibrium is disturbed, the position of equilibrium
shifts to counteract it
 𝐴 𝑔+ 2 𝐵 𝑔 ⇋ 𝐶 𝑔 + 𝐷 𝑔 ∆  𝐻 =−
• Change in concentration of products / reactants will shift the equilibrium
position to the side that will reduce the change in concentration (but will
not change K)
Addition of C or D to the reaction will shift the equilibrium to the reactant
side, while addition of A or B will result in shifting of the equilibrium to the
product side
• Change in pressure will shift the equilibrium position to the side that will
reduce the change in pressure (but will not change K)
Increase in pressure will result in shift to the product side, while a decrease
in pressure will result in a shift to reactant side
• Change in temperature will change K, and is dependent upon whether the
reaction is endothermic or exothermic
Increase in temperature will result in formation of reactants, while
decrease in temperature will result in formation of products
• Addition of a catalyst has no effect upon the equilibrium position or K
Experiment 2: Spectrophotometry
• Part 1. Verification of the Beer-Lambert Law and
Determination of the concentration of a solution
• Part 2. Determination of the Equilibrium Constant
for Formation of [Fe(NCS)]2+
 Part 1. Verification of the Beer-Lambert Law and
Determination of the concentration of a solution.

• Potassium permanganate (KMnO4) is a

strongly coloured salt when dissolved in
water
• A stock solution of unknown concentration
of KMnO4 solution is diluted to four different
concentrations
• The absorption of these solutions is
measured using a UV-Vis spectrometer and
is graphed relative to the absorption
• From the shape of this graph a linear
relationship between absorption and
concentration should be confirmed
Part 2. Determination of the Equilibrium Constant for
Formation of [Fe(NCS)]2+

• Upon addition of a thiocyanate solution to

an Fe3+ aqueous solution, the colour of the
solution changes from yellow to a blood
coloured solution, due to the formation of
the thiocyanate complex
• This reaction is in equilibrium and
therefore obeys Le Chatelier’ s Principle
• The UV-Vis absorption of [Fe(NCS)]2+ is
used as a means to determine the
concentration of this product and
therefore the equilibrium constant
• Different concentrations of Fe3+ is added to
the same concentration of SCN- which
results in a shift in the position of
equilibrium and therefore a different
concentration of [Fe(NCS)]2+