Dr.
Samar Mohammed 1st Lecture
Analytical chemistry: Specializes in studying the type and quantity of
elements and compounds found in the sample to analyze, with the help
of gravimetric, volumetric methods, spectral, electrical, or other
methods.
Classification of analytical methods:
Analytical methods are often classified as being either classical or
instrumental.
Classical methods: Involve separating the components in a sample by
precipitation, extraction or distillation.
In qualitative (what is present) classical methods, the separated
components treated with reagents can yield products recognized by their
colors, boiling points, melting points,
solubility in a series of solvents, odors, optical activities, or their refractive
index.
In quantitative (how much is present) classical methods, the amounts
of components are determined by gravimetric or titration methods. In
gravimetric analysis, the mass of components is determined. In titrimetric
analysis, the volume or mass of a standard reagent, required to react
completely with sample components is measured.
Instrumental methods:
Chemists began to use new methods for solving analytical problems.
Thus, measurement of physical properties of analysts such as-
conductivity, electrode potential, light absorption or emission, mass-to-
charge ratio and fluorescence.
Advantages of instrumental methods
• Analyze complex models
• Most of them are non-destructive methods where the model is not
destroyed
• High sensitivity and selectivity
• The analysis is quick and selective
• The sample is used in a low amount
Advantages of classical methods:
• The methods are simple • Low cost of analysis
Spectroscopic method of analysis:
Spectroscopy is the study of the interaction between matter and
electromagnetic radiation. It involves the analysis of the absorption,
emission, or scattering of electromagnetic radiation by atoms or
molecules in order to gain information about their physical and chemical
properties. Spectroscopy has many applications in fields such as
chemistry, physics, astronomy, and biology.
How Spectroscopy Works?
When a beam of electromagnetic radiation passes through a sample,
the photons interact with the sample, they may be absorbed,
reflected or refracted… etc.
Absorbed radiation affects the electrons and chemical bonds in a
sample.
Emitted and absorbed spectra can be used to gain information about the
matter
Electromagnetic radiation
A basic introduction to the electromagnetic field.
Electromagnetic (EM) radiation is a form of energy propagated
through free space or through a material medium in the form of
electromagnetic waves. EM radiation is so-named because it has electric
and magnetic fields that simultaneously oscillate in planes equally
perpendicular to each other and to the direction of propagation through
space.
Electromagnetic radiation has a dual nature:
It exhibits wave properties and particulate (photon) properties.
waves (the light travels in space as waves) and particles (the light’s
photons have a definite mass).
1- Wave nature of radiation: Radiation can be thought of as a traveling
transverse wave. The electric E and magnetic H fields oscillate in the x-y
plane and are perpendicular to the direction of propagation.
Wavelength: The distance between any two consecutive maxima
or minima of an electromagnetic wave (λ). The units of wavelength are
(m, μm, nm, A ), and the micrometer (1 μm = 10-6 m), usually called a
micron. The unit widely used in spectroscopy is angstrom (1A = 10-10m).
Wave number : the number of waves in one centimeter, and it
is reversible to the wavelength. It is measured by cm-1
Frequency: The number of oscillations of an electromagnetic
wave per second (ν)
If you increase the frequency, you must decrease the wavelength,
which means that if the wavelength is longer, the frequency is shorter.
For example, if red light had a wavelength of 650 nm, and green light
had a wavelength of 540 nm so green light has a higher frequency and a
shorter wavelength.
2- Particle properties:
To describe how electromagnetic radiation interacts with matter,
consider the beam of radiation as a train of photons. The energy of each
photon ( in joules) is proportional to the frequency ,wavelength or
wavenumber of a radiation by the equation:
The higher the frequency, the higher the energy of the light.
The light which has wavelengths of around 380 - 435 nm is seen as
a violet color. Various red colors have wavelengths around 625 - 740
nm. Which has the highest energy?
Where:
E: Photon energy
H: Planck constant (6.6261 x 10-34 J.S)
C: Speed of light (3x108 m/s)
Q/ Calculate the energy of a photon of red light with a wavelength 6.45 x10-5 cm
The Intensity of the beam radiation is proportional to the number
of photons and is independent of the energy of each photon. The intensity
is referred to the radiant power emitted by the source.
The Electromagnetic Spectrum:
The electromagnetic spectrum is composed of a large range of
wavelengths and frequencies (energies). It varies from highly energetic
gamma rays to very low energy radio-waves. The entire range of radiation
is commonly referred to as the electromagnetic spectrum. The table lists
the wavelength ranges for the regions of the spectrum that are important
for analytical purposes and, with the types of transitions.
Interaction of EMR with the matter
Electromagnetic radiation can interact with matter (atoms and
molecules) in several ways. When a substance is irradiated with
electromagnetic radiation, the energy of the incident photons may be
transferred to atoms and molecules raising their energy from ground state
level to excited state. This process is known as absorption and the
resultant spectrum is known as absorption spectrum. The process of
absorption can occur only when the energy difference between the two
levels E is exactly matched by the energy of the incident photons as given
by the equation.
The reverse process in which a portion of the internal energy of
matter is converted into radiant energy is called "emission". In the
emission process, species in an excited state can emit photons of
characteristic energies by returning to lower energy states or ground
states.
The radiation which passes into the matter may be scattered or
reflected or may be re-emitted at the same wavelength or a different
wavelength upon emerging from the sample. Radiation, which is neither
absorbed nor scattered, may undergo changes in orientation or
polarization as it passes through the sample.
1- Refraction of Radiation
When a beam of light passes from one medium to another of
different physical densities, a change in the direction of the beam will be
observed at the interface between the two media. and it occurs due to the
interference of the electric field of the radiation with the electrons of the
medium, which results in a decrease in the speed of the wave and perhaps
a change in the wavelength with no change in the energy of the radiation
due to the frequency value is constant.
θ1 is the angle of incidence; θ2 is the angle of refraction. n1 and
n2 are the two different mediums. V is the velocity.
Snell’s law is defined as “The ratio of the sine of the angle of
incidence to the sine of the angle of refraction is a constant, for the light
of a given color and for the given pair of media”. Snell’s law formula is
expressed as:
…. (1) OR n1 sin θ1 = n2 sin θ2 ...(2)
Dispersion of the radiation
The variation of the refractive index of a substance with
wavelength (or frequency) is called dispersion. indicates that light
of different frequencies is refracted at different angles. The
refractive index is an important property of transparent materials.
The characteristic dispersion of radiation by prisms both are of
significant value in the design of optical instruments.
Reflection of Radiation:
When a ray of light passes through the interface of a
medium with a different refractive index, the reflection will
occur. And the reflected part of the incident rays becomes
larger with the increase in the difference in the refractive
index (this means that the reflected rays increase with the
increase in the difference between the refractive indexes of
the two media), the percentage of the reflected radiation
increases, but slightly when the angle of the incidence is
greater than 60 degrees, but the percentage of the reflected
radiation increases rapidly and reaches 100% at the angle
90 degrees. The part of the reflected rays can be expressed
by the following equation:
Ir/ I0 = (n2-n1)2/ (n2+ n1)2
Whereas (Ir) is the intensity of the reflected radiation, (I0)
is the intensity of the incident radiation, (n1) and (n2 ) are
the refractive index of the medium
