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PHRM 309
UV VIS Spectroscopy
Spectroscopy is the study of the interaction between matter and radiated energy (light).
Electromagnetic radiation is a self-propagating wave in space with electric and magnetic components. EM radiation has an electric and magnetic field component which oscillate in phase perpendicular to each other and to the direction of energy propagation.
Radio waves have longest wavelength and Gamma rays have shortest! Since electromagnetic radiation (light) is a wave, it can be characterized by either a wavelength or frequency or wave numbers.
The electromagnetic wave consists of two fluctuating fieldsone electric and the other magnetic. The two vectors are at right angles to one another, and both are perpendicular to the direction of travel.
Wavelength ()
The distance between two consecutive peaks or troughs in a particular wave. Linear distance from any point on one wave to the corresponding point on the adjacent wave.
Increasing wavelength
1 > 2 > 3
Symbol: lambda () Unit: meter (m), practically measured in micrometers (m, a millionth of a meter) or nanometers (nm, a billionth of a meter )
Frequency ()
The number of waves which can pass through a given point in one second.
Decreasing frequency 1 < 2 < 3
Symbol: nu () Units: cycle/sec, may also be denoted as hertz (Hz)
Wave number
Wave number is defined as the total number of waves passing through a space of unit length (1cm or 1m). We can calculate the wave number by taking the reciprocal value of wave length of a radiation. i.e.
1 Wave number = Wavelength
Energy
Energy of a particular wave of the particular radiation can also be calculated by applying the relation:
E=h. = h. (c/) Here h = Plancks constant = 6.626x10-27 erg sec = Frequency of radiation c = Velocity of EM radiation = Wavelength
Electromagnetic spectrum
The arrangement of all types of electromagnetic radiations in order of their increasing wavelength or decreasing frequencies is known as complete electromagnetic spectrum. The full electromagnetic radiation spectrum is continuous and each region merges slowly into the next. For convenience of reference, definitions of the various spectral regions have been set by the Joint Committee on Nomenclature in Applied Spectroscopy:
Region
Far ultraviolet Near ultraviolet Visible Near infrared Middle infrared Far infrared Microwave
Wavelength (nm)
10-200 200-380 380-780 780-3000 3000-30,000 30,000-300,000 300,000-1,000,000,000
Absorption spectroscopy
It may be defined as the analysis of chemical substance by the measurement of the amount of radiation absorbed by this substance. Absorption spectroscopy refers to a range of techniques employing the interaction of electromagnetic radiation (EMR) with matter.
In absorption spectroscopy, the intensity of a beam of light measured before and after interaction with a sample is compared.
Absorption spectroscopy is widely used for both qualitative (is a chemical present?) and quantitative (how much?) and structural (is it degraded?) work in a wide range of fields.
While two atoms form chemical bond, their atomic orbital combine together to form molecular orbital. Bonding orbital and antibonding orbital
Bonding orbital energy level is always lower than that of the original atomic orbital
Antibonding orbital energy - higher
Bonding electron
Electrons which are involved in bond formation. They are present in the lower energy level in the molecule. They are of two types: -bond electrons (electrons in the single bond, electrons in saturated compounds)
-bond electrons (electrons in double and triple bond, electrons in unsaturated compounds)
Non-bonding electron
Paired electrons in outer most shell which are not involved in bond formation between atoms in molecule. They are present in the higher energy level in the molecule than bonding electrons. They are represented by n.
contains
nitrogen,
oxygen,
Anti-bonding electron
Electrons which are excited to a higher energy level by absorbing energy (EMR) are called anti-bonding electron. They are present in the higher energy level. They are represented by: Anti-bonding sigma (*) and
Anti-bonding pi (*)
*
Energy
UV/VIS
Electron transitions
UV-VIS spectroscopy
This is the spectroscopy. earliest method of molecular
Absorption of EMR results in electronic transition of a molecule, and electrons are promoted from ground state to higher electronic states.
The radiation which is absorbed has an energy which exactly matches the energy difference between the ground state and the excited state. These absorptions transitions. correspond to electronic
At room temperature, most of the atoms, molecules and electrons are in the lowest energy orbital called ground state. The electron of atom (molecule) at ground state can absorb EMR and transit to higher energy orbital called excited state.
Atom or molecule can absorb the radiation only when the energy of proton is equal to the energy difference of the two orbitals.
* Transitions
An electron in a bonding orbital is excited to the corresponding antibonding orbital. The energy required is large. For example, methane (which has only C-H bonds, and can only undergo * transitions) shows an absorbance maximum at 125 nm. Absorption maxima due to * transitions are not seen in typical UV-VIS spectra.
n * Transitions
Saturated compounds containing atoms with lone pairs (non-bonding electrons) are capable of n* transitions. These transitions usually need less energy than * transitions. They can be initiated by light whose wavelength is in the range 150 - 250 nm. The number of organic functional groups with n* peaks in the UV region is small.
n * and * Transitions
Most absorption spectroscopy of organic compounds is based on transitions of n or electrons to the * excited state. These transitions fall in an experimentally convenient region of the spectrum (200 - 700 nm). These transitions need an unsaturated group in the molecule to provide the electrons.
s* p*
Atomic orbital
Unoccupied levels
Energy
Atomic orbital
Occupied levels
p s
Molecular orbitals
pp*
max(Lambda max): For a given substance, the wave length at which maximum absorbance in the electromagnetic spectrum occurs is known as max.
Solvent
Chloroform Benzene
245 nm 280 nm
H2O 264.5
CH3OH 270
C2H5OH 272
CHCl3 277
C6H14 279
(nm)
Polarity
In chemistry, polarity refers to the dipole-dipole intermolecular forces between the slightly positivelycharged end of one molecule to the negative end of another or the same molecule.
Molecular polarity is dependent on the difference in electronegativity between atoms in a compound and the asymmetry of the compound's structure. For example, a molecule of water is polar because of the unequal sharing of its electrons in a "bent" structure, whereas methane is considered non-polar because the carbon shares the hydrogen atoms uniformly.
Hypsochromic Hypochromic
Hyperchromic Bathochromic
200 nm
700 nm
Chromophores:
Functional groups that give electronic transitions. 1. Chromophore containing electrons: ethylene
Auxochromes:
Substituents with unshared pair e's like OH, NH2, NHR, NR2 SH, OR, etc when attached to chromophore they generally move the max to longer and also increase the intensity of absorption. Combination of chromophore and auxochrome give rise to another chromophore Also known as color enhancing group.
NH2
NH3+
Bezene Aniline Protonated Aniline max 255 nm max 280 nm max 200 nm max 203 max 1430 max ???
Extending conjugation has a larger effect on lmax; shift is again to longer wavelengths H H
C
H
C H
lmax 170 nm
H C H H H3C C H C C
C
C H C
CH3
Lycopene
orange-red pigment in tomatoes
Lamberts Law
When a beam of monochromatic radiation passes through a homogenous absorbing medium, the intensity of the emitted radiation decreased exponentially as the thickness of the absorbing medium increases arithmetically.
Beers Law
When a beam of monochromatic radiation passes through a homogenous absorbing medium, the intensity of the emitted radiation decreased exponentially as the concentration of the absorbing substance increases arithmetically.
Beer-Lamberts Law
The intensity of emitted electromagnetic radiation through a sample at a given wavelength decreases exponentially with the sample thickness and concentration.
Beer-Lamberts Law
The Beer-Lambert Law is rigorously obeyed when a single species is present at relatively low concentrations.
Transmittance Transmittance is the percentage of incident light that passes through a sample of material. A= log 1/T A= absorbance T= transmittance If sample had a % transmitted light through sample of 80%. What is the absorbance of the sample? Ans: 0.096