Spectroscopy Flashcards
Electro-analytical methods
A class of techniques in analytical chemistry, which deals with study of an analyte (test solution) by using suitable instrumental techniques.
Spectrophotometry and Spectroscopy
A method to measure intensity of light
absorbed by a chemical substance when a beam of light passes
through a sample solution.
The branch of science that deal with the study of
interaction of matter with electromagnetic radiation of particular
wavelength and vice-versa
Lambert’s Law
When a monochromatic radiation is passed through a light absorbing species (solution), the decrease in the intensity of radiation with thickness of the a light absorbing species (solution)
is directly proportional to the intensity of incident light
Beer’s Law
The decrease in the intensity of incident radiation due to absorption is directly proportional
to the concentration of absorbing species.
Absorbance and Molar Extinction coefficient
Absorbance :
No Unit, It is the logarithm of the ratio of the incident light (I0) to the transmitted light (I).
Molar Extinction coefficient :
It is defined as the absorbance of that solution which has concentration of the absorbing species 1 mol.dm-3 and the path
length is 1 cm
A = ε . C . l
Where, ε = molar absorptivity, dm3mol-1cm-1
C = concentration, mol.dm-3
L = path length
A = 2- log10 %T
A = -log T = log (1/T)
Limitations of Lamberts and Beers
Linearity of the Beer-Lambert Law is limited by chemical and instrumental factors
Not valid for concentration greater than 10^-2
Molar extinction coefficient depends on the R.I. of the solution and changes with it.
Temperature fluctuations and stray light affect absorbance measurement.
Single beam spectrophotometer
Light source :
Deuterium and hydrogen lamps (190-400 nm) (For UV light)
Tungsten filament lamp (300-750 nm) (For visible light)
Sample containers :
Cuvettes (Quartz)
Mono - chromators :
Prisms can be used as mono - chromator
Diffraction gratings
Detectors :
Photomultiplier tube
Photodiode
Photodiode array
Working :
Monochromator
Through a quartz cuvette containing sample solution
Transmitted radiation falls on photoelectric cell which gives a electrical signal as absorbance reading.
Double beam Spectrophotometer
Light source :
Deuterium and hydrogen lamps (190-400 nm) (For UV light)
Tungsten filament lamp (300-750 nm) (For visible light)
Sample containers
Cuvettes (Quartz)
Beam splitters
Mirrors
Mono-chromators
Prisms can be used as mono-chromator
Diffraction gratings
Detectors
Photomultiplier tube
Photodiode
Photodiode array
Working :
Variation in intensity of light is compensated by splitting it.
One beam through blank soln and one through sample soln
And as in single beam the beam falls on photoelectric cell which converts radiation to electrical signal as absorbance.
Applications of UV Visible Spectroscopy
Detector in HPLC
To study absorbance of organic compounds
Magnitude of molar absorptivity
Identification of inorganic and organic species
Conductometric titration
Constant measuring of conductance of a mixture while reactant is being added, sudden change is the equivalence point.
When one electrolyte is added to another the conductance will alter if ionic reaction takes place, if not then conductance will simply increase.
Procedure for Conductometric titration
Definite volume of solution is pipetted out.
Dip type conductivity cell dipped in it, distilled water added if not completely dipped.
Cell connected to conductometer and conductance is measured.
Then titrant added to burette, small proportions added to solution and stirred.
7-8 reading beyond equivalence point.
Strong Acid with Strong Base
Before NaOH conductance is high due to hydrogen ions.
Then conductance drops due to addition of NaOH which causes OH and H ions to form undissociated water.
Once H ions are extinguished the Solution only contains NaCl, then addition of NaOH increases conductance due to presence of OH.
Weak Acid with Strong Base
Initial conductance low due to feeble ionization of acetic acid.
On adding base it decreases further due to replacement of H+ by Na+ and due to suppression of acetic acid due to common ion acetate.
Graph is curved near equivalence point due to hydrolysis of salt CH3COONa.
Conductance increases after point due to OH ions from NaOH.
Strong Acid Weak Base
Initially high, then decreases due to replacement of H+, after equivalence point the graph becomes almost horizontal as excess aqueous ammonia is not ionized in the presence of ammonium sulphate.
Weak Acid and Weak Base
Initial curve is similar to weak acid strong base up till the equivalence point. After point almost horizontal as weak base is feebly ionized and therefore not much conducting.