Instrumental Analysis Flashcards
any procedure that uses the interaction of EMR w/ matter to identify and/or to estimate an analyte
SPECTROSCOPY
molecules, ions, atoms, mixtures, solid, liquid, gas, solutions
MATTER
qualitative analysis
IDENTIFY
quantitative analysis
ESTIMATE
dual nature of light (both particles and waves)
EMR (Electromagnetic Radiation)
consists of perpendicular and oscillating electric and magnetic fields
LIGHT WAVES
distance from one wave peak to the next
WAVELENGTH
number of peaks that pass a given point per second
FREQUENCY
number of waves per cm
WAVENUMBER
what can the nature of light explain
REFLECTION, REFRACTION, AND DIFFRACTION
discrete packets of energy and particles of light or quanta of light
PHOTONS
E= hv
ENERGY
h
6.626 x 10^-34 J.s
The [ ] the energy, the [ ] the frequency and the wavenumber and the [ ] the wavelength
GREATER, HIGHER, SHORTER
what can the particle nature explain
ABSORPTION AND EMISSION OF LIGHT
a molecule that absorbs light photons will end up with?
INCREASED ENERGY
increased energy
MOLECULE IN EXCITED STATE
excited to ground state emitting the excess energy
FORM OF HEAT
rotation of compounds
MICROWAVE ENERGY
promote bond stretching
IR ENERGY
promotes electrons into higher orbitals
UV/Vis
ionizes molecules or even break bonds
SHORT-WAVELENGTH UV AND X-RAYS
what happens when a molecule absorbs UV-Vis radiations?
ELECTRONINC TRANSITIONS, ADDITIONAL VIBRATION AND ROTATION TRANSITIONS ALSO OCCUR
total energy absorbed
Eelec + Evib + Erot
a graph that shows how absorbance varies with wavelength
SPECTRUM
fraction of light that reaches a detector after passing through a sample
TRANSMITTANCE
formula of transmittance
T = I/Io
formula of absorbance
A= -log T
directly proportional to conc and path length of light
ABSORBANCE
heart of spectrophotometry; relation between absorbance and conc
BEERβS LAW / BEER-LAMBERT LAW
formula of Beerβs law
A= abc
unit for molar absorptivity
M^-1 cm^-1
characteristic for each substance at a particular wavelength
MOLAR ABSORPTIVITY
Transmittance decreases as conc increases
If all the light passes through a solution without any absorption, then absorbance is zero, and percent transmittance is 100%.
due to the limitations of beerβs law itself; when conc of analyte is high, analyte begins to behave differently due to interactions (h-bonding); creates a screen thereby shadowing them from the incident light
REAL DEVIATIONS
due to chemical species of the sample which is being analyzed; chemical phenomenon involving the analyte molecules due to association, dissociation and interaction w/ the solvent to produce a product w/ different absorption characteristics.
CHEMICAL DEVIATIONS
due to how the absorbance measurements are made
INSTRUMENT DEVIATION
radiation outside the selected wavelength
STRAY/SCATTERED RADIATION
analyte absorbs at the wavelength of the stray radiation
DUE TO PRESENCE OF STRAY RADIATION
if the cells holding the analyte and the blank solutions are having different paths, or unequal optical characteristics
DUE TO MISMATCHED CELLS/CUVETTES
occur when the sample absorbs some of the energy from the light
ABSORPTION
when we hit a sample w/ some light and it emits light of a different wavelength
EMISSION
an instrument for making relative measurements in the optical spectral region using light that is spectrally dispersed by the means of a dispersing element
SPECTROMETER
spectroscopic techniques
- ATOMIC ABSORPTION SPECTROSCOPY (AA)
- INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROSCOPY (ICPOES)
- MOLECULAR SPECTROSCOPY
an atom in the vapor will absorb light of certain frequencies as a unique characteristic of that specific atom; sequential technique; have to measure one element after the other by changing the lamp.
ATOMIC ABSORPTION SPECTROSCOPY (AA)
contains a small quantity of the analyte as a metal or a salt in a quartz bulb together with an inert gas (argon gas @ low pressure)
ELECTRODELESS DISCHARGE LAMP (EDL)
used in LS AAS (LS-line source) for background correction purposes
DEUTERIUM LAMPS
when a continuum sources radiation source is used for AAS, it is necessary to use a high resolution monochromator
CONTINUUM SOURCES
conversion of the analyte to a reproductible amount of gaseous atoms that appropriately represent the sample
ATOMIZATION
limits the accuracy, precision, and the limit of detection of the analytical instrument
SAMPLE ATOMIZATION
introduce analyte in a steady manner (for AAS, flame)
CONTINUOUS ATOMIZERS
introduce the analyte discontinuously (electrothermal atomizer)
DISCRETE ATOMIZERS
comprises a dispersive element, an entrance slit and mirrors to create a parallel beam similar to sunlight, and an exit slit and mirrors to xetract the monochromatic light
MONOCHROMATOR
generally uses an argon plasma to excite the atoms in the solution
INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROSCOPY (ICPOES)
Advantages of ICP over AAS
- CAN MEASURE MORE ELEMENTS ALL AT ONCE; MEASURE A WHOLE RANGE OF SUBSTABCES AT ONCE
UV-Vis spectroscopy covers the ultraviolet-vis range of the spectrum
MOLECULAR SPECTROSCOPY
a particular type of infrared spectroscopy; uses an interferometer to produce an IR spectrum
FOURIER TRANSFORM INFRARED SPECTROSCOPY
investigate tools used in many fields of science and engineering
INTERFEROMETER
some molecules can take high-energy ultraviolet light, absorb it, and then emit it back out at lower-energy, longer wavelengths
FLUORESCENSE SPECTROSCOPY
partner of IR spectroscopy; both technologies examine changes in vibration and rotation at the molecular level; measures the amount of light scattered
RAMAN SPECTROSCOPY
a large numbers of photons of certain wavelengths are absorbed by a molecule. These individual wavelengths are too numerous and too close to each other and a spectrum of broad bands of absorbed wavelengths are obtained
Po and P
Intensity or radiant power of EMR and Interaction with matter
Transmittance increases, absorbance decreases
Transmittance decreases, absorbance increases
it is common to use a polychromatic source of radiation with continuous distribution of wavelengths along with a monochromators to create a monochromatic beam from this source.
DUE TO POLYCHROMATIC RADIATION
The longer the path length, the more molecules there are in the path of the beam of radiation, therefore the absorbance goes up. Therefore, the path length is directly proportional to the concentration.
Path length dependence
Increase in conc, increase absorbance
Conc dependence
The blue solution do absorb the red radiation; The red solution can not absorb
the red radiation but it can absorb radiation that is complimentary to red
Wavelength dependence
Concentration = Absorbance / Slope
Relation between concentration and absorbance: Absorbance is directly proportional to the concentration of the substance. The higher the concentration, the higher its absorbance.
a region of the electromagnetic
spectrum covering the range from just above the visible (7.8 π₯ 10β7) to approximately 10β4 m
Infrared (IR)
- Wavelengths within the IR region are usually given in
micrometers (1ΞΌm = 10β6 m) - Frequencies are given in wavenumbers rather than in
hertz
Infrared (IR)
Wavenumber : π£ (ππβ1) = 1/ π(ππ)
spectroscopic method used for
identifying pure organic and inorganic compounds. With the
exception of some homonuclear molecules, all molecular
species absorb infrared radiation.
Infrared Spectroscopy
Advantages of IR spectroscopy:
- Qualitative and quantitative analysis
- Sample preparation
- Sensitive and Time-saving technique
- Itβs versatility
- Easy for interpretation
Why does a molecule absorb some wavelengths of IR radiation?
A pair of atoms joined by a covalent bond
can be thought of as being like balls on the
end of a vibrating spring. The bond can
vibrate with different amounts of energy at a
frequency that depends on the masses of the
atoms and the strength of the bond.
Why does a molecule absorb some wavelengths of IR radiation?
At room temperature, most bonds will vibrate
with the lowest possible amount of energy. But
if radiation of the right frequency is supplied,
the bond can absorb energy and vibrate with
greater amplitude.
is an instrument that uses infrared radiation to
obtain a complete spectrum of the analyte for qualitative
identification.
FTIR
identifies chemical bonds in a molecule by
producing an infrared absorption spectrum.
FTIR
Advantages of FTIR
- High sensitivity, resolution and speed of data
acquisition - All wavelengths are detected and measured
simultaneously using Michelson interferometer that can
be recorded as an interferogram and subsequently
decoded by Fourier transform which is a mathematical
operation that is conveniently carried out by the
computer. - The measured spectrum is complete with different
display options (%T, A, zoom, peak, height, and peak
area)
Parts of an Infrared Spectrum:
- Wavenumber
- Transmittance
- Peaks
- Functional Group Region
- Fingerprint Region
tells us about the very particular energy of infrared light.
Wavenumber
percentage of a [articular wavenumber that reaches the
detector
Transmittance
means that IR light that corresponds to that
wavenumber is not being absorbed by the sample.
100% transmittance
shows that the IR light of the particular wavenumber is not making
through to the detector and is being absorbed by the sample.
Peaks
region where most of the information is used to
interpret the IR spectrum (4000 β 1500 ππβ1)
Functional Group Region
fingerprint of a known substance in a database. This region
important in finding an exact match of the sample. (1500 - 400 ππβ1)
Fingerprint region
two major instruments used to measure IR absorption:
1.Dispersive spectrometer
2.Fourier Transform Infrared Radiation (FTIR) spectrometer
provided the robust instrumentation
required for the extensive application of
this technique.
Dispersive spectrometer
Dispersive spectrometer components
- Source of Radiation,
- Monochromator, and
- Detector
as temp increases, intensity of every emitted wavelength increases