Beruflich Dokumente
Kultur Dokumente
Video Lecture 1 2
Frequency ( R ) is the number of oscillations which occur within a given period of time (sec). The unit hertz (Hz) is often used for frequency and is equal to 1 cycle/sec. Wavelength ( P ) is the crest to crest distance of a wave. Angstroms (1010 m) are used for x-rays; nm (10-9 m) are used for Qv and visible; mQ (106 m) is used for IR. Wavenumber ( )is the reciprocal of wavelength (1/P and the unit is -1 cm . Wavenumbers are normally used in infrared spectrophotometry. Amplitude (a) is the height of a wave. Velocity ( V ) is dependent upon the medium through which radiation is passed is is measured in cm/sec. Velocity = wavelength x frequency = P x R
Example: What is the velocity of an ocean wave which has a length of 7.5 m and a frequency of 0.45 cycles/sec? V = P x R = 7.5 m/cycle x 0.45 cycles/sec = 3.38 m/sec Example: What is the frequency and wave number of radiation which has a wavelength of 1.58 x 10-6 cm in vacuum? Solve for frequency: V = P x R therefore R = V / P In a vacuum the velocity = 3 x 1010 cm/sec freq = c / P = 3 x 1010 cm/sec / 1.58 x 10-6 cm/cycle = 1.9 x 1016 cycles/sec wavenumber = =1/
ENERGY PROPERTIES
Radiant energy consists of small bundles called photons. Every photon of a specific wavelength possesses exactly the same energy as every other photon of that wavelength. A photon at a different wavelength does not possess the energy of some other wavelength. The relationship between the energy of particles and their wave nature is given by E = hR where
R = frequency in cycles/sec
h = Planck's constant = 6.62 x 10-27 erg sec If we substitute for c/P for the frequency ( R ), where c = velocity of light in a vacuum (3 x 1010 cm/sec).
Therefore the energy of a photon increases linearly with its frequency. Example: Calculate the wave number (cm-1), the frequency (sec-1) and energy of a photon in ergs of radiation which has a of 1.24 x 10-6 cm in vacuum. wavenumber = = 1/
freq = R = c / P = 3 x 1010 cm/sec / 1.24 x 10-6 cm = 2.42 x 1016 sec-1 energy = hR = 6.62 x 10-27 erg sec x 2.42 x 1016 sec-1 = 1.60 x 10-10 erg
SUMMARY OF UNITS
Parameter wavelength amplitude wavenumber frequency Symbol Units cm cm cm-1 Constants
P
a
cycles/sec
V c E h
RELATIONSHIPS
wavenumber = =1/P
gamma ray 0.0005 - 0.14 nm 0.01 - 10 nm X-ray uv-vis IR 180 - 780 nm 780 - 30000 nm
Absorption of Radiation absorption - a chemical species in a transparent medium selectively attenuates (reduces the intensity) certain frequencies of electromagnetic radiation.
Every elemental particle (atom, molecule, ions) has a specific set of energy states (whole number multiples of hR). Ground state - the lowest energy a particle exists at room temperature. Excited state - a higher energy state than the ground state (a whole number multiple of hR When a photon of radiation passes near an elementary particle, absorption can occur if the energy of the photon (hR is exactly the difference between the ground state and one of the excited states (higher energy states). Therefore, each particle only absorbs at selected wavelengths.
If absorption occurs, the energy of the photon is transferred to the elementary particle. When radiation is impinged upon these particles, electrons may be promoted from a lower energy state to a higher. Energy is transferred from the photon to the molecule (absorbed) and any excess radiation is transmitted. This raises the particle to an excited state. particle + hR ----> excited particle The electrons in chemical particles possess a limited number of discrete energy states. The particle only remains in this excited state for a brief period of time (10-6 to 10-9 sec). The excited particle relaxes back to its ground state.
The excess energy that was obtained from the photon is transferred to other atoms or molecules in the medium with a small increase in heat. excited particle -----> particle + heat The amount of heat generated is so small it is usually undetectable. The lifetime of the excited particle (species) is so short that its concentration is ordinarily negligible. The relaxation may also occur by photochemical decomposition of the excited species to form new species or by fluorescent or phosphorescent remission of radiation.
The molecules can only absorb the exact amount of energy from each photon. If the energy of the photon is not perfectly matched, there is no absorption.
Problems
1. The wavelength of a sodium line is 589 nm. Calculate: a) freq = v in cycles/sec
b) wavenumber = v = cm-1 c) energy in ergs 2. Calculate the velocity (v) of an ocean wave which has a length of 1000 cm and a frequency of one wave every 15 sec. 3. Calculate the energy of a photon in ergs which has a wavenumber of 2.2 x 10-4 cm in a vacuum. 4. What frequency of light will allow the correct amount of energy to raise the electron in the ground state to 1stenergy level? What is the of this photon (assume vacuum)?
Spectroscopy
Introduction
Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic radiation by matter to qualitatively or quantitatively study the matter or to study physical processes. The matter can be atoms, molecules, atomic or molecular ions, or solids. The interaction of radiation with matter can cause redirection of the radiation and/or transitions between the energy levels of the atoms or molecules.
y y
Absorption: A transition from a lower level to a higher level with transfer of energy from the radiation field to an absorber, atom, molecule, or solid. Emission: A transition from a higher level to a lower level with transfer of energy from the emitter to the radiation field. If no radiation is emitted, the transition from higher to lower energy levels is called nonradiative decay. Scattering: Redirection of light due to its interaction with matter. Scattering might or might not occur with a transfer of energy, i.e., the scattered radiation might or might not have a slightly different wavelength compared to the light incident on the sample.
FILTER PHOTOMETERS Filter photometers use filters to select the desired wavelength and are either single beam or double beam. A single beam instrument uses a single light
path for both the reference and the sample. A double beam uses separate light paths for the reference and sample.
SINGLE BEAM PHOTOMETERS Single beam photometers use the same light path for both the solvent (100 %T) and the solvent-sample. Typically, the light passes through a collimating lens that is directed at the entrance slit where the light is then passed through a filter. The unabsorbed light is passed through the sample holder, passes a closeable shutter (0 %T), to a photovoltaic cell which is attached to a readout device.
A stabilized power supply is very important. Using a stabilized power supply avoids errorsresulting from changes in the beam intensity during the time required to measure 100 %T and the %T of the analyte.
Normally, the process that is followed for the analysis of a sample at a predetermined wavelength (as per filter selection) is as follows:
1.
2. The sample holder is filled with the solvent (blank), the shutter is opened and 100 %T is adjusted. 3. The sample is added to the sample holder and %T is read.
variation in light intensity errors in %T light beam not monochromatic deviation from Beer's law %T and A are not "true" values not designed for spectral data
DOUBLE BEAM PHOTOMETERS Double beam photometers split the light path into two segments. One segment is used as a reference and the other as the working path. This allows the instrument to make automatic corrections for variations in light intensity.
When the voltages between the sample resistor (CD) and reference resistor (AB) are equal, no current flows through the galvanometer (null detector) since there is no voltage potential difference between the two resistors.
The 0 %T is set by moving contact A (between the meter and the reference resistor) to no resistance (contact B). The shutter is closed which blocks all light from hitting the phototubes. The null meter is mechanically set to read 0 %T since no current is produced by the phototubes. 100 %T is set by placing only the solvent in the sample container. The null meter's contact A (between the meter and the reference resistor) is set for maximum resistance (100 %T). The shutter is opened so that light does strike both phototubes (sample and reference). The null meter's contact D (between the meter and the sample resistor) is adjusted so that there is equal voltage difference between the two resistors (points AB and points CD). At that point, no current flows through the null meter and the meter reads 100 %T. The analyte and solvent is now placed in the sample container. The analyte will absorb some of the light passing through it which reduces the intensity of the light striking the sample phototube. Since less light is striking the sample phototube, the phototube produces less current. Less current means less voltage across the sample resistor. Now there is a voltage difference between the sample resistor (AB) and reference resistor (CD). Current now flows through the null meter (AD). To compensate, contact A (between the null meter and the contact reference resistor) is moved downward until the voltages are once again
equal and no current flows (AD). The %T is read directly from the meter. Advantages of double beam photometers
y y
light beam is not monochromatic deviation from Beer's law %T and A are not "true" values not designed for spectral data
Steps for the use of a single beam spectrophotometer 1. 2. 3. 4. Set the wavelength. Select readout display to the desired mode ( %T, A, Conc). Set the readout display to 0 %T (no light) (shutter closed). Insert the reference cell which contains the solvent and set the readout display to 100 %T (shutter open).
5.
Insert the sample dissolved in the solvent and read %T from the display.
Cannot easily be used for absorption spectra (point by point). Changes in light intensity cause variations in readout. Changes in solvent causes variations. Changes in wavelengths cause variations and % T and has to be reset at 0 %T and 100 %T.
DOUBLE BEAM SPECTROPHOTOMETERS Double beam spectrophotometers use a beam chopper to separate the reference beam from the sample beam. Beam Chopper The chopper is divided into three equal segments. One segment is clear which will pass light through the wheel, one segment is mirrored which will reflect light along a different path, and the third segment is opaque so that no light is transmitted nor reflected.
speed of operation automatic compensation for variation in lamp output solvent absorption at various 8 changes in detector sensitivity spectra scan
cost is higher
OTHER SELECTIONS ON INSTRUMENT Most instruments have various options and selections which can be made during an analysis. The mode switch allows the operator to choose what data the readout gives . The three major choices are absorbance (a log amplifier converts transmittance to absorbance), % T, or directly into concentration units.
The slit adjustment allows the operator to adjust the slit width of the instrument. For instruments which have gratings which can be automatically turned the scan speed (wavelength/min) can be adjusted. Higher scan speeds are used for surveys while slower speeds are used to look at areas in more detail. The chart recorder is used to record the data of scan instruments. The paper speed and range (mv) can be adjusted to match the output of the spectrophotometer to give a spectra scan.
SPECTRA SCAN Spectra scans have two coordinated: the X axis is normally wavelength, and the Y axis is either absorbance or transmittance. The resulting graph is called a spectra scan. A spectra scan is similar to a fingerprint of a compound.
PROBE TYPE PHOTOMETERS Dipping type photometers use fiber optics to transport light. The original light from a tungsten lamp travels down a fiber optic cable which is dipped into the solutions of interest.
The light then passes through the solution and a mirror reflects the light back to a return fiber optics cable. The cell path length is 2 times the distance between the ends of the optical cable and the mirror. Interference filters are provided to select wavelengths. The reflected light is then passed through a photodiode with an amplifier and an electronic chopper which is synchronized with the lamp. This results in the detector not responding to extraneous light.
PowerPoint
UV - VIS SPECTROPHOTOMETERS
LIGHT SOURCES visible (350 to 2200 nm) - heated tungsten filament ultraviolet (160 to 380 nm) - hydrogen or deuterium lamp using quartz windows
The deuterium lamp consists of a metal electrode and an oxide coated plate with a 40V regulated voltage source. D2 + e- ---> D2* -----> D + D + hR
WAVELENGTH SELECTION Wavelength selectors restrict the radiation being measured to a narrow band that is absorbed or emitted by the analyte. Narrow bandwidths increase the likelihood of adherence to Beer's Law. Each selector has a nominal effective bandwidth.
y
FILTERS Absorption Filters Absorption filters are normally less expensive than interference filters. Absorption filters are typically used in the visible range. Absorption filters have effective bandwidths from 30 to 250 nm. Filters with narrow bandwidths also absorb a significant portion of the light and have about 10% transmittance. Three types of absorption filters:
y y y
The filters absorb all wavelengths of light except for particular wavelengths which they pass.
Dyed gelatin filters do not last long and must be frequently replaced. A sharp cutoff filter consists of two filters put together.
Band Width is a filter characteristic of wavelength range over which transmission is greater than its maximum value.
Interference Filters Interference filters use optical interference to provide narrow bandwidths of radiation. The filter consists of a dielectric insulator which has essentially no charged current carrying particles (MgF2 or CaF2) which is sandwiched between two semitransparent metallic films. These three layers are then sandwiched between two plates of glass or transparent materials.
The thickness of the dielectric layer determines the wavelength of the transmitted radiation. When the beam of radiation strikes this filter, some of the radiation passes through the first metallic layer while the
rest is reflected. The remaining light then strikes the second metallic layer and some is passed while the rest is reflected. If the reflected light from the second layer is of the proper wavelength, it is partially reflected from the inside surface of the first layer in phase with incoming radiation of the same wavelength. The result is that the desired wavelength is reinforced while the others wavelengths, being out of phase, undergo destructive interference. Interference filters are used throughout the ultraviolet and visible regions and about 14 um into the IR region. MONOCHROMATORS For many methods it is desirable to vary the range of wavelengths of radiation. This varying of the wavelengths is called scanning.
entrance slit collimating lens or mirror prism or grating focusing and reflecting elements exit slit
PRISMS Prisms can disperse ultraviolet, visible, and infrared radiation. Two major types are:
y
Cornu prisms are typically constructed by cementing two 30 degree quartz blocks together. On block is left-handed quartz while the other is right-handed quartz.
Littrow prisms are more compact and are 30 degree prisms with mirrored backs. Refraction take place twice within the same segment.
DIFFRACTION GRATING Diffraction gratings (transmission gratings) are not typically used.
REFLECTION GRATING Reflection grating are used in most monochromators. The grating is consists of a hard optically flat polished surface. Onto this surface are etched parallel and closely spaced grooves. Gratings for visible and ultraviolet will typically have from 300 to 2000 grooves per mm with the typical grating having 1200 to 1400 grooves. Gratings for infrared may have 10 - 200 grooves per mm with the typical IR instruments (5 - 15 Qm) having about 100 grooves.
overlapping of orders - sometimes various overlapping wavelengths are diffracted in the same position (i.e. 600 nm, 300 nm, 200 nm). To cure the overlapping, filters are placed in the light path to eliminate the unwanted wavelengths.
COLLIMATING LENS
y y
Front face mirrors do not suffer from chromatic aberration Aluminized front mirror has no light absorption of UV.
Chromatic aberration in lens are caused when the light paths coming in are bent and focus on various points instead of one point.
SLITS The entrance slit of a monochromator is the source of the radiant energy. The image of the entrance slit is focused afterwards on the exit slit. By directing the entrance light to a rotating dispersing element, the light can be broken up into particular wavelengths which are then individually focused on the exit slit.
Slit Width
y
y y
narrow slits are selected for resolution of closely spaced absorption bands. But as the slit width becomes smaller, the radiant power going through the slit decreases. The S/N ration increases. slit widths are varied for quantitative analysis narrow slits are used for qualitative work
STRAY LIGHT Stray light is light of wavelengths different from those wanted. Sources of stray light
y y y
incompletely removed higher order wavelengths in grating instrument scattering of light by dust reflection of light by lens and grating mountings
first monochromator selects wavelengths and passes them to a second which refines the wavelengths
y
paint all components except for reflecting surfaces which are desired black enclose system to keep out dust
SAMPLE CONTAINER The sample cells or cuvettes that hold the sample must be made of a material which is transparent to the radiation of interest which is being passed through the sample.
y
y y
quartz or fused silica for UV (below 350 nm) and the visible region. NaCl for the IR region.
PHOTOSENSITIVE DETECTOR
y y
Photoelectric effect
When the photon hits the plate, an electron is released which strikes the cathode. The current is measured.
PHOTOMULTIPLIER TUBE
More and more electrons are knocked off each respective dyanode. Finally, at the last dyanode, there are sufficient electrons to give a good readout.
PHOTOVOLTAIC CELLS
Photovoltaic cells generate their own voltage on irradiation. Best used for photometers which use filters due to irregular response to various wavelengths.
READOUT
y y