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    Infrared Spectros

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    Crisa China

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    CAPE Analytical Methods and Separation Techniques “7 Infrared Spectroscopy INFRARED (IR) SPECTROSCOPY Infrared spectroscopy is a subset of spectroscopy that deals with the IR region (4000 — 600 cm’) of the clectromagnetc spectrum. Itis bound by the red end of the visible region at high frequencies andthe microwave region at low frequencies. The main goal of IR spectroscopic analysis is to determine the chemical functional groups in a sample. Infrared is a more powerful tool than UV/Vis spectroscopy in qualitative analysis but itis less satisfactory for quantitative analyses because the narrow peaks that characterize IR absorption usually lead to deviations from Beer’s Law and IR absorbance measurements are less precise. In addition to electronic transitions, molecules exhibit 2 other types of radiation-induced transitions: ~ Vibrational transitions - Rotational transitions IR radiation is not energetic enough to cause electronic transitions but can induce transitions in the vibrational and rotational states within the ground electronic state of the molecule. Ifyou shine a range of infra-red frequencies one ata time through a sample of an organic compound, you find that some frequencies get absorbed by the compound, A detector on the other side of the compound would show that some frequencies pass through the compound with almost no loss, but other frequencies are strongly absorbed. Each frequency has a certain amount of energy associated with it. If a particular frequency is being absorbed as it passes through the compound being investigated, it must mean that its energy is being transferred to the compound. Energies in infra-red radiation correspond to the energies involved in bond vibrations In covalent bonds, atoms aren't joined by rigid links - the two atoms are held together because both nuclei are attracted to the same pair of electrons. The two nuclei can vibrate backwards and forwards - towards and away from each other - around an average postion. Bonds ae vibrating all the time, butif you shine exactly the right amount of energy on a bond, you can kick it into a higher state of vibration. The amount of energy it needs to do this will vary from bond to bond, and so each different bond will absorb a different frequency (and hence energy) of infra-red radiation, Absorption in the rotational levels is often prevented in solid and li iquid samples and the effects of these energy changes are not detected. Modes of molecular vibrations: ~ Stretching - distance between 2 atoms increases or decreases (change in bond length) x qu symmetrical stretching asymmetrical stretching Page 1 of 14 ‘Scanned with CamScanner care: = ‘Analytical Methods and Separation-Techniques Infrared Spectroscopy ‘The energy involved in this vibration depends on the length of the bond and the mass of the atoms at either end. That means that each different bond will vibrate in a different way, involving different amounts of energy. Bonds are vibrating all the time, but if you shine exactly the right amount of energy on a bond, you can kick it into a higher state of vibration. The amount of energy it neds to do this will vary from bond to bond, and so each different bond will absorb a different frequency (and hence energy) of infra-red radiation. = Bending — position of the atom changes relative to the original bond axis (change in bond angle): scissoring, rocking, wagging and twisting ON ate ‘AX, ANTISYMMETRICAL stm Ae VP COON ‘AX; -INPLANE ‘AX:-ROCKING sem ae ExonNG s5,-ovr orate 6, oo orga somes secomneest acy ees Vibrational modes of CO, vs SO; CO; S02 Type of molecule Tinear ‘Non-linear Polar vs non-polar ‘Non-polar polar Vibrational mode (symmetric stretch) ‘Non IRactive | IRactive Vibrational mode (asymmetric stretch) TRactive TRactive Vibrational mode (bending) TRactive TRactive Since S03 is a polar molecule essentially all modes of vibration causes a cause Ia the di " : ipole and thus would be IR active. However a linear molecule like CO; would be non-polar but specific vibrational modes where the dipole is no longer symmetrical would result in IR absorption. Page 2 of 14 Scanned with CamScanner CAPE Analytical Methods and Separation Techniques Infrared Spectroscopy ‘When the frequency of a specific vibration is equal to the frequency of the IR radiation directed on the molecule, the molecule absorbs the radiation and the associated energy is converted into these types of motions, ‘The number of ways a molecule can vibrate depends on the number of atoms and hence the number of bonds in the molecule. ‘Not all bonds within a molecule absorb energy at IR wavelengths even though the frequency of the radiation exactly matches that of the bond vibration. A molecule only absorbs those frequencies of IR radiation that Match vibrations that cause a change in the dipole m« it of the molecule. The more polarised a bond is (large difference in electronegativity), the easier is the interaction with IR radiation. ‘Symmetrical bonds such as Na, Ha and Cla do not absorb IR because stretching does not change the dipole moment, and bending cannot occur with only 2 atoms in the molecule. More complex molecules allows for an increase in the number of possible vibrations. Sample analysis by IR spectroscopy Solid, liquid and gaseous samples can be analysed by IR spectroscopy. However, many materials are opagiue to IR radiation and must be dissolved or diluted in a transparent matrix in order to obtain spectra. Gaseous samples require little preparation beyond purification, but a sample cell with a long path length (typically 5-10 em) is normally needed, as gases show relatively weak absorbances. Infrared Spectrometer, [ee H — Sample In order to measure a sample, a beam of IR light is passed through the sample, and the amount of energy absorbed at each wavelength is recorded. This may be done by scanning through the spectrum with a monochromatic beam, which changes in wavelength over time, or by using a Fourier transform instrument (FT- IR) to measure all wavelengths at the same time. The result of which is a plot of transmittance versus wave number. This technique works exclusively on covalent bonds and clear spectra can be obtained from samples with few IR active bonds and high levels of purity. Analysis of solid samples There are 3 ways of analyzing solid samples; as a thin film, as a mull or disc. Thin film A drop of the sample is squeezed between two salt (NaCI) plates to form a film of about 0.01 mm in thickness. The sample can also be melted and squeezed between 2 plates Page 3 of 14 ‘Scanned with CamScanner CAPE Analytical Methods and Separation Techniques Infrared Spectroscopy Mulls ‘The sample is mixed with a few drops of paraffin oil/nujol and ground into a thick paste (<2um) and applied onto salt plates. A mull is a suspension of a solid in a liquid, To obtain full TR spectrum that is free of mulling agent bands, multiple mulls must be used (c.g. fluorolube and hexachlorobutadiene). The paste must contain particles less than 2 ym to avoid scattering of IR radiation. Discs Pellets are used for solid samples that are difficult to melt or dissolve in any suitable TR-transmittng solvent. The sample (Img) is finely ground and mixed with 100mg of KBr (any other alkali halide) dry powder. The mixture is then pressed into a transparent disc. A KBr pellet is a dilute suspension of a solid in a solid, Analysis of liquid and vapour samples Liquid samples are smeared between salt plates or by using a special liquid cell. Liquid samples should be prepared at a concentration of about 0.2M using a suitable organic solvent such as CCl, and carbon disulphide, ‘Water is never used in preparing samples for IR analysis because it damages the NaCl plates. A cell containing ure solvent is generally placed in the reference beam of the spectrometer, so that the solvent IR bands are not obtained in the desired spectrum, Gases are analysed in cells with ends made of NaCl, with a path length of about 10cm. ‘NaCl plates can be cleaned with dry methylene chloride or acetone. As much as possible, the purest samples are best for analysis. Limitations Note that to determine the structure of an unknown compound, IR Spectroscopy can only determine the functional groups present. In order to fully elucidate the structure, other techniques are required such as:- Mass. ‘Spectroscopy and NMR (Nuclear Magnetic Resonance) Spectroscopy. Infrared Spectrum The IR spectrum for a molecule is a graphical display of the frequencies of IR radiation absorbed (given in units of wavenumber, cm") and the % transmittance. How much of a particular frequency gets through the compound is measured as percentage transmittance. “A percentage transmittance of 100 would mean that all of that frequency passed straight through the compound without any being absorbed. In practice, that never happens - there is always some small loss, giving a transmittance of perhaps 95% as the best you can achieve. ‘A transmittance of only 5% would mean that nearly all of that particular frequency is absorbed by the compound, A very high absorption of this sort tells you important things about the bonds in the compound. Page 4 of 14 Scanned with CamScanner CAPE Analytical Methods and Separation Techniques, Infrared Spectroscopy Wavenumber is: wavenumber = aveiengihingn emt IR absorptions occur as a result of vibrational and rotational transitions within the molecule. Because only a few compounds exhibit pure rotational bands, the vibrational absorption bands are of more practical interest. The spectrum can be divided into 2 regions: ~ Fingerprint regions — unique for a molecule (<1200 cm", consists of many peaks due to the variations of the bending vibrations. These are difficult to interpret) ~ ‘Functional group region — similar for molecules with the same functional groups (located in the shorter wavelength region; 4000 — 1200 cm’) “Most of the information that is used to interpret an IR spectrum is obtained from the Functional Group Region. Example 1: Carbon monoxide == c—o Symmetrical stretch (IR active) Example 2: Carbon dioxide —=u_s> a t o—c—o Oo—cC—oO t ~ g Symmetrical stretch (IR inactive) Asymmetrical stretch (IR active) Bending (IR active) (2 degenerate modes @ right angles} ‘The 2 degenerate modes are equal-energy bending vibrations in CO. They ar identical except that one bending mode is in the plane of the paper and one is out of the plane. IR Spectrum for CO; ‘wransinttence Page 5 of 14 ‘Scanned with CamScanner cape ‘Analytical Methods and Separation Techniques Infrared Spectroscopy CO> only shows 2 absorption peaks because the symmetrical stretch of CO; causes no change in dipole thus no absorption occurs. Example 3: Sulphur dioxide t S 8, S. v™ YSN &> S77 ‘Asymmetrical stretch (Ractive) _ Symmetrical stretch (IR active) Bending (IR sctive) IR Spectrum of Sulphur ide 40 % Transmittance y 3 1800 1600 1400 1200 1000 9800 600 400 Wavenumber / cm Sulphur dioxide shows 3 absorption peaks because a change in dipole occurs in both bending and stretching, Interpreting Infrared Spectra IR spectroscopy is used for structural elucidation and compound identification. The interpretation of IR spectra involves the correlation of absorption bands in the spectrum of an unknown sample with the known absorption frequencies for types of bonds. Factors to consider when identifying the source of an absorption band: — Intensity (weak (w), medium (m), strong (s)) ~ Shape (broad (b), sharp (s)) — Position (em") It must be notes that if a reference IR spectrum is not available for an unknown molecule, then IR spectroscopy does not provide sufficient details for it to be used alone to identify a molecule. Pare 6 of 14 Scanned with CamScanner ee ‘Analytical Methods and Separation Techniques Infrared Spectroscopy *Polar bonds absorb strongly such as OH, C=O, C=N, C - O and non-polar bonds absorb weakly such as C=C, cc Example 1: IR spectrum of propan-1-ol, CHsCH;CH;0H energy absorbed due to the O-H bond stretching ‘energy absorbed due to C-Hbonds bending 100. ‘wansmitance (%) 4000 = 3000. 2000» 1500 = 1000S S00 ‘wavenumber (err!) ‘eneray absorbed due to C-Hbonds stretching In the diagram, three sample absorptions are picked out to show you the bond vibrations which produced them. Notice that bond stretching and bending produce different troughs in the spectrum. Alkenes * C=C stretch from 1680-1640 cm™ + =C-H stretch from 3100-3000 cm” + =C-H bend from 1000-650 cm ‘The IR spectrum of 1-octene is shown below. Note the band greater than 3000 om’ for the =C-H stretch and the several bands lower than 3000 cm’ for ~C-H stretch (alkanes). The C=C stretch band is at 1644 cm, Bands for C-H scissoring (1465) and methyl rock (1378) are marked on this spectrum; in routine IR analysis, these bands are not specific to an alkene and are generally not noted because they are present in almost sll organic molecules (and they are in the fingerprint region). Page 7 of 14 ‘Scanned with CamScanner care. Analytical Methods and Separation Techniques. Infrared Spectroscopy 2383, cs 4 tectene rad Qe alone CH ‘Wevenumbers(em-1) Alcohols + O-Hstretch, hydrogen bonded 3500-3200 em"! + C-O stretch 1260-1050 cm" (5) ‘The spectrum of ethanol is shown below. Note the very broad, strong band of the O-H stretch (3391) and the C-O stretches (1102, 1055). Page 8 of 14 ‘Scanned with CamScanner cee Analytical Methods and Separation Techniques Infrared Spectroscopy H asymmetnc NH (4 syometic NH ‘Stretch, higher wavenumber stretch, lower wavenumber H + N-Hstretch 3400-3250 em" © 1° amine: two bands from 3400-3300 and 3330-3250 cm™ © 2° amine: one band from 3350-3310 cm’! © 3° amine: no bands in this region + N-Hbend (primary amines only) from 1650-1580 cm"! + C-Nstretch (aromatic amines) from 1335-1250 cm" + CNstretch (aliphatic amines) from 1250-1020 em’! 1N-H wag (primary and secondary amines only) from 910-665 cm’! The spectrum of aniline is shown below. This primary amine shows two N-H stretches (3442, 3360); note the Shoulder band, which is an overtone of the N-H bending vibration. The C-N stretch appears at 1281 rather than at lower wavenumbers because aniline is an aromatic compound. Also note the N-H bend at 1619, \ shoulder band 3380 eee antine a any cn Om ete, 5 ed eo (primary amines) 1619 ni 0 Wavenumbers (emt) amines) ‘The spectrum of diethylamine is below. Note that this secondary amine shows only one N-H stretch (3288). The C-N stretch is at 1143, in the range for non-aromatic amines (1250-1020). Diethylamine also shows an N- H wag (733). Page 9 of 14 ‘Scanned with CamScanner Cais ‘Analytical Methods and Separation Techniques Infrared Spectroscopy ‘3208 N-H strotch (secondary amino) verTransranance dlethylamine grey at LG ‘stretch He 20 ‘Wavenumbers (cm-1) Triethylamine is a tertiary amine and does not have an N-H stretch, nor an N-H wag, The C-N stretch is at 1214 cm” (non-aromatic). note the ubsence ofa N-H stretch inthis compound, g ‘au fe c-N i stretch e Hetytamine e ones nyoe-a6 CHG, ‘Wvenurbers(em-1) Page 10 of 14 ‘Scanned with CamScanner ce ‘Analytical Methods and Separation Techniques Infrared Spectroscopy Ketones * C=O stretch: © aliphatic ketones 1715 cm” © a, B-unsaturated ketones 1685-1666 cm’? The spectrum of 2-butanone is shown below. This is a saturated ketone, and the C=O band appears at 1715. Note the C-H stretches (around 2991) of alkyl groups. Itis usually not necessary to mark any of the bands in the fingerprint region (less than 1500 em”), g = 281 5 : Hotere R 2-butanone 4 OW H ‘Wearenunbers (1) Aldehydes + H-C=0 stretch 2830-2695 cm™ + C=O stretch: © aliphatic aldehydes 1740-1720 cm™ o alpha, beta-unsaturated aldehydes 1710-1685 cm ‘The spectra of benzaldehyde and butyraldehyde are shown below. Note that the O=C stretch of the alpha, beta- unsaturated compound ~~ benzaldehyde ~ is at a lower wavenumber than that of the saturated butyraldehyde. Note the O=C-H stretches in both aldehydes in the region 2830-2695 cm’, especially the shoulder peak at 2725 ‘om’ in butyraldehyde and 2745 cm"! in benzaldehyde. Page 11 of 14 ‘Scanned with CamScanner CAPE Analytical Methods and Separation Techniques 275 ‘a 2 CHevetches 2 (aldahyees) 5 & : butyraldehyde 2376 ‘Wererumbers (em) sar \_ “25 cH stateh CH stetches . foray (aldehydes) = # benzaldehyde _Warerumbers (em) Carboxylic acids + O-Hstretch from 3300-2500 om” + C0 stretch from 1760-1690 cm"? Page 12 of 14 ‘Scanned with CamScanner Infrared Spectroscopy CAPE Analytical Methods and Separation Techniques Infrared Spectroscopy + C-O stretch from 1320-1210 cm™ + O-Hobend from 1440-1395 and 950-910 cm” The spectrum of hexanoic acid is shown below. Note the broad peak due to O-H stretch superimposed on the sharp band due to C-H stretch. Note the C=O stretch (1721), C-O stretch (1296), O-H bends (1419, 948), and C-O stretch (1296). 98 o-n 2 hexanolc acid 126 bend 2 1419 6-0 s WH HHO 0-H strotch 5 one 2 N-G-G-C-C-C-C-O-H Cd s rere y 5 WaaAA zn uH—_ O-Hstroieh (and C-H stretch) ACTIVITY: Using your data booklet, show how IR spectroscopy can be used to distinguish between the following. compounds HO InN. HsC A IN Page 13 of 14 ‘Scanned with CamScanner CAPE ‘Analytical Methods and Separation Techniques Infrared Spectroscopy Applications of IR Spectroscopy IR spectroscopy is widely applicable as a sensitive, rapid and highly specific tool for the monitoring of various ‘atmospheric pollutants including carbon disulphide, pyridine, sulphur dioxide, hydrogen cyanide and carbon dioxide, Peak Jem Minimum detectable concentration/ppm_ | Carbon disulphide 2200 05 Pyridine 704 02, Sulphur dioxide 1160 05 Hydrogen cyanide 3300. 0.4 ‘Modem IR spectrometers are used in: + Forensic composition of a paint sample can narrow the search + Torapidly identify different samples of polymers —this can help recycling, enabling separation of

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