Spectroscopy Atomic emission spectra UV/Vis spectra Infrared (IR) 1 Spectroscopy Atomic emission spectrum. Recall. 2 Spectroscopy An atomic light source may be obtained by burning an element over a flame (flame test). When this light hits a prism, the different wavelengths of light are refracted at different angles. 3 Spectroscopy Atomic emission spectrum. Recall. c = and E = h 4 Spectroscopy Absorption and Emission spectra Evidences to support the atomic model. 1. All atoms have a unique emission/absorption spectrum. This allows the identification of elements. 2. The spectra of the pure element is ALWAYS the same regardless of where is the spectrum obtained. This suggest that the separation of the energy levels for each atom is different but it is constant for that element. 3. Not all lines appear equally separated. It suggests that not all energy levels are equally separated. 4. The transition n=7 to n=1 releases more energy than the transition n=5 to n=1. Therefore the lines associated with these transitions will have different frequencies and wavelengths. 5 Energy Spectroscopy n=7 n=6 n=5 n=4 n=3 IR n=2 Vis n=1 UV 6 Ultraviolet/Visible or UV/Vis Spectroscopy It examines transitions in electronic energy levels. It is used in Lambert Beer’s law. 2 a 1.8 b 1.6 s 1.4 o 1.2 r 1 b 0.8 a 0.6 n 0.4 c 0.2 e 0 200 300 400 500 600 700 wavelength (nm) 800 The peaks correspond with energy transitions between MOs. Peaks at about 480 nm and 600 nm allows to calculate the energy transitions using c = and E = h 7 Ultraviolet/Visible or UV/Vis Spectroscopy 1.8 a b 1.6 s 1.4 o r 1.2 b 1 a n 0.8 c 0.6 e 0.4 0.2 0 100 150 200 250 300 wavelength (nm) This compound absorbs in the UV section and it is colorless. Any colored molecule can be used in UV/Vis spectroscopy experiments, as they will absorb light from the visual spectrum. 8 Ultraviolet/Visible or UV/Vis Spectroscopy Recall Lambert Beer’s law A=abc where: A is absorbance (amount of light absorbed by the sample) a: molar absorptivity (M-1 cm-1). Constant and specific to the atom, ion or molecule and to the wavelength. b: path length of sample (cm). Length from front to back of the cuvette that is used. Larger cuvettes absorb more as the light will encounter more particles. c: concentration (M). When concentration increases, absorbance increases as the light will encounter more particles. 9 IR Spectroscopy All covalent bonds in molecules experience vibrations within the bond. See animation This vibrational frequency falls in the IR section of the spectrum. Vibrational frequencies depend on the mass of the atoms and the strength of the bonds. Recall frequency is related to wavelength. c = Wavenumbers are the reciprocal of the wavelengths measured in cm-1. IR spectra is often plotted with wavenumbers along the top and wavelengths along the bottom, both in the x axis. 10 IR Spectroscopy Bond type Range of wavelengths (m) Range of wavenumbers (cm-1) -C-H 3.38 – 3.51 2960 - 2850 =C-H 3.23 – 3.33 3100 - 3000 C=C 5.95 – 6.17 1680 - 1620 O-H 2.74 – 4.00 3650 - 2500 N-H 2.94 – 3.13 3400 - 3200 C–O 7.69 – 10.00 1300 - 1000 C=O 5.56 – 6.13 1800 - 1630 Molecules that have the same functional groups such as alcohols (O-H) or carboxylic acids (-COOH) can be identified through IR since they will have peaks within the same range. Every compound have a unique IR spectrum that 11 allows its identification. IR Spectroscopy O ║ Acetone CH3 – C – CH3 12 IR Spectroscopy 13 Visit the webcast below for a better understanding of this important technique. http://media.collegeboard.com/dig italServices/swf/apwebcasts/chemistry/ap_chem_pe s.html 14