Atomic Spectra and Qualitative Spectral Analysis

Technical University of Cluj-Napoca Physics Department

which atoms cannot do. it occupies the lowest energy level. 2 Energy levels in atoms and atomic transitions. The different amounts of energy that an atomic electron is allowed are called energy levels. molecules have many ways to absorb energy. For example. Atomic electrons usually remain excited only a very small fraction of a second before returning to the ground state and thus emitting electromagnetic waves. He tried to unite the nuclear model with Einstein's quantum theory of light. That is. That is (see also fig. the molecular ones are band spectra. Bohr accepted the planetary arrangement of electrons but made the bold hypothesis that the laws of electromagnetism do not operate inside atoms. While atomic spectra are line spectra. This level is called the ground state. 1911. the energy of an electron in an atom is quantized. called the excited state. He noted that the specific wavelengths in an atomic spectrum mean that an atomic electron cannot absorb or emit just any wavelength of light. 1 Electron "orbits" in atoms 2 Fig. He postulated that an electron in a stable orbit does not radiate energy. Einstein's revolutionary theory of the photoelectric effect had not yet been confirmed and was not widely believed. The molecules also have discrete energy levels. As a result. the energy of a photon of light is given by: E = hν . Einstein says that the light photon has an energy hν . The electrons in excited states have larger orbits and thus higher energies. Therefore. Furthermore. The energy of the photon is equal to the energy difference between the excited and the ground states. the energy of an electron from an orbit near the nucleus is less than that of an electron in an orbit farther away. Work has to be done to move an electron from an orbit near the nucleus to one farther away. According to Einstein. When an electron has the smallest allowed amount of energy. Fig. Thus. 1 and 2): hν = E excited − E ground (1) When the electron makes the return transition to the ground state.THEORETICAL APPROACH The Danish physicist NIELS BOHR (1885-1962) worked on the problem of the atom. destroying the atom. the energy of an orbiting electron in an atom is the sum of the kinetic energy of the electron and the potential energy resulting from the attractive force between the electron and the nucleus. In that time. According to Bohr. molecules can emit a much wider variety of light frequencies than can atoms. a photon is emitted. Bohr postulated that the difference in the energy of the atomic electron before and after a photon is absorbed is equal to the energy of the photon. If an electron absorbs energy it can undergo a transition to a higher level. the electron does not spiral into the nucleus. an electron can emit or absorb only specific amounts of energy. Therefore. they can rotate and vibrate. . Bohr assumed that the light emitted by the hydrogen atoms accompanied changes in the energy of the electrons.

When a high voltage is applied across the tube. Similarly. electrons pass through the gas. if sodium chloride is put on a wire and held in a flame. A phosphorescent material contains atoms that. The light has a red colour. lithium salts emit red light. the substance is a phosphor. the electrons collide with the Hg atoms. The light given off comes from the atoms. When an atom of a fluorescent material is in the excited state. coated on the inner surface of the glass tube. Gas atoms can be made to emit their characteristic colours by a method shown in fig. The properties of individual atoms become apparent only when they are not tightly packed into a solid. In this spectroscope. 4. Some phosphors are nearly fluorescent. electronic excitation and photon excitation (see fig 3). There is no sharp dividing line between fluorescence and phosphorescence. Phosphorescence is a matter of degree. it is emitted in the form of light. greenish blue. The set of wavelengths of light emitted by an atom is called the emission spectrum of that atom. The ultraviolet photons are absorbed by the atoms in the phosphor. Thus. is another method of exciting atoms. once excited. transferring them energy. When they give up this extra energy. Generally. the coating of a fluorescent lamp emits light only when current flows through the tube. A glass tube containing neon gas (Ne) has metal electrodes at each end. emitting photons of visible rather than ultraviolet light. Atoms remain in higher energy levels only a bit longer than in fluorescent substances. However. and mercury. The emission spectrum of an atom can be studied in greater detail using the instrument shown in figure 4.Fluorescence and Phosphorescence There are three ways to cause the atoms to emit photons: thermal excitation. if an atom remains in a higher energy level for 10-3 seconds or longer. Nitrogen and argon emit a bluish colour. causing them to emit ultraviolet photons. 3 Ways of emitting photons by bodies 3 . These photons strike a material called a phosphor. Then the atoms can emit light that is characteristic for the elements making up the substance. For example. all incandescent solids emit the same spectrum. When a body is heated it becomes incandescent. then. and barium salts emit green light. the light passes Fig. a fluorescent reflector on an automobile will glow only while it is being irradiated by the photons from the headlights of another automobile. Collision with photons. The two types of substances differ in the time it takes their excited atoms to return to their normal energy levels. can remain in higher than normal energy levels for some time. Many substances can be vaporized by heating them in flame. The atoms and the molecules of the coated substance are excited. Thus. Let us consider a fluorescent lamp filled with mercury vapour. When a high voltage is applied across the tube. besides the thermal excitation and the electron collision. the sodium atoms will emit a bright yellow light. Atomic Spectra The puzzle of the arrangement of the electrons about the nucleus of the atom was clarified by studying the light emitted by atoms. Both fluorescent and phosphorescent materials contain atoms that are easily excited. The electrons collide with the neon atoms. The atoms have no stability in the higher energy levels. the atoms return to their normal energy levels at once.

For a certain colour. λ = λ (div ) . the spectrum of a gas is a series of lines of different colours. and the energy λ λ (Å ) Position (div) Data table 2 (Hg spectrum) Position (div) λ(Å ) ν (Hz ) E (eV) 4 . A lens system focuses the dispersed light for viewing through a telescope or a photographic plate. by using the spectroscope for positioning the lines and the calibration graph to find their wavelengths. All being gathered in Data table 1.Fig. Observing the emission spectrum of Ne. Data table 1 (Ne spectrum) c . 2. Observing the emission spectrum of an unknown gas and finding out the wavelengths in its spectrum. the coordinates of the coloured lines are read on the spectroscope scale. However. The spectrum of an incandescent body is a continuous band of colours from red through violet.6 10-19 J). with the prism spectroscope. The wavelengths of the lines in the Ne spectrum are given and. The emission spectra of atoms are characteristic features of the atoms of that gas. of wavelength. The second data table will be completed. Each line corresponds to a particular wavelength of light emitted by the atoms. Each wavelength of light forms an image of the slit. its frequency is ν = of the photon emitted with this frequency is E = hν (J). These data are then used to draw the calibration curve of the spectroscope. 4 A prism spectroscope through a slit and is then dispersed by passing through a prism. considering all these and that the energy of photons is better to be expressed in eV (1eV = 1. Experimental Procedure This experiment will focus on: 1.