Line Spectra

Advertisements
Advertisements

Related Posts:


This figure shows a colorful neon sign. The tubes are bent into various shapes.

Figure 1. Neon signs operate by exciting a gas at low partial pressure using an electrical current. This sign shows the elaborate artistic effects that can be achieved. (credit: Dave Shaver)

Line Spectra (OpenStax Chemistry 2e)

When solids, liquids, or condensed gases are heated sufficiently, they radiate some of the excess energy as light. Photons produced in this manner have a range of energies, and thereby produce a continuous spectrum in which an unbroken series of wavelengths is present. Most of the light generated from stars (including our sun) is produced in this fashion. You can see all the visible wavelengths of light present in sunlight by using a prism to separate them. As can be seen in Figure 2, sunlight also contains UV light (shorter wavelengths) and IR light (longer wavelengths) that can be detected using instruments but that are invisible to the human eye. Incandescent (glowing) solids such as tungsten filaments in incandescent lights also give off light that contains all wavelengths of visible light. These continuous spectra can often be approximated by blackbody radiation curves at some appropriate temperature.

A graph is shown with a horizontal axis labeled, “Wavelength ( n m ),” and a vertical axis labeled, “Spectral irradiance ( W divided by m superscript 2 divided by n m ).” The horizontal axis begins at 250 and extends to 4000 with markings provided every 250 n m. Similarly, the vertical axis begins at 0.00 and extends to 2.00 with markings every 0.25 units. Two vertical dashed lines are drawn. The first appears at about 400 nanometers and the second at nearly 700 nanometers. To the left of the first of these lines, the label, “U V,” appears at the top of the graph. Between these lines, the label, “Visible,” appears at the top of the graph. To the right of the second of these lines, the label, “Infrared,” appears at the top of the graph. A grey curve begins on the vertical axis at about 0.10. This curve increases steeply to a maximum value between the two vertical line segments of approximately 1.75 at about 625 nanometers. This curve decreases rapidly at first, then tapers off to reach a value of about 0 at the far right end of the graph. A golden colored curve traces along the same path as the grey curve, but shows a significant degree of variation in the region of the peak of the graph. In this general region, the gold curve is jagged and somewhat erratic. This curve reaches a maximum over 2.00 at around 475 nanometers. A key provided in the open space of the graph shows that the gold graph represents sunlight at the top of the atmosphere, and the grey curve represents the 5250 degrees C Blackbody spectrum.
Figure 2. The spectral distribution (light intensity vs. wavelength) of sunlight reaches the Earth’s atmosphere as UV light, visible light, and IR light. The unabsorbed sunlight at the top of the atmosphere has a distribution that approximately matches the theoretical distribution of a blackbody at 5250 °C, represented by the blue curve. (credit: modification of work by American Society for Testing and Materials (ASTM) Terrestrial Reference Spectra for Photovoltaic Performance Evaluation)

In contrast to continuous spectra, light can also occur as discrete or line spectra having very narrow line widths interspersed throughout the spectral regions such as those shown in Figure 3. Exciting a gas at low partial pressure using an electrical current, or heating it, will produce line spectra. Fluorescent light bulbs and neon signs operate in this way. Each element displays its own characteristic set of lines, as do molecules, although their spectra are generally much more complicated.

Each emission line consists of a single wavelength of light, which implies that the light emitted by a gas consists of a set of discrete energies. For example, when an electric discharge passes through a tube containing hydrogen gas at low pressure, the H2 molecules are broken apart into separate H atoms and we see a blue-pink color. Passing the light through a prism produces a line spectrum, indicating that this light is composed of photons of four visible wavelengths, as shown in Figure 3.

An image is shown with 5 rows. Across the top and bottom of the image is a scale that begins at 4000 angstroms at the left and extends to 740 angstroms at the far right. The top row is a continuous band of the visible spectrum, showing the colors from violet at the far left through indigo, blue, green, yellow, orange, and red at the far right. The second row, labeled, “N a,” shows the emission spectrum for the element sodium, which includes two narrow vertical bands in the blue range, two narrow bands in the yellow-green range, two narrow bands in the yellow range, and one narrow band in the orange range. The third row, labeled, “H,” shows the emission spectrum for hydrogen. This spectrum shows single bands in the violet, indigo, blue, and orange regions. The fourth row, labeled, “C a,” shows the emission spectrum for calcium. This spectrum shows bands in the following colors and frequencies; one violet, five indigo, one blue, two green, two yellow-green, one yellow, two yellow-orange, one orange, and one red. The fifth row, labeled, “H g,” shows the emission spectrum for mercury. This spectrum shows bands in the following colors and frequencies; two violet, one indigo, two blue, one green, two yellow, two orange, and one orange-red. It is important to note that each of the color bands for the emission spectra of the elements matches to a specific wavelength of light. Extending a vertical line from the bands to the scale above or below the diagram will match the band to a specific measurement on the scale.

Figure 3. Compare the two types of emission spectra: continuous spectrum of white light (top) and the line spectra of the light from excited sodium, hydrogen, calcium, and mercury atoms.

The origin of discrete spectra in atoms and molecules was extremely puzzling to scientists in the late nineteenth century, since according to classical electromagnetic theory, only continuous spectra should be observed. Even more puzzling, in 1885, Johann Balmer was able to derive an empirical equation that related the four visible wavelengths of light emitted by hydrogen atoms to whole integers. That equation is the following one, in which k is a constant:

Other discrete lines for the hydrogen atom were found in the UV and IR regions. Johannes Rydberg generalized Balmer’s work and developed an empirical formula that predicted all of hydrogen’s emission lines, not just those restricted to the visible range, where, n1 and n2 are integers, n1 < n2, and Ris the Rydberg constant (1.097 ×× 107 m−1).

Even in the late nineteenth century, spectroscopy was a very precise science, and so the wavelengths of hydrogen were measured to very high accuracy, which implied that the Rydberg constant could be determined very precisely as well. That such a simple formula as the Rydberg formula could account for such precise measurements seemed astounding at the time, but it was the eventual explanation for emission spectra by Neils Bohr in 1913 that ultimately convinced scientists to abandon classical physics and spurred the development of modern quantum mechanics.

Related Research: Research Article: Atomic Force Microscopy Study of Nano-Physiological Response of Ladybird Beetles to Photostimuli

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

Advertisements
Advertisements

Related External Link:

NMRKIN: simulating line shapes from two-dimensional spectra of proteins upon ligand binding