Spectroscopy
uses various forms of electromagnetic radiation for analysis. Electromagnetic
radiation consists of massless particles (photons) traveling in a wave-like
pattern and moving at the speed of light. Major difference between
types of electromagnetic radiation is the energy of the photons--radio
waves possess lowest while gamma-rays highest.
Spectroscopy comprises absorption, emission, or scattering.
The transition of an electron from lower to higher level is called absorption;
transition from higher to lower level is called emission; redirection of
light due to interaction with matter is called scattering (usually results
in slightly different wavelength l).
Spectrum
Discovery
Isaac
Newton (1666) passed a beam of sunlight through a prism and
produced a band of colors just like the rainbow. He then passed each of
these colors through other prisms and found they did not change.
When Newton passed the whole band of colored lights through a prism in
reverse order, the colored band became white sunlight again. Newton concluded
that white light is really a mixture of colored lights and each color bends
by a different amount when passing through the prism. The band of colored
lights discovered by Newton is called a spectrum; the rainbow is actually
a spectrum formed by sunlight passing through raindrops. Ironically,
Newton believed the spectrum to be his most important discovery.
Dispersion is the separation of light into its
colors by refraction (bending) of the light through a prism. Each of the
colors has its own wavelength which determines how much each color will
bend; red bends least and violet most.
Utilizing the dispersive
action of the prism, Gustav
Kirchhoff and Robert
Bunsen built the first spectroscope (1859) and studied the patterns
produced by elements vaporized in a Bunsen flame. Elements such as hydrogen,
lithium, and mercury exhibit the following bright-line spectra:
Using this method of spectrum analysis led to the discovery
of cesium/rubidium/thallium. Spectra
were soon obtained for the different elements and their lines charted.
English astronomer Norman
Lockyer (1868) noted lines in the solar spectrum which could
not be identified with charted lines of any known element. Lockyer believed
an unknown element existed in the sun and named it helium from the Greek
word for sun. From its spectrum, William
Ramsay (1895) identified the presence of helium on earth.
Spectral lines were believed to originate from the vibration
of atoms at different rates under the stimulus of heat. The faster
vibrations resulted in shorter waves causing lines to appear toward the
violet end of the spectrum while slower vibrations gave lines toward the
red end. In 1885 Johann
Balmer discovered through experimentation that the various rates
of vibration in a mass of glowing hydrogen gave a simple mathematical relation
to each other. This indicated that some one type of "mechanism " was at
work at varying rates within the hydrogen atom, giving off the different
wavelengths. Johannes
Rydberg developed the following equation to describe many observed
lines:
911A/l = 1/n2
- 1/m2
In 1913 Niels Bohr proposed the hydrogen atom consisted of an electron revolving around a central nucleus. Using Planck's constant and the Rydberg equation, Bohr explained the spectrum of hydrogen. As an atom absorbed energy, this orbit would enlarge by definite amounts. When energy was emitted, as in the form of light, the electron would fall by steps into inner orbits, and the frequency of the light would depend upon how many orbits were traversed.
Modern
spectroscopes vary considerably in function and design and are often quite
specialized for the specific substances they analyze. Teaching instruments
used in today's classrooms are the relatively simple prism spectroscopes
shown to the left. They consist of a collimator (tube for admitting light),
a glass prism, and a telescope. The collimator has a slit at one end to
admit light and a lens on the other to concentrate it. The lens directs
the light on the prism, which disperses the ray into its component colors.
Applications 
Analytical techniques based on infrared, ultraviolet,
and visible radiation are used in modern labs. The SPEC 20 can use
visible light to determine the concentration of CuSO4
solutions. Since CuSO4
transmits in the blue region (4000-4500A), it absorbs in the red region
(6500-7000A). If the concentration of sample #1(C1
= 1.00M) is known and its absorption measured (A1
= 0.600), the concentration of sample #2 (C2)
can be determined from its absorption (A2
= 0.300) and Beer's Law. Beer's Law describes how the intensity of light
diminishes as it passes through an absorbing media.
C2A1
= C1A2
C2 = (1.00M)(0.300)/(0.600)
= 0.500M
Infrared spectroscopy generates spectra by graphing absorbance
versus wavelength. The spectra for four salts are provided below.
Computers are able to quickly identify compounds by comparing the obtained
spectrum with known spectra.