Introduction to
Spectrochemical Methods
Chapter 7
Introduction
Spectrochemical methods
– Absorption or emission of light
More than half or all instrumental methods of analysis
– Spectroscopy or spectrometry
Science that deals with light
– Its absorption and emission by solutions
– Other material substances
Instrument used
– Spectrometer
When using a light sensor/phototube = spectrophotometer
– Spectrochemical analysis
Degree which light absorbed or the primary light emitted
– Related to the amount of analyte present in the sample
– Critical measurements!
Atomic spectroscopy
– Spectral differences between atoms
– Molecular spectroscopy
Characterizing Light
Dual nature of light
– Particles
Photons or quanta
– Particle theory of light
– Waves
Electromagnetic disturbances or electromagnetic waves
– Wave theory of light
– Dual nature not unlike modern description of
electrons
Described as particles
– To explain aspects of their behavior
For more accurate description
– Must be described as entities of energy and NOT particles
Characterizing Light
Wave theory of light
– Light travels in a fashion similar to that of a
series of repeating waves of water
Wave pool at an amusement park
– Electromagnetic waves
They are wave disturbances that have an electrical
component and a magnetic component
– Do NOT require matter to exist
Can travel through a vacuum
Characterizing Light
Wavelength, speed, frequency, energy,
and wavenumber
– Wavelength (λ)
The physical distance from a point on one wave, to
the same point on the next wave
– Measured in metric units
Characterizing Light
Wavelength, speed, frequency, energy,
and wavenumber
– Speed of light (c)
Speed in which electromagnetic waves move
– Speed of light in a Vacuum ≈ 3.00 x 1010 cm/sec
Accounts for instantaneous speed that light fills a
room when switch turned on
ALL ELECTORMAGNETIC WAVES TRAVEL AT
THE SAME SPEED IN A VACUUM REGARDLESS
OF THEIR WAVELENGTH
Characterizing Light
Wavelength, speed, frequency, energy, and
wavenumber
– Frequency (ν = nu)
Number of moving electromagnetic waves past a fixed point
in 1 second
– Expressed in waves or cycles per second
= hertz (Hz)
Units = sec-1
Wavelength, speed, frequency can be expressed
mathematically
C = λν units are cm x sec-1 or cm/sec
– Wavelength and frequency are inversely proportional
As one increases
Other decreases
Characterizing Light
Wavelength, speed, frequency, energy, and
wavenumber
– Energy
B/c light is a form of energy
– Each wavelength or frequency has certain amount of energy
– Considered to be the energy associated with a single photon of
light
.: particle theory and wave theory linked via energy
E = hν
E = energy, h = proportionality constant called Planck’s
constant
depends on units used-metric = 6.63 x 10-34 J/sec
.: E = hc/λ
Characterizing Light
Wavelength, speed, frequency, energy,
and wavenumber
– Wavenumber (ν)
Wavelength expressed in centimeters
– Characterized by the reciprocal of this wavelength
ν = 1/ λ (cm) Used in conjunction with infrared light.
The Electromagnetic Spectrum
The Electromagnetic Spectrum
Electromagnetic
spectrum
– So broad broken down
into regions
Visible light
– That portion of the
spectrum we see with
our eyes
≈ 350 nm to
≈750 nm
Very narrow
region
UV, infrared, x-ray,
radio, and television
The Electromagnetic Spectrum
Electromagnetic Spectrum
– UV, visible, and infrared regions
Mostly ones emphasized
– Nanometer and micrometer units used for wavelength
– Something to remember
Long wavelength = low energy
Infrared region
– Wavelengths extremely short
– Have higher energy than radio or television
– Cause no harm
Remotes for TVs, VCRs, etc
UV, x-rays, and gamma rays
– Very short wavelengths
– Very high energy
– Very dangerous!
Interaction of Light With Matter
Light striking matter causes different events
– Transmitted
Pass without interaction through the material
– Light passing through glass
– Reflected
Changes directions
– Light in a mirror
– Scattered
Deflected into many different directions
Occurs when light strikes a substance composed of many
individual, small particles
– Absorbed
Light fives up some or all of its energy to the material
Absorption Spectra
Instruments used to measure absorption
– Some in the UV and visible regions
– Others for the infrared region
– Methods used
Beam of light formed
Sample measured contained so that light passes
through
Absorption of the wavelengths present in light
beam measured by a sensor and signal processor
Absorption Spectra
An absorption spectrum
– Plot of the amount of light absorbed by a
sample vs. the wavelength of the light
Light absorbed called the absorbance (A)
Obtained by using a spectrometer to
– Scan a particular wavelength region
– To observe amount of light absorbed by the sample
along the way
– It’s a continuous spectrum (fig. 7.13, pg. 189)
The spectrum is an unbroken pattern
– Does not display breaks or sharp peaks
Absorption Spectra
Absorption vs. wavelength
– Can be displayed as a transmission spectrum
Plotting the amount of light transmitted by a sample
Rather than the light absorbed
– y-axis is transmittance (T) or percent transmittance instead of
the absorbance (fig. 7.16, pg. 191)
High transmittance = low absorbance and vice versa
– Absorption pattern
Differs from compound to compound
– “molecular fingerprint”
Often useful for identification
Detecting impurities
Other sample components
Absorption Spectra
Light Emission
– Matter will emit light
Molecular and ionic analytes
Useful for qualitative and quantitative analysis
Called an emission spectrum
– Plot of emission intensity vs. wavelength
– Product of the change in the energy level of an electron
From excited state to ground state (lowest energy level)
– Fluorescence
When molecules/complex ions emit light under certain
conditions
– When absorption of light in the UV region is followed by
emission of light in the visible region
– Involves the loss in energy from an excited state to a lower
state
Absorbance, Transmittance, and
Beer’s Law
A = εbc
– Beer’s Law
ε = extinction coefficient or absorptivity
– Units depends on other parameters
Absorbance is dimensionless quantity
b = path length
– Distance the light travels through the measured solution
Inside diameter of the sample container
Usually centimeters or millimeters
c = concentration
– Expressed in any concentration unit
– Usually expressed in molarity, ppm, or grams/100ml.
.: c= molarity, b = cm, then absorptivity = L mol-1 cm-1
Absorbance, Transmittance, and
Beer’s Law
Container to be used
– Varies according to the method
UV-VIS
– Small test tube or square tube with an inside path length
of 1 cm
Called a cuvette
IR
– Container called the IR liquid sampling cell
Sample contained in a space between two salt plates
Created with a thin spacer between the plates
Path length is the thickness of the spacer
Absorbance, Transmittance, and
Beer’s Law
Quantitative analyses by Beer’s law
– Prepared series of standard solutions
Measure absorbance of each in identical containers
Plotting the measured absorbance vs.
concentration
– Creates a standard curve
Absorbance of an unknown solution then
measured and concentration determined from the
standard data
