Chapter 6 – Introduction to Spectrometric
Methods
Read pp. 132-159 Problems: 1,2,3,4,7,8,9,14,15
Spectrometric methods = general term for the science that deals with
the interactions of various types of electromagnetic radiation (e.g., visible
light) with matter.
Sample What can happen to
the light intensity as it
Io I passes through the
sample?
For many measurements,
Ultraviolet = < 180 nm the amount of light
Ultraviolet/visible = 180 – 780 nm absorbed (only) is
Infrared = 0.78 – 300 μm related to the analyte
concentration!
E = h υ = hc/λ photon Iabs ~ [analyte]
Electromagnetic radiation (EMR) has
properties of a wave
energy E = hυ = hc/λ
Oscillating electric field
velocity vi = υλi
h = 6.62 x 10-34 Js
c = 3.00 x 108 m/s
Velocity slowed!
Velocity in vacuum
vvac,air = c = 3.00 x 108 m/s
Amplitude, frequency (s-1, Hz), period (time in s for passage of
successive maxima or minima), wave length (linear distance between
two equiv. Pts., nm), velocity of propagation (m/s).
Monochromatic means one wavelength of light (EMR).
y = magnitude of the electric field
A = amplitude or max value of y y = A sin (ωt + Φ)
ω = 2πν
What can happen to EMR when interacting
with matter (e.g., an analyte sample)?
• Diffraction
• Transmission Power = Energy/cm2-s
• Refraction
• Reflection Intensity = Power/angle
• Scattering
• Absorption (quantized event!)
P
T=P
Sample o
A = log Po
P0 P P
= - log T
b
Diffraction = process whereby a parallel beam of radiation is bent as it
passes a sharp barrier or through a narrow opening.
Transmission = rate at which radiation propagates through a
transparent medium is less than in vacuum and depends on kinds and
concentrations of atoms, ions and molecules making up the medium.
Refractive index = ηi = c/νi
Stepwise process that involves polarized atoms, ions or molecules.
Refraction = when radiation passes at an angle through the interface
between two transparent media that have different optical densities, an
abrupt change in the direction of propagation occurs.
θ1
M1 sin θ1 = η2 = ν2
sin θ2 = η1 = ν1
M2
θ2
Reflection = when radiation crosses an interface between media that
differ in refractive index, reflection occurs.
Ir = (η2 - η1)2
M1
Io = (η2 + η1)2
M2 > 60% ~ 100 % Ir
Scattering = small fraction of radiation is transmitted in all angles from
the original path.
1
Is α λ4
Transmission of radiation in matter can be pictured as a momentary
retention of the radiant energy. When atomic or molecular particles are
large with respect to the wavelength of light, radiation can be transmitted
in all directions. Scattered radiation increases with particle size.
Converting Light (Energy) Into Electricity
Ru(II) + hυ → Ru(II)* (*denotes and excited species)
Ru(II)* → Ru(III) + e- (injected into the TiO2)
I3- + 2e- → 3I-
3I- + 2Ru(III) → I3- + 2Ru(II) At Pt electrode
High surface area ~100-300 m2/g) TiO2
“support”
Major Classes of Spectrometric Methods
Class Radiant Power Conc. Method
Measured Relationship Types
Emission Emitted, Pe Pe = kC Atomic emission
Luminescence Luminescent, Pl Pl = kC Atomic and molecular
fluorescence and chemi-
luminescence
Scattering Scattered, Psc Psc = kC Raman spectroscopy
and turbidimetry
Absorption Incident, Po & A = -log P/Po Atomic and molecular
transmitted, P = εbC absorption
Quantized Nature of EMR and its Interaction
with Matter
hυ = eVo + ω When EMR is emitted or
(KE) (WF) absorbed, a permanent
transfer of energy from the
emitting object or to the
absorbing medium occurs.
1. Photocurrent proportional
to intensity of incident
radiation.
2. Magnitude of stopping
voltage depends on
frequency (energy) of
incident radiation.
3. Stopping voltage
depends on
photocathode material.
EMR is form of energy that releases electrons 4. Stopping voltage is
from metallic surfaces and imparts to these independent of intensity
electrons some kinetic energy. of incident radiation.
Quantized Nature of EMR and its Interaction
with Matter
• Etotal = Eelectronic + Evibrational +
Erotational + Etranslational
• Excitation photon, hυ, must
equal the energy difference
between the ground energy
state (lower) and the excited
energy state (higher).
• Energy differences are
unique for each chemical
species (atom or molecule).
• Relaxation from the excited
state – (i) radiative and (ii)
nonradiative.
Energy Level Diagram
Quantitative Aspects of Spectrochemical
Measurements
A = εbC = -log T = log Po/P
