Electromagnetic Energy

🠜 Radiant energy from short wavelength gamma rays to long wavelength radio waves. They are photon of energy
traveling in a wavelike manner:
Wavelength = Electromagnetic energy
🠜 Energy is transmitted via electromagnetic waves and is characterized by its frequency and wavelength
🠜 The relationship between Energy and Wavelength is described by PLANCK'S FORMULA:
E=hv
h: a constant 6.62 x 10-27 erg sec
v: frequency
Wavelength
🠜 Distance between 2 successive peaks and it is expressed in terms of nanometer

Frequency
🠜 The number of vibration of wave motion per second
🠜 The lower the wave frequency the longer the wavelength
1
W𝖺
𝐹 𝑎𝑛𝑑 𝐸

Light Spectra
1. Visible: 400 to 700 nm
2. Invisible:
A. UV region: <400nm
B. IR region: >700nm
B. IR region: >700 nm

Colorimetry
🠜 Two considerations:
1. Quality of the color
2. Intensity of the color
🠜 Kinds of Colorimetry
1. Visual Colorimetry
-uses the eye in determining end point

MELS 1055– Analytical Chemistry (Lecture) 7

 2. Photoelectric Colorimetry
A. Photometric/Filter Photometry
-measurement of light intensity WITHOUT consideration of wavelength
B. Spectrophotometric Measurement
E.g. Spectrophotometer, AAS, FEP

Spectrophotometry
🠜 Involves measurement of the light transmitted by a solution to determine the concentration of light absorbing
substances in the solution
🠜 Parts:
1. Light Source: -provides radiant energy (e.g., Hallow Cathode Lamp -Light source of AAS)

2. Monochromator
-isolates specific or individual wavelength
-Monochromatic light: Light radiation of single WL
-Types:
A. Prisms
-wedge shaped pieces of glass, quartz or NaCl
-a narrow light focused on a prism is refracted as it enters the denser glass
-can be rotated allowing only the desired WL to pass through an exit slit

B. Diffraction Gratings
-most commonly used; better resolution than prism
-based on the principle that WL are bent as they pass a sharp corner
-made by cutting grooves or slits into a surface of flat piece of crown glass

C. Filters -simple, least expensive but useful

3. Entrance Slit -minimizes unwanted stray light and prevents the entrance of scatteredlight into the
monochromator
***Stray Light: refers to any WL outside the band transmitted by the monochromator
-causes absorbance errors
-deleted by cut-off filters
-most common cause of stray light: scratches on optical surface and dust particles
4. Exit Slit
-controls the width of light beam (band pass)
-allows only narrow fraction of the spectrum to reach the sample cuvet
***Band pass: the range of WL between points at which transmittance is
half peak transmittance
5. Cuvet/Analytical Cell/Sample Cell
-holds the solution whose concentration is to be determined
-Types:
A. Borocate Glass Cuvet
-for solution that do not etch glass
-for strong alkaline solution
B. Alumina Silica Glass
-good for 340 nm and above (Visible)
-most commonly used
C. Soft Glass
-used for strong acidic solution
-cuvets with scratches scatter light so it must be discarded
6. Detector/Photodetector
-detects and converts transmitted light into photoelectric energy
-detects amount of light that passes through the sample in the cuvet

MELS 1055– Analytical Chemistry (Lecture) 8

 -Types:
A. Barrier Layer Cell/Photocell/Photovoltaic cell -simplest detector
B. Phototube/Photoemissive tube
C. Photomultiplier tube -most common type, excellent sensitivity and rapid response
D. Photodiode -excellent linearity

7. Meter or Read-out device

-galvanometer or ammeter
-displays output of the detection system
Principle: Beer's Law/Beer-Lambert/s Law
-states that C A
-Mathematically establishes the relationship between concentration and absorbance
-%T: ratio of the radiant energy transmitted (I) divided by radiant energy incident on the sample (Io)

𝑇
%𝑇 = 𝑥 100
𝐼

-In commercial spectrophotometer, it is measured as:

sample beam signal
%𝑇 = x 100
blank beam signal

-The amount of light absorbed at a particular wavelength depends on: Molecular type, Ion type, Ph,
Temperature
-Absorbance is mathematically derived from %T:
𝐼
1. 𝐴 = − log 10
𝑇
2. 𝐴 = log(100%) − log %𝑇
3. 𝐴 = 2 − log %𝑇
-Absorbance is also known as OPTICAL DENSITY
-Formula in Beer’s Law:
𝐴 = 𝑎𝑏𝑐

a: molecular absorptivity
b: length of light through the solution
c: concentration of absorbing molecules/solution

Quality Control of Spectrophotometer

• Wavelength Accuracy: the WL indicated in the dial is the actual WL of light passed by the

MELS 1055– Analytical Chemistry (Lecture) 9

 monochromator
• WL Accuracy checkers:
Didynium (600nm)
Holmium oxide filter (360nm)

Flame Emission Photometry

→ Measures the light emitted by a single atom burned in flame
→ Principle: Excitation of lower to higher energy state
→ Parts:
A. Light source: Flame (also serve as cuvet) -the purpose of flame in FEP:
− Breaks the chemical bonds to produce atoms
− Source of energy by the atoms to enter an excited state
B. Gases: mixture of H and O gas (acetylene propane, or natural gas)
C. Atomizer or Burner: breaks up the solution into finer droplets so that atom will absorbheat and get excited
D. Monochromator: Interference filters
Na filter- Yellow @ 589nm
K filter- Purple @ 767nm
Li filter- Red @ 761nm
E. Detector: Photocell

• Use: measurement of excited ions (Na and K)

• Internal standard: Lithium -Purpose: to achieve stability
• Note: if Li is the analyte, CESIUM is used as a standard

Atomic Absorption Spectrophotometry

• Absorption of EM radiation by atoms than molecules

• Measures the light absorbed by atoms dissociated by heat
• Principle: Element is not excited by merely dissociated form its chemical bond and placed in an unionized,
unexcited, ground state
• Most/more sensitive, very specific, accurate compared to FEP
• Used to measure unexcited trace metals Ca2+ and Mg2+
• Lanthanum or Strontium chloride is added to samples to form stable complexes with phosphate to avoid
Calcium interference.
Parts:
a. Light Source: Hallow Cathode Lamp
b. Mechanical Rotating Chopper -modulates the beam coming from the Hallow Cathode Lamp
c. Burner-uses flame to dissociate chemical bonds and form free, unexcited atoms
-alternative to burner: Electric furnace (uses Deuterium lamp as secondary LS)
d. Monochromator
e. Photodetector: PM tubes
f. Read-out Device/Meter

Fluorometry
• Determines the amount of light emitted by a molecule after excitation by EM radiation
• LS: Mercury Arc, Xenon lamp
• Light detector: PM tubes
• Uses 2 Monochromator-The WL that is best absorbed by the solution to be measured is selected by the
primary
• Filter. Secondary filter prevents incident light from striking the solution
• Measures the amount of light intensity present over zero background
• Affected by quenching

MELS 1055– Analytical Chemistry (Lecture) 10

Mass Spectrometry
In the mass spectrometer, analyte molecules are converted to ions by applying energy to them. The ions
formed are separated on the basis of their mass-to-charge ratio (m/z) and directed to a transducer that converts the
number of ions (abundance) into an electrical signal. The ion abundance plotted against mass-to-charge ratio is
called a mass spectrum.

END OF LESSON

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MELS 1055– Analytical Chemistry (Lecture) 12