FRICTION IS

MUST
TO GENERATE HEAT
Microwave Assisted Processes

Meghal

16 November 2018
Percy Spencer (19 July 1894 – 8 September 1970)
To develop and produce combat radar equipment for M.I.T.’s
Radiation Laboratory during World War II.

One day, while Spencer was working on building magnetrons for radar
sets, he was standing in front of an active radar set when he noticed the
candy bar he had in his pocket melted. Spencer wasn’t the first to notice
something like this with radars, but he was the first to investigate it.

Spencer then created what we might call the first true microwave oven by
attaching a high density electromagnetic field generator to an enclosed
metal box.

The company Spencer was working for, Raytheon, then filed a patent
on October 8, 1945 for a microwave cooking oven, eventually named
the Radarange.

This first commercially produced microwave oven was about 6 feet tall
and weighed around 750 pounds. The price tag on these units was about
$5000 a piece. It wasn’t until 1967 that the first microwave oven that was
both relatively affordable ($495) and reasonably sized (counter-top model)
became available.
 A Microwave

c

H


 = electric field
H = magnetic field
 = wavelength (12.2 cm for 2450 MHz)
c = speed of light (300,000 km/s)
 Electromagnetic Spectrum

Visible
X-Rays Ultraviolet Infrared Microwaves Radiowaves
Laser Radiation
10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 1
Wave Length (meters)
3x1012 3x1010 3x108 3x106 3x104 3x102
Frequency (MHz)

Molecular
vibrations
Inner-shell
electrons Outer-shell
(valence)
Molecular rotations
electrons
 Microwave Energy Versus
Other Electromagnetic Energy
Radiation Typical Quantum Chemical Chemical
Type Frequency Energy Bond Type Bond Energy
(MHz) (ev) (ev)
Gamma Rays 3.0 x 1014 1.24 x 106 H OH 5.2
X-Rays 3.0 x 1013 1.24 x 105 H CH3 4.5
Ultraviolet 1.0 x 109 4.1 H NHCH3 4.0
Visible Light 6.0 x 108 2.5 H3C CH3 3.8
Infrared Light 3.0 x 106 0.012 PhCH2 COOH 2.4
H
Microwaves 2450 0.0016 H H+ O 0.21
O (-) H
Radio 1 4 x 10-9 (-)
Material Interaction With Microwaves
Reflective
Conductor Metals reflect microwave energy
and do not heat.

Transparent
Insulator Numerous materials are transparent
to microwave energy and will not
heat but can be good insulators.

Absorptive
Dielectric .... These materials absorb microwave
energy and are heated.
 Molecular Heating
Liquids (such as mineral acids) heat
rapidly when exposed to microwave
energy. Absorption of microwave
energy occurs by two mechanism:

Dipole Rotation
Ionic Conduction
 Dipole Rotation
Microwave Electric Field Interaction with Water Molecule


+
Electric Field

0
t = 0 ns

 O
H H

The water dipole moment is aligned with the field.
 Dipole Rotation
Microwave Electric Field Interaction with Water Molecule


+
Electric Field

0
t = 0.1 ns

The dipole moment rotates in an attempt to follow the field.

 Dipole Rotation
Microwave Electric Field Interaction with Water Molecule


+
Electric Field

0
t = 0.3 ns


4.9 X 109 times per second

The dipole moment rotates in the opposite direction

trying to align with the field.
 Ionic Conduction
Microwave Electric Field Interaction with Chloride Ion In Water


+
Electric Field

0
t = 0 ns

 Cl -

The negative chloride ion migrates toward the positive field.

 Ionic Conduction
Microwave Electric Field Interaction with Chloride Ion In Water


+
Electric Field

Cl - t = 0.1 ns

The negative chloride ion migrates away from the

rising negative field.
 Ionic Conduction
Microwave Electric Field Interaction with Chloride Ion In Water


+
Electric Field

0
t = 0.3 ns
Cl -


The negative chloride ion migrates away

from the negative field.
 A Microwave
Electromagnetic Wave
Low energy photon (does not break chemical bonds)
Causes movement of molecules (dipole rotation)
Causes movement of ions (ionic conduction)
Will be reflected, transmitted or absorbed
Heats throughout an absorbing material
Non-ionizing (will not cause cellular or chromosome damage)
Sample Heating by Conduction

.
.. Convection currents
. .
.

Temperature on the outside surface is in excess

of the boiling point of liquid.
 Sample Heating by Microwaves
Liner, sleeve & frame Sample-acid mixture
transparent to MW (absorbs microwave
energy energy)

Gas

Vapor

Vessel Body Microwaves

Liquid

Localized
superheating
The energy dissipation factor or loss tangent (tanδ = ε’’/ ε’)
combines dielectric constant (ε’) and loss factor (ε’’) and
gives an idea of different materials to convert microwave
energy into thermal energy at given frequency.
 Variation of Penetration with Frequency
for Water at 25 oC
less efficient 100
50

1/2 Power depth (inches) 20

10
5
2
1
.5
.2
.1
.05
more efficient .02
100 915 2450 10,000 100,000
Frequency (MHz)
Copson, D.A. Microwave Heating: AVI 1975, Chapter 1
 Percent Microwave Power Absorbed by Water
100
90
80
70
60
% Power
Absorbed 50
40
30
20
10

300 600 900 1200 1500

600 Watt System Mass, Grams
Kingston H. M., Jassie L.B. Introduction to Microwave Sample Preparation: American
Chemical Society Profession Reference Book, 1988, Chapter 2.
 Dipole Moment
CCl4 0
CO 0.10
HCL 1.08
H2S 1.10
C3H8O 1.66
HF 1.82
H2O 1.85
CH3Cl 1.87
HNO3 2.17
HCN 2.93
CsF 7.87
 Dipole Moment and Dielectric
Constant for Liquids
Dipole Dielectric
Liquid Moment Constant
Acetone 2.77 20.70
Benzene 0 2.27
Methanol 1.68 33.62
Methylene Chloride 1.14 8.93
H2O 1.85 78.54
HNO3 2.17
HF 1.82 83.60
HCl 1.08 4.60
Heating of Organic Liquids by
Microwave Energy
Rapidly Heated
Acetone N,N’-Dimethylformamide
Methanol N,N’-Diethylacetamide
Ethanol 1,2,4 Trichlorobenze
1-Propanol 1-Methyl-2-Pyrrolidinone
2-Propanol Dimethylsulfoxide
Ethyl Acetate Propionaldehyde
M-Creosol Methyl Ethyl Ketone
Cyclohexanone Ethylene Glycol
 Temperature Rise for Microwave Heated Liquids
(100 mL heated at 100% power, 600 W)
200

150
LIQUID IDENTIFICATION
Temperature (oC)

1,2-Dichlorobenzene (ODCB)
N,N-Dimethylformamide (DMF)
100 1-Methyl-2-Pyrrolidinone (NMP)
Cyclohexanone
WATER
CONDITIONS m-Cresol
50 N,N' Dimethylacetamide (DMAA)
Power, 600 W
1,2,4-Trichlorobenzene (TCB)
5 vessels
each with 20 mL liquid Dimethylsulfoxide (DMSO)
0
0 1 2 3 4 5 6
Time (minutes)
Heating of Organic Liquids by
Microwave Energy
Heated Slightly or Not At All

Petroleum Ether Toluene

Natha Xylenes
Kerosene Benzene
Dichloromethane
Simultaneous Heating Rates of Acetone,
Hexane, and 1:1 Acetone:Hexane
200
Temperature (oC)

150

Acetone
100 Hexane
1:1 Acetone:Hexane
30 mL per vessel, 423 watts
50

0
0 2 4 6 8 10
Time (minutes)
Factors That Influence Solution Heating
Physical Properties of the Solution
• Viscosity
• Temperature
• Polarity
• Heat Capacity
• Dielectric
Wave Length
Ion Characteristics (conduction only)
• Concentration
• Charge
• Size
• Mobility
 Microwave Hardware Design
Objectives of Sample Preparation
• Ability to do multiple samples
• Ability to monitor & control reaction conditions
• Ability to do rapid sample throughput
• Automation
Problems
• Uniform distribution of energy to multiple samples
• Temperature & Pressure monitoring in Uw
• Strong microwave Transparent vessels
• Relief mechanism must be microwave immune
Components of a Microwave System
• Magnetron
• Waveguide
• Cavity
• Mode Stirrer
• Circulator
• Turntable
• Wavelength Attenuator Cutoff
• Duty Cycle
– Magnetron:
• Filament: Thorium and tungsten
• Anode: Copper
CEM Patented Magnetron Protection
Isolator waveguide
microwaves

reflected
microwaves
magnetron vessel
microwave
cavity
 Ceramic Floor Magnetron Protection

waveguide
microwaves

reflected
microwaves

magnetron
Turntable
microwave
cavity

Weflon Floor
Schematic of Microwave Pattern
Interaction with Pressure Vessels
waveguide

microwave
pattern

microwave
cavity
 Schematic of Home Microwave EM
Field Pattern

Low Em Field Intensity

Microwave High Em Field

Cavity Intensity
Comparison of Power Cycle Times for Analytical
and Appliance Grade Microwave Systems
700

600

500
Power (watts)

400

300
Appliance
200 Grade
Analytical
100
50% Power
0
0 1 2 3 4 5 6
Time (sec)
A Laboratory Microwave
• Chemical resistant
• Removes fumes from cavity
• Power available in small increments
• Constant power at level selected
• Control of reaction conditions
• Constant microwave field pattern
• Multiple, overlapping safety features
Advantages
• Amount of solvent used is very less.
• It allows full control of extraction parameters like time, power and
temperature.
• It reduces extraction time to the great extent.
• It is energy efficient method with enhanced extraction efficiency and
environment friendly nature.
• It leads to improved yield, quality of the extract, reduced production
• costs and reduced process-related hazards compared to the
conventional processes.
• Use of microwave in essential oil extraction causes fewer chemical
changes of original plant components like rearrangement, dehydration
and isomerization compared to hydrodistillation .
• Essential oil obtained by microwave irradiation has increased
antimicrobial as well as antioxidant activities compared to oil obtained
by HD
• How a Microwave Oven Works.mp3
 Applications

Acid digestion for Atomic Solvent extraction

Absorption (AA) and Emission for gas and liquid
(ICP) Spectroscopy chromatography

Hydrolysis of proteins Sample drying and

and peptides for Amino moisture
Acid Analysis determination
Polymer Dissolution for molecular Organic
weight determination via Gel Synthesis
Permeation Chromatography (GPC) Reactions
Acid digestion of reinforced Dry Ashing
composites for gravimetric
determination of fiber content
https://www.youtube.com/watch?v=FGdwEPEU61U

https://www.youtube.com/watch?v=kp33ZprO0Ck
 Special Note: PREVENTION

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