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HIGH RESOLUTION ULTRASOUND SPECTROSCOPY IN HUMIC RESEARCH
Miloslav Pekař Jiří Kučerík
Daniela Šmejkalová Martina Klučáková
Institute of Physical and Applied Chemistry
Faculty of Chemistry
Brno University of Technology
Brno, Czech Republic
? • ULTRASOUND SPECTROSCOPY • ?
TRADITIONAL SPECTROSCOPY
sample
electromagnetic wave
ULTRASOUND SPECTROSCOPY
ultrasound wave(mechanical)
ULTRASOUND INTERACTION WITH MATTER
intermolecular forces probe
microelasticity
ULTRASOUND FREQUENCY
method Hz
UV 1014-1016
VIS 1014
IR 1012-1014
NMR 106-108
US 106-108
ULTRASOUND PARAMETERS
• velocity ...
• amplitude (attenuation) ......
... elasticity, density •
...... energy loss •
ULTRASOUND VELOCITY
elastic response• dominating • sensitive to molecular organization, intermolecular interactions
v
solids
liquids
gasesrigidity . . . velocity
ULTRASOUND ATTENUATION
heterogeneous sample• scattering • particle sizing
homogeneous sample • local relaxation
HIGH RESOLUTION
RESOLUTIONhighnormal
ATTENUATION
VELOCITYVELOCITY
0.1 m/s 0.0001 m/s
(10-5%)
0.2% 0.2%
EXAMPLE – MICELLES
hydrophobic core . . . higher elasticity
EXAMPLE – CONFORMATION CHANGES
temperature ramp - polyacrylamide
EXAMPLE – LIGAND BINDING
Mg2+ to polyriboadenilic acid
EXAMPLE – AGGREGATION
carbonic anhydrase, temperature induced
EXAMPLE – MICROEMULSION
lipid+surfactant+cosurfactant and water
QUANTITATIVE INTERPRETATION – PRINCIPLES
velocity of sound
2/10)ρ/( Pu )/ρ)(ρ/1(β P
sound – longitudinal wave• causes local variation of the density, pressure
• finite compressibility energy transports across the space
compressibility
2/1)βρ/1(u
QUANTITATIVE INTERPRETATION – DECOMPOSITION
DILUTE SOLUTIONS
(adiabatic)
apparent molar volume
20
11V /)(φ nVnV
apparent molar compressibility
20
11KS /)ββ(φ nn
solution solute
solvent
hMV Δφ VV rhMKS Δφ KKK
M…solute h…hydration r…relaxationcontributions
QUANTITATIVE INTERPRETATION – CONCLUSION
concentration increment of ultrasound velocity
KM …constantKr …from frequency dependence of attenuationKh …evaluated
)ρ/()( 000 muuuA
solutionsolvent
molality
)β2/()Δ(Δ)Δ(ΔΔ 0hh KVA
NaHu - CONCENTRATION
NaHu + ACID … KINETICS
0.5g/L NaHu
pH: 7 3.5
NaHu + ACID … VELOCITY
-0.08
-0.06
-0.04
-0.02
0
0.01 0.05 0.08 0.1 0.2 0.5 0.8 1 2
NaHu concentration (g/L)
velo
city
cha
nge
(m/s
)
HCl
NaHu + ACID … VELOCITY
NaHu concentration (g/L)
velo
city
cha
nge
(m/s
)
-0.1
0
0.1
0.2
0.3
0.01 0.05 0.08 0.1 0.2 0.5 0.8 1 2
propionic
NaHu + PROPANOL … VELOCITY
NaHu concentration (g/L)
velo
city
cha
nge
(m/s
)
-0.2
-0.15
-0.1
-0.05
0
0.05
0.01 0.05 0.08 0.1 0.2 0.5 0.8 1 2
propanol
Cu2+ + SALYCILIC ACIDve
loci
ty (
m/s
ec)
1496
1498
1500
0 10000 20000 30000 40000
time (sec)
blank
sample
THANKS …
… for your attention