• Selected applications • „on-line“ process monitoring
Supercritical Fluid Chromatography Fourier-Transform-Infraredspectroscopy
SFC – FT-IR
SFC – FT-IR

IR PD APPLICATION; ANALYTICAL WORK
HYPHENATED TECHNIQUES
Albrecht Rager
HYPHENATED TECHNIQUES
Combinations realised with IR
• PART I • I.0I • I.II - FT-IR) • I.III • I.IV • I.V
OH
4000
3500
3000
2500 2000 1500 Wavenumber cm-1
1000
500
GC – FT-IR sensitivity
1/1 Transmittance Transmittance [%]
1/10
10/10
SENSITIVITY
GC – FT-IR sensitivity
Pressure / atm.
~ ~ fluid solid Triple Point vapour - 57 31 Temperature / °C
73.0
Pc
Supercritical
Tc
5.2
SFC – FT-IR
Fluid Tc (°C) Pc(atm.) ρc (g/ml) 31.3 36.5 132.5 196.6 152.0 45.5 16.6 111.8 25.9 72.9 72.5 112.5 33.3 37.5 37.1 58.4 40.7 46.9 0.47 0.45 0.24 0.23 0.23 0.74 1.10 0.56 0.52
(Pyrolysis-[GC] – FT-IR)
Pyrolysis GC – FT-IR
capillary column carrier gas
split vent septum retainer heater quartz sample tube and sample
Pyrolysis GC – FT-IR
7.) vitamine A-acid
8.) 4-nitrophenol
SFC – FT-IR
Si 3 µm 125 x 4 mm pressure gradient (linear) 150 - 350 bar, 28 bar/min flow: CO2, 2 ml/min modifier: 40 µl/min 0.003% citric acid in CH3OH oven temperature: 70°C detection: UV 220 nm
40 20
60
80
Ethylacetate
100 µm
3500 3000 2500 Wavenumber cm-1 2000 1500 1000
HPLC – FT-IR
LC flow
heated nitrogen
heater
Ge-disk
HPLC – FT-IR
HPLC – FT-IR
IR beam ZnSe window Flow through cell heater
4000
3500
3000 2500 2000 Wavenumber cm-1
1500
0.00
Gram Schmidt 0.20 0.10 OH-Strech 0.30
0 50 100
GS-trace
150 200 Seconds 250 300
Structural Isomers
OH OH OH Absorbance 0.2
IBMA
(METHACRYLIC ACID, ISOBUTYL ESTER)
4000
3500
3000
2500 2000 Wavenumber cm-1
1500
1000
500
Pyrolysis – [Gaschromatography] – Fourier-Transform-Infraredspectroscopy
-
O
+
N
b1,2 : base vectors s : sample vector t: Gram-Schmidt-value
b1
s
t=s-p
p
b2
Gaschromatography – Fourier-Transform-Infraredspectroscopy (GC –FT-IR)
1
Dimension
4000 4000
Sample
Wavenumber cm-1
2000 1000
Wavenumber cm-1
2000
1000
40Байду номын сангаас0
Wavenumber cm-1
2000
1000
Gram-Schmidt-Chromatogram calculation
M
M : base vectors N: dimension O: offset
UV Spectrometer
SFC – FT-IR
40 mm
Window
SFC/FT-IR-high pressure cell
SFC – FT-IR
TABLE: SFC-Applications Industrial: Synthetic oligomers, polymers/additives Surfactants (polyglycols) Oligo-,Poly-sacharides, sucrose polyesters Pesticides Isocyanates Dyes Waxes Biochemical: Stereoids Prostaglandins Fatty acids / lipids Antibiotics Drugs of abuse Fossil Fuels: Fractionation of petroleum and coal-derived fluids Hydrocarbon group analysis Simulated distillation
HPLC – FT-IR
100 Transmittance [%] 40 60 80
Cyclohexane
20
100 µm
3500 3000 2500 Wavenumber cm-1 2000 1500 1000
HPLC – FT-IR
100
blocked area
Transmittance [%]
SFC – FT-IR
Synthetic Mixture of Acidic Compounds
1.) 2-nitrophenol 2.) phenylbenzoate
3.) phenol
4.) salicylic acid 5.) 3-bomobenzoic acid 6.) 2-naphthoic acid
450
550
650
750
850 Pyr T/°C
High-performance-liquid-chromatography
Fourier-Transform-Infraredspectroscopy
HPLC – FT-IR
HPLC – FT-IR
Outlet
IR beam
IR window
Inlet
SFC
capillary columns packed columns
SFC – FT-IR
BRUKER IFS 88 HP 1084 SFC SFC Pump SFC IR-Cell Column
Oven
Heat exchanger
FTIR
In/Out Pressure stabiliser
Scheme of SFC/FTIR
Capillary column
Inlet
Gaschromatography – Fourier-Transform-Infraredspectroscopy (GC –FT-IR)
GS
0.0
500
1000
1500
2000
2500
3000
3500
Points
0
t/sec.
300
FT Reference
Ge-disk
Deposition
HPLC – FT-IR • Flow Cell
• Relatively low sensitivity (mobile phase absorption) • Direct Detection • Ease of operation, low maintenance • Cell must withstand high pressure
OH
OH
OH
4000
3500
3000
2500 2000 1500 Wavenumber cm-1
1000
500
Structural Isomers 1,2-Butanediole
1,4-Butanediole
OH OH
OH
1,3-Butanediole
OH
OH OH
OH
2,3-Butanediole
Gas
Liquid
10-3
10-4
10-2 5x10-4
10-1
1
0.3 - 1