![Page 1: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/1.jpg)
Tadeusz Górecki, Ahmed Mostafa, Matthew EdwardsDepartment of Chemistry, University of Waterloo (ON)
Journal of Chromatography A, 1255 (2012) 38Journal of Chromatography A, 1255 (2012) 38––5555
![Page 2: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/2.jpg)
• Analysis of volatile and semi-volatile compounds• Max. theoretical peak capacity: ~22 peaks/min
◦ (15m x 0.1mm x 0.1µm column, 50cm/s, n = 150000, 15 min analysis)
Carrier GasColumn
OvenSample
ElectrometerData Recorder
InjectorDetector
![Page 3: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/3.jpg)
3
Segment of a chromatogram of a sediment sample subjected to pyrolysis with TOF-MS detection (AIC)27 peaks visible
![Page 4: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/4.jpg)
4
Overlay of selected masses (magnified 20 - 40 x)95 peaks found through spectral deconvolution.
![Page 5: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/5.jpg)
nc ~ f x N 0.5 f < 2
tfirst tlast
Courtesy of Prof. Pat Sandra 5
![Page 6: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/6.jpg)
6
Column n Peak capacity
25 m x 0.25 mm 100.000 316 – 632
50 m x 0.25 mm 200.000 447 - 894
100 m x 0.25 mm 400.000 632 - 1264
80 m x 0.1 mm 800.000 895 - 1790
Slide courtesy of Prof. Pat Sandra
![Page 7: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/7.jpg)
T.A. Berger, Chromatographia 42 (1996) 63.
450 m x 0.25 mm x 0.25 µm PONA1,300,000 plates
Peak capacity over 1,000
100 min segments
![Page 8: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/8.jpg)
T.A. Berger, Chromatographia 42 (1996) 63.
450 m x 0.25 mm PONA30 m x 0.25 mm PONA
![Page 9: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/9.jpg)
9
… using the statistical theory of peak overlap …
… peak resolution is severely compromised when the number of components present in a sample overrates 1/3 of the peak capacity.J.M. Davis, J.C. Giddings, Anal. Chem. 55 (1983) 418
…in order to resolve 98% of the components, the peak capacity must exceed the number of components by a factor of 100.J.C. Giddings, J. Chromatogr. A 703 (1995) 3
100 analytes peak capacity should be 100 x 100 = 10.000, or N ca. 100.000.000 plates !!!
Slide courtesy of Prof. Pat Sandra
![Page 10: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/10.jpg)
Solvent 1 front
Firs
t dim
ensi
on e
lutio
n
Solvent 1 front
10
![Page 11: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/11.jpg)
Firs
t dim
ensi
on e
lutio
n
Solvent 1 front
First dimension elution11
![Page 12: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/12.jpg)
Sol
vent
1 fr
ont
Sec
ond
dim
ensi
on e
lutio
n
Solvent 2 front
Separated!
Solvent 2 front
First dimension elution12
![Page 13: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/13.jpg)
13
1st dimension retention time
2nd dimension chromatogram
![Page 14: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/14.jpg)
14
1st dimension retention time
2nd dimension chromatogram 2nd
dimension chromatogram
![Page 15: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/15.jpg)
15
1st dimension retention time
2nd dimension chromatograms
![Page 16: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/16.jpg)
1D-GCHeartcut GCGCxGC16
![Page 17: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/17.jpg)
• Interface traps effluent from 1st column and injects into 2nd
column• Times of injections are recorded• Second dimension is fast (0.5 - 10s)
InjectorCarrier Gas
PrimaryColumn
OvenSample
ElectrometerData Recorder
SecondaryColumn
Interface
Detector
1717
![Page 18: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/18.jpg)
1D: 30 m x 0.25 – 0.32 mm x 0.25 – 1 µm, non-polar 2D: 0.5 – 2 m x 0.1 mm x 0.1 µm, polar Modulation period resulting in 2.5 to 3 cuts per peak
All parameters treated somewhat independently
Can it really be that simple?
![Page 19: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/19.jpg)
Directly controllable
Green arrows: parameters whose values increase as the input parameter value increases
Red arrows: parameters whose values decrease as the input parameter value increases
1df 2df
2dc 1dc
1wh
Mass perModulation
Chance of overloading 1D
Chance of overloading 2D
1l 2l
Capacity of 2D
Capacity of 1D
2Δp 1Δp
1u 2u
2D retention
2Rs 1Rs
2wh
Allowed / Required 2D Space
Oven Programming Rate
Te
AnalysisTime
PM
1uopt
Inlet Pressure
1Δp
ΔpT
![Page 20: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/20.jpg)
Thermal modulators◦ heater-based ◦ cooling-based
cryogeniccryogen-free
Flow modulators
![Page 21: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/21.jpg)
Thermal modulators◦ Modulation period◦ Modulation temperature ◦ Stationary phase thicknessFlow modulators◦ Modulation period◦ Carrier gas flow rates
![Page 22: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/22.jpg)
Model 1D separation1st dimension peak width 24s
PM = 6 s (4-5 cuts)
PM = 12 s (2-3 cuts)
0 0.5 1 1.5
5
10
15
20
Retention Time (min)
Sig
nal I
nten
sity
0 0.5 1 1.5
500
1000
1500
2000
Retention Time (min)
Sig
nal I
nten
sity
0 0.5 1 1.5
500
1000
1500
2000
Retention Time (min)S
igna
l Int
ensi
ty
![Page 23: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/23.jpg)
L. Ramos, J. Sanz, in: D. Barcelo (Ed). Comprehensive Analytical Chemistry, Elsevier, Amsterdam, Netherlands, 2009, p. 283.
5 s 6 s 7 s
(1) indeno[1,2,3-cd]pyrene, (2) dibenzo[a,h]anthracene, (3) benzo[ghi]perylene
![Page 24: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/24.jpg)
Liquid-cooled thermal modulatorLibardoni et al., Anal. Chem. 2005, 77, 2786-2794
24
Constant heating voltage
Programmed heating voltage
![Page 25: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/25.jpg)
25
![Page 26: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/26.jpg)
26
![Page 27: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/27.jpg)
C40C16 C20
N-PAHs
120 min
5 s
![Page 28: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/28.jpg)
1D and 2D columns connected through a specially modified segment of a coated stainless steel capillaryCapillary is compressed between two passive coolersCapacitive discharge resistively heats the trapping capillary
2828
![Page 29: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/29.jpg)
2929
![Page 30: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/30.jpg)
30
![Page 31: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/31.jpg)
31
![Page 32: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/32.jpg)
![Page 33: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/33.jpg)
12.80 12.81 12.82 12.83 12.84 12.85 12.86 12.87 12.88 12.89 12.90
150000
200000
250000
300000
350000
400000
450000
500000
e
Signal: 12112204.D\FID1B.CH
25.20 25.21 25.22 25.23 25.24 25.25 25.26 25.27 25.28 25.29 25.30 25.31
120000
130000
140000
150000
160000
170000
180000
190000
200000
210000
220000
230000
240000
250000
260000
270000
280000
290000
300000
310000
e
Signal: 12112204.D\FID1B.CH
![Page 34: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/34.jpg)
LMCSQuad-jet modulatorDelay-loop modulator
![Page 35: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/35.jpg)
T
R
Longitudinally Modulated Cryogenic System (LMCS)
Kinghorn and Marriott (1998-2000)
3535
![Page 36: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/36.jpg)
Temperature difference between the oven and the trap crucialOptimum peak width in both dimensions when ΔT =~70 °C ◦ Smaller ΔT trapping inefficient◦ Larger ΔT release inefficient (peak broadening in
both dimensions)
![Page 37: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/37.jpg)
37
Built by LECO under license from Zoex Corporation
![Page 38: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/38.jpg)
10 °C 20 °C
40 °C 80 °C
![Page 39: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/39.jpg)
39
Carrier gas
![Page 40: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/40.jpg)
40
Carrier gas
![Page 41: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/41.jpg)
41
3.551300
3.5751300
3.61300
3.6251300
3.651300
3.6751300
3.71300
25000
75000
125000
175000
1st Time (s)2nd Time (s)
S2
2.65244
2.7244
2.75244
2.8244
2.85244
2.9244
10000
20000
30000
40000
50000
1st Time (s)2nd Time (s)
S2
100 Hz
60 ms
40 ms
![Page 42: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/42.jpg)
42
1184
3.5184
2188
0.5192
3192
1.5196
0200
2.5200
1204
3.5204
10000
20000
30000
40000
50000
1st Time (s)2nd Time (s)
S2
![Page 43: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/43.jpg)
43
![Page 44: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/44.jpg)
44
1: 2,3-butanediol; 2: n-decane; 3: 1-octanol; 4: 2-ethylhexanoic acid; 5: nonanal; 6: n-undecane; 7: 2,6-dimethylphenol; 8: 2,6-dimethylaniline; 9: methyl decanoate; 10: dicyclohexylamine; 11:
methylundecanoate; 12: methyl decanoate
![Page 45: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/45.jpg)
45
![Page 46: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/46.jpg)
Constant flow Programmed flow
46
![Page 47: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/47.jpg)
Adjustments to the modulation period usually require changes to the loop length or the carrier gas flow◦ When the loop is too short, the analyte band is not
refocused at the second cold spot (breakthrough) ◦ When the loop is too long, multiple injections from
the first cold spot could be present within the loop simultaneously (possible breakthrough, changes in 1D retention times)
47
![Page 48: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/48.jpg)
Journal of Chromatography A, 1218 (2011) 4952– 4959
◦ Analysis of 45 FAME
http://www.chem.agilent.com/cag/prod/GC/2DGC_amj2_05_02_07D1a.pdf
48
![Page 49: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/49.jpg)
Modulation period range limited by the fixed volume of the collecting loop◦ Too long modulation periods lead to loop
overfilling (breakthrough)Typical modulation periods ~2 s
◦ Larger loop volumes result in broader 2D peaksPossible artifacts when high concentration peaks elute
49
![Page 50: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/50.jpg)
(A) Reverse fill/flush (RFF) modulator: flow path of fill cycle. (B) Reverse fill/flush (RFF) modulator: flow path of flush cycle.
Griffith et al., J. Chromatogr. A 1226 (2012) 116– 123
50
![Page 51: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/51.jpg)
Griffith et al., J. Chromatogr. A 1226 (2012) 116– 12351
![Page 52: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/52.jpg)
1D (length m × i.d. µm) 2D (length m ×
i.d. µm) Analyte/sample Reference
Poly(ethylene glycol) (21 m × 250 µm) 100% Polydimethylsilocxane (PDMS) (1 m ×
100 µm)A hydrocarbon mixture and a coal liquids sample [7]
(SolGel + poly(ethylene glycol)) composite phase (SolGel-WAX (30 m ×
250 µm)
5% Phenyl polysilphenylene siloxane (1 m × 100 µm) Roasted coffee bean volatiles [72]
Poly(ethylene glycol) (30 m × 250 µm) 5% Phenyl polysilphenylene siloxane (1 m ×
100 µm)Lipids and roasted coffee bean volatiles [73, 74]
Polyethylene glycol (TPA-treated) (30 m × 250 µm)
35% Phenyl-polysilphenylenesiloxane (1 m × 100 µm) Food analysis [75]
(5%-Phenyl)(1%-Vinyl)- methylpolysiloxane (2 m ×
100 µm)
14% Cyanopropylphenyl) methylpolysiloxane (0.5 m × 100 µm) Test mixtures [35]
100% PDMS (30 m × 250 µm) (SolGel + Poly(ethylene glycol)) composite
phase (SolGel-WAX (1.5 m × 250 µm)Volatile components of Pinotage wines [65]
100% PDMS (50 m × 530 µm) 50% Phenyl-polysilphenylene siloxane (2.2
m × 150 µm)Volatile organic compounds in urban air [76]
100% Cyclodextrin directly bonded to PDMS (10 m ×
100 µm)
(50% Liquid crystal / 50% dimethyl) siloxane column (1 m × 100 µm) PCBs in environmental samples [77]
100% PDMS (1 m × 100 µm) 14% Cyanopropylphenyl)
methylpolysiloxane (2 m × 100 µm) Essential oils [78]
Polyethylene glycol (60 m × 250 µm) (14%-Cyanopropyl-phenyl)-
methylpolysiloxane (3 m × 100 µm) Cigarette smoke condensates [79]
Poly(5%-phenyl–95%-methyl)siloxane phase (40 m ×
100 µm)
1,12-Di (tripropylphosphonium) dodecane bis (trifluoromethanesulfonyl) imide (3 m × 100 µm)
PCBs [80]
Poly(methyltrifluoropropyl siloxane) (30 m ×
250 µm)
Poly(dimethyldiphenylsiloxane) (5 m × 250 µm)
Trace biodiesel in petroleum- based fuel [81]
![Page 53: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/53.jpg)
1D Length of BPX5 column*
Length of BP20 column*
A 20 0B 15 5C 10 10D 5 15E 0 20
D. Ryan, P. Morrison, P. Marriott, J. Chromatogr. A 1071 (2005) 47.
![Page 54: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/54.jpg)
1D Length of BPX5 column*
Length of BP20 column*
A 20 0B 15 5C 10 10D 5 15E 0 20
D. Ryan, P. Morrison, P. Marriott, J. Chromatogr. A 1071 (2005) 47.
![Page 55: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/55.jpg)
Typical 1D columns: 0.25 – 0.32 mm IDTypical 2D columns: 0.1 mm ID
This is not always optimal!
![Page 56: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/56.jpg)
0.1 mm ID
0.25 mm ID
Mixture of pure compounds 1,000 x dilution
![Page 57: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/57.jpg)
(15 m × 0.25 mm i.d) × (1.5 m × 0.1 mm i.d)
(30 m × 0.32 mm i.d) × (1.5 m × 0.18 mm i.d)
J. Beens, H. Janssen, M. Adahchour, U.A.T. Brinkman, J. Chromatogr. A 1086 (2005) 141.
![Page 58: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/58.jpg)
Pin (KPa) 1N 2N 1ū (cm/s) 2ū (cm/s) PRopt
30 m × 0.32 mm + 1.5 m × 0.18 mm
56 86000 9000 16 64 4
88 100000 8000 24 106 5
132 98000 6500 35 140 6
15 m × 0.25 mm + 1.5 m × 0.10 mm
112 44000 15000 10 80 4
224 65000 10000 18 160 7
400 40000 4000 30 280 12
J. Beens in cooperation with www.chromedia.org, Comprehensive Two-Dimensional Gas Chromatography the State-of-Separation-Arts Theory. Part 2, 2010.
![Page 59: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/59.jpg)
No split
35:65 split
P.Q. Tranchida, A. Casilli, P. Dugo, G. Dugo, L. Mondello, Anal. Chem. 79 (2007) 2266.
![Page 60: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/60.jpg)
Primary – IsothermalSecondary - Isothermal
Primary – IsothermalSecondary – Temperature incremented
Primary – Temperature programmedSecondary - Isothermal
Primary – Temperature ProgrammedSecondary – Temperature Incremented
![Page 61: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/61.jpg)
2D peaks very narrow – fast detectors requiredAt least 10 data points across a peak needed for quantitative determinations◦ Data acquisition rate of at least 50 Hz required Detectors must have low internal volume and short time constantsMost popular detectors: FID, TOF-MS
![Page 62: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/62.jpg)
Detector Analyte/sample References
µECD
Pesticides in sediments [116-118]PCBs/OCs/CBz in soils, sediments and sludges [119, 120]Dioxins and dioxin-like PCBs in food and feed [121]Chiral toxaphenes typically found in real-life samples [122]Polybrominated diphenyl ethers [123]Polychlorinated dibenzo-p-dioxins, dibenzofurans and PCBs in food [124, 125]Chiral PCBs in food [125]PCBs in Baltic grey seals [126]Toxaphene [127]Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and PCAs in a cod liver extract and a standard mixture [99]
NPD
Nitrogen-containing compounds in Brazilian heavy gas oil [128]
Volatile fraction of creosote-treated railway wood sleepers [129]Nanoparticles in roadside atmosphere [130]methoxypyrazines in coffee headspace [131]Fungicide residues in vegetable samples [132]Methoxypyrazines in wine [133]
SCD
Sulfur-containing compounds in straight run diesel oil [134]
Sulfur-containing compounds in heavy petroleum cuts [135]
Sulfur-containing compounds in middle distillates [136]Sulfur-containing compounds in crude oils [137]Sulfur compounds in diesel oils [138]Sulfur-containing compounds in diesel [139]
AED Sulfur-containing compounds in crude oil [140]MPDD Pyrolysis of gasoline (cracked naphtha) and pyrolysis of a polyethylene copolymer [141]
![Page 63: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/63.jpg)
TOF-MS most popular owing to very high data acquisition rates (up to 500 Hz)Quadrupole MS slower, but can be used for qualitative work (quantitative determinations often possible with narrower mass range)HRTOF-MS very promising
![Page 64: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/64.jpg)
Hopanes
Phenanthrenes
TIC
Sample and assistance provided by Jack Cochran and Michelle Misselwitz of Restek Corporation.Data provided by LECO Corporation using a prototype GCxGC-HRT system.
64
![Page 65: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/65.jpg)
Hopanes
Phenanthrenes
Sample and assistance provided by Jack Cochran and Michelle Misselwitz of Restek Corporation.Data provided by LECO Corporation using a prototype GCxGC-HRT system.
65
![Page 66: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/66.jpg)
Hopanes
Phenanthrenes
Sample and assistance provided by Jack Cochran and Michelle Misselwitz of Restek Corporation.Data provided by LECO Corporation using a prototype GCxGC-HRT system.
66
![Page 67: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/67.jpg)
Hopanes
Phenanthrenes
Sample and assistance provided by Jack Cochran and Michelle Misselwitz of Restek Corporation.Data provided by LECO Corporation using a prototype GCxGC-HRT system.
67
![Page 68: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/68.jpg)
HopanesFWHH 0.090 sec
191.179852.2 ppm error
191.179450.12 ppm error
191.17940-0.14 ppm error
191.179530.54 ppm error 191.18078
7.1 ppm error
68
![Page 69: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/69.jpg)
FWHH 0.060 sec
191.085881.8 ppm error
191.085841.6 ppm error
191.085700.91 ppm error
191.08526-1.4 ppm error
Phenanthrenes
69
![Page 70: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/70.jpg)
GCxGC approaches a mature status, but there is still room for improvementCareful optimization is required to reach the full potential of the techniqueGC×GC separation optimization is not as simple as in conventional 1D-GC because of the column coupling◦ any changes to the 1D column, flow rate, modulation,
oven temperature programming rate, etc., affect the separation in the 2D as well
70
![Page 71: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/71.jpg)
71
O. Panic, C. McNeish, T.N. Oldridge, A. Mostafa
◦ NSERC◦ RESTEK◦ LECO◦ SGE◦ DoE◦ Polymicro Technologies
![Page 72: Journal of Chromatography A, 1255 (2012) 38–55 · Tadeusz Górecki, Ahmed Mostafa, Matthew Edwards. Department of Chemistry, University of Waterloo (ON) Journal of Chromatography](https://reader033.vdocuments.us/reader033/viewer/2022042314/5f02d0ef7e708231d4062722/html5/thumbnails/72.jpg)
1df 2df
2dc 1dc
1wh
Mass perModulation
Chance of overloading 1D
Chance of overloading 2D
1l 2l
Capacity of 2D
Capacity of 1D
2Δp 1Δp
1u 2u
2D retention
2Rs 1Rs
2wh
Allowed / Required 2D Space
Oven Programming Rate
Te
AnalysisTime
PM
1uopt
Inlet Pressure
1Δp
ΔpT
72