gc/ms 의 원리 및 이론
DESCRIPTION
GC/MS 의 원리 및 이론. 부경대공실관 VOCs/ 냄새분석실. What is Mass Spectrometry?. Measure the masses of individual molecules & atoms which are converted into gas phase ions in terms of their mass to charge ratios. convert into gas (chromatographic separation). Inlet. Source. Analyzer. Detector. - PowerPoint PPT PresentationTRANSCRIPT
Cryo system with GC/MS for ppt level Analysis
GC/MS 의 원리 및 이론
부경대공실관 VOCs/ 냄새분석실
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Source
Measure the masses of individual molecules & atomswhich are converted into gas phase ions in terms of their mass to charge ratios
Inlet Analyzer Detector Data System
solidliquidgas
ionization sort ions by m/z
convert into gas(chromatographic separation)
mass spectrum
What is Mass Spectrometry?
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
▣ ▣ GCGC 의 기본 구성과 기능의 기본 구성과 기능
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
▣ ▣ 시료주입기와 주입방법시료주입기와 주입방법
1. 섬광기화 직접법
2. 섬광기화 분할법 (split)
3. 섬광기화 비분할법 (splitless)
4. 섬광기화 냉각법
5. 온도프로그래밍 기화법 (PTV)
6. 냉각 온 - 컬럼 주입법 (OCI)
7. 기타
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
▣ ▣ 컬럼오븐컬럼오븐
분리도와 머무름 재현성 향상을 위해서
1. 설정온도와 실제온도의 일치
2. 최저 및 최고 작동 온도의 범위의 확장
3. 오븐의 가온 · 냉각 속도가 정확
4. 오븐 온도의 평형 시간의 단축
5. 설정된 온도가 주기적인 변동없이 안정
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
▣ ▣ 컬럼온도에 따른 분리도 컬럼온도에 따른 분리도
30℃ 등온분석
100℃ 등온분석
30~200℃승온분석
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
▣ ▣ 검출기의 종류검출기의 종류
1. 이온화 검출기 (ionization detector) 불꽃이온화 검출기 (flame ionization detector;FID) 열이온화 검출기 (thermionic ionization detector;TID) 광이온화 검출기 (photo ionization detector;PID) 전자포획 검출기 (electron capture detector;ECD)
2. 물리적 성질 검출기 (bulk physical detector) 열전도도 검출기 (thermal conductivity detector;TCD)
3. 광학 검출기 (optical detector) 불꽃광도 검출기 (flame photometric detector;FPD) 원자방출 분광 검출기 (atomic emission detector;AED)
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
What is the Mass Spectrum?
mass to charge ratio
# o
f io
ns
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Inlet + Source : 시료도입 및 이온화 방법에 따라
EI, EI/DIP, CI, DCI, FD, FI, TI, FAB(LSIMS), LD, ESI, APCI, MALDI,GC-MS, LC-MS, CE-MS, etc.
Analyzer : 질량분석관에 따라
Sector, TOF, Q(quadrupole mass filter, 2D-Q)Quadrupole IT(ion trap, 3D-Q), ICR (FTMS)Hybrid MSs (Sector-TOF, QqTOF, TOF-TOF, QqQ, IT-TOF, etc)
Diverse Mass Spectrometric Systems
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Reservoir Inlet
DIP
FAB, LD, MALDI
Non-volatileVolatile
GC/MS
Thermally Stable Thermally labile
GC/MS
ESI, MALDI
Choice of MS Method I
ESI/APCI (but should be soluble in ESI/APCI compatible solvents)
FAB, APCI
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Choice of MS Method II
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Quantitation
InformationfromMS
Molecular Weight& Elemental Composition
molecular ion → molecular mass (M+Na)+=897 → M=874accurate mass → elemental composition 897.4976 → C48H74O14Naisotopic distrib’n → elemental composition
source of the sample
Molecular StructureFrom fragmentation
Non-covalent InteractionNon-covalent adduct(Ab-Ag, host-guest)
Information from Mass Spectrometry
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Advantage of MS detector
Information of chemical structure Identification of target compound Determination of molecular weight High sensitive and rapid analysis
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Identification
m/z
Retention time
Chromatogram
MS
Spec
trum
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Configuration of GCMS Configuration of GCMS
Mass Spectrometer
Gas Chromatograph
Interface
Ion source box
Data Store
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Flow Chart of GC-MS
Sample
Inlet System
Ion Source
Vacuum System
Mass Analyzer
Detector
Signal Processor
Print Out
GC Direct
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
MS analyzer
Magnetic sector type (sector type) Quadrupole type Time of flight type (TOF type) Ion Trap type
Quadrupole type of GCMS is very popular.
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Schematic of a Quadrupole MS systemSchematic of a Quadrupole MS system
Generation
Introduction
Selection
Detection
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Hardware structure of QP/MS
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Ion Source Box- Increased ionization efficacy -
Ion Source Box- Increased ionization efficacy -
Interface
Filament
Ion source box
Conventional ion source
QP2010 ion source High luminosity ion source
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Ion Source Box Ion Source Box
Extractor : This device can draw ion generated into the ion source box.
from GC
To QP
QP2010
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Optimum adjustment of the Lens system
QP
Software can optimize lens voltage in order to introduce more ions to Quadrupole.
X
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Quadrupole Rod - Minimize losses in transit to the Quadrupole -
Quadrupole Rod - Minimize losses in transit to the Quadrupole -
Main RodSpecific ion only can be passed by the electronic field into Quadrupole Rod which is controlled by PC.
Pre Rod
From ion sourceTo detector
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
rotary pump
Vacuum systemVacuum system- Minimize losses in transit to the Quadrupole -
turbo molecular pump [260 L/sec X 65 L/sec]
Dual turbo pumping system
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Low-noise Dynode multiplier - Increased detection of created ions -
EMDetector
Conversion dynode
Low noise detector unit
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
High Sensitivity High Sensitivity
Octaflouronaphthalene, 1pg : S/N > 60
Octafluoronaphthalene, 1pg : S/N > 30
QP-2010
QP-5050
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Modes of Ionization
EI : Electron Impact Hard Ionization, High Energy Structural information
CI : Chemical Ionization Soft Ionization, Low Energy Molecular weight information
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Ionization techniques available for GC/MS
Electron Impact Ionization (EI)
Positive Chemical Ionization
(PCI)
Negative Chemical Ionization
(NCI)
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Electron Impact Ionization (EI)Electron Impact Ionization (EI)
e-e-Sample
from GC
filament
++
+ +
Fragment ion
QPe-e-e-
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass SpectrometerElectron Impact Ionization
(EI)
Thermal electrons (ca. 70 eV) hit molecules and ionize them. Ample fragment ions = ample structural information “finger print”
EI spectrumMethylstearate M.W. 298
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Positive Chemical Ionization (PCI)
Positive Chemical Ionization (PCI)
from gas cylinder
filament
e-e-
e- e-e-
QP
CH4 CH5
+
C2H5+
Sample from GC
H+
-CH4
[M+1]-C2H4
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Positive Chemical Ionization (PCI)
Reagent gas molecules are ionized first. Sample molecules are ionized mainly by “proton
transfer”. Quasi molecular ions easily produced useful for
molecular weight verification.
+
PCI spectrumMethylstearate M.W. 298
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Comparison of EI and PCIComparison of EI and PCI
EI mode
PCI mode
Fragment
Molecular weight
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Negative Chemical Ionization - NCI -Negative Chemical Ionization - NCI -
filament
e-e- e-e-
Reagent Gas
Sample
NCI for highest sensitivity for electrophilic compounds
Sample
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Negative ion formation by electron capture (associative resonance capture)
MX + e- (~0 eV) MX-.
X: positive electron affinity part
CH4
e-
MX
CH4+
CH3
+H
CH4
CH4
CH4
e-
MX-
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Advantages of negative chemical ionization
Ion formation by electron capture
High sensitivity Close to GC-ECD sensitivity
High selectivity
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Application fieldfor negative chemical ionization
Environmental chlorinated pesticides phosphorus pesticides PCB etc.
Life science Drugs, steroids, bile acids
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Measurement Mode
Scan Mode SIM Mode (Selected Ion Monitoring)
mas
s n
um
ber
mas
s n
um
ber
Time Time[Scan] [SIM]
(Qualitative)(Qualitative) (Quantitative)(Quantitative)
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Scan Mode
m/z
Retention time
TIC : Scan Mode
72
54
152
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
SIM Mode
Retention time
m/z=72 m/z=152 m/z=54
Higher Sensitivity than Scan Mode.For quantitation purpose
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Adjustment of MS
All adjustment of the instrument can be carried out by Windows Software.
Sensitivity adjustment Resolution adjustment Correction of mass number Correction of relative intensity
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
MS TuningMS Tuning
PFTBA(perfluorotributylamine) is use for MS tuning.
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
PFTBAPFTBA
relative
m/z intensity
69 100.0131 26.0219 32.0414 2.0502 2.0614 0.4
CF3 -CF2 -CF2 -CF2 -N -C4F9
C4F9
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Direct Injection Mode (DIP)
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Operational Precaution Operational Precaution for GCMSfor GCMS
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Operation Precautions
• Sample• Pretreated sample• Know amount of components in the sample• Used the smallest appropriate sample volume• For unknown, screen on GC first
• Tools• Wear sanitary gloves when performing any work on IS or analyzer housing• Wipe/clean all the tools with acetone to minimize the background noise
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Operation Precautions
•Column• Avoid wide bore, thick film & dirty column.
•Use the recommended standard sample and column to evaluate the system performance.
•Perform preventive maintenance frequently to minimize problems.
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Sample Pretreatment
• Filtration• Centrifuge• Extraction
• HSG• Dynamic HS (Purge & Trap)• Static HS
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Extraction• LLE
• isolating organic compounds from aqueous samples
• SPE• isolating organic compounds from aqueous samples
• Soxhlet• extracting nonvolatiles and semivolatiles from solid samples
• Sonication• extracting nonvolatiles and semivolatiles from solid samples
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Sample Clean-up
• Acid-base partition • Sulfur clean-up• Adsorption column chromatography
• Alumina clean-up• Silica gel clean-up• Florisil clean-up
• GPC
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Typical GCMS Problem
•Poor sensitivity•Contamination•Vacuum leak•Dirty ion source•Untrained operator
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Troubleshooting for Poor Sensitivity
• Sample • Active• Thermal decomposition
• Injector• Septum leak• Seal rings/graphite damage• Glass insert broken
• GC parameters• Injection parameter
• MS parameters
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
• Possible Source• Carrier Gas• Injector - Dirty glass insert
- Septum bleed - Graphite bleed• Cleaning solvents• Fingerprints• Plasticizers
• Verify the source by isolating MS from GC• Identify the source
Troubleshooting for Troubleshooting for ContaminationContamination
부경대학교 공동실험실습관 VOCs/ 냄새분석실
Gas Chromatograph/Mass Spectrometer
Typical Contaminants
Mass (M/Z) Compound Classification Potential Source------------------------------------------------------------------------------------------------------------------18, 28, 32, 40, 44 Air H2O, N2, O2, Ar, CO231 Solvent Primary alcohol (MeOH)43, 58 Solvent Acetone77 Bz, Xyl85 Freons91, 92 Tol105, 106 Xyl22, 73, 147, 207, 281, 295, 355, 429 Dimethylpolysiloxane Septum/column41, 45, 55, 57, 71, 85, 99 Hydrocarbon Fingerprint/pump oil149 Phthalates Plasticizers