pid and process_gc_instrumentation_jack_driscoll
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Dr. Jack Driscoll
PID Analyzers, LLC
Seoul,Korea 2010copyright 2000-2011 PID
8/13/2011PID Analyzers, LLC
In 1974, Dr. Jack Driscoll developed the first
portable PID (> 25,000 sold worldwide)
In 1976, Dr. Jack Driscoll developed the first PID
for gas chromatography (> 15,000 sold)
The IR100 award was won for the PID in 1978
Dr Driscoll has published > 80 papers on
photoionization
Dr. Driscoll was awarded the Outstanding
Achievement Award by the Northeastern Section
of the ACS 2011 for developing the first hand
held PID for industrial hygiene
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R + h = R + + e-
where
R= molecule h = a photon with an energy > IP of R R+ = positive ion e- = electron
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Process
h
Linear dynamic range > 5 x107
Detection limit <0.5 ppb benzene
Non destructive; other detectors can be run in-series
Sensitivity increases as the carbon number increases (carbon counter)
For 10.2 eV lamp, responds to carbon aliphatic compounds > C4, all
olefins and all aromatics
The PID also responds to inorganic compounds such as H2S, NH3, Br2,
I2, PH3, AsH3, e.g. any compound with an ionization potential of < 10.6
eV
The PID is more sensitive than the FID; >200 x more sensitive for
aromatics, 80 times for olefins, & 30 times for alkanes > C6
Non destructive detector; other detectors can be run downstream
Concentration sensitive detector
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ppb Levels of VOC’s in Plant Atmospheres Process control of VOC’s ppb to ppt Levels of BTX in ambient air ppb Levels of BTX in beverage grade CO2Detection of VOCs under Texas Chapter 115 Carbon bed breakthrough for toxic
compounds at ppb levels ppb levels of S in process streams GC-
FPD
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8/13/2011PID Analyzers, LLC
GC Signal Schematic
PCRS232
Keyboard
Digital I/O- valvesDigital I/O Alarms
Diagnostics
DAC to 4-20 mA
ADC 16 bit
Display
Time clock, data calc & storage on hard drive
Detector
AMP
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Model 301-C
mouse
USB Port
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The GC firmware has been continuously
developed since its inception in 1990 as a DOS
based system. Now it is written in C++. PID
Analyzers is a Value Added Reseller of Microsoft .
The first process GC (20 point) was developed in
1980 for monitoring AsH3 and PH3 at ppb levels
in semiconductor plants. The 301C is the fifth
generation of that product.
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8/13/2011PID Analyzers, LLC Method
On-screen keyboard
PID 10.6 eV
8/13/2011PID Analyzers, LLC Calibration
8/13/2011PID Analyzers, LLC Detector Parameters
PID 10.6 eV- 3 ppb
3 Way Valve
PID
ChamberFilter
Switching
Valve
(2-position)Port
(point)
Column
Chromatographic Oven
Carrier
Gas (N2)Exhaust
Pump
Sample
Pump
Vent
Vent
Multipoint Module Main Analysis Module
Gas
① ②
③
④⑤ ⑥
⑦
⑧
⑨⑩
⑪
Pre column- to remove heavies, polar or non
polar species, protect analytical column
Inject time- can be varied to remove heavier
species
Detector- Selectivity- HNU has 6 detectors to
choose from;PID lamp energy can be varied
Packed and capillary columns can be mixed
Backflushing to remove heavies; foreflushing
to remove light compounds, heart cutting to
remove a compound during the run
Pressure programming- new option for 2004
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Analytical Column Mode for Specific Detection
Five detectors to choose from: Specific to
Universal
Minimum Maintainance
Data Processing of Concentrations
X (Div. 1) or Z purge (Div. 2)
Outdoor Locations-
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PID- hydrocarbons (>C4), inorganic species H2S, NH3, PH3, etc. at ppb to ppm levels (ppb-%)
FID- specific for hydrocarbons (ppm-%)FPD- specific for S or P (ppb)FUV- nearly universal detector (ppb to%)TCD- universal detector ( ppm to %)
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Photoionization Detector
• 1st commercial introduction in 1976 by HNU
(Driscoll)- 50x more sensitive than FID for
aromatics- low ppb
Far UV Absorbance Detector
• 1st commercial introduction in 1985 by HNU
(Driscoll)-low ppm sensitivity- nearly
universal
Flame Ionization Detector 1st commercial introduction in late 1950s-
hydrocarbons- sub ppm
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PID• Mechanical, chromatographic, electronic &
software-results: improved detection limits from 2 ppb to < 0.5 ppb
FUV• Electronic, chromatographic, & software-
results: improved detetion limits from 1-2 ppm to 25-100 ppb
FID• Electronic, chromatographic, & software-
results: from 100 ppb to 25-50 ppb
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PID Analyzers, LLC
Measures absorbance @ 124 nm-log
signal
Nearly Universal Response
Linear (Log) Range > 105
Low dead volume < 40 uL- fast response
Non- destructive
Environmental applications: freons, landfill
gases, O2, CO2, CH4 at same detection limit
as FID (0.1 ppm), VOCs
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8/13/2011PID Analyzers, LLC
h
Linear dynamic range > 2 x 106
Detection limit 50 ppb
Sensitivity increases as the carbon number increases
(carbon counter)
Sensitivity to substituted species depends on the
mass of carbon present and the ability to break the
carbon bonds
The FID is sensitive to hydrocarbons
Detector is destructive since sample is burned
Requires the use of zero grade (high purity) hydrogen
and air to produce the flame
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h
PID FUV FID
Species
Alkenes Y Y Y
Aromatics Y Y Y
Dynamic Range 5 x 10exp7 1 x 10exp5 1 x 10exp6
Detection Limits
Air
aromatics < 0.5 ppb 25-100 ppb 50-100 ppb
alkenes <5 ppb 25-100 ppb 50-100 ppb
alkanes < 10 ppb 25-100 ppb 50-100 ppb
Water
aromatics < 0.1 ppb 2.5-10 ppb 2.5-10 ppb
alkenes 0.1 ppb 2.5-10 ppb 2.5-10 ppb
alkanes 1 ppb 2.5-10 ppb 2.5-10 ppb
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Detectors and Characteristics
Multipoint Sequencer- 1, 4, 8 ,10, 20 points
Six detectors to choose from specific to universal
Analytical Column Mode for Specific Detection
Pre column to remove interferences & protect analytical
column
Built in Diagnostics
Long term reliability
Data Processing of Concentrations (1 Y storage)
X or Z purge- not necessary- in control room
Windows 2000 operating system PeakWorks Chromatography Software VGA color display Mouse (left & right buttons) On screen keyboard USB Port for accessories
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Model 301-C GC Standard Features … Single sample stream; autocalibration Single or dual detector capability, single or
dual columns, Outputs- 0-1V, RS232 (2), plus alarms (lo, high), 4-20 mA (optional), LAN
40 GByte hard drive for data storageVGA Color flat panel display, ASCII keyboardAutomatic report generation Extensive diagnostics
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The 301-C has a 16 channel ADC
Six are used for the 301-C
There are 10 additional channels for
sensor input
Sensors available are:
Electrochemical, IR, UV, Semiconductor
for more than 20 different species
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No support gases needed- just
carrier
Widest dynamic range of any
GC detector > 5 x 10 exp 7
PID is 50-100 x more sensitive
than the FID
Detection limit of benzene=
0.5 ppb
No response to C1-C4
aliphatic HC
PID is a concentration
sensitive detector so lower
flowrates further improve
sensitivty
Requires H2 (quarterly) and
zero air (monthly) or
generators
Dynamic range > 10 exp 6
Detection limit of benzene =
< 40 ppb
FID can detect C1-C4
aliphatic HC
FID is mass sensitive detector
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Hydrocarbon- a compound consisting of hydrogen and carbon atoms (CH4-methane)
Carbon Compound (organic compound)- a compound consisting of carbon and another atom(s) such as CS2 (carbon disulfide)
VOC- Volatile organic compound- could be a volatile version of either of the above two definitions
PID FID
Response to Hydrocarbons
Yes
Response to organic cpds
Yes – CS2, CCl4
Response to hydrides
Yes NH3, H2S, AsH3, PH3
Response to other cpds
Yes – Cl2, I2. HBr, HI
Yes
No
No
No
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8/13/2011PID Analyzers, LLC
The 301 C can have packed or capillary columns (0.53 or 0.32 mm or 0.18)
Typical cap column 30M x 0.53 or 0.32mm
We use PLOT for inorganic, fixed gases or light hydrocarbons
One or two columns packed or capillary
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8/13/2011PID Analyzers, LLC 3 ppb BTX
PID 10.6 eV
8/13/2011PID Analyzers, LLC 5 ppb BTX
PID 10.6 eV
PID
PID
PID
PID
FID
PID
Low Level Linearity of Benzene & Ethyl Benzene
y = 972.99x - 16.272
R2 = 0.9999 y = 389.31x - 8.112
R2 = 0.9999
0
5000
10000
15000
20000
25000
0 5 10 15 20 25
ppb Benzene/Ethyl Benzene
Pe
ak
Co
un
ts
TCD
Children’s Hospital Univ. of CA SF John Hopkins Smithsonian VA Hospital, Dallas Roosevelt Hospital Perrier Becton Dickinson Amoco EI DuPont Ohio State Univ. Hospital Aberdeen Proving Grounds Meriter Hospital American Medical Supp. Celanese Chemical Methodist Hospital
EtO from sterilization chemical production
Multicomponent monitoring of hazardous waste site
fencelines
H2S and mercaptans in air & stacks
Silicone compounds in process streams
Carbon breakthrough break detection of toxic gases
ppb levels of chlorinated HC’s
Fenceline monitoring from chemical & petrochemical
plants
Single point monitoring
Four point monitoring
IBM
Dow Chemical
Dow Corning
Rhone Poulenc
Ato Chem
BP
ICI
Johnson & Johnson
Becton Dickenson
Medtronics
Phillips Petroleum
Akzo Nobel
Union Carbide
Celanese Chemical
Solvents (PGMEA etc) in semiconductor plants EtO from sterilization chemical production Multicomponent monitoring of hazardous waste
sites H2S and mercaptans in air & stacks Carbon bed breakthrough of specific VOC’s Silicone compounds in process streams Carbon breakthrough break detection of toxic
gases ppb levels of chlorinated HC’s Fenceline monitoring from chemical &
petrochemical plants Multipoint monitoring 10-20 point
PRAXAIR- 50 UNITSSHELL CHEMIEELFTOTALATOCHEMSYNERGROATOFINAIBMINTELIBM CANADAHOECHST CELANESEALLIED SIGNAL
GLOBAL FOUNDRY
LINCOLN GENERAL HOSPITAL
USB RADIAN CORP. 4 UNITS
KOCH REFINING
EASTMAN KODAK
SHELL CHEMIE
CZECH MUSEUM
AKZO NOBEL
TENNESSEE EASTMAN
MINISTRY OF THE ENV. 6 BTX ANALYZERS
In the early 1980’s we developed a “Quickscan” method
to reduce the time to sequence 20 points of AsH3 & PH3
from 30 min to <10 min. We did this by eliminating the
column and when a preset level was exceeded, the
svstem would go into the chromatographic mode.
When many of the PELs were dropped to 1 ppm,
quickscan was dropped because we had no way to do
ppb levels, ony ppm.
Several years ago, we developed ppb capability for the
PID, now it is possible to have quickscan again, this time
with ppb measurements
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Quickscan is like having a Model 201 (no column) and
a Model 301 incorporated into the same instrument
with the best features of both incorporated.
It requires two separate detectors. The 201 can scan
each point in 20-30 sec. The analysis time is expected to
be 6-10 minutes for a 10 component system or, at best, 2
hours to scan a 20 point system. This compared to 10
minutes for the quickscan.
If a preset alarm level is exceeded, the system goes into
the chromatographic mode to analyze all the components.
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1. The PID is the most sensitive GC
detector available for VOCs and it has the
widest range of response for VOC’s
2. The incorporation of Quickscan in this
unique PID GC would provide
semiconductor workers with the safest
work environment possible.
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