Pid and process_gc_instrumentation_jack_driscoll

Dr. Jack Driscoll
PID Analyzers, LLC
Seoul,Korea 2010
copyright 2000-2011 PID

PID Analyzers, LLC 8/13/2011

 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

h

Process
 R + h = R + + e -

 where

 R= molecule
 h = a photon with an
 energy > IP of R
 R+ = positive ion
 e- = electron


 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


 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 CO2
 Detection of VOCs under Texas Chapter 115
 Carbon bed breakthrough for toxic
compounds at ppb levels
 ppb levels of S in process streams GC-
FPD


GC Signal Schematic
Detector
ADC 16 bit AMP

Keyboard
Display DAC to 4-20 mA
Diagnostics
PC RS232

Digital I/O Alarms Digital I/O- valves

Time clock, data calc & storage on hard drive

Model 301-C

mouse

USB Port


 TheGC 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.


PID 10.6 eV

On-screen keyboard

Method

Calibration

PID 10.6 eV- 3 ppb

Detector Parameters

Exhaust Carrier
Pump Gas (N2)

① ② ⑧
⑨ ⑪
Gas

③ ⑦ ⑩ Vent
④
Column PID
Chamber
⑤
Filter

Port
Switching
Valve
⑥
(point) (2-position) Sample
Vent
Pump
Chromatographic Oven
3 Way Valve

Multipoint Module Main Analysis Module

 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


 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-


 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 %)


 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


 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


 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


h


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


Detectors and Characteristics
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


 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


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 storage
 VGA Color flat panel display, ASCII keyboard
 Automatic report generation
 Extensive diagnostics


 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


 No support gases needed- just  Requires H2 (quarterly) and
carrier zero air (monthly) or
 Widest dynamic range of any generators
GC detector > 5 x 10 exp 7  Dynamic range > 10 exp 6
 PID is 50-100 x more sensitive
than the FID
 Detection limit of benzene=  Detection limit of benzene =
0.5 ppb < 40 ppb
 No response to C1-C4  FID can detect C1-C4
aliphatic HC aliphatic HC
 PID is a concentration
sensitive detector so lower  FID is mass sensitive detector
flowrates further improve
sensitivty


 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  Yes

 Response to organic cpds
 Yes – CS2, CCl4  No

 Response to hydrides
 Yes NH3, H2S, AsH3, PH3  No

 Response to other cpds
 Yes – Cl2, I2. HBr, HI  No


 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


PID 10.6 eV

3 ppb BTX

PID 10.6 eV

5 ppb BTX

Low Level Linearity of Benzene & Ethyl Benzene

25000

20000
y = 972.99x - 16.272
Peak Counts

15000 R2 = 0.9999 y = 389.31x - 8.112
2
R = 0.9999
10000

5000

0
0 5 10 15 20 25
ppb Benzene/Ethyl Benzene

 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

GLOBAL FOUNDRY
PRAXAIR- 50 UNITS LINCOLN GENERAL HOSPITAL
SHELL CHEMIE USB RADIAN CORP. 4 UNITS
ELF KOCH REFINING
TOTAL EASTMAN KODAK
ATOCHEM
SYNERGRO SHELL CHEMIE
ATOFINA CZECH MUSEUM
IBM AKZO NOBEL
INTEL TENNESSEE EASTMAN
IBM CANADA
HOECHST CELANESE MINISTRY OF THE ENV. 6 BTX ANALYZERS
ALLIED SIGNAL

 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

 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.

 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.


Pid and process_gc_instrumentation_jack_driscoll

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