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
PID Analyzers, LLC 8/13/2011

h

Process
  

R + h = R + + e where


   

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

PID Analyzers, LLC

8/13/2011

     

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

  

PID Analyzers, LLC

8/13/2011

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 GCFPD

PID Analyzers, LLC

8/13/2011

GC Signal Schematic
ADC 16 bit
Keyboard Display Diagnostics

Detector

AMP

PC

DAC to 4-20 mA RS232

Digital I/O Alarms

Digital I/O- valves

Time clock, data calc & storage on hard drive
PID Analyzers, LLC 8/13/2011

Model 301-C

mouse

USB Port

PID Analyzers, LLC

8/13/2011

PID Analyzers, LLC

8/13/2011

 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 . 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.

 The

PID Analyzers, LLC

8/13/2011

PID 10.6 eV

On-screen keyboard

PID Analyzers, LLC

8/13/2011

Method

PID Analyzers, LLC

8/13/2011

Calibration

PID 10.6 eV- 3 ppb

PID Analyzers, LLC

8/13/2011

Detector Parameters

Exhaust Pump

Carrier Gas (N2)

① Gas

② ③
Filter

⑧ ⑦ ④
Switching Valve (2-position)


Column


PID Chamber


Vent

Port (point)


Sample Pump

Vent

3 Way Valve Multipoint Module

Chromatographic Oven 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

PID Analyzers, LLC

8/13/2011

 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 Analyzers, LLC

8/13/2011

 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 %)

PID Analyzers, LLC

8/13/2011

 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 1950shydrocarbons- sub ppm
PID Analyzers, LLC 8/13/2011

 PID

• Mechanical, chromatographic, electronic &
 FUV

software-results: improved detection limits from 2 ppb to < 0.5 ppb results: improved detetion limits from 1-2 ppm to 25-100 ppb results: from 100 ppb to 25-50 ppb

• Electronic, chromatographic, & software FID

• Electronic, chromatographic, & software-

PID Analyzers, LLC

8/13/2011

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

PID Analyzers, LLC

8/13/2011

h

PID Analyzers, LLC

8/13/2011

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

PID Analyzers, LLC

8/13/2011

Detectors and Characteristics
PID Species Alkenes Aromatics Dynamic Range Detection Limits Air aromatics < 0.5 ppb 25-100 ppb 50-100 ppb Y Y 5 x 10exp7 Y Y 1 x 10exp5 Y Y 1 x 10exp6 FUV FID

alkenes
alkanes Water aromatics alkenes alkanes

<5 ppb
< 10 ppb

25-100 ppb
25-100 ppb

50-100 ppb
50-100 ppb

< 0.1 ppb 0.1 ppb 1 ppb

2.5-10 ppb 2.5-10 ppb 2.5-10 ppb
8/13/2011

2.5-10 ppb 2.5-10 ppb 2.5-10 ppb

PID Analyzers, LLC


  

  


     

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

PID Analyzers, LLC

8/13/2011

Model 301-C GC Standard Features …
 Single  Single

sample stream; autocalibration 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

PID Analyzers, LLC

8/13/2011

 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

PID Analyzers, LLC

8/13/2011

     

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

 

PID Analyzers, LLC

8/13/2011

 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) Volatile organic compound- could be a volatile version of either of the above two definitions

 VOC-

PID
   

FID

Response to Hydrocarbons Yes Response to organic cpds Yes – CS2, CCl4
Response to hydrides

Yes No No No
8/13/2011

  

Yes NH3, H2S, AsH3, PH3 Response to other cpds Yes – Cl2, I2. HBr, HI

PID Analyzers, LLC

PID Analyzers, LLC

8/13/2011

 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 Analyzers, LLC 8/13/2011

PID 10.6 eV

PID Analyzers, LLC

8/13/2011

3 ppb BTX

PID 10.6 eV

PID Analyzers, LLC

8/13/2011

5 ppb BTX

PID

PID

PID

PID

FID

PID

Low Level Linearity of Benzene & Ethyl Benzene
25000 20000

Peak Counts

15000 10000 5000 0 0

y = 972.99x - 16.272 R2 = 0.9999

y = 389.31x - 8.112 R = 0.9999
2

5

10

15

20

25

ppb Benzene/Ethyl Benzene

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 UNITS SHELL CHEMIE ELF TOTAL ATOCHEM SYNERGRO ATOFINA IBM INTEL IBM CANADA
HOECHST CELANESE

ALLIED 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
PID Analyzers, LLC 8/13/2011

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.
PID Analyzers, LLC 8/13/2011

 1. The

PID is the most sensitive GC detector available for VOCs and it has the widest range of response for VOC’s incorporation of Quickscan in this unique PID GC would provide semiconductor workers with the safest work environment possible.
PID Analyzers, LLC 8/13/2011

 2. The