PID and Process GC Instrumentation JackDriscoll

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


R + h = R + + e-

where

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


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


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



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


Model 301-C

mouse

USB Port


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.


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


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


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



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


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


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


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


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

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


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



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


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


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.


Documents

PID and Process GC Instrumentation JackDriscoll