Determination of Volatiles & PCBs in Transformer Oil by GC/PID

Pittcon March 11, 2012 Paper # 220-16P

Dr. J.N. Driscoll PID Analyzers, LLC Sandwich, MA http://www.hnu.com
PID Analyzers, LLC; Sandwich MA http://www.hnu.com

Introduction
Methods were needed to measure volatiles and semivolatiles (PCBs in used transformer oil). Initially two columns were used but the method was simplified so that only a single column was necessary. The method selected for the volatiles was headspace The method for PCBs was dilution followed by s direct injection These methods will be described in the following slides

PID

Photoionization Detector
Process
R + h = R + + e where

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

PID

PID Photo

GC Conditions Volatiles
PID Analyzers- Model GC322 with PID GC conditions Injector- 80C Oven- Isothermal 60oC Column 30M x 0.53 mm 0.5 m film Restek RTX-5 Carrier: N2 Flow 7 cc/min, 10 cc/min makeup Sample size: 1 cc gas-

GC322

Headspace Procedure
Using a 40 mL VOA vialAdd 25-30 mL of transformer oil & seal cap tightly Heat in oven @60C for 15 min Remove from oven Let stand for 15-20 min Using a 1 cc gas syringe remove a sample through the septum & inject into GC Inject a second 1 cc sample

Determination of Waiting time before HS sampling

Blank Transformer oil- Headspace

Headspace 5 min after removal from oven

Headspace 15 min after removal from oven

PCBs in Transformer Oil

PID Analyzers- Model GC322 with PID GC conditions Injector- 250oC Oven- Temp. Prog. 160oC for 1 min, 10oC/min To 225oC, hold 2 min. Column 30M x 0.53 mm m film Restek R Carrier: He Flow 8.5 cc/min, 10 cc/min makeup Sample size: 0.2uL sample + 0.2 uL hexane (dilution) Total analysis Time (with cool down): 13 min.

PID Response
PID Sensitivity for Organic Compounds Sensitivity increases as carbon number increases For n-alkanes, SM= 0.715n-0.457 where SM = molar sensitivity relative to benzene (benzene= 1.0) and n = carbon number Sensitivity for alkanes < alkenes < aromatics Sensitivity for alkanes < alcohols esters < aldehydes < ketones

PID

Sensitivity for cyclic compounds > non cyclic compounds Sensitivity for branched compounds > non branched compounds Sensitivity for fluorine substituted < chlorine substituted < bromine substituted < iodine substituted For substituted benzenes, ring activators (electron releasing groups) increase sensitivity For substituted benzenes, ring deactivators ( electron withdrawing groups) decrease sensitivity (exception: halogenated benzenes)

PID Response to PCBs Where Benzene Sensitivity = 1.0

1 ppm Arochlor 1016 in hexane -PID

ppm Arochlor 1016 in Transformer Oil

Arochlor 1016 in transformer oil 25 ppm
*10000 15

Clean Transformer Oil blank

*1000 0 -5 12 3 4

10

-10 -15

-20 -25

-30 -35

-5 2 1 -10 0:00 2:00 3

-40
5 6 4:00 7 11 13 15 891012 14 16 6:00 8:00 17 19 20 18 min 10:00

-45 -50 0:00 2:00 4:00 6:00 8:00 min 10:00

Statistics for 25 ppm PCBs in Oil

Total Area 32,379,272.00 41,605,638.00 38,087,952.00 33,710,864.00 41,825,388.00 37,521,823 -ave 4372870-std dev 11.7 CV% 5 replicates

Comparison of GC/PID chromatograms of PCBs @ 25 ppm in Transformer Oil

Conclusions
Two methods were developed using the same column but with different techniques. The volatiles required 15 minutes of heating in a VOC vial before analysis. The analysis time was 3 min. the precision was +/- 5% The SVOC sample was diluted 1:1 with hexane and injected. We could recognize the difference between various PCBs using the PID. The precision of the method was +/- 11% at 25 ppm.