Supelco: Capillary GC Troubleshooting: A Practical Approach

SUPELCO
Capillary GC Troubleshooting:
A Practical Approach
Katherine Stenerson
Gas Separations R&D
Supelco, Supelco Park, Bellefonte, PA 16823
Outline
❚ Basic Troubleshooting Strategy

❚ Preventing Problems
❚ Identifying Common Problems
❚ Recommended Reading
❚ Discussion
©1999 Sigma-Aldrich Co. SUPELCO

Troubleshooting Strategy
❚ Have appropriate equipment and

supplies on hand.
❚ Establish a systematic approach.
❚ Know what to look for first.
❚ Record what you did to correct the
problem.

Suggested Equipment to Have on
Hand for Troubleshooting:
Electronic Leak Detector

Flow Meter
“Test” Column
Replacement Accessories (Syringes, Ferrules, Septa)
Replacement Purifiers

Five Major Sources of
Chromatographic Problems:
❶Operator Error
❷The Sample
❸The Column
❹The GC Electrical System
❺The Gas Flow System (both internal and
external to the GC)

Approaching the Problem
❚ Check first to see if a “fix” for the

problem is already known.
❚ Check the Supelco Capillary GC
Troubleshooting Guide (Bulletin 853.)
❚ Check back in the instrument
maintenance record.
❚ Talk to others in your lab.

Isolate the Source of the Problem
OK Not OK
Check operating Correct the
Run Ref. Std.
parameters parameter
Not OK
OK
Problem was Install

sample Test
related Column
Not OK
OK Problem is in the Inlet
or with the carrier gas
OK
Problem
Cap off
was
Detector
Column related Problem is in the
Not OK
Detector

When reviewing operating method
parameters consider the following:
? Is my starting temp. low enough to allow

sufficient sample focusing?
? For splitless injections, is my splitter opening
at the appropriate time?
? Is my column flow set to give me maximum
efficiency at the most critical point?
? Are heated zones (injectors, detectors,
interfaces) set appropriately?

The Best Way to Solve Problems
is to Prevent Them!
❚ Install and maintain proper purification

for all gases in the GC system.
❚ Maintain the injector by periodically
inspecting and changing the liner,
septa, and seal (H/P™.)
❚ Use the proper injection technique-this
includes using the right liner for the job.
❚ When necessary, use a guard column to
protect the analytical column.

Gas Purification
❚ Carrier Gas
❙ At minimum, remove hydrocarbons, water, and oxygen.
❚ Hydrogen (FID)
❙ At minimum, remove hydrocarbons.
❚ Air (FID)
❙ At minimum, remove water and hydrocarbons.
❚ Nitrogen make-up (FID, ECD)
❙ At minimum, remove hydrocarbons.
❚ P-5 make-up (ECD)
❙ At minimum remove hydrocarbons (especially halogen-
containing), oxygen.

Acceptable Purity Levels for
Chromatography Grade Gases
Impurity / Maximum Concentration

Total
Gas O2 H2O CO2 CO Hydrocarbons
Helium <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Nitrogen <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Air 20-22% <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Hydrogen <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Argon/
Methane <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm

Suggested purifiers
Hydrocarbons Water Oxygen
Carrier Supelcarb HC Mole Sieve 5A OMI -2

Supelpure HC
H2
Air Mole Sieve 5A
N2 makeup
P-5 OMI -2 OMI -2
P-5

What are some signs that my
purifiers need to be changed?
Hydrocarbon Traps Molecular Sieve 5A

Noise in the baseline (FID) Increase in column bleed
Increase in background Water visible in MS
peaks on tune (MSD) background
Higher than normal Poor peak shapes for
baseline reading on FID gaseous VOCs (purge and
trap)
Extra peaks visible in run
Extra peaks visible in run
OMI™-2 color change

Injector Maintenance
❚ Change (as needed):

1. Liner and O-ring*
2. Seal and washer *
*H/P™ GCs
❚ Inspect the inlet periodically

-Look for contamination in the liner
-Look for residue on the seal

Using the right liner and injection
technique can also prevent problems:
❚ Split Injection
❙ used for concentrated samples
❙ high flow of carrier gas through liner
during injection
❙ should use liner designed for split injection
❚ Splitless Injection
❙ used for trace analysis
❙ low flow of carrier gas through liner during
injection
❙ inertness and internal volume of liner used
are critical
Some liners used for split
injection:
Cup (unpacked)
Cup (wool packed)
Split/splitless- wool packed

Some liners used for splitless
injection
2 mm ID, straight
Dual-tapered
Single-tapered

If you must clean a liner….
❚ Handle liners with gloves or forceps.

❚ Use clean compressed gas and/or a fine
brush to remove particles.
❚ Rinse liner in an appropriate solvent
and dry with clean compressed gas.
❚ Use mineral acid and/or detergent only
if absolutely necessary.

Using a Guard Column
❚ Choose a guard column which has been

deactivated.
❚ Usually, the ID of the guard matches
the analytical column.
❚ A 5-10 meter length is normally used.
❚ Connect with either a GlasSeal™ or butt
connector.

Common Problems
1 Poor Peak Shapes (either tailing,

fronting, or just generally ugly.)
2 Nonlinearity
3 Baseline Noise and /or Drift
4 Ghost Peaks
5 Missing Peaks / Poor Response
6 Insufficient Resolution
1. Poor Peak Shapes
❚ Fronting can indicate

column overload.
||
||
❚ Tailing can indicate

activity in the system
or improper column
installation.
1. Poor Peak Shapes (cont.)
❚ Generally ugly peaks, such

as a,a-
dimethylphenethylamine,
can be caused by a variety
of problems.

2. Nonlinearity
The most common causes are:
➨Column overload
➨Detector overload
➨Standards preparation
➨Poor peak shape resulting in improper
integration

An Example of Overload:
Peaks have broad bases,

fronting on last few visible in
run.

Preventing column overload for
splitless injections:
❚ Inject a smaller amount / use a 1 ul

syringe.
❚ Use a thicker film column.
❚ Use a column with a wider ID.
❚ Decrease upper limit of calibration
range.
❚ Use a column of slightly different
polarity.
An example of poor peak shape
affecting linearity:
❚ Benzoic acid is
typically of poor
shape when doing
splitless injections.

3. Common causes of baseline
noise / drift.
❚ Column bleed
❚ Dirty detector
❚ Contaminants in carrier gas / carrier
gas purity

Effect of carrier gas purity on baseline
noise:
12000
11500
11000
10500
10000
9500
9000
8500
8000
7500 H2 carrier from tank
7000
6500
6000
5500
5000
4500
4000
3500
3000
2500
2000
1500
1000
500
0
H2 carrier from a generator
1

Column bleed results from the
normal degradation of the
stationary phase.
❚ All columns bleed to some extent.

❚ Bleed increases with temperature.
❚ The amount of bleed will increase in the
presence of oxygen.

A Typical Bleed Profile:
Bleed measured as the

difference between 1 and 2.

Column Bleed on an MSD
❚ Visible as baseline rise in the TIC.

❚ Check spectra for key bleed ions:
❙ PTE™-5: 207, 281
❙ SPB™-1: 73, 207, 281
❙ SPB™-624: 207, 269
❚ Make sure interface temp. is < column
max. temp.

Ion 207 corresponds to a fragment known as D3:
CH 3 CH 3
Si
O O
+
Si Si
CH 3 O CH 3
CH 3

MS spectra of bleed from a PTE™-5 Column
Abundance
Scan 2895 (27.487 min): 1118015.D

207
6000
5500
207
5000
4500
4000
3500
3000
2500
281
2000
1500
73 281
96 133
1000 191
253
500 50
115 162 223 327 355

415
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400
m/z-->

MS spectra of bleed from an SPB™-1 Column
Abundance
Scan 1941 (28.793 min): 0122002.D

11500 73
11000
10500
10000
9500
9000 73
8500
8000
7500
7000
6500
44
6000
207
5500
5000
4500
4000
3500
207 281
3000
2500 147
2000
281
341
1500
1000
96 119 179
500 253 429
313 401
0
40 60 80 100120140160180200220240260280300320340360380400420
m/z-->

MS spectra of bleed from an SPB™-624 Column
Abundance
Scan 8581 (33.704 min): 1022006.D

24000 207
22000
20000 207
18000
16000
14000
269
12000
269
10000
8000
6000 44
253
4000 133 191
73 96
147 177
2000 283
119 322 343
59 163 223239
298
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
m/z-->

MS Spectra of Septa Bleed
Abundance
Scan 604 (7.460 min): 1201001.D

44000 73
42000
40000
38000
36000
73
34000
32000
30000
28000
26000 147
24000
22000
20000
147
281
18000
16000
281
14000
12000
10000
8000
6000
327
45
4000
207
2000 399415
131 191 251 343 383
95 115 163 223 297
0
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420
m/z-->

Prevent column bleed!
❚ Sufficiently purge column with carrier before

ramping it up in temperature.
❚ Make sure carrier gas is filtered for water and
oxygen.
❚ Check integrity of all fittings leading to the
column.
❚ Do not heat the column above its maximum
temp.
❚ Precondition the column prior to use.
4. Ghost Peaks
❚ Residue in the inlet liner and at the

head of the column
❚ Contaminated syringe / and or wash
solutions on an autosampler.
❚ Sample carryover
❚ Contaminated carrier gas

If pieces of septa get into an inlet liner...
2200000
2000000
1800000
1600000
Response test mix, before
1400000
1200000
1000000
800000
600000
400000
200000

…even a simple analysis can be ruined.
3500000
3000000
2500000
Response test mix, after
2000000
1500000
1000000
500000
Time-->

5. Missing Peaks / Poor
Response
❚ Sample decomposition
❙ Activity in the inlet or column
❙ Injection port temperature too high
❙ Sample not stable enough for GC
❙ Standards not stable
❚ Coelution
❚ Insufficient run time / final temperature
❚ Sample not volatile enough for GC
❚ Improper column installation
Nasty samples can damage a column
by creating active sites:
450000 Before Sample Injection

400000
2-methyl-3,5-dinitrophenol
pentachlorophenol
350000
2,4-dinitrophenol
300000 4-nitrophenol
250000
200000
150000
100000
50000

Here, the responses of some acids
were affected:
Abundance
After sample injection
2,4-DNP & 4-NP should be here

900000
Pentachlorophenol should be here

800000
2-methyl-3,5-dinitrophenol
700000
600000
500000
400000
300000
200000
100000
Time-->

Response can also be affected by the
position of the column in the inlet:
2800000
2600000
2400000
2200000
2000000
8 mm above top of ferrule
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000

Here, the column was not inserted far
enough:
2200000
2000000
1800000
1600000 5 mm above top of ferrule

1400000
1200000
1000000
800000
600000
400000
200000
0

Here, the column was inserted too far:
1800000
1600000
1400000
1200000
20 mm above top of ferrule
1000000
800000
600000
400000
200000

6. Insufficient Resolution
❚ Wrong column
❙ Longer columns increase resolution.
❙ Smaller ID columns increase resolution.
❙ A different phase altogether may be
needed.
❚ Wrong Conditions
❙ Carrier gas flow too fast or slow .
❙ Oven ramp rate too fast.

Recommended Reading
Supelco Bulletins
1. 741: The Supelco Guide to Leak-Free Connections
2. 783: Cleaning Flame Ionization Detectors
3. 853: Capillary Troubleshooting Guide
4. 875: Supelco Capillary GC Selection Guide
5. 895: Installation and Maintenance Instructions for
.25 mm and .32 mm ID Fused Silica Capillary
Columns
6. 897: Installation and Maintenance Instructions for
.53 mm ID Fused Silica Capillary Columns
7. 898: Gas Management Systems for GC
8. 899: Capillary GC Inlet Sleeve Selection Guide
9. 916: Purge and Trap System Guide
10. 918: Selecting Purifiers for Gas Chromatography
Help is just a phone call or
mouse click away!
❚ Supelco Technical Service

phone: 1-800-359-3041
email: techservice@supelco.sial.com
❚ Supelco Customer Service
phone: 1-800-247-6628
email: supelco@sial.com
❚ Sigma-Aldrich Website
www.sigma-aldrich.com

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SUPELCO

❚ Basic Troubleshooting Strategy

©1999 Sigma-Aldrich Co. SUPELCO

❚ Have appropriate equipment and

©1999 Sigma-Aldrich Co. SUPELCO

Electronic Leak Detector

©1999 Sigma-Aldrich Co. SUPELCO

©1999 Sigma-Aldrich Co. SUPELCO

❚ Check first to see if a “fix” for the

©1999 Sigma-Aldrich Co. SUPELCO

Problem was Install

©1999 Sigma-Aldrich Co. SUPELCO

? Is my starting temp. low enough to allow

©1999 Sigma-Aldrich Co. SUPELCO

❚ Install and maintain proper purification

©1999 Sigma-Aldrich Co. SUPELCO

©1999 Sigma-Aldrich Co. SUPELCO

Impurity / Maximum Concentration

©1999 Sigma-Aldrich Co. SUPELCO

Carrier Supelcarb HC Mole Sieve 5A OMI -2

Air Mole Sieve 5A

P-5 OMI -2 OMI -2

©1999 Sigma-Aldrich Co. SUPELCO

Hydrocarbon Traps Molecular Sieve 5A

©1999 Sigma-Aldrich Co. SUPELCO

❚ Change (as needed):

❚ Inspect the inlet periodically

©1999 Sigma-Aldrich Co. SUPELCO

Cup (wool packed)

Split/splitless- wool packed

©1999 Sigma-Aldrich Co. SUPELCO

©1999 Sigma-Aldrich Co. SUPELCO

❚ Handle liners with gloves or forceps.

©1999 Sigma-Aldrich Co. SUPELCO

❚ Choose a guard column which has been

©1999 Sigma-Aldrich Co. SUPELCO

1 Poor Peak Shapes (either tailing,

❚ Fronting can indicate

❚ Tailing can indicate

❚ Generally ugly peaks, such

©1999 Sigma-Aldrich Co. SUPELCO

The most common causes are:

©1999 Sigma-Aldrich Co. SUPELCO

Peaks have broad bases,

©1999 Sigma-Aldrich Co. SUPELCO

❚ Inject a smaller amount / use a 1 ul

©1999 Sigma-Aldrich Co. SUPELCO

©1999 Sigma-Aldrich Co. SUPELCO

©1999 Sigma-Aldrich Co. SUPELCO

❚ All columns bleed to some extent.

©1999 Sigma-Aldrich Co. SUPELCO

Bleed measured as the

©1999 Sigma-Aldrich Co. SUPELCO

❚ Visible as baseline rise in the TIC.

©1999 Sigma-Aldrich Co. SUPELCO

©1999 Sigma-Aldrich Co. SUPELCO

Scan 2895 (27.487 min): 1118015.D

115 162 223 327 355

©1999 Sigma-Aldrich Co. SUPELCO

Scan 1941 (28.793 min): 0122002.D

©1999 Sigma-Aldrich Co. SUPELCO

Scan 8581 (33.704 min): 1022006.D