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Manual For SP1 7890-0166 and G3445B Opt 524

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

Refinery Gas Analyzer for


Sour Gas samples up to
C6+

Specials and Solutions Group


For use with G3445 Option 524 and G3440 SP1 7890-0166
This manual only contains information specific to the special parts or
application ordered. Customers should first become familiar with the
Gas Chromatograph, ChemStation software or Mass Spectrometer by
using the documentation supplied with these products.

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General information
This GC is configured to analyze refinery gas containing high concentrations of hydrogen sulfide.
The analyzer is a four valve system using 1/8 inch packed columns with early back-flush of the C6+
components. A typical plumbing diagram is shown below. The GC has two channels, one dedicated
to hydrogen analysis and the other for permanent gases and hydrocarbons. Fig. 1 shows a
configuration with two pneumatics control modules (PCM) acting as flow sources. The instrument
can also be configured with a packed inlet (PPI) and a pneumatics control module (PCM) or two
packed inlets, although there is no technical advantage on doing so.


FLOW
Valve System
INJECTION VALVE COMPARTMENT
Date :
Order No :
S/N :

Item :
DETECTOR
OVEN LEFT SIDE
SOURCE PORT BLOCK 2 BLOCK 1

4/802/869 1/805/869

Col 5 Col 2
Back Aux

Ch 2 7 6 5 7 6 5
Side
8 4 8 4
PCM C OUT
9 3 9 3
Ch 1 SAMPLE
10
1
2 SAMPLE 10
1
2

IN
Back Inl Col 1
LOOP Back

TCD
(220)
Front Inl
Front

TCD
(220)
Col 4 Col 3
Front Aux 4 4
3 3
Ch 2 5 5
6 2 6
PCM A 1 1
2

Ch 1

3/702/868 2/702/868
Options SP1 options Remarks
2x220,2x309,2x503,2x702,754,802,805, 7890-0166
2x868,2x869

Fig. 1

The columns used in this analyzer are as follows. All are 1/8 inch nickel tubing.

Column #1 2Ft 20% Sebaconitrile column in nickel


Column #2 30Ft 20% Sebaconitrile column in nickel
Column #3 6Ft HayeSep Q 80/100 in nickel
Column #4 10Ft Molecular Sieve 13X in nickel
Column #5 4Ft Molecular Sieve 13X in nickel

All valves are in Hastelloy C for corrosion resistance requirements.


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Analysis Sequence
Permanent Gases and Hydrocarbons Channel
The diagrams below show the sequence of the analysis. The order of the columns is as follows:

30 ft Sebaconitrile 2ft Sebaconitrile HayeSep Q Mole Sieve 13X TCD

1. Injection and first minute of the run.

C5-C1,CO2,CO,N2 O2 C 6+

Note that the sample is injected onto the short Sebaconitrile column.

2. Backflush and reverse flow of the short Sebaconitrile.

C5-C2,CO2,CO,C1 N2 O2 C6+

C6 and heavier compounds come out early in the chromatogram as one peak.

3. Transfer of light compounds to the Mole Sieve column. Heavier compounds distribute along
the first two columns

C5-C3,CO2 C2 's H2S CO C1 N2 O2

Heavier compounds distribute along the first two columns

4. Start transfer hydrogen sulfide and ethane / ethylene into the HayeSep Q column. Light
compounds move further down into the MolSieve column.

C5 's C4 's C3 's CO2 C2 C2= H2S CO C1 N2 O2

Light compounds move further down into the MolSieve column.

5. Trapping of the light compounds in the MolSieve column. Hydrogen sulfide and C2
hydrocarbons elute form the Sebaconitrile columns into the HayeSep Q column.

C5 's C4 's C3 's CO2 C2 C2= H2S CO C1 N2 O2

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Hydrogen sulfide and C2 hydrocarbons elute form the Sebaconitrile columns into the HayeSep Q
column.

6. Trapping of the ethane / ethylene compounds and hydrogen sulfide in the HayeSep Q
column.

C5 's C4 's C3 's C2 C2= H2S CO C1 N2 O2 CO2

Start eluting carbon dioxide and hydrocarbons heavier than C2 into the TCD

7. Continue eluting hydrocarbons from propane to pentanes from the Sebaconitrile columns into
the TCD.

C2 C2= H2S CO C1 N2 O2 C5

8. Start eluting hydrogen sulfide and ethane / ethylene from the HayeSep Q column into the
TCD.

C2 C2= CO C1 N2 O2 H 2S

9. Finish eluting ethane from the HayeSep Q column into the TCD.

CO C1 N2 O2 C2

10. Release and elution of the light compounds from the MolSieve column into the TCD.

N2
CO C1 O2

11. End of the elution of light compounds from the MolSieve column and of the chromatography.

CO

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Installation.
Supply carrier and detector support gases to the GC. Connect helium to PCM A and front TCD.
Connect nitrogen to PCM C and back TCD and power up the GC.

If this is the only factory tested method, then the checkout method set up for the instrument will be
stored in “Method # 9” GC memory position”. Load the GC method pressing [LOAD] [METHOD] [9]
in the GC keyboard or enter the parameters by means of the GC keyboard. Allow the system to
stabilize. If an Agilent ChemStation is being used – bring it up and establish communication with the
GC. Do not resolve the “default” method loaded by ChemStation the first time. Instead “get” the GC
configuration using the “Instrument Configuration” option under the “Instrument” menu. Double click
in the “Agilent 7890A” module in the right side of the screen under “Selected Modules”. The tab
labeled “Connection” has a “Get GC Configuration” button that must be pressed. Close the “GC
Configuration” screen. Following this, go to the “Instrument” menu again and select “Upload method
from Agilent 7890A“ menu option or if the ChemStation is rev. C.01.02 or higher, then go to "Edit
Agilent 7890A Parameters" under the "Instrument" menu view and press the button labeled “Upload
from Instrument” at the bottom of the screen. Verify that the parameters coincide with the ones listed
in this manual or supplied documentation.
Load the method 78900166.M supplied on the CD-ROM disk. Resolve the method if necessary and
save it into the computer’s hard drive.

NOTE: Some conditions might not appear exactly as described here, specially the valve timing due
to column variability between the original design and your current instrument. Check the “Procedure
for a New Setup” section in case of doubt.
=====================================================================
Agilent 7890A
=====================================================================

Oven
Equilibration Time 1 min
Max Temperature 150 degrees C
Slow Fan Disabled
Oven Program On
60 °C for 41 min
Run Time 41 min

Column #1
Agilent RGA column set
150 °C: Packed
In: PCM A-1 He
Out: Front Detector TCD

Flow Program On
28 mL/min for 0 min
Run Time 41 min

Column #2
Agilent G3591-82012 4 ft. MolSieve 13X
150 °C: Packed
In: PCM C-1 N2
Out: Back Detector TCD

Flow Program On
28 mL/min for 0 min
Run Time 41 min

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Front Detector TCD
Heater On 250 °C
Reference Flow On 40 mL/min
Makeup Flow On 2 mL/min
Const Col + Makeup Off
Negative Polarity Off
Filament On

Back Detector TCD


Heater On 250 °C
Reference Flow On 40 mL/min
Makeup Flow On 2 mL/min
Const Col + Makeup Off
Negative Polarity On
Filament On

Valve 1
Other Off

Valve 2
Other Off

Valve 3
Other Off

Valve 4
Other Off

PCM A-1 He: Supplies Column 1

PCM A-2 N2
***Excluded from Affecting GC's Readiness State***
Pressure Program Off
32.225 psi for 0 min
Run Time 41 min

PCM C-1 N2: Supplies Column 2

PCM C-2 N2
***Excluded from Affecting GC's Readiness State***
Pressure Program Off
10 psi for 0 min
Run Time 41 min

Valve Box
Heater On 100 °C

Signals
Signal #1: Front Signal Save On
10 Hz
Signal #2: Back Signal Save On
10 Hz
Run Time Events
Time (min) Event Position Setpoint
0.01 Valve Valve 2 On
0.01 Valve Valve 3 On
0.04 Valve Valve 4 On
0.05 Valve Valve 1 On
0.60 Valve Valve 4 Off
2.00 Valve Valve 1 Off
5.05 Valve Valve 3 Off
6.05 Valve Valve 2 Off
7.05 Valve Valve 3 On

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7.20 Valve Valve 2 On
25.1 Valve Valve 2 Off
34.7 Valve Valve 3 Off
Procedure for a New Setup

This procedure will have to be carried out on a new GC or if new columns are installed or the
present columns are re-conditioned. If new columns are being installed, or present columns need to
be conditioned, condition columns as indicated in the Appendix A

Set up of needle valves


1. Ensure that you have the following conditions set up. Also ensure that you have about 120 psi as
the supply pressure for helium for the front inlet.

Oven Temp 60 C


Column flow 28 ml/min (Typically driven by PCM A)
Valve 1 OFF
Valve 2 OFF
Valve 3 OFF.

2. Monitor the head pressure of the columns by looking at the ‘Actual’ pressure for the main
channel of the Pneumatics Control Module or PCM A-1 (or the corresponding flow supply for the
permanent gases and hydrocarbons channel). When this is steady, note the value.

3. Turn Valve 3 ON by using the GC keyboard.

4. Adjust the needle valve associated with Valve 3 to give the same head-pressure noted in step 2
+/- 0.5 psi. The system may take some time to react to changes, be patient.

5. When this has been done, turn Valve 2 ON by using the GC keyboard.

6. Adjust the needle valve associated with Valve 2 to give the same head-pressure noted in step 2
+/- 0.5 psi. The system may take some time to react to changes, be patient.

Setting the backflush time for valve 4


1. Connect up a cylinder of Refinery Gas Sample, P/N 5080-8755, to the sample inlet line.

2. Clear the run table and then add the following

Valve 2 ON time 0.01


Valve 3 ON time 0.01
Valve 4 ON time 0.04.

3. Save the method as 78900166.M. Flush the sample loop with the gas mixture. Start the method.
As soon as the hydrogen peak has eluted, note the time and manually turn Valve 4 OFF by
means of the GC keyboard. Stop the run. The chromatogram should be similar to Fig. 2 below.

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Fig. 2

4. Enter into the run time table

Valve 4 OFF Backflush time noted.

Set backflush time for V1

5. Add the following to the run time table. Note that Valve 1 should turn ON after valve 4 to prevent
helium from diffusing into the sample loop of V4 and influencing the hydrogen analysis. Valve 2
and Valve 3 remain in ON position as in step 2 for this part of the procedure.

Valve 1 ON time 0.05


Valve 1 OFF time 1.70 minutes.

6. Flush the sample loop with the gas mixture and start the method. The chromatogram that you
get should be similar to that in Fig. 3 shown below.

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Fig. 3

7. When the run has finished, integrate the runs and make a note of the area of the trans-2-butene
peak and the area of the n-pentane peak.

8. An Excel spreadsheet will help in the task of setting up the valve 1 backflush timing. If Excel is
not available, make up a table shown in Fig. 4 below. The ratio column is the value of the trans-
2-butene peak area divided by the n-pentane peak area. The %Change column is the (change in
ratio/previous ratio) x 100 or ((previous ratio - current ratio)/previous ratio) x 100. Note: this
%Change calculation is valid upon the second run on this experiment.

9. Repeat the above run with Valve1 OFF time changing from 1.80 to 2.20 in 0.1 minute
increments. Note the areas of the trans-2-butene peak and the n-pentane peak for each new run
as you go.

10. Fill out the cells in the Excel spreadsheet you created. You only need to add the areas for the
trans-2-butene peak and the n-pentane peak.

11. When all of the data has been entered, note in the last column (%Change) the first cell from the
top where the number is less than 1%. Note the switch time. In the example below this would be
2.0 minutes. This means that the change of n-pentane peak area is no longer affected by the
backflush time of the valve (this is, is not being backflushed itself), but only by small area
changes found on both peaks run over run. Therefore, the whole n-pentane peak is clearing the
pre-column into the analytical column and into the detector.

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Fig. 4

12. Enter this time as the V1 OFF time in the events table of the method.

Set valve timings for V2 and V3


13. Load up the data file that holds the data for the switch time you have selected in the previous
steps. Note the following times in the chromatogram as shown in Fig. 5 below.

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Fig. 5
14. Define the following events:

-Time A = tick mark time for first peak – 0.5 minutes

Enter into the run time table

Valve 3 OFF Time A.


Valve 3 ON Time A +2 minutes

-Time B = this is the start tick mark time for the ethylene/ethane peak – 0.2 minutes

Enter into the run time table

Valve 2 OFF Time B

-Time C = this is the start tick mark time for the CO2 peak – 0.2 minutes.

Enter into the run time table

Valve 2 ON Time C

-Time D = this is the stop tick mark time for the n-pentane peak + 0.5 minutes

Enter into the run time table

Valve 2 OFF Time D.

Verify that the following entries are still present in the run time table

Valve 2 ON Time 0.01


Valve 3 ON Time 0.01

15. Save the method. Flush the sample loop with the gas mixture and start the method. The
chromatogram that you get should be similar to that in Fig. 6 shown below.

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Fig. 6

IMPORTANT: When the run has finished, manually turn Valve 3 OFF and allow the peaks to
elute from the MolSieve column as they were captured in the previous run and never released

16. Based in the resulting chromatogram from the previous step, define the following additional
events:

-Time E = this is the stop tick mark time for the Ethane peak + 0.5 minutes

Enter into the run time table

Valve 3 OFF Time E

17. Save the method once more. Flush the sample loop with the gas mixture again and start the
method. The chromatogram that you get should be similar to that in Fig. 7 shown below (for both
channels).

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Fig. 7

It is possible to present the chromatographic results merged into one window by superposing the
signals. With the latest ChemStation revisions and GC firmware is also possible to switch detector
signals after the elution of the hydrogen peak in the back TCD to the rest of the components of the
sample in the front TCD. Zeroing the signals and freezing the values between the signal switch
further contributes positively to the overall aspect of the chromatographic result.

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About hydrogen sulfide (H2S)
It is expected in this analyzer to determine the presence of hydrogen sulfide (H2S) in the samples or
standards. Agilent Technologies does not provide this compound in the Refinery Gas Sample, P/N
5080-8755 due to its reactive nature and limited shelf life. However, each instrument is ready and
tested for the presence of hydrogen sulfide in the analysis. The H2S peak is visible after the n-
pentane peak (right after Time D set in step 14 of this guide) and before the ethylene peak (not
present in the example chromatogram). A standard with a small amount of hydrogen sulfide is
shown below in Fig. 8.

Fig. 8

The tailing observed in the H2S peak is most likely due to the highly polar nature of this compound
and its strong tendency to reversibly interact with various materials, including stationary phases of
the analytical columns.

Calibration
Connect up a calibration gas to the GC, purge the sample loop with the calibration gas and allow the
pressure in the loop to come down to atmospheric pressure before starting the run. At the end of the
run, calibrate the GC.

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Tips on running the analyzer.
Sample introduction
To get reproducible results, do NOT start the GC when sample is flowing through the sample loop.
Always fill the loop and wait for about 15 seconds for the pressure in the sample loop to equilibrate
to atmospheric pressure before starting the run.

To run the GC as an analyzer automatically proceed as follows.

As stated above, it is not recommended to have flow through the sample loop when injecting the
sample into the GC. You will need a way to control the sample gas. One way is to use an external
solenoid valve controlled by the GC. The pressure of the sample to the valve should be in the 5 to
10 psi range (35 to 70 Kilopascals). The valve should be an ON/OFF type of valve. If you wish to
control this directly from the GC it should operate at 24 Volts DC and with a power rating of no more
than 1.8 watts.

Agilent cable P/N G1530-60590


Connect to
EVENT socket

White Black

Sample vent line

7890 GC
Sample in 24 V Solenoid
at 5-10 psi valve 1.8 W

The 7890 has the possibility to control 8 valves. Four of these, Valve 1 to Valve 4 are ‘internal’
valves and are used to control the valves installed on top of your instrument. The other 4 valve
controls are available at the rear of the GC through the EVENT socket. Valve 5 and Valve 6 are 24
Volt outputs (1.8 watts). Valve 7 and Valve 8 are contact closures. As shown on the diagram, the
solenoid valve would be controlled by the Valve 6 command.

To start the GC automatically, one Valve MUST be defined as a “Gas Sampling valve”. See
appendix B for information on how to configure valves.

The picture below shows a screen shot of the valve configuration screen where:

V1 to V3 are the switching valves used for the analysis


V5 is the “dummy” gas sample valve
V6 is used for the solenoid valve

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The sample can be controlled by entering Valve 6 ON, waiting about 15 seconds, then entering
Valve 6 OFF. Wait 10 seconds for the pressure in the sample loop to come down to ambient
pressure, and then press START run or start the method from the Chemstation.

A macro is supplied that will do this automatically. On the 7890 you must have ChemStation Rev
B.03.02 or higher. Copy the macro file valve6.mac from the CD disk into the CORE directory of the
chemstation (usually c:\chem32\core). To get this macro to run automatically from the chemstation,
go into the ‘Method and Run Control’ view and click the ‘Method’ menu item and then the resulting
‘Run Time Checklist’ menu. The following will appear.

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Click the ‘Pre-Run Command/Macro’ check box and enter the name of the macro, Valve6, into the
box as shown. Then press ‘OK’. A program listing of this macro is given in appendix C.

The GC, with the Agilent Chemstation, can be run in four different modes. These are (a) single
analysis, (b) a batch run, (c) continuous analysis and (d) timed analysis. All modes assume that you
have set up a valve to control the sample loading and a valve is configured as a Gas Sampling
Valve.

Single Run
From the chemstation just click the ‘Run method’ item in the ‘Run Control’ menu of the ‘Method and
Run Control’ screen.

Batch Run
This would be used for running a set number of runs one after the other. You will need to set up a
simple sequence. First, set up the sequence table which is accessed from the Sequence Menu in
the Method and Run Control screen.

Enter a Enter number of runs Enter ‘Sample’ for


value here you want here sample type

When this has been done, load up the Sequence Parameters screen as shown below which is also
accessed from the Sequence Menu. To make it easier to find your files it is suggested that you click
the Prefix/Counter radio button and enter a Prefix for your files and set the counter. You may also
set up a sub directory in which your files are stored.

To start the sequence, click the ‘Run Sequence’ item in the ‘Run Control’ menu.

Please note that if you have finished a sequence and wish to repeat it, the old data files will
be over written. Either change the subdirectory, the prefix or the starting position for the
counter.

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Continuous Run.
The easiest way is an extension of the Batch run method. You can set up a maximum number of 99
for the inj/location entry. If you need more than 99 runs, you enter a new line which also has 99 runs.
You can have 999 lines in the sequence table. This will give you 98,901 runs. For a 30 minute
analysis time, this is enough for 5 years!

Timed Analysis
This when you want to automatically make a run every hour, for example.

First set up the Sample Information screen.

Set to Prefix/Counter

Set Prefix and where the counter starts

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Set the Prefix /Counter button and then enter the Prefix for your files and where the counter should
start from.

Now start up the Chemstation Scheduler which you can access form the ‘View’ menu in the ‘method
and Run Control’ screen.

Set this to your instrument!!!!

Make sure that you have set the scheduler to your instrument. Enter the date and time that you wish
to start a run. For the command enter ‘runmethod’. For the ‘Mode’ enter ‘DoDaily’. Set the next entry
to be one hour later, for example. If you wish to run every hour, you will need 24 entries in the table.
The system will run as follows. If we take the first entry in the table above, the GC will inject the
sample at 15.00 hours on 9th March 2008. When it has finished, it will automatically add an entry
into the table for 15.00 on the 10th March 2008. This happens when you choose ‘DoDaily’ as the
mode.

When you have finished adding your entries, save by clicking the ‘disk’ icon and then minimize the
scheduler. The scheduler must be running for the entries to be executed.

The scheduler table can only hold 200 lines. If you are automatically adding lines, this can soon fill
up. You will need to go into the scheduler and remove any lines that have been executed. These will
be the lines that are ‘grayed’ out.

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Appendix A
Conditioning the columns.

Molecular Sieve 13 X column 10 Foot column

This column should be removed from the GC and installed into a similar GC oven which does not
have valves installed on the top and does not have any other columns installed in the oven.

If a second GC oven is not available, remove all other columns from the oven, remove the valve box
top so that the valves are exposed to atmospheric temperature and turn off the heat to the zones
that heat the valves.

Condition at 350°C for 8 hours with helium gas at 30-40ml/min.

HayeSep Q

You will also need to remove the other columns, but this can be conditioned in this GC. If the GC
has a packed inlet, connect one end of the column to the packed inlet and allow the other end to
hang free. If the GC does not have a packed inlet, remove the Sebaconitrile columns and connect
the HayeSep Q column to the line going to port 6 of Valve 1 or “Column 2 In” connection. Make sure
the Valve 1 remains in OFF position over the length of the conditioning process.

Condition at 225°C for 4 hours with helium gas at 30-40ml/min

Sebaconitrile columns

These columns can be conditioned in the oven with the other columns installed. However, ensure
that Valve 2 and Valve 3 are on the ON position.

Condition at 90°C for 4 hours with helium gas at 30-40ml/min.

Molecular Sieve 13 X column 4 Foot column

This column should be removed from the GC and installed into a similar GC oven which does not
have valves installed on the top and does not have any other columns installed in the oven.

If a second GC oven is not available, remove all other columns from the oven, remove the valve box
top so that the valves are exposed to atmospheric temperature and turn off the heat to the zones
that heat the valves.

Condition at 350°C for 8 hours with nitrogen or argon gas at 30-40ml/min.

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Appendix B

Configuring valves on the 7890.


Valves can be configured into the 7890 several ways, with some confusion. The choices are as
follows:

Gas Sampling
Switching
Other
MultiPosition
Not Installed.

Multiposition.

Used to configure a valve as a stream selection valve. Only ONE valve on the GC may be
configured as a multiposition valve.

Not Installed

Used to uninstall a valve.

Other

Used to define something that is not actually a valve. For example the valve control could be used
to switch a relay which controls some other piece of equipment. This still acts as a valve control for
all intents and purposes.

Switching

Used to control a valve. Valve can be controlled from the run table or from the keyboard. Turning
the valve on has no effect on the GC status (see Gas Sampling). Valve will NOT turn to its original
position at the end of the run. To do this you will need a Run Table entry.

If you have a valve hardware configured as a gas sampling valve but configured in the 7890 as a
switching valve, you cannot start the run remotely from the GC ChemStation.

Gas Sampling

Now this is where the confusion starts. If a valve is configured as a Gas Sampling valve, the
following will happen.

 The GC can be started remotely from the GC ChemStation providing the injection source has
been set to "GC Valve".
 An automatic sequence can be set up.
 The valve will return to the OFF position at the end of the run.

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 If you press "START" on the GC, the GC program will start but the Gas Sampling valve will NOT
inject the sample.
 If Valve 1 is configured as a Gas Sampling valve and from the GC keyboard you enter Valve 1
ON, you will inject the sample AND start a GC run. This can be a nuisance if you are trouble
shooting, as all events in the Run Table will also execute.
 The switch on time of the Gas Sample Valve will NOT appear in the Run Time Table.
 You cannot stagger injection times if you have two or more valves injecting samples.

So what is the best way to set up?

The 7890 has eight valve control functions. It is rare that all are used up. Normally valves 1 to 4 are
used to actually control valves on the GC. This leaves valve controls 5 to 8 free. So configure all of
the valves in your valve system as switching valves and configure one of the unused positions as a
Gas Sampling Valve. This will give the following advantages.

 You can control the GC remotely from the GC ChemStation.


 You can set up a sequence.
 If you press "START" on the GC, the GC will start AND your sample will be injected.
 If you enter "Valve 1 ON", valve 1 will switch on but the GC will NOT start a run.
 All switching times will appear in the Run Table.
 You can stagger injection times.

G3445 Option 524 and G3440 SP1 7890-0166 Printed Copies


Rev. A are Uncontrolled
Agilent Technologies, Inc. Page 24 of 24 Date Printed: 18 June 2015

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