Electron Capture Detector For GC-2010/2010Plus ECD

221-40824 Electron Capture Detector For GC-2010/2010Plus ECD-2010 Plus USER’S MANUAL Read the
instruction manual thoroughly before you use the product. Keep this instruction manual for future
reference. Since a radioisotope is used as the raiation source, check the laws and regulations before
installation. ? Shimadzu Corporation 2009. All rights are reserved, including those to reproduce this
publication or parts there of in any form without permission in writing from Shimadzu Corporation.
Information in this publication is subject to change without notice and does not represent a
commitment on the part of the vendor. Any errors or omissions which may have occurred in this
publication despite the utmost care taken in its production will be corrected as soon as possible, but not
necessarily immediately upon detection. Note that Shimadzu does not have any obligation concerning
the effects resulting from the application of the contents of this manual. MS-DOS and MS-Windows are
trademarks of the Microsoft Corporation. Precautions for Safe Operation The ECD-2010 Plus is a
detector for Shimadzu gas chromatograph GC-2010/2010Plus. For safe operation, observe the following
precautions. If not observed, the safety may be compromised. 1. Use the unit only for the purpose for
which it is intended. 2. Follow the procedures, warnings and precautions described in the mamual. 3. Do
not disassemble or modify the unit. 4. For repairs, contact our sales office or service representative.
THREE CATEGORIES OF DANGER SYMBOLS ARE USED THROUGHOUT THE MANUAL. WARNING CAUTION
NOTE Used for situations that may cause death or serious injury. Used for situations that may cause
slight injury or damage to the instrument. Emphasizes additional information or provides tips for easier
operation. Read the safety information in the instruction manual of the gas chromatograph before using
this unit. I 1. Corrosive gas and dust The vital section of the measuring circuit of this detector is shielded
in a case. In view of maintaining the service life and accuracy of the detector, avoid installing in a dusty
or corrosive environment. 2. Discharge of carrier gas Connect a vinyl or teflon tube to the exhaust port
(VENT) when using the detector, and set the other end of the tube on the roof of the building or other
place where no person is likely to come within 1 m from the tube end. 3. Application name plates Stick
the name plates at the position shown below: ECD VENT ECD VENT GC-2010 Plus RADIOISOTOPE
NUCLIDE QUANTITY 63Ni 370Mbq (10mCi) RADIOISOTOPE NUCLIDE QUANTITY 63Ni 370MBq (10mCi) II
Contents Precautions for Safe Operation 1 1.1 1.2 Outline Principle of the ECD (Electron capture
Detector) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Response Characteristics of the Detector . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 2 2 2.1 Parts List Parts List . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . 5 3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 Basic Operation Introduction . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Gas used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 8 Checking the glass insert and the injection inlet septum . . . . . . . . . . . . . . . .
. . . . . . . . 9 Mounting the column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Setting
the flow rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Setting the flow rate of
detector gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 Starting the system . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Setting the detector temperature . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . 14 Setting the temperatures of the column oven and injection port . . . . . . . . . . . . . . . . .
15 Checking the baseline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 Setting the
current value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 Setting the range/attenuation . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 Caution during analysis . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 19 Stopping the system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . 20 3.10 3.11 3.12 3.13 3.14 4 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Key Operation Setting the detector . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Selecting the detector . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 29 Selecting the detector gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 30 Detector ON/OFF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Setting
the range/attenuation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 Setting the current value . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 Zero adjustment . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 35 5 5.1 5.2 5.3 5.4 Service/Maintenance Checking the ECD cell . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 How to Keep the ECD Cell Clean . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 40 Cleaning procedure for ECD Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . 42 Actions to Be Taken in Case There Is the Doubt of Break . . . . . . . . . . . . . . . . . . . . . 44 ECD-2010
Plus i Contents 6 6.1 6.2 Troubleshooting Troubleshooting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 45 Error Message . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49 7 7.1 Disuse Cautions at Disuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 8
8.1 Maintenance Parts Maintenance Parts List . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. 53 9 9.1 Specifications Specifications of the ECD-2010 Plus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . 55 10 Appendix 10.1 10.2 10.3 Structure of ECD Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 57 Calibration Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Conditioning of Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 ii ECD-2010 Plus 1.1
1. 1 Outline 1.1 Principle of the ECD (Electron capture Detector) Radiation (Beta-ray) from the radiation
source (63Ni) sealed in the ECD cell ionizes an inert gas (N2). If a pulse voltage is applied to the electrode
in the cell, electrons are captured, allowing current to flow. If electrophilic molecules enter the cell, the
molecules absorb the electrons to be negatively ionized. Negatively-charged molecules move more
slowly than free electrons and take longer to reach the positive electrode. Additionally, they are more
likely to be bonded with positive ions again. Accordingly, the electrons density in the detector drops so
that a fewer number of electrons to be constant by increasing the pulse. The total number of electrons
to be captured in a unit time (and thus the current) can be maintained constant by increasing the pulse
frequency as the number of electrons decreases ; the variation in the number of pulses is proportional
to the density of the electrophilic molecules passing through the detector1). 1) R.J. Maggs et al., Anal.
Chem. 43 (1971),1966 ΔF = f - f 0 = Ka f : Pulse frequency f0 : Pulse frequency when carrier gas alone is
allowed to flow (Basic frequency) K : Constant determined by electron capture rate and other factors a :
Concentration of electron captivating substance The construction of the system is schematically shown
below. Chromatopac ECD cell Pulse shaper Carrier gas System Block Diagram Amplifier E compares the
average pulse current from the ECD cell with reference current IR and outputs a voltage to the voltage-
frequency converter (VFC) to make the two currents equal. The pulse from the VFC is shaped to have
appropriate width and height before being sent to the ECD cell, closing a control loop. ECD-2010 Plus 1
1.2 1. 1 Outline 1.2 Response Characteristics of the Detector The electron capture detector has an
extremely peculiar response characteristic. The response varies largely depending upon the kind of
compound. Even with the same kind of compound, the response may change largely with minor
differences in the molecular structure, e.g., with racemates. For reference, relative sensitivities for
various compounds are listed below. For the same component, response may vary depending upon the
structure of the detector, temperature, applied voltage, etc. Therefore, the figures below should be
considered as just relative standards. Relative sensitivity for various compounds (example 1)*
Compound 1-chlorobutane 2-chlorobutane 1-chloro-2-methyl propane 2-chloro-2-methyl propane 1-
chloropentane 1-chlorohexane 1-chloroheptane 1-chlorooctane 1, 2-dichloroethane 1, 4-dichlorobutane
1, 1-dichlorobutane trans-1, 2-dichloroethylene cis-1, 2-dichloroethylene chloroform carbon
tetrachloride 1-bromopropane 1-bromobutane bromocyclopentane 1-bromopropene-2 (allyl bromide)
1, 1-dibromoethane 1-iodobutane benzene toluene 2-fluorotoluene 4-fluorotoluene chlorobenzene
bromobenzene 1-butanol di-n-butyl ether acetone methyl butyrate 2, 3-butanedione n-heptyl
trifluoroacetate n-propyl pentafluoropropionate Sensitivity (Unit is arbitrary) 1.0 2.0 1.7 12 1.0 1.1 1.5
1.6 190 15 110 370 90 6 × 104 4 × 105 255 280 280 4 × 103 1.1 × 105 9 × 104 0.06 0.2 0.55 0.55 75 450
1.0 0.6 0.5 0.9 5 × 104 4.5 450 2 ECD-2010 Plus 1 Outline 1.2 Response Characteristics of the Detector
Relative sensitivity for various compounds (example 2)** Compound Hexane Heptane Octane Decane
Chlorobenzene Atrazine Dichloroethane Lead Tetraethyl Benzophenone 2, 4D Tedion Malathion Diethyl
Maleate Thioctane 2, 4, 5, T Kelthane DDD D D T (para, para) DDE Heptachlor Dieldrin Aldrin Lindane
Dibromoethane Fluothane Carbon Tetrachloride Sensitivity (Unit is arbitrary) 0.9 1.2 1.5 2.6 5.5 3,000
20,000 30,000 100,000 125,000 180,000 250,000 550,000 600,000 800,000 1,600,000 2,000,000
2,000,000 3,200,000 4,800,000 8,000,000 10,000,000 11,000,000 11,000,000 16,000,000 400,000,000 *
Phillippe Devaux, Georges Guiochon ; in “Advances in Gas Chromatography 1967”,A.Zlatikis,ed. ** K. P.
Dimik, H.Hartmann ; presented at ACS Winter Meeting Cincinnati, Ohio January 13-18,1963 ECD-2010
Plus 3 1 Outline 1.2 Response Characteristics of the Detector This page is intentionally left blank. 4 ECD-
2010 Plus 2.1 2. 2 Parts List 2.1 Parts List This unit consists of the following contents. Confirm these
contents. List of parts for the ECD-2010 Plus Control unit for the ECD-2010 Plus (excluding the detector
unit) : part No. 221-47733-42 Part name ECD control unit User’s manual (this document) APC flow
controller Thermal insulation cup Label, RI Label, ECD vent Accessories and mounting parts for ECD-2010
Plus Consists of: Screw (2-point Semus) M4 × 8 Washer M4 Column packing, aluminum Pipe insert, G6
Pipe, MN2W-GN2W L350 Molecular sieve filter MS-5A filter Signal cable Pipe MM-GF 300 mm Branch
pipe MM-MF-MF Graphite ferrule adjuster for the ECD-2010 Plus Part No. 221-48455-41 221-40824 221-
73343-41 221-44671 221-07755 221-29747 Qty. 1 1 1 1 2 1 020-46147 023-66140-01 201-35183 201-
36364-01 201-48560-35 221-34121-94 201-36992-84 221-00816-03 201-48561-30 221-72658-92 221-
48610-03 2 2 1 1 1 1 1 1 1 1 1 ECD-2010 Plus 5 2 Parts List 2.1 Parts List This page is intentionally left
blank. 6 ECD-2010 Plus 3.1 3. 3 Basic Operation 3.1 Introduction Chapter 3 covers the basic operational
procedure of the ECD. The key sequence described in this chapter assumes that the parameters are set
prior to the start of the GC in accordance with “6. Analysis flow chart” in the instruction manual for the
GC-2010/2010Plus (CD-ROM version). For the details of operations and key sequence for the gas
chromatograph, refer to the instruction manual for the GC-2010/2010Plus (CD-ROM version). ■
Operation procedure for the ECD <Key sequence> Set the detector gas. ↓ Set the temperature of the
injection port, column oven, and detector nearly at the room temperature. ↓ Press the [Start GC] key
(PF menu) to start the control. ↓ Wait until the air in the ECD cell has been substituted by carrier gas
and makeup gas. ↓ Set the detector temperature and current values. ↓ After the detector temperature
has reached the set value, wait for 10 minutes or more and then set the injection port and column oven
temperatures. ↓ After the baseline has been stabilized, press the [Zero Adj.] key (PF menu) on the
MONIT screen to make the zero adjustment. ↓ Start the analysis. ECD-2010 Plus 7 3.2 3. 3 Basic
Operation 3.2 Gas used Since the ECD is a detector with a high sensitivity, even slight impurities
contained in the carrier gas may affect the stability of the baseline. A Gas Filter (option: 221-05619-01)
and Oxygen trap (option: 221-46985-91) should be mounted along the flow route to clear impurities
from the carrier gas. Both the carrier gas and make-up gas should meet the following purity standard: ■
Carrier gas (supply pressure : 300~980pa) ◎ Helium (most suitable) Purity 99.9999% or higher
(applicable when purity is 99.999% or more) ○ Nitrogen (can be used) Purity 99.999% or higher
(99.9999% or more is recommended) ○ Argon + Methane (5%) (can be used) ■ Make -up gas (supply
pressure: 300~980kpa) ◎ Nitrogen (most suitable) Purity 99.9999% or higher (applicable when purity is
99.999% or more) ○ Argon + Methane (5%) (can be used) 8 ECD-2010 Plus 3.3 3. 3 Basic Operation 3.3
Checking the glass insert and the injection inlet septum For the procedural details, refer to “12. Injection
port” of the instruction manual for the GC-2010/2010Plus. WARNING High temperature You might
suffer burns. Prior to start the work, check that the temperature at each part is below 50°C. CAUTION
In order to prevent seizure or the like, do not turn the screw when the temperature is high. The glass
insert for the injection port differs in shape depending on the injection port type and the split mode.
Check that the proper insert for the sample injection mode is selected, that the silica wool is positioned
properly, that there is no contamination, and that the O-ring for the glass insert has not yet deteriorated
in quality. For split analysis For splitless/WBI analysis Fig. 3.3.1 Glass insert Replace the injection inlet
septum, in principle, when the number of injections reaches one hundred. ECD-2010 Plus 9 3.4 3. 3 Basic
Operation 3.4 Mounting the column For the detailed procedure for mounting the column, refer to “4.
Installing the column” in the instruction manual for the GC-2010/2010Plus. The graphite ferrule shall be
placed in the position (37 mm) indicated in the following figure. This placement is possible using the
supplied graphite ferrule adjuster (P/N. 221-4861003) for the ECD-2010 Plus. Split/splitless injection port
ECD-2010 plus 34mm 37mm Graphite ferrule Capillary column Fig. 3.4.1 Position in which to retain the
graphite ferrule In order to prevent the ECD-2010 Plus from being contaminated, connect the properly
conditioned column. ■ Conditioning the column Mount the column on the injection port only. Send the
gas as in the analytical conditions. Set the column temperature at the analysis temperature plus 20°C
(without exceeding the maximum operating temperature in the isothermal analysis) and then allow the
column to stand for approximately 12 hours. NOTE While the column is conditioned, the detector shall
be sealed. 10 ECD-2010 Plus 3.5 3. 3 Basic Operation 3.5 Setting the flow rate Set the flow rate of the
carrier gas on the screen that is displayed by pressing the [FLOW] key Also set the column and purge. For
the procedural details, refer to “12. Injection Port” of the instruction manual for the GC-2010/2010Plus.
Fig. 3.5.1 ECD-2010 Plus 11 3.6 3. 3 Basic Operation 3.6 Setting the flow rate of detector gas Set the
flow rate of the makeup gas in the following procedure: Press the [DET] key to display the detector’s
condition setting screen. If multiple detectors are mounted, press the [Next Det] in the PF menu to go to
the ECD screen. Press the [Det Gas] key in the PF menu to go to the Makeup gas flow rate setting screen.
Enter the gas type and its flow rate. Turn On the flow controller. In case of the capillary column, set the
flow rate of the makeup gas to 15~60 ml/min. NOTE The detection sensitivity of the ECD-2010 Plus
depends upon the sample concentration in the carrier gas containing the makeup gas. Unless the peak
range expands, the sensitivity increases as the flow rate of the makeup gas decreases. For the
quantitative analysis, make sure to set the flow rate as that of the last analysis. Fig. 3.6.1 12 ECD-2010
Plus 3.7 3. 3 Basic Operation 3.7 Starting the system Press the [SYSTEM] key when the GC-
2010/2010Plus stops. The GC Start Sequence screen will appear. Set the start time to 10 minutes or
more. CAUTION In order to avoid any damage to the ECD cell, set the start time so that the detector
temperature starts increasing after the air in the ECD cell has entirely been substituted with the carrier
gas and makeup gas. Before starting the system, set the temperatures of the column oven and injection
port to nearly the room temperature (25°C). After setting the parameters for starting the GC-
2010/2010Plus, press the [Start GC] key in the PF menu. The GC will start and the control will be
performed for the temperatures at various parts and the flow rates of gases. The control of the ECD
control unit will not be started unless the detector is On. For further details of this procedure, refer to
“7. Starting and Stopping GC” in the instruction manual for the GC-2010/2010Plus. Fig. 3.7.1 ECD-
2010 Plus 13 3.8 3. 3 Basic Operation 3.8 Setting the detector temperature To set the temperature of
the ECD detector, press the [DET] key to display the DET screen. CAUTION In order to prevent the cell
from being contaminated, set the detector temperature to a value higher by at least 20°C than the
maximum temperature of the column oven during the analysis. Using the cursor keys (UP and DOWN),
move the cursor to the temperature row. Enter a value with numeric keys and then press the [ENTER]
key. If the indicated detector is not the ECD-2010 Plus, press the [Next Det] key in the PF menu to
change the detector. (Pressing the toggle key allows you to change the PF menu.) Fig. 3.8.1 NOTE The
detector temperature can be set via either the [SET] or [DET] screen. The value set on either screen will
be reflected on the other screen. To check the baseline, set the range to ×10-1 (×2-3 for attenuation)
and the current value to 1 nA. For the output of digital signals via the GCsolution or other, set the
current value only. To change the current value, move the cursor to the current value on the [DET]
screen using the UP or DOWN cursor keys. Enter a value and then press the [ENTER] key. To change the
range, move the cursor to the range on the [DET] screen. Using the LEFT or RIGHT cursor keys, change
the displayed range value and then press the [ENTER] key. (The attenuation can also be changed in a
similar procedure.) 14 ECD-2010 Plus 3.9 3. 3 Basic Operation 3.9 Setting the temperatures of the
column oven and injection port Press the [DET] key and check that the detector temperature has
reached the set value. After the detector temperature has reached the set value, it takes some time
until the temperature in the ECD cell is equilibrated. Wait for approximately 10~20 minutes and then set
the temperatures of the column oven and injection port. For the detailed procedure, refer to “11.
Column Oven” and “12. Injection Port” in the instruction manual for the GC-2010/2010Plus. For the
injection port, press the [INJ] key to display the Injection Port screen and then set the temperature. For
the column oven, press the [COL] key to display the Column Oven screen and then set the temperature.
Pressing the [SET] key also allows you to set the temperatures. However, the temperature program
cannot be set. CAUTION In order to prevent the ECD cell from being contaminated with matter eluting
from the column, maintain the detector at a temperature higher by at least 20°C than the column
temperature. Fig. 3.9.1 ECD-2010 Plus 15 3.10 3. 3 Basic Operation 3.10 Checking the baseline 3 1. Set
the attenuation of the Chromatopac (analog input) to 3 (2 ) and check that the baseline is stabilized to
the extent that becomes almost flat. For digital signals via the GCsolution or other, set the full-scale
value to 6.4×104 ?V. Fig. 3.10.1 Stabilized baseline 2. If the baseline is not stabilized as shown in
Fig.3.10.2 or if it deflects from the range, see “6.1 Troubleshooting”. Noise Meander Positive drift Others
Negative drift Fig. 3.10.2 Various abnormal baselines Zero adjustment Press the [MONIT] key and also
press the [Zero Adj.] in the PF menu. The signal output will become 0 ?V. If the indication on the
Chromatopac or other deviates from 0 ?V after the zero adjustment has been completed on the GC,
additionally make the zero adjustment on the Chromatopac. For further details, see “4.7 Zero
adjustment”. NOTE The “zero adjust” of the GCsolution is same as the zero adjustment on the GC. But
the Chromatopac can not adjust the detector output signal of GC. The zero adjustment should be done
on the GC before the zero adjustment on the Chromatopac. 16 ECD-2010 Plus 3.11 3. 3 Basic Operation
3.11 Setting the current value The detector current value can be set in a range between 0.00 nA and
3.50 nA (for GC-2010, between 0.00 nA and 2.00 nA). As the current value increases, the signal output
becomes larger. Set a current value for which zero adjustment is possible. In general, the current value
should be large when background is low (e.g. when the detector is still relatively new) and it should be
small when background is high (e.g. when the detector is contaminated). For highsensitivity analysis, the
current value is sometimes set to a large value, however this may increase the background too much,
disabling zero adjustment. To avoid this, set the current value to 2 nA maximum. If the current value is
too small, the output signal becomes so low that it cannot be detected in some cases. Setting a small
current value when background is low sometimes makes the baseline unstable. To set the current value,
move the cursor to the current value line on the [DET] screen using the UP or DOWN cursor key. Enter a
value and then press the [ENTER] key to validate the value. Fig. 3.11.1 ECD-2010 Plus 17 3.12 3. 1.
Analog output 3 Basic Operation 3.12 Setting the range/attenuation If the analog output is connected to
a data processing unit, two types of analog signal output, wide range and linear range are available. To
connect the analog output to a data processing unit compatible with the wide range (the analog input to
the C-R7A, C-R7Aplus, or C-R8A), set the analog signal type to “Wide”. To connect it to any other data
processing unit, set the analog signal type to “Linear”. If Wide is selected, no range selection is required.
However, if the attenuation control on the data processing unit does not work (e.g., an error peak
occurs), the attenuation can be changed on the [DET] screen. There are five attenuation levels from ×1
(2-0) to ×2-4. When the exponential value increases by 1, the output becomes 1/2. Prior to using this
function, calibrate the data processing unit. (See “2.7 Connecting cables to the extended devices” of GC-
2010/2010Plus instruction manual.) If Linear is selected, the range (amplification factor of the amplifier)
can be set in five levels from ×1 (100) to x10-4. The range ×1 provides the largest amplification factor of
the amplifier. The range ×10-1 provides 1/10 that amplification factor, the range ×10-2, 1/100, the range
×10-3, 1/1000, and the range ×10-4, 1/10000. For the high-sensitivity analysis, therefore, use a small
range (×1 or ×10-1). Otherwise, use a large range (×10-2, ×10-3, or ×10-4). Set the signal range of the
detector and the analog signal type on the screen that is displayed by pressing the [DET] key. Fig. 3.12.1
2. Digital output If the digital output is connected a data processing unit compatible with digital signals
(the digital input to the GCsolution and so on), the digital signals are always output at ×1, which means
that no range selection is required. 18 ECD-2010 Plus 3.13 3. 3 Basic Operation 3.13 Caution during
analysis CAUTION Caution on sample 1. Clean up the sample as far as possible, if it is from a biological
source, and then inject it to the gas chromatograph. 2. Do not use a strong electrophilic compound, e.g.,
carbon tetrachloride or chloroform as a solvent. This would cause the baseline to deflect from the range,
requiring longer time before the baseline becomes stable again. NOTE 1. In general, the sensitivity
becomes the highest when the column flow rate of the carrie gas plus the flow rate of the makeup gas is
30~60 ml/min. 2. If helium is used as the carrier gas, the baseline level becomes too high and unstable
when the widebore capillary column or packed column in which the carrier gas flows at a high flow rate
is used. This difficulty in analysis is attributable to the fact that the ionization efficiency per unit time of
nitrogen sent as the makeup gas to the ECD cell decreases. In this case, set the flow rate of the makeup
gas to a slightly larger value. ECD-2010 Plus 19 3.14 3. 3 Basic Operation 3.14 Stopping the system 1. For
completely stopping the GC-2010/2010Plus Select [Stop GC] from the PF menu on the screen that is
displayed by pressing the [SYSTEM] screen. The GC-2010/2010Plus will enter into the stopping sequence
in accordance with the set stop time and flow off time. If the stop time is set, the temperature control,
the background current control for the detector will be stopped after the stop time has elapsed. If the
program operation is used, they will be stopped after the stop time has elapsed following the end of the
program. The control of the carrier gas will continue for the time period specified by the flow off time
after the stop time has elapsed. The flow off time means the time period from stopping the temperature
control to stopping the carrier gas. If this time period is short and if the supply of the carrier gas is
stopped when the column oven temperature remains high, the liquid phase in the column might be
damaged. Set the flow off time considering the time when the column temperature becomes low
enough. The initial value is not set for the flow off time, but set to “Cont.” Therefore, the carrier gas will
continue to flow. When the temperature at each part decreases sufficiently, stop the GC-2010/2010Plus
by turning OFF the power switch located at the lower right part of the GC-2010/2010Plus. For the details
of stopping the GC-2010/2010Plus, refer to the instruction manual for the GC-2010/ 2010Plus. To restart
the GC-2010/2010Plus that has been stopped by the above sequence, do as described in “3.7 Starting
the system”. If the GC-2010/2010Plus is stopped for a long period, close the main valves on the gas
cylinders. Fig. 3.14.1 20 ECD-2010 Plus 3 Basic Operation 3.14 Stopping the system 2. For continuous
operation For the continuous operation, the stopping operation is not required. In the split analysis,
however, the carrier gas can be saved if the split ratio is set to a smaller value. NOTE The cell and flow
path can be maintained to be clean by sending the makeup gas to the cell even if the ECD2010 Plus is
not used. The baseline will become stable earlier when the system is restarted, than in the case where
the makeup gas is stopped completely. ECD-2010 Plus 21 3 Basic Operation 3.14 Stopping the system
This page is intentionally left blank. 22 ECD-2010 Plus 4.1 4. 4.1.1 4 Key Operation 4.1 Setting the
detector Description on the screen Press the [DET] key to display the main screen shown in Fig.14.1.1
and to set the detector temperature, the detector gas flow rate, etc. When the detector is configured in
the line, the setting of the output signal appears in the lower half portion of the screen. For the detector
signal output, refer to “13.5 Setting the Output Signals” of Instruction Manual for GC-2010/2010Plus.
Fig. 4.1.1 Main screen of [DET] key 4.1.2 Set item list DETECTOR CONTROLLER Selection: On/Off,
Default: On When a detector is set to “On”, its current and voltage are controlled. When a detector is
selected in a line and set to “On” here, the detector is used. However, even if a detector is set to “Off”
here, the gas flow and the temperature rises and reaches the setup value if the detector is configured in
a line. TEMP Range: 0.0 ～ 350.0°C, Default: 25.0°C Set the detector temperature. Set usually the
detector temperature to a value a little higher (by approximately 30°C) than the column oven
temperature (final temperature in temperature program) so that adhesion of substances of high boiling
point inside the detector can be prevented. For setting of the maximum temperature, refer to “16.6.4
Setting of maximum temperature” in “16.6 GC Configuration” of Instruction Manual for GC-
2010/2010Plus. ECD-2010 Plus 23 4 Key Operation 4.1 Setting the detector Current Setting range:
0.00~3.50 nA, default value: 0.00 nA Set the value for the current sent to the detector. (for GC-2010,
between 0.00 nA and 2.00 nA) FILTER TIME CONSTANT Selection: 4 ms/5 ms/10 ms/20 ms/50 ms/100
ms/200ms/500 ms/1 s/2 s, Default: 200 ms This is the effect of the signal processing on the detector
signal. As the time constant is larger, noise is smaller and the peak height is lower. Select the optimum
value in accordance with the peak half width. (Refer to “13.4 Time Constant of Filter Signal” of
Instruction Manual for GC-2010/2010Plus.) SIGNAL OUTPUT PORT Selection: Off/Ch1/Ch2/Ch3/Ch4,
Default: (Channel is automatically assigned.) Set the channels for digital and analog signals output from
the gas chromatograph. There are four channels. However, in the case of analog output, only Ch1 and
Ch2 are offered as standard. BACKGROUND SIG. SAVE Selection: Off/Buff 1/Buff 2, Default: Off You can
store fluctuation of the base line as the background in the waveform memory of the gas chromatograph.
BACKGROUND SIG COMP. Selection: Off/Buff 1/Buff 2, Default: Off You can subtract the base line stored
as the background from the actual base line. By this subtraction, stable base line can be output even if
the base line considerably fluctuates. DET SIG SUBTRACTION Selection: Off/DET# 1/DET# 2/DET# 3/DET#
4, Default: Off You can subtract the signal output from another detector from the signal output from the
detector. This function is mainly used in a dual column flow line to subtract the data acquired by analysis
without sample injection from the data acquired by analysis with sample injection so that the
background is eliminated. For the details of “SIGNAL OUTPUT PORT”, “BACKGROUND SIG. SAVE”,
“BACKGROUND SIG COMP.” and “DET SIG SUBTRACTION”, refer to “13.5 Setting the Output Signals” of
Instruction Manual for GC-2010/2010Plus. SIGNAL RANGE Selection: ×1/×10-1/×10-2/×10-3/×10-4,
Default: /×10-1 You can multiply the analog signal by the coefficient “10-x” when the analog signal type
is linear. If the peak is saturated in the data processing unit, change the setting from “×1” to “×101”,
from “×10-2” to “×10-3”, for example. In case of the digital signal, the signal is always output with “×1”.
SIGNAL ATTENUATION Selection: ×1/×2-1/×2-2/×2-3/×2-4, Default: /×2-1 You can multiply the analog
signal by the coefficient “2-x” when the analog signal type is wide. If the peak is saturated in the data
processing unit, change the setting from “×1” to “×2-1”, from “×2-2” to “×2-3”, for example. In case of
the digital signal, the signal is always output with “×1”. 24 ECD-2010 Plus 4 Key Operation 4.1 Setting the
detector ANALOG SIGNAL TYPE Selection: Linear/Wide, Default: Linear Set this item when the GC is
connected to the chromatopac in the analog format. Wide ... Select it when connecting the GC to the C-
R8A/C-R7A/C-R7A plus. The signal raised to the “1/2” power is output from the GC, then the signal
received by the chromatopac is squared. When connecting the GC to the C-R8A/C-R7A/CR-7A plus for
the firs time or replacing the chromatopac, set the detector signal output to “Off” and perform
calibration. For the calibration procedure, refer to “2.6 Connection of External Unit” of Instruction
Manual for GC-2010/2010Plus. Linear ... Select it when connecting the GC to any chromatopac other
than the C-R8A/CR7A/C-R7A plus. When connecting the GC to the C-R8A/C-R7A/C-R7A plus and setting
“ANALOG SIGNAL TYPE” to “Linear”, the optional signal cable (linear, P/N 221-47251-92) is required.
4.1.3 PF menu list Description Sets the flow rate of makeup gas. Changes over to setup screen for
another installed detector. You can change over screen by pressing [DET] key on detector screen. PF
menu Det Gas Next Det ECD-2010 Plus 25 4 Key Operation 4.1 Setting the detector 4.1.4 Checking the
installation state setting Pressing the [FUNC] key and selecting “7. Service/Maintenance” in the screen
that appears displays the sub-screen shown in the figures. 1. Installation state setting (position) Pressing
the numerical key [1] or using the cursor key (up/down), place the cursor on “1. Installation (Position)”
and press the [ENTER] key. Fig. 4.1.2 1) Check that the ECD-2010 Plus has been recognized. When ECD
is not displayed, control unit may not be installed correctly or a failure may have occurred. 2) Confirm
that the installation position of the unit is set correctly. When changing, move the cursor to the
applicable column using the cursor keys (up/ down), input numerical values, and press the [ENTER] key.
The relation between the installation position and the number is as follows: 26 ECD-2010 Plus 4 Key
Operation 4.1 Setting the detector (0 = Not installed, 9 = Installed at the position other than those in the
figure.) 8 7 6 4 3 2 1 Top view Fig. 4.1.3 2. Setting the installation state (piping) If “7.
Service/Maintenance” is selected on the screen that is displayed by pressing the [FUNC] key, the
subscreens shown below will appear. Press the numeric key [2], or position the cursor on “2. Installation
(Piping)” using the cursor keys (UP and DOWN) and then press the [ENTER] key. Check that the flow
controller for the detector gas (makeup gas) is set properly. Fig. 4.1.4 Cont. Type The control unit type
is automatically recognized and displayed. When this is not displayed, the control unit may not be
mounted correctly or a failure may have occurred. ECD-2010 Plus 27 4 Key Operation 4.1 Setting the
detector Slot No. Select the APC slot number connected to the detector. The DET APC No. and Unit type
are automatically displayed when SLOT is set. Also, “APC (1ch)” is used for ECD. Heater port This is the
temperature control port of the detector to which flow controller set in the slot is connected. Set DET 1
when the DET1 is connected to the ECD detector and DET2 when connected to DET2. For the details,
refer to “16.7 Service and maintenance” in GC-2010/2010Plus Instruction Manual (CD-ROM version).
4.1.5 Checking the detector setting of line configuration Press the [SET] key and display the SET key
screen. Press [Line Confg] of the PF menu and display the sub-screen of the line configuration. Fig. 4.1.5
Confirm that ECD in the detector column is set to an appropriate line. When changing the line
configuration, move the cursor to the ECD line using the cursor keys (up/ down), select the line number,
and determine the selection by pressing the [ENTER] key. For the details, refer to “8. Setting the
Analytical Parameters and File Management” in the GC2010/2010Plus Instruction Manual (CD-ROM
version). 28 ECD-2010 Plus 4.2 4. 4 Key Operation 4.2 Selecting the detector The key operation and the
screen display when selecting the detector are as follows: Pressing the [DET] key displays the setting
screen of the detector. When more than one detector is loaded, the setting screen of the currently
selected detector will be displayed. Press the toggle key to select the PF menu. Pressing the [Next Det]
can select the other detectors. When no detector is connected, pressing the [DET] displays “Detector is
not installed”. When changing from FID of DET#1 to ECD of DET#2, the screen is changed as follows: Fig.
4.2.1 ECD-2010 Plus 29 4.3 4. 4 Key Operation 4.3 Selecting the detector gases Press the [DET] key to
display the [DET] screen. Select Detector Gas from the PF menu. The [DET Gas] screen will appear. Set
the type of gas to “N2”. Set the flow rate of the makeup gas using the following values as guidelines: ■
For the capillary column: makeup gas (N2) -- 15 to 40 ml/min (50 to 100 kPa) ■ For the packed column:
makeup gas (N2) -- 5 to 10 ml/min (20 to 40 kPa) Fig. 4.3.1 PF key Return: Returns to the detector
setting screen. Program: Goes to the detector gas flow rate program screen. On/Off: Toggles between
turning ON and OFF the control for the flow rates of detector gases NOTE 1. The detection sensitivity of
the ECD-2010 Plus depends upon the sample concentration in the carrier gas containing the makeup
gas. Unless the peak range expands, the sensitivity increases as the flow rate of the makeup gas
decreases. For the quantitative analysis, make sure to set the flow rate as that of the last analysis. 2. To
purge the detector connecting part of the column, send the makeup gas to even the packed column. 3.
The cell and flow path can be maintained to be clean by sending the makeup gas to the cell even if the
ECD-2010 Plus is not used. The baseline will become stable earlier when the system is restarted, than in
the case where the makeup gas is stopped completely. 30 ECD-2010 Plus 4 Key Operation 4.3 Selecting
the detector gases Flow rate program for detector gases The flow rate program may be set for a
maximum of seven stages. To set the program, do as in the case with the carrier gas program. For
further information, refer to “13.2.3.4 Flow rate program for detector gas” of the instruction manual
(CD-ROM version) for the GC-2010/2010Plus. Fig. 4.3.2 Under the general analytical conditions, the
flow rate program for the detector gases is not necessary to use. ECD-2010 Plus 31 4.4 4. 4 Key
Operation 4.4 Detector ON/OFF Using the UP and DOWN cursor keys, position the cursor on the desired
item. Select ON or OFF by horizontally moving the cursor, and then press the [ENTER] key. Fig. 4.4.1
32 ECD-2010 Plus 4.5 4. 4 Key Operation 4.5 Setting the range/attenuation Position the cursor on the
indicated item with the UP and DOWN cursor, change the range with the LEFT and RIGHT cursors, and
then press the [ENTER] key. Normally, use ×10-1. For the high-sensitivity analysis, use ×1. If the analog
signal type is Wide, use ×2-1. Digital signals are output as ×1 regardless of the above setting. Fig. 4.5.1
ECD-2010 Plus 33 4.6 4. 4 Key Operation 4.6 Setting the current value The value for the current sent to
the detector can be set in units of 0.01 nA in the range of 0.00 to 3.50 nA (for GC-2010, between 0.00 nA
and 2.00 nA). The default value is 0.00 nA. The output signal increases as the current value becomes
larger. However, the noise level simultaneously becomes higher. Move the cursor to the row for the
current value using the UP or DOWN cursor key. Enter a value with numeric keys and then press the
[ENTER] key. Fig. 4.6.1 34 ECD-2010 Plus 4.7 4. 4 Key Operation 4.7 Zero adjustment Zero adjustment
procedure 1. Select the detector to perform zero adjustment. 2. Perform key operation. 3. Make zero
adjustment of the data processing unit. (For the operation method, refer to the instruction manual of
the data processing unit such as Chromatopac.) Selecting the detector to perform zero point
adjustment. Zero adjustment is performed on the Monitor screen. This section describes zero
adjustment only. For the details of the monitor screen, refer to “9. Monitor” in the GC-2010/2010Plus
Instruction Manual. Pressing the [MONIT] key displays the main screen. When the displayed line
configuration does not include the ECD, press [Chng Line] of the PF menu and change the line. Fig. 4.7.1
ECD-2010 Plus 35 4 Key Operation 4.7 Zero adjustment Key operation No. 1: Automatic zero adjustment
Pressing the [Zero Adj] in the PF menu changes the display on the screen to 0 ?V and the baseline moves
to the zero point of the GC. However, depending on the range of the detector and the attenuation of
the Chromatopac, baseline cannot be accommodated within the screen of Chromatopac. NOTE The
“zero adjust” of the GCsolution is same as the zero adjustment on the GC. But the Chromatopac can not
adjust the detector output signal of GC. The zero adjustment should be done on the GC before the zero
adjustment on the Chromatopac. Fig. 4.7.2 [Zero adj.] Z key on the Chromatopac Zero point on the
Chromatopac If the baseline is stable, the analysis possible. 36 ECD-2010 Plus 4 Key Operation 4.7 Zero
adjustment Key operation No. 2: Zero point adjustment Pressing [Up][Down] of the PF menu changes
the baseline level upward/downward. Fig. 4.7.3 Example: Chromatopac screen [Down] [Up] Z key on
the Chromatopac Zero point on the Chromatopac The baseline has decreased to the The zero point is
negative side since the [Down] key adjusted for the has been held down too long. Chromatopac. If the
baseline is stable, the analysis is possible. ECD-2010 Plus 37 4 Key Operation 4.7 Zero adjustment Key
operation No. 3: Releasing zero adjustment Pressing the [Zero Free] of the PF menu returns the baseline
to the level before zero adjustment is performed. Fig. 4.7.4 When the level does not move with key
operation, it is exceeding upper or lower limit. In such a case, refer to “6.1 Troubleshooting”. 38 ECD-
2010 Plus 5.1 5. 5 Service/Maintenance 5.1 Checking the ECD cell If the sample or other accumulates on
the inside of the ECD cell, the baseline level becomes higher. Even in this case, the analysis can be
performed so far as the baseline does not deflect from the range when the [Zero Adj] key is pressed. If
the current value is decreased, the baseline can be lowered. In this case, however, the output signal
(peak) becomes smaller. For the daily service, check the ECD cell for contamination in the following
steps: 1. Set the temperatures of the column mounted and other parts, the flow rate, and the current
value as during the analysis. 2. Wait until the baseline has become stable enough. 3. Press the [MONIT]
key to display the MONIT screen (if the ECD-2010 Plus is not included in the displayed line, press the
Chng Line key in the PF menu to change the displayed line). 4. Press the [Zero Free] key in the PF menu
and then read the detector signal level indicated. 5. In principle, the signal level (?V) in the above step 4.
falls below the following value against the set current value, the cell contamination is regarded as within
the acceptable level: Set current value (nA) × 90000 ?V (e.g., the set current value is 1 nA, the limit is
90000 ?V). (27000 ?V, if see current valve is less than 0.3 nA.) However, even if this limit is exceeded,
the analysis can be performed so far as the satisfactory peak can be obtained when the current is set to
a smaller value. When the standard diagnostic function is used: 1. Press the [DIAG] key to display the
Diagnosis menu. 2. Select “1.Standard Diagnosis” 3. Press the [DiagParam] in the PF menu to display the
“Diagnosis Parameters” screen. 4. Move the cursor to the ECD Frequency item and then set it to “Yes.”
All the items that are set to “Yes” will be diagnosed. To check the ECD-2010 Plus only, set all the other
items to “No.” 5. Press the [Return] key in the PF menu. You will return to the Main screen for the
standard selfdiagnosis. Press the [StartDiag] key in the PF menu to start the diagnosis. 6. When the
diagnosis is completed, the comprehensive diagnostic result and the number of anomalies will be
displayed. 7. If the diagnostic result for the ECD frequency is Not Good, it is recommended that the cell
be cleaned (the radiation source be replaced). (see “5.3 Cleaning Procedure for ECD Cell.”) For the
details of the self-diagnosis, refer to Chapter “14. Diagnosis” in the instruction manual for the GC-
2010/2010Plus (CD-ROM version). NOTE In the standard self-diagnosis, the default value for the
threshold of the ECD frequency is 40 kHz at 2 nA. This value can be changed if the standard value for the
system check is selected in the system configuration of the GCsolution for the ECD-2010 Plus. However,
it cannot be changed on the GC-2010/2010Plus alone. The ECD frequency is in proportion to the
detector signal level, and the output frequency of 40 kHz is equivalent to the signal level of 2,500,000
?V. ECD-2010 Plus 39 5.2 5. 5 Service/Maintenance 5.2 How to Keep the ECD Cell Clean The following
cautions should be exercised in order to keep the ECD cell clean: 1. Use a column with excellent heat
resistance A major factor causing contamination of the ECD cell is the accumulation of the liquid phase
vapor of the column. Use of a column with excellent heat resistance is recommended. Also, the life of
the ECD cell can be lengthened when it is used at a temperature 20~30°C lower than its max.
temperature. 2. Use a column with less quantity liquid phase Use of a column with less quantity liquid
phase is also recommended to prevent accumulation of the liquid phase on the ECD cell. Although
capillary columns are hardly affected, care should be exercised when using a packed column. 3. Use a
column which has been sufficiently conditioned The column to be used should be sufficiently
conditioned in order to prevent impurities from accumulating on the ECD cell. It is recommended that
the column be conditioned without connecting it to the ECD cell in order to prevent deterioration of the
operational life of the ECD cell. 4. Condition the injection port sufficiently The injection port should also
be sufficiently conditioned, in the same way as the column in step (3) above. Check the injection port
(glass insert) for contamination and carry out sufficient conditioning. (Refer to “10.3 Conditioning of
Equipment”.) 5. Reduse impurities in the carrier gas and make-up gas The carrier gas and make-up gas
containers of the ECD should be of high purity. Flow route parts (pipes, flow controller, etc.) should also
be clean. A gas filter and oxygen trap are effective for removing impurities. 6. Condition the ECD cell
periodically Condition the ECD cell periodically. When conditioning, the temperature of the ECD cell
should be set as close to the max. operation temperature, 350°C, as possible (for instance 340°C). (Refer
to “10.3 Conditioning of Equipment”) When conditioning the ECD cell with the column connected, the
temperature of the column oven shoud be one given below: Capillary column : Max. temperature
Packed column : (Max. temperature) -30°C When a packed column with a low boiling point of the liquid
phase is used at a high temperature, conditioning the ECD cell immediately after use is an effective
method for extending the operational life of the ECD cell. 7. Set the detector temperature to a value
higher than that of the column oven. The liquid phase of the column does not accumulate on the ECD
cell if the detector temperature is higher than the column oven temperature. Set the detector
tremperature to a value 20~50°C higher than that of the column oven. However, beware that the max.
operation temperature of the ECD is 350°C. (Refer to “3.8 Setting the detector temperature”.) 40 ECD-
2010 Plus 5 Service/Maintenance 5.2 How to Keep the ECD Cell Clean 8. In case of contimuous
operation, lower the temperature. Many analyses carried out using the ECD cell are contimuous. In such
cases, if the analysis is carried out with the column oven heated to a high temperature, the liquid phase,
in particular of the packed temperartures of the column oven and the injection port be lowered if
possible. However, neither the carrier gas nor the make-up gas shoud be stopped. (Refer to “3.14
Stopping the system”.) 9. When ECD is not used When the ECD is not used, close the column connection
of the ECD cell and supply the make-up gas. When the column is removed, blank off with the graphite
ferrule and the column nut. The make up gas is not flow, while the power is off. Install the blind (G-type
nut) to the ECD vent to keep the radiation source clean, when the power is turned off. ECD-2010 Plus 41
5.3 5. 5 Service/Maintenance 5.3 Cleaning procedure for ECD Cell The ECD cell used for gas
chromatography may through long service, be contaminated with samples, column packing or
liquidphase, causing sensitivity to drop, abnormal peck shapes or inverted peaks, etc. In such a case
contact our company for cleaning (repair) of the ECD cell in the following procedure: CAUTION For the
mounting and removing the ECD unit, contact our service engineer. 1. Ask our Sales office for a “Request
for a Cleaning ( Repairing ) ECD Cell” slip. 2. Write the necessary information including your special
request on the slip and send it to us (Sales office). 3. Remove the ECD unit from the gas chromatograph
main body. 4. The ECD unit must be sent by the user himself directly to our office by mail according to
the law. (For the mailing method and the address, please contact our Sales office.) 5. The ECD unit sent
from you will be cleaned (or repaired) by us according to the information on the slip. 6. After having
been cleaned or repaired, the ECD unit will be sent back to you by mail. 7. Mount the ECD unit on the
main body. NOTE In cleaning the ECD cell, it is unavoidable to handle the nonsealed source. Therefore, if
the user wants to clean the cell on his side, it is essential that he observe the applicable national, state
and/or local laws and regulations regarding the handling of radioactive materials. 42 ECD-2010 Plus 5
Service/Maintenance 5.3 Cleaning procedure for ECD Cell User Shimadzu corporation Request for
cleaning. Call us. Request for cleaning (Repairing) ECD cell Branch office or agent Mail the request slip
Fill out the slip We will explain how to pack and mail the ECD unit. Request slip GC-2010/2010Plus
Remove the ECD unit. Use the box the ECD unit originally came in for mailling. Pack Mail Shimadzu
corporation RI acceptance card RI acceptance card is sent. Cleaning Repair Mail GC-2010/2010Plus
Remount the ECD unit. Completed. Fig. 5.3.1 Cleaning the ECD cell (replacing the radiation source)
ECD-2010 Plus 43 5.4 5. 5 Service/Maintenance 5.4 Actions to Be Taken in Case There Is the Doubt of
Break If there is a doubt of break of the ECD, the measurement with the survey meter must be carried
out. If there is any abnormality such as the disuse of the ECD etc. NOTE Refer to “7 Disuse”. 44 ECD-2010
Plus 6.1 6. 6 Troubleshooting 6.1 Troubleshooting This chapter covers causes of and countermeasures
against troubles encountered when using the ECD. Troubles which are attributable to the gas
chromatograph main unit are covered in “Troubleshooting” in the instruction manual of the gas
chromatograph. If a trouble cannot be cleared by the countermeasure given hereafter, or if a troubles
other than outlined in this chapter occurs, contact Shimadzu office or agent which is nearest to you. 1.
Abnormal baseline ■ Significant noise occurs in the baseline. Noise Cause The electrical connector is not
securely connected. There is a large quantity of impurities in the carrier gas or make-up gas.
Countermeasures Check the connector and connect securely. ? Purge the air inside the flow line
completely. (Refer to “10.3 Conditioning of Equipment”) ? Replace the filter (molecular sieve filter, gas
filter or oxygen trap). ? Replace the plumbing parts. ? Replace the gas container, changing to a gas of
higher purity. Check for gas leakage and correct any joints from which gas is leaking. Check the cell for
contamination. If necessary, send the ECD unit to our Company for cleaning. (Refer to “5.
Service/Maintenance”.) Contact our sales office or service company. Gas leakage The cell is
contaminated. The APC does not work. ECD-2010 Plus 45 6 Troubleshooting 6.1 Troubleshooting ■
Baseline drift, meander, etc. (Positive) drift (Negative) drift Meander Others Cause Air is trapped in the
flow line. The carrier gas or make-up gas is not flowing and air is mixed in. Injection port (glass insert) or
column is contaminated. Countermeasures Purge the air completely. (Refer to “10.3 Conditioning of
Equipment”.) Correct the flow conditions of the carrier gas or makeup gas. ? Clean the glass insert or
replace it. (Refer to “3.3 Checking the glass insert and the injection inlet septum”.) ? Condition the
column. (Refer to the instruction manual of the gas chromatograph.) Monitor the temperature of each
section on the monitor screen ([MONIT] key). Contact our branch office or agent if the temperature will
not stabilize. Monitor the pressure and flow rate on the monitor screen ([MONIT] key). Contact our
branch office or agent if the temperature will not stabilize. Check the cell for contamination. If
necessary, send the ECD unit to our company for cleaning. (Refer to “5. Service/Maintenance”.)
Temperature of each section is unstable. The flow rate is unstable. The cell is contaminated. 2. Zero
adjustment does not work. Exceeding the limit. Cause Air is trapped in the flow route. The carrier gas or
make-up gas is not flowing and air is mixed in. The cell is contaminated. Countermeasure Purge the air
completely. (Refer to “10.3 Conditioning of Equipment”.) Correct the flow conditions of the carrier gas
or makeup gas. Check the cell for contamination. If necessary, send the EDC unit to our company for
cleaning. (Refer to “5. Service/Maintenance”.) Set a smaller current value. The current value is too large.
46 ECD-2010 Plus 6 Troubleshooting 6.1 Troubleshooting 3. Peak is too small (or the sensitivity is too
low.) Cause The carrier gas is leaking. The split ratio is too large. (in case of split analysis) The quantity of
the sample injected is too small, or the sample concentration is too low. Countermeasures Check for gas
leakage and correct any piping joints from which gas is leaking. Reduce the split ratio. Increase quantity
or concentration of injected sample. NOTE 1. Injecting too much sample may contaminate the injection
port. 2. High-concentration samples may contaminate the detector. The value of current, range or
attenuation is inappropriate. The capillary column has been connected in the wrong way. An incorrect
column is used. There is a large quantity of impurities in the carrier gas or make-up gas. Set the range or
attenuation to ×1 or current. Mount the column in the correct way. (Refer to “3.4 Mounting the
column”.) Replace the column in the correct one, taking the polarity into consideration. ? Purge the air
inside the flow route completely. (Refer to “10.3 Conditioning of Equipment”.) ? Replace the filter
(molecular sieve filter, gas filter or oxygen trap). ? Replace the plumbing parts. ? Replace the gas
container, changing to a gas of higher purity. Check the cell for contamination. If necessary, send the
ECD unit to our company for cleaning. (Refer to “5. Service/Maintenance”.) Replace the glass insert with
an inert one (optional). Replace it with an acid-treated or alkali-treated one for some components. The
cell is contaminated. A component has stuck to the glass insert. ECD-2010 Plus 47 6 Troubleshooting 6.1
Troubleshooting 4. The linearity of the calibration curve has become significantly poor. (Refer Curve”.)
to “10.2 Calibration Calibration curve Cause There is a large quantity of impurities in the carrier gas or
make-up gas . Countermeasures ? Purge the air inside the flow route completely. (Refer to “10.3
Conditioning of Equipment”.) ? Replace the filter (molecular sieve filter, gas filter or oxygen trap). ?
Replace the plumbing parts. ? Replace the gas container. (changing to a gas of higher purity.) ? Condition
the column. (Refer to the instruction manual of the gas chromatograph.) Check the cell for
contamination. If necessary, send the ECD unit to our company for cleaning. (Refer to “5.
Service/Maintenance”.) Lower the current value. Note that lowering the current value lowers the
detection sensitivity. Increase the makeup gas flow rate. Note that increasing the makeup gas flow rate
lowers the detection sensitivity. The column is contaminated . The cell is contaminated. The current
value is too large. Makeup gas flow rate is too low. 5. Other abnormal phenomena As for the
phenomena shown below , refer to “Troubleshooting” in the instruction manual of the gas
chromatograph. ○ The pressure meter does not indicate the set value. ○ Gas leakage does not stop. ○
The temperature does not rise. ○ Column inlet pressure or total flow rate connot be set, or the
difference is severe. ○ Ghost peak. ○ Abnormal peak shape. ○ Reproducibility of retention time is low. ○
Reproducibility of peak area is low. 48 ECD-2010 Plus 6.2 6. ■ OVER TEMP error 6 Troubleshooting 6.2
Error Message Error messages specific to the ECD are explained in this section. As for the error messages
relating to the gas chromatograph main unit , refer to “19.2 Error Messages” in the instruction manual
of the gas chromatograph. The DET temperature has exceeded the upper limit. If the unit for which the
temperature is controlled exceeds the upper limit for its operating temperature, the confirmation
screen appears prompting you to reset the error with the above message displayed. When the ECD is
used, the max. temperature of the detector is set to 350°C or less. For the ECD, if the detector
temperature exceeds 350°C, the safety function operates automatically and it becomes OVER TEMP.
error. Therefore, if an attempt to set the detector temperature to over 350°C, this OVER TEMP error
returns. Beware that, even when the detector temperature has been set to less than 350°C, the
temperature may exceed 350°C momentary on the way to the set value. If this error occurs, move the
cursor to “Ignore Error” and then press the [ENTER] key. Eliminate the cause of the error by changing
the settings or taking any other action. Several 10 seconds after the [ENTER] key has been pressed, the
confirmation screen appears. Position the cursor on “Reset Error” and then press the [ENTER] key. If you
return to the confirmation screen when you are changing the settings, select “Ignore Error” again. ECD-
2010 Plus 49 6 Troubleshooting 6.2 Error Message This page is intentionally left blank. 50 ECD-2010 Plus
7.1 7. 7 Disuse 7.1 Cautions at Disuse When disusing the used ECD etc., you must take legal
administrative procedures at the same time. Also, in the case of disposing the gas chromatograph
equipped with the ECD, be sure to remove the ECD and take the measures mentioned above. NOTE
When removing the ECD from the gas chromatograph, contact our service engineer. * When removing
the ECD unit, plug the hole with the heat insulating material which was cut off at installation. ECD-2010
Plus 51 7 Disuse 7.1 Cautions at Disuse This page is intentionally left blank. 52 ECD-2010 Plus 8.1 8. 8
Maintenance Parts 8.1 Maintenance Parts List Part name Silicon rubber septum (20 pcs.) Glass insert (for
split injection) Glass insert (for splitless injection) Inert silica wool (2 grams) Fluoride rubber O-ring (5
pcs.) Graphite ferrule 0.5 mm (10 pcs.) Graphite ferrule 0.8 mm (10 pcs.) Aluminum packing (500 pcs.)
Molecular sieve filter Trap (SPLIT) Trap (PURGE) Part No. 201-35584 221-41444-01 221-48335-01 221-
48600 036-11203-84 221-32126-05 221-32126-08 201-35183-84 221-34121-94 221-42559-92 221-
42559-92 Remarks Injection port septum For split injection method For splitless injection method
Stuffing for glass insert For fitting the glass insert For mounting the capillary column For mounting the
wide-bore column Packing for the piping joint For removing contamination in carrier gas and makeup
gas Split flow line trap Septum parge flow line trap ECD-2010 Plus 53 8 Maintenance Parts 8.1
Maintenance Parts List This page is intentionally left blank. 54 ECD-2010 Plus 9.1 9. 9 Specifications 9.1
Specifications of the ECD-2010 Plus : : : : : : : : : Frequency-controlling , constant current type 63Ni
370MBq Coaxial type electrode with purging line 0.00 - 3.50 nA (for GC-2010, between 0.00 nA and 2.00
nA) 104 (with γ - BHC) 6 fg / s 350°C 5 steps of ×1, ×10-1, ×10-2, ×10-3, and ×10-4 (at analog and linear
output) 5 steps of ×1, ×2-1, ×2-2, ×2-3, and ×2-4 (at analog and wide output) Type Radiation source Cell
Cell current Dynamic range Detection limit Max. temperature Range Attenuation ECD-2010 Plus 55 9
Specifications 9.1 Specifications of the ECD-2010 Plus This page is intentionally left blank. 56 ECD-2010
Plus 10.1 10. 10 Appendix 10.1 Structure of ECD Cell Electrode Radioactivity mark To VENT Radiation
source Input of make-up gas ECD cell body Heating block Capillary adaptor Fig. 10.1.1 Structure of the
ECD unit ECD-2010 Plus 57 10.2 10. 10 Appendix 10.2 Calibration Curve This chapter covers the
explanation of linearity of calibration curve which has been described in 6.1 “Troubleshooting”.
Calibration curve The “Calibration curve” refers to the graph shown in Fig.10.2.1. this graph shows the
relationship between the sample quantity and the area of the peak. Dynamic Range Dynamic range
refers to the ratio between the minimum and maximum sample quantities that allow observing changes
in output signal with respect to increases in sample quantity. In the example shown in Figure 10.2.1,
peak area increases along with sample quantity between the minimum detection limit of about 2.5 × 10-
1 pg and about 2.5 × 103 pg, but beyond that range, the increase in peak area is significantly smaller
compared to increases in sample quantity. In this case, the dynamic range is equivalent to 2.5 × 10-1 pg
divided by 2.5 × 103 pg, or about 104. The linearity of a calibration curve refers to the range over which
the graph is considered linear. Quantitativity Within the linear range of calibration curves, the peak area
(or height) is proportional to the sample quantity. In other words, within that range, quantitative
analysis is possible using a single-point calibration curve method. Even if the calibration is not linear, if it
is within the dynamic range, quantitative analysis is possible using a two-point calibration curve method.
Note, however, that quantitative analysis is not possible beyond the dynamic range. Characteristics of
the ECD Fig. 10.2.1 is an example of the calibration curve. This calibration curve is one when the ECD cell
is in the best condition. Dynamic range 10 6 10 Peak area 5 10 4 10 3 10 2 -1 0 1 2 3 4 10 10 10 10 10 10
(Pg) Detection limit ( 2.5×10-1) Sample quantity 2.5×10 3 58 ECD-2010 Plus 10.3 10. 10 Appendix 10.3
Conditioning of Equipment After the installation of equipment or after the replacement of pipings, air is
trapped inside the flow line. If air is mixed in the gas inside the flow line, the base line, the base line
connot be stabilized and analysis cannot be performed correctly. Equipment must be conditioned prior
to starting analysis. Given in this section is an example of settings of equipment conditioning . As for the
details of the operational procedure, refer to “3. Basic Operation”. It is recommended to condition the
equipment in the following settings : 1. Glass insert in the injection port Same glass insert as that used
for analysis (Confirm the kind glass inserts. Check the glass insert for contamination and for damage.)
(Refer to “3.3 Checking the glass insert and the injection inlet septum”.) 2. Column Use of an empty
column (column without liquid phase) is recommended. (to prevent the liquid phase of the column from
being accumulated on the ECD cell) When a normal column is connected, use a column with an excellent
heat resistance Also, a packed column should not be used for the conditioning of equipment since its
liquid phase quantity is large. ■ In case of a capillary column : A fused silica tube (option : for instance
FQ tube 0.2 mmID×2 m, P/N 221-25964-02) is conveniently used. ■ In case of a packed column : Pipe
MF-MF (option:P/N 201-48555-**, -** is the length. For instance if the pipe is 30 cm, it is expressed as -
30 cm, If it is 1m. It is expressed as-00.) It can be used as a empty column. 3. Temperature setting
Column over temperature : 340°C (empty column) Injection port temperature : 340°C Detector
temperature : 340°C NOTE When a normal column is connected, the column oven temperature should
be set lower than max. temperature of the column by 30°C and more. 4. Flow rate setting The flow rate
of both carrier gas and make-up gas should be set to the same rates as those for analysis . NOTE When
the FQ tube (0.2 mmID×2 m) mentioned above is connected, conditioning can be performed if the flow
rate is within the control range of the flow controller and if the carrier gas is flowing to the column. 5.
Detector settings Range=1 , Current=1 nA (Check the baseline by changing the values if necessary.) 6.
Conditioning time ~half a day (This time depends on the period during which the ECD has not been
used.) ECD-2010 Plus 59 10 Appendix 10.3 Conditioning of Equipment This page is intentionally left
blank. 60 ECD-2010 Plus