Antec Scientific

Hoorn 131
2404 HH Alphen a/d Rijn
The Netherlands

DECADE Elite/Lite
User Manual

175.0010, Edition 13, 2022

T +31 172 268888 | [email protected] | www.AntecScientific.com

All functionality, specs and warnings in the manual where the DECADE ELITE is mentioned apply to
all models of DECADE Elite: SCC, DCC and including the DECADE Lite. Except for the few model
design differences in features, such as the keyboard, display, Pulse and Scan mode not being avail-
able in the Lite.

Copyright ©2022, Antec, The Netherlands. Contents of this publication may not be reproduced in any form or by any means
(including electronic storage and retrieval or translation into a foreign language) without prior agreement and written consent
from the copyright of the owner. Antec reserves the right to make changes to the design and specifications of the instrument
and this manual without prior notice.

DECADE Elite, DECADE Lite, ROXY, ALEXYS, ROXY Exceed, INTRO, FlexCell, ReactorCell, µ-PrepCell, ISAAC, HyREF,
SenCell and SynthesisCell are trademarks of Antec Scientific. Whatman™ (word and device) and Whatman™ (word only) are
trademarks of Whatman international Ltd. SOLVENT IFD™ and AQUEOUS IFD™ are trademarks of Arbor Technologies, Inc.
Clarity®, DataApex® are trademarks of DataApex Ltd. Microsoft® and Windows™ are trademarks of Microsoft Corporation. Ex-
cel is a registered trademark of the Microsoft Corporation. Thermo Scientific ChromeleonTM is a trademark of ThermoFisher
Scientific. EmpowerTM is a trademark of Waters Corporation. Agilent OpenLabTM is a trademark of Agilent Technologies Inc.
All other trademarks are the property of their respective owners.

The software and the information provided herein is believed to be reliable. Antec shall not be liable for errors contained
herein or for incidental or consequential damages in connection with the furnishing, performance, or use of software or this
manual. All use of the software shall be entirely at the user’s own risk.
 Declaration of conformity

We Antec Scientific, Alphen a/d Rijn, The Netherlands, declare that the product:

DECADE Elite / Lite™ Electrochemical Detector type 175 and 176

to which this declaration relates, is in conformity with the following CE directives:

2014/35/EU Low Voltage Directive (LVD)

2014/30/EU Electromagnetic Compatibility Directive (EMC)
2015/863/EU Directive on Restriction of the use of certain Hazardous Substances (RoHS)
2012/19/EU Directive on Waste Electrical and Electronic Equipment (WEEE)

Product standards used for demonstration of compliance:

EN 61010-1:2010
Safety requirements for electrical equipment for measurement, control, and laboratory use; part 1:
General Requirements.

EN 61010-2-010:2014
Safety requirements for electrical equipment for measurement, control, and laboratory use; part 2-
010: Particular requirements for laboratory equipment for the heating of materials.

EN 61326-1:2013
Electrical equipment for measurement, control and laboratory use - EMC requirements; part 1: Gen-
eral Requirements (Class B equipment).

EN 55032:2015
Electromagnetic compatibility of multimedia equipment
Emission requirements (Class B equipment).

Only use manufacturer-supplied cable(s) to connect with other devices. Thoroughly connect
shielding to common. Manufacturer will not accept any liability for damage, direct or indirect,
caused by connecting this instrument to devices and with cables which do not meet relevant
safety standards. All cables used should not exceed a length of 3 meters.

This DoC applies to above-listed products (2020 model). A 2020 model can be identified by the letter
B in the part number. For older models see previous revision of this manual.

Date: June 29th, 2020

Dr. N.J. Reinhoud (managing Director)
4 175_0010 - DECADE Elite / Lite user manual - rev 13

Table of contents
Symbols 7
Intended use 9
WEEE 10
ROHS 10
ISO 10
Safety instructions 11

CHAPTER 1 - Introduction 15
Instrument description 16
DECADE Elite – Front side 16
DECADE Lite – Front side 17
DECADE Elite – Back side 18
DECADE Elite – Oven compartment 19

CHAPTER 2 - Installation 21
Storage requirements 21
Site Preparation Requirements 21
Personal Computer 21
Laboratory requirements 22
Electrical and power requirements 24
Chemicals 25
Unpacking 26
Mains connection 28
PC connection 28
Software 32
Dialogue Elite 33
Clarity Chromatography software 34
HPLC fluid connections 37
Tubing connectors 37
Mobile Phase 39
Installation & start-up 41

CHAPTER 3 - Maintenance & shutdown 45

Maintenance 45
Periodic check for leakage 45
Periodic check of the oven temperature 45
Flow cell 46
Cleaning 46
Replacement of fuses 46
Shutting down the system 47

CHAPTER 4 - DECADE Elite controller 49

Introduction 49
Overview of DECADE Elite screens 50
DC mode 50
Pulse mode 51
SCAN mode 52
CONFIG menu 53
CHAPTER 1 Table of contents 5

DIAG menu 54
Parameters 55
Dialogue Elite 60
Clarity CDS 62
Chromeleon CDS 63
OpenLab CDS 64
Empower CDS 65

CHAPTER 5 - Detection & parameters 66

Introduction 66
Three-electrode configuration 66
Internal organization 68
Dual flow cell control (Elite only) 68
Serial mode detection 69
Parallel mode detection 69
Navigation in dual cell menu 70
Parameters 71
Range 71
Offset 72
Polarity 73
Filter 73
DC mode 73
Pulse mode 74
MPAD mode 74
Autozero 75

CHAPTER 6 - Measurement modes 77

DC mode 77
Pulse mode 78
MPAD mode 80
Scan mode 81

CHAPTER 7 - Advanced Digital Filtering (ADF) 83

CHAPTER 8 - Pulsed Amperometric Detection (PAD) 93

Introduction 93
High pH of mobile phase 95
Pulse settings 96

CHAPTER 9 - Optimization of the working potential 99

Hydrodynamic voltammogram 101
Scanning voltammogram 102

CHAPTER 10 - Specifications 111

Environmental, dimensions, weight & power requirements 111
General 112
DC mode 113
PULSE mode 113
MPAD mode 113
SCAN mode 113
6 175_0010 - DECADE Elite / Lite user manual - rev 13

CHAPTER 11 - Rear panel I/O 115

USB B connector 116
LAN connector 116
VALVE connector 116
Valve connector layout 117
Inject marker 117
Electrical valve configuration 117
Valve status & control 119
ANALOG DATA connector 122
DAC output 124
I/E output 124
Digital I/O connector 125
TTL inputs & outputs 126
Relays 126
AUX 126
Overload 126
Cell on, Cell off 128
Autozero 128
Start 128
Chassis grounding stud 134

CHAPTER 12 - Troubleshooting 135

Instrument errors 135
Analytical troubleshooting 138
Dummy cell test 139
Stop flow test 144
Known issues 149

CHAPTER 13 - Detector accessories 150

Detector accessory kit 150
Optional AD convertor cables 151
Optional grounding kit for ECD 153

INDEX 155
CHAPTER 1 Table of contents 7

Symbols
The following symbols might be used in this guide or may be found on the
instrument:

This sign warns about the risk of electric shock. It calls

attention to a procedure or practice which, if not adhered
to, could result in loss of life by electrocution. Do not pro-
ceed beyond a danger sign until the indicated conditions
are fully understood and met.

The warning sign denotes a hazard. It calls attention to a

procedure or practice which, if not adhered to, could re-
sult in severe injury, loss of life or damage or destruction
of parts or all of the equipment. Do not proceed beyond a
warning sign until the indicated conditions are fully under-
stood and met.

The caution sign denotes a hazard. It calls attention to a

procedure or practice which, if not adhered to, could re-
sult in damage or destruction of parts or all of the equip-
ment and/or erratic results. Do not proceed beyond a
cautions sign until the indicated conditions are fully un-
derstood and met.

The biohazard sign draws attention to the fact that use

of biological materials, viral samples may carry a signifi-
cant health risk.

The toxic hazard sign draws attention to the fact that use
of toxic solvents or samples may carry a significant
health risk.
8 175_0010 - DECADE Elite / Lite user manual - rev 13

The hot surface sign calls attention to parts in the

instrument that must not be touched, as they may
cause burns.

This symbol indicates electrostatic discharge (ECD

hazard), damages to system, device, or components
can occur if not properly grounded.

This symbol indicates that the waste of electrical and

electronic equipment must not be disposed as un-
sorted
municipal waste and must be collected separately.
Please contact the manufacturer or authorized repre-
sentative of the manufacturer for information con-
cerning the decommissioning of equipment.

A device or system marked with CE fulfills the prod-

uct specific requirements described in the European
directives. This is confirmed in a Declaration of Con-
formity.

Certification marking for Canada and the USA issued

by MET labs, a Nationally Recognized Testing La-
boratory (NRTL). The certified device complies to
the relevant UL and CSA safety (61010-1) stand-
ards.

Frame or chassis ground terminal, which can be

used as to make additional external grounding con-
nection.

The note sign signals additional information. It pro-

vides advice or a suggestion that may support you in
using the equipment.

The attention sign signals relevant information. Read

this information.
CHAPTER 1 Table of contents 9

Intended use
The DECADE Elite /Lite Electrochemical Detector is used in combination
with (Ultra) High Performance Liquid Chromatography for the electrochem-
ical detection of suitable analytes in liquid samples. With this technique the
amount of electroactive substances in mobile phase can be quantified. The
instrument can be used for the chromatographic analysis of a wide range
of electroactive analytes in the fields of for example:

• Bioanalytical analyses
• Food analyses
• Environmental analyses

For research purposes only. While clinical applications may be shown,

this instrument is not tested by the manufacturer to comply with the In
Vitro Diagnostics Directive.

Operation of an electrochemical detector can involve the use of hazardous

materials including corrosive fluids and flammable liquids. The instrument
should only be operated by users with the following expertise:

• Completed degree as chemical laboratory technician or

comparable vocational training
• Fundamental knowledge of liquid chromatography and equipment
• Participation in an installation of the system performed by the
manufacturer or a company authorized by the manufacturer and
suitable training on the system and chromatography software.
• Knowledge and experience in the safe handling of toxic and
corrosive chemicals and knowledge of the application of fire
prevention measures prescribed for laboratories.

Information on safety practices is provided with your instrument and opera-

tion manuals. Before using your instrument or accessories, you must thor-
oughly read these safety practices. This manual is written for laboratory
technicians/scientists skilled in the art, who use the DECADE Elite / Lite
detector for (U)HPLC analysis.

Unskilled, improper, or careless use of this instrument can create fire

hazards, or other hazards which can cause death, serious injury to
personnel, or severe damage to equipment and property. Observe all
relevant safety practices at all times. Only use the device for
applications that fall within the scope of the specified intended use.
Else the protective and safety equipment of the device could fail.
10 175_0010 - DECADE Elite / Lite user manual - rev 13

WEEE
All equipment of Antec Scientific which are subjected to the WEEE di-
rective shipped after August 13, 2005 are compliant with the WEEE mark-
ing requirements. Such products are labelled with the “crossed out
wheelie”, depicted on the left site.

The symbol on the product indicates that the product must not be
disposed as unsorted municipality waste.

Collection & recycling information

Please ship the instrument back to the manufacturer (Antec Scien-
tific, the Netherlands) at the end-of-life time of the product. The man-
ufacturer will take care of the proper disposal and recycling of the in-
strument at its facilities. For more info: [email protected].

Shipping address for the end-of-life products:

Antec Scientific
Hoorn 131
2404 HH Alphen a/d Rijn
The Netherlands

In case of questions, or if further information is required about the collec-

tion & recycling procedure, please contact your local distributor.

ROHS

The DECADE Elite/Lite is ROHS compliant and in conformity with Di-

rective EU 2015/863 Restricted use of Hazardous Substances in electrical
and electronic Equipment (ROHS).

ISO

Antec Scientific is an ISO 9001:2015 certified company.

CHAPTER 1 Table of contents 11

Safety instructions
Adhere to the following standard quality control procedures and the follow-
ing equipment guidelines when using the DECADE Elite / Lite detector.
The following safety practices are intended to ensure safe operation of the
instrument.

Working environment & safety

The intended use of the instrument is to detect electroactive substances in
liquid samples in combination with a (U) HPLC system in a GLP-approved
environment. Operators using the system should have the appropriate ed-
ucation an extensive understanding of GLP rules and be skilled in the art.
Use this system ONLY for the intended use. Use of the system for any
other purpose might cause unsafe situations.

System Operation
To assure optimal performance keep of the detector we recommend that
the instrument is checked regularly and maintenance procedures are car-
ried out. Preventive maintenance contracts are available for that purpose.
Please contact your local dealer or the nearest sales office for more infor-
mation.

Electrical safety
The removal of protective panels on the instrument can result in exposure
to potentially dangerous voltages. Therefore, disconnect the instrument
from all power sources before disassembly.

Untrained personnel should not open the instrument, this may only be
done by authorized service engineers. Replace or repair faulty insula-
tion on power cords immediately after discovery of the fault. Check that the
actual power voltage is the same as the voltage for which the instruments
are wired. Make sure power cords are connected to correct voltage
sources: grounded AC power source, line voltage 100 – 240 VAC. The in-
strument should be connected to a protective earth via a ground socket.
12 175_0010 - DECADE Elite / Lite user manual - rev 13

The DECADE Elite must only be used with appliances and power sources
with proper protective grounding to prevent damage through build-up of
static electricity. The power source should exhibit minimal power transients
and fluctuations. If necessary connect to a filtered mains socket.

USE ONLY WITH 250 V FUSES

EMPLOYER UNIQUEMENT
AVEC DES FUSIBLES DE 250V

Replace blown fuses with fuses of proper type and rating as indicated on
the rear panel and as listed in the list of accessories and spares (appendix
D). The fuse holder is integrated in the mains connector. Ensure that the
instrument is never put in operation with fuses of a different type. This
could cause fire.

Only use manufacturer-supplied I/O cable(s) to connect with other

devices.

Thoroughly connect shielding to common. Manufacturer will not accept

any liability for damage, direct or indirect, caused by connecting this instru-
ment to devices and with cables which do not meet relevant safety stand-
ards. Place the detector on a flat and smooth surface. Do not block the
ventilation holes located at the bottom and lower rear panel of the detector.
Blocking these holes may impair the cooling capability of the power supply.

Solvents
The solvents used may be flammable, toxic or corrosive. The room in
which the system is installed should be well ventilated to prevent that sol-
vent vapors cause poisoning or ignite and cause a fire. Use of open fire in
the vicinity of this system must be strictly prohibited. Do not install the sys-
tem in the same room with any other equipment that emits or could poten-
tially emit sparks. Provide protective equipment near the instrument, when
solvent gets into the eyes or on the skin, it must be flushed away immedi-
ately. Provide equipment, such eye wash stations and safety showers, as
close to system as possible. Use proper eye and skin protection when
CHAPTER 1 Table of contents 13

working with solvents. Additional safety requirements or protection may be

necessary depending on the chemicals used in combination with this
equipment. Make sure that you understand the hazards associated with
the chemicals used and take appropriate measures with regards to safety
and protection. Sample containers (vials) should be sealed to minimize
any risks related to solvent vapor.

Biological Hazard
When you analyze biological fluids you need possible precautions and
treat all specimens as potentially infectious. Always wear protective
And gloves when handling toxic or biologically infectious samples to pre-
vent bio hazards or hazards while working with the DECADE Elite .If nec-
essary the instrument must be decontaminated before decommis-
sioning or shipment of the instrument for repair to Antec or its repre-
sentatives. When shipped to Antec every instrument must be accompa-
nied with a decontamination form which should be completely filled in and
signed by the customer. Without this decontamination form the instrument
will not be processed by Antec (either repaired or disposed).

Waste disposal
Perform periodic leak checks on LC tubing and connections. Do not close
or block the drain in the oven compartment. Do not allow flammable and/or
toxic solvents to accumulate. Follow a regulated, approved waste
Disposal program. Never dispose of flammable and/ toxic solvents through
the municipal sewage system.

Applications: quality control

It is recommended that you routinely run several quality control samples.
Quality control samples should represent low, average and high levels of a
compound. Make sure that quality control sample results are within
An acceptable range, and evaluate precision from day to day and run to
run. Data collected when quality control samples are out of range may not
be valid. Do not report this data until you are certain that system
performance is acceptable. Apart from use of quality control samples, we
Recommend that you use blanks. The blanks will help you assess whether
carry-over is within an acceptable range and monitor the integrity of your
data.

Using the DECADE Elite / Lite in other ways than indicated in the
manual or defined by good laboratory practice may result in erratic or
unsafe operation.
14 175_0010 - DECADE Elite / Lite user manual - rev 13
CHAPTER 1 Introduction 15

C H A P T E R 1

Introduction
Congratulations on your purchase of the DECADE Elite or DECADE Lite.
This detector enables you to perform all (U)HPLC applications using elec-
trochemical detection. The DECADE Elite includes a highly stable Fara-
day-shielded oven compartment accommodating column and flow cell.
This flow cell has surprised researchers for its unsurpassed S/N ratio and
therefore you now possess the best possible combination for extremely
sensitive EC analyses. The DECADE Elite has 3 operational measurement
modes: DC, SCAN and PULSE mode. Furthermore, a Diag(nostics) and
Config(uration) mode are available. In addition, crucial parameters can be
controlled by either relays or TTL. The DECADE Elite can support up to 3
flow cells (optional), which makes it possible to perform 3 independent
measurements with one detector. The DECADE Lite (right side) is a “light”
version of the Elite with a front panel without keyboard and display, it is for
single flow cell operations in DC mode only. For the DECADE Lite PC soft-
ware for parametric control and data-acquisition is required.

This manual covers the installation, set-up and operation of the

DECADE Elite / DECADE Lite only. Detailed operation instructions for
other peripheral LC equipment and parts such as flow cells, pumps,
auto samplers, valves, column heaters etc. are given in the manuals
accompanying those accessories. From this point onwards the
abbreviation DECADE Elite will be used when the information applies
for both types of detectors (Elite and Lite). In case it only applies to one
of the models it will be specifically mentioned (DECADE Elite or Lite).
16 175_0010 - DECADE Elite / Lite user manual - rev 13

Instrument description
DECADE Elite – Front side

# Description # Description
1 Instrument housing 7 '+' and '-' value keys
2 LC tubing inlet/outlet 8 Cursor keys
3 Instrument door panel 9 Door handle (for opening door)
4 4 x 40 Ch LCD display
5 Function keys
6 <Enter> key
CHAPTER 1 Introduction 17

DECADE Lite – Front side

# Description # Description
1 Instrument housing
2 LC tubing inlet/outlet
3 Instrument door panel
4 Door handle (for opening door)
18 175_0010 - DECADE Elite / Lite user manual - rev 13

DECADE Elite – Back side

# Description # Description
1 Instrument rear panel 7 USB connector (USB B)
2 Type label (PN, SN etc.) 8 Fuse & power rating
3 Digital I/O connector (25-p sub-D fem) 9 Mains switch/inlet
4 Analog data (9-pins sub-D fem) 10 Grounding stud
5 Valve connector (9-pins sub-D male) 11 Ventilation holes
6 LAN connector (RJ45 jack) 12 Fuse compartment
CHAPTER 1 Introduction 19

DECADE Elite – Oven compartment

# Description # Description
1 Cell cabinet 8 Door lock
2* Cell connector (9-pin sub-D) 9 Mounting hole M4 (cell clamp)
3 Top fan heater (intake) 10 Bottom fan heater (exhaust)
4 Door sensor 11 Mounting hole M3 (column clamp)
5 Mounting plate 12 Drain
6 Column clamp 13 Door panel, rear
7 Flow cell clamp (SenCell) 14 Type label
*) The Lite version has 1 flow cell (1 cell connector) only.
20 175_0010 - DECADE Elite / Lite user manual - rev 13
CHAPTER 2 Installation 21

C H A P T E R 2

Installation
Storage requirements

The DECADE Elite is shipped in one box to your facility with the following
dimensions:

Equipment Dimensions storage box

DECADE Elite 59 (D) x 41 (W) x 56 (H) cm (23.2 x 16.1 x 22.0 in)

Make sure to have sufficient space to store the packed instrument under
the following storage conditions:

Parameter Requirement
Storage temperature -25 – 50 °C (-14 – 122 °F)
Storage humidity 20 – 80%, non-condensing

Site Preparation Requirements

It is evident that (for as far it is not specified in this document) the

installation site must comply with all applicable local laws and
regulations with regard to electrical and mechanical installations,
building safety, and use of potentially hazardous materials/chemical
and disposal thereof, etc.

For a successful onsite installation of the instrument, please arrange the

following requirements at your location in advance:

Personal Computer
In case the instrument is used via remote control by PC software (Dialogue
Elite, DataApex Clarity, Waters Empower, Agilent OpenLab CDS, Agilent
OpenLab Chemstation or Thermo Chromeleon CDS) or a firmware (FW)
update needs to be performed a desktop computer is required with the fol-
lowing requirements:
22 175_0010 - DECADE Elite / Lite user manual - rev 13

• Free LAN port (onboard, PCI, PCI express or PCI-X)

• Free USB port (required for FW updates)
• Microsoft Windows 7 Operating System or higher*

*) An US or European Microsoft® Windows™ version is recommended. The

Windows operating system should be updated with the latest Service Packs.

Further information about software packages and requirements please visit

the Antec website www.antecscientific.com.

Installing software requires a computer with administrator access.

Make sure that the PC and its USB ports is authorized/able to install
third-party software. Inform your IT department well in advance to
arrange authorization to avoid unnecessary delays during the
installation.

For uninterrupted operation of a DECADE Elite system and control

software Antec advises to turn off:

- Screensavers
- (USB, LAN) hibernate mode
- Auto hard disk shut down (energy saving)
- Automatic Windows updates
- Avoid exhaustive scanning by virus scanners*

*) In your antivirus SW, turn off the option "Check Files

at Change" for the relevant Dialogue Elite data storage directory.

The PC for control and data-acquisition of the system should be placed in

the vicinity of the DECADE Elite, within a distance of max 2.5 meter.

Laboratory requirements
Your instrument is intended for indoor use only in an industrial or commer-
cial environment (EN55011 group 1 class B ISM equipment). It is suitable
for the following categories: Installation category II, Pollution degree 2,
equipment class I.
CHAPTER 2 Installation 23

Table I. Environmental specifications

Parameter Requirement
Operating temperature 10 – 35 °C (50 – 104°F)
Maximum Altitude < 2000 meter (< 7500 ft)
Operating humidity 20 – 80%, non-condensing

For optimum analytical performance it is recommended that the

ambient temperature of the laboratory be between 20-25 °C and be held
constant to within ± 2 °C throughout the entire working day. Note: that
for optimal temperature stability of the cell cabinet the oven
temperature should be set to a temperature at least 7 degrees higher as
ambient temperature.

Do not place the system next to heating or cooling pipes or expose the
instrument to direct sun light or expose it to air drafts (AC system /
open windows).

Requirements for the laboratory bench on which the instrument will be in-
stalled:

• Stabile, clean, flat and smooth surface.

• Enough mechanical strength to hold at least the weight of the

detector. A DECADE Elite SCC without cell weights 14.4 kg (31.7
lbs.). A full-dressed potentiostat with flow cells and peripherals
columns and valves may weigh up to 20 kg or more.

• A DECADE Elite detector has the following dimensions 44 (H) x 22

(W) x 43 (D) cm = 17.3” (D) x 8.7” (W) x 16.9” (H). Take into
account that additional space is necessary on all sides to prevent
obstruction of ventilation holes and allow sufficient heat
dissipation. Keep at least 15 cm free at the back. Keep at least 5
cm distance, if there is another device on one side. Keep at least
10 cm distance, if there are devices on both sides.
24 175_0010 - DECADE Elite / Lite user manual - rev 13

Electrical and power requirements

The customer is responsible for providing appropriate electrical power

and power outlets in the laboratory.

1. The installation of electrical supplies and fixtures in the laboratory

must be in compliance with all local regulations and safety stand-
ards.

2. The power source should exhibit minimal power transients and

fluctuations. The AC mains supply voltage source should not fluc-
tuate more than +/- 10% from the nominal voltage. If your mains
voltage is unstable ( >10% of nominal voltage use an Uninter-
ruptable Power Supply (UPS) The mains supply must include a
correctly installed protective earth conductor.

To protect against power transients (voltage spikes and power surges)

it is advised to connect the equipment over an electrical surge
protector.

3. The DECADE Elite is equipped with an universal AC/DC switched-

mode power adapter rated for 100–240 V AC and 50/60 Hz. Every
potentiostat is delivered with a set of 2 power cords for the follow-
ing regions:

• EUR (CEE7/7 plug to IEC60320 C13 plug)

• US (NEMA 5-15 plug to IEC60320 C13 plug)

For regions with deviating mains plugs/sockets like (for example UK,
Switzerland, Brazil etc.) make sure to have the appropriate power
cords available on-site at the date of installation. Make sure these
power cables are properly grounded and meet the relevant safety
standards which apply in your country. In case of questions contact
your local distributor.

4. The maximum power consumption of the DECADE Elite on full

power) is < 200 Watt. The typical power consumption is < 50 Watt.

5. Connect the detector to a grounded AC wall socket with a line volt-

age of 100 – 240 VAC (as specified in the sections above) using
the supplied power cables. The instrument should be connected to
a protective earth via the socket. Make sure the detector is placed
CHAPTER 2 Installation 25

in such a way that the mains power connection can be reached

easily to disconnect it from the mains power by removing the
power cable.

Only use manufacturer-supplied cable(s) to connect with other

devices. Thoroughly connect shielding to common. Manufac-
turer will not accept any liability for damage, direct or indirect,
caused by connecting this instrument to devices and with cables
which do not meet relevant safety standards.

Chemicals
Mobile phase and flush/storage solutions must be clean as it is in direct
contact with the working electrode of the electrochemical reactor cell. High
purity chemicals including water is a prerequisite. So all chemicals should
be electrochemically clean, HPLC grade or better. For water used for the
preparation of mobile phases a water purification apparatus is advised
which is able to supply high purity deionized water with resistivity of >18
MOhm.cm and low TOC level (<10 ppb).
26 175_0010 - DECADE Elite / Lite user manual - rev 13

Unpacking
Inspect the transport box for possible damage as it arrives. Immediately in-
form the transport company in case of damage, otherwise she may not ac-
cept any responsibility. Keep the transport box as it is designed for opti-
mum protection during transport and it may be needed again. Carefully un-
pack the system and inspect it for completeness and for possible damage.
Contact your supplier in case of damage or if not all marked items on the
checklist are included. Prior to shipment, your detector has been thor-
oughly inspected and tested to meet the highest possible demands. The
results of all tests are included.

See check list below for reference:

(1) Delivery is in accordance with order O

(2) Delivery is undamaged O
(3) All items on checklist(s) are included O
(4) Certificates of performance are included:
- detector O
- flow cell(s)* O
(5) User manual(s) is (are) included on USB stick O

*) Note that flow cells are not part of the DECADE Elite detector and have
to be ordered separately.

To unpack the detector, lift it from its box by both hands (Fig. 1). Never lift
the detector at its front door, but at its sides.

Fig. 1. Lift instructions DECADE Elite.

CHAPTER 2 Installation 27

With both hands under the instrument lift the detector and bring it to its op-
eration location. Install the detector in an area which meets the environ-
mental conditions.

Fig. 2. Location of ventilation holes in the DECADE Elite (bottom & rear).

Remove the protective tape from the detector LCD screen. Leave the in-
strument to adopt ambient temperature for at least half an hour in the
place of installation.

In case the instrument was stored cold (< 10°C) and switched on immedi-
ately, the oven might not work. This is by design (at temperatures below
10°C the heater is switched off in the embedded software). Remedy: just
allow the detector (electronics) to warm up a little longer to adopt ambient
before switching on the oven.

Use the detector indoors only. Place the potentiostat upright (on its
instrument feet) on a stable, flat and smooth surface. Do not place the
instrument in an area subject to excessive dust or shocks.
Do not place it near a source of heat or in direct sun light, as this may
influence the heating capabilities of the instrument. Make sure the
potentiostat is placed in such a way that the mains power connection
can be reached easily to disconnect it from the mains power by
removing the Mains power cable. Do not block the ventilation holes at
the back and bottom of the instrument (Fig. 2.). Blocking might impair
the cooling capability of the power supply.

Do not place heavy object/instruments on top of the detector. Objects can

be placed on any side of the potentiostat; however, make sure these ob-
jects are placed at a distance of 5 cm from the potentiostat, in case that
28 175_0010 - DECADE Elite / Lite user manual - rev 13

objects are placed at only one side of the instrument. and 10 cm from the
instrument, if objects are placed on both sides of the instrument.

Mains connection
Check that fuses and voltage range on the rear side of the instrument
match that for the power outlet to be used.

Power supply and protective earth: The system must be connected to a

suitable mains power supply with a correctly installed protective earth
conductor. Never use the system without a properly connected
protective earth conductor.

Leave the instrument powered off until specifically mentioned in the proce-
dure below.

PC connection
Follow the instructions in this paragraph when the instrument is used with
PC control over LAN using the Dialogue Elite, DataApex Clarity, Agilent
OpenLab CDS, Agilent OpenLab Chemstation or Thermo Chromeleon
CDS. This section can be skipped if the instrument is used stand-alone
(DECADE Elite only). To be able to communicate over LAN a computer is
required with a free (PCI, PCI Express or PCI-X) LAN port.

The DECADE Elite has a fixed IP address: 192.168.5.1, with subnet mask:
255.255.255.0. Gateway and DNS are not filled in.

The instrument is standard delivered with a special crossover LAN (UTP)

cable (pn 250.0170) which is part of the DECADE Elite accessory kit (pn
175.0200).

To ensure stable and error-free communication only use the

manufacturer-supplied LAN cable to connect the DECADE Elite to LAN.
Create a small dedicated local area network to connect the DECADE
Elite to the PC. Do not connect the DECADE Elite over a company Local
Area Network. If needed a second network adapter with a different
(unique) IP address range can be applied.
CHAPTER 2 Installation 29

In the following section the procedure to connect the instrument to the PC

using the crossover UTP cable is described. Configure the IP address of
the PC LAN network card by executing the following steps (in this example
the Windows 10 OS is used, in an older Windows OS the example screens
may look different):

1. Right click on the Network icon in the bottom right of the Windows
taskbar and open the menu 'Network & Internet settings'. Alterna-
tive: open Windows start menu, open Setting menu and open Net-
work & Internet menu.

2. Open the menu 'Change adapter settings' on the right panel of the
'Network & Internet window.
30 175_0010 - DECADE Elite / Lite user manual - rev 13

3. Right click on the Local Area Connection icon of the LAN card in
your PC and click on properties to open the Network card setting.

4. Open the menu 'Internet Protocol Version 4 (TCP/IPv4)' menu

(double click).
CHAPTER 2 Installation 31

5. Configure the network IP address and subnet mask as depicted in

the screen dump below (IP 192.168.5.10, Subnet mask:
255.255.255.0). Gateway and DNS fields are not filled.
6. Close the menu(s) by clicking the 'OK' buttons. The network IP ad-
dress of the LAN network card is now set up for communication
with the DECADE Elite.
7. Connect the crossover (UTP) cable to the RJ45 Jack of the LAN
card of your PC (typically located on the backside of a desktop
PC).
8. Connect the other end of the crossover LAN (UTP) cable to the
LAN port on the rear panel of the DECADE Elite as depicted on
the photograph.
9. Switch on the DECADE Elite. Set the detector temperature to
35°C if an Operational Qualification (OQ) will be executed, or set it
to the temperature at which your ECD application is running. Allow
the instrument to stabilize for at least half an hour before starting
experimental work or performing an OQ. The OQ is described in a
separate manual available on the Antec website.

Fig. 3. Example of LAN connection between PC and DECADE Elite. A di-

rect connection requires the special crossover UTP cable delivered in the
detector ship kit. With a Ethernet switch any regular UTP cable can be
used.
32 175_0010 - DECADE Elite / Lite user manual - rev 13

Software
The DECADE Elite can be used remote in combination with PC control
software. The following software packages are available for control of the
DECADE Elite electrochemical detector:

Vendor Software Version†

Antec Dialogue Elite 2.20.2.1
DataApex Clarity CDS 8.3
Agilent OpenLab CDS1 2.3
Agilent OpenLab CDS, Chemstation Ed.1 C.01.09
1,2
Thermo Chromeleon CDS 7.2 SR 5
Waters Empower1,3 3

1) Besides a valid CDS license an additional (paid) license is required to enable the detector
control driver in the CDS. Contact Antec Scientific for detailed info and pricing.
2) The Chromeleon CDS license should include an Instrument class 3 license to be able to
control the DECADE Elite.
3) The Empower 3 license should also include a Agilent LC control license to be able to
control the DECADE Elite. Empower ICF Support Layer V3.5 or higher is required.
†) Version compatibility: compatible with the listed version and up.

In the chromatography CDS drivers only DC and Pulse mode are sup-
ported (no SCAN mode support), and up to a maximum of two flow cells
can be controlled (exception: in Clarity up to 3 flow cells). Only DECADE
Elites with FW version 1.09 or higher can be controlled with the CDS soft-
ware.

The Antec Dialogue Elite software is used for instrument control and Quali-
fications and is also required for the upload of new firmware (= embedded
software controlling the DECADE Elite electronics). In this section the in-
stallation of Dialogue Elite and configuration is shortly described. Note: this
is by no means a replacement of the installation documentation available
for the software packages. Please refer to the software documentation for
details.

Ensure you have Administrator access rights in your system before

you start with the installation of the software packages. Dialogue Elite
users must have read/write access to all software (sub) folders.
CHAPTER 2 Installation 33

Dialogue Elite
To install the software:

• Download the latest version of the Dialogue Elite from the Antec
website www.antecscientific.com (register to get access).
• Double click on the setup.exe file to start the installation wizard
• Follow the instructions of the installation wizard for successful
installation of the software.
• Insert the Dialogue Elite license dongle to get full access to the
software (without dongle it will operate in demo mode).
• Make sure that the LAN connection is configured and the LAN
cable is connected.
• Power up the detector by means of the mains switch on the rear
panel.
• Start the program Dialogue Elite from the Windows start menu.
• During start-up the ‘Select devices’ menu will pop-up as shown
below.

• When a DECADE Elite detector is available it is automatically

detected and the IP address is shown in the port settings box. If
not press port scan or type in the default IP address 192.168.5.1.
34 175_0010 - DECADE Elite / Lite user manual - rev 13

• The pull down field shows all responding devices with their IP and
MAC address. In case of doubt check the device unique MAC
address on the rear panel IO connector.
• Type OK. The instrument will connect and is ready for use.

Clarity Chromatography software

In the case an ALEXYS Analyzer was purchased which includes preconfig-
ured Clarity software installation files please refer to the installation infor-
mation shipped with the ALEXYS system, otherwise, see instruction below
to install the software:

• Open the official installer of the Clarity Chromatography software

on the supplied Antec Scientific USB memory stick.
• For disk space requirements and detailed installation information
see the official Clarity ‘Getting Started’ manual. It can be
downloaded from the DataApex website www.dataapex.com.
• Select the INSTALL.EXE file and double click it (if installation does
not automatically start.
• The software installation wizard will guide you through the
installation process including creation of a Clarity menu in the
Windows start menu and a Clarity quick start icon on the PC
desktop.
• When asked during the installation fill in the license key code of
the Clarity license dongle purchased. To be able to control the
DECADE Elite you need to have at least the following Clarity
modules: single instrument SW module + the LC control module.
• Insert the license dongle.
• Make sure that the LAN connection is configured and the LAN
cable is connected.
• Power up the detector by means of the mains switch on the rear
panel.
• Start Clarity by double clicking on the quick start icon on the
desktop.
• Open the ‘Configuration’ menu from the ‘system’ pull-down menu
in the Clarity main window:
• Add (button bottom left field) the DECADE Elite control module
(listed under detectors).
• The detector set-up menu will open (see figure on the next page).
Select LAN communication (checkbox) and fill in the IP address
192.168.5.1.
CHAPTER 2 Installation 35

• By clicking ‘Auto detect’ the instrument will be automatically

connected and the number of available sensor boards shown.
• Set the desired heater temperature. For valve control check the
‘valve connected’ box.

• The instrument has a CRC-32 check on the data communication

to correct for transmission errors. It is advised to have the CRC-32
check switched on.
• For use of the analog start trigger to start a run using an external
device, open the ‘Digital Inputs’ and select ‘Sensor 1 – start in’.
36 175_0010 - DECADE Elite / Lite user manual - rev 13

Connect the relay (contact closure) of the external device which

functions as inject trigger to the ‘digital IO connector on the rear
panel of the detector to pin 21 (start 1) and pin 25 (ground). For
sensor board 2 or 3 use pin 22 (start 2) and pin 23 (start 3) re-
spectively.

• Add the DECADE Elite device to the Clarity instrument by clicking

the right arrow button (encircled) and select Ext. Start. Dig. Input
‘Device DECADE Elite, Number 1’ to enable an external start
trigger.
• In case an ALIAS, SINEAS, AS 110 auto sampler is used to trigger
a run digitally (via RS232, LAN, USB etc) please refer to the
corresponding Clarity instruction manual of the specific control
module.
• Type OK and login to your Clarity instrument to connect and the
DECADE Elite is ready for use.
CHAPTER 2 Installation 37

HPLC fluid connections

In this section the installation & priming of all relevant fluidic connections
are described to be able to use the DECADE Elite for the analysis of sub-
stances with (U)HPLC-ECD. When working with HPLC solutions and mo-
bile phases take the following precautions:

Use proper eye and skin protection when working with solvents. The
solvents used may be flammable, toxic or corrosive. Organic sol-
vents are toxic above a certain concentration. Ensure that work areas
are always well-ventilated! Use of open fire in the vicinity of this sys-
tem must be strictly prohibited. Do not install the system in the same
room with any other equipment that emits or could potentially emit
sparks. Wear protective gloves, safety glasses and other relevant
protective clothing when working on the device!

With respect to third-party (U)HPLC equipment, such as LC pumps, auto

samplers, injection valves, column heaters etc. used in combination with
the DECADE Elite Detector. The equipment connected to the system
should be specifically designed for use in (Ultra) High Performance Liquid
Chromatography and capable of delivering flow rates typically in the range
between 1 µL/min up to 2 mL/min.

The manufacturer will not accept any liability for damage, direct or
indirect, caused by connecting this instrument to devices that do not
meet the relevant safety standards.

Tubing connectors
For optimal operation it is of the utmost importance that all tubing connec-
tions on the injection valve, columns and flow cells of the injection valves
are made without introducing dead volumes to minimize peak broadening,
carry-over etc.

Use only the original polymeric fingertights supplied by Antec with the
purchased flow cell to make LC connections on the flow cells inlet and
outlet. Do not use metal tubing on the flow cell because it may lead to
damage or incorrect operation of the flow cell. Use PEEK, PEEKsil or
Fused Silica tubing (with FEP sleeves).

For columns and injection valves etc. use only nuts, ferrules or finger tights
recommend by the respective manufacturer of the parts. So for Vici Valco
38 175_0010 - DECADE Elite / Lite user manual - rev 13

valves use Valco nuts and ferrules, for Rheodyne valves use Rheodyne
valves etc. The use of unsuitable connectors may lead to damage of the
parts or the introduction of dead volumes. In case the DECADE Elite was
purchased as a part of an ALEXYS HPLC-ECD analyzer, the instrument is
shipped with a complete set of dedicated tubing assemblies (LC connec-
tion kits) tailor-made for the application the analyzer was specifically de-
fined for.

Please note that the tubing length (length L below) required to make a
good connection differs for each brand of connection. If length L is not cor-
rect, this will result in faulty peaks and carry-over. Essentially, when you
create a connection the ferrule on the tubing is compressed into the valve
to make sure that the connection is leak-tight. Take the following into ac-
count when creating the connection:

If L is too long, the ferrule cannot form a seal in the connection. This may
cause
Irreparable damage port of the valve, column or other part, as:

• Part of the tubing may end up in the connection port internals

• Internals of the port may be damaged.
CHAPTER 2 Installation 39

If L is too short, this may result in:

• Leakage
• Dead volume at the end of the ferrule (a ‘mixing chamber’).

Every ferrule type needs an appropriate length of tubing for connecting it to

the type of connection port, depending on the depth of the connection port.
Refer to the information provided by the manufacturer for specific infor-
mation.

Mobile Phase
Electrochemical detection is a sensitive detection technique characterized
by extremely low detection limits. A typical detection limit of 100 pmol/L or
lower for catecholamines is no exception. Improving detection limits will al-
ways be limited by the weakest link in an LC-EC system. In daily practice a
couple of ‘rules’ must be obeyed to fully exploit the incredible linear dy-
namic range and low detection limits of an EC detector. These are not only
hardware related, but also refer to mobile phase composition, degassing,
temperature and pH stability and several other issues.

Mobile phase requirements:

• Electrochemically clean, HPLC grade or better

• Ion strength 20 - 200 mmol/L
• Buffer pH near pKa
• In-line 0.2 µm filter & degassing of mobile phase
• EDTA for trapping of metal ions

Mobile phase must be clean as it is in direct contact with the working elec-
trode in EC detection. High purity chemicals including water is a pre requi-
site. In some applications EDTA is added to the mobile phase to traps
electrochemically metals such as Fe2+ by forming an inactive complex.
40 175_0010 - DECADE Elite / Lite user manual - rev 13

However at higher working potentials (typically > 1.2 V vs. salt bridge AgCl
ref) also EDTA can become electrochemically active and is not recom-
mended. In that case only a passivation step with 15% HNO3 is recom-
mended (see installation guide).
Electrolytes assure contact between 3 electrodes in an electrochemical
flow cell. Low ion strength destabilizes an EC system and noise will in-
crease. Extremely high buffer concentrations cause problems of salt for-
mation. Therefore concentrations between 20 and 200 mmol/L are recom-
mended.

Also constant pH is important for baseline stability and reproducible re-

sults. Stability of pH is best when close to pKa of a buffer ion. Often used
buffers are phosphate, carbonate, acetate and citrate. Modifiers such as
methanol, propanol and acetonitrile can be used without problems in DC
amperometry, but not in pulsed amperometric detection as peaks are
strongly attenuated. In our experience the quality and expiration date of or-
ganic modifiers can be a problem resulting in increased noise levels.
Metal inlet frits in mobile phase bottles are not advised as metal ions are
introduced that increase baseline noise. Instead 0.2 µm nylon inlet filters
are recommended.

Vacuum degassing: Considerable amounts of the gases N2, O2 and CO2

may be dissolved in HPLC mobile phases. Whenever the temperature
changes, solvents are mixed or a pressure reduction occurs, these gases
may show up as very small air bubbles. To avoid noisy baselines an in-line
Teflon AF vacuum degasser has been integrated in the ALEXYS analyzer.
It has a low dead volume (less than 0.5 mL) and high degassing efficiency.
The advantage over helium degassing is that the degasser does not
change the mobile phase composition.

Helium degassing: Degassing using helium is an effective and universally

applicable method but only recommended when working in reductive elec-
trochemical detection and pulsed electrochemical detection (analysis of
carbohydrates using anion-exchange chromatography with NaOH as mo-
bile phase). All gases except helium are removed completely. Helium is
not EC active and does not change the mobile phase properties signifi-
cantly. To prevent mobile phase contamination, only high-purity helium
must be used.
CHAPTER 2 Installation 41

Installation & start-up

Please carefully follow the next steps for a successful installation and start-
up:

1. The installation of the flow cell and column is shown in Fig. 4.

2. If a manual injector is applied with position sensor, the sensor
cable must be connected to the VALVE connector on the rear
panel to enable INJECT/LOAD functions. In the CONFIG screen
the valve option should be set to 'Valve = present' manually.
3. An electrically actuated valve of Vici Valco (type E2CA, EHCA)
can be connected & controlled by the DECADE Elite. For that
purpose a serial valve cable is required. The serial cable should
be connected to the VALVE connector on the rear panel of the
instrument to enable INJECT/LOAD functions. This presence of
this valve is automatically detected and no further configuration
has to be performed.

Fig. 4. Installation of flow cell and column in the DECADE Elite.

4. Prior to connection of the HPLC system to the detector all metal
parts should preferably be passivated with 15% nitric acid during
42 175_0010 - DECADE Elite / Lite user manual - rev 13

20 min. The acid is flushed through the pump, the pump tubing,
the dampener, the injector (in load and inject position) and to
waste

Make sure that all parts that are not acid-resistant such as: nylon inlet
filters, column and flow cell are not connected during this step.

5. After flushing with nitric acid, the system must be thoroughly

flushed with demi water. Make sure that no traces of nitric acid are
left in the tubing or pulse dampener (check with pH paper). Flush
the system with HPLC buffer.

If an ISAAC™ reference electrode is used, make sure that the mobile

phase contains at least 2 mmol/l chloride (KCl or NaCl) ions.

6. Before connecting a new column read the manufacturer’s

instructions. Our experience is that thorough pre-conditioning of a
column is always required. Only a pre-conditioned column is
electrochemically clean. If not, the background current may be
unacceptably high and substantial fouling of the working electrode
occurs. For reversed phase columns flushing with 50% methanol
in water for 3 days at a low flow rate is highly recommended.
Before switching to mobile phase, flushing with water (10 column
volumes) is recommended to prevent precipitation of buffer salts.

7. Passage of air bubbles through the flow cell will lead to

unacceptable noise levels and ‘spikes’. Therefore, the use of an
in-line degasser is strongly recommended. In our experience, a
one-time degassing step of the HPLC buffer is almost never
sufficient. If the DECADE Elite is used for reductive ECD (at a
negative working potential) additional steps should be taken to
remove oxygen from the mobile phase. These include degassing
with Helium and the use of stainless steel tubing.

8. Consult your flow cell manual for detailed information about the
installation of the flow cell. Although the oven of the detector can
be operated in a temperature range from 7 °C above ambient to
60°C, do not operate the flow cells above 50°C.

Do not use the flow cells at temperatures above 50°C, higher

temperatures might lead to damage of the cell. Do not touch the metal
parts inside the oven compartment because they could be hot and may
cause burns.
CHAPTER 2 Installation 43

9. See figure 5 for reference how to make the electrical and fluid
connections. Connect the flow cell to the corresponding cell
connector in the oven compartment. All cell connectors are
marked with a label for identification. In case of a DECADE Elite
SCC connect the flow cell to the cell connector on the left side
marked “Cell 1”.

The cell connector inside the oven compartment is ESD sensitive. Make
sure that the flow cell is OFF when removing or connecting the cell
cable.

Never switch ON the flow cell when:

(1) the cell cable is not correctly connected,

(2) the cell is only partly (or not at all) filled with mobile phase,
(3) the outside of the flow cell is wet, particularly the part between the
auxiliary and working electrode connection, because substantial
damage to the working electrode or electronics may occur.

Fig. 5. Left: SenCell with ISAAC reference mounted under an angle of ap-
proximately 45° in the detector. [1] Cell clamp, [2] Cell Inlet (tubing connec-
tion from column–to–cell), [3] Cell outlet (tubing connection from cell-to-
waste) make sure that the outlet is positioned on the top side to prevent
entrapped air bubbles, [4] WE contact (red), [5] AUX contact (blue), [6]
REF contact (black). Top-right: electrical connections of WE (red con-
nector) and AUX electrode (blue connector). Bottom-right: SenCell with
Salt Bridge reference electrode.
44 175_0010 - DECADE Elite / Lite user manual - rev 13

10. Before switching ON the flow cell, make sure that the mobile
phase contains sufficient electrolyte (buffer ions). A stable
baseline will never be obtained if the cell is switched ON with only
water or another non-conducting mobile phase. Also be sure that
no air bubbles are trapped in the flow cell.

11. The outlet tubing from the flow cell should lead to a reservoir that
is at a higher level than the flow cell. This ensures a small back
pressure which prevents air-bubble entrapment. The outlet tubing
should be under the liquid level, to avoid electrical noise induced
by ‘dripping’ of mobile phase.

12. Set the cell potential (see page 99 for optimization of the
potential), switch ON the flow cell and allow the system to stabilize
for approximately 30 min. A ‘good’ stabilization curve shows a
mono-exponential decline without jumps and/or spikes.

13. Connect the DECADE Elite to the PC control software (Clarity or

Elite Dialogue). In the case the instrument is used stand-alone
connect an external A/D converter or recorder to the ‘Analog data
output’ (1 V full scale) on the rear panel. Refer to the
documentation of the third-party software controlling the A/D
converter for detailed instruction how to set up a measurement
with the A/D device.

Your system is now ready for use. The DECADE Elite has been developed
for continuous operation. For maximum stability it is advised to leave the
system ON continuously. If preferred, the flow cell may be switched OFF at
night.
CHAPTER 3 Maintenance & Shutdown 45

C H A P T E R 3

Maintenance & Shutdown

Maintenance
In this paragraph all maintenance is described which can be performed by
the end-user, all other maintenance & service procedures may only be per-
formed by authorized service engineers only.

Periodic check for leakage

Perform leak checks on LC tubing, flow cells and connections on a daily
basis and check if the drain on the bottom of the oven compartment is not
blocked or closed. Do not allow flammable and/or toxic solvents to accu-
mulate. Follow a regulated, approved waste disposal program. Empty and
clean waste container regularly. Never dispose of such products through
the municipal sewage system. Check daily that the mobile phase bottles
contain enough mobile phase for the number of analysis planned to be
Executed.

Periodic check of the oven temperature

The operator should perform regular checks to verify if the actual oven
temperature is in accordance with the set temperature of the DECADE
Elite.

In case the actual temperature exceeds 70°C switch off the potentiostat
immediately do not touch the metal parts inside the oven compartment
because they could be hot, and contact the manufacturer or its
representatives for service. Do not use/switch on the instrument before
the instrument is serviced at the factory.

In the event of a heater defect and the temperature exceeds 70°C the in-
strument will come up with an error message (Err 23).
46 175_0010 - DECADE Elite / Lite user manual - rev 13

Flow cell
Check the performance of the detector & flow cell on a daily basis by eval-
uating background current, noise and signal. An increase in background
current, noise and/or loss of sensitivity may be a sign of contamination of
the working electrode (WE) and/or a sign that maintenance is required on
the reference electrode (REF) of the flow cell. If necessary perform mainte-
nance on the flow cell. Detailed information about flow cell maintenance in-
structions are described in the user manual supplied with the specific flow
cell (SenCell, VT-03 or FlexCell) purchased in combination with your de-
tector.

Cleaning
In general, the DECADE Elite needs very little maintenance. The outside
of the detector may be cleaned with a non-aggressive cleaning liquid.

Do not use any organic solvents to clean the exterior of the detector,
because this may lead to damage of the paint layer.

In case of leakage in the cell cabinet (tubing, connectors, cell, column etc.)
remove the spilled mobile phase or other solutions as soon as possible be-
cause this may damage the paint layer, or result in the deposition of salt
crusts (in case of buffered mobile phases), which could block the drain in
the bottom of the cell cabinet. Remove any dust on the protective screens
that cover the fans in the oven compartment.

Replacement of fuses
Replace blown fuses with fuses of proper type and rating as stipulated on
the rear panel and specified in the installation section of this manual. The
fuse holder is integrated in the mains connector. Ensure that the instru-
ment is never put in operation with fuses of a different type. This could
cause fire.

In case the fuses blow out repetitively contact Antec or its representatives
for instructions and/or service of the instrument.
CHAPTER 3 Maintenance & Shutdown 47

Shutting down the system

There are a couple of steps to take to switch off an LC system with electro-
chemical detector for a longer period of time. Shutting down is not different
from most other HPLC systems. Perform the following procedure:

• Switch off the flow cell using the keyboard (standalone) or via the
software (Clarity or Dialogue Elite).
• Check the column(s) documentation for the appropriate storage
liquid, apply this and make sure the column is properly flushed. A
reversed phase C18 column is usually stored with 50%
Acetonitrile/water.
• Take out the column, mount the corresponding end-caps and store
the column in an appropriate place.

Avoid precipitation of high salt concentrations in organic solvent, first

wash out salts with water if necessary.

• Flush and store the system with 50% water/acetonitrile (or

methanol). Switch the injector valve between load and inject a few
times. Make sure all tubing, filters etc. are flushed so no traces of
salt are left that could precipitate and clog the system.
• Remove the flow cell from the system by disconnecting the inlet
and outlet capillary.
• Open the cell, flush with water, use some tissues to carefully dry
the cell. Be careful not to damage the spacer in the case of a VT-
03 or FlexCell (the SenCell does not have a spacer).
• Close the cell and store dry. In case of salt bridge REF, store the
REF separately with a cap on it to prevent drying out. Alternatively,
put the sb-REF in a 10 mL vial under a KCl solution and close the
vial with a cap.
• Switch off the detector (and other LC equipment) via the mains
switch (switch to position ‘0’) on the rear panel.
48 175_0010 - DECADE Elite / Lite user manual - rev 13
Chapter 4 DECADE Elite controller 49

C H A P T E R 4

DECADE Elite controller

Introduction
The DECADE Elite has been designed for maximum functionality and ease
of use. The control of ECD parameters via the keyboard & LCD display
(DECADE Elite only) is such that without reading this chapter, it should be
possible to operate the detector. This chapter is intended as a reference
guide in case questions arise during operation.
The information shown in the numerous screens is presented in alphabeti-
cal order. For each item an explanation is given, together with the item’s
nature and the screen(s) of appearance. The nature of an item can be:
1. Control: parameters with a cursor box (‘’) can be attained via
cursor buttons and changed by the ‘value’ button.
2. Status: without a cursor box a parameter reflects the current
status.
3. Functions: parameters in CAPITALS are commands accessible via
function buttons F1 - F5.
4. The 'Enter' button is only used to accept changes in cell potential
and range.
In the top right corner of each screen the name of the present screen is
displayed. If available, the bottom left function button displays a previous
screen, and the bottom right one the next screen.

Fig. 6. DECADE Elite keyboard. The cursor is on ‘Range’ which allows

changes using the value buttons ‘+’ and ‘-’. The ‘Enter’ button is only used
to confirm changes in potential (Ec) and range.
50 175_0010 - DECADE Elite / Lite user manual - rev 13

Overview of DECADE Elite screens

DC mode
Chapter 4 DECADE Elite controller 51

Pulse mode
52 175_0010 - DECADE Elite / Lite user manual - rev 13

SCAN mode
Chapter 4 DECADE Elite controller 53

CONFIG menu
54 175_0010 - DECADE Elite / Lite user manual - rev 13

DIAG menu
Chapter 4 DECADE Elite controller 55

Parameters
Explanation: Type S is status, F is function and C is control.

Parameter Screen Description Type

28 > 30˚C dc stat Displays the actual (left value) S
pulse stat and the pre-set oven
scan stat temperature (right value).
run
AZERO pulse stat dc Sets the output voltage to 0 V, or F
stat, run, pulse to the offset voltage. Control
stat, scan stat Comp = off changes to Comp =
on. If cell current exceeds the
max. compensation a message
“cell current exceeds max.
compensation” appears. In that
case max. compensation will be
applied, which may not be the 0
Volt level but higher.
Boot system Displays boot firmware version S
CELL=ON/ dc stat, pulse Toggles between cell ‘ON’ and F
OFF stat, scan setup, ‘OFF’. Confirmation is required
scan stat “Switch cell on (off)?” Switching
on resets the clock to 0.00. Pulse
mode: pulsation occurs as long
as the cell is on, irrespective
which screen is selected. Scan
mode: potential E1 is applied.
Checksum system Displays checksum S
Comp dc stat, pulse Toggles between ‘ON’ and ‘OFF’, C
stat releases auto zero offset.
Switches ON if AZERO is
pressed. Affects auto zero
compensation only, not the %
offset!
CONFIG main Enters config screen F
Contrast config Sets the contrast of display C
56 175_0010 - DECADE Elite / Lite user manual - rev 13

Parameter Screen Description Type

Cyc scan setup Controls the nature of the cycle: C
half, full and continuous. ‘Half’
means that the cell potential runs
from E1 to E2 and stops at E2 (/|
). ‘Full’ means that the cell poten-
tial runs from E1 to E2, and back
to E1, and then stops (/\). ‘Cont’
means that the cell potential runs
from E1 to E2 and back to E1
continuously (/\/\/\/\……..). Press-
ing “STOP” or finishing the cycle,
sets the potential to E1.
DIAG main Enters Diag screen F
DISPL test Enters DISP screen for display F
test.
E1, E2, E3, pulse setup2 Controls the cell potential C
E4, E5 pulse setup3 settings of the pulse. Can be set
between +2.50 and –2.50 V with
10 mV steps. Can only be set or
changed after confirmation with
the ‘enter’ button.
Ec dc setup Controls the cell potential, can be C
set between +2.50 and –2.50 V
with 10 mV steps. Can only be
set or changed after confirmation
with the ‘enter’ button.
Ec run (dc only), Reflects the set cell potential. S
scan stat (during Displays the actual cell potential
scanning) in the scan mode.
Filt dc setup, dc stat Filter settings: RAW (100 Hz), C
(DC mode) Off (10 Hz) and 1 Hz to 0.001 Hz
cut off frequency, in 1, 2, 5 steps.
Filt pulse setup, Filter settings: Off and 0.5 Hz to C
(PULSE pulse stat 0.001 Hz cut off frequency, in 1,
mode) 2, 5 steps. (Fcut-off / filter
coefficients based on 1 Hz input
frequency in pulse mode )
Filt run Reflects the actual filter setting. S
Firmware system Displays firmware version S
Hold run, scan stat Toggle, holds or resumes S
resume execution of scan.
Chapter 4 DECADE Elite controller 57

Parameter Screen Description Type

HOLD=0,1 run, scan stat Holds or continues execution of S
scan. Toggles between 1 and 0.
Pressing hold again continues
scan were it has been hold.
Ic stat (dc, pulse, Displays the true, non- F
scan), , run, compensated cell current,
noise unaffected by auto zero or offset.
ID1 master config Sets sensor board 1 as master. F
When this setting is set to ‘yes’
all parameter settings from
sensor board 1 are automatically
copied/transferred to all other
sensor boards present.
IO Config Enter IO menu S
INJ=I/L dc stat, pulse Displays or switches the position C
stat of the injection valve, toggles
between inject (I) and load (L). If
a manual injector with position
sensor is applied, it echoes the
position of the injector. If an
electrically actuated injector is
used (optional) it is possible to
switch the injector with this
function button.
KEYB test Enters ‘KEYB’ screen, for F
keyboard test. Press 2x F1 to
leave.
MARK dc stat, pulse Triggers a marker signal on F
stat output.
MaxComp dc setup, pulse Maximum cell current that can be S
setup1 compensated for using auto
zero.
Next several screens Enter next screen F
NOISE test Enters NOISE screen for F
performance test.
Offs dc setup, dc Percentage offset, can be set C
stat, prog, pulse between -50 and +50%.
setup1, pulse
stat, scan setup,
scan stat
58 175_0010 - DECADE Elite / Lite user manual - rev 13

Parameter Screen Description Type

POLAR dc setup, pulse Inverts output polarity, toggle F
setup2 between + and -. Requires
confirmation.
PREV several screens Return to previous screen F
P11(OVLD) IO Programmable output: can be C
configured that the overload
(OVLD) signal of cell 1, 2 or 3
only is present on pin 11 when
active or ALL cells.
P12(C-ON) IO Programmable input: can be C
configured that only cell 1, 2 or 3
is switched ON when active, or
ALL cells.
P15(C-OFF) IO Programmable input: can be C
configured that only cell 1, 2 or 3
is switched OFF when active, or
ALL cells.
P18(AZERO) IO Programmable input: can be C
configured that the signal of cell
1, 2 or 3 is zeroed when active,
or ALL cells.
P21(START) IO Programmable input: can be C
configured that the data-
acquisition on sensor board 1, 2
or 3 is started when active, or on
ALL sensor boards.
Range dc setup, dc Range setting, varying from 10 C
stat, prog, pulse pA to 200 µA full scale, in 1, 2
setup1, pulse and 5 steps. In the pulse and
stat, scan setup, scan mode 10 nA to 200 µA full
scan stat scale can be used.
S scan setup Scan speed, can be set from 1 - C
100 mV/s in 1, 2, 5 steps.
SPD scan stat Scan speed, can be set from 1 - C
100 mV/s in 1, 2, 5 steps.
START scan stat Starts a scan in scan mode. F
STOP scan stat Scan mode: STOP aborts scan F
and resets cell potential to E1.

SYSTEM diag Enter SYSTEM menu F

Chapter 4 DECADE Elite controller 59

Parameter Screen Description Type

t pulse setup2, Displays the total duration of one S
pulse stat pulse (t1 + t2 + t3 + t4 + t5).
t1, t2, t3, t4, pulse setup2 Duration of potential step E1, E2, C
t5 pulse setup3 E3, E4 and E5. Time can be set
between 0 (t2 – t5) or 100 (t1)
and 2000 ms in 10 ms
increments. Maximum pulse
duration is 9999 ms.
Temp config Controls the temperature of the C
oven. Range: off, 15 - 60˚C,
selectable in 1˚C steps. The
oven is stable from 7˚C above
ambient oven temperature.
ts pulse setup2 Controls the duration of the C
sampling time in the pulse mode.
The time can be set between 20
ms and maximum t1-60ms with
20 ms increments.
Tsensor system Displays active temperature S
sensor
Valve config User confirmation whether a S
manual valve is connected to
phone jack C on rear panel. If
present: INJ=I or INJ=L appears
in DC/Pulse Status screen
Vout stat (dc, pulse, Displays output signal. S
scan), run, noise
Vout source config Sets the output source from the S
analog data output: DAC
(processed digital signal after 16-
bit AD conversion) or I/E (true
analog signal from the I/E
converter)
60 175_0010 - DECADE Elite / Lite user manual - rev 13

Dialogue Elite
Dialogue Elite for Windows is a multi-functional program to control the
DECADE Elite and DECADE Lite electrochemical detector.

Fig. 8. DECADE Elite Detector window in Dialogue Elite. On the detector

tab the main measurement conditions can be set/controlled (measurement
mode & potential settings)

Dialogue Elite is a tool for:

• Controlling all operational parameters

• Programming timed events in one run or sequence*
• Scanning voltammetry
• Firmware upgrades using the FW upgrade wizard
• OQ, PQ and dummy cell measurements
• Device calibration

*) An example of an simple event table is shown on the next page. This

event table will execute an autozero after 0.10 minutes after start of a run.
The start of the event table is triggered by a hardware TTL trigger. Pin 21
‘Start’ on the digital IO connector on the rear panel.
Chapter 4 DECADE Elite controller 61

Fig. 9. Example event table.

There are no tools for further data analysis, therefore Dialogue cannot be
considered as fully featured chromatography software package. The free
demo version of this program has already all functionality implemented,
functionality is unlocked by a license dongle.

The free version is primarily used for controlling all operational parame-
ters of the detector. The free version cannot be used for starting a run, run-
ning a calibration or OQ. The DECADE Lite does not have a keyboard and
display, and are fully controlled by the free Dialogue software.

For details about the use and functionality of the Dialogue Elite software
please refer to document 175.0015 Dialogue Elite user manual which can
be downloaded from the Antec website (www.antecscientific.com).
62 175_0010 - DECADE Elite / Lite user manual - rev 13

Clarity DECADE Elite control module

Full control and data acquisition of the DC and Pulse measurement mode
for both the DECADE Elite and Lite is supported in the Clarity chromatog-
raphy software.

Fig. 10. DECADE Elite method window in Clarity. On the main tab the
main measurement conditions can be set/controlled (measurement mode
& potential settings).

Within a Clarity method it is possible to execute timed event by program-

ming time lines under the Time table tab. Running a Time table enables
time-based, automated parametric control of the electrochemical detection
(ECD) during a run. This is particularly useful when during a run settings
have to be changed such as the sensitivity, auto zero or control of external
equipment.

The SCAN mode is not supported in Clarity. Scanning Voltammetry is

supported in the Elite Dialogue software.
Chapter 4 DECADE Elite controller 63

Chromeleon CDS
Full control and data acquisition of the DC and Pulse measurement mode
for the DECADE Elite is supported in Chromeleon CDS version 7.2 SR5
and higher (ThermoFisher Scientific, USA).

Fig. 11. Chromeleon console showing a ECD e-panel with method settings
and acquisition window.

Within a Chromeleon instrument method it is possible to execute timed

event by programming time lines. Running a Time table enables time-
based automated parametric control of the Exceed potentiostat. This is
particularly useful when during a run, parameters such as the cell potential
settings have to be changed, to set for example the optimal oxidation po-
tential for different target compounds eluting during a run.

The SCAN mode is not supported in Chromeleon CDS. Scanning

Voltammetry is supported in the Dialogue Elite software only.

For details about the requirements, use and functionality of the DECADE
Elite control driver in Chromeleon please refer to document 176.0108
DECADE Elite driver for Chromeleon CDS user manual, which can be
downloaded from the Antec website (www.antecscientific.com).
64 175_0010 - DECADE Elite / Lite user manual - rev 13

OpenLab CDS
Full control and data acquisition of the DC and Pulse measurement mode
for the DECADE Elite is supported in OpenLab CDS version 2.3 and
higher (Agilent, USA). The DECADE Elite is supported in OpenLab Chem-
station version C.01.09 and higher.

Agilent OpenLab CDS is a fully featured data acquisition software. The

DECADE Elite driver adds full instrument control for Electrochemical De-
tection (ECD) up to 2 channels in a single time base. Supported is the DC
mode with constant potential measurement for most applications, and
the PULSE mode for special applications such as carbohydrate and ami-
noglycosides. A time table is supported for time based control of several
operational parameters and triggers for external devices by switching re-
lays. Also an external electric valve can be controlled via the Elite in case
of special applications such as column switching during
an analysis.

Fig. 12. Agilent Status window showing the Instrument status and acquisi-
tion window showing the acquired data.

For details about the requirements, use and functionality of the DECADE
Elite control driver in OpenLab and OpenLab Chemstation edition please
refer to document 176.0102 and 176.0102C DECADE Elite driver for
OpenLab CDS user manual, respectively. The documents can be down-
loaded from the Antec website (www.antecscientific.com).

The SCAN mode is not supported in OpenLab CDS. Scanning

Voltammetry is supported in the Dialogue Elite software only.
Chapter 4 DECADE Elite controller 65

Empower CDS
Empower™ CDS is a fully featured data acquisition software from Waters
Corporation. Full control and data acquisition of the DC and Pulse meas-
urement mode for the DECADE Elite is supported in Empower 3.0 (with
Empower ICF Support Layer v3.5) and higher.

The DECADE Elite driver adds full instrument control for Electrochemical
Detection (ECD) up to two flow cells (DCC). Supported is the DC mode
with constant potential measurement for most applications, and the
PULSE mode for special applications such as carbohydrates and amino-
glycosides. A time table is supported for time based control of several op-
erational parameters and triggers for external devices by switching relays.
Also, an external electric valve can be controlled with the DECADE Elite
case of special applications such as column switching during an analysis.

Fig. 13. Empower ECD instrument status window.

For details about the requirements, use and functionality of the DECADE
Elite control driver in Empower OpenLab please refer to document
176.0112 Waters ECD driver for Empower 3 user manual. The documents
can be downloaded from the Antec website (www.antecscientific.com).

The SCAN mode is not supported in Empower. Scanning Voltammetry

is supported in the Dialogue Elite software only.
66 175_0010 - DECADE Elite / Lite user manual - rev 13

C H A P T E R 5

Detection and Parameters

Introduction
One of the characteristics of electrochemical detection is its tremendous
dynamic range. In amperometric detection peak heights may vary from mi-
cro-amperes down to the pico-ampere range. The DECADE Elite covers
such a wide range from 200 µA down to 10 pA full scale, without being lim-
ited by electronic noise. For this reason the DECADE Elite is equipped
with a 24-bit ADC and 16-bit DAC for analogue data output. One of the key
features is that data can be sampled with data collection rates up to 100
Hz (100 pts/sec) in DC mode which assures that fast peak responses typi-
cal for UHPLC can be detected with sufficient resolution.

Three-electrode configuration
The circuitry of the DECADE Elite detector is designed for operation with
electrochemical flow cells with a three-electrode configuration (Fig. 14).
The working potential is set between the working electrode (WE) and the
auxiliary electrode (AUX). The AUX is kept at a precisely defined reference
electrode (REF) potential by means of the so-called voltage clamp. This is
an electronic feedback circuit that compensates for polarization effects at
the electrodes.

At the WE, which is kept at virtual ground, the electrochemical reaction

takes place, i.e. electrons are transferred at the WE. This results in an
electrical current to the I/E converter, which is a special type of operational
amplifier. The output voltage of the I/E converter is digitized in the instru-
ment by means of a 24-bit A/D converter and processed, and the resulting
output current Ic can be acquired digitally by PC control software (Elite Di-
alogue or Clarity) or analog using the ‘Analog Data output’ on the rear
Chapter 5 Detection and Parameters 67

panel connected to a recorder or an external A/D converter.

Fig. 14. Schematic representation of an electrochemical cell with a three-

electrode configuration.

Essentially, for the oxidation or reduction reaction it would be sufficient to

use only two electrodes. However, the three-electrode configuration has
several advantages over a two-electrode configuration. If the working po-
tential would be applied only over an AUX versus the WE (without REF),
the working potential would continuously change due to polarization effects
at the electrodes, resulting in highly unstable working conditions.
If the working potential would be applied only over the REF versus the WE
(without AUX), the working potential would be very well defined. However,
the potential of a REF is only well defined if the current drawn is extremely
low (pico-amperes) resulting in a very limited dynamic range.
A three-electrode configuration, combines the best of both electrodes. The
REF stabilizes the working potential and the AUX can supply high cur-
rents. This results in the tremendous dynamic range of a three-electrode
system.
68 175_0010 - DECADE Elite / Lite user manual - rev 13

Internal organization
At the working electrode (WE) in the electrochemical flow cell the electron
transfer takes place due to an oxidation or reduction reaction. The result-
ing electrical current is amplified by the current-potential (I/E) converter
(Fig. 15).

Fig. 15. DECADE Elite signal processing from electrochemical flow cell to
output.

The signal from the I/E converter can be compensated with auto zero or
offset, and is digitized using a 24-bits ADC. In the CPU the signal is pro-
cessed, for example noise filtering, or more complex data processing in
PAD. Finally after the 16-bits DAC the signal is set to a 1 V full scale ana-
log data output (by default Output = ADC). Also the true analog signal from
the I/E converter (before AD conversion) is available via the ‘Analog data
output’ connector. This output can be selected in the CONFIG menu by
setting the parameter Output = I/E.

Dual flow cell control (Elite only)

The DECADE Elite electronics are located on 2 different PCB's (printed
circuit boards). The control board and the sensor board. The control board
is dedicated to communication with PC (LAN) and keyboard & display. It
has a processor with a so called 'event handler' that takes care of all user
commands and hardware interrupts. The sensor board is fully dedicated to
data acquisition and flow cell control. By using this architecture it is possi-
ble to extend the functionality of the detector to more than one flow cell by
simply adding a sensor board (DECADE Elite only). The control board and
other hardware is prepared for more than one sensor board. Typically, a
two flow cell configuration can be used in serial or parallel mode detection.
Chapter 5 Detection and Parameters 69

Serial mode detection

In serial mode one LC system is used, with 2 flow cells in series. For data
acquisition 2 data channels are applied with the same time base. Serial
mode detection is especially suitable for OX-RED or RED-OX applications,
examples are analysis of vitamin K and nitro-tyrosine, using micro HPLC.
The first flow cell is a FlexCell that converts the analyte of interest in a de-
tectable substance. The second flow cell is a SenCell or VT-03 cell which
is used for detection. Note that it is necessary to work with micro HPLC be-
cause the conversion rate of the reactor cell is too small when using stand-
ard HPLC.

Fig. 16. Typical configuration for serial mode detection. Cell 1 is a FlexCell,
cell 2 is a SenCell for detection. Channel 1 and 2 use the same time base
of system 1.

Parallel mode detection

In parallel mode 2 HPLC systems are used with 2 flow cells. In fact, the
DECADE Elite is operated as if 2 independent detectors are in one hous-
ing.

Fig. 17. Typical configuration for parallel mode detection. Two independent
HPLC systems with dual channel support from OR 110, DECADE Elite and
Clarity software.
70 175_0010 - DECADE Elite / Lite user manual - rev 13

In Chromeleon, Empower and OpenLab CDS a DECADE Elite DCC with

2 cells in a parallel configuration cannot be operated on two
independent HPLC systems. One time base only (one HPLC system).

Fig. 18. DECADE Elite with 2 columns and 2 SenCell flow cells for parallel
detection.

Navigation in dual cell menu

All menus for a dual flow cell system are similar to a single cell system with
2 exceptions. First, in the top right corner a number is visible which indi-
cates the active cell in display. Toggle with the “+” and “-“ buttons between
sensor boards. If the board number does not change it means that the sec-
ond sensor board is not installed or not properly recognized. Second, a
Chapter 5 Detection and Parameters 71

new status screen is available in dual cell systems which indicates the sta-
tus of both cells in a single screen. However, for convenience it is advisa-
ble to use PC control from the Clarity Chromatography software or Dia-
logue Elite software when working with 2 flow cells.

M A I N 1 2

E C D e t e c t o r 1 . 1 0

# C O N F I G > D C P U L S E S C A N D I A G

QCC 1 D I c = + 2 3 . 4 5 n A R E M O T E 10A

2 P I c = + 1 2 0 . 6 n A
2 5 > 3 0 ° C
P R E V

Fig. 19. DECADE Elite main menu (top) with active cell indicator in top
right corner. Multi-STAT screen showing cell 1 (DC mode) and cell 2
(PULSE mode).

Parameters
Operational parameters are controlled from the SETUP screens in the
DECADE Elite. Parameters are filter, cell potential and offset. Temperature
is set in CONFIG menu.

T e m p = 3 0 ° C C o n t r a s t = 2 0 C O N F I G
V a l v e = 3 V o u t s o u r c e = D A C
I D 1 m a s t e r = n o
P R E V I O

R a n g e = 5 0 n A M a x C o m p = 2 . 5 µ A D C 1
E c = + 0 . 5 0 V # O f f s = + 1 0 % S E T U P
F i l t = . 0 0 2 H z
P R E V P O L A R = + E V E N T S N E X T

Fig. 20. Selection of parameters in the ‘DC SETUP’ screen. Temperature

is set in CONFIG menu.

Range
Range selection is done in the ‘SETUP’ or ‘STAT’ screen in DC, PULSE
and SCAN mode. A number of ranges can be selected; the maximum cur-
rent that can be compensated for using auto zero and offset differs. The
high sensitivity ranges (10 pA - 5 nA) have the best noise specifications. In
fact, there is a trade-off between best noise specification at sensitive
ranges, and maximum compensation at the less sensitive ranges. This is
72 175_0010 - DECADE Elite / Lite user manual - rev 13

an inevitable consequence of the tremendous dynamic range that is cov-

ered by electrochemical detection. The info listed in the tables below are
valid for DECADE Elite detectors with FW version 1.09 and higher.

Table II. DC ranges and maximum compensation.

Range Max comp Range Max comp
200 µA 2.5 mA 20 nA 2.5 µA
100 µA 2.5 mA 10 nA 2.5 µA
50 µA 2.5 mA 5 nA 250 nA
20 µA 250 µA 2 nA 250 nA
10 µA 250 µA 1 nA 25 nA
5 µA 250 µA 500 pA 25 nA
2 µA 25 µA 200 pA 25 nA
1 µA 25 µA 100 pA 25 nA
500 nA 25 µA 50 pA 25 nA
200 nA 25 µA 20 pA 25 nA
100 nA 25 µA 10 pA 25 nA
50 nA 2.5 µA

In the PULSE and SCAN mode (available in the DECADE Elite only), cur-
rent is much higher than in DC mode. Therefore it is not possible to select
pA ranges.

Table III. PAD ranges and maximum compensation.

Range Max comp Range Max comp
200 µA 2.5 mA 500 nA 25 µA
100 µA 2.5 mA 200 nA 25 µA
50 µA 2.5 mA 100 nA 25 µA
20 µA 250 µA 50 nA 2.5 µA
10 µA 250 µA 20 nA 2.5 µA
5 µA 250 µA 10 nA 2.5 µA
2 µA 25 µA
1 µA 25 µA

Offset
A maximum offset of +50% and - 50% in 5% steps can be set. For exam-
ple, 20% is a 200 mV offset when the maximum output is 1.0 Volt.
Chapter 5 Detection and Parameters 73

Polarity
The polarity of the output can be inversed. Oxidative and reductive anal-
yses generate opposite currents. For data acquisition, traditionally chroma-
tographic peaks have a positive amplitude. Therefore selection of polarity
is useful.

Filter
High frequency noise is efficiently removed and chromatographic peaks
can be detected with better signal to noise ratio.

Fig. 21. Signal to noise ratio is improved using a filter (A vs. B).

The DECADE Elite is equipped with ADF (Advanced Digital Filter) as a tool
to filter the acquired signal and improve the sensitivity of the analysis (Sig-
nal-to-noise ratio). In the next chapter the filter setting is explained includ-
ing detailed background information about filtering.

DC mode
In the tables below the available filter settings for the DC mode are listed
with the corresponding data rate of the output. Data rate is expressed as
number of data points per second (Hz). In the DC mode the data rate is
not an adjustable parameter but is coupled to the filter setting, except for
RAW. RAW is special, the incoming data are not filtered and a data rate
between 1 and 100 Hz can be selected.
74 175_0010 - DECADE Elite / Lite user manual - rev 13

Table IV. DC mode filter setting and corresponding data rate.

Filter setting DC mode (Hz) Data rate (Hz)
RAW 100(default), 50, 20, 10, 5, 2, 1
10 100
5 50
2, 1 20
OFF 10
0,5 0.2, 01 10
0.05 5
0.02 2
0.01, 0.005, 0.002, 0.001 1

Filter OFF is also a special case. The data rate is fixed to 10 Hz, and the
data is not filtered. Setting OFF is therefore the same as RAW at 10 Hz.

Pulse mode
In the pulse mode the working electrode is dynamically and continuously
regenerated by a series of potential steps in a cyclic manner. Data is pro-
cessed differently, and the data rate is defined by the total duration of the 5
potential steps in a pulse: t1 + t2 + t3 + t4 + t5. Usually the typical pulse
duration is between 0.5 and 2s (data rate between 2 – 0.5 Hz). Filter set-
tings in the pulse mode are therefore selectable between 0.5 and 0.001
Hz, and OFF.

Pulse 2 mode (available in remote control only)

In the pulse 2 mode filter settings are selectable between 0.5 and 0.001
Hz, and OFF.
Chapter 5 Detection and Parameters 75

Autozero
In the STAT screen the Autozero function (F4) is available. For the DC
mode this screen is shown below.

V o u t = + 0 . 5 0 0 V I c = + 2 . 5 0 0 n A D C 1 12

R a n g e = 5 n A E c = + 0 . 8 0 V S T A T
F i l t = o f f C o m p = O F F 3 5 → 3 5 ° C 2 1 1 . 2 0
P R E V C E L L = O N M A R K A Z E R O N E X T

V o u t = + 0 . 0 0 0 V I c = + 2 . 5 0 0 n A D C 1 12

R a n g e = 5 n A E c = + 0 . 8 0 V S T A T
F i l t = o f f C o m p = O N 3 5 → 3 5 ° C 2 1 1 . 2 0
P R E V C E L L = O N M A R K A Z E R O N E X T

Fig. 22. Stat screen in DC mode. Top: compensation off. Bottom: after ex-
ecuting an Autozero (Function button F4).

The Autozero function can be used to set the output voltage of the I/E con-
verter (signal) to 0 Volt. This is done by means of an compensation ampli-
fier in the analog measurement circuitry, see Fig. 15. This compensation
circuitry enables the possibility to measure small current signals (analyte
peaks) in a sensitive range even if the background cell current is high. For
example with a background current of 20 nA one can still do measure-
ments in the 1 nA range, because the maximum compensation for that
range is 25 nA.
Applying an Autozero will set the baseline (close) to 0 nA level. The full
scale is available for data acquisition. The Icell does not change, it is the
uncompensated current.

Do not execute an autozero, offset or range change when the cell

current is not stabile or the baseline did not stabilize.

In case an Autozero, Offset or a change of range is initiated on an instable

or changing current signal (baseline), this may lead to the display of an er-
ratic current value or erratic offset in current. This is expected behavior. An
Autozero, offset or change of measurement range will trigger an internal
calculation procedure in the detector based on the actual cell current. This
is an iterative process and the cell current is measured several times dur-
ing the calculation process. In case the cell current is not stable during the
calculation process this might lead to errors.

Remedy: In the event it does happen, the issue can be simply solved by
setting the Compensation to OFF (Comp = OFF) in the STAT screen or
76 175_0010 - DECADE Elite / Lite user manual - rev 13

CDS control software. Subsequently, wait till the background current is sta-
ble/stabilized and execute an Autozero again. The detector should now
display the correct current again.
In case event tables are programmed in LC methods in the CDS
software with an Autozero action, make sure that the autozero is pro-
grammed in a part of the chromatogram were the signal is stable. So at the
beginning of the run, during the hold-up time (so before the unretained/sol-
vent peak elutes). Or at the end of the run.
Chapter 6 Measurement modes 77

C H A P T E R 6

Measurement modes

DC mode
In Direct Current (DC) mode a static potential is constantly applied to the
EC flow cell to establish an electrochemical oxidation or reduction reaction
of an suitable analyte. In DC mode the resulting current signal is continu-
ously measured and sent to the detector output.

Fig. 23. Top: Plot of cell potential versus time. Bottom: DC mode method
settings window in Dialogue Elite. The potential (top right) can be set be-
tween -2.5 and +2.5 Volt.
78 175_0010 - DECADE Elite / Lite user manual - rev 13

The DC mode can be used for detection using relatively inert working elec-
trode (WE) materials such as Glassy Carbon (GC) or Boron-Doped Dia-
mond. Suitable analytes in this case are typically aromatic compounds with
functional groups which can be easily oxidized at relatively low potentials.
In addition, one other requirement for successful operation in DC mode is
that the target compounds and reaction products should not easily absorb
or contaminating the electrode surface leading to inactivation of WE elec-
trode activity and subsequent loss of response.

Pulse mode
Besides the DC mode the DECADE Elite can also be operated in Pulse
mode. The pulse mode is quite different from the DC mode. Instead of a
constant potential, a series of potential steps is applied in a cyclic manner.
The signal is sampled during a fraction of the total pulse cycle. During the
sampling time (ts) the signal is collected and this value is sent to the detec-
tor output. The frequency of data output is determined by the pulse dura-
tion: t1 + t2 + t3 + t4 + t5. Typically the duration is between 0.5 and 2s
(data rate between 2 – 0.5 Hz).

Fig. 24. Pulse mode example: Plot of a three-step potential waveform

(grey curve) versus time. Red part: time during which the current signal is
measured.

This mode is particularly useful for certain applications where the working
electrode is rapidly fouled due to adsorption of reactant or reaction prod-
ucts or/and when using metal electrodes like gold, platinum, titanium elec-
trodes etc. Metal electrodes are the electrodes of choice for oxidation/re-
duction of aliphatic compounds with functional groups. Such compounds
are hard to oxidize on inert electrode materials. Due to surface adsorption
of the target compound on metal electrodes the activation energy barrier
Chapter 6 Measurement modes 79

for the reaction is lowered allowing oxidation/reduction at much lower po-

tential. Due to the fact that the reactant remains at the WE surface or a
metal oxide layer is formed the electrode is deactivated and needs a
pulsed potential to continuously clean and regenerate an oxide-free metal
surface for the reaction.

Fig. 25. Pulse mode method settings window in Dialogue Elite. The poten-
tial waveform settings are shown on the right side.

Fig. 26. Potential steps in pulse mode. During t1 the measurement poten-
tial is applied, the actual current measurement occurs during ts. Steps t2,
t3 and t4 are for regenerating the electrode. This process repeats itself
continuously as soon as the cell is on.
80 175_0010 - DECADE Elite / Lite user manual - rev 13

In pulse mode up to five potential steps can be defined. The sampling in-
terval (period at which the current is measured) is applied at the end of E1.
More detailed information about pulsed amperometric detection is availa-
ble in chapter 8 of this user manual.

MPAD mode
In the DECADE Elite (FW 1.09 and up) an Multistep Pulsed Amperometric
Detection (MPAD) mode is available also known as pulse mode 2. In
MPAD mode it is possible to program a multi-step waveform, with up to 30
time, potential (t,E) coordinates with a maximum pulse duration of 4 sec-
onds, see figure below.

Fig. 27. The new pulse mode 2 with freely programmable t,E table. In red
the sampling of data for acquisition.
Chapter 6 Measurement modes 81

The measurement time interval in which the current is measured, marked

by a ‘Begin’ and ‘End’ marker, is free programmable in the pulse table.
This new pulse mode extends the application areas of the Elite to analysis
using PAD detection with more sophisticated potential waveforms like for
instance used in amino acid analysis.

The MPAD mode is not available in manual operation using keyboard/dis-

play. The new pulse mode can only be used through software control (Dia-
logue Elite or Clarity, Chromeleon and OpenLab CDS software). When dis-
connecting the device from the CDS it will automatically switch back to the
standard pulse mode and a warning message will appear in the display.

Scan mode
For method development the scan mode is available. In the scan mode the
cell potential is swept between two pre-set values (E1 and E2) using a cer-
tain scan speed (in mV/s) and the current is measured during the sweep.
This method can be used to study the REDOX behavior and to determine
the optimum detection potential of a pure analyte dissolved in mobile
phase.

Fig. 28. Scan mode example: plot of cell potential versus time in scan
mode (two full scans).
82 175_0010 - DECADE Elite / Lite user manual - rev 13

Fig. 29. Scan mode method settings window in Dialogue Elite. Continuous
scan (10 scans) between 0.20 and 1.20V with a scan rate of 50 mV/s.

The scan mode can be used in method development but is not a measure-
ment mode used in HPLC-ECD analysis itself. Therefore it is only available
in Dialogue Elite and in stand-alone operation. In Clarity, Chromeleon,
OpenLab and OpenLab Station Ed. CDS the scan mode is not available.

See chapter 9 describing the details how to optimize the working potential
for detection using scanning voltammetry.
Chapter 7 Measurement modes 83

C H A P T E R 7

Noise suppression: ADF™

Introduction
Besides for its tremendous linear dynamic range and selectivity, electro-
chemical detection is well-known for its very low limits of detection. To fur-
ther improve these detection limits the Antec engineers have developed
ADF (Advanced Digital Filter) and the DECADE Elite has been equipped
with it as a standard. The improvement factor in signal-to-noise (S/N) ratio
depends on the frequency relation of signal and baseline noise. S/N im-
provements from a factor 5 up to more than 100 have been obtained.
To understand how a digital filter works, first the importance of frequencies
in chromatographic analysis will be explained. Then we will look at peak
width, filter settings, cut off frequency, amplitude response plots and finally
at a few chromatograms before and after applying ADF.

Frequency
A scientific definition of frequency is “the number of completed alterations
per unit time”. It has two dimensions: count and time. Frequency is usually
expressed in Hz, which is counts per second.
The counts themselves can run in a regular, evenly spaced manner, as
with sine waves whose curve shapes do not change. Alternatively, the
counts can run in an irregular manner within the specified unit of time. If
the latter happens, frequencies would vary if broken down into t smaller
units of time.
In the example of Fig. 30 a signal is shown with a frequency of 12 altera-
tions in 5 minutes. To express its frequency in a more scientific way a full
period is precisely determined and expressed in Hertz (or s-1). It is a sine
wave with a frequency of 0.04 Hz (Fig. 31).
84 175_0010 - DECADE Elite / Lite user manual - rev 13

400000

300000

200000

100000

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
-100000

-200000

-300000

-400000

Fig. 30. Example of a signal with regular evenly spaced alterations: a sine.

400000

300000

200000

100000

0
4.0 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 5.0
-100000
t (min)
-200000

-300000 4.15 4.56

-400000

Fig. 31. Sine of Fig. 30. A full period is 0.41 min (25 s) which corresponds
to a frequency of 1/25 = 0.04 Hz.

Frequency of signal and noise

Also a chromatographic peak can be expressed in terms of frequencies.
The way to determine this frequency is the same. The duration of the full
peak is measured and expressed in Hz.

540000

3.8 4.05
440000

340000

240000

140000

40000
3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0

Fig. 32. Frequency tells how often something happens: 1 peak in about
0.25 min (15 s), f = 1/15 = 0.07 Hz.
Chapter 7 Measurement modes 85

This is further illustrated by an overlay of the same chromatographic peak

with a sine of 0.07 Hz (Fig. 33).

540000

440000

340000

240000

140000

40000
3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0

Fig. 33. Overlay of a chromatographic peak with 0.07 Hz sine.

Typically in chromatography narrow peaks are in front of a chromatogram
while peaks with longer retention times get wider. As a consequence fre-
quencies are not constant but vary between 0.1 – 0.01 Hz, which corre-
sponds to 10 – 100 s peak width.

698000 ADF

598000 10 s 40 s
0.10 Hz 0.025 Hz
498000

398000
h

298000

198000

98000

-2000
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0

min

Fig. 34. Typical chromatogram with peak widths between 10 – 100 s.

Noise in chromatography can come from different sources. Pump pulsa-

tions are typically shown as a very regular noise pattern, while electronic
86 175_0010 - DECADE Elite / Lite user manual - rev 13

noise has a more random character. This is illustrated in Fig. 35 where a

noise trace is shown with an overlay of a 10 and 0.4 Hz sine.

20
sine f = 10 Hz

15

10 sine f = 0.4 Hz
I (pA)

-5
30 31 32 33 34 35 36 37 38 39 40
t (s)

Fig. 35. Typical random noise in chromatography (lower trace). Both fre-
quencies (0.4 and 10 Hz) can be recognized amongst others.
Looking closely to the lower noise trace both frequencies (and others) can
be recognized. This is typical for noise in chromatography: a collection of
more or less random frequencies.

Low pass noise filters

The way noise filters work is by suppressing certain frequencies in the ac-
quired signal. Typically low pass filters allow chromatographic peaks (low
frequency) to pass, while high(er) frequency noise is attenuated. No matter
how advanced, it is impossible to use a low pass filter successfully if there
is no difference in frequency of signal and noise.
Analogue filters are made of hardware, from capacitors, resistors and am-
plifiers (opamps). Digital filters are mathematical routines to process an ac-
quired signal.
Traditionally, in many detectors for chromatography an analogue low-pass
filter is applied (rise time filter). A ‘passive’ RC filter consists of resistors
and capacitors. An active higher order filter can be considered as a num-
ber of these RC filters in series. In a 4th order filter the signal coming from
the first filter is filtered again in a second, third and fourth filter. During
these steps, loss of signal occurs simply because of all the resistors that
are applied. Operational amplifiers, which are ‘active’ components, are ap-
plied in each stage to restore the signal to its original value.
With the availability of powerful processors, digital signal processing has
become an excellent alternative for hardware filters. In its most simple
Chapter 7 Measurement modes 87

form a running average filter takes the average of n data points to create a
new data point. For example in a 5-points running average filter output
data point y[80] is calculated from measured data points x[80] – x[84] as:

Each input data point has the same weighting factor of 1/5. In more ad-
vanced digital signal processing a more complicated equation is used to
calculate the output data point y[n]:

In contrast to the previous equation, each data point has a different

weighting factor a. Sum of these weighting factors a0…n will always be 1.
Characteristic of noise filters is that processing the signal will result in a
delay. This is inevitable, as the mathematics of digital signal processing re-
quires a number of previous data points to process a new data point.
The filter characteristic in DSP is often named after the scientist who ‘in-
vented’ the mathematics behind the signal processing routine. Well-known
names in this field are Bessel, Chebychev, Savitsky, Golay, Hamming and
many others.

Amplitude response plot

1.2
pass
1
Amplitude

0.8
0.6

0.4
0.2
filte r block
0
0 1 2 3 4 5
Freq uency (Hz)

Fig. 36. Amplitude response plot of an ideal low pass filter with a cut-off
frequency of 1 Hz.
There are several ways to describe the filter characteristics. An amplitude
response plot gives important information on filter behavior. Suppose our
signal of interest has a frequency between 0 - 1 Hz, and all higher frequen-
cies are noise. An ideal filter is shown in Fig. 36 where signal frequencies
88 175_0010 - DECADE Elite / Lite user manual - rev 13

between 0 – 1 Hz completely pass while frequencies of higher than 1 Hz

are completely blocked.

In practice filters behave a bit different from the ideal situation. Amplitude
response plot shows a more gradual attenuation profile at higher fre-
quency. This cut off frequency is where the output signal amplitude is 70%
of the input signal, also known as 3 dB point.

1.2

1
Amplitude

0.8
0.6

0.4
B A
0.2
C
0
0 1 2 3 4 5
Freq uency (Hz)

Fig. 37. An amplitude response plot of a low pass filter with a cut-off fre-
quency of 1 Hz. It is a 2 (A), 4 (B) and 8 (C) pole Bessel filter.
In Fig. 37 it is shown that the number of poles is important, a filter behaves
more ideal with increasing number of poles. In a hardware filter the num-
ber of poles is the number of filter circuits that are placed in series.

Fig. 38. Analogue 6 pole Bessel filter.

Chapter 7 Measurement modes 89

A digital filter does not have poles, but it is characterized by the number of
input data points used to calculate a new output data point. For example a
9-point digital filter (Savitzky-Golay) is given as:

Y[1] = -0.090909091 X[1] + 0.060606061 X[2] +

0.168831169 X[3] + 0.233766234 X[4] +
0.255411255 X[5] + 0.233766234 X[6] +
0.168831169 X[7] + 0.060606061 X[8] +
-0.090909091 X[9]

Note that the sum of coefficients is exactly 1. Y[n] is the output data point,
X[n] are input data points. Generally spoken, the performance of a digital
filter improves with more input data points, but also more processor capac-
ity is required for the large number of calculations.
90 175_0010 - DECADE Elite / Lite user manual - rev 13

Applying ADF in chromatography

If noise frequencies in LC-EC differ from the frequency of the signal, noise
can be suppressed. Using the right filter setting (cut-off frequency) will spe-
cifically attenuate noise and improve the signal-to-noise (S/N) ratio. No
matter how ‘advanced’ a filter is, it is only possible to apply low pass filter-
ing if noise frequencies are higher than the frequency of the signal.

400000

300000

200000

100000

0 0
0 5 10 15 5 6 7 8 9 10

400000

300000

200000

100000

0 0
0 5 10 15 5 6 7 8 9 10

400000

300000

200000

100000

0 0
0 5 10 15 5 6 7 8 9 10

Fig. 39. From top to bottom filter setting of 0.5, 0.02 and 0.002 Hz. Narrow
peaks in front of the chromatogram are deformed at 0.005 Hz, whereas
wider peaks show hardly any deformation (see peak at t~ 13 min). Attenu-
ation of noise is shown in the close up on the right.

Prerequisite for a ‘good’ noise filter for data acquisition in liquid chromatog-
raphy is that it improves the S/N ratio without significant distortion of the
Chapter 7 Measurement modes 91

signal of interest. This is particularly difficult if the frequency of the signal is

close to the frequency of the noise.
The DECADE Elite has a number of filter settings to optimize for best pos-
sible signal-to-noise ratio. The width of the peaks of interest is important
because wider peaks allow stronger filter settings simply because of the
lower frequency of such peaks. Advised filter setting to start further optimi-
zation is given as:

Filter setting = 1 / [2 * (peak width)]

So at a 10 s peak width a 0.05 Hz filter setting is advised. If peaks are 50 s

a 0.01 Hz filter is advised to start with. Note that if a chromatogram has in-
teresting peaks of 10 s as well as 50 s, it may not be possible to work with
one filter setting. In that case it is advisable to switch to a stronger filter
setting for the second half of the chromatogram using a timed event. To
optimize for the best S/N ratio, use the lowest acceptable cut-off fre-
quency.
After optimization, do not change the cut-off frequency setting during anal-
ysis of a calibration sequence. Use the same settings for analysis of sam-
ples and calibration standards.

Fig. 40. Analysis of 20 pmol/L 5-hydroxytryptophan, 5-HIAA and 5-HT us-

ing ADF for improving detection limits.

The S/N improvement depends on the composition of the frequency spec-

trum. Improvement up to a factor 100 may be obtained compared to an un-
filtered signal. As high frequency noise is suppressed, remaining noise
components will be in the same frequency range as chromatographic
92 175_0010 - DECADE Elite / Lite user manual - rev 13

peaks. As suppressing noise will always result in (some) suppression of

signal it is advised to switch the DECADE Elite to the highest acceptable
sensitivity.
Chapter 8 Measurement modes 93

C H A P T E R 8

Pulsed Amperometric Detection (PAD)

Introduction
The DECADE Elite can operate in PAD mode (Not available in the
DECADE Lite). In pulsed amperometric detection (PAD) the working elec-
trode (WE) is regenerated at a frequency of 0.5 - 3 Hz by the application of
a series of potential changes. This is particularly useful for certain applica-
tions where the working electrode is rapidly fouled due to adsorption of in-
soluble reaction products. A well-known application area of PAD is the
analysis of carbohydrates (Fig. 41) [1].

Fig. 41. Carbohydrate analysis in the pulse mode.

94 175_0010 - DECADE Elite / Lite user manual - rev 13

Pulse vs. DC mode

The pulse mode is quite different from the DC mode. Instead of a constant
potential, a series of potential steps is applied in a cyclic manner. The sig-
nal is sampled during a fraction of the total pulse cycle. During the sam-
pling time (ts) the signal is collected and this value is sent to the detector
output. The frequency of data output is determined by the pulse duration:
t1 + t2 + t3 + t4 + t5. Usually the duration is between 0.5 and 2s (data rate
between 2 – 0.5 Hz). The background or cell current is usually considera-
bly higher (100 - 1000 nA) than in the DC mode. Therefore, only nano- and
microampere ranges are available in the pulse mode. Typically, the back-
ground current is between 0.1 – 2 µA.
When the frequency of the data acquisition system (integrator) is higher
than the pulse frequency a typical stepwise pattern may appear in the
chromatogram. This is called ‘oversampling’ and these steps are usually
only visible after considerable magnification of the chromatogram. In case
a AD converter is used to record the analog signal it is recommended to
keep the sampling rate of the AD converter in pace with the data rate of
the detector. For example: for a waveform with a pulse duration of 0.5
seconds (2 Hz data rate) use a sampling rate of 2 Hz on your AD
convertor. Or in case this is not selectable the closest possible higher
sampling rate.

In FW1.09 and extended pulse mode, pulse mode 2, was introduced in

addition to the existing pulse mode. In the pulse mode 2 it is possible to
program a multi-step waveform, with up to 30 time, potential (t,E)
coordinates with a maximum pulse duration of 4 seconds. The
measurement time interval in which the current is measured (marked by a
‘Begin’ and ‘End’ marker), is free programmable in pulse table. This new
pulse mode extends the application areas of the Elite to analysis using
PAD detection with more sophisticated potential waveforms like for
instance used in amino acid analysis. See chapter 6 for more details.
Chapter 8 Measurement modes 95

High pH of mobile phase

In carbohydrate analysis another ‘special’ consideration has to be taken
into account. Detection is done in the pulse mode using a flow cell with
gold electrode. For separation an anion exchange column is used with a
mobile phase of around 20-100 mmol/L sodium hydroxide. The pH is
between 12 and 14. This puts some demands on the HPLC system, and
flow cells. After prolonged use of the flow cell with a gold working electrode
(WE) in the pulse mode, the gold oxide which is generated at the WE,
precipitates on the auxiliary electrode (AUX). This gold oxide coating may
electrically isolate the AUX and result in an increase of the noise. Cleaning
the AUX electrode with metal wool is a way to remove this coating.
The reference electrodes of the Ag/AgCl type are not suitable for
carbohydrate analysis. Due to silver oxide formation they require regular
(monthly) maintenance. HyREF reference electrodes are maintenance free
under these conditions and are therefore particularly suited.
If a mobile phase is used with a high pH (pH>10, carbohydrate analysis),
the standard Vespel rotors from the injection valve should be replaced by
Tefzel rotors which are pH resistant. For carbohydrate analysis, only CO2-
free sodium hydroxide should be used since carbonate anions may disturb
the ion exchange chromatography. It forms CO32- which is a strong
modifier. The CO2-free sodium hydroxide is available from several
suppliers as a 50% solution (19.2 mol/L). NaOH pellets are not
recommended because of their high CO2 content. Organic modifiers
(acetonitrile) strongly attenuate the signal of most carbohydrates in PAD
and are therefore not recommended.
96 175_0010 - DECADE Elite / Lite user manual - rev 13

Pulse settings
In PAD of carbohydrates a series of potentials is applied in a continuous
cyclic manner. During time interval t1 the detection potential is applied.
The data collection occurs within t1, during time interval ts (sampling time).
The time difference t1 - ts is the stabilization time.

Fig. 42. Potential steps in pulsed amperometric detection. During t1 the

detection potential is applied, detection occurs during ts. Steps t2, t3 and
t4 are for regenerating the electrode. This process repeats itself continu-
ously as soon as the cell is on.

During the next time intervals (t2..t4) the electrode is ‘cleaned’ by reductive
and oxidative potential steps.

Optimization of wave forms

LaCourse and Johnson [2-4] have published several papers on optimiza-
tion of wave forms in PAD. Several considerations are important for the
choice of the pulse duration. Optimization is depending on the working
electrode material, the sample constituents and the required detection fre-
quency. The impression may arise that the number of variables, 5 potential
Chapter 8 Measurement modes 97

steps and 6 time settings, may lead to a time-consuming optimization pro-

cedure. In practice, the pulse mode is more straightforward and published
in several excellent review papers and application notes.

Output frequency
An important difference between the DC and the pulse mode is the fre-
quency of the output signal. In the DC mode the signal has a 1-100 Hz fre-
quency, in the pulse mode the frequency is determined by the duration of
the pulse. Once every cycle, the ts signal is sent to the output.
If a stepwise pattern in the chromatogram is seen when zooming in, it
means that the data acquisition has an unnecessarily high sampling fre-
quency. This leads to large data files, but certainly not to a better chroma-
togram. Usually, data acquisition at 1 Hz is sufficient.

Fig. 43. A detailed part of a chromatogram acquired at different data fre-

quencies. The data rate is (A) 5x, (B) 2.5x, (C) 1.2x, (D) 0.6x and (E) 0.3x
the frequency of the pulse. C is 1 Hz data rate.

Working electrode material

Gold and platinum are used as working electrodes for PAD. Glassy carbon
appears to be unsuitable due to the high electric capacitance of this mate-
rial. Furthermore, resurfacing of the noble metal working electrode is
98 175_0010 - DECADE Elite / Lite user manual - rev 13

based on formation and removal of a (metal-) oxide layer. This is impossi-

ble with glassy carbon.

References
1. D.C. Johnson, D. Dobberpuhl, R. Roberts and P. Vandenberg, Review.
Pulsed amperometric detection of carbohydrates, amines and sulphur spe-
cies in ion chromatography - the current state of research, J. Chromatogr.
640 (1993) 79-96
2. D.C. Johnson, W.R. LaCourse, LC with pulsed ECD at gold and plati-
num electrodes, Anal. Chem., 62 (1990) 589A-597A
3. W.R. LaCourse, D.C. Johnson, Optimization of waveforms for pulsed
amperometric detection of carbohydrates following separation by LC, Car-
bohydrate Research, 215 (1991) 159-178
4. W.R. LaCourse, D.C. Johnson, Optimization of waveforms for pulsed
amperometric detection of carbohydrates based on pulsed voltammetry,
Anal. Chem. 65 (1993) 50-55
Chapter 9 Measurement modes 99

C H A P T E R 9

Optimization of the working potential

Introduction
A current - voltage (I/E) relationship, or voltammogram, characterizes an
analyte. It gives information on the optimum working potential, which can
be used to improve detection sensitivity and selectivity.
There are several ways to obtain a voltammogram:

• A hydrodynamic voltammogram is obtained in the DC mode by

running several chromatograms at different working potentials.
Both peak height and background current are plotted against the
working potential. A hydrodynamic voltammogram has as an ad-
vantage that the I/E relationship of all analytes of interest can be
obtained simultaneously in one set of experiments (boundary con-
dition: all analytes should be sufficiently separated under the ap-
plied LC conditions). Furthermore, under real chromatographic
conditions reliable information about the S/N ratio is obtained.
• A scanning voltammogram is obtained in the so-called scan mode
of the DECADE Elite: the voltage runs between two pre-set poten-
tial values (E1 and E2) and scan speed (in mV/s) and the current
is measured. The SCAN mode is not available in the DECADE
Lite.

Optimization of the working potential and the construction of a voltammo-

gram is described.

Electrochemical reactions
In electrochemical detection (ECD) a reaction of the analyte at an elec-
trode surface is monitored. This distinguishes ECD from most other detec-
tion techniques where detection is based on the physical properties of an
analyte (i.e. mass spectrometry: molecular mass, absorbance detection:
molar absorptivity). For electrochemically active compounds, the potential
between reference electrode (REF) and working electrode (WE) deter-
mines the reactivity of the analyte at the WE. The potential difference sup-
100 175_0010 - DECADE Elite / Lite user manual - rev 13

plies the energy level needed to initiate or enhance the electrochemical re-
action. Different analytes may have different oxidation or reduction poten-
tials, which determines the selectivity of ECD.

Fig. 44. Oxidation/reduction reaction of norepinephrine.

An example of an electrochemical reaction is shown in Fig. 44, norepi-

nephrine is converted into a quinone by oxidation at the WE. Two elec-
trons are transferred at the WE resulting in an electrical current that is am-
plified by the controller.
Chapter 9 Measurement modes 101

Hydrodynamic and scanning voltammogram

Hydrodynamic voltammogram
A hydrodynamic voltammogram is constructed when the pure analyte is
not available and separation over an analytical column is required. Further-
more, under real chromatographic conditions reliable information about the
S/N ratio is obtained. The peak heights obtained from the sequence of
chromatograms are plotted against the working potential used. Also the
background current (I-cell) is plotted.

10 A
Icell (nA)

0
0.0 0.5 E1 1.0 1.5

Ecell (V)
Fig. 45. Hydrodynamic voltammogram of norepinephrine (A) at a glassy
carbon working electrode, and the current of the baseline (B). At E1 the
electrochemical signal becomes diffusion limited.
102 175_0010 - DECADE Elite / Lite user manual - rev 13

Scanning voltammogram
An alternative for the chromatographic construction of an I/E relationship is
the application of scanning voltammetry (DECADE Elite only). In a scan-
ning voltammetry experiment the working electrode potential is ramped up
and down between two preset potentials (E1 and E2) and the current is
measured while the analyte is continuously flushed through the flow cell.
This is repeated as many times as desired. The rate of voltage change
over time is defined as the scan rate (mV/s).

Scanning Voltammetry Waveform

E2
)
Working Potential (V)

(V/s
nrate
Sca

E1

t0 t1 t2
Time (Seconds)

Fig. 46. Scanning voltammetry potential waveform.

The current is plotted against the working potential to give a voltammo-

gram (I/E curve). An example is shown in Fig. 47. A difference with a hy-
drodynamic
In scanning voltammetry, no HPLC separation is involved. The signal is
the sum of all EC active substances. It takes only a few minutes to con-
struct a scanning voltammogram. This is an advantage, especially when a
number of analytes have to be characterized. However, it is a prerequisite
to have the pure analyte dissolved in buffer. A scan of the buffer (blank)
should be used to distinguish between solvent peaks and analyte peaks.

Any contamination in the buffer may lead to artefacts.

Chapter 9 Measurement modes 103

As can be seen in both Fig. 45 and Fig. 47, when the working potential is
increased the electrochemical reaction is enhanced hence the signal in-
creases. At a certain potential the I/E curve flattens. All analyte molecules
that reach the working electrode are converted at such a high rate that the
analyte supply becomes the limiting factor. At the working electrode sur-
face a stagnant double layer exists, where molecular transport takes place
by diffusion only. Therefore, the current at (and beyond) this potential is
called the diffusion limited current.

A
10

B
Icell (nA)

0
0.0 0.4 0.8 1.2

Ecell (V)
Fig. 47. Scanning voltammetry of 1.0 µmol/L norepinephrine (A) at a
glassy carbon working electrode, at a scan speed of 10 mV/s. Scan (B) is
the blank solvent.

With respect to sensitivity, a high working potential is important. However,

at higher working potentials, more analytes are detectable. So, as to selec-
tivity, a low working potential will be favorable.
Working at a potential on the slope of the I/E curve will result in less repro-
ducibility in HPLC. A small fluctuation in the applied potential, or any
change in the system (like for instance a pH change) may result in a differ-
ences in measured peak height. In practice the choice of the working po-
tential is a compromise between sensitivity, selectivity and reproducibility.
In the example of Fig. 45 a working potential (E1) of 0.8 V is chosen.
104 175_0010 - DECADE Elite / Lite user manual - rev 13

Optimization using a voltammogram

Sometimes, when interfering peaks appear in the chromatogram, it is pos-
sible to optimize the method with regard to selectivity. If the interfering
compound has a higher oxidation potential, a working potential is chosen
that gives the best selectivity, i.e. the largest difference in peak height. In
the example of Fig. 48 the selectivity for compound X is improved consid-
erably by decreasing the potential to E2 or E1. Obviously, if compound Y is
the compound of interest, optimization of selectivity in this way is not pos-
sible and the chromatography has to be optimized.
Electrochemical detection differs from most other LC detection methods in
that a reaction takes place in the detection cell. Due to reaction kinetics an
increased temperature speeds up the oxidation/reduction reaction. How-
ever, this not only holds for the analyte but also for the background current
and possible interferences. An elevated temperature will therefore not au-
tomatically lead to a better detection. A constant temperature is of para-
mount importance for a stable baseline and reproducible detection condi-
tions.

Fig. 48. Selectivity in LC-EC of compound X and Y is optimised by choos-

ing the working potential with the largest difference in peak height.
Chapter 9 Measurement modes 105

Electrochemical reactions are pH sensitive (Fig. 49). For norepinephrine

the I/E curve is shifted to a lower potential at higher pH. When the working
potential is high (E2), and the signal is diffusion limited, an increase in pH
will result only in a small increase of the peak height. When the working
potential is lower (E1), and the signal is not diffusion limited, the signal will
strongly increase at higher pH. In both cases the background current in-
creases at a higher pH.

Fig. 49. At a higher pH the I/E curve of norepinephrine is shifted to the left.

Reaction kinetics predict that electrochemical detection is mass flow de-

pendent. When the LC flow is stopped in LC-EC, the analyte will be oxi-
dized completely and the signal decreases rapidly. This means that the
flow rate not only affects temporal peak width and analysis time but also
peak height. Also the background signal is sensitive towards fluctuations
in the flow rate. Therefore, it is important to use a pulse-free solvent deliv-
ery system like in the Antec ALEXYS LC-EC analyzer.
106 175_0010 - DECADE Elite / Lite user manual - rev 13

Construction of a hydrodynamic voltammogram

Before a hydrodynamic voltammogram can be obtained, the chromato-
graphic conditions should be optimized. Then the following steps are
taken:
1. A solution of the analyte at a concentration between 1 - 100
µmol/L, is prepared in mobile phase.
2. The electrochemical detector is stabilized in the DC mode at a
high potential. After stabilization the background current is read
from the display of the detector (I-cell) and the noise is measured.
3. The run is started by injecting the compound. When at the high
working potential no signal is obtained, it may be concluded that
the compound is not electrochemically active. In such a case
derivatization of the compound may be an option.
4. If a peak is measured, the working potential is decreased by 50 or
100 mV and step 2 to 4 is repeated until the lowest potential
setting (Fig. 50).
5. The peak heights and the background currents are plotted against
the working potential (Fig. 45).
The working potential which gives the best sensitivity is obtained by
plotting the signal-to-noise ratio against the working potential.

Fig. 50. Construction of a hydrodynamic voltammogram for norepine-

phrine. Chromatograms are obtained at cell potentials ranging from 1.0 V
(back) to 0.4 V (front), with 100 mV steps.
Chapter 9 Measurement modes 107

Construction of a scanning voltammogram

A scanning voltammogram can be recorded using the DECADE Elite scan
mode. The scan mode is programmed in the ‘SCAN SETUP’ screen of the
DECADE Elite. Depending on the data acquisition software that is used
and the experimental set-up, a full, half or continuous scan cycle can be
chosen.
E 1 = + 0 . 0 0 V E 2 = + 1 . 0 0 V S C A N 1 33

R a n g e = 2 µ A S p d = 2 0 m V / s S E T U P
O f f s = + 0 % C y c = h a l f
P R E V C E L L = O F F N E X T

Fig. 51. Programming the scan mode in the 'SCAN SETUP' screen.

With the Elite Dialogue control software a scanning voltammogram can be

programmed under the ‘Detector’ tab in the main window.

Fig. 52. Programming a scan in the Elite Dialogue software, half sweep.
In the above example a ‘half’ scan is programmed, sweeping the potential
from 0 V to 1.0 V. A full scan would include the reverse scan, i.e. from 0 V
to 1.0 V and back to 0 V. In the continuous mode the voltage is swept up
and down between both potentials for a pre-defined run time.
108 175_0010 - DECADE Elite / Lite user manual - rev 13

A convenient way to record a scanning voltammogram is by direct infusion

of analyte in the flow cell using a syringe pump. In the figure below a scan-
ning voltammetry set-up is shown.

Fig. 53. DECADE Elite scanning voltammetry set-up with a syringe pump.

The Antec dual syringe infusion pumps (pn 188.0035, 36 and 37) which
can be obtained as accessory has as an advantage that it can be con-
trolled in Dialogue Elite software as well.

Fig. 54. Programming the Antec infusion pump in Elite Dialogue.

Chapter 9 Measurement modes 109

In the example below a half scan is shown at a flow rate of 10 µL/min of a

20 µM Serotonin (5-HT) standard in mobile phase.

Fig. 55. Scan (cycle: half) of a 20 µM Serotonin in mobile phase at a

glassy carbon working electrode. Scan speed 20 mV/s.

The following procedure is advised to record scanning voltammogram of

analytes:

• Use a voltammetry set-up as shown in figure 54 (preferably) in

combination with the Elite Dialogue software and a syringe pump
for direct infusion of analyte in the flow cell.

If Dialogue is not used, connect an A/D converter to the analog output

of the detector to record the cell current. Set the A/D converter
sampling rate to 1 Hz. This is the same frequency as the voltage steps
during the scan. If a higher sampling frequency is chosen a typical
stepwise pattern may appear. Note that with such set-up only ‘I versus
t’ curves can be obtained.

• Prepare a solution of the pure compound dissolved in (preferably)

the HPLC buffer with a concentration in the range of 10-100 µM.
• Set the lower (E1) and upper potential (E2), the scan rate (Spd),
range and scan cycle in the ‘SCAN SETUP’ menu or under the
‘detector’ tab in Dialogue.
110 175_0010 - DECADE Elite / Lite user manual - rev 13

Typical scan settings to start with: E1 0 mV, E2 1000 mV, scan

speed 10 mV/s, range 5 µA/V. Optimize the settings if required for
your specific compounds.
• Prime a 1 mL glass syringe with analyte solution and install it in
the syringe holder of the pump.
• Program the syringe diameter and flow rate in the syring pump
settings menu. In case a syringe pump is used which can be con-
trolled in Dialogue the settings can be programmed under the ‘S
pump’ tab. A typical flow rate to start with is 10 µL/min. Optimize
the flow rate if required during the scan experiments.
• Start the syringe pump and before scanning assure that the flow
cell is sufficiently primed with analyte solution.
• A scan can be started (stand-alone) by pressing the ‘START’ but-
ton in the ‘SCAN STAT’ menu or by starting a single run in Dia-
logue: press the ‘F5’ button or click ‘start single run’ under the ‘Op-
tions’ menu.
• To record a background (blank) scan repeat the experiment with
the pure HPLC buffer in which the analyte was dissolved.

When scanning with the Elite Dialogue software (‘continuous’) all scans
are displayed and can be selected individually.

Fig. 56. Example of multiple scans (‘continuous’) of Amodiaquine.

CHAPTER 10 Specifications DECADE Elite / Lite 111

C H A P T E R 1 0

Specifications DECADE Elite / Lite

Environmental, dimensions, weight & power requirements

Working temperature 10 - 35°C (indoor use only)

Storage temperature –25 - +50°C
Humidity 20 - 80% RH
Safety and EMC CE (CB Scheme), UL, CSA (cMETus approval)
Equipment group & class Group 1, Class B*
Installation category II
Pollution degree 2
Dimensions 43 (D) x 22 (W) x 44 (H) cm = 16.9” (D) x 8.7”
(W) x 17.3” (H)
Weight 14.4 kg (32 lbs) without flow cell and column
(SSC version)
Installation Install upright on flat & smooth surface, keep
space under the potentiostat free.
Power requirements 100-240 VAC, 50/60 Hz, 260 VA, auto-sensing
Mains fuse 2.5 AT / 250V, 5x20 mm, IEC 60127-2
For safety reasons, any other internal fuse or
circuit breaker is not operator accessible, and
should be replaced only by Antec authorized
personnel. Only use manufacturer-supplied
fuses.
*) Only valid for (E)lite 2020 model (with B in part number). The older model produced be-
tween 2015 – 2020 is Group 1, Class A equipment.

For optimum analytical performance it is recommended that the

ambient temperature of the laboratory be between 20-25 °C and be held
constant to within ± 2 °C throughout the entire working day. Note: that
for optimal performance of the oven the oven temperature should be
set at least 7 degrees higher as ambient temperature.
112 175_0010 - DECADE Elite / Lite user manual - rev 13

General

Operating modes DC, PULSE, PULSE 2, SCAN (Lite: DC mode

only)
Other mode CONFIG, DIAG and SERVICE
Sensors 1 flow cell (SCC), up to max. of 3 flow cells
(TCC)
Autozero triggered by keyboard (Elite only), rear panel
TTL, or remote PC control (LAN)
Max. current compensa- 25 nA - 2.5 mA in DC and PULSE mode de-
tion (Autozero) pendent on range setting
Offset +50% to - 50% of max. output voltage, 5%
steps
PC control Parametric control and data-acquisition via
LAN port (USB service port)
Embedded software Flash technology, upgradeable via PC (USB)
Oven +7°C above ambient to 60°C, accuracy 0.5°C,
stability 0.1°C; accommodates column and
flow cell(s)
Rear panel connectors 1x IEC inlet (Mains), 1x USB B, 1x RJ45 LAN,
1x 9-pins sub-D Male (Valve), 1x 9-pins sub-
D Female (Analog output), 1x 25-pins sub-D
Female (Digital I/O)
Analog output (DAC) -1 to +1 V full scale (via 16-bit D/A converter)
Analog output (I/E) -2.5 to +2.5 V full scale (unprocessed I/E con-
verter signal)
Digital I/O (HW) 2x Relay, 5x TTL outputs (CMOS 3.3V logic),
13 TTL inputs (programmable), 1x GND
Programmable I/O func- Cell on, Cell off, Autozero, Start, Overload,
tionality Relay, Auxiliary
Valve control VICI Valco 2-pos electrically-actuated valve
(E2CA, EHCA) via serial cable, Manual
valve, 1x inject marker output
CHAPTER 10 Specifications DECADE Elite / Lite 113

DC mode

Range 10 pA - 200 µA in 1, 2, 5 increments

Filter (ADF) RAW (100 Hz), OFF (10Hz) , 10 - 0.001 Hz in
1, 2, 5 increments
Potential (Ec) -2.50 V to + 2.50V with 10 mV increments
Data Rate 1 - 100 Hz in 1, 2, 5 increments, dependent
on filter setting
Noise < 2 pA with dummy cell (load of 300 MΩ/470
pF) in 1 nA range, filter off, Ec +800mV and
temperature of 35 °C.

PULSE mode (Elite only)

Range 10 nA - 200 µA in 1, 2, 5 increments

Filter (ADF) 0.5 - 0.001 Hz in 1, 2, 5 increments
OFF: for unprocessed data
Potential (Ec) -2.50 V to + 2.50 V with 10 mV increments
Data Rate 1/(pulse duration) Hz
Waveform Max 5 potential steps
Pulse times (t1-t5) t1: 100 ms - 2000 ms; t2, t3, t4, t5: 0 - 2000
ms in 10 ms increments
Sampling times (ts) 20 ms – [t1 – 60] ms

MPAD mode (available by PC control only)

MPAD is the abbreviation of Multistep Pulsed Amperometric Detection.
Range 10 nA – 200 µA in 1, 2, 5 increments
Filter (ADF) 0.5 - 0.001 Hz in 1, 2, 5 increments
OFF: for unprocessed data
Potential (Ec) -2.50 V to + 2.50 V with 10 mV increments
Data Rate 1/(pulse duration) Hz
Waveform Free programmable multi-step waveform with
up to 30 time-potential (t, E) coordinates and
max. pulse duration of 4 s. Time points in 10
ms increments.
Sampling time Sampling interval is free programmable, de-
fined by a ‘Begin’ and ‘End’ marker

SCAN mode (Elite only)

Range 10 nA - 200 µA in 1, 2, 5 increments

Potential (Ec) -2.50 V to + 2.50V with 10 mV increments
Data Rate 1 Hz
Scan rate 1 - 100 mV/s in 1, 2, 5 increments
Cycle Half, Full, Continuous
114 175_0010 - DECADE Elite / Lite user manual - rev 13
CHAPTER 11 Rear panel I/O 115

C H A P T E R 1 1

Rear panel I/O

In this chapter all rear panel functionality is described. The DECADE Elite
has besides the mains inlet in total 5 connectors on the rear panel for com-
munication, data output and I/O. A photo of the rear panel connectors is
shown below for reference.

Fig. 57. DECADE Elite rear panel.

116 175_0010 - DECADE Elite / Lite user manual - rev 13

USB B connector
USB type B connector for serial instrument control over USB, for service
use only:

• Based on USB-to-serial UART interface using the FT232R chip

from FTDI (Future Technology Devices International Ltd).
• FT232R is fully compliant with USB 2.0 specifications.
• Fixed communication baud rate: 921600 bps.
• Communication over USB is used for software (FW) update of the
instrument only using Antec boot loader FW upload utility.

LAN connector
RJ-45 bus for serial instrument control over LAN:

• 10Base-T or 100Base-TX (Auto-Sensing) serial-to-ethernet

connectivity.
• Network configuration of Xport via web browser.
• Fixed communication baud rate: 921600 bps
• Communication over LAN is used for parametric instrument control
and data-acquisition.

To establish communication over LAN, the LAN cable must be

connected when starting the detector using the mains power switch on
the rear panel. If no communication cable (either LAN or USB) is
connected during start-up, communication via USB is enabled (default).

Please consult the installation section for details about configuration and
set-up of communication over LAN.

VALVE connector
Serial D9 (9-pins subD male) valve control connector for electrical (Vici)
and manual valves:

• Serial (RS232) valve control of Vici 2-position electrically actuated

valves via pin 1 - 3 (see Vici technical note tn413.pdf on the official
www.vici.com web site). Compatible with the E2CA and EHCA
actuator control module.
CHAPTER 11 Rear panel I/O 117

• Automatic detection of electrically actuated Vici valve, valve

control in: STAT screen and Command ID 30 (0=load, 1=inject).
• Manual valve status (load/inj) read-out via pin 5 and 6 (contact
closure).
• Inject Marker (pin 9) TTL output. Default: high 3.3V (load), on
inject event: low (0 V) for 2000 ms.

Valve connector layout

In the table below the connector layout is shown for the Valve connector.

Table V. Valve connector lay-out.

Pin Layout
1 GND
2 TRANSMIT(TxD)
3 RECEIVE (RxD)
4 -
5 GND
6 SWITCH (Hand valve)
7 -
8 -
9 INJECT MARKER

For a manual valve the status (LOAD/INJ) read-out is established by con-

necting the LOAD/INJ sensor wires/leads of a manual valve to pin 5 and 6
(contact closure).
Inject marker
A connected valve enables the inject marker (pin 9)|. The contact is high
when the valve is in ‘load’ position (3.3V), and low (0V) in the ‘inject’ posi-
tion. On an inject event the contact will go to 0V (low) for 2000 ms, It can
for example be used to start the integration software when injection is
done.

Electrical valve configuration

A Vici electrically-actuated 2-position valve is automatically detected dur-
ing start-up of the instrument. Automatically the Valve parameter in the
DECADE Elite IO menu is set to Valve = Present.

T e m p = 3 5 ° C C o n t r a s t = 2 0 C O N F I G
V a l v e = P r e s e n t V o u t s o u r c e = D A C
I D 1 m a s t e r = n o
P R E V I O
118 175_0010 - DECADE Elite / Lite user manual - rev 13

Not ‘hot swappable’: Always restart the detector (by re-powering via the
mains switch on the rear panel) when connecting the valve for correct
initialization of an electrically-actuated Vici valve.

In the case an electrical Vici valve is detected, the Dialogue Elite software
automatically shows the presence of the electrical valve in the device set-
tings window (EC device) and valve control buttons will appear in the de-
tector window.

Fig. 58. Dialogue Elite Device settings.

Fig. 59. DECADE Elite detector window with Valve control.

CHAPTER 11 Rear panel I/O 119

Manual valve configuration

In case of a manual Valve the valve present parameter has to be set man-
ually. Configuration of a manual valve can be done via the LCD screen
(DECADE Elite only) or the Dialogue Elite software.

LCD display: Configuration of a manual valve can be done by setting the

Valve parameter in the IO menu manually to Valve = ‘Present’.

Dialogue Elite: Go to the device settings and the EC device tab and check
the manual valve check box.

Fig. 60. Dialogue Elite EC device settings, manual valve check box.

Valve status & control

In stand-alone mode (Elite only) the valve status for both an electrically-ac-
tuated valve and manual valve is displayed in the STAT screens on the
LCD display. For example see the screen dumps of the STAT screen for a
DECADE Elite SCC (top) and TCC detector. INJ=L represents the LOAD
position (position A on the actuator control module of an electrically-actu-
ated valve) and INJ=I represents the INJECT position (B on the actuator
control module). The LOAD position is the default position at start-up of the
instrument in the case of an electrically-actuated valve.
120 175_0010 - DECADE Elite / Lite user manual - rev 13

In stand-alone mode the valve position can be controlled via the F5 func-
tion button in the STAT screen. In the case of a manual valve the infor-
mation above the F5 button (INJ=L) in the STAT screen shows the status
(position) of the valve only, no valve control is possible with this type of
valve.

Make sure that the valve flow path is connected correctly and LOAD
corresponds with position A and INJECT with position B. See example
in the figure below for a 6-port valve.

Fig. 61. Example of the valve flow path of a 6-port valve.

In Dialogue Elite the valve status/position is shown under the monitor tab.
To make it visible in the left table, check the valve position checkbox in the
item selector (by default the valve position is not show).
CHAPTER 11 Rear panel I/O 121

Fig. 62. Dialogue Elite Monitor tab with valve status (position) displayed.

An electrically-actuated VICI valve can also be controlled via Dialogue

Elite under the detector tab, see figure 60. Note that the valve will switch
immediately after a change from Load to Inject (checkboxes) or vice versa,
no ‘Send to device’ action is required.

An electrically-actuated VICI valve can also be controlled via timed events

under the events tab in Dialogue Elite. In the Event editor the event ‘valve
position’ is available to switch the valve in the Load/inject position See ex-
ample below in the figure on the next page.
122 175_0010 - DECADE Elite / Lite user manual - rev 13

Fig. 63. Dialogue Elite Events tab with an example of two programmed
events switching the valve to Inject (t = 0.01 min) and back to Load (t =
0.05 min).

For more detailed information about valve control of the electrically-

actuated VICI valves in the Clarity chromatography software or
Dialogue Elite please refer to the corresponding user manuals.

ANALOG DATA connector

The DECADE Elite is equipped with an analog data output connector to
provide the measured signals in millivolts (mV) for users who work stand-
alone without PC control with the instrument. The ANALOG DATA con-
nector (D9-female) can either be connected to an X-Y recorder or A/D con-
verter. The ANALOG DATA output can supply either a non-manipulated
signal directly from the I/E converter, or the processed data signal by the
CPU of the DECADE Elite. The type of output can be selected from the
CONFIG screen by setting the parameter Vout source to either DAC or I/E
(DECADE Elite only, for Lite use Dialogue Elite to set value).
CHAPTER 11 Rear panel I/O 123

T e m p = 3 5 ° C C o n t r a s t = 2 0 C O N F I G
V a l v e = P r e s e n t V o u t s o u r c e = D A C
I D 1 m a s t e r = n o
P R E V I O

Fig. 64. Top: CONFIG screen. Bottom: DECADE Elite signal processing
from electrochemical flow cell to output. R is a selectable I/E resistor of
100M, 10M, 1M, 100K, 10K or 1K in the I/E converter circuit.

The output parameter Vout source can also be selected/set using Dialogue
Elite. Go to the device settings menu and Acquisition tab and set the ana-
logue output to DAC or I/E converter. The instrument is by default set to
DAC. For regular measurements it is advised to use the DAC output.

Fig. 65. Dialogue Elite Acquisition tab analog Output setting.

124 175_0010 - DECADE Elite / Lite user manual - rev 13

DAC output
The DAC output is the processed signal by the DECADE Elite’s CPU and
is identical to that of the digital cell current signal obtain via data-acquisi-
tion over LAN using the Elite Dialogue or the Clarity Chromatography soft-
ware.

The signal in mV from this output is directly related to the range setting of
the DECADE Elite. So for example in the case the 200 µA measurement
range is selected ‘Range = 200 µA’ the DAC signal on the analog data
connector corresponds with +1000 mV = +200 µA and -1000 mV = -200
µA (so +/- 1V full scale). To convert the signal in mV to the actual cell cur-
rent in nA use the following calculation:

Ic (nA) = Vout (mV) x Range setting (nA)

1000 mV

So for example a signal on the output of 250 mV in the 200 nA range cor-
responds with an actual cell current of (250/1000)*200 nA = 50 nA.

I/E output
The I/E output is the unprocessed analog signal from the I/E converter cir-
cuit. This signal is a true analog signal which is as close as practically pos-
sible to the working electrode (WE). The maximum output voltage of the
I/E output is +/- 2.5V under all conditions and is independent of the detec-
tor range setting. The signal in mV is related to the selectable I/E resistor
of 100M, 10M, 1M, 100K or 1K in the I/E converter circuit. The actual cell
current can be calculated from the analog I/E output in Volt using the fol-
lowing formula:

Ic (Ampere) = Vout (Volt)

RI/E (Ohm) x 10

So for example an I/E output signal of 250 mV in the 5 nA range (RI/E = 10

MΩ) corresponds to an actual cell current of 0.25V/(10 x 1E7Ω) = 2.5E-9A
= 2.5 nA. In the table below, the I/E resistor value is listed for every range
setting.
CHAPTER 11 Rear panel I/O 125

Table VI. DECADE Elite I/E converter resistors (valid for FW1.09 or higher)
Current Ranges I/E Resistor (Ohm)
10pA, 20pA, 50pA, 100pA, 200pA, 500pA and 1nA 100M
2nA, 5nA 10M
10nA, 20nA, 50nA 1M
100nA, 200nA, 500nA, 1µA, 2µA 100K
5µA, 10µA, 20µA 10K
50µA, 100µA, 200µA 1k

In the detector accessory kit a dedicated Output cable, D9 male – open,

2m (pn 250.0128A) is supplied. It is advised to use this manufacturer-sup-
plied cable for this type of measurements. See chapter 13 for optional ded-
icated output cable for Agilent, Shimadzu and Waters AD converters.

For reference, the layout of the analog data out connector is shown in the
table below.

Table VII. Analog data output connector lay-out.

Pin Layout
1 Vout 1
2 Vout 2
3 Vout 3
4 Vout 4
5 Vout 5
6-9 GND

To measure for example the analog signal of cell 1 with an external A/D
converter:

• Connect the signal wire, lead of pin 1 (Vout 1), to the analog
measurement channel of the A/D converter.
• Connect the GND wire, lead of pin 6 (or 7-9V), to the
corresponding analog ground connection of the A/D converter.

Digital I/O connector

The detector has one 25-pins digital I/O connector which enables control
of (or by) external equipment. The IO connector contains 18 TTL contacts
(5 outputs and 13 inputs, 3.3V CMOS logic), 2 RELAYS (contact closure)
and 1 ground (GND connection).
126 175_0010 - DECADE Elite / Lite user manual - rev 13

TTL inputs & outputs

Both the TTL inputs and outputs are default = high (3.3 Volt). The TTL in-
puts are level triggered: the contacts require a minimum TTL-low pulse du-
ration of 100 ms. If multiple activations are required the next pulse should
be given after 100 ms TTL high. When the input is kept low, only one acti-
vation will occur.

Relays
The DECADE Elite has 2 free programmable contact closure outputs:

• Relay1: pin 1 normally closed, pin 2 normally open, pin 3 common.

• Relay2: pin 4 normally closed, pin 5 normally open, pin 6 common.

The maximum rating for these contact closure outputs are 24 VDC (switch-
ing voltage) and 0.25 A. The relays can be controlled in the Elite Dialogue
software and Clarity Chromatography software.

AUX
The DECADE Elite has 4 free programmable TTL outputs AUX1 – AUX4
(pin 7 – 10). These contacts are default ‘high’ 3.3V (inactive), when active
the status is ‘low’ 0V.

Overload
The overload output (pin 11) can be used to monitor if the cell current goes
out of range during a chromatographic run. An ‘Out of range’ error appears
when the cell current Icell exceeds the limit of the current range at which the
measurement is performed. See figure on the next page.
CHAPTER 11 Rear panel I/O 127

Fig. 66. Example of a chromatogram were the cell current exceeds the
maximum current level and the signal is ‘out of range’.

It is important to recognize an ‘out of range’ (overload) situation,

because it may lead to erratic results when quantifying analyte
concentrations in samples.

If for instance the cell current goes in out of range during the recording of
an analyte peak, it can be (in most cases) easily recognized by a flat top of
the peak and a very abrupt transition to the flat top at the edges.

By default the status of the overload output is ‘high’ 3.3V. When the cell
current has the status ‘out of range’ the overload output will change status
to ‘low’ 0 Volt, until the cell current returns to a value within the measure-
ment range again. The overload output (pin 11) is one of the configurable
I/O’s.

P 1 1 ( O V L D ) = 1 P 1 8 ( A Z E R O ) = 1 I O
P 1 2 ( C - O N ) = A L L P 2 1 ( S T A R T ) = A L L
P 1 5 ( C - O F F ) = 2
P R E V

The configurable I/O’s can be programmed in the IO menu, which is a sub-

menu of the CONFIG menu. By default, the overload output is assigned to
cell 1: ‘P11 (OVLD) = 1’. This means that only when the cell current of cell
1 is ‘out of range’ the status of the overload output will change to ‘low’ 0V.
For all other cells present in the DECADE Elite (in case of a DCC or TCC
version of the instrument) an out of range situation will not trigger a re-
sponse on pin 11.
128 175_0010 - DECADE Elite / Lite user manual - rev 13

The following options can be selected for the configuration of pin 11 (in
case of a DECADE Elite TCC) :

P11(OVLD) = 1 Overload output active for cell 1 only

P11(OVLD) = 2 Overload output active for cell 2 only
P11(OVLD) = 3 Overload output active for cell 3 only
P11(OVLD) = Overload output inactive
P11(OVLD) = All* Overload output active for all cells present

*) When this option is selected, the overload output will be active for all
cells present in the DECADE Elite. If the cell current of either one of those
cells will go ‘Out of range’ the overload input pin 11 will become active.

Cell on, Cell off

The DECADE Elite has 3 TTL inputs to switch on cells (pin 12 – 14) and
also 3 inputs to switch off cells (pin 15 -17) AUX1 – AUX4 (pin 7 – 10).
This input command can be used for example to switch on and stabilize
the flow cell early in the morning by means of a timer. Two of the inputs
are configurable (pin 12, pin 15, cell on and off respectively) in the IO
menu (see previous chapter about the overload output). The configuration
settings of these inputs are: 1, 2, 3, 4, 5,’ ‘, and all. In case ‘all’ is selected
all cells present in the DECADE Elite will be switched on or off when the
corresponding input is triggered.

Autozero
The DECADE Elite has 3 TTL inputs (pin 18 – 20) available to autozero
the cell current of the cell(s). Triggering these inputs enables external acti-
vation of the auto zero command. This function is active only when the ‘I-
cell’ is displayed. One autozero input is configurable (pin 18) in the IO
menu (see previous chapter about the overload output). The configuration
settings of this input are: 1, 2, 3, 4, 5,’ ‘, and all. In case ‘all’ is selected the
cell current of all cells present in the DECADE Elite will be zeroed when
the input is triggered.

Start
The DECADE Elite has 4 TTL inputs (pin 21 – 24) available to start data-
acquisition and/or start a scan. One start input is configurable (pin 21) in
the IO menu and can be used for example to start the data-acquisition of
all cells synchronously using only one trigger input when the setting ‘All’ is
selected.
CHAPTER 11 Rear panel I/O 129

The manufacturer will not accept any liability for damage, direct or
indirect, caused by connecting this instrument to devices that do not
meet the relevant safety standards.

Programming outputs
In the Dialogue Elite software the DECADE Elite/Lite outputs (Relays and
AUX) can be controlled and programmed. This can be done via the Detec-
tor tab on the main window and via timed event tables. By default the I/O is
hidden and not shown in the monitor tab. To be able to see the status and
control buttons for the I/O go to the Device settings window (settings tab)
and check the ‘Show status outputs’ checkbox under the controls section.

Fig. 67. Dialogue Elite Detector tab with I/O status and control buttons.

The status of the Relays and TTL inputs can be set to active () or inac-
tive (). The selected state of the outputs will be activated after clicking
the ‘Send to device button’.

The outputs can also be switched via timed events under the events tab.
By opening a ‘New event’ under the Events pull-down menu, a new Event
table/file can be created. Subsequently, the Event editor will open. Select
130 175_0010 - DECADE Elite / Lite user manual - rev 13

the event ‘Output A’ and assign a time at which the output should be
switched and select which output should be activated (Relay, Aux) under
the value field. See example below in the figure below. Make sure to pro-
gram a second step to inactivate the Output again and put it back in its ini-
tial inactive state again.

Fig. 68. Dialogue Elite Event Editor window. Programming of output A.

Fig. 69. Dialogue Elite Event table window with an example of program-
ming timed events for output A (in this case Relay 1).
CHAPTER 11 Rear panel I/O 131

Table VIII. DIGITAL I/O connector layout.

Pin Type I/O Function Configurable Description
(default) I/O
1,2,3 Relay 1 Relay 1 - Contact between 3
(common) and 1
(default), activated by
time file Outp 0100 or
Command 47
4,5,6 Relay 2 Relay 2 - Contact between 6
(common) and 4
(default), activated by
time file Outp 0001 or
Command 47
7 TTL OUT AUX 1 - Free programmable TTL
output, activated by time
file Outp 0001,
Command 47
8 TTL OUT AUX 2 - Free programmable TTL
output, activated by time
file Outp 0010,
Command 47
9 TTL OUT AUX 3 - Free programmable TTL
output, activated by
Command 47
10 TTL OUT AUX 4 - Free programmable TTL
output, activated by
Command 47
11 TTL OUT Overload A*, 1-3 Active in case of signal
overload (‘OUT OF
RANGE’, 'PAD OVLD')
12 TTL IN Cell on 1 A, 1-3 Trigger to switch the cell
on
13 TTL IN Cell on 2 - Trigger to switch the cell
on
14 TTL IN Cell on 3 - Trigger to switch the cell
on
15 TTL IN Cell off 1 A, 1-3 Trigger to switch the cell
off
16 TTL IN Cell off 2 - Trigger to switch the cell
off
17 TTL IN Cell off 3 - Trigger to switch the cell
off
132 175_0010 - DECADE Elite / Lite user manual - rev 13

Table VIII. DIGITAL I/O connector layout.

Pin Type I/O Function Configurable Description
(default) I/O
18 TTL IN Autozero 1 A,1-3 Trigger to zero/null the
cell current
(compensation Ic)
19 TTL IN Autozero 2 - Trigger to zero/null the
cell current
(compensation Ic)
20 TTL IN Autozero 3 - Trigger to zero/null the
cell current
(compensation Ic)
21 TTL IN Start 1 A,1-3 Trigger to start a Scan
and Data-acquisition
22 TTL IN Start 2 - Trigger to start a Scan
and Data-acquisition
23 TTL IN Start 3 - Trigger to start a Scan
and Data-acquisition
25 GND GND - Ground connection
*) A = All boards.

In the detector accessory kit (pn 175.0200) a dedicated I/O cable is sup-
plied with an I/O connector board with screw terminal connections for easy
connection of open-ended electrical wiring for I/O:

pn 250.0131B DECADE Elite I/O conn. Board

pn 250.0131C DECADE Elite I/O cable 25M-25M, 1.8m

For use, connect the I/O cable to the 25-pins I/O connector on the detector
rear panel, subsequently connect the I/O connector board to the end of the
I/O cable.

On the rear side of the I/O connector board a label is adhered for
reference with the lay-out of the digital I/O connector.
CHAPTER 11 Rear panel I/O 133

Fig. 70. Top: DECADE Elite with I/O screw terminal board installed. Bot-
tom-left: back side of screw terminal board.
134 175_0010 - DECADE Elite / Lite user manual - rev 13

Chassis grounding stud

On the rear panel a chassis grounding stud is available at the lower right-
side, next to the ventilation holes of the power supply compartment. This
grounding stud which is connected to the central grounding point of the in-
strument can be used for shielding purposes. For example, to shield the
flow cell outlet from external electrical interferences (troubleshooting noise
issues), or to shield the flow cell from other equipment which might be cou-
pled in series with the electrochemical detector such an MS.

Fig. 71. Left: DECADE Elite rear panel grounding stud. Right: example of
shielding the flow cell by grounding the solvent outlet tubing.

Use the chassis grounding stud for shielding only, not for safety
grounding .
CHAPTER 12 Troubleshooting 135

C H A P T E R 1 2

Troubleshooting

Even though great care was taken in the design of the DECADE Elite,
problems may occur during operation of the instrument. The information in
this chapter may help you to identify and solve the source of the problems.
Errors can be categorized in two types:

• Instrument errors
• Analytical problems

In the next sections both types of errors are described. In the event that
the problems cannot be solved after following the instructions in this trou-
bleshooting section, contact your local supplier for further assistance.

Instrument errors
Incidental fault conditions may occur in any instrument. The DECADE Elite
will generate an error message containing an error number with a short de-
scription for several hardware fault conditions, which will be shown in the
instruments LCD display.

Table VIII. Error messages.

Error Message
11 Checksum error
12 Temperature sensor 1 error
13 Disconnect flow cell x
14 Control board SDRAM error
20 No sensor board detected
23 Heater defect, turn off instrument immediately,
disconnect power cord, call for service

Error 23: In case the actual temperature exceeds 70°C switch off the
potentiostat immediately do not touch the metal parts inside the oven
compartment because they could be hot, and contact the manufacturer
or its representatives for service. Do not use/switch on the instrument
before the instrument is serviced at the factory.
136 175_0010 - DECADE Elite / Lite user manual - rev 13

Make sure that maintenance is performed on a regular basis. Please con-

tact your local supplier if one of the above errors occur for further instruc-
tions. In the case the instrument does not power up at all check the follow-
ing remedies.

No detector response
Possible cause Remedy
No power Check line voltage setting, plug in power cord
Power switch off Turn this switch ON (at the rear panel)
Faulty fuse Replace fuse
Divergent mains voltage Check line voltage

Make sure the DECADE Elite is connected to a grounded power source

with a line voltage which is within the specified ratings. If the DECADE
Elite does not respond, a fuse in the mains inlet may be blown.

Furthermore the following messages can be displayed on the LCD screen

or PC control software during a measurement:

Table IX. Messages.

Message Advice
01 Out of range* Output is either above +1.0V or below –1.0V.
Pressing AZERO may give an adequate read-
out again. If the message remains after
pressing AZERO, the autozero function is
unable to compensate the background cell
current. Advice: use a less sensitive range in
the SETUP menu.
02 PAD overload Charging current in pulse mode out of range.
Pressing AZERO may give an adequate read-
out again. If not, it is advisable to change the
pulse settings (increase t1) or use a less
sensitive range.

*) An ‘Out of range’ error appears when the cell current Icell exceeds the
limit of the current range at which the measurement is performed. See fig-
ure on the next page.
CHAPTER 12 Troubleshooting 137

Fig. 72. Example of a chromatogram were the cell current exceeds the
maximum current level and the signal is ‘out of range’.

It is important to recognize an ‘out of range’ (overload) situation,

because it may lead to erratic results when quantifying analyte
concentrations in samples.

Erratic cell current value or offset after current compensation

In case an Autozero, Offset or a change of range is initiated on an instable
or changing current signal (baseline), this may lead to the display of an er-
ratic current value or erratic offset in current. This is expected behavior. An
Autozero, offset or change of measurement range will trigger an internal
calculation procedure in the detector based on the actual cell current. This
is an iterative process and the cell current is measured several times dur-
ing the calculation process. In case the cell current is not stable during the
calculation process this might lead to errors.

Do not execute an autozero, offset or range change when the cell

current is not stabile or the baseline did not stabilize.

Remedy: In the event it does happen, the issue can be simply solved by
setting the Compensation to OFF (Comp = OFF) in the STAT screen or
CDS control software. Subsequently, wait till the background current is sta-
ble/stabilized and execute an Autozero again.

In the case event tables are programmed in LC methods in the CDS soft-
ware with an Autozero action, make sure that the autozero is programmed
in a part of the chromatogram were the signal is stable. So at the begin-
ning of the run, during the hold-up time (so before the unretained/solvent
peak elutes). Or at the end of the run.
138 175_0010 - DECADE Elite / Lite user manual - rev 13

Analytical troubleshooting
Analytical problems like loss of signal, increase in noise level, high cell cur-
rent, loss in sensitivity etc. may occur in any (U)HPLC-ECD system. It may
be hard to find the cause and several checks need to be performed to
eliminate the source of the problem. The first step is to determine whether
the problem is caused by the DECADE Elite electrochemical detector or
the rest of the (U)HPLC system. For that purpose two basic checks should
be performed by the end-user:

• Dummy cell test

• Stop flow test

Dummy cell test: The outcome of the dummy cell test, which is described
in the next paragraph will give an indication if the problems are caused by
the detector hardware (electronics).

Stop flow test: The stop flow test will eliminate if the problems are caused
by the electrochemical flow cell, or is originating from the rest of the
(U)HPLC system (pump, autosampler, pulse damper, column, mobile
phase etc.)
CHAPTER 12 Troubleshooting 139

Dummy cell test

External dummy cell
A successful dummy cell test confirms that the controller, including the cell
cable, functions properly. A full dummy cell test consists of a reading of the
cell current, and a 15 min noise measurement.
An external dummy flow cell (pn 250.0040) is shipped with every DECADE
Elite instrument for troubleshooting purposes and maintenance checks.
The dummy cell test is fully automated in Antec’s Dialogue Elite software.
The resulting report shows if the detector is passed or failed.
It is also possible to perform a dummy cell test by using data acquisition
software. The ‘current reading’ can be obtained from the LCD display or
CDS software. For a full dummy cell test a 15 min noise measurement is
needed as well, without injection (by-passing the AS). If the result of the
current reading (Ic) and noise measurement with the dummy cell is within
specs, the controller is excluded in a troubleshooting procedure.

Fig. 73. Left: cell cable with external dummy flow cell (pn 250.0040). Right:
detector with external dummy flow cell.
140 175_0010 - DECADE Elite / Lite user manual - rev 13

The dummy flow cell consists of a resistor of 300 MOhm and a capacitor of
0.47 µF in parallel. The current is measured over the resistor according to
Ohm’s law (V = I * R), hence with a working potential of 0.80 V the current
will be about 2.67 nA.
Small differences are due to the tolerance of the resistor. The capacitor
functions as a ‘noise generator’ and resembles the capacitance of a flow
cell in an (U)HPLC set-up. The noise should be less than 2 pA, provided
that the dummy cell is within the fully closed Faraday shielded instrument
at the same position as the flow cell. The cell and cable must be positioned
in such way that it is not in the air flow of an oven fan.

Table X. Dummy cell test settings.

Parameter Setting
Mode DC
Cell potential 0.80 V
Oven 35 °C, door closed, stable*
Filter Off
Range 1 nA/V
Data rate noise measurement ≤ 10 Hz
Cell and cable position Not in full air flow of an oven fan

* It is allowed to run a dummy cell test at a lower temperature (incl oven off) or with shorter
stabilization time if the instrument appears stabilized. However, in case ‘failed’, repeat the test
under above conditions to rule out short stabilization or temperature issue.

Noise measurement
A baseline trace is obtained for 15 minutes to measure the noise. Evalua-
tion of the noise level is done by averaging 30 peak to peak values from
segments of 30 s (total of 15 min) using appropriate software.

n1 + n2 + n3 ................. + n30
noise =
30

This procedure is fully automated in Antec’s Dialogue Elite software. In

case no software tools are available, an estimate can be made. Provided
the baseline is stable without significant drift, two lines through the aver-
aged maximum and minimum values are drawn. The noise is obtained by
subtraction:

noise = Imax - Imin

CHAPTER 12 Troubleshooting 141

However, in case ‘failed’ or near 2 pA value, repeat the test with 30 seg-
ments to rule out an error in the estimated value.

When a DA convertor is used for data acquisition without any conversion

factor, the data unit is in (micro, milli-) Volt. With a range setting of 1 nA,
which is 1 nA/V actually, the noise value is easily converted: 1 mV = 1 pA.

Fig. 74.Baseline noise measurement from 30 segments (left) and an

estimate (right). The noise in both cases is 0.8 pA.
142 175_0010 - DECADE Elite / Lite user manual - rev 13

Steps to perform a dummy cell test

In case a CDS (Chromeleon, Clarity, OpenLab etc.) is used to perform the
dummy cell test, take the following steps to obtain the Icell and noise read-
ing:
1. Switch off the cell and disconnect the flow cell from the cable.
2. Leave the flow cell in place, and connect a dummy cell as shown
in the previous page(s).
3. Set measurement conditions as per above Table X “Dummy cell
test settings” and switch on the cell.
4. Wait until the cell current (baseline) stabilizes. It may take some
time for the dummy cell to be at measurement temperature (about
20 min).
5. Start the measurement. When done, evaluate the noise on the
ECD data channel. Take the Icell reading from the direct control
window in the CDS, or from the Elite display.

Test criteria

• I cell = 2.67 ± 0.05 nA

• Noise < 2 pA (< 2 mV @ 1 nA range)

The results (cell current and noise) of the dummy cell test should be
within the above mentioned test criteria. If the current value Icell and
the noise are not within the criteria it is an indication that something
could be wrong with the detector hardware. Please consult your local
representative.
CHAPTER 12 Troubleshooting 143

Internal dummy cell

In case the external dummy cell fails, or no external dummy cell is availa-
ble, the ECD also has the option to run an internal dummy cell test for fur-
ther troubleshooting. No cell cable or dummy cell are connected, the inter-
nal dummy cell is integrated on the sensor board.
To start the test, in MAIN select DIAG, followed by NOISE. This activates a
timer in the NOISE screen, and after 10 seconds of stabilization auto zero
is activated and the dummy cell test ‘current reading’ is ready. The inter-
nal dummy cell test is a visual check. Both the cell current and noise are
assessed from the LCD screen. For the noise estimation the Ic is moni-
tored for half a minute and the min and max value written down. The differ-
ence between min and max should not exceed more than 0.004 nA (4 pA).

The Vout of 0.538V reflects the analog output signal of the ECD. In case
an AD converter is used for data acquisition this value should correspond
with what is acquired in the chromatogram. If applied, any conversion or
multiplier factor in the CDS should be considered as well.
The range setting of the internal dummy cell test is 5 nA/V, to facilitate this
Output test. At 1 nA/V the signal would run of scale completely. The visu-
ally checked noise spec at 5 nA/V range is 4 pA.

No display
For a DECADE Lite (ECD without keyboard and display) the internal
dummy cell test can be performed with the Dialogue Elite software. See
figure below. First, start “Options/Dummy cell noise test”. When the script
has started, in ‘monitor’ tab check () the Internal dummy cell checkbox.
The cell on/off will automatically uncheck, which is correct because the ex-
ternal cell circuit must be off.

Evaluate the cell current in the monitor window. The internal dummy cell
current and noise level should fall within the criteria specified on the previ-
ous page. Make sure to uncheck the Internal dummy cell option again from
the device settings menu after the test.
144 175_0010 - DECADE Elite / Lite user manual - rev 13

Fig. 75. After starting the “Dummy cell noise test”, the internal dummy cell
must be checked. Note that the (external) cell is off.

Stop flow test

The stop flow test is a basic test to check if the problems are related to ei-
ther the flow cell or the rest of our (U)HPLC system. Perform the following
steps to execute the stop flow test:

• Switch off the (U)HPLC pump.

• Disconnect the tubing connection from the column outlet (see
figure below).
CHAPTER 12 Troubleshooting 145

• Disconnect the outlet tubing from the flow cell.

• Connect the other end of the tubing (of the tubing connected to the
inlet of the flow cell) to the outlet of the flow cell.
• The fluidic path of the flow cell is now completely isolated from the
rest of the LC system.
• Record a run (without injection of sample) to measure/evaluate the
background cell current (Icell) and noise.
• Compare the obtained values of the cell current and noise with the
values observed before the stop flow with the pump on.

Results:

Icell: In case a significant drop in Icell is observed, for example a drop of

more than 50%, it is an indication that the problem is not flow cell related
but originates from other parts of the LC system. The most obvious rea-
sons for a high background current are electrochemically active contami-
nants in the mobile phase, column bleeding, leaking pulse damper. This
causes can be systematically eliminated by replacing the mobile phase or
disconnecting column or pulse damper etcetera, and re-evaluate the cell
current.

Noise: If a significant drop of the noise only is observed it could be signa-

ture of for example pump problem (check valves, air in pump head, com-
pressibility issues or leaking seals).
146 175_0010 - DECADE Elite / Lite user manual - rev 13

In case no significant drop in noise or cell current is observed service

or replace the cell. In case you still cannot solve the problem contact
your local representative.

Please bear in mind that analytical problems may also be caused by exter-
nal Influences like temperature, unstable samples. Make sure that the ap-
plication was running trouble-free before and that no changes have been
made to the system. A number of causes and possible solutions for analyt-
ical problems is listed below. Contact your local representative if you need
further help.

No detector response
Possible cause Remedy
No power Check line voltage setting, plug in power cord
Power switch off Turn this switch ON (at the rear panel)
Faulty fuse Replace fuse
Divergent mains voltage Check line voltage
Cell disconnected, or Check connection
switched off
Output disconnected Check connection
Fouled WE Clean WE
CHAPTER 12 Troubleshooting 147

High cell current

Possible cause Remedy

Contaminated buffer Replace buffer, do not recycle the buffer
High WE potential Optimize potential, if possible: use smaller WE
diameter
Salt bridge in REF not Refill with wetted KCl crystals
saturated
Retained peaks from Wait for elution of these (very) broad peaks
previous runs
Column is ‘bleeding’ Replace column
High amount of Fe2+ in Add EDTA to buffer, rinse metal parts with 15%
buffer HNO3

Noisy baseline

Possible cause Remedy

Salt bridge in REF not Refill with saturated KCl, add wetted KCl
saturated crystals
Air bubble in REF or in cell Remove air bubble, continuously degas the
mobile phase
Slow temperature Isolate detector cell, set oven temperature
fluctuations
Fouled WE Clean WE
Leaking REF or cell Tighten connections with care

Decreased sensitivity (low S/N ratio)

Possible cause Remedy

Fouled WE by dirty Clean WE, if possible: dilute samples
samples
Cell potential too low Optimize potential
Contaminated buffer Replace buffer, do not recycle the buffer
(high Icell)
148 175_0010 - DECADE Elite / Lite user manual - rev 13

Saturation of output

Possible cause Remedy

Damaged REF Check with spare REF, replace if necessary
Damaged WE Replace cell block
Cell incorrectly connected Check connections (REF: black, WE: red, AUX:
blue)
Cell potential too high Optimize cell potential

Base line oscillations

Possible cause Remedy

Malfunctioning pump Check pump (seals, valves)
(regular pattern)
Over-tightened cell bolts Adjust cell bolts, check pump pressure
Air bubbles in cell or REF Maintenance REF
Temperature oscillations Set oven temperature
Contaminated buffer (high Replace buffer, do not recycle the buffer
Icell)
Electromagnetic Connect grounding kit for ECD*
interferences
Fouled WE Clean WE
High concentration of Fe2+ Add EDTA, passivate metal parts with HNO3
in buffer
*) See Chapter 13 optional detector accessories.
CHAPTER 12 Troubleshooting 149

Solved issues
In FW version 1.11.16 the known issues listed below are solved. For us-
ers with a DECADE Elite running on FW version 1.09.12 we advise to up-
date the FW to version 1.11.16 or us the work arounds advised in the table
below. In the second column (instr.) the type of instrument to which the is-
sue applies is indicated. SCC = Single Cell control (standard product),
DCC = Dual Cell control (option).

It is advised to update the FW of your instrument to version 1.11.16

# Instr. Description Work around

1 DCC Not all pulse mode parameter (E4, Set these specific
E5, t4 and t5) of sensor board 1 will parameters for board 2 in
be updated to sensor board 2 in the PULSE2, SETUP3
enslave mode (CONFIG menu). menu
2 SCC, Maximum compensation current The maximum current
DCC values (Max Comp) shown in the which can be compensated
SETUP menu are incorrect for the in these ranges is 25 µA.
200 nA and 500 nA range. See table II and III in
Chapter 3 for an overview
of the maximum
compensation for all
selectable ranges in the DC
and pulse mode.
3 SCC, In Pulse mode - 2 the 0.005, 0.002 Select an ADF filter setting
DCC and 0.001 Hz are selectable from in the range of 0.5 – 0.01
the method window of the CDS Hz for the Pulse mode - 2.
control drivers (Dialogue Elite,
Chromeleon), but must not be used.
It can lead to noise and regular
spikes in the chromatogram.
4 DCC Related to issue #3: If one of the Select an ADF filter setting
cells is operated in Pulse mode - 2, in the range of 0.5 – 0.01
and the other in either DC or pulse Hz for both cell 1 and 2.
mode: do not use an ADF filter
setting of 0.005, 0.002 and 0.001 Hz
on both cells. These filter settings
can affect the performance of the
cell operated in Pulse mode - 2.
150 175_0010 - DECADE Elite / Lite user manual - rev 13

C H A P T E R 1 3

Detector accessories

Detector accessory kit

The electrochemical detector is shipped together with a number of parts.
The listing in Table below may not be complete, see check list of delivery
for complete listing.

Table XI. Accessory kit (pn 175.0200) DECADE Elite detector.

Part number Description
250.0040 External dummy flow cell
250.0107 Column clamp 12 mm
250.0102* Cell clamp kit 40 mm
250.0113 Fuse 2.5 AT 250 V
250.0170 LAN (UTP) cable, crossed, 3 meter
250.0175 USB cable, A-B, 3 meter
250.0131B I/O conn. Board
250.0131C I/O cable 25M-25M, 1.8m
250.0128A Output cable, D9 male – open, 2m
250.0116 Mains cable (Europe)
250.0118 Mains cable (USA)
250.0126A Cell cable
*) for the VT-03 flow cell pn 250.0102 Cell clamp kit 40 mm is available in the accessory kit.

For a Vici Valco electrically-actuated 2-position valve, with an E2CA,

EHCA actuator a serial cable is available for control via the DECADE Elite
detector: pn 250.0190 Serial valve cable, Valco, 2m.

For these and other DECADE Elite parts or flow cells contact your local
supplier.
CHAPTER 13 Detector accessories 151

Optional AD convertor cables

For several types of ADC converters of third party (U)HLPC systems there
are dedicated output cables available. With these cables a hassle free di-
rect connection can be made between the DECADE Elite data output (ana-
log signal) and AD converter.

Fig. 76. Left: pn 250.128A DECADE Elite SCC output cable D9 - Shi-
madzu ADC for connection to for example (right) an Shimadzu CBM-20A
equipped with a PC-55N AD board.

Table XII. Dedicated analog output cables for AD convertors of Agilent,

Shimadzu and Waters.
Part number Description
250.0128A DECADE Elite SCC output cable D9- Agilent ADC- 3m
250.0128AD DECADE Elite DCC output cable D9- Agilent ADC-3m
250.0128U DECADE Elite SCC output cable D9 - Shimadzu ADC
250.0128UD DECADE Elite DCC output cable D9 - Shimadzu ADC
250.0128W DECADE Elite SCC output cable D9 - Waters ADC - 1.8m
250.0128WD DECADE Elite DCC output cable D9 - Waters ADC - 1.8m

The cables are compatible with the following AD converters:

• Agilent AD converters: 35900E, 35900E series II and 1200 Infinity

series universal interface box (UIB).
• Shimadzu PC-55N AD convertor board (for CBM20A or SCL-
10AVP controller)
• Waters e-SAT/IN Module
152 175_0010 - DECADE Elite / Lite user manual - rev 13

For Agilent LC systems also some dedicated trigger and autozero cables
are available which can be connected to free remote ports on any of the
Agilent LC modules

Table XIII. Trigger and IO (autozero) cables for Agilent LC systems.

Part number Description
250.0129B DECADE Elite ERI remote cable D25 - AZero - Agilent
250.0032G DECADE Elite ERI remote trigger cable - Agilent
250.0129A DECADE Elite AGP remote cable D25 - AZero - Agilent
250.0032H DECADE Elite AGP remote trigger cable - Agilent

The parts 250.0129B and 250.0032G are for Agilent Infinity II LC systems
with 15-pins ERI remote interface. Part 250.0129A and 32H for Infinity I or
older LC systems with 9-pins AGP remote interface. For more information
contact your local Antec Scientific distributor.
CHAPTER 13 Detector accessories 153

Optional grounding kit for ECD

In the case electromagnetic interferences are present in the vicinity of the

electrochemical detector, they may be transmitted into the flow cell via the
mobile phase in the connected tubing. This may lead to an increase in
noise or random oscillations in the detector baseline which in turn will re-
sult in a loss of performance. The grounding kit pn 250.0035C is a tool
which may help to eliminate/suppress the problem of electromagnetic in-
terferences in electrochemical detection. The kit consists of two grounding
leads:

250.0035A Outlet tubing grounding lead for ECD

250.0035B Column grounding lead for ECD

250.0035A Outlet tubing grounding lead for ECD

This part consist of an metal union with two 10-32 fingertights connectors.
The union has an electrical ground wire which can be connected to the
grounding stud on the rear panel of a DECADE II / SDC and DECADE
Elite / Lite. The grounding stud is connected to instrument ground and in
such a manner the mobile phase passing through the union is grounded.

How to connect the grounding lead (DECADE II/SDC and DECADE

Elite/Lite) in the LC flow path:

Cut the waste line (outlet tubing from the cell going to the waste bottle)
with a PEEK tubing cutter and fix the union in between as depicted below.
154 175_0010 - DECADE Elite / Lite user manual - rev 13

250.0035B Column grounding lead for ECD

This part consist of an grounding lead with an alligator clip on one side and
a faston connector on the other end. This grounding lead is used inside the
detector oven compartment. The alligator clip can be clipped onto a col-
umn with a metal housing (stainless steel) or a metal T-splitter. See pic-
tures below. T-splitters are used in HPLC-ECD applications based on post-
column addition of sodium hydroxide (the splitter is than a part of the post-
column mixing assembly). The faston connector can be connected to the
grounding point in the oven compartment (faston tab) located at the top
side (centered) of the oven compartment.
CHAPTER 13 Detector accessories 155
156 175_0010 - DECADE Elite / Lite user manual - rev 13

Index
 Index 157

ADC, 66
ADF, 83
Amplitude response, 87
ANALOG DATA, 122
Applications: quality control, 13
auxiliary electrode, 66
Biological Hazard, 13
Buffer pH, 39
buttons DECADE Elite keyboard, 49
Carbohydrate analysis, 93
cleaning of detector, 46
column, 42
compensation, 71
cut off frequency, 88
DAC output, 124
degassing mobile phase, 42
digital filter, 86
digital I/O connector, 125
DSP, 87
dual flow cell control, 68
dual flow cell navigation, 70
dummy cell
external, 139
internal, 140
dummy cell test, 138
EDTA, 39
Electrical safety, 11
electrochemical reaction, 100
Environmental specifications, 23
filter, 73, 86
frequency, 83
fuses
replacement of, 12, 46
Helium degassing, 40
I/E converter, 66, 68
I/E output, 124
I/E relationship, 99
inject marker, trigger, 117
installation
DECADE Elite, 21, 148
Instrument description, 16
integrator
158 175_0010 - DECADE Elite / Lite user manual - rev 13

connection of trigger, 117

Intended use, 9
internal dummy cell test, 141
Ion strength, 39
IP address, 28
ISO, 10
keyboard DECADE Elite, 49
LAN, 116
LC tubing, 45
license dongle, 61
maintenance
cleaning of detector, 46
maximum compensation, 71
mobile phase requirements, 39
noise, 42, 44, 95, 106, 145
noise filters, 86
offset, 72
output
frequency, 97
pulse mode, 97
overload, 126
Parallel mode detection, 69
passivation with nitric acid, 41
pH, 40
polarity, 73
potential
optimisation, 99
pulse mode
characteristics, 94
literature references, 98
optimisation, 96
output frequency, 97
potential settings, 96
working electrode, 97
pulsed amperometric detection, 93
range, 71
reference electrode, 66
ROHS, 10
rotor Tefzel, 95
rotor Vespel, 95
S/N ratio, 106, 145
Safety instructions, 11
scan mode
 Index 159

example, 107
scanning voltammogram, 102
Serial mode detection, 69
Solvents, 12
specifications DECADE Elite, 111, 115
stop flow test, 138
Symbols, 7
System Operation, 11
Tefzel rotor, 95
three-electrode configuration, 66
Time table, 62
transport box, 26
ts, 94
USB, 116
Vacuum degassing, 40
valve configuration, 117
Vespel rotor, 95
Vici Valco, 41
voltage clamp, 66
voltammogram
construction, 101, 106
introduction, 99
warning sign, 7
Warning Symbols, 7
Waste disposal, 13
WEEE directive, 10
working electrode, 66
material, 97
Working environment & safety, 11