ADI 2045VA Process Analyzer

Trace metal and plating bath analysis

 Voltammetric analysis goes online

02 Voltammetric trace analysis (VA) is used for determining

the type and amount of electrochemically active sub-
speciation analysis. Voltammetry is often used for
supplementing and validating spectroscopic methods
stances in a liquid sample on the basis of a current-volt- and is characterized by:
age relationship. These can be inorganic or organic ions,
or even neutral organic compounds. This electrochemi- • Low equipment costs
cal technique is mostly used for trace metal analysis as • Comparably low investment and operating costs
well as quality control of plating baths. • Short analysis times

Voltammetric analyzers, developed based on many years The infrastructure needed for a voltammetric measure-
of laboratory experience, are installed online in many in- ment system requires hardly any expenditure. All it needs
dustries for fast and efficient process control, which an is electricity and in some cases a supply of nitrogen.
in-house laboratory cannot provide. Ventilation, flammable gases and associated safety re-
quirements are no issues. In the case of the Multi-Mode
Sensitive, accurate trace analysis Electrode pro (MME), the mercury used is contained in a
The importance of voltammetry is based on its high de- hermetically sealed reservoir for safe handling.
gree of accuracy and sensitivity, and the possibility of

Online analyzers from Metrohm Process Analytics

Metrohm Process Analytics is the brand name repre- Due to the close collaboration with Metrohm AG, a
senting the well-known Applikon wet chemistry process world leader in ion analysis, Metrohm Applikon has ac-
analyzers as well as the Metrohm NIRSystems instru- cess to a large database of applications for laboratory-
ments for process analysis. Under this brand name we based measurements and instrument technology that
offer analytical systems for titration, spectroscopy, elec- can be used as a basis for online applications.
trochemistry, photometry, ion chromatography, TOC, as
well as ion selective measurements. Metrohm Process Analytics takes the famous Metrohm
laboratory solutions a step further. Fully automated, on-
Metrohm Applikon B.V. has over 40 years of experience line customizable analyzers facilitate process monitoring
with online measurements in the chemical industry, across a wide array of applications. Drawing on our core
waste­­water treatment plants, power plants, refineries, competencies in a wide range of analytical techniques,
semi­­conductor manufacturers, and more. All of the ana- we leverage our applications knowledge to create re-
lyzers are used directly in the process and are able to run liable solutions for process analysis that optimize effi­
24 hours a day to continuously monitor the components ciency, decrease chemical consumption and create a
of interest, keeping processes running smoothly. safer work environment.
Basis of Voltammetric Analysis

Voltammetry is an electrochemical technique in which

a current as a result of an electron transfer is measured.
Due to the fact that a kind of preconcentration step (the
deposition of the metal) is used in this process, cathodic
03
A potential that varies in time is applied to an electrode, and anodic stripping voltammetry (CSV and ASV) are ca-
a redox reaction will take place of which the current is pable of achieving very low detection limits.
then measured.
Easily measure chemical speciation
Stripping voltammetry Voltammetry allows to distinguish between free and
By applying a discrete potential over a period of time, bound metal ions or between their different oxidation
metal(s) are deposited on the electrode. In a second states as well as to specify the biological availability of
step the potential is swept and the metal is stripped off heavy metals. This makes voltammetry into an essential
the electrode surface. The currents measured during the tool for environmental analysis. Comparable insights
sweep are directly related to the metal concentration in can only be gained by spectroscopy after complicated
solution. separation of the metal species.

Example of a determination with the Computrace of heavy metals Zn, Cd, Pb, and Cu present in tap water
according to DIN 38406 Part 16. Voltammograms (left) and standard addition curves (right) are shown.

Typical Detection limits Concentration range of ADI 2045VA electrodes

Antimony Sb(III)/Sb(V) 200 ppt
Arsenic As(III)/As(V) 100 ppt
Bismuth Bi 500 ppt
Cadmium Cd 50 ppt
Chromium Cr(III)/Cr(VI) 25 ppt
Cobalt Co 50 ppt
Copper Cu 50 ppt
Iron Fe(II)/Fe(III) 50 ppt
Lead Pb 50 ppt
Manganese Mn 2 ppb
Mercury Hg 100 ppt
Molybdenum Mo(IV)/Mo(VI) 50 ppt
Nickel Ni 50 ppt
Platinum Pt 0.1 ppt
Rhodium Rh 0.1 ppt
Selenium Se(IV)/Se(VI) 300 ppt
Thallium Tl 50 ppt
Tungsten W 200 ppt
Uranium U 25 ppt
Zinc Zn 50 ppt
 ADI 2045VA Process Analyzer

04 Metrohm is the world market leader in voltammetry.

Hardly any other method is better suited to detect even
Suitable for a variety of industries
• Semiconductor production
the smallest traces of heavy metals in water. The Metrohm • Mining applications
Applikon ADI 2045VA analyzer is an online Process Ana- • Water quality control
lyzer based on the principle of voltammetric analysis,
which has routinely been applied in the lab for several
decades.

The ADI 2045VA system is built in the same rugged hous­

ing as our other established and proven multipurpose
analyzers. Its analytical heart is the 797 Computrace VA
system of Metrohm, the most well-known laboratory VA
system.

The advantage of this setup is that the same methods

can be used as are being developed and used in the lab.

Working Electrodes
• Multi-Mode Electrode pro (MME)
• Rotating Disk Electrodes (RDE)
• scTRACE Gold sensor

Flexibility enables many different applications

Depending on the application the so-called wet part can
be configured choosing the right modules like sampling
valves, tubing pumps, dosinos, valves, and more.

Depending on the application, the number of burettes

may change, or a sample digester (UV or thermal) may
or may not be present.

Digestion Capabilities: UV or Thermal

When performing metal analysis, often a part of the
metals are bound in (organic) compounds. A digester
module is used to release these metals by exposing the
sample to UV radiation, possibly in combination with an
oxidizer and acid. Now all metals are determined in a
subsequent VA analysis, and the amount of free vs. total
metals can be calculated.

Eliminate interfering substances

Interfering compounds such as peroxide are simply de-
structed to inactive molecules like water and carbon di-
oxide.

Additionally, a thermal digester module is available for

ins­­tances where the UV digester is not sufficient.
Operation

The system is controlled by an Industrial PC (IPC) in com-

bination with a programmable logic controller (PLC). The
pointing device can be connected via a USB port. The
operation bar gives a number of options while the sta-
05
PLC controls all external and wet part devices, while the tus bar shows system status at every moment. The user
Computrace and Dosino burettes are driven directly by is informed about relevant events, such as result limit
the IPC. alarms, by means of a pop-up window that can be ac-
knowledged. All external and wet part devices can be
The analyzer includes a touch screen display, making manually operated for maintenance purposes.
operation easy and intuitive. An optional keyboard and

Result display, trend graph

Results are presented in a list or in a graphical view.
The appearance can be modified, i.e. scales, colors and
pointers to indicate set point and alarm limits in a trend
graph and bar graph.

Events can be logged for later inspection

• Occurred result alarms
• Device warnings and errors
• Control actions
• Configuration changes, etc.

Relevant system information, like analysis results, log-

book events, system configuration info, action lists and
data can be exported in XML-format on a removable
memory stick connected to the easily accessible USB
port on the front of the analyzer cabinet.

Standards and Accepted Methods for VA

Parameter Standard Matrix

Zn, Cd, Pb, Cu, Tl, Ni, Co DIN 38406-16 Drinking and wastewater
CN – Sample preparation acc. to DIN 38405-13 Drinking and wastewater
UVI DIN 38406-17 Ground-, raw-, and drinking water
EDTA, NTA DIN 38413-5 Wastewater, sludge
Cu2+ EN 15376 , ASTM D 4806, ASTM D 5798 Bioethanol
Fumaric acid AOAC 968.16 Fruit and vegetable juices
Saccharin SLB 41-2.5 Fruit and vegetable juices
Pb2+ AOAC 979.13, AOAC 979.17 Dairy, Fruit and vegetable juices
 Working Electrodes for the ADI 2045VA

06 MME, Multi-Mode Electrode pro

As a working electrode for the system, small mecury
drops are formed at the end of a capillary. The Multi-
Mode Electrode pro has a hermeti­cally sealed mercury
reservoir of 6 mL and is ideally suited for (heavy) metal
analysis. This reliable electrode for polarography and
voltammetry can be operated as DME, SMDE or HMDE.

Key points of the Multi-Mode Electrode pro

• New electrode surface for every measurement
• Enough mercury for > 10,000 analyses, or 200 days
• Collection of mercury for safe disposal
• 10 years of measurement at 50 analyses per day
requires 100 mL mercury in total
Metrohm Multi-Mode Electrode pro
Safety always comes first with Hg reservoir and capillary
During and after the analysis, mercury is collected on
the bottom of the analysis vessel and is then drained off
into a mercury trap. It is always kept under liquid, so no
mercury vapor is allowed to escape and the safety risk
for the user is thus minimized. The mercury trap can be
emptied on occasion, so that the collected mercury can
be disposed of correctly.

scTRACE Gold sensor

Anodic stripping voltammetry (ASV) using the scTRACE
Gold sensor offers a straightforward, highly affordable
alter­native to the spectroscopic determination of arse-
The scTRACE Gold can detect nic, dis­ tinguishing between As(total) and As(III). The
trace amounts of As and Hg
limit of detection is significantly lower than international
in water
ma­­xi­­mum allowable limits.

• Also suitable for trace inorganic mercury detection

Many different important applications Example applications for the ADI 2045VA
Online use of voltammetric analysis is of importance in • Mining for Au, Cu, Zn, and other metals
many industries. In Zinc mining for example, the tech- • Electroplating bath quality
nique can be applied during smelting, purification, • Water quality control (drinking, river, surface, and
electrolysis or in the control of the process water. waste water)
• Monitoring trace metal concentrations
Cyclic Voltammetric Stripping

Production control of electroplating baths

Cyclic Voltammetric Stripping Analysis (CVS) and Cyclic
Pulse Voltammetric Stripping Analysis (CPVS) are wide-
spread methods in the electroplating industry for the de-
termination of organic additives in electroplating baths.

Rotating Disk Electrode (RDE)

The RDE induces a flux of analyte to the electrode by ro­­
tating in a controlled manner during experiments. There­­
fore the boundary layer is continually refreshed from the
bulk sample. For many technical coatings, particularly
in the manufacture of PCBs and semiconductor com-
ponents, this method is an essential part of production
control.

• Solid state platinum electrode, no mercury

• Organic additive determinations under process
circumstances
• Accurately measures brighteners, levelers, and
suppressors
• Concentrations in mL additive per L bath liquid Cell with electrodes for CVS analysis of a Cu bath

With CVS or CPVS methods, the concentration of orga­nic

Determination of suppressor in acid copper with calibration curve
DT determination of suppressor additives can be determined accurately. This gu­­a­­­­rantees
Suppressor Suppressor
c = 12.774 +/- 0.111 mL/L (0.87%)
continuous and interference-free operation of the plat-
15.0m 1.00 Z = 16.224 +/- 0.131 uL/L
ing bath. In particular, the accuracy of the analytical re-
800m
sults has helped the method to become well accepted in
the electroplating industry.
Q/Q(0)

10.0m 600m
0.13 0.16
I (A)

400m

5.00m 200m The most important application fields for CVS

0
• Acidic copper baths
0 5.00e-2 1.00e-1 1.50e-1 2.00e-1
V (m L)
• Tin-lead baths and tin baths
0
• Alkaline zinc baths

-5.00m

0 0.50 1.00 1.50

U (V)

Precise measurements even in saline conditions

The particular challenge for analysis in the electroplating
sector are the large quantities of salts typically found in
electroplating samples. For such samples, many measur-
ing techniques can at best provide unsatisfactory results;
others cannot provide any results at all.

Here, electrochemical analysis is able to demonstrate its

strengths; the disadvantage for other methods is trans-
formed into a big advantage: large amounts of salt equal
good conductivity, which is a prerequisite for electro-
chemical analysis.
 Technical information

Dimensions (H x W x D) 870 x 700 x 500 mm

Weight 85 kg
Power supply 100–120 V / 200–240 V
Power consumption 50–60 Hz / 600 W
IP protection IP65 / NEMA4
Ambient temperature 5–40 °C

Other specifications

Applied Analysis methods

• DP (Differential Pulse)
• SQW (Square Wave)
• CVS (Cyclic Voltammetric Stripping)
• CPVS (Cyclic Pulse Voltammetric Stripping)

Sampling and sample streams

Sampling batchwise
Sample frequency programmable
Analysis time typically 15–30 minutes
Sample streams maximum 4
Sample volume 0.2–50 mL
Sample temperature 5–45 ºC
Sample pressure 0–2 BarG / 0–28 PSIG (without preconditioner)

Connectivity
Discrete I/O:
Analog Result Output 4–20 mA, max 16 ea.
Digital Remote Control 24 VDC, Start, Stop, Continue, Sample Override 1, 2, 3, 4
Digital Detector Input 24 VDC, max 12 ea. (Leak, Reagent Level, etc,)
Digital Relay Output max. 2 A, Power On, Sequence Running, Warning, Error, Result Alarm 1, 2, 3, 4, Service

Serial ports:
Ethernet for remote control by Windows functionality
RS232 remote control by Windows functionality
USB for keyboard, pointing device and removable memory media

General
Touch screen operation
Housing material: Electronics cabinet: Zinc plated steel, epoxy coated
Wet part door: Polystyrene, epoxy coated
Designed by Alyson Lanciki, Metrohm Applikon B.V.

Maintenance
Weekly visual inspection www.metrohm.com
Monthly reagents supply
Biannual maintenance check
8.000.5206EN – 2016-11
Subject to modifications