ADI 2045VA Process Analyzer Trace metal and plating bath analysis Voltammetric analysis goes online 02 Voltammetric trace analysis (VA) is used for determining speciation analysis. Voltammetry is often used for the type and amount of electrochemical y active sub-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 instal ed online in many in-ment system requires hardly any expenditure. All it needs dustries­for­fast­and­efficient­process­control,­which­an­ is electricity and in some cases a supply of nitrogen. in-house laboratory cannot provide. Ventilation,­ flammable­ gases­ and­ associated­ safety­ requirements 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-hermetical y 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 col aboration with Metrohm AG, a senting the wel -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. Ful y 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, semi conductor 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 effi24 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 Due to the fact that a kind of preconcentration step (the 03 a current as a result of an electron transfer is measured. deposition of the metal) is used in this process, cathodic 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 al ows 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. Suitable for a variety of industries Hardly any other method is better suited to detect even • Semiconductor production the smal est 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 wel -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-cal ed wet part can be­configured­choosing­the­right­modules­like­samplingvalves, 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. Additional y, a thermal digester module is available for ins­tances­where­the­UV­digester­is­not­sufficient. Operation The system is control ed by an Industrial PC (IPC) in com-pointing device can be connected via a USB port. The 05 bination with a programmable logic control er (PLC). The operation bar gives a number of options while the sta-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 manual y 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. The­appearance­can­be­modified,­i.e.­scales,­colors­andpointers 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 •­Configuration­changes,­etc. Relevant system information, like analysis results, log-book­events,­system­configuration­info,­action­lists­anddata 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 capil ary. The Multi-Mode Electrode pro has a hermeti cal y sealed mercury reservoir of 6 mL and is ideal y 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 col ected 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 al owed to escape and the safety risk for the user is thus minimized. The mercury trap can be emptied on occasion, so that the col ected mercury can be disposed of correctly. scTRACE Gold sensor Anodic stripping voltammetry (ASV) using the scTRACE Gold sensor offers a straightforward, highly affordable alter native 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 limit­of­detection­is­significantly­lower­than­internationalin water ma xi mum 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 determination of organic additives in electroplating baths. Rotating Disk Electrode (RDE) The­RDE­induces­a­flux­of­analyte­to­the­electrode­by­rotating in a control ed manner during experiments. There - fore the boundary layer is continual y refreshed from the bulk sample. For many technical coatings, particularly in the manufacture of PCBs and semiconductor components, 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 orga nic Determination of suppressor in acid copper with calibration curve DT determination of suppressor additives can be determined accurately. This gu a rantees Suppressor Suppressor continuous and interference-free operation of the plat-c = 12.774 +/- 0.111 mL/L (0.87%) 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 10.0m 0) 600m the electroplating industry. Q( 0.13 0.16 Q/ )(A 400m I 5.00m The most important application fields for CVS 200m • Acidic copper baths 0 0 5.00e-2 1.00e-1 1.50e-1 2.00e-1 V (mL) • 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 chal enge for analysis in the electroplating sector are the large quantities of salts typical y found in electroplating samples. For such samples, many measur-ing techniques can at best provide unsatisfactory results; others cannot provide any results at al . 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 electrochemical 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 typical y 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 V. Maintenance Weekly visual inspection www.metrohm.com ohm Applikon B. Monthly reagents supply 11 Biannual maintenance check ­modifications ­to Subject Designed by Alyson Lanciki, Metr 8.000.5206EN – 2016-