アプリケーション（技術資料）

UV/VIS detection is one of the most sensitive detection techniques in trace-level chromatography. Sometimes, however, spectrophotometric detection lacks sensitivity, selectivity or reproducibility and chemical derivatizations are required. By using Metrohm`s rugged and versatile flow-through reactor, single- or multi-step derivatizations can be done fully automatically, in either pre- or post-column mode at any temperature between 25…120 °C. The variable reactor geometry allows to adjust the reactor residence time of the reactants according to derivatization kinetics. The flexibility of the reactor is demonstrated by optimizing four widespread post-column techniques: the relatively slow ninhydrin reaction with amino acids and the fast derivatizations of silicate, bromate and chromate(VI).

The poster presents the ion chromatographic determination of organic degradation products such as glycolate, formate and acetate besides the standard anions fluoride, chloride, nitrate and sulfate.

The presented IC system with inline sample preparation allows the determination of traces of lithium and sodium (ppt) in the presence of ppm quantities of ammonium and ethanolamine.

The Combustion IC system presented allows the automated determination of organic halogen and sulfur compounds in all flammable samples. Both combustion digestion, which is automatically controlled with a flame sensor, and the professional Liquid Handling guarantee highest precision and trueness. This poster describes the determination of the halogen and sulfur content in a certified polymer standard, a coal reference material as well as in latex and vinyl gloves.

核発電所の一次冷却系、ニッケルめっき浴、光学ガラス製造、洗剤、肥料などで使用されるホウ酸およびホウ素化合物の電位差滴定装置・温度滴定装置による定量法を紹介します。酸分解を行うことで他のホウ素化合物にも適用できます。

This Bulletin describes the fully automated determination of uranium according to the method of Davies and Gray: Uranium(VI) is reduced in concentrated phosphoric acid solution with iron(II) to form Uranium(IV). With molybdenum as a catalyst, the excess iron(II) is oxidized with nitric acid. The nitrous acid that is formed is destroyed with sulfamic acid before uranium(IV) is titrated with a potassium dichromate solution in the presence of a vanadium catalyst.

このApplication Bulletinでは、マンデル酸を錯化剤として用いた吸着ストリッピングボルタンメトリー (AdSV) によるチタンの測定について説明しています。このメソッドは、チタン濃度が重要とされる地下水、飲料水、海水、地表水、および冷却水の分析に適しています。このメソッドはもちろん、他のマトリックスの微量分析にも用いることができます。検出限界はおよそ 0.5 µg/L です。

Determination of zinc, lithium, cobalt, sodium, ammonium, potassium, manganese, magnesium, and calcium in power plant feed water stabilized with 7 ppm monoethanolamine using cation chromatography with direct conductivity detection.

Determination of magnesium, strontium, and barium in produced water using cation chromatography with direct conductivity detection.

Determination of trace levels of lithium, sodium, ammonium, potassium, magnesium, and calcium in boiler feed water using cation chromatography with direct conductivity detection.

Determination of traces of zinc and iron(II) in the presence of lithium, sodium, ammonium, potassium, calcium, and magnesium in boiler water using cation chromatography with direct conductivity detection.

Methylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) in methylpyrrolidone using Metrohm Inline Matrix Elimination.

Determination of monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) using cation chromatography with direct conductivity detection.

Determination of lithium, sodium, ammonium, and monoethanolamine (MEA) using cation chromatography with direct conductivity detection and Metrohm Inline Preconcentration and Inline Calibration.

Water chemistry of the water-steam cycle is crucial for maintaining plant reliability and for ensuring optimal plant operational conditions. Impurities such as corrosion products in ionic, colloidal, or oxide forms are ubiquitous in feedwater, condensate, and reactor coolant. This application shows the determination of sub-ppb levels of Cu, Ni, Zn and standard cations (e.g., Na +, NH 4+, Mg 2+, Ca 2+) in the water-steam cycle of a BWR.

In pressurized water reactors (PWRs), light water is used as primary coolant. Boron (as boric acid) readily absorbs neutrons and is added to the coolant to control reactivity. Lithium hydroxide assures a pH value greater than 7 to prevent corrosion. This application allows to measure sub-ppb levels of zinc, nickel, calcium, and magnesium besides high boric acid and lithium hydroxide concentrations.

Water in steel-based cooling systems requires a pH value slightly above 7 to prevent corrosion. Often ammonium or organic amines are applied for pH adjustement. This application shows the separation of typical amines besides inorganic cations. Sample preconcentration applies combined Inline Preconcentration and Matrix Elimination (MiPCT-ME).

In pressurized water reactors (PWRs), light water is used as coolant in the primary side. Boron (as boric acid) is added to the coolant to absorb neutrons, thus controlling reactivity. Lithium hydroxide assures the alkaline pH value to prevent corrosion. This application allows to measure lithium content besides high boric acid concentrations. AN-C-138 shows the respective trace metal determination on the same system setup.

N-メチルジエタノールアミン、ピペラジンは、天然ガス処理過程などにおいて、スクラバー溶液中で使用されます。イオンクロマトグラフィーによるこのタイプのサンプルの検査では、良好な分離度および標準陽イオンからのアミンの分離が必要となります。この分離は、直接電気伝導度検出を使用して、カラム Metrosep C 4 - 150/4.0 で行うことができます。

天然ガスの液化プロセスの前に、ピペラジンおよびN-メチルジエタノールアミン (MDEA) を含むスクラバー溶液によって炭酸塩、硫化水素を取り除く必要があります。この 2 つの成分の濃度比は、直接電気伝導度検出を使用して、カラム Metrosep C 4 - 150/4.0 でイオンクロマトグラフィーによって測定することができます。

Harmful industrial flue gases like H2S and CO2 cause corrosion of pipes and damage the environment. Adding the correct amount of amines in scrubber solutions, e.g. ethanolamines and methylamines, will neutralize these gases («gas sweetening»). Non-suppressed cation analysis with direct conductivity detection is a straightforward and robust technique for the quantification of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) via ion chromatography. Thanks to the high capacity of the Metrosep C 6 column, large volumes can be injected without compromising the peak shapes. The analytical technique can be used at laboratory scale but also for process analysis.

製薬産業または半導体産業のための超純水の生産には高品質なイオン交換体が必要です。陰イオン交換体物質の純度の検査には、燃焼法イオンクロマトグラフィシステムは不可欠なツールです。

石炭が燃焼すると、ハロゲンで大気が汚染されます。フッ素と塩素は石炭の自然の構成成分ですが、同様の臭化物は水銀排出を少なくするためにしばしば臭化カルシウムとして投入されます。この 技術資料では、異なる臭化物含有量を示す3つの石炭サンプルを燃焼法イオンクロマトグラフィシステムを使用して燃焼分解の結果を紹介しています。

石炭には一定量のフッ素、塩素、硫黄化合物が含まれています。石炭の燃焼中、これらの成分は腐食性の酸 (フッ化水素酸など) を放出します。火力発電所はフッ化水素酸の大量生産を防ぐため、低フッ素の石炭を要望しています。この技術資料では、燃焼法イオンクロマトグラフィシステムを使用して石炭中のフッ素含有量を測定しています。

ボイラー給水は、火力発電における機能の要です。腐食を抑制するため、pH 値は低アルカリの範囲に保つべきであり、そのために給水にアミンが追加されます。この追加は定期的にチェックしなければなりません。同様に重要なのが、ナトリウム濃度のモニタリングです。この値が下がるとコンデンサー内の冷却水が侵入する恐れがあるからです。連続サプレッション後に電気伝導度検出器を備えたイオンクロマトグラフに、サンプル自動濃縮およびマトリックス自動除去をおこなうことで、モニタリングに最適なシステムとなります。

Determination of ferrous ions in heat exchanger and vessel acid wash solutions, for measuring the effectiveness of acid inhibitors used in the solutions. Depending on the condition of the sample, the lower practical limit for the determination will vary from approximately 20-100mg/Kg Fe2+. Samples with high silicic acid contents require relatively large amounts of dilution water to render them mobile, and this limits the aliquot size and hence the amount of Fe2+ which can be analyzed.

Determination of free acid in sulfuric acid («acid shot») solutions employed in the removal of silicate scale in heat exchangers. This method is suitable for acid shot solutions where the silicic acid content is so high that the solutions have gelled.

石炭粉塵の水分含量は、サンプルの水分が少ないため、水分気化装置（窒素、270℃）と電量法水分計を使用して測定されます。

Urea is not a typical analyte for ion chromatography. In combination with MS, however, IC is the method of choice for the trace analysis of urea in ultrapure water. This Application Note shows the determination of urea concentrations in the ppb range using the Metrosep C 6 - 250/4.0 column.

純水中のシリカ（ケイ酸塩として）の濃縮前処理後における、陰イオンクロマトグラフィーおよび直接電気伝導度検出による定量（ポストカラム反応を行わない方法）を紹介します。

Determination of silicate and borate and their limits of determination (LOD) and quantification (LOQ) according to the EPA procedure for method detection limit (MDL) using anion chromatography with direct conductivity detection and Metrohm Inline Calibration.

Determination of borate in a borate effluent using anion chromatography with direct conductivity detection.

Conventional methods used to analyze moisture, ash, fixed carbon, and volatile content in coal samples, are time consuming and costly. Near-infrared (NIR) spectroscopy is excellently suited to determine all parameters simultaneously in less than one minute without any sample preparation.

Determination of boric acid and acetic acid in process water using ion-exclusion chromatography with conductivity detection after chemical suppression.

Scrubber solutions for scrubbing flue gas often contain amines for absorbing acid gases, e.g., sulfur dioxide (SO2). 1-(2-hydroxyethyl)piperazine and 1,4- Bis(2-hydroxyethyl)piperazine from gas scrubber solutions are separated in the Metrosep Carb 2 - 150/4.0 column and then determined using pulsed amperometric detection.

炭素回収システムは、排ガスから二酸化炭素を除去します。アミンと二酸化炭素のプロセスオンライン分析により、アミンの使用効率が向上し、運用コストが削減できます。

Boric acid requires precise monitoring in the primary circuit to control nuclear reactor reactivity. The 2060 TI Process Analyzer monitors boric acid online in near-real time.

This Process Application Note deals with the online monitoring of calcium and sulfate in flue gas scrubbing solutions using titration. Other contaminants that can be measured are sulfite, chloride, and chlorine. Low concentrations of heavy metals such as cadmium, zinc, copper, and lead can be measured in the ppb/ppm range with the ADI 2045VA Process Analyzer using voltammetry.

Excessive silica concentrations in the boiler feed water can lead to deposits on turbine blades and must therefore be avoided. Silica analysis is carried out via differential photometry using a leading-edge technology thermostatic cuvette module for non-sample contact at the detector. Typical concentration ranges for silica are 0–50 ppb and 0–1 ppm or higher.

Corrosion in the water-steam circuit of power plants leads to shorter lifetimes of most metal components and potentially dangerous situations. Flow Accelerated Corrosion (FAC) is a specific case, leading to thinned pipes and elevated Fe concentrations in the circuit. Additionally, metal transport issues such as with Cu from copper heat exchangers can lead to deposition on the high pressure turbine blades, decreasing their efficiency. Current methods can monitor but not prevent these issues, and analysis times are extremely long (up to three weeks). In combination with the power plant’s Distributed Control System (DCS), online monitoring of Fe and Cu with the 2060 Process Analyzer from Metrohm Process Analytics ensures that corrosion can be controlled before it affects the power plant efficiency, ultimately decreasing downtime and lowering maintenance costs. Results are offered within 20 minutes, allowing fast adjustments to the water-steam circuit to protect company assets.

火力発電所において熱伝導の効率を最大限に高めるための方法の1つが、冷却回路中の水化学の管理です。弱アルカリ性の冷却水により、金属管中の酸化皮膜が守られます。しかし冷却水のアルカリ度が高過ぎると、沈着物形成の可能性が高くなります。そのため、冷却水を炭酸塩（CO32-）および 重炭酸塩（HCO3-）で緩衝します。冷却水を pH 値 4.5 まで滴定すると、Mアルカリ度（メチルオレンジアルカリ度）、すなわち総アルカリ度が得られます。このpH 値ではそれほど高いアルカリ度は示されず、ただ遊離酸（H+）、炭酸（H2CO3）、CO2のみが見られます。

火力発電所は、タービンを回転させるために高圧で高純度の蒸気を使用して、大量の水を必要とします。 独立した冷却水回路が実装されており、タービンの後で蒸気が凝縮するときに真空を形成するのに役立ちます。 最適な凝縮パラメータでこの真空を維持することは、発電所の効率にとって重要です。 銅製コンデンサーはアンモニアによる腐食の影響を受けやすく、冷却水中でEPRIによって設定された2mg /LNH3の上限につながります。 復水器の小さな亀裂と蒸気回路と冷却水回路の大きな圧力差が相まって、ボイラー内の高純度水を汚染し、大きな問題を引き起こし、プラントのメンテナンスのためにシャットダウンする必要があります。 メトロームのプロセス分析計を使用することで、冷却水中のアンモニア（NH3）をオンラインで監視することで、事前にトラブルを防ぐことができます。

Measures to monitor or prevent corrosion are crucial in nuclear power plants, where significant risks to health and safety can occur if corrosion is left unchecked. Anions corrode metals under high temperature and pressure, therefore their concentrations must be monitored at all times. The analytical challenge in the primary circuit is detection of anions in the μg/L range alongside gram quantities of boric acid and lithium hydroxide. Precise, reliable trace analysis requires the method to be automated as much as possible. The 2060 IC Process Analyzer from Metrohm Process Analytics can measure several anions from a single injection, with combined Inline Preconcentration and Inline Matrix Elimination to measure low anion concentrations precisely and reliably time after time.

発電所において、腐食は高額かつ重大な稼働停止の主な要因となっています。 原子力発電所では、加圧水型原子炉（PWR）と呼ばれる独立した水回路が放射性物質の封じ込めを行いながら、他の回路へ熱とエネルギーを伝達しています。 このPWR回路には、特にホウ酸および水酸化リチウムが添加されますが、これらの成分は他の分析測定を複雑化させる場合があります。 リチウムは腐食防止の役割を果たし、亜鉛、ニッケル、アンモニウムイオンなどとともにモニタリングが必要です。 これらの陽イオンを単一分析でサブµg/Lレベルの感度でオンライン測定するために、2060 ICプロセスアナライザーが、インライン前濃縮およびインラインマトリックス除去機能と組み合わせて提供されています。 複数の陽イオンを1回の注入で分析でき、自動化された試料前処理により、正確かつ信頼性の高い測定が容易になります。

Neutralizing amines are added to adjust pH levels within the water-steam circuit of power plants to avoid corrosion-inducing conditions. This preventive maintenance can reduce costly and critical downtimes due to corrosion, however frequent monitoring of the amine chemistry is necessary to ensure conditions stay optimal. The 2060 IC Process Analyzer featuring the Metrohm intelligent Partial Loop Technique (MiPT) option is ideal for this application, with the ability to measure trace amounts of the analytes precisely and reliably through an automated method. The benefit of using IC is that multiple analytes can be monitored simultaneously, and here the ability to measure the presence of sodium next to the high ammonium or amine concentrations could indicate that cooling water is seeping into the circuit, indicating a problem upstream.

Copper is used widely in industrial cooling water systems for its heat transfer properties, although it is susceptible to corrosion. Corrosion can cause a loss of efficiency and eventually a failure of equipment, leading to costly maintenance, replacement, and downtime. Corrosion inhibitors (triazoles) can be added to the water chemistry, which form sparingly soluble protective layers on the surface of the metal. Triazole concentrations must be maintained to protect the copper, which necessitates regular concentration determinations in cooling water. The 2060 IC Process Analyzer with UV/VIS detection is well-suited for this application, able to precisely and reliably measure multiple ionic and UV-active compounds simultaneously in cooling water.

In power plants, corrosion is the greatest enemy. If corrosive impurities are present in the circuit streams (e.g., chlorides and hydroxides), deposition of an insulating layer of scale on the heat transfer surfaces occurs, resulting in costly and critical downtimes. To ensure high throughput of power plants, online analysis of critical parameters such as sodium is highly advantageous for safety, protection, and process optimization. With the 2035 Process Analyzer from Metrohm Process Analytics, operators gain the information they need to accurately identify trends, reduce downtimes, and address operational issues before costly problems arise.

電気めっき浴液中の錯化剤を高精度で分析するには、インラインラマン分光法が有効です。本アプリケーションノートでは、2060ラマンアナライザーを用いた一例をご紹介します。

Determination of trace levels of chloride, nitrate, phosphate, and sulfate in boiler feed water using anion chromatography with conductivity detection after chemical suppression.

A setup that allows online sampling is crucial for immediate and contamination-free analysis of power plant water samples. This application recommends a setup that facilitates simultaneous anion/cation determinations. Automated inline sample preparation combines variable preconcentration (MiPCT) and calibration with a single multi-ion standard. AN-Q-005 shows the respective anion results.

A setup that allows online sampling is crucial for immediate and contamination-free analysis of power plant water samples. This application recommends a setup that facilitates simultaneous anion/cation determinations. Automated inline sample preparation combines variable preconcentration (MiPCT) and calibration with a single multi-ion standard. AN-Q-004 displays the respective cation results.

この技術資料では、可変濃縮とInline Matrix Elimination ( MiPCT-ME ) を組み合わせたInline Neutralization（ インライン中和 ）を使用することにより、注入前にほう酸を自動除去してからイオンクロマトグラフで微量アニオンを直接分析しています。

A combination of the 850 Professional IC and the 872 Extension Module Liquid Handling opens the field of Metrohm’s online monitoring by IC. In this application, Inline Preconcentration is coupled to Matrix Elimination (MiPCT-ME). By removing excess matrix components, corrosive anions can be sensitively determined. Additionally, this technique allows automated calibration using a single multi-ion standard solution. Online trace analysis for chloride and sulfate is possible for several different sample lines.

Determination of fluoride, chloride, nitrite, nitrate, phosphate, and sulfate in cooling water using anion chromatography with conductivity detection after chemical suppression.

Determination of chloride, nitrate, and sulfate in ultrapure water after sample preconcentration using anion chromatography with conductivity detection after chemical suppression.

Determination of traces of fluoride, chloride, bromide, nitrate, and sulfate in a boiler feed water containing 10 mg/L ammonia using anion chromatography with conductivity detection after chemical suppression and inline sample preparation by cation exchange.

Determination of trace levels of chloride, nitrate, phosphate, and sulfate in a boiler feed water using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, chloride, nitrite, nitrate, and sulfate in a closed cooling water system using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, chloride, nitrate, phosphate, and sulfate in a borate effluent using anion chromatography with conductivity detection after chemical suppression.

Determination of fluoride, chloride, nitrate, sulfate, and oxalate in a perfluorocarbon material using anion chromatography with conductivity detection after chemical suppression.

加圧水型原子炉（PWR）一次冷却水中のフッ素イオン、グリコール酸イオン、酢酸イオン、蟻酸イオン、塩化物イオン、亜硝酸イオン、硝酸イオンおよび硫酸イオンを、化学抑制後の導電率検出法を用いた陰イオンクロマトグラフィーにより定量し、Metrohm インラインキャリブレーションにて校正を行った。

Boiler water analysis is an important task in power plant applications. Under the given conditions, the "Metrosep A Supp 10 - 100/4.0" column separates sulfite and sulfate without any organic modifier in the eluent. Even without any stabilizer, sulfite can be determined with a high reproducibility.

Water of the water-steam cycle of boiling water reactors (BWR) needs to be free of corrosive anions. Analyzing these trace anions allows the parallel determination of chromate, which is a potential corrosion product. Automated sample preparation includes variable Inline Preconcentration (MiPCT) and automatic calibration with a single multi-ion calibration standard.

Formate, acetate, propionate, and butyrate in addition to standard anions are determined in a coal extract. To improve the separation of the early eluting organic acid anions, a Dose-in Gradient is applied. Due to the limited sample volume available, Metrohm intelligent Pick-up Technique (MiPuT) is also utilized.

FDG gypsum originates from flue gas desulfurization systems in power plants. VGB-M 701 E (2008) describes aqueous extraction methods for determining chloride in FDG gypsum using ion chromatography. The sample preparation described in the VGB permits the determination of other anions besides chloride.

複合ガラスpH電極を用いた硫酸による電位差滴定により、アルカノールアミン含有ガス洗浄液のアルカリ度を定量します。

この技術資料では、ASTM D1287に準拠したエンジン冷却液および防錆剤のpH値を電位差測定によって評価する方法を解説します。試料を水に溶解しProfitrodeで撹拌後の安定値を測定する手順や、リザーブアルカリ度・水分量測定にも拡張できるOMNIS Basic滴定装置のシステム構成についても紹介します。

この技術資料では、ASTM D1121に準拠したエンジン冷却液のリザーブアルカリ度を電位差滴定によって測定する方法を解説します。試料を水に溶解しpH値を測定したのち、標準化した塩酸でpH5.5の終点まで滴定する手法や、OMNIS全自動システムによるヒューマンエラー低減と作業効率化についても紹介します。

FOS/TAC値は、時にVFA/TAと呼ばれ、バイオガスプラントの消化装置における嫌気性消化プロセスの現在の状況と発展過程の両方を評価するのに重要なパラメータです。この値を知ることは、消化プロセス全体がコストのかかるクラッシュを起こしかねない酸性化の問題のリスクを抑えるのに役立つことがあります。そのため、FOS/TAC 値の正確かつ信頼度の高い測定は、効率的かつコストパフォーマンスが高い生産操業のために重要です。この値は、酸塩基滴定によって測定されます。Ecotrode plus 電極を装備したメトロームの自動滴定装置 Ecoタイトレータ―を用いることで、FOS/TAC 値の再現性がある正確な測定が可能となります。

Feedwater for steam generation in boiling water reactors (BWR) needs to be analyzed for corrosion products. Presence of transition metals, mainly nickel and iron, indicates corrosion problems. Traces of these ions are determined using Inline Preconcentration (MiPCT). After separation, post-column reaction with 4-(2-pyridylazo)resorcinol (PAR) allows VIS detection at 510 nm.

In industrial cooling water systems, copper and its alloys are widely used because of their superior heat transfer properties. These materials are, however, susceptible to corrosion. Azoles are commonly used to protect copper and its alloys from corrosion. These corrosion inhibitors are quantified by ion chromatography with UV/VIS detection.

Simultaneous determination of Sb and Bi in an alkaline ZnO solution.

Determination of Al in alkaline ZnO solution with Eriochrome Blue Black R at 60 °C.

Accurate determination of Fe(II) and Fe(III) in water is crucial for many industries. Cathodic sweeping voltammetry (CSV) offers a robust, cost-effective solution.

ボイラー給水中の鉄濃度は、水–蒸気系の信頼性と安全な運転を確保するために監視する必要があります。さまざまなガイドラインにおいて、鉄分の最大含有量には上限が設けられています。 ボイラー給水中の全鉄濃度は、錯化剤として 2,3-ジヒドロキシナフタレン（DHN）を用いた吸着ストリッピングボルタンメトリー（AdSV）により、高感度に測定することが可能です。 ボルタンメトリーは、鉄の定量において、原子吸光分析（AAS）や誘導結合プラズマ（ICP）と比べて装置投資が比較的少なく、ランニングコストも低い、実用的で高度な設備を要しない代替手法です。

This White Paper presents four different «green» sensors: the scTRACE Gold, screen-printed electrodes, the glassy carbon electrode, and the Bi drop electrode from Metrohm that can be used to determine low concentrations of heavy metals in different sample matrices, such as boiler feed water, drinking water, and sea water.

OMNISクライアント/サーバーは、拡張性のあるサーバー管理により業務効率を向上させ、拠点全体のハードウェア、エネルギー使用量、保守コストを削減することでコスト削減を実現します。