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Passion. Power. Productivity.

MSQ and MSQ Plus are trademarks of Thermo Fisher Scientific.

Venture is a trademark of W. R. Grace and Co.

DCMSLink, Reagent-Free, RFIC, and ultra are trademarks and Acclaim, ASE,

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trademarks of Dionex Corporation.

© 2010 Dionex Corporation

LPN 2388 10M 01/10 Printed in U.S.A.

Related Dionex Applications LiteratureDionex has an extensive library of methods and techniques for determining a wide variety of analytes im-portant to chemical industries. Below is a selected list of applications covered in this brochure. For more in-formation, please visit www.dionex.com, click on the Markets tab, and select Chemicals. All of the literature below and more can be found by clicking the Documents tab and selecting Application Notes and Updates, or by contacting your local Dionex representative.

CHEMICAL AnALySIS LITERATURE

Contaminant Matrix Resource

Alcohols, carbohy-drates, glycols

Fermentation brothsAN 122: The Determination of Carbohydrates, Alcohols, and Glycols in Fermentation Broths

Alcohols, glycols Fermentation brothsAN 188: Determination of Glycols and Alcohols in Fermentation Broths Using Ion-Exclusion Chromatography and Pulsed Amperometric Detection

Amines, cations Hydrogen peroxideAU 155: Determination of Cations and Amines in Hydrogen Peroxide by Ion Chromatography Using a RFIC (Reagent-Free) System

Amines, cations WastewaterAN 141: Determination of Inorganic Cations and Ammonium in Environmental Waters by Ion Chromatography Using the IonPac CS16 Column

Anions Concentrated acid AN 78: Determination of Trace Anions in Concentrated Hydrofluoric Acid

Anions Concentrated baseAN 93: Determination of Trace Anions in Concentrated Bases Using AutoNeutralization Pretreatment/Ion Chromatography

Anions Organic solventsAU 163: Determination of Trace Anions in Organic Solvents Using Matrix Elimination and Preconcentration

Anions Toothpaste AN 156: Determination of Anions in Toothpaste by Ion Chromatography

Anions Wastewater AN 135: Determination of Inorganic Anions in Wastewater by Ion Chromatography

Anions, organic acids Fermentation brothsAN 123: The Determination of Inorganic Anions and Organic Acids in Fermentation Broths

Anions, organic acids Personal care AN 104: Analysis of Personal Care Products by Ion Chromatography

Anions, oxalate Bayer liquor AN 206: Determination of Oxalate and Other Anions in Bayer Liquor Using IC

Anions, perchlorate Fertilizer AN 144: Determination of Perchlorate in High Ionic Strength Fertilizer Extracts by IC

Aromatic antioxidants Polymers AN 331: Accelerated Solvent Extraction (ASE) of Additives from Polymer Materials

Carbohydrates Alternative fuels AN 363: Using Accelerated Solvent Extraction in Alternative Fuel Research

Carbohydrates BiomassAN 225: Rapid Method for the Estimation of Total Free Monosaccharide Content of Corn Stover Hydrolysate Using HPAE-PAD

Cations BiodieselAN 203: Determination of Cations in Biodiesel Using a Reagent-Free Ion Chromatography System with Suppressed Conductivity Detection

Cations Concentrated acidsAN 94: Determination of Trace Cations in Concentrated Acids Using AutoNeutralization Pretreatment/Ion Chromatography

Chloride, sulfate Ethanol AU 161: Determination of Sulfate and Chloride in Ethanol Using Ion Chromatography

Chloride, sulfate Methanol AN 201: Determination of Chloride and Sulfate in Methanol Using Ion Chromatography

Chromium (VI) WastewaterAN 80: Determination of Dissolved Hexavalent Chromium in Drinking Water, Ground-water, and Industrial Wastewater Effluents by Ion Chromatography

Corrosion inhibitors Engine coolants AN 204: Improved Method for Determination of Corrosion Inhibitors in Engine Coolants

Cyanide Alkaline solutions AU 107: Determination of Cyanide in Strongly Alkaline Solutions

Ethanolamines Industrial waters AU 138: Determination of Ethanolamines in Industrial Waters by Cation-Exchange

Halides, Sulfur All Brochure: Combustion IC System

Phenols Wastewater AU 119: Determination of Phenols

Plasticizers Polyvinyl chlorideAN 336: Accelerated Solvent Extraction (ASE) of Plasticizers from Poly(vinyl chloride) Polymer

Metal cyanides Wastewater AU 147: Direct Determination of Metal Cyanides by IC with UV Absorbance Detection

Sulfate Brine AN 53: Method for the Determination of Trace Sulfate in Brine

Thiosulfate, thiocyanate

Wastewater AN 138: Determination of Thiosulfate in Refinery and Other Wastewaters

Transition metals Complex matrices TN 25: Determination of Transition Metals in Complex Matrices by Chelation IC

wesrawlins

Thermo

Quality, Safety, and the Environment

page 2

Industrial manufacturers such as petroleum refineries and chemical producers struggle to obtain reliable, low-cost sources of raw materials for their process needs. Trace contaminants present in solvents or starting reagents such as bases, acids, or feed gasses used during manufacturing can introduce contaminants, which can not only cause corrosion damage to costly chemical infrastructure and reduce product yields, they can be potentially dangerous.

Ensuring the quality of monomers used in food-grade plastics, as well as the chemical formulations used in the production of consumer products like adhesives, paints, inks, cosmetics, detergents, and many pharmaceutical products is extremely

important to ensure product quality and safety. For example, phthalates used as plasticizers are potential carcinogens. Cation contamination of acids, such as phosphoric acid used in the production of soft drinks, has been linked to increased urinary calcium which is associated with hypertension. Ions such as bromate or chromium VI are carcinogenic at very low concentrations.

The pollution emitted by internal combustion engines greatly impacts the quality of our air. With more stringent regulatory standards by the US EPA limiting the sulfur content of fuels such as diesel, gasoline, and ethanol, the analysis of total sulfur and individual sulfur-containing components is becoming more challenging and important.

Chemical manufacturers are under increasing pressure to expand their markets and launch new products in the face of tough environmental and economic conditions. This puts renewed focus on process improvement, quality assurance, and the challenge to develop new analytical methods that ensure the safety and efficacy of chemicals and the products that are made from them.

Dionex has developed products and solutions that address the challenging task of isolating and identifying contaminants in chemical and petrochemical products to protect manufacturing equipment, increase productivity, and ensure only safe, reliable products come to market. Dionex innovation coupled with years of experience working with industry and regulatory experts has produced a broad range of liquid sample prep, extraction, IC, and HPLC solutions for the analysis of trace-level contaminants in raw materials, chemical intermediates, and finished products.

page 3

System Solutions

Solvent ExtractionExtraction of plasticizers from PVC polymers, water-soluble compounds in plant biomass, azo dyes in textiles, and active ingredients in consumer product formulations, including adhesives, paints, inks, cosmetics, detergents and many pharmaceutical products, is required to ensure the safety and efficacy of industrial products. Dionex Accelerated Solvent Extraction (ASE®) systems use elevated temperatures and pressures to extract analytes quickly and efficiently. Alternative techniques, including Soxhlet extraction, microwave-assisted extraction, and supercritical fluid extraction, are not only much slower than ASE systems, they also require the handling and disposal of large volumes of hazardous organic solvents, and additional cleaning steps after extraction.

• Extraction of sample sizes from 1 to 100 g in minutes, not hours

• Automation reduces operator time and labor

• Dramatic solvent reduction compared to traditional extraction methods

• Compatible with a wide variety of matrices, including acidic and alkaline

Ion ChromatographyIon chromatography (IC) is well established as a routine analytical technique, and is specified in many required ASTM regulatory methods for the production of fuels and chemicals. Dionex is the leading provider of IC instrumentation, with innovative solutions that fit your workflow and your budget.

• Reagent-Free™ IC (RFIC™) systems reduce eluent and regenerant preparation while providing greater reproducibility and confidence in your results

• Dual systems allow double throughput and simultaneous analysis

• Configurable for on-line process monitoring using Integral™ process analytical systems

• Suppressed conductivity, pulsed amperometry, UV-vis, fluorescence, and MS detectors

• Ion-exchange, ion-exclusion, carbohydrate, and organic acid columns

• Integrated control and data processing with the Chromeleon® Chromatography Data System

Liquid ChromatographyThe Dionex UltiMate® 3000 series of liquid chromatography systems are ideally suited for the determination of monomer quality for polymer production, PAHs in fuels, chemical formulations in consumer products such as herbicides, disinfectants, and cosmetics, and monitoring workplace contaminants to ensure compliance with regulatory methods. Dionex offers a wide variety of modules, detectors, and configurations to suit your application needs.

• Excellent retention time precision, detector sensitivity, linearity, and drift specifications

• x2 dual systems for doubled throughput or multidimensional separations

• Rapid Separation LC (RSLC) systems for fast, high flow-rate, ultrahigh-pressure applications

• Configurable for on-line process monitoring using Integral process analytical systems

• Reversed-phase, ion-exchange, mixed-mode (HILIC, reversed-phase, and ion-exchange combinations), and monolith columns

• Diode array, multi-wavelength, fluorescence, electrochemical, and MS detectors

UltiMate Series HPLC/RSLC Analytical Systems

ICS Series IC/RFIC Analytical Systems

ASE Series Solvent Extractors

Fine and Specialty Chemicals

page 4

Analysis of Ionic LiquidsIonic liquids (IL) are a new generation of solvents with a substantial potential for replacing conventional organic solvents in numerous technical applications. They are organic salts with a melting point below 100 °C. They have very low vapor pressure and flammability, conduct electric current, and have selective dissolving properties. Modifying the functional groups of the cation or the anion allows ILs to be used as tailor-made solvents, modifiers, and reagents in organic synthesis and homogeneous catalysis.

Process monitoring during IL production and process control during their use require ef-ficient qualitative and quantitative analysis. The inherent charges of ILs make IC with suppressed conductivity detection an ideal analytical method for determining these com-plex electrolyte systems. Chromatographic separations of ILs can be optimized by varying the acidic or basic eluent concentra-tion, adding an organic modifier, and using an elevated separation column temperature.

Fine and specialty chemical manufacturers produce a broad range of products used in many different industrial applications. From reagents and solvents to monomers for acrylates and other polymeric materials, from intermediate chemicals such as alcohols, amides, ethers, and acids to pigments, inks, paints, adhesives, and coatings. Dionex provides instrumentation to separate, isolate, and identify components and contaminants for a variety of chemicals.

Effect of column temperature on retention time of structurally similar cations in ionic liquids, using an IonPac® CS17 column and suppressed conductivity detection.

Trace Anions in Organic SolventsAnion contamination introduced during manufacturing processes can damage equipment and ruin final products. This is especially important in the manufacturing of semiconductors and computer components, where trace contaminants can cause short circuits, defects in deposition, and corrosion, reducing yields and increasing manufacturing costs and waste. IC with automated eluent generation provides a convenient method to successfully determine trace anions from high ng/L to low μg/L concentrations in solvents. Automated matrix elimination prevents column fouling, and analyte concentration improves detection limits. The method easily meets the Semiconductor Equipment and Materials International (SEMI®) specifications for solvents.

Trace anionic contaminants found in a 2-propanol sample, after automated concentration and matrix elimination.

0 5 10 15 20 24-2

0

2

5

7

10

Minutesκ/

µS/c

m

EMIM

BMIM HMIM

OEIM

30 °C

40 °C

50 °C

60 °C

70 °C

26772

N+N

N+ N

N+ N

N+ N

24441

Peaks: 1. Acetate ND* µg/L 2. Formate ND 3. Lactate ND 4. Chloride 3.00 5. Nitrite ND 6. Carbonate ND 7. Sulfate 1.88 8. Nitrate 1.34

0.6

3.0

12

4

56

78

3

Minutes

µS

5 10 20 30 4015 25 35

*ND = not determined

page 5

Contaminants in Acids and BasesDetermination of ions and metals in concentrated acids and bases is important to many industries, including chemical, electronics, pharmaceutical, food, and beverage manufacturing, as well as industrial plating, environmental monitoring, and mining. Ionic contaminants can combine with their respective counterions to form insoluble compounds that can cause manufacturing defects. Calcium in phosphoric acid enhances the extraction of uranium, but when present in phosphate fertilizers may contaminate soil. Excessive amounts of potassium and sodium in foods can be a health risk. Contaminants in concentrated acids and bases must be monitored for safety and quality control.

Direct injection of concentrated acid or base samples often results in overloading of the IC column, resulting in poor chromatography and unreliable quantification. Sample dilution can reduce column overloading, but sacrifices detection limits. An AutoNeutralization™ suppressor eliminates the need to dilute concentrated acids or bases to avoid column

Trace cations in 24% sulfuric acid spiked with the Combined Six Cation Standard-II. The acid is automatically neutralized using the CSRN II suppressor, and then injected directly onto an IonPac CS16 column.

overloading, permitting the determination of μg/L and ng/L concentrations of anions and cations.

Chelation IC is ideal for determination of transition metals in organic solvents and concentrated acids and bases.

Ions and Amines in H2O2Hydrogen peroxide is an essential chemical used in a number of manufacturing processes. For polymerization and especially for semicunductor manufacturing, purity is critical. An IonPac CS17 column can be used to separate amines without the organic modifiers required with older cation-exchange columns, and an RFIC system with eluent generation permits gradient separation with the ease of use of an isocratic system, using Chromeleon software to program the gradient.

Cations or anions can be determined using the online matrix elimination technique described in Dionex Application Update 163. However, exposure to hydrogen peroxide may reduce the concentrator column lifetime.

Trace amines and cations found in a hydrogen peroxide sample, after treatment with platinum to remove the H2O2.

24533

1.4 10 20 30 350.35

0.75

Minutes

1

23

4

6

7

8

910

5

Peaks µg/L1. System –2. Lithium 13.83. Sodium 62.44. Ammonium ND5. Methylamine ND6. Dimethylamine ND7. Potassium 133.38. Magnesium 69.29. Trimethylamine ND10. Calcium 137.3

µS

23233

Peaks: 1. Sodium 0.28 µg/L 2. Ammonium (from blank) 3. Potassium 0.13 4. Unknown — 5. Unknown — 6. Trimethylamine 0.26 7. Magnesium 0.25 8. Calcium 2.0

µS

Minutes0 10 20 30 40 50

0.5

–0.1

12

3 456 7

8

page 6

Surfactant AnalysisBenzalkonium chloride is a cation surfactant sometimes used as an antiseptic in consumer products. It has applications in products such as fungicides, antiseptics, and anti-bacterial consumer products. Cationic surfactants have traditionally been difficult to analyze by reversed-phase HPLC. That changed with the introduction of the Acclaim Surfactant column. While the Acclaim Surfactant column was designed to analyze all classes of surfactants, it was especially designed for cationic surfactants. The Acclaim Surfactant column and an UltiMate 3000 system can be used to determine both the quantity and the polymeric distribution of benzalkonium chloride in a range of consumer products, for example disinfectant sprays, eye drops, and sterile elastic bandages.

Consumer Products

Chemical formulations are combinations of compounds that do not react and are designed to yield a mixture with specific desired characteristics. Many common consumer products, such as adhesives, paints, inks, cosmetics, and detergents, have complex formulations. They require precise amounts of active ingredients, plus inert ingredients, such as surfactants, to ensure product safety, consistency, and applicability. The UltiMate 3000 systems with Acclaim® columns, and Dionex IC systems with IonPac columns, are ideal for separating components of product formulations for process monitoring, quality control, safety, and regulatory compliance.

Comparison of urea and allantoin separation on A) a polar-embedded reversed-phase column, B) a C18 reversed-phase column, and C) an Acclaim Mixed-Mode HILIC-1 column. The Mixed-Mode column operated in the HILIC mode is the best choice for retention and resolution of urea and allantion.

Allantoin and Urea in CosmeticsAllantoin is frequently added to preparations used to treat minor cuts, scrapes, burns, sunburn, fever blisters, diaper rash and chapped skin and lips, and to cosmetic products to support skin protection and regeneration. Urea is frequently added as an antiseptic to prevent the growth of bacteria, mildew, and yeast in creams, shampoos, lotions, and cosmetics. However, when used in large quantities in the raw materials, they may adversely affect health and must be analyzed for quality control purposes.

Reversed-phase C18 and polar-embedded reversed-phase columns retain urea and allantoin poorly, and demonstrate limited resolution. An Acclaim Mixed-Mode HILIC-1 column operated in the HILIC mode is the best choice for retention and resolution of urea and allantion.

Separation of benzalkonium chloride homologs in two eye drop samples using the Acclaim Surfactant column.

25504

Peaks: 1. Allantoin (25 ppm) 2. Urea (200 ppm)

300

mAU

–500 1 2 3

Minutes4 5 6

C

B

A

12

1 2

1,2

26154Minutes

0 2 4 6 8 10 12 14

14

15

1

1

n-C12

n-C14

0 2 4 6 8 10 12 15

2

n-C12

A

B

200

mAU

–20

200

mAU

–20

page 7

Glyphosate in Consumer Weed Killer FormulationsGlyphosate is a popular herbicide available in many formulations. Waterproofing agents are often present in the formulation along with glyphosate, which are hydrophobic, and can interfere with glyphosate retention. The Acclaim Mixed-Mode WAX-1 column cleanly separates glyphosate from the other ingredients. Glyphosate’s lack of a UV chromophore and high concentration in the sample make detection by evaporative light scattering a convenient option.

Engine Coolant Corrosion InhibitorsCorrosion inhibitors are added to ethylene glycol coolant soutions because glycolic acid can erode cooling systems, especially if copper ions are present. No single inhibitor can protect against all corrosive agents; therefore, multiple inhibitors are typically added to antifreeze formulations. The Acclaim Mixed-Mode WAX-1 column can be used to separate glycolic acid and numerous corrosion inhibitors, including benzotriazole (BT), tolyl-triazole (TT), 2-mercaptobenzothiazole (MBT), sebacic acid, 2-ethyl hexanoic acid, and benzoic acid, in a single injection.

Consumer Products

Anions in Toothpaste and APFFluoride is well known to play a critical role in preventing tooth decay. The U.S. Food and Drug Administration has approved the use of three decay-preventing compounds in toothpaste: stannous fluoride, sodium fluoride, and sodium monofluorophosphate (MFP). However, fluoride can react with other ingredients in toothpaste to form insoluble compounds, and MFP can hydrolyze during storage, interfering with the efficacy of the product. Acidulated phosphate fluoride (APF) is approved for use as a topical solution or gel, and has strict requirements for fluoride concentration. Therefore, the determination of fluoride and MFP in toothpastes and APF is important for quality control purposes. IC provides a convenient and simple method for the direct determination of fluoride and MFP in a single analysis, with minimal sample preparation.

Separation of anions in a commercially available toothpaste using direct injection on an IonPac AS18 column.

24553

0.0 2.5 5.0 7.5 10.0

0

800

mV

Minutes

Glyphosate

Determination of glyphosate in a commercially available weed killer using the Acclaim Mixed-Mode WAX-1 column and evaporative light scattering detection (ELSD).

19344

Peaks: 1. Fluoride 0.018% 2. Acetate – 3. Chloride 0.002 4. Carbonate – 5. MFP 0.81 6. Sulfate 0.23 7. Benzoate 0.096 8. Phosphate 0.07

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 300

25

µS

Minutes

1

23 4

5

6

78

Sulfur SpeciationThe measurement and characterization of total sulfur content, as well as identification of sulfur species at trace levels, is important in several industrial processes. Catalytic hydrotreating processes, for example hydrodesulfurization, remove sulfur compounds from refinery product streams, and sweetening processes remove sulfur compounds or convert them to disulfides, as in the case of mercaptans. This can be a challenging application given their redox chemistry, and the tendency of many sulfur-containing species to readily react with each other, decompose over time, or oxidize in the presence of air. They are also very sensitive to the solution pH, which would affect the distribution of the species over time. All of these factors make the determination of these sulfur-containing anions a very challenging task. Traditional wet chemical methods for sulfur speciation are often unreliable for quantification at trace levels concentrations. However, modern IC provides an accurate and convenient method for the speciation of sulfur-containing species. OnGuard® single-use or InGuard™ in-line multiuse sample preparation cartridges can be used to help remove matrix ions and reduce solution pH to improve chromatographic separation.

Industrial Processing

page 8

Manufacturing processes are often complex, and depend on steps that use chemicals or produce byproducts that can affect product quality, worker health, or environmental safety. Dionex IC and HPLC systems and columns are used in a number of industries to help monitor process intermediates, occupational exposure, and waste streams for process control and regulatory compliance.

Determination of sulfur species in calcium polysulfide, after sample pretreatment using OnGuard H and Na cartridges, and separation on an IonPac AS17-C column with an electrolytically generated gradient.

Overlay of three consecutive runs of a Bayer liquor sample separated using an IonPac AS17 column. The on-line sample preparation and automatically generated eluent yield highly reproducible results.

Oxalate in Bayer LiquorTo isolate alumina, bauxite is dissolved in sodium hydroxide, forming a solution referred to as Bayer liquor. Aluminum hydroxide is precipitated and used in the aluminum smelting process. After precipitation, only the large crystals are put into the kiln for calcination; small crystals are returned to the precipitator. Oxalate can interfere with crystal formation, and therefore measurement of the oxalate concentration helps predict the success of forming large crystals from a given Bayer liquor. The high ionic strength and metal content typically present in these solutions make it a challenging sample. Dionex has developed a direct injection method using an RFIC system with in-line sample cleanup to accurately and reproducibly measure oxalate in Bayer liquor.

26247

0

25

10 15 20 2550Minutes

µS

1 2 3

5

4

20.00

40.00

65.00

Concentration: 2.00 mM

Peaks: 1. Sulfide 2. Sulfite 3. Sulfate 4. Thiosulfate 5. Unknown

25653

0 3 6 9 12 15 18–20

µS

100

Minutes

2

3

4

5

1Peaks: 1. Fluoride 0.1% NaF 2. Chloride 34.47 mg/L 3. Malonate 11.93 4. Sulfate 44.84 5. Oxalate 16.77

Industrial Processing

page 9

Analysis of Cations in WastewaterTo prevent nutrient enrichment and the undesirable ecological impacts associated with them, anionic and cationic species must be closely monitored in chemical wastewater streams. IC has proven to be a useful technique for the determination of amines and their breakdown products (usually other smaller amines and ammonium), as well as Group I and Group II metals. Alternate techniques using GC and HPLC require derivitization for separation and detection. Typically, these samples are water based since amines are used extensively as organic bases for pH adjustment in aqueous process streams, for example boiler water, or product formulations (scale inhibitor). IC with suppressed conductivity detection offers the convenience of analyzing water based systems with excellent sensitivity and minimal effort. The IonPac CS16 column can separate these cations rapidly and reliably using electrolytically generated methanesulfonic acid (MSA) eluent, and is compliant with ASTM Method D6919-03.

Occupational Safety

Analysis of DiisocyanatesToluene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) are commonly used in the manufacture of urethane polymers, are highly toxic by inhalation, and are carcinogenic. OHSA method 42 is a standard method for testing workplace air for contamination. The Acclaim RSLC PolarAdvantage II (PA2) 2.2 μm column not only provides suitable selectivity for these diisocyanates but also allows an acceleration of about eightfold over the conventional method. Elevated temperature improves resolution while reducing backpressure to about 210 bar.

Analysis of AzodicarbonamideAzodicarbonamide (ADC) is a blowing agent used in the production of foamed rubber and plastics, and as a flour bleaching agent that also promotes stable, even baking. But ADC is also a known respiratory sensitizer, and occupational exposure is monitored with air filters. The collected ADC is dissolved in EtOAc:DMSO and then quantified by HPLC. As ADC is not retained by reversed-phase or ionic interactions, the Acclaim Mixed-Mode WAX-1 column can be used in normal-phase mode for analysis of the filter extracts. The 3 μm, 3.0 × 150 mm format column provides excellent resolution and reduces solvent consumption as compared to 4 mm columns.

Determination of ammonium and cations in a high-sodium wastewater sample.

Fast determination of diisocyanates using the Acclaim PA2 2.2 µm column.

16268

0 10 20Minutes

0.25

0.55

µS

2

3

4

5

1

Peaks*: 1. Sodium 26,345 mg/L (ppm) 2. Ammonium 5.6 3. Potassium 45.3 4. Magnesium 11.3 5. Calcium 5.5 *Calc. (in original sample)

25773

Peaks 1. 2,6-Toluenediisocyanate 2. 1,6-Hexamethylenediisocyanate 3. 2,4-Toluenediisocyanate

Samples: A. Reagent blank B. 0.16 µg/mL in matrix C. 8.0 µg/mL each in acetonitrile

1

2

3

0 0.5 1.0 1.5 2.0 2.6

0

75

mAU

Minutes

CBA

Combustion Ion ChromatographyFluorine, chlorine, bromine and sulfur can cause corrosion in many industrial processes, decreasing the lifetime of many catalysts and causing environmental pollution. Combustion IC permits automated qualitative and quantitative analysis of halogens and sulfur in petrochemicals, coal-based chemicals, and construction materials, chemicals, and polymers. Solid or semisolid samples are pyrolyzed, absorbed in an aqueous solution, and injected onto an IC system for analysis of the combustion products. This system can be used to identify and measure:

• Sources of contaminants in production and manufacturing

• Additives for fire retardants and antioxi-dants (plastics, polymers, textiles)

• Environmental impact of use (coal), dis-posal and recycling (plastics and solvents)

• Product specification and QC/QA

For example, total halides and sulfur can be determined in an LPG (liquefied petroleum gas) sample, to monitor HF alkylation unit effectiveness.

Petroleum Refining and Exploration

page 10

The refining and use of fossil fuels in a number of industries poses challenging analytical problems. Raw materials and finished products must be tested for quality to ensure product yields, protect refinery equipment, increase the lifetimes of engines or equipment using the fuels, and to protect the environment. Dionex has developed equipment and applications for testing raw material and product quality, and for compliance with regulations for fuel production and use.

Determination of sulfur and halogens in a liquified petroleum gas sample, using combustion IC with an IonPac AS11-HC column and suppressed conductivity detection.

Determination of heat-stable salts in a gas conditioning scrubbing solution, using an IonPac AS11-HC column and suppressed conductivity. Gradient elution accelerates the elution of strongly retained species, such as thiocyanate.

Refinery Heat-Stable Salt MonitoringAlkanolamine is a gas-conditioning scrubbing solution used in petroleum refineries to remove H2S and CO2 that may be present in the feed gas. Heat stable salts (HSSs) can form from amines in these solutions. While H2S and CO2 gasses are retained when they are passed through the amine stripper and later removed by heat, inorganic cations such as formate, acetate, glycolate, sulfite, and chloride can not be removed. The buildup of HSSs in the amine unit decreases the acid gas carrying capacity of the amine, increases solution viscosity, and can cause corrosion and foaming problems, thus increasing operating costs.

IC is the preferred technique for monitoring several points throughout the amine unit. It can unambiguously identify and quantify trace-level organic acids such as acetate, formate, and glycolate while simultaneously resolving sulfur species from sulfite and sulfate to the strongly retained anions such as thiosulfate and thiocyanate, within a single chromatographic run.

19007-01

0 2 4 6 8 10 12–0.5

0

3.0

µS

Minutes

1

2

3

4

Peaks: 1. Fluoride 1.5 mg/L2. Chloride 0.0193. S as Sulfate 3.04. Phosphate 2.0 (int. std)

26830

µS

Minutes

912

3

4

5

6

7 8

0 10 20 30 40 50-0.50

4.0

Peaks: 1. Acetate 4 ppm 2. Glycolate 4 3. Formate 4 4. Chloride 4 5. Sulfite 4 6. Sulfate 4 7. Oxalate 4 8. Thiosulfate 4 9. Thiocyanate 4

Petroleum Refining and Exploration

page 11

Analysis of Polycyclic Aromatic Hydrocarbons in Fuel OilThe content of polycyclic aromatic hydrocarbons (PAHs) in diesel fuels is regulated, and most often determined using standard methods EN-12916 or ASTM D-6591. Not only does the presence of aromatic hydrocarbons pose a health risk because they are known carcinogens, they also affect fuel quality and performance. To ensure optimum engine performance and lifetime, the amount of PAHs in diesel fuel should be as low as possible. For this reason it is necessary to be able to detect and quantify trace-level PAHs in complex matrices such as petroleum distillates. The UltiMate 3000 x2 dual system facilitates the automation of on-line sample preparation and matrix elimination, permitting direct injection of complex samples using a split in-line loop injection.

Determination of PAHs in diesel fuel. Split in-line loop injection using isocratic elution provides baseline separation of all analytes.

Determination of amines and cations at concentrations from 0.5–5 ppm in a wastewater sample using an IonPac CS16 column and suppressed conductivity detection.

Anticorrosion Amines and CationsEfficient management of process streams in petrochemical production requires frequent monitoring for contamination prior to use or disposal. For example, natural gas liquids (NGL) and liquid petroleum gas (LPG) streams are typically washed with dilute caustic, 2–14 wt% NaOH, to remove residual organic sulfur compounds, such as mercaptans. Alkanolamine solutions are used to remove acidic components (H2S, CO2) from these hydrocarbon streams. Caustic washing may also be employed to neutralize the acid alkylation process effluents to minimize corrosion of plant piping and mechanical components. IC is an effective analytical tool for measuring cation contaminants, for example alkali and alkaline earth metals, ammonium, and alkanolamines in spent caustic washes, alkanolamine solutions, and other process streams such as wastewater.

26829

10 20 30 40 500.20

3.00

1 23

45

67

8

9

1112

13

14

15

16 17

µS

Minutes

10

Peaks: 1. Lithium 2. Sodium 3. Ammonium 4. Monoethanolamine 5. Methylamine 6. Diethanolamine 7. Ethylamine 8. Potassium

9. Dimethylamine 10. Triethanolamine 11. Methyldiethanolamine 12. Dimethylethanolamine 13. Morpholine 14. 1-methoxypropylamine 15. Dimethylamino-2-propanol 16. Magnesium 17. Calcium

26882

µRIU

Minutes

Peaks: 1. Parafins 2. Toluene 3. Napthalene 4. Phenanthrene 5. Pyrene 6. Nitrobenzene

0 5 10 139

181

2

3

45

6

page 12

Chloride and Sulfate in AlcoholsThe National Institute of Standards and Technology (NIST) recently made recommendations for the minimum acceptable limit for contamination of ethanol with ions such as sulfate and chloride, with the goal of harmonizing US, European Union, and Brazilian standards for biofuels quality assurance. Excessive amounts of sulfate and chloride anions can clog automobile filters and fuel injector nozzles, negatively impacting engine performance. The NIST study recommends IC as the preferred analytical method for determining sulfate and chloride in ethanol, and also recommends lowering the regulated limit of chloride ion to more closely match the specification of 1 ppm adopted by Brazil.

Using the matrix elimination method with the Dionex ICS-3000 ICS system, chloride and sulfate ions are concentrated automatically for detection limits as low as 1 ppm chloride and sulfate in denatured ethanol, methanol, and alcohol-gasoline blends, without arduous sample preparation. Dionex IonPac AS24 and AS22 columns provide accurate, reproducible results in even the most complex matrices. Choose between hydroxide (IonPac AS24) or carbonate (AS22) electrolytically generated eluents for fast run times (<12 min) with excellent retention time stability.

Alternative Fuels and Chemicals

Today, biology is transforming the way fuels and chemicals are manufactured, from biodiesel, bioethanol, and cellulosic biofuels to fine and specialty chemicals. The greatest challenge is to develop analytical methods tailored to deliver fast, accurate results. Dionex has developed a number of systems and methods for analyzing raw materials, in-process samples, and finished products.

Determination of 1 mg/L chloride and sulfate in reagent-grade ethanol containing 5% gasoline. Anions were separated using an IonPac AS22 column and carbonate/bicarbonate eluent after concentration on a TAC-ULP1 concentrator column.

Determination of cations in A) B20 and B) B99 biodiesel mixtures using an IonPac CS12-5µm column, MSA eluent, and suppressed conductivity detection.

Cations in BiodieselBiodiesel is produced by reacting plant or animal oils with an alcohol in the presence of a catalyst to produce the desired methyl esters and the byproduct glycerol. Basic catalysts, for example, sodium or potassium hydroxide or alkoxides, are most commonly used, and leave residual sodium or potassium that must be removed. Magnesium and calcium contamination can also occur if hard water is used in the manufacturing process. These cations can form soaps and ash that can clog engines.

ASTM D6751 and EN 14214 standards set a limit for these cations at <5 ppm combined sodium and potassium, and <5 ppm combined magnesium and calcium, and limits as low as <0.3 ppm total combined cations are required for a 6% biodiesel blend. The methods specified in these standards, ICP-OES and atomic absorption spectroscopy, suffer from matrix interference, difficulty in simultaneously determining contaminants, and complicated sample preparation. IC can quickly and specifically determine multiple cations simultaneously, with direct injection after only a simple water extraction and filtration. Detection limits are routinely at the 1 ppm level, far below the 5 ppm concentrations specified in the standard methods.

24069

Peaks: 1. Fluoride ND 2. Chloride 1.0 mg/L 3. Nitrate ND 4. Sulfate 1.0

0 2.5 5.0 7.5 10.0 12.5 15.010

35

Minutes

1

2

3

4µS

25494

0.5

0.20.7

µS

0.2

µS

1

150 5 Minutes

A

B

2

3 45

10

3

4

5

1

Peaks: mg/L1. Sodium 0.0472 0.9562. Unknown — —3. Potassium 0.0046 0.00534. Magnesium 0.0065 0.03625. Calcium 0.0314 0.183

page 13

Carbohydrate Profiling of BiomassAccurate, precise compositional analysis of biomass is critical for understanding and assessing biomass conversion technology. Analytical methods that provide a high degree of confidence are required for accurate yield and mass balance calculations, which in turn are necessary for sound cost estimates for biofuels production. The Dionex method for monosaccharide analysis permits determination of carbohydrates by direct injection using high-performance anion-exchange chromatography with pulsed amperometric detection (HPAE-PAD). Our new low-volume microloop injection valve technology provides baseline-resolved separation of highly concentrated samples (up to 100 g/L) without dilution, thus eliminating dilution errors while delivering stellar performance.

Fermentation Process MonitoringPrecise monitoring of fermentation in ethanol production is critical for maximizing fermentation rates and minimizing organic acid inhibitors. A key requirement is determining three different analyte classes—carbohydrates, organic acids, and alcohols—in a single analytical run. For this application, the Dionex Integral Process Analytical System using HPLC with refractive index detection, permits simultaneous monitoring of multiple analyte classes.

Determination of carbohydrates in corn stover hydrolysate using a CarboPac PA1 column and pulsed amperometric detection. Direct injection without dilution still shows excellent resolution and sensitivity, saving time and labor.

Simultaneous separation and determination of carbohydrates, organic acids, and alcohols at time zero and after 2 hours.

Lipid Profiling of Algal BiomassMany plants, including algae, store large amounts of oil as carbon storage reserves, making them an important biomass feedstock for the development of alternative fuels. Profiling of the mixture of microalgal lipids is critical in order to screen out polar phospholipids from the feedstock because they can contaminate the precious metal refining catalysts used in the production of a form of biodiesel known as renewable diesel.

The Corona® ultra™ with Charged Aerosol Detection® (CAD®) technology permits detection of multiple lipid classes including neutral lipids such as triacylglycerols and sterols, polar lipids such as phospholipids, as well as the non-acyl lipids including phytols in a single analytical run. Methods based on charged aerosol detection are more convenient than older, ELSD technology, often requiring multiple different chemistries, from normal-phase to reversed-phase chromatography, employing more complex method development, and the need for multiple analytical runs.

26006Minutes

nC

250

-1000 5037.52512.5

B

A

1

2

3

4

5 67

Peaks: 1. Glycerol 2. Galactose 3. Sucrose 4. Xylose 5. Mannose 6. Fructose 7. Cellobiose

26033

–5

200

µRIU

1 2 3

4

0 2 4 6 8 10 12 14 16 18 20 22 25 Minutes

5 6 7 8

9 10

11

0 2 4 6 8 10 12 14 16 18 20 22 25 –0.50

5.00

µRIU

Minutes

t = 0

t = 2 hr

Peaks: 1. Dextrin 7. Lactic acid 2. Maltotriose 8. Glycerol 3. Maltose 9. Acetic acid 4. Glucose 10. Methanol 5. Fructose 11. Ethanol 6. Succinic acid

page 14

Bisphenol-A Diglycidyl Ether (BADGE) and Related ImpuritiesBADGE is a widely used epoxy monomer derived from bisphenol-A. It is used to manufacture many kinds of coatings, such as powder coatings, solid coatings, solvent-based coatings, and anti-corrosive coatings. The purity of the monomer is critical because it is used to produce polycarbonate, epoxy, phenolic, polyester, and other resins. Residues of epoxies used in food-contact applications are of great health concern, because they are endocrine disruptors. For these reasons, it has become necessary to examine the quality of the raw materials of such monomers prior to polymerization and scale-up for industrial purposes. Most analytical methods for these contaminants use organic solvent-water gradients and a relatively long column to provide acceptable selectivity. The high flow-pressure footprint of the UltiMate 3000 RSLC system permits use of Acclaim RSLC columns with smaller particle sizes, such as the 2.2 μm Acclaim RSLC C18 2.1 mm i.d. column. This column can resolve BADGE and related impurities in less than 5 min, a quarter of the time necessary to resolve the same components using the conventional 5 μm Acclaim 120 C18 column.

Plastics and Polymers

Plastics and polymers are widely used in the manufacture of industrial products. Monomers, oligomers, plasticizers, and stabilizers must all meet strict quality standards to ensure product quality. Because of health hazards associated with plasticizers and other additives, their presence must be limited in products which come into contact with food, for example water bottles, or human skin, as in consumer products, for example absorbent diapers and cosmetics.

Separation of BADGE and related impurities using A) conventional LC: Acclaim 120 C18, 5 µm. 4.6 × 150 mm column and B) UHPLC: Acclaim RSLC C18, 2.2 µm, 2.1 × 150 mm column, and detected using UV absorbance.

Separation of acrylic acid monomers and oligomers using an Acclaim OA column, with detection by UV absorbance. A) Acrylic acid sample showing dimer and trimer impurities. B) Separation of a mixture of acrylic acid oligomers.

Acrylic Acid and OligomersAcrylic acid is an important monomer that can be polymerized to yield a class of hydrophilic polymers with high absorption capacity for aqueous solutions. Hydrophilic polymers are capable of absorbing several times their own weight in water, transforming them into gels with agricultural, horticultural, and sanitary applications. Ensuring the purity of the acrylic acid monomer is critically important to meet the demanding market requirements for products which come into contact with food, beverages, or human skin. Acrylic acid can also spontaneously form oligomers that can affect the properties of the finished product. The Acclaim Organic Acid (OA) column is well suited for quality-control assays related to this important class of polymers.

Peaks: 1. BADGE + 2H2O 50 µg/mL 2. Bisphenol-A 50 3. BADGE + H2O 50 4. BADGE + HCl + H2O 50 5. BADGE 50 6. BADGE + HCl 50 7. BADGE + 2HCl 50

25398Minutes0 5 10 15 20

0

125

mAU 1

2

3 56 7

R1,2 = 2.69

R1,2 = 4.55

B

A

4

20029

0 5 10 15 20

2

1

2

3

4567

3

1

AU

Minutes

O

OHAcrylic acid (Aldrich)

Acrylic acid oligomers(Aldrich)

OO

HO On

Peaks: 1. Monomer 2. Dimer 3. Trimer 4. Tetramer 5. Pentamer 6. Hexamer 7. Heptamer

A

B

page 15

Extraction of Plasticizers from PVCPoly(vinyl chloride) PVC is a popular, versatile polymer used in many different products including water pipes, toys, and shower curtains. PVC is typically composed of resins, stabilizers, pigments, and plasticizers. Platsicizers soften the polymer, aid in the manufacturing process, and provide form and function to various PVC materials. Plasticizers may account for 30-35% of the PVC formulation. Extraction and determination of plasticizers in a PVC material are critical steps in evaluating a polymer for an intended use. Traditionally, plasticizers are extracted from PVC using a 6 h Soxhlet method and identified using infrared spectrometry or gas chromatography. Compared to Soxhlet extractions, ASE methods decrease extraction times from hours to minutes and reduce solvent consumption while delivering equivalent recoveries.

Determination of a polymer UV stabilizer and three antioxidant additives, after extraction using an ASE system. Additives were separated using an Acclaim 120 C18 column and detected using UV absorption.

Analysis of Polymer Additives

Polymer additives are used as processing and long-term thermal stabilizers to protect the polymer from breakdown caused by UV light or oxidation. These antioxidant additives are critical to maintain the lifetime of consumer products containing thermoplastic polyurethane (TPU) resins. Tinuvin® is a common UV stabilizer used as an additive (for example, in polyethylene and polypropylene). Irganox® is the trade name for a class of phenolic-based antioxidants used widely as additives (for example, in PET and polyolefins). In order to control formulation levels and to conduct stability studies, the additive content of the polymer must be determined.

An ASE system is ideal for extraction of additives from in-process materials and final products. The additives can be separated using an UltiMate 3000 HPLC system with the Acclaim 120 C18 column using a CH3CN/H2O gradient. For identification and analysis of decomposition products of polymer additives, MS detection by positive ion APCI is required.

24205

0

1

2

3

4

700

40

mAU

Minutes

Peaks: 1. Irganox 245 2. Tinuvin 234 3. Irganox 259 4. Irganox 1010

242100 70

0

1.0 × 106

Counts

Minutes

Irganox 245Tinuvin 234

Irganox 259

Irganox 1010

Peaks: 1. Irganox 1010 488 m/z 2. Irganox 259 471 3. Irganox 245 587 4. Tinuvin 234 448

Overlay of selected ion mode (SIM) chromatograms of a polymer UV stabilizer and three antioxidant additives.