-------M393-0085D '. Total Organic Carbon Analyzer TOC-5000/5050 ,r PIN 638-90216 \Instruction Manual (kef 1'1 5t'lf Sljl, *:-CJII 8e'ff/ (113) ( S t ft: (Ufl LI f- (1 t3) 4b7- I 1 ) / -[,/7 _-vc l-100 - y 71- \'Z. 7.. ry f V-' yOO::1-' r:.: ef \) \ c..e. r'V\.cc '" u.J - 3z, ... l',. .. t"* 5000 . ( v .. .; t!' ~ , ~ : ...; .:: . . , ~ ? 1 ro,; t:. Copyright Shimadzu Corporation 1991. All rights are reserved, including those to reproduce this publication or parts thereof in any form without permission in writing from Shimadzu Corporation. Information in this publication is subject to change without notice and does not represent a commitment on the part of the vendor. Any errors or omissions which may have occurred in this publication despite the utmost care taken in its production will be corrected as soon as possible, but not necessarily immediately upon detection. 1 3 5 Table of Contents 1 Introduction 2 Inspection 3 Installation 3.1 Installation site .5 3.1.1 Placement and space requirements .5 3.1.2 Environmental requirements .5 3.2 Unpacking .6 3.3 Power Connection and Grounding .6 3.4 Change of supply voltage .7 3.5 Gas requirements .7 3.6 Gas connection .8 3.7 Connection of drain tubing .9 4 Instrument preparation 11 4.1 Filling dehumidifier drain vessel 11 4.2 Preparing humidifier 12 4.3 Preparing soda lime scrubber 12 4.4 Filling TC combustion tube with TC catalyst 13 4.4.1 Procedure for regular sensitivity catalyst 13 4.4.2 Procedure for high-sensitivity catalyst 14 4.5 Connecting TC combustion tube 14 4.6 Loading chart paper in printer 16 4.7 Preparing IC reagent reservoir 17 4.8 Preparing IC reaction vessel 17 +.9 Mounting microliter syringe 18 5 Keypad and LCD unit 21 5.1 Key functions 21 5.2 LCD unit 22 236 Screen displays and functions .23 6.1 INITIAL START screen (Normal Start) 6.2 INITIAL START screen (ALL RESET Start) .24 .26 6.3 MAIN MENU screen ..... 6.4 CALIBRATION/CONDITIONS screen .29 6.5 MEASUREMENT START screen (for Calibration) .32 6.6 DATA PROCESSING STANDARD screen .34 6.7 CALIBRATION CURVE screen . . . . .37 6.8 SAMPLE MEASUREMENT/CONDITIONS screen .39 6.9 MEASUREMENT START screen (at Sample Measurement) .42 6.10 DATA PROCESSING SAMPLE screen .44 6.11 GENERAL CONDITIONS Screen . . .48 6.12 CALIBRATION CURVE FILE LIST screen . 51 6.13 DATA REPORT screen .54 6.14 MONITOR screen .57 6.15 STANDBY OPTIONS screen .59 6.16 MAINTENANCE screen .62 7 Analysis preparation 67 7.1 Supplying carrier gas . .67 7.2 Setting syringe size (GENERAL CONDITIONS screen) .67 7.3 Turning on TC furnace (GENERAL CONDITIONS screen) .67 7.4 Zero point detection of syringe pump (MAINTENANCE screen) .68 7.5 Setting date and time (in MAINTENANCE screen) . . . . .68 7.6 Regeneration of TC catalyst (also in MAINTENANCE screen) .68 7.7 Regeneration of IC solution (MAINTENANCE screen) .69 7.8 Preparation of standard solutions . . . . . .69 7.8.1 Preparation of TC (TOC) standard solution .69 7.8.2 Preparation of IC standard solution .70 7.8.3 Storage of standard solutions .70 718 Analysis 718.1 Calibration 718.1.1 Preparation for calibration 718.1.2 Calibration procedure 728.2 Sample measurement 8.2.1 Measurement procedure 72 8.3 High-sensitivity measurement 73 8.3.1 Handling of TC combustion tube with high-sensitivity catalyst 73 8.3.2 Handling of purified water or samples with ultra-low carbon content 74 8.3.3 Dedicated microliter syringe 74 8.3.4 IC removal in high-sensitivity measurement 75 8.3.5 TC Blank Check 75 8.4 Measurement of samples with high IC content 75 8.4.1 Acidification 76 8.4.2 Sparging 76 8.5 Measurement of samples with suspended solids 78 8.6 Measurement of samples containing acid, alkali or salts 78 8.6.1 Chloric acids and salls 79 8.6.2 Non-chloric acids and salls 79 8.6.3 Alkali samples . 80 8.6.4 Samples containing salts 80 9 MAINTENANCE 81 9.1 Daily inspection 81 9.2 Zero adjustment of infrared gas analyzer (NDIR) optical system 82 9.2.1 Adjustment procedure 82 9.2.2 Causes of sudden deviation of baseline position 84 9.2.3 Causes of gradual and chronic deviation of baseline position 84 9.3 Regeneration procedures 85 9.3.1 Regeneration of TC catalyst 85 9.3.2 Regeneration of IC solution . 87 9.3.3 Regeneration of TC catalyst and IC solution . 88 9.4 Maintenance procedures . 88 9.4.1 Replacement of high purity air (in cylinder) . 88 9.4.2 Cleaning/replacement of syringe plunger tip . 88 9.4.3 Cleaning and replacing the sampling needle . 88 9.4.4 Replacing O-rings in sliding TC sample injection block (monthly) . 89 9.4.5 Replacing O-ring between injection block and TC combustion tube . 90 9.4.6 Replacing O-rings in IC reaction vessel sliding sample injection block . 90 9.4.7 Cleaning and replacing sample injection needle . 91 9.4.8 Replacement of soda lime scrubber (annually) . 93 9.4.9 Replacement of halogen scrubber and membrane filter . 93 9.4.10 Supply of IC reagent . 94 9.4.11 Repositioning silicon tube in IC drain pinch valve (once a month) . 94 9.4.12 Replacement of ferrules in TC combustion tube outlet connector . 95 9.4.13 Washing or replacement ofTC combustion tube .95 9.4.14 Washing or replacing TC catalyst . 95 9.4.15 Replacement of high-sensitivity TC catalyst . 96 9.4.16 TC Blank Check . 96 9.5 MECHANICAL CHECK screen . 98 9.6 Consumable parts . 100 10 Principles of operation 101 10.1 Measurement of TC (Total Carbon) 101 10.2 Measurement of IC (Inorganic Carbon) 101 10.3 Measurement of TOC (Total Organic Carbon) 101 10.4 Measurement of NPOC (Non-purgeable Organic Carbon) 102 10.5 Electronic Signal Processing 102 10.6 Peak Area Measurement 102 10.7 Calibration Curve 103 10.7.1 One-point calibration curve 103 10.7.2 Multi-point calibration curve . 104 10.7.3 Shifting to origin . 104 10.7.4 Sparging process in measurement of standard solution . 105 10.8 Quantitative calculation . 106 10.9 Calculation of Mean Value, Standard Deviation and Coefficient of Variation . 106 10.10 Voiding abnormal values/performing additional measurement . 106 10.11 Automatic setting ofrange and injection volume . 107 10.12 Automatic selection of optimum calibration curve . 108 10.13 Automatic change ofrange and injection volume . 111 10.13.1 Automatic change of range . 111 10.13.2 Automatic change of injection volume .111 10.14 Measurement based on carbon equivalent . 112 10.15 Automatic regeneration of IC solution . 114 11 TROUBLESHOOTING 115 11.1 Error Messages . 115 11.2 Troubleshooting . 119 12 Specifications 123 Table of Figures Figure 2.1 Outside Dimensions of TOC-SOOO . . 5 Figure 3.1 Gas Tubing for TOC-SOOO ..... . 9 Figure 4.1 Internal View of TOC-SOOO . . . . . .11 Figure 4.2 Filling TC Combustion Tube with Catalyst . .13 Figure 4.3 Combustion Tube/Swage Union Connection .14 Figure 4.4 TC Sample Injecting Block Assembly .15 Figure 4.S Positioning of 3-Way Cock .17 Figure 4.6 Plunger Holder Assembly . .19 Figure 5.1 TOC-SOOO Keypad . .21 Figure 6.1 INITIAL START Screen (Normal Start) .23 Figure 6.2 INITIAL START Screen (ALL RESET Start) .24 Figure 6.3 MAIN MENU Screen . . . . . . . . . . . . . .26 Figure 6.4 CALIBRATION/CONDITIONS Screen ... .29 Figure 6.S MEASUREMENT START Screen (for CALIBRATION) .32 Figure 6.6 DATA PROCESSING STANDARD Screen . .34 Figure 6.7 CALIBRATION CURVE Screen . .37 Figure 6.8 SAMPLE MEASUREMENT/CONDITIONS Screen .39 Figure 6.9 MEASUREMENT START Screen (at Sample Measurement) .42 Figure 6.10 DATA PROCESSING SAMPLE Screen .. .44 Figure 6.11 GENERAL CONDITIONS Screen ..... .48 Figure 6.12 CALIBRATION CURVE FILE LIST Screen .51 Figure 6.13 DATA REPORT Screen . .54 Figure 6.14 MONITOR Screen . .57 Figure 6.15 STANDBY OPTIONS Screen .59 Figure 6.16 FINISH Screen . .59 Figure 6.17 RUNNING Screen . .59 Figure 6.18 MAINTENANCE Screen .. .62 Figure 9.1 Top Internal View of TOC-5000 .83 Figure 9.2 MAINTENANCE Screen .... .85 Figure 9.3 REGENERATION OF TC CATALYST Screen .86 Figure 9.4 Sample Injection Patterns . . . . . . . .91 Figure 9.5 Proper Positioning of Injection Needle .92 Figure 9.6 Halogen Scrubber . . . ..... .93 Figure 9.7 MECHANICAL CHECK Screen ... .98 Figure 10.1 Peak Area Processing Method . . . . .103 Figure 10.2 Shifting Calibration Curve to Origin .104 Table of Tables Table 2.1 Standard Accessories . . 3 Table 2.2 Optional Accessories , . . 4 Table 4.1 Microliter Syringe and Concentration Range .18 Table 9.1 Consumable Parts List . .100 Table 10.1 Absorption of C02 by Distilled Water ... .105 This page intentionally left blank. 1 Introduction Thank you for your purchase of the Shimadzu Total Organic Carbon Analyzer TOC-5000/5050. The TOC-5000 Analyzer Series measures the levels of total carbon (TC), inorganic carbon (IC), total organic carbon (TOC) and non-purgeable organic carbon (NPOC) in water. The measurement system is based on the combustion/non-dispersive infrared gas analysis method widely employed for TOC measurement. The advanced design of the TOC-5000/5050 Analyzer enables precision analysis and convenient operation. However, to ensure trouble-free operation and accurate results, it is strongly recommended that the operator refer closely to this manual and observe proper laboratory procedures in preparing standards, samples and other materials. Strict adherence to periodic maintenance will also playa significant role in ensuring long-term satisfactory operation. Note on the TOCSOSO (Available only in U.S., Canada and Europe) To enable smooth reading of the manual, all occurrences of the term "TOC-5000" apply equally to the TOC-5050, except where specifically stated. The TOC-5050 is recommended only for users not intending to routinely perform ultra-high sensitivity analysis, i.e., below 300 - 500ppb. In addition, any descriptions or procedures which do not apply to the TOC-5050 will be identified with a "shaded" background, as follows: - 1 This page intentionally left blank. -22 Inspection The TOC-SOOO shipping container consists of the TOC-SOOO main unit with a box of standard accessories placed on a wooden pallet. After unpacking the containers, confirm that all parts and standard accessories listed below are included in the shipment. (Note: Refer to Sec. 3.2 for proper unpacking procedure. Also, the packing materials should be saved for possible transport of the instrument in the future.) Table 2.1 Standard Accessories Part Name Part No. Q'ty Accessory kit (TOC-5000) for U.S. 638-90217-03 or 1for Europe 638-90217-05 Accessory kit (TOC-5050) for U.S. 638-90217-02 or for Europe 638-90217-04 [Brea kdown] 1 Overflow cup 638-14305 1 2 Humidifier 638-52813 1 3 Soda lime scrubber (C02 absorber) 630-00999 1 4 Soda lime container holder 631-26482 1 5 Shaft 631-28177 1 6 Chart paper 630-08913 1 7 Connecting cable 071-60814-01 1for Europe 071-60814-02 8 Combustion tube 631-41524 2 9 TC catalyst set 638-92069-01 1 Idmi9....se .. . .Vl . .... . . . ..... .flSl ... ... pC.a. T.. ;':-:';':';';':';';':':':':':':';':';'::':-:':':::':;:'";:::::::::;:::;::::::;;.:.;..;.:....11 IC reagent 630-00710 1 12 IC reagent reservoir 630-02657 1 13 O-ring for adapter 036-11216 1 14 Microliter syringe, 250f,l1 630-02591-04 1 16 Half union, 5304, 1/8 CM4 035-55026-02 1 17 Template for LCD 631-51959 1 18 Plastic tube, 9 mm ID, 12 mm OD 630-00315-09 2m 19 Sparging tube pack 630-00337 1 20 Catalyst filling rod 638-16023 1 21 Cleaning wire, for needle 638-30002 1 22 O-ring (inj. slide) 036-11209 1 23 O-ring (inj. slide, Teflon) 036-11408 1 24 O-rin C port 630-01566 -00 1 - 3 Part Name Part No. Q'ty 25 O-ring (IC vessel) 036-11222 1 26 Needle (sample injection) 630-01565 2 27 Plunger tip for 250!!1 630-02546-45 1 29 Flanged tube, O.5mm ID, 1.5mm 638-41269 1 OD, 400mm long 30 2N-hydrochloric acid 630-00998 1 31 Silicon grease (for high vacuum) 017-30812-01 1 32 Potassium hydrogen phthalate 25g 630-00635-01 1 33 Sodium carbonate 25g 630-00962-01 1 34 Sodium hydrogen carbonate 25g 630-00963-01 1 Instruction Manual M393-0085 1 Additional items are available as optional accessories, as listed in Table 2.2. These items must be ordered separately. Table 2.2 Optional Accessories Part Name Part No. Remarks Adsorption type gas purifier 638-52824-02 High purity air cylinder 630-00960 To be supplied by user in U.S. Mf] . H. 500 T .... .. .... .... ..... .... ... .... .... .... .... ... ..... .... .... . .... ...... :::::::::::::::::::::::::::::::: :':: :': ... :.:: ::. . .:... :3: : ...... :.: ...:Q.: :... ,:.".l ... ::.... sr.: .: :. . ...... :: :... :..... :' ... :1.:.06.: .. ... : .. .... :...... :... :... :. .... ': ..... ..... ...... .... .... .... .... ..... .... ..... .. ..... ..... .. ... .. .... ::.:.: . .. ... .. :.0: .... :... :. .. ... 9:... :1.: :... :5.: . ..... :' : ... U3 9 Plunger tip (3 pes. in a set) 638-60734-06 For 500ul microliter syringe Plunger tip (3 pes. in a set) 638-60734-07 For l,OOOul microliter syringe RS-232C interface (25P) 638-72376 For output to RS-232C RS-232C interface (9P) 638-72376-01 For output to RS-232C (For IBM PC/AT and compatible computers) Optional board mounting kit 638-70292 Required for mounting RS-232C interface - 4 3 Installation 3.1 Installation site 3.1.1 Placement and space requirements The TOe-5000 should be installed on a sturdy, level surface convenient to a grounded power source of the appropriate voltage. An installation width of approximately 1 meter is recommended for convenient operation and maintenance. If the soda lime container holder is to be mounted (at rear of instrument), at least 137 mm (5 in.) of space must be allowed beyond the rear panel of the instrument. If space at the rear is limited, the soda lime may be placed at the side of the instrument. The outside dimensions are as indicated in Figure 2.1. ~ _ 5 2 2 ? -~ ~ ;:;;::= 0 """D [ About 480 mm J .. ~ L 0 l::..J ::::1 :::1 00 About 520 mm ~ E E 0 00 v :; 0 ~ CJI-About 80 mm Figure 2.1 Outside Dimensions of TOG-5000 3.1.2 Environmental requirements Select an installation site which is free from corrosive or organic gas and dust. For high sensitivity measurement in particular, contaminated atmosphere may cause erroneous measurement. Ambient temperature must be stable. Do not install the instrument where it will be exposed to direct sunlight, heat from a local heat source, drafts from an air-conditioner, etc. Do not install the equipment where use of fire is prohibited. Do not install the instrument in the vicinity of strong magnetic or electric fields or high frequency waves. - 5 -3.2 Unpacking 1) After removing the shipping bands, lift off the cardboard container to reveal the main unit and standard accessories box. NOTE: Retain all shipping materials for future transport of the instrument. Lift the TOC-SOOO main unit carefully from the pallet, taking care not to lift using the door or putting pressure on the LCD screen. NOTE: Two people should lift the unit. 2) Remove the 2 screws securing the top cover at the rear of the instrument. Then lift off the top cover and remove the 2 Styrofoam blocks above the furnace. 3) Remove the plastic bag covering the sampling tube assembly which exits through the door. At the same time, remove the outer Teflon tube covering the sampling tube during transport. This outer Teflon tube (inner diam. 2mm, outer diam. 3mm) is fitted over the sampling tube again when sparging is to be performed during operation (see Sec. 8.4.2). 4) Remove the door fixing screw at the lower left below the door. After opening the door, the door fixing bracket may be swiveled up to the side by loosening the screw in the door rear panel, and secured in place by tightening the screw. Remove one more Styrofoam block situated beneath the furnace, and the three plastic bags covering the drain tube at lower right, the IC reservoir bottle cap and the TC combustion tube union. 5) Remove the 2 screws which secure the LCD monitor unit. These are located at about mid-height in the door rear panel, offset to the right and left. When these are removed, the LCD unit may be tilted up and down. 3.3 Power Connection and Grounding This instrument is preset to a specified source voltage before shipment according to the power supply at the destination. The set voltage is indicated on the label affixed at the lower right on the rear panel. Confirm that the source voltage to be used corresponds with that indicated on label before connecting the power cord. -6NOTE: The power supply must be stable to ensure reliable operation. Unstable voltage may adversely affect results in high-sensitivity measurement. The power cord included in the standard accessories is equipped with a 3P grounded connector. A 2P adapter connector is also provided with an attached grounding wire. NOTE: Complete grounding is essential not only for safety but also to protect the logic circuit and microcomputer. The TOC-SOOO is equipped with a thermal breaker instead of a fuse. A power surge will activate the circuit breaker and cause the power switch to be turned off automatically. Power may be supplied again by simply turning ON the power switch. However, if the thermal breaker is frequently activated, preventive measures should be taken to determine and eliminate the cause of the over-current. 3.4 Change of supply voltage If the supply voltage is to be changed due to relocation or other reasons, it will be necessary to change the wiring connection to the supply voltage-adjusting terminal board and to modify the settings on the main board to conform to the new supply voltage. In this case, contact your Shimadzu Service Representative. 3.5 Gas requirements The TOC-SOOO requires air or oxygen as a carrier/combustion gas. The TOC is an ultra-sensitive measuring device which absolutely requires a high quality carrier/combustion gas to ensure accurate, reproducible data. The use of gases that do not meet the specifications will result in poor data quality and, in severe cases, prevent the instrument from coming to the "READY" condition. The following minimum gas specifications must be observed: Regular Sensitivity Catalyst Operation C02 ~ 1.0ppm CO :5 l.Oppm THC* :5 l.Oppm (*total hydrocarbons) - 7 High Sensitivity Catalyst Operation C02 s l.Oppm CO s l.Oppm THC* s O.lppm (*total hydrocarbons) CAUTION: To ensure that the carrier gas meets the above specifications, do not rely on names such as "pure', "ultra-pure", "high purity", etc. A guaranteed analysis, which most gas suppliers will provide, should be requested. NOTE: Use of optional adsorption type gas purifier The use of a 13x molecular sieve and ascarite filter additions with lower quality gas is not recommended. Rapid deterioration of the purifier may occur depending upon the levels and types of impurities and the amount of moisture in the gas. A purifier may, however, be useful in high-sensitvity measurement. I ~ A U T I O N : Under no circumstances may untreated, compressed, atmospheric air be used as a carrier/combustion gas for the TOC-SOOO. 3.6 Gas connection Connect a two-stage pressure regulator to the carrier/combustion gas cylinder to ensure stable gas supply to the instrument at about 8Spsi (6 kg/cm2) [lOOpsi max. (7 kg/cm2 max.)]. Clean copper, stainless steel (1/8" 0.0.) or the optional air piping set may be used between the pressure regulator and the gas inlet at the rear of the TOC-SOOO (see Fig. 3.1). A half union connection adapter is provided as standard for connection using 1/8" metal tubing. Quick-connect half unions for nylon tubing is also available. Check for gas leakage Open the gas cylinder valve and use Snoop, Leak-tee, etc. at all tubing and regulator connections (outside the instrument) to check for gas leakage. All gas leaks must be eliminated to prevent rapid depletion of carrier/combustion gas in the cylinder. 8o 00 I Pressure regulator Pressure regulator (8S - lOOpsi) [2200psi min. (200kglcm2) (6 Carrier/combustion gas Air cylinder 1/8" (00) tubing 7kglcm2) TOC-SOOO gas inlet Figure 3.1 Gas Tubing for TOC-5000 NOTE: Be sure to monitor the carrier/combustion gas cylinder pressure frequently, and replace the cylinder when the pressure reaches 200psi to prevent moisture or residues from passing into the TOC-SOOO. 3.7 Connection of drain tubing Drainage is collected from the dehumidifier drain vessel, the IC reaction vessel and from the rinse tubes for TC and IC into a single drain tube at the lower right inside the instrument. Pass one end of the provided plastic tubing (pIN 630-00315-09) through the round opening at the lower right side of the instrument and fit it onto the unused "leg" of the Y-shaped drain collection tube. Insert the external end of the drain tubing into an appropriate drain container placed at a level lower than that of the instrument. Since the drainage may contain acids, a polyethylene container with a capacity of 1 - 2 gallons (5 - 10 liters) is recommended. -9This page intentionally left blank. - 10 4 Instrument preparation Carrier gas_ flow meter Microliter syringe Humidifier Dehumidifier drain vessel 3-way valve Figure 4.1 Internal View of TOG-SOOO 4.1 Filling dehumidifier drain vessel 1) Remove the cap of the plastic dehumidifier drain vessel secured by flexible clasps in the instrument at the lower right (see Fig. 4.1). 2) Add water to the level of drain outlet (upper opening) on the wall of the vessel. 3) Cap the drain vessel and set it in its original position inside the flexible clasps. - 11 4.2 Preparing humidifier 1) Fill the humidifier vessel (PIN 638-52813; shipped in standard accessories box) with a .3N NaOH solution to the upper line through port on the side wall. For high-sensitivity catalyst measurement, use water as low as possible in TC content to prepare the solution. 2) Fit the reducing union of the Teflon tube labeled "L" (originating at carrier gas flow meter and passing through opening at upper part of Toe-sooo internal divider) onto the longer glass tube that extends into the humidifier vessel. Fit the reducing union of the Teflon tube labeled "S" (from check valve on internal divider) onto the other glass tube of the humidifier vessel. 3) Set the humidifier inside the flexible clasps mounted on the right side of the TOC-5000 internal divider. NOTE: Check the liquid level in the humidifier every 2 -3 weeks and supply more purified water when necessary. The water level should never fall below the lower line, nor should it be filled to above the upper line. 4.3 Preparing soda lime scrubber 1) Mount the soda lime scrubber holder (pIN 631-26482; shipped in standard accessories box) with the 2 screws near the central lower part of the instrument rear panel. (If there is insufficient space at the rear of the the soda lime scrubber may be placed alongside the instrument withoUl the holder.) 2) Use a cutter to cut the ends of two tubes in the cap of the soda lime scrubber. 3) Fit the end of the flexible tube labeled "L" (passing through the opening at the upper part of the rear panel) onto the tube in the soda lime cap which extends into the container, and the tube labeled" S" ooto the other tube in the cap. 4) Place the soda lime scrubber in the mounted holder, taking care that the flexible tubes are not pinched. -12 4.4 Filling TC combustion tube with TC catalyst Two kinds of catalyst are available for use with the TOC-SOOO, the TC catalyst for regular sensitivity measurement (PIN 017-42801-01), standard accessory) and TC catalyst for high-sensitivity measurement (PIN 630-00996-00), standard with TOC-5000, optional with TOC-5050). Select the appropriate catalyst according to the intended measurement referring to Sec. 8.3. ~ . , .... , . ~ C\:t ,/,' i Filling of High-sensitivity TC CatalystFilling of TC Catalyst TC combustion tube (PIN 631-41524) TC catalyst (Alumina spherical support) (PIN 017-42801-01) E E o C') ...... DI EE o C') ..--l High-sensitivity I T(PIN 630-00996) Quartz wool (PIN 630-00557) Platinum screens (2) Platinum screens (2) (PIN 630-00105-01) Figure 4.2 Filling TC Combustion Tube with Catalyst 4.4.1 Procedure for regular sensitivity catalyst Fill the TC combustion tube with TC catalyst as shown in Fig. 4.2. One full bottle (20 grams) of TC catalyst is required for each combustion tube. NOTE: When filling the tube, be sure that the catalyst is not contaminated with foreign substances. Contamination of the catalyst may cause high blank values or abnormal measurement. - 13 4.4.2 Procedure for high-sensitivity catalyst Fill the TC combustion tube with the high-sensitivity TC catalyst (pIN 638-92070-01) as shown in Fig. 4.2. Two cylinders of catalyst are required for each TC combustion tube. Remove the caps from both ends of the cylinders. Using the supplied catalyst filling rod, empty the contents of the catalyst container into the TC combustion tube by pushing catalyst from the opening on one side of the container into the combustion tube. Add the second cylinder, and then tamp the catalyst to the proper level (130mm). NOTE: Whenever the TC combustion tube is filled with new TC catalyst or high sensitivity TC catalyst, execute the REGENERATION OF TC CATALYST function in the MAINTENANCE screen once or twice (see Sec. 9.3.1). 4.5 Connecting TC combustion tube 1) Lift off the instrument top cover by removing the two screws on the rear panel. 2) Disconnect the sliding TC sample injecting block assembly above the TC furnace by removing the 2 knurled thumb screws in the mounting plate. Shift the disconnected assembly to the left side to gain access to the furnace. 3) Carefully insert the TC combustion tube (narrow tube portion first) into the center opening in the furnace. 4) *For the TOC-5050, connect the tube projecting from the bottom of the TC furnace to the elbow connector attached to the Teflon tubing. - 14 CAUTIONS: . .-: .:-:-.;:':-'.;.". . " " ........" -: -:.:.' -:-:.;". -:.:." ". ." '.". :-:-:-:.:-:-:.:-:.:::::-:.:.;. -,'. -,' .- . ' outer sudaces the combustion tube lower end, inner surface of Swage lock fitting, ferrules and other gas contact surfaces from grease, oils and other organic substances, particularly when high-sensitivity measurement is conducted. 6) Apply a thin coat of the supplied high vacuum silicon grease on the outer surface of the combustion tube upper end, and fit the TC port (with O-ring) of the sliding TC sample injecting block assembly onto the coated upper end of the combustion tube. Align the sample injecting block assembly and re-mount it using the screws, but do not fully tighten the screws yet. drain tube slider sample injection needle sample injecting block Figure 4.4 Te Sample Injecting Block Assembly .:.; ... :. ..;....... ..' .... ": :-:::.;.;.;:;):-:-:.:.:-: ...... - 15 8) Finally, tighten the screws to securely mount the sample injecting block assembly (see Fig. 4.4). NOTE: Take care not to exert downward force on the slider, adversely affecting the airtightness between the slider and O-ring in the sample injecting block. 4.6 Loading chart paper in printer 1) Open the printer cover on the top of the TOe-SOOo and set a chart paper roll (with shaft (PIN 631-28177) inserted through roll) in the chart paper holder. The ends of the shaft should be seated in the lateral slots of the chart paper holder. The roll must be mounted so that the paper will feed from below the roll. 2) Fold or cut the leading edge of the paper on a slant and guide it forward under the paper feed roller of the printer. Turn ON the power switch and press the IFEED I key to feed the paper into the printer until the leading edge emerges from the printer cutter section. 3) Correct the paper alignment if necessary. Then turn OFF the power switch. NOTE: The appearance of a red streak along the edge of the chart paper indicates that the paper roll is nearly used up. Since a single roll contains 40m of chart paper, the paper will last about 14 days with a daily paper consumption of 2.Sm. CAUTION: Do not actuate the printer without properly setting the chart paper. Operating the printer without chart paper will damage the printer head. - 16 4.7 Preparing Ie reagent reservoir 1) Set the IC reagent overflow cup on the floor inside the front door of the instrument, so that the 2 projections on the bottom of the cup fit into the corresponding holes in the floor. 2) Fill the IC reagent reservoir bottle (pIN 630-02657) with 120 - 130ml of the provided IC reagent (PIN 630-00710). 3) Carefully apply a small amount of the provided silicon grease to the O-ring on the adapter inside the cap of the IC reagent reservoir bottle, preventing any grease from contacting other parts. The IC reagent reservoir bottle adapter is pre-connected to 2 tubes, a black IC reagent carrier gas tube and a thin plastic tube leading up to the IC reagent vessel. Confirm that these tubes are snug in the adapter, and then securely screw the cap on the IC reagent reservoir bOLlle. The thin plastic tube should reach to the bottom of the IC reagent reservoir bottle. 4) Place the IC reagent reservoir bottle in the IC reagent overflow cup. 4.8 Preparing Ie reaction vessel 1) Dismount the IC reaction vessel (see Fig. 4.1) by first removing the 2 screws securing the IC reaction vessel bracket below the vessel. Then, holding the main body of the vessel, twist the vessel while pulling downward until it comes loose from the injection block above it. Take care not to apply pressure to the plastic tubes attached to the vessel 2) Position the 3-way cock as shown in B of Figure 4.5, and confirm that it is securely connected to the IC reaction vessel. 3) Fill the vessel with purified water (or deionized water) up to the drain tube on the right wall of the vessel. A B 4) Apply a very thin coat of grease on the outer surface of the upper part of the Figure 4.5 Positioning of vessel, and insert the upper part of the 3-Way Cock vessel back into the sliding IC sample injection block. 5) Remount the IC reaction vessel bracket below the vessel and position the 3-way cock as shown in A of Figure 4.5 -17 4.9 Mounting microliter syringe ..anmQ:i.] .. ...i.. .: .... ...... ..: . ..D:I 11..Uj ..@.r.... . . :: : :.:.:.:-:.:.:-:- "." :.:.:.:...:.:-:.;.:.;.:.:.;.;TC Concentration Injection IC Concentration Plunger tip Size Part No. volume (f!l) range range PIN (f!l) 250 630-02591-04 630-60734-05 4 - 250 100ppb - 4000ppm 100ppb - 5000ppm . .:. :. Table 4.1 Microliter Syringe and Concentration Range NOTE: The TOC-SOOO employs a Type C (threaded) fitting on the syringe. Only this type of syringe fitting may be used. Procedure 1) Washing: The syringe must be washed thoroughly before mounting. To wash the syringe, pump the plunger 10 - 20 times with the end of the syringe immersed in acid (such as the provided 2N HCl) or in quality soap or detergent for laboratory glassware. Then rinse the syringe thoroughly using running water and finally purified water (or deionized water, or reverse osmosis water). 2) Confirm that the instrument is OFF. Lower the plunger holder assembly (see Fig. 4.6) manually to its lowest position. Remove the plunger holder assembly from the injector by unscrewing the black knob. 3) Unscrew the plunger holder cap (used to secure the plunger head in the plunger holder). Pass the microliter syringe plunger through the plunger holder cap (from the threaded side). Replace the plunger holder cap onto the plunger holder assembly. 4) Working the plunger, draw purified water into the microliter syringe, confirming the absence of bubbles in the syringe near the plunger tip. -18 Sparging connector Sampling tube Microliter syringe Plunger holder assembly Figure 4.6 Plunger Holder Assembly 5) Reposition the plunger holder assembly onto the injector assembly. Do not tighten the black knob yet. 6) Manually raise the assembly until the microliter syringe can be screwed to the 4-port valve. Hand-tighten the syringe fitting to secure the syringe. Do not over-tighten. Take care not to lower the plunger causing air to enter the syringe. NOTE: At this time, confirm that the plunger holder assembly is properly aligned. If necessary, re-align the plunger holder assembly, and re-tighten the black securing knob. 7) Pass the end of the sampling tube through the opening in the front door and close the front door. Place a beaker of purified water on the sample platform mounted on the front door and immerse the end of the sampling lube in the purified water. 8) Turn the TOe-5000 on using the power switch on the lower righl side of lhe instrument. - 19 NOTE: If leakage is ever noticed at the line connections of the 4-port valve, the cause may be a severely clogged injection needle or tubing leading to the needle. Check the condition of the injection needle, referring to Sec. 9.4.7, and clean or replace the injection needle as required. DO NOT USE A TOOL TO TIGHTEN THE CONNECTIONS AT THE 4-PORT VALVE IN CASE OF LEAKAGE. This will damage the 4-port valve, requiring replacement. These connectors must be hand-tightened only. 20 r 5 Keypad and LCD unit ENTER Figure 5.1 TOC-5000 Keypad r 5.1 Key functions 1) ISTART/STOP I key The ISTART/STOP I key is used to start and stop measurement. 2) F1 - F6 keys The "function keys" are used to perform functions indicated at the bottom of the LCD screen, with the functions varying from screen to screen. When a function key is indicated in this manual, it will be shown as the function designation (as named on the LCD screen) enclosed in a double box. For example, "press the NU key" requires the operator to press the appropriate function key (Fl - F6) corresponding to the designation at the bottom of the LCD screen. NOTE: A function key template (PIN 631-51959) is provided to facilitate identification of the appropriate function key number. This template should be affixed to the TOC unit below the LCD screen when the instrument is turned ON so that the keys on the template correspond to those shown on the screen. - 21 3) []] OJ EJ B keys The "cursor keys" are used to move the screen cursor to a desired position, so that parameters may be selected, inserted or changed 4) [Q] - [}] keys The "numeric keys" are used to input numeric values. They can also be used to bring the cursor directly to a menu item instead of using the cursor keys, and to select among parameters for setting conditions. 5) IENTER I key The I ENTER I key is used to validate an entry or a selected condition. NOTE: When entering values, it is necessary to press IENTER I to validate each entry. After keying in a value, use of the cursor keys will move the cursor in the indicated direction, however, the keyed-in entry will not become valid. 6) ICE!key The ICE Ikey is used to clear or delete a key entry which has not yet been validated using the I ENTER I key. 7) IFEED I key The IFEED Ikey is used to feed the chart paper through the printer. Chart paper continues to be fed as long as the IFEED I key is depressed. 5.2 LCD unit The LCD unit employs a high contrast backlit screen with 640 x 400 dots. The unit itself may be rotated vertically about 10 for adjustment of the viewing angle. Contrast and brightness adjustment Contrast and brighness of the image are adjusted for optimum viewing before shipment, however, these may be adjusted via the 2 adjustment screws recessed in the 2 small holes at the right of the LCD unit. The upper screw adjusts the brightness of the backlight, while the lower screw adjusts the image contrast. NOTE: Operation under extreme ambient temperatures may cause deterioration of the image display, but this is remedied with return to normal ambient temperature. Protect the plastic-coated LCD screen from damage by preventing contact with organic solvents and sharp-pointed objects. - 226 Screen displays and functions The TOC-SOOO operation is controlled through the various screens on the LCD. These screens and their associated functions will be introduced in this chapter. In general, functions are carried out using the keys on the keypad as described in the previous chapter. All items listed in the various screens may be selected for their respective functions, except those function keys which display "*,, before their indicated function. These functions are "locked out" while the * is displayed. 6.1 INITIAL START screen (Normal Start) INITIAL 8TART 06(JUN)-22-1989 2l: 26 21--+-----------TOC-5000 ~ __-------- VERSION 2.00 3 r INITlALIZING 4 TC FURNACE OFF 5 Copr.1989 Shimadzu Corporation IND Figure 6.1 INITIAL START Screen (Normal Start) When the instrument is turned on using the power switch alone, the screen appears as shown above. In this case, all previously stored calibration files, date and time settings and syringe zero point remain valid. - 23 6 6.2 INITIAL START screen (ALL RESET Start) INITIAL START 00(**)-00-0000 00: 00 RAM OK ROM OK TOC-SooO VERSION 2.00 81-+--------------ALL RESET TC FURNACE OFF FIND SYRINGE ZERO POINT ON DfSPLAY (#8) 9 \---1-------{ LSF:T DATF: & TIMF: ON "MAINTENANCE" DISPLAY (#8) Copr. 1989 Shimadzu Corporation 11-:1Figure 6.2 INITIAL START Screen (ALL RESET Start) When the instrument Power Switch is turned ON while the IENTER I key is depressed or if there is an abnormality detected in the RAM memory, lhe TOC-5000 slarts up in the ALL RESET mode. In this case, all previously stored calibration files, date and lime settings and syringe zero point are deleted from memory (RAM) and must be reset. 1) Screen item descriptions 1. Screen title "INITIAL START" is displayed. 2. Instrument model name is displayed. 3. Version number of ROM is displayed. 4. The syringe pump and other mechanical components move to their "home positions". During this process, the message "INITIALIZING" is displayed, and when the entire process is completed, lhe message "INITIALIZED" is displayed. 5. The READY message indicates that the temperature of the TC furnace and electric dehumidifier, and the position, fluctuation and noise - 24r r conditions of the baseline have all met the preset conditions for measurement (warm-up is completed). "WARMING UP" is displayed during the period prior to the display of "READY", If the TC furnace is not turned on, "TC FURNACE OFF" is displayed. 6. Date and hour are displayed. When the operation starts in the ALL RESET mode, all displayed digits are 0 (zero). 7. Results of the RAM and ROM check are displayed. If an error is found, either RAM ERROR or ROM ERROR is displayed, and other messages are cleared form the screen. 8. Indicates ALL RESET condition, (reset has been performed). 9. Messages: FIND SYRINGE ZERO POINT ON "MAINTENANCE" DISPLAY (#8) SET DATE & TIME ON "MAINTENANCE" DISPLAY (#8) Select MAINTENANCE on the MAIN MENU screen. Carry out zero point detection of the microliter syringe and set the date and time as described in Sec. 7.4, 7.5. 2) Operations Purpose Key Operation Function Proceed to next step. Press II NEXT II Proceeds to MAIN MENU. Carry out any operations indicated in ALL RESET screen. 3) NOTE When the instrument is turned ON, the date and time it was last turned OFF are printed oul along with the current date and time. - 259 6.3 MAIN MENU screen MAIN MENU