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Preface This manual describes operation of the combination type calcium ion selective electrode. Be sure to read this manual before using the product to ensure proper and safe operation of the product. Also safely store the manual so it is readily available whenever necessary. Please contact HORIBA Advanced Techno if any points regarding safety come to your attention during use.
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For your safety Hazard classification and warning symbols Warning messages are described in the following manner. Read the messages and follow the instructions carefully. Hazard classification This indicates an imminently hazardous situation which, if not avoided, will result in death or serious injury.
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Safety precautions This section provides precautions for using the product safely and correctly and to prevent injury and damage. The terms of DANGER, WARNING, and CAUTION indicate the degree of imminency and hazardous situation. Read the precautions carefully as it contains important safety messages. Precautions for chemicals Solutions used for calibration and measurement must not come in contact with the skin, or consumed.
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Product handling information Operational precautions Use of the product in a manner not specified by the manufacturer may impair the protection provided by the product. And it may also reduce product performance. Exercise the following precautions: Use the supplied internal solution for the reference electrode. Using any other internal solutions may cause measurement errors.
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Manual information Description in this manual The following explains the icons used in this manual. Icon Meaning This interprets the necessary points for correct operation and notifies the important points for handling the product. Note Note This indicates reference information. This indicates the part where to refer for information.
efore Use This chapter describes what you should know before using the product. Confirmation of the items included in the package ........2 About this product ......3 Product features............3 System configuration ...........3 Names of parts.............4 Measurement procedure ....5...
onfirmation of the items included in the package Open the package and make sure that the following items are included. 1000 mg/L standard solution (50 mL) Main unit 100 mg/L standard solution (50 mL) of electrode Internal solution Ion electrode tip (2 units) (50 mL) Instruction manual...
bout this product Product features The combination type calcium ion selective electrode is an electrode that combines a tip type ion electrode with a reference electrode. This product has the following features. Ion concentration can be measured with this one electrode. There is no need to use a pair of an ion selective electrode and reference electrode.
Names of parts This product consists of the parts shown in the figure below. Cable Electrode cap Protective cap Internal solution fill port Internal solution chamber Electrode connector (BNC connector) Ion electrode tip Support pipe Ion selective membrane Liquid junction Rubber cap Protective pipe * When the ion electrode tip is...
easurement procedure The following figure shows the procedure for measuring the Ca concentration. Measurement preparation Rinse with pure water. page 15) Fill with internal solution. page 12) Attach the ion electrode tip. page 10) Meter Connect the electrode to the meter. page 16)
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Calibration Measurement Prepare two types of Prepare the sample solution. solutions for calibration. page 32) page 19) Perform calibration. page 22) In the following cases, perform conditioning of the electrode before calibration. Before the first use Perform measurement. Before use after storage for two page 33) weeks or longer ...
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After measurement Discharge the internal solution from the electrode. Rinse the electrode page 39) with pure water. page 40) When the electrode will not be used for two weeks or longer, store it as described on page 44. Note Note...
lectrode Preparation This chapter describes the preparation that must be performed before using the product. Assembling the electrode (only when use for first time)......10 Filling with internal solution ..12 Rinsing the electrode..... 15 Connecting the electrode to the meter ..........
ssembling the electrode (only when use for first time) When using the product for the first time, assemble the View video View video electrode as described in the following procedure. Item to be prepared Ion electrode tip Remove the protective cap. Protective cap Remove the rubber cap.
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Attach the ion electrode tip by turning it clockwise. Ion electrode tip...
illing with internal solution Be sure to fill the electrode with internal solution as View video View video described in the following procedure before use. Be sure to fill with internal solution before use. If measurement is performed in the state in which there is not much internal solution, an inflow of sample solution into the electrode will result in accurate...
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Make sure that there is no internal solution remaining. If there is any internal solution remaining, remove it all. Steps 1 to 2 of “How to clean the electrode” (pages 38 to 39.)) Open the rubber stopper of the internal solution fill port. Rubber stopper Fill the internal solution with a dropper.
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Make sure that the inside of the electrode moves up and down and that internal solution oozes out from the liquid junction. View video View video The internal solution oozes out from the liquid junction. It is best that the internal solution oozes out slightly. If the outflow is extremely little, the potential of the reference electrode will become unstable and susceptible to stir.
insing the electrode Make sure that no dirt and other foreign matters have View video View video adhered to the electrode before measurement. If dirt and other foreign matters have adhered to the electrode, rinse the electrode as described in the following procedure.
onnecting the electrode to the meter Connect the electrode to the meter. View video View video For details on the connector of the meter to which the electrode will be connected, refer to the instruction manual of the meter. Connect the electrode connector to the meter. When disconnecting the electrode from the meter, disconnect it in the opposite direction from step 1.
tandard solutions The following standard solutions are used for calibration and measurement. 1000 mg/L Ca standard solution Use the standard solution included in the package or available as consumables by HORIBA Advanced Techno. 100 mg/L Ca standard solution Use the standard solution included in the package or available as consumables by HORIBA Advanced Techno.
alibration operation Measure standard solutions in ascending order of ion concentration to create calibration curves in the meter ( “Measurement principle of ion selective electrode” (page 56)). Perform calibration once every day or before measurement as appropriate. Before operation Be sure to fill with internal solution and rinse the electrode before the calibration operation.
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Set the meter as shown below. Setting item Setting value Set the valence as shown in the table on the right. Valence Prepare the standard solutions. Prepare the two types of standard solution to create Ca concentration ratio 1:10. For example, if the sample solution concentration is 250 mg/L, prepare standard solutions of 100 mg/L and 1000 mg/L.
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It is best to control the stirring speed so that the stir bar will rotate 3 or 4 turns per second. If swirling occurs on the surface, the stirring speed is too fast. Reduce the speed to a level where swirling does not Note Note occur.
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Rinse the electrode with pure water. Wipe off the moisture. Wipe off the moisture using soft and clean lint-free paper, or cloth. Open the rubber stopper of the internal solution fill port. Rubber stopper...
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Conditioning of the electrode In the following cases, perform conditioning of the electrode before Standard calibration. solution Before the first use Before use after storage for two weeks or longer If the electrode is less responsive Note Note An electrode is conditioned by soaking it in a standard solution for 1 hour or longer.
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Do not touch the stir bar with the electrode. It may damage the electrode. Make sure that the rubber stopper of the internal solution fill port is open during calibration. If it is closed, the internal Note Note solution does not ooze out very much from the liquid junction.
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When the first calibration is finished, take out the electrode from the solution for calibration. Rinse the electrode with pure water. Wipe off the moisture. Wipe off the moisture using soft and clean lint-free paper, or cloth. Soak the electrode in the second solution for calibration prepared in step 4.
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Do not touch the stir bar with the electrode. It may damage the electrode. Make sure that the rubber stopper of the internal solution fill port is open during calibration. If it is closed, the internal Note Note solution does not ooze out very much from the liquid junction.
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Perform the second calibration. Wait for a stable reading and perform the second calibration as described in the Meter Instruction Manual. When the second calibration is finished, the slope (%) of the electrode is displayed. Check the slope (%) on the meter. For details on how to check the slope (%), refer to the Meter Instruction Manual.
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Rinse the electrode with pure water. Wipe off the moisture. Wipe off the moisture using soft and clean lint-free paper, or cloth. When disposing of the standard solution, and paper or cloth soaked in the standard solution, follow the local rules and regulations.
easurement This chapter describes measurement. Requirements for sample and standard solutions ......30 Measurement hints ......31 Measurement units ......31 Measurement operation....32...
Requirements for sample and standard solutions The requirements for sample solutions and standard solutions are as follows: Sample solutions shall not contain organic substances. It may cause electrode deterioration. The temperatures of sample solution and standard solution shall be kept at 50°C or less.
easurement hints A gradual rise in solution temperature due to the magnetic stirrer generating heat may cause an apparent potential drift. When it happens, reduce the influence of the temperature changes by covering the magnetic stirrer with heat insulation such as polystyrene foam or using a thermostatic bath.
easurement operation Before operation The calibration characteristics vary depending on the temperature. The standard solution in calibration and the sample solution in measurement shall have almost the same temperature. Match Note Note the temperature as close as possible by, for example, using a thermostatic bath.
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(1) Put 50 mL of sample solution (250 mg/ L) in a 100 mL beaker. ISA: (2) Add 1 mL of ISA. 1 mL (3) Stir the solution slowly with a magnetic stirrer. It is best to control the stirring Sample solution Beaker: speed so that the stir bar will...
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Open the rubber stopper of the internal solution fill port. Rubber stopper Soak the electrode in the sample solution prepared in step 1. Place the electrode fully into the sample solution so that the solution comes up to the liquid junction. ...
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It is recommended to place the electrode in the electrode stand. If gravel or other foreign matters gets in the sample solution, for example, in outdoor measurement, attach the protective pipe. It will protect the ion selective membrane from foreign matters in the sample solution.
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Close the rubber stopper of the internal solution fill port. Rinse the electrode with pure water. Wipe off the moisture. Wipe off the moisture using soft and clean lint-free paper, or cloth.
ow to clean the electrode Clean the electrode after use as described in the following View video View video procedure. Item to be prepared Dropper Open the rubber stopper of the internal solution fill port. Rubber stopper...
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Remove the internal solution in one of the following ways. <Discharging from the liquid junction> Spread soft and clean lint-free paper, or cloth beneath the electrode and then press the electrode against it from above. The inside of the electrode moves up and The internal solution down.
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Close the rubber stopper of the internal solution fill port. Rinse the electrode with pure water. Wipe off the moisture. Wipe off the moisture using soft and clean lint-free paper, or cloth. Make sure that there are no dirt and crystals of internal solution adhered to the area around the liquid junction.
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Attach the protective cap. Do not get water and foreign matters inside of the protective cap when attaching it to the electrode. It may shorten the lifespan. Note Note...
aintenance This chapter describes the storage procedure of the electrode as well as the lifespan and replacement procedure of each part. Storage..........44 Main unit of electrode..........44 Consumables........45 Consumables and replacement periods ....45...
torage When the electrode will not be used for two weeks or longer, store it as described in the following procedure. Main unit of electrode Clean the electrode and discharge the internal solution. “After Measurement” (page 37)) Attach the protective cap. ...
onsumables Consumables and replacement periods The consumables that need to be replaced and the replacement periods are as follows. Replace each part at the appropriate timing to ensure accurate measurement. approx. 1 year approx. 1 year approx. 1 year Replace Service life Ion electrode tip...
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Single piece of the electrode main unit is not available for sale. When replacing the main unit of electrode, purchase the combination type calcium ion selective electrode including Note Note the ion electrode tip (Part number:3200697410). Use this up before the expiration date displayed on the bottle.
roubleshooting This chapter describes the measures to take when accurate measurement is not possible. When accurate measurement is not possible........... 48...
hen accurate measurement is not possible When accurate measurement is not possible, check the following. Table 2 Check list Check item Solution View in video Are the temperatures The standard solution in of the standard calibration and the sample solution and sample solution in measurement shall solution the same? have almost the same...
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Check item Solution View in video Is the temperature of A gradual rise in solution the solution being temperature due to the magnetic stirred rising? stirrer generating heat may cause an apparent potential drift. Reduce the influence of the ― temperature changes by covering the magnetic stirrer with heat insulation such as polystyrene...
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Check item Solution View in video Has the internal Replace the internal solution solution been before each measurement. replaced? If not, the internal solution concentration will change and it will cause measurement errors. “How to clean the electrode” (page 38)) Is there a sufficient Make sure that the surface of the amount of internal...
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Check item Solution View in video Has the composition If the standard solution has and the expired, replace it with a new one. concentration of the Use up the standard solution standard solution within approximately 3 months ― changed? after opening the bottle. Do not return the standard solution to its bottle once it has come out of the bottle.
eference This chapter describes general matters regarding ion selective electrodes. Ion selective electrodes....54 Measurement principle of ion selective electrode ............56 About activity..............58 Characteristics of calcium ion selective electrode ......60 Measurement range...........60 Impact of pH...............61 Impact of temperature ..........62 Impact of stirring............63 Impact of coexistent ions..........63 Response time ............65...
on selective electrodes The ion concentration is measured as the potential difference between an ion selective electrode and a reference electrode which are soaked into the sample solution and connected with an ion meter or a meter with an ion measurement function.
Mechanism with which the reference electrode maintains a stable potential The reference electrode generates the potential that is used as the reference against the potential measured with the V ≈ 0 ion selective electrode. The generated potential needs to be stable with very little variation no matter what kind of Fig.
easurement principle of ion selective electrode If specific ions exist in the sample solution, the ion selective membrane of the ion selective electrode generates a potential that corresponds to the concentration of those ions. The generated potential is measured as the potential difference on the basis of the reference electrode using an ion meter or meter with an ion measurement function.
If the ion concentration (activity) is set to the logarithmic axis, a linear relationship like in the graph below is created between the electrode potential measured with the ion selective electrode and the ion concentration (activity). ∆2.303 RT/nF Potential gradient 59.16 mV/decade (at 25ºC) Ion concentration (activity) Fig.
About activity The ion concentration can be accurately measured by performing calibration and measurement using an ISA. The following describes the relationship between the ion concentration and activity and the reason for adding an ISA. Distance Distance The concentration increases The number of solvent Solvent...
The activity is a concentration of ions in the solution that is corrected using a coefficient called the activity coefficient, and the relationship between them can be expressed with the following relational expression. Activity (a) = Activity coefficient () · Ion concentration (C) Table 4 shows the relationship between the ion concentration and the activity coefficient.
haracteristics of calcium ion selective electrode Measurement range The range where linearity is established between the logarithm of the ion concentration and the electromotive force is called the measurement range. In general, the range for measuring ion concentration using ion selective electrodes is a maximum of around 110 mol/L and a minimum of around 110...
Impact of pH The usable pH range is determined depending on the type and structure of the ion selective electrode. In general, this range is smaller when the concentration of the ions to be measured is lower. Also, depending on the ion selective electrodes, the components of the ion selective membrane may be dissolved depending on the pH or the electrode potential may change due to the impact of the pH.
Impact of temperature The potential gradient measured by the ion electrode method is impacted by the temperature of the sample solution in accordance with the Nernst equation. The higher the temperature is, the larger the potential gradient is. The lower the temperature is, the smaller the potential gradient is. The standard solution in calibration and the sample solution in measurement shall have almost the same temperature.
If the temperature of the sample solution in measurement differs from the temperature of the standard solution in calibration, perform calibration again. When the electrode is moved to a place that has a different temperature, wait until the temperature of the electrode becomes same as the temperature of that place before using the electrode.
About interfering ions in Ca concentration measurement When a high concentration of cations exists, the calcium ion selective electrode will be affected by, for example, measurement errors and electrode drift due to the interference by cations. The following table lists the cations that cause a 10% error with respect to the Ca concentration, and their corresponding concentrations.
Response time The response times of ion selective electrodes differ depending on factors such as the type and structure of the electrode, and type and concentration of ions. In general, the response time tends to be shorter when the ion concentration is high and longer when the ion concentration is low.
Standard solutions Selecting standard solutions Perform calibration using standard solutions of 100 mg/L and 1000 mg/L. Approximate concentrations can be measured. For more accurate measurements, prepare standard solutions which have the following concentration relationship for calibration. Standard solution with low concentration <...
aterial This chapter describes the specifications, external dimensions, and consumables of the product. Specifications......... 68 External dimensions ...... 69 Consumables........70...
pecifications The following table shows the specifications of the product. Table 8 Specifications of combination type calcium ion selective electrode Item Description Operating temperature range 0°C to 50°C Internal electrode Ag/AgCl (silver/silver chloride) electrode Internal solution 3 mol/L NH Liquid junction Movable sleeve type Wetted part (part contacting PVC, PSU...
500 mL 3200697177 electrode inner filling -IFS solution ISA for calcium ion 500-CA 500 mL 3200697178 selective electrode -ISA Distributed by: ABQ Industrial LP USA Tel: +1 (281) 516-9292 / (888) 275-5772 eFax: +1 (866) 234-0451 Web: https://www.abqindustrial.net E-mail: info@abqindustrial.net...
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31, Miyanonishi-cho, Kisshoin Minami-ku, Kyoto 601-8306, Japan http://www.horiba-adt.jp For any questions regarding this product, please contact your local agency, or inquire from the following website. http://global.horiba.com/contact_e/index.htm...