JPH11108917A - Titration control method - Google Patents
Titration control methodInfo
- Publication number
- JPH11108917A JPH11108917A JP28284497A JP28284497A JPH11108917A JP H11108917 A JPH11108917 A JP H11108917A JP 28284497 A JP28284497 A JP 28284497A JP 28284497 A JP28284497 A JP 28284497A JP H11108917 A JPH11108917 A JP H11108917A
- Authority
- JP
- Japan
- Prior art keywords
- titration
- change
- physical quantity
- control method
- test liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004448 titration Methods 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000012085 test solution Substances 0.000 claims description 17
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 101001121315 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) Oxysterol-binding protein homolog 3 Proteins 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Automatic Analysis And Handling Materials Therefor (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
(57)【要約】
【課題】 被検液に滴定試薬を滴加し、被検液の化学量
又は物理量の変化をセンサにより検出し、その変化量に
応じて常に適切な間隔にて滴定試薬を滴加し、滴定時間
の短縮を達成することができ、更には、終点付近で変化
が大きくなった場合でも、終点の検出を確実におこな
い、高精度にて滴定を行うことのできる滴定制御方法を
提供する。
【解決手段】 滴定試薬を滴加して所定の待ち時間経過
した後の被検液の化学量又は物理量変化の大きさに応じ
て、次に滴定試薬を滴加した後のセンサによる被検液の
化学量又は物理量検出のための待ち時間の大きさを制御
する。
(57) [Summary] [Problem] A titration reagent is added dropwise to a test liquid, a change in the chemical or physical quantity of the test liquid is detected by a sensor, and the titrant is constantly changed at an appropriate interval according to the change. Titration control that can shorten the titration time by dropping, and even if the change becomes large near the end point, the end point can be detected reliably and titration can be performed with high accuracy Provide a way. SOLUTION: According to the magnitude of change in the stoichiometric or physical quantity of the test liquid after a predetermined waiting time has elapsed after dropping the titrant, the test liquid by the sensor after the drop of the titrant is next added. The amount of waiting time for detecting the stoichiometry or physical quantity of the target is controlled.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一般に、食品の酸
度、塩分測定、メッキ液の濃度管理、石油の中和価測定
などにて利用可能な滴定制御方法に関し、特に被検液の
反応速度に応じた滴定を自動的に行うことのできる滴定
制御方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to a titration control method which can be used for measuring the acidity and salt content of food, controlling the concentration of a plating solution, measuring the neutralization value of petroleum, etc., and particularly relates to the reaction rate of a test solution. The present invention relates to a titration control method capable of automatically performing titration in accordance with the titration.
【０００２】[0002]
【従来の技術】従来、被検液に滴定試薬を少量ずつ滴加
し、被検液の濃度を測定する滴定は、化学成分の濃度を
測定するために有効で、汎用性の高い分析方法であり、
食品の酸度、塩分測定、メッキ液の濃度管理、石油の中
和価測定など様々の産業分野で利用されている。2. Description of the Related Art Conventionally, titration, in which a titration reagent is added little by little to a test solution and the concentration of the test solution is measured, is an effective and versatile analytical method for measuring the concentration of chemical components. Yes,
It is used in various industrial fields such as measurement of acidity and salt content of food, concentration control of plating solution, and measurement of neutralization value of petroleum.
【０００３】滴定を行う場合、被検液に対して滴定試薬
を滴加し、被検液の化学量又は物理量変化をセンサによ
り検出し、滴定の終点を自動的に判別する自動滴定装置
が実用化されている。このような自動滴定装置で滴定の
終点を判断する場合、（１）滴定試薬の滴加量に対して
被検液の化学量又は物理量変化が直線的に変化せず、特
に滴定の終点付近において変化量が大きくなる場合があ
ること、（２）被検液の化学量又は物理量変化を検出す
るセンサのレスポンスが実際の変化に対して遅れる場合
があること、（３）滴定の種類によっては化学反応の反
応時間が異なること、（４）被検液と滴定試薬を混合す
るためにある程度時間を要すること、などの問題があ
り、滴定試薬を一定の速度で滴加すると、終点の検出を
見間違うことがあった。[0003] In performing titration, an automatic titrator is used in which a titration reagent is added dropwise to a test liquid, and a chemical or physical quantity change of the test liquid is detected by a sensor to automatically determine the end point of the titration. Has been When the end point of the titration is determined by such an automatic titrator, (1) the change in the stoichiometric or physical quantity of the test solution does not change linearly with the amount of titration reagent added, and especially near the end point of the titration. The amount of change may be large, (2) the response of the sensor that detects the change in chemical or physical quantity of the test liquid may be delayed from the actual change, and (3) the chemical may vary depending on the type of titration. When the titration reagent is added dropwise at a constant rate, the end point is detected when the reaction time of the reaction is different and (4) it takes a certain amount of time to mix the test liquid and the titration reagent. There was something wrong.
【０００４】この場合、滴定試薬の１回の滴加量を極力
少なくしたり、滴定試薬の滴加間隔を十分にとることに
より終点の検出が確実に行えるが、滴定が終了するまで
の時間が長くなり、迅速性を損なう要因となっていた。[0004] In this case, the end point can be reliably detected by minimizing the titration amount of the titration reagent at a time or by taking a sufficient interval between the titration reagents. It became longer and became a factor that impaired quickness.
【０００５】[0005]
【発明が解決しようとする課題】そこで、上記問題を解
決するために、被検液の化学量又は物理量変化が大きい
場合には滴定試薬の滴加量を少なくし、その変化量が小
さい場合には滴定試薬の滴加量を大きくするというフィ
ードバック制御により、なるべく滴定時間を短くする方
法や、濃度がある程度分かっている被検液の場合には予
め予備滴加してから滴定を行う方法などを採用し、でき
るだけ滴定時間を短くするための工夫が成されてきた
が、それだけでは不十分な場合があった。又、これらの
場合においてもセンサのレスポンスなどを考慮し、滴定
試薬を滴加してから次の滴加を行うまでの間隔をある程
度余裕を持って設定する必要があり、滴定時間を長くす
る要因になっていた。Therefore, in order to solve the above-mentioned problems, the amount of titration reagent added is reduced when the chemical or physical quantity of the test liquid is large, and when the change is small. For example, a method of reducing the titration time as much as possible by feedback control to increase the titration amount of the titration reagent, or a method of performing preliminary titration beforehand for a test solution with a known concentration, etc. Although it has been devised to reduce the titration time as much as possible, it has been insufficient in some cases. Also, in these cases, it is necessary to set the interval between the dropping of the titration reagent and the next dropping with some allowance in consideration of the response of the sensor, etc. Had become.
【０００６】従って、本発明の目的は、被検液に滴定試
薬を滴加し、被検液の化学量又は物理量の変化をセンサ
により検出し、その変化量に応じて常に適切な間隔にて
滴定試薬を滴加し、滴定時間の短縮を達成することがで
き、更には、終点付近で変化が大きくなった場合でも、
終点の検出を確実におこない、高精度にて滴定を行うこ
とのできる滴定制御方法を提供することである。Accordingly, an object of the present invention is to add a titration reagent to a test solution, detect a change in the chemical or physical quantity of the test solution with a sensor, and always at appropriate intervals in accordance with the change. The titration reagent can be added dropwise to shorten the titration time, and even if the change increases near the end point,
An object of the present invention is to provide a titration control method capable of reliably detecting an end point and performing titration with high accuracy.
【０００７】[0007]
【課題を解決するための手段】上記目的は本発明に係る
滴定制御方法にて達成される。要約すれば、本発明は、
被検液に滴定試薬を少量ずつ滴加し、被検液の化学量又
は物理量の変化をセンサにて測定する滴定における制御
方法であって、滴定試薬を滴加して所定の待ち時間経過
した後の被検液の化学量又は物理量変化の大きさに応じ
て、次に滴定試薬を滴加した後の前記センサによる被検
液の化学量又は物理量検出のための待ち時間の大きさを
制御するようにしたことを特徴とする滴定制御方法であ
る。The above object is achieved by a titration control method according to the present invention. In summary, the present invention provides:
A titration reagent is added dropwise to a test liquid little by little, and this is a control method in titration in which a change in the stoichiometric or physical quantity of the test liquid is measured by a sensor, and a predetermined waiting time has elapsed after the titrant was added dropwise. The magnitude of the waiting time for detecting the chemical or physical quantity of the test liquid by the sensor after the titration reagent has been added is controlled in accordance with the magnitude of the change in the stoichiometric or physical quantity of the test liquid later. The titration control method is characterized in that the titration control method is performed.
【０００８】本発明の一実施態様によると、前記被検液
の化学量又は物理量変化が大きい場合には、次に滴定試
薬を滴加した後の被検液の化学量又は物理量検出のため
の待ち時間を大きくし、前記被検液の化学量又は物理量
変化が小さい場合には前記待ち時間を小さくする。According to one embodiment of the present invention, when the change in the stoichiometry or physical quantity of the test liquid is large, the stoichiometric or physical quantity of the test liquid after the titration reagent is added dropwise is detected. The waiting time is increased, and when the change in the chemical or physical quantity of the test liquid is small, the waiting time is reduced.
【０００９】本発明によれば、前記滴定は、中和滴定、
非水中和滴定、酸化還元滴定、沈殿滴定、キレート滴定
又は温度滴定であり、前記滴定に使用するセンサは、ｐ
Ｈ電極、ＯＲＰ電極、電導度電極、イオン電極、吸光度
センサ又は温度センサであり、前記被検液の化学量又は
物理量は、液の電気的な量、呈色又は温度である。According to the present invention, the titration comprises a neutralization titration,
Non-aqueous neutralization titration, redox titration, precipitation titration, chelate titration or temperature titration, and the sensor used for the titration is p
An H electrode, an ORP electrode, a conductivity electrode, an ion electrode, an absorbance sensor, or a temperature sensor, wherein the stoichiometric or physical quantity of the test liquid is an electric quantity, color, or temperature of the liquid.
【００１０】[0010]
【発明の実施の形態】以下、本発明に係る滴定制御方法
を図面に則して更に詳しく説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a titration control method according to the present invention will be described in more detail with reference to the drawings.
【００１１】実施例１ 本発明の滴定制御方法は、中和滴定、非水中和滴定、酸
化還元滴定、沈殿滴定、キレート滴定、温度滴定などの
あらゆる滴定に適用することができ、検出に用いるセン
サとしては、ｐＨ電極、ＯＲＰ電極、電導度電極、イオ
ン電極、吸光度センサ、温度センサなど、滴定に使用で
きる全てのセンサを使用することができる。Embodiment 1 The titration control method of the present invention can be applied to all kinds of titrations such as neutralization titration, non-aqueous neutralization titration, redox titration, precipitation titration, chelate titration, and temperature titration, and a sensor used for detection. Examples of the sensor include all sensors that can be used for titration, such as a pH electrode, an ORP electrode, a conductivity electrode, an ion electrode, an absorbance sensor, and a temperature sensor.
【００１２】本実施例では、本発明の滴定制御方法を、
センサとしてｐＨ電極を用いた硫酸の水酸化ナトリウム
による中和滴定に適用するものとして説明する。In the present embodiment, the titration control method of the present invention
The description will be given as applied to neutralization titration of sulfuric acid with sodium hydroxide using a pH electrode as a sensor.
【００１３】図１に、本発明を実施する自動滴定装置の
概略構成を示す。自動滴定装置１は、被検液Ｌを収容す
る被検液容器２を備え、この容器２内にはｐＨ電極３と
比較電極４が挿入され、各電極３、４は、それぞれリー
ド線５、６にて自動滴定装置本体７に接続されている。
又、容器２内には、撹拌子８が配置され、スターラ９に
より回転可能とされる。FIG. 1 shows a schematic configuration of an automatic titration apparatus embodying the present invention. The automatic titrator 1 includes a test solution container 2 containing a test solution L, in which a pH electrode 3 and a reference electrode 4 are inserted. At 6, it is connected to the main body 7 of the automatic titrator.
Further, a stirrer 8 is arranged in the container 2 and is rotatable by a stirrer 9.
【００１４】又、自動滴定装置１は、更に、シリンジ１
０及びこのシリンジ１０に嵌合したピストン１１を備
え、ピストン１１は、ピストン１１に連結された駆動装
置１２によりシリンジ１０内を往復動可能とされる。駆
動装置１２は、装置本体７にケーブル１４にて接続さ
れ、装置本体７からの信号により駆動制御される。前記
シリンジ１０は、滴定試薬Ａを収容した滴定試薬容器１
５に、導入管１６、３方コックの第１の弁１３ａ及び第
２の弁１３ｂ、更に、導入管１７を介して接続されてい
る。従って、駆動装置１２によりピストン１１を駆動す
ることにより、容器１５内の滴定試薬Ａは、導入管１
６、３方コックの第１の弁１３ａ及び第２の弁１３ｂ、
そして、導入管１７を介してシリンジ１０内へと導入さ
れる。又、前記３方コック１３の第３の弁１３ｃは、導
入管１８を介して、容器２内に挿入されたノズル１９に
接続されている。The automatic titrator 1 further includes a syringe 1
0 and a piston 11 fitted to the syringe 10, and the piston 11 can be reciprocated in the syringe 10 by a driving device 12 connected to the piston 11. The driving device 12 is connected to the device main body 7 by a cable 14, and is driven and controlled by a signal from the device main body 7. The syringe 10 includes a titration reagent container 1 containing a titration reagent A.
5 is connected to an introduction pipe 16, a first valve 13 a and a second valve 13 b of a three-way cock, and further through an introduction pipe 17. Therefore, by driving the piston 11 by the driving device 12, the titration reagent A in the container 15 is transferred to the introduction tube 1
6, a three-way cock first valve 13a and second valve 13b,
Then, it is introduced into the syringe 10 through the introduction pipe 17. The third valve 13 c of the three-way cock 13 is connected to a nozzle 19 inserted into the container 2 via an introduction pipe 18.
【００１５】次に図２を参照して、上記構成の自動滴定
装置１を使用して、本発明の制御方法に従って中和滴定
を行う場合について説明する。Next, a case where the neutralization titration is performed by using the automatic titration apparatus 1 having the above-described configuration according to the control method of the present invention will be described with reference to FIG.
【００１６】本実施例では、先ず、滴定試薬容器１５に
滴定試薬Ａとして０．１Ｎ水酸化ナトリウムを入れ、３
方コック１３を切り換えて弁１３ａ、１３ｂを開とし、
滴定試薬容器１５とシリンジ１０とを導入管１６、１７
にて接続する。次いで、駆動装置１２を付勢し、ピスト
ン１１を図面にて下方へと動かし、滴定試薬Ａをシリン
ジ１０内に導入する。滴定試薬導入後、３方コック１３
を切り換えて、弁１３ｂ、１３ｃを開とし、シリンジ１
０とノズル１９とを導入管１７、１８を介して接続す
る。次いで、駆動装置１２でピストン１１を図面にて上
方へと駆動して、シリンジ１０の上方に溜まった空気を
ノズル１９から捨て、シリンジ１０、導入管１７、１８
及びノズル１９を滴定試薬で満たす。In this embodiment, first, 0.1N sodium hydroxide is added as a titration reagent A to
The cock 13 is switched to open the valves 13a and 13b,
The titration reagent container 15 and the syringe 10 are introduced into the introduction tubes 16 and 17.
Connect with. Next, the drive device 12 is energized, the piston 11 is moved downward in the drawing, and the titrant A is introduced into the syringe 10. After introduction of titration reagent, 3-way cock 13
To open the valves 13b and 13c, and set the syringe 1
0 and the nozzle 19 are connected via introduction pipes 17 and 18. Next, the piston 11 is driven upward in the drawing by the driving device 12, and the air accumulated above the syringe 10 is discarded from the nozzle 19, and the syringe 10, the introduction pipes 17 and 18 are discharged.
And the nozzle 19 is filled with the titration reagent.
【００１７】次いで、被検液容器２に被検液Ｌとして、
本実施例では約０．１Ｎの硫酸をホールピペットで１０
ｍｌ正確に秤量して入れ、イオン交換水約５０ｍｌを加
えた。容器２内に配置した撹拌子８をスターラ９により
回転し、被検液Ｌとイオン交換水とを良く撹拌する。ス
ターラ９は滴定の間常に回転させておく。この状態で、
先ず、ｐＨ電極３と比較電極４からの信号に基づき装置
本体７で、被検液Ｌの電気的な量、本実施例では電位Ｅ
１を検出し、この電位を保存する（ステップ１、２）。Next, as a test liquid L in the test liquid container 2,
In this embodiment, about 0.1 N sulfuric acid is added to the solution with a whole pipette.
ml was accurately weighed and added, and about 50 ml of ion-exchanged water was added. The stirrer 8 arranged in the container 2 is rotated by the stirrer 9 to stir the test liquid L and the ion-exchanged water well. The stirrer 9 is always rotated during the titration. In this state,
First, based on signals from the pH electrode 3 and the comparison electrode 4, the electric amount of the test liquid L, the electric potential E in this embodiment,
1 is detected and this potential is stored (steps 1 and 2).
【００１８】電位Ｅ１を検出した後、駆動装置１２によ
りピストン１１を上方に動かして、滴定試薬Ａを所定量
Ｍ、容器２内へと滴加する（ステップ３）。滴定試薬Ａ
の滴加量Ｍも電位変化により制御することができるが、
本発明の効果を明確にするために、本実施例では、１回
の滴加量Ｍを０．１ｍｌに固定して滴定を行った。待ち
時間ＴINT を所定の時間Ｔ１に設定し（ステップ４）、
滴定試薬滴加Ｔ１後の被検液電位Ｅ２を検出し、この電
位を保存する（ステップ５、６、７）。After detecting the potential E1, the piston 11 is moved upward by the driving device 12, and a predetermined amount M of the titrant A is dropped into the container 2 (step 3). Titration reagent A
Can also be controlled by changing the potential,
In order to clarify the effect of the present invention, in the present example, titration was performed by fixing the amount of single addition M at 0.1 ml. The waiting time T INT is set to a predetermined time T1 (step 4),
The test solution potential E2 after the titration reagent addition T1 is detected, and this potential is stored (steps 5, 6, and 7).
【００１９】次いで、（前回保存した電位Ｅ１−今回保
存した電位Ｅ２）の絶対値ＥＳと、予め設定された電位
変化ＥＳ１とを比較し、（Ｅ１−Ｅ２）の絶対値ＥＳが
電位変化ＥＳ１に対して、ＥＳ＜ＥＳ１の場合には、前
にステップ４で設定した待ち時間Ｔ１を所定時間△Ｔ、
例えば１秒短くする（ステップ９）。逆に、ＥＳ≧ＥＳ
１の場合には、待ち時間Ｔ１を所定時間△Ｔ、例えば１
秒長くする（ステップ１０）。Next, the absolute value ES of (the previously stored potential E1-the currently stored potential E2) is compared with a preset potential change ES1, and the absolute value ES of (E1-E2) is converted to the potential change ES1. On the other hand, when ES <ES1, the waiting time T1 previously set in step 4 is changed to the predetermined time ΔT,
For example, it is shortened by one second (step 9). Conversely, ES ≧ ES
In the case of 1, the waiting time T1 is set to a predetermined time ΔT, for example, 1
Seconds are extended (step 10).
【００２０】このとき、微分値（滴定試薬滴加毎の電位
変化量）から滴定の終点を判断し（ステップ１１）、終
点と判断すると、滴定作業を終了する。もし、終点でな
いと判断したときは、上記ステップ３に戻り、再度滴定
試薬Ａを所定量Ｍだけ被検液容器２内へと滴加する（ス
テップ３）。待ち時間ＴINT は、上記ステップ９、１０
に基づき、Ｔ１−△Ｔか、或いはＴ１＋△Ｔに再設定さ
れており（ステップ４）、今回は、滴定試薬滴加後Ｔ１
−△Ｔ或いはＴ１＋△Ｔ経過後の被検液電位Ｅ３を検出
し、この電位を保存する（ステップ５、６、７）。At this time, the end point of the titration is determined from the differential value (the amount of potential change for each drop of the titration reagent) (step 11). When the end point is determined, the titration operation is terminated. If it is determined that it is not the end point, the process returns to step 3 and the titration reagent A is again dropped by a predetermined amount M into the sample liquid container 2 (step 3). The waiting time T INT is determined in steps 9 and 10 described above.
Is reset to T1-ΔT or T1 + ΔT (step 4).
The test solution potential E3 after the lapse of −ΔT or T1 + ΔT is detected, and this potential is stored (steps 5, 6, and 7).
【００２１】次いで、（前回保存した電位Ｅ２−今回保
存した電位Ｅ３）の絶対値ＥＳと、予め設定された電位
変化ＥＳ１とを比較し（ステップ８）、（Ｅ２−Ｅ３）
の絶対値ＥＳが電位変化ＥＳ１に対して、ＥＳ＜ＥＳ１
の場合には、待ち時間Ｔ１−△Ｔ或いはＴ１＋△Ｔに、
所定時間△Ｔだけ加えるか或いは引くことにより（ステ
ップ９、１０）、前にステップ４にて設定した待ち時間
ＴINT を設定し直す。Next, the absolute value ES of (previously stored potential E2−currently stored potential E3) is compared with a preset potential change ES1 (step 8), and (E2−E3).
Of the potential change ES1, ES <ES1
In the case of, the waiting time T1-ΔT or T1 + ΔT,
By adding or subtracting a predetermined time ΔT (steps 9 and 10), the waiting time T INT previously set in step 4 is reset.
【００２２】続いて、前回と同様に、滴定の終点を判断
し、滴定を終了するか、或いは、ステップ３に戻って、
上記手順に従って滴定作業を続ける。Subsequently, as in the previous case, the end point of the titration is determined, and the titration is terminated, or the process returns to step 3,
Continue the titration procedure according to the above procedure.
【００２３】このようにして滴定を行うと、電位変化Ｅ
Ｓが大きい場合には、待ち時間ＴIN T を長くし、電位変
化ＥＳが小さい場合には、待ち時間ＴINT を短くするこ
とができるために、終点付近で変化量が大きくなって
も、滴定試薬を入れすぎたりすることがなくなり、常に
最短の待ち時間で滴定を行うことができ、滴定終了まで
の時間を短くすることができる。When the titration is performed in this manner, the potential change E
If S is large, a longer waiting time T IN T, when the potential change ES is small, in order to be able to shorten the waiting time T INT, also the amount varies around the end point is increased, titration The reagent is not excessively added, the titration can always be performed with the shortest waiting time, and the time until the completion of the titration can be shortened.
【００２４】本実施例では、これに限定されるものでは
ないが、上記待ち時間Ｔ１は３秒とし、調整時間△Ｔは
１秒とし、電位ＥＳ１として２ｍＶを設定することによ
り好結果を得ることができた。In this embodiment, although not limited to this, good results can be obtained by setting the waiting time T1 to 3 seconds, setting the adjustment time ΔT to 1 second, and setting the potential ES1 to 2 mV. Was completed.
【００２５】本実施例における滴定試薬Ａの総滴加量と
滴定時間を表１に示す。表１の値は、滴定を５回行った
ときの平均値である。Table 1 shows the total amount of titration reagent A and the titration time in this example. The values in Table 1 are the average values when the titration was performed 5 times.
【００２６】比較例１ 実施例１で説明した自動滴定装置を使用し、待ち時間Ｔ
１を３秒に固定して滴定した以外は、実施例１で説明し
たと同じ材料及び方法にて滴定を行った。Comparative Example 1 Using the automatic titrator described in Example 1, the waiting time T
Titration was performed using the same materials and method as described in Example 1 except that titration was performed with 1 fixed at 3 seconds.
【００２７】比較例における滴定試薬Ａの総滴加量と滴
定時間を表１に示す。表１の値は、滴定を５回行ったと
きの平均値である。Table 1 shows the total amount of titration reagent A and the titration time in Comparative Example. The values in Table 1 are the average values when the titration was performed 5 times.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１にて、ＣＶ値（％）とは、測定値に対
する繰り返し性を意味し、 ＣＶ値（％）＝（標準偏差）÷（滴定試薬滴加量平均
（ｍｌ））×１００ にて求められる。In Table 1, the CV value (%) means repeatability with respect to the measured value. CV value (%) = (standard deviation) ÷ (average of titrant addition amount (ml)) × 100 Required.
【００３０】表１に示す結果から、本発明に基づく実施
例１と、比較例１とは、滴定試薬滴加量平均値はほぼ一
致しており、又、繰り返し性を示すＣＶ値は、共に０．
２５％以下であり、終点検出が正確に繰り返し性良く行
われていることが分かった。一方、滴定時間は、実施例
１では、２分１３秒であるのに対して、比較例１では５
分２７秒と２倍以上の滴定時間を必要としており、本発
明の滴定制御方法は、滴定時間を大幅に短縮し得ること
が分かった。From the results shown in Table 1, it can be seen that the average value of the titration reagent titration of Example 1 according to the present invention and Comparative Example 1 are almost the same, and that the CV values indicating the repeatability are both the same. 0.
25% or less, indicating that the end point detection was accurately performed with good repeatability. On the other hand, the titration time was 2 minutes and 13 seconds in Example 1, whereas the titration time was 5 minutes in Comparative Example 1.
A titration time of twice as long as 27 minutes was required, and it was found that the titration control method of the present invention can greatly reduce the titration time.
【００３１】[0031]
【発明の効果】以上説明したように、本発明の滴定制御
方法は、滴定試薬を滴加して所定の待ち時間経過した後
の被検液の化学量又は物理量変化の大きさに応じて、次
に滴定試薬を滴加した後のセンサによる被検液の化学量
又は物理量検出のための待ち時間の大きさを制御する構
成とされるので、（１）被検液に滴定試薬を滴加し、被
検液の化学量又は物理量の変化をセンサにより検出し、
その変化量に応じて常に適切な間隔にて滴定試薬を滴加
することができ、滴定時間の短縮を達成することができ
る。更には、（２）終点付近で変化が大きくなった場合
でも、終点の検出を確実におこない、高精度にて滴定を
行うことができる。という効果を奏し得る。As described above, according to the titration control method of the present invention, the titration reagent is added dropwise, and after a predetermined waiting time has elapsed, the stoichiometric or physical quantity of the test solution is changed according to the magnitude of the change. Next, since the size of the waiting time for detecting the chemical or physical quantity of the test liquid by the sensor after the titrant is dropped is controlled, (1) the titrant is added dropwise to the test liquid. Then, a change in the chemical or physical quantity of the test solution is detected by a sensor,
The titration reagent can always be added at appropriate intervals according to the amount of change, and the titration time can be shortened. Furthermore, (2) even if the change becomes large near the end point, the end point can be reliably detected, and the titration can be performed with high accuracy. The effect can be obtained.
【図１】本発明の滴定制御方法を実施するための自動滴
定装置の概略構成図である。FIG. 1 is a schematic configuration diagram of an automatic titrator for performing a titration control method of the present invention.
【図２】本発明の滴定制御方法の作動を説明するフロー
図である。FIG. 2 is a flowchart illustrating the operation of the titration control method of the present invention.
１ 自動滴定装置 ２ 被検液容器 ３ ｐＨ電極 ４ 比較電極 ７ 装置本体 １０ シリンジ １１ ピストン １２ 駆動装置 １３ ３方コック １５ 滴定試薬容器 DESCRIPTION OF SYMBOLS 1 Automatic titration apparatus 2 Sample liquid container 3 pH electrode 4 Reference electrode 7 Main body 10 Syringe 11 Piston 12 Drive device 13 Three-way cock 15 Titration reagent container
Claims (3)
検液の化学量又は物理量の変化をセンサにて測定する滴
定における制御方法であって、滴定試薬を滴加して所定
の待ち時間経過した後の被検液の化学量又は物理量変化
の大きさに応じて、次に滴定試薬を滴加した後の前記セ
ンサによる被検液の化学量又は物理量検出のための待ち
時間の大きさを制御するようにしたことを特徴とする滴
定制御方法。1. A titration control method in which a titration reagent is added dropwise to a test solution little by little, and a change in the chemical or physical quantity of the test solution is measured by a sensor. Depending on the magnitude of the change in the stoichiometry or physical quantity of the test liquid after the elapse of the waiting time, the waiting time for detecting the stoichiometric or physical quantity of the test liquid by the sensor after the titration reagent is added dropwise. A titration control method characterized by controlling the size of the titration.
きい場合には、次に滴定試薬を滴加した後の被検液の化
学量又は物理量検出のための待ち時間を大きくし、前記
被検液の化学量又は物理量変化が小さい場合には前記待
ち時間を小さくする請求項１の滴定制御方法。2. When the stoichiometric or physical quantity change of the test solution is large, the waiting time for detecting the stoichiometric or physical amount of the test solution after the titrant is added dropwise is increased, and 2. The titration control method according to claim 1, wherein the waiting time is reduced when the change in the chemical or physical quantity of the test liquid is small.
酸化還元滴定、沈殿滴定、キレート滴定又は温度滴定で
あり、前記滴定に使用するセンサは、ｐＨ電極、ＯＲＰ
電極、電導度電極、イオン電極、吸光度センサ又は温度
センサであり、前記被検液の化学量又は物理量は、液の
電気的な量、呈色又は温度である請求項１又は２の滴定
制御方法。3. The titration includes a neutralization titration, a non-aqueous neutralization titration,
Redox titration, precipitation titration, chelate titration or temperature titration, wherein the sensor used for the titration is a pH electrode, an ORP
3. The titration control method according to claim 1, wherein the titration control method is an electrode, a conductivity electrode, an ion electrode, an absorbance sensor, or a temperature sensor, and the chemical quantity or physical quantity of the test liquid is an electric quantity, color, or temperature of the liquid. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28284497A JP3813006B2 (en) | 1997-09-30 | 1997-09-30 | Titration control method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28284497A JP3813006B2 (en) | 1997-09-30 | 1997-09-30 | Titration control method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11108917A true JPH11108917A (en) | 1999-04-23 |
| JP3813006B2 JP3813006B2 (en) | 2006-08-23 |
Family
ID=17657813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28284497A Expired - Fee Related JP3813006B2 (en) | 1997-09-30 | 1997-09-30 | Titration control method |
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| Country | Link |
|---|---|
| JP (1) | JP3813006B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006071355A (en) * | 2004-08-31 | 2006-03-16 | Kyoto Electron Mfg Co Ltd | Automatic titrator |
| KR20120055472A (en) | 2010-11-22 | 2012-05-31 | 가부시키가이샤 호리바 세이사꾸쇼 | Apparatus for titration |
| CN107741469A (en) * | 2017-10-30 | 2018-02-27 | 王梓任 | An automatic titration chemical analysis system and its application method |
| CN113917072A (en) * | 2021-10-11 | 2022-01-11 | 聚光科技(杭州)股份有限公司 | Detection method based on reaction process control |
| JP2022510518A (en) * | 2019-07-15 | 2022-01-27 | 王飛 | Spectral potential temperature multidimensional titration analyzer and its usage |
| CN115586297A (en) * | 2022-09-27 | 2023-01-10 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Efficient and accurate component titration device |
| JP2024001828A (en) * | 2022-06-22 | 2024-01-10 | 東亜ディーケーケー株式会社 | Automatic titrator |
| EP4414701A1 (en) * | 2023-02-09 | 2024-08-14 | Eurosmart | System for monitoring the evolution of at least one characteristic of a reactive mixture in a container |
-
1997
- 1997-09-30 JP JP28284497A patent/JP3813006B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006071355A (en) * | 2004-08-31 | 2006-03-16 | Kyoto Electron Mfg Co Ltd | Automatic titrator |
| KR20120055472A (en) | 2010-11-22 | 2012-05-31 | 가부시키가이샤 호리바 세이사꾸쇼 | Apparatus for titration |
| CN107741469A (en) * | 2017-10-30 | 2018-02-27 | 王梓任 | An automatic titration chemical analysis system and its application method |
| JP2022510518A (en) * | 2019-07-15 | 2022-01-27 | 王飛 | Spectral potential temperature multidimensional titration analyzer and its usage |
| CN113917072A (en) * | 2021-10-11 | 2022-01-11 | 聚光科技(杭州)股份有限公司 | Detection method based on reaction process control |
| JP2024001828A (en) * | 2022-06-22 | 2024-01-10 | 東亜ディーケーケー株式会社 | Automatic titrator |
| CN115586297A (en) * | 2022-09-27 | 2023-01-10 | 内蒙古电力(集团)有限责任公司内蒙古电力科学研究院分公司 | Efficient and accurate component titration device |
| EP4414701A1 (en) * | 2023-02-09 | 2024-08-14 | Eurosmart | System for monitoring the evolution of at least one characteristic of a reactive mixture in a container |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3813006B2 (en) | 2006-08-23 |
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