JP3526371B2 - Residual chlorine concentration measurement device - Google Patents
Residual chlorine concentration measurement deviceInfo
- Publication number
- JP3526371B2 JP3526371B2 JP14962796A JP14962796A JP3526371B2 JP 3526371 B2 JP3526371 B2 JP 3526371B2 JP 14962796 A JP14962796 A JP 14962796A JP 14962796 A JP14962796 A JP 14962796A JP 3526371 B2 JP3526371 B2 JP 3526371B2
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- Japan
- Prior art keywords
- residual chlorine
- chlorine concentration
- electrical conductivity
- apparent
- sample water
- 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.)
- Expired - Fee Related
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Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/182—Specific anions in water
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】この発明は浄水場の水質，給
水配管末端の水質，下水処理水質といった水道分野での
水質測定、水泳用プールの水質などの測定に利用される
残留塩素濃度測定装置に係り、特に無試薬式のポーラロ
グラフ法を用いる残留塩素濃度測定装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a residual chlorine concentration measuring device used for measuring water quality in waterworks such as water quality at water purification plants, water quality at the ends of water supply pipes and sewage treatment water, and water quality in swimming pools. In particular, the present invention relates to a residual chlorine concentration measuring device using a reagentless polarographic method.
【０００２】[0002]
【従来の技術】塩素は強力な酸化力とその残留性に特徴
があり、水道分野ではこの特性を利用して浄水場におけ
る殺菌をはじめ、窒素，鉄，マンガン，藻類，臭気の除
去，給水配管中での無菌状態の保持，排水に対する殺菌
処理などを行っている。残留塩素濃度測定装置は種々の
水質測定装置の中でも衛生上の観点から特に重要な計器
となっている。2. Description of the Related Art Chlorine is characterized by its strong oxidizing power and its residual property. In the water supply field, this property is utilized for sterilization in water purification plants, removal of nitrogen, iron, manganese, algae, odors, and water supply piping. It maintains the aseptic condition inside and sterilizes wastewater. The residual chlorine concentration measuring device is a particularly important instrument from the viewpoint of hygiene among various water quality measuring devices.
【０００３】従来の残留塩素濃度測定方法には比色法，
電流滴定法，ヨウ素滴定法などがあるが、連続測定器と
して一般的に実用化されているのはポーラログラフ法で
ある。以下に単に残留塩素濃度測定装置という場合はポ
ーラログラフ法を用いる測定装置を指す。The conventional residual chlorine concentration measuring method is a colorimetric method,
Although there are amperometric titration method, iodometric titration method, etc., the polarographic method is generally used as a continuous measuring instrument. Hereinafter, when simply referred to as a residual chlorine concentration measuring device, it means a measuring device using a polarographic method.
【０００４】ポーラログラフ法を用いる残留塩素濃度測
定装置は試料水内に２つの電極を対向させて一定電圧を
印加し、電極間に流れる電流により残留塩素濃度を測定
する。ポーラログラフ法残留塩素濃度測定装置には酢酸
−酢酸ナトリウム緩衝液に臭化カリウムを加えた試薬を
内蔵する有試薬式と、試薬を内蔵しない無試薬式の２つ
のタイプがある。The residual chlorine concentration measuring device using the polarographic method measures the residual chlorine concentration by applying a constant voltage to the sample water with two electrodes facing each other and applying a constant current between the electrodes. There are two types of polarographic residual chlorine concentration measuring devices: a reagent-containing type that contains a reagent in which potassium bromide is added to an acetic acid-sodium acetate buffer solution, and a reagentless type that does not contain a reagent.
【０００５】[0005]
【発明が解決しようとする課題】有試薬式では試薬の作
用により、残留塩素濃度測定値が試料水のｐＨ、電気伝
導率の影響を受けない。しかしながら試薬の補充を約１
月に一度の頻度で行う必要が生じることや送液ポンプの
交換などメンテナンスが煩雑になるという問題点があ
り、長期間の無保守連続運転が望まれるケースでは無試
薬式に対する需要が多い。さらに装置の小型化，低価格
化の観点からも無試薬式は優れている。しかしながら無
試薬式には以下のような問題点があった。In the reagent-containing formula, the residual chlorine concentration measured value is not affected by the pH and electric conductivity of the sample water due to the action of the reagent. However, the reagent replenishment is about 1
There is a problem that maintenance needs to be performed once a month and maintenance such as replacement of the liquid feed pump becomes complicated, and there is a great demand for a reagentless system in the case where long-term maintenance-free continuous operation is desired. Furthermore, the reagentless type is also superior from the viewpoints of downsizing and cost reduction of the device. However, the reagentless method has the following problems.
【０００６】・試料水のｐＨ変動により測定値が影響を
受ける。
・試料水の電気伝導率変動により測定値が影響を受け
る。
ｐＨ変化により残留塩素濃度測定値が変化するのは下記
の理由による。すなわち、残留塩素は試料水中にアンモ
ニア性窒素が含まれない場合には、遊離残留塩素と呼ば
れるＣｌ2 ，ＨＯＣｌ，ＯＣｌ- という３種類の形態で
存在しており、それらの存在比はｐＨによって変化す
る。残留塩素濃度測定装置の電極上での還元反応はＣｌ
2 ，ＨＯＣｌ，ＯＣｌ- 各々で反応性が異なる。このた
めにｐＨ変化によって残留塩素濃度測定装置の指示値が
影響を受ける。試料水中にアンモニア性窒素が含まれる
場合には、遊離残留塩素の他に結合残留塩素と呼ばれる
ＮＣｌ3 ，ＮＨＣｌ2 ，ＮＨ2 Ｃｌが生成するが、ｐＨ
変化による残留塩素濃度測定値への影響は遊離残留塩素
の場合と同様な理由で発生する。The measured value is affected by the pH fluctuation of the sample water.・ Measured values are affected by changes in electrical conductivity of sample water. The residual chlorine concentration measured value changes due to pH change for the following reasons. That is, when the sample water does not contain ammoniacal nitrogen, residual chlorine exists in three forms called Cl 2 , HOCl, and OCl − called free residual chlorine, and their abundance ratios change depending on pH. To do. The reduction reaction on the electrode of the residual chlorine concentration measuring device is Cl
2 , HOCl, OCl - each have different reactivity. Therefore, the change in pH affects the indicated value of the residual chlorine concentration measuring device. When the sample water contains ammonia nitrogen, NCl 3 , NHCl 2 and NH 2 Cl called combined residual chlorine are generated in addition to free residual chlorine,
The influence of the change on the measured residual chlorine concentration occurs for the same reason as in the case of free residual chlorine.
【０００７】電気伝導率変化による残留塩素濃度測定値
の変化は以下の理由による。すなわち、ポーラログラフ
法では、電極反応を支配する作用極（金電極）と対極
（銀電極）との間に電圧をかけ、以下の反応によって流
れる電流から残留塩素濃度を測定している。
（金電極） ＨＯＣｌ＋ ｅ- → 1/2 Ｈ2 ＋ＯＣｌ-
（銀電極） Ａｇ → Ａｇ+ ＋ ｅ-
Ａｇ+ ＋ＯＣｌ- → ＡｇＣｌ＋ 1/2Ｏ2
試料水の電気伝導率変化は、電極間溶液抵抗値が変化す
ることを意味し、残留塩素の還元に寄与すべき電極電位
が変化する。このために残留塩素濃度測定値が変化す
る。The change in the residual chlorine concentration measured value due to the change in electric conductivity is due to the following reasons. That is, in the polarographic method, a voltage is applied between the working electrode (gold electrode) and the counter electrode (silver electrode) that control the electrode reaction, and the residual chlorine concentration is measured from the current flowing by the following reaction. (Gold electrode) HOCl + e − → 1/2 H 2 + OCl − (Silver electrode) Ag → Ag + + e − Ag + + OCl − → AgCl + 1 / 2O 2 The change in the electrical conductivity of the sample water is the solution resistance value between the electrodes. Changes, and the electrode potential that should contribute to the reduction of residual chlorine changes. As a result, the residual chlorine concentration measurement value changes.
【０００８】このために無試薬式の残留塩素濃度測定装
置ではｐＨおよび電気伝導率が一定の場所でしか精度を
保証できず、使用環境が限定されるという欠点があっ
た。この発明は上述の点に鑑みてなされその目的は、残
留塩素濃度測定値に対するｐＨ、電気伝導率の一方また
は両者の影響を補正することにより、小型，低価格でメ
ンテナンスが不要な上に測定精度に優れる無試薬式の残
留塩素濃度測定装置を提供することにある。For this reason, the reagentless residual chlorine concentration measuring device has a drawback that the accuracy can be guaranteed only in a place where the pH and the electric conductivity are constant, and the use environment is limited. The present invention has been made in view of the above points, and an object thereof is to correct the influence of one or both of pH and electric conductivity on a residual chlorine concentration measurement value, thereby making it compact, low-priced, maintenance-free, and accurate in measurement. An object of the present invention is to provide a reagentless residual chlorine concentration measuring device which is excellent in performance.
【０００９】[0009]
【課題を解決するための手段】上述の目的はこの発明に
よれば無試薬式のポーラログラフ法を用い、残留塩素濃
度計と、ｐＨ 測定手段あるいは電気伝導率測定手段の
いずれかと、信号処理部とを有し、残留塩素濃度計は試
料水の見かけの残留塩素濃度を測定し、ｐＨ 測定手段
は試料水のｐＨ を測定し、電気伝導率測定手段は試料
水の電気伝導率を測定する残留塩素濃度測定装置におい
て、信号処理部は、残留塩素濃度の真値に対して正規化
した見かけの残留塩素濃度のｐＨ依存性あるいは電気伝
導率依存性に関し、試料水の測定されたｐＨのｘ 1 に対
応する、近似式 ( １ ) から求められる補正係数ｙ 1 あるい
は、試料水の測定された電気伝導率ｘ 2に対応する、近
似式 ( ２ ) 〜 ( ３ ) のいずれかから求められる補正係数ｙ 2
を決定して求めた補正曲線に基づいて、試料水の測定さ
れた見かけの残留塩素濃度を少なくとも一つの補正係数
で除して真の残留塩素濃度を算出することにより達成さ
れる。According to the present invention, the above-mentioned object is achieved by using a reagentless polarographic method and using a residual chlorine concentration meter and a pH measuring means or an electric conductivity measuring means .
The residual chlorine concentration meter measures the apparent residual chlorine concentration of the sample water, the pH measuring means measures the pH of the sample water, and the electrical conductivity measuring means measures the sample water. Residual chlorine concentration measuring device for measuring electrical conductivity
Te, the signal processing section related to the pH-dependent or electrical conductivity dependence of the residual chlorine concentration of apparent normalized to the true value of the residual chlorine concentration, pairs x 1 of the measured pH of the sample water
To respond, there correction coefficient y 1 obtained from the approximate expression (1) have
Corresponds to the measured electrical conductivity x 2 of the sample water , near
Correction coefficient y 2 obtained from any one of the similar expressions ( 2 ) to ( 3 )
Is calculated by dividing the measured apparent residual chlorine concentration of the sample water by at least one correction coefficient based on the correction curve obtained by determining the true residual chlorine concentration.
【００１０】[0010]
【００１１】[0011]
【数４】ｙ1 =ａ( ｘ 1) ３ +ｂ( ｘ 1) ２ +ｃ( ｘ 1) +ｄ （０ を含むａ 〜ｄは定数） （１）## EQU4 ## y1 = a ( x1 ) 3 + b ( x1 ) 2 + c ( x1 ) + d (a to d including 0 are constants) (1)
【００１２】[0012]
【数５】 ｙ2 =ｇ ・ｌｎ(ｘ2 )+ｈ （ｇ 、ｈ は定数） （２)[Equation 5] y2 = g.ln (x2) + h (g and h are constants) (2)
【００１３】式（３）は、補正曲線を電気伝導率に対し
複数の区間に分割し、各区間について直線近似できる一
次関数の近似式で表される。 Equation (3) is a correction curve for electrical conductivity.
One that can be divided into multiple sections and linearly approximated for each section
It is expressed by the approximation formula of the following function.
【数６】
ｙ2 =ｉ・ｘ2 +ｊ ， （ｉ 〜ｊ は各区間で異なる定数）（３）
ｐＨと電気伝導率に対する補正係数はそれぞれ独立に決
定される。また補正係数は残留塩素濃度に左右されない
ので残留塩素濃度の真値に対して正規化した単一の補正
曲線を用いて補正係数を求める。## EQU00006 ## y2 = i.multidot.x2 + j, (i to j are different constants in each section) (3) The correction factors for pH and electrical conductivity are independently determined. Since the correction coefficient does not depend on the residual chlorine concentration, the correction coefficient is calculated using a single correction curve normalized to the true value of the residual chlorine concentration.
【００１４】残留塩素濃度の真値に対して正規化した補
正曲線は式（１），式（２），または式（３）を用いて
精度の高い近似がなされる。The correction curve normalized with respect to the true value of the residual chlorine concentration is approximated with high accuracy by using the equation (1), the equation (2) or the equation (3).
【００１５】[0015]
【発明の実施の形態】残留塩素濃度計は無試薬式のポー
ラログラフ法を用いる濃度計で見かけの残留塩素濃度を
与える。真値の残留塩素濃度は、見かけの残留塩素濃度
である残留塩素濃度計の出力をｐＨと電気伝導率に対す
る各補正係数の積で除して求めることができる。また単
独の補正係数を用いるときはｐＨまたは電気伝導率に対
する補正がなされる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The residual chlorine concentration meter gives an apparent residual chlorine concentration in a concentration meter using a reagentless polarographic method. The true residual chlorine concentration can be obtained by dividing the output of the residual chlorine concentration meter, which is the apparent residual chlorine concentration, by the product of each correction coefficient for pH and electrical conductivity. Further, when a single correction coefficient is used, pH or electric conductivity is corrected.
【００１６】補正係数は補正曲線の近似式を信号処理部
に入力しておき、この近似式に測定されたｐＨまたは電
気伝導率を代入して決定することができる。補正曲線の
近似式には高次の多項式，対数関数，一次式等のうちか
ら最も良い近似を与えるものが選択される。これらの近
似式の定数は水質や用いる計器の特性に従って定められ
る。The correction coefficient can be determined by inputting an approximate expression of the correction curve into the signal processing unit and substituting the measured pH or electric conductivity into the approximate expression. As the approximation formula of the correction curve, the one that gives the best approximation is selected from high-order polynomials, logarithmic functions, linear equations, and the like. The constants of these approximate expressions are determined according to the water quality and the characteristics of the measuring instrument used.
【００１７】[0017]
【実施例】図１は本発明の実施例に係る残留塩素濃度測
定装置を示すブロック図である。残留塩素濃度計１が見
かけの（あるいは補正前の）残留塩素濃度を与える。信
号処理部２は残留塩素濃度計１とｐＨ計３と電気伝導率
計４の各信号に基づいて補正された残留塩素濃度を算出
する。1 is a block diagram showing a residual chlorine concentration measuring apparatus according to an embodiment of the present invention. The residual chlorine concentration meter 1 gives an apparent (or uncorrected) residual chlorine concentration. The signal processing unit 2 calculates a corrected residual chlorine concentration based on the signals of the residual chlorine concentration meter 1, the pH meter 3, and the electric conductivity meter 4.
【００１８】ｐＨ変化による残留塩素濃度測定値変化は
残留塩素の各形態の存在比がｐＨにより変化することに
起因するが通常の水質測定で対象となる濃度範囲では、
各形態の存在比はｐＨにのみ依存し、残留塩素濃度には
依存しない。従って測定値の変化量は残留塩素濃度に比
例して増減するが、測定値の変化率に着目すると、ｐＨ
変化による影響は残留塩素濃度によらず一定となる。こ
のために残留塩素濃度に関係なくｐＨによる残留塩素濃
度変化率を与える単一の近似式を得ることができる。The change in residual chlorine concentration measurement value due to pH change is caused by the change in the abundance ratio of each form of residual chlorine depending on pH, but in the concentration range targeted for ordinary water quality measurement,
The abundance ratio of each form depends only on pH, not on the residual chlorine concentration. Therefore, the amount of change in the measured value increases or decreases in proportion to the residual chlorine concentration.
The effect of the change is constant regardless of the residual chlorine concentration. Therefore, it is possible to obtain a single approximate expression that gives the rate of change of the residual chlorine concentration depending on the pH regardless of the residual chlorine concentration.
【００１９】図２はこの発明の実施例に係る補正前の正
規化した残留塩素濃度と補正後の正規化した残留塩素濃
度につきｐＨ依存性を示す線図である。残留塩素を含む
標準液を希釈して濃度の異なる残留塩素試料を調製し、
それぞれについてｐＨを変化させた３系列を準備し、３
系列全ての測定点について、手分析結果により正規化し
た残留塩素濃度計出力をｐＨに対してプロット（黒の三
角）した。次いで正規化した残留塩素濃度計出力につい
て近似式を求めた。得られた近似式より補正係数を求
め、１を補正係数で除して補正された正規化残留塩素濃
度を得た。ｘ1 をｐＨ、ｙ1 を補正係数とするときに残
留塩素濃度計出力値（黒の三角）が式（４）の３次多項
式FIG. 2 is a diagram showing the pH dependence of the normalized residual chlorine concentration before correction and the normalized residual chlorine concentration after correction according to the embodiment of the present invention. Diluting standard solution containing residual chlorine to prepare residual chlorine samples with different concentrations,
Prepare 3 series with different pH for each.
The residual chlorine densitometer output normalized by the result of the hand analysis was plotted against pH (black triangle) for all measurement points in the series. Then, an approximate expression was obtained for the normalized residual chlorine concentration meter output. A correction coefficient was obtained from the obtained approximate expression, and 1 was divided by the correction coefficient to obtain a corrected normalized residual chlorine concentration. When x 1 is pH and y 1 is the correction coefficient, the residual chlorine concentration meter output value (black triangle) is the third-order polynomial of equation (4).
【００２０】[0020]
【数７】
ｙ1= -0.0478（ｘ1)3 + 0.9626(ｘ1)2 - 6.4709(ｘ1)+ 15.509 （４）
で近似できること、および補正係数が残留塩素濃度に依
存しないことがわかる。また式（４）の近似式により補
正した正規化残留塩素濃度（○）のばらつきが、補正前
の正規化した残留塩素濃度のばらつきの約半分に縮小さ
れていることがわかる。It can be seen that y 1 = -0.0478 (x 1 ) 3 + 0.9626 (x 1 ) 2 -6.4709 (x 1 ) + 15.509 (4) can be approximated and that the correction coefficient does not depend on the residual chlorine concentration. Further, it can be seen that the variation of the normalized residual chlorine concentration (◯) corrected by the approximate expression of the equation (4) is reduced to about half the variation of the normalized residual chlorine concentration before the correction.
【００２１】図３はこの発明の実施例に係る残留塩素濃
度計（△）と標準液手分析（■）による残留塩素濃度の
ｐＨ依存性を示す線図である。図４はこの発明の実施例
に係る残留塩素濃度測定装置（○）と標準液手分析
（■）による残留塩素濃度のｐＨ依存性を示す線図であ
る。図５はこの発明の異なる実施例に係る残留塩素濃度
計（△）と標準液手分析（■）による残留塩素濃度のｐ
Ｈ依存性を示す線図である。FIG. 3 is a diagram showing the pH dependence of the residual chlorine concentration by the residual chlorine concentration meter (Δ) and the standard liquid manual analysis (■) according to the embodiment of the present invention. FIG. 4 is a diagram showing the pH dependence of the residual chlorine concentration by the residual chlorine concentration measuring device (◯) according to the embodiment of the present invention and the standard liquid manual analysis (■). FIG. 5 is a residual chlorine concentration p obtained by a residual chlorine concentration meter (Δ) and a standard liquid manual analysis (■) according to another embodiment of the present invention.
It is a diagram which shows H dependence.
【００２２】図６はこの発明の異なる実施例に係る残留
塩素濃度測定装置（○）と標準液手分析（■）による残
留塩素濃度のｐＨ依存性を示す線図である。図７はこの
発明のさらに異なる実施例に係る残留塩素濃度計（△）
と標準液手分析（■）による残留塩素濃度のｐＨ依存性
を示す線図である。図８はこの発明のさらに異なる実施
例に係る残留塩素濃度測定装置（○）と標準液手分析
（■）による残留塩素濃度のｐＨ依存性を示す線図であ
る。FIG. 6 is a diagram showing the pH dependence of the residual chlorine concentration by the residual chlorine concentration measuring device (∘) and the standard liquid manual analysis (■) according to different embodiments of the present invention. FIG. 7 shows a residual chlorine concentration meter (Δ) according to another embodiment of the present invention.
FIG. 3 is a diagram showing the pH dependence of residual chlorine concentration by a standard solution manual analysis (■). FIG. 8 is a diagram showing the pH dependence of the residual chlorine concentration by the residual chlorine concentration measuring device (◯) and standard solution manual analysis (■) according to a further different embodiment of the present invention.
【００２３】式（４）の近似多項式を利用して補正係数
を求め、残留塩素濃度計出力を補正して残留塩素濃度測
定装置出力としている。これらの線図から残留塩素濃度
に関係なく単一の近似式で補正係数を求めてよいことが
わかる。補正後の残留塩素濃度は手分析による残留塩素
濃度と良い一致を示すことがわかる。図９はこの発明の
実施例に係る補正前の正規化した残留塩素濃度と補正後
の正規化した残留塩素濃度につき電気伝導率依存性を示
す線図である。A correction coefficient is obtained using the approximation polynomial of the equation (4), and the output of the residual chlorine concentration meter is corrected to obtain the output of the residual chlorine concentration measuring device. It is understood from these diagrams that the correction coefficient may be obtained by a single approximate expression regardless of the residual chlorine concentration. It can be seen that the corrected residual chlorine concentration shows good agreement with the residual chlorine concentration obtained by manual analysis. FIG. 9 is a diagram showing the electrical conductivity dependence of the normalized residual chlorine concentration before correction and the normalized residual chlorine concentration after correction according to the example of the present invention.
【００２４】残留塩素を含む標準液を希釈して濃度の異
なる残留塩素試料を調製し、それぞれについて電気伝導
率を変化させた２系列を準備し、２系列全ての測定点に
ついて、手分析結果により正規化した残留塩素濃度計出
力を電気伝導率に対してプロット（黒の三角）した。次
いで正規化した残留塩素濃度計出力について近似式を求
めた。得られた近似式より補正係数を求め、１を補正係
数で除して補正された正規化残留塩素濃度を得た。ｘ2
を電気伝導率、ｙ2 を補正係数とするときに残留塩素濃
度計出力（黒の三角）が式（５）の対数式で近似できる
こと、補正曲線は残留塩素濃度の影響を受けず単一に定
まること、および式（５）の近似式により補正した正規
化残留塩素濃度（○）のばらつきが、補正前の正規化し
た残留塩素濃度のばらつきの約３分の１に縮小されてい
ることがわかる。Standard solutions containing residual chlorine were diluted to prepare residual chlorine samples having different concentrations, and two series with different electric conductivity were prepared for each of the two series. The normalized residual chlorine concentration meter output was plotted against electrical conductivity (black triangle). Then, an approximate expression was obtained for the normalized residual chlorine concentration meter output. A correction coefficient was obtained from the obtained approximate expression, and 1 was divided by the correction coefficient to obtain a corrected normalized residual chlorine concentration. x 2
Where the electrical conductivity is and y 2 is the correction coefficient, the residual chlorine concentration meter output (black triangle) can be approximated by the logarithmic expression of equation (5), and the correction curve is not affected by the residual chlorine concentration and is single. And that the variation of the normalized residual chlorine concentration (○) corrected by the approximate expression of the equation (5) is reduced to about one-third of the variation of the normalized residual chlorine concentration before the correction. Recognize.
【００２５】[0025]
【数８】
ｙ2= 0.1251 ｌｎ( ｘ2) + 0.311 （５）
図１０はこの発明の異なる実施例に係る補正前の正規化
した残留塩素濃度と補正後の正規化した残留塩素濃度に
つき電気伝導率依存性を示す線図である。電気伝導率10
0 μS/cmを区切りとして、測定結果を２つの区間に分
け、ｘ2 を電気伝導率、ｙ2 を補正係数とするときに残
留塩素濃度計出力（黒の三角）が式（６）の直線で近似
できること、補正曲線は残留塩素濃度の影響を受けず単
一に定まること、および式（６）の近似式により補正し
た正規化残留塩素濃度（○）のばらつきが、補正前の正
規化した残留塩素濃度のばらつきの約６分の１に縮小さ
れていることがわかる。Y 2 = 0.1251 ln (x 2 ) +0.311 (5) FIG. 10 is a graph showing the normalized residual chlorine concentration before correction and the normalized residual chlorine concentration after correction according to different embodiments of the present invention. It is a diagram which shows a conductivity dependence. Electrical conductivity 10
The measurement result is divided into two sections with 0 μS / cm as the delimiter. When x 2 is the electrical conductivity and y 2 is the correction coefficient, the residual chlorine concentration meter output (black triangle) is the straight line of equation (6). Can be approximated by, the correction curve can be set to a single value without being affected by the residual chlorine concentration, and the variation in the normalized residual chlorine concentration (○) corrected by the approximate expression of equation (6) is normalized before correction. It can be seen that the residual chlorine concentration is reduced to about 1/6.
【００２６】[0026]
【数９】 ｙ2= 0.0042 ｘ2 + 0.5338 ｙ2= 0.0002 ｘ2 + 0.9671 （６）[Formula 9] y 2 = 0.0042 x 2 + 0.5338 y 2 = 0.0002 x 2 + 0.9671 (6)
【００２７】[0027]
【発明の効果】この発明によれば残留塩素濃度計と、ｐ
Ｈ測定手段あるいは電気伝導率測定手段と、信号処理部
を有して、信号処理部は、残留塩素濃度の真値に対して
正規化した見かけの残留塩素濃度のｐＨ依存性あるいは
電気伝導率依存性に関する補正曲線に基づいて、試料水
の測定されたｐＨあるいは電気伝導率に対応する補正係
数を決定し、試料水の測定された見かけの残留塩素濃度
を少なくとも一つの補正係数で除して真の残留塩素濃度
を算出するものであるので、小型，低価格でメンテナン
スが不要な上に測定精度に優れる無試薬式のポーラログ
ラフ法による残留塩素濃度測定装置が得られる。According to the present invention, a residual chlorine concentration meter and p
An H measuring unit or an electric conductivity measuring unit and a signal processing unit are provided, and the signal processing unit has a pH dependence of the apparent residual chlorine concentration normalized to the true value of the residual chlorine concentration, or A correction factor corresponding to the measured pH or electrical conductivity of the sample water is determined based on the correction curve for the electrical conductivity dependence, and the measured apparent residual chlorine concentration of the sample water is determined by at least one correction factor. Since the true residual chlorine concentration is calculated by dividing the total residual chlorine concentration, a reagentless polarographic residual chlorine concentration measuring device that is compact, low-priced, maintenance-free, and excellent in measurement accuracy can be obtained.
【図１】本発明の実施例に係る残留塩素濃度測定装置を
示すブロック図FIG. 1 is a block diagram showing a residual chlorine concentration measuring apparatus according to an embodiment of the present invention.
【図２】この発明の実施例に係る補正前の正規化した残
留塩素濃度と補正後の正規化した残留塩素濃度につきｐ
Ｈ依存性を示す線図FIG. 2 is a graph showing a normalized residual chlorine concentration before correction and a normalized residual chlorine concentration after correction according to an embodiment of the present invention.
Diagram showing H dependence
【図３】この発明の実施例に係る残留塩素濃度計（△）
と標準液手分析（■）による残留塩素濃度のｐＨ依存性
を示す線図FIG. 3 is a residual chlorine concentration meter (Δ) according to an embodiment of the present invention.
Diagram showing pH dependence of residual chlorine concentration by manual analysis with standard solution (■)
【図４】この発明の実施例に係る残留塩素濃度測定装置
（○）と標準液手分析（■）による残留塩素濃度のｐＨ
依存性を示す線図FIG. 4 is a pH of residual chlorine concentration measured by a residual chlorine concentration measuring device (○) according to an embodiment of the present invention and a standard liquid manual analysis (■).
Diagram showing dependency
【図５】この発明の異なる実施例に係る残留塩素濃度計
（△）と標準液手分析（■）による残留塩素濃度のｐＨ
依存性を示す線図FIG. 5: Residual chlorine concentration pH by residual chlorine concentration meter (△) and standard liquid manual analysis (■) according to different embodiments of the present invention
Diagram showing dependency
【図６】この発明の異なる実施例に係る残留塩素濃度測
定装置（○）と標準液手分析（■）による残留塩素濃度
のｐＨ依存性を示す線図FIG. 6 is a diagram showing the pH dependence of residual chlorine concentration by a residual chlorine concentration measuring device (○) and standard liquid manual analysis (■) according to different examples of the present invention.
【図７】この発明のさらに異なる実施例に係る残留塩素
濃度計（△）と標準液手分析（■）による残留塩素濃度
のｐＨ依存性を示す線図FIG. 7 is a diagram showing pH dependence of residual chlorine concentration by residual chlorine concentration meter (Δ) and standard liquid manual analysis (■) according to another embodiment of the present invention.
【図８】この発明のさらに異なる実施例に係る残留塩素
濃度測定装置（○）と標準液手分析（■）による残留塩
素濃度のｐＨ依存性を示す線図FIG. 8 is a diagram showing the pH dependence of residual chlorine concentration by a residual chlorine concentration measuring device (○) and standard liquid manual analysis (■) according to a further different embodiment of the present invention.
【図９】この発明の実施例に係る補正前の正規化した残
留塩素濃度計出力と補正後の正規化した残留塩素濃度に
つき電気伝導率依存性を示す線図FIG. 9 is a diagram showing electrical conductivity dependence of a normalized residual chlorine concentration meter output before correction and a normalized residual chlorine concentration after correction according to an embodiment of the present invention.
【図１０】この発明の異なる実施例に係る補正前の正規
化した残留塩素濃度計出力と補正後の正規化した残留塩
素濃度につき電気伝導率依存性を示す線図FIG. 10 is a diagram showing electric conductivity dependence of a normalized residual chlorine concentration meter output before correction and a normalized residual chlorine concentration after correction according to another embodiment of the present invention.
１ 残留塩素濃度計 ２ 信号処理部 ３ ｐＨ計 ４ 電気伝導率計 1 Residual chlorine concentration meter 2 Signal processing unit 3 pH meter 4 Electrical conductivity meter
───────────────────────────────────────────────────── フロントページの続き (72)発明者 多田 弘 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 原田 健治 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 外山 文生 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (72)発明者 金井 秀夫 神奈川県川崎市川崎区田辺新田１番１号 富士電機株式会社内 (56)参考文献 実開 昭62−162662（ＪＰ，Ｕ) 実開 平５−59304（ＪＰ，Ｕ) 実開 平５−40872（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 27/416 G01N 33/18 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroshi Tada 1-1 Tanabe Shinden, Kawasaki-ku, Kawasaki-shi, Kanagawa Fuji Electric Co., Ltd. (72) Kenji Harada 1 Nitta Tanabe, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 Fuji Electric Co., Ltd. (72) Inventor Fumio Sotoyama No. 1 Tanabe Shinden, Kawasaki-ku, Kawasaki-shi, Kanagawa Fuji Electric Co., Ltd. (72) Hideo Kanai No. 1 Tanabe Nitta, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 within Fuji Electric Co., Ltd. (56) References: 62-162662 (JP, U): 5-59304 (JP, U): 5-40: 72-72 (JP, U) Field (Int.Cl. 7 , DB name) G01N 27/416 G01N 33/18
Claims (3)
塩素濃度計と、ｐＨ 測定手段と、信号処理部とを有
し、残留塩素濃度計は試料水の見かけの残留塩素濃度を
測定し、ｐＨ測定手段は試料水のｐＨ を測定する残留
塩素濃度測定装置において、前記 信号処理部は、残留塩素濃度の真値に対して正規化
した見かけの残留塩素濃度のｐＨ依存性に関する、ｐＨ
をｘ 1 、補正係数をｙ 1 とするときの式（１ ）の３次多
項式で表される近似式による補正曲線に基づいて、試料
水の測定されたｐＨに対応する補正係数を決定し、試料
水の測定された見かけの残留塩素濃度を少なくとも一つ
の補正係数で除して真の残留塩素濃度を算出するもので
あることを特徴とする残留塩素濃度測定装置。 【数１】ｙ1=ａ( ｘ 1 ) 3 +ｂ( ｘ 1 ) 2 +ｃ( ｘ 1 ) +ｄ （０ を含むａ 〜ｄは定数） （１）1. A reagentless polarographic method is used , which has a residual chlorine concentration meter, a pH measuring means, and a signal processing unit, and the residual chlorine concentration meter measures the apparent residual chlorine concentration of the sample water, The pH measuring means is a residue for measuring the pH of the sample water.
In chlorine concentration measurement device, said signal processing unit relates the pH dependence of the residual chlorine concentration of apparent normalized to the true value of the residual chlorine concentration, pH
Where x 1 is the correction coefficient and y 1 is the correction coefficient. ) 3rd order
A correction coefficient corresponding to the measured pH of the sample water is determined based on the correction curve by the approximate expression represented by the term expression, and the measured apparent residual chlorine concentration of the sample water is divided by at least one correction coefficient. The residual chlorine concentration measuring device is characterized by calculating the true residual chlorine concentration. ## EQU1 ## y1 = a ( x1 ) 3 + b ( x1 ) 2 + c ( x1 ) + d (a to d including 0 are constants) (1)
塩素濃度計と、電気伝導率測定手段と、信号処理部とを
有し、残留塩素濃度計は試料水の見かけの残留塩素濃度
を測定し、電気伝導率測定手段は試料水の電気伝導率を
測定する残留塩素濃度測定装置において、 前記信号処理部は、残留塩素濃度の真値に対して正規化
した見かけの残留塩素濃度の電気伝導率依存性に関す
る、 電気伝導率をｘ2 、補正係数をｙ2 とするときの近
似式が式（２ ）で表される補正曲線に基づいて、試料
水の測定された電気伝導率に対応する補正係数を決定
し、試料水の測定された見かけの残留塩素濃度を少なく
とも一つの補正係数で除して真の残留塩素濃度を算出す
るものであることを特徴とする残留塩素濃度測定装置。 【数２】 ｙ2 =ｇ ・ｌｎ(ｘ2)+ｈ （ｇ 、ｈ は定数） （２）2. A reagentless polarographic method is used to
A chlorine concentration meter, electrical conductivity measuring means, and signal processing unit
The residual chlorine concentration meter has an apparent residual chlorine concentration in the sample water.
The electrical conductivity measuring means measures the electrical conductivity of the sample water.
In the residual chlorine concentration measuring device for measurement, the signal processing unit normalizes the true value of the residual chlorine concentration.
The dependence of apparent apparent residual chlorine concentration on electrical conductivity
That the electrical conductivity x2, based on the correction curve approximation formula when the correction coefficient and y2 are expressed by the formula (2), the sample
Determine a correction factor corresponding to the measured electrical conductivity of water
To reduce the apparent residual chlorine concentration measured in the sample water.
Calculate the true residual chlorine concentration by dividing by one correction coefficient
A residual chlorine concentration measuring device characterized by being a thing. ## EQU00002 ## y2 = g.ln (x2) + h (g and h are constants) (2)
塩素濃度計と、電気伝導率測定手段と、信号処理部とを
有し、残留塩素濃度計は試料水の見かけの残留塩素濃度
を測定し、電気伝導率測定手段は試料水の電気伝導率を
測定する残留塩素濃度測定装置において、 前記信号処理部は、残留塩素濃度の真値に対して正規化
した見かけの残留塩素濃度の電気伝導率依存性に関する
補正曲線を、電気伝導率に対し複数の区間に分割し、各
区間について電気伝導率をｘ2 、補正係数をｙ2とする
ときの近似式が式（３）で表される補正の一次関数式に
基づいて、試料水の測定された電気伝導率に対応する補
正係数を決定し、試料水の測定された見かけの残留塩素
濃度を少なくとも一つの補正係数で除して真の残留塩素
濃度を算出するものであることを特徴とする残留塩素濃
度測定装置。 【数３】 ｙ2 =ｉ ・ｘ2 +ｊ （ｉ 〜ｊ は各区間で異なる定数）（３）3. A reagentless polarographic method is used to
A chlorine concentration meter, electrical conductivity measuring means, and signal processing unit
The residual chlorine concentration meter has an apparent residual chlorine concentration in the sample water.
The electrical conductivity measuring means measures the electrical conductivity of the sample water.
In the residual chlorine concentration measuring device for measurement, the signal processing unit normalizes the true value of the residual chlorine concentration.
Was <br/> correction curve relating to electrical conductivity dependence of the residual chlorine concentration of the apparent were, into a plurality of sections with respect to electrical conductivity, the electrical conductivity for each section x2, the correction coefficient when the y2 The approximate expression is a linear function expression of the correction expressed by the expression (3).
Based on the measured electrical conductivity of the sample water.
Determine the apparent coefficient and measure the apparent residual chlorine in the sample water.
True residual chlorine by dividing the concentration by at least one correction factor
Concentration of residual chlorine characterized by calculating concentration
Degree measuring device. [Mathematical formula-see original document] y2 = i x2 + j (i to j are different constants in each section) (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14962796A JP3526371B2 (en) | 1996-06-12 | 1996-06-12 | Residual chlorine concentration measurement device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14962796A JP3526371B2 (en) | 1996-06-12 | 1996-06-12 | Residual chlorine concentration measurement device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09329577A JPH09329577A (en) | 1997-12-22 |
| JP3526371B2 true JP3526371B2 (en) | 2004-05-10 |
Family
ID=15479364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14962796A Expired - Fee Related JP3526371B2 (en) | 1996-06-12 | 1996-06-12 | Residual chlorine concentration measurement device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3526371B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7189314B1 (en) * | 2002-09-06 | 2007-03-13 | Sensicore, Inc. | Method and apparatus for quantitative analysis |
| JP4377197B2 (en) | 2003-10-22 | 2009-12-02 | 株式会社タニタ | Residual chlorine meter |
| JP5305021B2 (en) * | 2009-01-16 | 2013-10-02 | 横河電機株式会社 | Residual chlorine meter |
| JP7709160B2 (en) * | 2021-08-12 | 2025-07-16 | 慶應義塾 | Dissolved hydrogen concentration measuring device, electrode for the dissolved hydrogen concentration measuring device, and method for measuring dissolved hydrogen concentration |
-
1996
- 1996-06-12 JP JP14962796A patent/JP3526371B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09329577A (en) | 1997-12-22 |
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