JPH0220062B2 - - Google Patents
Info
- Publication number
- JPH0220062B2 JPH0220062B2 JP57228148A JP22814882A JPH0220062B2 JP H0220062 B2 JPH0220062 B2 JP H0220062B2 JP 57228148 A JP57228148 A JP 57228148A JP 22814882 A JP22814882 A JP 22814882A JP H0220062 B2 JPH0220062 B2 JP H0220062B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- seawater
- residual chlorine
- sample water
- chlorine
- 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 - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 33
- 229910052801 chlorine Inorganic materials 0.000 claims description 33
- 239000013535 sea water Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 238000010612 desalination reaction Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- -1 bromine ions Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4166—Systems measuring a particular property of an electrolyte
- G01N27/4168—Oxidation-reduction potential, e.g. for chlorination of water
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】
本発明は海水淡水化による製品水を被検液とし
て該被検液中に残存する塩素を回転金属電極によ
るポーラログラフ法により直接定量測定する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for directly quantitatively measuring chlorine remaining in a test liquid using product water produced by desalination of seawater by a polarographic method using a rotating metal electrode.
塩素は殺菌のため飲料水や下水、プール水等に
添加したり、ボイラーの腐食防止に用いたヒドラ
ジンの分解のためにその廃液中に注入したりし
て、各種の産業分野で広く用いられている。 Chlorine is widely used in various industrial fields, such as by adding it to drinking water, sewage water, pool water, etc. for sterilization, and injecting it into waste liquid to decompose hydrazine used to prevent corrosion in boilers. There is.
そして飲料水の殺菌および給水末端に至るまで
の清浄性の維持など塩素注入の目的を効果的に達
成するためには塩素注入後の試料中の残留塩素濃
度を常時測定し、その濃度が適切な範囲に保たれ
るよう制御する必要がある。 In order to effectively achieve the purpose of chlorine injection, such as sterilizing drinking water and maintaining cleanliness all the way to the end of the water supply, the residual chlorine concentration in the sample after chlorine injection must be constantly measured to ensure that the concentration is appropriate. It is necessary to control it so that it is kept within a range.
残留塩素濃度の測定法としては、(1)０−トリジ
ンにより発色させて吸光度測定により測定する方
法、(2)試料水によう化カリウムや臭化カリウムを
含む溶液を加え、遊離したよう素または臭素を、
回転金属電極を用いるポーラログラフ法、(3)試料
水に試薬を加えることなく、試料水を直接、回転
金属電極によるポーラログラフ法、などがある。
これらのうち、(1)は０−トリジンが発がん性物質
であるため次第に利用されなくなり、現在は(2)お
よび(3)の方法が連続測定が容易な点もあいまつて
ひろく利用されている。特に(3)の方法は、試薬の
定期的調製・補給の手間がない上、測定計器の価
格も(2)に比し低廉となるので、広く使われるすう
勢にある。 The residual chlorine concentration can be measured by (1) developing color with 0-tolidine and measuring absorbance; (2) adding a solution containing potassium iodide or potassium bromide to the sample water and measuring the free iodine or Bromine,
There are polarographic methods that use a rotating metal electrode, and (3) polarographic methods that use a rotating metal electrode to directly apply sample water without adding reagents to the sample water.
Among these, method (1) is gradually no longer used because 0-tolidine is a carcinogenic substance, and methods (2) and (3) are now widely used, partly because continuous measurement is easy. In particular, method (3) does not require the periodic preparation and replenishment of reagents, and the price of the measuring instrument is lower than that of method (2), so it is on the verge of becoming widely used.
しかし、(3)の方法で精度のよい残留塩素濃度測
定が行なえるためには、試料水がある程度以上の
導電率を持つていることが必要である。そこで本
発明者らは(3)の方法における試料水の導電率が残
留塩素濃度測定に及ぼす影響を調べ第１図の如き
結果を得た。 However, in order to be able to accurately measure the residual chlorine concentration using method (3), the sample water must have a certain level of electrical conductivity. Therefore, the present inventors investigated the influence of the electrical conductivity of sample water on the measurement of residual chlorine concentration in method (3) and obtained the results shown in FIG. 1.
これからわかるように、試料水導電率が約
200μS／cm以上あれば測定誤差は殆んどないが、
試料水導電率が150μS／cm程度から誤差があらわ
れはじめ30μS／cmになると極めて大きな誤差が
生じることがわかる。 As you can see, the sample water conductivity is approximately
If it is 200 μS/cm or more, there will be almost no measurement error, but
It can be seen that errors begin to appear when the sample water conductivity reaches about 150 μS/cm, and extremely large errors occur when it reaches 30 μS/cm.
そこでこのような低導電率の試料水の残留塩素
濃度を測定する場合は、例えば硫酸ナトリウム溶
液を少量づつ試料水に添加しながら導電率を高め
て測定を行なう方法が採られてきた。この方法は
硫酸ナトリウムがよう化カリウムに比べて非常に
低廉であるから、よう化カリウム溶液を用いる(2)
の方法に比べてメリツトはあるが、試薬溶液の定
期的調製・補給というわずらわしさは解決されな
い。 Therefore, when measuring the residual chlorine concentration in sample water with such low conductivity, a method has been adopted in which, for example, a sodium sulfate solution is added little by little to the sample water to increase the conductivity. This method uses potassium iodide solution because sodium sulfate is much cheaper than potassium iodide (2).
Although this method has advantages over the previous method, it does not solve the trouble of regularly preparing and replenishing reagent solutions.
さて飲料水は従来主として河川水を浄化して製
造されてきたが、水資源の不足化傾向や、河川水
や降水量の少ない中近東などにおける飲料水の確
保のため海水の淡水化が次第にひろく行なわれる
ようになつてきた。この場合でも海水の淡水化プ
ラントにおいて製造された製品水（飲料水）に塩
素注入を行つて消毒・滅菌が行なわれており、そ
の残留塩素濃度測定は同様に重要である。 Drinking water has traditionally been produced primarily by purifying river water, but as water resources tend to become scarce and in order to secure drinking water in the Middle East and elsewhere, where river water and rainfall are low, desalination of seawater is gradually becoming more widespread. It has started to be practiced. Even in this case, the product water (drinking water) produced in a seawater desalination plant is disinfected and sterilized by injecting chlorine, and measurement of the residual chlorine concentration is equally important.
この海水淡水化によつて得られた製品水の導電
率は50μS／cm以下で、場合によつては25μS／cm
程度の場合も多く、そのまゝ(3)の方式で残留塩素
濃度測定を行なうことはできず、硫酸ナトリウム
溶液などを添加しながらの測定が必要となる。し
かしこのようなプラントは降雨量の少ない地域に
おける建設が多い。そしてこれらの地域の国は発
展途上国が大部分で、化学薬品が乏しく貴重品で
あり、またこれを所定の濃度に定期的に調製し、
補給作業を期待するのは必ずしも現実的ではな
い。 The electrical conductivity of the product water obtained through this seawater desalination is less than 50 μS/cm, and in some cases 25 μS/cm.
In many cases, it is not possible to measure the residual chlorine concentration using method (3) as is, and it is necessary to measure while adding a sodium sulfate solution or the like. However, such plants are often constructed in areas with little rainfall. Most of the countries in these regions are developing countries, and chemicals are scarce and valuable, and they are regularly prepared to a predetermined concentration.
It is not necessarily realistic to expect replenishment operations.
本発明は、海水淡水化プラント周辺に無尽蔵に
存在する海水を、試料水の導電率増加に利用すれ
ば、硫酸ナトリウムなどの試料の入手、溶液の定
期的調製・補給などの操作が不要となり、連続測
定上大きなメリツトになることから自現したもの
である。 The present invention proposes that if the seawater that exists inexhaustibly around seawater desalination plants is used to increase the conductivity of sample water, operations such as obtaining samples such as sodium sulfate and periodic preparation and replenishment of solutions will become unnecessary. This was realized because it offers a great advantage in continuous measurement.
さて海水の導電率は40000μS／cmであり、試料
水に対し１／200量以上を添加すれば試料水の導
電率は約200μS／cm以上に高まり、導電率的には
(3)方法による残留塩素測定において誤差が生じな
いことになる。 Now, the electrical conductivity of seawater is 40,000 μS/cm, and if more than 1/200 of the amount is added to the sample water, the electrical conductivity of the sample water increases to about 200 μS/cm or more, and in terms of electrical conductivity,
(3) Errors will not occur in residual chlorine measurement using this method.
一方、海水中には塩化ナトリウムから生じてい
るナトリウムイオン、塩素イオンのほか、臭素イ
オン、硫酸イオン、炭酸水素イオン、ふつ素イオ
ン、マグネシウムイオン、カルシウムイオンなど
が少量ではあるが含まれている。そこでこれらの
共存物質が残留塩素濃度測定に際して影響を及ぼ
さないかどうか、導電率の低い試料水に実際に海
水を１／100の割合で添加して、残留塩素計に導
びき誤差の有無を調べてみた。その結果は第２図
に示したとおりであり、計器指示は真の濃度と極
めてよく一致した。 On the other hand, seawater contains small amounts of bromine ions, sulfate ions, bicarbonate ions, fluoride ions, magnesium ions, calcium ions, etc. in addition to sodium ions and chloride ions produced from sodium chloride. Therefore, in order to check whether these coexisting substances have any effect on the measurement of residual chlorine concentration, we actually added seawater at a ratio of 1/100 to sample water with low conductivity and introduced it into a residual chlorine meter to check for errors. I tried it. The results are shown in Figure 2, and the meter readings were in excellent agreement with the true concentrations.
この結果から、海水淡水化による淡水製造にお
け残留塩素濃度測定など、海水が手軽に得られる
場合においては、硫酸ナトリウムの購入、溶解調
製、補給の操作を行なうことなく、海水を試料水
に対し１／100程度の割合で添加しつつ残留塩素
計に導びくことにより精度よく測定を行なうこと
ができ、実用上その効果大である。 Based on this result, when seawater is easily obtained, such as when measuring residual chlorine concentration in freshwater production by seawater desalination, it is possible to use seawater as a sample water without purchasing, dissolving, or replenishing sodium sulfate. By adding chlorine at a ratio of about 1/100 and introducing it into a residual chlorine meter, accurate measurements can be made, which is very effective in practice.
なお、海水中には塩素を消費する物質が含まれ
ている場合があるが、その添加量は試料の１／
200程度と少ないので通常は無視できる。若し無
視できない程度である場合には海水淡水化プラン
トの工程において塩素を添加して塩素消費物質を
なくする工程があるので、その後のパイプから淡
水化中間水を分取し、これを試料水に添加する方
法をとればよい。この場合の添加海水中の残留塩
素濃度は低い上に、添加率も小さいので何ら問題
はない。 Note that seawater may contain substances that consume chlorine, but the amount added is 1/1 of the sample.
Since it is small at around 200, it can usually be ignored. If the level is not negligible, there is a step in the seawater desalination plant to add chlorine to eliminate chlorine-consuming substances, so the desalination intermediate water is separated from the subsequent pipe and used as sample water. What is necessary is to add it to In this case, the residual chlorine concentration in the added seawater is low and the addition rate is also small, so there is no problem.
第３図は本発明の実施例である。一点鎖線より
上に記したの部分は公知の試料薬残留塩素計、
一点鎖線より下に記したの部分が本発明を実施
するために付加した部分である。試料水入送入ポ
ンプ１と海水送入ポンプ２による試料水３と海水
４のそれぞれの流量比は200以下：１程度に選ぶ
のが適当である。又定流量ポンプ１，２を使用せ
ず、それぞれヘツドタンクを用い、適当な絞りに
よつて流量比を200以下：１程度にし、測定槽５
に導びく方法をとつてもよい。 FIG. 3 shows an embodiment of the invention. The part written above the dashed line is a known sample drug residual chlorine meter,
The parts written below the dashed line are the parts added to carry out the present invention. It is appropriate that the flow rate ratio of the sample water 3 and seawater 4 by the sample water inlet pump 1 and the seawater inlet pump 2 is approximately 200:1 or less. Also, without using constant flow pumps 1 and 2, use a head tank for each, and set the flow rate ratio to 200 or less: 1 with an appropriate restriction, and the measuring tank 5
You may find a way to lead to this.
なお、図中６は回転金属電極、７はその検知
極、８は対極、９は電極６を回転するモターで、
１０は残留塩素濃度指示計を示す。 In the figure, 6 is a rotating metal electrode, 7 is its detection electrode, 8 is a counter electrode, and 9 is a motor that rotates the electrode 6.
10 indicates a residual chlorine concentration indicator.
第４図は本発明の例の実施例を示し、この例で
は海水淡水化プラントＣにおける塩素添加後のパ
イプから淡水化中間水をパイプ１１を通して分取
し、残留塩素計Ａに添加している。１２は塩素注
入機、１３はポンプ、１４は海水淡水化プラント
Ｃへの海水採取管、１５は試料水添加用海水採取
管である。また１６は製品水ライン、１７はその
供給ラインである。 FIG. 4 shows an example of the present invention. In this example, desalinated intermediate water is collected from a pipe after chlorine addition in a seawater desalination plant C through a pipe 11, and is added to a residual chlorine meter A. . 12 is a chlorine injection machine, 13 is a pump, 14 is a seawater sampling pipe to seawater desalination plant C, and 15 is a seawater sampling pipe for adding sample water. Further, 16 is a product water line, and 17 is its supply line.
第１図は試料水の導電率と残留塩素濃度との関
係を示す図表、第２図は本発明法による場合の誤
差の有無を調べた結果を示す図表、第３図及び第
４図は本発明法の各実施例を示す説明図である。
Ａ……無添加残留塩素計、Ｂ……海水添加装
置、Ｃ……海水淡水化プラント、１，２……定量
ポンプ、６……回転金属電極、１１……塩素注入
後海水を試料水に添加する場合の配管。
Figure 1 is a chart showing the relationship between the conductivity of sample water and the residual chlorine concentration, Figure 2 is a chart showing the results of examining the presence or absence of errors when using the method of the present invention, and Figures 3 and 4 are from this book. It is an explanatory view showing each example of an invention method. A... Additive-free residual chlorine meter, B... Seawater addition device, C... Seawater desalination plant, 1, 2... Metering pump, 6... Rotating metal electrode, 11... Seawater after chlorine injection as sample water Piping when adding.
Claims (1)
中の残留塩素を直接回転金属電極によるポーラロ
グラフ法によつて測定するに当り、上記試料水に
原料海水またはその淡水化中間水を添加してその
残留塩素を測定することを特徴とする残留塩素測
定方法。1. When measuring the residual chlorine in product water from seawater desalination as sample water by the polarographic method using a direct rotating metal electrode, raw seawater or its desalination intermediate water is added to the sample water to measure the residual chlorine. A residual chlorine measuring method characterized by measuring chlorine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57228148A JPS59116537A (en) | 1982-12-24 | 1982-12-24 | Measuring method of residual chlorine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57228148A JPS59116537A (en) | 1982-12-24 | 1982-12-24 | Measuring method of residual chlorine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59116537A JPS59116537A (en) | 1984-07-05 |
| JPH0220062B2 true JPH0220062B2 (en) | 1990-05-08 |
Family
ID=16871975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57228148A Granted JPS59116537A (en) | 1982-12-24 | 1982-12-24 | Measuring method of residual chlorine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59116537A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6340415B1 (en) | 1998-01-05 | 2002-01-22 | Applied Materials, Inc. | Method and apparatus for enhancing a sputtering target's lifetime |
-
1982
- 1982-12-24 JP JP57228148A patent/JPS59116537A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59116537A (en) | 1984-07-05 |
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