JP2659631B2 - Sulfuric acid concentration measuring device - Google Patents
Sulfuric acid concentration measuring deviceInfo
- Publication number
- JP2659631B2 JP2659631B2 JP3160429A JP16042991A JP2659631B2 JP 2659631 B2 JP2659631 B2 JP 2659631B2 JP 3160429 A JP3160429 A JP 3160429A JP 16042991 A JP16042991 A JP 16042991A JP 2659631 B2 JP2659631 B2 JP 2659631B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- acid concentration
- polymer compound
- compound
- measuring device
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 148
- 229920000642 polymer Polymers 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 37
- -1 aromatic amine compound Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920000775 emeraldine polymer Polymers 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
-
- 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
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0042—SO2 or SO3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
- H01M10/484—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte for measuring electrolyte level, electrolyte density or electrolyte conductivity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/569—Constructional details of current conducting connections for detecting conditions inside cells or batteries, e.g. details of voltage sensing terminals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Immunology (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Secondary Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Tests Of Electric Status Of Batteries (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、硫酸の濃度、特に鉛蓄
電池の電解質に用いられている硫酸の濃度を容易に測定
できる硫酸濃度測定装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfuric acid concentration measuring apparatus capable of easily measuring the concentration of sulfuric acid, particularly the concentration of sulfuric acid used in the electrolyte of a lead storage battery.
【０００２】[0002]
【従来技術及びその問題点】硫酸は工業的に広範囲にお
いて使用されており、その使用に際しては硫酸の濃度を
把握することが要求される場合が多い。従って硫酸濃度
を測定することは工業的に非常に意義のあることであ
る。例えば鉛蓄電池では、下記の化２のように充放電に
伴なって硫酸濃度が変化するので、硫酸濃度を測定する
ことによって鉛蓄電池の充放電電気量を測定することが
できる。また簡単に測定できれば、鉛蓄電池の充放電電
気量を制御することができる。鉛蓄電池の充放電におい
ては、硫酸濃度は通常８〜４５％程度の範囲で変化する
ので、この濃度範囲における測定が特に重要とされる。2. Description of the Related Art Sulfuric acid is widely used industrially, and it is often required to ascertain the concentration of sulfuric acid. Therefore, measuring sulfuric acid concentration is of great industrial significance. For example, in a lead-acid battery, the concentration of sulfuric acid changes with charge and discharge as shown in Chemical Formula 2 below. Therefore, by measuring the concentration of sulfuric acid, the amount of charge / discharge of the lead-acid battery can be measured. If the measurement can be easily performed, the charge / discharge electricity amount of the lead storage battery can be controlled. In charge and discharge of a lead storage battery, the sulfuric acid concentration usually varies in the range of about 8 to 45%, so that measurement in this concentration range is particularly important.
【０００３】[0003]
【化２】 Embedded image
【０００４】従来、硫酸濃度を測定する方法としては、
比重測定法、屈折率測定法が知られている。しか
し、の方法では、浮子を用いて測定するので、自動読
取が困難であり、制御系に電気信号として取出すのが困
難であった。またの方法では、測定対象とする硫酸溶
液中に比較的長い光路を必要とし、また光を電気に変換
する必要があり、このため測定装置が大規模で高価とな
っていた。Conventionally, methods for measuring the concentration of sulfuric acid include:
A specific gravity measuring method and a refractive index measuring method are known. However, in the method, since the measurement is performed using the float, it is difficult to perform automatic reading, and it is difficult to extract the electric signal to the control system. In addition, the method requires a relatively long optical path in the sulfuric acid solution to be measured, and it is necessary to convert light into electricity, which makes the measuring apparatus large and expensive.
【０００５】更に簡便な方法として、硫酸溶液中の電気
伝導度を測定する方法が古くから知られている。しかし
硫酸水溶液の電気伝導度は約３０％の濃度で極大値を示
すので、硫酸濃度は電気伝導度の一価関数にはならず
（ジョン ウィレーアンドサンズ社発行、“エンサイク
ロペディア オブ ケミカル テクノロジ”、第２版、
１９巻、４４６頁、１９６９年（Ｊｏｈｎ Ｗｉｌｅｙ
＆ Ｓｏｎｓ社発行、“Ｅｎｃｙｃｌｏｐｅｄｉａ
ｏｆ Ｃｈｅｍｉｃａｌ Ｔｅｃｈｎｏｌｏｇｙ”、ｓ
ｅｃｏｎｄ ｅｄｉｔｉｏｎ、１９巻、４４６頁、１９
６９年））、電気伝導度の値から硫酸濃度を一義的に求
めることはできなかった。As a simpler method, a method for measuring electric conductivity in a sulfuric acid solution has been known for a long time. However, since the electric conductivity of the sulfuric acid aqueous solution shows the maximum value at a concentration of about 30%, the sulfuric acid concentration does not become a monovalent function of the electric conductivity ("Encyclopedia of Chemical Technology, published by John Wiley and Sons Co., Ltd."", 2nd edition,
19, 446, 1969 (John Wiley
& Sons, Inc., “Encyclopedia
of Chemical Technology ”, s
second edition, 19, 446, 19
1969), the concentration of sulfuric acid could not be uniquely determined from the value of electric conductivity.
【０００６】[0006]
【発明の目的】本発明は、硫酸の濃度を容易に測定でき
る硫酸濃度測定装置を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a sulfuric acid concentration measuring device capable of easily measuring the concentration of sulfuric acid.
【０００７】[0007]
【目的を達成するための手段】本発明は、上記のような
問題点に鑑みて、硫酸濃度の変化をその変化に対して一
価関数的な相関関係のある電気的変化量として捕えよう
としてなされたものである。即ち、本発明の硫酸濃度測
定装置は、硫酸溶液中にセンサー部を浸漬し、センサー
部に電流を流してセンサー部の導電率を求めることによ
って硫酸濃度を求める硫酸濃度測定装置であって、セン
サー部として、硫酸が付加される性質を有し且つ硫酸の
付加量の変化に伴なって一価関数的に導電率が変化する
性質を有する高分子化合物を用い、該高分子化合物は、
芳香族アミン化合物が窒素原子と芳香環との結合を介し
て重合された構造を有する重合物であることを特徴とす
るものである。SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention aims at capturing a change in sulfuric acid concentration as an electrical change having a monovalent correlation with the change. It was done. That is, a sulfuric acid concentration measuring device of the present invention is a sulfuric acid concentration measuring device for immersing a sensor portion in a sulfuric acid solution, flowing an electric current through the sensor portion and determining the conductivity of the sensor portion to determine the sulfuric acid concentration. As a part, a polymer compound having a property that sulfuric acid is added and having a property that conductivity is monovalently changed with a change in the added amount of sulfuric acid is used.
It is a polymer having a structure in which an aromatic amine compound is polymerized through a bond between a nitrogen atom and an aromatic ring.
【０００８】ここで用いる高分子化合物は、硫酸が付加
される性質を有し且つ硫酸の付加量の変化に伴なって一
価関数的に導電率が変化する性質を有し且つ芳香族アミ
ン化合物が窒素原子と芳香環との結合を介して重合され
た構造を有する重合物であれば、特に制限はない。しか
し硫酸溶液がある程度の導電率を有することから、高分
子化合物は相当大きな導電率を示すものであることが必
要である。The polymer compound used herein has a property of adding sulfuric acid, a property of changing the conductivity monovalently with the change of the added amount of sulfuric acid, and an aromatic amine compound. Is not particularly limited as long as it is a polymer having a structure polymerized through a bond between a nitrogen atom and an aromatic ring. However, since the sulfuric acid solution has a certain degree of conductivity, it is necessary that the polymer compound has a considerably large conductivity.
【０００９】上記高分子化合物としては、例えば下記の
化３〜化７に示すような芳香族アミン化合物を電気化学
的に又は酸化剤を用いて化学的に酸化して得られる重合
物が好ましく用いられる。これらの重合物は分子中に酸
と反応する窒素原子を有するという特徴を有している。As the above-mentioned polymer compound, for example, a polymer obtained by electrochemically oxidizing an aromatic amine compound as shown in the following chemical formulas 3 to 7 electrochemically or using an oxidizing agent is preferably used. Can be These polymers are characterized by having a nitrogen atom that reacts with an acid in the molecule.
【００１０】[0010]
【化３】 Embedded image
【００１１】[0011]
【化４】 Embedded image
【００１２】[0012]
【化５】 Embedded image
【００１３】[0013]
【化６】 Embedded image
【００１４】[0014]
【化７】 Embedded image
【００１５】例えば化３に示すアニリンの酸化によって
得られるポリアニリンの内、下記の化８に示すエメラル
ディン塩基型構造体は殆んど電気を通さないが、下記の
化９に示すエメラルディン酸型構造体は１０Ｓcm-1（ジ
ーメンス毎センチメートル）程度の大きな導電性を有す
ることが知られている（例えばＦ．−Ｌ．Ｌｕ等、
「ジャーナル オブ アメリカン ケミカル ソサイエ
ティ（Ｊｏｕｒｎａｌｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅ
ｍｉｃａｌ Ｓｏｃｉｅｔｙ）」、１０８巻、８３１１
頁、１９８６：緒方直哉編、「導電性高分子」、講談
社サイエンティフィク刊、７５頁、１９９０：山本隆
一，松永孜著、「ポリマーバッテリー」、共立出版刊、
３４頁、１９９０）。For example, among the polyanilines obtained by the oxidation of aniline shown in Chemical formula 3, the emeraldine base structure shown in Chemical formula 8 below hardly conducts electricity, but the emeraldine acid type structure shown in Chemical formula 9 below. It is known that the structure has a large conductivity of about 10 Scm -1 (Siemens per centimeter) (for example, F.-L.L.
"Journalof American Chem Society
medical Society) ", 108 volumes, 8311
1986: Naoya Ogata, Ed., “Conductive Polymers”, Kodansha Scientific, 75 pages, 1990: Ryuichi Yamamoto, Azusa Matsunaga, “Polymer Battery”, Kyoritsu Shuppan,
34, 1990).
【００１６】[0016]
【化８】 Embedded image
【００１７】[0017]
【化９】 Embedded image
【００１８】また例えば化４に示す化合物は酸化して重
合させると、下記の化１０に示すエメラルディン塩基型
類似構造体となり、これに酸が付加すると、下記の化１
１に示すエメラルディン酸型類似構造体となり、センサ
ー部に有効に用いられる。もちろんセンサー部に用いら
れる高分子化合物は、芳香族アミンの酸化以外の方法に
よって合成されたものでも有効である。For example, when the compound shown in Chemical formula 4 is oxidized and polymerized, it becomes an emeraldine base type analogous structure shown in Chemical formula 10 below, and when an acid is added thereto, the following chemical formula 1
It becomes an emeraldinic acid type analogous structure shown in 1 and is effectively used for a sensor part. Of course, the polymer compound used for the sensor portion is also effective if synthesized by a method other than the oxidation of the aromatic amine.
【００１９】[0019]
【化１０】 Embedded image
【００２０】[0020]
【化１１】 Embedded image
【００２１】なお上記芳香族アミンは芳香環にアルキル
基、アルコキシ基、アミド基、カルボキシル基等を有す
るものでもよい。また本発明に用いる高分子化合物とし
ては、上記のもののほか、ポリ（ピロール−２，５−ジ
イル）、ポリ（チオフェン−２，５−ジイル）、ポリ
（アリーレンビニレン）などのπ共役高分子やそれらの
置換誘導体の内、硫酸と反応し硫酸濃度の変化と共に一
価関数的に導電率を変化させるものを用いてもよい。上
記高分子化合物において、芳香環や置換基の種類を適宜
選択すれば、その高分子化合物の塩基性や、硫酸濃度の
測定範囲や測定感度がコントロールされる。The aromatic amine may have an aromatic ring having an alkyl group, an alkoxy group, an amide group, a carboxyl group or the like. Examples of the polymer compound used in the present invention include, in addition to the above, π-conjugated polymers such as poly (pyrrole-2,5-diyl), poly (thiophen-2,5-diyl), and poly (arylenevinylene). Among these substituted derivatives, those which react with sulfuric acid and change the conductivity monovalently with the change in sulfuric acid concentration may be used. In the above-mentioned polymer compound, by appropriately selecting the kind of the aromatic ring or the substituent, the basicity of the polymer compound, the measurement range and the measurement sensitivity of the sulfuric acid concentration are controlled.
【００２２】また上記高分子化合物の酸付加反応のコン
トロール、硫酸溶液中での上記高分子化合物の安定性の
コントロール等の目的に応じて、上記高分子化合物を、
汎用高分子化合物（例えばナイロン等）である他の高分
子化合物やセラミック等で被覆したり、これらと混合し
たりして用いてもよい。Further, the above-mentioned polymer compound may be used in accordance with the purpose of controlling the acid addition reaction of the above-mentioned polymer compound, controlling the stability of the above-mentioned polymer compound in a sulfuric acid solution, and the like.
It may be used by being coated with another polymer compound such as a general-purpose polymer compound (for example, nylon or the like), ceramic, or the like, or by being mixed with these.
【００２３】センサー部に加える電流は、目的に応じて
直流、交流のいずれでもよい。またセンサー部の導電率
は、センサー部即ち上記高分子化合物を流れる電流値又
は電気抵抗値を測定することにより得られる。The current applied to the sensor unit may be either DC or AC depending on the purpose. The conductivity of the sensor unit can be obtained by measuring a current value or an electric resistance value flowing through the sensor unit, that is, the polymer compound.
【００２４】鉛蓄電池においては硫酸濃度が８〜４５％
の範囲で変化するので、この範囲に硫酸濃度がある場合
に本発明の装置を用いることは、意義のあることであ
る。In the lead storage battery, the sulfuric acid concentration is 8 to 45%
It is significant to use the apparatus of the present invention when the sulfuric acid concentration is in this range.
【００２５】なお本発明の装置は、硫酸水溶液中の硫酸
濃度の測定に限定して用いられるものではなく、有機溶
媒中の硫酸濃度の測定にも用い得るものである。また化
９において塩酸が付加しているように、本発明の装置
は、硫酸に限らず、他の酸（例えば塩酸等）の濃度測定
にも用い得るものである。The apparatus of the present invention is not limited to the measurement of the concentration of sulfuric acid in an aqueous sulfuric acid solution, but can be used for measuring the concentration of sulfuric acid in an organic solvent. Further, as in the case of adding hydrochloric acid in Chemical formula 9, the apparatus of the present invention can be used not only for sulfuric acid but also for concentration measurement of other acids (for example, hydrochloric acid).
【００２６】[0026]
【作用】本発明に用いる高分子化合物の導電率は硫酸濃
度に対応している。従ってセンサー部即ち高分子化合物
の導電率を求めれば、硫酸濃度が求められることとな
る。The conductivity of the polymer compound used in the present invention corresponds to the concentration of sulfuric acid. Therefore, if the conductivity of the sensor part, that is, the polymer compound is determined, the sulfuric acid concentration is determined.
【００２７】芳香族アミン化合物に由来する重合物は、
分子中に硫酸が付加する窒素原子を有しているので、高
濃度の硫酸水溶液であっても硫酸の付加が確定的に生
じ、導電率の変化がはっきりと生じる。The polymer derived from the aromatic amine compound is
Since the molecule has a nitrogen atom to which sulfuric acid is added, the addition of sulfuric acid is definitely caused even in a high-concentration aqueous solution of sulfuric acid, and the conductivity is clearly changed.
【００２８】上記高分子化合物を、他の高分子化合物で
被覆したり、他の高分子化合物と混合したりして用いる
と、上記高分子化合物への酸の接近がコントロールされ
ることとなるので、上記高分子化合物の酸付加反応や、
硫酸溶液中での上記高分子化合物の安定性等がコントロ
ールされる。When the above-mentioned polymer compound is used after being coated with another polymer compound or mixed with another polymer compound, the approach of the acid to the polymer compound is controlled. An acid addition reaction of the polymer compound,
The stability and the like of the polymer compound in a sulfuric acid solution are controlled.
【００２９】[0029]
【実施例】まず、阿部等によって報告されている方法
（例えば高分子学会予稿集、３８巻、２１３９頁、１９
８９）によって、Ｎ−メチルピロリドンに可溶なポリア
ニリンを合成した。即ち、アニリンを、硫酸及び塩酸を
含む水溶液中でペルオキソ二硫酸アンモニウムを用いて
酸化重合させて粉末状高分子を得、これをアンモニア水
で処理してエメラルディン塩基型のポリアニリンを得
た。EXAMPLES First, a method reported by Abe et al. (For example, Proceedings of the Society of Polymer Science of Japan, 38, 2139, 19
89), polyaniline soluble in N-methylpyrrolidone was synthesized. That is, aniline was oxidatively polymerized using ammonium peroxodisulfate in an aqueous solution containing sulfuric acid and hydrochloric acid to obtain a powdery polymer, which was treated with aqueous ammonia to obtain an emeraldine base type polyaniline.
【００３０】次に、このポリアニリンをＮ−メチルピロ
リドンに溶解し、得られた溶液を基板上に展開し、溶媒
を真空下で気化させて除いて黒ないし濃紫色の厚さ８９
μｍのフィルムを得た。このフィルムを７．２ｍｍ×１
０．５ｍｍの長方形に切取り、切取ったフィルムの短い
方の２辺を導電性カーボンペースト（フルウチ化学株式
会社製）を用いてそれぞれ白金線（直径０．２５ｍｍ）
に接続してセンサー部を作製した。Next, the polyaniline is dissolved in N-methylpyrrolidone, the resulting solution is spread on a substrate, and the solvent is removed by vaporization under vacuum to remove a black or dark purple film.
A μm film was obtained. This film is 7.2mm x 1
Cut into 0.5 mm rectangles, and use the conductive carbon paste (Furuuchi Chemical Co., Ltd.) to form a platinum wire (0.25 mm diameter) on each of the two shorter sides of the cut film.
To make a sensor unit.
【００３１】このセンサー部を１９℃の硫酸水溶液中に
浸し、センサー部の２本の白金線の間に０．５０Ｖの直
流電圧を印加した時の電気抵抗値を測定し、この測定値
からセンサー部のフィルムの導電率を求めた。なお０．
５０Ｖの印加電圧では、硫酸水溶液中の水の電気分解に
よる電流は殆んど無視できる。また硫酸水溶液に浸す前
のフィルムは、１０-3Ｓcm-1以下の導電率を示し、事実
上絶縁体であった。その結果、硫酸濃度を、８％、１５
％、２０％、２５％、３０％、３５％、４０％、４５％
と増加させるにつれて、上記フィルムの導電率は、２．
４Ｓcm-1、３Ｓcm-1、３．１Ｓcm-1、３．２Ｓcm-1、
３．３Ｓcm-1、３．４Ｓcm-1、３．４Ｓcm-1、３．５Ｓ
cm-1と略単調に増加した。またその後に、センサー部を
８％の硫酸水溶液に浸すと、フィルムの導電率は略元の
値（２．４Ｓcm-1）に戻った。The sensor was immersed in a 19 ° C. sulfuric acid aqueous solution, and the electric resistance was measured when a DC voltage of 0.50 V was applied between the two platinum wires of the sensor. The conductivity of the film in each part was determined. Note that 0.
At an applied voltage of 50 V, the current due to the electrolysis of water in the aqueous sulfuric acid solution is almost negligible. The film before immersion in the aqueous sulfuric acid solution showed a conductivity of 10 -3 Scm -1 or less, and was practically an insulator. As a result, the sulfuric acid concentration was increased to 8% and 15%.
%, 20%, 25%, 30%, 35%, 40%, 45%
As the conductivity of the film increases, 2.
4 Scm -1 , 3 Scm -1 , 3.1 Scm -1 , 3.2 Scm -1 ,
3.3 Scm -1 , 3.4 Scm -1 , 3.4 Scm -1 , 3.5 S
cm -1 increased almost monotonically. After that, when the sensor section was immersed in an 8% aqueous sulfuric acid solution, the conductivity of the film returned to substantially the original value (2.4 Scm -1 ).
【００３２】このように、上記センサー部のフィルムの
導電率は、硫酸濃度と一価関数的な相関関係にあり、硫
酸濃度の変化と共に変化する。従ってフィルムの導電率
を求めることによって、硫酸濃度を求めることができ
る。As described above, the conductivity of the film in the sensor section has a univalent function correlation with the sulfuric acid concentration, and changes with the change in the sulfuric acid concentration. Therefore, by determining the conductivity of the film, the sulfuric acid concentration can be determined.
【００３３】[0033]
【発明の効果】以上のように本発明の硫酸濃度測定装置
によれば、センサー部の導電率を求めることにより硫酸
濃度を求めることができる。センサー部の導電率は容易
に求めることができるので、本発明の装置によれば、硫
酸濃度を容易に測定することができる。As described above, according to the sulfuric acid concentration measuring apparatus of the present invention, the sulfuric acid concentration can be determined by determining the conductivity of the sensor section. Since the conductivity of the sensor section can be easily obtained, the sulfuric acid concentration can be easily measured according to the apparatus of the present invention.
【００３４】しかも、芳香族アミン化合物に由来する重
合物は、分子中に硫酸が付加する窒素原子を有している
ので、高濃度の硫酸水溶液であっても硫酸の付加が確定
的に生じ、導電率の変化がはっきりと生じる。従って、
硫酸濃度を正確に測定することができる。Moreover, since the polymer derived from the aromatic amine compound has a nitrogen atom to which sulfuric acid is added in the molecule, sulfuric acid is definitely added even in a high-concentration aqueous sulfuric acid solution. A change in conductivity clearly occurs. Therefore,
The sulfuric acid concentration can be accurately measured.
【００３５】上記高分子化合物を、他の高分子化合物で
被覆したり、他の高分子化合物と混合したりして用いる
と、上記高分子化合物の酸付加反応や、硫酸溶液中での
上記高分子化合物の安定性等をコントロールすることが
できる。従って硫酸濃度の測定を安定した状態で行なう
ことができる。When the above-mentioned polymer compound is used after being coated with another polymer compound or mixed with another polymer compound, an acid addition reaction of the above-mentioned polymer compound or the above-mentioned high polymer in a sulfuric acid solution is caused. The stability of the molecular compound can be controlled. Therefore, the measurement of the sulfuric acid concentration can be performed in a stable state.
【００３６】硫酸濃度が８〜４５％の範囲にある場合に
本発明の装置を用いれば、鉛蓄電池の充放電電気量の測
定、制御に当たって意義のある測定を行なうことができ
る。When the apparatus of the present invention is used when the sulfuric acid concentration is in the range of 8 to 45%, meaningful measurement can be performed in measuring and controlling the amount of charge / discharge of the lead storage battery.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−42047（ＪＰ，Ａ) 特開 昭62−11159（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-42047 (JP, A) JP-A-62-11159 (JP, A)
Claims (5)
サー部に電流を流してセンサー部の導電率を求めること
によって硫酸濃度を求める硫酸濃度測定装置であって、 センサー部として、硫酸が付加される性質を有し且つ硫
酸の付加量の変化に伴なって一価関数的に導電率が変化
する性質を有する高分子化合物を用い、該高分子化合物
は、芳香族アミン化合物が窒素原子と芳香環との結合を
介して重合された構造を有する重合物であることを特徴
とする硫酸濃度測定装置。1. A sulfuric acid concentration measuring device for immersing a sensor part in a sulfuric acid solution and applying a current to the sensor part to determine the conductivity of the sensor part to determine the sulfuric acid concentration, wherein sulfuric acid is added as the sensor part. A polymer compound having a property of being changed and having a property that the conductivity changes monovalently with a change in the added amount of sulfuric acid, wherein the aromatic amine compound is replaced with a nitrogen atom An apparatus for measuring the concentration of sulfuric acid, which is a polymer having a structure polymerized through a bond with an aromatic ring.
はこれを酸化して得られる化合物で 【化１】 （Ｒは水素基又は炭化水素基、ｎは２以上の整数であ
る）ある請求項１記載の硫酸濃度測定装置。2. The polymer compound is a compound represented by the formula 1 or a compound obtained by oxidizing the compound. The sulfuric acid concentration measuring device according to claim 1, wherein R is a hydrogen group or a hydrocarbon group, and n is an integer of 2 or more.
化によって重合させて得られた重合物である請求項１記
載の硫酸濃度測定装置。3. The sulfuric acid concentration measuring device according to claim 1, wherein the polymer compound is a polymer obtained by polymerizing an aromatic amine compound by oxidation.
し又は他の高分子化合物と混合して用いる請求項１ない
し３のいずれかに記載の硫酸濃度測定装置。4. The sulfuric acid concentration measuring device according to claim 1, wherein the polymer compound is coated with another polymer compound or mixed with another polymer compound.
項１ないし４のいずれかに記載の硫酸濃度測定装置。5. The sulfuric acid concentration measuring device according to claim 1, wherein the sulfuric acid concentration is in the range of 8 to 45%.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3160429A JP2659631B2 (en) | 1991-07-01 | 1991-07-01 | Sulfuric acid concentration measuring device |
| US07/904,324 US5273841A (en) | 1991-07-01 | 1992-06-25 | Sulfuric acid concentration sensor and lead acid battery equipped with sulfuric acid concentration sensor |
| DE4221189A DE4221189C2 (en) | 1991-07-01 | 1992-06-27 | Sensor for the sulfuric acid concentration and lead accumulator equipped with the sensor for the sulfuric acid concentration |
| KR1019920011323A KR100211089B1 (en) | 1991-07-01 | 1992-06-27 | Sulfuric acid concentration sensor and lead acid battery equipped with sulfuric acid concentration sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3160429A JP2659631B2 (en) | 1991-07-01 | 1991-07-01 | Sulfuric acid concentration measuring device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0510908A JPH0510908A (en) | 1993-01-19 |
| JP2659631B2 true JP2659631B2 (en) | 1997-09-30 |
Family
ID=15714744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3160429A Expired - Lifetime JP2659631B2 (en) | 1991-07-01 | 1991-07-01 | Sulfuric acid concentration measuring device |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2659631B2 (en) |
| KR (1) | KR100211089B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1679507B1 (en) | 2003-10-22 | 2014-03-05 | Murata Manufacturing Co. Ltd. | Proton acceptance type gas sensor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4717673A (en) * | 1984-11-23 | 1988-01-05 | Massachusetts Institute Of Technology | Microelectrochemical devices |
| JPS6242047A (en) * | 1985-08-19 | 1987-02-24 | Toyota Central Res & Dev Lab Inc | Sulfuric acid concentration detector |
-
1991
- 1991-07-01 JP JP3160429A patent/JP2659631B2/en not_active Expired - Lifetime
-
1992
- 1992-06-27 KR KR1019920011323A patent/KR100211089B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0510908A (en) | 1993-01-19 |
| KR930003457A (en) | 1993-02-24 |
| KR100211089B1 (en) | 1999-07-15 |
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