JPH0510908A - Apparatus for measuring concentration of sulfuric acid - Google Patents
Apparatus for measuring concentration of sulfuric acidInfo
- Publication number
- JPH0510908A JPH0510908A JP3160429A JP16042991A JPH0510908A JP H0510908 A JPH0510908 A JP H0510908A JP 3160429 A JP3160429 A JP 3160429A JP 16042991 A JP16042991 A JP 16042991A JP H0510908 A JPH0510908 A JP H0510908A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- compound
- concentration
- acid concentration
- conductivity
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 230000000379 polymerizing effect Effects 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 22
- 229920002521 macromolecule Polymers 0.000 abstract 6
- HFMDLUQUEXNBOP-UHFFFAOYSA-N n-[4-amino-1-[[1-[[4-amino-1-oxo-1-[[6,9,18-tris(2-aminoethyl)-15-benzyl-3-(1-hydroxyethyl)-12-(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-hydroxy-1-oxobutan-2-yl]amino]-1-oxobutan-2-yl] Chemical compound OS(O)(=O)=O.N1C(=O)C(CCN)NC(=O)C(NC(=O)C(CCN)NC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)CCCCC(C)CC)CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C1CC1=CC=CC=C1 HFMDLUQUEXNBOP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229920000775 emeraldine polymer Polymers 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group 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
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 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
- 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
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002791 soaking Methods 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
- 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)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Secondary Cells (AREA)
- Tests Of Electric Status Of Batteries (AREA)
Abstract
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 device capable of easily measuring the concentration of sulfuric acid, particularly the concentration of sulfuric acid used in the electrolyte of lead acid batteries.
【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 necessary to know the concentration of sulfuric acid when using it. Therefore, measuring the sulfuric acid concentration is very significant industrially. For example, in a lead-acid battery, the sulfuric acid concentration changes with charge and discharge as shown in Chemical Formula 2 below, and therefore the amount of charge and discharge of the lead-acid battery can be measured by measuring the sulfuric acid concentration. Further, if it can be easily measured, it is possible to control the charge / discharge electric quantity of the lead storage battery. During charge / discharge of a lead-acid battery, the sulfuric acid concentration usually changes in the range of about 8 to 45%, so measurement in this concentration range is particularly important.
【０００３】[0003]
【化２】 [Chemical 2]
【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, as a method for measuring the sulfuric acid concentration,
A specific gravity measuring method and a refractive index measuring method are known. However, in the method of (1), since the measurement is performed using the float, it is difficult to read automatically and it is difficult to take out as an electric signal to the control system. In the other method, a relatively long optical path is required in the sulfuric acid solution to be measured, and it is necessary to convert light into electricity. Therefore, the measuring device is large-scale 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 of measuring electric conductivity in a sulfuric acid solution has long been known. However, since the electric conductivity of sulfuric acid aqueous solution shows a maximum value at a concentration of about 30%, the sulfuric acid concentration does not become a single-valued function of the electric conductivity (published by John Willie & Sons, “Encyclopedia of Chemical Technology”). ", 2nd edition,
Volume 19, 446, 1969 (John Wiley
& Sons, "Encyclopedia
of Chemical Technology ", s
second edition, vol. 19, p. 446, 19
1969)), the sulfuric acid concentration could not be uniquely determined from the electric conductivity value.
【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 It is an object of the present invention 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、硫酸と反応する性質を有し且つ硫酸濃度
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たことを特徴とするものであ
る。In view of the above problems, the present invention intends to capture a change in sulfuric acid concentration as an electrical change amount having a monovalent functional correlation with the change. It was made. That is, the sulfuric acid concentration measuring device of the present invention is a sulfuric acid concentration measuring device for determining the sulfuric acid concentration by immersing the sensor part in a sulfuric acid solution, and applying an electric current to the sensor part to determine the conductivity of the sensor part. As a part, a polymer compound having a property of reacting with sulfuric acid and having a property of changing its conductivity in a monovalent function with a change in sulfuric acid concentration is used.
【０００８】ここで用いる高分子化合物は、硫酸と反応
する性質を有し且つ硫酸濃度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ものであれば、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 here is not particularly limited as long as it has a property of reacting with sulfuric acid and a property of changing its conductivity in a monovalent function with a change in sulfuric acid concentration. . However, since the sulfuric acid solution has a certain degree of conductivity, the polymer compound needs to have 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 represented by the following Chemical formulas 3 to 7 electrochemically or using an oxidizing agent is preferably used. To be These polymers are characterized by having a nitrogen atom which reacts with an acid in the molecule.
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】[0013]
【化６】 [Chemical 6]
【００１４】[0014]
【化７】 [Chemical 7]
【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 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 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.Lu et al.
"The Journal of American Chemical Society (Journalof American Che
medical Society) ", Volume 108, 8311
Page, 1986: "Conductive Polymers" edited by Naoya Ogata, published by Kodansha Scientific, page 75, 1990: Ryuichi Yamamoto, Takeshi Matsunaga, "Polymer Battery", published by Kyoritsu Shuppan,
34, 1990).
【００１６】[0016]
【化８】 [Chemical 8]
【００１７】[0017]
【化９】 [Chemical 9]
【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。Further, for example, when the compound shown in Chemical formula 4 is oxidized and polymerized, it becomes an emeraldine base type similar structure shown in Chemical formula 10 below.
It becomes the emeraldonic acid type similar structure shown in 1 and is effectively used for the sensor part. Of course, the polymer compound used in the sensor portion is also effective if it is synthesized by a method other than the oxidation of aromatic amine.
【００１９】[0019]
【化１０】 [Chemical 10]
【００２０】[0020]
【化１１】 [Chemical 11]
【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 alkyl group, an alkoxy group, an amide group, a carboxyl group or the like in the aromatic ring. As the polymer compound used in the present invention, in addition to the above, π-conjugated polymers such as poly (pyrrole-2,5-diyl), poly (thiophene-2,5-diyl), and poly (arylenevinylene), Among these substituted derivatives, those which react with sulfuric acid to change the conductivity in a monovalent function with the change of the sulfuric acid concentration may be used. In the above-mentioned polymer compound, the basicity of the polymer compound, the measurement range of the sulfuric acid concentration and the measurement sensitivity can be controlled by appropriately selecting the kind of the aromatic ring or the substituent.
【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, depending on 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, etc., the above-mentioned polymer compound is
It may be used by being coated with another polymer compound which is a general-purpose polymer compound (for example, nylon etc.), ceramics 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 section may be either direct current or alternating current depending on the purpose. Further, the conductivity of the sensor portion can be obtained by measuring the value of electric current or the electric resistance value flowing through the sensor portion, 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 a lead acid battery, the sulfuric acid concentration is 8 to 45%
Therefore, it is significant to use the device 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
８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 being used for measuring the concentration of sulfuric acid in a sulfuric acid aqueous solution, but can also be used for measuring the concentration of sulfuric acid in an organic solvent. Further, as hydrochloric acid is added in Chemical formula 8, the device 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 sulfuric acid concentration. Therefore, if the conductivity of the sensor portion, that is, the polymer compound is calculated, the sulfuric acid concentration can be calculated.
【００２７】請求項２記載の高分子化合物及び請求項３
記載の芳香族アミン化合物を酸化して得られた重合物
は、分子中に酸と反応する窒素原子を有しているので、
硫酸との反応が確定的に生じ、導電率の変化がはっきり
と生じる。The polymer compound according to claim 2 and claim 3
The polymer obtained by oxidizing the aromatic amine compound described has a nitrogen atom that reacts with an acid in the molecule,
The reaction with sulfuric acid takes place deterministically, and the change in conductivity is apparent.
【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 polymer compound is used by being coated with another polymer compound or mixed with another polymer compound, the access of acid to the polymer compound is controlled. , An acid addition reaction of the above polymer compound,
The stability of the polymer compound in a sulfuric acid solution is 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, the method reported by Abe et al. (For example, Proceedings of the Polymer Society 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 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, this polyaniline is dissolved in N-methylpyrrolidone, the resulting solution is spread on a substrate, and the solvent is evaporated under vacuum to remove it, and the thickness is from black to dark purple 89.
A film of μm was obtained. This film is 7.2mm x 1
Cut into a rectangle of 0.5 mm, and use the conductive carbon paste (Furuuchi Chemical Co., Ltd.) on the two shorter sides of the cut film to form platinum wires (diameter 0.25 mm).
And the sensor part was produced.
【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。This sensor part was immersed in a sulfuric acid aqueous solution at 19 ° C., and an electric resistance value was measured when a direct current voltage of 0.50 V was applied between two platinum wires of the sensor part. The conductivity of each part of the film was determined. In addition, 0.
At an applied voltage of 50 V, the current due to electrolysis of water in sulfuric acid aqueous solution is almost negligible. The film before soaking in the sulfuric acid aqueous solution exhibited a conductivity of 10 -3 Scm -1 or less, and was practically an insulator. As a result, the sulfuric acid concentration was changed to 8%, 15
%, 20%, 25%, 30%, 35%, 40%, 45%
The electrical conductivity of the film increases as 2.
4Scm -1 , 3Scm -1 , 3.1Scm -1 , 3.2Scm -1 ,
3.3Scm -1 , 3.4Scm -1 , 3.4Scm -1 , 3.5S
It increased almost monotonically with cm -1 . After that, when the sensor portion was dipped in an 8% sulfuric acid aqueous solution, the conductivity of the film returned to 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 of the sensor section has a monovalent functional correlation with the sulfuric acid concentration, and changes with the change of 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 device of the present invention, the sulfuric acid concentration can be obtained by obtaining the conductivity of the sensor section. Since the conductivity of the sensor portion can be easily obtained, the sulfuric acid concentration can be easily measured by the device of the present invention.
【００３４】特に請求項２記載の高分子化合物及び請求
項３記載の芳香族アミン化合物を酸化して得られた重合
物は、分子中に酸と反応する窒素原子を有しているの
で、硫酸との反応が確定的に生じ、導電率の変化がはっ
きりと生じる。従って上記重合物を用いれば、硫酸濃度
をより正確に測定することができる。In particular, the polymer obtained by oxidizing the polymer compound according to claim 2 and the aromatic amine compound according to claim 3 has a nitrogen atom capable of reacting with an acid in the molecule, and therefore, sulfuric acid. The reaction with and occurs definitely, and the change in conductivity is obvious. Therefore, if the above-mentioned polymer is used, the sulfuric acid concentration can be measured more accurately.
【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 by being coated with another polymer compound or mixed with another polymer compound, the acid addition reaction of the polymer compound or the above-mentioned increase in a sulfuric acid solution is performed. The stability of the molecular compound can be controlled. Therefore, the sulfuric acid concentration can be measured 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%, it is possible to perform meaningful measurement in measuring and controlling the charge / discharge electric quantity of the lead storage battery.
Claims (5)
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、硫酸と反応する性質を有し且つ硫酸濃
度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たことを特徴とする硫酸濃
度測定装置。1. A sulfuric acid concentration measuring device for determining the sulfuric acid concentration by immersing the sensor part in a sulfuric acid solution and applying an electric current to the sensor part to determine the conductivity of the sensor part, wherein the sensor part reacts with sulfuric acid. An apparatus for measuring a sulfuric acid concentration, which uses a polymer compound having the property of changing the conductivity and having the property of changing the conductivity in a monovalent function with the change of the sulfuric acid concentration.
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 Chemical formula 1 or a compound obtained by oxidizing the same. 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 used by being coated with another polymer compound or mixed with the other 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 |
| KR1019920011323A KR100211089B1 (en) | 1991-07-01 | 1992-06-27 | 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 |
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 true JPH0510908A (en) | 1993-01-19 |
| JP2659631B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040781A1 (en) * | 2003-10-22 | 2005-05-06 | Toyo Ink Mfg. Co., Ltd. | Proton acceptance type sensor, hydrogen gas sensor and acid sensor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6211159A (en) * | 1984-11-23 | 1987-01-20 | マサチユ−セツツ・インステイテユ−ト・オブ・テクノロジ− | Microelectronic device for molecular base |
| JPS6242047A (en) * | 1985-08-19 | 1987-02-24 | Toyota Central Res & Dev Lab Inc | Sulfuric acid concentration detection device |
-
1991
- 1991-07-01 JP JP3160429A patent/JP2659631B2/en not_active Expired - Lifetime
-
1992
- 1992-06-27 KR KR1019920011323A patent/KR100211089B1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6211159A (en) * | 1984-11-23 | 1987-01-20 | マサチユ−セツツ・インステイテユ−ト・オブ・テクノロジ− | Microelectronic device for molecular base |
| JPS6242047A (en) * | 1985-08-19 | 1987-02-24 | Toyota Central Res & Dev Lab Inc | Sulfuric acid concentration detection device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040781A1 (en) * | 2003-10-22 | 2005-05-06 | Toyo Ink Mfg. Co., Ltd. | Proton acceptance type sensor, hydrogen gas sensor and acid sensor |
| US8268250B2 (en) | 2003-10-22 | 2012-09-18 | Murata Manufacturing Co., Ltd. | Proton acceptance type sensor, hydrogen gas sensor and acid sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2659631B2 (en) | 1997-09-30 |
| KR930003457A (en) | 1993-02-24 |
| KR100211089B1 (en) | 1999-07-15 |
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