JPH034160A - Measurement end point deciding method in water measuring instrument - Google Patents
Measurement end point deciding method in water measuring instrumentInfo
- Publication number
- JPH034160A JPH034160A JP13991189A JP13991189A JPH034160A JP H034160 A JPH034160 A JP H034160A JP 13991189 A JP13991189 A JP 13991189A JP 13991189 A JP13991189 A JP 13991189A JP H034160 A JPH034160 A JP H034160A
- Authority
- JP
- Japan
- Prior art keywords
- end point
- amount
- measurement
- water
- sample
- 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
- 238000005259 measurement Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 29
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 238000004448 titration Methods 0.000 abstract description 7
- 238000000954 titration curve Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WXDJHDMIIZKXSK-UHFFFAOYSA-N iodine dioxide Inorganic materials O=I=O WXDJHDMIIZKXSK-UHFFFAOYSA-N 0.000 description 1
- -1 iodine ions Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は水分測定装置における、測定終点の判定方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for determining the end point of a measurement in a moisture measuring device.
一般に固体、液体又は気体中に含まれる微量水分を測定
する方法としてカールフィッシャー測定法が知られてい
る。この測定法はメタノール及びピリジンの存在下（該
メタノール、ピリジン含有液を発生液という）で、水が
ヨウ素及び亜硫酸ガスと次の化学式に示すように定量的
に反応することを利用したものである。Karl Fischer measurement is generally known as a method for measuring trace amounts of moisture contained in solids, liquids, or gases. This measurement method utilizes the fact that water reacts quantitatively with iodine and sulfur dioxide gas in the presence of methanol and pyridine (the solution containing methanol and pyridine is called the generated solution) as shown in the following chemical formula. .
ｓｏ、＋ｌ、＋Ｈ１ｏ＋３ｃｓ １−ｒｓ Ｎ→２
Ｃｓ Ｈｓ Ｎ −ＨＩ ＋Ｃｓ Ｈｓ Ｎ
−５ｏｉｌＣｓ Ｈｓ Ｎ−５Ｏｓ ＋ ＣＨ２
０Ｈ→Ｃ％ Ｈｓ Ｎ −Ｈ３０４ＣＨ。so, +l, +H1o+3cs 1-rs N→2
Cs Hs N -HI +Cs Hs N
-5oilCs Hs N-5Os + CH2
0H→C% Hs N -H304CH.
上記ヨウ素は、滴定液またはヨウ素イオンを含む発生液
の電気分解によって与えられ、該滴定量または電気量に
よって水分量が計算できることになる。The above-mentioned iodine is provided by electrolysis of a titrant solution or a generated solution containing iodine ions, and the amount of water can be calculated from the titration amount or amount of electricity.
測定の終点は発生液に浸した２本の白金電極間に微少な
電流を流して分極させ、ヨウ素の過剰によって生ずる電
位変化を検出するいわゆるデッド・ストップ（Ｄｅａｄ
５ｔｏｐ ）法により検出する。The end point of the measurement is the so-called dead stop, in which a minute current is passed between two platinum electrodes immersed in the generated solution to polarize them, and the change in potential caused by excess iodine is detected.
5top) method.
第４図は上記原理に基づいた水分測定装置の要部を示す
ものである。第４図において測定フラスコｌに対して滴
定液の注入口２が設けられ、滴定液がビユレット５から
パルプ６を介して測定フラスコ１に注入される。このビ
ユレット５はマイクロコンピュータ２０で作動されるビ
ユレット制御部２１によって制御されている。また該測
定フラスコｌには測定終点検出用の戻口金電極３が設け
られ、この電極３による検出電圧は検出部２２を介して
マイクロコンピュータ２０に入力され、上記滴定の制御
に利用される。測定フラスコ１には試料注入口４が設け
られ、以下のようにして試料が注入される。FIG. 4 shows the main parts of a moisture measuring device based on the above principle. In FIG. 4, the measuring flask 1 is provided with an inlet 2 for the titrant, and the titrant is injected into the measuring flask 1 from the billet 5 through the pulp 6. This billet 5 is controlled by a billet control section 21 operated by a microcomputer 20. The measuring flask 1 is also provided with a return cap electrode 3 for detecting the end point of the measurement, and the voltage detected by this electrode 3 is inputted to the microcomputer 20 via the detecting section 22 and used for controlling the above-mentioned titration. The measurement flask 1 is provided with a sample injection port 4, and a sample is injected in the following manner.
固体に含有される水分、あるいは結晶水等を測定する場
合は直接発生液に試料を投入しても発生液中に測定すべ
き水分が溶出拡散し難いので、測定可能な状態にならな
い、そのため第４図に示すように加熱炉１１に試料を入
れ、加熱して水分を分離し、乾燥キャリアーガスＡによ
って上記測定フラスコ１に導く、いわゆる間接法が用い
られている。また液体に含有される水分のように発生液
中に拡散し易い場合には上記注入口４から注射器を用い
て測定フラスコ１内に注入される、いわゆる直接法が用
いられている。When measuring water contained in solids or water of crystallization, even if the sample is directly poured into the generated liquid, the water to be measured is difficult to elute and diffuse into the generated liquid, making it impossible to measure. As shown in FIG. 4, a so-called indirect method is used in which a sample is placed in a heating furnace 11, heated to separate moisture, and introduced into the measuring flask 1 using a dry carrier gas A. In addition, when water is easily diffused into the generated liquid, such as water contained in the liquid, a so-called direct method is used in which the water is injected into the measurement flask 1 through the injection port 4 using a syringe.
そして、戻口金電極３に直流、交流、あるいはパルス信
号を印加して微弱電流を流し電極３間の分極電位を測定
する０滴定試薬の滴定量（あるいは電気量）に対する白
金電極間の電位の変化を滴定曲線として描けば、その形
状は直接法においては第５図で示す曲ｗＡ（Ｃ）のよう
になる、そこで、滴定の際、予め曲線（Ｃ）を推定し、
さらに測定終点電位（Ｖｏ）を設定しておいて（ＶＯ）
に達するまでカールフィッシャー試薬を滴定していけば
よい。Then, a direct current, alternating current, or pulse signal is applied to the return port gold electrode 3 to flow a weak current and measure the polarization potential between the electrodes 3. Changes in the potential between the platinum electrodes with respect to the titration amount (or quantity of electricity) of the zero titration reagent If is drawn as a titration curve, its shape will be like the curve wA(C) shown in Figure 5 in the direct method.Therefore, during titration, estimate the curve (C) in advance,
Furthermore, set the measurement end point potential (Vo) (VO)
Simply titrate the Karl Fischer reagent until it reaches .
第６図は上記間接法で水分量を測定した場合の時間と水
分量／時間の関係を示すものである。間接法は前述のよ
うに固形物を炉に入れ該固形物に含まれる水分を加熱し
、分離させて発生液に乾燥キャリアーガスと共に注入さ
れるようになっている。従って、滴定曲線は第６図に示
すように、初期には水分が大量に分離されが、時間とと
もにその後徐々に減少する傾向を示す、この測定方法に
於いて、単位時間ｔｏ当たりの積分水分量Ｍ、が所定値
以下になったときを測定の終点として、測定を自動的に
打ち切るようになっている。FIG. 6 shows the relationship between time and moisture content/time when the moisture content is measured by the above-mentioned indirect method. In the indirect method, as described above, the solid material is placed in a furnace, the water contained in the solid material is heated, separated, and injected into the generated liquid together with a dry carrier gas. Therefore, as shown in Figure 6, the titration curve shows a tendency for a large amount of water to be separated at the beginning, but then to gradually decrease over time.In this measurement method, the integrated water amount per unit time to The measurement is automatically terminated when M becomes less than a predetermined value as the end point of the measurement.
（発明が解決しようとする課題〕
第２図（ｂ）は上記方法（従来法）によって同一物質（
含水量一定）に対して、試料量を異にした場合（試料量
ａ＜ｂ＜ｃ）の測定結果である。(Problem to be solved by the invention) Figure 2(b) shows that the same material (
These are the measurement results when the sample amount was varied (sample amount a<b<c) with respect to the case where the water content was constant).
元来試料の量は変化しても測定結果は同じでなければな
らないが、上記のように単位時間ｔｏ当たりの積分水分
量Ｍ１が所定値以下となるように測定終点を決定すると
試料量の影響をうけて水分測定結果がａ＜ｂ＜ｃとなる
。なぜならば、測定終点での積算水分量Ｍと単位時間当
たりの積分水分量Ｍ１との関係を考えると各試料の積算
水分量はＭ ａ ＜ Ｍ ｂ ＜ Ｍ ｃであるため、
となることからも明らかである。Originally, the measurement result must be the same even if the sample amount changes, but if the measurement end point is determined so that the integrated moisture content M1 per unit time to is less than a predetermined value as described above, the sample amount will affect the measurement result. As a result, the moisture measurement result becomes a<b<c. This is because, considering the relationship between the cumulative moisture content M at the measurement end point and the integral moisture content M1 per unit time, the cumulative moisture content of each sample is M a < M b < M c.
It is clear from this.
また、第３図（ｂ）は同一物質に対して試料量を同一に
した場合（試料量ａ＝ｂ＝ｃ）の測定結果である０元来
同一時間で測定が終了するはずであるが、上記方法（従
来法）によると終点にばらつきが生じ、測定結果もばら
ついた状態になる。In addition, Fig. 3(b) shows the measurement results when the sample amount is the same for the same substance (sample amount a = b = c).Originally, the measurement should have finished in the same time. According to the above method (conventional method), variations occur in the end points, and the measurement results also vary.
特にこの傾向は滴定曲線が緩やかな測定に於いて顕著で
ある。なぜならば、従来の終点判断は積算水分量Ｍの大
きさに依存することなく単位時間当たりの積分水分量Ｍ
１だけで判断しているためである。This tendency is particularly noticeable in measurements where the titration curve is gentle. This is because the conventional end point determination does not depend on the size of the integrated water content M, but rather the integrated water content M per unit time.
This is because the judgment is based on only 1.
この発明は上記従来の事情に鑑みて提案されたものであ
って、測定値が試料の量に影響を受けることなく、また
再現性が高い終点判別方法を提供することを目的とする
ものである。This invention was proposed in view of the above-mentioned conventional circumstances, and aims to provide an end point determination method in which the measured value is not affected by the amount of sample and has high reproducibility. .
同一物質に対して試料量を異にした場合、本発明の方法
によると現時点までの単位重量当たりの積算水分量をｍ
、現時点での単位時下ｔｏ当たりで、且つ単位重量当た
りの積分水分量をｍｌ、試料の量（重りをＮとするとき
、（１１式にあてはめると、
ｍＸＮ
× １００
従って、
となって、本発明の終点判断には重量の要素は相殺され
、影響されないことが明らかである。When different sample amounts are used for the same substance, according to the method of the present invention, the accumulated water content per unit weight up to the present time can be calculated as follows:
, when the current integral water content per unit time is ml, and the amount of sample (weight is N), (applying to equation 11, mXN × 100, so, It is clear that the weight factor cancels out and is unaffected in determining the endpoint of the invention.
また、同一物質に対して試料量を同一にした場合、終点
判断は単位期間当たりの積分水分量Ｍ。In addition, when the sample amount is the same for the same substance, the end point judgment is the integral moisture content M per unit period.
たけてなく積算水分量Ｍの大きさに依存するため、特に
滴定曲線が緩やかな測定に於いて有効となり、実験上良
好な再現性が得られている。Since it is extremely dependent on the magnitude of the cumulative water content M, it is particularly effective in measurements where the titration curve is gentle, and good reproducibility has been obtained experimentally.
第１図はこの発明の一実施例を示す図である。 FIG. 1 is a diagram showing an embodiment of the present invention.
測定曲線そのものは従来と変わるところはない。The measurement curve itself remains the same as before.
まず、滴定試薬の滴定総量から現時点までの総水分量Ｍ
が求められる。同時に現時点での単位時間ｔｏ当たりの
積分水分量（Ｍｌ）を測定する。これらの水分量Ｍ％Ｍ
、より
を計算してこの値がＲ（一定値）以上になったとき、す
なわち、Ｍｌ ／Ｍが一定値以下になったときに測定終
点とするものである。First, from the total amount of titration reagent to the current amount of water M
is required. At the same time, the integral moisture content (Ml) per unit time to is measured at the present time. These moisture contents M%M
, twist is calculated, and when this value becomes equal to or greater than R (a constant value), that is, when Ml /M becomes less than a constant value, the measurement end point is determined.
第２図（ａ）はこの発明を用いて同一物質（含水量一定
）に対して重量（試料量）を変えて（試料１ｉａ＜ｂ＜
ｃ）測定したものである。上記総積算水装置Ｍは単位重
量当たりの総積算水分量をｍ、重量をＮとしたときｍＸ
Ｎで表すことができ、現時点での単位時間ｔｏ当たりの
積分水分量は単位重量あたりで且つ単位時間ｔｏ当たり
の積分水分量をｍｌとしたときｍ、ＸＮで表すことがで
き、従って（１）式は
となり重量の要素は相殺される。従って、測定結果も試
料の量に依存することはなくなる。FIG. 2(a) shows that using this invention, the weight (sample amount) of the same material (constant water content) was changed (sample 1ia<b<
c) It was measured. The above total integrated water device M is mX when the total integrated water content per unit weight is m and the weight is N.
It can be expressed as N, and the current integral moisture content per unit time to can be expressed as m, XN when the integral moisture content per unit weight and per unit time to is ml, and therefore (1) The equation becomes: The weight factor cancels out. Therefore, the measurement results are no longer dependent on the amount of sample.
例えば、試料ａの終点判断は１１）式に当てはめると、 ａ の計算値がＲ（一定値）以上になったときである。For example, when determining the end point of sample a, applying equation 11), a This is when the calculated value of is equal to or greater than R (constant value).
測定結果は試料量に影響されることなく、再現性が得ら
れている。The measurement results are not affected by the amount of sample and are reproducible.
次に、第３図（ａ）は滴定曲線が緩やかな同一物質に対
して試料量を同一にした場合に、ついての３回（ａ＋
＊ ａｚ ｒ ａｓ ）の水分測定結果を示すもの
である。３回の終点はほぼ同一時刻になっており、従来
のようなばらつきがなくなり、測定結果は再現性が得ら
れている。Next, Fig. 3(a) shows three times (a+
* Shows the results of moisture measurement of az ra as ). The end points of the three measurements were at almost the same time, eliminating the conventional variations and ensuring reproducibility of the measurement results.
上記に於いて単位時間ｔｏは、例えば１０Ｓｅｃ”１２
０ｓｅｃの間で任意に設定できるが、時間が短いほど、
精度が低くなる。更に、上記所定値Ｒは例えば９９．９
以上１００までの値が採られる。In the above, the unit time to is, for example, 10Sec”12
It can be set arbitrarily between 0 seconds, but the shorter the time, the
Accuracy decreases. Further, the predetermined value R is, for example, 99.9.
Values above 100 are taken.
以上間接法についてのみ説明したが、直接法でも試料か
ら発生液への水分の溶出拡散に時間がかかるときには、
間接法と同様な滴定曲線を描くこととなり、この方法を
適用できる。Although only the indirect method has been explained above, when the elution and diffusion of water from the sample to the generated liquid takes time even with the direct method,
A titration curve similar to that of the indirect method will be drawn, and this method can be applied.
以上説明したようにこの発明は現時点での単位時間当た
りの積分水分量と現時点までの積算水分量との比を採っ
ているので測定結果が試料の量に影響されることがなく
なり、また再現性も高くなる。As explained above, this invention calculates the ratio between the current integrated moisture content per unit time and the cumulative moisture content up to the current time, so the measurement results are not affected by the amount of sample, and the reproducibility is It also becomes more expensive.
第１図はこの発明の一実施例を示すグラフ、第２図は試
料の量を変えた場合にこの発明の方法を従来の方法と対
比した状態を示すグラフ、第３図は同一量の複数回の試
料に対するこの発明の方法を従来の方法と対比した状態
を示すグラフ、第４図はこの発明が適用される装置の概
念図、第５図は直接法による測定結果を示すすグラフ、
第６図は間接法による従来の測定結果を示すグラフであ
２傅υ′時間
（ａ）
７に倒し補間
第
図
１、事件の表示
平成 １年特許願第１３９９１１号
２、発明の名称
水分測定装置における測定終点判定方法３、補正をする
者
事件との関係 特許出願人
住 所 京都市南区吉祥院新田二ノ段町６８４、代理人
補正の内容
２、特許請求の範囲
（１）測定開始から現時点までの積算水分量に対する、
現時点での単位時間当たりの積分水分量の比が所定値以
下であるとき測定終点とすることを特徴とする水分測定
装置における測定終点判定方法。
〔２〕測定開始から現時点までの積算水分量をＭ、現時
点での単位時間当たりの積分木立１奎Ｍ ＋ としたと
き
が所定値より大きくなったときを測定終点とする、が所
定値より大きくなつたときを測定装置における測定終点
判定方法。
明細書の「特許請求の範囲」の欄。Fig. 1 is a graph showing an embodiment of the present invention, Fig. 2 is a graph showing a comparison between the method of the present invention and the conventional method when the amount of sample is changed, and Fig. 3 is a graph showing multiple samples of the same amount. FIG. 4 is a conceptual diagram of an apparatus to which this invention is applied; FIG. 5 is a graph showing measurement results by the direct method;
Figure 6 is a graph showing the conventional measurement results using the indirect method. Method for determining the end point of measurement in the device 3, Relationship with the case of the person making the amendment Patent applicant address: 684 Nitta Ninodan-cho, Kisshoin, Minami-ku, Kyoto City, Contents of amendment by agent 2, Claims (1) From the start of measurement Regarding the cumulative moisture content up to the present time,
A method for determining a measurement end point in a moisture measuring device, characterized in that the measurement end point is determined when the current ratio of the integrated moisture content per unit time is less than or equal to a predetermined value. [2] The measurement end point is when the cumulative moisture content from the start of the measurement to the present time is M, and the integral grove per unit time at the present time is M+, and the measurement end point is set to be greater than a predetermined value. A method for determining the end point of measurement using a temperature measuring device. The “Claims” column of the specification.
Claims (1)
現時点での単位時間当たりの積分水分量の比が所定値以
下であるとき測定終点とすることを特徴とする水分測定
装置における測定終点判定方法。 〔２〕測定開始から現時点までの積算水分量をＭ、現時
点での単位時間当たりの積分水分量の比をＭ＿１とした
とき Ｍ−Ｍ＿１／Ｍ×１００・・・・・・・・・（１） が
所定値より大きくなったときを測定終点とする、請求項
１に記載の水分測定装置における測定終点判定方法。[Claims] [1] Regarding the cumulative moisture content from the start of measurement to the present time,
A method for determining a measurement end point in a moisture measuring device, characterized in that the measurement end point is determined when the current ratio of the integrated moisture content per unit time is less than or equal to a predetermined value. [2] M-M_1/M×100 (1 2. The method for determining a measurement end point in a moisture measuring device according to claim 1, wherein the measurement end point is determined when .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13991189A JP2793841B2 (en) | 1989-05-31 | 1989-05-31 | Determination method of measurement end point in moisture measurement device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13991189A JP2793841B2 (en) | 1989-05-31 | 1989-05-31 | Determination method of measurement end point in moisture measurement device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH034160A true JPH034160A (en) | 1991-01-10 |
| JP2793841B2 JP2793841B2 (en) | 1998-09-03 |
Family
ID=15256509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13991189A Expired - Fee Related JP2793841B2 (en) | 1989-05-31 | 1989-05-31 | Determination method of measurement end point in moisture measurement device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2793841B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6026723A (en) * | 1997-03-31 | 2000-02-22 | Sharp Kabushiki Kaisha | Roll paper feeding apparatus |
| WO2000011460A1 (en) * | 1998-08-18 | 2000-03-02 | Mitsubishi Chemical Corporation | Method of constant-current polarization voltage and apparatus for karl-fischer technique |
-
1989
- 1989-05-31 JP JP13991189A patent/JP2793841B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6026723A (en) * | 1997-03-31 | 2000-02-22 | Sharp Kabushiki Kaisha | Roll paper feeding apparatus |
| WO2000011460A1 (en) * | 1998-08-18 | 2000-03-02 | Mitsubishi Chemical Corporation | Method of constant-current polarization voltage and apparatus for karl-fischer technique |
| US6315888B1 (en) | 1998-08-18 | 2001-11-13 | Mitsubishi Chemical Corporation | Method of constant-current polarization voltage and apparatus for Karl-Fischer technique |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2793841B2 (en) | 1998-09-03 |
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