JPS62167456A - Electric conductivity detector - Google Patents

Electric conductivity detector

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Publication number
JPS62167456A
JPS62167456A JP27046385A JP27046385A JPS62167456A JP S62167456 A JPS62167456 A JP S62167456A JP 27046385 A JP27046385 A JP 27046385A JP 27046385 A JP27046385 A JP 27046385A JP S62167456 A JPS62167456 A JP S62167456A
Authority
JP
Japan
Prior art keywords
signal
output
correction
reference resistor
difference
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.)
Pending
Application number
JP27046385A
Other languages
Japanese (ja)
Inventor
Shuzo Maruyama
秀三 丸山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shimadzu Corp
Original Assignee
Shimadzu Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shimadzu Corp filed Critical Shimadzu Corp
Priority to JP27046385A priority Critical patent/JPS62167456A/en
Publication of JPS62167456A publication Critical patent/JPS62167456A/en
Pending legal-status Critical Current

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  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

PURPOSE:To enable efficient detection by performing the correction of a background level within a short time, by performing correction only by a feedback circuit consisting of an adder, a comparator and a microcomputer (MC). CONSTITUTION:The voltage of an AC power source 1 is applied to a measuring cell 22 and reversed by a phase reversal device 8 to be inputted to a reference resistor and further inputted to an amplifying circuit 14. The circuit 14 outputs the difference between the current flowing to the measuring cell 2 and the current flowing to the reference resistor 7, that is, a signal e1 wherein a background level is substracted. The signal e1 is detected by a detector 15 and smoothed by a smoothing circuit 16 and added to the correction signal E2 from MC24 by an adder 17 to be outputted as a signal E0. The signal E0 is compared with the earth potential by a comparator 31 and the comparing result is inputted to MC24 and, if the signal E0 is zero, the correction of the background level is completed. The background level after the start of measurement is generally narrow in a variation range and corrected only by a feedback circuit consisting of the adder 17, the comparator 31 and MC24 and, therefore, correction is performed rapidly.

Description

【発明の詳細な説明】 (イ)産業上の利用分野 この発明は、主にイオンクロマトグラフィーにおいて用
いられる電気伝導度検出器に関する。
DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to an electrical conductivity detector mainly used in ion chromatography.

(ロ)従来の技術 従来のイオンクロマトグラフィー(とくに、ノンサプレ
ッサ方式のもの)に使用される電気伝導度検出器におい
ては、試料イオンの電導度にくらべて溶離液イオンの電
導度が大きいため、溶離液イオンの電導度(バックグラ
ンドレベル)を自動的に打消す回路を設けて試料イオン
の電導度のみを出力するようにしている。
(B) Conventional technology In electrical conductivity detectors used in conventional ion chromatography (especially non-suppressor type ones), the electrical conductivity of the eluent ions is greater than that of the sample ions. A circuit is provided to automatically cancel the electrical conductivity (background level) of the eluent ions, so that only the electrical conductivity of the sample ions is output.

(ハ)発明が解決しようとする問題点 ところで、電導度の測定には、測定セル内における分極
の発生を避けるために、交流電圧を測定セルに印加する
方法が用いられるので、電気伝導度検出器は測定セルか
ら得られる交流信号を直流信号に変換して出力する必要
があり、検波回路やローパスフィルタなどの遅延回路を
含んでいる。
(c) Problems to be Solved by the Invention By the way, when measuring electrical conductivity, a method is used in which an alternating current voltage is applied to the measuring cell in order to avoid the occurrence of polarization within the measuring cell. The device needs to convert the AC signal obtained from the measurement cell into a DC signal and output it, and includes a delay circuit such as a detection circuit and a low-pass filter.

従って、分析中にバックグランドレベルを打消す操作が
行われ検出器の出力が変動すると、平滑回路による遅延
のため、その出力が安定するまでに長い時間を要し、そ
の間、精度のよい検出が行われないという問題点があっ
た。
Therefore, if an operation is performed to cancel the background level during analysis and the detector output fluctuates, it will take a long time for the output to stabilize due to the delay caused by the smoothing circuit, and during that time, accurate detection will not be possible. The problem was that it wasn't done.

この発明は、このような事情を考慮してなされたもので
、バックグランドレベルの消去を短時間で行い、能率よ
く検出することが可能な電気伝導度検出器を提供するも
のである。
The present invention has been made in consideration of the above circumstances, and it is an object of the present invention to provide an electrical conductivity detector that can eliminate background levels in a short time and perform efficient detection.

に)問題点を解決するための手段 第1図はこの発明の構成を示す構成図であり、(l01
)は一対の電極を備えた測定セル、(l02)は段階的
に抵抗値が調整可能な参照抵抗器。
Figure 1 is a block diagram showing the configuration of the present invention.
) is a measurement cell equipped with a pair of electrodes, and (l02) is a reference resistor whose resistance value can be adjusted in steps.

(loo)は測定セル(l01)と参照抵抗器(l02
)に並列に出力を印加する交流電源、(l03)は測定
セル(l01)と参照抵抗器(l02)に流れる電流の
差を増幅して出力する減算増幅手段、(l04)は減算
増幅手段(l03)の出力を検波する検波手段、(l0
5)は検波手段(l04)の出力を平滑する平滑手段、
(l06)は平滑手段<  ios>の出力に、必要な
補正電圧を加算する加算手段、(l07)は加算手段(
l0G)の出力と接地電位とを比較する第1比較手段、
(l08)は第1比較手段(l07)の比較で差がある
とき、その差がゼロになるよう前記補正電圧を出力する
第1U!j整手段、(l09)は前記減算増幅手段(+
03)の出力を所定位相でサンプリングして接地電位と
比較する第2比較手段、(l10)は前記第1調整手段
(l08)が調整可能な全範囲の補正電圧を出力しても
第1比較手段(l07)の差がゼロにならない時、第2
比較手段(l09)の差が小となるように参照抵抗器(
l02)を調整する第2調整手段、(l11)は第1お
よび第2調整手段(l08)  (l10)の作動をオ
ン・オフさせる指令手段である。
(loo) is the measuring cell (l01) and the reference resistor (l02)
), (l03) is a subtraction amplification means that amplifies and outputs the difference between the currents flowing through the measurement cell (l01) and the reference resistor (l02), and (l04) is a subtraction amplification means ( detection means for detecting the output of (l03);
5) smoothing means for smoothing the output of the detection means (l04);
(l06) is an adding means for adding the necessary correction voltage to the output of the smoothing means <ios>, and (l07) is an adding means (
a first comparison means for comparing the output of 10G) and the ground potential;
(l08) is the first U! which outputs the correction voltage so that when there is a difference in the comparison by the first comparing means (l07), the difference becomes zero! j adjustment means (l09) is the subtraction amplification means (+
A second comparison means (l10) samples the output of the first adjustment means (l08) at a predetermined phase and compares it with the ground potential; When the difference in means (l07) is not zero, the second
The reference resistor (
The second adjusting means (l11) is a command means for turning on and off the operation of the first and second adjusting means (l08) and (l10).

(ホ)作 用 測定セル(l01)および参照抵抗器(l02)に交流
電源(l03)の出力電圧が印加されると、各々に流れ
る電流の差が減算増幅手段(l03)で演譚され、検波
手段(l04)で検波されると共に、平滑手段(l05
)で平滑されて加算手段(l06)に入力される。加算
手段(l06)はその入力に第1調整手段(l08)か
らの補正電圧を加算して、測定セル(l01)の試料イ
オンの電気伝導度に対応する信号を出力する。測定中の
適当な時点でバックグランドレベルの調整のため、指令
手段(+11)がオンになると、まず第1調整手段(l
08)が作動して、第1比較手段(l07)の比較結果
力旨う加算手段(loe)への補正電圧を調整して加専
手段(l06)の出力を直らにゼロに修正する。第1調
整手段(iog)が全調整範囲にわたって補正電圧調整
しても第1比較手段(l07)の差がゼロにならない、
すなわち加算手段(l06)の出力がゼロにならない時
には、第2比較手段(l09)における差が小となるよ
うに第2調整手段(710)が作動して参照抵抗器(l
02)の抵抗値を調整し、その結果が検波手段(l04
)および平滑手段(l05)を介して加算手段(l07
)に入力される。第1調整手段(l08)は第1比較手
段(l07)の比較結果から調整した補正電圧を加算手
段(l06)に入力し、その出力をゼロにする。
(e) Effect When the output voltage of the AC power supply (l03) is applied to the measurement cell (l01) and the reference resistor (l02), the difference in the current flowing through each is calculated by the subtraction amplification means (l03), The wave is detected by the detection means (l04), and the wave is detected by the smoothing means (l05).
) and then input to the adding means (l06). The adding means (l06) adds the correction voltage from the first adjusting means (l08) to its input, and outputs a signal corresponding to the electrical conductivity of the sample ions in the measurement cell (l01). When the command means (+11) is turned on to adjust the background level at an appropriate point during measurement, first the first adjustment means (l) is turned on.
08) is activated, the comparison result of the first comparing means (107) is used to adjust the correction voltage to the adding means (LOE), and the output of the specializing means (106) is immediately corrected to zero. Even if the first adjustment means (iog) adjusts the correction voltage over the entire adjustment range, the difference in the first comparison means (l07) does not become zero;
That is, when the output of the adding means (l06) does not become zero, the second adjusting means (710) operates so that the difference in the second comparing means (l09) becomes small.
02), and the result is detected by the detection means (l04).
) and the addition means (l07) via the smoothing means (l05).
) is entered. The first adjusting means (l08) inputs the corrected voltage adjusted from the comparison result of the first comparing means (l07) to the adding means (l06), and sets the output to zero.

このようにして、バックグランドレベルの消去が自動的
に行われる。第2調整手段(l10)まで作動させて調
整すると、その結果は検波回路(l04)や平滑回路(
l05)によって遅延され定常値に安定するまで比較的
長い調整時間を要するが、通常測定中のバックグランド
レベルの変動範囲は、第1調整手段(l08)の調′!
!i範囲に納まるため、はとんど第1調整手段(l08
)のみの作動によってバックグランドレベルが調整され
、その出力が速やかに安定する。従って、その調整に時
間を要することがない。
In this way, the background level is automatically erased. When the second adjustment means (l10) is activated and adjusted, the result is the detection circuit (l04) and the smoothing circuit (
105), and it takes a relatively long adjustment time to stabilize at a steady value, but the fluctuation range of the background level during normal measurement is limited by the adjustment of the first adjustment means (108).
! Since it falls within the i range, the first adjustment means (l08
), the background level is adjusted and the output quickly stabilizes. Therefore, no time is required for the adjustment.

くべ)実施例 以下、図面に示す実施例に基づいてこの発明を詳述する
。なお、これによってこの発明が限定されるものではな
い。
Example) The present invention will be described in detail below based on the example shown in the drawings. Note that this invention is not limited to this.

第2図はこの発明の一実施例を示す電気回路図であり、
(l)は交流電源、(2]は測定セル、(7)は参照抵
抗器、(7a)はマイクロコンピュータ(以下マイコン
という) (24+からの入力により抵抗器(3)〜(
6)を切換えるアナログスイッチ、(8)はオペアンプ
(g)と抵抗器001 (l11からなる位相反転器、
■)はオペアンプ面と帰還抵抗器(l3)からなり信号
(el)を出力する増幅回路、(l5]は検波回路、(
l6)は平滑回路、面はオペアンプ(l81と抵抗器s
〜@からなり平滑回路Q6)からの出力(El)にマイ
コン24]からの補正電圧(E2)を加算する加算器、
因はマイコン(24)の入出力を変換するI10ボート
、(至)はコンパレータ囚と比較用電源(27)からな
り交流電源(l)の出力の所定位相を検出する位相検出
回路、囚は増幅回路(l4)の出力(el)を位相検出
回路(至)の出力に同期してサンプリングし、信号(e
2)を出力するサンプルアンドホールド回路、田はサン
プルアンドホールド回路の出力(e2)を接地電位と比
較してその結果をマイコン24+に入力するコンパレー
タ、c31)は加算器面の出力<EO)と接地電位との
比較結果をマイコン(24)に入力するコンパレータ、
叡)はバックグランドレベル消去のタイミング用信号を
マイコン(24)に入力する信号発生器である。
FIG. 2 is an electrical circuit diagram showing an embodiment of the present invention.
(l) is an AC power supply, (2) is a measurement cell, (7) is a reference resistor, (7a) is a microcomputer (hereinafter referred to as a microcomputer) (by input from 24+, resistors (3) to (
(6) is a phase inverter consisting of an operational amplifier (g) and resistor 001 (l11),
■) is an amplifier circuit consisting of an operational amplifier surface and a feedback resistor (l3) that outputs a signal (el), (l5] is a detection circuit, (
l6) is a smoothing circuit, and the plane is an operational amplifier (l81 and resistor s
an adder that adds the correction voltage (E2) from the microcomputer 24 to the output (El) from the smoothing circuit Q6);
The reason is the I10 board that converts the input and output of the microcomputer (24), the phase detection circuit that consists of a comparator and a power supply for comparison (27), and which detects a predetermined phase of the output of the AC power supply (l), and the stage is an amplification circuit. The output (el) of the circuit (l4) is sampled in synchronization with the output of the phase detection circuit (to), and the signal (e
2) is a sample-and-hold circuit that outputs, ta is a comparator that compares the output (e2) of the sample-and-hold circuit with the ground potential and inputs the result to the microcomputer 24+, and c31) is the output of the adder surface <EO). a comparator that inputs the comparison result with the ground potential to the microcomputer (24);
叡) is a signal generator that inputs a timing signal for background level erasure to the microcomputer (24).

このような構成において、交流電源(l)の電圧が測定
セル(2)に印加されると共に、位相反転器(8)によ
って反転された交流電源(l)の電圧が参照抵抗器(′
7)に印加され増幅回路(l4)に入力されると、増幅
器(l4)は、測定セル(2)に流れる電流と参照抵抗
器(7)に流れる電流との差すなわちバンクグランドレ
ベルを差引いた信号(el)を出力する。そして、信号
(el)は、検波回路051および平滑回路(l6)に
よって検波・平滑され、加算器側によってマイコンr2
4)からの補正信号(E2)と加算されて信号(EO)
として出力される。
In such a configuration, the voltage of the alternating current source (l) is applied to the measuring cell (2), and the voltage of the alternating current source (l) inverted by the phase inverter (8) is applied to the reference resistor ('
7) and input into the amplifier circuit (l4), the amplifier (l4) subtracts the difference between the current flowing through the measuring cell (2) and the current flowing through the reference resistor (7), that is, the bank ground level. Outputs a signal (el). The signal (el) is detected and smoothed by the detection circuit 051 and the smoothing circuit (l6), and the adder side detects and smoothes the signal (el) by the microcomputer r2.
4) is added to the correction signal (E2) from signal (EO).
is output as

第3図は第2図においてバックグランドレベル調整を行
う場合のフローチャートを示し、以下第3図と共に動作
を説明する。測定セル(2)に溶離液のみが存在すると
き、信号発生器(支)がオンされると(ステップ201
)、コンパレータc31)によって信号(EO)がゼロ
、プラス又はマイナスのいずれかであるかが判別され(
ステップ202,203) 、ゼロであれば、バックグ
ランドレベル調整は終了する。プラスの場合には、補正
信号(E2)が下限でないことが確認されると(ステッ
プ204) 、補正信号(E2)が減少され、ステップ
(202)へ戻る。ステップ(203)において信号(
EO)がマイナスの場合には、補正信号(E2)が上限
でないことが確認されるとくステップ206)、補正信
号〈E2)が増加され、ステップ(202)へ戻る。ス
テップ(204)又は(206)において補正信号(E
2)が下限又は上限値の場合には、それに対応してアナ
ログスイッチ(7a)が1段階切換えられ、ルーチンは
再びステップ(202>から開始される。ステップ(2
02)において信@(EO)がゼロになると、アナログ
スイッチ(7)や補正信号(E2〉はその状態に保持さ
れバックグランドレベル調整が終了する。
FIG. 3 shows a flowchart when background level adjustment is performed in FIG. 2, and the operation will be explained below with reference to FIG. 3. When only the eluent is present in the measuring cell (2), the signal generator (support) is turned on (step 201).
), the comparator c31) determines whether the signal (EO) is zero, plus or minus (
Steps 202, 203), if zero, the background level adjustment ends. If positive, if it is confirmed that the correction signal (E2) is not at the lower limit (step 204), the correction signal (E2) is decreased and the process returns to step (202). In step (203), the signal (
If EO) is negative, it is confirmed that the correction signal (E2) is not at the upper limit, and in step 206), the correction signal <E2) is increased and the process returns to step (202). In step (204) or (206), the correction signal (E
If 2) is the lower limit or upper limit, the analog switch (7a) is switched one step correspondingly, and the routine starts again from step (202>).Step (2)
When the signal @(EO) becomes zero at step 02), the analog switch (7) and the correction signal (E2> are held in that state, and the background level adjustment is completed.

このようにして、バックグランドレベル補正が行われる
が、測定開始後におけるバックグランドレベルは一般に
変動範囲が小さく、加算器0力、コンパレータ(31)
そしてマイコン24)から成る帰還回路のみによって補
正される。従って、帰還回路には時間遅れ要素をほとん
ど含まないので、バックグランドレベルの補正が速やか
に行われ、測定の能率が向上する。
In this way, background level correction is performed, but the background level after the start of measurement generally has a small fluctuation range, and the adder has zero output and the comparator (31)
Then, correction is performed only by a feedback circuit consisting of a microcomputer 24). Therefore, since the feedback circuit contains almost no time delay elements, the background level can be quickly corrected, improving measurement efficiency.

(ト)発明の効果 この弁明によれば、バックグランドレベル調整が速やか
に行われるので、測定能率の高い電気伝導度検出器が提
供される。
(G) Effects of the Invention According to this defense, since background level adjustment is performed quickly, an electrical conductivity detector with high measurement efficiency is provided.

【図面の簡単な説明】[Brief explanation of drawings]

第1図はこの発明の構成を示′?t′構成図、第2図は
この発明の一実施例を示す電気回路図、第3図は第2図
の要部の動作を示すフローチャー1〜である。 (l)・・・・・・交流電源、 (2)・・・・・・測
定セル、(7)・・・・・・参照抵抗器、 (8)・・
・・・・位相反転器、暑)・・・・・・増幅回路、  
(l5)・・・・・・検波回路、(5)・・・・・・平
滑回路、  (l7)・・・・・・加算器、(24)・
・・・・・マイクロコンピュータ、(至)・・・・・・
位相検出回路、 囚・・・・・・サンプルアンドホールド回路、(l)0
1)・・・・・・コンパレータ。 第3図
Figure 1 shows the configuration of this invention. t' configuration diagram, FIG. 2 is an electric circuit diagram showing one embodiment of the present invention, and FIG. 3 is a flowchart 1 to 1 showing the operation of the main part of FIG. 2. (l)...AC power supply, (2)...Measurement cell, (7)...Reference resistor, (8)...
...phase inverter, heat) ...amplifier circuit,
(l5)...Detection circuit, (5)...Smoothing circuit, (l7)...Adder, (24)...
・・・・・・Microcomputer, (to)・・・・・・
Phase detection circuit, prisoner... Sample and hold circuit, (l) 0
1)...Comparator. Figure 3

Claims (1)

【特許請求の範囲】 1、(a)一対の電極を備えた測定セル、 (b)段階的に抵抗値が調節可能な参照抵抗器、(c)
測定セルと参照抵抗器に並列に出力を印加する交流電源
、 (d)測定セルと参照抵抗器に流れる電流の差差を増幅
して出力する減算増幅手段、 (e)減算手段の出力を検波する検波手段、(f)検波
手段の出力を平滑する平滑手段、(g)前記平滑手段の
出力に必要な補正電圧をを加算する加算手段、 (h)加算手段の出力と接地電位とを比較する第1比較
手段、 (i)第1比較手段の比較で差があるとき、その差がゼ
ロになるよう前記補正電圧を出 力する第1調整手段、 (j)前記減算増幅手段の出力を所定位相でサンプリン
グして接地電位と比較する第2 比較手段、 (k)前記第1調整手段が調整可能な全範囲の補正電圧
を出力しても第1比較手段の差 がゼロにならない時、第2比較手段の差 が小となるように前記参照抵抗器を調整 する第2調整手段、 (l)第1および第2調整手段の作動をオン・オフさせ
る指令手段、 から構成された電気伝導度検出器。
[Claims] 1. (a) A measurement cell equipped with a pair of electrodes, (b) A reference resistor whose resistance value can be adjusted in steps, (c)
an AC power supply that applies an output in parallel to the measurement cell and the reference resistor; (d) subtraction amplification means that amplifies and outputs the difference between the currents flowing through the measurement cell and the reference resistor; (e) detection of the output of the subtraction means. (f) smoothing means for smoothing the output of the detection means; (g) addition means for adding a necessary correction voltage to the output of the smoothing means; (h) comparing the output of the addition means with a ground potential; (i) when there is a difference in the comparison of the first comparison means, the first adjustment means outputs the correction voltage so that the difference becomes zero; (j) the output of the subtraction amplification means is adjusted to a predetermined value; (k) when the difference in the first comparing means does not become zero even if the first adjusting means outputs a correction voltage in the entire adjustable range; a second adjusting means for adjusting the reference resistor so that the difference between the two comparing means is small; (l) a command means for turning on and off the operation of the first and second adjusting means; Detector.
JP27046385A 1985-11-30 1985-11-30 Electric conductivity detector Pending JPS62167456A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27046385A JPS62167456A (en) 1985-11-30 1985-11-30 Electric conductivity detector

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27046385A JPS62167456A (en) 1985-11-30 1985-11-30 Electric conductivity detector

Publications (1)

Publication Number Publication Date
JPS62167456A true JPS62167456A (en) 1987-07-23

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JP27046385A Pending JPS62167456A (en) 1985-11-30 1985-11-30 Electric conductivity detector

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3943346A1 (en) * 1988-12-29 1990-07-05 Hitachi Ltd DEVICE FOR MEASURING THE ELECTRICAL CONDUCTIVITY OF LIQUIDS
JP2012027027A (en) * 2010-07-26 2012-02-09 Mettler-Toledo Thornton Inc Calibration of conductivity measurement system
WO2017208561A1 (en) * 2016-05-31 2017-12-07 株式会社島津製作所 Measuring device
WO2019155592A1 (en) * 2018-02-09 2019-08-15 株式会社島津製作所 Electrical conductivity detector and method for determining phase adjustment value for background subtraction signal

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58122465A (en) * 1981-09-18 1983-07-21 ダイオネツクス・コ−ポレ−シヨン Conductivity detector and its method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58122465A (en) * 1981-09-18 1983-07-21 ダイオネツクス・コ−ポレ−シヨン Conductivity detector and its method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3943346A1 (en) * 1988-12-29 1990-07-05 Hitachi Ltd DEVICE FOR MEASURING THE ELECTRICAL CONDUCTIVITY OF LIQUIDS
US5138264A (en) * 1988-12-29 1992-08-11 Hitachi, Ltd. Apparatus for measuring electrical conductivity
JP2012027027A (en) * 2010-07-26 2012-02-09 Mettler-Toledo Thornton Inc Calibration of conductivity measurement system
WO2017208561A1 (en) * 2016-05-31 2017-12-07 株式会社島津製作所 Measuring device
CN109196344A (en) * 2016-05-31 2019-01-11 株式会社岛津制作所 Measuring appliance
WO2019155592A1 (en) * 2018-02-09 2019-08-15 株式会社島津製作所 Electrical conductivity detector and method for determining phase adjustment value for background subtraction signal

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