JPS6252259B2 - - Google Patents
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- Publication number
- JPS6252259B2 JPS6252259B2 JP53156825A JP15682578A JPS6252259B2 JP S6252259 B2 JPS6252259 B2 JP S6252259B2 JP 53156825 A JP53156825 A JP 53156825A JP 15682578 A JP15682578 A JP 15682578A JP S6252259 B2 JPS6252259 B2 JP S6252259B2
- Authority
- JP
- Japan
- Prior art keywords
- standard solution
- measurement
- calibration curve
- concentration standard
- ion
- 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
Links
- 238000005259 measurement Methods 0.000 claims description 31
- 239000012086 standard solution Substances 0.000 claims description 31
- 238000012937 correction Methods 0.000 claims description 25
- 238000011088 calibration curve Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
Description
【発明の詳細な説明】
本発明は、イオン電極によるイオン活量測定方
法の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a method for measuring ion activity using an ion electrode.
従来のイオン電極によるイオン活量測定方法
は、第１図に示した如く、イオン電極１及び参照
電極２を測定槽３内の検体４中に浸漬し、これら
電極１及び２に発生する電位を増幅器５で増幅し
た後その電位図示しない表示器によりイオン濃度
単位で表示するものであつて、その場合はネルン
ストの式
Ｖ＝ＶO＋Clog ａ
を用いていた。但し、ａはイオン濃度、Ｃは勾配
を表わす定数、ＶOは電極によつて定まる定数、
Ｖは測定電位である。 In the conventional method for measuring ion activity using ion electrodes, as shown in FIG. After being amplified by an amplifier 5, it is displayed in ion concentration units on a display (not shown), using the Nernst equation V=V O +Clog a. However, a is the ion concentration, C is a constant representing the gradient, V O is a constant determined by the electrode,
V is the measured potential.
そして、この方法によるイオン活量測定方法に
ついてより詳しく説明すれば、まず下記の如くイ
オン電極１の検量線を求める。即ち、検体４を測
定する前に、ピペツト６等で高濃度標準液（イオ
ン濃度の高い液）を測定槽３に注入して測定する
と、その測定電位は、
ＶH＝ＶO＋ClogH (1)
となる。但し、ＶHは高濃度標準液の測定電位、
Ｈは所定の高濃度標準液のイオン濃度である。次
に高濃度標準液を廃棄し洗浄した後、低濃度標準
液（イオン濃度の低い液）をピペツト６等で測定
槽３に注入して測定すると、その測定電位は、
ＶL＝ＶO＋ClogL (2)
となる。但し、ＶLは低濃度標準液の測定電位、
Ｌは所定の低濃度標準液のイオン濃度である。次
に図示しない演算回路により式(1)と(2)から定数Ｖ
Oを消去して勾配Ｃを求めると、
Ｃ＝ＶＨ−ＶＬ／ｌｏｇＨ／Ｌ (3)
となり、この匂配Ｃを図示しないメモリに記憶し
ておく。次に、低濃度標準液を廃棄し洗浄した
後、検体４をピペツト６等で測定槽３に注入して
測定すると、そのイオン濃度の測定電位は、
ＶX＝ＶO＋ClogX (4)
と出力される。但し、ＶXは検体４の測定電位、
Ｘは検体４のイオン濃度である。次に式(2)と(4)か
ら定数ＶOを消去すると、
ＶX＝ClogX−CogL＋ＶL (5)
となり、これが第２図にて実線で示した検量線と
なる。又、この式(5)をイオン濃度Ｘについて整理
すれば、
となり、この式（5′）にメモリに記憶されていた
勾配Ｃの値と測定電位ＶXの値を入れて演算し表
示すれば、検体４のイオン濃度Ｘの値を知ること
が出来る。 To explain in more detail how to measure ion activity using this method, first, a calibration curve of the ion electrode 1 is determined as follows. That is, if a high concentration standard solution (liquid with high ion concentration) is injected into the measurement tank 3 using a pipette 6 or the like before measuring the sample 4, the measured potential is V H =V O +ClogH (1) becomes. However, V H is the measured potential of the high concentration standard solution,
H is the ion concentration of the predetermined high concentration standard solution. Next, after discarding and washing the high-concentration standard solution, a low-concentration standard solution (a solution with low ion concentration) is injected into the measurement tank 3 using a pipette 6, etc., and measured. The measured potential is V L = V O + ClogL. (2) becomes. However, V L is the measured potential of the low concentration standard solution,
L is the ion concentration of the predetermined low concentration standard solution. Next, an arithmetic circuit (not shown) calculates the constant V from equations (1) and (2).
When O is deleted and the gradient C is obtained, C=V H -V L /logH/L (3), and this gradient C is stored in a memory (not shown). Next, after discarding and washing the low-concentration standard solution, the sample 4 is injected into the measurement tank 3 using a pipette 6, etc., and measured. The measurement potential of the ion concentration is output as V X =V O +ClogX (4) be done. However, V X is the measured potential of specimen 4,
X is the ion concentration of sample 4. Next, by eliminating the constant V O from equations (2) and (4), we obtain V X =ClogX-CogL+V L (5), which becomes the calibration curve shown by the solid line in FIG. Also, if we rearrange this equation (5) with respect to the ion concentration X, we get By inserting the value of the slope C stored in the memory and the value of the measured potential V X into equation (5'), calculating and displaying the result, the value of the ion concentration X of the specimen 4 can be determined.
上記測定方法は、高濃度標準液と低濃度標準液
とによつて決定された検量線を一回引くと、それ
以後は何も補正しない方法だが、外部条件（例え
ば温度）及び電極の変化等によりこの検量線を補
正してやる必要性が出てくる。その為、本来なら
一検体を測定する度に高濃度標準液と低濃度標準
液とによつて検量線を引き直せば良いのぞある
が、この方法は極めて煩しい為、通常は低濃度標
準液のみを使用して、一検体測定後に必ずこの低
濃度標準液により補正する方法がとられる。但
し、この場合、勾配Ｃは常に一定とみなして最初
の高濃度標準液と低濃度標準液とによつて決定さ
れた値即ち式(3)による値を用いる。又、装置内に
保持する低濃度標準液は、補正液と称し、最初の
低濃度標準液と較べてイオン濃度が全く同じであ
るのに外部条件の変化等により測定電位が変化す
るので該低濃度標準液と区別する。従つて、毎検
体測定後に補正液による補正を行うと、式(5)は
ＶX＝ClogX−ColgL＋ＶC (6)
となり、これが第２図にて点線で示した補正後の
検量線となる。但し、ＶCは補正液の測定電位で
ある。又、この式(6)をイオン濃度Ｘについて整理
すれば、
となり、この式（6′）に上記と同様に勾配Ｃの値
と測定電位ＶXの値を入れて演算し表示すれば、
検体４のイオン濃度Ｘの値を正しく知ることが出
来る。即ち、第２図に示した如く、外部条件変化
後に検体４の測定電位ＶXに対応するイオン濃度
を求めようとする場合、最初の検量線（実線）を
そのまま用いると誤つたイオン濃度ＸOが求めら
れてしまうのに対して、補正後の検量線（点線）
を用いれば正しいイオン濃度Ｘが求められるので
ある。 The above measurement method is a method in which a calibration curve determined by a high concentration standard solution and a low concentration standard solution is drawn once, and no correction is made after that. Therefore, it becomes necessary to correct this calibration curve. Therefore, it would normally be possible to redraw the calibration curve using high-concentration standard solutions and low-concentration standard solutions each time one sample is measured, but since this method is extremely troublesome, it is usually A method is used in which only the standard solution is used, and after each sample measurement, correction is made with this low concentration standard solution. However, in this case, the slope C is always assumed to be constant, and the value determined by the initial high concentration standard solution and low concentration standard solution, that is, the value according to equation (3) is used. In addition, the low concentration standard solution held in the device is called a correction solution, and even though the ion concentration is exactly the same compared to the initial low concentration standard solution, the measured potential changes due to changes in external conditions, etc. Distinguish from concentration standard solution. Therefore, if correction is performed using a correction solution after each sample measurement, equation (5) becomes V X =ClogX-ColgL+V C (6), which becomes the corrected calibration curve shown by the dotted line in FIG. However, V C is the measured potential of the correction liquid. Also, if we rearrange this equation (6) with respect to the ion concentration X, we get Then, if we insert the value of slope C and the value of measured potential V
The value of the ion concentration X of the sample 4 can be accurately known. That is, as shown in FIG. 2, when trying to find the ion concentration corresponding to the measured potential V X of the specimen 4 after a change in external conditions, if the initial calibration curve (solid line) is used as is, the ion concentration X O will be incorrect. is calculated, whereas the corrected calibration curve (dotted line)
By using , the correct ion concentration X can be found.
ところが、この補正液の注入をピペツトを用い
てやつていた場合は上記方法だけで正しいイオン
濃度が得られたが、毎検体測定後の補正液の注入
操作を自動化して能率をあげるためにローリング
ポンプ７等から成る装置を用いた場合、上記方法
だけでは正しいイオン濃度が得られなくなつてし
まつた。そして、その原因としては補正液の注入
方法とか注入タイミングの相違等の微妙なシーケ
ンスの違いが影響していることが考えられた。 However, if the correction solution was injected using a pipette, the correct ion concentration could be obtained using only the above method, but in order to automate the injection of the correction solution after each sample measurement and increase efficiency, rolling When a device consisting of the pump 7 and the like is used, it is no longer possible to obtain the correct ion concentration using only the above method. It was thought that the cause of this was due to subtle differences in the sequence, such as differences in the injection method and injection timing of the correction liquid.
本発明は、上記問題点に鑑み、勾配Ｃ決定時に
補正液の測定電位を加味することを上記方法に付
加することによつて、ローリングポンプ等から成
る装置を用いた場合でも正しいイオン濃度が得ら
れるようにしたイオン活量測定方法を提供せんと
するものであつて、その内容について第３図及び
第４図に基づき説明する。まず、最初に高濃度標
準液をピペツト６等で測定槽３に注入して測定電
位ＶHを得る。次に高濃度標準液を廃棄し洗浄し
た後、補正液をローリングポンプ７等により測定
槽３に注入して測定電位ＶCH（高濃度標準液測定
時とほとんど同時に測定したという意味でこの記
号とする。）を求める。次に補正液を廃棄し洗浄
した後、低濃度標準液をピペツト６等で測定槽３
に注入して測定電位ＶLを得る。次に低濃度標準
液を廃棄し洗浄した後、補正液をローリングポン
プ７等により測定槽３に注入して測定電位ＶCL
（本来ＶCL＝ＶCHであるはずだが、注入タイミン
グ及び雰囲気の違い等により異つているものと考
える。）を求める。次に上記各電位ＶH，ＶCH，Ｖ
L，ＶCL及び各イオン濃度Ｈ，Ｌにより上記従来
方法と同様に演算回路を用いて勾配Ｃを求める
と、
Ｃ＝（ＶＨ−ＶＣＨ）−（ＶＬ−ＶＣＬ）／ｌｏｇＨ
／Ｌ(7)
となる。尚、この場合ＶCH＝ＶCLならば、式(7)は
上記式(3)と全く同じになる。又、この勾配Ｃを有
する検量線は第３図にて一点鎖線で示した如くに
なる。即ち、この勾配Ｃの中には、高濃度標準液
及び低濃度標準液の各々に続いて測定される補正
液の測定電位ＶCH，ＶCLが加味されているので、
該勾配Ｃの値は実際の検体測定に近い状態の勾配
値となつている。次に外部条件の変化等を考慮し
て上記検量線を補正すると、それは第４図にて二
点鎖線で示した如くになり、この検量線によるイ
オン濃度Ｘは、
となる。但し、ＶCXはイオン濃度Ｘの検体測定に
つづいて測定した補正液の測定電位である。即
ち、従来方法の式（6′）によりイオン濃度Ｘを求
めたものが検量線グラフの一点でのみ補正するだ
けで勾配Ｃは一定であるとしていたのに対して、
この式(8)によりイオン濃度Ｘを求めたものは検量
線グラフの二点以上で補正することにより勾配Ｃ
の補正も行つているので、測定精度が良くなつて
いる。 In view of the above problems, the present invention adds to the above method the measurement potential of the correction liquid when determining the gradient C, thereby making it possible to obtain correct ion concentration even when using a device such as a rolling pump. The purpose of this invention is to provide a method for measuring ion activity, the contents of which will be explained based on FIGS. 3 and 4. First, a high concentration standard solution is injected into the measurement tank 3 using a pipette 6 or the like to obtain a measurement potential V H . Next, after discarding and washing the high-concentration standard solution, a correction solution is injected into the measurement tank 3 using the rolling pump 7, etc., and the measured potential V CH (this symbol means that the measurement was made almost at the same time as when measuring the high-concentration standard solution). ). Next, after discarding and washing the correction solution, pipette the low concentration standard solution into the measuring tank 3.
to obtain the measured potential V L . Next, after discarding and washing the low-concentration standard solution, a correction solution is injected into the measurement tank 3 using a rolling pump 7, etc., and the measurement potential V CL is
(Originally, V CL = V CH should be true, but it is assumed that the difference is due to differences in injection timing, atmosphere, etc.). Next, each of the above potentials V H , V CH , V
L , V CL and each ion concentration H, L, when calculating the slope C using an arithmetic circuit in the same way as in the conventional method described above, C = (V H - V CH ) - (V L - V CL )/log H.
/L(7). In this case, if V CH =V CL , equation (7) becomes exactly the same as equation (3) above. Further, the calibration curve having this slope C is as shown by the dashed line in FIG. That is, since the gradient C takes into account the measured potentials V CH and V CL of the correction solution measured subsequent to the high concentration standard solution and the low concentration standard solution,
The value of the gradient C is a gradient value close to the actual sample measurement. Next, when the above calibration curve is corrected in consideration of changes in external conditions, etc., it becomes as shown by the two-dot chain line in Fig. 4, and the ion concentration X according to this calibration curve is becomes. However, V CX is the measured potential of the correction solution measured following the measurement of the ion concentration X in the sample. That is, in contrast to the conventional method in which the ion concentration
The ion concentration
The measurement accuracy has also been improved.
次に本測定方法における検体測定手順について
説明すれば、まず上記方法にて検量線の設定を行
つておく。そして、検体測定を行う場合検体４を
ピペツト６等で測定槽３内に注入して測定電位Ｖ
Xを得る。次に検体４を廃棄し洗浄した後、補正
液をローリングポンプ７等により測定槽３に注入
して測定電位ＶCXを得る。次に、測定電位ＶX，
ＶCXの値を式(8)の演算回路に入力演算し、検体４
のイオン濃度Ｘの値を求める。最後にこの値を図
示しない表示器により表示する。 Next, the sample measurement procedure in this measurement method will be explained. First, a calibration curve is set using the above method. When performing sample measurement, the sample 4 is injected into the measurement tank 3 using a pipette 6, etc., and the measurement potential V
Get X. Next, after discarding and washing the specimen 4, a correction liquid is injected into the measurement tank 3 using a rolling pump 7 or the like to obtain a measurement potential V CX . Next, the measured potential V x ,
The value of V CX is input to the calculation circuit of formula (8) and calculated.
Find the value of the ion concentration X. Finally, this value is displayed on a display (not shown).
以上のように、本発明によるイオン活量測定方
法によれば、毎検体測定時の補正液の注入にロー
リングポンプを用いたとしても、検量線の勾配値
を実際の検体測定に近い状態の勾配値に補正し、
而も検体測定時にイオン濃度算出式にも補正を与
えているので、イオン濃度を極めて精度良く求め
ることが出来る。 As described above, according to the ion activity measurement method of the present invention, even if a rolling pump is used to inject the correction solution during each sample measurement, the slope value of the calibration curve can be adjusted to a slope close to that of the actual sample measurement. correct to the value,
Moreover, since the ion concentration calculation formula is also corrected when measuring the sample, the ion concentration can be determined with extremely high accuracy.
第１図はイオン電極によるイオン活量測定装置
の要部を示す概略図、第２図は従来方法における
検量線の補正を示す図、第３図は本発明によるイ
オン活量測定方法における検量線の設定を示す
図、第４図は本発明方法における検量線の補正を
示す図である。
１……イオン電極、２……参照電極、３……測
定槽、４……検体、５……増幅器、６……ピペツ
ト、７……ローリングポンプ。
Figure 1 is a schematic diagram showing the main parts of an ion activity measuring device using an ion electrode, Figure 2 is a diagram showing calibration curve correction in the conventional method, and Figure 3 is a calibration curve in the ion activity measuring method according to the present invention. FIG. 4 is a diagram showing the calibration curve correction in the method of the present invention. 1... Ion electrode, 2... Reference electrode, 3... Measurement tank, 4... Sample, 5... Amplifier, 6... Pipette, 7... Rolling pump.
Claims (1)
設定すると共に、毎検体測定時に該低濃度標準液
と同一の補正液により前記検量線を補正するよう
にしたイオン電極によるイオン活量測定方法にお
いて、前記検量線設定時にピペツト等により測定
槽に注入した高濃度標準液及び低濃度標準液の各
測定電位から、夫々の該電位測定後にローリング
ポンプ等により測定槽に注入した前記補正液の各
測定電位を夫々差し引くことにより、前記検量線
の勾配値を実際の検体測定に近い状態の勾配値に
補正するようにしたことを特徴とするイオン活量
測定方法。1. A method for measuring ion activity using an ion electrode, in which a calibration curve is set using a high-concentration standard solution and a low-concentration standard solution, and the calibration curve is corrected using the same correction solution as the low-concentration standard solution during each sample measurement. , from each measurement potential of the high-concentration standard solution and low-concentration standard solution injected into the measurement tank with a pipette or the like when setting the calibration curve, each of the correction solutions injected into the measurement tank with a rolling pump or the like after measuring the respective potentials. A method for measuring ion activity, characterized in that the slope value of the calibration curve is corrected to a slope value close to the actual sample measurement by subtracting the measured potentials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15682578A JPS5583846A (en) | 1978-12-21 | 1978-12-21 | Ion activity measuring method dependent upon ion electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15682578A JPS5583846A (en) | 1978-12-21 | 1978-12-21 | Ion activity measuring method dependent upon ion electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5583846A JPS5583846A (en) | 1980-06-24 |
| JPS6252259B2 true JPS6252259B2 (en) | 1987-11-04 |
Family
ID=15636163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15682578A Granted JPS5583846A (en) | 1978-12-21 | 1978-12-21 | Ion activity measuring method dependent upon ion electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5583846A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228909A (en) * | 1979-06-21 | 1980-10-21 | The Continental Group, Inc. | Squeeze-off closure with tamper indicating band |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5444593A (en) * | 1977-09-14 | 1979-04-09 | Hitachi Ltd | Ion concentration analytical apparatus |
-
1978
- 1978-12-21 JP JP15682578A patent/JPS5583846A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5444593A (en) * | 1977-09-14 | 1979-04-09 | Hitachi Ltd | Ion concentration analytical apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5583846A (en) | 1980-06-24 |
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