CN107219284A - A kind of adulterated method of fluoride ion electrode detection milk - Google Patents

A kind of adulterated method of fluoride ion electrode detection milk Download PDF

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Publication number
CN107219284A
CN107219284A CN201710429940.6A CN201710429940A CN107219284A CN 107219284 A CN107219284 A CN 107219284A CN 201710429940 A CN201710429940 A CN 201710429940A CN 107219284 A CN107219284 A CN 107219284A
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China
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milk
electrode
fluoride ion
adulterated
value
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李胜利
张娟
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Cangzhou Medical College
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Cangzhou Medical College
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333Ion-selective electrodes or membranes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/4163Systems checking the operation of, or calibrating, the measuring apparatus

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

The invention discloses a kind of adulterated method of fluoride ion electrode detection milk, fluorine ion chemical property is very active, it is widely present in various environment, the method for determining content of fluoride ion, current most sensitive simplest method is electrode method, this method equipment is simple, easy to carry, sample consumption is small, operates very simple, very sensitive, multiple samples can be once handled, can particularly be operated to working site.It because Oil repellent is extremely low in milk, can not typically be detected, some drink the milk cow of high-fluorine water, also be not in high fluorine phenomenon in milk, because milk has a good barrier action to fluorine.Normal milk in buffer solution typically will not reading, when having adulterated, the fluorine in adulterant can just be detected by fluoride electrode.No matter the adulterated of any mode can all be detected.If it is known that during the Oil repellent of adulterant, such as water, by electrode reading, watering quantity can be calculated, the instrument qualitative can also can not only be quantified.

Description

A kind of adulterated method of fluoride ion electrode detection milk
Technical field
The present invention relates to a kind of method for detecting that milk is adulterated, more particularly to a kind of fluoride ion electrode detection milk is adulterated Method, belongs to technical field of food safety.
Background technology
Adulterated milk is always the problem of milk foods are safe, in current milk detection of adulterations to select hydrometer method, the party more Method is simple and easy to apply, and graduated cylinder, a densimeter can be completed.But milk adulterated and double-doped vacation can be divided into, it is necessary to butterfat The use of meter, this method needs larger centrifuge, and operate burdensome, can not directly arrive Site Detection.If more multiple Miscellaneous is adulterated, and the above method can not be determined.If determining the source of fat, that will be an extremely complex process, the country one As laboratory can not complete.
The content of the invention
The technical problem to be solved in the present invention is that there is provided a kind of fluorine ion for the defect that overcomes milk detection of adulterations process complicated The adulterated method of electrode detection milk.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme:
The invention provides a kind of adulterated method of fluoride ion electrode detection milk, before the start of the measurement, first by two kinds The standard liquid of concentration known to electrode carry out demarcation correction, both standard liquids be by 1000ppm standard liquid or it Dilution constitute, complete fluoride ion selective electrode demarcation trimming process, it is necessary to be equipped with a series of standard liquid, Its fluorinion concentration(F)Respectively:1000ppm, 100ppm, 10ppm, 1ppm;In demarcation timing, electrode is successively put into Know in the standard sample liquid 1 and standard sample liquid 2 of fluorinion concentration and detect, apparatus measures mode is then switched to measurement of concetration On shelves, pin the prompting of the sound of right button etc. three blow a whistle sound and blank screen show after unclamp button, instrument is shown " PC1 xx.xx ";PC1 tables Show secondary display window show value xx.xx be standard sample liquid 1 concentration it is negative to measured value, utilization can go up lower key increase or reduce PC1 value, makes it identical with the concentration negative logarithm of standard sample liquid 1, upper lower key is the automatic carry using key press time as foundation Key, i.e. short time press upper (lower) key, and numerical value lowest order can be made to add and (subtract) 1, and upper (lower) key is pinned for a long time, can make numerical value highest Position plus (subtracting) 1, medium while press (under) key, numerical value second or the 3rd can be made to add (subtracting) 1, key press time length it is right The plus-minus position answered can be indicated by the cursor of secondary indicating window, can also be pointed out by sound of blowing a whistle;Press upper (lower) key blowing a whistle, two sound, Unclamped after three sound or the four tones of standard Chinese pronunciation, can make first of numerical value, second, the 3rd or the 4th plus (subtracting) 1, PC1 sets afterwards by the right side Key instrument is shown " PC2 xx.xx ";PC2 represents that secondary display window show value xx.xx is the negative logarithm of the concentration of standard sample liquid 2 Value, PC2 is set to be shown by right button instrument afterwards " PCA1 xx.xx ";It represents that pair display window show value xx.xx is that analog signal is defeated Go out corresponding PC values at 0 volt, PCA1 is set to be shown by right button instrument afterwards " PCA2 xx.xx ";Here xx.xx is that analog signal is defeated Go out corresponding PC values at 5 volts, finally completing demarcation correction by right button instrument is set;A certain amount of milk to be measured is got out afterwards, The pH value of milk is detected, if its pH value is not in the range of 4-8, prepares the background ions intensity adjustment cushioning liquid of equivalent, PH value is adjusted in the range of 4-8;Finally will fluoride ion electrode insert milk in detection milk in content of fluoride ion, by fluorine from Whether the content of son determines adulterated and adulterated using which kind of method in milk.
As a preferred technical solution of the present invention, the standard liquid is the NaF solution containing 1000ppm F- (2.886 grams of NaF are dissolved in 1000 milliliters of volumetric flasks in pure water).
As a preferred technical solution of the present invention, it should be made pottery when the fluoride ion electrode is used electrode front portion is enclosed on Rubber ring rubber stopper on porcelain core and outer reference liquid filling opening is removed, and outer the too low of reference liquid level drop should supplement outer reference at any time Liquid.
As a preferred technical solution of the present invention, the used time can not steep in potassium chloride containing 3M and 0.053M electrode in short term Deposited in NaF solution, the used time should not dry external water and put that rubber ring rubber stopper is dry to be put for a long time.
As a preferred technical solution of the present invention, the time that milk soln is put into during the fluoride ion electrode detection should More than 10S.
As a preferred technical solution of the present invention, the normal detection temperature of the fluoride ion electrode is 5 DEG C -80 DEG C, Optimum temperature is 25 DEG C.
The beneficial effect that is reached of the present invention is:Dairy products are the major issue for being related to city's health, milk safely Adulterated is most common safety problem, traditional milk detection of adulterations, it is impossible to solve whole issue, and instrument is more complicated, Labor intensive, material resources and time.Fluoride ion selective electrode method, can in a short period of time i.e. it could be assumed that, and with instrument Device is simple to operate, very convenient to carry, and sample consumption is few, detection sample time it is short, processing sample it is many, to it is any it is adulterated can Detection, to some samples, qualitative can also can not only be quantified, and be the adulterated preferable means of current detection milk.
Embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
The invention provides a kind of adulterated method of fluoride ion electrode detection milk, before the start of the measurement, first by two kinds The standard liquid of concentration known to electrode carry out demarcation correction, both standard liquids be by 1000ppm standard liquid or it Dilution constitute, complete fluoride ion selective electrode demarcation trimming process, it is necessary to be equipped with a series of standard liquid, Its fluorinion concentration(F)Respectively:1000ppm, 100ppm, 10ppm, 1ppm;In demarcation timing, electrode is successively put into Know in the standard sample liquid 1 and standard sample liquid 2 of fluorinion concentration and detect, apparatus measures mode is then switched to measurement of concetration On shelves, pin the prompting of the sound of right button etc. three blow a whistle sound and blank screen show after unclamp button, instrument is shown " PC1 xx.xx ";PC1 tables Show secondary display window show value xx.xx be standard sample liquid 1 concentration it is negative to measured value, utilization can go up lower key increase or reduce PC1 value, makes it identical with the concentration negative logarithm of standard sample liquid 1, upper lower key is the automatic carry using key press time as foundation Key, i.e. short time press upper (lower) key, and numerical value lowest order can be made to add and (subtract) 1, and upper (lower) key is pinned for a long time, can make numerical value highest Position plus (subtracting) 1, medium while press (under) key, numerical value second or the 3rd can be made to add (subtracting) 1, key press time length it is right The plus-minus position answered can be indicated by the cursor of secondary indicating window, can also be pointed out by sound of blowing a whistle;Press upper (lower) key blowing a whistle, two sound, Unclamped after three sound or the four tones of standard Chinese pronunciation, can make first of numerical value, second, the 3rd or the 4th plus (subtracting) 1, PC1 sets afterwards by the right side Key instrument is shown " PC2 xx.xx ";PC2 represents that secondary display window show value xx.xx is the negative logarithm of the concentration of standard sample liquid 2 Value, PC2 is set to be shown by right button instrument afterwards " PCA1 xx.xx ";It represents that pair display window show value xx.xx is that analog signal is defeated Go out corresponding PC values at 0 volt, PCA1 is set to be shown by right button instrument afterwards " PCA2 xx.xx ";Here xx.xx is that analog signal is defeated Go out corresponding PC values at 5 volts, finally completing demarcation correction by right button instrument is set;A certain amount of milk to be measured is got out afterwards, The pH value of milk is detected, if its pH value is not in the range of 4-8, prepares the background ions intensity adjustment cushioning liquid of equivalent, PH value is adjusted in the range of 4-8;Finally will fluoride ion electrode insert milk in detection milk in content of fluoride ion, by fluorine from Whether the content of son determines adulterated and adulterated using which kind of method in milk.
The standard liquid is that (2.886 grams of NaF are dissolved in 1000 milliliters of volumetric flasks the NaF solution containing 1000ppm F- In pure water).The fluoride ion electrode should be being enclosed on the anterior ceramic core of electrode and outer reference liquid filling opening when using Rubber ring rubber stopper remove, the too low of outer reference liquid level drop should supplement outer reference liquid at any time.The electrode short-term not used time can be with Bubble is deposited in potassium chloride containing 3M and 0.053M NaF solution, and the used time should not dry external water and put rubber ring rubber for a long time Plug is dry to be put.The time that milk soln is put into during the fluoride ion electrode detection should be greater than 10S.The fluoride ion electrode it is normal Detection temperature is 5 DEG C -80 DEG C, and optimum temperature is 25 DEG C.
Concrete operating principle:Fluorine ion chemical property is very active, is widely present in various environment, determines fluorine ion and contains The method of amount, current most sensitive simplest method is electrode method, and this method equipment is simple, easy to carry, and sample consumption is small, behaviour Make very simple, it is very sensitive, multiple samples can be once handled, can particularly be operated to working site.
It because Oil repellent is extremely low in milk, can not typically be detected, some drink the milk cow of high-fluorine water, will not also go out High fluorine phenomenon in existing milk, because milk has a good barrier action to fluorine.Normal milk will not typically be read in buffer solution Number, when having adulterated, the fluorine in adulterant can just be detected by fluoride electrode.No matter the adulterated of any mode can all be detected Go out.If it is known that during the Oil repellent of adulterant, such as water, by electrode reading, watering quantity can be calculated, the instrument is not only It qualitative can also quantify, be to judge the adulterated good means of milk at present.
In the detection, because fluoride electrode is more sensitive, require to pay special attention in cleaning, it should when there are enough cleanings Between, also there is corresponding requirement to the preparation of buffer solution.
The beneficial effect that is reached of the present invention is:Dairy products are the major issue for being related to city's health, milk safely Adulterated is most common safety problem, traditional milk detection of adulterations, it is impossible to solve whole issue, and instrument is more complicated, Labor intensive, material resources and time.Fluoride ion selective electrode method, can in a short period of time i.e. it could be assumed that, and with instrument Device is simple to operate, very convenient to carry, and sample consumption is few, detection sample time it is short, processing sample it is many, to it is any it is adulterated can Detection, to some samples, qualitative can also can not only be quantified, and be the adulterated preferable means of current detection milk.
Finally it should be noted that:The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic. Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's Within protection domain.

Claims (6)

1. a kind of adulterated method of fluoride ion electrode detection milk, it is characterised in that before the start of the measurement, first by two The standard liquid of kind of concentration known carries out demarcation correction to electrode, both standard liquids be by 1000ppm standard liquid or What its dilution was constituted, a complete fluoride ion selective electrode demarcation trimming process is, it is necessary to which to be equipped with a series of standard molten Liquid, its fluorinion concentration(F)Respectively:1000ppm, 100ppm, 10ppm, 1ppm;In demarcation timing, electrode is successively put Detected in the standard sample liquid 1 and standard sample liquid 2 that enter known fluorinion concentration, apparatus measures mode is then switched to concentration Measure on shelves, pin the prompting of the sound of right button etc. three blow a whistle sound and blank screen show after unclamp button, instrument is shown " PC1 xx.xx "; PC1 represent secondary display window show value xx.xx be standard sample liquid 1 concentration it is negative to measured value, utilization can go up lower key increase Or reduce PC1 value, make it identical with the concentration negative logarithm of standard sample liquid 1, upper lower key is oneself by foundation of key press time Dynamic carry key, the i.e. short time presses upper (lower) key, numerical value lowest order can be made to add and (subtract) 1, upper (lower) key is pinned for a long time, can make number Value highest order adds and (subtracted) 1, medium while press (under) key, numerical value second or the 3rd plus (subtracting) 1 can be made, key press time is long Short corresponding plus-minus position can be indicated by the cursor of secondary indicating window, can also be pointed out by sound of blowing a whistle;Upper (lower) key is pressed to blow a whistle, Unclamped after two sound, three sound or the four tones of standard Chinese pronunciation, first of numerical value, second, after the 3rd or the 4th plus (subtracting) 1, PC1 sets can be made Shown by right button instrument " PC2 xx.xx ";PC2 represents that secondary display window show value xx.xx is negative pair of the concentration of standard sample liquid 2 Numerical value, PC2 is set to be shown by right button instrument afterwards " PCA1 xx.xx ";It represents that pair display window show value xx.xx is analog signal Corresponding PC values at 0 volt are exported, PCA1 is set to be shown by right button instrument afterwards " PCA2 xx.xx ";Here xx.xx is analog signal Corresponding PC values at 5 volts are exported, finally completing demarcation correction by right button instrument is set;A certain amount of ox to be measured is got out afterwards Milk, detects the pH value of milk, if its pH value is not in the range of 4-8, and the background ions intensity adjustment buffering for preparing equivalent is molten In the range of liquid, regulation pH value to 4-8;Fluoride ion electrode is finally inserted into the content of fluoride ion in milk in detection milk, passed through Whether the content of fluorine ion determines adulterated and adulterated using which kind of method in milk.
2. a kind of adulterated method of fluoride ion electrode detection milk according to claim 1, it is characterised in that the standard Solution is the NaF solution containing 1000ppm F- (2.886 grams of NaF are dissolved in 1000 milliliters of volumetric flasks in pure water).
3. a kind of adulterated method of fluoride ion electrode detection milk according to claim 1, it is characterised in that the fluorine from Sub-electrode should remove the rubber ring rubber stopper being enclosed on the anterior ceramic core of electrode and outer reference liquid filling opening when using, outer ginseng Too low than liquid level drop should supplement outer reference liquid at any time.
4. the adulterated method of a kind of fluoride ion electrode detection milk according to claim 1, it is characterised in that electrode is short-term The used time can not steep deposits in potassium chloride containing 3M and 0.053M NaF solution, and the used time should not dry outside water jacket for a long time Upper rubber ring rubber stopper is dry to be put.
5. a kind of adulterated method of fluoride ion electrode detection milk according to claim 1, it is characterised in that the fluorine from Sub-electrode is put into milk soln time when detecting should be greater than 10S.
6. a kind of adulterated method of fluoride ion electrode detection milk according to claim 1, it is characterised in that the fluorine from The normal detection temperature of sub-electrode is 5 DEG C -80 DEG C, and optimum temperature is 25 DEG C.
CN201710429940.6A 2017-06-09 2017-06-09 A kind of adulterated method of fluoride ion electrode detection milk Pending CN107219284A (en)

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US20140065712A1 (en) * 2012-08-28 2014-03-06 Piramal Enterprises Limited (PEL). Rapid detection of urea in adulterated milk using thread based microfluidic system
KR20150095461A (en) * 2014-02-13 2015-08-21 (주) 휴마스 The method for analysis of Fluoride ion and apparatus in water
CN105241944A (en) * 2015-09-25 2016-01-13 浙江大学 Method for electrochemical detection of antibiotics in milk based on vertical and ordered micelle enrichment
CN106018513A (en) * 2016-06-23 2016-10-12 陕西科技大学 Fingerprint method for detecting adulteration of dairy products
JP2017064569A (en) * 2015-09-28 2017-04-06 水ing株式会社 Method and apparatus for treating fluorine-containing wastewater
CN106770512A (en) * 2016-11-17 2017-05-31 江南工业集团有限公司 The assay method of fluohydric acid content in a kind of nitric hydrofluoric acid type Acidwash solution

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140065712A1 (en) * 2012-08-28 2014-03-06 Piramal Enterprises Limited (PEL). Rapid detection of urea in adulterated milk using thread based microfluidic system
CN103399163A (en) * 2013-08-15 2013-11-20 四川大学 Online phosphorus and fluorine content measuring analyzer
KR20150095461A (en) * 2014-02-13 2015-08-21 (주) 휴마스 The method for analysis of Fluoride ion and apparatus in water
CN105241944A (en) * 2015-09-25 2016-01-13 浙江大学 Method for electrochemical detection of antibiotics in milk based on vertical and ordered micelle enrichment
JP2017064569A (en) * 2015-09-28 2017-04-06 水ing株式会社 Method and apparatus for treating fluorine-containing wastewater
CN106018513A (en) * 2016-06-23 2016-10-12 陕西科技大学 Fingerprint method for detecting adulteration of dairy products
CN106770512A (en) * 2016-11-17 2017-05-31 江南工业集团有限公司 The assay method of fluohydric acid content in a kind of nitric hydrofluoric acid type Acidwash solution

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Title
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