CN101078709A - Glass fluorinion content measuring method - Google Patents
Glass fluorinion content measuring method Download PDFInfo
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- CN101078709A CN101078709A CN 200710069261 CN200710069261A CN101078709A CN 101078709 A CN101078709 A CN 101078709A CN 200710069261 CN200710069261 CN 200710069261 CN 200710069261 A CN200710069261 A CN 200710069261A CN 101078709 A CN101078709 A CN 101078709A
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Abstract
The invention provides a measuring method for fluorine ion content in glass. The measuring equipment adapting the measuring method comprises selecting electrode of fluorine ion, reference electrode, PH acidimeter and magnetic stirrer. Reagent comprises sodium hydroxide, phenolphthalein indicator, hydrochloride and regulating buffering solution of total ion intensity. The measuring method comprises following procedures that sample is washed and dried; sample of sodium hydroxide is melted; melted sample is immerged by hot de-ionized water; the regulating and buffering solution of total ion intensity is added; potential value is measured by the selecting electrode of fluorine ion; logarithm value of fluorine ion concentration is found on the calibration curve; fluorine ion concentration is calculated according to the formula of F-%=[(VXCX10) /(GX1000)]X100=(VXC)/G. Where: V--cubage of sample detecting solution (ml); G--sample weight (g); C-logarithm value of fluorine ion concentration found on the calibration curve. The invention is simple, quick and low cost compared with prior technology.
Description
Technical field
The present invention relates to the measuring method of content of fluoride ion in a kind of glass.
Background technology
Fluorine ion is measured in the glass, national standard method adopt GB T1549-94 distillation---spectrophotometric method (I method).Sample is through the NaOH fusion, and with the perchloric acid distillation, fluorine generates hydrofluosilicic acid and distillates; Utilize the zirconium in the orange red complex of the blue or green R-zirconium of fluorine and Yi Lai chromium to generate more stable colourless complex then; According to color fading reaction spectrophotometry fluorine.This method operation steps is more, and minute is longer.
Measure at present in the glass fluorine ion generally adopt national standard method GB T1549-94 precipitation---spectrophotometric method (II method).Sample is removed sulfate radical through the NaOH fusion with barium chloride, uses hartshorn salt precipitate and separate such as silicon, iron, titanium, aluminium, calcium, magnesium again; Utilize fluorine and the color fading reaction spectrophotometry fluorine of complying with the blue or green R-zirconium complex of chromium.This method needs about 6 hours from claiming sample to going out the result.
Summary of the invention
Technical matters to be solved by this invention is to seek a kind of measuring method and relevant device and the reagent that can measure content of fluoride ion in the glass easy, quick, low-cost, exactly.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: tested glass leaches frit with NaOH fusion sample, cooling back with hot deionized water, uses fluorine ion selective electrode determining then.
Cardinal principle of the present invention is as follows:
Ion-selective electrode is a kind of electrochemical sensor, and it converts the activity of specific ion in the solution to corresponding current potential.When fluoride electrode (making indicator electrode) and saturated calomel electrode (contrast electrode) are inserted when forming working battery in the detected solution, the potential value of battery (E) under certain condition with the logarithm value relation of being in line of fluorine ion activity; When the total ionic strength adjustment buffer degree of solution was constant, the activity coefficient of ion was a certain value, then the concentration C of potential value (E) and fluorine ion
F-The logarithm value relation of being in line, i.e. E=K-(2.303RT/F) * lgC
F-Therefore,, add the enough indifferent electrolytes of equivalent in be everlasting standard solution and the sample solution simultaneously and make total ionic strength adjustment buffer degree adjusting buffer solution, make their total ionic strength adjustment buffer degree identical in order to measure the concentration of fluorine ion.
Working battery is expressed as follows:
Ag|AgCl, Cl
-(0.33mol/L), F
-(0.001mol/L) | LaF
2‖ test solution ‖ contrast electrode.
The inventive method compared with prior art has characteristics such as easy, quick, low cost.
Embodiment
Measuring method (equipment, method, step etc.):
1, equipment and reagent
Equipment
(1) fluoride ion selective electrode;
(2) saturated calomel electrode or silver chloride electrode;
(3) pH acidometer (possessing temperature compensation function) is accurate to 0.1mV;
(4) magnetic stirring apparatus;
(5) other general experimental facilities.
Reagent
(1) NaOH: solid (AR), 6mol/L;
(2) phenolphthalein indicator: 10g/L alcoholic solution;
(3) hydrochloric acid: 1+1,1+10;
(4) the total ionic strength adjustment buffer degree is regulated buffer solution (TISAB-1):
At first in the 1000ml beaker, add 500ml deionized water and 57ml glacial acetic acid, 58g sodium chloride, 12g sodium citrate, be stirred to dissolving.Beaker is placed in the cold water, slowly adds the 6mol/L sodium hydroxide solution, (check) between 6.0～6.5 until the pH value to change in the 1000ml volumetric flask, be diluted to graticule (1000ml) with deionized water with pH meter.
(5) fluoride standard stock solution:
Take by weighing 0.2210 gram benchmark sodium fluoride (in advance prior to 105～110 ℃ of dryings 2 hours), in the volumetric flask that changes 1000ml behind the deionized water dissolving over to, be diluted to graticule (1000ml), shake up, be stored in the polyethylene bottle.0.10 milligram of every milliliter of fluoride ion of this solution.
Use pipette, extract fluorine ion standard stock solution 10.00ml again, inject the volumetric flask of 100ml, be diluted to graticule (100ml), shake up.0.01 milligram of every milliliter of fluoride ion of this solution.
2, typical curve is drawn
With suction pipe get 1.00,2.00,3.00,5.00,10.00 respectively, 20.00ml fluoride standard solution, place the volumetric flask of 50ml, add 10ml total ionic strength adjustment buffer degree and regulate buffer solution, water is rare to graticule, shakes up.Move into respectively in the tygon beaker of 100ml, each adds a plastics stirrer, is order with low concentration to high concentration, inserts electrode respectively successively, continuous stirring solution, treat that current potential is stable after, reading potential value (E) under continuing to stir.Before measuring each time, all want water that electrode washing is clean, and absorb water with filter paper.On coordinate paper by E that records (mV) and logc
F-Relation draw calibration curve.
3, actual measurement process:
Take by weighing 0.1 gram sample, be accurate to 0.0001 gram, place nickel crucible.Add 1.5 gram NaOH, heating and melting on electric furnace decomposes sample fully., cool off in the beaker of 250ml with hot deionized water leaching frit the cooling back.Move in the 250ml volumetric flask, be diluted to graticule (250ml), shake up with deionized water.Draw the test solution of 25.00ml, place the volumetric flask of 50ml, add 1 phenolphthalein, drip 1+10 hydrochloric acid extremely just to colourless, the total ionic strength adjustment buffer degree that adds 10ml is regulated buffer solution, is diluted with water to graticule (50ml), shakes up.Solution moves in the tygon cup of 100ml, adds a plastics stirrer, inserts electrode, continuous stirring solution, treat that current potential is stable after, continuing reading potential value (E) under the stirring.Before measuring each time, all to fully wash electrode, and blot with filter paper with deionized water.According to the potential value that records (E), by the logarithm value logc that checks in fluorinion concentration on the calibration curve
F-(C), try to achieve fluorinion concentration F
-%.
4, the result calculates:
F
-％＝〖(V×C×10)÷(G×1000)〗×100＝(V×C)÷G
In the formula: V---test portion is measured the volume of solution, unit milliliter (ml);
G-sample mass, unit gram (g);
C-by the logarithm value logc that checks in fluorinion concentration on the calibration curve
F-, try to achieve fluorinion concentration F
-% (mg/ml);
5, test result
The test of standard sample:
The contained fluorine of c-glass marble standard specimen (JBW 04-2-1), the results are shown in Table (1) of carrying out 12 replicate determinations by electrode method of the present invention.
Table (1)
| Standard value | Measured value | Mean value | Absolute deviation | Standard deviation |
| 0.57 ±0.02 | 0.56 0.58 0.58 0.55 0.57 0.57 0.58 0.58 0.57 0.58 0.56 0.58 | 0.58 | 0.03 | 0.01 |
Content of fluoride ion is respectively each 1 fluorine that the c-glass marble sample is contained of high, medium and low third gear, by electrode method of the present invention and national standard method GB T1549-94 precipitate---spectrophotometric method (II method) is carried out the results are shown in Table (2) of 8 replicate determinations.
Table (2)
| Middle alkali glass standard specimen | Assay method | Measured value | Mean value | Exhausted poor | Standard deviation |
| High | The electrode method | 0.92 0.95 0.94 0.94 0.94 0.93 0.93 0.95 | 0.94 | 0.03 | 0.01 |
| Spectrophotometric method | 0.92 0.93 0.94 0.94 0.93 0.93 0.93 0.92 | 0.93 | 0.03 | 0.01 | |
| In | The electrode method | 0.65 0.66 0.64 0.67 0.65 0.65 0.66 0.65 | 0.65 | 0.03 | 0.01 |
| Spectrophotometric method | 0.67 0.65 0.65 0.68 0.65 0.66 0.66 0.65 | 0.66 | 0.03 | 0.01 | |
| Low | The electrode method | 0.35 0.34 0.34 0.34 0.33 0.33 0.35 0.33 | 0.34 | 0.02 | 0.01 |
| Spectrophotometric method | 0.33 0.32 0.34 0.34 0.32 0.34 0.32 0.32 | 0.33 | 0.02 | 0.01 |
C-glass marble standard specimen (JBW 04-2-1) fluorine content standard value in the table (1), be according to national standard method GB T1549-94 precipitation---spectrophotometric method (II method) is surveyed, use determination of electrode of the present invention fluorine in the alkali glass standard sample in these then, mean value shows that precision of measurement of the present invention is good within the permissible error scope of this standard sample.
From table (2) as can be seen, with national standard method GB T1549-94 precipitation---the high, medium and low third gear sample (every grade of 8 replicate determination) of spectrophotometric method (II method) and electrode method centering alkali glass fluorinated volume of the present invention is measured, the mean value of two kinds of methods, absolute deviation and relative deviation are basic identical, so the mensuration of accuracy of centering alkali glass and precision, electrode method of the present invention can obtain precipitation---the test result that spectrophotometric method is identical.
Contained fluorine in the alkali-free glass ball sample (JBW 04-1-1), the results are shown in Table (3) of carrying out 12 replicate determinations with electrode method of the present invention.
Table (3)
| Standard value | Measured value | Mean value | Exhausted poor | Standard deviation |
| 0.30 ±0.007 | 0.305 0.306 0.303 0.300 0.306 0.299 0.307 0.297 0.298 0.299 0.300 0.295 | 0.303 | 0.010 | 0.004 |
Content of fluoride ion is respectively each 1 fluorine that the e-glass marble sample is contained of high, medium and low third gear, by electrode method of the present invention and national standard method GB T1549-94 precipitate---spectrophotometric method (II method) is carried out the results are shown in Table (4) of 8 replicate determinations.
Table (4)
| The alkali-free glass standard specimen | Assay method | Measured value | Mean value | Exhausted poor | Standard deviation |
| High | The electrode method | 1.02 1.04 1.00 1.04 1.03 1.02 1.05 1.03 | 1.03 | 0.05 | 0.02 |
| Spectrophotometric method | 1.05 1.02 1.01 1.04 1.04 1.06 1.03 1.03 | 1.04 | 0.05 | 0.02 | |
| In | The electrode method | 0.54 0.56 0.55 0.53 0.53 0.55 0.56 0.55 | 0.55 | 0.03 | 0.01 |
| Spectrophotometric method | 0.57 0.55 0.55 0.58 0.55 0.56 0.56 0.55 | 0.56 | 0.03 | 0.01 | |
| Low | The electrode method | 0.25 0.24 0.24 0.24 0.23 0.23 0.25 0.23 | 0.24 | 0.02 | 0.01 |
| Spectrophotometric method | 0.23 0.22 0.24 0.24 0.22 0.24 0.22 0.22 | 0.23 | 0.02 | 0.01 |
Alkali-free glass ball sample (JBW 04-2-1) fluorine content standard value in the table (3), be according to national standard method GB T1549-94 precipitation---spectrophotometric method (II method) is surveyed, use the fluorine in these alkali-free glass standard samples of determination of electrode of the present invention then, mean value shows that precision of measurement of the present invention is good within the permissible error scope of this standard sample.
From table (4) as can be seen, with national standard method GB T1549-94 precipitation---the high, medium and low third gear sample (every grade of 8 replicate determination) of spectrophotometric method (II method) and electrode method centering alkali glass fluorinated volume of the present invention is measured, the mean value of two kinds of methods, absolute deviation and relative deviation are basic identical, so to alkali-free glass fluorine content measurement result, electrode method of the present invention can obtain precipitation---the test result that spectrophotometric method is identical.
Mensuration according to above two kinds of glass bead standard specimens can confirm that the accuracy of measuring method of the present invention and precision all have good measurement effect in the scope usually for middle alkali glass and alkali-free glass content of fluoride ion.
Conclusion:
The inventive method (fluorine ion in the selective Electrodes Method For The Determination glass) accuracy of measurement, precision in the scope of this test is better. The inventive method for AAS, have easy, fast, characteristics cheaply, Measuring Time is less than 3 hours, and do not need spectrophotometer etc. than expensive instrument.
Claims (2)
1, the measuring method of content of fluoride ion in a kind of glass, it is characterized in that: the measuring equipment of described measuring method comprises fluoride ion selective electrode, contrast electrode, the pH acidometer, magnetic stirring apparatus, reagent comprises NaOH, phenolphthalein indicator, hydrochloric acid, the total ionic strength adjustment buffer degree is regulated buffer solution, described measuring method may further comprise the steps: sample cleans, oven dry, the NaOH fusing sample, with the sample after the hot deionized water leaching fusion, add the total ionic strength adjustment buffer degree and regulate buffer solution, record potential value with fluoride ion selective electrode, by checking in fluorinion concentration logarithm value, by formula F on the calibration curve
-(V * C) ÷ G calculates fluorinion concentration to %=" (V * C * 10) ÷ (G * 1000) " * 100=, in the formula; V---test portion is measured the volume of solution, unit milliliter (ml); The G-sample mass, unit gram (g); C-is by the logarithm value of the fluorinion concentration that checks on the calibration curve.
2, the measuring method of content of fluoride ion in the glass according to claim 1 is characterized in that: described contrast electrode adopts saturated calomel electrode or silver chloride electrode.
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|---|---|---|---|
| CN 200710069261 CN101078709A (en) | 2007-06-12 | 2007-06-12 | Glass fluorinion content measuring method |
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|---|---|---|---|
| CN 200710069261 CN101078709A (en) | 2007-06-12 | 2007-06-12 | Glass fluorinion content measuring method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104730139A (en) * | 2015-03-31 | 2015-06-24 | 清华大学 | Method for analyzing fluorine ion concentration under radioactive condition |
| CN105548280A (en) * | 2015-12-30 | 2016-05-04 | 东旭科技集团有限公司 | Method for determining uniformity of mixed batch for alkali-free glass and method for preparing mixed batch |
| CN105651851A (en) * | 2015-12-29 | 2016-06-08 | 中核北方核燃料元件有限公司 | Measuring method of fluorine content in thorium tetrafluoride |
| CN106442663A (en) * | 2016-11-30 | 2017-02-22 | 江西洪都航空工业集团有限责任公司 | Analysis method for hydrofluoric acid content in pickling solution |
| 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 |
| CN107192629A (en) * | 2017-04-27 | 2017-09-22 | 甘肃东兴铝业有限公司 | A kind of ion regulating agent and its application in aluminum fluoride in fluorine content determination method |
| CN107271530A (en) * | 2017-07-17 | 2017-10-20 | 云南云天化股份有限公司 | A kind of method of Oil repellent in fluorine-containing organic solvent of Accurate Determining |
| CN107727715A (en) * | 2017-09-12 | 2018-02-23 | 河南中源化学股份有限公司 | A kind of content of fluoride ion assay method of soda ash product and bittern |
| CN109813783A (en) * | 2019-03-28 | 2019-05-28 | 山东省产品质量检验研究院 | A kind of detection method improving wire and cable fluorine content measurement precision |
| CN111337558A (en) * | 2020-04-06 | 2020-06-26 | 东莞正大康地饲料有限公司 | Method for measuring sodium content in feed by using ion selective electrode |
| CN111505153A (en) * | 2020-05-06 | 2020-08-07 | 连云港海关综合技术中心 | Method for measuring fluorine and chlorine in high-silicon silver concentrate |
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2007
- 2007-06-12 CN CN 200710069261 patent/CN101078709A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104730139A (en) * | 2015-03-31 | 2015-06-24 | 清华大学 | Method for analyzing fluorine ion concentration under radioactive condition |
| CN104730139B (en) * | 2015-03-31 | 2017-06-30 | 清华大学 | The analysis method of fluorinion concentration under a kind of radioactivity |
| CN105651851A (en) * | 2015-12-29 | 2016-06-08 | 中核北方核燃料元件有限公司 | Measuring method of fluorine content in thorium tetrafluoride |
| CN105651851B (en) * | 2015-12-29 | 2018-07-27 | 中核北方核燃料元件有限公司 | The assay method of fluorine content in a kind of thorium tetrafluoride |
| CN105548280B (en) * | 2015-12-30 | 2018-06-08 | 东旭科技集团有限公司 | The method for measuring the uniformity and deployment and conjugation material of alkali-free glass batch |
| CN105548280A (en) * | 2015-12-30 | 2016-05-04 | 东旭科技集团有限公司 | Method for determining uniformity of mixed batch for alkali-free glass and method for preparing mixed batch |
| 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 |
| CN106442663A (en) * | 2016-11-30 | 2017-02-22 | 江西洪都航空工业集团有限责任公司 | Analysis method for hydrofluoric acid content in pickling solution |
| CN107192629A (en) * | 2017-04-27 | 2017-09-22 | 甘肃东兴铝业有限公司 | A kind of ion regulating agent and its application in aluminum fluoride in fluorine content determination method |
| CN107271530A (en) * | 2017-07-17 | 2017-10-20 | 云南云天化股份有限公司 | A kind of method of Oil repellent in fluorine-containing organic solvent of Accurate Determining |
| CN107727715A (en) * | 2017-09-12 | 2018-02-23 | 河南中源化学股份有限公司 | A kind of content of fluoride ion assay method of soda ash product and bittern |
| CN109813783A (en) * | 2019-03-28 | 2019-05-28 | 山东省产品质量检验研究院 | A kind of detection method improving wire and cable fluorine content measurement precision |
| CN111337558A (en) * | 2020-04-06 | 2020-06-26 | 东莞正大康地饲料有限公司 | Method for measuring sodium content in feed by using ion selective electrode |
| CN111337558B (en) * | 2020-04-06 | 2023-03-28 | 正大康地农牧集团有限公司 | Method for measuring sodium content in feed by using ion selective electrode |
| CN111505153A (en) * | 2020-05-06 | 2020-08-07 | 连云港海关综合技术中心 | Method for measuring fluorine and chlorine in high-silicon silver concentrate |
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