CN110133067A - The measuring method of fluorine in a kind of calcirm-fluoride - Google Patents
The measuring method of fluorine in a kind of calcirm-fluoride Download PDFInfo
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- CN110133067A CN110133067A CN201910518382.XA CN201910518382A CN110133067A CN 110133067 A CN110133067 A CN 110133067A CN 201910518382 A CN201910518382 A CN 201910518382A CN 110133067 A CN110133067 A CN 110133067A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 38
- 239000011737 fluorine Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000523 sample Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000012488 sample solution Substances 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000872 buffer Substances 0.000 claims description 10
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 7
- 239000012086 standard solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- -1 bromine cresols Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 10
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 239000000037 vitreous enamel Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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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 Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of measuring methods of fluorine in calcirm-fluoride, the specific steps are as follows: in Muffle furnace, calcirm-fluoride is decomposed in silver crucible under the action of potassium hydroxide；Slag in crucible is leached with hot water, diluted hydrochloric acid dissolution to it is limpid, be filtered, washed and constant volume；Dividing takes sample solution at 25 DEG C using saturated calomel electrode as reference electrode, the fluorine in solution is measured with fluoride ion selective electrode, so as to find out the content of fluorine in calcirm-fluoride sample.This method advantage is: analysis is simple and efficient, as a result accurately and reliably.
Description
Technical field
The present invention relates to a kind of analysis test method, in particular to the measuring method of fluorine in a kind of calcirm-fluoride.
Background technique
Fluorine is one of element widely distributed in nature, mainly with CaF2Form exist, and be enriched in firefly extensively
In stone, rock phosphate in powder.CaF at present2It is mainly used for metallurgy, chemical industry and the big industry of building materials three, but with fluorination work comprehensive utilization technique
Develop in depth and breadth, CaF2Application in other industry is also constantly being expanded, and strategic position and significance also become more
Exacerbation is wanted.In metallurgical industry, CaF2With the fusing point that can reduce infusibility substance, promotes clinker flowing, keep slag and metal fine
The features such as separating, desulfurization, dephosphorization in smelting process, enhancing the forging property and tensile strength of metal.Therefore, it is as fluxing agent
It is widely used in smelting iron and steel and ferroalloy production, changes iron process and non-ferrous metal metallurgy.In building materials industry, CaF2It is wide
General to be applied in the productions of products such as glass, ceramics, cement, dosage accounts for the 2nd in China, wherein in glass industry,
CaF2It is added as fluxing agent, opacifier, it can promote the fusing of glass raw material；In manufacture of cement, CaF2As mineralizer plus
Enter.CaF2The sintering temperature of furnace charge can be reduced, clinker liquid phase viscosity when reducing fuel consumption, while can also enhance sintering promotes
The formation of tricalcium silicate；In ceramic industry, CaF2It is mainly used as enamel, it can be played in enamel production process helps color and help
Molten effect；CaF2It is also applied in porcelain enamel industry and cast stone production, but either in metallurgy industry, building material industry, can all exist
High-temperature lower part is divided calcirm-fluoride to decompose and form gaseous fluorides and is escaped, and not only causes the pollution of environment, also will form corrosivity
Stronger hydrofluoric acid and corrode equipment, reduce the service life of production equipment.Therefore, it realizes to various source different content fluorine
Precise determination, strict control CaF2Additional amount then becomes most important.
However up to the present, the measurement of fluorine is to survey after calcium arbitration law measures calcium content to convert by calcirm-fluoride in calcirm-fluoride
Gained, method is cumbersome, and time-consuming, and this method is on the basis of carrying out pretreated to sample with flux potassium hydroxide, knot
Fluoride ion selective electrode method is closed, has accomplished the simple and efficient Accurate Determining of fluorine content in calcirm-fluoride.
Summary of the invention
The purpose of the present invention is to provide a kind of measuring methods of fluorine in calcirm-fluoride, it is characterised in that uses flux potassium hydroxide
On the basis of pretreated to sample progress, in conjunction with fluoride ion selective electrode method, accomplish that the simplicity of fluorine content in calcirm-fluoride is fast
Prompt Accurate Determining.
Realize that the work step of the object of the invention measuring method is as follows:
(1) sample ore to be determined is crushed, ground, granularity≤200 mesh.
(2) above-mentioned sample ore is placed in Muffle furnace, under the action of flux potassium hydroxide, is decomposed in silver crucible.
(3) slag in crucible is leached with hot water, diluted hydrochloric acid dissolution to it is limpid, be filtered, washed and constant volume.
(4) it is divided to and takes sample solution that five drop citric acid-sodium citrate buffers and two drop bromines are added in 50ml volumetric flask
The green indicator solution of cresols, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5)
Solution is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water,
It is poured into dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, stirred in the constant speed of magnetic stirring apparatus
Under, potential value when balance is measured, E1 is recorded as.Addition 1mg/ml fluorine standard solution 0.5ml measures its potential value again and is recorded as
E2。
Fluorine content (w) is calculated as follows
In formula: m1- addition fluorine standard solution is equivalent to fluorine quality, g；
59.16-with the theoretical value of this special slope of the energy that measures of experiment (59.16 at 25 DEG C)；
M-absorption sample solution is equivalent to the quality of sample, g；
The potential difference (i.e. E2-E1) that Δ E-front and back measures twice, mV；
Arclog-antilogarithm.
All calcirm-fluoride arbitration law first measures calcirm-fluoride to fluorine measuring method in a conventional manner always in calcirm-fluoride so far
Amount, finally converse fluorine content, but existing chemical method surveys calcirm-fluoride and operates shadow relatively complicated, vulnerable to interfering ion
Ring, result that time-consuming inaccuracy, this method using flux potassium hydroxide to sample progress it is pretreated on the basis of, in conjunction with fluorine ion
Electrodes selective method has accomplished the measurement of fluorine content in calcirm-fluoride, the advantage is that time-consuming short, process is simple and direct, as a result accurately may be used
It leans on.
Specific embodiment
Example 1
It weighs 0.3999g 1# calcirm-fluoride (granularity≤200 mesh) and is accurate to 0.0001, (doing reagent blank with sample), which is placed in, to be filled
It in the silver crucible of 6.0052 g potassium hydroxide, covers crucible and stays a gap, be placed in high temperature and decomposed 8 minutes at 680 DEG C, take out
Crucible and rotate it is slightly cold, be placed in 500ml beaker, be added 20~50ml hot water, cap upper surface ware, falls off to fusant immediately
Afterwards, crucible and lid (being cleaned with the glass bar with rubber tip) are cleaned with hot water and a small amount of 1:5 hydrochloric acid solution.It drips under constant stirring
Add hydrochloric acid solution until solution is limpid.Beaker is removed, rinses surface plate and wall of cup with deionized water, it is cooling, it is dry with Medium speed filter paper
It filters and is washed with deionized acid non-soluble substance 5 times or more, collect filtrate and cleaning solution is settled to 500mL.
Take 10ml sample solution that five drop citric acid-sodium citrate buffers and two drop bromine first are added in 50ml volumetric flask
The green indicator solution of phenol, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5) molten
Liquid is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, inclines
Enter in dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus,
Potential value when balance is measured, is recorded as -158.Be added 1mg/ml fluorine standard solution 0.5ml measure again its potential value be recorded as-
150。
Fluorine content (w) is calculated as follows
=17.11%
Example 2
It weighs 0.2009g 2# calcirm-fluoride (granularity≤200 mesh) and is accurate to 0.0001, (doing reagent blank with sample), which is placed in, to be filled
It in the silver crucible of 4.0031 g potassium hydroxide, covers crucible and stays a gap, be placed in high temperature and decomposed 10 minutes at 700 DEG C, taken
Out crucible and rotate it is slightly cold, be placed in 500ml beaker, be added 20~50ml hot water, cap upper surface ware, falls off to fusant immediately
Afterwards, crucible and lid (being cleaned with the glass bar with rubber tip) are cleaned with hot water and a small amount of 1:3 hydrochloric acid solution.It drips under constant stirring
Add hydrochloric acid solution until solution is limpid.Beaker is removed, rinses surface plate and wall of cup with deionized water, it is cooling, it is dry with Medium speed filter paper
It filters and is washed with deionized acid non-soluble substance 5 times or more, collect filtrate and cleaning solution is settled to 500mL.
Take 5ml sample solution that five drop citric acid-sodium citrate buffers and two drop bromine first are added in 50ml volumetric flask
The green indicator solution of phenol, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5) molten
Liquid is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, inclines
Enter in dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus,
Potential value when balance is measured, is recorded as -162.Be added 1mg/ml fluorine standard solution 0.5ml measure again its potential value be recorded as-
148。
Fluorine content (w) is calculated as follows
=34.41%
Example 3
It weighs 3# calcirm-fluoride 0.1005g (granularity≤200 mesh) and is accurate to 0.0001, (doing reagent blank with sample), which is placed in, to be filled
It in the silver crucible of 2.0052 g potassium hydroxide, covers crucible and stays a gap, be placed in high temperature and decomposed 15 minutes at 720 DEG C, taken
Out crucible and rotate it is slightly cold, be placed in 500ml beaker, be added 20~50ml hot water, cap upper surface ware, falls off to fusant immediately
Afterwards, crucible and lid (being cleaned with the glass bar with rubber tip) are cleaned with hot water and a small amount of 1:1 hydrochloric acid solution.Under constant stirring after
It is continuous that 1:1 hydrochloric acid solution is added dropwise until solution is limpid.Beaker is removed, rinses surface plate and wall of cup with deionized water, it is cooling, use middling speed
Filter Paper Dry is filtered and is washed with deionized acid non-soluble substance 5 times or more, collects filtrate and cleaning solution is settled to 500mL.
Take 5ml sample solution that five drop citric acid-sodium citrate buffers and two drop bromine first are added in 50ml volumetric flask
The green indicator solution of phenol, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then is adjusted with the nitric acid solution of (1+5) molten
Liquid is in yellow just.The citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, inclines
Enter in dry 50ml beaker, is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus,
Potential value when balance is measured, is recorded as -163.Be added 1mg/ml fluorine standard solution 0.5ml measure again its potential value be recorded as-
143。
Fluorine content (w) is calculated as follows
=42.23%
Fluorine content analyzes result in 1 calcirm-fluoride of table
| Embodiment | Different samples | Potential changing value | Fluorine content (%) | Theoretical value (%) | Relative error |
| 1 | Calcirm-fluoride 1# | 8 | 17.11 | 17.13 | 0.12% |
| 2 | Calcirm-fluoride 2# | 14 | 34.41 | 34.68 | 0.78% |
| 3 | Calcirm-fluoride 3# | 20 | 42.19 | 42.60 | 0.96% |
Illustrate: the theoretical value of calcirm-fluoride sample is converted after measuring fluorination calcium value by calcirm-fluoride arbitration law in table 1.
It can be seen from Table 1 that this analysis method is preferable for the measurement reproducibility of fluorine in different calcirm-fluoride, relative error
Between 0.12%~0.96%.
Claims (5)
1. the measuring method of fluorine in a kind of calcirm-fluoride, it is characterised in that key step is as follows:
(1) sample ore to be determined is crushed, ground, granularity≤200 mesh；
(2) above-mentioned sample ore is placed in Muffle furnace, under the action of flux potassium hydroxide, is decomposed in silver crucible；
(3) slag in crucible is leached with hot water, diluted hydrochloric acid dissolution to it is limpid, be filtered, washed and constant volume；
(4) it is divided to and takes sample solution that five drop citric acid-sodium citrate buffers and two drop bromine cresols are added in 50ml volumetric flask
Green indicator solution, is neutralized to that solution is blue with the sodium hydroxide solution of 200 g/L, then adjusts solution with the nitric acid solution of (1+5)
Just it is in yellow, the citric acid-sodium citrate buffer 20ml that pH value is 5 is added and is diluted to scale with deionized water, is poured into
In dry 50ml beaker, it is inserted into fluoride ion selective electrode and saturated calomel electrode, under the constant speed stirring of magnetic stirring apparatus, is surveyed
Potential value when must balance, is recorded as E1；
Addition 1mg/ml fluorine standard solution 0.5ml measures its potential value again and is recorded as E2；
Fluorine content (w) is calculated as follows:
In formula: m1- addition fluorine standard solution is equivalent to fluorine quality, g；
59.16-with the theoretical value of this special slope of the energy that measures of experiment (59.16 at 25 DEG C)；
M-absorption sample solution is equivalent to the quality of sample, g；
The potential difference (i.e. E2-E1) that Δ E-front and back measures twice, mV；
Arclog-antilogarithm.
2. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: accurately weigh calcirm-fluoride sample
0.1~0.8g of product, flux 2~10g of potassium hydroxide, is accurate to 0.0001g.
3. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: using potassium hydroxide to examination
Sample is decomposed, and decomposition temperature is 650~750 DEG C, the resolving time 8~15 minutes.
4. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: slag is soaked with hot water
Out, with 1:5~1:1 diluted hydrochloric acid dissolution to limpid.
5. the measuring method of fluorine in a kind of calcirm-fluoride according to claim 1, it is characterised in that: with flux potassium hydroxide
On the basis of pretreated to sample progress, in conjunction with fluoride ion selective electrode method, accomplish that the simplicity of fluorine content in calcirm-fluoride is quasi-
Really measurement.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113776904A (en) * | 2021-08-27 | 2021-12-10 | 柳州钢铁股份有限公司 | Method for measuring calcium fluoride in fluorite |
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|---|---|---|---|---|
| EP0125368A1 (en) * | 1983-12-05 | 1984-11-21 | Pharmacia ENI Diagnostics Inc. | A method of immunoassay detection by reaction-rate potentiometry using fluoride ion-selective electrode |
| CN108344789A (en) * | 2017-01-24 | 2018-07-31 | 华北理工大学 | A kind of method of fluorine content in measurement continuous casting covering slag |
| CN109596683A (en) * | 2018-11-05 | 2019-04-09 | 包头钢铁（集团）有限责任公司 | A method of fluorine content in measurement gypsum, silica |
-
2019
- 2019-06-15 CN CN201910518382.XA patent/CN110133067A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125368A1 (en) * | 1983-12-05 | 1984-11-21 | Pharmacia ENI Diagnostics Inc. | A method of immunoassay detection by reaction-rate potentiometry using fluoride ion-selective electrode |
| CN108344789A (en) * | 2017-01-24 | 2018-07-31 | 华北理工大学 | A kind of method of fluorine content in measurement continuous casting covering slag |
| CN109596683A (en) * | 2018-11-05 | 2019-04-09 | 包头钢铁（集团）有限责任公司 | A method of fluorine content in measurement gypsum, silica |
Non-Patent Citations (4)
| Title |
|---|
| 商检群: "《氟石检验》", 31 October 1978, 中国财政经济出版社 * |
| 李强 等: "氟离子选择电极法测定磷酸中的氟", 《磷肥与复肥》 * |
| 马列: "《化学检验（水泥）》", 30 November 2006, 中国建材工业出版社 * |
| 高德池: "氟离子选择电极法测定磷酸中氟含量", 《磷肥与复肥》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113776904A (en) * | 2021-08-27 | 2021-12-10 | 柳州钢铁股份有限公司 | Method for measuring calcium fluoride in fluorite |
| CN113776904B (en) * | 2021-08-27 | 2024-03-01 | 柳州钢铁股份有限公司 | Method for determining calcium fluoride in fluorite |
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Application publication date: 20190816 |