CN109813783A - A kind of detection method improving wire and cable fluorine content measurement precision - Google Patents
A kind of detection method improving wire and cable fluorine content measurement precision Download PDFInfo
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- CN109813783A CN109813783A CN201910240494.3A CN201910240494A CN109813783A CN 109813783 A CN109813783 A CN 109813783A CN 201910240494 A CN201910240494 A CN 201910240494A CN 109813783 A CN109813783 A CN 109813783A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 49
- 239000011737 fluorine Substances 0.000 title claims abstract description 49
- 238000001514 detection method Methods 0.000 title claims abstract description 28
- 238000005259 measurement Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 239000000872 buffer Substances 0.000 claims abstract description 8
- 239000000779 smoke Substances 0.000 claims abstract description 7
- 238000002485 combustion reaction Methods 0.000 claims abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000008595 infiltration Effects 0.000 claims abstract description 3
- 238000001764 infiltration Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 112
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 65
- 239000007788 liquid Substances 0.000 claims description 20
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 13
- 239000012490 blank solution Substances 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 3
- 150000004683 dihydrates Chemical class 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012556 adjustment buffer Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 241001411320 Eriogonum inflatum Species 0.000 description 6
- 241000208125 Nicotiana Species 0.000 description 6
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229940053652 fluorinse Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MZQZQKZKTGRQCG-UHFFFAOYSA-J thorium tetrafluoride Chemical compound F[Th](F)(F)F MZQZQKZKTGRQCG-UHFFFAOYSA-J 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002028 dodecanols Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 halogen flame-retardant series Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to a kind of detection methods for improving wire and cable fluorine content measurement precision, include the following steps: that (1) takes quantitative sample, and by sample comminution, sample powder is made；(2) sample powder is mixed into infiltration with dodecanol, it is placed on filter paper, full combustion under the conditions of closed, pure oxygen, with sodium hydroxide solution adsorbing smoke, then it will be mixed with buffer with the solution after the remnants and adsorbing smoke after burning, distilled water constant volume；(3) fluorinion concentration gradient solution is prepared respectively, then draws concentration curve, obtains fitting equation；(4) fluorine content in sample is calculated according to formula.The precision of wire cable insulating, sheath and the detection of filler fluorine content is greatly improved by the way of burning sample, and by optimizing relevant testing conditions in the present invention, more existing conventional detection mode, it is easy to implement, and testing cost is low, is convenient for large-scale promotion application.
Description
Technical field
The present invention relates to a kind of detection methods for improving wire and cable fluorine content measurement precision, belong to chemical detection technique neck
Domain.
Background technique
It being shown according to many scientific researches, halogen-system fire retardant has become the pollutant spread everywhere in surroundings,
The fire retardant do not simply fail to recycling use, and burning with heating process in can discharge harmful substance, to human immune system,
All there is far-reaching influence in endocrine system, reproduction and development and environmental pollution.In national standard and professional standard, electric wire electricity
Cable is not recommended mostly to use halogen-system fire retardant in fire-retardant class product.But in reality, many wire and cable enterprises hinder to improve
Performance and cost performance are fired, still uses and contains halogen-system fire retardant.
The one kind of fluorine element as halogen, detection value is up to 0.1% in low-smoke non-halogen flame-retardant series wire and cable.And
In the detection of the fluorine content of wire cable insulating, sheath and filler, general there are two types of detection methods, first is that fluoride ion selects
Electrode method is selected, another kind is alizarin fluoro-blue method.The most commonly used is the first, Fluoride ion selective electrode method.Such as Chinese patent literature
CN105651851A (application number 201511019875.7) discloses a kind of measuring method of fluorine content in thorium tetrafluoride, step
Rapid: (1) sample dissolves；(2) elimination of aluminium element interference；(3) standard addition method measures.The present invention has been successfully established ion selection
The detection method of fluorine content in property determination of electrode thorium tetrafluoride, using hydrochloric acid-alchlor and nitric acid solution dissolved samples,
Then the fluorine element in solution is measured with fluorescence spectrophotometric method.Utilize the experiment enumerated in technical solution of the present invention
Condition can accurately measure the content of fluorine in thorium tetrafluoride, quoted accurate detection data, effectively cooperated research and production
It carries out.
But with regard to the detection method can not suitable for wire and cable fluorine element detection, mainly due to the sample of wire and cable
Product are not readily dissolved in above-mentioned lysate；And other modes are used, due to the drafting of standard solution curve and the ignition method of sample
The problem of, cause measurement accuracy not high.Therefore, a kind of method for finding raising wire and cable fluorine content measurement precision is current is somebody's turn to do
Field problem in the urgent need to address.
Summary of the invention
In view of the deficiencies of the prior art, the present invention proposes a kind of method for drafting of new standard solution curve and the points of sample
Burning method, and then wire and cable fluorine content measurement precision is improved, to meet the accuracy requirement of inspection and scientific research.
Realize the technical solution of the object of the invention:
A kind of detection method improving wire and cable fluorine content measurement precision, includes the following steps:
(1) quantitative sample is taken, by sample comminution, sample powder is made；
(2) sample powder made from step (1) is mixed into infiltration with dodecanol, be placed on filter paper, in closed, pure oxygen item
Full combustion under part then will be with after the remnants and adsorbing smoke after buffer and burning with sodium hydroxide solution adsorbing smoke
Solution mixing, distilled water constant volume；
(3) compound concentration is 1 × 10 respectively-1mol/L、1×10-2mol/L、1×10-3mol/L、5×10-4mol/L、2×
10-4mol/L、1×10-4mol/L、1×10-5mol/L、1×10-6The fluorinion concentration gradient solution of mol/L；Successively with fluorine from
Sub-electrode measures the potential value of above-mentioned fluorinion concentration gradient solution, then draws concentration curve, and it is as follows to obtain fitting equation:
Y=a+bA
In formula: Y is the potential value of measurement, and a is zero potential value, and b is electrode slope, and A is the logarithm of sample fluorine content；
(4) blank solution theoretical value X is calculated separately according to the following formula0With sample to be tested theoretical value X, formula is as follows:
In formula: Y0For the potential value of blank solution, a is zero potential value, and b is electrode slope；
X=10A
In formula: A is the logarithm of sample fluorine content；
And sample concentration C is calculated according to the following formula:
In formula: m is sample mass；
According to above-mentioned sample concentration C calculate sample in fluorine content to get.
It is preferred according to the present invention, in the step (1), take quantitative sample that precision is used to be claimed for the balance of 0.1mg
Amount.
Preferred according to the present invention, in the step (1), the partial size of sample powder is not more than 500 μm.
It is preferred according to the present invention, in the step (2), the mass volume ratio of sample powder and dodecanol is 0.15~
0.3g/ml。
Preferred according to the present invention, in the step (2), the mode that sample is lighted is to light every bottle laser, laser lamp
The minimum 5000mw of power.
Preferred according to the present invention, in the step (2), concentration of sodium hydroxide solution is 0.35~0.6mol/L；Into one
Step is preferred, in the step (2), concentration of sodium hydroxide solution 0.5mol/L.
Preferred according to the present invention, in the step (2), sodium hydroxide solution dosage is 5~6mg/ml.
Preferred according to the present invention, in the step (2), the buffer is that total ionic strength adjusts buffer solution, often
It is as follows to rise component:
Sodium Citrate, usp, Dihydrate Powder (analysis is pure) 58.8000g, sodium nitrate 85.000g (analysis is pure), HCl adjusts pH to 5~6, water
It is settled to 1000mL.
Preferred according to the present invention, in the step (3), fluorinion concentration gradient solution is prepared using following steps:
It takes 4.2000g to analyze pure sodium fluoride, is dissolved in distilled water, is settled to 1000mL, this solution is 1 × 10-1Mol/L's
Fluoride solution；Take the 1 × 10 of 100mL-1The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10-2mol/L
Fluoride solution；Take the 1 × 10 of 100mL-2The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10- 3The fluoride solution of mol/L；Take the 1 × 10 of 100mL-3The fluoride solution of mol/L, is diluted to 1000mL, this solution be 1 ×
10-4The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 200mL, this solution is 5
×10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 500mL, this solution is
2×10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 1000mL, this solution
It is 1 × 10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-5The fluoride solution of mol/L, is diluted to 1000mL, this is molten
Liquid is 1 × 10-6The fluoride solution of mol/L.
Beneficial effect
Electric wire electricity is greatly improved by the way of burning sample, and by optimizing relevant testing conditions in the present invention
The precision of cable insulation, sheath and the detection of filler fluorine content, more existing conventional detection mode is easy to implement, and testing cost is low,
Convenient for large-scale promotion application.
Detailed description of the invention
Fig. 1 is according to embodiment 1 according to the analogous diagram of the data calculating and plotting of measurement；
Fig. 2 is according to embodiment 2 according to the analogous diagram of the data calculating and plotting of measurement；
Specific embodiment
Technical solution of the present invention is further elaborated combined with specific embodiments below, but institute's protection scope of the present invention
It is without being limited thereto.
Test sample is the wire cable insulating using the known fluorinated volume 0.05% of preparation in embodiment 1 and comparative example 1
Standard sample, the preparation method of sample such as: weigh known not fluorine-containing wire cable insulating sample 37.958g, shredded to
Partial size weighs 0.0420g and analyzes pure sodium fluoride, be stirred for uniformly less than 500 μm.
Buffer in embodiment is that total ionic strength adjusts buffer solution, and every liter of component is as follows:
Sodium Citrate, usp, Dihydrate Powder (analysis is pure) 58.8000g, sodium nitrate 85.000g (analysis is pure), HCl adjusts pH to 5~6, water
It is settled to 1000mL.
Laser lamp power used in embodiment is 5000mw or more.
Embodiment 1
The standard sample 30.0mg that fluorinated volume 0.05% is accurately weighed with electronic balance, it is with knife or scissors that its is fine crushing to grain
Diameter is less than 500 μm.
The sample handled well is put into the filter paper of tobacco pipe shape, tobacco pipe shape filter paper is put into the platinum filament lower end of bottle stopper welding,
Add 3 drop dodecanols on sample, the sodium hydroxide solution of dropwise addition 5mL 0.5mol/L is to bottom of bottle as absorbefacient.
With clean sebific duct in Molotov cocktail exit, sebific duct is inserted into Molotov cocktail absorbing liquid upper end, rapidly leads to oxygen 2min, and
Sebific duct is gradually carefully moved into bottleneck by absorbing liquid upper end, sebific duct not touch bottle wall and liquid level, and sebific duct removal moves back remote to elsewhere
From oxygen cylinder, bottleneck is covered with surface plate immediately later.It will be rapidly inserted into Molotov cocktail with the bottle stopper of sample, by tight bottle stopper,
And with a small amount of water seal bottleneck.
It is directed at tobacco pipe shape filter paper using laser lamp, laser lamp is opened, lights sample, after all burnt, Molotov cocktail is rocked, allows
Smog is settled and is absorbed by liquid absorption.In oxygen cylinder material and liquid move into a 50mL volumetric flask in, then to
5mL buffer reagent is added in aforesaid liquid, is diluted to graduation mark with distilled water.
It takes 4.2000g to analyze pure sodium fluoride, is dissolved in distilled water, is settled to 1000mL, this solution is 1 × 10-1Mol/L's
Fluoride solution；Take the 1 × 10 of 100mL-1The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10-2mol/L
Fluoride solution；Take the 1 × 10 of 100mL-2The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10- 3The fluoride solution of mol/L；Take the 1 × 10 of 100mL-3The fluoride solution of mol/L, is diluted to 1000mL, this solution be 1 ×
10-4The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 200mL, this solution is 5
×10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 500mL, this solution is
2×10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 1000mL, this solution
It is 1 × 10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-5The fluoride solution of mol/L, is diluted to 1000mL, this is molten
Liquid is 1 × 10-6The fluoride solution of mol/L.
Each 100mL of the Fluorinse of various concentration is taken, its potential value is successively measured with fluoride ion electrode, and record data
The results are shown in Table 1:
Table 1
| Concentration mol/L | 1×10-6 | 1×10-5 | 2×10-5 | 5×10-5 | 1×10-4 | 1×10-3 | 1×10-2 | 1×10-1 |
| Fluorine content x μ g | 1.9 | 19 | 38 | 95 | 190 | 1900 | 19000 | 190000 |
| The logarithm A of fluorine content | 0.2788 | 1.2788 | 1.5798 | 1.9777 | 2.2788 | 3.2788 | 4.2788 | 5.2788 |
| Potential value Y mV | -296.2 | -280.1 | -265.4 | -251.2 | -230.7 | -178.6 | -122.5 | -64.4 |
According to nernst equation, Yx=Y0+S×log(CX+Cb)
In formula, YxThe equilibrium potential of~sample to be tested；
Y0The potential value of~blank solution；
S~electrode slope；
CXThe concentration value of~sample to be tested；
Cb~blank concentration value
Simplify Nernst equation, Y=a+bA.
Curve is drawn according to the data of measurement, calculates its curvilinear equation, analogous diagram and related coefficient.Its curvilinear equation uses
MATLAB is calculated, and formula is specifically shown in down:
A=[log10 (1.9), log10 (19), log10 (38), log10 (95), log10 (190), log10 (1900),
log10(19000),log10(190000)]；
B=[- 296.2, -280.1, -265.4, -251.2, -230.7, -178.6, -122.5, -64.4]；
P=polyfit (A, b, 1)
A1=0:0.5:6；
B1=polyval (p, A1)；
plot(A,b,'*r',A1,b1,'-b')
corrcoef(A,b)
Calculated result: a=-335.6058, b=49.2212, correlation coefficient r=0.9878, analogous diagram are as shown in Figure 1.
Its fitting equation Y=a+bA, according to the calculated a of MATLAB, b value obtains linear equation in two unknowns Y=-
335.6058+49.2212A
(4) the potential value Y for measuring 50mL absorbing liquid sample is -276.6mV, and pair of its fluorine content is calculated according to curvilinear equation
Numerical value A,
Its formula are as follows:
According to the logarithm A=1.1990 of its fluorine content, its fluorine content X=15.812 is found out；
Measure the potential value Y of 50mL blank solution0For -322.4mV, the logarithm A of its fluorine content is calculated according to curvilinear equation0
=0.2633, calculate blank solution theoretical value X0=1.834；
Sample fluorine content calculation formula is
Above-mentioned data are substituted into, calculating and obtaining sample fluorine content is C=0.0466%.
Embodiment 2
The standard sample 25.0mg that fluorinated volume 0.05% is accurately weighed with electronic balance, it is with knife or scissors that its is fine crushing to grain
Diameter is less than 1000 μm.
The sample handled well is put into the filter paper of tobacco pipe shape, tobacco pipe shape filter paper is put into the platinum filament lower end of bottle stopper welding,
Add 3 drop dodecanols on sample, the sodium hydroxide solution of dropwise addition 5mL 0.5mol/L is to bottom of bottle as absorbefacient.
With clean sebific duct in Molotov cocktail exit, sebific duct is inserted into Molotov cocktail absorbing liquid upper end, rapidly leads to oxygen 2min, and
Sebific duct is gradually carefully moved into bottleneck by absorbing liquid upper end, sebific duct not touch bottle wall and liquid level, and sebific duct removal moves back remote to elsewhere
From oxygen cylinder, bottleneck is covered with surface plate immediately later.It will be rapidly inserted into Molotov cocktail with the bottle stopper of sample, by tight bottle stopper,
And with a small amount of water seal bottleneck.
It is directed at tobacco pipe shape filter paper using laser lamp, laser lamp is opened, lights sample, after all burnt, Molotov cocktail is rocked, allows
Smog is settled and is absorbed by liquid absorption.In oxygen cylinder material and liquid move into a 50mL volumetric flask in, then to
5mL buffer reagent is added in aforesaid liquid, is diluted to graduation mark with distilled water.
It takes 0.4200g to analyze pure sodium fluoride, is dissolved in distilled water, is settled to 100mL, this solution is 1 × 10-1Mol/L's
Fluoride solution；Take the 1 × 10 of 10mL-1The fluoride solution of mol/L, is diluted to 100mL, this solution is 1 × 10-2Mol/L's
Fluoride solution；Take the 1 × 10 of 10mL-2The fluoride solution of mol/L, is diluted to 100mL, this solution is 1 × 10-3Mol/L's
Fluoride solution；Take the 1 × 10 of 10mL-3The fluoride solution of mol/L, is diluted to 100mL, this solution is 1 × 10-4Mol/L's
Fluoride solution；Take the 1 × 10 of 50mL-4The fluoride solution of mol/L, is diluted to 100mL, this solution is 5 × 10-5Mol/L's
Fluoride solution；Take the 1 × 10 of 20mL-4The fluoride solution of mol/L, is diluted to 100mL, this solution is 2 × 10-5Mol/L's
Fluoride solution；Take the 1 × 10 of 10mL-4The fluoride solution of mol/L, is diluted to 100mL, this solution is 1 × 10-5Mol/L's
Fluoride solution；Take the 1 × 10 of 10mL-5The fluoride solution of mol/L, is diluted to 100mL, this solution is 1 × 10-6Mol/L's
Fluoride solution.
The 100mL Fluorinse potential value of various concentration is successively measured with fluoride ion electrode, and records data result such as
Shown in table 2:
Table 2
| Concentration mol/L | 1×10-6 | 1×10-5 | 2×10-5 | 5×10-5 | 1×10-4 | 1×10-3 | 1×10-2 | 1×10-1 |
| Fluorine content x μ g | 1.9 | 19 | 38 | 95 | 190 | 1900 | 19000 | 190000 |
| The logarithm A of fluorine content | 0.2788 | 1.2788 | 1.5798 | 1.9777 | 2.2788 | 3.2788 | 4.2788 | 5.2788 |
| Potential value Y mV | -295.7 | -278.6 | -264.7 | -251.0 | -229.6 | -178.5 | -123.1 | -64.8 |
According to nernst equation, Yx=Y0+S×log(CX+Cb)
In formula, YxThe equilibrium potential of~sample to be tested；
Y0The potential value of~blank solution；
S~electrode slope；
CXThe concentration value of~sample to be tested；
Cb~blank concentration value
Simplify Nernst equation, Y=a+bA.
Curve is drawn according to the data of measurement, calculates its curvilinear equation, analogous diagram and related coefficient.Its curvilinear equation uses
MATLAB is calculated, and formula is specifically shown in down:
A=[log10 (1.9), log10 (19), log10 (38), log10 (95), log10 (190), log10 (1900),
log10(19000),log10(190000)]；
B=[- 295.7, -278.6, -264.7, -251.0, -229.6, -178.5, -123.1, -64.8]；
P=polyfit (A, b, 1)
A1=0:0.5:6；
B1=polyval (p, A1)；
plot(A,b,'*r',A1,b1,'-b')
corrcoef(A,b)
Calculated result: a=-334.4066, b=48.9002, correlation coefficient r=0.9881, analogous diagram are as shown in Figure 2；
Its fitting equation Y=a+bA, according to the calculated a of MATLAB, b value show that linear equation in two unknowns is Y=-
334.4066+48.9002A
(4) the potential value Y for measuring 50mL absorbing liquid sample is -279.7mV, and pair of its fluorine content is calculated according to curvilinear equation
Numerical value A,
Its formula are as follows:
According to the logarithm A=1.1187 of its fluorine content, its fluorine content X=13.1444 is found out；
Measure the potential value Y of 50mL blank solution0For -322.4mV, the logarithm A of its fluorine content is calculated according to curvilinear equation
=0.2633, calculate blank solution theoretical value X0=1.834；
Sample fluorine content calculation formula is
Above-mentioned data are substituted into, calculating and obtaining sample fluorine content is C=0.0452%.
Comparative example 1
The standard sample 30.0mg of fluorinated volume 0.05% is accurately weighed with electronic balance.
Specific sample handling processes after lighting sample outside Molotov cocktail, move into combustion referring to embodiment 1, ignition way
Flask.The drafting of its standard curve, prepares 1 × 10 respectively-1mol/L、1×10-2mol/L、1×10-3mol/L、1×10-4mol/
L、1×10-5mol/L、1×10-6The fluoride solution of mol/L concentration.
Each 100mL of the Fluorinse of above-mentioned various concentration is taken, its potential value is successively measured with fluoride ion electrode, and record
Data result is as shown in table 3:
Table 3
| Concentration mol/L | 1×10-6 | 1×10-5 | 1×10-4 | 1×10-3 | 1×10-2 | 1×10-1 |
| Fluorine content x μ g | 1.9 | 19 | 190 | 1900 | 19000 | 190000 |
| The logarithm A of fluorine content | 0.2788 | 1.2788 | 2.2788 | 3.2788 | 4.2788 | 5.2788 |
| Potential value Y mV | -296.4 | -281.3 | -233.4 | -178.4 | -124.2 | -65.7 |
Fitting equation Y=-329.9310+47.9943A of its binary
The potential value for measuring 50mL absorbing liquid sample is -274.7mV, calculates referring to calculation formula in embodiment 1 and obtains sample
Product fluorine content is C=0.0411%.Its measurement result is than embodiment 1 low 11.8%.
Comparative example 2
The standard sample 30.0mg of fluorinated volume 0.05% is accurately weighed with electronic balance.
Specific sample handling processes after lighting sample outside Molotov cocktail, move into combustion referring to embodiment 1, ignition way
Flask.The drafting of its standard curve, referring to fitting equation Y=-335.6058+49.2212A of its binary of embodiment 1
The potential value for measuring 50mL absorbing liquid sample is -278.2mV, calculates referring to calculation formula in embodiment 1 and obtains sample
Product fluorine content is C=0.0428%.Its measurement result is than embodiment 1 low 8.2%.
Comparative example 3
The standard sample 30.0mg of fluorinated volume 0.05% is accurately weighed with electronic balance.
Specific sample handling processes and ignition way are referring to embodiment 1.The drafting of its standard curve, referring to comparative example 1 its
Fitting equation Y=-329.9310+47.9943A of binary
The potential value for measuring 50mL absorbing liquid sample is -277.2mV, calculates referring to calculation formula in embodiment 1 and obtains sample
Product fluorine content is C=0.0451%.Its measurement result is than embodiment 1 low 3.2%.
Interpretation of result
It is analyzed by the Comparative result of embodiment 1 and comparative example 1-3 as can be seen that when detecting mark of the fluorinated volume for 0.05%
When quasi- sample, the detection knot closer to true value only can be just obtained using the sample handling characteristics of the application and data processing method
Fruit, and it is changed to other sample handling characteristics and data processing method, data accuracy can significantly reduce.
Claims (10)
1. a kind of detection method for improving wire and cable fluorine content measurement precision, which comprises the steps of:
(1) quantitative sample is taken, by sample comminution, sample powder is made；
(2) sample powder made from step (1) is mixed into infiltration with dodecanol, be placed on filter paper, under the conditions of closed, pure oxygen
Full combustion, with sodium hydroxide solution adsorbing smoke, then by with buffer with it is molten after the remnants and adsorbing smoke after burning
Liquid mixing, distilled water constant volume；
(3) compound concentration is 1 × 10 respectively-1mol/L、1×10-2mol/L、1×10-3mol/L、5×10-4mol/L、2×10- 4mol/L、1×10-4mol/L、1×10-5mol/L、1×10-6The fluorinion concentration gradient solution of mol/L；Successively use fluorine ion
Then the potential value of the above-mentioned fluorinion concentration gradient solution of electrode measurement draws concentration curve, it is as follows to obtain fitting equation:
Y=a+bA
In formula: Y is the potential value of measurement, and a is zero potential value, and b is electrode slope, and A is the logarithm of sample fluorine content；
(4) blank solution theoretical value X is calculated separately according to the following formula0With sample to be tested theoretical value X, formula is as follows:
In formula: Y0For the potential value of blank solution, a is zero potential value, and b is electrode slope；
X=10A
In formula: A is the logarithm of sample fluorine content；
And sample concentration C is calculated according to the following formula:
In formula: m is sample mass；
According to above-mentioned sample concentration C calculate sample in fluorine content to get.
2. detection method as described in claim 1, which is characterized in that in the step (1), take quantitative sample use precision for
The balance of 0.1mg is weighed.
3. detection method as described in claim 1, which is characterized in that in the step (1), the partial size of sample powder is not more than
500μm。
4. detection method as described in claim 1, which is characterized in that in the step (2), sample powder and dodecanol
Mass volume ratio is 0.15~0.3g/ml.
5. detection method as described in claim 1, which is characterized in that in the step (2), the mode that sample is lighted is every bottle
Laser is lighted, the minimum 5000mw of the power of laser lamp.
6. detection method as described in claim 1, which is characterized in that in the step (2), concentration of sodium hydroxide solution is
0.35~0.6mol/L.
7. detection method as claimed in claim 6, which is characterized in that in the step (2), concentration of sodium hydroxide solution is
0.5mol/L。
8. detection method as described in claim 1, which is characterized in that in the step (2), sodium hydroxide solution dosage is 5
~6mg/ml.
9. detection method as described in claim 1, which is characterized in that in the step (2), the buffer is total ionic strength adjustment buffer
Degree adjusts buffer solution, and every liter of component is as follows:
Sodium Citrate, usp, Dihydrate Powder 58.8000g, sodium nitrate 85.000g, HCl adjust pH to 5~6, and water is settled to 1000mL.
10. detection method as described in claim 1, which is characterized in that in the step (3), fluorinion concentration gradient solution
It is prepared using following steps:
It takes 4.2000g to analyze pure sodium fluoride, is dissolved in distilled water, is settled to 1000mL, this solution is 1 × 10-1The fluorine of mol/L from
Sub- solution；Take the 1 × 10 of 100mL-1The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10-2The fluorine of mol/L
Solion；Take the 1 × 10 of 100mL-2The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10-3Mol/L's
Fluoride solution；Take the 1 × 10 of 100mL-3The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1 × 10-4mol/L
Fluoride solution；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 200mL, this solution is 5 × 10-5mol/
The fluoride solution of L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 500mL, this solution is 2 × 10- 5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-4The fluoride solution of mol/L, is diluted to 1000mL, this solution be 1 ×
10-5The fluoride solution of mol/L；Take the 1 × 10 of 100mL-5The fluoride solution of mol/L, is diluted to 1000mL, this solution is 1
×10-6The fluoride solution of mol/L.
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