CN106841342B - A kind of mercury-nitric acid amino mercury reference electrode and its preparation method and application - Google Patents
A kind of mercury-nitric acid amino mercury reference electrode and its preparation method and application Download PDFInfo
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- CN106841342B CN106841342B CN201710204959.0A CN201710204959A CN106841342B CN 106841342 B CN106841342 B CN 106841342B CN 201710204959 A CN201710204959 A CN 201710204959A CN 106841342 B CN106841342 B CN 106841342B
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- -1 mercury-nitric acid amino mercury Chemical compound 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 37
- 238000011049 filling Methods 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- 229910017604 nitric acid Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YUCJFSWWUVRFED-UHFFFAOYSA-N aminomercury Chemical compound [Hg]N YUCJFSWWUVRFED-UHFFFAOYSA-N 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 229920001971 elastomer Polymers 0.000 claims description 17
- 239000005060 rubber Substances 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 7
- 229920000297 Rayon Polymers 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000002964 rayon Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 6
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003411 electrode reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 235000008645 Chenopodium bonus henricus Nutrition 0.000 description 1
- 244000138502 Chenopodium bonus henricus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- VRJVVIKEWDDYOG-UHFFFAOYSA-N mercury;nitric acid Chemical compound [Hg].O[N+]([O-])=O VRJVVIKEWDDYOG-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
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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)
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- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
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Abstract
The invention discloses a kind of mercury-nitric acid amino mercury reference electrodes and its preparation method and application.By chemically synthesized method, it is prepared for the mercury that can be stabilized in ammonium hydroxide-nitric acid amino mercury paste Hg (NH2)NO3White solid, and mercury-nitric acid amino mercury paste has been made with Elemental Mercury mixed grinding in it.The paste and the electrode potential for the electrode reaction that ammonium hydroxide is formed are sufficiently stable, it can provide accurately potential reference, and ionic soil will not be caused to measuring medium, while also having many advantages, such as that production is simple, at low cost, it is particularly suitable for the electrochemical measurement of the pure aquatic system containing ammonia.
Description
Technical field
The invention belongs to electrochemical measuring technology fields, and in particular to a kind of novel mercury-nitric acid amino mercury reference electrode and
Preparation method and application.
Background technique
Electrochemical measuring technology is the important means of metal erosion Yu primary battery performance detection, such as dynamic potential scanning, electrification
The technologies such as impedance spectrum, electrochemistry noise, volt-ampere polarization are learned to be widely used.When implementing electro-chemical test, elder generation is needed
Establish measuring electrode system, the most commonly used is three-electrode systems: working electrode, reference electrode and auxiliary electrode, wherein reference is electric
The effect of pole is to provide potential reference for working electrode, is disturbed with ensuring that measuring instrument can apply accurate current potential to working electrode
It is dynamic.Therefore, the quality of reference electrode performance directly affects the accuracy of electrochemical measurements.Reference electrode generally needs to meet
Following technical conditions: (1) in locating solution medium have good potential stability, by effects of ion, temperature etc. because
Element influences small；(2) the interior filling liquid of electrode or electrode material will not pollute interference to test system.Currently used reference
Electrode is basically divided into: hydrogen electrode and metal-metal difficulty soluble salt or two class of oxide electrode.Hydrogen electrode is because of inconvenient to use, hydrogen
The defects of gas is inflammable and explosive, in the application less use.Metal-metal difficulty soluble salt or oxide electrode are also known as second kind electrode,
Due to manufacture craft simplicity, performance stablize, it is easy to use the advantages that and be widely applied, such as calomel electrode, silver-chlorination
Silver electrode, mercury-mercurous sulfate electrode, mercury-mercuric oxide electrode etc..
The media environment that every kind of reference electrode has its applicable, as calomel electrode because containing saturation potassium chloride in filling liquid due to compared with
Mostly suitable for the solution of chloride ion-containing, mercury-mercurous sulfate electrode is suitable for the solution of containing sulfate radicals.And without these from
When carrying out electro-chemical test in the aqueous solution of son, when such as studying corrosion of metal in the pure water that ammonification adjusts pH, calomel electrode
The chloride ion of interior filling liquid can be diffused into pure water, and Contamination measurement solution causes measurement result to be distorted, other a few money reference electrodes
All there is a problem of same.To widen electrochemical method in the research application in metal erosion field, it is necessary to invent a kind of special
Novel electrode suitable for the pure water containing ammonia.
Summary of the invention
The object of the present invention is to provide a kind of novel mercury-nitric acid amino mercury reference electrodes.Novel electrode of the invention is special
Suitable for the electrochemical corrosion measurement of the pure aquatic system containing ammonia, ionic soil will not be caused to pure water, reference electrode can be eliminated to survey
Measure the influence of result.
A kind of mercury of the invention-nitric acid amino mercury reference electrode: electrode is by outer glass pipe 1, interior glass bushing 2, Elemental Mercury
3, mercury-nitric acid amino mercury paste 4, permeable plug 5, platinum filament 6, sealing-plug 7, stomata 8, porous plug 9, interior filling liquid 10
Composition；
Wherein, interior glass bushing 2 is sleeved in outer glass pipe 1, and one end of interior glass bushing 2 and outer glass pipe 1 is firm
It is adhered on sealing-plug 7；The permeable plug of plug 5 is at the nozzle of interior 2 other end of glass bushing；One is plated on permeable plug 5
Layer mercury-nitric acid amino mercury paste 4；Mercury-one layer of 4 upper berth of nitric acid amino mercury paste Elemental Mercury 3；Platinum filament 6 passes through sealing-plug 7 and stretches
Enter into mercury -4 layers of paste of nitric acid amino mercury, the platinum filament 6 being exposed at outside sealing-plug 7 is used for and external connection；On outer glass pipe 1
Portion, the position higher than permeable plug 5 are provided with stomata 8, and outer glass pipe 1 is provided with interior filling liquid 10, the liquid level of interior filling liquid 10
More than rayon balls 5, it is lower than stomata 8；The other end of outer glass pipe 1 is sealed with porous plug 9.
The mercury-nitric acid amino mercury reference electrode, the stomata 8 are provided with the rubber stopper 11 for closure；It is porous
Rubber sleeve 12 is provided with outside the sealing of plug 9.
The mercury-nitric acid amino mercury reference electrode, the interior filling liquid 10 are the ammonium hydroxide of 10-15%.
The mercury-nitric acid amino mercury reference electrode, the filling of the mercury-nitric acid amino mercury paste 4 and Elemental Mercury 3
Height ratio is 2:1.
The mercury-nitric acid amino mercury reference electrode,
The described selection of permeable plug 5 can be permeable, and chemical property is stablized, and not with mercury-nitric acid amino mercury paste 4 and
The material that interior filling liquid 10 is reacted；
The sealing-plug 7 selects chemical property to stablize, and the material not reacted with Elemental Mercury 3 and interior filling liquid 10；
The porous plug 9 selects interior filling liquid 10 can be allowed slowly to flow out, chemical property to stablize, and does not fill out with interior
The material that filling liquid 10 reacts.
The permeable plug 5 selects rayon balls；The sealing-plug 7 selects polyethylene, glass or ceramics；It is preferred that
Polyethylene；The porous plug 9 selects porous ceramics.
The mercury-nitric acid amino mercury reference electrode, the platinum filament 6 is used for and external connection.
It is a further object to provide above-mentioned mercury-nitric acid amino mercury reference electrode preparation methods.The preparation side
Method is easy to operate, at low cost, electrochemical corrosion measurement of the product prepared especially suitable for the pure aquatic system containing ammonia, will not be right
Pure water causes ionic soil, can eliminate influence of the reference electrode to measurement result.
Mercury of the invention-nitric acid amino mercury reference electrode is the preparation method is as follows: in interior glass bushing 2, from the bottom up
Successively fill permeable plug 5, mercury-nitric acid amino mercury paste 4 and Elemental Mercury 3；Load 2 upper end of interior glass bushing that finishes with
After 7 secure adhesion of sealing-plug, interior 2 housing outer glass pipe 1 of glass bushing, and make 7 jail of upper end and sealing-plug of outer glass pipe 1
By bonding；Filling liquid 10 in injecting in outer glass pipe 1 again, interior 10 liquid level of filling liquid are lower than stomata 8, are higher than permeable plug 5；
The sealing-plug 7 that platinum filament 6 passes through punching is extend into mercury -4 layers of paste of nitric acid amino mercury.
The mercury-nitric acid amino mercury reference electrode preparation method: stomata 8 is clogged with rubber stopper 11, with rubber sleeve 12
Entangle the porous plug 9 of 1 lower end of outer glass pipe.
The mercury-nitric acid amino mercury reference electrode preparation method, the mercury-nitric acid amino mercury paste 4 system
It is standby as follows:
(1)HNO3HgO solid powder is added in solution, and constant temperature water bath, agitating solution dissolves HgO solid quickly, to solution
It is middle that excessive ammonium hydroxide is added, until the amount of the white solid of Precipitation is not further added by；White precipitate is separated by filtration, is used repeatedly
Demineralized water cleaning, low temperature drying, obtained white solid powder are nitric acid amino mercury；
(2) nitric acid amino mercury powder is mixed with mercury simple substance, and a few drop concentrated ammonia liquors is added dropwise, the fine grinding in mortar, directly
Uniformly to mixture grinding, it is spontaneously dried in vent cabinet, obtains mercury-nitric acid amino mercury paste 4.
The mercury-nitric acid amino mercury reference electrode preparation method: the mercury-nitric acid amino mercury paste 4 system
It is standby specific as follows:
(1) to equipped with 1-2mol/L HNO3Addition HgO solid powder in the beaker of solution, 50 DEG C -60 DEG C of constant temperature water bath,
HNO3It is 2:1 with HgO molar ratio；Agitating solution dissolves HgO solid quickly；After HgO is completely dissolved, it is added into solution excessive
Ammonium hydroxide, until the amount of white solid of Precipitation is not further added by；White precipitate is separated by filtration, is cleaned repeatedly with demineralized water
It is greater than 6 to pH value, low temperature drying, obtained white solid powder is nitric acid amino mercury；
(2) nitric acid amino mercury powder is mixed with mercury simple substance, and a few drop concentrated ammonia liquors is added dropwise, the fine grinding in mortar, directly
Uniformly to mixture grinding, 2h is spontaneously dried, mercury-nitric acid amino mercury paste 4 of moisture content 8%~12% is obtained；Nitric acid ammonia
Base mercury: mercury simple substance: with NH4The mass ratio of the ammonium hydroxide of OH meter is (9.5-10.5): (2.3-2.7): (0.8-1.0), preferably 10:
2.5:1.
Final object of the present invention is to provide mercury-nitric acid amino mercury reference electrode application method: as
Reference electrode is used for the electrochemical corrosion measurement of the pure aquatic system containing ammonia.Ionic soil will not be caused to pure water, reference electricity can be eliminated
Extremely to the influence of measurement result.
When in use, rubber stopper 11 and rubber sleeve 12 are extracted for electrode of the present invention, then are put the electrodes into test solution, i.e.,
It can be used.
Mercury of the present invention-forms electrode between nitric acid amino mercury paste 4 and interior filling liquid 10 (10% ammonium hydroxide) anti-
It answers:
Hg(NH2)NO3+ 2e=Hg+NH2 -+NO3 - Eθ=-0.13mV； (1)
Wherein NH2 -With water power from H+In conjunction with:
NH2 -+H+=NH3； (2)
Due under the alkaline atmosphere of ammonium hydroxide, H of the water power from generation+Amount it is very small, cause react (2) be difficult to carry out,
NH2 -Reaction (1) is set to be difficult to carry out to the right in accumulation.Therefore the electrode potential of reaction (1) is sufficiently stable, when as reference electrode
Stable ground potential reference can be provided for working electrode.Simultaneously because the NO that reaction (1) generates3 -Amount it is extremely limited, therefore also not
Ionic soil can be caused to measuring medium.
The present invention has the advantages that being prepared for the mercury-nitric acid that can be stabilized in ammonium hydroxide by chemically synthesized method
Amino mercury paste Hg (NH2)NO3White solid, and mercury-nitric acid amino mercury paste has been made with 3 mixed grinding of Elemental Mercury in it
Object 4.The paste and the electrode potential for the electrode reaction that ammonium hydroxide is formed are sufficiently stable, it is possible to provide accurately potential reference, and not
Ionic soil can be caused to measuring medium, while also have many advantages, such as that production is simple, at low cost, be particularly suitable for the pure water containing ammonia
The electrochemical measurement of system.
Detailed description of the invention:
Fig. 1 is reference electrode structural schematic diagram of the invention；
Mark in Fig. 1 are as follows:
1-outer glass pipe；2-interior glass bushings；3-Elemental Mercuries；4-mercury-nitric acid amino mercury paste；5-permeable envelopes
Stifled object；6-platinum filaments；7-sealing-plugs；8-stomatas；9-porous plugs；10-interior filling liquids；11-rubber stoppers；12-rubbers
Set；
Fig. 2 is that the Q235 steel that measures using mercury-nitric acid amino mercury electrode as reference electrode is linear in the demineralized water of pH9.5
Polarization curve；
Fig. 3 is the linear polarization of the Q235 steel that measures by reference electrode of saturated calomel electrode in the demineralized water of pH9.5
Curve.
Specific embodiment:
The present invention is further illustrated below by embodiment.The embodiment of the present invention is for illustrating rather than pair
Limitation of the invention.
A kind of mercury of the invention-nitric acid amino mercury reference electrode: electrode is by outer glass pipe 1, interior glass bushing 2, Elemental Mercury
3, mercury-nitric acid amino mercury paste 4, permeable plug 5 (preferably rayon balls), platinum filament 6, sealing-plug 7 (preferably polyethylene), gas
Hole 8, porous plug 9 (preferably porous ceramics), interior filling liquid 10 form；
Wherein, interior glass bushing 2 is sleeved in outer glass pipe 1, and one end of interior glass bushing 2 and outer glass pipe 1 is firm
It is adhered on sealing-plug 7；Permeable plug 5 is tightly filled at the nozzle of interior 2 other end of glass bushing, and effect is to prevent upper layer
Substance drops out interior glass bushing 02；One layer of mercury-nitric acid amino mercury paste 4 is plated on permeable plug 5；Mercury-nitric acid amino mercury
One layer of 4 upper berth of paste Elemental Mercury 3；Platinum filament 6 passes through sealing-plug 7 and extend into mercury -4 layers of paste of nitric acid amino mercury, is exposed at close
Platinum filament 6 outside blocking 7 is used for and external connection；On 1 top of outer glass pipe, the position higher than permeable plug 5 is provided with stomata 8,
Stomata 8 can maintain 01 inside of outer glass pipe to balance with external pressure, eliminate draught head.Outer glass pipe 1 is provided with interior filling liquid 10,
The liquid level of interior filling liquid 10 is more than rayon balls 5, is lower than stomata 8；Porous plug 9 is filled in the another port of outer glass pipe 1；Its
Effect is to make the interior slowly outflow of filling liquid 10, reduces the consumption of interior filling liquid 10.The stomata 8 is provided with the rubber for closure
Rubber plug 11；Rubber sleeve 12 is provided with outside the sealing of porous plug 9.
Embodiment 1
Hg(NH2)NO3Synthesis: in 500mL beaker prepare 1mol/L HNO3Solution 300mL, claims on an electronic balance
HgO powder 32.5g is measured, HNO is poured into3In solution.Beaker is put into water-bath, 55 DEG C of constant temperature, is made with glass bar agitating solution
HgO sufficiently dissolves.After 30min, HgO has been completely dissolved.25% (mass fraction) ammonium hydroxide 20mL is added dropwise into solution, in solution
A large amount of white precipitate is generated, continues that ammonium hydroxide 20mL is added dropwise, the amount of the white solid of precipitation does not obviously increase.Solution is naturally quiet
Set, make to precipitate complete sedimentation, outwell supernatant, with demineralized water repeated flushing white precipitate, until flushing water pH be greater than
6.0.Finally white precipitate is filtered, is put into baking oven, dry at 60 DEG C, obtained drying solid powder is nitric acid amino
Mercury (Hg (NH2)NO3)。
Embodiment 2
The development of mercury-nitric acid amino mercury paste: electronic balance weighing nitric acid amino mercury powder 5.00g, mercury simple substance are used
The two is put into quartzy mortar and mixes by 1.25g, and 25% ammonium hydroxide of 8-10 drop is added dropwise with dropper, and grinding is until mixture grinding is equal
It is even, the paste that grinding obtains is put into vent cabinet and spontaneously dries 2h.Finally obtain mercury-nitric acid amino mercury paste.
Embodiment 3
The assembling of electrode: in a both ends open, length 10mm, in the interior glass bushing of internal diameter about 5mm, with absorbent cotton bulb stopper
Tight lower port, a few drop demineralized waters are dripped on degreasing cotton keeps it wet.Mercury-nitric acid in rayon balls upper berth embodiment 2
Amino mercury paste about 2.0g, then in mercury -3 about 1.0g of nitric acid amino mercury paste upper berth Elemental Mercury.By interior glass bushing housing
The upper end of outer glass pipe, outer glass pipe and interior glass bushing is bonded in polymeric seal beyond the Great Wall with seccotine, close in polyethylene
Blocking central punch perforates platinum filament in insertion mercury-nitric acid amino mercury paste, then with glass cement by the hole of polymeric seal plug
Sealing.Porous ceramics is filled in outer glass pipe lower end, injects 10% ammonium hydroxide, liquid level to stomata lower edge by stomata.Rubber stopper beyond the Great Wall
And rubber sleeve, reference electrode are completed.
Embodiment 4
1% potassium nitrate solution of 300mL is prepared in electrolytic cell, is inserted into mercury-prepared by saturated calomel electrode and embodiment 3
Nitric acid amino mercury electrode, makees reference with saturated calomel electrode, measures the potential difference between two electrodes with milivoltmeter, result is
0.107V, i.e. mercury-nitric acid amino mercury electrode relative saturation calomel electrode current potential are 0.107V.
Embodiment 5
Using demineralized water as tested media, after the completion of ammonification aqueous solution adjusts pH to 9.5, pH adjusting, demineralized water conductance is measured
Rate is 5.41us/cm.Mercury-nitric acid amino mercury electrode of the production of embodiment 3 is inserted into as reference electrode, Q235 steel electrode is work
Electrode, platinum electrode are auxiliary electrode, measure linear polarisation curves of the Q235 steel in demineralized water with electrochemical workstation, as a result such as
Shown in Fig. 2.Linear polarisation curves in Fig. 2 are smooth, linear good, show that reference electrode current potential is stablized during the test.It surveys
After examination, measurement desalination water conductivity is 5.54us/cm, shows that mercury-nitric acid amino mercury reference electrode does not have Contamination measurement body
System.
Embodiment 6
Change the mercury in embodiment 5-nitric acid amino mercury electrode into saturated calomel electrode, it is same to measure the linear of Q235 carbon steel
Polarization curve, result are as shown in Figure 3.Linear polarisation curves data point in Fig. 3 is at random, linear poor.After test, measurement
Desalination water conductivity is 67.10us/cm, chloride ion content 1.2mg/L.This is because filling liquid is saturation in saturated calomel electrode
KCl solution, chlorine ion binding capacity leads to the potential fluctuation of Q235 steel into demineralized water, to disturb the survey of linear polarisation curves
Amount.
Claims (12)
1. a kind of mercury-nitric acid amino mercury reference electrode, it is characterised in that: for electrode by outer glass pipe (1), interior glass bushing (2) is single
Matter mercury (3), mercury-nitric acid amino mercury paste (4), permeable plug (5), platinum filament (6), sealing-plug (7), stomata (8), porous envelope
Stifled object (9), interior filling liquid (10) composition；
Wherein, interior glass bushing (2) is sleeved in outer glass pipe (1), and one end of interior glass bushing (2) and outer glass pipe (1) is equal
It is firm to be adhered on sealing-plug (7)；Permeable plug (5) plug is at the nozzle of interior glass bushing (2) other end；Permeable plug
(5) one layer of mercury-nitric acid amino mercury paste (4) is plated on；Mercury-nitric acid amino mercury paste (4) one layer of upper berth Elemental Mercury (3)；
Platinum filament (6) passes through sealing-plug (7) and extend into mercury-nitric acid amino mercury paste (4) layer, is exposed at the platinum filament (6) of sealing-plug (7) outside
For with external connection；On outer glass pipe (1) top, the position for being higher than permeable plug (5) is provided with stomata (8), outer glass pipe
(1) it is provided with interior filling liquid (10), the liquid level of interior filling liquid (10) is more than permeable plug (5), is lower than stomata (8)；Outer glass
The other end for managing (1) is sealed with porous plug (9).
2. mercury according to claim 1-nitric acid amino mercury reference electrode, it is characterised in that:
The stomata (8) is provided with the rubber stopper (11) for closure；Rubber sleeve is provided with outside the sealing of porous plug (9)
(12)。
3. mercury according to claim 1-nitric acid amino mercury reference electrode, it is characterised in that: the interior filling liquid (10)
For the ammonium hydroxide of 10-15%.
4. mercury according to claim 1-nitric acid amino mercury reference electrode, it is characterised in that: the mercury-nitric acid amino mercury
The filling height ratio of paste (4) and Elemental Mercury (3) is 2:1.
5. mercury according to claim 1-nitric acid amino mercury reference electrode, it is characterised in that:
Described permeable plug (5) selection can be permeable, and chemical property is stablized, and not with mercury-nitric acid amino mercury paste (4) and
The material of interior filling liquid (10) reaction；
The sealing-plug (7) selects chemical property to stablize, and the material not reacted with Elemental Mercury (3) and interior filling liquid (10)；
The porous plug (9) selects interior filling liquid (10) can be allowed slowly to flow out, chemical property to stablize, and does not fill out with interior
The material of filling liquid (10) reaction.
6. mercury according to claim 5-nitric acid amino mercury reference electrode, it is characterised in that:
The permeable plug (5) selects rayon balls；The sealing-plug (7) selects polyethylene, glass or ceramics；It is described
Porous plug (9) select porous ceramics.
7. mercury according to claim 1-nitric acid amino mercury reference electrode, it is characterised in that: platinum filament (6) with outside for connecting
It connects.
8. the described in any item mercury of claim 1-7-nitric acid amino mercury reference electrode preparation method, it is characterised in that:
In interior glass bushing (2), successively fill from the bottom up permeable plug (5), mercury-nitric acid amino mercury paste (4) and
Elemental Mercury (3)；After loading interior glass bushing (2) upper end finished and sealing-plug (7) secure adhesion, interior glass bushing (2) is outside
It covers outer glass pipe (1), and makes upper end and sealing-plug (7) secure adhesion of outer glass pipe (1)；The note in outer glass pipe (1) again
Enter interior filling liquid (10), interior filling liquid (10) liquid level is lower than stomata (8), is higher than permeable plug (5)；Platinum filament (6) passes through punching
Sealing-plug (7) extend into mercury-nitric acid amino mercury paste (4) layer.
9. mercury according to claim 8-nitric acid amino mercury reference electrode preparation method, it is characterised in that: use rubber stopper
(11) stomata (8) are clogged, the porous plug (9) of outer glass pipe (1) lower end is entangled with rubber sleeve (12).
10. mercury according to claim 8-nitric acid amino mercury reference electrode preparation method, it is characterised in that: described
Mercury-nitric acid amino mercury paste (4) prepares as follows:
(1)HNO3HgO solid powder, constant temperature water bath is added in solution, and agitating solution dissolves HgO solid quickly, is added into solution
Excessive ammonium hydroxide, until the amount of the white solid of Precipitation is not further added by；White precipitate is separated by filtration, uses demineralized water repeatedly
Cleaning, low temperature drying, obtained white solid powder are nitric acid amino mercury；
(2) nitric acid amino mercury powder is mixed with mercury simple substance, and a few drop concentrated ammonia liquors is added dropwise, the fine grinding in mortar, until mixed
It closes object grinding uniformly, is spontaneously dried in vent cabinet, obtain mercury-nitric acid amino mercury paste (4).
11. mercury according to claim 10-nitric acid amino mercury reference electrode preparation method, it is characterised in that: described
Mercury-nitric acid amino mercury paste (4) prepares as follows:
(1) to equipped with 1-2mol/L HNO3Addition HgO solid powder in the beaker of solution, 50 DEG C -60 DEG C of constant temperature water bath, HNO3With
HgO molar ratio is 2:1；Agitating solution dissolves HgO solid quickly；After HgO is completely dissolved, excess of ammonia is added into solution
Water, until the amount of the white solid of Precipitation is not further added by；White precipitate is separated by filtration, is cleaned repeatedly with demineralized water to pH
Value is greater than 6, and low temperature drying, obtained white solid powder is nitric acid amino mercury；
(2) nitric acid amino mercury powder is mixed with mercury simple substance, and a few drop concentrated ammonia liquors is added dropwise, the fine grinding in mortar, until mixed
It closes object grinding uniformly, spontaneously dries 2h, obtain mercury-nitric acid amino mercury paste (4) of moisture content 8%~12%；Nitric acid amino
Mercury: mercury simple substance: with NH4The mass ratio of the ammonium hydroxide of OH meter is (9.5-10.5): (2.3-2.7): (0.8-1.0).
12. the described in any item mercury of claim 1-7-nitric acid amino mercury reference electrode application method, it is characterised in that: as
Reference electrode is used for the electrochemical corrosion measurement of the pure aquatic system containing ammonia.
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| EP0313657B1 (en) * | 1986-07-10 | 1994-05-25 | Terumo Kabushiki Kaisha | Reference electrode |
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| DE59406380D1 (en) * | 1993-02-04 | 1998-08-13 | Hoechst Ag | pH glass electrode |
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