CN107315064A - A kind of method of cuprous oxide content in golden corrosion product for quantitative determining copper - Google Patents
A kind of method of cuprous oxide content in golden corrosion product for quantitative determining copper Download PDFInfo
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- CN107315064A CN107315064A CN201710133786.8A CN201710133786A CN107315064A CN 107315064 A CN107315064 A CN 107315064A CN 201710133786 A CN201710133786 A CN 201710133786A CN 107315064 A CN107315064 A CN 107315064A
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- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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Abstract
The invention belongs to inorganic chemical analysis technical field, in particular it relates in a kind of corrosion product for quantitative determining copper cuprous oxide content method.Under anaerobic, the cuprous oxide on detected sample is dissolved in ammoniacal liquor, the ferrum sulfuricum oxydatum solutum of sulfuric acid acidifying is added after dissolving, cuprous ion is oxidized to copper ion by ferric sulfate, and itself is reduced to ferrous sulfate.It is ferrous with Standard Potassium Permanganate Solution titrated sulfuric acid then in aerobic environment, the content of cuprous oxide is calculated by the content meter of ferrous sulfate.The inventive method can quantitative determine the content of cuprous oxide, and measurement error is within ± 3%.Suitable for the research of the corrosion mechanism of copper.
Description
Technical field
The invention belongs to inorganic chemical analysis technical field, in particular it relates to a kind of corruption for quantitative determining copper
Lose the method for cuprous oxide content in product.
Background technology
Under natural environment, the corrosion product of copper has oxide, sulfate, carbonate and chloride etc. several, big compression ring
Border is different, and corrosion product is also different.But no matter which kind of atmospheric environment, it is general all sub- containing oxidation in the corrosion product of copper
Copper, and cuprous oxide is all one of main corrosion product that copper surface is formed.Therefore, the content of quantitative analysis cuprous oxide,
It is very important for the corrosion for studying copper.At present, cuprous oxide in the atmospheric corrosion products of copper can quantitatively be divided
The persevering current cathode reducing process of method of analysis, weightless and weightening rule of three, infrared absorption spectroscopy etc., these methods have deficiency
Part.Constant current cathode reduction method is in the case of unsymmetrical corrosion, it is impossible to the content of Accurate Determining cuprous oxide；Weightless and weightening
Rule of three, infrared absorption spectroscopy can only sxemiquantitative explanation cuprous oxide content.And in natural environment, the corrosion one of copper
As be cuprous oxide content in unsymmetrical corrosion, therefore a kind of corrosion product that can quantitative determine copper of research method have it is non-
Chang Xianshi meaning.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide cuprous oxide in a kind of corrosion product that can quantitative determine copper
The method of content.
To achieve the above object, the present invention takes following technical scheme：
A kind of method of cuprous oxide content in corrosion product for quantitative determining copper, under anaerobic, by test sample to be checked
In product immersion ammonia spirit, the corrosion product (cuprous oxide and cupric compound) on sample is set to be dissolved in ammonia spirit
In, the ferrum sulfuricum oxydatum solutum of sulfuric acid acidifying is added after dissolving, cuprous ion in corrosion product cuprous oxide is oxidized to copper by ferric sulfate
Ion, itself is reduced to ferrous sulfate, then in aerobic environment, ferrous with Standard Potassium Permanganate Solution titrated sulfuric acid, by
The content meter of ferrous sulfate calculates the content of cuprous oxide.
Specifically：
1) detected sample is immersed in ammonia spirit under anaerobic, it is through vibrating that the corrosion product on copper sheet surface is molten
Solution forms the solution of the ion containing copper ammonia complexation into ammonia spirit；
2) ferrum sulfuricum oxydatum solutum of sulfuric acid acidifying is added into the solution of above-mentioned cupric ammonia complexing ion, under anaerobic,
Using the oxidisability of ferric ion in ferric sulfate, cuprous ion in corrosion product cuprous oxide is oxidized to copper ion, and certainly
Body is reduced to ferrous sulfate, then in aerobic environment, and the ferrous sulfate of above-mentioned formation is titrated with Standard Potassium Permanganate Solution,
According to the volume of the potassium permanganate of consumption and the concentration of potassium permanganate, the quality of cuprous oxide in corrosion product is finally given.
The oxygen free condition is is continually fed into high pure nitrogen (99.99%) to system, and flow is 30-200mL/min.
The ammonia spirit concentration is 1wt%-10wt%；The ferrum sulfuricum oxydatum solutum concentration of sulfuric acid acidifying is
0.001mol/L-1mol/L。
The experimental principle of institute's foundation is：
Cu2O+4NH3+H2O=2Cu (NH3)2 ++2OH-
3H2SO4+2OH-+2Cu(NH3)2 +=Cu2SO4+2(NH4)2SO4+2H2O
Fe2(SO4)3+Cu2SO4=2FeSO4+2CuSO4
2KMnO4+10FeSO4+8H2SO4=K2SO4+5Fe2(SO4)3+2MnSO4+8H2O
Advantage for present invention：
The present invention can more accurately determine the content of cuprous oxide in the corrosion product of copper, and measurement error is ± 3%
Within.It is measured because the cuprous oxide in whole copper specimen surface corrosion product can be dissolved down by the present invention, therefore,
, still can be with the content of cuprous oxide in Accurate Determining its corrosion product for corroding uneven copper sample.It is sub- according to oxidation
Copper ratio shared in corrosion product, can be analyzed the corrosion mechanism of copper.
The present invention is solved in the atmospheric corrosion products of quantitative determination copper at this stage in the method for cuprous oxide content, in corruption
The problem of degree of accuracy is not high in the case that erosion is uneven, has very important significance.
Brief description of the drawings
Fig. 1 is the experiment flow figure for the measure cuprous oxide content that the embodiment of the present invention 1 is provided.
Fig. 2 is the XRD that the surface for the preparation that the embodiment of the present invention 1 is provided only has the corrosion copper sheet sample of cuprous oxide
Fig. 3-it is the SEM figures that the surface for the preparation that the embodiment of the present invention 1 is provided only has the corrosion copper sheet sample of cuprous oxide.
Fig. 4-for the embodiment of the present invention 1 provide by step 1) 2) after, remove surface oxidation it is cuprous after copper sheet XRD
Figure.
Embodiment
Below in conjunction with the accompanying drawings, the present invention, but do not limit the invention in any way are further described by example.
Embodiment 1
It is quick to prepare the corrosion copper sheet sample that surface only has cuprous oxide：By the fine copper that size is 25mm × 10mm × 1mm
Piece is polishing to 3000 mesh with SiC rubbing down paper, is then polished to 1 μm using diamond grinding polishing agent.The good pure copper sheet of rubbing down is put into
1h is stood in the copper/saturated copper sulphate solution of boiling, then the copper sheet examination of corrosion is taken out with deionized water rinsing from copper-bath
Sample, and each ultrasonic oscillation 20s of corrosion copper sheet positive and negative is removed into the sulfuric acid DDTC that surface is stained with, deionization is then used repeatedly
Water is rinsed, and is dried, and the cuprous oxide film of one layer of even compact is made on copper sheet surface (referring to Fig. 2, Fig. 3).Weigh corrosion copper
Tablet quality is 3.961267g
According to flow shown in Fig. 1：
1) dissolving of corrosion copper sheet surface corrosion product：Deoxygenation 1h is carried out using high pure nitrogen (99.99%), flow is
100mL/min, then persistently leads to the anaerobic state that high pure nitrogen keeps system, and concentration is added for 6.5wt% ammonia spirit
Into the bottle equipped with corrosion copper sheet, the corrosion product on copper sheet surface is dissolved down by ultrasonic oscillation.In cuprous oxide it is cuprous from
Son and ammonia complexing, form monovalence copper ammonia complexation ion.
2) remove after corrosion product, the cleaning of copper sheet:Under anaerobic, the copper sheet rope after corrosion product will be removed
Pull, the copper sheet removed after corrosion product is then cleaned with deionized water (referring to Fig. 4).
3) oxidation of cuprous ion：After cleaning is finished, persistently lead to high pure nitrogen, make " oxidation of cuprous ion " step in nothing
Carried out under the conditions of oxygen, the ferrum sulfuricum oxydatum solutum being acidified with 0.01mol/L sulfuric acid (1.8mol/L) is by step 1) in obtained solution
Monovalence ammoniacal copper complex ion is oxidized to bivalent cupric ion, and itself is reduced to ferrous sulfate.
4) ferrous ion is titrated：After above-mentioned oxidation processes, stop logical high pure nitrogen, be 1.1325 × 10 with concentration-3mol/L
Ferrous ion in the solution that liquor potassic permanganate titration step 3 is obtained, the volume of the potassium permanganate of consumption is 4.87ml.According to
The potassium permanganate volume of consumptionAnd the concentration of potassium permanganateThe quality of cuprous oxide in corrosion product is finally given,
2KMnO4~10Fe2+~5Cu2O,
5) weigh step 2) clean after copper sheet quality be 3.959259g, corrosion copper sheet is weightless for 0.002008g.
Then the cuprous oxide quality of said determination is contrasted with corrosion weight loss, to verify the degree of accuracy of the inventive method
(referring to table 1).
The degree of accuracy for the cuprous oxide that table 1 is determined
| Soak time (h) | 1 |
| Copper sheet weightlessness (g) | 0.001973 |
| Titration measures cuprous oxide quality (g) | 0.002008 |
| Titrate percentage (compared to more weightless) | 98.3% |
Claims (4)
1. a kind of method of cuprous oxide content in corrosion product for quantitative determining copper, it is characterised in that：Under anaerobic, will
In detected sample immersion ammonia spirit, the corrosion product (cuprous oxide and cupric compound) on sample is set to be dissolved in ammonia
In the aqueous solution, the ferrum sulfuricum oxydatum solutum of sulfuric acid acidifying is added after dissolving, ferric sulfate is by cuprous ion oxygen in corrosion product cuprous oxide
Copper ion is turned to, ferrous sulfate itself is reduced to, it is sub- with Standard Potassium Permanganate Solution titrated sulfuric acid then in aerobic environment
Iron, the content of cuprous oxide is calculated by the content meter of ferrous sulfate.
2. the method for cuprous oxide content in the corrosion product of the quantitative determination copper as described in claim 1, it is characterised in that：
1) detected sample is immersed in ammonia spirit under anaerobic, be dissolved to the corrosion product on copper sheet surface through vibrating
In ammonia spirit, the solution of the ion containing copper ammonia complexation is formed；
2) ferrum sulfuricum oxydatum solutum of sulfuric acid acidifying is added into the solution of above-mentioned cupric ammonia complexing ion, under anaerobic, is utilized
The oxidisability of ferric ion in ferric sulfate, copper ion is oxidized to by cuprous ion in corrosion product cuprous oxide, and itself quilt
Ferrous sulfate is reduced to, then in aerobic environment, the ferrous sulfate of above-mentioned formation is titrated with Standard Potassium Permanganate Solution, according to
The volume of the potassium permanganate of consumption and the concentration of potassium permanganate, finally give the quality of cuprous oxide in corrosion product.
3. the method for cuprous oxide content in the corrosion product of the quantitative determination copper as described in claim 2, it is characterised in that：Institute
State oxygen free condition to be continually fed into high pure nitrogen (99.99%) to system, flow is 30-200mL/min.
4. the method for cuprous oxide content in the corrosion product of the quantitative determination copper as described in claim 2, it is characterised in that：Institute
Ammonia spirit concentration is stated for 1wt%-10wt%；The ferrum sulfuricum oxydatum solutum concentration of the sulfuric acid acidifying is 0.001mol/L-1mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108333295A (en) * | 2017-11-30 | 2018-07-27 | 山东东岳有机硅材料股份有限公司 | A kind of chemical analysis method of Ternary copper ternary component |
| CN112051356A (en) * | 2020-09-11 | 2020-12-08 | 山东博苑医药化学股份有限公司 | Method for analyzing content of various forms of copper in copper-containing waste |
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| CN102156159A (en) * | 2011-05-18 | 2011-08-17 | 云南烟草科学研究院 | Method for detecting starch content in tobacco |
| CN106404996A (en) * | 2016-09-06 | 2017-02-15 | 国网天津市电力公司 | Method for measuring ferrous oxide in corrosion product |
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2017
- 2017-03-08 CN CN201710133786.8A patent/CN107315064A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102156159A (en) * | 2011-05-18 | 2011-08-17 | 云南烟草科学研究院 | Method for detecting starch content in tobacco |
| CN106404996A (en) * | 2016-09-06 | 2017-02-15 | 国网天津市电力公司 | Method for measuring ferrous oxide in corrosion product |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108333295A (en) * | 2017-11-30 | 2018-07-27 | 山东东岳有机硅材料股份有限公司 | A kind of chemical analysis method of Ternary copper ternary component |
| CN112051356A (en) * | 2020-09-11 | 2020-12-08 | 山东博苑医药化学股份有限公司 | Method for analyzing content of various forms of copper in copper-containing waste |
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Application publication date: 20171103 |