CN110702845B - Titration analysis method for copper and nickel in pyrophosphate-citrate copper-nickel alloy plating solution - Google Patents
Titration analysis method for copper and nickel in pyrophosphate-citrate copper-nickel alloy plating solution Download PDFInfo
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Abstract
The invention discloses a titration analysis method for copper and nickel in pyrophosphate-citrate copper-nickel alloy plating solution. Masking copper ions by combining thiourea and ascorbic acid, masking iron by using the ascorbic acid, adjusting the pH of the test solution by using a hexamethylenetetramine-hydrochloric acid buffer solution with the pH being 5.4, adding an EDTA standard solution, using xylenol orange as an indicator, back-titrating excessive EDTA by using zinc sulfate, and calculating the nickel content in the plating solution. The citrate and pyrophosphate are destroyed according to the method, ascorbic acid is added to mask iron, then sodium hydroxide solution is added to adjust the test solution to weak acidity, ammonia-ammonium chloride buffer solution with pH of 10 is added to adjust the pH of the test solution, ammonium prussiate is used as indicator, EDTA standard solution is used to titrate the total amount of copper and nickel, and the content of copper is calculated by differential subtraction.
Description
Technical Field
The invention relates to a method for analyzing a plating solution, in particular to a method for titrating and analyzing copper and nickel in a copper-nickel alloy plating solution containing pyrophosphate and a citrate complexing agent.
Background
The pyrophosphate-citrate copper-nickel alloy plating solution has more complex components, and has certain difficulty in analyzing copper and nickel in the plating solution. For the analysis of the mixed solution of copper and nickel, documents [1-3] report an EDTA volumetric method for measuring nickel, document [1] uses thiourea to mask copper, uses xylenol orange as an indicator, and directly titrates nickel by using an EDTA standard solution under the condition of pH 5.5. Document [2] discloses that the method is also not applicable when the determination of nickel is interfered by pyrophosphate and citrate, as shown by experiments, in which copper is first masked by ascorbic acid and thiourea, PAN-6S is used as an indicator, nickel is titrated by EDTA under the condition that the pH is 2.3, then copper is deblocked by adding hydrogen peroxide, and then copper is titrated by EDTA. Document [3] reports a method for measuring nickel by zinc sulfate back titration using xylenol orange as an indicator under a condition of pH 5.4; tests have shown that citrate interferes strongly with the determination of nickel, and this method is not feasible.
The citrate has strong oxidation resistance, and the citrate is difficult to be effectively damaged by ammonium persulfate, hydrogen peroxide and sodium hypochlorite solution, thereby bringing great difficulty to the analysis of the content of copper and nickel in the pyrophosphate-citrate copper-nickel alloy plating solution.
Among them, references:
[1] xuhong was turned, Zhoudu electroplating solution analysis technique [ M ]. Beijing chemical industry Press, 2003: 300-302.
[2] Sanyusheng (PAN-6S) as a complexometric titration indicator for continuous copper and nickel determination [ J ]. proceedings of the chemical institute of sheng, 2004, 18 (4): 309-312.
[3] Analysis of nickel sulfate in mucigera, guo chongwu pyrophosphate copper-nickel alloy baths [ J ] plating and finishing, 2016, 38 (6): 36-38.
Disclosure of Invention
Based on this, it is necessary to develop a method for titrimetric analysis of copper and nickel in pyrophosphate-citrate copper nickel alloy plating solutions.
The citric acid has strong oxidation resistance, and the citrate can not be effectively destroyed by using a strong oxidant ammonium persulfate under the acidic and heating conditions; under the condition of no copper ion catalysis, the citrate can not be effectively destroyed by hydrogen peroxide under the heating condition; citrate is also not effectively destroyed with sodium hypochlorite.
The invention utilizes the catalytic action of copper ions to destroy citric acid by using hydrogen peroxide with higher concentration under the conditions of alkalinity and heating.
The pyrophosphate-citrate copper-nickel alloy plating solution is used for electroplating metal coins, the used metal is steel, the plating solution contains iron impurities, and the interference of the iron impurities on the measurement is eliminated by masking the iron with ascorbic acid.
The invention discloses a titration analysis method of copper and nickel in pyrophosphate-citrate copper-nickel alloy plating solution, which comprises the steps of destroying citrate by using hydrogen peroxide, strengthening acid to hydrolyze pyrophosphoric acid to generate orthophosphoric acid, jointly masking copper ions by using thiourea and ascorbic acid, masking iron by using ascorbic acid, adjusting the pH of the test solution by using hexamethylenetetramine-hydrochloric acid buffer solution with the pH being 5.4, adding EDTA standard solution, using xylenol orange as an indicator, back titrating excessive EDTA by using zinc sulfate, and calculating the content of nickel in the plating solution. The citric acid and pyrophosphoric acid are destroyed by the method, then sodium hydroxide solution is added to adjust the test solution to be weakly acidic, ascorbic acid is added to mask iron, ammonia-ammonium chloride buffer solution with the pH value of 10 is added to adjust the pH value of the test solution, ammonium prussiate is used as an indicator, EDTA standard solution is used for titrating the total amount of copper and nickel, and the content of copper is calculated by a differential subtraction method.
The invention solves the problem that the prior art can not use an EDTA volumetric method to measure the content of copper and nickel in the pyrophosphate-citrate copper-nickel alloy plating solution.
The technical scheme of the invention is realized as follows: the titration analysis method for copper and nickel in pyrophosphate-citrate copper-nickel alloy plating solution comprises the following steps:
(a) absorbing pyrophosphate-citrate copper-nickel alloy plating solution to be detected into a conical flask, adding 5mL of hydrogen peroxide with the mass fraction of 30% and 10mL of sodium hydroxide solution with the mass concentration of 8-12 g/L, heating for reaction for 1min (timing after bubbles are generated), completely destroying citrate, then adding dilute sulfuric acid with the volume concentration of 180-220 mL/L, heating to boil for 0-20 s, hydrolyzing pyrophosphoric acid to generate orthophosphoric acid, cooling, adding water for dilution, dropwise adding 25% of sodium hydroxide solution until the sample solution is slightly turbid, adding thiourea solution, ascorbic acid and hexamethylenetetramine-hydrochloric acid buffer solution, and then sequentially adding EDTA standard solution A and xylenol orange indicator to obtain a yellowish green sample solution; sucking the volume ratio of the plating solution to be detected to the added sodium hydroxide solution, the diluted sulfuric acid, the thiourea solution, the hexamethylenetetramine-hydrochloric acid buffer solution and the EDTA standard solution A to be 1: 5, and sucking the volume mass ratio of the plating solution to be detected to the added ascorbic acid to be 1: 0.1-0.2) (mL/g);
(b) titrating with a zinc sulfate standard solution until the yellow-green test solution in the step (a) is converted into purple red as an end point;
(c) calculating the mass concentration of nickel sulfate hexahydrate in the pyrophosphate-citrate copper-nickel alloy plating solution: rho (NiSO)4·6H2O)＝262.8(c1V1-c2V2)/V0Where ρ (NiSO)4·6H2O) represents the mass concentration (g/L) of nickel sulfate hexahydrate in the plating solution, 262.8 is the molar mass (g/mol) of nickel sulfate hexahydrate, c1The quantity concentration (mol/L) of a substance which is an EDTA standard solution A, V1Volume (mL) for addition of EDTA Standard solution, c2The quantity concentration (mol/L) of a substance which is a standard solution of zinc sulfate, V2Volume (mL) of standard solution of zinc sulfate to be consumed, V0Absorbing the volume (mL) of the pyrophosphate-citrate copper-nickel alloy plating solution to be detected;
(d) absorbing pyrophosphate-citrate copper-nickel alloy plating solution to be detected into a conical flask, adding 5mL of hydrogen peroxide with the mass fraction of 30% and 10mL of sodium hydroxide solution with the mass concentration of 8-12 g/L, heating for reaction for 1min (timing after bubbles are generated), then adding 10mL of dilute sulfuric acid with the volume concentration of 180-220 mL/L, heating to boil for 0-20 s, cooling, adding water for dilution, dropwise adding 25% of sodium hydroxide solution until the test solution is turbid, adding an ammonia-ammonium chloride buffer solution after adding ascorbic acid, and adding an ammonium diuranate indicator to obtain a yellow-green test solution; sucking the volume ratio of the plating solution to be detected to the added sodium hydroxide solution, the diluted sulfuric acid and the ammonia-ammonium chloride buffer solution to be 1: 5, sucking the volume-mass ratio of the plating solution to be detected to the added ascorbic acid to be 1: 0.1-0.2 (mL/g), wherein the volume of the pyrophosphate-citrate copper-nickel alloy plating solution to be detected is the same as the sucking amount in the step (a);
(e) titrating by using an EDTA standard solution B until the yellow-green test solution in the step (d) is converted into purple red as an end point;
(f) calculating the mass concentration of copper sulfate pentahydrate in the pyrophosphate-citrate copper-nickel alloy plating solution: rho (CuSO)4·5H2O)＝249.7(c3V3-c1V1+c2V2)/V0Where ρ (CuSO)4·5H2O) represents the mass concentration (g/L) of copper sulfate pentahydrate, 249.7 is the molar mass (g/mol) of copper sulfate pentahydrate, c3The quantity concentration (mol/L) of the substance being EDTA standard solution B, V3To consume EDVolume of TA Standard solution B (mL), c1The quantity concentration (mol/L) of a substance which is an EDTA standard solution A, V1Volume (mL) of EDTA Standard solution A added in step (a), c2The quantity concentration (mol/L) of a substance which is a standard solution of zinc sulfate, V2Volume (mL), V, of standard solution of zinc sulfate to be consumed in step (b)0To draw up the volume (mL) of pyrophosphate-citrate copper nickel alloy plating solution to be tested.
In some of these embodiments, the ascorbic acid is a solid.
In some embodiments, the thiourea solution is a thiourea aqueous solution with a mass concentration of 40-80 g/L.
In some of these embodiments, the xylenol orange indicator is formulated as follows: 0.15-0.25 g of xylenol orange is weighed and dissolved in 100mL of water.
In some of these examples, the hexamethylenetetramine-hydrochloric acid buffer solution is prepared as follows: 160g of hexamethylenetetramine was dissolved in 400mL of water, and 40mL of concentrated hydrochloric acid was added.
In some of the embodiments, the substance of the EDTA standard solution A is in a concentration of 0.08 mol/L.
In some of these examples, the zinc sulfate standard solution has a mass concentration of 0.05 mol/L.
In some of these embodiments, the ammonium diuranate indicator is formulated as follows: 0.15-0.25 g of ammonium diuranate and 100g of sodium chloride are ground and mixed uniformly.
In some of these embodiments, the ammonia-ammonium chloride buffer solution is formulated as follows: dissolving 15g of ammonium chloride in 300mL of water, adding 100mL of concentrated ammonia water with the mass fraction of 25-28%, uniformly mixing, and adding water to 500 mL.
In some of the embodiments, the substance of the EDTA standard solution B is in a concentration of 0.05 mol/L.
The invention has the beneficial effects that:
1. the invention utilizes the catalytic action of copper ions, and uses hydrogen peroxide with higher concentration to completely destroy citrate under the alkaline and heating conditions, thereby effectively eliminating the interference of the citrate on the determination of copper and nickel;
2. according to the method, pyrophosphoric acid is hydrolyzed by strong acid under the heating condition to generate orthophosphoric acid, so that the interference of pyrophosphate on the measurement is effectively eliminated;
3. according to the invention, thiourea and ascorbic acid are adopted to jointly mask copper, an EDTA standard solution is added under the condition that the pH value is 5.4, then xylenol orange is used as an indicator, and the content of nickel is determined by a zinc sulfate back titration method, so that the blocking effect of nickel ions on the xylenol orange indicator is effectively eliminated;
4. the method fills the blank of the titration analysis method of copper and nickel in the pyrophosphate-citrate copper-nickel alloy plating solution, and has the advantages of simplicity and high accuracy.
Detailed Description
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The chemical reagents used were as follows:
1. sodium hydroxide solution: the mass concentration is 10 g/L;
2. 25% sodium hydroxide solution: 100g of sodium hydroxide is dissolved in 300g of water;
3. hydrogen peroxide: the mass fraction is 30 percent;
4. dilute sulfuric acid: the volume concentration is 200 mL/L;
5. thiourea solution: the mass concentration is 50 g/L;
6. ascorbic acid: a solid;
7. xylenol orange indicator: weighing 0.2g of xylenol orange to dissolve in 100mL of water;
8. ammonium taurocyanate indicator: 0.2g of ammonium diuranate and 100g of sodium chloride are ground and mixed uniformly;
9. hexamethylenetetramine-hydrochloric acid buffer solution: 160g of hexamethylenetetramine is dissolved in 400mL of water, and 40mL of concentrated hydrochloric acid is added;
10. ammonia-ammonium chloride buffer solution: dissolving 15g of ammonium chloride in 300mL of water, adding 100mL of concentrated ammonia water with the mass fraction of 25-28%, uniformly mixing, and adding water to 500 mL;
11. EDTA standard solution a: the mass concentration of the substance is 0.08 mol/L;
12. EDTA standard solution B: the mass concentration of the substance is 0.05mol/L
13. Zinc sulfate standard solution: the mass concentration of the substance is 0.05 mol/L;
example (b):
1. preparing pyrophosphate-citrate copper-nickel alloy plating solution:
accurately weighing 60.00g of analytically pure nickel sulfate hexahydrate and 10.50g of copper sulfate pentahydrate, dissolving in 700mL of water, adding 200g of potassium pyrophosphate, 60g of sodium citrate and 1g of ferrous sulfate heptahydrate, stirring for dissolving, transferring into a 1000mL volumetric flask, adding water for diluting to a scale, and shaking up.
2. And (3) determining the mass concentration of the nickel sulfate:
absorbing 2mL of pyrophosphate-citrate copper-nickel alloy plating solution into a 300mL conical flask, adding 5mL of hydrogen peroxide and 10mL of sodium hydroxide solution, heating for reaction for 1min (timing when bubbles are generated), adding 10mL of dilute sulfuric acid, heating to boil for 0-20 s, cooling, adding 50mL of water for dilution, dropwise adding 25% of sodium hydroxide solution until the test solution is slightly turbid, adding 10mL of thiourea solution, 0.3g of ascorbic acid and 10mL of hexamethylenetetramine-hydrochloric acid buffer solution, accurately adding 10mL of EDTA standard solution A by using a pipette, adding 2-3 drops of xylenol orange indicator, and titrating by using zinc sulfate standard solution until the test solution is changed from yellow green to purple red.
According to the formula rho (NiSO)4·6H2O)＝262.8(c1V1-c2V2)/V0Calculating the mass concentration of nickel sulfate hexahydrate, wherein rho (NiSO)4·6H2O) represents the mass concentration (g/L) of nickel sulfate hexahydrate in the plating solution, 262.8 is the molar mass (g/mol) of nickel sulfate hexahydrate, c1The quantity concentration (mol/L) of a substance which is an EDTA standard solution A, V1Volume (mL) for addition of EDTA Standard solution, c2The quantity concentration (mol/L) of a substance which is a standard solution of zinc sulfate, V2Volume (mL) of standard solution of zinc sulfate to be consumed, V0To suck the sample to be testedVolume of pyrophosphate-citrate cupronickel bath (mL).
3. And (3) measuring the mass concentration of the copper sulfate:
absorbing 2mL of pyrophosphate-citrate copper-nickel alloy plating solution into a 300mL conical flask, adding 5mL of hydrogen peroxide and 10mL of sodium hydroxide solution, heating for reaction for 1min (timing after bubbling is generated), adding 10mL of dilute sulfuric acid, heating to boil for 0-20 s, cooling, adding 70mL of water for dilution, dropwise adding 25% of sodium hydroxide solution until the test solution is turbid, adding 0.3g of ascorbic acid, adding 10mL of ammonia-ammonium chloride buffer solution, adding 0.2-0.3 g of ammonium taurate indicator, and titrating with an EDTA standard solution B until the test solution is changed from yellow green to purple red.
According to the formula rho (CuSO)4·5H2O)＝249.7(c3V3-c1V1+c2V2)/V0Calculating the mass concentration of the copper sulfate pentahydrate, wherein rho (CuSO)4·5H2O) represents the mass concentration (g/L) of copper sulfate pentahydrate, 249.7 is the molar mass (g/mol) of copper sulfate pentahydrate, c3The quantity concentration (mol/L) of the substance being EDTA standard solution B, V3To consume volume (mL) of EDTA Standard solution B, c1The quantity concentration (mol/L) of a substance which is an EDTA standard solution A, V1To determine the volume (mL) of EDTA Standard solution A added to Nickel sulfate, c2The quantity concentration (mol/L) of a substance which is a standard solution of zinc sulfate, V2To determine the volume (mL) of zinc sulfate standard solution consumed in nickel sulfate, V0To draw up the volume (mL) of pyrophosphate-citrate copper nickel alloy plating solution to be tested.
The results obtained by 6 replicates in the manner described are given in Table 1. The analysis method provided by the invention has higher precision and accuracy.
TABLE 1 precision and recovery of analytical methods
Test example 1:
preparing a test solution: 60g/L of nickel sulfate hexahydrate and 120g/L of sodium citrate.
Sucking 2mL of the test solution into a 500mL conical flask, adding 80mL of water for dilution, adding 10mL of dilute sulfuric acid, adding 1g of sodium persulfate, heating and boiling for 5min, cooling the test solution, and then dropwise adding a 25% sodium hydroxide solution until the pH value is 10, wherein no nickel hydroxide precipitate is generated in the test solution.
Tests have shown that sodium persulfate, a strong oxidant, is not effective in destroying citric acid under strongly acidic and heated conditions.
Test example 2:
preparing a test solution: 60g/L of nickel sulfate hexahydrate and 120g/L of sodium citrate.
And (3) sucking 2mL of the test solution into a 500mL conical flask, adding 80mL of water for dilution, dropwise adding 25% sodium hydroxide solution until the pH value is 11, adding 5mL of hydrogen peroxide, heating and boiling for 5min, wherein no nickel hydroxide precipitate is generated in the test solution.
Experiments show that the citric acid cannot be effectively destroyed by using hydrogen peroxide under the alkaline condition.
Test example 3:
preparing a test solution: 60g/L of nickel sulfate hexahydrate, 10g/L of copper sulfate pentahydrate and 120g/L of sodium citrate.
Sucking 2mL of the test solution into a 500mL conical flask, adding 60mL of water for dilution, dropwise adding a 25% sodium hydroxide solution until the pH value is 11, adding 5mL of hydrogen peroxide, heating and boiling for 3min, generating copper hydroxide and nickel hydroxide precipitates in the test solution, cooling, adding 50mL of water, and filtering with quantitative filter paper to obtain a filtrate.
10mL of 10g/L sodium dimethyldithiocarbamate solution was added to the filtrate, and a small amount of brown precipitate was formed in the sample solution.
Tests show that under the catalysis of copper ions and the heating condition, the citric acid can be destroyed by using hydrogen peroxide with lower concentration, but the coordination ability of the citric acid cannot be completely lost.
Test example 4:
preparing a test solution: 60g/L of nickel sulfate hexahydrate, 10g/L of copper sulfate pentahydrate and 120g/L of sodium citrate.
Sucking 2mL of the test solution into a 300mL conical flask, adding 5mL of hydrogen peroxide, adding 10mL of 10g/L sodium hydroxide solution, heating for reacting for 1min, cooling, adding 50mL of water for diluting, adding 50mL of copper hydroxide and nickel hydroxide in the test solution for precipitation, adding 50mL of water for supplement, and filtering with quantitative filter paper to obtain a filtrate.
10mL of 10g/L sodium dimethyldithiocarbamate solution was added to the filtrate, and no precipitate was formed in the sample solution.
Tests show that under the catalysis and heating conditions of copper ions, the citric acid can be completely destroyed by using hydrogen peroxide with higher concentration.
Test example 5:
preparing pyrophosphate-citrate copper-nickel alloy plating solution: 60.00g/L of analytically pure nickel sulfate hexahydrate, 10.50g/L of copper sulfate pentahydrate, 200g/L of potassium pyrophosphate, 60g/L of sodium citrate and 1g/L of ferrous sulfate heptahydrate.
Absorbing 2mL of the plating solution into a 500mL conical flask, adding 80mL of water, adding 10mL of dilute sulfuric acid, heating and boiling for 2min, cooling, dropwise adding 25% sodium hydroxide solution to adjust the pH value to 11-12, adding 5mL of hydrogen peroxide, heating and boiling for 3min, dropwise adding dilute sulfuric acid to adjust the pH value to 6-7, adding 10mL of thiourea solution, 0.3g of ascorbic acid and 10mL of hexamethylenetetramine-hydrochloric acid buffer solution, accurately adding 10mL of EDTA standard solution A by using a pipette, adding 2-3 drops of xylenol orange indicator, titrating by using zinc sulfate standard solution, slowly changing the color of the test solution when the end point is approached, and recording the volume of the zinc sulfate standard solution consumed when the end point is titrated to red. Calculated according to the calculation formula of nickel sulfate in the embodiment to obtain rho (NiSO)4·6H2O) ═ 54.32g/L, the recovery was 90.53%.
Tests show that under the condition that the citric acid is not completely destroyed, the determination result is obviously lower, and the endpoint is not easy to observe.
Sucking 2mL of the plating solution into a 300mL conical flask, adding 80mL of water, adding 0.3g of ascorbic acid, adding 10mL of ammonia-ammonium chloride buffer solution, adding 0.2g of ammonium diuranate indicator, titrating with an EDTA standard solution B, slowly changing color when the endpoint is approached, and recording the volume of the EDTA standard solution B consumed when the titration is red. Calculated according to the calculation formula of copper sulfate in the embodiment to obtain rho (CuSO)4·5H2O) — 15.67g/L, with a recovery of 149.24%.
Tests show that pyrophosphate and citrate lead the discoloration range of the titration end point to be elongated, the end point is difficult to judge, and the measurement result of copper sulfate is seriously higher due to the obvious low measurement result of nickel sulfate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The titration analysis method for copper and nickel in pyrophosphate-citrate copper-nickel alloy plating solution is characterized in that the determination of the content of nickel sulfate comprises the following steps:
(a) absorbing pyrophosphate-citrate copper-nickel alloy plating solution to be detected into a conical flask, adding 5mL of hydrogen peroxide with the mass fraction of 30% and 10mL of sodium hydroxide solution with the mass concentration of 8-12 g/L, heating for reaction, timing for 1min after bubbles are generated, completely destroying the citrate, then adding 10mL of dilute sulfuric acid with the volume concentration of 180-220 mL/L, heating to boil for 0-20 s, hydrolyzing the pyrophosphoric acid to generate orthophosphoric acid, cooling, adding water for dilution, dropwise adding the sodium hydroxide solution with the mass fraction of 25% until the test solution is slightly turbid, adding thiourea solution, ascorbic acid and hexamethylenetetramine-hydrochloric acid buffer solution, and then sequentially adding EDTA standard solution A and xylenol orange indicator to obtain a yellow-green test solution; sucking the volume ratio of the plating solution to be detected to the added sodium hydroxide solution, the diluted sulfuric acid, the thiourea solution, the hexamethylenetetramine-hydrochloric acid buffer solution and the EDTA standard solution A to be 1: 5, and sucking the volume mass ratio of the plating solution to be detected to the added ascorbic acid to be 1: 0.1-0.2 mL/g;
(b) titrating with a zinc sulfate standard solution until the yellow-green test solution in the step (a) is converted into purple red as an end point;
(c) calculating the mass concentration of nickel sulfate hexahydrate in the pyrophosphate-citrate copper-nickel alloy plating solution:ρ(NiSO4·6H2O)=262.8(c 1 V 1-c 2 V 2)/V 0whereinρ(NiSO4·6H2O) represents the mass concentration g/L of nickel sulfate hexahydrate in the plating solution, 262.8 is the molar mass g/mol of nickel sulfate hexahydrate,c 1is the quantity concentration mol/L of the substance of the EDTA standard solution A,V 1to add a volume mL of EDTA standard solution a,c 2is the quantity concentration mol/L of the zinc sulfate standard solution,V 2to consume a volume mL of the zinc sulfate standard solution,V 0absorbing the volume mL of the pyrophosphate-citrate copper-nickel alloy plating solution to be detected;
(d) absorbing pyrophosphate-citrate copper-nickel alloy plating solution to be detected into a conical flask, adding 5mL of hydrogen peroxide with the mass fraction of 30% and 10mL of sodium hydroxide solution with the mass concentration of 8-12 g/L, heating for reaction, timing for 1min after bubbles are generated, then adding 10mL of dilute sulfuric acid with the volume concentration of 180-220 mL/L, heating to boil for 0-20 s, cooling, adding water for dilution, dropwise adding 25% of sodium hydroxide solution until the test solution is turbid, adding an ammonia-ammonium chloride buffer solution after adding ascorbic acid, and adding an ammonium diuranate indicator to obtain a yellowish green test solution; sucking the volume ratio of the plating solution to be detected to the added sodium hydroxide solution, the diluted sulfuric acid and the ammonia-ammonium chloride buffer solution to be 1: 5, sucking the volume-mass ratio of the plating solution to be detected to the added ascorbic acid to be 1: 0.1-0.2 mL/g, wherein the volume of the pyrophosphate-citrate copper-nickel alloy plating solution to be detected is the same as the suction amount in the step (a);
(e) titrating by using an EDTA standard solution B until the yellow-green test solution in the step (d) is converted into purple red as an end point;
(f) calculating the mass concentration of copper sulfate pentahydrate in the pyrophosphate-citrate copper-nickel alloy plating solution:ρ(CuSO4·5H2O)=249.7(c 3 V 3-c 1 V 1+c 2 V 2)/V 0whereinρ(CuSO4·5H2O) represents the mass concentration g/L of copper sulfate pentahydrate, 249.7 is the molar mass g/mol of copper sulfate pentahydrate,c 3is the quantity concentration mol/L of the substance of the EDTA standard solution B,V 3to consume a volume mL of EDTA standard solution B,c 1is the quantity concentration mol/L of the substance of the EDTA standard solution A in the step (a),V 1to add a volume mL of EDTA standard solution a in step (a),c 2is the quantity concentration mol/L of the zinc sulfate standard solution,V 2in order to consume the volume mL of the zinc sulfate standard solution in the step (b),V 0the volume mL of the pyrophosphate-citrate copper-nickel alloy plating solution to be measured is sucked.
2. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the ascorbic acid is a solid.
3. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the thiourea solution is a thiourea aqueous solution with the mass concentration of 40-80 g/L, and the xylenol orange indicator is prepared by the following method: 0.15-0.25 g of xylenol orange is weighed and dissolved in 100mL of water.
4. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the hexamethylene tetramine-hydrochloric acid buffer solution is prepared by the following method: 160g of hexamethylenetetramine was dissolved in 400mL of water, and 40mL of concentrated hydrochloric acid was added.
5. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the substance quantity concentration of the EDTA standard solution A is 0.08 mol/L.
6. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the mass concentration of the zinc sulfate standard solution is 0.05 mol/L.
7. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the ammonium diuranate indicator is prepared by the following method: 0.15-0.25 g of ammonium diuranate and 100g of sodium chloride are ground and mixed uniformly.
8. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the ammonia-ammonium chloride buffer solution is prepared by the following method: dissolving 15g of ammonium chloride in 300mL of water, adding 100mL of concentrated ammonia water with the mass fraction of 25-28%, uniformly mixing, and adding water to 500 mL.
9. The method for the titrimetric analysis of copper and nickel in a pyrophosphate-citrate copper nickel alloy plating bath as set forth in claim 1, characterized in that: the substance quantity concentration of the EDTA standard solution B is 0.05 mol/L.
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| CN103499542A (en) * | 2013-09-30 | 2014-01-08 | 中粮生物化学（安徽）股份有限公司 | Method for detecting calcium ion content of citric acid-containing substance |
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| Cu-Sn alloy microtube assembly fabricated by electroless plating on polyester nonwoven fabric and its lithiation-delithiation performance;YutakaFujiwara;《Applied Surface Science》;20190702;第493卷;第112-124页 * |
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