CN101639449B - Method for rapidly detecting main component in active lime and passivated lime - Google Patents
Method for rapidly detecting main component in active lime and passivated lime Download PDFInfo
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Abstract
The invention relates to the field of analytical chemistry and discloses a method for rapidly detecting a main component in active lime and passivated lime. The method comprises the following steps: 1, weighing a proper amount of active lime and passivated lime samples and carrying out a blank test along with the samples; placing the samples into a heating container; adding a proper amount of hydrochloric acid solution; heating till the samples are completely decomposed; cooling a few undissolved substances of the passivated lime sample to the room temperature; after the solution is filled into a volumetric flask to fix volume, respectively extracting two parts of proper amount of test solution; and 2, respectively titrating calcium oxide and magnesium oxide or calcium and magnesium. Theinvention has the characteristics that the sample decomposition is simplified, and a measurement error is reduced and the analysis time is shortened by controlling the titer of EDTA and EGTA titrand within the burette volume range; two separately added indicating agents are prepared into a mixed indicating agent to be added once when the calcium and magnesium or magnesium oxide is directly titrated so as to reduce the operation time; and the final result is obtained by adding the experience correction coefficient in the passivated lime sample.
Description
Technical field
The present invention relates to the analytical chemistry field.
Background technology
Active lime is lime stone a kind of high-quality soft burnt lime behind 900 ℃～1200 ℃ temperature lower calcinations in special rotary kiln, in order to keep the activity degree of active lime composition, the active lime surface is carried out obtaining passive lime after the Passivation Treatment.They all are the modern requisite auxiliary materials in the production of smelting.
Active lime has as the slag former of making steel shortens the heat, and improves molten steel degree of purity and recovery rate, reduces lime and fluorite consumption, improves advantages such as converter lining life-span.World developed country all adopts active lime steel-making, and Iron and Steel Enterprises in China also uses active lime to replace general metallurgy lime gradually, and has obtained better economic benefits.Along with the raising of iron and steel output and the quickening of smelting cycle, the output of the lime that steel mill uses smelting slag making and the requirement of quality are more and more stricter, particularly the research and development of active lime are more and more paid attention to, the lime consumption of using according to the cubage smelting slag making of the major component of active lime for example, obtain the R﹠D work that passive lime and effective constituent do not reduce etc. after the Passivation Treatment, so active lime, major component calcium oxide in the passive lime, one of important technology index of its quality discrimination when magnesian content is R﹠D work and use and trade is to active lime, calcium oxide in the passive lime, magnesian simple, fast, accurately measure and proposed requirement.
The EDTA titrimetry has been widely used in principal element calcium oxide in lime, lime stone, the rauhkalk, magnesian mensuration, but the processing majority of sample all is to carry out titrimetry after the mixed flux fusion, has restricted analysis speed.Wang Qiuhui with sour molten SAMPLE METHOD EDTA titration determination the calcium oxide in the unslaked lime; Yu Jianhua, Mao Xingxian have measured the chemical constitution of lime stone with calcination-hydrochloric acid decomposition method; Du Yungui, Liu Yi etc. disclose a kind of measurement lime stone CaCO
3, MgCO
3The process patent of composition, patent content are with the lime stone dissolving with hydrochloric acid, measure CaCO with the EDTA standard solution titration respectively
3, the EDTA standard solution is crossed titration and ZnSO
4The standard solution back titration is measured MgCO
3Content.But at present calcium oxide, the molten rapid chemical analytical approach of magnesian acid in active lime, the passive lime are not appeared in the newspapers.
The said method that prior art adopted has the following disadvantages:
In the active lime of former usefulness, the passive lime in calcium oxide, the magnesian assay method decomposition of test portion be the alkali fusion method, analysis time is long, the energy consumption height.
2.EDTA, the concentration of EGTA, CyDTA titrand is 0.01mol/L, titration for the calcium oxide of high-load in active lime, the passive lime, if it is 25.00mL that branch is got titration test solution amount, the vs that has surpassed a buret amount, it is 15.00mL that branch is got titration test solution amount, titration error is amplified, and has strengthened the uncertainty in the analytical test.
3. the magnesium oxide of low content 0.01mol/L CyDTA titrand titration, titration milliliter number is too little, has strengthened the uncertainty in the analytical test.
Summary of the invention
Technical matters to be solved by this invention provides the method for major component in a kind of fast measuring active lime, the passive lime, it has the decomposition method of simplifying sample, titer by control EDTA, EGTA titrand is within the range of capacity of buret, reduce measuring error and improve the accuracy of analyzing, and shortened analysis time; When carrying out calcium, magnesium resultant or magnesium oxide direct titration, two kinds of indicator that separately add are made into mixed indicator once add, reduced the running time, a plurality of links alleviate the characteristics of analyst's labour intensity.
For solving the problems of the technologies described above, the method for major component is characterized in that in a kind of fast measuring active lime provided by the invention, the passive lime, may further comprise the steps:
Step 1, claim the active lime of an amount of granularity less than 0.125mm, the passive lime sample, accurately to 0.0001g, carry out blank test in company with sample, place heating container, add hydrochloric acid solution, sample size is corresponding with the hydrochloric acid consumption, when sample weighting amount after a little while, the molten sample of hydrochloric acid solution of a spot of or low concentration ratio of corresponding usefulness, heating and decomposition sample are to fully, and the passive lime sample has a little insolubles, be cooled to room temperature, solution is moved in the volumetric flask, be diluted with water to scale, mixing behind the constant volume, extract two parts of an amount of test solutions respectively, guarantee to divide and to get that sample size is 0.05g in the test solution;
Step 2,
The titration of calcium oxide content: in the described test solution of portion, add 3mL～15mL concentration and be 1 to 1 triethanolamine solution mixing, the potassium hydroxide solution that adds 200g/L, or sodium hydroxide solution, or the pH value of other solution when guaranteeing titration is greater than 12, and do not influence the strong alkali solution 20mL of follow-up titration step and analysis result, the calcon-carboxylic acid that adds 4～5 5g/L, mixing, becoming sapphirine to test solution by redness with the EGTA standard titration solution titration of 0.02mol/L is terminal point, and the EGTA standard titration solution volume that consume this moment is V
1, blank test solution adds the magnesium oxide standard solution of 3～4 1.00mg/mL before titration, and by formula (1) calculates the content of calcium oxide:
In the formula: w
CaO---CaO massfraction, %;
V
1---calcium oxide consumes the volume of EGTA standard titration solution, mL in the titration test solution;
V
01---calcium oxide consumes the volume of EGTA standard titration solution, mL in the titration blank test solution;
C---the concentration of EGTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g;
For the calcium oxide in the passive lime, the result of formula (1) is added 0.3% correction coefficient, calcium oxide content in the passive lime that gets final product to the end, that is:
Magnesian titration: in the described test solution of another part, add 3mL～15mL concentration and be 1 to 1 triethanolamine solution mixing, the EGTA standard solution that adds 0.02mol/L, the milliliter number of the EGTA standard solution that consumes when its addition equals the titration calcium oxide, and excessive 0.2mL, after adding the ammonia buffer solution of 15mL～30mL pH 10, add 2 5g/L acid chromium blue k solution and 5～6 5g/L naphthol green B solution respectively, mixing, becoming pewter to test solution by redness with the CyDTA standard titration solution titration of 0.005mol/L is terminal point, the CyDTA standard titration solution volume V that consume this moment
2, use V
2By formula (3) calculate magnesian content:
In the formula: w
MgO---MgO massfraction, %;
V
2---magnesium oxide consumes the volume of CyDTA standard titration solution, mL in the titration test solution;
V
02Magnesium oxide consumes the volume of CyDTA standard titration solution, mL in the-titration blank test solution;
C---the concentration of CyDTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g.
Another preferred version to said method is,
Step 2 is, can also adopt following mode of operation for magnesium oxide greater than 1% sample,
The titration of calcium oxide content: in operation steps and account form thereof the step 2 as claimed in claim 1 the titration of calcium oxide content described, just titrimetric standard solution changes the EDTA standard titration solution into;
The titration of calcium oxide, magnesium oxide resultant: in the described test solution of another part, add 3mL～15mL concentration and be 1 to 1 triethanolamine solution mixing, after adding the ammonia buffer solution of 15mL～30mL pH 10, acid chromium blue k solution and 5～6 5g/L naphthol green B solution of adding 2 5g/L respectively, mixing, becoming pewter to test solution by kermesinus with the EDTA standard titration solution titration of 0.02mol/L is terminal point, the EDTA standard titration solution volume V that consume this moment
3, by formula (4) calculate magnesian content:
In the formula: w
MgO---MgO massfraction, %;
V
3---calcium oxide, magnesium oxide resultant consume the volume of EDTA standard titration solution, mL in the titration test solution;
V
03---calcium oxide, magnesium oxide resultant consume the volume of EDTA standard titration solution, mL in the titration blank test solution;
V
1---calcium oxide consumes the volume of EDTA standard titration solution, mL in the titration test solution;
V
01---calcium oxide consumes the volume of EDTA standard titration solution, mL in the titration blank test solution;
C---the concentration of EDTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g.
To being optimized for of aforesaid operations method,
Step 1 is, take by weighing 0.1g～0.50g, accurately to 0.0001g, granularity is less than the active lime of 0.125mm, the passive lime sample, carry out blank test in company with sample, place 100mL～250mL heating container, adding 30mL～100mL concentration ratio is the hydrochloric acid solution of 1 to 1 to 1 to 5 scope, sample size and hydrochloric acid consumption are corresponding, when sample weighting amount after a little while, the molten sample of hydrochloric acid solution of a spot of or low concentration ratio of corresponding usefulness, the heating and decomposition sample is to fully, the passive lime sample has a little insolubles, be cooled to room temperature, solution is moved in the volumetric flask, be diluted with water to scale, mixing behind the constant volume extracts two parts of test solutions respectively.
The aforesaid operations method further is optimized for,
Step 1 is when the sample size that takes by weighing is 0.50g, to be settled to the 200mL volumetric flask, two parts of extraction 20.00mL test solutions; Be settled to the 250mL volumetric flask, extract two parts of 25.00mL test solutions; Be settled to the 500mL volumetric flask, extract two parts of 50.00mL test solutions; When the sample size that takes by weighing is 0.40g, be settled in the 200mL volumetric flask, extract two parts of 25.00mL test solutions; When the sample size that takes by weighing is 0.20g, be settled in the 100mL volumetric flask, extract two parts of 25.00mL test solutions; When the sample size that takes by weighing is 0.10g, be settled in the 100mL volumetric flask, get two parts of 50.00mL test solutions.
The aforesaid operations method further is optimized for,
Step 1 is to take by weighing 0.50g, accurately to 0.0001g, granularity is carried out blank test less than active lime, the passive lime sample of 0.125mm in company with sample, places the 150ml beaker, adding 100mL concentration is 1 to 3 hydrochloric acid solution, the heating and decomposition sample is to complete, and the passive lime sample has a little insolubles, is cooled to room temperature, solution is moved in the 250mL volumetric flask, be diluted with water to scale, mixing behind the constant volume extracts two parts of 25.00mL test solutions respectively;
Step 2 is,
The titration of calcium oxide content: in the described test solution of portion, add 5mL concentration and be 1 to 1 triethanolamine solution mixing, the potassium hydroxide solution 20mL that adds 200g/L, the calcon-carboxylic acid that adds 4～5 5g/L, mixing, becoming sapphirine to test solution by redness with the EGTA standard titration solution titration of 0.02mol/L is terminal point, and the EGTA standard titration solution volume that consume this moment is V
1, blank test solution adds the magnesium oxide standard solution of 3～4 1.00mg/mL before titration, and by formula (1) calculates the content of calcium oxide;
For the calcium oxide in the passive lime, the result of formula (1) is added 0.3% correction coefficient, calcium oxide content in the passive lime that gets final product to the end;
Magnesian titration: in the described test solution of another part, add 5mL concentration and be 1 to 1 triethanolamine solution mixing, the EGTA standard solution that adds 0.02mol/L, the milliliter number of the EGTA standard solution that consumes when its addition equals the titration calcium oxide, and excessive 0.2mL, add 20mL, behind the ammonia buffer solution of pH 10, add 2 5g/L acid chromium blue k solution and 5～6 5g/L naphthol green B solution respectively, mixing, becoming pewter to test solution by redness with the CyDTA standard titration solution titration of 0.005mol/L is terminal point, the CyDTA standard titration solution volume V that consume this moment
2, use V
2By formula (3) calculate magnesian content.
To further being optimized for of another optimal technical scheme,
Step 2 is, can also adopt following mode of operation for magnesium oxide greater than 1% sample,
The titration of calcium oxide content: in operation steps and account form thereof the step 2 as claimed in claim 1 the titration of calcium oxide content described, just titrimetric standard solution changes the EDTA standard titration solution into;
Titration to calcium oxide, magnesium oxide resultant: in the described test solution of another part, add 5mL concentration and be 1 to 1 triethanolamine solution mixing, add 20mL, the ammonia buffer solution of PH10, acid chromium blue k solution and 5～6 5g/L naphthol green B solution of adding 2 5g/L respectively, mixing, becoming pewter to test solution by kermesinus with the EDTA standard titration solution titration of 0.02mol/L is terminal point, the EDTA standard titration solution volume V that consume this moment
3, by formula (4) calculate magnesian content.
The aforesaid operations method further is improved to,
In step 2, the acid chromium blue k solution and the naphthol green B solution that behind the ammonia buffer solution that adds 15mL～30mL pH 10, are added, soluble in water according to 0.5g naphthol green B and 0.2g acid chromium blue k, the method that is diluted with water to 70mL is made magnesium mixed indicator solution in advance, once adds 4～5 when titration.
The invention has the advantages that:
1. the invention discloses the method for major component in a kind of fast measuring active lime, the passive lime, by simplifying the decomposition method of sample, the titer of control EDTA, EGTA titrand is within the range of capacity of buret, reduce measuring error and improve the accuracy of analyzing, and shortened analysis time.When carrying out calcium, magnesium resultant or magnesium oxide direct titration, two kinds of indicator that separately add are made into mixed indicator once add, also reduced the running time, a plurality of links have alleviated analyst's labour intensity.Solved the decomposition employing alkali fusion method of test portion in the prior art, analysis time is long, the energy consumption height, and also the concentration of EDTA, EGTA, CyDTA titrand is 0.01mol/L, titration for the calcium oxide of high-load in active lime, the passive lime, if claim sample 0.50g, constant volume 250mL, it is 25.00mL that branch is got titration test solution amount, the vs that has surpassed a buret amount, it is 15.00mL that branch is got titration test solution amount, and titration error is amplified, and has strengthened the problem of the uncertainty in the analytical test.
2. during with CyDTA titrand titration magnesium oxide, adopt EGTA to shelter calcium, CyDTA direct titration magnesium, avoided difference to subtract a large amount of calcium are measured small amount of magnesium in the titrimetry influence and propagation of error, simultaneously, because the content of magnesia in the sample is lower, by reducing the concentration of CyDTA, increase titration milliliter number, thereby improved accuracy.Solved the magnesium oxide of low content 0.01mol/L CyDTA titrand titration in the prior art, titration milliliter number is too little, has strengthened the problem of the uncertainty in the analytical test.
3. the present invention adopts directly with hydrochloric acid active lime, passive lime sample is carried out constant volume after the heating for dissolving, carry out the method for part test solution titration, because the Passivation Treatment of passive lime contains a spot of insolubles, pass through with sample sample number abundant more than 30, adopt this method and national standard analytical approach result to contrast the correction coefficient that obtains after the statistics, calcium oxide result to passive lime acid after molten carries out after experience factor proofreaies and correct, obtain the accurate content of calcium oxide in the passive lime, can access accuracy with national standard analytical approach basically identical.
4. because the calcium oxide and the calcium magnesium resultant of high-load, select the EDTA standard titration solution titration of 0.02mol/L, allow the volume milliliter numerical control of vs below 50mL, avoided the vs of low concentration to make the volume milliliter number of titration greater than 50 milliliters, liquid feeding carries out reading to zero point and titration has once more influenced analysis speed, increase the uncertainty of measuring simultaneously, and then influenced the accuracy of analyzing.
5. when titration calcium magnesium resultant or direct titration magnesium oxide, two kinds of indicator with adding directly are made into the disposable adding of mixed indicator, have simplified operation steps, and mixed indicator is put in the refrigerator and can preserves more than three months.
7. the method by major component in fast measuring active lime provided by the present invention, the passive lime, analyze calcium oxide and magnesium oxide in an active lime, the passive lime sample, need 30 minutes approximately, and the alkali fusion method that prior art adopts needs 2 hours approximately, obviously shorten analysis time, alleviated analyst's labour intensity.
8. analytical approach agents useful for same provided by the present invention is few, and is economical, simple, quick, shortened analysis time greatly, and accuracy and precision can satisfy the express-analysis requirement well.
The invention provides and a kind ofly directly active lime, passive lime sample are carried out constant volume after the heating for dissolving with hydrochloric acid, carry out the titration of part test solution and measure the method for major component in active lime, the passive lime, through repeatedly test and obtain the correction coefficient of passive lime, can obtain and the basic the same accuracy of national standard analytical approach after calibrated; Select EDTA or the titration of EGTA standard titration solution of 0.02mol/L, select the combination of sample weighting amount, constant volume and the branch amount of getting, the sample size that allows branch get in the test solution is 0.05g, and the volume milliliter numerical control that makes vs has improved the accuracy of analyzing below 50mL; When carrying out titration calcium magnesium resultant or direct titration magnesium oxide, two kinds of indicator that separately add are made into mixed indicator once to add, avoid the repetition liquid feeding all to reduce the running time jointly with the concentration of front acid decomposition samples and control criterion volumetric soiutions, reduce analyst's labour intensity; During with CyDTA titrand titration magnesium oxide, replace minusing titration magnesium, reduced error transfer, improved accuracy of measurement with direct titrimetric method.Simultaneously, take to reduce the concentration of CyDTA, directly low content oxidation magnesium in the sample is carried out titration, increase titration milliliter number, further improved the accuracy of measuring.
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Embodiment
Take by weighing 0.1g～0.50g, 0.5000g preferably, (accurately to 0.0001g) has been prepared as granularity less than 0.125mm, place the active lime of air-tight bottle, the passive lime sample, carry out blank test in company with sample, place the heating container of 100mL～250mL, preferably adopt 150mL baked cup for heating container, adding 30mL～100mL concentration ratio is the hydrochloric acid solution of 1 to 1 to 1 to 5 scope, sample size and hydrochloric acid consumption are corresponding, when sample weighting amount after a little while, the molten sample of hydrochloric acid solution of a spot of or low concentration ratio of corresponding usefulness, be preferably 100mL concentration and be 1 to 3 hydrochloric acid, if sample decomposes not exclusively, can add 10mL concentration at every turn and be 1 to 3 hydrochloric acid, or select the hydrochloric acid and the consumption dissolved samples of other concentration, decomposition samples is to complete on well heater, the passive lime sample has a little insolubles, is cooled to room temperature, and solution is moved in the volumetric flask, be diluted with water to scale, mixing behind the constant volume extracts two parts of test solutions respectively, when the sample size that takes by weighing is 0.50g, be settled to the 200mL volumetric flask, extract two parts of 20.00mL test solutions; Be settled to the 250mL volumetric flask, extract two parts of 25.00mL test solutions; Be settled to the 500mL volumetric flask, extract two parts of 50.00mL test solutions; When the sample size that takes by weighing is 0.40g, be settled in the 200mL volumetric flask, extract two parts of 25.00mL test solutions; When the sample size that takes by weighing is 0.20g, be settled in the 100mL volumetric flask, extract two parts of 25.00mL test solutions; When the sample size that takes by weighing is 0.10g, be settled in the 100mL volumetric flask, get two parts of 50.00mL test solutions; Divide behind the different in a word sample weighting amount constant volume different volumes and get that sample size is 0.05g in the test solution.
The branch amount of getting of the amount of taking by weighing of sample, constant volume and test solution has certain relation, guarantee to divide and to get that sample size is that 0.05g gets final product in the test solution, to get in the test solution sample size too little because divide, enlarged analytical error during calculating, divide that to get in the test solution sample size too big, the titer of standard titration solution surpasses the buret range of capacity easily, and liquid feeding and reading easily increase measuring error and analysis time once more.For example during sample weighting amount 0.5000g,, get 25.00mL respectively,, get 20.00mL respectively if be settled in the 200mL volumetric flask if be settled in the 250mL volumetric flask; If be settled in the 500mL volumetric flask, get 50.00mL respectively; During sample weighting amount 0.4000g, be settled in the 200mL volumetric flask, get 25.00mL respectively and can guarantee that branch gets that sample size is 0.05000g in the test solution; Control divides and to get that sample size is 0.05000g in the test solution in these examples of enumerating, be convenient to the calculating of formula 1～formula 4, other sample weighting amount, constant volume and branch get branch that the test solution amount obtains get in the test solution sample size for 0.05000g (sample weighting amount 0.4987g for example, constant volume 250mL divides and gets 25.00mL; Sample weighting amount 0.4015g, constant volume 200mL divides and to get 25.00mL or the like) situation do not enumerate one by one.Preferably be settled in the 250mL volumetric flask, get the 25.00mL test solution respectively.
If specimen preparation is even, representative, composition measurement to the varying number level, general sample weighting amount is 0.1g～1g, and owing to calcium oxide and calcium magnesium resultant content in active lime, the passive lime sample are higher, sample weighting amount is decided to be 0.1g～0.50g, but guarantee the representativeness of starting material sample powder-like again, get the concentration of sample weighting amount and the increasing standard titration solution of 0.50g, can avoid the consumption of the unnecessary buret of volumetric soiutions and the expansion of titration error, guarantee the representativeness of sample analysis simultaneously.
The preferred sample 0.5000g that claims, molten sample under optimum condition is settled in the 250mL volumetric flask, gets the 25.00mL test solution respectively.
The titration of calcium oxide content is: add 3mL～15mL in the described test solution of portion, 5mL preferably, concentration is 1 to 1 triethanolamine solution mixing, the potassium hydroxide solution that adds 200g/L, or sodium hydroxide solution, or the pH value of other solution when guaranteeing titration is greater than 12, and do not influence the strong alkali solution 20mL of follow-up titration step and analysis result, the potassium hydroxide solution of preferred 200g/L, the calcon-carboxylic acid that adds 4～5 5g/L, mixing, becoming sapphirine to test solution by redness with the EGTA standard titration solution titration of 0.02mol/L is terminal point, the EGTA standard titration solution body that consume this moment is V
1, blank test solution adds the magnesium oxide standard solution of 3～4 1.00mg/mL before titration, and by formula (1) calculates the content of calcium oxide:
In the formula: w
CaO---CaO massfraction, %;
V
1---calcium oxide consumes the volume of EGTA standard titration solution, mL in the titration test solution;
V
01---calcium oxide consumes the volume of EGTA standard titration solution, mL in the titration blank test solution;
C---the concentration of EGTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g;
For the calcium oxide in the passive lime, the result of formula (1) is added 0.3% correction coefficient, calcium oxide content in the passive lime that gets final product to the end, that is:
Magnesian titration: in the described test solution of another part, add 3mL～15mL, 5mL preferably, concentration is 1 to 1 triethanolamine solution mixing, the EGTA standard solution that adds 0.02mol/L, the milliliter number of the EGTA standard solution that consumes when its addition equals the titration calcium oxide, and excessive 0.2mL, add 15mL～30mL, the ammonia buffer solution of the pH 10 of 20mL preferably, add 4～5 soluble in water by 0.5g naphthol green B and 0.2g acid chromium blue k, be diluted with water to the magnesium indicator solution of 70mL, becoming pewter to test solution by redness with the CyDTA standard titration solution titration of 0.005mol/L is terminal point, the CyDTA standard titration solution volume V that consume this moment
2, use V
2By formula (3) calculate magnesian content:
In the formula: w
MgO---MgO massfraction, %;
V
2---magnesium oxide consumes the volume of CyDTA standard titration solution, mL in the titration test solution;
V
02---magnesium oxide consumes the volume of CyDTA standard titration solution, mL in the titration blank test solution;
C---the concentration of CyDTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g.
Can also adopt following mode of operation for magnesium oxide greater than 1% sample,
The titration of calcium oxide content: in its operation steps and account form and the leading portion titration of calcium oxide content described consistent, just titrimetric standard solution changes the EDTA standard titration solution into, so repeat no more;
The titration of calcium oxide, magnesium oxide resultant is: add 3mL～15mL in the described test solution of another part, preferably 5mL concentration is 1 to 1 triethanolamine solution mixing, add 15mL～30mL, the ammonia buffer solution of the PH10 of 20mL preferably, add 4～5 soluble in water by 0.5g naphthol green B and 0.2g acid chromium blue k, be diluted with water to the magnesium indicator solution of 70mL, becoming pewter to test solution by kermesinus with the EDTA standard titration solution titration of 0.02mol/L is terminal point, the EDTA standard titration solution volume V that consume this moment
3, by formula (4) calculate magnesian content:
In the formula: w
MgO---MgO massfraction, %;
V
3---calcium oxide, magnesium oxide resultant consume the volume of EDTA standard titration solution, mL in the titration test solution;
V
03---calcium oxide, magnesium oxide resultant consume the volume of EDTA standard titration solution, mL in the titration blank test solution;
V
1---calcium oxide consumes the volume of EDTA standard titration solution, mL in the titration test solution;
V
01---calcium oxide consumes the volume of EDTA standard titration solution, mL in the titration blank test solution;
C---the concentration of EDTA standard titration solution, mol/L;
M---divide and get the suitable sample size of test solution, g.
In line with the analytical reactions condition certain selectable range is arranged all, often near the condition the selectable range center all is the best of reaction and guarantees condition, use reagent simultaneously less as far as possible, so the optimum condition great majority are near the conditions the selectable analysis condition scope center, guarantee the top condition of finishing and reacting of analytical reactions.
It is related using concentration and the volume of reagent in analytic process, as long as the solute amount unanimity in the reagent that adds, reaction finishes that the while does not influence the subsequent analysis step and analytical accuracy gets final product in the time of many.For example, in the reality, add 20mL potassium hydroxide solution (200g/L), when the concentration of potassium hydroxide solution became 400g/L by 200g/L, the amount of its adding reduced by half and also can reach identical effect.
Follow the amphitypy social construction principle of current promotion in this analysis method; vigorously advocate environmental protection analytical chemistry; can reach the same effect of reaction with few amount of reagent of trying one's best; should advocate and use up a spot of amount of reagent; if according to this method scaled down or amplify reagent dosage and sample size also can reach purpose of the present invention, also should be within the present invention's scope required for protection.
Below, adopt the method for major component in a kind of fast measuring active lime provided by the present invention, the passive lime that 5 active limes and passive lime sample are analyzed, the result contrasts as following table 1～table 4.
Table 1: active lime sample calcium oxide analysis result (%)
| Method name | 1# | 2# | 3# | 4# | 5# |
| National Standard Method | 89.87 | 92.20 | 93.54 | 93.66 | 90.63 |
| This law | 89.36 | 92.42 | 93.08 | 93.34 | 90.59 |
| Standard deviation | 0.34 | / | / | 0.26 | / |
| Relative standard deviation | 0.38 | / | / | 0.28 | / |
Table 2: active lime sample magnesium oxide analysis result (%)
| Method name | 1# | 2# | 3# | 4# | 5# |
| National Standard Method | 1.95 | 1.12 | 1.04 | 0.99 | 1.74 |
| This law | 1.81 | 1.19 | 0.93 | 0.94 | 1.83 |
| Standard deviation | 0.051 | / | / | 0.054 | / |
| Relative standard deviation | 2.82 | / | / | 5.74 | / |
Table 3: calcium oxide analysis result (%) in the passive lime sample
| Method name | 6# | 7# | 8# | 9# | 10# |
| National Standard Method | 92.21 | 88.60 | 69.97 | 89.93 | 88.35 |
| This law (not proofreading and correct) | 91.87 | 87.94 | 69.32 | 89.77 | 87.67 |
| This law (proofreading and correct the back) | 92.17 | 88.24 | 69.62 | 90.07 | 87.97 |
| Standard deviation | 0.37 | / | 0.45 | / | / |
| Relative standard deviation | 0.40 | / | 0.65 | / | / |
Table 4: magnesium oxide analysis result (%) in the passive lime sample
| Method name | 6# | 7# | 8# | 9# | 10# |
| National Standard Method | 0.24 | 0.33 | 1.52 | 0.50 | 0.28 |
| This law | 0.27 | 0.28 | 1.42 | 0.51 | 0.24 |
| Standard deviation | 0.021 | / | 0.036 | / | / |
| Relative standard deviation | 7.78 | / | 2.54 | / | / |
The national standard analytical approach standard GB/T3286.1-1998 of lime stone, rauhkalk is to calcium oxide and magnesian tolerance scope following (%): CaO≤70.00, tolerance 0.50, CaO 〉=70.00, tolerance 0.60; MgO 0.10～0.50, tolerance 0.05, MgO＞0.50～1.00, tolerance 0.08, MgO＞1.00～2.50, tolerance 0.15.Contrasting data as can be known from table, this law and National Standard Method have consistance preferably, standard deviation and relative standard deviation data presentation, the inventive method have good precision, can satisfy calcium oxide in active lime, the passive lime, magnesian express-analysis requirement fully.
When actual analysis, if adopt technical scheme disclosed in this invention, sample size is lower than 0.05g in the test solution of getting but divide, or other concentration standard solution that is lower than 0.02mol/L concentration comes titration, or used the volume of the unnecessary buret range of capacity of standard titration solution amount, operate through those of ordinary skill in the art, the requirement that in general accuracy of analyzing and precision can be lower than the inventive method, but the operating personnel that analytical technology is very consummate utilize himself operation skill and experience, as long as follow operation steps disclosed in this invention, also may reach this analysis method accuracy and precision.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all also should be encompassed in the middle of the claim scope of the present invention.
Claims (10)
1. the method for major component in fast measuring active lime or the passive lime is characterized in that, may further comprise the steps:
Step 1, claim active lime or the passive lime sample of an amount of granularity less than 0.125mm, accurately to 0.0001g, carry out blank test in company with sample, place heating container, add hydrochloric acid solution, sample size is corresponding with the hydrochloric acid consumption, when sample weighting amount after a little while, the molten sample of hydrochloric acid solution of a spot of or low concentration ratio of corresponding usefulness, heating and decomposition sample are to fully, and the passive lime sample has a little insolubles, be cooled to room temperature, solution is moved in the volumetric flask, be diluted with water to scale, mixing behind the constant volume, extract two parts of an amount of test solutions respectively, guarantee to divide and to get that sample size is 0.05g in the test solution;
Step 2,
The titration of calcium oxide content: adding 3mL～15 mL concentration in the described test solution of portion is 1 to 1 triethanolamine solution mixing, the potassium hydroxide solution that adds 200g/L, or sodium hydroxide solution, or the pH value of other solution when guaranteeing titration is greater than 12, and do not influence the strong alkali solution 20mL of follow-up titration step and analysis result, the calcon-carboxylic acid that adds 4～5 5g/L, mixing, becoming sapphirine to test solution by redness with the EGTA standard titration solution titration of 0.02mol/L is terminal point, and the EGTA standard titration solution volume that consume this moment is V
1, blank test solution adds the magnesium oxide standard solution of 3～4 1.00mg/mL before titration, and by formula (1) calculates the content of calcium oxide:
In the formula:
w CaO---CaO massfraction, %;
V
1---calcium oxide consumes the volume of EGTA standard titration solution, mL in the titration test solution;
V
01---calcium oxide consumes the volume of EGTA standard titration solution, mL in the titration blank test solution;
C---the concentration of EGTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g;
For the calcium oxide in the passive lime, the result of formula (1) is added 0.3% correction coefficient, calcium oxide content in the passive lime that gets final product to the end, that is:
＋0.3 （2）
Magnesian titration: adding 3mL～15 mL concentration in the described test solution of another part is 1 to 1 triethanolamine solution mixing, the EGTA standard solution that adds 0.02mol/L, its addition during than the titration calcium oxide milliliter number of the EGTA standard solution that consumes many 0.2mL, after adding 15mL～30 mL PH values and be 10 ammonia buffer solution, add 2 5g/L acid chromium blue k solution and 5～6 5g/L naphthol green B solution respectively, mixing, becoming pewter to test solution by redness with the CyDTA standard titration solution titration of 0.005 mol/L is terminal point, the CyDTA standard titration solution volume V that consume this moment
2, use V
2By formula (3) calculate magnesian content:
In the formula: w
MgO---MgO massfraction, %;
V
2---magnesium oxide consumes the volume of CyDTA standard titration solution, mL in the titration test solution;
V
02---magnesium oxide consumes the volume of CyDTA standard titration solution, mL in the titration blank test solution;
C---the concentration of CyDTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g.
2. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 1 or the passive lime,
Step 2 is, greater than 1% sample, described step 2 replaces with following operation steps for magnesium oxide,
The titration of calcium oxide content: in operation steps and account form thereof the step 2 as claimed in claim 1 the titration of calcium oxide content described, just titrimetric standard solution changes the EDTA standard titration solution into;
The titration of calcium oxide, magnesium oxide resultant: in the described test solution of another part, add 3mL～15mL concentration and be 1 to 1 triethanolamine solution mixing, after adding 15mL～30 mL pH values and be 10 ammonia buffer solution, acid chromium blue k solution and 5～6 5g/L naphthol green B solution of adding 2 5g/L respectively, mixing, becoming pewter to test solution by kermesinus with the EDTA standard titration solution titration of 0.02mol/L is terminal point, the EDTA standard titration solution volume V that consume this moment
3, by formula (4) calculate magnesian content:
（4）
In the formula:
w MgO---MgO massfraction, %;
V
3---calcium oxide, magnesium oxide resultant consume the volume of EDTA standard titration solution, mL in the titration test solution;
V
03---calcium oxide, magnesium oxide resultant consume the volume of EDTA standard titration solution, mL in the titration blank test solution;
V
1---calcium oxide consumes the volume of EDTA standard titration solution, mL in the titration test solution;
V
01---calcium oxide consumes the volume of EDTA standard titration solution, mL in the titration blank test solution;
C---the concentration of EDTA standard titration solution, mol/L;
M---divide the sample size of getting in the test solution, g.
3. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 1 or 2 or the passive lime,
Step 1 is, take by weighing 0.1g～0.50g, accurately to 0.0001g, granularity is less than active lime or the passive lime sample of 0.125mm, carry out blank test in company with sample, place 100mL～250mL heating container, adding 30mL～100 mL concentration ratios is the hydrochloric acid solution of 1 to 1 to 1 to 5 scope, sample size and hydrochloric acid consumption are corresponding, when sample weighting amount after a little while, the molten sample of hydrochloric acid solution of a spot of or low concentration ratio of corresponding usefulness, the heating and decomposition sample is to complete, the passive lime sample has a little insolubles, is cooled to room temperature, and solution is moved in the volumetric flask, be diluted with water to scale, mixing behind the constant volume extracts two parts of test solutions respectively, guarantee to divide to get that sample size is 0.05g in the test solution.
4. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 3 or the passive lime,
Step 1 is, when the sample size that takes by weighing is 0.50g, is settled to 200 mL volumetric flasks, extracts two parts of 20.00 mL test solutions; Be settled to 250 mL volumetric flasks, extract two parts of 25.00 mL test solutions; Be settled to 500 mL volumetric flasks, extract two parts of 50.00 mL test solutions; When the sample size that takes by weighing is 0.40g, be settled in the 200mL volumetric flask, extract two parts of 25.00mL test solutions; When the sample size that takes by weighing is 0.20g, be settled in the 100mL volumetric flask, extract two parts of 25.00mL test solutions; When the sample size that takes by weighing is 0.10g, be settled in the 100mL volumetric flask, get two parts of 50.00mL test solutions.
5. as the sharp method that requires major component in 1 described a kind of fast measuring active lime or the passive lime, it is characterized in that,
Step 1 is to take by weighing 0.50g, accurately to 0.0001g, granularity is carried out blank test less than active lime or the passive lime sample of 0.125mm in company with sample, places the 150ml beaker, adding 100mL concentration is 1 to 3 hydrochloric acid solution, and the heating and decomposition sample is to complete, and the passive lime sample has a little insolubles, be cooled to room temperature, solution is moved in the 250mL volumetric flask, be diluted with water to scale, mixing behind the constant volume, extract two parts of 25.00mL test solutions respectively, guarantee to divide and to get that sample size is 0.05g in the test solution;
Step 2 is,
The titration of calcium oxide content: in the described test solution of portion, add 5mL concentration and be 1 to 1 triethanolamine solution mixing, the potassium hydroxide solution 20mL that adds 200g/L, the calcon-carboxylic acid that adds 4～5 5g/L, mixing, becoming sapphirine to test solution by redness with the EGTA standard titration solution titration of 0.02mol/L is terminal point, and the EGTA standard titration solution volume that consume this moment is V
1, blank test solution adds the magnesium oxide standard solution of 3～4 1.00mg/mL before titration, and by formula (1) calculates the content of calcium oxide;
For the calcium oxide in the passive lime, the result of formula (1) is added 0.3% correction coefficient, calcium oxide content in the passive lime that gets final product to the end;
Magnesian titration: in the described test solution of another part, add 5 mL concentration and be 1 to 1 triethanolamine solution mixing, the EGTA standard solution that adds 0.02mol/L, its addition during than the titration calcium oxide milliliter number of the EGTA standard solution that consumes many 0.2mL, add 20 mL, pH value is behind 10 the ammonia buffer solution, add 2 5g/L acid chromium blue k solution and 5～6 5g/L naphthol green B solution respectively, mixing, becoming pewter to test solution by redness with the CyDTA standard titration solution titration of 0.005 mol/L is terminal point, the CyDTA standard titration solution volume V that consume this moment
2, use V
2By formula (3) calculate magnesian content.
6. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 2 or the passive lime,
The titration of calcium oxide content: in operation steps and account form thereof the step 2 as claimed in claim 1 the titration of calcium oxide content described, just titrimetric standard solution changes the EDTA standard titration solution into;
Titration to calcium oxide, magnesium oxide resultant: in the described test solution of another part, add 5mL concentration and be 1 to 1 triethanolamine solution mixing, add 20mL, pH value is 10 ammonia buffer solution, acid chromium blue k solution and 5～6 5g/L naphthol green B solution of adding 2 5g/L respectively, mixing, becoming pewter to test solution by kermesinus with the EDTA standard titration solution titration of 0.02mol/L is terminal point, the EDTA standard titration solution volume V that consume this moment
3, by formula (4) calculate magnesian content.
7. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 1 or 2 or the passive lime,
In step 2, adding acid chromium blue k solution and the naphthol green B solution that is added after 15mL～30 mL pH values are 10 ammonia buffer solution, soluble in water according to 0.5g naphthol green B and 0.2g acid chromium blue k, the method that is diluted with water to 70mL is made magnesium mixed indicator solution in advance, once adds 4～5 when titration.
8. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 3 or the passive lime,
In step 2, adding acid chromium blue k solution and the naphthol green B solution that is added after 15mL～30 mL pH values are 10 ammonia buffer solution, soluble in water according to 0.5g naphthol green B and 0.2g acid chromium blue k, the method that is diluted with water to 70mL is made magnesium mixed indicator solution in advance, once adds 4～5 when titration.
9. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 4 or the passive lime,
In step 2, adding acid chromium blue k solution and the naphthol green B solution that is added after 15mL～30 mL pH values are 10 ammonia buffer solution, soluble in water according to 0.5g naphthol green B and 0.2g acid chromium blue k, the method that is diluted with water to 70mL is made magnesium mixed indicator solution in advance, once adds 4～5 when titration.
10. the method for major component is characterized in that in a kind of fast measuring active lime as claimed in claim 5 or the passive lime,
In step 2, adding acid chromium blue k solution and the naphthol green B solution that is added after the 20mL pH value is 10 ammonia buffer solution, soluble in water according to 0.5g naphthol green B and 0.2g acid chromium blue k, the method that is diluted with water to 70mL is made magnesium mixed indicator solution in advance, once adds 4～5 when titration.
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