CN105067758A - Method for measuring content of carbonyl oxygen-containing functional groups on surface of carbon black - Google Patents

Abstract

The invention relates to a method for measuring the content of carbonyl oxygen-containing functional groups on the surface of carbon black. The method aims at solving the problems that in the prior art, when an existing method for measuring the content of carbonyl oxygen-containing functional groups on the surface of carbon black is used, large devices are needed and calculation is complex. The method includes the steps of firstly, configuring and calibrating a standard solution; secondly, measuring a carbon black sample; thirdly, calculating the content of carbonyl oxygen-containing functional groups on the surface of unit carbon black according to the result. The method is completed through a chemical tritration method, experiment steps and calculation steps are simple, no large devices need to be used, the method is easy to implement, and the measurement result is accurate. The method is suitable for measuring the content of carbonyl oxygen-containing functional groups on the surface of carbon black.

Description

A kind of method measuring carbon blacksurface carbonyl oxygen-containing functional group content

Technical field

The present invention relates to a kind of assay method of carbonyl oxygen-containing functional group content.

Background technology

The surface chemical property of carbon black is often referred to the type and content etc. of hydrogen richness, oxygen content, volatile matter, pH value and surface functional group, and the oxygen-containing functional group of carbon blacksurface is the most remarkable to the property effect of carbon black.As can be seen from Fourier transform infrared spectroscopy figure, be combined with the major surfaces oxygen-containing functional groups such as carbonyl, phenolic hydroxyl group, carboxyl and lactone group at the huge aromatic condensed ring periphery of carbon black.These oxy radicals are hydrophilic, and are easy to form hydrogen bond inside water-based system.The increase of these group contents, is conducive to carbon black stable dispersion in water-based system.

At present, domestic perfect not containing quantifier elimination to carbon black oxygen-containing functional group, the content of element in carbon black can be measured by x-ray photoelectron power spectrum (XPS) spectrum analysis, again by very complicated series of computation, the general content that can hammer out group, but the data that this method obtains are inaccurate, and calculation of complex.Employing fourier transform infrared spectroscopy can measure the oxygen-containing functional group that carbon blacksurface contains, and but cannot measure the content of functional group.Patent CN104359907A (2015.02.18), the titration method recorded in " evaluation of activated carbon surface oxygen-containing functional group " solves the problem measuring activated carbon surface carboxyl, lactone group, phenolic hydroxyl group oxygen-containing functional group content, but carbon black is not illustrated, and the mensuration of carbonyl content is not also illustrated.The academic dissertation " oxidation modification of black carbon and the research to fragrant pollutant absorption behavior thereof " of Zhejiang Polytechnical University Ruan Chu Qi has measured the content of black carbon surface carboxyl, lactone group, phenolic hydroxyl group acidic functionality and basic functionality, but to carbonyl not research.University Of Tianjin thanks to the academic dissertation " research of carbon blacksurface graft modification and dispersion stability thereof " raised and uses sodium bicarbonate, sodium carbonate, NaOH and TBAH to indicate highly acid carboxyl, faintly acid carboxyl, the respective content of phenolic hydroxyl group three functional groups and the total content of other faintly acid group, the content of this functional group of carbonyl is not tested, be not specifically described yet.

Summary of the invention

The present invention will solve the problem that method that prior art measures carbon blacksurface carbonyl oxygen-containing functional group content needs main equipment, calculation of complex, and provides a kind of method utilizing chemistry titration to measure carbon blacksurface carbonyl oxygen-containing functional group content.

A kind of method measuring carbon blacksurface carbonyl oxygen-containing functional group content of the present invention follows these steps to realize:

The configuration of step one, standard solution and demarcation

Prepare respectively and demarcate the NaOCH of the HCl standard solution of 0.1mol/L, the NaOH standard solution of 0.1mol/L and 0.1mol/L ₂cH ₃standard solution;

Step 2, sample determination

1., get the carbon black of the carbon black of particle diameter≤75 μm, in vacuum drying chamber, dry 36h for 120 DEG C, put in exsiccator and preserve;

2., take 2 parts of carbon black samples with electronic balance and be placed in No. 1 flask and No. 2 flasks respectively; The NaOCH of excessive 0.1mol/L is added in No. 1 flask ₂cH ₃standard solution, adds excessive 0.1mol/LNaOH standard solution in No. 2 flasks, respectively by the solution ultrasound wave dispersion 20min in two flasks, backflow 1.5h ~ 3h; The NaOCH of described excessive 0.1mol/L ₂cH ₃standard solution is the NaOCH added in flask ₂cH ₃the amount of standard solution complete reaction can fall carbon blacksurface oxygen-containing functional group, and after reacting completely, the solution in flask is still in alkalescence; The NaOH standard solution of described excessive 0.1mol/L is that the amount of the NaOH standard solution added in flask complete reaction can fall carbon blacksurface oxygen-containing functional group, and after reacting completely, the solution in flask is still in alkalescence;

3. HCl standard solution to the solution in flask, then adding 0.1mol/L in two flasks is respectively acidity, stir solution in beaker adding HCl standard solution simultaneously, finally with the NaOH standard solution of 0.1mol/L, solution in two flasks is titrated to pH=7 respectively; Described be accurate to 0.0001g when taking the quality of carbon black with electronic balance; Described carbon black is the carbon black of surface containing carbonyl; The carbon black that carbonyl is contained on described surface is colour carbon black, conductive black or oxidation modification carbon black; Described oxidation modification carbon black is the colour carbon black of salpeter solution oxidation modification or the conductive black of salpeter solution oxidation modification;

Step 3, result calculate

Carbon black sample is adding NaOCH ₂cH ₃after standard solution, the oxygen-containing functional group of unit mass carbon blacksurface consumes NaOCH ₂cH ₃amount N ₁, be calculated as follows, unit is mmol/g:

N ₁＝(C ₁V ₁+C ₁₁V ₁₁-C ₁₂V ₁₂)/W ₁；

In above-mentioned formula:

C ₁-the NaOCH that adds in carbon black sample ₂cH ₃the concentration of standard solution, unit is mol/L;

V ₁-the NaOCH that adds in carbon black sample ₂cH ₃the volume of standard solution, unit is mL;

C ₁₁-the concentration of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mol/L;

V ₁₁-the volume of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mL;

C ₁₂-adding the concentration of the HCl standard solution in No. 1 flask, unit is mol/L;

V ₁₂-adding the volume of the HCl standard solution in No. 1 flask, unit is mL;

W ₁-adding the quality of the carbon black sample in No. 1 flask, unit is g;

Carbon black sample is after adding NaOH standard solution, and the oxygen-containing functional group of unit mass carbon blacksurface consumes the amount N of NaOH ₂, being calculated as follows unit is mmol/g:

N ₂＝(C ₂V ₂+C ₂₁V ₂₁-C ₂₂V ₂₂)/W ₂

In above-mentioned formula:

C ₂-the concentration of NaOH standard solution that adds in carbon black sample, unit is mol/L;

V ₂-the volume of NaOH standard solution that adds in carbon black sample, unit is mL;

C ₂₁-the concentration of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mol/L;

V ₂₁-the volume of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mL;

C ₂₂-adding the concentration of the HCl standard solution in No. 2 flasks, unit is mol/L;

V ₂₂-adding the volume of the HCl standard solution in No. 2 flasks, unit is mL;

W ₂-adding the quality of the carbon black sample in No. 2 flasks, unit is g;

Finally calculate the calculating namely completing carbon blacksurface carbonyl oxygen-containing functional group assay according to the following formula:

N _RCOR＝N ₁–N ₂

In above-mentioned formula:

N _rCORthe carbonyl oxygen-containing functional group content of-unit mass carbon blacksurface, unit is mmol/g.

Wherein, in described step one, the configuration of HCl standard solution is carried out according to the following steps with demarcation:

One, the concentrated hydrochloric acid measuring 8.4mL massfraction 37% adds in 1000mL distilled water, shakes up and obtains hydrochloric acid solution;

Two, at 270 DEG C by natrium carbonicum calcinatum calcination to constant weight, and take 0.2g, be accurate to 0.0001g, be dissolved in 50mL distilled water, drip 10 bromcresol green-methyl red mixed indicators;

Three, be titrated to solution with the hydrochloric acid solution prepared and become kermesinus from green, boil 2min, continue titration after cooling and make solution again in kermesinus;

Four, blank test: add 50mL distilled water in conical flask, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the hydrochloric acid solution prepared, and continues titration and make solution again in kermesinus after cooling;

Five, hydrochloric acid standard solution concentration is calculated as follows:

$C_{HCl}=\frac{m}{(V_a-V_b)\×0.05299}$

In above-mentioned formula:

C _hCl-hydrochloric acid standard solution substance withdrawl syndrome, unit is mol/L;

M-natrium carbonicum calcinatum quality, unit is g;

V _a-hydrochloric acid solution consumption, unit is mL;

V _b-blank test hydrochloric acid solution consumption, unit is mL;

The quality of 0.05299-suitable with 1.00mL, the 1.000mol/L hydrochloric acid standard solution natrium carbonicum calcinatum represented with gram (g).

In described step one, the configuration of NaOH standard solution is carried out according to the following steps with demarcation:

One, take the NaOH of 4.0g, be accurate to 0.0001g, be placed in plastic beaker, inject 1000mL without the water of carbon dioxide, make it shake up and obtain NaOH solution after dissolving;

Two, at 110 DEG C, benchmark Potassium Hydrogen Phthalate is dried to constant weight, and take 0.6g, be accurate to 0.0001g, be dissolved in 50mL volume without in the water of carbon dioxide, add 2 instructions phenolphthalein solutions, carry out titration by the NaOH solution of preparation in step one, be titrated to solution pinkiness and keep 30s colour-fast;

Three, blank test: add the water of 50mL without carbon dioxide in conical flask, adds 2 instructions phenolphthalein solutions, carries out titration, be titrated to solution pinkiness and keep 30s colour-fast by the NaOH solution of preparation in step one;

Four, NaOH concentration of standard solution is calculated as follows:

$C_{NaOH}=\frac{m}{(V_c-V_d)\×\mathrm{0.0.2042}}$

In above-mentioned formula:

C _naOH-NaOH standard solution substance withdrawl syndrome, unit is mol/L;

M-Potassium Hydrogen Phthalate quality, unit is g;

V _c-NaOH standard solution consumption, unit is mL;

V _d-blank test NaOH standard solution consumption, unit is mL;

The quality of 0.2042-suitable with 1.00mL, the 1.000mol/LNaOH standard solution Potassium Hydrogen Phthalate represented with gram (g).

NaOCH in described step one ₂cH ₃the configuration of standard solution is carried out according to the following steps with demarcation:

One, 6.8g anhydrous Na OCH is taken ₂cH ₃, be dissolved in 1000mL absolute ethyl alcohol, shake up, obtain NaOCH ₂cH ₃solution;

Two, the NaOCH configured in 30mL step one is measured ₂cH ₃solution, adds 20mL absolute ethyl alcohol, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the HCl standard solution of 0.1mol/L, continues to be titrated to solution again in kermesinus after cooling;

Three, NaOCH ₂cH ₃the concentration of standard solution is calculated as follows:

$C_{{\mathrm{NaOCH}}_2{\mathrm{CH}}_3}=C_{HCl}\×\frac{V_e}{V_f}$

In above-mentioned formula:

C _naOCH2CH3-NaOCH ₂cH ₃standard solution substance withdrawl syndrome, unit is mol/L;

C _hCl-HCl standard solution substance withdrawl syndrome, unit is mol/L;

V _e-hydrochloric acid standard solution consumption, unit is mL;

V _f-measuring caustic alcohol standard solution consumption, unit is mL.

The present invention comprises following beneficial effect:

Present invention utilizes NaOCH ₂cH ₃this strong alkaline substance, can react with acid oxygen-containing functional groups such as the carboxyl of carbon blacksurface, lactone group, phenolic hydroxyl group, carbonyls, and NaOH can react with acid oxygen-containing functional groups such as the carboxyl of carbon blacksurface except carbonyl, lactone group, phenolic hydroxyl groups, consumes NaOCH respectively according to unit mass carbon black ₂cH ₃amount be easy to the difference of amount consuming NaOH the content calculating carbon blacksurface carbonyl.The method design that the present invention measures carbon blacksurface carbonyl oxygen-containing functional group content is reasonable, and completed by chemistry titration method, experimental procedure is simply easy to implement; Assay method of the present invention goes for measuring arbitrarily containing the content of the carbon blacksurface carbonyl functional group of carbonyl, applied widely; Assay method of the present invention can exempt the use of large-scale instrument, simple to operate, is very easy to implement, and testing cost is lower; Assay method calculation procedure of the present invention is simple, and calculated amount is little, improves work efficiency; Assay method test result of the present invention is accurate, can be as accurate as 0.0001.

Embodiment

Embodiment one: the method that present embodiment measures carbon blacksurface carbonyl oxygen-containing functional group content follows these steps to implement:

The configuration of step one, standard solution and demarcation

Prepare respectively and demarcate the NaOCH of the HCl standard solution of 0.1mol/L, the NaOH standard solution of 0.1mol/L and 0.1mol/L ₂cH ₃standard solution;

Step 2, sample determination

1., get the carbon black of particle diameter≤75 μm, in vacuum drying chamber, dry 36h for 120 DEG C, put in exsiccator and preserve;

2., take 2 parts of carbon black samples with electronic balance and be placed in No. 1 flask and No. 2 flasks respectively; The NaOCH of excessive 0.1mol/L is added in No. 1 flask ₂cH ₃standard solution, adds excessive 0.1mol/LNaOH standard solution in No. 2 flasks, respectively by the solution ultrasound wave dispersion 20min in two flasks, backflow 1.5h ~ 3h;

3. HCl standard solution to the solution in flask, then adding 0.1mol/L in two flasks is respectively acidity, stir solution in beaker adding HCl standard solution simultaneously, finally with the NaOH standard solution of 0.1mol/L, solution in two flasks is titrated to pH=7 respectively;

Step 3, result calculate

Carbon black sample is adding NaOCH ₂cH ₃after standard solution, the oxygen-containing functional group of unit mass carbon blacksurface consumes NaOCH ₂cH ₃amount N ₁, be calculated as follows, unit is mmol/g:

N ₁＝(C ₁V ₁+C ₁₁V ₁₁-C ₁₂V ₁₂)/W ₁；

In above-mentioned formula:

C ₁-the NaOCH that adds in carbon black sample ₂cH ₃the concentration of standard solution, unit is mol/L;

V ₁-the NaOCH that adds in carbon black sample ₂cH ₃the volume of standard solution, unit is mL;

C ₁₁-the concentration of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mol/L;

V ₁₁-the volume of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mL;

C ₁₂-adding the concentration of the HCl standard solution in No. 1 flask, unit is mol/L;

V ₁₂-adding the volume of the HCl standard solution in No. 1 flask, unit is mL;

W ₁-adding the quality of the carbon black sample in No. 1 flask, unit is g;

Carbon black sample is after adding NaOH standard solution, and the oxygen-containing functional group of unit mass carbon blacksurface consumes the amount N of NaOH ₂, being calculated as follows unit is mmol/g:

N ₂＝(C ₂V ₂+C ₂₁V ₂₁-C ₂₂V ₂₂)/W ₂

In above-mentioned formula:

C ₂-the concentration of NaOH standard solution that adds in carbon black sample, unit is mol/L;

V ₂-the volume of NaOH standard solution that adds in carbon black sample, unit is mL;

C ₂₁-the concentration of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mol/L;

V ₂₁-the volume of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mL;

C ₂₂-adding the concentration of the HCl standard solution in No. 2 flasks, unit is mol/L;

V ₂₂-adding the volume of the HCl standard solution in No. 2 flasks, unit is mL;

W ₂-adding the quality of the carbon black sample in No. 2 flasks, unit is g;

Finally calculate the calculating namely completing carbon blacksurface carbonyl oxygen-containing functional group assay according to the following formula:

N _RCOR＝N ₁–N ₂

In above-mentioned formula:

N _rCORthe carbonyl oxygen-containing functional group content of-unit mass carbon blacksurface, unit is mmol/g.

The method design of present embodiment is reasonable, and completed by chemistry titration method, experimental procedure is simply easy to implement; Assay method of the present invention goes for measuring arbitrarily containing the content of the carbon blacksurface carbonyl functional group of carbonyl, applied widely; Assay method of the present invention can exempt the use of large-scale instrument, simple to operate, is very easy to implement, and testing cost is lower; Assay method calculation procedure of the present invention is simple, and calculated amount is little, improves work efficiency; Assay method test result of the present invention is accurate, can be as accurate as 0.0001.

Embodiment two: present embodiment and embodiment one are carried out with demarcating according to the following steps unlike the configuration of: the HCl standard solution described in step one:

One, the concentrated hydrochloric acid measuring 8.4mL massfraction 37% adds in 1000mL distilled water, shakes up and obtains hydrochloric acid solution;

Two, at 270 DEG C by natrium carbonicum calcinatum calcination to constant weight, and take 0.2g, be accurate to 0.0001g, be dissolved in 50mL distilled water, drip 10 bromcresol green-methyl red mixed indicators;

Three, be titrated to solution with the hydrochloric acid solution prepared and become kermesinus from green, boil 2min, continue titration after cooling and make solution again in kermesinus;

Four, blank test: add 50mL distilled water in conical flask, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the hydrochloric acid solution prepared, and continues titration and make solution again in kermesinus after cooling;

Five, hydrochloric acid standard solution concentration is calculated as follows:

$C_{HCl}=\frac{m}{(V_a-V_b)\×0.05299}$

In above-mentioned formula:

C _hCl-hydrochloric acid standard solution substance withdrawl syndrome, unit is mol/L;

M-natrium carbonicum calcinatum quality, unit is g;

Va-hydrochloric acid solution consumption, unit is mL;

Vb-blank test hydrochloric acid solution consumption, unit is mL;

The quality of 0.05299-suitable with 1.00mL, the 1.000mol/L hydrochloric acid standard solution natrium carbonicum calcinatum represented with gram (g).Other step is identical with embodiment one.

Embodiment three: present embodiment and embodiment one or two are carried out with demarcating according to the following steps unlike the configuration of: the NaOH standard solution described in step one:

One, take the NaOH of 4.0g, be accurate to 0.0001g, be placed in plastic beaker, inject 1000mL without the water of carbon dioxide, make it shake up and obtain NaOH solution after dissolving;

Two, at 110 DEG C, benchmark Potassium Hydrogen Phthalate is dried to constant weight, and take 0.6g, be accurate to 0.0001g, be dissolved in 50mL volume without in the water of carbon dioxide, add 2 instructions phenolphthalein solutions, carry out titration by the NaOH solution of preparation in step one, be titrated to solution pinkiness and keep 30s colour-fast;

Three, blank test: add the water of 50mL without carbon dioxide in conical flask, adds 2 instructions phenolphthalein solutions, carries out titration, be titrated to solution pinkiness and keep 30s colour-fast by the NaOH solution of preparation in step one;

Four, NaOH concentration of standard solution is calculated as follows:

$C_{NaOH}=\frac{m}{(V_c-V_d)\×\mathrm{0.0.2042}}$

In above-mentioned formula:

C _naOH-NaOH standard solution substance withdrawl syndrome, unit is mol/L;

M-Potassium Hydrogen Phthalate quality, unit is g;

V _c-NaOH standard solution consumption, unit is mL;

V _d-blank test NaOH standard solution consumption, unit is mL;

The quality of 0.2042-suitable with 1.00mL, the 1.000mol/LNaOH standard solution Potassium Hydrogen Phthalate represented with gram (g).Other step is identical with embodiment one or two.

Embodiment four: one of present embodiment and embodiment one to three are unlike NaOCH described in step one ₂cH ₃the configuration of standard solution is carried out according to the following steps with demarcation:

One, 6.8g anhydrous Na OCH is taken ₂cH ₃, be dissolved in 1000mL absolute ethyl alcohol, shake up, obtain NaOCH ₂cH ₃solution;

Two, the NaOCH configured in 30mL step one is measured ₂cH ₃solution, adds 20mL absolute ethyl alcohol, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the HCl standard solution of 0.1mol/L, continues to be titrated to solution again in kermesinus after cooling.

Three, NaOCH ₂cH ₃the concentration of standard solution is calculated as follows:

$C_{{\mathrm{NaOCH}}_2{\mathrm{CH}}_3}=C_{HCl}\×\frac{V_e}{V_f}$

In above-mentioned formula:

C _naOCH2CH3-NaOCH ₂cH ₃standard solution substance withdrawl syndrome, unit is mol/L;

C _hCl-HCl standard solution substance withdrawl syndrome, unit is mol/L;

V _e-hydrochloric acid standard solution consumption, unit is mL;

V _f-measuring caustic alcohol standard solution consumption, unit is mL.Other step is identical with one of embodiment one to three.

Embodiment five: one of present embodiment and embodiment one to four unlike: described in step 2 take the quality of carbon black with electronic balance time be accurate to 0.0001g.Other step is identical with one of embodiment one to four.

Embodiment six: one of present embodiment and embodiment one to five are the carbon black of surface containing carbonyl unlike: the carbon black described in step 2.Other step is identical with one of embodiment one to five.

Embodiment seven: present embodiment and embodiment six unlike: the carbon black that carbonyl is contained on described surface is colour carbon black, conductive black or oxidation modification carbon black.Other step is identical with embodiment six.

Embodiment eight: present embodiment and embodiment seven unlike: described oxidation modification carbon black is the colour carbon black of salpeter solution oxidation modification or the conductive black of salpeter solution oxidation modification.Other step is identical with embodiment seven.

Embodiment nine: one of present embodiment and embodiment one to eight unlike: get the carbon black that particle diameter is 75 μm in step 2, in vacuum drying chamber 120 DEG C dry 36h, put in exsiccator and preserve.Other step is identical with one of embodiment one to eight.

Embodiment ten: one of present embodiment and embodiment one to nine unlike: get the carbon black that particle diameter is 25 μm in step 2, in vacuum drying chamber 120 DEG C dry 36h, put in exsiccator and preserve.Other step is identical with one of embodiment one to nine.

Embodiment 11: one of present embodiment and embodiment one to ten unlike: reflux in step 2 2h.Other step is identical with one of embodiment one to ten.

Embodiment one:

The present embodiment measures Cabot Co., Ltd M1300 colour carbon black surface carbonyl oxygen-containing functional group content, and assay method follows these steps to realize:

The configuration of step one, standard solution and demarcation

Prepare respectively and demarcate the NaOCH of the HCl standard solution of 0.1mol/L, the NaOH standard solution of 0.1mol/L and 0.1mol/L ₂cH ₃standard solution;

Step 2, sample determination

1., get M1300 colour carbon black (particle diameter is 13nm), in vacuum drying chamber, dry 36h for 120 DEG C, put in exsiccator and preserve;

2., take 2 parts of carbon black samples with electronic balance and be placed in No. 1 flask and No. 2 flasks respectively; The NaOCH of excessive 0.1mol/L is added in No. 1 flask ₂cH ₃standard solution, adds excessive 0.1mol/LNaOH standard solution in No. 2 flasks, respectively by the solution ultrasound wave dispersion 20min in two flasks, backflow 3h;

3. HCl standard solution to the solution in flask, then adding 0.1mol/L in two flasks is respectively acidity, stir solution in beaker adding HCl standard solution simultaneously, finally with the NaOH standard solution of 0.1mol/L, solution in two flasks is titrated to pH=7 respectively;

Step 3, result calculate

Carbon black sample is adding NaOCH ₂cH ₃after standard solution, the oxygen-containing functional group of unit mass carbon blacksurface consumes NaOCH ₂cH ₃amount N ₁, be calculated as follows, unit is mmol/g:

N ₁＝(C ₁V ₁+C ₁₁V ₁₁-C ₁₂V ₁₂)/W ₁；

In above-mentioned formula:

C ₁-the NaOCH that adds in carbon black sample ₂cH ₃the concentration of standard solution, unit is mol/L;

V ₁-the NaOCH that adds in carbon black sample ₂cH ₃the volume of standard solution, unit is mL;

C ₁₁-the concentration of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mol/L;

V ₁₁-the volume of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mL;

C ₁₂-adding the concentration of the HCl standard solution in No. 1 flask, unit is mol/L;

V ₁₂-adding the volume of the HCl standard solution in No. 1 flask, unit is mL;

W ₁-adding the quality of the carbon black sample in No. 1 flask, unit is g;

Carbon black sample is after adding NaOH standard solution, and the oxygen-containing functional group of unit mass carbon blacksurface consumes the amount N of NaOH ₂, being calculated as follows unit is mmol/g:

N ₂＝(C ₂V ₂+C ₂₁V ₂₁-C ₂₂V ₂₂)/W ₂

In above-mentioned formula:

C ₂-the concentration of NaOH standard solution that adds in carbon black sample, unit is mol/L;

V ₂-the volume of NaOH standard solution that adds in carbon black sample, unit is mL;

C ₂₁-the concentration of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mol/L;

V ₂₁-the volume of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mL;

C ₂₂-adding the concentration of the HCl standard solution in No. 2 flasks, unit is mol/L;

V ₂₂-adding the volume of the HCl standard solution in No. 2 flasks, unit is mL;

W ₂-adding the quality of the carbon black sample in No. 2 flasks, unit is g;

Finally calculate the calculating namely completing carbon blacksurface carbonyl oxygen-containing functional group assay according to the following formula:

N _RCOR＝N ₁–N ₂

In above-mentioned formula:

N _rCORthe carbonyl oxygen-containing functional group content of-unit mass carbon blacksurface, unit is mmol/g.

Wherein, in described step one, the configuration of HCl standard solution is carried out according to the following steps with demarcation:

One, the concentrated hydrochloric acid measuring 8.4mL massfraction 37% adds in 1000mL distilled water, shakes up and obtains hydrochloric acid solution;

Two, at 270 DEG C by natrium carbonicum calcinatum calcination to constant weight, and take 0.2g, be accurate to 0.0001g, be dissolved in 50mL distilled water, drip 10 bromcresol green-methyl red mixed indicators;

Three, be titrated to solution with the hydrochloric acid solution prepared and become kermesinus from green, boil 2min, continue titration after cooling and make solution again in kermesinus;

Four, blank test: add 50mL distilled water in conical flask, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the hydrochloric acid solution prepared, and continues titration and make solution again in kermesinus after cooling;

Five, hydrochloric acid standard solution concentration is calculated as follows:

$C_{HCl}=\frac{m}{(V_a-V_b)\×0.05299}$

In above-mentioned formula:

C _hCl-hydrochloric acid standard solution substance withdrawl syndrome, unit is mol/L;

M-natrium carbonicum calcinatum quality, unit is g;

V _a-hydrochloric acid solution consumption, unit is mL;

V _b-blank test hydrochloric acid solution consumption, unit is mL;

The quality of 0.05299-suitable with 1.00mL, the 1.000mol/L hydrochloric acid standard solution natrium carbonicum calcinatum represented with gram (g).

After demarcating, the concentration of HCl standard solution is 0.0977mol/L.

In described step one, the configuration of NaOH standard solution is carried out according to the following steps with demarcation:

One, take the NaOH of 4.0g, be accurate to 0.0001g, be placed in plastic beaker, inject 1000mL without the water of carbon dioxide, make it shake up and obtain NaOH solution after dissolving;

Two, at 110 DEG C, benchmark Potassium Hydrogen Phthalate is dried to constant weight, and take 0.6g, be accurate to 0.0001g, be dissolved in 50mL volume without in the water of carbon dioxide, add 2 instructions phenolphthalein solutions, carry out titration by the NaOH solution of preparation in step one, be titrated to solution pinkiness and keep 30s colour-fast;

Three, blank test: add the water of 50mL without carbon dioxide in conical flask, adds 2 instructions phenolphthalein solutions, carries out titration, be titrated to solution pinkiness and keep 30s colour-fast by the NaOH solution of preparation in step one;

Four, NaOH concentration of standard solution is calculated as follows:

$C_{NaOH}=\frac{m}{(V_c-V_d)\×\mathrm{0.0.2042}}$

In above-mentioned formula:

C _naOH-NaOH standard solution substance withdrawl syndrome, unit is mol/L;

M-Potassium Hydrogen Phthalate quality, unit is g;

V _c-NaOH standard solution consumption, unit is mL;

V _d-blank test NaOH standard solution consumption, unit is mL;

The quality of 0.2042-suitable with 1.00mL, the 1.000mol/LNaOH standard solution Potassium Hydrogen Phthalate represented with gram (g);

After demarcating, the concentration of NaOH standard solution is 0.0985mol/L.

NaOCH in described step one ₂cH ₃the configuration of standard solution is carried out according to the following steps with demarcation:

One, 6.8g anhydrous Na OCH is taken ₂cH ₃, be dissolved in 1000mL absolute ethyl alcohol, shake up, obtain NaOCH ₂cH ₃solution;

Two, the NaOCH configured in 30mL step one is measured ₂cH ₃solution, adds 20mL absolute ethyl alcohol, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the HCl standard solution of 0.1mol/L, continues to be titrated to solution again in kermesinus after cooling;

Three, NaOCH ₂cH ₃the concentration of standard solution is calculated as follows:

$C_{{\mathrm{NaOCH}}_2{\mathrm{CH}}_3}=C_{HCl}\×\frac{V_e}{V_f}$

In above-mentioned formula:

C _naOCH2CH3-NaOCH ₂cH ₃standard solution substance withdrawl syndrome, unit is mol/L;

C _hCl-HCl standard solution substance withdrawl syndrome, unit is mol/L;

V _e-hydrochloric acid standard solution consumption, unit is mL;

V _f-measuring caustic alcohol standard solution consumption, unit is mL.

NaOCH after demarcating ₂cH ₃the concentration of standard solution is 0.0994mol/L.

In experimentation, in strict accordance with correct experimental implementation requirement, to guarantee the accuracy of testing, experimental error to be reduced as far as possible.

Mensuration and the result of calculation of the present embodiment mensuration Cabot Co., Ltd M1300 colour carbon black surface carbonyl oxygen-containing functional group content are as shown in table 1.

Table 1

The method design that the present embodiment measures carbon blacksurface carbonyl oxygen-containing functional group content is reasonable, and completed by chemistry titration method, experimental procedure is simply easy to implement; The present embodiment assay method goes for arbitrarily containing the content of the carbon blacksurface carbonyl functional group of carbonyl, applied widely; The present embodiment assay method can exempt the use of large-scale instrument, simple to operate, is very easy to implement, and testing cost is lower; The present embodiment assay method calculation procedure is simple, and calculated amount is little, improves work efficiency; It is 0.1601mmol/g that the present embodiment measures M1300 colour carbon black surface carbonyl oxygen-containing functional group content.

Embodiment two:

The present embodiment measures the Cabot Co., Ltd M1300 colour carbon black surface carbonyl oxygen-containing functional group content of salpeter solution modification, and assay method follows these steps to realize:

The configuration of step one, standard solution and demarcation

Prepare respectively and demarcate the NaOCH of the HCl standard solution of 0.1mol/L, the NaOH standard solution of 0.1mol/L and 0.1mol/L ₂cH ₃standard solution;

Step 2, sample determination

1., getting M1300 colour carbon black puts in the beaker of 250mL, add the salpeter solution that 150mL massfraction is 8.125%, reaction 24h, filter, and be washed with distilled water to neutrality, in vacuum drying chamber, dry 36h for 120 DEG C, it is 75 μm that salpeter solution modification M1300 carbon black is ground to particle diameter, puts in exsiccator and preserves;

2., take 2 parts of carbon black samples with electronic balance and be placed in No. 1 flask and No. 2 flasks respectively; The NaOCH of excessive 0.1mol/L is added in No. 1 flask ₂cH ₃standard solution, adds excessive 0.1mol/LNaOH standard solution in No. 2 flasks, respectively by the solution ultrasound wave dispersion 20min in two flasks, backflow 3h;

3. HCl standard solution to the solution in flask, then adding 0.1mol/L in two flasks is respectively acidity, stir solution in beaker adding HCl standard solution simultaneously, finally with the NaOH standard solution of 0.1mol/L, solution in two flasks is titrated to pH=7 respectively;

Step 3, result calculate

Carbon black sample is adding NaOCH ₂cH ₃after standard solution, the oxygen-containing functional group of unit mass carbon blacksurface consumes NaOCH ₂cH ₃amount N ₁, be calculated as follows, unit is mmol/g:

N ₁＝(C ₁V ₁+C ₁₁V ₁₁-C ₁₂V ₁₂)/W ₁；

In above-mentioned formula:

C ₁-the NaOCH that adds in carbon black sample ₂cH ₃the concentration of standard solution, unit is mol/L;

V ₁-the NaOCH that adds in carbon black sample ₂cH ₃the volume of standard solution, unit is mL;

C ₁₁-the concentration of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mol/L;

V ₁₁-the volume of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mL;

C ₁₂-adding the concentration of the HCl standard solution in No. 1 flask, unit is mol/L;

V ₁₂-adding the volume of the HCl standard solution in No. 1 flask, unit is mL;

W ₁-adding the quality of the carbon black sample in No. 1 flask, unit is g;

Carbon black sample is after adding NaOH standard solution, and the oxygen-containing functional group of unit mass carbon blacksurface consumes the amount N of NaOH ₂, being calculated as follows unit is mmol/g:

N ₂＝(C ₂V ₂+C ₂₁V ₂₁-C ₂₂V ₂₂)/W ₂

In above-mentioned formula:

C ₂-the concentration of NaOH standard solution that adds in carbon black sample, unit is mol/L;

V ₂-the volume of NaOH standard solution that adds in carbon black sample, unit is mL;

C ₂₁-the concentration of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mol/L;

V ₂₁-the volume of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mL;

C ₂₂-adding the concentration of the HCl standard solution in No. 2 flasks, unit is mol/L;

V ₂₂-adding the volume of the HCl standard solution in No. 2 flasks, unit is mL;

W ₂-adding the quality of the carbon black sample in No. 2 flasks, unit is g;

Finally calculate the calculating namely completing carbon blacksurface carbonyl oxygen-containing functional group assay according to the following formula:

N _RCOR＝N ₁–N ₂

In above-mentioned formula:

N _rCORthe carbonyl oxygen-containing functional group content of-unit mass carbon blacksurface, unit is mmol/g.

Wherein, in described step one, the configuration of HCl standard solution is carried out according to the following steps with demarcation:

One, the concentrated hydrochloric acid measuring 8.4mL massfraction 37% adds in 1000mL distilled water, shakes up and obtains hydrochloric acid solution;

Two, at 270 DEG C by natrium carbonicum calcinatum calcination to constant weight, and take 0.2g, be accurate to 0.0001g, be dissolved in 50mL distilled water, drip 10 bromcresol green-methyl red mixed indicators;

Three, be titrated to solution with the hydrochloric acid solution prepared and become kermesinus from green, boil 2min, continue titration after cooling and make solution again in kermesinus;

Four, blank test: add 50mL distilled water in conical flask, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the hydrochloric acid solution prepared, and continues titration and make solution again in kermesinus after cooling;

Five, hydrochloric acid standard solution concentration is calculated as follows:

$C_{HCl}=\frac{m}{(V_a-V_b)\×0.05299}$

In above-mentioned formula:

C _hCl-hydrochloric acid standard solution substance withdrawl syndrome, unit is mol/L;

M-natrium carbonicum calcinatum quality, unit is g;

V _a-hydrochloric acid solution consumption, unit is mL;

V _b-blank test hydrochloric acid solution consumption, unit is mL;

The quality of 0.05299-suitable with 1.00mL, the 1.000mol/L hydrochloric acid standard solution natrium carbonicum calcinatum represented with gram (g).

After demarcating, the concentration of HCl standard solution is 0.0977mol/L.

In described step one, the configuration of NaOH standard solution is carried out according to the following steps with demarcation:

One, take the NaOH of 4.0g, be accurate to 0.0001g, be placed in plastic beaker, inject 1000mL without the water of carbon dioxide, make it shake up and obtain NaOH solution after dissolving;

Two, at 110 DEG C, benchmark Potassium Hydrogen Phthalate is dried to constant weight, and take 0.6g, be accurate to 0.0001g, be dissolved in 50mL volume without in the water of carbon dioxide, add 2 instructions phenolphthalein solutions, carry out titration by the NaOH solution of preparation in step one, be titrated to solution pinkiness and keep 30s colour-fast;

Three, blank test: add the water of 50mL without carbon dioxide in conical flask, adds 2 instructions phenolphthalein solutions, carries out titration, be titrated to solution pinkiness and keep 30s colour-fast by the NaOH solution of preparation in step one;

Four, NaOH concentration of standard solution is calculated as follows:

$C_{NaOH}=\frac{m}{(V_c-V_d)\×\mathrm{0.0.2042}}$

In above-mentioned formula:

C _naOH-NaOH standard solution substance withdrawl syndrome, unit is mol/L;

M-Potassium Hydrogen Phthalate quality, unit is g;

V _c-NaOH standard solution consumption, unit is mL;

V _d-blank test NaOH standard solution consumption, unit is mL;

The quality of 0.2042-suitable with 1.00mL, the 1.000mol/LNaOH standard solution Potassium Hydrogen Phthalate represented with gram (g); After demarcating, the concentration of NaOH standard solution is 0.0985mol/L.

NaOCH in described step one ₂cH ₃the configuration of standard solution is carried out according to the following steps with demarcation:

One, 6.8g anhydrous Na OCH is taken ₂cH ₃, be dissolved in 1000mL absolute ethyl alcohol, shake up, obtain NaOCH ₂cH ₃solution;

Two, the NaOCH configured in 30mL step one is measured ₂cH ₃solution, adds 20mL absolute ethyl alcohol, drips 10 bromcresol green-methyl red mixed indicators, is titrated to solution and becomes kermesinus from green, boil 2min with the HCl standard solution of 0.1mol/L, continues to be titrated to solution again in kermesinus after cooling;

Three, NaOCH ₂cH ₃the concentration of standard solution is calculated as follows:

$C_{{\mathrm{NaOCH}}_2{\mathrm{CH}}_3}=C_{HCl}\×\frac{V_e}{V_f}$

In above-mentioned formula:

C _naOCH2CH3-NaOCH ₂cH ₃standard solution substance withdrawl syndrome, unit is mol/L;

C _hCl-HCl standard solution substance withdrawl syndrome, unit is mol/L;

V _e-hydrochloric acid standard solution consumption, unit is mL;

V _f-measuring caustic alcohol standard solution consumption, unit is mL.

NaOCH after demarcating ₂cH ₃the concentration of standard solution is 0.0994mol/L.

Mensuration and the result of calculation of the Cabot Co., Ltd M1300 colour carbon black surface carbonyl oxygen-containing functional group content of the present embodiment mensuration salpeter solution modification are as shown in table 2.

Table 2

In experimentation, in strict accordance with correct experimental implementation requirement, to guarantee the accuracy of testing, experimental error to be reduced as far as possible.

The method design that the present embodiment measures carbon blacksurface carbonyl oxygen-containing functional group content is reasonable, and completed by chemistry titration method, experimental procedure is simply easy to implement; The present embodiment assay method goes for arbitrarily containing the content of the carbon blacksurface carbonyl functional group of carbonyl, applied widely; The present embodiment assay method can exempt the use of large-scale instrument, simple to operate, is very easy to implement, and testing cost is lower; The present embodiment assay method calculation procedure is simple, and calculated amount is little, improves work efficiency; The M1300 colour carbon black surface carbonyl oxygen-containing functional group content that the present embodiment measures salpeter solution modification is 0.3661mmol/g.

Claims (5)

1. measure a method for carbon blacksurface carbonyl oxygen-containing functional group content, it is characterized in that the method realizes according to the following steps:

The configuration of step one, standard solution and demarcation

Prepare respectively and demarcate the NaOCH of the HCl standard solution of 0.1mol/L, the NaOH standard solution of 0.1mol/L and 0.1mol/L ₂cH ₃standard solution;

Step 2, sample determination

1., get the carbon black of particle diameter≤75 μm, in vacuum drying chamber, dry 36h for 120 DEG C, put in exsiccator and preserve;

2., take 2 parts of carbon black samples with electronic balance and be placed in No. 1 flask and No. 2 flasks respectively; The NaOCH of excessive 0.1mol/L is added in No. 1 flask ₂cH ₃standard solution, adds the NaOH standard solution of excessive 0.1mol/L in No. 2 flasks, respectively by the solution ultrasound wave dispersion 20min in two flasks, backflow 1.5h ~ 3h;

3. HCl standard solution to the solution in flask, then adding 0.1mol/L in two flasks is respectively acidity, stir solution in beaker adding HCl standard solution simultaneously, finally with the NaOH standard solution of 0.1mol/L, solution in two flasks is titrated to pH=7 respectively;

Step 3, result calculate

Carbon black sample is adding NaOCH ₂cH ₃after standard solution, the oxygen-containing functional group of unit mass carbon blacksurface consumes NaOCH ₂cH ₃amount N ₁, be calculated as follows, unit is mmol/g:

N ₁＝(C ₁V ₁+C ₁₁V ₁₁-C ₁₂V ₁₂)/W ₁；

In above-mentioned formula:

C ₁-the NaOCH that adds in carbon black sample ₂cH ₃the concentration of standard solution, unit is mol/L;

V ₁-the NaOCH that adds in carbon black sample ₂cH ₃the volume of standard solution, unit is mL;

C ₁₁-the concentration of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mol/L;

V ₁₁-the volume of NaOH standard solution used when solution in No. 1 flask being titrated to pH=7, unit is mL;

C ₁₂-adding the concentration of the HCl standard solution in No. 1 flask, unit is mol/L;

V ₁₂-adding the volume of the HCl standard solution in No. 1 flask, unit is mL;

W ₁-adding the quality of the carbon black sample in No. 1 flask, unit is g;

Carbon black sample is after adding NaOH standard solution, and the oxygen-containing functional group of unit mass carbon blacksurface consumes the amount N of NaOH ₂, being calculated as follows unit is mmol/g:

N ₂＝(C ₂V ₂+C ₂₁V ₂₁-C ₂₂V ₂₂)/W ₂

In above-mentioned formula:

C ₂-the concentration of NaOH standard solution that adds in carbon black sample, unit is mol/L;

V ₂-the volume of NaOH standard solution that adds in carbon black sample, unit is mL;

C ₂₁-the concentration of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mol/L;

V ₂₁-the volume of NaOH standard solution used when solution in No. 2 flasks being titrated to pH=7, unit is mL;

C ₂₂-adding the concentration of the HCl standard solution in No. 2 flasks, unit is mol/L;

V ₂₂-adding the volume of the HCl standard solution in No. 2 flasks, unit is mL;

W ₂-adding the quality of the carbon black sample in No. 2 flasks, unit is g;

Finally calculate the calculating namely completing carbon blacksurface carbonyl oxygen-containing functional group assay according to the following formula:

N _RCOR＝N ₁–N ₂

In above-mentioned formula:

N _rCORthe carbonyl oxygen-containing functional group content of-unit mass carbon blacksurface, unit is mmol/g.

2. a kind of method measuring carbon blacksurface carbonyl oxygen-containing functional group content according to claim 1, is characterized in that being accurate to 0.0001g when taking carbon black with electronic balance in step 2.

3. a kind of method measuring carbon blacksurface carbonyl oxygen-containing functional group content according to claim 1, is characterized in that in step 2, carbon black is the carbon black of surface containing carbonyl.

4. a kind of method measuring carbon blacksurface carbonyl oxygen-containing functional group content according to claim 3, is characterized in that the carbon black that carbonyl is contained on described surface is colour carbon black, conductive black or oxidation modification carbon black.

5. a kind of method measuring carbon blacksurface carbonyl oxygen-containing functional group content according to claim 4, is characterized in that described oxidation modification carbon black is the colour carbon black of salpeter solution oxidation modification or the conductive black of salpeter solution oxidation modification.