CN106596877A - Method and reagent composition for measuring chemical oxygen consumption in water - Google Patents
Method and reagent composition for measuring chemical oxygen consumption in water Download PDFInfo
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- CN106596877A CN106596877A CN201610017904.4A CN201610017904A CN106596877A CN 106596877 A CN106596877 A CN 106596877A CN 201610017904 A CN201610017904 A CN 201610017904A CN 106596877 A CN106596877 A CN 106596877A
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- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 389
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 245
- 238000000034 method Methods 0.000 title claims abstract description 117
- 239000000126 substance Substances 0.000 title claims abstract description 103
- 230000036284 oxygen consumption Effects 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 122
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000005070 sampling Methods 0.000 claims description 95
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 claims description 41
- 229940074994 mercuric sulfate Drugs 0.000 claims description 41
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims description 41
- 230000002378 acidificating effect Effects 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 33
- 238000003149 assay kit Methods 0.000 claims description 23
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical group [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 23
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910001430 chromium ion Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004457 water analysis Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 19
- 238000005259 measurement Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- 239000011651 chromium Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- YUVLVONHNMXKBW-UHFFFAOYSA-L [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O YUVLVONHNMXKBW-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- JKNZUZCGFROMAZ-UHFFFAOYSA-L [Ag+2].[O-]S([O-])(=O)=O Chemical class [Ag+2].[O-]S([O-])(=O)=O JKNZUZCGFROMAZ-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical group [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- CIWXFRVOSDNDJZ-UHFFFAOYSA-L ferroin Chemical compound [Fe+2].[O-]S([O-])(=O)=O.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 CIWXFRVOSDNDJZ-UHFFFAOYSA-L 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Medicinal Chemistry (AREA)
- Food Science & Technology (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Biodiversity & Conservation Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to the technical field of water analysis, in particular to a method and reagent composition for measuring chemical oxygen consumption in water. The method for measuring the chemical oxygen consumption in the water comprises the steps that 1, a water sample to be measured and a reagent I are mixed, the reagent I contains potassium dichromate, concentrated sulfuric acid and a catalyst, the concentration of potassium dichromate ranges from 0.062 g/L to 13.7 g/L, and the sample introduction volume of the reagent I is smaller than or equal to 5 mL; 2, the obtained mixture is decomposed at the temperature higher than 90 DEG C; 3, the chemical oxygen consumption in the water is obtained through calculation. According to the method and the reagent composition, the precision and accuracy of the chemical oxygen consumption detecting result can be effectively improved, meanwhile, the sample introduction volume, especially the sample introduction volume of concentrated sulfuric acid can be effectively reduced, and a water sample with high chemical oxygen consumption concentration can be detected. The method and the reagent composition can be especially suitable for a micro sample introduction mode, and the smaller the sample introduction volume is, the more obvious the advantages of the method and the reagent composition are.
Description
Technical field
The present invention relates to water analysis technical field, in particular it relates to a kind of determine chemistry consumption in water body
The reagent composition that the method and the method for oxygen amount is used.
Background technology
Chemical oxygen consumption (COC) refers to that the reducing substances in water body is oxidized agent and aoxidizes consumed oxidant
Amount, represents, chemical oxygen consumption (COC) is also known as chemical oxygen demand with oxygen demand weight mg/L of unit volume water body
Amount, reflects in water by the pollution level of reducing substances, is monitoring item conventional in water quality detection
Mesh, is the important indicator for evaluating water pollution.Determining the most commonly used method of chemical oxygen consumption (COC) at present is
Dichromate titration, with the principle of the method chemical oxygen consumption (COC) is defined for：Under certain condition,
The process of Jing potassium dichromate oxidations, the potassium bichromate phase that the dissolved matter and suspension in water sample is consumed
The mass concentration of corresponding oxygen, 1mol potassium bichromate (1/6K2Cr2O7) equivalent to 1mol oxygen (1/2O).
Prior art determine chemical oxygen consumption (COC) in water body generally according to GB/T 11914-1989 and
The method and reagent that HJ/T399-2007 recommends is carried out.
The method of GB/T 11914-1989 mainly includes：Add the potassium bichromate of known quantity molten in water sample
Liquid, and catalyst is made with silver salt under strong acid media, Jing after boiling reflux, with ferroin to indicate
Agent, with the potassium bichromate not being reduced in iron ammonium sulfate Titration Water Sample by the iron ammonium sulfate for consuming
Amount be converted into consume oxygen mass concentration, and in detection process in order to go interference, in addition it is also necessary to add
Mercuric sulfate removes the chloride in water sample.As can be seen that the method for GB/T 11914-1989 is more applicable
In the titration method in laboratory, the volume of the water sample to be measured that the method needs is more, in requisition for
The amount of reagent for arriving is also more, such as when concrete water quality to be measured is 20mL, the volume before titration can reach
140mL.This method give when sample size is 10-50mL and distinguish corresponding amount of reagent, such as the institute of table 1
Show.
Table 1
The method of HJ/T399-2007 mainly includes：Add the potassium bichromate of known quantity molten in the sample
Liquid, in strength sulfuric acid medium, using silver sulfate as catalyst, Jing after High-temperature Digestion, uses spectrophotometric
Method determine biochemical oxygen demand value, and in detection process in order to go interference, in addition it is also necessary to add mercuric sulfate
Remove the chloride in water sample.As can be seen that the method for HJ/T399-2007 is AAS, should
Method can be used for laboratory, but be at present more as common use Water Test Kits
Learn the reference of the instrument detection method of oxygen demand detection.
At present, with increasingly serious, the pay attention to day by day to environmental protection of pollution, chemical oxygen consumption (COC) is detected
Requirement also more and more higher, using general both states of GB/T 11914-1989 and HJ/T399-2007
The reagent of standard configuration, detects that chemical oxygen consumption (COC) has a lot, example on analytical instrument of water quality
Such as, (1) concentrated sulfuric acid consumption is too high, brings serious secondary pollution：It is known in the art that in instrument inspection
In survey method, the used in amounts of the concentrated sulfuric acid at least will add the sampling volume of other main agents with water sample to be measured
Sum is roughly the same, under the premise of this, current water sample to be measured and potassium bichromate sampling volume very
In the case of difficult further reduction, the sampling volume of the concentrated sulfuric acid also is difficult to further reduction, so as to chemistry
The amount of the concentrated sulfuric acid that oxygen demand detection process is discharged is considerable, and environment can be brought very
Serious secondary pollution；(2) time efficiency is too low：It is similarly subjected to sampling volume and is difficult further reduction
Impact, the time required for chemical oxygen consumption (COC) detection process is also generally longer, and no matter right time efficiency is
All it is very important parameter for industrial production or for monitoring water quality, relatively low time efficiency
Often mean that the loss of thousands of or even hundreds thousand of units；(3) generally compared to Manual analysis, less water
Sample sampling volume, the precision and stability of analytical instrument of water quality measurement is poor：The phase of existing measurement result
It is larger to standard deviation, and with the reduction of sampling volume, the precision and stability of measurement is also more next
It is poorer.
Therefore, it is all extremely important and urgent for this area to solve above-mentioned these problems.
The content of the invention
It is an object of the invention to overcome prior art to determine the above-mentioned deficiency of the method for chemical oxygen consumption (COC),
The reagent composition that a kind of method and the method for determining chemical oxygen consumption (COC) in water body is used is provided.
The method of the present invention and reagent composition can effectively improve weight chromium when using on analytical instrument of water quality
The feed liquor precision of sour potassium, makes chemical oxygen consumption (COC) testing result more precise and stable, and is ensureing dichromic acid
On the premise of potassium feed liquor precision, reagent sampling volume can be effectively reduced, especially reduce entering for the concentrated sulfuric acid
Sample volume, so as to reducing the pollution to environment and the time efficiency that chemical oxygen consumption (COC) is detected being improved.
The method of the present invention and reagent composition are particular enable to be applied to reagent when using on analytical instrument of water quality
The less micro- sample introduction pattern of sampling volume, and reagent sampling volume is less, and the advantage of the present invention is all the more
Substantially.
First aspect present invention provides a kind of method of chemical oxygen consumption (COC) in measure water body, the method bag
Include following steps：
(1) enter water sample to be measured and reagent I respectively and optional reagent II is mixed, wherein, institute
State in reagent I containing potassium bichromate, the concentrated sulfuric acid and catalyst, the potassium bichromate in the reagent I it is dense
Spend for 0.062-13.7g/L, the sampling volume≤5mL of the reagent I, in the reagent II sulfuric acid is contained
Mercury；
(2) step (1) gained mixture is cleared up at a temperature of more than 90 DEG C；
(3) determination step (2) gained clears up the three of remaining hexavalent chromium concentration in product or generation
Valency chromium ion concentration, the chemical oxygen consumption (COC) being then calculated in water body.
Second aspect present invention provide it is a kind of for determining water body in chemical oxygen consumption (COC) method reagent
Composition, the reagent composition includes：
Reagent I, contains potassium bichromate, the concentrated sulfuric acid and catalyst in reagent I, wherein, in reagent I
The concentration of potassium bichromate is 0.062-13.7g/L, preferably 0.186-6.85g/L.
Third aspect present invention provides a kind of method of chemical oxygen consumption (COC) in measure water body, the method bag
Include following steps：
(1) enter water sample to be measured, reagent i and reagent ii respectively and optional reagent iii mixed,
Wherein, in the reagent i containing potassium bichromate and the concentrated sulfuric acid, the potassium bichromate in the reagent i it is dense
Spend for 0.062-13.7g/L, catalyst contained in the reagent ii, in the reagent iii mercuric sulfate is contained,
Sampling volume≤the 5mL of the reagent i；
(2) step (1) gained mixture is cleared up at a temperature of more than 90 DEG C；
(3) determination step (2) gained clears up the three of remaining hexavalent chromium concentration in product or generation
Valency chromium ion concentration, the chemical oxygen consumption (COC) being then calculated in water body.
Fourth aspect present invention provide it is a kind of for determining water body in chemical oxygen consumption (COC) method reagent
Composition, the reagent composition includes：
Reagent i, containing potassium bichromate and the concentrated sulfuric acid, the concentration of the potassium bichromate in reagent i in reagent i
For 0.062-13.7g/L, preferably 0.186-6.85g/L；
Reagent ii, in the reagent ii catalyst is contained.
The present inventor has found that the present invention determines chemical oxygen consumption (COC) in water body through further investigation
Method and reagent composition at least have advantages below：
1. by the way that potassium bichromate (and silver sulfate) is first dissolved in into the concentrated sulfuric acid in, on analytical instrument of water quality
When using, the sampling volume of potassium bichromate is measured by feed liquor together with the concentrated sulfuric acid, independent with prior art
The concentration of preparation is larger, but the less potassium bichromate solution of sampling volume is compared, and the present invention can make weight chromium
The concentration of sour potassium solution is significantly reduced, and the liquid inlet volume of potassium bichromate is dramatically increased, so that dichromic acid
The feed liquor error of potassium significantly reduces (the feed liquor precision that improve potassium bichromate), and stability is significantly carried
Height, and then significantly improve the accuracy and stability of measurement result.In addition, potassium bichromate solution
Volume increases, and concentration is reduced so that the total amount of potassium bichromate can in interior adjustment in a big way, so as to
Enable the invention to measure the very high water sample of chemical oxygen consumption (COC) content.
2. by the way that potassium bichromate (and silver sulfate) is first dissolved in into the concentrated sulfuric acid in, it is not necessary to be again dichromic acid
The extra reagent preparation of potassium (and silver sulfate), therefore the present invention can require (bag reaction system is ensured compliance with
Include water sample plus the cumulative volume after other reagents needs to meet approximate 1 with the volume proportion of the concentrated sulfuric acid:1) before
Put, reduce the liquid inlet volume of the concentrated sulfuric acid so that the sampling volume sum of water sample and reagent is significantly subtracted
It is few.And the reduction of water sample and reagent sampling volume sum can greatly shorten sample injection time and water sample and
Reaction time between reagent, so as to improve the time efficiency of chemical oxygen consumption (COC) detection.
3. the method for the present invention and reagent composition can be particularly well-suited to be detected on analytical instrument of water quality
Chemical oxygen consumption (COC).
4. also it is particular enable to fit when the method for the present invention and reagent composition are used on analytical instrument of water quality
For the less micro- sample introduction pattern of sampling volume, and sampling volume is less, and the advantage of the present invention is all the more
Substantially.
5. the reagent composition of the present invention facilitates preparation, storage and the transport of reagent.
6. the reagent composition of the present invention compares the reagent of GB preparation, reduces amount of reagent, makes this
Invention reagent composition reduces number of injections when using on analytical instrument of water quality, so as to shorten sample introduction
Time.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification,
It is used to explain the present invention together with detailed description below, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 be for 30mg/L normal concentration chemical oxygen consumption (COC) water samples, the experimental group of embodiment 1-4 and
The relative standard deviation scatter diagram of control group gained testing result.
Fig. 2 be for 300mg/L normal concentration chemical oxygen consumption (COC) water samples, the experimental group of embodiment 1-4 and
The relative standard deviation scatter diagram of control group gained testing result.
Fig. 3 is for 1800mg/L normal concentration chemical oxygen consumption (COC) water samples, the experimental group of embodiment 1-4
With the relative standard deviation scatter diagram of control group gained testing result.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
First aspect present invention provides a kind of method of chemical oxygen consumption (COC) in measure water body, the method bag
Include following steps：
(1) enter water sample to be measured and reagent I respectively and optional reagent II is mixed, wherein, institute
State in reagent I containing potassium bichromate, the concentrated sulfuric acid and catalyst, the potassium bichromate in the reagent I it is dense
Spend for 0.062-13.7g/L, the sampling volume≤5mL of the reagent I, in the reagent II sulfuric acid is contained
Mercury；
(2) step (1) gained mixture is cleared up at a temperature of more than 90 DEG C；
(3) determination step (2) gained clears up the three of remaining hexavalent chromium concentration in product or generation
Valency chromium ion concentration, the chemical oxygen consumption (COC) being then calculated in water body.
The method of the present invention can be applied to the Water Test Kits of various large volume sample injections and small size sample introduction
Device, particularly under micro- sample introduction pattern, can significantly decrease sampling volume and effectively improve sample introduction
Precision and measurement stability.Micro- sample introduction pattern of the present invention refers to the liquid of all sample introductions
The sampling volume of (including the various reagents required for water sample to be measured and measurement) should meet
≤ 5mL, in situations where it is preferred, the sampling volume of the liquid of all sample introductions all needs to meet≤2mL.
Because the sampling volume of the concentrated sulfuric acid (herein equivalent to reagent I) should be maximum, in preferred sample introduction
Under pattern, the sampling volume≤2mL of reagent I, the sampling volume of water sample to be measured is 0.5-1.2mL, other
The sampling volume of reagent (if any) amounts to≤0.5mL.
In the present invention, the water sample to be measured and the sampling volume ratio of the reagent I can be 1：
0.8-3, preferably 1：0.9-1.5, more preferably 1：1-1.1.In the art, in instrument detection side
In method, the consumption of the concentrated sulfuric acid should be more than or equal to water sample to be measured add other main agents sampling volume it
With, on the premise of ensureing to clear up, the consumption for reducing the concentrated sulfuric acid to try one's best, in the present invention, institute
The volume ratio of the liquid of sample introduction preferably meets as far as possible：The sampling volume of reagent I with addition to reagent I other
Total sampling volume substantially 1 of liquid (including water sample to be measured and other reagents)：1 relation.Generally
In the case of, the sampling volume of other reagents in addition to reagent I is less, calculates for convenience, can make into
The volume ratio of the liquid of sample meets as far as possible：The sampling volume of water sample to be measured meets with the sampling volume of reagent I
Substantially 1：1 relation, for example, 1：1-1.2, preferably 1：1-1.1, is most preferably close to as far as possible
1：1.
The present invention by the way that potassium bichromate is dissolved in the concentrated sulfuric acid, the concentration individually prepared with prior art compared with
Greatly, but the less potassium bichromate solution of sampling volume is compared, the concentration of potassium bichromate can be substantially reduced,
Increase the sampling volume of potassium bichromate so that the sample introduction precision of potassium bichromate is greatly improved, so as to significantly
Improve the accuracy and stability of detection.In the present invention, in the reagent I potassium bichromate concentration
Can be 0.062-13.7g/L, more preferably preferably 0.186-6.85g/L, 1.2-6g/L.Potassium bichromate
Concentration can be selected according to the size of chemical oxygen consumption (COC) in water sample to be measured, usually, when to be measured
When chemical oxygen consumption (COC) is higher in water sample, higher potassium bichromate concentration is selected as far as possible, otherwise select relatively low
Potassium bichromate concentration.
In the present invention, can also be containing catalyst so as to further reducing the body of sample introduction in the reagent I
Product, in reagent I the concentration of catalyst can be 1-20g/L, preferably 5-12g/L, more preferably
8-10g/L；Preferably, the catalyst is silver sulfate.
In the present invention, the condition cleared up is carried out according to conventional the clearing up in this area, the temperature cleared up
Degree is typically larger than 90 DEG C, preferably 120-180 DEG C, more preferably 140-170 DEG C.The time cleared up can
To be configured according to the easily degree of clearing up of chemical oxygen consumption (COC) composition in water sample to be measured, can clear up completely i.e.
Can.Under micro- sample introduction pattern of the present invention, the time cleared up generally can be controlled within 15min.
In the present invention, reagent II is optional can to use the reagent that can not also be used, the examination
Contain mercuric sulfate in agent II, the mercuric sulfate is mainly used in shielding the chlorion in water sample, therefore whether adds
Entering the addition of mercuric sulfate and mercuric sulfate can be selected according to the content of Chloride Ion In Water to be measured
Select.Mercuric sulfate, acidic materials and water can be contained in the reagent II.Preferably, the reagent II
Preparation method be：First acidic materials and water are made into into acid solution, then to be added thereto to mercuric sulfate molten
Solution.The acidic materials are preferably liquid acidic material, and liquid acidic material is preferably sulfuric acid, is secondly
There is no particular limitation for the amount ratio of nitric acid, the acidic materials and water, can be completely molten by mercuric sulfate
Solution, such as described acidic materials can be 1 with the consumption volume ratio of water：3-9, preferably 1：
5-9.The sampling volume of the reagent II can be with the ratio of the sampling volume of the water sample to be measured
0.05-0.5：1, preferably 0.05-0.4：1.The concentration of mercuric sulfate is without special limit in the reagent II
It is fixed, for example can be 1-120g/L, preferably 30-90g/L.
In the present invention, the potassium bichromate can also additionally be dissolved in other in addition to reagent I
In reagent, such as when needing to use reagent II, in the reagent II potassium bichromate can also be contained, should
The concentration of potassium bichromate has no particular limits, can phase with the concentration of potassium bichromate in the reagent I
Together can also be different, and preferably, when also potassium bichromate is contained in reagent II, weight in reagent I
The concentration of potassium chromate can be reduced suitably.
In the present invention, the Loading sequence of the water sample to be measured, reagent I and reagent II is without special limit
It is fixed, can sample introduction in any order.
Method described in first aspect present invention is carried out preferably in Water Test Kits, the Water Test Kits
There is no particular limitation, can be the various large volume sample injections and/or little of can realizing that this area can use
The Water Test Kits of Injection volumes.It is more obvious due to working as sampling volume more hour advantage of the invention, therefore
The sampling volume that the Water Test Kits can be realized is less, and sample introduction precision is higher, more excellent in the present invention
Choosing.As the Water Test Kits of the present invention, for example, it can be Wuhan Ju Zheng Environmental Protection Technology Co., Ltd
JZ-CG01 type COD online automatic monitors, Jiangxi Xia Shi spring and autumn environmental investments Co., Ltds
CQ-X/C type COD on-line computing models and Hebei Hua Houtian are into environmentally friendly Technology Co., Ltd.
CODcrType COD on-line determination instrument.
Second aspect present invention provide it is a kind of for determining water body in chemical oxygen consumption (COC) method reagent
Composition, the reagent composition includes：
Reagent I, contains potassium bichromate, the concentrated sulfuric acid and catalyst in reagent I, wherein, in reagent I
The concentration of potassium bichromate be 0.062-13.7g/L, preferably 0.186-6.85g/L, more preferably
1.2-6g/L。
In the present invention, the concentration of the catalyst in the reagent I can be 1-20g/L, preferably
5-12g/L, more preferably 8-10g/L；Preferably, the catalyst is silver sulfate.
In the present invention, the reagent composition can also include：
Reagent II, in the reagent II mercuric sulfate is contained, and the concentration of the mercuric sulfate in reagent II is
1-120g/L, preferably 30-90g/L.
In the present invention, in situations where it is preferred, containing mercuric sulfate, acidic materials in the reagent II
And water；The acidic materials are preferably sulfuric acid, are secondly the consumption body of nitric acid, the acidic materials and water
Product ratio can be 1：3-9, preferably 1：5-9.
In the present invention, the potassium bichromate can also additionally be dissolved in other in addition to reagent I
In reagent, such as can also contain potassium bichromate in described reagent II, the concentration of the potassium bichromate is without spy
The concentration of the potassium bichromate in other restriction, with the reagent I can be the same or different, and excellent
Selection of land, when also potassium bichromate is contained in reagent II, the concentration of potassium bichromate can be appropriate in reagent I
Reduce.
The feature and selection mode of each reagent and the present invention the in the reagent composition of second aspect present invention
The feature of correspondence reagent is identical with selection mode in the method for one side, will not be described here.
Third aspect present invention provides a kind of method of chemical oxygen consumption (COC) in measure water body, the method bag
Include following steps：
(1) enter water sample to be measured, reagent i and reagent ii respectively and optional reagent iii mixed,
Wherein, in the reagent i containing potassium bichromate and the concentrated sulfuric acid, the potassium bichromate in the reagent i it is dense
Spend for 0.062-13.7g/L, catalyst contained in the reagent ii, in the reagent iii mercuric sulfate is contained,
Sampling volume≤the 5mL of the reagent i；
(2) step (1) gained mixture is cleared up at a temperature of more than 90 DEG C；
(3) determination step (2) gained clears up the three of remaining hexavalent chromium concentration in product or generation
Valency chromium ion concentration, the chemical oxygen consumption (COC) being then calculated in water body.
The method of the present invention can be applied to the method and instrument of various large volume sample injections and small size sample introduction
Device, particularly under micro- sample introduction pattern, can significantly decrease sampling volume and effectively improve sample introduction
Precision and measurement stability.Micro- sample introduction pattern of the present invention refers to the liquid of all sample introductions
The sampling volume of (including the various reagents required for water sample to be measured and measurement) should meet
≤ 5mL, in situations where it is preferred, the sampling volume of the liquid of all sample introductions all needs to meet≤2mL.
Due to the concentrated sulfuric acid (should be maximum in sampling volume herein equivalent to reagent i), in preferred sample introduction
Under pattern, the sampling volume≤2mL of reagent i, the sampling volume of water sample to be measured is 0.5-1.2mL, reagent
Sampling volume≤the 0.5mL of ii, the sampling volume of other reagents (if any) amounts to≤0.5mL.
In the present invention, the sampling volume ratio of the water sample to be measured, reagent i and reagent ii can be 1：
0.8-3：0.01-1, preferably 1：0.9-1.5：0.05-0.5, more preferably 1：1-1.1：0.05-0.4.
In the art, in instrument detection method, the consumption of the concentrated sulfuric acid should add more than or equal to water sample to be measured
The sampling volume sum of other main agents, on the premise of measurement effect is ensured, in order to reduce as far as possible
The consumption of the concentrated sulfuric acid, in the present invention, the volume ratio of the liquid of institute's sample introduction preferably meets as far as possible：Reagent i
Sampling volume with addition to reagent i other liquid (including water sample to be measured, reagent ii and other reagents)
Total sampling volume substantially 1：1 relation.Under normal circumstances, other reagents in addition to reagent i enter
Sample small volume, calculates for convenience, and the volume ratio that can make the liquid of sample introduction meets as far as possible：It is to be measured
The sampling volume of water sample meets substantially 1 with the sampling volume of reagent i：1 relation, for example, 1：
1-1.2, preferably 1：1-1.1, most preferably as far as possible close 1：1.
The present invention by the way that potassium bichromate is dissolved in the concentrated sulfuric acid, the concentration individually prepared with prior art compared with
Greatly, but the less potassium bichromate solution of sampling volume is compared, the concentration of potassium bichromate can be substantially reduced,
Increase the sampling volume of potassium bichromate so that the sample introduction precision of potassium bichromate is greatly improved, so as to significantly
Improve the accuracy and stability of detection.In the present invention, in the reagent i potassium bichromate concentration
Can be 0.062-13.7g/L, more preferably preferably 0.186-6.85g/L, 1.2-6g/L.Potassium bichromate
Concentration can be selected according to the size of chemical oxygen consumption (COC) in water sample to be measured, usually, when to be measured
When chemical oxygen consumption (COC) is higher in water sample, higher potassium bichromate concentration is selected as far as possible, otherwise select relatively low
Potassium bichromate concentration.
In the present invention, the catalyst can not be prepared in concentrated sulfuric acid, but individually be formulated in examination
In agent ii, in reagent ii the concentration of catalyst can be 1-20g/L, preferably 5-12g/L, more preferably
8-10g/L；Preferably, the catalyst is silver sulfate.It is molten used by catalyst solution (i.e. reagent ii)
There is no particular limitation for agent, can be completely dissolved catalyst, for example, can be the concentrated sulfuric acid, dense nitre
Acid or other acidic materials；The preferably concentrated sulfuric acid.In the present invention, the condition cleared up is according to ability
Conventional the clearing up in domain is carried out, and the temperature cleared up is typically larger than 90 DEG C, preferably 120-180 DEG C, more preferably
For 140-170 DEG C.The time cleared up can be according to the easily degree of clearing up of chemical oxygen consumption (COC) composition in water sample to be measured
It is configured, can clears up completely.Under micro- sample introduction pattern of the present invention, the time cleared up leads to
Often can control within 15min.
In the present invention, reagent iii is optional can to use the reagent that can not also be used, the examination
Contain mercuric sulfate in agent iii, the mercuric sulfate is mainly used in shielding the chlorion in water sample, therefore whether adds
Entering the addition of mercuric sulfate and mercuric sulfate can be selected according to the content of Chloride Ion In Water to be measured
Select.Mercuric sulfate, acidic materials and water can be contained in the reagent iii.Preferably, the reagent iii
Preparation method be：First acidic materials and water are made into into acid solution, then to be added thereto to mercuric sulfate molten
Solution.The acidic materials are preferably liquid acidic material, and the liquid acidic material is preferably sulfuric acid, its
There is no particular limitation for the secondary amount ratio for nitric acid, the acidic materials and water, can be complete by mercuric sulfate
CL, such as described acidic materials can be 1 with the consumption volume ratio of water：3-9, preferably
1：5-9.The sampling volume of the reagent iii can be with the ratio of the sampling volume of the water sample to be measured
0.05-0.5：1, preferably 0.05-0.4：1.The concentration of mercuric sulfate is without special in the reagent iii
Limit, for example, can be 1-120g/L, preferably 30-90g/L.
In the present invention, the potassium bichromate can also additionally be dissolved in other in addition to reagent i
In reagent, such as can also contain potassium bichromate in described reagent ii, and ought need to use reagent iii
When, can also contain potassium bichromate in reagent iii.Dichromic acid in the reagent ii or described reagent iii
The concentration of potassium has no particular limits, and the concentration of the potassium bichromate in reagent i, reagent ii and reagent iii can
With it is identical can also be different；And preferably, when also containing dichromic acid in reagent ii and/or reagent iii
During potassium, the concentration of potassium bichromate can be reduced suitably in reagent i.
In the present invention, the Loading sequence of the water sample to be measured, reagent i, reagent ii and reagent iii does not have
It is special to limit, can sample introduction in any order.
Method described in third aspect present invention is carried out preferably in Water Test Kits, the Water Test Kits
There is no particular limitation, can be the various large volume sample injections and/or little of can realizing that this area can use
The Water Test Kits of Injection volumes.It is more obvious due to working as sampling volume more hour advantage of the invention, therefore
The sampling volume that the Water Test Kits can be realized is less, and sample introduction precision is higher, more excellent in the present invention
Choosing.As the Water Test Kits of the present invention, for example, it can be Wuhan Ju Zheng Environmental Protection Technology Co., Ltd
JZ-CG01 type COD online automatic monitors, Jiangxi Xia Shi spring and autumn environmental investments Co., Ltds
CQ-X/C type COD on-line computing models and Hebei Hua Houtian are into environmentally friendly Technology Co., Ltd.
CODcrType COD on-line determination instrument.
Fourth aspect present invention provide it is a kind of for determining water body in chemical oxygen consumption (COC) method reagent
Composition, the reagent composition includes：
Reagent i, containing potassium bichromate and the concentrated sulfuric acid in reagent i, the potassium bichromate in reagent i it is dense
Spend for 0.062-13.7g/L, preferably 0.186-6.85g/L；
Reagent ii, in the reagent ii catalyst is contained.
In the present invention, the concentration of catalyst can be 1-20g/L in the reagent ii, preferably
5-12g/L；Preferably, the catalyst is silver sulfate.
In the present invention, the reagent composition can also include：
Reagent iii, in the reagent iii mercuric sulfate is contained, and the concentration of the mercuric sulfate in reagent iii is
1-120g/L, preferably 30-90g/L.
In the present invention, in situations where it is preferred, containing mercuric sulfate, acidic materials in the reagent iii
And water；The acidic materials are preferably sulfuric acid, are secondly the consumption body of nitric acid, the acidic materials and water
Product is than being 1：3-9, preferably 1：5-9.
In the present invention, the potassium bichromate can also additionally be dissolved in other in addition to reagent i
In reagent, such as can also contain potassium bichromate in described reagent ii, and ought need to use reagent iii
When, can also contain potassium bichromate in reagent iii.Dichromic acid in the reagent ii or described reagent iii
The concentration of potassium has no particular limits, and the concentration of the potassium bichromate in reagent i, reagent ii and reagent iii can
With it is identical can also be different；And preferably, when also containing dichromic acid in reagent ii and/or reagent iii
During potassium, the concentration of potassium bichromate can be reduced suitably in reagent i.
The feature and selection mode of each reagent and the present invention the in the reagent composition of fourth aspect present invention
The feature of correspondence reagent is identical with selection mode in the method for one side, will not be described here.
In order that those skilled in the art more fully understands technical scheme, with reference to tool
The present invention is described in further detail for body embodiment.
In the examples below, the concentrated sulfuric acid used is 98% concentrated sulfuric acid.The water sample to be measured for using is change
Learn the normal concentration chemical oxygen consumption (COC) that oxygen demand concentration is respectively 30mg/L, 300mg/L and 1800mg/L
Water sample, without chloride ion interference in water sample.
Embodiment 1-2 is used to illustrate a first aspect of the present invention and second aspect.
Embodiment 1
Experimental group：
(1) reagent preparation
Reagent I：The reagent I that three groups of constituents are potassium bichromate, the concentrated sulfuric acid and silver sulfate is prepared, point
It is not designated as reagent Ia～Ic, specifically, reagent IaThe concentration of middle potassium bichromate is 0.54g/L, silver sulfate
Concentration is 5.12g/L；Reagent IbThe concentration of middle potassium bichromate is 3.63g/L, and the concentration of silver sulfate is
11.04g/L；Reagent IcThe concentration of middle potassium bichromate is 5.98g/L, and the concentration of silver sulfate is 15.96g/L.
(2) chemical oxygen consumption (COC) detection
30mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, three Water Test Kits is taken (
For the JZ-CG01 type COD online automatic monitors of Wuhan Ju Zheng Environmental Protection Technology Co., Ltd),
Same following operation is carried out respectively：
1) the 30mg/L normal concentration chemical oxygen consumption (COC) water samples and 5mL reagent I of 5mL are extracted respectivelyaExtremely
Mix in digestion instrument；
2) gained mixture is cleared up；
3) determination step 2) gained clear up remaining hexavalent chromium concentration or the trivalent chromium of generation in product
Ion concentration, the chemical oxygen consumption (COC) being then calculated in water body, as 30mg/L normal concentrations chemistry
The chemical oxygen consumption (COC) testing result of oxygen demand water sample；Every Water Test Kits measures 4 data, altogether
12 data, successively (i.e. the 1-4 data for First instrument measurement data, the 5-8 data
For the measurement data of second instrument, the 9-12 data is the measurement data of the 3rd instrument, below
All same) remember in table 2.
300mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method for learning oxygen demand water sample is identical, except that, using reagent IbReplace reagent Ia, gained
12 data are remembered in table 2.
1800mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method of chemical oxygen consumption (COC) water sample is identical, except that, using reagent IcReplace reagent Ia, institute
Obtain 12 data to remember in table 2.
Control group：
(1) reagent preparation
Prepared according to the reagent in national standard HJT399-2007, obtain concentration and be respectively c
(1/6K2Cr2O7The potassium bichromate solution of)=0.120mol/L, 0.160mol/L and 0.500mol/L, with
And concentration is the silver sulfate-sulfuric acid solution of 10g/L.
(2) chemical oxygen consumption (COC) detection
It is right respectively on analytical instrument of water quality according to the reagent in national standard HJT399-2007
The normal concentration chemical oxygen consumption (COC) water sample of 30mg/L, 300mg/L and 1800mg/L detected, in order to
It is easy to compare with experimental group, the volume of water sample to be measured and each reagent is scaled up so that water to be measured
The sampling volume of sample is 5mL.12 data are respectively obtained, is remembered in table 2.
Table 2
According to table 2,12 data obtained by experimental group and control group are calculated into respectively relative standard deviation σ
(%) the absolute value A of the difference of, mean value X (mg/L), and mean value X and normal concentration
(mg/L), remember in table 3, and by the sampling volume and volume of water sample to be measured and agents useful for same and remember in
In table 3.
Table 3
Under the premise of the water sample identical to be measured of experimental group and control group, using the experiment of the method for the present invention
The sampling volume of group and (10mL) entering significantly less than the control group of the method using GB preparation of reagents
Sample volume and (16.7mL), and the sampling volume (5mL) of the experimental group concentrated sulfuric acid is only control group
(10mL) half.Experimental group is by potassium bichromate by dissolving in the concentrated sulfuric acid so that potassium bichromate enters
Sample volume (5mL) is much larger than control group (1.7mL), and the concentration of potassium bichromate also far below control
Group, so as to the sample introduction error of the potassium bichromate of sample introduction is reduced so that measuring accuracy is improved, and measurement is stable
Property improve.It can be seen from Table 3 that, using the reagent composition and method of the present invention, with national standard
The method of preparation of reagents is compared, and relative standard deviation σ value can be reduced to less than half, illustrates what is measured
Stability is significantly improved, and A values can be reduced to less than half even below 1/7, illustrate what is measured
The degree of accuracy is also significantly improved.
Embodiment 2
Experimental group：
(1) the reagent I that reagent I is prepared using the experimental group of embodiment 1a～Ic。
(2) chemical oxygen consumption (COC) detection
30mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, three Water Test Kits is taken (
For the CQ-X/C type COD on-line computing models of Jiangxi Xia Shi spring and autumn environmental investments Co., Ltd),
Same following operation is carried out respectively：
1) the 30mg/L normal concentration chemical oxygen consumption (COC) water samples and 1mL reagent I of 1mL are extracted respectivelyaExtremely
Mix in digestion instrument；
2) gained mixture is cleared up；
3) determination step 2) gained clear up remaining hexavalent chromium concentration or the trivalent chromium of generation in product
Ion concentration, the chemical oxygen consumption (COC) being then calculated in water body, as 30mg/L normal concentrations chemistry
The chemical oxygen consumption (COC) testing result of oxygen demand water sample；Every Water Test Kits measures 4 data, altogether
12 data, remember in table 4.
300mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method for learning oxygen demand water sample is identical, except that, using reagent IbReplace reagent Ia, gained
12 data are remembered in table 4.
1800mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method of chemical oxygen consumption (COC) water sample is identical, except that, using reagent IcReplace reagent Ia, institute
Obtain 12 data to remember in table 4.
Control group：
(1) reagent preparation
Prepared according to the reagent in national standard HJT399-2007, obtain concentration and be respectively c
(1/6K2Cr2O7The potassium bichromate solution of)=0.120mol/L, 0.160mol/L and 0.500mol/L, with
And concentration is the silver sulfate-sulfuric acid solution of 10g/L.
(2) chemical oxygen consumption (COC) detection
It is right respectively on analytical instrument of water quality according to the reagent in national standard HJT399-2007
The normal concentration chemical oxygen consumption (COC) water sample of 30mg/L, 300mg/L and 1800mg/L detected, in order to
It is easy to compare with experimental group, it is the volume of water sample to be measured and each reagent is scaled so that water to be measured
The sampling volume of sample is 1mL.Three kinds of water samples respectively obtain 12 data, remember in table 4.
Table 4
According to table 4,12 data obtained by experimental group and control group are calculated into respectively relative standard deviation σ
(%) the absolute value A of the difference of, mean value X (mg/L), and mean value X and normal concentration
(mg/L), remember in table 5, and by the sampling volume and volume of water sample to be measured and agents useful for same and remember in
In table 5.
Table 5
Under the premise of the water sample identical to be measured of experimental group and control group, using the experiment of the method for the present invention
Sample introduction of the sampling volume and (2mL) of group significantly less than the control group of the method using GB preparation of reagents
Volume and (3.3mL), and the sampling volume (1mL) of the experimental group concentrated sulfuric acid is only control group (2mL)
Half.Experimental group by potassium bichromate by dissolving in the concentrated sulfuric acid so that the sampling volume of potassium bichromate
(1mL) control group (0.3mL) is much larger than, and the concentration of potassium bichromate is also far below control group, from
And the sample introduction error of the potassium bichromate of sample introduction is reduced so that measuring accuracy is improved, measurement stability is improved.
It can be seen from Table 5 that, using the reagent composition and method of the present invention, with national standard preparation of reagents
Method compare, relative standard deviation σ value can be reduced to less than half less than even 1/4, illustrate survey
The stability of amount is significantly improved, and A values can be reduced to less than half or even 1/7 or so, illustrates to survey
The degree of accuracy of amount is also significantly improved.
Embodiment 3-4 is used to illustrate a third aspect of the present invention and fourth aspect.
Embodiment 3
Experimental group：
(1) reagent preparation
Reagent i：The reagent i that three groups of constituents are potassium bichromate and the concentrated sulfuric acid is prepared, examination is designated as respectively
Agent ia～ic, specifically, reagent iaThe concentration of middle potassium bichromate is 0.32g/L, reagent ibMiddle potassium bichromate
Concentration is 3.08g/L, reagent icThe concentration of middle potassium bichromate is 13.32g/L.
Reagent ii：The aqueous solution for preparing three groups of silver sulfates is designated as respectively iia、iibAnd iic, the concentration of silver sulfate
For 6.38g/L, the concentration of silver sulfate is 14.95g/L, and the concentration of silver sulfate is 18.65g/L.
(2) chemical oxygen consumption (COC) detection
30mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, three Water Test Kits is taken (
For Hebei Hua Houtian into environmentally friendly Technology Co., Ltd. CODcrType COD on-line determination instrument), enter respectively
The same following operation of row：
1) 30mg/L normal concentration chemical oxygen consumption (COC) water samples, the reagent of 0.3mL of 2mL are extracted respectively
iiaWith the reagent i of 2mLaMix into digestion instrument；
2) gained mixture is cleared up；
3) determination step 2) gained clear up remaining hexavalent chromium concentration or the trivalent chromium of generation in product
Ion concentration, the chemical oxygen consumption (COC) being then calculated in water body, as 30mg/L normal concentrations chemistry
The chemical oxygen consumption (COC) testing result of oxygen demand water sample；Every Water Test Kits measures 4 data, altogether
12 data, remember in table 6.
300mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method for learning oxygen demand water sample is identical, except that, using reagent ibReplace reagent ia, use
Reagent iibReplace reagent iia, 12 data of gained are remembered in table 6.
1800mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method of chemical oxygen consumption (COC) water sample is identical, except that, using reagent icReplace reagent ia, make
Use reagent iicReplace reagent iia, 12 data of gained are remembered in table 6.
Control group：
(1) reagent preparation
Prepared according to the reagent in national standard HJT399-2007, obtain concentration and be respectively c
(1/6K2Cr2O7The potassium bichromate solution of)=0.120mol/L, 0.160mol/L and 0.500mol/L, with
And concentration is the silver sulfate-sulfuric acid solution of 10g/L.
(2) chemical oxygen consumption (COC) detection
It is right respectively on analytical instrument of water quality according to the reagent in national standard HJT399-2007
The normal concentration chemical oxygen consumption (COC) water sample of 30mg/L, 300mg/L and 1800mg/L detected, in order to
It is easy to compare with experimental group, it is the volume of water sample to be measured and each reagent is scaled so that water to be measured
The sampling volume of sample is 2mL.Three kinds of water samples respectively obtain 12 data, remember in table 6.
Table 6
According to table 6,12 data obtained by experimental group and control group are calculated into respectively relative standard deviation σ
(%) the absolute value A of the difference of, mean value X (mg/L), and mean value X and normal concentration
(mg/L), remember in table 7, and by the sampling volume and volume of water sample to be measured and agents useful for same and remember in
In table 7.
Table 7
Under the premise of the water sample identical to be measured of experimental group and control group, using the experiment of the method for the present invention
The sampling volume of group and (4.3mL) entering significantly less than the control group of the method using GB preparation of reagents
Sample volume and (6.7mL), and the sampling volume (2mL) of the experimental group concentrated sulfuric acid is only control group (4mL)
Half.Experimental group by potassium bichromate by dissolving in the concentrated sulfuric acid so that the sampling volume of potassium bichromate
(2mL) control group (0.7mL) is much larger than, and the concentration of potassium bichromate is also far below control group, from
And the sample introduction error of the potassium bichromate of sample introduction is reduced so that measuring accuracy is improved, measurement stability is improved.
It can be seen from Table 7 that, using the reagent composition and method of the present invention, with national standard preparation of reagents
Method compare, relative standard deviation σ value can be reduced to less than half less than even 1/3, illustrate survey
The stability of amount is significantly improved, and A values can be reduced to less than half even below 1/6, illustrates to survey
The degree of accuracy of amount is also significantly improved.
Embodiment 4
Experimental group：
(1) reagent preparation
Reagent i：The reagent i prepared using the experimental group of embodiment 3a～ic。
Reagent ii：The reagent ii prepared using the experimental group of embodiment 3a～iic。
(2) chemical oxygen consumption (COC) detection
30mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, three Water Test Kits is taken (
For Hebei Hua Houtian into environmentally friendly Technology Co., Ltd. CODcrType COD on-line determination instrument), enter respectively
The same following operation of row：
1) 30mg/L normal concentration chemical oxygen consumption (COC) water samples, the reagent of 0.1mL of 0.5mL are extracted respectively
iiaWith the reagent i of 0.5mLaMix into digestion instrument；
2) gained mixture is cleared up；
3) determination step 2) gained clear up remaining hexavalent chromium concentration or the trivalent chromium of generation in product
Ion concentration, the chemical oxygen consumption (COC) being then calculated in water body, as 30mg/L normal concentrations chemistry
The chemical oxygen consumption (COC) testing result of oxygen demand water sample；Every Water Test Kits measures 4 data, altogether
12 data, remember in table 8.
300mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method for learning oxygen demand water sample is identical, except that, using reagent ibReplace reagent ia, use
Reagent iibReplace reagent iia, 12 data of gained are remembered in table 8.
1800mg/L normal concentration chemical oxygen consumption (COC) water samples are detected, with 30mg/L normal concentrations
The detection method of chemical oxygen consumption (COC) water sample is identical, except that, using reagent icReplace reagent ia, make
Use reagent iicReplace reagent iia, 12 data of gained are remembered in table 8.
Control group：
(1) reagent preparation
Prepared according to the reagent in national standard HJT399-2007, obtain concentration and be respectively c
(1/6K2Cr2O7The potassium bichromate solution of)=0.120mol/L, 0.160mol/L and 0.500mol/L, with
And concentration is the silver sulfate-sulfuric acid solution of 10g/L.
(2) chemical oxygen consumption (COC) detection
It is right respectively on analytical instrument of water quality according to the reagent in national standard HJT399-2007
The normal concentration chemical oxygen consumption (COC) water sample of 30mg/L, 300mg/L and 1800mg/L detected, in order to
It is easy to compare with experimental group, it is the volume of water sample to be measured and each reagent is scaled so that water to be measured
The sampling volume of sample is 0.5mL, and the reagent of wherein potassium bichromate+mercuric sulfate is scaled to be should be
0.25mL, however, to ensure that the precision and stability of potassium bichromate sample introduction is in acceptable scope,
The volume of the reagent is set to into acceptable minimum volume, i.e. 0.5mL.Three kinds of water samples are respectively obtained
12 data, remember in table 8.
Table 8
According to table 8,12 data obtained by experimental group and control group are calculated into respectively relative standard deviation σ
(%) the absolute value A of the difference of, mean value X (mg/L), and mean value X and normal concentration
(mg/L), remember in table 9, and by the sampling volume and volume of water sample to be measured and agents useful for same and remember in
In table 9.
Table 9
Under the premise of the water sample identical to be measured of experimental group and control group, using the experiment of the method for the present invention
Sample introduction of the sampling volume and (1mL) of group significantly less than the control group of the method using GB preparation of reagents
Volume and (1.67mL), and the sampling volume (0.5mL) of the experimental group concentrated sulfuric acid is only control group (1mL)
Half.Experimental group by potassium bichromate by dissolving in the concentrated sulfuric acid so that the sampling volume of potassium bichromate
(0.5mL) control group (0.17mL) is much larger than, and the concentration of potassium bichromate is also far below control group,
So as to the sample introduction error of the potassium bichromate of sample introduction is reduced so that measuring accuracy is improved, measurement stability is carried
It is high.It can be seen from Table 9 that, using the reagent composition and method of the present invention, with national standard reagent
The method of preparation is compared, and relative standard deviation σ value can be reduced to less than half even below 1/3, say
The stability of bright measurement is significantly improved, and A values can be reduced to less than half even below 1/6, say
The degree of accuracy of bright measurement is also significantly improved.
In embodiment 1-4, using the inventive method experimental group used by the concentrated sulfuric acid and potassium bichromate
The sampling volume of reagent I or reagent i is respectively 4mL, 1mL, 2mL and 0.5mL.In order to compare this
Measurement of the method for invention from national standard preparation of reagents method under different concentrated sulfuric acid sampling volumes is stablized
Property, respectively by experimental group in embodiment 1-4 corresponding to three kinds of normal concentration chemical oxygen consumption (COC) water samples and right
Remember in Fig. 1 (30mg/L), Fig. 2 (300mg/L) according to the relative standard deviation of the test result of group and
In Fig. 3 (1800mg/L).Comprehensive Fig. 1, Fig. 2 and Fig. 3 can be seen that the feed liquor of reagent I or i
Amount is less, and the relative standard deviation that the embodiment of the present invention is measured is carried than the relative standard deviation that the world is measured
High multiple is more, it will thus be seen that determining chemistry in water body using the present invention on Water Test Kits
During oxygen demand, under conditions of the micro- sample introduction of reagent is ensured, i.e., in the reagent i or examination for only needing extraction≤5mL
Under conditions of agent ii, compared to the method for GB preparation of reagents, the assay method for applying the present invention is surveyed
Amount result is substantially more precise and stable；On the other hand, in existing reagent sampling volume and Instrument measuring precision
On the premise of requirement, the present invention can also reduce by 2-3 times of reagent dosage, save use cost；Reduce
The secondary pollution discharge of waste liquid.
Embodiment 5
(1) reagent preparation
Five group reagent I (including potassium bichromate, the concentrated sulfuric acid and silver sulfate) are prepared, reagent is designated as respectively
I1～I5.Reagent I1～I5The concentration of middle potassium bichromate be respectively 0.062g/L, 0.186g/L, 1.37g/L,
6.85g/L and 13.7g/L, the concentration of silver sulfate be respectively 1g/L, 5g/L, 8g/L, 12g/L and
20g/L。
(2) water sample is prepared
Prepare the water sample of 5 groups of variable concentrations, water sample concentration be respectively 10mg/L, 30mg/L,
160mg/L, 1000mg/L and 2200mg/L, without chloride ion interference in water sample.
(3) chemical oxygen consumption (COC) detection
Method according to experimental group in embodiment 2 carries out chemical oxygen consumption (COC) detection to every kind of water sample respectively, often
Plant water sample and obtain 6 testing results, be shown in Table 10.
Table 10
As can be seen from Table 10, for the water sample of variable concentrations, using the reagent and method of the present invention
Good accuracy and stability can be realized；And the reagent and method of the present invention can detect chemistry
Oxygen demand it is dense such as the water sample of more than 2000mg/L, and remain to keep good accuracy and steady
It is qualitative.
Embodiment 6
(1) reagent preparation
Five group reagent i (including potassium bichromate and the concentrated sulfuric acid) are prepared, reagent i is designated as respectively1～i5.Reagent
i1～i5The concentration of middle potassium bichromate be respectively 0.072g/L, 0.194g/L, 1.41g/L, 6.91g/L and
13.8g/L。
Five group reagent ii (silver sulfate solution) are prepared, reagent ii is designated as respectively1～ii5.Reagent ii1～ii5
The concentration of middle silver sulfate is respectively 1g/L, 5g/L, 8g/L, 12g/L and 20g/L.
(2) water sample is prepared
Prepare the water sample of 5 groups of variable concentrations, water sample concentration be respectively 10mg/L, 30mg/L,
160mg/L, 1000mg/L and 2200mg/L, without chloride ion interference in water sample.
(3) chemical oxygen consumption (COC) detection
Method according to experimental group in embodiment 3 carries out chemical oxygen consumption (COC) detection to every kind of water sample respectively, often
Plant water sample and obtain 6 testing results, be shown in Table 11.
Table 11
As can be seen from Table 11, for the water sample of variable concentrations, using the reagent and method of the present invention
Good accuracy and stability can be realized；And the reagent and method of the present invention can detect chemistry
Oxygen demand it is dense such as the water sample of more than 2000mg/L, and remain to keep good accuracy and steady
It is qualitative.
Embodiment 7
(1) reagent preparation
Reagent I：Using five group reagent I of embodiment 51～I5。
Reagent II：By the concentrated sulfuric acid and water with 1:6 volume ratio prepares acidic aqueous solution, then takes appropriate sulphur
Sour mercury is completely dissolved in the acidic aqueous solution so that the concentration of mercuric sulfate is 40g/L, obtains mercuric sulfate
Solution, is designated as reagent IIa。
(2) water sample is prepared
Prepare the water sample of 5 groups of variable concentrations, water sample concentration be respectively 10mg/L, 30mg/L,
160mg/L, 1000mg/L and 2200mg/L, the concentration of Chloride Ion In Water is 1500mg/L.
(3) chemical oxygen consumption (COC) detection
Method according to experimental group in embodiment 2 carries out respectively chemical oxygen consumption (COC) detection, institute to every kind of water sample
Except for the difference that, the reagent II of 0.15mL is especially added in experimental group and control groupa, every kind of water sample obtains
6 testing results, are shown in Table 12.
Table 12
As can be seen from Table 12, for the water sample of variable concentrations, using the reagent and method of the present invention
Good accuracy and stability can be realized；And the reagent and method of the present invention can detect chemistry
Oxygen demand it is dense such as the water sample of more than 2000mg/L, and remain to keep good accuracy and steady
It is qualitative.
Embodiment 8
(1) reagent preparation
Reagent I：Using five group reagent I of embodiment 51～I5。
Reagent II：By the concentrated sulfuric acid and water with 1:7 volume ratio prepares acidic aqueous solution, then takes appropriate sulphur
Sour mercury is completely dissolved in the acidic aqueous solution so that the concentration of mercuric sulfate is 80g/L, obtains mercuric sulfate
Solution, is designated as reagent IIb。
(2) water sample is prepared
Prepare the water sample of 5 groups of variable concentrations, water sample concentration be respectively 10mg/L, 30mg/L,
160mg/L, 1000mg/L and 2200mg/L, the concentration of Chloride Ion In Water is 3000mg/L.
(3) chemical oxygen consumption (COC) detection
Method according to experimental group in embodiment 3 carries out respectively chemical oxygen consumption (COC) detection, institute to every kind of water sample
Except for the difference that, the reagent II of 0.35mL is especially added in experimental group and control groupb, every kind of water sample obtains
6 testing results, are shown in Table 13.
Table 13
As can be seen from Table 13, for the water sample of variable concentrations, using the reagent and method of the present invention
Good accuracy and stability can be realized；And the reagent and method of the present invention can detect chemistry
Oxygen demand it is dense such as the water sample of more than 2000mg/L, and remain to keep good accuracy and steady
It is qualitative.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.In addition
It should be noted that each particular technique feature described in above-mentioned specific embodiment, not
In the case of contradiction, can be combined by any suitable means, in order to avoid unnecessary weight
Multiple, the present invention is no longer separately illustrated to various possible combinations.Additionally, the present invention it is various not
Can also be combined between same embodiment, as long as its thought without prejudice to the present invention, its
Content disclosed in this invention should be equally considered as.
Claims (34)
1. it is a kind of determine water body in chemical oxygen consumption (COC) method, it is characterised in that the method include it is following
Step：
(1) enter water sample to be measured and reagent I respectively and optional reagent II is mixed, wherein, institute
State in reagent I containing potassium bichromate, the concentrated sulfuric acid and catalyst, the potassium bichromate in the reagent I it is dense
Spend for 0.062-13.7g/L, the sampling volume≤5mL of the reagent I, in the reagent II sulfuric acid is contained
Mercury；
(2) step (1) gained mixture is cleared up at a temperature of more than 90 DEG C；
(3) determination step (2) gained clears up the three of remaining hexavalent chromium concentration in product or generation
Valency chromium ion concentration, the chemical oxygen consumption (COC) being then calculated in water body.
2. method according to claim 1, wherein, methods described is entered under micro- sample introduction pattern
OK, the water sample to be measured of institute's sample introduction and the sampling volume of various reagents all need to meet≤5mL；
Preferably, the water sample to be measured of institute's sample introduction and the sampling volume of various reagents all need to meet≤2mL.
3. method according to claim 1 and 2, wherein, the water sample to be measured and the reagent I
Sampling volume ratio be 1：0.8-3, preferably 1：0.9-1.5, more preferably 1：1-1.1.
4. method according to claim 1, wherein, the potassium bichromate in the reagent I it is dense
Spend for 0.186-6.85g/L.
5. method according to claim 1, wherein, the concentration of the catalyst in the reagent I
For 1-20g/L, preferably 5-12g/L；
Preferably, the catalyst is silver sulfate.
6. method according to claim 1, wherein, the temperature cleared up is 120-180 DEG C.
7. method according to claim 1, wherein, water sample to be measured, reagent I and examination are entered respectively
Agent II carries out the mixing.
8. method according to claim 7, wherein, mercuric sulfate, acid are contained in the reagent II
Property material and water；
Preferably, the acidic materials are sulfuric acid, and the acidic materials are 1 with the consumption volume ratio of water：
3-9。
9. the method according to claim 1 or 7, wherein, the mercuric sulfate in the reagent II
Concentration is 1-120g/L, and the sampling volume of the reagent II is with the ratio of the sampling volume of the water sample to be measured
0.05-0.5：1；
Preferably, the concentration of the mercuric sulfate in the reagent II is 30-90g/L, and the reagent II's enters
Sample volume is 0.05-0.4 with the ratio of the sampling volume of the water sample to be measured：1.
10. the method according to claim 7 or 8, wherein, contain dichromic acid in the reagent II
Potassium.
11. methods according to claim 1, wherein, methods described is carried out in Water Test Kits.
12. it is a kind of for determining water body in chemical oxygen consumption (COC) method reagent composition, the reagent set
Compound includes：
Reagent I, contains potassium bichromate, the concentrated sulfuric acid and catalyst in reagent I, wherein, in reagent I
The concentration of potassium bichromate is 0.062-13.7g/L, preferably 0.186-6.85g/L.
13. reagent compositions according to claim 12, wherein, the catalysis in the reagent I
The concentration of agent is 1-20g/L, preferably 5-12g/L；
Preferably, the catalyst is silver sulfate.
14. reagent compositions according to claim 12, wherein, the reagent composition is also wrapped
Include：
Reagent II, in the reagent II mercuric sulfate is contained, and the concentration of the mercuric sulfate in reagent II is
1-120g/L, preferably 30-90g/L.
15. reagent compositions according to claim 14, wherein, contain sulphur in the reagent II
Sour mercury, acidic materials and water；
Preferably, the acidic materials are sulfuric acid, and the acidic materials are 1 with the consumption volume ratio of water：
3-9。
16. reagent compositions according to claim 14, wherein, containing weight in the reagent II
Potassium chromate.
17. it is a kind of determine water bodys in chemical oxygen consumption (COC) methods, it is characterised in that the method include with
Lower step：
(1) enter water sample to be measured, reagent i and reagent ii respectively and optional reagent iii mixed,
Wherein, in the reagent i containing potassium bichromate and the concentrated sulfuric acid, the potassium bichromate in the reagent i it is dense
Spend for 0.062-13.7g/L, catalyst contained in the reagent ii, in the reagent iii mercuric sulfate is contained,
Sampling volume≤the 5mL of the reagent i；
(2) step (1) gained mixture is cleared up at a temperature of more than 90 DEG C；
(3) determination step (2) gained clears up the three of remaining hexavalent chromium concentration in product or generation
Valency chromium ion concentration, the chemical oxygen consumption (COC) being then calculated in water body.
18. methods according to claim 17, wherein, methods described is entered under micro- sample introduction pattern
OK, the water sample to be measured of institute's sample introduction and the sampling volume of various reagents all need to meet≤5mL；
Preferably, the water sample to be measured of institute's sample introduction and the sampling volume of various reagents all need to meet≤2mL.
19. methods according to claim 17 or 18, wherein, the water sample to be measured, reagent i
It is 1 with the sampling volume ratio of reagent ii：0.8-3：0.01-1, preferably 1：0.9-1.5：0.05-0.5,
More preferably 1：1-1.1：0.05-0.4.
20. methods according to claim 17, wherein, the potassium bichromate in the reagent i
Concentration is 0.186-6.85g/L.
21. methods according to claim 17, wherein, the catalyst in the reagent ii it is dense
Spend for 1-20g/L, preferably 5-12g/L；
Preferably, the catalyst is silver sulfate.
22. methods according to claim 17, wherein, the temperature cleared up is
120-180℃。
23. methods according to claim 17, wherein, water sample to be measured, reagent i, examination are entered respectively
Agent ii and reagent iii are mixed.
24. methods according to claim 23, wherein, in the reagent iii containing mercuric sulfate,
Acidic materials and water；
Preferably, the acidic materials are sulfuric acid, and the acidic materials are 1 with the consumption volume ratio of water：
3-9。
25. methods according to claim 23 or 24, wherein, the sulfuric acid in the reagent iii
The concentration of mercury is 1-120g/L, the sampling volume of the sampling volume of the reagent iii and the water sample to be measured
Ratio be 0.05-0.5：1；
Preferably, the concentration of the mercuric sulfate in the reagent iii is 30-90g/L, and the reagent iii's enters
Sample volume is 0.05-0.4 with the ratio of the sampling volume of the water sample to be measured：1.
26. methods according to claim 17, wherein, contain potassium bichromate in the reagent ii.
27. methods according to claim 23 or 24, wherein, containing weight in the reagent iii
Potassium chromate.
28. methods according to claim 17, wherein, methods described is entered in Water Test Kits
OK.
29. it is a kind of for determining water body in chemical oxygen consumption (COC) method reagent composition, the reagent set
Compound includes：
Reagent i, containing potassium bichromate and the concentrated sulfuric acid, the concentration of the potassium bichromate in reagent i in reagent i
For 0.062-13.7g/L, preferably 0.186-6.85g/L；
Reagent ii, in the reagent ii catalyst is contained.
30. reagent compositions according to claim 29, wherein, the catalysis in the reagent ii
The concentration of agent is 1-20g/L, preferably 5-12g/L；
Preferably, the catalyst is silver sulfate.
31. reagent compositions according to claim 29 or 30, wherein, the reagent composition
Also include：
Reagent iii, in the reagent iii mercuric sulfate is contained, and the concentration of the mercuric sulfate in reagent iii is
1-120g/L, preferably 30-90g/L.
32. reagent compositions according to claim 31, wherein, contain sulphur in the reagent iii
Sour mercury, acidic materials and water；
Preferably, the acidic materials are sulfuric acid, and the acidic materials are 1 with the consumption volume ratio of water：
3-9。
33. reagent compositions according to claim 29, wherein, containing weight in the reagent ii
Potassium chromate.
34. reagent compositions according to claim 31 or 32, wherein, in the reagent iii
Containing potassium bichromate.
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