KR20020043132A - COD Vials and determination methods for chemical oxygen demand analysis - Google Patents
COD Vials and determination methods for chemical oxygen demand analysis Download PDFInfo
- Publication number
- KR20020043132A KR20020043132A KR1020000072615A KR20000072615A KR20020043132A KR 20020043132 A KR20020043132 A KR 20020043132A KR 1020000072615 A KR1020000072615 A KR 1020000072615A KR 20000072615 A KR20000072615 A KR 20000072615A KR 20020043132 A KR20020043132 A KR 20020043132A
- Authority
- KR
- South Korea
- Prior art keywords
- cod
- test tube
- water
- measuring
- measurement
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 title claims abstract description 11
- 238000004458 analytical method Methods 0.000 title claims description 4
- 238000012360 testing method Methods 0.000 claims abstract description 54
- 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 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 229910000367 silver sulfate Inorganic materials 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000011368 organic material Substances 0.000 claims abstract 2
- 238000005259 measurement Methods 0.000 claims description 24
- 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 9
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 7
- 238000003556 assay Methods 0.000 claims description 5
- 238000011161 development Methods 0.000 claims description 5
- 229940074994 mercuric sulfate Drugs 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000000691 measurement method Methods 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- RQPCXPDUSNVHSU-UHFFFAOYSA-N [O].[K] Chemical compound [O].[K] RQPCXPDUSNVHSU-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 238000011088 calibration curve Methods 0.000 description 10
- 244000005700 microbiome Species 0.000 description 7
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000010421 standard material Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 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
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Biodiversity & Conservation Biology (AREA)
- Biomedical Technology (AREA)
- Emergency Medicine (AREA)
- Molecular Biology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
산소요구량은 수질 시료중의 유기오염물질의 영향을 결정하는 중요한 지표이다. 자연계에서 미생물들이 이들 유기오염물질을 분해하면서 수중의 산소를 소모하게 되고, 산소의 고갈은 수중의 생태계에 막대한 부작용을 미치기 때문이다. 산소요구량을 측정하는 방법으로 크게 두 가지 방법이 널리 사용되어 왔으며, 이것이 생물학적 산소요구량(BOD; Biochemical Oxygen Demand, 이하 BOD)과 화학적 산소요구량(COD; Chemical Oxygen Demand, 이하 COD)이다. 국내 환경관련법규에서도 폐수 배출시설의 오염물질배출에 대해 BOD와 COD의 수치로서 규제를 해오고 있다.Oxygen demand is an important indicator for determining the impact of organic pollutants in water samples. In nature, microorganisms decompose these organic pollutants to consume oxygen in the water, and the depletion of oxygen has a huge side effect on the ecosystem of the water. Two methods have been widely used to measure the oxygen demand, which is a biological oxygen demand (BOD) and a chemical oxygen demand (COD). Domestic environmental legislation has also regulated BOD and COD values for pollutant emissions from wastewater discharge facilities.
BOD는 물속의 유기물질이 산소를 필요로 하는 미생물의 작용에 의해 안정화하고 자연히 정화되는 과정에서 소비되는 산소량으로 ppm(part per million; 백만분의 일)으로 표시한다. 다시말해서 BOD는 유기물질의 함량을 간접적으로 나타내는 지표인데 BOD가 높다고 하는 것은 이들 유기물질이 과도로 유입되어 물속의 산소를 결핍시키면서 물을 썩게 만들어 환경 및 생태계를 파괴 시키는 것이다.BOD is the amount of oxygen consumed in the process of stabilizing and naturally purifying organic matter in water by the action of microorganisms that require oxygen, expressed in parts per million (ppm). In other words, BOD is an indirect indicator of the content of organic matter. High BOD means that these organic substances are excessively inflowed, depleting oxygen in the water, causing water to rot and destroying the environment and ecosystem.
미생물에 의한 산화작용을 이용하는 BOD의 측정은 주로 습식방법(적정법)에 의한 방법으로 이루어지며, 다음과 같은 단점으로 인해 각종 산업현장에서의 활용도가 떨어지고 있다. 우선 측정시간이 5일간으로 길기 때문에 오늘의 상황을 5일 후에나 결과를 알 수 있으며, 측정대상 수질시료중에 미생물에 독성을 미치는 독성 물질이 존재할 경우 미생물을 사멸시켜 유기오염물질의 분해가 불가능하게 된다. 또한 독성이 없는 물질이라 하여도 미생물에 의해 분해되가 잘 되지않는 난분해성 물질의 경우 5일동안의 배양기간에도 분해되지 않으므로 정확한 유기물 농도를 측정할 수 없다. 또한 실험시 측정대상시료의 유기물 농도를 잘못 예측하여 실험 BOD의 산소량을 고갈시킬 수도있으며, 실험시 여러단계를 거치는 동안 오차유발 요인이 계속하여 존재하므로 실험 결과의 정확성 및 재현성에 문제가 있는 실정이다.The measurement of BOD using oxidation by microorganisms is mainly performed by the wet method (titration method), and its utilization in various industrial sites is declining due to the following disadvantages. First of all, the measurement time is 5 days long, so you can know the result after 5 days. If there is a toxic substance that is toxic to the microorganisms in the water sample, the microorganisms are killed and the decomposition of organic pollutants becomes impossible. . In addition, even non-toxic substances that are difficult to be degraded by microorganisms cannot be decomposed by the microorganisms during the five days of incubation period, and thus, accurate organic concentration cannot be measured. In addition, the concentration of oxygen in the test BOD may be depleted by incorrectly predicting the concentration of the organic substance in the sample to be measured during the experiment, and there is a problem in the accuracy and reproducibility of the test result because the error-causing factors continue to exist during the various steps in the experiment. .
COD는 BOD와 더불어 주로 유기물질을 간접적으로 나타내는 지표로서 산화제를 이용하여 물속의 피산화물을 산화하는데 요구되는 산소량을 ppm단위로 표시한다. COD 측정방법에는 산화제의 종류에 따라 과망간산칼륨법과 중크롬산칼륨법의 두 종류가 있으며, 국내의 법적규제는 수질오염공정시험법상의 과망간산칼륨법을 이용한 습식방법(적정법)에 따라 이루어지고 있다. 과망간산칼륨법에 의한 COD 측정은 독성물질이나 난분해성물질이 함유되어 있는 폐수시료에 대해서도 측정할 수 있는 장점이 있어 공장폐수등의 다양한 수질시료의 분석에 활용되고 있으나, 시료의 염소이온 농도에 따라 산성법 및 알칼리법(염소이온 다량 함유 시료)으로 구분하여 측정방법을 달리해야 하고, 시료의 전처리에서부터 시약조제, 가열반응, 적정에 이르기까지 여러단계의 실험을 하는 과정에서 오차유발 요인이 계속하여 존재하므로 실험 결과의 정확성 및 재현성에 문제가 있는 실정이다.COD, in addition to BOD, is an indirect indicator of organic substances. It indicates the amount of oxygen required to oxidize the pioxid in water using an oxidant in ppm. There are two types of COD measurement methods, potassium permanganate and potassium dichromate, depending on the type of oxidant. Domestic legal regulations are made by wet method using potassium permanganate method in water pollution test method. COD measurement by potassium permanganate method has the advantage of being able to measure wastewater samples containing toxic or hardly decomposable substances, so it is used to analyze various water samples such as factory wastewater. The measurement method should be divided into the acid method and the alkali method (samples containing a large amount of chlorine ions), and the error-prone factors will continue to occur during the multi-step experiments from pretreatment of the sample to reagent preparation, heating reaction, and titration. There exists a problem in the accuracy and reproducibility of the experimental results.
중크롬산칼륨법을 이용한 습식방법은 과망간산칼륨법에 비하여 산화력이 크므로 수중 유기물의 총량에 가까운 값을 얻는다는 장점이 있으나, 이 방법 역시도 시료의 전처리에서부터 시약조제, 시약주입, 가열반응, 적정에 이르기까지 여러단계의 실험을 하는 과정에서 오차유발 요인이 계속하여 존재하므로 실험 결과의 정확성 및 재현성에 문제가 있는 실정이다.The wet method using the potassium dichromate method has the advantage of obtaining a value close to the total amount of organic matter in the water because the oxidizing power is greater than that of the potassium permanganate method, but this method also includes the pretreatment of the sample, reagent preparation, reagent injection, heating reaction, and titration. There is a problem in the accuracy and reproducibility of the experimental results because the error-causing factors continue to exist in the process of several stages until the experiment.
현재 국내 각종 산업시설, 연구소등지에서 수중의 오염물질 농도를 측정하기 위한 수단으로 정확성이 높아 중크롬산칼륨법의 COD 를 널리 이용하고 있는 실정이다. 국내의 수질오염공정시험방법에도 중크롬산칼륨법이 1997년에도입되었으며, 매립지 침출수의 배출허용기준으로는 중크롬산칼륨법이 2001년 6월 31일까지는 과망간산칼륨법과 함께 적용되며, 2001년 7월 1일 이후부터는 중크롬산칼륨법에 의한 배출허용기준을 적용받게 된다. 현재 과망간산칼륨법은 한국과 일본에서만 적용되고 있는 방법으로 최근에는 국내의 수질오염 법적규제를 중크롬산칼륨법에 의한 적용을 검토중이어서 중크롬산칼륨법에 의한 COD 측정이 보편화될 전망이다.Currently, the COD of the potassium dichromate method is widely used as a means for measuring the concentration of pollutants in water at various industrial facilities and research institutes in Korea. The potassium dichromate method was introduced in 1997 in the water pollution process test method in Korea, and the potassium dichromate method is applied together with the potassium permanganate method until June 31, 2001 as the allowable discharge standard of landfill leachate. After that, the emission limit under the potassium dichromate method will be applied. Currently, the potassium permanganate method is applied only in Korea and Japan. Recently, the domestic law on water pollution is under consideration by the potassium dichromate method, and the COD measurement by the potassium dichromate method is expected to become common.
이에 본 발명은 COD 시험관내에 산화제 및 반응촉매제, 측정시 방해가되는 물질인 염소이온의 영향을 제거하기 위한 방지제등 산화반응을 위해 필수적인 시약들을 적정비율로 미리 조제하여 둠으로써, COD측정시 단순히 측정하고자하는 시료를 COD 시험관에 넣는 것만으로 COD 측정이 가능하도록 실험방법의 편리성을 높이는데 있다.Accordingly, the present invention prepares the reagents necessary for the oxidation reaction in advance in an appropriate ratio, such as an oxidizing agent and a reaction catalyst in a COD test tube, and an inhibitor for removing the influence of chlorine ion, which is a material that interferes with the measurement. It is to increase the convenience of the test method so that COD measurement is possible simply by putting the sample to be measured in the COD test tube.
또한 습식방법으로 측정되고 있는 중크롬산칼륨법의 적정방법을 흡광광도법 및 색도비교법으로 개선하여 적정시 개인에 따라 발생할 수 있는 오차유발요인을 없앰으로서 측정값의 정확성 및 재현성을 높이려는데 있다.In addition, the titration method of potassium dichromate method, which is measured by the wet method, has been improved by absorbance and chromaticity comparison methods to remove the error-caused factors that can occur in each individual during the titration, thereby improving the accuracy and reproducibility of the measured values.
도 1 은 화학적산소요구량 측정용 시험관의 구성도,1 is a block diagram of a test tube for measuring the chemical oxygen demand,
도 2 는 고농도 측정용 COD 시험관의 검량선 그래프,2 is a calibration curve graph of a COD test tube for high concentration measurement,
도 3 은 저농도 측정용 COD 시험관의 검량선 그래프이다.3 is a calibration curve graph of a COD test tube for low concentration measurement.
<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>
1: 테프론으로 처리된 속마개를 갖고있는 불활성마개로 닫혀지는 시험관의 목부분1: neck of test tube closed with inert stopper with Teflon treated stopper
2: 분광계용 석영질 시험관2: Quartz test tube for spectrometer
3: 미리 조제되어 있는 분석시약3: preprepared assay reagent
4: 테프론으로 처리된 속마개를 갖고있는 불활성마개4: inert stopper with teflon treated stopper
상기 COD 시험관은 내부에 COD 분석을 위한 분석시약이 미리 조제되어 들어 있고, 시험관 재질은 분광계용 석영질(Borosilicate)이며, 시험관의 입구는 마개를 돌려 막을 수 있도록 나사산이 만들어져 있다. 시험관의 마개는 산성에 대해 내성이 있는 테프론처리된 고무 속마개가 들어있는 내열성 마개를 사용하며, 시험관을 가열시 내용물이 유출되지 않도록 시험관을 밀폐할 수 있다. 사용되는 COD 시험관은 필요에 따라 크기가 16mmX100mm, 20mmX150mm, 25mmX150mm(외경 X 높이)인 시험관을 사용한다.In the COD test tube, an analytical reagent for COD analysis is pre-prepared, and the test tube material is made of quartz for spectrometer (Borosilicate), and the inlet of the test tube is made of a thread so as to be closed by turning a stopper. The test tube closure is a heat resistant stopper containing an acid resistant Teflonized rubber stopper and can be sealed to prevent the contents from leaking out when the test tube is heated. The COD test tubes used are test tubes of size 16mmX100mm, 20mmX150mm, 25mmX150mm (outer diameter X height) as required.
상기 COD 시험관 내부에 들어있는 분석시약은 물속의 오염물질을 산화시키기 위한 시약들의 혼합물로 주요성분은 중크롬산칼륨(K2Cr2O7), 황산은(Ag2SO4), 황산수은(HgSO4), 진한황산, 그리고 증류수로 되어있다.The analytical reagent contained in the COD test tube is a mixture of reagents for oxidizing contaminants in water. The main components are potassium dichromate (K2Cr2O7), silver sulfate (Ag2SO4), mercury sulfate (HgSO4), concentrated sulfuric acid, and distilled water. have.
상기 시약중 중크롬산칼륨(K2Cr2O7)은 물속의 오염물을 산화시키기 위한 산화제로 첨가하며, 가열반응에 의해 오염물이 산화되면서 중크롬산이온(Cr2O72-)이 크롬산이온(Cr3+)으로 환원되며 이 과정에서 발색이 된다.Potassium dichromate (K2Cr2O7) is added as an oxidizing agent to oxidize contaminants in water, and dichromate ions (Cr2O7 2- ) are reduced to chromium ions (Cr 3+ ) as the contaminants are oxidized by heating. It becomes a color development.
상기 시약중 황산은(Ag2SO4)은 직쇄형 탄화수소를 산화시키기 위한 촉매로 첨가하며, 물속에 Cl, Br, I 같은 할로겐원소가 존재할 경우 은 이온이 이들 할로겐원소와 반응하여 침전을 형성하므로 산화반응을 촉진하는데 방해가 된다.Silver sulfate (Ag 2 SO 4 ) in the reagent is added as a catalyst for oxidizing the linear hydrocarbon, and when a halogen element such as Cl, Br, I is present in water, silver ions react with these halogen elements to form a precipitate. It interferes with promoting the oxidation reaction.
상기 황산은(Ag2SO4)의 촉매작용을 방해하는 할로겐원소의 영향을 제거하기 위해 황산수은(HgSO4)을 첨가하는데, 황산수은은 할로겐원소와 복합체를 형성하여 할로겐원소의 방해작용을 제거한다. 상기 COD 시험관의 경우 Cl-ion의 농도가 2000ppm까지는 영향을 받지 않도록 황산수은을 첨가하였다.Mercury sulfate (HgSO 4 ) is added to remove the effect of halogen elements that interfere with the catalytic action of silver (Ag 2 SO 4 ), mercury sulfate forms a complex with the halogen element to remove the interference of the halogen element do. In the case of the COD test tube, mercuric sulfate was added so that the concentration of Cl - ion was not affected until 2000 ppm.
상기 COD 시험관 내부에 존재하는 분석시약의 성분별 조성은 측정하고자 하는 시료의 유기물농도에 따라 다르며, 1500ppm까지 측정할 수 있는 고농도용과 150ppm까지 측정할 수 있는 저농도용으로 구분된다. 고농도용 COD 시험관의 제조시 각 성분의 몰비율은 중크롬산칼륨:황산수은:황산은:진한황산:물의 몰비율이 1:1.0∼2.0:2.0∼3.0:400∼500:130∼160 범위이며, 저농도용 COD 시험관의 제조시 각 성분의 모비율은 중크롬산칼륨:황산수은:황산은:진한황산:물의 몰비율이 1:10∼20:20∼30:4000∼5000:1300∼1600 범위이다.The composition of each component of the analytical reagent present in the COD test tube depends on the organic concentration of the sample to be measured, and is divided into a high concentration that can be measured up to 1500 ppm and a low concentration that can be measured up to 150 ppm. The molar ratio of each component in the production of COD test tubes for high concentrations ranges from 1: 1.0 to 2.0: 2.0 to 3.0: 400 to 500: 130 to 160 with a molar ratio of potassium dichromate: mercuric sulfate: silver sulfate: concentrated sulfuric acid: water. The molar ratio of each component in the production of the COD test tube for use is in the range of 1:10 to 20:20 to 30: 4000 to 5000: 1300 to 1600: potassium dichromate: mercuric sulfate: silver sulfate: concentrated sulfuric acid: water.
상기와 같이 제조된 COD 시험관을 이용한 측정방법은 다음과 같다. COD 시험관의 마개를 열고, 측정하고자하는 시료를 적정농도로 희석한후 피펫을 이용하여 2mL를 시험관에 넣는다. 아래위로 시험관을 잘 흔들어 섞은 후 가열기에서 150℃로 2시간 가열하고 꺼내어 상온으로 식힌다. COD 시험관의 표면을 깨끗한 헝겁으로 잘 닦은후 분광계를 이용한 흡광광도법이나 색도비교표를 이용한 색도비교법으로 시료의 유기물 농도를 읽는다.The measurement method using the COD test tube manufactured as described above is as follows. Open the stopper of the COD test tube, dilute the sample to be measured to an appropriate concentration, and put 2 mL into the test tube using a pipette. Shake the test tube up and down well, heat it to 150 ℃ in a heater for 2 hours, remove it, and let it cool to room temperature. Clean the surface of the COD test tube with a clean cloth, and then read the organic concentration of the sample by using the spectrophotometer or the color comparison method using the chromaticity comparison table.
상기 시험관의 반응 후 발색강도를 측정하는 방법이 고농도용 COD 시험관과 저농도용 COD 시험관이 다르다. 고농도용 COD 시험관의 경우 산화반응후 생성된 Cr3+의 양에 따른 발색강도를 측정하며, 분광계를 이용한 측정파장은 600∼620nm범위이다. 저농도용 COD 시험관의 경우 산화반응후 소비되지않고 남아있는 Cr6+의 양에 따른 발색강도를 측정하며, 분광계를 이용한 측정파장은 400∼450nm범위이다. 또한 상기 시험관의 발색강도를 측정하는 방법에 있어서 또 다른 방법이 있는데, 고농도용 및 저농도용 COD 시험관에 대한 표준물질의 농도별 발색정도를 근거로 제작된 농도별 색도비교표를 이용한 색도비교법으로 측정할 수 도 있다.The method of measuring the color intensity after the reaction of the test tube is different from the high concentration COD test tube and the low concentration COD test tube. In the case of high concentration COD test tubes, the color intensity is measured according to the amount of Cr 3+ produced after the oxidation reaction, and the measurement wavelength using the spectrometer is in the range of 600 to 620 nm. In the case of low concentration COD test tubes, the color intensity is measured according to the amount of Cr 6+ remaining after consumption, and the measurement wavelength using the spectrometer is in the range of 400-450 nm. In addition, there is another method for measuring the color intensity of the test tube, which is to be measured by the chromaticity comparison method using the concentration chromaticity comparison table produced on the basis of the concentration of the concentration of the standard material for high concentration and low concentration COD test tube Can also be.
이하, 본 발명을 실시예를 통하여 상세히 설명한다. 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해영향을 받는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not affected by these examples.
실시예 1: 고농도 측정용 COD 시험관의 검량선 작성Example 1: Preparation of calibration curve of COD test tube for high concentration measurement
고농도 측정용 COD 시험관의 표준물질에 대한 검량선을 구하기 위하여, 표준물질로 Potassium hydrogen phthalate(KHP ; HOOCC6H4COOK, 이하 KHP)를 사용하여 다음과 같은 방법으로 농도별 표준용액을 제조하였다.In order to obtain a calibration curve for the standard of the COD test tube for high concentration measurement, a standard solution for each concentration was prepared by the following method using Potassium hydrogen phthalate (KHP; HOOCC 6 H 4 COOK, hereinafter KHP) as a standard.
우선 KHP를 항량이 되도록 120℃에서 밤새도록 건조시킨후, KHP 425mg을 증류수에 녹여 1000mL가 되게 한다. KPH의 이론 COD는 1.176mg O2/mg KHP이므로, 이 용액의 이론적 COD는 500mg O2/L이다.First, the KHP is dried overnight at 120 ° C. to a constant dose, and then 425 mg of KHP is dissolved in distilled water to make 1000 mL. The theoretical COD of KPH is 1.176 mg O 2 / mg KHP, so the theoretical COD of this solution is 500 mg O 2 / L.
위와 같은 방법으로 하여 아래 표1과 같이 각각의 농도별 표준용액을 제조하여 고농도 측정용 COD 시험관의 검량선을 작성하였다. 상기 표준용액은 냉장보관 시 3개월 유효하다.In the same manner as described in Table 1 below to prepare a standard solution for each concentration was prepared a calibration curve of the COD test tube for high concentration measurement. The standard solution is valid for 3 months when refrigerated.
표2 및 도2에서 나타난 결과에서 볼 수 있듯이 고농도 측정용 COD 시험관의 경우 표준물질에 대한 검량선의 R-제곱값이 0.9997로 이론COD와 측정COD사이에 매우 상관성이 있는 측정값을 보여주었다.As can be seen from the results shown in Table 2 and FIG. 2, in the case of high concentration COD test tubes, the R-squared value of the calibration curve for the standard material was 0.9997, which showed a very correlated measurement value between the theoretical COD and the measured COD.
실시예 2: 저농도 측정용 COD 시험관의 검량선Example 2: Calibration curve of COD test tube for low concentration measurement
상기 고농도 측정용 COD 시험관의 표준물질에 대한 검량선을 구할때와 마찬가지 방법으로 표3에서와 같은 농도별 표준용액을 제조하여, 저농도 측정용 COD 시험관의 검량선을 작성하였다.The standard solution for each concentration was prepared in the same manner as in Table 3, and the calibration curve for the low concentration COD test tube was prepared in the same manner as when the calibration curve for the standard material of the high concentration COD test tube was obtained.
표4와 도3의 결과에서 볼 수 있듯이 저농도 측정용 COD 시험관의 경우에도 표준물질에 대한 검량선의 R-제곱값이 0.9988로 이론COD와 측정COD사이에 매우 상관성이 있는 측정값을 보여주었다.As can be seen from the results of Table 4 and FIG. 3, even in the case of COD test tubes for low concentration measurement, the R-squared value of the calibration curve for the standard material was 0.9988, which showed a very correlated measurement value between the theoretical COD and the measured COD.
COD 시험관의 개발로 인해 각종 산업현장에서 배출되는 폐수의 오염물 농도를 특별한 환경관련 지식이 없는 작업자라 하여도 간편하고 정확한 측정이 가능하도록 함으로써 배출수 및 각종 폐수의 원천관리를 보다 효율적으로 할 수 있다.Due to the development of COD test tubes, the pollutant concentration of wastewater discharged from various industrial sites can be easily and accurately measured even by workers without special environmental knowledge, so that the source and discharge of wastewater can be more efficiently managed.
현재 국내에서 사용되고 있는 COD 시험관은 전량 외국에서 수입되고 있으며 가격이 고가이기 때문에 많은 사업장에 널리 보급되지 못한 실정이다. 이러한 이유로 국내에서 COD 시험관이 개발되므로써 현재 연간 수십억원에 달하는 수입대체 효과를 가져올 뿐만아니라 국내 법적 규제가 중크롬산칼륨법으로 전환될 경우 수입대체 효과는 현재의 10배 이상으로 늘어날 것이다. 또한 공급가격을 대폭 낮추어 보다 많은 사업장에서 활용하게 함으로써 국내 환경정책에 일조를 할 수 있으리라 생각된다.Currently, COD test tubes used in Korea are all imported from foreign countries, and because of their high price, they are not widely used in many workplaces. For this reason, the development of COD test tubes in Korea will not only bring about billions of annual import substitution effects, but will also increase the import substitution effect by more than 10 times if domestic legal regulations are converted to potassium dichromate law. In addition, it is expected to contribute to domestic environmental policy by drastically lowering the supply price so that it can be utilized in more workplaces.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000072615A KR20020043132A (en) | 2000-12-01 | 2000-12-01 | COD Vials and determination methods for chemical oxygen demand analysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000072615A KR20020043132A (en) | 2000-12-01 | 2000-12-01 | COD Vials and determination methods for chemical oxygen demand analysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20020043132A true KR20020043132A (en) | 2002-06-08 |
Family
ID=27679134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020000072615A KR20020043132A (en) | 2000-12-01 | 2000-12-01 | COD Vials and determination methods for chemical oxygen demand analysis |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20020043132A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100475429B1 (en) * | 2002-04-23 | 2005-03-10 | 주식회사 드림바이오스 | Automatic On-line COD Analyzer use multi-syringe of injecting & sending System |
| CN102156182A (en) * | 2011-03-25 | 2011-08-17 | 杭州泽天科技有限公司 | Method and device for judging H2SO4 invalidation in COD (chemical oxygen demand) online monitor |
| CN103616276A (en) * | 2013-10-23 | 2014-03-05 | 洛阳高新开发区双阳仪器有限公司 | Digestion determination method of chemical oxygen demand |
| CN108169225A (en) * | 2017-12-28 | 2018-06-15 | 青岛路博建业环保科技有限公司 | A kind of analytical reagent and its preparation method of COD quick analytic instruments |
| CN112292599A (en) * | 2018-07-04 | 2021-01-29 | 哈希朗格有限公司 | Method for determining Chemical Oxygen Demand (COD) of high-chloride sample |
| CN112485099A (en) * | 2020-11-23 | 2021-03-12 | 陕西彩虹新材料有限公司 | Preparation method of COD mixed digesting agent |
| CN117825646A (en) * | 2023-11-08 | 2024-04-05 | 浙江迪特西科技有限公司 | Mixed reagent for COD detection, COD detection reagent tube and COD detection method |
-
2000
- 2000-12-01 KR KR1020000072615A patent/KR20020043132A/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100475429B1 (en) * | 2002-04-23 | 2005-03-10 | 주식회사 드림바이오스 | Automatic On-line COD Analyzer use multi-syringe of injecting & sending System |
| CN102156182A (en) * | 2011-03-25 | 2011-08-17 | 杭州泽天科技有限公司 | Method and device for judging H2SO4 invalidation in COD (chemical oxygen demand) online monitor |
| CN103616276A (en) * | 2013-10-23 | 2014-03-05 | 洛阳高新开发区双阳仪器有限公司 | Digestion determination method of chemical oxygen demand |
| CN108169225A (en) * | 2017-12-28 | 2018-06-15 | 青岛路博建业环保科技有限公司 | A kind of analytical reagent and its preparation method of COD quick analytic instruments |
| CN112292599A (en) * | 2018-07-04 | 2021-01-29 | 哈希朗格有限公司 | Method for determining Chemical Oxygen Demand (COD) of high-chloride sample |
| CN112485099A (en) * | 2020-11-23 | 2021-03-12 | 陕西彩虹新材料有限公司 | Preparation method of COD mixed digesting agent |
| CN117825646A (en) * | 2023-11-08 | 2024-04-05 | 浙江迪特西科技有限公司 | Mixed reagent for COD detection, COD detection reagent tube and COD detection method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Boyles | Chemical oxygen demand | |
| Ma | Determination of chemical oxygen demand in aqueous samples with non-electrochemical methods | |
| Visco et al. | Organic carbons and TOC in waters: an overview of the international norm for its measurements | |
| Miro et al. | Application of flowing stream techniques to water analysis. Part I. Ionic species: dissolved inorganic carbon, nutrients and related compounds | |
| CN107037045B (en) | Method for rapidly measuring content of hydrogen peroxide in solution | |
| Florescu et al. | Validation procedure for assessing the total organic carbon in water samples | |
| Aguilar-Torrejón et al. | Relationship, importance, and development of analytical techniques: COD, BOD, and, TOC in water—An overview through time | |
| Zhang et al. | A novel method for the determination of hydrogen peroxide in bleaching effluents by spectroscopy | |
| US11280778B2 (en) | Determining chemical oxygen demand | |
| Korenaga et al. | Continuous-flow injection analysis of aqueous environmental samples for chemical oxygen demand | |
| KR20020043132A (en) | COD Vials and determination methods for chemical oxygen demand analysis | |
| Miller et al. | Chemical oxygen demand analysis of wastewater using trivalent manganese oxidant with chloride removal by sodium bismuthate pretreatment | |
| Alves et al. | Photo-assisted electrochemical degradation of textile effluent to reduce organic halide (AOX) production | |
| Jensen et al. | Interferences by monochloramine and organic chloramines in free available chlorine methods. 2. N, N-Diethyl-p-phenylenediamine | |
| Taromsary et al. | Quantifying the organic content of saline wastewaters: is chemical oxygen demand always an achievable parameter? | |
| KR101208190B1 (en) | Analizing methods of chemical oxygen demand(cod) using ultrasound digestion and oxidation-reduction potential based titration | |
| Song et al. | Low consumption and portable technology for dithionite detection based on potassium ferricyanide differential spectrophotometry method in related advanced oxidation processes | |
| Kalogerakis et al. | A high-throughput and cost-effective microplate reader method for measuring persulfates (peroxydisulfate and peroxymonosulfate) | |
| Yang et al. | Field speciation of chromium with a sequential injection lab-on-valve incorporating a bismuthate immobilized micro-column | |
| Carbajal-Palacios et al. | Replacing dichromate with hydrogen peroxide in the chemical oxygen demand (COD) test | |
| Knechtel et al. | Determination of chlorine dioxide in sewage effluents | |
| TWI665439B (en) | A method for determining chemical oxygen demand of a water sample | |
| Messenger | Comparisons of sealed digestion chamber and standard method COD tests | |
| Monbet et al. | Phosphates | |
| Harrafi et al. | Determination of chemical oxygen demand in spent caustic by potentiometric determination |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Withdrawal due to no request for examination |