4.3.3 Procedure
Draw a working diagram of a standard series. Place 0, 0.10, 0.20, 0.40 …. 1.40 potassium nitrate standard solution, respectively, in 250 Erlenmeyer flasks. The concentration is 0–140 mg NO3-N/m3. Pour 50 ml nitrogen-free seawater, or seawater with low nitrogen content and add 1.0 ml 0.32 N acetic acid and 80 mg zinc powder or 2.5 g zinc particles. Shake for 7 minutes for reduction and let stand for 2–3 minutes. (With zinc powder, let it sink but with zinc particles proceed further.) Pour this solution into 2 ml graduated vessels or color comparison tubes, mix well, let stand for 30 minutes and draw a density relationship graph of the nitrate concentration and the light.
Measuring the seawater sample. Pour 50 ml seawater in 250 ml Erlenmeyer flask and add 1.0 ml 0.32 N acetic acid and 80 mg zinc particles. Reduction or color-forming may be attained with the above-described method. Measure the light intensity with photo-electric calorimeter or compare with a standard series.
4.4. Biochemical Oxygen Demand (BOD)
4.4.1 Principle
Determination of the BOD can be done as follows. Agitate a sample of water in a large container (provide aeration) and transfer to 2 clean glass bottles for oxygen measurement. Determine the dissolved oxygen immediately in one bottle. The other bottle should be measured after allowing it to stand for 5 weeks in a thermostat at 20 °C. BOD is the difference between the amount determined in the sampled water and the oxygen demand of a 1-litre water during its stay in the thermostat for 5 weeks.
4.4.2 Procedure
For determining the actual level of BOD, collect a water sample in a 1.5 litre sealed glass beaker. The temperature of sampled water should be as near as possible to 0 °C. Transfer the sampled water to a large flask, heat up to 20 °C and shake well for a minute for oxygen saturation. Transfer the water into 2 glass bottles for oxygen measurement. Place one bottle in a thermostat at 20 °C while measuring the amount of oxygen in the second bottle. Measure the oxygen content in the former bottle five weeks later. The difference of oxygen contents in these two bottles is the BOD. The error of thermostat's temperature is deemed at ± 1 °C.
4.5 Chemical Oxygen Demand (COD)
4.5.1 Principle
The degree of water oxidation may be determined based on the fact that potassium permanganate (KMnO4) consumes oxygen for the oxidation of organic substance.
In acid media, reductor potassium permanganate is reduced.
2KMnO4 + 3H2SO4 = 3H2O + 2MnSO4 + K2SO4 + 50
When excessive potassium permanganate solution is added to the sampled water, the extra potassium permanganate which does not take part in the oxidation of organic substance is decomposed (reduced by a certain amount of oxalic acid C2H2O4).
2KmnO4 + 5C2H2O4 + 3H2SO4 -- 8H2O + 1OCO2 + 2MnSO4 + K2SO4
2H2SO4 + K2MnO4 + 2H2C2O4 -- MnSO4 + 4CO2 + 4H2O + K2SO4
Titrate the remaining oxalic acid with a certain amount of KMnO4 solution after reducing the excess KMnO4.
The presence of oxides (iron sub-oxide, nitrous acid) increases the titration result of potassium permanganate.
Permanganic acid (MnO4) monomolecule in the alkaline media reacts with hydroxy monomolecule, producing free hydroxy. The hydroxy is unstable and therefore it soon decomposes producing nascent oxygen. A strong oxidizer as it is, this nascent oxygen reacts with the organic matter in water completely oxidating it.
KmnO4 + KOH = K2MnO4 + OH
2OH → H2O + (O),
i.e., 2KMnO4 + 2KOH + H2O → 2MnO4 + 4KOH + 3O
4.5.2 Reagents
0.01 N oxalic acid (C2H2O4.2H2O) solution. Dissolve 0.6302 mg oxalic acid in water, the total volume to be 1 litre.
25 % sulfuric acid (H2SO4) solution.
50% caustic soda (NaOH). 0.01 N potassium permanganate (KMnO4) solution.
2KMnO4 + 3H2SO4 = 2MnSO4 + K2SO4 + 3H2O + 5O
In the acid solution, the bimolecular potassium permanganate produces a penta atom oxygen. Therefore, 0.01 N potassium permanganate solution will be:
If 0.316 g potassium permanganate is dissolved in 1 litre distilled water, 1 ml 0.01 N solution can separate 0.08 mg of oxygen.
4.5.3 Procedure
a) In acid media. Pour 100 ml distilled water into a clean flask and add 5 ml 0.01 N potassium permanganate solution and 5 ml diluted sulfuric acid. Boil for 3–5 minutes to remove reductive substance sticking on the inner walls and wash the flask two to three times. Place in the flask 100 ml water sample by using a pipette, add 5 ml diluted sulfuric acid, and heat. When water begins to boil, add 10 ml 0.01 N potassium permanganate solution. Boiling should be for 10 minutes from the time it begins to boil. If, at the end of boiling, the liquid in the flask is reddish-pink, this means that enough of the potassium permanganate has been added for the oxidation of oxides contained in the water sample.
If the solution is colorless or of a distinct brown, do not go further, and dilute the sampled water with distilled water two to three times or add more potassium permanganate solution.
When its color is reddish-pink, add 10 ml 0.01 N oxalic acid solution into the flask. The color of the liquid in the flask disappears when shaken. When discoloration is completed, titrate excessive oxalic acid again with potassium permanganate solution and oxidize until the liquid is faint rosy-red when observed.
2KMnO4+5(C2H2O4.2H2O)+2H2SO4 = K2SO4+2MnSO4+18H2O2+10CO2
b) In alkaline media. Place a 100 ml water sample in a flask and heat until it boils. Add 0.5 ml caustic soda solution and 100 ml 0.01 N potassium permanganate solution. Boil for 10 minutes from the time it begins to boil. Cool the water to about 60 °C and add diluted sulfuric acid and 100 ml 0.01 N oxalic solution. When the liquid is completely discolored, titrate with the potassium permanganate solution until it becomes light pink.
4.3.3 ขั้นตอนวาดไดอะแกรมการทำงานของชุดมาตรฐาน วาง 0, 0.10, 0.20, 0.40 ... 1.40 ประสิวโซลูชันมาตรฐาน ตามลำดับ ในน้ำ Erlenmeyer 250 ความเข้มข้นเป็น 0 – 140 mg NO3-N/m3 เทน้ำทะเลฟรีไนโตรเจน 50 ml หรือทะเลที่ มีไนโตรเจนต่ำเนื้อหา และเพิ่มกรดอะซิติก N 1.0 ml $ 0.32 และ 80 มิลลิกรัมสังกะสีผงหรือ 2.5 g สังกะสีอนุภาค จับเวลา 7 นาทีสำหรับการลด และให้ยืน 2 – 3 นาที (สังกะสีผง ปล่อยให้มันจม แต่มี อนุภาคดำเนินต่อไป) เทโซลูชั่นนี้ลงในหลอด 2 มล.ที่จบศึกษาหรือหลอดเปรียบเทียบสี ลาบ ให้ยืน 30 นาที และวาดเป็นกราฟความสัมพันธ์ความหนาแน่นของความเข้มข้นของไนเตรตและแสงวัดตัวอย่างน้ำทะเล เททะเล 50 ml ใน 250 ml Erlenmeyer หนาว และเพิ่มกรดอะซิติก N 1.0 ml $ 0.32 และอนุภาคสังกะสี 80 มิลลิกรัม ลดหรือขึ้นรูปสีอาจจะได้ ด้วยวิธีที่อธิบายข้างต้น วัดความเข้มแสงกับแคลอรีมิเตอร์ไฟฟ้าภาพ หรือเปรียบเทียบกับชุดมาตรฐาน4.4 การ Biochemical ออกซิเจนอุปสงค์ (BOD)4.4.1 หลักความมุ่งมั่นของเพนกวินสามารถทำได้ดังนี้ กวนตัวอย่างน้ำในภาชนะขนาดใหญ่ (ให้ aeration) และโอนย้ายไปที่ 2 ทำความสะอาดขวดแก้วสำหรับวัดออกซิเจน กำหนดปริมาณออกซิเจนละลายใน 1 ขวดทันที ขวดอื่น ๆ ที่ควรวัดหลังจากที่อนุญาตให้ยืนใน 5 สัปดาห์ในอุณหภูมิที่ 20 องศาเซลเซียส BOD คือ ผลต่างระหว่างยอดเงินที่กำหนดในตัวอย่างน้ำและความต้องการออกซิเจนของน้ำ 1 ลิตรอุณหภูมิการเดินของสัปดาห์ที่ 54.4.2 ProcedureFor determining the actual level of BOD, collect a water sample in a 1.5 litre sealed glass beaker. The temperature of sampled water should be as near as possible to 0 °C. Transfer the sampled water to a large flask, heat up to 20 °C and shake well for a minute for oxygen saturation. Transfer the water into 2 glass bottles for oxygen measurement. Place one bottle in a thermostat at 20 °C while measuring the amount of oxygen in the second bottle. Measure the oxygen content in the former bottle five weeks later. The difference of oxygen contents in these two bottles is the BOD. The error of thermostat's temperature is deemed at ± 1 °C.4.5 Chemical Oxygen Demand (COD)4.5.1 PrincipleThe degree of water oxidation may be determined based on the fact that potassium permanganate (KMnO4) consumes oxygen for the oxidation of organic substance.In acid media, reductor potassium permanganate is reduced.2KMnO4 + 3H2SO4 = 3H2O + 2MnSO4 + K2SO4 + 50When excessive potassium permanganate solution is added to the sampled water, the extra potassium permanganate which does not take part in the oxidation of organic substance is decomposed (reduced by a certain amount of oxalic acid C2H2O4).2KmnO4 + 5C2H2O4 + 3H2SO4 -- 8H2O + 1OCO2 + 2MnSO4 + K2SO42H2SO4 + K2MnO4 + 2H2C2O4 -- MnSO4 + 4CO2 + 4H2O + K2SO4Titrate the remaining oxalic acid with a certain amount of KMnO4 solution after reducing the excess KMnO4.The presence of oxides (iron sub-oxide, nitrous acid) increases the titration result of potassium permanganate.Permanganic acid (MnO4) monomolecule in the alkaline media reacts with hydroxy monomolecule, producing free hydroxy. The hydroxy is unstable and therefore it soon decomposes producing nascent oxygen. A strong oxidizer as it is, this nascent oxygen reacts with the organic matter in water completely oxidating it.KmnO4 + KOH = K2MnO4 + OH2OH → H2O + (O),i.e., 2KMnO4 + 2KOH + H2O → 2MnO4 + 4KOH + 3O4.5.2 Reagents0.01 N oxalic acid (C2H2O4.2H2O) solution. Dissolve 0.6302 mg oxalic acid in water, the total volume to be 1 litre.25 % sulfuric acid (H2SO4) solution.50% caustic soda (NaOH). 0.01 N potassium permanganate (KMnO4) solution.2KMnO4 + 3H2SO4 = 2MnSO4 + K2SO4 + 3H2O + 5OIn the acid solution, the bimolecular potassium permanganate produces a penta atom oxygen. Therefore, 0.01 N potassium permanganate solution will be:If 0.316 g potassium permanganate is dissolved in 1 litre distilled water, 1 ml 0.01 N solution can separate 0.08 mg of oxygen.4.5.3 Procedurea) In acid media. Pour 100 ml distilled water into a clean flask and add 5 ml 0.01 N potassium permanganate solution and 5 ml diluted sulfuric acid. Boil for 3–5 minutes to remove reductive substance sticking on the inner walls and wash the flask two to three times. Place in the flask 100 ml water sample by using a pipette, add 5 ml diluted sulfuric acid, and heat. When water begins to boil, add 10 ml 0.01 N potassium permanganate solution. Boiling should be for 10 minutes from the time it begins to boil. If, at the end of boiling, the liquid in the flask is reddish-pink, this means that enough of the potassium permanganate has been added for the oxidation of oxides contained in the water sample.If the solution is colorless or of a distinct brown, do not go further, and dilute the sampled water with distilled water two to three times or add more potassium permanganate solution.When its color is reddish-pink, add 10 ml 0.01 N oxalic acid solution into the flask. The color of the liquid in the flask disappears when shaken. When discoloration is completed, titrate excessive oxalic acid again with potassium permanganate solution and oxidize until the liquid is faint rosy-red when observed.2KMnO4+5(C2H2O4.2H2O)+2H2SO4 = K2SO4+2MnSO4+18H2O2+10CO2b) In alkaline media. Place a 100 ml water sample in a flask and heat until it boils. Add 0.5 ml caustic soda solution and 100 ml 0.01 N potassium permanganate solution. Boil for 10 minutes from the time it begins to boil. Cool the water to about 60 °C and add diluted sulfuric acid and 100 ml 0.01 N oxalic solution. When the liquid is completely discolored, titrate with the potassium permanganate solution until it becomes light pink.
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