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DISSOLVED OXYGEN
TITLE
To determine the amount of Dissolved Oxygen (DO) in water. DISSOLVED OXYGEN The dissolved oxygen (DO) is oxygen that is dissolved in water. The oxygen dissolves by diffusion from the surrounding air; aeration of water that has tumbled over falls and rapids; and as a waste product of photosynthesis. A simplified formula is given below: Photosynthesis (in the presence of light and chlorophyll): Carbon dioxide + Water --------------> Oxygen + Carbon-rich foods CO2 H2O O2 C6H12O6 Fish and aquatic animals cannot split oxygen from water (H2O) or other oxygencontaining compounds. Only green plants and some bacteria can do that through photosynthesis and similar processes. Virtually all the oxygen we breathe is manufactured by green plants. A total of three-fourths of the earths oxygen supply is produced by phytoplankton in the oceans. Fish, invertebrates, plants, and aerobic bacteria all require oxygen for respiration. Much of the dissolved oxygen in water comes from the atmosphere. After dissolving at the surface, oxygen is distributed by current and turbulence. Algae and rooted aquatic plants also deliver oxygen to water through photosynthesis. The main factor contributing to changes in dissolved oxygen levels is the build-up of organic wastes. Decay of organic wastes consumes oxygen and is often concentrated in summer, when aquatic animals require more oxygen to support higher metabolisms. Depletions in dissolved oxygen can cause major shifts in the kinds of aquatic organisms found in water bodies. Temperature, pressure, and salinity affect the dissolved oxygen capacity of water. The ratio of the dissolved oxygen content (ppm) to the potential capacity (ppm) gives the percent saturation, which is an indicator of water quality.

METHODS OF DETERMINATION OF DO IN WATER:

(1) (2) (3) (4) Winkler Method Azide modification of Winkler Method Rideal Stewart method DO-meters

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(1) Winkler Method Its principle is that oxygen oxidizes manganese (Mn+2) to higher oxidation state then this higher oxidation state manganese converts iodide ion (I-1) to iodine I2 and amount of free iodide librated is equivalent to DO Mn+2 + 2OH-1 Mn(OH)2 + 1/2O2 MnO2 + 2I-1 + 4H+1 Mn(OH)2 MnO2 + H2O Mn+2 + I2 + H2O

Then by titration with S2O3-2, thiosulphate ion (thiosulphate ion comes from sodium thiosulphate), iodine can be calculated. 2S2O3-1 + I2 S4O6-2 + 2I-1

If we use 0.025 N Na2S2O3 then 1ml of titrant = 1mg of DO (2) Azide modification of Winkler Method If nitrites NO2 will present in water, they will change the results because they convert iodide ions to iodine before performance of experiment. To remove NO2-1 sodium azides are added.
-1

PROCEDURE 1. 2. 3. 4. Take BOD bottle (300 ml volume) Fill the bottle with water sample. Add 1 ml MnSO4 solution to it and mix uniformly with the help of pipette. Add 1ml alkali azide iodide solution. On addition, if white ppts. are formed, then there is no DO in water. Formation of Reddish brown ppts. Indicates the presence of DO. If Reddish brown ppts are formed, stopper the bottle and shake it upside down for 20 times and allow the ppts. To settle down for about 2 inches. Add 1 ml Concentrated H2SO4 and again shake for about 8 times. Take 200 ml of this water sample in a titration flask and titrate it with 0.025 N Na2S2O3 till the appearance of light yellow color. Then add 1ml starch solution. The color of solution becomes blue on this addition. Again titrate it with 0.025N Na2S2O3 till the disappearance of blue color. Note the volume of titrant used. ml of titrant used = DO in mg/liter The above formula is applicable if we use 200ml of water sample solution and 0.025N Na2S2O3. General formula is given by

5. 6. 7. 8. 9. 10.

DO (mg/l)

mean vol of titrant used x N x 8000 F x vol of sample in ml

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Where,

vol of BOD bottle - vol of reagents used vol of BOD bottle

Dissolved Oxygen (DO) Observations And Calculations

Sample description Sample no. Mean Volume Dissolved Dissolved of titrant Oxygen oxxygen (Na2S2O3) (DO) (DO)
(ml) (mg/l) (mg/l)

sample volume
(ml)

1 2 3

Lab prepared Lab prepared Lab prepared

200 100 200 100

6.7 3.4 6.2 2.9

6.767 6.868 6.26 5.85

6.8 6.06

No Dissloved Oxygen

Questions
Q.1. What is importance of PALE YALLOW colour in titration for estimation of dissolved oxygen? The Starch-Iodine complex is not very much soluble in water, so the starch is added near the end point of an Iodine titration, when the iodine concentration is low. This eliminates error due the fact that some iodine remains absorbed on the complex and goes undetected. we add starch only near the end point when the color of the solution is pale yellow so that the starch should not complex and go lumpy. This also tells us whether the experiment is proceeding in the right direction. Like if starch is added before this pale yellow, resulting color would be black. And if it is added after that it would go colorless. Q.2. Give applications of dissolved oxygen in Civil Engineering. This test can help in making a decision that whether the water coming out from the treatment plant is good for drinking or the intend use or not. Which is itself is an engineering application of it. The water that is good for drinking is good for construction as well. Hence, Meanwhile clan water will help cement developing a good bond.

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what are various sources of oxygen by which it can dissolve in water and wastewater? Sources of oxygen are:

Atmosphere: A great part of oxygen that is present in water comes from Atmosphere. After dissolving at the surface, oxygen is distributed by current and turbulence. Algae and rooted plants: they also are a cause of DO mainly due to the photosynthesis. Aeration: Water falls and similar situations may provide a chance of aeration when contact area of water and air considerably increased and oxygen has more chances to dissolve itself in the water.

Q.4.

What will be DO of solution if 10mL of 0.2N sodium thiosulphate solution is used in titration? (F=0.99) Given Data: D.O = ? A = Volume of Titrant used = 10 ml Solution: N = 0.2 of Na2S2O3 Volume of Sample = 300 ml

= 53.87 mg/l
Q.5. What will be DO of solution if 6.3mL, 6.2mL and 6.3mL of 0.2N sodium thiosulphate solution is used in each of 100mL titration of solution ? (F=0.99) Given Data: D.O = ? N = 0.2 of Na2S2O3 A = Volume of Titrant used = (6.3+6.2+6.3) ml = 18.8 ml Volume of Sample = (100+100+100) ml = 300 ml Solution:

= 101.28 mg/l COMMENTS

DO of sample 1 is more than of sample 2 which makes it better for aquatic life and photosynthesis in green plants under water. Sample 3 contained no dissolved oxygen.

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BIOCHEMICAL OXYGEN DEMAND (BOD)

TITLE
To determine the amount of Biochemical Oxygen Demand (BOD) in domestic waste water. Biochemical Oxygen Demand (BOD) The amount of oxygen required by the bacteria while stabilizing decomposable organic matter under aerobic conditions. Decomposable means that organic matter can serve as food for the bacteria and energy is derived from its oxidation. Biochemical oxygen demand is a measure of the quantity of oxygen used by microorganisms (e.g., aerobic bacteria) in the oxidation of organic matter. Natural sources of organic matter include plant decay and leaf fall. However, plant growth and decay may be unnaturally accelerated when nutrients and sunlight are overly abundant due to human influence. Urban runoff carries pet wastes from streets and sidewalks; nutrients from lawn fertilizers; leaves, grass clippings, and paper from residential areas, which increase oxygen demand. Oxygen consumed in the decomposition process robs other aquatic organisms of the oxygen they need to live. Organisms that are more tolerant of lower dissolved oxygen levels may replace a diversity of more sensitive organisms.

BOD Level (in ppm) 1-2 3-5 6-9 10+

Water Quality Very Good-not much organic waste present Moderately clean Somewhat polluted Very polluted

Importance of BOD Test in Environmental Engineering The BOD test is used to determine the relative oxygen requirements of wastewaters, effluents, and polluted waters. The test measures the oxygen utilized during a specified incubation period for the biochemical degradation of organic material. It is also used to determine treatment plant efficiency.

Determination of BOD
Principle The method consists of filling with sample, to overflowing, an airtight bottle of the specified size and incubating it at the specified temperature for 5 days. Dissolved oxygen Environmental Engineering-II (Lab Manual) Page 5

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is measured initially and after incubation, and the BOD is computed from the difference between initial and final DO. Because the initial DO is determined shortly after the dilution is made, all oxygen uptake occurring after this measurement is included in the BOD measurement. Sampling and Storage Sample for BOD analysis may degrade significantly during storage between collection and analysis, resulting in low BOD values. Minimize reduction of BOD by analyzing sample promptly or by cooling it to near-freezing temperature during storage. However, even at low temperature, keep holding time to a minimum. Warm chilled samples to 20 3C before analysis. Apparatus Incubation bottles: Use glass bottles having 60 mL or greater capacity (300mL bottles having ground-glass stopper and a flared mouth are preferred). Air incubator or water bath, thermo-statistically controlled at 20 1C. Exclude all light to prevent possibility of photosynthetic production of DO. Reagents Prepare reagents in advance but discard if there is any sign of precipitation or biological growth in the stock bottles. a. Phosphate buffer solution: Dissolve 8.5 g KH2PO4, 21.75 g K2HPO4, 33.4 g Na2HPO4.7H2O, and 1.7 g NH4CI in about 500 mL distilled water and dilute to 1 Lit. The pH should be 7.2 without further adjustment. Alternatively, dissolve 42.5 g KH2PO4 or 54.3 g K2HPO4 in about 700 mL distilled water. Adjust pH to 7.2 with 30% NaOH and dilute to I Lit. Magnesium sulfate solution: Dissolve 22.5 g MgS04.7H20 in distilled water and dilute to 1 L. Calcium chloride solution: Dissolve 27.5 CaCl2 in distilled water and dilute to 1 L. Ferric Chloride solution: Dissolve 0.25 g FeCl3.6H2O in distilled water and dilute to 1 L. Acid and alkali solution, 1N, for neutralization of caustic or acidic waste samples. 1) Acid-Slowly and while stirring, add 28 mL cone. Sulfuric acid to distilled Water. Dilute to 1 L. 2) Alkali-Dissolve 40 g sodium hydroxide in distilled water. Dilute to 1 L. Sodium sulfate solution: Dissolve 1.575 g Na2SO3 in 1000 mL distilled water. This solution is not stable; prepare daily. Nitrification inhibitor: 2-chloro-6-(trichloromethyl) pyridine (if nitrification inhibition desired). Page 6

b. c. d. e.

f. g.

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i.

j.

Glucose-glutamic acid solution: Dry reagent-grade glucose and reagent-grade glutamic acid at 103C for 1 h. Add 150 mg glucose and 150 mg glutamic acid to distilled water and dilute to 1 L. Prepare fresh immediately before use. Ammonium chloride solution: Dissolve 1.15 g NH4CI in about 500 mL distilled water, adjust pH to 7.2 with NaOH solution and dilute to 1 L. Solution contains 0.3 mg N mL-1 Dilution water: Use demineralized, distilled, tap, or natural water for making sample dilutions.

Procedure: (with out seeding) 1) First of all it is important to know the amount of samples to be used for test. For this purpose the source of sample is to be recorded which will indicate the approximate value of BOD5 for the sample. (i) Domestic sewage BOD5 =100-500mg/L (ii) Effluent from treatment plant= 20-80mg/L (iii) River water = 2-4mg/L 2) Take 9 BOD bottles note their numbers and arrange them in 3 groups. 3) Fill each bottle half with dilution media ensuring that no air gets mixed with the media while fill in as in DO test. 4) Add 2ml sample in each of the three bottles marked as first group; 5 ml in each bottle of 2nd group and 10ml in each bottle of the 3rd group. 5) Fill the bottle completely with dilution media and place the stopper such that no air bubbles are trapped. 6) Now take one bottle from each set and estimate its DO. This will be DO initial or DO 0days. 7) For comparison prepare two more bottles with blank dilutions media (with out sewage sample) and find the DO from one bottle. 8) Place the rest of the six bottles with sewage samples and one bottle for blank in the incubator at 200C. 9) After 5 days find out DO in all bottles. 10) That value of oxygen depletion should be considered correct which gives an oxygen depletion of at least 2 mg/L. and which have at least 0.5 mg/L DO after 5 days of incubation. 11) Calculate BOD5 at 200C. for the sample using following relationship . BOD(mg/L) = DO depletion (mg/L) *300 Volume of sample in bottle (ml)

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BOD5 Observations And Calculations

AT ZERO DAYS

sample added

volume of sample

bottle no.

Volume of Na2S2O3
(ml) 9.2 10.7 10.7

Mean Dissolved Dissolved oxygen oxygen

(mg/l) 6.195 7.205 6.87 7.205 (mg/l)

(ml) 315 135 418 2 5 10 BLANK

(ml) 300 300 300

AT FIVE DAYS

volume of sample

bottle no.

Volume of Na2S2O3
(ml) 8.3 8.6 7.1 9.3 8 6.8 BLANK

Mean Dissolved Dissolved oxygen oxygen

(mg/l) 5.59 5.695 5.8 4.78 5.52 6.26 5.38 4.98 4.58 (mg/l)

sample added
(ml) 2 2 5 5 10 10

(ml) 300 300 300 300 300 300

12 10 92 25 126 70

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DO DEPLETION Bottle no. sample added (ml) 2 5 10 DO at zero days (mg/l) 6.195 7.205 7.205 BLANK DO at 5 days (mg/l) 5.695 5.52 4.98 DO Depleted (mg/l) 0.5 1.685 2.225 BOD5 (mg/l) 75 101.1 66.75

315, 12, 10 135, 92, 25 418,126,70

MEAN BOD5 = 80.95 mg/l

Questions
Q.1. What is the role of chemicals added in dilution media?

Bacteria derive energy for growth and other metabolites utilizing variety of carbon and nitrogenous sources through oxidation and fermentation. Studies of such activities are possible with bio-chemical media only carbon and nitrogen as supplemented as exclusive nutrient sources to basal medium (like peptane) e.g. sugar at 0.5-1% leve;s are added to peptone water along with an indicator which imparts different color to a medium at acidic and alkaline pH. Q.2. Why aeration is important for dilution media?

Bacteria produce large quantities of acetic acid if the growth medium contains little or no oxygen causing the growth medium to reach pH 4 and lower. At this pH, bacteria growth slows down or even stopps. Thats why aeration is important for dilution media. Q.3. Give any FOUR differences between COD and BOD.

COD is the total measurement of all chemicals in the water that can be oxidized while BOD is supported to measure the amount of food or organic carbons that bacteria can oxidized. Permissible limit of COD is 250-500 ppm but for BOD is 30 mg/l. COD is always greater than BOD. COD is not not different b/w bi-logically available and inert organic matter and it measure total quantity of oxygen required to oxidize all organic matter into CO2 and H2O.

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Q.4.

What will be DO depletion after five days, if 12.1mL and 6.3mL of sodium thiosulphate (0.025N) were used at zero day and at five day, respectively? Volume of sample is 3mL.F= 0.99
Volume of sample 300 300 Volume of Na2S2O3 12.1 At zero days 6.3 At five days Dissolved oxygen 8.148 4.242 DO Depletion

Sample Added 3 3

3.90

Q.5.

What will be BOD after five days, if 12.1mL and 6.3mL of sodium thiosulphate (0.025N) were used at zero day and at five day, respectively? (Volume of sample is 3mL &F= 0.99)
Volume of sample 300 300 Volume of Na2S2O3 12.1 At zero days 6.3 At five days Dissolved oxygen 8.148 4.242 DO Depletion BOD (mg/l) 390

Sample Added 3 3

3.90

COMMENTS
Value of DO after 5 days decreases because some oxygen is used by organic matter and micro organisms. BOD5 is greater than 10 ppm so sample is highly polluted. BOD5 for effluent of treatment plant must be less than 80, so if the sample is a effluent of treatment plant, results are OK.

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CHEMICAL OXYGEN DEMAND (COD)

TITLE
Determination of amount of Chemical Oxygen Demand (COD) in water. Chemical Oxygen Demand (COD) The Chemical Oxygen Demand, or COD, is a measurement of the amount of material that can be oxidized (combined with oxygen) in the presence of a strong chemical oxidizing agent. Since the COD test can be performed rapidly, it is often used as a rough approximation of the water's BOD, even though the COD test measures some additional organic matter (such as cellulose) which is not normally oxidized by biological action. As with the BOD test, the COD test is reported as mg/Lit of oxygen used. There is a specific normal range of COD found in various kinds of domestic wastewater. Keep in mind that the addition of industrial waste can cause these values to vary widely. Biochemical oxygen demand is a measure of the quantity of oxygen used by microorganisms (e.g. aerobic bacteria) in the oxidation of organic matter.

METHODS OF DETERMINATION OF COD

1. Open Reflux Titrimetric Method Principle In this method known amount of strong oxidizing agent is being added. Then reaction takes place to form CO2 and H2O. Then remaining amount of oxidizing agent is being determined by titration. The amount of oxidizing agent to be added depends upon the COD of sample which can roughly be known by knowing the source of sample. Equipment: Caution: The presence of minute traces of organic matter on the equipment will cause large errors in the test results. So clean all equipment thoroughly before using. Erlenmeyer flask Small beaker Titration apparatus: 25 or 50 mL burette, graduated in 0.1 mL burette support 100 mL graduated cylinder rubber-tipped stirring rod, or magnetic stirrer and stir bar white porcelain evaporating dish, 4.5 inches in diameter Reflux apparatus:

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500 or 250 mL Erlenmeyer flasks with ground glass 24/40 neck 300 mm jacket Liebig, West, or equivalent condenser with 24/40 ground-glass joint hot plate with sufficient power to produce at least 1.4 W /cm2 of heating surface Blender Pipets Glass beads Fume hood

Reagents Standard potassium dichromate solution, 0.25N or O.025N Sulfuric acid reagent containing silver sulfate catalyst Standard ferrous ammonium sulfate titrant Ferroin indicator solution Mercuric sulfate crystals Sulfamic acid Concentrated sulfuric acid Distilled water

Theory of Titration The COD analysis, by the dichromate method, is more commonly used to control and continuously monitor wastewater treatment systems, The COD of an effluent is usually higher than the BOD5 since the number of compounds that can be chemically oxidized is greater than those that can be degraded biologically, It is also common to make a correlation of BOD5 versus COD and then use the analysis of COD as a rapid means of estimating the BOD5 of a wastewater. This may be convenient since only about three hours are needed for a COD determination while a BOD5 takes at least 5 days. However, this procedure can be used only for specific situations where there is low variability in the composition of a wastewater, and the results of a system cannot be used reliably in other cases. The method of COD which uses dichromate as oxidant is carried out by heating under total reflux a wastewater sample of known volume in an excess of potassium dichromate Environmental Engineering-II (Lab Manual) Page 12

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(K2Cr2O7) in presence of sulphuric Acid (H2SO4) for a fixed period (usually two hours) in presence of silver sulphate (Ag2SO4) as catalyst. The organic matter present is oxidized and, as a result, the dichromate ion (orange colour) is consumed and replaced by the chromic ion (green colour):
Cr2O7-2 + 14H+ + 6e2Cr3+ + 7H2O

The COD is calculated by titrating the excess of dichromate or by spectrophotometrically measuring the Cr+3 ions at 606 nm. Another possibility is to measure the excess dichromate spectrophotometrically at 440 nm. Titration requires more work but is considered more precise. The presence of silver sulphate as catalyst is needed for complete oxidation of aliphatic carbon compounds. The standard method implies cooling of the sample after the two hour digestion period, adding a few drops of indicator (ferroin) solution and titrating the excess dichromate with a solution of ferrous ammonium sulphate of known concentration, until the colour changes from brilliant green to reddish brown. The titration reaction corresponds to the oxidation of the ferrous ammonium sulphate by the dichromate:
Cr2O7-2 + 14H+ + 6Fe+2 2Cr3+ + 6Fe+3 + 7H2O

The change in colour corresponds to the formation of the complex ferrous ion phenanthroline which occurs when all the dichromate ion has been reduced to Cr3+.
(Fe(C12H8N2)3)3+ + e (Fe(C12H8N2)3)2+

Ferric Phenanthroline (Green Blue)

Ferrous Phenanthroline (Reddish Brown)

Interferences A common interference factor in the COD test is the presence of chlorides. If seawater is used at some point in the processing or salt brines are used for some "curing" operations, chlorides will most probably appear in the wastewater causing interference while they are oxidized by the dichromate:
Cl- + Cr2O72- + 14H+ 3Cl2 + 2Cr3+ + 7H2O

This interference causes erroneously high values of COD which can be prevented by the addition of mercuric sulphate (HgSO4) which reacts to form mercuric chloride and precipitates:
Hg2+ + 2ClHgCl2

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Procedure: 1) Place 50ml sample in 500ml refluxing flask (for samples with COD>900mg/L use a smaller sample diluted to 50ml). 2) Add 1g HgSO4 and several glass beeds. 3) Add slowly 5ml H2SO4 reagent while mixing to dissolve HgSO4 4) Cool while mixing to avoid the loss of volatile materials. 5) Add 25 ml 0.25N K2 Cr2O7 solution and mix. 6) Attach the flask to the condenser and turn on cooling water. 7) Add remaing H2SO4 (70ml) through open end of the condenser continue mixing while adding H2SO4. 8) Reflux the mixture for 2 hrs and cool to room temperature, after diluting the mixture to about twice its volume with distilled water. 9) Titrate excess of K2 Cr2O7 with Ferrous ammonium sulfate using 2,3 drops of ferrion indicator. The end point will be from blue green to reddish brown. 10) Reflux and titrate in the same manner a blank containing the reagents and the voume of the distilled water will be equal to that of sample.

COD Observations And Calculations

COD (mg/l) = (A-B)xNx8000/(Vol. of sample, ml) N=0.25 Volume of sample = 50 ml volume of titrant used for sample Description of Sample

Serial no.

Volume of Titrant used for Blank

A 16.1

Chemical Oxygen Demand COD

(mg/l) 304

B 1 Sample-1 8.5

Sample-2

12.5

18

220

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Questions
1. Calculate COD of an industrial solution if 5mL sample is used against FAS. The volume of FAS (0.25N) used against sample is 12.34mL while for blank it is 23.1mL. A = 23.10 ml B = 12.34 ml N = 0.25 N

= 4304 mg/l
2. What will be the volume of FAS for sample if COD of sample is 424.5mg/L if FAS volume for blank is 30.1mL? Use standard procedure for calculations. (N=0.25) COD = 424.5 mg/l A = 30.1 ml B=? Vol. of sample = 50 ml N = 0.25 N

B = 19.487 ml 3. Chloride ions produce interference in COD measurements. It can be removed either by silver or mercury salts. Why only these two salts are used? Can we use any other salt? The most common interference is the chloride ions. Chlorides react with silver ions to make ppt. silver chloride and thus inhibit the catalytic activity of silver. Bromides, iodides and any other reagents that inactivates the silver ions can infer similarly. The interfernces are negative in that they tend to restrict the oxidizing action of dichromate ions itself. However, under the rigorous digestion procedures for analysis, Cl-,Br-,I- can react with dichromate to produce different chemical forms of halogens and the chromic ion too. Results then are on higher side.

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4. Write any FOUR applications of COD. COD is used to measure: The Chemical Oxygen Demand, or COD, is a measurement of the amount of material that can be oxidized (combined with oxygen) in the presence of a strong chemical oxidizing agent. Indirectly measures the amount of organic compounds present in water. Determines the total amount of organic pollutants and oxygen consumption is any water body like lakes or river and in the waste water samples (Before and After treatments) Indirect Idea of BOD. Since the COD test can be performed rapidly, it is often used as a rough approximation of the water's BOD 5. Why COD values are always higher than BOD values? BOD contains only biodegradable while The COD test measures some additional organic matter (such as cellulose) which is not normally oxidized by biological action. Thats why COD values are higher than BOD. As with the BOD test, the COD test is reported as mg/Lit of oxygen used.

COMMENTS
COD value for Sample 1 is greater than for Sample 2 which shows that Sample 1 contains more concentration of oxidizable matter i.e. organic matter in it. COD values suggest that BOD values will also be quite high even though always lesser than COD value.

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Kjeldhal Nitrogen
Title
To determine the amount of nitrogen in given water sample.

General
All nitrogen present in the organic compounds may be considered as organic nitrogen. This includes amino acids, amines, amides, nitroderivatives and no of other organic compounds. In waters and waste water the form of nitrogen of greatest intrest are organic N and ammonia-N, nitrates and nitrites. Organic nitrogen is defined functionally as organically bound nitrogen in tri negative state. In wastewaters organic-N include such natural materials like proteins, peptides , nucleic acids, urea and numerous synthetic organic materials. Organic nitrogen and ammonia can be determined together and have been refered as kjeldhal nitrogen.

Principle:
In the presence of H2SO4 , K2 S04 and CuSO4. Ammonia nitrogen of many organic materials is converted to ammonium sulfate. Free ammonia and ammonia nitrogen also are converted to ammonium sulfate. During sample digestion a cuppric ammonia complex is formed. After this mercury ammonia complex in the digestion has been decomposed by sodium thiosulfate, the ammonia is distilled from an alkaline layer and absorbed in boric acid.

Basic Steps involved:

1) Digestion 2) Distillation 3) Titration.

Titration theory:
The organic nitrogen is converted to ammonia nitrogen during the digestion. Boric acid is an excellent buffer. It combines with ammonia in the distillate to form ammonia and borate ions. NH3 + H3 BO3-- NH4++ H2BO3The ammonia then is measured by back titration with strong acid such as sulfuric acid. Actually the acid measures the amount of boric ion present in the solution as follows. H2BO3- +H+- H3BO3

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Reagents:
1) Digestion reagent ( dissolve 134g K2SO4 and 7.3g CuSO4 in about 800ml water carefully add 134ml coc H2SO4. Cool to room temperature, dilute to 1 lit with water . mix well keep at temp 200C to prevent vaporization). 2) Phenolphthalein indicator 3) Sodium hydroxide 4) Mixed indicator solution 5) Indicating boric acid solution 6) Standard sulfuric acid titrant. 7) Hydroxide thiosulfate reagent.

Procedure:
Digestion 1. Take 280ml of sample in a kjeldhal flask. 2. Add few glass beads to it then add 50ml digestion reagent 3. Mix, heat and continue boiling until solution remains 25-50ml. 4. Cool it and add distilled water to it to make the volume 300ml. 5. Add 0.5 ml phenolphthalein indicator. 6. Add 50 ml thiosulfate hydroxide reagent solution. If pink color does not appear then add more 50ml thiosulfate hydroxide reagent solution. Distillation 1. In collect the distillate in a flask containing boric acid solution. 2. Collect 200ml distillate into 50ml boric acid solution. Titration 1. Titrate it against 0.02N H2SO4 solution until color changes from purple to green. 2. Carry the blank titration, following all steps of procedure.

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Kjeldhal Nitrogen Observations And Calculations

Total Nitrogen (mg/L) =

(A-B)* 280 ml of sample

Volume of Sample = 140 ml A= volume of H2SO4 used for sample = 55 ml B= Volume of H2SO4 used for blank = 0.5 ml Total nitrogen (mg/L)= 109 mg/l

Questions
1) What is Kjeldhal nitrogen? The total Kjeldhal nitrogen assay is an analytical chemistry method for the quantitative determination of nitrogen in chemical substances, developed by John Kjeldhal. Organic nitrogen and ammonia determined together are referred as Kjeldhal nitrogen. 2) What is blue baby disease? Nitrates also react directly with hemoglobin in human blood and other warm blooded animals to produce methemoglobin. Methemoglobin destroys the ability of red blood cells to transport oxygen. This condition is much severe in babies of age 3 months. This is known as methemoglobinemia or blue baby syndrome. 3) How ammonia nitrogen can be determined? Ammonia nitrogen can be determined by several different methods. Selection of specific method must be based upon concentration level and amount and type of interferences present. In drinking water and some highly purified waste water effluent, it may be possible to determine ammonia concentration directly by colorimetric methods. However, the approved method for waste water is preliminary distillation of the

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ammonia into an acid adsorbing solution for colorimetric, titrimetric or specific ion electrode determination. 4) Why hydroxide thiosulfate reagent is added in above experiment? Na2S2O3 is added to neutralize the residual chlorine in the sample. 5) Write the significance of nitrogen test in Environmental Engineering. Nitrogen is no doubt an essential component of all the living things. Excessive concentrations of certain nitrogen substances in some compartments of the environment can lead to significant hazards and problems. So in order to deal with these issues, first of all determination of concentration is vital.

COMMENTS
Value of total nitrogen is 109 mg/l. Organic nitrogen and ammonia combine together and give Kjeldhal nitrogen. More Kjeldhal nitrogen means more nitrogenous compounds are present in the sample.

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CHLORIDES
TITLE
Determination of chloride concentration in different water samples. Chlorides Chloride is a salt compound resulting from the combination of the gas chlorine and a metal. Some common chlorides include sodium chloride (NaCl) and magnesium chloride (MgCl2) and calcium chloride (CaCl2). Chlorine alone as Cl2 is highly toxic, and it is often used as a disinfectant. In combination with a metal such as sodium it becomes essential for life. Small amounts of chlorides are required for normal cell functions in plant and animal life. Chlorides in Water Almost all natural waters contain chloride and sulfate ions. Their concentrations vary considerably according to the mineral content of the earth in any given area. In small amounts they are not significant. In large concentrations they present problems. Usually chloride concentrations are low. Sulfates can be more troublesome because they generally occur in greater concentrations. Low to moderate concentrations of both chloride and sulfate ions add palatability to water. In fact, they are desirable for this reason. Excessive concentrations of either, of course, can make water unpleasant to drink. The EPA Secondary Drinking Water Regulations recommend a maximum concentration of 250 mg/lit for chloride ions and 250 mg/lit for sulfate ions (expressed as Cl- and S04-2, not as CaC03). Chlorides give water a salty taste. At what concentrations this becomes noticeable again depends upon the individual. In large concentrations chlorides cause a brackish, briny taste that definitely is undesirable. Although chlorides are extremely soluble, they possess marked stability. This enables them to resist change and to remain fairly constant in any given water unless the supply is altered by dilution or by industrial or human wastes. Both chlorides and sulfates contribute to the total mineral content of water. As indicated above, the total concentration of minerals may have a variety of effects in the home. High concentrations of either sulfate or chloride ions add to the electrical conductivity of water. Chlorides and sulfates can be substantially removed from water by reverse osmosis. Deionization (demineralization) or distillation will also remove chlorides and sulfates from water, but these methods are less suitable for household use than reverse osmosis.

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Methods of determination of Chlorides 1. Mohrs method or Argentometric method 2. Mercuric Nitrate method 3. Potentiometeric method MERCURIC NITRATE METHOD General Discussion a. Principle: Chloride can be titrated with mercuric nitrate, Hg(N03)2 because of the formation of soluble, slightly dissociated mercuric chloride. In the pH range 2.3 to 2.8, diphenyl carbazone indicates the titration end point by formation of a purple complex with the excess mercuric ions. Xylene cyanol FF serves as a pH indicator and end-point enhancer. Increasing the strength of the titrant and modifying the indicator mixtures extend the range of measurable chloride concentrations. b. Interference: Bromide and iodide are titrated with Hg(N03)2 in the same manner as chloride. Chromate, ferric, and sulfite ions interfere when present in excess of 10 mg/lit. Procedure

A. for Titration of chloride concentrations less than 100 mg/lit:

i. Take a 100-ml of chloride containing solution in titration flask (100ml chloride containing sample is taken because of this sample contains less amount of chlorides) Add 1.0 ml indicator-acidifier reagent. It is a mixture of diphenyl carbazone and Xylene cyanol. If pH<2.30 pH=2.30 to 3.80 pH>3.80 iii. iv. then the color of the solution will be green then the color of the solution will be bluish green then the color of the solution will be blue

ii.

v. vi. vii. viii. ix.

Titrate this sample with 0.0141N Hg(N03)2 titrant till a definite purple end point color achieved. We can use high strength 0.141N Hg(N03)2 instead of 0.0141N Hg(N03)2 as a titrant but after few drops the definite purple end point color will be achieved. So it requires very care. Take three readings and determine mean volume. Take 100-ml distilled water in titration flask. Add indicator (diphenyl carbazone + Xylene cyanol) + 10mg Na2C03. Titrate this sample with 0.0141N Hg(N03)2 titrant till a definite purple end point color achieved. Take only reading and determine volume of the titrant Hg(N03)2 used Page 22

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Chloride ions concentration can be determined from following formula

(A B) x N x EqW of Cl - x 10000 vol of sample in ml (A B) x N x 35.4 x 10000 Cl - in mg/l 100 Cl - in mg/l

where: A = mean volume of Hg(N03)2 in ml used to titrate the sample B = mean volume of Hg(N03)2 in ml used to titrate the distilled water N = normality of Hg(N03)2 i.e 0.0141N Hg(N03)2

B. for Titration of chloride concentrations greater than 100 mg/lit:

i. ii. iii. iv. v. vi. vii. viii. ix. x. Take a 50-ml of chloride containing solution in titration flask Add 0.5 ml mixed indicator. It is a mixture of diphenylcarbazone and bromphenol. If Add few drops of 0.1N HN03 till color become yellow Titrate this sample with high strength 0.141N Hg(N03)2 titrant till a definite purple end point color achieved Take three readings and determine mean volume. Take 50-ml distilled water in titration flask. Add indicator Titrate this sample with 0.0141N Hg(N03)2 titrant till a definite purple end point color achieved. Take only reading and determine volume of the titrant Hg(N03)2 used Chloride ions concentration can be determined from following formula (A B) x N x MW of Cl - x 10000 Cl - in mg/l vol of sample in ml

Cl - in mg/l
where:

(A B) x N x 35.4 x 10000 50

A = mean volume of Hg(N03)2 in ml used to titrate the sample B = mean volume of Hg(N03)2 in ml used to titrate the distilled water N = normality of Hg(N03)2 i.e 0.10N Hg(N03)2

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CHLORIDES Observations And Calculations

Sample no.

final volume

Initial Volume

Difference
(ml) 4.3 5.5 1.7

chloride concentration
(mg/l) 429.26 549.05 169.7

(ml) 1 2 2 6 1 10.5

(ml) 10.3 6.5 12.2

Questions
1) What is the WHO guideline value for chlorides? Health based guideline for chlorides in drinking water were proposed in 1993. The EPA Secondary Drinking Water Regulations recommend a maximum concentration of 250 mg/lit for chloride ions and 250 mg/lit for sulfate ions (expressed as Cl- and S04-2, not as CaC03). 2) What is the significance of chlorides test for construction purposes? Water soluble chlorides, in combination with oxygen and moisture can cause corrosion of embedded metal in concrete. Unfortunately, chlorides are among the most abundant materials on the earth. Therefore, it is not practically possible to have no chlorides present in the water of concrete mix. Due to the fact, ACI has established some practical limits regarding this. Usually upto 500 mg/lit concentration is acceptable. 3) How chlorides gain access to natural waters? Chlorides gain access to natural waters in many ways. Water has the ability to dissolve chlorides from top soils and deep formations. Plus occurrence of chlorides can be natural as well as anthropogenic. Use of inorganic fertilizers is also a source of entering chlorides in water. Landfill leaches, septic tank effluents, animal feeds, industrial effluent, irrigation drainage and sea water intrusions are coastal reasons.

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4) What would be the role of mixed indicator in this titration? Chloride can be titrated with mercuric nitrate, Hg(N03)2 because of the formation of soluble, slightly dissociated mercuric chloride. In the pH range 2.3 to 2.8, diphenyl carbazone indicates the titration end point by formation of a purple complex with the excess mercuric ions. Xylene cyanol FF serves as a pH indicator and end-point enhancer. Increasing the strength of the titrant and modifying the indicator mixtures extend the range of measurable chloride concentrations. 5) Why different procedures are used depending upon chlorides concentration? The chloride content of natural surface waters will depend upon geology of the area. In a limestone area like Richmand, natural surface waters will have very little chlorides in it. (10-50) mg/l . Appreciable higher chloride concentrations would suggest contaminations. Concentration of chlorides can be damaging to metal pipes as well as agricultural crops. Different procedures are used depending upon concentration is due to the fact that chloride ions with Hg+2 to form HgCl2 (in concentrations greater than 100 mg/l) which white ppts are insoluble and will faint the color complex and end point can not be indicated properly.

COMMENTS
The chloride ion concentration for sample 1 and sample 2 is 429.26 mg/l and 549.05 mg/l respectively. Which is greater than 250 mg/l. since 250 mg/l is a threashold value given by WHO guidelines so both sample 1 and 2 are rejected. Sample 3 is suitable because Cl- concentration is less than 250 mg/l. Sample 2 and sample 3 may be used for concrete mix because their concentration is less than 500 mg/l.

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