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UNIVERSITY INSTITUTE OF TECHNOLOGY, RAJIV GANDHI PROUDYOGIKI VISHWAVIDHYALAYA, BHOPAL LABORATORY MANUAL

ENVIRONMENTAL ENGINEERING
(DEPARTMENT OF CIVIL ENGINEERING)

SAMPLING PROCEDURES FOR WATER & WASTE WATER ANALYSIS

1. Sampling A sample has to representative and valid both in time and space. The parameters in the sample at the time of analysis should have the same value and those at time and place of sampling. A sample will be representative depending upon the sampling techniques and preservations. A sample is valid if represents the true picture of water quality at the sampling point. Quality of water depends on place, time and its estimation depends on frequency of sampling. Conditions at each sample source vary widely and sampling programmed needs to be worked on the merits of the source. 2. Frequency of Sampling Quality of water, flowing or stagnant, seldom remains the same in time. The larger the number of samples from which the mean is derived the narrower will be limits of the probable difference between the observed and true value of the mean. In order to double the reliability of a mean value, the number of samples must be increased four-fold, because confidence limits are proportional to the square of the number of samples, hence a confidence between the increase reliability of data measured by confidence limits and the cost of its collection has to be reached. Effluent or water quality changes depending on the mass inputs and changes in the rate of

Population served
Upto20000 20000-500000 50000-100000 More than 100000

Maximum interval Minimum no. of sampling to the taken between successive from entire distribution system sampling
one month two week four days one day One sample per 5000 of population per month --- do------ do---One sample per 10000 of population per month

water flow or on volume. Characteristics of water quality vary (a)Randomly e.g. during from, spillages in factory and process, on of samples to be collected from a distribution systems should be as under: (b)

Cylindrically due to rainfall pattern. Also they vary with the production pattern in manufacture

3. Number of samples

Frequency of sampling can be worked out as under: Confidence level of an arithmetic mean of normally distributed values is the percentage of occasions (p %) on which true mean may be expected to lie with in a given range of values. The range in the confidence interval which is bounded by the confidence limits. Presume 95% confidence limits at 10, and then the probability is that on 95% occasion out of 100, the observed mean will not differ from the true mean by more than 10.Normally: P % = x E : L = KS / N Where S = Std. Deviation, K = Factor depending on p. Confidence 99 level% K 2.58 98 2.38 95 2.96 Table 1 90 1.64 80 1.2 68 1.0 50 6.67

If N 30, put students t in place of K. 4. Sampling Procedure: The determinants fall into three groups: (a) (b) (c) (d) Conservative, not changing with time. Non-conservative, change with time out can be. Stabilized for 24 hours by proper treatment Non-conservative, change rapidly with time and cannot be preserved e.g. temperature , pH, D.O. Table 2 gives the preservation required for some commonly required parameters.

Table No.2

Parameter 1 Acidity/Alkalinity BOD Calcium COD Colour Cyanide Do Metales,total Dissolved metals Amm. Nitrogen Kjeldahal Nitrogen Nitrate-Nitrite Oil& Grease Organic Carbon Phenolics Phosphorus Sulphates Sulphide Silica

Container 2 Glass ---do--Plastic Glass ------------------Glass Plastic/Glass --do ---do --do Glass/Plastic ----------Glass ---------Glass Plastic/Glass ---------Plastic

Preservative 3 Refrigeration ---do--Not required 2ml H2SO4/ 1 Ph-2 Refrigeration PH 10 by NaOH On site 5ml HNO3/1 40 fileration:3ml 1:1 HNO3/ l 40 mgHgCl2 / liter 40oC ---do--40 mgHgCl2/ liter 40oC 2ml/liter H2SO4 40oC 2ml H2SO4 /l- (pH-2) 1 g CuSO4 + H3Po4: 4.04oC 40mg MgCL2 /1-4oC 4oC 2mlZn Acetate/ 1 Filter on site then 4oC

Max.holdingperiod 4 24 hours 6 hours -----7 days 24 hours 24 hours None 6 months 6 months 7 days Unstable 7 days 24 days 7 days 24 hours 7 days 7 days 7 days --do--

5. COMPOSITE SAMPLES

It is a general practice to mix discrete samples lo form a composite sample.Time based composite or weighted composite sample is one, when individual samples are mixed in equal portions, or in portions according the flow at the time of sampling. Analysis of a composite sample wills he the average over the time of sampling. This will not give any indication of maximum or minimum values over the sampling period. Manual sampling is economically reliable. Composite samples are not possible for DO, pH, temperature, CN, metals and bacteria. These changes with time or due to chemical interactions. Each sample should carry a tag or label as under: (a)Source (b)Date (c)Time (d)Preservation added (e)Collectors identity Polluted Liquid Sampling When the liquid to be sampled contains oily or tarry matter or solids like those in sewage, it is difficult to collect representative samples. At sewerage works, sampling should not be done before screening. It should be done at a point in sewer where considerable turbulence is present. Oily substances form a film over the liquid and special procedure showed under these circumstances. Sample for Physical and Chemical Analysis: Samples should he collected in containers of Pyrex glass or other inert material like polythene. Sample bottles must be carefully cleaned before use. Glass bottles may be rinsed with a chromic acid cleaning mixture, made by adding one liter of concentrated sulphuric acid slowly with string to 35 ml saturated sodium dichromate solution, or with an alkaline permanganate solution followed by an oxalic acid solution. After having been cleaned, bottles must be rinsed thoroughly with tap water and then with distilled water. About 2.5 liters of the sample is required for analysis prior to filling, the sampling bottle should be rinsed out two or three times with water to be collected. Care should be taken to obtain a sample that is truly representative of existing conditions and to handle it in such a way that it does not deteriorate or become contaminated before it reaches the laboratory. The sample should reach the place of analysis within 72 hours of collection. The time elapsed between collection and analysis should be recorded on the laboratory report. Some determinations are likely to be affected by storage of samples. Walls of glass containers are likely to absorb cations like aluminum, cadmium, chromium, Copper, Iron, Lead, Manganese, Silver or Zinc which are best collected in a separate bottle and acidified by concentrated hydrochloric or nitric acid to a pH approximately 3.5 to minimize precipitation and absorption on the walls of the container. Certain parameters like to temperature, pH, dissolved gases like carbon di-oxide, hydrogen sulphite, chlorine and oxygen may change significantly during transportation. For this reason, determination of pH carbon di-oxide, dissolved oxygen and chlorine

should be carried out on the spot. Hydrogen sulphide can be preserved by fixing it with zinc acetate until the sample is ready for analysis. Hot samples collected under pressure should be cooled while under pressure, Samples from wells should be collected only after the well has been pumped for a sufficient time to ensure that the sample will be representative of the ground water. For collection of sample at different depths. Specific equipment should he used. SAMPLING FROM A WATER WORKS SVSTME & DISTRIBUTION SYSTEM In order to find out whether the processes of treatment are satisfactory, a number of sampling points at different locations of water works system arc selected. The samples from distribution system should be drawn from different mains and periphery of the distributory system. For taking sample sterilized stand pipe must be used. Before taking sample the pipe line should be hushed for a sufficient period 10 get a representative sample. SAMPLEING FOR BACTERIOLOGICAL ANALYSIS Sterilized glass bottles provided with ground glass stopper having an overlapping rim should be used. The stopper and the neck of (he bottle should be protected by brown paper. The sterilization is carried out in an autoclave at 1 kg/cm 2 Pressure for 15 minutes or two hours under steam and some space should be left in the bottle after sample is collected, Dechlorination is necessary for chlorinated water samples. For this, sodium thiosulpate should be added to the clean, dry sampling bottle before sterilization in an amount to provide an approximate concentration of 100 mg/l in the sample. This can be done by adding 0.2 ml of 10% thiosulphate solution to a 250 ml bottle. The bottle is than sterilized by either dry or moist heal. A mini volume of 250 ml should be taken for bacteriological exam. PRESERVATION AND STORAGE Water sample should be examined immediately after collection forever, this is seldom practical and hence it is recommended that the samples should be preferable analyzed within one hour after collection and in no case this time should exceed 24 hours. During transit, the temperature of the sample should be maintained as close as possible to that of the source of the sample, at the time of sampling. The time and temperature of storage of all samples should be recorded since they will be considered in the interpretation of the laboratory results. If they can not be analyzed within 24 hours the samples must be preserved in ice; until analysis No sample is 111 for bacteriological analysis after 72 hours. SAMPLING FOR BIOLOGICAL ANALYSIS For this purpose, two samples should be collected in clean two liter wide mouthed bottles with a glass stopper or a bakelite screw cap. In making the collection the bottle. Alter I he stopper is removed, is thrust as far as possible, mouth downward into dir water. It is then inverted and allowed to fill. To another bottle add 5 ml of commercial formalic

to every 100 ml of water sample immediately after collection Both the bottles should be dispatched with the label on the sample stating the one with formalin
7.4 Preservation and storage Water sample should be examined immediately after collection. However, this is seldom practical and hence it is recommended that the sample should be preferably analyzed within one hour after collection and in no cases this time should extended 24 hour .During transits, the temperature of the sample should be maintained as close as possible be that source of the sample ,at the time of sampling .The time and temperature of storage of al the sample should be recorded since they will be considered in the interruption of the laboratory results. If they can not analyzed within 24 hour ,the samples be preserved in ice until analysis. No sample is fit for bacteriological analysis after 72 hours. 8. Sampling for Biological Analysis For this purpose , two sample, should be collected in clean two liter wide mouthed bottle with glass stopper or bakelite screw cap. In making the collection, the bottle, after the stopper is removed, is thrust as far as possible mouth downward into the water. It is than inverted and allowed to fill. one bottle is stopped such .To another bottle ad 5 ml commercial formalin to every 100 ml of water sample immediately after collection . both the bottle should dispatched with the label on the sample stating the one with in formation. It two liter of sample could not be collected even 200 ml of the sample may be collected as above the formation added to one sample (0 ml of formation added to 200 ml of water) STANDER TESTS The standard test that are employed in the analysis of water are as follows : 1. Physical Examination: The parameter tested are temperature, turbidity, colour, and odour. 2. Chemical Examination: a) this include test for chemicals that affects the health of the consumers and the portability of the water viz. pH ,acidity, manganese, copper, Zink, aluminium, sulphates ,fluoride ,colloids, total dissolved and suspended solids. b) Test for efficiency of treatment viz chloride free and combined residual chlorine ,coagulants dosages. c) Test for chemical which are indicators of pollution such as total nitrogen and nitrogen in various forms like ammonia, nitrite, phosphate, dissolved oxygen and BOD. d) Test for TOXIS chemical substance lead, arsenic, mercury, selenium, chromium, cyanide, pesticides and hydrocarbons and e) Test of radio activity 3. Bacteriological Examination: This comprise of plate count, coli form count tests for fecal streptococci clostridium and salmonella. 4. Biological Examination: Microscopic tests for identification and enumeration of micro organism other then bacteria are included in this category.

5. Schedule of tests: The schedule of laboratory test followed by a particular undertaking will very with the size of plant and character of water treated, tough the ordinary plant the minimum schedule should include turbidity, color, alkalinity, pH, hardness, residual chloride, bacterial count at 37*C and coli form bacteria number, both presumptive and confirmed. Occasionally specia tests may be necessary such as residual alum , iron, and manganese tests and odore and other residual chlorine should be tested at each major stage of treatment .Chlorine demand tests should be carried out n row water. METHOD OF EXAMINATION The physical, chemical, bacteriological and biological procedure for analytic laboratory examinations given in the manual of methods for the examinations of water, sewage and industrial wastes published by the Indian council of Medical Research are to be followed. for procedure reading trace and other element not covered by ICMR, the procedure recommended in the W.H. O. publication International Standard for Drinking Water. Third Edition (1971) may be followed. Conformity to standard analytical methods is important of the result of the test carried out by different laboratories are to be meaningful. 1. Reporting of results: Specimen forms for reporting results of a short chemical examination, a complete chemical examination and bacteriological examinations of water, are given in appendix. For purpose of uniformity standard expression should be clearly stated in the report. The expression part per million (ppm), still used to express chemical concentration, should be replaced by milligram per liter(mg/l) , which is much more appropriate, unless their special need to some other chemicals concentration unit like miliequivalent per liter(per me/l) of microgram of several anions or cations responsible for imparting a particular characteristic to the water like hardness. Volume are expressed in milli-liters (ml) and to temperature in degree is centigrade (*C) . The total number of micro organism developing on solid media should be given in significant numbers per ml of water, the medium, time and temperature of incubation being started. The number of coli form organism and other organism indicator of pollution should be expressed in term of Most Probable Number(MPN)per 100 ml or as determined number obtained by direct plotting procedures. In biological examinations, the concentration of organisms per ml of sample is expressed in many instances as a simple more usually in term of a real standard units or numerical count. Occasionally the result is express in mg/l, but volumetric standard units. Reporting analytical results of a particular examination should be including the proper use of significant figures and the expression of confidence limit, where appropriate.

1.2 Physical and chemical standard for drinking water in India


S.No. Characterstics Acceptable Cause for rejection 10 25 Unobjectionable 6.5 to 9.2 1500 600 1000 400 1.5 45 200 150

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12..

Turbidity ( units on J. T. U. scale ) Colour (units on platinum cobalt scale ) Taste and Odour pH Total dissolved solids (mg/l) Total hardness (mg/l) (as CaCO3) Chlorides (as Cl ) (mg/l) Sulphates (as SO4 ) (mg/l) Fluorides (as F) (mg/l) Nitrates (as NO3) (mg/l) Calcium (as Ca) (mg/l) Magnesium (as Mg) (mg/l)

2.5 5.00 Unobjectionable 7.0 to 8.5 500 200 200 200 1.0 45 75 30

13. 14. 15 16. 17. 18.

If there are 250 mg/l of sulphates, Mg contents can be increased to a maximum of 125 mg/l with the reduction of sulphate at the rate of 1 unit per every 2.5 units of sulphates Iron (as Fe) (mg/l) 0.1 1.0 Manganese (as Mn) (mg/l) Copper (as Cu) (mg/l) Zinc (as Zn) (mg/l) Phenolic compounds (as phenol ) (mg/l) Anionic detergents (as MBAS) (mg/l) 0.05 0.5 5.00 0.001 0.2 0.5 1.5 15.0 0.002 1.0

19. Mineral oil (mg/l) TOXIC MATERIAL

20. 21.

Arsenic (as As) (mg/1)


Cadmium (as Cd) (mg/1)

0.05 0.0 1

0.05 0.0 1

22. 23. 24. 25. 26. 27.

Chromium (as hexavalent Cr) (mg/1) Cyanides (as CN) (mg/1) Lead (as Pd) (mg/1) Selinium (as Se) (mg/1)
Mercury (total as Hg) (mg/1)

0.05 0.05 0.1 0.01 0.001 0.1 / ug /l

0.05 0.05 0.1 0.01 0.001 0.2/ ug /l

Polynuclear aromatic hydrocarbons (PAH)

RADIO ACTIVITY
28. 29. Gross Alpha activity Gross Beta activity Pci = pico curie 3 pCi /1 30 pCi / 1 3 p Ci/ 1 30 p Ci/ l

Notes:
1*. The figures indicated under the column "acceptable1 are the limits upload which the water is generally acceptable to the consumers. 2* Figures in excess of those mentioned under 'acccpiablc1 render the water not acceptable but still may be tolerated in the absence of alternative and better source but up to the limits indicated under column cause for rejection1 above which the supply will have to be rejected.
3.

It is possible that come mine and spring waters may exceed these radio activity limits and in such eases. It is a necessary to analyze the individual radio nuclides in order to assess the acceptability or otherwise for public consumption.

APPENDIX TEST CHARACTERSTICS FOR DRINKING WATER

S.No

Substance of characteristic

W.H.O Guideline value (1885)

CPHEEO Recommendation 1991


Desirable value Maximum Tolerable value 10.0 JTU 25.0 6.5 9.2 1500 800 1.0 1000 200

IS : 10500 : 1991
Desirable value 5 NTU 5 Hazen U.O U.O 6.5 8.5 500 300 0.3 250 0.2 75 Maximum Tolerable value 10 NTU 25 Hazen 6.5 8.5 2000 600 1.0 1000 200

1. 2. 3. 4. 5. 6.

Turbidity Colour Taste Odour pH value Total dissolved solids (mg/l) Total hardness
(as CaCO3mg/l)

5 NTU 15 TCU I.O I.O 6.5 8.5 1000 500 0.3 250

2.5 NTU 5.0 U.O U.O 7.5 8.5 500 200 0.10 200 75

7. 8. 9. 10. 11.

Iron (as mg/l) Chlorides


(as CI mg/l)

Residual free chlorine (mg/l) Calcium


(as Ca mg/l)

12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29.

Copper (as Cu mg/l) Magnesium (as Mn mg/l) Sulphate (as SO4 mg/l) Nitrate (as NO3 mg/l) Fluoride (as F mg/l) Phynolic compounds
(as C6H5OH mg/l)

1.0 0.1 400 45 1.5 0.001 0.005 0.01 0.05 0.05 5.0 0.10

0.05 0.05 200 45 1 0.001 0.001 0.01 0.01 0.05 0.10 0.05

1.5 0.5 400 100 1.5 0.005 0.001

0.05 0.1 200 45 1 0.001 0.001 0.01 0.01 0.05 0.05 5.0 0.05 0.2

1.5 0.3 400 100 1.5 0.002 0.001 0.01 0.01 0.05 0.05 15.0 0.05 1.0

Mercury (as Hg mg/l) Cadmium (as Cd mg/l) Selenium (as Se mg/l) Arsenic (as As mg/l) Lead (as Pb mg/l) Zinc (as Zn mg/l) Cyanide (as CN mg/l) Anionic detergents
(as MBAS mg/l)

Chromium (as Cr mg/l) Polynuclear aeromatic hydrocarbons (mg/l) Pesticides mg/l Radio active materials
(a) - emitters Ba/l (b) -emitters Pci/l

0.05

0.05 0.2

0.05 Absent

0.05 0.001

0.1 1.00 0.2 200

3.0

0.1 1.0 200 0.03 1.0 0.01

600 0.2 5.0 0.03

30. 31. 32. 33. 34.

Alkalinity mg/l Aluminium (as Al mg/l) Boron mg/l Mineral oil mg/l Sodium mg/l

EFFLUENT STANDARDS These standards fix the limits of wastewater (after treatment) depending upon the mode of

final disposal viz : a) Discharge into inland surface water. b) Discharge on land for irrigation purpose.
c) Discharge into public sewers.

Acceptable limits according to IS-2490-1963, 1S-3307-1965 and 1S-3306-1965 are:


S.No.

Characteristics

Standards for water discharge


Into inland surface water On land for irrigation purpose Into public sewers

1
1. 2. 3. 4. 5. 6.

2
R.O. (for 5 days at 20aC) Suspended solids pH Temperature

3 30-100 mg/l
100 mg/l 5.5-9.0 4C

4
500 mg/1 --

5
500 mg/1 600 mg/1 5.5-9.0 45C 1 00 mg/1 2.0 mg/1 2100 mg/1 1000mg/1

5.5-9.0 30 mg/1 2100 mg/1 1000mg/l 600 mg/1 60% 2 mg/1

Oil and grease


Cunides

16mg/l 0.2 mg/1 2.0 mg/1

7.
8.

Sulphides

Total residua! chlorine 1.0 mg/l Flouride


Arsenic Total dissolved solids Sulphates

9.
10, 11. 12.

2.0mg/l
1.0 mg/1 -

13. 14. 15.

Chlorides
Sodium %

600 mg/1 60% 2 mg/1

Boron

16.

Gross and radio activity Gross activity Lead Copper Zinc Hexavalent compound Nickel Phenolic compound Amonical nitrogen and radio

10-8 /cu/ml

10-9/uc/l

10-7/uc/ml 10-6 /cu/ml 1 mg/1 3 mg/1 15 mg/1 2mg/l


2 mg/1 5mg/l

17. 18. 19. 20. 21, 22. 23.


24.

10-3 /cu/ml -

50 mg/1

TOXIC MATERIAL 20. 21. 22. 23. 24. 25. 26. 27. Arsenic (as As) {nig/1)
Cadmium (as Cd) (mg/1) 0.0 1 0.05 0.05 0.1 0.001 0.003 0.1/ug/1 0.05 0.05 0.0 1 0.05 0.05 0.1 0.01 0.001 0.2/ug/1

Chromium (as hexavalent Cr) (mg/1) Cyanides (as CN) (mg/1) Lead (as Pd) (mg/1) Selenium (as Se) (mg/1)
Mercury (total as Hg) (mg/1)

Polynuclear aromatic hydrocarbons (PAH)

RADIO ACTIVITY
28. 29, Gross Alpha activity Gross Beta activity Pci = pico curie 3p Ci/ 1 30p Ci/ 1 3p Ci/ 1 30pCi/l

Notes:
1*. The figures indicated under the column "acceptable1 are the limits upload which the water is generally acceptable to the consumers. 2* Figures in excess of those mentioned under 'acccpiablc1 render the water not acceptable but still may be tolerated in the absence of alternative and better source but up to the limits indicated under column cause for rejection1 above which the supply will have to be rejected. 3- It is possible that come mine and spring waters may exceed these radio activity limits and in such eases. It is a necessary to analyze the individual radio nuclides in order to assess the acceptability or otherwise for public consumption.

17

1.2 Physical and chemical standard for drinking water in India. S.No
.

Characterstics

Acceptabl Cause e for rejection


2.5 5.00 Unobjectionable 7.0 to 8.5 500 200 200 200 1.0 45 75 30 10 25 Unobjectionable 6.5 to 9.2 1500 600 1000 400 1.5 45 200 150

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12..

Turbidity ( units on J. T. U. scale ) Colour (units on platinum cobalt scale ) Taste and Odour pH Total dissolved solids (mg/l) Total hardness (mg/l) (as CaCO3) Chlorides (as SO4) (mg/l) Sulphates (as SO4) (mg/l) Fluorides (as F) (mg/l) Nitrates (as NO3) (mg/l) Calcium (as Ca) (mg/l) Magnesium (as Mg) (mg/l)

13. 14. 15 16. 17. 18. 19.

if there are 250 mg/l of sulphates, Mg contents can be increased to a maximum of 125 mg/l with the reduction of sulphate at the rate of 1 unit per every 2.5 units of sulphates Iron (as Fe) (mg/l) 0.1 1.0 Manganese (as Mn) (mg/l) Copper (as Cu) (mg/l) Zinc (as Zn) (mg/l) Phenolic compounds (as phenol ) (mg/l) Anionic detergents (as MBAS) (mg/l) Mineral oil (mg/l)

0.05 0.5 5.00 0.001 0.2


0.05 0.05

0.5 1.5 15.0 0.002 1.0


0.05 0.05

26.

Chromium (as Cr mg/l)

27. 28. 29.

Polynuclear aeromatic hydrocarbons (mg/l) Pesticides mg/l Radio active materials a) emitters Ba/l b) emitters Pci/l

0.2

Absent

0.001

0.1 1.00 0.2 200

3.0

0.1 1.0 200 0.03 1.0 0.01

600 0.2 5.0 0.03

30. 31. 32. 33. 34.

Alkalinity mg/l Aluminium (as AI mg/l) Boron mg/l Mineral oil mg/l Sodium mg/l

APPENDIX
TEST CHARACTERSTICS FOR DRINKING WATER
S.No Substance of W.H.O CPHEEO Recomm. IS : 10500 : 1991 characteristic Guideline 1991 value (1885) Desirable Maximum Desirable Maximum value Tolerable value Tolerable

value
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. Turbidity Colour Taste Odour pH value Total dissolved solids (mg/l) Total hardness (as CaCO3mg/l) Iron (as mg/l) Chlorides (as CI mg/l) Residual free chlorine (mg/l) Calcium (as Ca mg/l) 5 NTU 15 TCU I.O I.O 6.5 8.5 1000 500 0.3 250 2.5 NTU 5.0 U.O U.O 7.5 8.5 500 200 0.10 200 75 10.0 JTU 25.0 6.5 9.2 1500 800 1.0 1000 200 5 NTU 5 Hazen U.O U.O 6.5 8.5 500 300 0.3 250 0.2 75

value
10 NTU 25 Hazen 6.5 8.5 2000 600 1.0 1000 200

12. Copper (as Cu mg/l) 13. Magnesium (as Mn mg/l)

1.0 0.1

0.05 0.05

1.5 0.5

0.05 0.1

1.5 0.3

14. Sulphate (as SO4 mg/l) 15. Nitrate (as NO3 mg/l) 16. Fluoride (as F mg/l) 17. Phynolic compounds (as C6H5OH mg/l) 18. Mercury (as Hg mg/l) 19. Cadmium (as Cd mg/l) 20. Selenium (as Se mg/l) 21. Arsenic (as As mg/l) 22. Lead (as Pb mg/l) 23. Zinc (as Zn mg/l) 24. Cyanide (as CN mg/l) 25. Anionic detergents (as MBAS mg/l)

400 45 1.5 0.001 0.005 0.01 0.05 0.05 5.0 0.10

200 45 1 0.001 0.001 0.01 0.01 0.05 0.10 0.05

400 100 1.5 0.005 0.001

200 45 1 0.001 0.001 0.01 0.01 0.05 0.05 5.0 0.05 0.2

400 100 1.5 0.002 0.001 0.01 0.01 0.05 0.05 15.0 0.05 1.0

BACTERIOLOGICAL STANDARDS
1. Water entering the distribution system

Coli form count in any sample of 100 should be zero. A sample of the water entering the distribution system the docs not conform to this standard calls for an immediate investigation into both the efficiency of the purification process and the method of sampling.

2.
-

Water in the distribution system shall satisfy all three criteria indicated below:
B.Coli count in 100 ml of any sample should be zero,

Colifom organisms not more than 10 per 100ml shall be present in any sample. Coli form organisms should not be detectable in 10 nil of any two consecutive samples or more than 50% of the sample collected for the year.

3. Individual or small community supplies B. Coil count should be zero in any sample of 100 ml and a coli form organisms should not be more than 3 per 100 ml. (If repeated samples show the presence of coli form organisms, steps should be taken to discover and remove the source of the pollution. If coli form exceed 3 per 100 ml, the supply should be disinfected).

VIROLOG1CAL ASPECTS
0.5 mg/i of free chloride residual for one hour is sufficient to inactive virus, even in water that was originally polluted. This free chloride residual is to be insisted in all disinfected supplies in areas suspected of endcmicity of infections hepatitis to take care of the safety of the supply from virus point of view which incidentally takes care of the safety from the bacteriological point of view as well. For other areas mg/I of free chlorine residual for half an hour should be insisted-

SAMPLING: INSTRUCTION & DETAILS

INTRODUCTION For the proper working of plants, effluent with in prescribed quality, collection of proper sample and its analysis is a must, the present experiment aims at describing important methodology, preservation techniques and frequency. A sample has to be representative and valid both in time and space. The parameters in the sample at the time of analysis should have the same values as those at the time and place of sampling. A sample will be representative depending upon the sampling techniques and preservation. A sample is valid if it _represents _the true picture of water/waste water quality at the sampling point. Quality of water depends on place, time and its estimation depends on frequency of sampling. Conditions at each sample source very widely and sampling programmed needs to be worked on the merits of the source.

FREQUENCY OF SAMPLING Quality of water, flowing or stagnant, seldom, remains the same in time. The longer the number of samples from which the mean is derived the narrower will be tin: limits of the probable difference between the observed and true value of the mean. In order to double the

reliability of a mean value, the number of samples must hi: increased fourfold, because confidence limits are proportional to the square of the number of samples, hence a confidence between the increased reliability of data measured by confidence limits and the cost of its collection has to be reached. Effluent or waste water quality changes depending on the mass inputs and changes in rate of water flow or on volume. Characteristics of water quality vary (a) randomly e.g. during form, spillages in factory, and (b) cyclically due to rain Fall pattern. Also they vary with the production pattern in manufacture process, or depending upon the sources, say a river or a lake.

The minimum number of samples to be collected from a distribution system should be as under : Table No. 1 Population served Maximum interval between successive sampling One Month Two weeks Four Days One Day Minimum NO. of samples to be taken from entire distribution system One sample per 5000 of population per month ----do---------do----One sample per 10000 of population per month

up to 20000 20000 to 50000 50000 to 100000 More than 100000

SAMPLING PROCEDURE Procedure will depend on the type of sample i.e. its quality and & grouped accordingly a) b) c) Non-conservative changes with time. Stabilized for 24 hours by proper treatment. Non-conservative, i.e. changes rapidly with time and can not he preserved e.g. Temperature, pH, DO requiring fixation or determination on site. Table2: Gives the preservation required for some only requiredparameters. Table:2

Parameter 1 Acidity/Alkalinity BOD Calcium COD Colour Cyanide Do Metales,total Dissolved metals Amm. Nitrogen Kjeldahal Nitrogen Nitrate-Nitrite Oil& Grease Organic Carbon Phenolics Phosphorus Sulphates Sulphide Silica

Container 2 Glass ---do--Plastic Glass ------------------Glass Plastic/Glass --do ---do --do Glass/Plastic ---------Glass ------------Glass Plastic/Glass ----------Plastic

Preservative 3 Refrigeration ---do--Not required 2ml H2SO4/ 1 pH-2 Refrigeration pH 10 by NaOH On site 5ml HNO3/1 40 filerate:3ml 1:1 HNO3/ l 40 mgHgCl2 / liter 40oC ---do--40 mgHgCl2/ liter 40oC 2ml/liter H2SO4 -40oC 2ml H2SO4 / l- (pH-2) 1 g CuSO4 + H3Po4: 4.04oC 40mg MgCL2 /1-4oC 4oC 2mlZn Acetate/ 1 Filter on site then 4oC

Max. holding period 4 24 hours 6 hours -----7 days 24 hours 24 hours None 6 months 6 months 7 days Unstable 7 days 24 days 7 days 24 hours 7 days 7 days 7 days --do--

COMPOSITE SAMPLE It is a general practice to mix discrete samples lo form a composite sample.

Time based composite or weighted composite sample is one, when individual samples are mixed in equal portions, or in portions according the flow at the time of sampling. Analysis of a composite sample wills he the average over the time of sampling. This will not give any indication of maximum or minimum values over the sampling period. Manual sampling is economically reliable. Composite samples are nut possible for DO, pH temperature. CN, metals and bacteria. These change with time or due to chemical interactions. Each sample thus collected should carry information such as source, time of collection, preservative added, collector's identity and other useful information at site. SAMPLING FOR PHYSICAL AND CHEMICAL ANALYSIS Samples should he collected in containers of Pyrex glass or other inert material like polythene. Sample bottle must be carefully cleaned before use. Glass bottles may be rinsed with a chromic acid cleaning mixture, made by adding one liter of concentrated sulphuric acid slowly with string to 35 ml saturated sodium dichromate solution, or with an alkaline paramagnet solution foil wed by an oxalic acid solution. After having cleaned, bottles must be rinsed thoroughly with tap water and then with distilled water. About 2 5 liters of the sample is required for analysis Prior to filling the sampling bottle should be rinsed out two or three times with water to be collected. Care should be taken to obtain a sample that is truly representative of existing s and to handle it in .such a way that it does not deteriorate or become contaminated before it reaches the laboratory. The sample should reach the plate of analysis within 72 hours of collection. The time elapsed between collection and analysis should be recorded on the laboratory report.

Some determinations are likely to be affected by storage of samples. Walls of glass containers are likely lo absorb cations like aluminum cadmium, chromium. Copper, Iron, Lead, Manganese. Silver or Zinc which arc best collected in a separate bottle and acidified by concentrated hydrochloric or nitric acid to a pH approximately 3.5 to minimize precipitation and absorption on the walls of he container. Hot samples collected under pressure should be cooled while under pressure, Samples from wells should be collected only after the well has been pumped for a sufficient time to ensure that the sample will be representative of the ground water. For collection of sample at different depths. Specific equipment should he used.

SAMPLING FROM A WATER WORKS SYSTEM & DISTRIBUTION SYSTEM In order to find out whether the processes of treatment are satisfactory, a number of sampling points at different locations of water works system arc selected. The samples from distribution system should be drawn from different mains and periphery of the distributors system. For taking sample sterilized stand pipe must be used. Before taking sample the pipe line should be hushed for a sufficient period 10 get a representative sample.

SAMPLEING FOR BACTERIOLOGICAL ANALYSIS Sterilized glass bottles provided with ground glass stopper having an overlapping rim should be used. The stopper and the neck of (he bottle should be protected by brown paper. The sterilization is carried out in an autoclave at 1 kg/cm 2 Pressure for 15 minutes or two hours under steam and some space should be left in the bottle after sample is collected, Dechlorination is necessary for chlorinated water samples. For this, sodium thiosulpate should be added to the clean, dry sampling bottle before sterilization in an amount to provide an approximate concentration of 100 mg/l in the sample. This can be done by adding 0.2 ml of 10% thiosulphate solution to a 250 ml bottle. The bottle is than sterilized by either dry or moist heal. A mini volume of 250 ml should be taken for bacteriological exam. PRESERVATION AND STORAGE Water sample should be examined immediately after collection forever, this is seldom practical and hence it is recommended that the samples should be preferable analyzed within one hour after collection and in no case this time should exceed 24 hours. During transit, the temperature of the sample should be maintained as close as possible to that of the source of the sample, at the time of sampling. The time and temperature of storage of all samples should be recorded since they will be considered in the interpretation of the laboratory results. If they can not be analyzed within 24 hours the samples must be preserved in ice; until analysis No sample is 111 for bacteriological analysis after 72 hours. SAMPLING FOR BIOLOGICAL ANALYSIS

For this purpose, two samples should be collected in clean two liter wide mouthed bottles with a glass stopper or a bakelite screw cap. In making the collection the bottle. Alter I he stopper is removed, is thrust as far as possible, mouth downward into dir water. It is then inverted and allowed to fill. To another bottle add 5 ml of commercial formalic to every 100 ml of water sample immediately after collection both the bottles should be dispatched with the label on the sample stating the one with formalin.

EXPERIMENT No. 1
pH -VALUE
OBJECT

To determine the pH value of given sample of water. To calculate the dose of chemical for adjusting the pH to a specific value for treating 10 MLD of water.
APPARATUS

Burette, Pipette, Conical flask and Glazed tile.


REAGENTS

0.02 N NaOH solution, Universal pH-indicator and pH paper.


THEORY

pH is a term used rather universally to express the intensity of the acid or alkaline condition of a solution. More exactly, it is a way of expressing the

hydrogen-ion-concentration, as a number, which indicate the logarithm or reciprocal of hydrogen-ion-concentration. The concept of pH evolves from a series of developments that led to a fuller understanding of acids and bases. Water containing no acid or alkali has a pH value of 7, which is termed the neutral pH-value, and pH values 1 to 7 indicate acidic and 7 to 14 indicate alkalinity. The hydrogen electrode was found to be a very suitable device for measuring hydrogen-ion-concentration, with its uses, it was found that pure water dissociates to yield a concentration of hydrogen ions equal to 10-7 mole / litre. H2O = H+ + OHSince water dissociates to produce one hydroxyl ion for each hydrogen ion, it is obvious that 10-7 mole of hydroxyl ion is produced simultaneously. Applying Law of Mass Action, [H+] [OH ] = K [H2O] But, since the consumption of water is so extremely large and is diminished, so very little by the slight degree if ionization. It may be considered as constant and the above equation can be rewritten as [H+] [OH-] = Kw , add for pure water at about 25 C [H+] [OH-] = 10-14 (Ion Product for Water) Hence, for neutral water [H+] = 10-7 and [OH ] = 10-7 Expression of Hydrogen-ion concentration in terms of molar concentration is rather cumbersome. In order to overcome this difficulty, Sorenson proposed to express such values in terms of their negative logarithms and designated such values as pHx, this x symbol has been superseded by the simple designation pH. This term is represented by-

pH = -log [H+] or pH = log 1/ [H+] pH-scale is usually represented as ranging from 0 to 14 with pH-7 representing the absolute neutrality. Acid Range 0 7 Alkaline Range 14

It is important to remember that the [OH-] or [H] can never be reduced to zero, no matter how acidic or basic the solution may be.
MEHTODS OF DETERMINATION

pH can be determined by the following two methods1. Electrometric Method 2. Colorimetric Method
ELECTROMETRIC GLASS ELECTRODE METHOD THEORY OF TEST

pH is a measure of the relative acidity or alkalinity of water. It may be measured by determining with a potentiometer the voltage developed by two electrodes, which are in contact with the solution. The voltage of one electrode known as calomel half-cell is fixed. While the voltage of the other electrode varies with the pH of the sample. The glass electrodes system is based on the fact that a change of 1 pH unit produces an electrical charge of 59.1 milivolts at 25C and is the most accurate method for determining the pH of a wide variety of solution.
COLORIMETRIC METHOD THEORY OF TEST

Colorimetric method depends on the use of an indicator whose colour in solution is characteristics of the pH values of the solution. The colour produced is compared in a pH colour comparator with standards. PROCEDURE (a) Electrometric Method

Standardize the pH electrometer by using a buffer solution of known pH approaching that of the sample, and adjust the temperature correction. The glass electrode and the calomel electrode should be thoroughly wetted and prepared for use in accordance with the manufacturers instructions. Insert the glass electrode in the water sample and read the pH directly on the dial of the instrument. (b) Colorimetric Method Place 10 ml of the sample into each of the two or three tubes provided wit the pH colour comparator. To one tube add the appropriate quantity of the indicator solution. Place the tubes in the comparator, compare the colour with the standards and read the pH. Directions for making the determination of pH will be found with the particular pH colour comparator beings used. (c) Adjustment of pH (1) Take 20 ml of sample and determine its initial pH by Colorimetric Method. (2)Add NaOH to the above sample so as to raise its pH to 10 or 11. (3)Note the volume of NOH required. (4)Take two concurrent readings. OBSERVATIONS S. No. 1. 2. 3. 4. 5. Volume of Sample Initial Burette Final Burette Reading Reading Volume of NaOH (cc)

SAMPLE CALCULATION

The initial pH of Sample is Amount of NaOH required in mg/lt. = Volume of NaOH x 1000 x 40 Volume of Sample Kg / day = mg /1 x MLD
RESULT

= =

Amount of NaOH required in mg/lt.

= mg/lt. = Kg/day

CONCLUSION
We required . mg / lt or kg / day of NaOH to raise its Ph 7 to 10. The exact volume of NaOH of given sample is to be come 7.0 but due to some practical errors & personal error, it comes 6.6 ml. We determine by pH acidity or alkalinity of sample. The public water supply has range of pH from 6.5 to 8.5 by knowing initial pH of sample we can determine the dose of chemical for particular sample. SIGNIFICANCE pH determination is of importance in practically every phase of sanitary Engg. Practice. In the field of water supplies, it is a factor must be considered in chemical coagulation, disinfection, water softening and corrosion control. In chemical coagulation it helps in selecting a proper coagulant, because different coagulants are most effective in specific pH ranges. Also, optimum dose of coagulant is a function of pH.

In disinfection of water by Chlorine, pH again plays an important role. The action of chlorine as disinfectant is maximum in a specific pH-range, so for achieving an efficient disinfection that pH is to be maintained. In water softening by lime soda process the process is controlled in part by the test for pH. Corrosiveness of water is a function of pH and can often be corrected by decreasing the acid intensity by addition of alkali, which is usually controlled by determination of pH-value. Similarly, the deposition or dissolving of scale or pipes can be controlled by changing the reaction of alkalinity and pH value by addition of lime or soda ash, also controlled by pH-determinations. In sewage and industrial waste treatment employing biological processes, pH must be controlled within a range favourable to the particular organisms involved, chemical processes used to coagulate sewages or industrial waste, dewater sludge or oxidize certain substances, such as cyanide ion, required that the pH be controlled within rather narrow limits.

EXPERIMENT No. 2
ACIDITY OBJECT

To determine the acidity of the given sample of water.


APPARATUS

Burette, Pipette, Conical flask and Glazed tile.


REAGENTS

0.02N NaOH solution, Methyl orange solution and Phenolphthalein solution.

THEORY

The acidity of water may be used by presence of uncombined carbon-di-oxide, mineral acids and salts of strong acid and weak bases. It is defined as the capacity of a solution to neutralize a standard alkali. It can be noted that for carbonic acid the starchiometric end point is not reached until the pH has been raised to about 8.5 which indicates that all waters, having a pH lower that 8.5 contains acidity. Usually, the phenolphthalein end point at pH 8.2 to 8.4 is taken as the reference point. Inspection of curve further indicates that at pH 7.0 considerable carbon-di-oxide remains to be neutralized but alone CO2 will not depress the pH below a value of about 4.5 Considering the nature of the curve which is for a strong acid, it may be concluded that neutralization of acid is essentially complete at pH 4.5. It is incidentally, the methyl orange end point. Thus, it becomes obvious that the acidity of neutral water is caused by carbon dioxide or by strong mineral acids. Titration to methyl orange end point (pH = 4.5) is defined as the acidity which gives a measures of relatively strong acids such as mineral acids and titration to the phenolphthalein end point (pH = 8.3) is defined as totally acidity and it includes also the weak acids, acids salts and some acidity due to hydrolysis. 1 2 3 4 5 6 7 8 9 10 11

Practical Range of Mineral PROCEDURE (a) Total Acidity

Range of CO2 Acidity

Its determination should be made on spot; on a fresh sample collected in a bottle and stoppered immediately to prevent escape of carbon dioxide. Take 50 ml to 100 ml of the sample in an Erlenmeyer flask, add 3 drops of phenolphthalein indicator and titrate over a white surface with 0.02 N NaOH until faint colour appears.

(b) Mineral Acid Acidity Take 50 ml. or 100 ml of the sample in an Erlenmeyer flask, add 2 drops of Methyl orange indicator, and titrate over a white surface with 0.02 N NaOH until colour changes to faint orange. Brome-Cresol green indicator can also be used in lace of methyl orange; it gives a sharp end point.
OBSERVATIONS

S. No.

Volume of Sample

Initial Burette Final Burette Reading Reading

Volume of NaOH required

(A)Total Acidity - Indicator phenolphthalein 1. 2. 3. 4. 5. .

(B) Mineral Acidity - Indicator methyl orange S. No. 1. 2. 3. 4. 5. Volume of Sample Initial Burette Final Burette Reading Reading Volume of NaOH required

CALCULATION
(a) Total Acidity Mg / lt. total acidity as CaCO3 = = ml. 0.02 N NaOH x 1000 x 50 = ml. of Sample

(b) Mineral acid acidity Mg / lt. total mineral acid acidity = = ml. 0.02 N NaOH x 1000 x 50 = ml. of Sample

RESULT

The total acidity of sample B with initial pH.. .is found to be mg/lt. and mineral acidity is mg / lt. The acidity of sample A (Tap Water) is mg / lt. The total acidity is due to mineral acidity & weak acids. For pH range more than 8.5 the acidity due to OH ions

SIGNIFICANCE
Acidity is of little concern from a statutory or public health view point , carbon dioxide is present in malt and carbonate beverages in concentration greatly in excess of any concentration known In natural waters , and no deleterious effects due to the carbon dioxide have been recognized . Water that contains mineral acidity is usually so unpalatable that problems related to human consumption are non-existent. Acid water is of concern to Sanitary engineer because of their corrosive characteristics and the expenses involved in removing or controlling the corrosion producing substances. The corrosive factor in most water is carbon dioxide, but in many industrial wastes it is mineral acidity. Carbon dioxide must be reckoned with water softening problems where the lime or lime soda ash method is employed.

EXPERIMENT No . 3 ALKALINITY OBJECT To determinate alkalinity of given sample of water. APPARATUS Burette, Pipette, Conical flask and Glazed tile. REAGENTS 0.02 N H2SO4 solution, Phenolphthalein indicator and Methyl orange indicator. THEORY Alkalinity is the measure of the basic constituents of water and is defined the capacity of a solution to neutralize a standard acid. In natural water it is usually present as the carbonate and bicarbonate salts of calcium, magnesium, sodium and potassium. Bicarbonates represent the major form of alkalinity since they are formed in considerable amounts from the action of carbon dioxide upon basic materials in the soil. Under certain conditions natural water may contain appreciable amount of carbon and hydroxide alkalinity. Chemically treated water, particularly those produced in lime or lime soda ash softening of water, contain carbonates and excess hydroxide. Thus it is obvious that alkalinity is caused by three major classes of materials may be ranked in order of their effect on pH as hydroxides, carbonates, bicarbonates and other salts of weak acids. Alkalinity is determined by titration with a standard with a standard solution of a strong acid to certain end points as given by indicator solutions. Phenolphthalein is satisfactory indicator for the first end point (pH approx 8.3) contributed by hydroxide and carbonate. Methyl orange is used for the second end point (pH approx 4.5) contributed by bicarbonates. The phenolphthalein end point of titration is defined as P alkalinity and the end point observed by continuing the titration with same solution using methyl orange indicator is known as total or T-alkalinity. Following table can be used for working out OH, CO3 and HCO3 alkalinity individually after completing titration. Table

Result of Titration P=0 P < (T/2) P = (T/2) P > (T/2) P=T

Value of radical expressed in term of Calcium Carbonate OH0 0 0 2P-T T CO3-0 2P 2P 2(T-P) 0 HCO3T T-2P 0 0 0

PROCEDURE Phenolphthalein alkalinity The 50 or 100 ml of sample in an Erlenmeyer flask, add two drops of phenolphthalein indicator and titrate over a white tile with 0.02 N H2SO4 until the pink colour just disappears. Total or methyl orange alkalinity Add two drops of methyl orange indicator to the same sample in which phenolphthalein alkalinity has been determine previously and titrate with 0.02 N H2SO4 until the colour changes from yellow to faint orange. OBSERVATIONS (a) Sample .

(b) Initial pH of given sample is .

Table for phenolphthalein alkalinity S.No. 1. 2. 3. Volume of Sample Initial burette reading Final burette Reading Volume of H2SO4

Table for methyl orange alkalinity

Volume of sample S.No. 1. 2. 3. CALCULATIONS

Initial burette reading

Final burette reading

Volume of H2SO4

Initial pH of the sample is.. Mg/lt. phenolphthalein alkalinity as CaCO3 (ml. of 0.02N H2SO4 x 10 0 0 x 5 0) = = ..ml. of sample

Mg/lt. of total or methyl orange alkalinity as CaCO3 = Total ml. of 0.02 N H2SO4 x 1000 x 50 RESULT Methyl orange alkalinity as CaCO3 is ............mg/lt. and Phenolphthalein alkalinity is .. mg/lt. Total alkalinity due to bicarbonate is got by using methyl orange indicator it comes .. . mg/lt. CONCLUSION Since alkalinity of tap water mg/lt. which is very large/moderate/low. Thus it can be used/not used as drinking water because according to IS-10500:1991 range of alkalinity for drinking water is 200-600 mg/lt. OH- ion is mainly responsible for alkalinity. Due to only OHion alkalinity has range of pH 8.3 to 14 and practical range of alkalinity comes pink to colorless solution of alkalinity above 600 mg/lt. is not good for human point of view. =ml. of sample.

SIGNIFICANCE With in regional limit alkalinity has sanitary significance, but it is very important in connection with coagulation, softening and corrosion preservation, Alum used in coagulation is an acid salt which when added in small quantity to natural water, reacts with alkalinity present to form flocs. If insufficient alkalinity is present to react with all the alum, coagulation will be

incomplete and soluble alum will be left in the water. It may therefore, be necessary to add alkalinity in the form of soda ash or lime to complete the coagulation or to maintain sufficient alkalinity to prevent the coagulated water fro being corrosive. Ordinarily the total alkalinity determined with methyl orange indicator; gives sufficient information for the control of coagulation and corrosion prevention when pH is also determined. Many regulatory agencies prohibit the discharge of waste containing caustic alkalinity to receiving water. Municipal authorities usually prohibit discharge of waste containing caustic alkalinity to sewers. Alkalinity as well as pH is an important factor in determining the amenability of waste water to biological treatment. Lastly from public health point of view, alkaline water is usually unpalatable and consumer tends to seek other supplies Chemically treated water some time have rather pH values, which have met with some objections on the part of consumers. For these reasons, standards are some times established on chemically treated water. Where biological processes of treatment are used the pH must ordinarily be maintained within the range of 6 to 9.5. This criterion often requires adjustment of pH to favorable levels and calculations of the amount of chemical needed is based upon acidity values in most cases.

EXPERIMENT No. 4 CHLORIDE TEST OBJECT To determine the amount of chlorides in the given sample. APPARATUS Burette, Pipette and Conical flask, Silver nitrate (N/71), Potassium chromate indicator, chemicals for pH adjustments. THEORY

Chlorides occur in all natural water in widely varying concentrations. This chloride content normally increases as the mineral content increases and it is usually associated with Na + ion. The sources which contribute most of the increase of chlorides in natural water are: (i) (ii) (iii) (iv) (v) Due to the formation of minute salt crystals resulting from evaporation of ocean water and then its spraying over inland areas. Due to the solvent power of water which dissolves chlorides from top soil and deeper formations. Due to sea water intermixing with river water and due to over pumping that causes sea water intrusion in group water. Due to discharge of sewage effluents in surface water as the chloride content of urine are about 6gms. per person per day. Due to discharge of industrial wastes in surface sources or due to seepage in ground water.

PROCEDURE (i) (ii) (iii) (iv) (v) (vi) Clean the burette, pipette and conical flask with the tap water. Adjust the pH of sample between 7.0 and 8.0. Take 50 ml well mixed sample adjusted to pH 7.0 -8.0 and add 1.0 ml K2CrO4. Note initial burette reading. Titrate with standards AgNO3 solution till Ag2CrO4 starts precipitating giving red color. Note final burette reading. Repeat the procedure till the concurrent readings are obtained. Determine the blank reading with the same procedure using distilled water.

OBSERVATIONS The initial pH of the sample is .. S. No. Volume of sample Volume of AgNO3 ( ml ) Net volume of

AgNO3 (ml) Initial reading A. Tap water 1. 2. 3. B. Distilled water 1. 2. 3. Final reading

SAMPLE CALCULATIONS Initial pH is for tap water. Mg/lt. = (A-B) x 0.5 x 1000 =ml. of sample

Where AgNO3 for sample is = Where AgNO3 for Blank is Where A = ml. of AgNO3 for sample, RESULT The chloride content of given sample is found to be mg/lt. as Cl. CONCLUSION In a given sample ..mg/lt chlorides present, which is Harmful / not harmful. In first AgNo3 react with salt which has chlorides and make white precipitate and AgCl then (indicator K2CrO4) react with AgNO3 and given brick red color. Thus at last end point comes brick red precipitate. SIGNIFICANCE = . B = ml of AgNO3 for blank

Chlorides are not harmful as such but when it exceed beyond 250 mg/l it imparts a peculiar taste to water rendering it unacceptable from aesthetic point of view for drinking purpose. Presence of chlorides above the usual background concentration water source is also used as an indicator for pollution by domestic sewage. Before the development of bacteriological testing procedures, chemical tests for chloride and for nitrogen, in its various forms, served as the basis of detecting contamination of ground water by sewage. Chlorides are used to some extent as tracers in sanitary engineering practices. Where brackish water has to be used for domestic purposes, the amount of chlorides present in the source is an important factor in determining the type of desalting apparatus to be used. The chloride determination is used to control pumping of ground water from locations where intrusion of sea water is a problem. EXPERIMENT No. 5 HARDNESS TEST OBJECT To determine the total hardness and calcium hardness of a given sample of water. APPARATUS Burette, Pipette, Conical flask, etc. REAGENTS Standard EDTA solution (N/50), Ammonia buffer solution and NaOH solution, Eriochrome black T indicator and Murex indicator (dry power), inhibitor. THEORY Water that consumes considerable quantity of soap to produce lather and or produces scale in hot-water pipes, heater, boilers and utensils used for cooking is called hard water. Harness is caused by divalent metallic anions that are capable of reacting with soap to form precipitates with cations present in water to form scale. Principal actions causing hardness and the major anions associated with them are as listed below: CATIONS Ca++ Mg++ Sr++ Fe++ Mn++ ANIONS HCO3SO4-ClNO3SiO3--

Calcium and magnesium are primarily the constituents of chalk and limestone. When rain falls it takes up carbon dioxide from the atmosphere and forms a weak acid and this percolates underground, it then dissolves calcium and magnesium forming hard water. IN general hard water originates in the areas where the topsoil is thick and limestone formations are present. Soft water originates in areas where the topsoil is thin and limestone is either sparse or absent. The scale of hardness from consumers point of view may be taken as below: 0 50 100 150 Over 50 ppm 100ppm 150ppm 250 ppm 250 ppm Soft Moderately soft Slightly hard Moderately hard Hard

Hardness may be classified as: (a) Carbonate and non carbonate hardness (b) Calcium and magnesium hardness, and (c) Temporary and permanent hardness. PRINCIPLE In alkaline condition EDTA (Ethylene-diamine tetra acetic acid) or its sodium salt forms a soluble chelated complex, which is stable with Ca and Mg. Also Ca and Mg form a weak complex with the indicator Eriochrome black T, which has wine red color. During titration when all free hardness ions are complexed by Eriochrom black T indicator end point. The pH has to maintain at 10+0.1. At higher pH i.e. about 12.0 mg ion precipitates and only Ca++ ions remain in solution. At this pH murex indicator from a pink colour with Ca++, gets complexed resulting in a change from pink to purple, which indicates and point of the reaction. INTERFERENCE Metal ions do interfere but can overcome by addition of inhibitors.

PROCEDURE A. TOTAL HARDNESS 1. Rinse burette, pipette, and flask, etc. 2. Take 25 or 50 ml of well-mixed sample in a flask. 3. Add 1-2 ml buffer solution followed by 1 ml inhibitor. 4. Add a pinch of Eriochrome black T and titrate with standard EDTA solution till wine red colour changes to blue. Note down the volume of EDTA required. B. CALCIUM HARDNESS 1. Take 25 ml of sample in a flask. 2. Add 2-3 drops of NaOH (N/10) to raise pH to 12 and a pinch of indicator. Note initial burette readings. 3. Titrate with EDTA till pink colour changes to purple . Note the final burette readings. 4. Repeat the procedure for other sample s till concurrent readings are obtained. C. MAGNESIUM HARDNESS 1. Take 100 ml of sample , add 1.5 ml of the buffer solution and 2.3 ml of a saturated solution of ammonia oxalate. 2. Mix the solution and allow it to stand for two hours or overnight if possible. 3. Filter , using a No. 42 Watman filter paper. 4. Pipette out 25 ml from the filtered solution and add Eriochrome black tT indicator (1-2 drops) and titrate with EDTA solution till the colour changes from wine red to blue. 5. Take two concurrent readings. OBSERVATIONS FOR TOTAL HARDNESS S.No. Volume of sample Initial reading Final reading Net volume of EDTA (ml) Total hardness mg/lt. as CaCO3

1. 2. 3. 4. OBSERVATIONS FOR CALCIUM HARNDNESS

S.No. 1. 2. 3. 4.

Volume of sample

Initial reading

Final reading

Net volume of EDTA (ml)

Calcium hardness mg/lt.

SAMPLE CALCULATIONS (a) Total harndness: Total hardness (mg/litre) (b) Calcium harndness : Calcium hardness (mg/litre) = ml. of EDTA x 1 x 1000 ml. of sample (c) Magnesium harndness: Magnesium hardness (mg/litre) = Total hardness - Ca RESULT For the given tap water sample the hardness is found to be mg/lt., Calcium hardness is . mg/lt. and Magnesium hardness is mg/lt. CONCLUSION As the total hardness and calcium hardness are below/above the maximum tolerable value i.e. 600 and 200 respectively. The water can be used/not used for domestic purposes. SIGNIFICANCE The determination of hardness is helpful in deciding the suitability of water for domestic and industrial purpose. The design of softening process depends upon the relative amounts of carbonate and non-carbonate hardness present in water. The amount of calcium and magnesium hardness decides the suitability of water for boiler use. EXPERIMENT No. 10 DETERMINATION OF AVAILABLE CHLORINE FROM BLEACHING POWDER CaOCl AND RESIDUAL 2 CHLORINE IN THE GIVEN SAMPLE OF WATER = ml. of EDTA x 1 x 1000 ml. of sample

OBJECT 1. To determine the available chlorine in bleaching powder. 2. To determine the residual chlorine in given sample of water. APPARATUS Burette, Pipette, Conical flask, Stirrer. REAGENTS KI solution, Glacial acetic acid, Distilled water, Starch, Sodium thiosulphate solution.

THEORY In small water works, chlorine required for disinfections is usually obtained from bleaching powder. For this purpose iodometric method i.e. oxidation-reducation method is employed. The iodometric method is more precise when the residual chlorine concentration is greater than one ppm . Chlorine will liberate free iodine from KI solution when its pH is 8 or less. The liberated iodine is titrated against standard solution of sodium thiosulphate using starch as indicator. When blue colour disappears then all the liberated iodine will have reacted. This indicates the end point.

PROCEDURE 1.5 gram of bleaching powder is taken and dissolved in 1 liter of distilled water. The solution thus prepared is to be tested for available chlorine. 20 ml. of 10% KI is taken in a clean, dry conical flask, 2 ml of glacial acetic acid is added into the flask to reduce pH 3 to 4.12. 12 5 ml of bleaching powder solution is then pipetted out and is added in the flask. The colour of the solution will be brown. Tritrate this solution

against N/40 sodium thiosulphate solution, till pale or straw yellow colour is developed. At this stage, add 2 drops of freshly prepared starch solution, which results in appearance of blue colour. The titration against sodium thiosulphate solution is continued till the blue colour disappears. This indicates the end point. Initial reading and final reading of sodium thiosulphate solution in the burette is noted, the difference is then found out. The whole experiment is repeated and the mean difference is taken. OBSERVATIONS S. No. Burette Reading Initial 1. 2. 3. CALCULATIONS Quantity of chlorine in mg/lt. in the water sample Chlorine of given sample = = Number of ml. of thiosulphate solution of N/40 normality remove the blue colour N (Na2S2O3) X Volume of Na2S2O3 Final Difference Mean difference

= mg/lt. as chlorine Quantity of chlorine in mg/lt. in the sample = .(ml.of sodium thiosulphate as required)

CHLORINATION Chlorine is widely used for disinfection of water for removing odour since it is a powerful oxidizing agent and is cheaply available. It can be used in molecular from or in hypochlorite form. For effective disinfection, does of chlorine, optimum contact period and residual chlorine are required to be found out. PRINCIPLE

Chlorine combines with water to form hypochlorous and hydrochloric acid. Hypochlorous acid dissociates to give OCl- ion. Quantities of OCl- and HOCL- depend on pH of the solution. Hypochloricdes also gives the OCl- ions, HOCl- rupture the cell membrane of microbes, the disease producing organisms. These also reacts with the impurities like ammonia, oxidisable inorganic matter like ferrous ion, nitrites etc. to from chloramines and stable ions of the latter respectively. INTERFERENCE Oxidisable organic and inorganic matter.

REAGENTS 1. Bleaching powder

2. Concentrated acetic acid


3. Potassium iodide crystals

4. Standard sodium thiosulphate 0.1 N-- Dissolve 25g Na2S2O3.5 H2O and dilute to
1000ml in freshly boiled and cooled distilled water. Add about 5ml chloroform as a preservative.

5. Starch indicator : Prepare slurry by adding small quantity of water to 1g starch


powder. Add it to 100ml boiling water and continue boiling for few minutes then cool and uses.

6. Standard chlorine solution : Procedure outlined under analysis of bleaching


powder. REACTION When chlorine is added to water it forms hypochlorous acid or hypochlorine ions. Cl2 + H2O
pH > 5

HOCl + HCl

Hypochlorus acid is unstable and may break into hydrogen ions & hypochlorite ions. HOCl
pH > 8 pH < 7

H+ + OCl-

More over the chlorine will immediately react with ammonia present in water to from various chloramines. NH3 + HOCl NH2 Cl2 + H2O

PROCEDURE 1. Take 1000ml sample in 12 stoppered bottles. 2. Add standardized chlorine solution in ascending order. If chlorine demand of treated water is being estimated, doses from 0 to 300mg Cl2/l. 1 will be found useful. However, if the sample is polluted, doses from 0.1 mg to 3 mg Cl2/l may be required as in case of treated effluents etc. 3. Allow a contact period of 30 minutes of probable water and suitably higher for polluted water, or secondary effluents. 4. Estimate residual chlorine iodometrically as described under analysis of "bleaching powder"

5. Plot residual chlorine versus chlorine added. In case of organically polluted samples, a
distinct break point can be obtained. But in case of treated water sample, it is possible that only a straight line is obtained in absence of any ammonium. A residual 0.2 mg Cl2/lt. after the break point is recommended.

CONCLUSION We have found the result in the above test is . mg/lt. chlorine that chlorine is satisfied / not satisfied as compare to permissible limit. The permissible limit is 0.2 according to IS: 10500, hence given sample of water does not required to drinking purpose. The amount of available chlorine in a sample indicates that bacteria are reduced up to safer limits but when it increases above the permissible limit. It may lead to the water born disease. In this water sample the chlorine is below / average / above/ as per permissible limit. So it is fit / not fit for drinking and can be accepted / rejected. RESULT The amount of available chlorine in given sample of water is mg/lt. as chlorine.

SIGNIFICANCE If the amount of available chlorine present in water is more to the permissible limit than the water should be unpleasant taste characteristics. But if it present within limit forms hydrochlorous acid and killed the bacteria present in the water as it has been described earlier.

EXPERIMENT No.11 BREAK POINT CHLORINATION OBJECT


To determine the break point chloride demand of given sample of water.

APPARATUS
A number of bottles with stoppers, pipette, O.T. test comparator, stock solution of Cl2 of known strength.

THEORY
The determination of break point chlorine demand of water is in effect the extension of experiment already performed for determination of chlorine demand of water. As discussed already in the said experiment the residual chlorine appears only after the demand has been met after adding a particular dose of chlorine, at definite period of contact. In the absence of ammonia or its derivatives in water, the residual chlorine is the free available chlorine in the form of HOCL and/or OCI which are oxidants and react with orthotolidine to show residual chlorine. Thus once the residual appears, it will go on increasing with increase in applied dose. However, when ammonia is present, the hypochlorus acid i.e. HOCL reacts with it form chlorine's first mono and then dichlormine if excess of HOCL is available

HOCl+NH3
and

NH2Cl+H2O

HOCl+NH3Cl

NHCl2+H2O

Both dichloromine and monochloromine are oxidizing agents as if HOCL and react with orthotolidine to show residual chlorine. Hence, in the presence of ammonia in water, the residual chlorine is the sum total of the action of HOCL and chloromines is called the "Combined available chlorine" and the total residual of chloride is both due to free and combined available chlorine. An interesting stage comes in when all the ammonia present has been converted into monochloromine with addition of Cl2. At this stage further addition of chlorine will not results in increase of residual because of the following reaction: NHCl2+HOCl =NCl3+H2O

The conversion of NHCl2 to NCl3 rather results in drop of residual chlorine from the level already attained. This is due to the fact that NCl3 is non-oxidizing and does not react with O.T. and thus the drop in NHCl2 results in drop of residual chlorine with added does of chlorine. Thus once against the chlorine demand goes on increasing because of consumption of chlorine in producing NCl3, which does not show any residual. A stage reaches when all the NCHCl2 present is converted into NCl3 and there is no combined available chloride at all, the chlorine demand is maximum at this product. This is called the break point" in chlorination. Further addition of Cl2 will again show residual but this will be in the from of free chlorine i.e. HOCl and OCI as all the NH3 has been converted into NCl3 or oxidized to free nitrogen

or other gases at the break point.

SIGNIFICANCE OF THE BREAK POINT


The form of chlorine available as residual after break point is entirely free available chlorine and under controlled conditions of pH it may be entirely available as HOCL (and not as OCI because at lower pH values, the ionization of HOCl will be minimum).Which is the most efficient as bactericide, the chloramines and OCl being poor in action as disinfectants. The break point chlorination therefore achieves: a) Complete oxidation of ammonia and other compound b) Destruction of tastes and odors of biological and chemical nature c) Removal of Color due to organic matter. d) Removal of Manganese e) Improved bacteriological quality of water and destruction of virus infection.

PROCEDURE A number of sample bottles are taken and to each of them water sample (containing NH3 and its derivatives) in equal quantity, say 100 ml is put. to those sample are added at 5 minutes interval one by one gradual increasing does of Cl solution from a stock solution of chlorine of known strength. Residual chlorine is tested in each bottle after a contact time of 10 minutes by means of O.T. reagent and comparators.

OBSERVATIONS Strength of chlorine stock solution = --------------- ppm. Therefore 0.1 ml

contains = ----------- ppm --------- ml added to 1.00 ml contributes ------ ppm chlorine.

Sample No. 1

ml of Cl2

Solution added

Dose of Cl2 in ppm 4

Residual chlorine after 10 minutes 5

CALCULATIONS

CONCLUSION AND RESULT

SIGNIFICANCE

EXPERIMENT NO. 17 CHEMICAL OXYGEN DEMOND OBJECT To determine the chemical oxygen demand of a given sample of sewage. APPARATUS Pipette, Burette, Conical flasks, Condenser, Hot plate. REAGENTS K2Cr2O7 solution, Conc. H2SO4 , Ferrous ammonium sulphate, Ferrous indicator, distilled water etc. THEORY

Chemical Oxygen Demand (C.O.D.) is also referred to as the Dichromate oxygen consumed. The C.O.D. test is quick method of estimating the approximate amount of organic matter in sewage and industrial wastes. In C.O.D. determination, the organic matter is oxidized by dichromate in the presence of sulphuric acid. A catalyst such as Silver sulphate is used to help the oxidation of the organic matter. The excess of dichromate is liberated by ferrous ammonium sulphate solution. It may be noted that C.O.D. values are not directly correlated with B.O.D. values.
PROCEDURE Take 50 ml of the sample on an aliquot diluted to 50 ml in a 300 ml round bottom flask with ground glass neck and fitted with a Friedriche reflux condenser. The amount of sample taken should have a C.O.D. less than 1,000 mg/ liter. Add 25 ml of 0.25 N K2Cr207 solution, and 7.5 ml of conc. H2SO4 .The acid should be added in small amounts carefully mixing after each addition. Add a few glass beads or pumice granules to the mixture to avoid bumping. Attach the flask to the condenser and reflux for 2 hours. For some industrial wastes, a shorter period of refluxing is sufficient. Cool and wash down the reflux condenser with 25 ml of distilled water. Transfer the content to a 500 ml. Erlenmeyer flask rinsing 4 or 5 times with distilled water. Dilute the mixture to about 350 ml with distilled water. Titrate with Ferrous ammonium sulphate solution using 2 to 3 drops of ferrous indicator. The colour change is from blush-green to reddish blue at the end point.

Carry out a blank determination using 50ml distilled water and the same volume of reagents. It may be necessary to used silver sulphate as catalyst for the complete oxidation of many organic compounds such as straight chain acids and alcohols. In such case, 1gm of Ag2SO4 crystals should be added directly to the mixture before refluxing. CALCULATION mg /lt. of C.O.D. = (X Y) x Normality of FeSO4 (NH4)2SO4 x 8000 ml.of sample Where , C.O.D. = Oxygen consumed from K2Cr2O7 X = ml. of FeSO4 (NH4)2 SO4 Y = ml. of FeSO4 (NH4)2 SO4 When Silver sulphate is not used, the chloride contents of the sample have to be determined and correction applied as follows: Chloride correction = mg / liter chloride x 0.23

REACTION Organic Matter + K2Cr207 Conc. H2SO4 ------------> CO2 + H20

OBSERVATION

S.No. 1. 2.

Sample Blank Sample

Volume of Sample

F.B.R.

Vol. of SO4

FeSO4 (NH4)2

RESULTS The C.O.D. of given sample is found to be mg/l as O2.

CONCLUSION

SIGNIFICANCE This test is a measure of oxygen present in organic matter in sewage. It is useful in identifying the performance of various steps of treatment plants. It is also useful in determining the strength of industrial waste in sewage which can't be determined by B.O.D. test. This test has advantage of being fast & less time consuming.

EXPERIMENT No.18 BIOCHEMICAL OXYGEN DEMAND OBJECT

To determine the biochemical oxygen demand of the given sample of sewage.


APPARATUS

B.O.D. incubator, Burette, Pipette, and Flasks.


REAGENTS Manganese sulphate solution, Alkaline azide iodide solution, Concentrated sulphuric acid, N/40 Sodium thiosulphate, starch solution, FeCl3, MgSO4, CaCl2, Na2CO3 and Phosphate buffer. THEORY

The biochemical oxygen demand may be defined as the amount of oxygen required by bacteria to stabilize organic matter under aerobic condition. The B.O.D. test is widely used to determine the pollution strength of the sewage, industrial waste etc. It is a test of prime importance in the evaluation of the purifying capacity of receiving bodies of water. It is a device test. It involves the measurement of the dissolved oxygen contents of a sample before and after a bioassay process in which living organism serve as a medium for the oxidation of organic matter to carbon-dioxide and water. It therefore is possible to interpret B.O.D. in terms of organic matter as well as the amount of oxygen used during its oxidation, under atmospheric conditions. Nitrogen is nearly twice as soluble in water as in oxygen. Most of the critical conditions related to dissolved oxygen deficiency in Sanitary Engineering practice occur in periods of high temperature. The kinetics of B.O.D. reaction indicate that they are first order reaction, in which the rate of the reaction is proportional to the amount if oxidisable organic matter remaining at any time as modified by population of active organisms.

This can be expressed in the form of an equations, thus Y = L (1 - 10-kt) , where Y = B.O.D. at any time and Y = (I 10-kt). Experiments have shown that a reasonably large % (68 -70) of the B.O.D. is exerted in the first five days incubation. The test is, therefore, carried out with incubation for five days. For samples having a very high B.O.D. value, dilution to appropriate value is essential. So that oxygen depletion of at least mg/l is the end of incubation period. The minimum D.O. in the sample bottle of the end of incubation period is 0.5 mg/l. PROCEDURE Take well aerated distilled water and to it add nutrients such as FeCl3, MgSO4, CaCl2, Na2CO3 and phosphate buffer in approximated quantity to serve as food for growth bacteria and for buffer action. Take three portions of sample of known volume and dilute in three B.O.D. bottles to obtain 0.5%, 1% and 2% of the sewage with aerated water containing nutrients also take one blank B.O.D.bottle containing aerated water. Keep all the four bottles in incubation at 200C for 5 days and determine the dissolved oxygen of sample and blank. OBSERVATION (A) For zero day S. Sampl N. e N/40 Sodium thiosulphate
Initial reading Final reading

Volum D.O. in ppm= e volume consumed

O2consumed=D.O. of Blank D.O.of diluted sample

1. 2. 3.

4.

OBSEVATION TABLE S.N. Sample N/40 Sodium Thiosulphate


Initial reading

(B) For 5days Volume D.O. in ppm = volume consumed


O2 consumed = D.O. of BlankD.O. of diluted sample

Final reading

1. 2. 3. 4.

CALCULATION BOD At 20 C in mg/lt. = O2 consumed / Dilution factor O2 consumed in 5th day in (1) (2) (3) RESULTS BOD for the Sample in 5 day at 200C is as following(1) (2) (3) 1% dilution = ..mg/lt as O2 2% dilution = mg/lt as O2 3% dilution = mg/lt as O2 1% Sample = = mg/lt as O2 2% Sample = 4.4 / 6/300 = mg/lt as O2 3% Sample = 6.2 / 9/300 = ..mg/lt as O2

COMMENTS B.O.D. (Biochemical Oxygen Demand) is the amount of oxygen required by micro-organism while stabilizing biologically decomposable organic matter in a waste under aerobic conditions. The BOD is always less than C.O.D. The interferences in the test are lack of acclimated seed organisms, presence of heavy metals RCl2. The standard condition is pH near to 7 nutrients supply absence of microbial growth inhibiting substance. REACTION Micro Organism ----------------------->

Organic Matter

+ O2

New cells + CO2 + H2O + Stable Products

( If O2 is not present ) Micro Organism -----------------------> Anaerobic

Dry Matter

New Cells + CO2 + H2O + CH4, H2S, NH3 (Unstable product which produced bed smell)

SIGNIFICANCE BOD test is used to determine: (1)Pollution load of waste water. (2)Degree of pollution in lakes and stream at any time and there self purification capacity. (3)Efficiency of waste water treatment methods.

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