Laboratory Manual For Waste-Water Analysis and Testing Water

CE-441 Environment Engineering Lab-II Lab-

Department of Civil Engineering

Maulana Azad National Institute of Technology

Bhopal-462007

INDEX

S.No. 1

Name of Experiment

Page No. 2

Determination of total, dissolved, volatile, and fixed residue in a sewage

Determination of turbidity

Estimation of pH

Estimation of chloride concentration

Determination of dissolved oxygen and percentage saturation

Determination of biochemical oxygen demand of waste water

12

Estimation of chemical oxygen demand

15

1. DETERMINATION OF TOTAL, SUSPENDED, DISSOLVED, VOLATILE AND FIXED RESIDUE IN A SEWAGE/WATER SAMPLE
The methods are gravimetric..Great care must be taken to obtain a representative sample .the quantity of sample to be taken depends on the amount of suspended matter. Water 100ml to 500 ml Sewage 50 ml to Water effluent 50 ml to 100 ml PROCEDURE (A) TOTAL RESIDUE Place the required quantity of the sample in a dry constant weight dish or crucible. Evaporate to dryness in an oven at 103*C-105*C and dry to constant weight. Cool the dish in a desicator. Weigh and note the increase in weight.
Total residue in mg/l =

(weight of crucible with residue - weight of empty crucible)1000 sample (in ml)

(B) total solids : volatile and fixed Ignite the residue obtained in (a) at 600 degree celcius in a muffle furnace (15 - 20 min), cool ad weigh. Total volatile residue in mg/l = (wt. of crucible with total residue wt. of empty crucible) ( wt. of crucible with residue heated to 600*c) mg 1000))/ Sample(in ml) Fixed residue mg/l = total residue - volatile residue
(c) Suspended and dissolved solids:

Filter the sample through whatman filter paper no 44 or 41. Take a suitamle quantity in a weighed dry dish/crucible/corning or pyrex beaker. Evaporate to dryness at 103*C -105*C . Cool container to a constant weight. Weigh and note the increase in weight.

3 Dissolved residue mg/l = (weight of crucible with reside weight of empty crucible)mg 1000/ sample(in ml) Suspended residue mg/l = total residue (a)-dissolved residue(c)

Sample details Source

Type residue volume

of Empty beaker

weight With residue Mg/l residue

Total residue volatile residue fixed residue dissolved residue Suspended residue

Remarks

2. DETERMINATION OF TURBIDITY

Four turbidimeters are commonly employed in measurements. Standard Jackson candle turbidimeter = 25 Baylis turbidimeter Heliges / Aplab turbidimeter Nephlometer / Hachs turbidimeter =0 =0 =1 1000 Units (J.T.U.) 2 Units (J.T.U.) 150 Units (J.T.U) 1000 N.T.U.

Standard Jackson Candle Turbidimeter

It consists of three parts: a calibrated glass tube, a holder and a candle (bees wax candle designed to burn within the limits of 114 to 125 grains/hour). The glass tube and the candle are supported in a vertical position so the centre line of the tube passes through the centre line of the candle. The top of the support of the candle must be 7.6 cm below the bottom of the glass tube. Pour the sample in the glass tube until the image in the glass tube disappears. Note the light path in cm (measure from inside bottom of the glass tube) and read in the table for turbidity units. For turbidity exceeding 1000 units dilute the sample with turbidity free water and proceed. Cm. 2.3 2.6 2.9 3.2 3.5 3.8 4.1 4.5 4.9 5.5 5.6 Turbidity 1000 900 800 700 650 600 550 500 450 400 390 Cm. 5.8 5.9 6.1 6.3 6.4 6.6 6.8 7.0 7.3 7.5 7.8 Turbidity 380 370 360 350 340 330 320 310 300 290 280 Cm. 8.1 8.4 8.7 9.1 9.5 9.9 10.3 10.8 11.4 12.5 12.7 Turbidity 270 260 250 240 230 220 210 200 190 180 170 Cm. 13.5 14.4 15.4 16.6 18.0 19.6 21.5 22.6 23.8 25.1 26.7 Turbidity 160 150 140 130 120 110 100 95 90 85 80 Cm. 28.1 29.8 31.8 34.1 36.7 39.8 43.5 48.1 54.0 61.8 72.9 Turbidity 75 70 65 60 55 50 45 40 35 30 25

Nephlometer
A turbidimeter consisting of a Nephlometer with a light source and one or more photoelectric detectors and a read out mechanism at right angles to the path of light. There are various commercial models available. Elico-Hach. The equipment is calibrated with commercially available hydrazine sulphate suspensions. Measurements are made directly up to 40 NTU. If the turbidity is more, the sample is diluted.

Calculation
NTU = A (B+C)/C where A = NTU of diluted sample B = Volume of dilution water, ml C = Sample of volume taken for dilution, ml.

Jacksons Turbidimeter
Sample details Source Observations Length path cm

Turbidity JTU

Hach/Heliges/Aplab turbidimeter/ Nephlometer

No. of bulb

Type of filter

Reading on scale

Turbidity

3. ESTIMATION OF pH
MATERIALS REQUIRED: Waste water and pH indicator THEORY: pH is the negative logarithm of hydrogen ion. For neutral water pH is 7 and acidic water pH is less than 7 and more than 7for basic water. Generally fresh sewage is alkaline in nature (pH>7) but as time passes its pH tends to fall due to production of acids by bacterial action in anaerobic and nitrification processes. The pH however rises upon the treatment of sewage. There are two general methods for determination of pH 1. Colorimetric method or use of indicators A number of pH indicators have been used. They are unreliable for measuring pH below 3 and above 10 2. Electrometric method A number of electrodes have been suggested for the electrometric method of pH measurement. The glass electrode is the standard electrode. PROCEDURE: Colorimetric method: 10 ml of the sample is placed in each of the tubes of the pH comparator The appropriate of PH indicator as indicated in the kit (0.3 ml of phenol red) is added to one of them It should be checked that the same indicator disc is fitted to the comparator The tube in the comparator is placed in such a way that the colour standards are opposite to the tube not containing the indicator The tube is compared with the colour standards and colour nearest to the sample The pH is noted. Electrometeric method: The pH meter is standardized by immersing the electrode in buffer solution of known pH normally 4 and 9.2 The pH is read and adjusted correctly with the control knob, till the meter needle indicates the correct value for the pH of the buffer solution The electrodes is rinsed in distilled water and immersed in the sample and the needle is settled at one point and pH value is read.

1. 2.

3. 4.

5. 6. 1.

2.

3.

sample details Colorimetric

Indicator

Observations Qty. of Colour indicator

Ph

Elecrometric

pH

Buffer used

4. ESTIMATION OF THE CHLORIDE CONCENTRATION

Chlorides occur in all natural waters varying concentrations. Upland and mountain streams are usually low in chloride concentration. Chlorides gain access in many ways viz solvent power of water dissolve salts from top soil. Spray from ocean, seas invading fresh waters during tides, underground formation and seepage, human excreta, industrial wastes etc. Reagents (i)Potassium chromate indicator (8) (ii)N/35.5 Silver nitrate solution (9) Procedure Take 100ml sample in two conical flasks. Add to both one drop of potassium chromate indicator. Titrate with standard N/35.5 AgNO3 solution in one and compare with other to distinguish change from yellow to brick red. Note the amount of titrant used. The first permanent change of color should be noted. Chlorides as Cl- = ml of AgnO3 used for sample X 1000 ml of sample The pH should be between 6-8 Chemical reactions XClAgNO3 Ag+ + Cl-2Ag+ + CrO4

X+ + ClAg+ + NO3AgCl Ag2CrO4

Data Sheet 4.7 Estimation of chloride concentration Sample details Observation Source Volume Initial Final burette ml AgNO3 burette reading Solution reading used

Chlorides Chlorides mg/l

Remarks: The chloride values are normally low in surface inland waters. Ground waters have comparatively higher values. Chlorides have sanitary significance in waters of low chloride values.

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5. DETERMINATION OF DISSOLVED OXYGEN AND PERCENTAGE SATURATION Dissolved oxygen vary in nature and waste waters to a large extent, from the state of no oxygen to saturation level. The saturation values change with temperature, pressure, altitude and chloride concentration. The test is very delicate for assessment of pollutional load.

Reagents

(i) Manganous sulfate solution (10) (ii) Alkaline potassium iodide (11) (iii) N/40 Sodium thiosulphate solution (12) (iv) Conc. Sulphuric acid (v) Starch indicator Procedure Alsterberg modification of Winklers method Find out the exact capacity of the bottle in ml. Collect the sample in a narrow mouth flat stoppered reagent bottle of approximate 300 ml capacity. It is always preferable to collect the sample through D.O sampler to avoid contact with air. The bottle should be completely filled. Add 1.0 ml manganous sulphate solution by a pipette, dipping the end blow the surface. Some water would overflow. Add 1.0ml alkaline potassium iodide solution. Insert the stopper and mix thoroughly. Let the precipitate settle. Add 2.0 ml conc. sulphuric acid. Dissolve the precipitate by vigorous shaking. Take the calculated amount of aliquot as calculated below:

200 x exact capacity of bottle = exact capacity of bottle -4

.ml

Titrate with N/40 sodium thiosulphate solution using starch as indicator. Record the ml titrant used. Calculations Since 1ml of N/40 Na2S2O3 = 0.2 mg oxygen, the ml of this solution used is equivalent to mg/litre of dissolved oxygen. Determine the temperature and chloride concentration and by reference to solubility table on the next page find out the saturation value. Calculate percent saturation.

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Chemical reactions MnSO4 Mn++ + SO4- Alk K K+ + I- + OHMn++ + 2OH- Mn(OH)2 White precipitate means oxygen absent Mn++ + 2OH- + 1/2O2 MnO2 + H2O Brown precipitate means oxygen present This is referred to as oxygen fixation. MnO2 + 4H+ + 2I IO2 + Mn++ + 2 H2O Released I2 + 2 Na2S2O3 Na2S4O6 + 2NaI Solubility table oxygen at various temperatures (pressure 760 mm) Temp Chloride mg/litre Chloride mg/litre Temp C 0 5000 Diff. per 100 C 0 5000 Diff. per 100 Mg/litre Mg/litre 0 14.62 13.79 0.0165 16 9.95 9.46 0.0098 1 14.23 13.41 0.0160 17 9.74 9.26 0.0095 2 13.84 13.05 0.0154 18 9.54 9.07 0.0092 3 13.48 12.72 0.0149 19 9.35 8.89 0.0089 4 13.13 12.41 0.0144 20 9.17 8.73 0.0088 5 12.80 12.09 0.0140 21 8.99 8.57 0.0086 6 12.48 11.79 0.0135 22 8.83 8.42 0.0084 7 12.17 11.51 0.0130 23 8.68 8.22 0.0083 8 11.87 11.24 0.0125 24 8.53 8.12 0.0082 9 11.59 10.97 0.0121 25 8.38 7.96 0.0081 10 11.33 10.73 0.0118 26 8.22 7.81 0.0080 11 11.08 10.49 0.0114 27 8.07 7.67 0.0079 12 10.83 10.28 0.0110 28 7.92 7.53 0.0078 13 10.60 10.05 0.0107 29 7.77 7.39 0.0076 14 10.37 9.85 0.0104 30 7.63 7.25 0.0074 15 10.15 9.65 0.0100 -

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Sample details Source Temp

Capacity of Bottle

Volume Titrated

Initial burette Reading

Observations ml n/40 Final burette Na2S2O3used reading

Dissolved Oxygen mg/l

Remarks: Dissolved oxygen is one parameter which indicates the health of a stream. More oxygen better is the health (except when blooming with algae).

6.DETERMINATION OF BIOCHEMICAL OXYGEN DEMAND

(BOD) OF WASTE WATER

The biochemichal oxygen demand (BOD) is the amount required by bacteria while stabilizing decomposable organic matter under aerobic conditions. The quantity of oxygen required may be taken as a measure of its content of decomposable organic matter. The rate of BOD exertion is governed by the characteristics of its sewage, its decomposable organic content, bacterial population and its temperature. The progressive BOD exertion takes place in two stages

a. Carbonaceous b. Nitrification

It has been observed that a large percentage of the total BOD is exerted is 5 days at 20 degrees Celsius. The value of 5 days at 20 deg celcius is to a reasonable extent comparable to 4 days at 30 deg celcius and at 35 deg celcius. The first stage BOD reaction is represented as:

Y=L(1-10^(-kt)) Where Y=BOD at any time L=ultimate BOD K=reaction rate T=time, days Reagents 1)Phosphate buffer 2)Magnesium sulphate solution 3)Calcium chloride solution 4)Ferric chloride solution 13 14 15 16

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5)Manganous sulphate solution 6)Alkaline potassium iodide solution 7)N/40 sodium thiosulphate solution 8)Conc. Sulphuric acid 9)starch indicator 10 11 12

BOD measurable with different various dilutions Range of BOD 200-700 100-350 40-140 20-70 10-35 4-40 %Mixture 1.00 2.00 5.00 10.00 20.00 50.00

Procedure: Preapare dilution water by adding 1.0 ml of phosphate buffer solution, magnesium sulphate solution, calcium chloride solution and ferric chloride solution to 1.0 litre of distilled water. Add 2.0 ml settled sewage and aerate. .Determine the exact capacity of three BOD bottles. Find out the DO of undiluted sample as in 4.8 and designate Dos

Prepare the desired percent mixture by adding sample in dilution water. Fill up one bottle with the mixture and the other one with dilution water blank. Incubate at a fixed temperature for a definite time(20 deg celcius,5 days:30 deg celcius,4 days and 35 deg celcius,3 days).Find out DO in both the bottles after incubation and designate: Mixture as (DOi) Blank(DOb) Calculations BOD mg/l=[(DOb- DOi) 100%-(DOi- DOs)]

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Sample details

%mixture

DO3

DO2

DO1

BOD

mg/l

Data sheet 4.9 Determination of BOD

Remarks: The sensitivity of test is dependent on the type of seed used. It is advisable to use settled and acclimatized at 20 deg celcius seed. Checking also is possible by using a synthetic sample mixture(mixture of glucose and glutamic acid, in equal amounts).1 mg of glucose would be approximately equal to 1 mg TOD or 0.8 of BOD.

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7.ESTIMATION OF CHEMICAL OXYGEN DEMAND

COD test is widely used for measuring the pollution strength of waste waters. All aoganic compounds with few exceptions can be oxidized to carbon dioxide and water by the action of strong oxidizing agents regardless of biological assimilability of subsantances. Reagents (1)standard potassium dichromate 0.25N (17) (2)Sulphuric acid (with 1 gm of silver sulphate in every 0.75 ml acid (3)Ferroin indicator solution (18) (4)Standard ferrous ammonium sulphate solution (19)

Standardization procedure Dilute 25 ml standard potassium dichromate solution 250ml with distilled water. Add 20ml conc Sulphuric acid. Titrate with ferrous ammonium sulphate using Ferroin indicator to red end point. Normality of FeSO4(NH4)2 SO4 = ml of K2Cr2O70.25/ml of FeSO4(NH4)2 SO4 Procedure The procedures are either through open reflux or closed treatment Open reflux method Take 50ml sample or a smaller amount diluted to 50.0ml in a refluxing flask, add boiling chips and 1gm HgSO4. Cool the mixture. Add 0.25ml of 0.25N K2Cr2O7 solution and mix again. Attach the condenser and start cooling water. Add remaining acid (70ml) through the open end of the condenser, mix the reflux mixture. Apply heat and reflux the mixture for two hour cool Dilute the mixture to about 300ml and titrate excess of dichromate with Standard ferrous ammonium sulphate solution using Ferroin indicator. The colour will change from yellow to green blue and finally red. Record the ml of titrant used. Reflux in the same manner a blank consisting of distilled water, equal to the volume of the sample and the reagents. Titrate the sample. Record the ml of titrant used. Closed reflux method Place 5ml or fraction diluted to 100ml of sample with distilled water in hard glass bottle and add 25ml standard potassium dichromate solution. Carefully add 75ml conc sulphuric acid mixing after each addition. Digest the mixture in pressure cooker or autoclave for 30min. repeat the procedure with 100ml distilled water and same reagent. Transfer the contents to 500ml conical flask. Dilute the mixture to 350ml. titrate excess of dichromate with Standard ferrous ammonium sulphate solution using Ferroin indicator. The end point is red.

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Table reagents quantities and normality for various sample sizes

Sample 0.25N size(ml) K2Cr2O7 (ml) 10 5 20 10 30 15 40 20 50 25

Conc. H2SO4. with AgSO4.ml 15 30 45 60 75

HgSO4. Normality of ML FeSO4(NH4)2 SO4 0.2 0.05 0.4 0.1 0.6 0.15 0.8 0.20 1.0 0.25

Final vol before titration ml 70 140 210 280 350

Calculation COD (mg/l)= (A-B)C8000/ml of sample Where A = ml of FeSO4(NH4)2 SO4 for blank. B = ml of FeSO4(NH4)2 SO4 for sample C = Normality of FeSO4(NH4)2 SO4 solutions determined above. Data sheet for estimation of of COD Sample detail Sample source Normality of K2Cr2O7 Amount of K2Cr2O7 Added Normality of FeSO4(NH4)2 SO4 Ml of FeSO4(NH4)2 SO4 COD (MG/L)