CHHATRAPATI SHIVAJI MAHARAJ

INSTITUTE OF TECHNOLOGY

ENVIRONMENTAL ENGINEERING
LABORATORY MANUAL
DEPARTMENT OF CIVIL ENGINEERING
SEM VI
 CONTENT

Sr. No Name of the Experiment

1 Determination Of pH of Sewage

2 Solid waste: Determination of pH

3 Solid waste: Determination of Moisture Content

4 Determination of Total Solid, Suspended solids, dissolved Solids &

Volatile Solids

5 Determination of Dissolved Oxygen

6 Determination of Chlorides

7 Determination of Chemical Oxygen Demand of Sewage sample

8 Determination of Bio Chemical Oxygen Demand of Sewage sample

1. Sampling
The objective of sampling is to collect a portion of water which is small enough in volume
to be transported conveniently and handled in the laboratory while still representative of the
characteristics of the water available in that water body. Water is a dynamic system .Its
constituents vary with time
1.1. Planning of Sampling
Ask yourself the purpose of study (?), what data are needed (?) and then select most
suitable location that can provide the required information.
Site location for river
 Upstream of the industrial and domestic discharge points
 Immediately downstream of industrial and domestic discharge points.
 At a place of abstraction for industrial use and public water supply.
 Base line stations where water is available in natural state.
1.2. Types of Samples

 Grab Samples
 Composite Samples
 Integrated Samples
Grab Samples
A sample collected at a particular time and place can represent only the composition of the
source at that time and place. It shows only the prevailing conditions at the time of sampling
and does not represent the average conditions.
Sampling of water from sources such as wells, rivers, streams, lakes, oceans and reservoir
for chemical, physical and bacteriological analysis.

 When a source is known to be constant over a considerable time period, in that case a
single grab sample should be considered as representative.
 If the sources are known to vary with time, grab sample should be collected at suitable
intervals of time and analyzed separately.
 The results can be documented in terms of mean, standard deviation, frequency, and
duration of variations. When the source composition varies in space (in different
locations), collect samples from appropriate locations.

Composite Samples
The term composite refers to a mixture of grab samples collected at the same sampling point
at different times. A composite sample of 24 h period is considered standard for most of the
determination. It provides more meaningful data than the grab samples.
Sometimes a composite sample representing one shift or a shorter time period ora complete
cycle of a period operation may be preferable.
Take at least 120-150mL of sample in each h, in some cases even at intervals of30 min (if
composition varies within an hour) and mix at the end of sampling period or combine in a single
bottle as collected
Integrated Samples
They represent the mixture of grab samples collected from different points simultaneously
and mixed in equal volumes.
 Such samples are useful for rivers or streams that vary in composition across the width
anddepth.Forcollectionofintegratedsamples,specialsamplingdeviceisneeded.
 Sample is collected at a known depth without disturbing the surface water.
1.3. Sample Container
The sampling bottle may be made of either glass or plastic, usually polyethylene. It must
be capable of being tightly sealed either by stopper or cap.

 The bottles should be soaked with 10% HCI for 24 h and then thoroughly cleaned and
rinsed with distilled water.
 Cleaning solution; acid dichromate: Prepare a saturated water solution of potassium
dichromate (K2Cr2O7). Add 32 mL of this K2Cr2O7 solution in 1L of concentrated
H2SO4 (sp. gr.1.84).
1.4. Sample Collection

 Wherever possible, the container should be rinsed 2 to 3 times with the sample to be
examined.
 Sample where water is well mixed.
 Avoid large non-homogeneous matter such as leaves, rags, twigs and other floating
material in the sample.
 Provide complete information about the source and the conditions under which the
sample was collected.
 Sample preferably at 20cm depth in a shallow channel (Fig.1). Depths > 60 cm collect 2
samples at 20% and 80% below the surface.
 Sampling from dug wells and similar sources: Prepare the sampling device bottle with
the help of a string and attach a weight at the bottom(Fig.2).
Fig. 1: Collecting a Sample
from surface water
1.5. Transportation of Sample

Sample containing bottles should be placed in a box for transportation to the laboratory.
Sturdy, insulated wooden or plastic boxes will protect samples from sunlight, prevent the
breakage of bottles and should allow a temperature of 4°C to be maintained during transport.

1.6. Labeling of Container

Each sampling bottle must be provided with an identification label on which the following
information is legibly and indelibly written (Given below Table).

A Typical Label-Sheet of Container

1. Name of Study :
Sample No./Sample Station:
2. identification No.
:
3. Source/location of sampling point

4. Date and time of collection :

5. Volume of sample :

6. Nature of collection : Grab/Composite sample

7. Given any preservative : Yes/No

8. Purpose of analysis : Drinking water/Effluent discharge

: Temperature, pH, DO, or any other
9. Field measured parameters parameters
Purpose of sampling (please tick :
10.
which is applicable)
Sample to be refrigerated and used :
11
for general analysis.
.
Sample to be used for heavy metals :
12.
analysis
Sample to be refrigerated and used :
13.
 for bacteriological analysis.
Brief details of weather any unusual :
14.
condition was prevailing at the time
of sampling.
:
15. Name of the person and signature

Safety Rules & Experiment Instruction

1. Do not add water to concentrated acid. A concentrated acid should be added carefully to
water.

2. Do not handle chemicals with bare hands.

3. Do not blowout the last drop from the pipette when the liquid is drained out completely
.Touch the tip of pipette to the inner surface of the vessel.

4. Read the level of the curve (Miniscus) in all volumetric glass coarse with the eye
approximately the same level as the curve of the solution.

5. Clean all the apparatus used with distilled water before and after the experiment.

Techniques in Preparation Solution:

Normality (N): The number of gram equivalent weight of substance dissolved in 1

literofwateriscalledNormality.ForExample:ThegramequivalentweightofHClis

36.5 grams. So, if 36.5 grams of HClis added to 1 liter of water, it gives a solution of 1N.
Similarly for oxalic acid = 90/2 = 45 grams in 1 liter of water, it gives a solutionof1N.

Molarity (M): The number of gram molecular weight of the substance dissolved in 1 liter of
water is called Molarity. For Example: The gram molecular weight of oxalic acid is 90 grams. If
90 grams of Oxalic acid is dissolved in 1 liter of waterit is called1 molar solution.(1M)

Molality: The number of gram moles of substance dissolved in 1 Kg (1000 grams) of the
solvent. For Example: If 40 grams of NaOH (Molecular weight = 40) of Sodium hydroxide is
dissolved in 1 Kg of water, the molarity of the solution is 1.
Percent by weight: To make up a solution based on percentage by weight, one would simply
determine what percentage was desired.

As an example, let's consider a 12% by weight sodium chloride solution. Such asolution would
have 12 grams of sodium chloride for every 100 grams of solution. To make such a solution, you
could weigh out 12 grams of sodium chloride, and then add 88 grams of water, so that the total
mass for the solution is 100 grams. Since mass (unlike volume) is conserved, the masses of the
components of the solution, the solute and the solvent, will add up to the total mass of the
solution

Percent by volume: Solutions based on percent by volume are calculated the same as for
percent by weight, except that calculations are based on volume. Thus one would simply
determine what percentage was desired

For example, rubbing alcohol is generally 70% by volume isopropyl alcohol. That means that
100 mL of solution contains 70 mL of isopropyl alcohol. That also means that a liter (or 1000
ml) of this solution has 700 mL of isopropyl alcohol plus enough water to bring it up a total
volume of 1 liter, or 1000 mL

Percent by weight/volume: Another variation on percentage concentration is weight/volume

percent or mass/volume percent. This variation measures the amount of solute in grams but
measures the amount of solution in milliliters.

An example would be a 5% (w/v) NaCl solution. It contains 5 gm of NaCl for every100 mL

ofsolution.

Dilution: Dilution is the mixing of a small accurately measured sample with a large volume of sterile
water or normal saline called (diluents or dilution blank).
 Experiment 1

Aim : Determination Of pH of Sewage

Theory: pH of aqueous solutions can be defined as negative logarithm of hydrogen ion

concentration. pH values ranging from 0 to 7 are acidic, and from 7 to 14 are alkaline. The
effect of pH on the chemical and biological properties of liquids makes its determination
very important. It is used in several calculations in analytical work. The pH determinationis
usually done by electrometric method which is the most accurate method and free of
interference.
Environmental Significance:
Determination of pH is one of the important objectives in biological treatment of the
wastewater. In anaerobic treatment, if the pH goes below 5 due to excess accumulation of
acids, the process is severely affected. Shifting of pH beyond 5 to 10 upsets the aerobic
treatment of the wastewater. In these circumstances, the pH is generally adjusted by addition
of suitable acid or alkali to optimize the treatment of the wastewater. pH value or range is of
immense importance for any chemical reaction. A chemical shall be highly effective at a
particular pH. Chemical coagulation, disinfection, water softening and corrosion control are
governed by pH adjustment.
Dewatering of sludges, oxidation of cynides and reduction of hexavalent chromium into
trivalent chromium also need a favorable pH range. It is used in the calculation of carbonate,
bicarbonate, CO2 corrosion, stability index and acid base equilibrium.
Lower value of pH below 4 will produce sour taste and higher value above 8.5 a bittertaste.
Higher values of pH hasten the scale formation in water heating apparatus and also reduce
the germicidal potencial of chlorine. High pH induces the formation of trihalomethanes,
which arecausing cancer in human beings.

Standard: pH of drinking water should be between 6.5 and 8.5

Requirements: pH Meter, Flask, Magnetic Stirrer, Funnel, Beaker, Wash Bottle

Electrometric Method:
The pH is determined by measurement of the electromotive force of a cell comprising an
indicator electrode (an electrode responsive to hydrogen ions such as glass electrode)
immersed in the test solution and a reference electrode or a combined electrode. The contact
between the test solution and the reference electrode is usually achieved by means of a
liquid junction. The emf of this cell is measured with pH meter. This is a high impedance
electrometer calibrated in terms ofpH.

Reagents: Calibrates the electrode system against standard buffer solution of known pH.
Buffer tablets having pH 4.0, 7.0 and 9.2 are available.
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Reagents:

pH4,pH7,pH9.2BufferSolutions:DissolvebuffertabletofpH4in100mlofdistilled
water to get pH 4 buffer solution. Similarly other buffer solutions can be
prepared by dissolving corresponding buffertablets.

Procedure:

1. Prepare buffers of pH 4, 7 and9.2.

2. Rinse the electrode thoroughly with distilled water.
3. Standardize pH meter electrode with any two of these buffers.
4. Dip the electrode in the sample for test.
5. Letthereadingonscreenstabilize;noteitaspH&temperatureofyoursample.

Results:

Sr. No. Sample pH Temperature (°C)

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Experiment 2

AIM: To determine the pH of the solid waste sample using pH electrode.

MATERIALS REQUIRED: Buffer solutions of pH 4.0 and pH 7.0, beaker, pH meter, distilled
water, dried solid waste sample.

THEORY: The pH of solid waste is of much importance while disposing solid waste an
aerobically. The pH value of the digester content is an important indicator of the performance
and the stability of an anaerobic digester. In a well-balanced anaerobic digestion process, almost
all products of a metabolic stage are continuously converted into the next breaking down product
without any significant accumulation of intermediary products such as different fatty acids
which would cause a pH drop.

Many aspects of the complex microbial metabolism are greatly influenced by pH variations in
the digester. Although acceptable enzymatic activity of acid forming bacteria can occur at pH
5.0, methanogenesis proceeds only at a high rate the pH is maintained in the neutral range. Most
anaerobic bacteria including methane forming bacteria function in a pH range Of 6.5 to 7.5, but
optimally at a pH Of 6.8 to 7.6, and the rate of methane production may decrease if the pH is
lower than 6.3 or higher than 7.8.

PROCEDURE:

A) SAMPLE PREPARATION
1. 20 g of solid waste was weighed and transferred into 100 mL beaker.
2. 40 mL distilled water was added and stirred well with a glass rod.
3. This was allowed to stand for half an hour with intermittent stirring.
4. Collect the supernatant to measure the pH.

B) pH MEASUREMENT

I) CALIBRATION OF ELECTRODE

1. Dip the combined electrode in a 7 pH buffer solution.

2. Set the “TEMPERATURE C” at to the temperature of the selected buffer
solution.
3. Set the function selector switch to pH position and adjust “CALIBRATE” control
until the meter displays the precise pH value of the buffer solution.
4. Now set the Function Select or Switch to STAND BY.
5. Remove the electrode from the buffer solution, wash with distilled water.
6. Dip the combined electrode into another buffer solution (say 4 pH value).
7. Set the “TEMPERATURE C” control to the buffer solution Temperature.
8. Set the Function Selector Switch to pH position. Adjust the "SLOPE" Correction
Controls until the meter displays the pH value of the selected buffer solution,
Check that the correct readings are obtained with both solutions without further
adjustment.

II) pH MASUREMENTS
Dip the combined electrode in a suitable buffer solution.
Set the "TEMPERATURE C” Control to the buffer solution Temperature.
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Set the Function Selector Switch to the pH position and adjust the
“CALIBRATE” control until the meter displays the pH value of the buffer
solution.
Return the function Selector Switch to the STANDBY position. It is a good
practice to do this between measurements.
Remove the electrode from the buffer solutions wash with distilled water, and
immerse in the solution under test.
Set the “TEMPERATURE C” Control to the temperature of the test solution.
Set the function selector switch to the pH position. The meter wilt display pH
value of the test solution.

RESULTS: The pH of given samples

Experiment 3
 Page 4
AIM :To estimate the overall moisture content of the solid waste.

APPARATUS:

 oven
 analytical balance
 pre-weighed dish
SAMPLE:

domestic waste (food waste)

INTRODUCTION:

A man or a woman ceases to generate waste only when he or she is in a state to be disposed off
as waste. Solid wastes are all the waste arising from human and animal activities that are
normally solid and are discarded as useless or unwanted. It encompasses the heterogeneous mass
of throwaways residence and commercial activities as well as the more homogeneous
accumulations of single industrial activities. They are generated by almost every activities and
the amount varies by source, season, geography and time.The management and control of wastes
at all stages of production, collection, transportation, treatment and ultimate disposal is a
relatively social imperative.

Moisture content is defined as the percentage of water in a product or object. Moisture in

some form and amount is found in almost everything and can have different effects on the
object. In some cases, moisture is good, but in others, it can cause problems.The moisture
content of solid waste is expressed as the mass of moisture per unit mass of water or dry
materials. The moisture content which results from oven drying method depends on the type of
foodstuff used. The determination of moisture in a food is done for many purposes
such assessment of quality, quality control, quality assurance, detection and
estimation of adulteration, conformity with food standards and other statutory requirement,
calculation of total food solids content, assessment of stability, shelf life and storage life. The
shelf life of the product depends on water activity. Moisture can be determined by
using following methods, Thermal Drying method; D r y i n g e i t h e r h o t a i r o v e n a t
105°C in 2-3 hours or in vacuum ovens which is widely used for sugar
b a s e d f o o d s . T h e m e a s u r e m e n t o f t h e w e i g h t l o s s w h i c h results due to the
evaporation of H2O at or near boiling point is taken here. The loss in weight depend on the
particle size, weight of the sample used, type of the dish and temperature variation in
the ovens. Next is, chemical assay. This is based on the non-stoichiometric reaction of water.
Lastly, physical method It involves physical and physicochemical reaction in food. O v e n
 Page 5
drying method is widely used. The weight loss due to the removal of
w a t e r b y heating under specific conditions is considered here. The loss of weight due to
drying is considered as a measure of the moisture content of the sample.

PROCEDURE :

1. The sample waste was placed in pre-weighed dish by separating each type of wastes.
2. The sample/wet weight was weighed.
3. The sample was dried in an oven at 105°C to a constant weight.
4. After cool at room temperature, the dry waste was weighed again.
5. The moisture content are calculated.
Domestic Waste Mass of pre-weighed dish + Mass of pre-weighed dish +
wet waste (g) dry waste (g)

Food Waste 72.900 65.070

RESULTS :

CALCULATIONS :

M=[( w - d ) / w] × 100

M: moisture content (%)

w: initial weight (wet weight),g

d: weight of sample after drying at 105°C,g

DISCUSSION:

With oven drying, the sample is heated under specified conditions, and the loss of weight is used
to calculate the moisture content of the sample. Water is removed due to heating at 105 °C.
Loss of weight due to vaporization of water is taken as weight of moisture. In
principle, the moisture content of a sample can therefore be determined accurately by measuring
the number or mass of water molecules present in a known mass of sample. It is not possible to
 Page 6
directly measure the number of water molecules present in a sample because of the huge number
of molecules involved. A number of analytical techniques commonly used to determine the
moisture content of sample are based on determinations of the mass of water present in a known
mass of sample. The accuracy of results of moisture determination is affected by,
drying temperature, relative humidity, particle size of sample, handling method of sample,
amount of sample ,type of evaporation dish, variation in temperature inside the oven.
To minimize these errors various precautions should be taken. The rate and extent of
moisture removal depends on the size and shape of the sample, and how finely it is ground. The
greater the surface area of material exposed to the environment, the faster the rate of moisture
removal. If the temperature of drying is too high, or the drying is carried out for too long, there
may be decomposition of some of the heat-sensitive components. This will cause a change in the
mass of the sample matrix and lead to errors in the moisture content determination. It is therefore
normally necessary to use a compromise time and temperature, which are sufficient to remove
most of the moisture, but not too long to cause significant thermal decomposition of the sample
matrix.

CONCLUSION :From the experiment ,it can be deduced that food waste has the highest
moisture content while plastics has the lowest moisture content. The overall moisture content for
the solid waste can be calculated.
 Page 7
Experiment 4

Aim: To determine the total solid and total suspended solid in water samples
RELATED TEXT TOPICS
Discussion on total solid, total suspended solid and volatile suspended solid in a water samples
INTRODUCTION
All matter except the water contained in liquid materials is classified as solid matters. The solid
content of water is one of the most significant parameters. It is used in the design of water
treatment plant.
Total solid
The most important physical parameter of water is total solids content. The total solids content is
composed of floating material, settleable matter, colloidal matter and mater in solution. Total
solid content are the residue remaining after a water sample has been evaporated and dried at a
specified temperature (103 to 105οC)
Total suspended solid
Solids suspended in water may consist of inorganic and organic particles or of immiscible
liquids. A suspended solid are objectionable in water as it is aesthetically displeasing and
provides sites chemical and biological agents. Most suspended solids can be removed from
water by filtration. Portion of the total solids retained on the filter with a specified pore size
(1.58µm), measured after being dried at 105οC
Total Volatile Suspended Solid
Total volatile solids are those solids that can be volatilized and burned off when the TSS are
ignited at 500 ± 50οC.
EXPERIMENTAL PROCEDURE
List of glassware/apparatus
1. Evaporating dish
2. Measuring cylinder , 10 ml
3. Oven
4. Dessicator
5. Etc.
Sample Handling and Preservation
1. Use resistant glass or plastic bottles provided that the material in suspension does not
adhere to container walls
2. Begin analysis as soon as possible.
3. Refrigerate sample at 4οC up to the time of analysis to minimize microbiological
decomposition of solids.
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4. Preferably, do not hold samples without analysis more than 24 h.
Procedure:
You will make measurements of total solids andtotal suspended solids from two river water
samples. Work in groups. After you are done, compare your results with others. This will give
you a check of your precision.
Total Solids
1. Put 30 ml of sample into a tared porcelain weighing dish that has been cleaned and dried.
2. Evaporate the majority of the water on the steam table (this usually takes over an hour);
3. Complete evaporation to dryness in the oven at 103oC.
4. Cool in the desiccators and weigh.
5. The difference in weight from the tare weight represents the amount of total solids.
Suspended Solids
1. Prewash the filters by filtering about 50 ml of distilled water through the filters, drying
them in the 103 oC oven for at least one hour, and cooling them in a dessicator.
2. After cooled, filter as much of a known quantity of the sample as can be easily filtered
through a prewashed and dried tared glass microfibre filter. (Too small a sample size
will result in loss of precision - do not predetermine your sample size before you
start filtering.)
3. Use a clean filter flask and save water for dissolved solids analysis (described below).
4. Dry filter for 1 hour at 103oC.
5. Cool in desiccator and weigh.
6. Perform procedure in triplicate
7. The difference in weight is the weight of suspended solids. Remember to report your
results in units of mg/l.
 For total suspended solid, please use the procedure according to the lab experiment
that you have done yesterday.
Total Volatile Solids
1. Dry the porcelain dish further at 500oC for 1 hour in the muffle furnace.
2. After drying, cool in the dessicator and weigh.
3. The amount of weight lost corresponds to material lost by volatilization, roughly
comprising the organic fraction.
Dissolved Solids
1 i) Take 100 ml filtrate from suspended solids procedure.
2 ii) Dry first on evaporating dish, then in 103oC oven. - Cool and weigh.
3 iii) Difference in weight is weight of dissolved solids.
 Page 9
 Total volatile solid and dissolved solid mentions above are just for your
information. No need to put in your lab report.

Experiment 5

Aim: To determine chloride ion concentration in a water sample.

 Page
Theory: Chloride in the form of chloride (Cl) ion is one of the major inorganic anions in
10 water

and wastewater. The chloride concentration is higher in wastewater than in raw water because
sodium chloride is a common article of diet and passes unchanged through the digestive system
(Average estimate of excretion: 6 g of chlorides/person/day; additional chloride burden due to
human consumption on wastewater: 15 mg/L). Along the sea coast chloride may be present in
high concentration because of leakage of salt water into the sewage system. It also may be
increased by industrial process. In potable water, the salty taste produced by chloride
concentration is variable and depends on the chemical composition of water. Some waters
containing 250 mg/L Cl may have a detectable salty taste if sodium cation is present. On the
other hand, the typical salty taste may be absent in waters containing as much as 1000 mg/L
when the predominant cations are calcium and magnesium. In addition, a high chloride contents
may harm metallic pipes and structures as well as growing plants.

The measured chloride ions can be used to know salinity of different water sources. For brackish
water (or sea water or industrial brine solution), it is an important parameter and indicates the
extent of desalting of apparatus required. It also interferes with COD determination and thus it
requires a correction to be made on the basis of amount present or else a complexing agent, such
as HgSO4 can be added. Further, chloride ions are used as tracer ions in column studies to model
fate of different contaminants in soil and liquid media.

Procedure: The Mohr Method uses silver nitrate for titration (normality: 0.0141) (method
applicability: 0.15 to 10 mg/L chloride ions). This corresponds to 1 mL of 0.0141 equals to 1 mg
chloride in solution. The silver nitrate solution is standardized against standard chloride solution,
prepared from sodium chloride (NaCl). During the titration, chloride ion is precipitated as white
silver chloride (Eq.1): Ag+ +Cl<=>AgCl (Solubility product constant, Ksp=3×10-10) (1) the
indicator (potassium chromate) is added to visualize the endpoint, demonstrating presence of
excess silver ions. In the presence of excess silver ions, solubility product of silver chromate
exceeded and it forms a reddish-brown precipitate (Eq.2). This stage is taken as evidence that all
chloride ions have been consumed and only excess silver ions have reacted with chromate ions:
2Ag+ +CrO42-<=> Ag2CrO4 (Ksp=5×10-12) (1)

Apparatus: Burette, conical flask, pipette, measuring cylinder Reagents: Potassium chromate
indicator solution, standard silver nitrate titrant. 19 Steps:

1. Take 25 ml sample in a conical flask. Measure sample pH.

2. Add 1.0ml indicator solution,

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3. Titrate with standard silver nitrate solution to pinkish yellow end point and note down11
volume
of titrant used. Also measure sample pH.

4. Calculate chloride ion concentration using

Eq.(3): Chloride Ion Concentration (mg/L) = (A×N ×35.45)*1000 / V sample (3) Where: A =
volume of titrant used, N is normality of silver nitrate (here we used N/71 or 0.0141 N), and
Vsample is volume of sample used (mL).

Result- The concentration of Chloride ion in Given Water Sample is _____________mg/L

Experiment 6

Aim: Determination of Dissolved oxygen

Theory

All gases of the atmosphere are soluble in water to some degree. Oxygen is classified as poorly
soluble, and its solubility is affected both by atmospheric pressure, and physical and chemical
properties of water such as temperature, salinity, pollutants, etc. The solubility of atmospheric
oxygen in fresh waters ranges from 14.6 mg/L at 0o C to about 7 mg/L at 35o C under 1 atm. of
pressure. Most of the critical conditions related to dissolved-oxygen deficiency, both in natural
waters and biological wastewater treatment, occur during the warmer months when temperatures
are high and solubility of oxygen is at a minimum. The low solubility of oxygen is a major factor
 Page
limiting the purification capacity of natural waters. In aerobic biological treatment processes,
12 the

limited solubility of oxygen is also of great importance, because it governs the rate at which
oxygen will be absorbed by the medium and therefore the cost of aeration. Hence, DO analysis
is a key test both in natural waters and water pollution control practice.

Equipment

The use of DO probes or electrodes which allow in-situ measurements to be made has become
standard practice in recent years. They are especially useful for taking DO profiles of reservoirs
and streams, for monitoring DO levels in aerobic biological wastewater treatment processes, and
for conducting BOD analyses. An inert metal such as gold or platinum serves as the cathode, and
silver is used for the anode. These are electrically connected with a potassium chloride solution,
and the cell is separated from the sample by means of a gas-permeable membrane, usually
polyethylene. The membrane shields the cathode and anode from contamination by interfering
liquids and solids. When a potential of about 0.5 to 0.8 volt is applied across the anode and
cathode, any oxygen which passes through the membrane will be reduced at the cathode, causing
a current to flow. The magnitude of the current produced is proportional to the amount of
oxygen in the sample. Dissolved-oxygen electrodes are very sensitive to temperature, and thus
either temperature measurements must be made along with dissolved-oxygen measurements so
that a correction can be applied, or else instruments which are equipped with a thermistor or
other device to compensate automatically for temperature changes must be used.

Procedure

Dissolved oxygen measurements using DO probe (i) Remove glass stopper of the BOD bottle,
and place DO probe into the sample. (ii) Switch on the stirrer of the DO probe. (iii) Read the DO
value in mg/L when the meter reading has stabilized.

Result

Sr. NO Source of Sample DO[mg/L]

Experiment- 7

Aim: To determine the Chemical Oxygen Demand.

BACKGROUND AND PRINCIPLE:The chemical oxygen demand (COD) determines

the amount of oxygen required for chemical oxidation of organic matter using a strong
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chemical oxidant, such as, potassium dichromate under reflux conditions. This test is13widely
used to determine:

a) Degree of pollution in water bodies and their self-purification

capacity, b) Efficiency of treatment plants,
c) Pollution loads, and

d) Provides rough idea of Biochemical oxygen demand (BOD) which can be

used to determine sample volume for BOD estimation.
The limitation of the test lies in its inability to differentiate between the
biologically oxidizable and biologically inert material and to find out the system rate
constant of aerobic biological stabilization.
Most of the organic matters are-destroyed when boiled with a mixture of
potassium dichromate and sulphuric acid producing carbon dioxide and water. A sample is
refluxed with a known amount of potassium dichromate in sulphuric acid medium and the
excess of dichromate is titrated against ferrous ammonium sulphate. The amount of
dichromate consumed is proportional to the oxygen required to oxidize the oxidizable
organic matter.
SELECTION OF METHODS

There are two methods available for COD determination namely open reflux and closed

reflux.

Open Reflux Principle:

• Suitable for a wide range of wastes with a large sample size.

• Due to it higher oxidizing ability dichromate reflux method is preferred over

other procedures using other oxidants (e.g. potassium permanganate).
• Oxidation of most organic compounds is up to 95-100% of the theoretical value.

Closed Reflux Principle:

• This method is conducted with ampules and culture tubes with pre-
measured reagents.

• Measurement of sample volume and reagent volume are critical

 • This method is economical in the use of metallic salt reagents and
generate smaller quantity of hazardous wastes.

• Volatile organic compounds (VOC) gets completely oxidized in a closed

system than the open because of longer contact time with oxidants.

REAGENTS:

Standard Potassium dichromate (K2Cr2O7) digestion solution, 0.01667M: Add to about

500 mL distilled water 4.903 g K2Cr2O7, primary standard grade, previously dried at
150°C for 2 h, 167 mL conc. H2SO4, and 33.3 g HgSO4. Dissolve, cool to room
temperature, and dilute to 1000 mL.

Sulfuric acid reagent:Add H2SO4 at the rate of 5.5 g Ag2SO4/kg H2SO4 or 10.12 g
silver sulphate/L H2SO4. Let stand 1 to 2 d to dissolve and mix. This accelerates the
oxidation of straight- chain aliphatic and aromatic compounds.

(1 Kg = 543.47826 mL of H2 SO4 and take 20.24 g of Ag2SO4 to 2 L of H2

SO4 or 22.264 g of Ag2SO4 to 2.2 L of H2 SO4)

Ferroin Indicator solution This indicator is used to indicate change in oxidation-

reduction potential of the solution and indicates the condition when all dichromate has
been reduced by ferrous ion. It gives a very sharp brown color change which can
3+
be seen in spite of blue color generated by the Cr ions formed on reduction of the
dichromate.

Standard ferrous ammonium sulfate titrant (FAS), approximately 0.10M:

Dissolve 39.2 g Fe (NH4)2(SO4)2.6H2O in distilled water. Add 20 mL

conc. H2SO4, cool, and dilute to 1000 mL. Standardize solution daily against standard
K2Cr2O7 digestion solution as follows: Pipet 5.00 mL digestion solution into a small beaker.
Add 10 mL reagent water to substitute for sample. Cool to room temperature. Add 1 to
2 drops diluted Ferroin indicator and titrate with FAS titrant.

Molarity of FAS solution = [VK2Cr2O7 ×0.1] /

(VFAS)

Where: VK2Cr2O7 = volume of K2Cr2O7 (mL); VFAS = volume of

FAS (mL
PROCEDURE:

1. Wash culture tubes and caps with 20% H2SO4 before using to prevent contamination.

2. Place sample (2.5 mL) in culture tube and Add K2Cr2O7 digestion solution (1.5 mL).
3. Carefully run sulphuric acid reagent (3.5 mL) down inside of vessel so an acid layer is
formed under the sample-digestion solution layer and tightly cap tubes or seal
ampules, and invert each several times to mix completely.
4. Place tubes in block digester preheated to 150°C and reflux for 2 h behind a protective
shield.

5. Cool to room temperature and place vessels in test tube rack. Some mercuric sulfate
may precipitate out but this will not affect the analysis.
6. Add 1 to 2 drops of Ferroin indicator and stir rapidly on magnetic stirrer while titrating
with standardized 0.10 M FAS.
7. The end point is a sharp color change from blue-green to reddish brown,
although the blue green may reappear within minutes.
8. In the same manner reflux and titrate a blank containing the reagents and a volume
of distilled water equal to that of the sample.
9. COD is given by

COD (mg O2 /L) = [(A-B) × M ×8000) / (V sample)

Where: A = volume of FAS used for blank (mL)

B = volume of FAS used for sample

(mL) M = molarity of FAS

8000 = milli equivalent weight of oxygen (8) ×1000

mL/L.
Experiment No 8