CHEMICAL

ENGINEERING
LABORATORY MANUAL

DIVISION OF SAFETY AND FIRE ENGG

SOE, CUSAT
 SAFETY INSTRUCTIONS IN CHEMICAL
ENGINEERING LAB

➢ Do not use mouth suction for pipetting or starting a siphon. Filling

pipette with your mouth is extremely hazardous. Use approved filler.
➢ Work with strong acid and bases only in a properly functioning
chemical fume hood. Slowly add acids and bases to the water (with
constant stirring) to avoid splattering.
➢ Wear protective gloves while handling corrosive or hazardous
chemicals. Gloves protect your hands, use the particular kind
recommended for the job in hand.
➢ It is better to wear shoes all the time in the laboratory, but do not
wear sandals or perforated shoes.
➢ Wash your hands regularly and thoroughly when working with
chemicals particularly before eating or leaving the laboratory.
➢ Wipe up any reagent spills, liquids or powder as soon as they occur.
Rinse the area with sponge/towel, and then pat dry.
➢ The workbench and the area around should be kept clean from
chemicals and apparatus not in use. Use instruments/equipment only
after obtaining permission.
➢ Never leave a machine unattended.

1
 INDEX
Sl.No Name of the Experiment Page
No.
1. Determination of BOD. 3

2. Determination of COD. 7

3. Determination of pH 11

4. Determination of turbidity 15

5. Determination of total hardness 19

6. Determination of total solids. 24

7. Determination of dissolved oxygen. 29

8. Determination of the optimum coagulant dose for water 32

treatment using jar test apparatus.

9. Determination of order and rate constant (k) of a reaction 34

using isothermal batch reactor.

10. Determination of the area of a continuous thickener using 38

batch sedimentation test.

11. Simple leaching experiment to compare the actual recovery 49

with the theoretical recovery.

12. Verification of Freundlich equation for adsorption isotherm. 55

13. Frequency response of first order systems. 63

14. Frequency response of second order systems. 68

2
Experiment No: Date

DETERMINATION OF BIOLOGICAL OXYGEN

DEMAND

Aim

To determine the Biological Oxygen Demand (BOD) of the given

waste water sample.

Reagents Required

Standard manganese sulphate solution (2M)

N/40 Sodium thiosulphate

Concentrated H2S04 acid

Starch indicator

Phosphate buffer solution

Preparation of Dilution water: Add 1ml of each of phosphate

buffer, magnesium sulphate, calcium chloride and ferric chloride
per litter of water. In the case of waste waters which are not
expected to have sufficient bacterial population, add seed to the
dilution water. Generally, 2 ml of settled sewage is sufficient for
1000 ml of diluted water.

3
Apparatus Required

1000mL of graduated cylinder, mixing rod,300mL BOD bottles,

pipette, BOD incubator, conical flask, burette.

Theory

BOD is defined as the amount of oxygen required by bacteria to

stabilize decomposition of organic matter under aerobic condition.
This BOD test may be considered as Wet Oxidation Procedure in
which the living organism serve as the medium for oxidation of the
organic matter to carbon dioxide and water. BOD is the major
criteria used in water pollution control where organic loading is
restricted to maintain desired oxygen level. It involves the
determination of dissolved oxygen content of the sample. Before
and after 5 days incubation at 20 0 C.

Procedure

• A known volume (10 ml) of waste water sample was being

taken in 300ml of BOD bottle and made up to 300ml by using
dilution water.
• Add 2 ml MnSO4 and 2 ml Alkali-Iodide Azide solution in the
working solution for the liberation of iodine. Put the stopper
of BOD bottle and mix it thoroughly for several times.

4
 • If the solution becomes white precipitate, it indicates the
absence of oxygen. If the solution turns to brown precipitate,
allow sufficient time to settle.
• Remove the stopper and add 2 ml of Con. Sulphuric acid and
mix thoroughly.
• The solution becomes yellow in colour.
• Take 203 ml of working solution and titrate against 0.025 N
Na2S2O3 till brownish violet colour turns colourless. Starch
can be used as an indicator.
• The same procedure needs to be followed for blank.

Result

BOD of the given water sample is found out to be ……..mg/L

Inference

A water supply with a BOD level of 3 to 5 ppm is considered

to be moderately clean. In water with a BOD level of 6 to 9
ppm, the water is considered somewhat polluted because there
is usually organic matter present and bacteria are decomposing
this waste. The given water sample has a BOD of …..ppm
which indicates that it is ……..

5
Observations and Calculations

Initial Dissolved Oxygen (DO) on 1st day

Table 1 Volume of Na2S2O3 required to quantify the amount of oxygen present in water sample

Volume of water sample Burette reading Volume of Na2S2O3

S. No (mL) Initial Final (mL)
1
Sample 2
1
Blank 2

Final Dissolved Oxygen (DO) Value on 5th day

Table 1 Volume of Na2S2O3 required to quantify the amount of oxygen present in water sample

Volume of water sample Burette reading Volume of Na2S2O3

S. No (mL) Initial Final (mL)
1
Sample 2
1
Blank 2

Calculations

DissolvedO2=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑆𝑜𝑑𝑖𝑢𝑚 𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑×𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑝ℎ𝑎𝑡𝑒×1000×8
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑊𝑎𝑡𝑒𝑟 𝑆𝑎𝑚𝑝𝑙𝑒

Volume consumed×Normality of thiosulphate×1000×8

Initial DO =
Volume of sample

=
Volume consumed×Normality of thiosulphate×1000×8
Final DO =
Volume of sample

(Initial DO−Final DO)×Volume of Sample×1000

BOD = =
Volume of Dilute Solution

6
Experiment No: Date:

DETERMINATION OF CHEMICAL OXYGEN

DEMAND

Aim
To determine the Chemical Oxygen Demand (COD) of the given waste
water sample by open reflux method.

Apparatus Required
Reflux apparatus (Round bottom flask with its neck connected to spiral
condenser), burette.

Reagents Required
Potassium dichromate solution, 0.25N
Sulphuric acid reagent
Ferrous Ammonium sulphate (FAS) solution
Ferroin indicator
Mercuric sulphate

Theory
The waste water sample is refluxed with a known excess of K2Cr2O7 in
a 50% H2SO4solution in presence of AgSO4 (as catalyst) and HgSO4
(to eliminate interference of Cl), then the organic matter of sample is
oxidized to H2O, CO2 and NH3, the excess dichromate remaining
unreacted. The solution is then treated with standard solution of FAS
to determine the COD.

7
Procedure

• Add 0.4 gm of HgSO4 in the reflux flask.

• Add 20 ml of sample (or an aliquot diluted to 20 ml)
• 10 ml of more concentrated dichromate solution are placed into
flask together with glass beads.
• Add slowly 30 ml of H2SO4 containing Ag2SO4 and mix
thoroughly.
• Connect the flask to refluxing condenser. Mix the condense
thoroughly before heating.
• Reflux for a minimum period of 2 hours. Cool and wash down the
condenser with distilled water.
• Dilute the sample to make up to 150 ml and cool.
• Titrate with 0.1 N FAS solution using ferroin indicator till the red
colour appears after the intermediary green colour. (Note: While
refluxing if the colour changes to green discard the mixture as
Potassium Dichromate is not sufficient to oxidize the solution).
For small volumes i.e, 10,20,30,40 ml of samples, proportionate
reduction of Potassium dichromate and Sulphuric acid may be
done.

8
Result
COD of the given sample by open reflux method is found out to be
………. mg/L.

Inference
The chemical oxygen demand for drinking water according to the
Indian Standards for Drinking water Specification should be nil. The
given sample has a COD of…….. mg/L which is suitable/not suitable
for drinking as it contains harmful pollutants. The given sample was of
river water and the COD for inland surface water for rivers, lakes can
go upto 250 mg/L.

9
Observations and Calculations

Sl. No. Volume of Burette Burette Vol. of 0.25N FAS

water sample Reading Reading (mL)
(mL) Initial Final
1.(Blank) 25 0
2.(Sample) 25 0

Calculations
Volume of FAS,V1 (Sample) = mL

Volume of FAS, V2 (Blank) = mL

COD of the given sample = (V2-V1 X 0.1 X 8 ) / V

10
Experiment No: Date:

DETERMINATION OF pH

Aim
To determine the pH of given sample using pH meter and pH
paper.

Apparatus and Reagents required

• pH Meter
• pH Paper
• Buffer solution
• Beakers

Theory
The quantitative measurement of the acidity or basicity of a
solution is called pH of the solution. It is defined as the negative
logarithm of hydrogen ion concentration of a solution.

pH = -log [ H+ ]

If the pH of a solution is 7, the solution is called neutral. The

pH of pure water is 7. Neutral solution has an equal quantity of H+ &
OH− ions in pure water. The following relation exists.
pH determination In logarithmic form:
pH + pOH = 14
Hence
pH = 7 & pOH = 7

11
If the pH of solution is < 7, the solution is called acidic.
If the pH of solution is > 7, the solution is basic.

Procedure
pH measurement using pH Meter

• Calibrate the electrode of the pH meter with standard buffer

solutions of pH 4 and 7 (i.e., Two point calibration)
• Rinse the electrode with distilled water and carefully wipe with
tissue paper.
• Dip the electrode into the sample solution
• Reading is taken after the indicated value remains constant for
few seconds.
pH measurement using pH Paper
• Dip the pH paper into the solution taken in the beaker.
• Observe the colour change.
• The change of colour is compared with the colour chart.
• Take the appropriate value from the colour chart.

12
Result
pH of the given sample is determined using pH meter and pH paper.

Inference
pH of sample I is ……..; it is ……… in nature.
pH of sample II is……..; it is ……….in nature.
pH of sample III is ……..; it is ………in nature.

13
Observations

pH measured by
Sample pH Meter pH Paper

14
Experiment No: Date:

DETERMINATION OF TURBIDITY

Aim
• To determine the Turbidity of the given sample using Digital
Nephelometer

Apparatus required
• Digital Nephelometer

Theory
Water is said to turbid when it is seen containing materials of
suspension inside it. While turbidity may be defined as the measure of
visible material in suspension in water, turbidity may be caused by
algae or other organisms. It is generally caused by silt or clay. The
amount and character of turbidity depends upon two things:
1. Type of soil over which flows
2. The velocity of flowing water
When water becomes stationary, the heavier and larger suspended
particles settle down quickly and the lighter and finely divided particles
settles very slowly and even takes months.
Ground water is less turbid because of low velocity of water.
turbidity may be helpful for controlling growth of paganisms by not
allowing proper sunlight to water which is necessary for their growth
on the other hand it is harmful as the organisms are handling to the
suspended particles. When water becomes stationary, the heavier and
larger suspended particles settle down quickly and the lighter and finely
divided particles settles very slowly and even takes months. Ground
water is less turbid because of low velocity of water. Turbidity may be

15
helpful for controlling growth of paganisms by not allowing proper
sunlight to water which is necessary for their growth on the other hand
it is harmful as the organisms are handling to the suspended particles.

Procedure

• Allow sufficient warm up period after switching on the

instrument.
• Take the test tube with distilled water or blank solution. Place it
in the test tube holder and close the test tube holder cover. Make
sure that the mark on the test tube coincides with the mark on the
panel.
• Adjust the display to 00.0 by adjusting the set zero knob.
• Do the calibration by using 10 NTU and 100 NTU solutions.
• Take its measurement and set the display to the value of the
standard suspension with the Calibrate Knob.
• Again check the display zero with the test tube containing
distilled water.
• For measurements of turbidity less than 20 NTU thoroughly
shake the sample, wait until bubbles disappear. Put range switch
on 20 NTU and put the sample into the test tube. Take the reading
directly from the digital display.
• For measurement of turbidity above 200 NTU, put the range
switch to 200 NTU, dilute the sample with known volumes of
16
 turbidity free water until the turbidity falls within 200NTU. Then
compute the turbidity of the original sample from the turbidity of
the diluted sample and dilution factor.

Result
Turbidity of the given samples are measured.

Inference
Turbidity of sample I is …….
Turbidity of sample II is…….
Turbidity of sample III is ……

17
Observations

Sample Turbidity measured

I
II
III

18
Experiment No: Date:

DETERMINATION OF TOTAL HARDNESS

Aim

To determine the Total hardness of the given sample of water.

Reagents required

• Ammonia buffer solution

• Eriochrome Black T indicator
• Standard EDTA titrant (0.01 M)

Theory

Hard waters are generally considered to be those waters that

require considerable amounts of soap to produce foam or lather and that
also produce scale in hot water pipes, heaters, boilers, and other units
in which the temperature of water is increased materially. Hardness is
caused by multivalent metallic cations. Such ions are capable of
reacting with soap to form precipitates and with certain anions present
in the water to form scale. The principal hardness causing cations are
the divalent calcium (Ca2+), magnesium (Mg2+), strontium (Sr2+),
ferrous ion (Fe2+) and contributing to the hardness of water. However,
their solubility is very limited.

19
 The hardness of water varies considerably from place to place. In
general surface waters are soften than ground waters. Waters are
commonly classified in terms of the degree of hardness as follows.

Hardness
Degree of hardness
(mg/L)
Soft
0-75
Moderately hard
75-150
Hard
150-300
Very hard
>300

Types of Hardness
Total hardness is defined as the sum of calcium and magnesium
concentrations, both expressed as calcium carbonate, in milligrams per
liter.

Calcium and Magnesium Harness

Most of the harness in natural waters is due to these two cations. In
some situations, it is important to know the amounts of calcium and
magnesium hardness in water separately. For example, it is necessary
to know the magnesium hardness or the amount of Mg2+ ion in order
to calculate lime requirements in lime-soda ash softening.

20
Carbonate and Non-carbonate Hardness
The part of the total harness that is chemically equivalent to the
bicarbonate plus carbonate alkalinities present in a water is considered
to be carbonate harness. Since the alkalinity and harness are both
expressed in terms of CaCO3, the carbonate harness can be found as
follows.

❖ When Alkalinity < Total hardness:

Carbonate hardness (mg/L) = Alkalinity (mg/L)

❖ When Alkalinity > Total hardness:

Carbonate hardness (mg/L) =Total hardness (mg/L)
The amount of harness which is in excess of the carbonate harness is
called non-carbonate harness and can be estimated as follows:
Non Carbonate Harness (NCH) = Total hardness- Carbonate hardness.

Principle
Ethylenediamine tetra-acetic acid (EDTA) and its sodium salts
form a soluble compound when added to a solution of metal cations. If
a small amount of dye called Eriochrome Black –T is added to a
solution containing calcium and magnesium ions at a pH of 10, the
solution will become wine red. If EDTA is added then calcium and
magnesium will be complexed. When all these ions are complexed, the
solution will turn blue. This is the end point of titration.

21
Procedure
1. Take a sample volume of 25ml.
2. Dilute 25ml of the sample in Erlenmeyer flask to 50ml by adding
25ml of distilled water.
3. Add 1 mL of ammonia buffer to bring the pH to 10±0.1.
4. Add 1 or 2 drops of the indicator (Eriochrome Black T) solution.
If there is Ca or Mg hardness the solution turns wine red.
5. Add EDTA titrant to the sample with vigorous shaking till the
wine-red colour just turns blue.
6. Note the volume of titrant added (A).
7. Run a reagent blank, using distilled water of the same volume as
the sample, to which identical amounts of buffer and indicator
have been added. Note down the volume of EDTA required for
blank (B).
8. Calculate the volume of EDTA required for the sample as V= A-B

Result
Hardness of the given sample =

22
Observations

Sample Volume Burette reading (ml) Volume Hardness,

of of mg/L as
sample EDTA CaCO3
(ml) required
Sample Blank for
Initial Final Initial Final sample
(ml)

Calculation
Hardness, mg/L as CaCO3 = (V*1000/Sample)

23
Experiment No: Date:

DETERMINATION OF TOTAL SOLIDS

Aim

To determine the total solids, suspended solids and dissolved solids of

the given sample.

Apparatus required

• Filtration apparatus
• Evaporating dish made up of porcelain, platinum or high silica
glass.
• Drying oven
• Desiccator
• Measuring cylinder
• Whatman filter paper No.44
• Electronic weighing balance

Theory

The term solids refer to the matter either filterable or non-filterable that
remains as residue upon evaporation and drying in oven at 103 0C to
1050C. Various kinds of solids present in water and waste water are
shown below.

24
 TOTAL SOLIDS

SUSPENDED DISSOLVED
(REMAINED IN FILTER PAPER) (FILTRATE)

VOLATILE FIXED VOLATILE FIXED

Total solids is the sum of dissolved and suspended solids expressed in

mg/l. Suspended solids or matter in surface water may consists of
inorganic (silt and others) or organic matter (plant fibers, algal and
phytoplankton, metal chelates etc.) These materials are often natural
contaminants resulting from erosive action of water flowing over land
surface. Ground water contains negligible quantity of suspended solids
and being filtered out by soil strata through mechanical straining action.
In natural waters, dissolved solids consist mainly of inorganic salts
such as carbonates, bicarbonates, chlorides, sulphates, phosphate and
nitrates of calcium, magnesium, sodium, potassium, iron etc. and small
amount of organic matter and dissolved gases.
Principle
Total solids are determined as the residue left after evaporation and
drying of the unfiltered sample. Total suspended solids are determined

25
as the residue left on Gooch crucible or a glass fiber filter after drying
in an oven. Total dissolved solids are determined as the residue left
after evaporation and drying of the filtered sample. Fixed solids is the
residue left behind after igniting the total residue for 1 hour, at a
temperature of 5500C.

Environmental significance
Total solids determination is used to assess the suitability of potential
supply of water for various uses. In cases, in which water softening is
needed, the type of softening procedure used may be dicated by the
total solid content. Suspended material is aesthetically displeasing and
provides adsorption sites for chemical and biological agents.
Suspended organic solids, which are degraded anaerobically, may
release abnoxious odours. Dissolved minerals, gases and organic
constituents may produce aesthically displeasing colour, taste, and
odour. Some dissolved organic chemicals may deplete the dissolved
oxygen in the receiving waters and may be inert to biological oxidation.

Procedure
Total Solids: - Heat a clean dish to 1030C to 1050C for 1 hour. Store
and cool the dish in a desiccator until needed. Weigh immediately
before use (A). Transfer a measured volume of well mixed sample to
the pre-weighed dish. Evaporate the sample to dryness at 103 0C in a
drying oven. Dry evaporated sample for at least 1 hour in an oven at
the same temperature, and weigh (B). Repeat cycle of drying, cooling,
desiccating, and weighing till a constant weight is obtained.
Suspended Solids: - Dry a clean filter paper in an oven at 1030C to
1050C. After partial cooling in the air, cool in a desiccator and weigh
(A). Pour a suitable volume of well mixed sample on the filter paper
which is kept on filter flask. After filtration, dry the filter paper in an
oven at 1030C to 1050C. Cool in a desiccator and take weight (B).

26
Repeat cycle of drying, cooling, desiccating, and weighing till a
constant weight is obtained.
Dissolved solids: - Heat a clean dish or crucible to 180±20C for 1 hour
in an oven. After partial cooling in air, cool in a desiccator and weigh
immediately before use (A). Transfer the filtrates obtained above to the
weighed dish and evaporate to dryness. Dry evaporated sample for at
least 1 hour in an oven at 180±20C, cool in a desiccator to balance
temperature, and weigh (B).

Result
Total solids present in the sample =
Suspended solids present in the sample =
Dissolved solids present in the sample =

27
Observations
Sample Volume of Initial weight of Final weight Solids
details sample dish/filter paper of dish/filter (B-A)*1000/V
( V) ml (A) mg paper (B) mg

Total
solids
Suspended
solids

Dissolved
solids

Calculations
Total solids (mg/l) = (B-A)-1000/V
A = initial weight of dish in mg
B = final weight of dish in mg
V = volume of sample taken in ml

Suspended solids (mg/l) = (B-A)-1000/V

A = initial weight of filter paper in mg
B = final weight of filter paper in mg
V = volume of sample taken in ml

Dissolved solids (mg/l) = Total solids – Suspended solids

28
Experiment No: Date:

DETERMINATION OF DISSOLVED OXYGEN

Aim

To determine the Dissolved oxygen of the given sample.

Reagents required

• Manganese sulphate
• Alkali-iodide azide reagent
• Concentrated sulphuric acid
• Standard sodium thiosulphate solution (0.025N)
• Starch indicator solution

Theory
All gases in atmosphere are soluble in water to some degree.
Oxygen is poorly soluble and its solubility is directly proportional to
its partial pressure. The solubility of oxygen varies greatly with
temperature. The solubility of atmospheric oxygen in fresh water
ranges from 14.6 mg/l at 00C to about 7 mg/l at 350C under 1 atm
pressure. Solubility varies directly with atmospheric pressure at any
given temperature
In aerobic biological treatment, the limited solubility of oxygen
is of great importance, as it grows the rate at which oxygen will be
absorbed by the medium and therefore the cost of aeration. A minimum

29
of dissolved oxygen if 4.5 mg/l is desirable for the growth and survival
of aquatic life. Drinking water should be rich in D.O for good taste.

Principle
Most methods for the determination of dissolved oxygen depends
on amount of iodine equivalent to the amount of oxygen originally
present with subsequent measurement of amount of iodine released by
means of a standard solution of a reducing agent. All the reactions in
the determination of oxygen involve oxidation and reduction. The
Wrinkler or Idometry methods and its notifications are the standard
volumetric procedure for determining the D.O at the present time.
The test depends upon the fact that oxygen oxidizes Mn2+ to a
higher state of valence under alkaline conditions and that manganese in
higher state of valence is capable of oxidizing I- to I2 under acidic
conditions. Thus amount of I2releasd is equal to D.O originally present.
The iodine is measured with standard sodium thiosulphate solutions
(reducing agent) and interpreted in terms of D.O .Starch is the end point
indicator.

Procedure
1. Fill the BOD bottle with sample.
2. Add 2 ml of manganese sulphate and 2 ml of alkali-iodide azide
reagent to the bottle. The tip of bottle should be well below the
liquid level.
3. Stopper with care to exclude air bubbles, if any, completely, and
mix by inverting the bottle several times.
If no oxygen is present the manganese ion reacts with hydroxide
ion to form white precipitate of Mn (OH)2.
If oxygen is present, some Mn2+ is oxidized to Mn4+ and
precipitate as a brown hydrated oxide.
4. After shaking the samples for a time sufficient to allow all oxygen
to react, the floc is allowed to settle so as to leave at least 5
30
 cm(100ml) of clear liquid(supernatant) carefully remove the
stopper and immediately add 2 ml con.H2SO4 allowing the acid
to run down the neck of the bottle. Under the low pH conditions
that results, the MnO2 oxidizes I- to produce I2.
5. Restopper the bottle and mix by gentle inversions until the
suspension is completely dissolved and the yellow colour of
iodine is uniform throughout the bottle.
6. A volume of 203ml is taken into the conical flask and titrate
against 0.25 N Na2S2O3 solution until yellow coloured iodine
turns to a pale straw colour. At this time 1 to 2 ml of starch
solution is added as indicator, which forms a blue coloured
complex.
7. Continue titration till the first disappearance of the blue colour.

Result
o Dissolved Oxygen of given sample at 0C =
o Dissolved Oxygen of tap water at 0C =

31
Experiment No: Date:

DETERMINATION OF THE OPTIMUM

COAGULANT DOSE FOR WATER TREATMENT
USING JAR TEST APPARATUS.
Aim
To find out the optimum amount of coagulant required to treat the
turbid water.
Theory
The solids may vary in size from 1 millimicron to 200 millimicrons and
broad in characteristics between the suspended and dissolved salts.
They are small enough to exhibit stability by virtue of the slight residual
electrical charge, but large enough to interfere with passage of light and
therefore cause turbidity. They will not settle physically unless
destabilized, coagulated and flocculated into larger mass with
sufficiently greater densities than water.
Coagulants employed are normally those electrolytes possessing
strong positive changes when dissolved in water. For example, salt of
Al+++ and Fe+++. The coagulant appears to react simultaneously with OH-
and negative colloidal Impurities. Both are reduced substantial by the
reaction.
Alum is generally used as coagulant for coagulation of water and
reaction are as follows:
Al2 (S04)3. 18 H₂0+3Ca (OH)2 3 CaSO4 + 2Al (OH)3+6C0₂+ 18H2O

PRINCIPLE
Metal salts hydrolyse in the presence of natural alkalinity to form
metal hydroxide. The divalent cations can reduce the zeta potential,
while the metal hydroxides are good adsorbents and hence remove the
suspended particles, by enmeshing them.

32
REAGENT
• Alum solution.

PROCEDURE
1. Analyse the raw water for pH, turbidity and alkalinity after
filtering through a screen.
2. Take IL of sample into each of the 6 beakers.
3. Switch on the motor and adjust the speed of paddles to 100 rpm
4. Add varying does of alum to different batches simultaneously

Use the following doses.

I 0 10 20 30 40 50 mg/L
II 0 50 75 100 125 150 mg/L
III 0 150 175 200 250 300 mg/L

5. Allow flash mix for 1 minute

6. Reduce the speed of paddles to 30 rpm and continue mixing for
20 min.
7. Switch off the motor and allow 20 min for setting.
8. Collect the supernatant without disturbing the sediment and find
the turbidity of each using Nephelometric turbidity meter.
9. Repeat the experiment with higher dose of alum, if Satisfactory
results are not obtained.
10.Note the ideal dose of the coagulants for excellent flux formation.
11. Draw the graph of Amount of alum Vs Turbidity, and find the
optimum dose of alum
Result
Optimum dose of coagulant required to treat the turbid water = mg/L

33
Experiment No: Date:

DETERMINATION OF ORDER AND RATE

CONSTANT (k) OF A REACTION USING
ISOTHERMAL BATCH REACTOR
Aim
To determine the reaction rate constant(k) for the given saponification
reaction of ethyl acetate in aqueous sodium hydroxide solution.

Theory
A batch reactor is a closed system with no input and output streams. It
can operate under the following conditions
• Isothermal (temperature of reaction mass remains constant)
• Perfectly mixed (composition of the reaction mixture is uniform
throughout)
• Constant volume (volume of the reaction mixture within the reactor remains
constant, there is appreciable change in density of reaction mass)
In a homogeneous reaction, all the reactants remain in single
phase. The rate of reaction for such a reaction is as moles of product
formed per unit volume of reaction mixture per unit time.
For a first order unidirectional reaction:
A Product
For a unidirectional reaction of order k:

Ak Products

34
Rate of reaction can also be expressed as moles of A disappearing per
unit volume per unit time. Here the reaction is of the form:

A+B Product

-rA= 1/V(dNA/dt) = kCACB

NA =NA0(1-XA)

dNA/dt = - NA0 dXA/dt

For a second order reaction :

-rA= kCACB = k CA2 (if CA0 = CB0)

- dCA/dt = k CA2

1/CA0 - 1/CA = -kT

1/CA = kT + 1/CA0
According to Arrhenius equation :
K = k0 e-Ea/RT
ln (k2/k1) = Ea/R (1/T1-1/T2)

Procedure
1. Set the water bath temperature of reactor at T1.
2. Take 0.2 M ethyl acetate and 0.2 M sodium hydroxide
separately.
3. Pour the content into the batch reactor and switch on the stirrer.
4. Take the sample from the reactor at regular intervals as
underflow and conduct the titration using phenolphthalein
indicator.

35
5. Plot the graph between 1/CA Vs T to get k.
6. Using k, calculate volume of mixture at different intervals of
time.

Result
Graph was plotted between 1/CA Vs T and the value of k has been
found out. k =
The volume of reaction mixture was found to be

36
Observations and calculations
Sl.No Time Volume of Volume of Volume of
(min) HCl (ml) mixture (ml) NaOH (ml)
1. 2 10 20
2. 4 10 20
3. 6 10 20
4. 8 10 20
5. 10 10 20
6. 12 10 20

At T = 2 min
V, = (N x V) HCl /NaOH
XA = 1- (CA/CA0)

From graph:
k=
Now, V = NA0/ (XA/ (1-XA)) * (1/kT)

Sl.No Time(min) CA (mol/l) XA 1/CA V (l)

(l/mol)
1. 2
2. 4
3. 6
4. 8
5. 10
6. 12

Plot the graph 1/CA Vs Time.

37
 Experiment No: Date:

DETERMINATION OF AREA OF A CONTINUOUS

THICKENER USING BATCH SEDIMENTATION TEST

Aim
To find the area of a continuous thickener from a batch
sedimentation test to concentrate 20 g/l of slurry to 100 g/l at a rate of 10
tons/day of dry solids.

Equipment/Apparatus:

• 1 L graduated jar
• Beakers
• Weighing balance
• Stirrer
• Stop watch

Theory
Very fine particles which normally do not settle or settle at very low
velocity must be agglomerated or flocculated to large particles that do
possess a reasonable settling velocity. Many slimes consisting of particles
that carry electrical charges tend to remain dispersed because of the
mutual repulsion of like charges. If an electrolyte is added, the neutralized
particles may then agglomerate to form flocs each containing many
particles. Other methods of flocculation include the use of surface-active
agents and the addition of materials such as glue, lime or alumina that drag
down the slime particles with them. In a properly treated slime, the flocs
are visible to the naked eye.
38
 Flocculated particles possess two important settling characteristics.
The first one is the complicated structure of the flocs. Although initially
flocs settle in either free or hindered settling and the usual equations apply
in principle, it is not practical to use the laws of settling quantitatively
because the diameter and the shape of the flocs are not readily definable.
The second one is the complexity of its settling mechanism.
If a uniformly flocculated sludge is subjected to settling, a
concentration decrease will take place at the top and a concentration increase
will take place at the bottom. After some time, four zones can be demarcated
(1) A clear liquid zone at the top, (2) a zone of initial concentration, (3) a
transition zone with a varying concentration, (4) a compression zone at the
bottom. As settling continues initial concentration zone and then the
transition zone vanishes and only two zones exist. At this stage portion of the
liquid which has accompanied the flocs into the compression zone is expelled
and the liquid spurts out of the zone, when the weight of the deposit breaks
down the structure of the flocs. Finally, when the weight of the solid reaches
mechanical equilibrium with the compressive strength of the flocs, the
settling process stops. The entire process is called sedimentation.
The mass settling rate of the particles in the initial concentration zone
and the final compression zone are higher. But there is a layer in between
these two zones whose mass settling rate of the particles is the minimum.
Such a layer is called the capacity limiting layer (C. L. L.).

The properties of the CLL are:

1) Its concentration is greater than the initial concentration zone.
2) The settling velocity of the particles through the layer is less than that
at the initial concentration zone.
3) Its concentration is less than the final compression zone.
39
 4) The settling velocity of particles through the layer is greater than that
at the final compression zone.
5) The rate of input to the layer will always be greater than the rate output
from the layer since the solid handling capacity of the layer is the
minimum in a batch sedimentation operation.
6) As soon as the layer is formed its concentration increases and it is no
longer the layer.
7) The layer first forms at the bottom since any increase in concentration
is at the bottom.
8) The layer propagates to the top till it reaches the interface with the
clear liquid.
9) All the particles in the slurry passes through the C.L.L. by the time
the C.L.L. reaches the interface with clear liquid

Kynch Theory: Kynch has proposed that the rate of upward

propagation of the capacity limiting layer is constant if throughput exceeds
the limit.
From a batch sedimentation test the C.L.L. is found out and
the concentration settling rate of the particles in the C.L.L. is determined.
This information is used to calculate the minimum area of the continuous
thickener

For the batch Sedimentation Test

Co ─ Initial concentration of the Slurry
CL ─ Concentration of the C. L. L.

40
 vL ─ Settling rate of the particles through the C. L.L.

vL ─ Rate of upward propagation of the C. L.L.

θL ─ time required fro the C.L.L. to reach the interface.
Zo ─ initial height of the slurry in the test jar.
ZL ─ height of the slurry, when the C.L.L. reaches the interface.
Zi ─ the intercept of the tangent at ZL with y-axis.
a ─ area of cross section of the test jar.

For the continuous thickener

Co – Feed concentration.
Cu – Final concentration.
F – Feed rate of solids in the slurry.
A – Area of the thickener.
ρP – Density of the solid.

Total solids in the slurry = CoZoa

Slurry passing through the C.L.L. = ( vL + v L ) θL CL a

:.Co Zo a = ( v L θL + v L θL) C L a

Co Zo = ( v L θL+ v L θ L) C L

vL = (dz/ dθ)

= (Zi - ZL)/ θL

41
 :. v L θL = Zi - ZL

v L θL = ZL
(Since v L is constant
as per kynch theory)
CoZo = (Zi - ZL + ZL) CL
= Z i CL
CO Z O
:.CL =
Zi

For different values of θ, the corresponding values of VL and CL are

calculated.

Determination of thickener area

Volume of liquid associated with unit mass of solid at the C. L. L

CL
1−
P  P − CL
= =
CL  PCL

Volume of the liquid associated with unit mass of solid in the underflow
Cu
1−
P  P − Cu
= =
Cu  P Cu

:. Volume of liquid moving upwards through the C.L.L. per unit mass of
solid
 P − C L  P − Cu
= −
 P .C L  P Cu

 P ( Cu − CL )
=
 P.Cu.CL

42
 = ( Cu − CL )
Cu.CL

 Total volume of the liquid moving upwards through the C.L.L. in the
continuous thickener.
(Cu − CL )
= F
Cu CL

F (Cu − C L )
Upward velocity of the liquid =
A Cu C L

This upward velocity should be less than or equal to the settling velocity of
the particle through the C.L.L
F (Cu − C L )
 vL
A Cu C L

F (Cu − C L )
A 
v L Cu C L

F

 
 V 
 L

 1 1 
C −C 
 L u 

43
:. The minimum area of the thickener is given by

F
A =
 
 V 
 L

 1 − 1 
C C 
 L u 

VL
From the batch sedimentation test 1 1
is calculated for different
−
C L Cu
VL
values of v L and CL and the minimum value of 1 1
is substituted in
−
C L Cu

the equation
F
 A=
 
 V 
 L

 1 − 1 
C C 
 L u  min

Procedure

A slurry of barium sulphate of required concentration is prepared by

reacting barium chloride with sodium sulphate in the stoichiometric
proportion.

Ba Cl2.2H2O + Na2 SO4 ➔ BaSO4 + 2 NaCI +2H2O

44
 Barium chloride and sodium sulphate are transferred into two separate
beakers and dissolved in water. Barium chloride solution is transferred to a
1 litre graduated jar. Sodium sulphate solution is now added slowly and
mixed thoroughly and made up to 1 litre. When the concentration is uniform,
mixing is stopped and a stopwatch is started. The particles in the suspension
start settling and the height of the interface with the clear liquid is noted with
time cumulatively for every one cm or 1/2 cm fall of the interface. This is
continued till there is no more settling.
A graph of height Vs time is plotted. From this the settling rate at
different times and the corresponding slurry concentration are found.
VL
Another plot of Vs VL or θL is plotted.
 1 1 
 − 
 CL Cu 

VL
The minimum value of is noted and the area of
 1 1 
 − 
 CL Cu 

the thickener is calculated.

Conclusion

The area of the thickener =

45
Observation:

Amount of BaCl2 taken mg :

Amount of Na2SO4 taken mg :
Initial slurry concentration, Co mg/l :
Concentration of the under flow, Cu mg/l :
Initial height of the slurry, Zo cm :

Height of the Time Height of Time Height of Time

interface, the interface the
θ (s.) θ(s.) θ (s.)
interface,
Z (cm) Z (cm)
Z (cm)

46
Sl.No. θL ZL Zi CL=
CO Z O
VL =
( Zi − Z L ) VL
Zi L  1 1 
 − 
 CL Cu 

47
Calculation

Volume of slurry = 1000 ml.

Amount of BaSO4 = 20 g.
Eq. weight of BaCl2.2H2O =
Eq. weight of Na2SO4 =
Weight of BaCl2.2H2O required =
Weight of Na2SO4 required =

VL
from the graph =
 1 1 
 − 
 CL Cu  min

F
:. Minimum area of the thickener =
 
 V 
 L

 1 1 
C −C 
 L u  min

48
Experiment No: Date:

SIMPLE LEACHING EXPERIMENT TO COMPARE

THE ACTUAL RECOVERY WITH THE
THEORETICAL RECOVERY.
Aim
To draw the percentage actual recovery Vs, solvent to feed ratio
(constant) curve i.e., percentage actual recovers Vs the number of
stages curve keeping the solvent to feed ratio constant and to compare
the actual recovery with the theoretical recovery.

Apparatus/ Chemicals required

• Weighing balance
• Sand
• Sodium carbonate
• Phenolphthalein indicator
• Butter paper
• Beaker (250 ml) -10 nos
• Measuring cylinder (250 ml, 100 ml,50 ml)
• Glass rod
• Volumetric flask
• Burette
• Pipette (10 ml)

Theory
The methods of removing one constituent from a solid or liquid mixture
by a liquid solvent fall into two categories. If the soluble matter is
dissolved from its mixture by an insoluble sold, the operation is called

49
leaching or solid extraction. The second, called liquid extraction, is
used to separate two miscible liquids by the use of a solvent.
The following are some terms connected with leaching. The mixture
of the insoluble carrier solid and the solute, which is to be separated, is
called the feed. The feed is contacted with the solvent and the mixture
is separated into two streams. The solvent rich product of the operation
is called the extract or overflow and the stream that contains the bulk
of the carrier solid is called the leached solids or underflow. A unit of
equipment in which the above-mentioned operation is carried out is
called a stage. In simple batch leaching operation, if sufficient amount
of solvent is used, all the solute can ultimately be dissolved in the
solvent. The mount of solute that comes out with the extract based on
this assumption is called the theoretical recovery. But actual recovery
will be less than the theoretical recovery because
• The solute may be incompletely dissolved because of inadequate
contact time and
• Solids leaving the stage retain some of the solute.
The method of operation of leaching can be classified into batch wise
(unsteady-state) and continuous (steady-state). Here in this
experiment, we study the principles of batch leaching.

Procedure
Prepare a 10% by weight mixture of sodium carbonate and sand by
accurately weighing about 45gms. of sand and 5gms. of sodium
carbonate. Add 50cc of distilled water to this mixture. This is the feed.
Prepare the feed in five beakers. Extract the solute from each beaker
with 200cc of water but vary number of stages from 1 to 5. This is done
as follows. To beaker 1, add 200cc of water, stir the contents are well,
allow the sand to settle and pipette out 200cc of clear solution. Titrate
it against HCl. To beaker 2, add 100cc of water and pipette out 100cc

50
of clear solution into a clean beaker. Now, add 100cc of fresh water
again to the slurry and after mixing well, pipette out 100cc of clear
solution and mix it with earlier extract. Find strength of this combined
extract by titrating against HCl solution.
Beaker 3 ---------- Extracted 3 times using 66.6 cc of water each time.
Beaker 4 ----------- Use 50cc of water four times.
Beaker 5 ----------- Use 40cc of water five times.
A standard solution of sodium carbonate approximately 0.2 N is
prepared and this is used to standardize the HCl used.

Result
The graph for theoretical and actual recovery Vs number of stages is
plotted.

51
Observations

Beaker Sodium Sand Water Extract Number Total

No. carbonate per stage of stages amount
gm Cc
gm of solvent
cc
used for
extraction

Strength of extract
Beaker Extract Made up Volume taken Titre value of HCl cc
No. used for volume for titration.
Tit.1 Tit.2 Tit.3
dilution
Cc cc
cc

52
STANDARDIZATION OF HCl

Weight of sodium carbonate =

Made up volume of sodium carbonate solution =

Volume of Titre value of HCl cc

Na2CO3 soln.
Tit 1 Tit 2 Tit 3
taken cc

Calculations

Normality of standard Na2CO3 solution and HCl solution are

determined
Weight liter of Na2CO3, W1 =

Eq. Weight of Na2CO3, M1 =

Normality of Na2CO3, N1 = (W1/M1)
Normality of HCI, N2 = V1.N1/V2

The normality of extract in each case is found out.

53
Normality of made-up solution =
Normality of extract =

Calculation of theoretical recovery for varying number of stages is as

follows. If R1 is % theoretical recovery at the end of Ith stage, E, is the
vol.of extract from Ith stage Vi is the volume of feed and solvent in ith
stage,
R1 = (E1/V1)*100
R2 = (100-R1)*(E2/V2)
Or, Rn = (100- Rn-1)*En/Vn

Beaker Normality Solute % Actual % Theoretical

No. of extract Extracted gm recovery recovery

In the graph theoretical and actual % recoveries are plotted against

number of stages.

54
Experiment No: Date:

VERIFICATION OF FREUNDLICH EQUATION FOR

ADSORPTION ISOTHERM.

Aim
To verify the applicability of the Freundlich equation for adsorption of
acetic acid on activated carbon and to determine the value of the
constant k and n in equation for for adsorption at room temperature .

Apparatus
• Reagent bottles (5 nos)
• Shaking incubator
• Burette
• Filtering funnel (5 nos)
• Conical flask (250cc. 5 nos)
• Pipettes (10ml. 20ml)
• Volumetric flasks (100ml, 250ml. 2nos)
• Weighting tube (25cc)

Chemicals:
• Acetic acid
• Activated carbon
• Approximately 0.1N NaOH
• Oxalic acid

55
Theory

Adsorption operations exploit the ability of certain solids

preferentially to concentrate specific substances from solution to their
surfaces. In this component of either liquid or gaseous solutions may
be separated from each other. Some applications of adsorption in
gaseous separations are dehumidification of air and other gases,
removal of objectionable odours and impurities from industrial gases,
recovery of valuable solvent vapors form dilute mixtures with air and
other gases and fractionation of mixtures of hydrocarbon gases
containing such substances like methane, ethylene, ethane, and
propylene. Typical liquid separations are removal of moisture
dissolved in gasoline, decolourisation of petroleum products and
aqueous sugar solutions, removal of objectionable taste and odour from
water and fractionation of mixture of aromatic and paraffinic
hydrocarbons. Adsorption can be physical or chemical
(chemisorption). Physical adsorption or “Vander Waals” adsorption
can be readily reserved and is the result of intermolecular forces of
attraction between molecules of solid and the substance adsorbed. The
equilibrium partial pressure of the substance adsorbed equals that of the
contacting gas phase. This is lower than the vapor pressure and so
adsorption is not simple condensation. By lowering the pressure of the
gas phase or by raising the temperature, the adsorbed gas is readily
removed or desorbed in unchanged from. Reversible adsorption is seen
in liquids as well. Chemisorption or activated adsorption is the results
of chemical interaction between the solid and the adsorbed substance.
The process is frequently irreversible, and on adsorption, the original
substance will be found to have undergone a chemical change.
Chemisorption finds applications in catalysis. The usual adsorbents are
fuller’s earth, activated clays, bauxite, alumina, bone charcoal,
56
decolorizing carbon, gas adsorbent carbon, silica gel, zeolites, and
metal aluminosilicates.

Adsorption equilibria
The amount of substance adsorbed depends on the concentration
of the contacting gas or liquid phase, the temperature and pressure. A
relationship among these variables is called “adsorption equilibria “.
Data on adsorption equilibria are essential for designing adsorption
unit. Equilibrium data expressed for a particular temperature is called
“adsorption Isotherm”

In liquid adsorption isotherms are important since no appreciable

volume changes of the liquid occur which might be used as a measure
of adsorption. Withdrawal of the solid and weighting it, as can be done
in the case of gases, will not distinguish between the adsorbed liquid
and that which is mechanically occluded. When adsorbent is mixed
with a binary solution, adsorption in both solute and solvent occurs.
Since the total adsorption cannot be measured, the relative or apparent
adsorption can be determined instead. The customary procedure is to
57
treat a known volume of solution with a known weight of adsorbent, V
cm3 of solution /gm of adsorbent. As a result of preferential adsorption
of solute, the solute concentration of the solution is observed to fall
from the initial value c0 to the final value c* in the liquid (c-
concentration expressed in gms . of solute per cm3 of solution) . The
apparent adsorption of solute, neglecting any adsorption of solvent is
V (c0 - c*) gms of solute adsorbed per gram of adsorbent. This is
satisfactory for dilute solutions where the fraction of the original
solvent, which may be adsorbed, is small. Over a small concentration
range and particularly for dilute solutions, the adsorption isotherm may
be described by an empirical expression usually attributed to
Freundlich.
C*=k [V (c0 - c*) ]n

Where k and n are constants at a particular temperature. It is to be

noted that n is independent of units used and k has units same as that
used for c* or c 0 . Sometimes this curve may show deviation from
linearity. This may be due to appreciable adsorption of the solvent or
simply the general inapplicability of the Freundlich expression.

Procedure
Record the room temperature. Weigh about 25 grams of acetic
acid exactly in weighting tube and transferred completely by repeated
washings to a 250 ml volumetric flask (F1) .Make up the volume with
distilled water. Pipette out 10 ml of this solution in to a 250 ml
volumetric flask (F2) and the volume is made up. Weigh about 5gms of
activated carbon in to a reagent bottle (B1) (by differential weighting).
Add 200ml of solution from flask (F2) to this bottle. Repeat the same
58
procedure with bottles numbered (B2) (B3) (B4) (B5) with the
difference that the volumes of solution pipette out from the flask (F1)
are 20ml, 30ml, 40ml, and 50ml respectively. Shake the bottles well for
one hour using the bottle shaker for adsorption to come to equilibrium.
Meanwhile, prepare a standard solution of Oxalic acid (approx. .0.IN)
and use this to standardize the supplied NaOH solution. Filter the
solutions in the 5 bottles. Take the solution in the burette and titrate it
against 10ml NaOH.

Result
A graph of log C* Vs log (V (Co-C*)) is plotted.
The value of n =
k=

59
Observations
Room temperature =
Weight of weighting tube =
Weight of weighting tube + acetic acid =
Weight of acetic acid taken in 25 ml flask (F1) =

Preparation of mixtures
Vol.of Wt. of Wt. of
Vol. taken
solution paper paper Wt. of
from F1 to
Bottle No transferred +carbon +carbon carbon
250cc
to bottle before after taken
flask F2
from F2 transferring transferring

Weight of oxalic acid taken =

Volume of solution prepared =

Volume of NaOH
Titre value of oxalic acid
solution cc.

Tit1 Tit2 Tit3

60
 Titration of filtered solution
Volume of
Titre value of acetic acid
solution Volume
Bottle Diluted
used for of NaOH
No volume
dilution, taken cc Tit 1 Tit 2 Tit 3
ccs

Calculation

The normality of given NaOH solution =

The value of v (cm3 of solution /gms of adsorbent) and c0 in each of the
five bottles are calculated.
The value of c*in each of the original filtered solution is found out by

C*= NNaOH X volume of NaOH Eq.Wt of acetic acid/1000

X
Titre value of acetic acid

61
Bottle V (cm3 soln .gm C* (gm of solute/cm3
C0 (solute/cm3 soln)
No adsorbent) solution )

A graph of log C* Vs log (V (Co-C*)) is plotted and the value of n and

k are found from the slope and intercept respectively.

62
Experiment No: Date:

FREQUENCY RESPONSE OF FIRST ORDER SYSTEM

Aim
To obtain the time constant of the given thermometer from the step
response curve

Equipment/Apparatus

• Thermometer ( 0 to110 0C )
• Water bath
• Stop watch

Theory

A thermometer without thermo well is a first order dynamic

Y (s) 1
system whose transfer function is = and for a step
X (s)  s + 1

change of magnitude A, the response is

 −
t

y (t ) = A 1 − e 
 where τ is the time constant. For such a
 
system, 63.2 % of the step response will be completed within a time
period equal to one time constant.

63
0.632
Y(t)
A

 t/τ

Procedure

Boil water in a beaker, keeping the thermometer immersed in it

by suspending it from a stand and allow the thermometer to reach
steady boiling temperature. A step decrease in input can be affected by
taking it out from the boiling water and keeping it in atmospheric air.
A record of the thermometer reading against time will be the step
response data. Since rate of drop of mercury level is very fast in the
beginning, the following procedure can be adopted.

Tie a coloured thread around the thermometer at the 900C

mark. Take out the thermometer from the bath and simultaneously start
a stopwatch. Note the time to reach the thread mark. Keep the
thermometer again in boiling water to bring it back to the original
steady state temperature. The time to reach the thread mark is noted
twice more by following the same procedure. The average value of the
time is recorded. The whole procedure is repeated for observing the
time to reach 850C, 800C and 750C. From 750C onwards, the drop in

64
temperature can be noted along with the time in a continuous manner.
Use the response data to find the time constant.

Result

The step response curves are drawn.

Time constant (thermometer without thermowell) τ =

65
Observations and Calculations

Temperature, Time, s Deviation Y(t)/A

0
C

66
Room temperature =

Magnitude of step change, A =

A graph of Y(t) /A Vs time is plotted and the time constant is

determined.

Time constant = time taken for the response to reach 63.2 % of

the final value =

67
Experiment No: Date:

FREQUENCY RESPONSE OF SECOND ORDER

SYSTEM.

To obtain the time constant of the given thermometer with thermo well
using the step response curve

Equipment/Apparatus

Thermometer, Thermo well, 500ml beaker, Stopwatch,

Heating System

Theory

A thermometer without thermo well is a first order dynamic

system whose transfer function is

Y (s) 1
=
X (s)  s + 1

And for a step change of magnitude A, the response is Y(t) =

A{1-e-t/τ}, where τ is the time constant. For such a system, 63.2 % of
the step response will be completed within a time period equal to one
time constant. In the case when a thermo well is also used, the nature
of dynamics changes to second order over damped system whose
transfer function is

68
 Y ( s) 1
= where τ1 and τ2 are the effective time
X ( s ) ( 1s + 1)( 2 s + 1)

constants which can be determined by various methods like semi log

method, method of cold well and Oldenboung method. The semi log
plot method is described below.

Semi log plot method

In this method, (Reference P 297-298, Process System
Analysis and Control, Coughanowr) the logarithm of incomplete
response is plotted against time. This applies for systems with τ1 τ2.
The step by step procedure can be outlined as follows.

1. Plot the incomplete response against time and take the time at
which the process reaction curve first departs from time axis as
transportation lag τd.

2. Plot the fractional incomplete response I, against shifted time t1

starting from τd .
Bu − Y
I = = 1−
Y (t )
, t1 = t - d and Bu = the ultimate value
Bu A

of response.

3. The tangent through large values of t1 (Ia) is extended and its

intersection with

the vertical axis at t1 = 0 is taken as P.

4. The time constant is the time at which Ia = 0.368 P

69
 5.  = Ia – I is plotted against shifted time t1. For second order
systems, it will fall on a straight line intersecting the vertical axis
at t1 = 0 at R

6. Time constant is the time at which  = 0.368 R

Procedure
By suspending the thermometer with thermowell from a stand,
keep it immersed in water taken in a beaker. Boil the water and allow
the thermometer to reach steady boiling temperature.
A step decrease in input can be effected by taking it out from
the boiling water and keeping it in atmospheric air. A record of the
thermometer reading against time will be the step response data.
Record the response till steady state at room temperature.

Result
The process reaction curve is drawn.

Time constant (thermometer with thermowell τ1 =

τ2 =

70
Observations and Calculations

Thermometer With Thermowell

Temperature Time Deviation Y(t)/A %

0 incomplete
C
response

The Semi log plot is made for the system. From the plot,

P =

0.368 P =

71
τ1 =

R =

0.368 R =

τ2 =

72