Department of Fuel, Minerals and Metallurgical Engineering

PROCESS METALLURGY LAB

FMC 552

309, Third Floor, FMME Front Building

IIT(ISM) Dhanbad
 List of Experiments
Exp. Name of the experiment Page
No. No.
1. Pressure drop across a packed bed 3
2. Determination of minimum fluidization velocity of a bed of solid particles 6
Calibration of a thermocouple and determination of uniform temperature 10
3.
zone
To determine the angle of repose as affected by particle size, shape, surface 13
4.
condition and moisture content.
To study the reduction behaviour of iron ore pellets in the bed of 15
5.
coal/coke/graphite powder and CO gas used as reductant.
To determine the crushing strength and drop strength of green iron ore 17
6. pellets by varying percentage (%) of bentonite (1, 2, 3, 4, 5) additives
keeping 12% (OMC) moisture.
Determine the crushing strength and drop strength of green iron ore pellets 19
7. by varying % of water addition (8, 9, 10, 12, and 14 %) keeping 2%Na-
based bentonite.
Measurement of Thermodynamic Functions during the gas solid equilibrium 21
8.
of Calcination of Calcium Carbonate
Roasting kinetics of zinc sulphide at high temperature in oxidizing 23
9.
atmosphere
10. Effect of time on leaching of copper and determination of percent recovery 26
Effect of pulp density on leaching of copper and determination of percent 27
11.
recovery
Solvent extraction of Cu and Zn with determination of distribution co- 29
12.
efficient & separation factor

13. Study the effect of pH on solvent extraction of Cu 32

14. Electrowinning of copper from copper sulphate solution 34

15. Estimation of copper from copper ore 36

16. Estimation of percentage of the Fe in the given Iron-ore 37
17. Estimation of Silica (SiO2) in Ore 39

2
 E XPERIM ENT NO. 1

PRESSURE DROP ACROSS A PACKED BED

1. OBJECTIVE: To determine the pressure drop of a gas passing through a bed of spherical
solid particles of different sizes.
2. EQUIPMENT USED: Air compressor, rotameter, diaphragm pressure gauge, packing
particles, cylindrical tube, flow control valve.
3. THEORY: Ergun’s equation describes the flow of gases through packed beds/columns. The
pressure drop (Δܲ) across a bed of length ‫ ܮ‬can be obtained as
Δܲ 1−߳ 1
= ݂൬ ൰ቆ ቇ ߩ ܷଶ
‫ܮ‬ ߳ ߶݀௣ ௚ ௢
(1)

Where ݂ is the friction factor, which is empirically obtained as

150
݂= ܴ݁ < 0.1
ܴ݁
150
݂ = 1.75 + 10 < ܴ݁ < 2500
ܴ݁
(2)

160
݂= + 3.1ܴ݁ ଴.ଵ ܴ݁ > 2500
ܴ݁

ܴ݁ is the Reynolds number for the flow of gases through the particle bed and is given by
ߩ௚ ܷ௢ ݀௣
ܴ݁ =
ߤ௚ (1 − ߳)
(3)

Where ߳ is the void fraction, ߶ is the shape factor, ݀௣ is the diameter of the spherical particle,
ߩ௚ is the density of the gas, ܷ௢ is the empty-tube velocity of the gas.

The value of ߳ can be obtained from the bulk density, and the true density values as
ߩ௦,஻௨௟௞
߳ = 1−
ߩ௦,்௥௨௘
(3)

Where, ߩ௦ is the density of the solid particles. Also, for the spherical particles, the shape
factor ߶ = 1.

3
 Figure 1. Schematic illustrating the flow arrangement in the packed bed setup

4. EXPERIMENTAL PROCEDURE:
a. Fix the mesh at the bottom of the cylindrical tube and fill the solid particles up to 25 cm,
to form a packed bed.
b. Determine the packing fraction of the bed by measuring the bulk density and the true
density of the solid particles.
c. Connect the pressure gauges, rotameter, and the air compressor as shown in the figure
above.
d. Ensure that the flow rate and pressure indicators are all in zero position, and then switch
on the air compressor.
e. Slowly open the inflow control valve to allow airflow through the bed.
f. Record the airflow rate and the corresponding pressure readings from the rotameter and
the pressure gauges after near-stabilized conditions.
g. Repeat steps (e) and (f) for different values of the airflow rates till the onset of fluidization.
h. Refill the bed to increase the initial bed height to 50 cm and repeat the above procedure
to obtain the pressure drop across the bed.
i. Calculate the pressure drop vs. inflow rate from Ergun’s equation and compare it with the
experimental data for both cases.

4
5. OBSERVATIONS:

Table 1. Pressure distribution within the bed at different flow rates

Pressure (Pa)
S. No. Flow Rate (LPM)
1 2 3 4 5 6
1
2
3
4
5
6
7
8
9
10

6. EXERCISE SHEET (if any):

5
 E XPERIM ENT NO. 2

DETERMINATION OF THE MINIMUM FLUIDIZATION VELOCITY OF A BED

OF SOLID PARTICLES

1. OBJECTIVE: To determine the minimum fluidization velocity required for the fluidization
of a fixed bed.
2. EQUIPMENT USED: Air compressor, rotameter, diaphragm pressure gauge, packing
particles, cylindrical tube, flow control valve.
3. THEORY: Ergun’s equation describes the flow of gases through packed beds/columns. The
pressure drop (Δܲ) across a bed of length ‫ ܮ‬can be obtained as
Δܲ 1−߳ 1
= ݂൬ ൰ቆ ቇ ߩ ܷଶ
‫ܮ‬ ߳ ߶݀௣ ௚ ௢
(1)

Where ݂ is the friction factor, which is empirically obtained as

150
݂= ܴ݁ < 0.1
ܴ݁
150
݂ = 1.75 + 10 < ܴ݁ < 2500
ܴ݁
(2)

160
݂= + 3.1ܴ݁ ଴.ଵ ܴ݁ > 2500
ܴ݁

ܴ݁ is the Reynolds number for the flow of gases through the particle bed and is given by
ߩ௚ ܷ௢ ݀௣
ܴ݁ =
ߤ௚ (1 − ߳)
(3)

Where ߳ is the void fraction, ߶ is the shape factor, ݀௣ is the diameter of the spherical particle,
ߩ௚ is the density of the gas, ܷ௢ is the empty-tube velocity of the gas. The value of ߳ can be
obtained from the bulk density, and the true density values as
ߩ௦,஻௨௟௞
߳ = 1−
ߩ௦,்௥௨௘
(3)

Where, ߩ௦ is the density of the solid particles. Also, for the spherical particles, the shape
factor ߶ = 1.

6
 At the onset of fluidization, all the particles are suspended in the flow medium and are not
in contact. At the condition, the pressure forces and the gravity forces (buoyancy) are in
equilibrium, i.e.,
Δܲ
= (1 − ߳)൫ߩ௦ − ߩ௚ ൯݃
‫ܮ‬
(4)

The minimum fluidization velocity ൫ܷ௠௙ ൯ can be theoretically determined from equations
(1) and (4).

Figure 1. Schematic illustrating the fluidized bed experimental setup

4. EXPERIMENTAL PROCEDURE:
a. Fix the mesh at the bottom of the cylindrical tube and fill the solid particles up to 15 cm,
to form a packed bed.
b. Determine the packing fraction of the bed by measuring the bulk density and the true
density of the solid particles.
c. Connect the pressure gauges, rotameter, and the air compressor as shown in the figure
above.

7
 d. Ensure that the flow rate and pressure indicators are all in zero position, and then switch
on the air compressor.
e. Slowly open the inflow control valve to allow airflow through the bed.
f. Record the airflow rate and the corresponding pressure readings from the rotameter and
the pressure gauges after near-stabilized conditions.
g. Measure and record the average height of the bed.
h. Repeat steps (e) and (g) for different values of the airflow rates until and beyond the onset
of fluidization.
i. Slowly close the control valve to reduce the inflow rate and repeat steps (f) to (h) until the
inflow rate is zero.
j. Plot the pressure/height vs. superficial velocity during both ascension and fall of the
inflow rate.
k. Calculate the void fraction of the bed at the onset of fluidization by using the experimental
data.
l. Calculate the minimum fluidization velocity required and compare it with the
experimental data.

5. OBSERVATIONS:

Table 1. Pressure distribution within the bed at increasing flow rates

Pressure (Pa)
S. No. Flow Rate (LPM)
1 2 3 4 5 6
1
2
3
4
5
6
7
8
9
10

8
Table 2. Pressure distribution within the bed at decreasing flow rates
Pressure (Pa)
S. No. Flow Rate (LPM)
1 2 3 4 5 6
1
2
3
4
5
6
7
8
9
10

6. EXERCISE SHEET (if any):

9
 E XPERIM ENT NO. 3

CALIBRATION OF A THERMOCOUPLE AND DETERMINATION OF UNIFORM

TEMPERATURE ZONE

1. OBJECTIVE: To calibrate a given thermocouple and determine the temperature profile

inside a tube furnace.
2. EQUIPMENT USED: Tube furnace, standard thermocouple, non-standard thermocouple,
multi-meter.
3. THEORY: Thermocouples work based on the Seebeck effect or thermoelectric effect; i.e.,
when two dissimilar metals are joined, and the two junctions are held at different
temperatures, electric current flows through the closed-loop. Suppose only one end of the
metal wires is joined. In that case, an electromotive force (emf) is developed across the open
ends of the wires, which is a measure of the temperature difference between the hot and the
cold junctions, respectively.

Metal 1

Cold (ܶ‫) ܥ‬ Hot Junction (ܶ‫) ܪ‬

Metal 2
Figure 1. Schematic illustrating the thermocouple arrangement

Standard tables are available that relate the emf to the hot junction temperature, provided that
the cold junction is at 0 oC. If the cold junction is at a finite temperature, then the measured
emf must be corrected using the standard voltage (from the data tables) corresponding to the
cold junction temperature.
்݂݁݉௥௨௘ = ݂݁݉ெ௘௔௦௨௥௘ௗ + ݂݁݉஼௢௥௥௘௖௧௜௢௡ (1)
Thermocouples are calibrated against set standard temperatures, such as boiling point of water,
melting point of pure metals, etc. Once a thermocouple is calibrated, it can then be used to test
and calibrate other thermocouples. Depending on the materials used and the operating
temperatures, thermocouples are standardized into several kinds, as shown in Table-1.

10
 Table 1. Standard types of thermocouples
Thermocouple Material Temperature Range (࢕ ࡯)
B type Platinum/Rhodium 870 – 1700
E type Chromel/Constantan 0 – 870
J type Iron/Constantan 0 – 760
K type Chromel/Alumel 0 – 1260
N type Ncrosil/Nisil 0 – 1260
R type Platinum/Rhodium 870 – 1450
S type Platinum/Rhodium 980 – 1450
T type Copper/Constantan -200 – 370

4. EXPERIMENTAL PROCEDURE:
a. Tie a standard and a non-standard thermocouple together.
b. Connect the cold ends of the standard thermocouple to the temperature indicator.
c. Connect the cold ends of the non-standard thermocouple to a voltmeter.
d. Switch on the tube furnace and Place both the thermocouples at the center of the furnace.
e. Every 10 minutes, note down the actual temperature data and the emf across the cold ends
of the non-standard thermocouple using the voltmeter until the furnace reaches a steady
state of operation.
f. Slide the standard thermocouple aside by a few centimetres and measure the temperature
along the axis of the tube.
g. Slide the thermocouple radially and measure the temperature along the radius of the tube
at the center.
h. Draw a plot of actual temperature vs. emf to calibrate the non-standard thermocouple.
i. Draw a plot of axial distance vs. temperature and radial distance vs. temperature to obtain
the thermal profile and determine the uniform temperature zone of the furnace.

11
5. OBSERVATIONS:

Table 1. Thermocouple Calibration

S. No. Time (min) Hot junction temperature (࢕ ࡯) Emf (volts)

1
2
3
4
5
6
7
8
9
10

Table 2. Temperature Profile inside the furnace

S. No. Axial position (cm) Radial position (cm) Temperature (࢕ ࡯)

1
2
3
4
5
6
7
8
9
10

6. EXERCISE SHEET (if any):

12
 E XPERIM ENT NO. 4
To determine the angle of repose as affected by particle size, shape, surface condition and
moisture content.

1. OBJECTIVE: To study the effect of (a) shape, (b) size,(c) surface,(d) moisture on the
angle of repose of a given raw materials.
2. EQUIPMENT USED: Angle of repose set up, Tray, Open ends Perspex cylinder,
Weighing balance, Surfaces to be used (Steel, Rubber, Canvas, and Wood).
3. RAW MATERIALS:
a. Different raw materials of same size (iron ore, Limestone, Pellets etc. of 12 mm size.)- For
effect of Shape.
b. One Raw Material of different size (iron Ore of -21+18 mm , -18+15 mm , -15+12 mm, -
12+8 mm etc.)-For effect of size.
c. One raw material of particular size with different surface (-6+3 mm iron ore in Steel,
rubber, Canvas, Wood surfaces)-For effect of surface.
d. One raw material of particular size (i.e.-6+3 mm) with different moisture addition (say,
iron ore in steel surface and adding moisture 2, 3, 4, 5, %.) -For effect of moisture.

4. THEORY: When materials are dropped freely to form a conical heap then the slop of the
surface to horizontal is known as Angle of repose (θ). The granular particles on the conical heap
tend to roll down the inclined surface under gravitational force (G) opposed by frictional force
(F) between the rolling particles and particles lying on the heap surface. If the frictional force
(F) exceeds the value of (G), then the material roll down less and locate at the top region of the
heap giving higher (θ) value, if it locate lower region it gives lower (θ) value.

5. EXPERIMENTAL PROCEDURE:
(a) Keep the perpex cylinder in an enamel tray.
(b) Locate the Angle of repose set up in such a position, and tilt after taking the material
above it, such a way that particles fed on the chute slide and strike the inner side of the
wall before falling down.
(c) Measure the height of materials inclined surface at lower (h) and upper end (H) from
its base. The difference (H-h) would give the height of the inclined surface while
diameter (D) of the Perspex cylinder gives the base of a triangle to calculate the angle
(θ).
(d) Study the effect of different surface by fitting steel, canvas, rubber, sheet above the
Angle of repose set up bottom.
(e) Study the effect of moisture content add water with measuring cylinder (2%,3%,4%
,5% etc.)

13
6. OBSERVATIONS:

Sl No. Material Size %Moisture H h H-h (θ)

7. RESULTS AND DISCUSSION

Discuss your observation by plotting
(1) Angle of repose Vs Particle size
(2) Angle of repose Vs Moisture

8. PRECAUTIONS:

9. INDUSTRIAL SIGNIFICANCE

10. EXERCISE SHEET (if any):

14
 EXPERIMENT NO-05
To study the reduction behaviour of iron ore pellets in the bed of coal/coke/graphite powder
and CO gas used as reductant.

1. OBJECTIVE:
To study the effect of reduction time on the degree of reduction (%R) and Reduction
swelling (%S) of iron ore pellets reduced in a bed of reductant (e.g., Fines of Coal,
Coke, Wood char, Graphite etc.) at ~1000 °C and to study the effect of solid and
gaseous reductant on the reduction behaviour of iron ore pellets.

2. EQUIPMENT AND MATERIAL:

Resistance furnace (~1000°C), Digital balance, MS Crucibles, Slide Calliper, Hardened
Pellets, Reductant (Coke/ Coal / Charcoal/Graphite etc.), Vertical TGA setup,
Reductant CO gas.

3. THEORY:
When iron oxide pellet is kept in a bed of reductant at ~1000°C, then first the Carbon
is gasified by oxygen trapped in the bed and CO is formed. This CO reacts with iron
oxide which is reduced to lower oxide with formation of CO2. This CO2 in turn
combines with C of the bed with the formation of CO. This gasification of C and
reduction of oxide continuous till all iron is reduced in metallic form .The rate of this
reaction will depend upon mass transportation of gaseous phase and gasification
reaction. The reduction of iron oxide is accompanied with change in volume which is
due to growth of iron fiber (whiskers).

4. PROCEDURE:
Solid State reduction with Carbon
a. Take four dry almost uniform size without cracks iron ore pellets and accurately weight
them individually. (W1)
b. Take four iron crucibles and number them. (1 to 4).
c. Keep a bed of 20 mm reductant before feeding a pellet.
d. Place the pellets over the reductant layer and add more reductant in each crucible to
have about 15 mm thick bed over the pellets.
e. Now feed refractory material (groge) to have 10 mm bed over coke layer to prevent its
oxidation.
f. After marking the crucibles place them in Furnace at 1000°C. Mark their position on
table as place inside the furnace.
g. When the temperature reach 1000 °C note down the time and after 30 minutes withdraw
first crucible.
h. Then after every 10 minutes interval withdraw remaining crucibles.
i. Allow to cool the crucible , pour out ,separate pellets, clean them and weight
individually.(W2)
Solid State reduction with Gas (CO)
a. Start TGA setup and reach at 1000°C and flow nitrogen gas
b. Put the pellets in the TGA setup
c. Start the flow of CO gas from the cylinder
d. Note the readings carefully

15
 5. OBSERVATIONS:

SL Time Initial Final Loss of Oxygen % of dR/dt

No ( in min) Weight Weight weight present in Reduction =
(W1) (W2) (W1-W2 ) ore (W 0 ) (R/t)
(t) gm gm gm gm (R)

1
2
3
4

6. RESULTS and DISCUSSION

Plot the graphs (1) R Vs Time
(2) dR / dt Vs Time

7. PRECAUTIONS:
(1) Do not keep hot crucible on wooden bench.
(2) Handle hot object carefully.
(3) Handle reduced pellets carefully. They may break by careless handling.
(4)Switch off furnace during withdrawal and placing of crucibles to avoid electric
shock.

8. Industrial significance:

9. EXERCISE SHEET (if any):

16
 EXPERIMENTS No. 06
To determine the crushing strength and drop strength of green iron ore pellets by varying
percentage (%) of bentonite (1, 2, 3, 4, 5) additives keeping 12% (OMC) moisture.

1. OBJECTIVE:
To determine the crushing strength and drop strength of green iron ore pellets
by varying % of bentonite (1, 2, 3, 4, 5) additives keeping 12% moisture

2. MATERIAL:
Iron ore fines (-300mesh/-50micron), Sodium based bentonite and Water

3. EQUIPMENT:
Pelletizer, Crushing strength testing unit, steel sieve with 12mm apertures, a 2mm
thick steel plate (200mmx200mm), balance, weighing balance, enamel steel tray
(400mmx300mm), 100ml pipette, meter scale.

4. THEORY:
Pellets are balls prepared from concentrate and natural iron ore fines. The
production of pellets are carried out in three steps, i.e. i) Preparation of feed,
(addition of bentonite/water, ii) balling (by hand or machine) and iii) hardening (by
heating). During balling, the concentrate fines with binder (bentonite) are rolled
with addition of wetting liquid (water) in suitable device such as drum or disc
pelletizer or by hand. The balls thus formed are called as “green pellets”.
Mechanism of balling has demonstrated the extreme dependence of ball formation
on moisture content. This critical moisture content for balling is essential to initiate
the formation of nuclei. The green ball growth curve shows a characteristic S shape.
The agglomeration of fines, after first forming of nuclei proceeds through three
stages of growth which is termed as nuclei coalescence, transition and ball growth
region. Drop strength-The no. of drops sustained without breaking a green or dry
pellets when dropped on a steel plate from a height of 450mm is termed as its drop
strength. Average value of ten pellets is accepted as drop strength. The minimum
desirable value is 4 drops.

5. PROCEDURE:
a) Take five trays and mark 1 to 6,
b) Weight and put 200g iron ore fines in each of the five trays,
c) Weight and transfer bentonite to get 0, 1, 2, 3, 4 and 5wt% in respective trays
from 1-6,
d) Now mix ore and bentonite in dry state to have a homogeneous mixture,
e) Now take the material in a tray (say no.-1) and add 24cc water with the help of
burette to get 12% OMC water addition.
f) After preparation of pellets perform the green crushing strength and drop test
with the respective machines.

17
 6. OBSERVATIONS:

Tray Additives Green strength of Iron ore pellets

No.
% Bentonite %Moisture Drop Strength (nos.) Crushing strength(kg/g)
[average of 3 balls] [average of 3 balls]
Avg. Avg.
1 0 12
2 1 12
3 2 12
4 3 12
5 4 12

7. RESULTS AND DISCUSSION:

Draw a plot between drop no. /crushing strength vs. bentonite content to note
the behaviour of strength.
Discuss the result in light of bonding behaviour affected by increased bentonite
content

8. PRECAUTION:
a) Take minimum time to perform experiment to avoid moisture evaporation
from pellets.
b) Handle green pellets/ball carefully
c) Perform testing just after forming pellets to avoid drying.

9. INDUSTRIAL SIGNIFICANCE:

10. EXERCISE SHEET (if any):

18
 EXPERIMENT No. 07

Determine the crushing strength and drop strength of green iron ore pellets by varying %
of water addition (8, 9, 10, 12, and 14 %) keeping 2%Na-based bentonite.

1. OBJECTIVE:
To optimize the amount of moisture addition in the iron ore for pellet preparation by
determining the crushing strength and drop strength of green iron ore pellets by varying %
age of water addition (8, 9, 10, 12, 14 %) keeping 2%Na-based bentonite.

2. MATERIAL:
Iron ore fines (-300mesh/-50micron), Sodium based bentonite and Water

3. EQUIPMENT:
Pelletizer, Crushing strength testing unit, steel sieve with 12mm apertures, a 2mm thick
steel plate (200mmx200mm), balance, weighing balance, enamel steel tray
(400mmx300mm), 100ml pipette, meter scale.

4. THEORY:
Pellets are balls prepared from concentrate and natural iron ore fines. The production of
pellets are carried out in three steps, i.e. i) Preparation of feed, (addition of bentonite /water,
ii) balling (by hand or machine) and iii) hardening (by heating). During balling, the
concentrate fines with binder (bentonite) are rolled with addition of wetting liquid (water)
in suitable device such as drum or disc pelletizer or by hand. The balls thus formed are
called as “green pellets”. Mechanism of balling has demonstrated the extreme dependence
of ball formation on moisture content. This critical moisture content for balling is essential
to initiate the formation of nuclei. The green ball growth curve shows a characteristic S
shape. The agglomeration of fines, after first forming of nuclei proceeds through three
stages of growth which is termed as nuclei coalescence, transition and ball growth region.
Drop strength-The no. of drops sustained without breaking a green or dry pellets when
dropped on a steel plate from a height of 450mm is termed as its drop strength. Average
value of ten pellets is accepted as drop strength. The minimum desirable value is 4 drops.

5. PROCEDURE:
a) Take five trays and mark 1 to 5,
b) Weight and put 200g iron ore fines in each of the five trays,
c) Add 2% bentonite in all trays mix properly to have a homogeneous mixture. d) Add 16cc
(tray no.1), 20cc, 24cc, 28cc water with the help of burette to get 8, 9, 10, 12, 14% water
addition in ore mixed respectively.
e) Mix water and ore mix properly by hand to get a green mix.
f) Now make pellets by hand rolling to get 12mm size pellets (more than 6 in nos.) and
keep them in covered desiccator holding water. The water in place of normal CaCl2 will
prevent water evaporation in the pellets.
g) First test 3 pellets for drop strength and then proceed for crushing strength for remaining
3 pellets.
h) Now repeat above steps for materials in tray nos.2,3,4 and 5 one by one.
6. OBSERVATIONS

Tray Additives Green strength of Iron ore pellets

No.

19
 %Bentonite %Moisture Drop Strength (nos.) Crushing strength(kg/g)
(2% [average of 3 balls] [average of 3 balls]
bentonite)
Avg. Avg.
1 2 8
2 2 9
3 2 10
4 2 12
5 2 14

7. RESULTS AND DISCUSSION:

Draw a plot between drop no./ crushing strength Vs. Moisture content to note the behaviour
of strength. Discuss the result in light of bonding behaviour affected by moisture content.

8. PRECAUTION:
a) Take minimum time to perform experiment to avoid moisture evaporation from pellets.
b) Handle green pellets/ball carefully
c) Perform testing after forming pellets to avoid drying.

9. INDUSTRIAL SIGNIFICANCE:
10. EXERCISE SHEET (if any):

20
 Experiment No 08
Measurement of Thermodynamic Functions during the gas solid equilibrium of Calcination
of Calcium Carbonate

1. OBJECTIVE: Measurement of standard free energy (߂‫ ܩ‬௢ ), Enthalpy (߂‫ܪ‬௢ ), and
Entropy of formation (߂ܵ ௢ ) of calcium carbonate through pressure measurement
technique.
2. EQUIPMENT: Horizontal Tube Furnace, Calcium Carbonate, Nitrogen gas.
3. THEORY:
Decomposition of CaCO3 can be written as following:
CaCO3 (s) = CaO (s) + CO2 (g)
Equilibrium constant can be written as: K=


2 =


2 w.r.t. 1 atm. Pressure
of gas as the standard state. If solids are pure (in their standard state) then the activity
of the solids can be assumed as 1. It is assumed that the temperature we will be
dealing with will not melt the solid. In that case the calculation becomes more
complex.


2 is the equilibrium gas pressure of CO2 at that temperature in atm.
unit.

The Thermodynamic functions can be written as following:

߂

= -RTln


2 (1)

From the Thermodynamic relations one can write:

(





2 )
߂

=− =





(2)

From Gibb’s -Helmholtz equation one can write:

(


/
)

(




2 )

߂

=
(1/
)
=−
(1/
)
(3)

Through measuring the equilibrium gas pressure of


2 at each temperature and
using the Eq. (1), (2) and (3) one can find out the ߂

,߂

and ߂

.

4. PROCEDURE:
1. Place about 20g of Calcium Carbonate in the silica tubing one end closed.

2. Keep the reaction tube in the furnace and bring it to around 300°C.

3. Evacuate the system using the vacuum pump to around 0.1 mm Hg level.

21
4. Close the stopcock connection to the vacuum pump.

5. Set the temperature controller of the furnace at 750°C

6. Record the changes in the temperature of the furnace and levels of

mercury in the two legs of manometer at regular intervals of 2 minutes.

7. Repeat the experiment at 800°C and 850°C

From the fluid statics one can write that the partial pressure of carbon dioxide in the reaction
tube at any instant is related to the difference in the mercury levels in two legs of the manometer
as follows:

= [barometer pressure in mm Hg – manometer reading in mm Hg] / 760

Barometer pressure (one leg is in equilibrium with the atmospheric pressure) may be obtained
from the barometer fixed in the walls of the laboratory.

5. OBSERVATIONS:

Below table may be useful to tabulate the experimental result:

Manometer Manometer
Time, Temperature, Temperature, Pressure
Left Right Leg,
min K Difference,m
°C Leg,mm Hg
mm Hg m Hg

6. RESULTS & DISCUSSION

1. Plot of (





2 ) w.r.t. T to find the ߂

(check Eqn. 2)

2. Plot of (




2 ) w.r.t. (1/T) to find the ߂

(check Eqn.3)
3. Find the std. Decomposition temperature of CaCO3.

std. Decomposition temperature : The temperature at which the CaCO3 decomposes at 1 atm
in equilibrium condition.

22
 EXPERIMENT NO 9
ROASTING KINETICS OF ZINC SULPHIDE AT HIGH TEMPERATURE IN
OXIDIZING ATMOSPHERE

1. OBJECTIVE: To study the kinetics of roasting of ZnS by Thermogravimetric method.

2. EQUIPMENT: Vertical tube furnace (TGA), ZnS, Nitrogen gas.
3. THEORY: The sulphide ores are in general difficult to reduce to metal. Therefore, it is
desirable to convert the sulphide form of the ore to oxide form, which is suitable for reduction
with cheaply available reducing agents like H2 or Carbon. This conversion is carried out by
heating the sulphide ore below its fusion temperature with excess air (amount of air more than
stoichiometric requirement).

2ZnS+ 3O2 = 2ZnO+ 2SO2

Roasting is a metallurgical process in the extraction circuit wherein the ore is heated below the
fusion point of its constituents under such conditions such that the metal component of the ore
which is sought to recover will be chemically as well as physically changed from to some other
form which will be amenable to same definite subsequent treatment for extraction of the metal.
There are various types of roasting operations possible. Some important ones are the following:

(i) oxidizing roasting,

(ii) reduction roasting,
(iii) sulphate roasting and
(iv) chloridizing roasting.
(v) Volatilizing roasting

In industrial practice, roasting operations are carried out in various types of furnaces such as
shaft furnace, hearth roaster, rotary kilns and fluidized bed reactors. All roasting operations
involve heterogeneous chemical reaction, that is to say, gas-solid reactions in which a solid
reacts with a gas to produce another solid and gas, and therefore, the kinetics of a roasting
operation should conform to the kinetics of gas solid reactions. In addition, this roasting
reaction is exothermic leading to significant rise of sample in-situ temperature during
oxidation. This situation sometimes may lead to local sintering.

23
 4. PROCEDURE:

1. Materials required for this experiment includes (a) Any (Zinc) sulfide, (b) oxygen and
(c) nitrogen/ argon.
2. Weigh about 0.60 gm of the dry ZnS pieces, in the wire mesh basket.
3. Flush nitrogen/argon in the furnace tube already heated to give a steady state
temperature for 5 minutes to drive out air from it.
4. With the help of a thin nichrome wire slowly lower the basket containing zinc sulfide
into the furnace. The other end of the wire is attached to the pan of a balance which is
used to measure weight loss of the concentrate during the roasting operation by
removing it from the furnace. The wire should be freely suspended into the furnace.
(This is in general the TGA setup)
5. Note down the weight reading on the balance.
6. Switch off nitrogen/argon and start flushing oxygen at a given slow rate taking care to
avoid any carry over of the ZnS particles.
7. Immediately start taking the weight readings at intervals of 2 minutes till almost a
constant weight reading is obtained.
8. Note the temperature and oxygen flow rates before and after the experiments. Try to
maintain them constant as far as possible throughout the experiment. In case of
variation, average values of temperature and oxygen flow rates may be used. (This is
an isothermal reaction)
9. Repeat the above for two other temperatures with the same flow rate of Oxygen.
(Suggested temperature 600oC, 650oC and 700oC)

Upon roasting of ZnS, any of the following 3 products are likely to form according to phase
equilibria in Zn-S-O system.

Reaction Log K (K is equilibrium constant)

T = 900K T = 1000K T = 1100K

ZnS+ 3O2 = ZnO+ SO2 (1) 21.77 19.19 17.07

24
 ZnS+ 2O2 = ZnSO4 (2) 26.61 22.16 18.61

3ZnS+ 11O2 = ZnO. ZnSO4 + SO2 75.84 64.35 54.97

(3)

T. R. Ingraham and H.H. Kellogg: Trans. of Met. Soc. AIME, Vol.227(1963), p.1419

1. Assuming the product to be ZnO, calculate fractional conversion (F) as function of time
from your weight loss data.

2. From oxygen flow rate and weight loss data, calculate the average value of PSO2 in exit
gas at one of the temperatures.

For example, consider reaction 1: From the weight loss of the sample one can calculate how
much SO2 is generated through the stoichiometry. One can find out the partial pressure of O2
and SO2 from that data.

3.Then do thermodynamic calculations to predict the product.

Write the equilibrium constant value as a function of partial pressure of O2 and SO2 for
reaction (1). Does that match with the reported data of K at that temperature? If yes, reaction
(1) is the correct reaction. Otherwise follow the same steps for reaction (2) and (3).

5. OBSERVATIONS:
Following table may be useful to record the experimental data:

Initial Time Temperature Weight Fraction Fraction Fraction

Temperature recorded of the conversion conversion conversion
sample reaction 1 reaction 2 reaction 3

6. RESULTS & DISCUSSION:

25
 EXPE RIM ENT NO. 10
Effect of time on leaching of copper and determination of percent recovery

1. OBJECTIVE: To conduct the leaching of copper ore for different time interval and
determine the percent recovery
2. EQUIPMENT USED: Electronic balance, beaker, filter paper, magnetic pellet,
3. THEORY: Leaching is a hydrometallurgical unit process. Leaching is used to selectively
dissolve the desired metals or impurities in the aqueous solution from ore/mineral. A variety
of acids/alkali are used to dissolve the metal in the solution. The leaching recovery depends
on various parameters such as type of reagent, concentration of reagent, leaching time,
stirring speed, pulp density (solid to liquid ratio), temperature etc.
4. PROCEDURE:
a. Take 5 g of roasted copper ore in a beaker (100 ml)
b. Add leaching reagent to the beaker by maintaining pulp density 100 g/L
c. Place the magnetic pellet in the beaker gently
d. Stir the solution for 60 minutes
e. Take out the 2 ml of leach solution at the interval of 15, 30 and 45 minutes
f. At completion of 60 minutes, filter the leach solution from undissolved solid
g. Keep the undissolved solid in oven for drying
h. Weigh the solid after drying
i. Estimate the weight of residue by determining the difference in initial and final
weight of ore
j. Analyse the leach liquor collected at different time interval to determine the Cu
concentration
k. Plot %Recovery of Cu vs time in the graph
5. OBSERVATIONS:
Table 1. Effect of leaching time on recovery of Cu
Concentration of Cu % Recovery of Cu
Time duration Observation (Colour) in leach solution
(mg/L)
15 min
30 min
45 min
60 min

26
 EXPE RIM ENT NO. 11
Effect of pulp density on leaching of copper and determination of percent recovery

1. OBJECTIVE: To conduct the leaching of copper ore at different pulp density and
determine the percent recovery
2. EQUIPMENT USED: Electronic balance, beaker, filter paper, magnetic pellet,
3. THEORY: Leaching is a hydrometallurgical unit process. Leaching is used to selectively
dissolve the desired metals or impurities in the aqueous solution from ore/mineral. A
variety of acids/alkali are used to dissolve the metal in the solution. The leaching recovery
depends on various parameters such as type of reagent, concentration of reagent, leaching
time, stirring speed, pulp density, temperature etc. The pulp density defined as the amount
of solid used in per litre of the solution. It represent the solid to liquid ratio during leaching
experiments.
4. PROCEDURE:
a. Take 4 beakers and add 5 g of roasted copper ore in each beaker
b. Add leaching reagent to the beaker by maintaining pulp density 50 g/L, 70 g/L, 100
g/L and 150 g/L.
c. Place the magnetic pellet in the beaker gently
d. Stir the solution for 30 minutes
e. At completion of 30 minutes, filter the leach solutions from undissolved solids
f. Keep the undissolved solids in oven for drying
g. Weigh the solids after drying
h. Estimate the weight of residue by determining the difference in initial and final
weight of ores
i. Analyse the leach liquor collected at different time interval to determine the Cu
concentration
j. Plot %Recovery of Cu vs pulp density in the graph

27
5. OBSERVATIONS:

Table 1. Effect of pulp density on leaching recovery of Cu

Pulp density Observations Concentration Wt. of leach % Recovery
of Cu in leach residue
solution (mg/L)
50 g/L
70 g/L
100 g/L
150 g/L

6. EXERCISE SHEET (if any):

28
 EXPE RIM ENT NO. 12
Solvent extraction of Cu and Zn with determination of distribution co-efficient &
separation factor

1. OBJECTIVE: To conduct the solvent extraction (Liquid-liquid extraction) experiment for

the separation of Cu and Zn from the sulphate solution by using LIX64N as extractant
2. EQUIPMENT USED: Beaker, separating funnel, pH meter
3. THEORY: Solvent extraction is a method to separate compounds or metal complexes, based
on their relative solubilities in two different immiscible liquids, usually water and an organic
solvent. The phase enriched in solute after extraction called “Extract” and feed solution
depleted in solute called “Raffinate”. It is one of the most commonly used hydrometallurgical
techniques for the separation of metals. The extent of distribution depends on the nature of
solvent and diluents, and the extraction conditions viz., equilibrium pH, concentration of
metal ions, temperature, etc. In the solvent extraction process, the extraction percentage
(%E), distribution coefficients (D) and separation factors (β) are calculated using equations
(1) to (3):
(M i - M f ) × 100
%E = (1)
Mi
(M i - M f )
D= (2)
Mf
D1
S.F = (3)
D2

where Mi and Mf represent the initial concentration of metal ions in the aqueous feed and final
concentration of metal ions in the raffinate, respectively. The extraction percentage (%E)
determines the efficiency of the extraction. The distribution coefficient (D) represents the ratio
of metal ions transferred to organic phase to remaining metal ions in the raffinate. The
separation factor (S.F) determines the selectivity of one metal ion over other, where D1 and D2
are the distribution coefficient of metal ions 1 and 2, respectively.

4. PROCEDURE:
a. Aqueous phase preparation: Prepare 100 ml of mixed solution of Cu and Zn of
concentration 1g/L each by dissolving the appropriate amount of CuSO4 and ZnSO4
in distilled water.

29
b. Organic phase preparation: Take the appropriate amount of extractant (LIX64N)
in a volumetric flask (100ml). Add kerosene as diluent upto the mark to maintain the
required volume of volumetric flask. Mix the organic solution by gentle shaking.
c. Take out a beaker and add 25 ml of aqueous solution.
d. Maintain the pH =2.5 for the aqueous solution by adding dilute H2SO4/NaOH
solution and observing the pH reading using pH meter.
e. Pour this solution in a separating funnel (before pouring ensure that stopcock is
closed)
f. Add 25 ml of organic solution in the same separating funnel to maintain the O/A
ratio 1:1.
g. Closed the cap of separating funnel and gently shake the funnel for 5 minutes for
proper mixing of two phases.
h. After mixing, keep the separating funnel in standing position for 2-3 minutes for
better separation of aqueous and organic phases.
i. Open the stopcock slowly and separate out the raffinate phase in a beaker.
j. Analyse the Cu and Zn concentration in the raffinate
k. Determine the concentration of Cu and Zn loaded in the organic phase from mass
balance.
l. Determine the distribution co-efficient value Cu and Zn extraction
m. Calculate the separation factor (βCu/Zn) value for the separation of Cu and Zn

30
5. OBSERVATIONS:

Table 1. Solvent extraction separation study of Cu and Zn

pH [Cu]raffinate [Zn]raffinate [Cu]org [Zn]org %ECu %EZn DCu DZn βCu/Zn

6. EXERCISE SHEET (if any):

31
 EXPE RIM ENT NO. 13
Study the effect of pH on solvent extraction of Cu

1. OBJECTIVE: To study the effect of pH on solvent extraction by using LIX64N as

extractant
2. EQUIPMENT USED: Beaker, separating funnel, pH meter
3. THEORY: Solvent extraction is a method to separate compounds or metal complexes,
based on their relative solubilities in two different immiscible liquids, usually water and an
organic solvent. The phase enriched in solute after extraction called “Extract” and feed
solution depleted in solute called “Raffinate”. It is one of the most commonly used
hydrometallurgical techniques for the separation of metals. The extraction of metals from
aqueous to organic phase depends very much on pH of the aqueous solution, especially when
cation exchange extractants is used. The pH0.5 depicts the pH value at which 50% of
extraction takes place
4. PROCEDURE:
a. Aqueous phase preparation: Prepare 100 ml of solution of Cu of concentration
1g/L each by dissolving the appropriate amount of CuSO4 in distilled water.
b. Organic phase preparation: Take the appropriate amount of extractant (LIX64N)
in a volumetric flask (100ml). Add kerosene as diluent upto the mark to maintain the
required volume of volumetric flask. Mix the organic solution by gentle shaking.
c. Take out 5 beaker and add 20 ml of aqueous solution in each
d. Maintain the pH value of 1, 2, 3, 4, and 5 for the aqueous solution by adding dilute
H2SO4/NaOH solution and observing the pH reading using pH meter.
e. Pour this solution in a separating funnel (before pouring ensure that stopcock is
closed)
f. Add 20 ml of organic solution in the same separating funnel to maintain the O/A
ratio 1:1.
g. Closed the cap of separating funnel and gently shake the funnel for 5 minutes for
proper mixing of two phases.
h. After mixing, keep the separating funnel in standing position for 2-3 minutes for
better separation of aqueous and organic phases.
i. Open the stopcock slowly and separate out the raffinate phase in a beaker.
j. Analyse the Cu in the raffinate
k. Determine the concentration of Cu in the organic phase from mass balance.

32
 l. Determine the %E of Cu. Plot %ECu Vs pH.
m. From the graph, determine the pH0.5 value for extraction of Cu.

5. OBSERVATIONS:
Table 1. Effect of pH on extraction of Cu
Exp. No. pH meter reading [Cu]raffinate [Cu]org %E

33
 EXPE RIM ENT NO. 14
Electrowinning of copper from copper sulphate solution

1. OBJECTIVE: To conduct the leaching of copper ore and determine the percent recovery
2. EQUIPMENT USED: Beaker, electrolysis set-up, power supply, pH meter
3. THEORY: Electrowinning is an electrolysis process which is used to produce metals from
their salts (metal ions) present in the aqueous solution. Metals that appear above H2O on the
electrochemical series are produced using aqueous electrowinning. In the electrowinning
of copper, anode (lead alloy) and cathode (stainless steel or copper sheet) are connected
through an external power supply for the electrolysis process. Oxidation occurs at the anode
and reduction of copper ions takes place at cathode. The solid copper metal is deposited at
cathode and oxygen gas evolved at anode. The reactions involved in the electrowinning of
copper are:
At cathode: Cu2+ + 2e-
Cu

At anode: H2O
2H+ + ½O2+ 2e-

Overall reaction: Cu2+ + H2O
Cu + 2H+ + ½O2

4. PROCEDURE:
a. Prepare an electrolyte of sulphuric acid of appropriate concentration
b. The weight of the cathode weight was noted.
c. The anode and cathode plates are placed inside the beaker. The distance between
the anode and cathode is maintained at 1 cm.
d. Electrolyte was poured in the beaker.
e. The electrolysis set up was completed by connecting the anode and cathode to
power supply.
f. The electrolysis experiment is performed for fixed duration.
g. After completion of electrolysis, the final weight of cathode was noted.
h. Calculate the actual weight of copper deposited using difference in cathode weight
before and after electrolysis.
i. Calculate the theoretical expected weight of copper deposition using Faraday’s Law
(W = ZIt), where W, Z, I and t are theoretical weight of copper deposited, equivalent
weight of copper, current (ampere) and time (second).
j. Determine the current efficiency using C.E = (w/W) x 100, where w = weight of
actual copper deposited.

34
5. OBSERVATIONS:

Initial wt. of Wt. of cathode after Cuactual Cutheoretical Current

cathode electrolysis (w) (W) efficiency

35
 EXPE RIM ENT NO. 15
Estimation of copper from copper ore

1. OBJECTIVE: Estimation of copper in copper ore

2. MATERIAL USED: Copper ore, HNO3/HCl, Potassium iodide, K2Cr2O4 solution,
Na2S2O3.5H2O, Urea, Starch solution, Ammonium bifluoride

3. THEORY: The analysis of copper is important to determine its concentration in the

aqueous solution. Titration is an absolute method to analyse the liquor with good accuracy.
4. PROCEDURE:
a. 0.5 gm of copper ore was taken
b. Aqua regia (one part of conc HNO3 and three part of conc HCL) was added to the ore
c. 3. The solution was heated over hot plate for around three hours
d. 4. After digestion it was filtered, filtrate was collected
e. Preparation of 250 ml Na2S2CO3 solution- find the equivalent weight for 250 ml
solution and solution is prepared
f. Standardization of Na2S2O3 solution
g. Titration of copper ore with Na2S2O3 solution
h. Filtrate was collected from filtration of digested copper ore and aquaregia solution
i. Add Urea and Ammonium bifluoride
j. 2 g KI was added
k. It was titrated with Na2S2O3 solution, paint yellow colour was observed at the end
point
l. Starch indicator was added and it was further titrated
m. Milky white colour was observed at end
n. Note the reading

5. OBSERVATIONS:

36
 EXPERIMENT NO. 16
Estimation of percentage of the Fe in the given Iron-ore
1. OBJECTIVE: To estimate the percentage of the Fe in the given Iron-ore sample
2. EQUIPMENT: Iron ore sample , Concentrated HCl , Distilled water, K2Cr2O7, SnCl2
solution, HgCl2 solution, Mix of H2SO4 and H3PO4, & Diphenylamine indicator.
3. PROCEDURE:
a) Digestion of ore in acid
• Take 0.50 g Fe-ore in a beaker (200ml)
• Then add 50 ml concentrated HCl
• Covered with watch glass
• Finally put on hot tray for about 1 hr for digestion
• If digestion is not complete within stipulated time, then again add 10 cc HCl and keep it for
digestion
b) Preparation of stock solution
• After digestion filtered in 250 ml measuring flask. Wattman 40 filter paper was used
• Washed the filter paper with distilled water several times. Made the volume 250 ml- This is
stock solution
(Reaction involved is Fe2O3 + 6HCl → 2FeCl3 + 3H2O)
c) Reduction of Fe 3+ into Fe 2+
• Take 25 ml stock solution in a beaker
• Added 12 ml concentrated HCl, Solution was boiled gently (50-60°C)
• Then hot solution was reduced with SnCl2 solution, add drop by drop . Colour changes
from yellow to colourless
• 2FeCl3 + SnCl2 → 2FeCl2 + SnCl4 ( Fe 3+ → Fe 2+)
• Add 5 ml HgCl2 solution and 10 ml distilled water. This had taken care of excess SnCl2
and a silky white precipitate is obtained
SnCl2 + HgCl2 → Hg + SnCl4
SnCl2 + 2HgCl2 → Hg2Cl2 + SnCl4
• Preparation of K2Cr2O7 solution
• Take 1.2257 g of K2Cr2O7 powder
• Dissolve in 250 cc water
• Light orange colour appears

37
d) Titration with K2Cr2O7 solution
Add 15 ml acid Mix of H2SO4 and H3PO4
Add 4-5 drops of diphenyl amine indicator
Titrated against K2Cr2O7 solution, end product was blue-violet
Finally note down the amount of K2Cr2O7 solution consumed (say x ml)
6FeCl2 + K2Cr2O7 + 14 HCl → 6FeCl3 + 2KCl + 2CrCl3 + 7H2O
4. OBSERVATIONS:

Table 1. Observation of colour change in Burette

S. No Observation (Colour)

5. CALCULATION:
%Fe = ( Burete Reading * Normality * 0.5585 / Wt of sample )

38
 EXPERIMENT NO: 17
Estimation of Silica (SiO2) in Ore
1. OBJECTIVE: Estimation of Silica in Iron Ore
2. EQUIPMENT: Beaker, Measuring Cylinder, Hot plate, Platinum crucible, Furnace,
Whatmann filter paper no. 40, Concentrated HCl, Distilled water.
3. PROCEDURE:
a. Take 0.5 g Ore (200 mesh) in a beaker
b. Then add 20ml concentrated HCl
c. Covered with watch glass
d. Finally put on hot tray for about 2-3 hours for digestion
e. If digestion is not complete within stipulated time then again add 10ml HCl and keep
it for digestion
f. After digestion filtered in 250ml measuring flask. Wattman 40 filter paper was used
g. Wash the residue with hot water to make it free from acid
h. Take the dry mass in a weighed platinum crucible and keep it for ignition in a furnace
at 1000°C for 1 hour.
i. Take it out. Cool it.
j. Find the weight of the residue
k. Repeat the above procedure for 5 times.

4. OBSERVATIONS:
Table 1. Observation Table
S. No Observation

39