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1. Objective
To verify the Reyleigh equation for a differential distillation in a binary system.
3. Chemicals required
1. Distilled water
2. Methanol
4. Theory
The word distillation refers to the physical separation of a mixture into two or more fractions that
have different boiling points. In this method components of a solution are separated depending
upon distribution of the substances between a gas and a liquid phase, applied to cases where all
components are present in both phases. Distillation differs from absorption and stripping in that
the second fluid phase is usually created by thermal means (vaporization and condensation)
rather than by the introduction of a second phase that may contain an additional component or
components not present in the feed mixture. There are three main methods used in distillation
practice. These are: (a) differential distillation or simple distillation (b) flash or equilibrium
distillation, and (c) rectification.
In the case of a differential distillation, the vapor at any time is in equilibrium with the liquid
from which it rises but changes continuously in the composition. Thus the mathematical
approach used must be differential. A block diagram for distillation process is shown in Figure 1.
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2 Department of Chemical Engineering Date: _____________
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= ¿
W xW
−x
Equation (6) after rearrangement can be written in the form known as Reyligh’s equation, as
follows:
xF
F dx (7)
ln W =∫ ¿
x y −x
W
F=D+W (8)
x F F=x D D+ x W W (9)
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3 Department of Chemical Engineering Date: _____________
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Set up consists of Heating Mantle, Distillation Flask, Condenser and a Distillate collector. A
mixture of known components A and B is fed in the distillation flask and constant heating rate is
supplied by heating mantle. Vapors escaping from the flask are passed through the condenser and
collected in the distillate collector. The schematic diagram for differential distillation is shown in
Figure 2.
7. Observations
Data from literature
1. Molecular weights of A and B are _________ and ________, respectively.
2. Refractive indices of A and B _________ and ________, respectively.
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Table 1 Calibration data for mole fraction vs. Table 2 Equilibrium data for methanol and
density at 25 0C. water system
Sr. no. Mole fraction of Density T (⁰C) x y
methanol 100 0 0
1. 0.1 0.9578 96.4 0.02 0.134
2. 0.2 0.9498 93.5 0.04 0.230
3. 0.3 0.9319 91.2 0.06 0.304
4. 0.4 0.9196 89.3 0.08 0.365
5. 0.5 0.9032 87.7 0.10 0.418
6. 0.6 0.8839 84.4 0.15 0.517
7. 0.7 0.8710 81.7 0.20 0.579
8. 0.8 0.8407 78.0 0.30 0.665
9. 0.9 0.8105 75.3 0.40 0.729
10. 1.0 0.7912 73.1 0.50 0.779
71.2 0.60 0.825
69.3 0.70 0.870
67.5 0.80 0.915
66.0 0.90 0.958
65.0 0.95 0.979
64.5 1.00 1.000
0−dD=dL
Figure 2 Calibration curve for density vs composition of a methanol-water system.
8. Calculation
1. Calculate D (amount of distillate), from weighed 30 ml sample, and xD (distillate
composition) from density of 30 ml sample, for each sample.
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2. Calculate W (amount of residue still left in the flask) and xW (composition of residue)
using equation 7 and 8 for each fraction.
3. Calculate y* (vapor phase composition) for each sample (from density of 8 drops
collected.)
4. Calculate x (liquid phase composition in equilibrium with y*) using Raoults law.
5. Complete the following table.
xF
ln( F / W ) dx /( y * x)
% Error *100
xW
ln( F / W )
10. Nomenclature
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6 Department of Chemical Engineering Date: _____________
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(i) Heating should be regulated to be sufficiently slow that it can be assumed that the vapors
issuing from the liquid mixture are at all times in equilibrium with the liquid.
12. References
(i) McCabe, WL, Smith, JC, Harriott, P, “Unit Operations in Chemical Engineering”, 5th
Edition, McGraw–Hills International Edition, pp. 810–837.
(ii) Geankoplis, CJ, “Transport Processes and Separation Process Principles”, 4th ed.
Introduction to adsorption processes, Ch.12, pp. 760–771, 2003.
(iii) Coulson & Richardson, “Chemical Engineering Vol. 2, 4 th edition, Asian Books Pvt. Lt.,
ND, 1991, Page: 451-454, 427-434.
(iv) Treybal, RE, “Mass Transfer Operations”, 3rd Edition, pp. 477–485, 1981.
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7 Department of Chemical Engineering Date: ______________
Indian Institute of Technology Roorkee Page no.: ___________
1. Objective
To carryout steam distillation of toluene-benzil mixture and compare the experimental results
with those theoretically predicted.
(i) Heating mantle, three-neck round bottom flask, condenser, separatory funnel and
graduated cylinder.
(ii) Electricity Supply: Single Phase, 220 V AC, 50 Hz, 6.5 kW with earth connection.
(iii) Water supply
3. Chemicals required
4. Theory
In distillation, two or more components are separated based on the difference in their boiling
points. The temperature sensitive materials, such as oils, resins, hydrocarbons, etc., which are
insoluble in water and may decompose at their boiling point are typically separated using steam
distillation. Steam distillation enables a compound or mixture of compounds to be distilled at a
temperature substantially below that of the boiling point(s) of the individual constituent(s).
Essential oils contain substances with boiling points up to 200°C or higher temperatures. In the
presence of steam or boiling water, however, these substances are volatilized at a temperature
close to 100°C at atmospheric pressure. In case of essential oil extraction, fresh or dried, flower
petals or leaves are placed in a still, or on screen above still, and the steam is allowed to pass
through it under pressure which softens the cells and allows the essential oil to escape in vapor
form. The temperature of the steam must be high enough to vaporize the oil present, yet not so
high that it destroys the plants or burns the essential oils. As it release, the tiny droplets of
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essential oil evaporate and, together with the steam molecules, travel through a condenser. As the
steam cools, it condenses into water. The essential oil forms a separate layer on the surface of the
water. The essential oil is then separated from the water.
In laboratories, steam distillation is used for purification of starting materials, solvents, and
products. In steam distillation, the amount of water required for separation of a given amount of
organic material can be estimated by considering Dalton’s law and assuming that more volatile
material occupies more vapors as follows:
nW pW
nOM = pOM
where n and p refers to number of moles and vapor pressure, respectively, and subscripts W and
OM refers to water and the organic material, respectively. Given that the partial pressure of the
organic material then must be equal to 760 – pW. Therefore the weight of water required per gram
for the distillation of an organic volatile material is
18× pW
WW=
MW OM × ( 760− pW )
where WW and MW are the weight of water per gram of volatile material (Toluene) and molecular
weight of Organic material, respectively. Vapor pressure of water is given in Table 1, for
calculation of weight of water per gram of volatile material. In the present experiment, a mixture
of two miscible organic compounds (toluene and benzil) is separated using steam distillation.
A very simple experimental setup used for steam distillation is shown in Figure 1. A known
amount of toluene–benzil mixture is placed in the distillation flak with known amount of distilled
water. The mixture was heated in a heating mental at a constant heating rate. Mixed vapors of
water and toluene are passed through the water cooled condenser. The distillate containing
toluene and water are received in a receiver. The resulting distillate then kept in a separatory
funnel where they form two immiscible layers of toluene and water.
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9 Department of Chemical Engineering Date: ______________
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(i) Prepare a mixture of toluene (90 gm) and benzil (10 gm) and put it into a distillation flask.
(ii) Add 200 gm of water in the distillation flask, which is already having 100 gm toluene–
benzil mixture.
(iii) Start cooling water in condenser at such a rate so that it condenses all the vapors passing
through it.
(iv) Start heating the mixture. When the temperature of the distillation remains constant (the
azeotrope), collect about (but not more than) 100 mL of the distillate in a receiver flask.
(v) Note down this temperature and replace the receiver flask with a new one.
(vi) Transfer the collected distillate from the first receiver flask to a graduated cylinder, and
measure the volumes of water and toluene.
(vii) Determine the weight of water per gram of toluene.
(viii) Compare the experimental result with the theoretical value determined from the vapor
pressure of water at its azeotrope temperature.
7. Observations
Data from literature
(i) Molecular weights of water = 18.00
Molecular weights of toluene = 92.14
Molecular weights of benzil = 210.23
(ii) Vapor pressure data for water at atmospheric pressure (Table 1).
(iii) Volume of water collected in the receiver = ………………ml.
(iv) Volume of toluene collected in the receiver= ………………ml.
(v) Weight of water collected in the receiver = ………………gm.
(vi) Weight of toluene collected in the receiver = ………………gm.
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10 Department of Chemical Engineering Date: ______________
Indian Institute of Technology Roorkee Page no.: ___________
8. Calculation
Calculate the weight of water per gram of novolatile material using the following equation:
18 × pW
WW=
nOM × (760− pW )
(i) Volume of water and toluene collected in the receiver are …………ml and …………
ml, respectively.
(ii) The amount of weight of water per gram of nonvolatile material is _________.
10. Nomenclature
(i) Heating should be regulated to be sufficiently slow that it can be assumed that the
vapors issuing from the liquid mixture are at all times in equilibrium with the liquid.
(ii) Ensure that no vapor loss takes place from the setup.
12. References
(i) McCabe, WL, Smith, JC, Harriott, P, “Unit Operations in Chemical Engineering”, 5 th
Edition, McGraw–Hills International Edition, pp. 810–837.
(ii) Geankoplis, CJ, “Transport Processes and Separation Process Principles”, 4th ed.
Introduction to adsorption processes, Ch.12, pp. 760–771, 2003.
(iii) Coulson & Richardson, “Chemical Engineering Vol. 2, 4th edition, Asian Books Pvt. Lt.,
ND, 1991, Page: 451-454, 427-434.
(iv) Treybal, RE, “Mass Transfer Operations”, 3rd Edition, pp. 477–485, 1981.
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11 Department of Chemical Engineering Date: ______________
Indian Institute of Technology Roorkee Page no.: ___________
Table 1. Vapor pressure of water (in mmHg) for temperatures between 65–101 0C. (R.C. Weast
(Ed). CRC Handbook of Chemistry and Physics, CRC Press, Baton Rouge, FL p D-232 (1978).
Temperature (oC) p (mm of Hg) Temperature (oC) p (mm of Hg) Temperature (oC) p (mm of Hg)
65 187.54 78 327.3 91 546.05
66 196.09 79 341.00 92 566.99
67 204.96 80 355.10 93 588.60
68 214.17 81 369.70 94 610.90
69 223.73 82 384.90 95 633.90
70 233.7 83 400.60 96 657.62
71 243.9 84 416.8 97 682.07
72 254.6 85 433.6 98 707.27
73 265.7 86 450.9 99 733.24
74 277.2 87 468.7 100 760.00
75 289.1 88 487.1 101 787.57
76 301.4 89 506.1
77 314.1 90 525.76
1. Objective
To study the Liquid–Liquid Extraction and determine distribution coefficient for water (A)–
toluene (B) –acetic Acid (C), with one pair only partially soluble.
3. Chemicals required
1. Distilled water
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2. Acetic acid
3. Toluene
4. NaOH
5. Phenolphthalein Indicator
4. Theory
Liquid extraction sometimes called solvent extraction is the separation of the constituents of a
liquid solution by contact with another insoluble/sparingly soluble liquid. If the substances
constituting the original solution distribute themselves differently between the two liquid phases,
a certain degree of separation will result. In this operation, the solution which is to be extracted is
called the feed, and the liquid with which the feed is contacted is the solvent. The solvent rich
phase is called the extract phase and the residual liquid from which solute has been removed is
the raffinate phase. Liquid-Liquid extraction involves three stages:
a) Bringing the feed mixture and the solvent into intimate contact,
b) Separation of the resulting two phases after certain contacting time, and
c) Estimation of solute concentration in each phase
a. where distillation would require excessive amounts of heat, such as, for example, when the
relative volatility of the components to be separated is near unity,
b. when the formation of azeotropes limits the degree of separation obtainable in distillation,
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c. when the feed is highly volatile and the heat supply is avoided, and
d. when the components to be separated are quite different in nature
In the present experiment acetic acid, water and toluene system has been considered, which is
most commonly encountered in liquid-liquid extraction. Acetic acid (C) is completely miscible in
toluene (A) and water (B), but A and B dissolves only to a limited extent in each of other, at
prevailing operating conditions of temperature, to give rise to two distinct liquid solutions. Such
systems are easy to analyze because the two liquid binary phases are pseudo binary systems as
the concentration of B in A rich phase is limited to very low saturation value and similarly that of
A is again limited in B rich phase.
5. Procedure
1. Prepare five samples, each of 25 ml of acetic acid–water solution in the range of 20% to
90% acetic acid in 100 ml conical flask with stopper.
2. To each flask add 25 ml of toluene slowly.
3. Shake the mixture well after fixing the stopper to remove the turbidity and allow the
mixture to separate in two clear phases.
4. Separate A– and B– rich phases and measure the volume and weight of both lower and
upper layers. Analyze acetic acid concentration by titrating it with NaOH solution.
5. Draw the distribution curve in weight percent of C in raffinate phase (x) and weight
percent of C in Extract phase (y), and calculate the distribution coefficient.
6. Observations
7. Calculation
(i) Toluene rich phase: Extract (y) in wt% of acetic acid in toluene phase, i.e. top layer
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(ii) Water rich phase: Raffinate (x) in wt% acetic acid in water phase, i.e. bottom layer
(iii) Water density @room temperature = _________ gm/cc (using density bottle)
(iv) Acetic acid density @ room temperature = ________ gm/cc (using density bottle)
(v) Weight of acetic acid in water rich phase (gm) =
Volume of NaOH required Normality of NaOH 60
(vi) Weight of water (gm) = Total weight – weight of acetic acid
(vii) Volume of water (ml) = weight of water/density of water
(viii) Volume of acetic acid (ml) = Total volume – volume of water
(ix) Weight of acetic acid in toluene rich phase (gm) =
Volume of NaOH required Normality of NaOH 60
(x) Weight of toluene (gm)= Total weight – weight of acetic acid
(xi) Volume of acetic acid (ml) = weight of acetic acid/density of acetic acid
Acetic acid NaOH Weight of Weight of Total Acetic Volume Volume Total Acetic
in water volume acetic acid water weight acid of acetic of water volum acid
(Vol.%) (ml) (gm) (gm) (gm) (wt%) acid (ml) e (Vol.%)
20%
40%
60%
80%
90%
Acetic acid NaOH Weight of Weight of Total Acetic Volume Volume of Total Acetic
in water volume acetic toluene weight acid of acetic toluene volum acid
(Vol.%) (ml) acid (gm) (gm) (gm) (wt%) acid (ml) (ml) e (Vol.%)
20%
40%
60%
80%
90%
Kd = [wt% acetic acid in solvent rich phase] / [wt% acetic acid in water rich phase] =y/x
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9. Precaution
10. References
1. McCabe, WL, Smith, JC, Harriott, P, “Unit Operations in Chemical Engineering”, 5th
Edition, McGraw–Hills International Edition, pp. 810–837.
2. Geankoplis, CJ, “Transport Processes and Separation Process Principles”, 4th ed.
Introduction to adsorption processes, Ch.12, pp. 760–771, 2003.
3. Seader, JD, Henley, EJ, “Separation Process Principles”, Αdsorption, Ion Exchange,
Chromatography, Ch 15, pp. 778–789, 794–806, 820–824, 1998.
4. Treybal, RE, “Mass Transfer Operations”, 3rd Edition, pp. 477–485, 1981.
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1 Department of Chemical Engineering Date:
6 ______________
Indian Institute of Technology Roorkee Page
no.:___________
1. Objective
Estimate the percent oil recovery from a given sample.
3. Chemicals required
1. Hexane
2. Mustered oil cake
4. Theory
Leaching is concerned with the extraction of a soluble constituent from a solid by means of a
solvent. The process may be used either for the production of a concentrated solution of a
valuable solid material, or in order to remove an insoluble solid, such as a pigment, from a
soluble material with which it is contaminated.
The method used for the extraction is determined by the proportion of soluble constituent
present, its distribution throughout the solid, the nature of the solid and the particle size.
1. If the solute is uniformly dispersed in the solid, the material near the surface will be
dissolved first, leaving a porous structure in the solid residue. The solvent will then have to
penetrate this outer layer before it can reach further solute, and the process will become
progressively more difficult and the extraction rate will fall.
1 Department of Chemical Engineering Date:
7 ______________
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no.:___________
2. If the solute forms a very high proportion of the solid, the porous structure may break
down almost immediately to give a fine deposit of insoluble residue, and access of solvent
to the solute will not be impeded.
Any one of these three processes may be responsible for limiting the extraction rate, though the
first process usually occurs so rapidly that it has a negligible effect on the overall rate.
Percent recovery:
(W −W )
% Recovery = W × XO ×100
O
The experiment can be repeated for different solvent temperature, different particle size of oil
cake and different solvent rates.
1 Department of Chemical Engineering Date:
8 ______________
Indian Institute of Technology Roorkee Page
no.:___________
5. Procedure
1. We reduced the mustered oil cake in to finer particles with the help of a crusher.
2. We measured the weight of dry filter paper and conical flask (250 ml).
3. We took three flask of 250 ml capacity and added100 ml hexane in each.
4. We added 10 gm of mustered oil cake in each flask containing 100 ml hexane.
5. We shook all the flasks into an incubator shaker at 263 rpm and 40 oC for a required contact
time (15, 30 and 60 minutes).
6. After shaking, we filtered the sample by using filter paper and the filter paper was put in
hot air oven at 80oC.
7. We weighed the particle remaining in the conical flask after drying it in a hot air oven at
80oC.
8. When constant weight of filter paper and conical flask was obtained, we noted down the
readings.
6. Observations
Weight of
Total weight (gm) Initial Final
Weight of Weight of oil
S. Time weight of weight of
dried filter dried recovered
No. (min) Sample + Sample sample sample
paper (gm) flask (gm) (Wo – W),
filter paper + flask (WO), (gm) (W), (gm)
(gm)
1
2
3
7. Calculation:
(i) Initial weight of dry cake = _________ gm
(ii) Initial amount of oil in seeds = ________
(iii) Oil in feed = 10 10/100 = ________ gm
(iv) Weight of dry cake after leaching = ________ gm
(v) Weight of oil collected = ________ gm
(vi) % of oil recovery from cake = ________
(i) Percent recovery of oil from mustered–oil cake using hexane for contact time of
…………min is ……………%.
(ii) Discuss the effect of time on percent recovery of oil.
(iii) What will happen if the extraction temperature and particle size of cake is increased
or decreased?
9. Precaution:
(i) Complete drying of samples in the hot air oven should be considered only until
constant weight is achieved.
(ii) Carefully filter the sample to avoid lose of solid sample.
10. References:
(i) McCabe, WL, Smith, JC, Harriott, P, “Unit Operations in Chemical Engineering”, 5 th
Edition, McGraw–Hills International Edition, pp. 810–837.
(ii) Treybal, RE, “Mass Transfer Operations” 3rd Edition, McGraw–Hills International
Edition, pp. 717–744.
1. Objective
2 Department of Chemical Engineering Date:
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(a) To determine the activity coefficient for a binary system and compare it with activity
coefficient models, such as Van Laar and Wilson.
(b) Plot Txy diagram from the experimental observation.
3. Chemicals required
1. Distilled water
2. Methanol
4. Theory
The set of activity coefficients of the components in a fluid (gas or liquid) mixture is a measure
of departure of the thermodynamic properties of that mixture from those of the ideal mixture.
An ideal mixture is defined as one for which:
μi ( P , T , x́ ) =μ0i ( P , T ) + Ŕ T ln x́ i (1)
But for real mixtures differ from the ideal, the above equation is modified to give the real
mixture equation:
where
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a i= x́ l γ i (3)
This equation can be regarded as the defining equation for activity coefficient. There will be an
activity coefficient for each component in the mixture and, although it is not explicitly stated in
the above equation, each of the activity coefficients will be a function of P, T and x́ i . A necessary
condition on γi is that
γ i=1 at x́ i=1 (4)
As methanol is soluble in water, it makes the nearly ideal aqueous solution. Hence we can use
Roult’s Law rather than Henry’s law. The non-ideality is accounted by the factor “activity
coefficient γ i . So modified Roult’s law is :
y i P= x́ i γ i P isat (5)
sat
The vapour pressure of a pure liquid (Pi ¿ is a function of temperature and can be calculated
using the Antoine equation, i.e.
B
log 10 p= A− C +T (6)
The experimental setup is shown in Figure 1. It consists of insulated vessel, three valves (V 1, V2,
V3), a condenser, two thermocouples and heating element with variac. A mixture of methanol and
water is fed from the top of the vessel and heating rate is controlled by variac to set the desired
temperature. Vapors escaping from top of the vessel, after heating, are passed through the
condenser and reflux back to the vessel.
2 Department of Chemical Engineering Date:
2 ______________
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no.:___________
Figure 1 Experimental setup for determination of activity coefficient, where T 1 and T2 are
thermocouples for measuring temperatures at specific locations, V1, V2 and V3 are valves for
collecting vapor condensate sample, feed for liquid solution and for collection of liquid samples,
respectively, and CW is cooling water.
4. Procedure
(i) We prepared the methanol-water solutions of known compositions (40% by volume)
and found out their refractive index and composition (mole fraction of methanol).
(ii) We took 500 ml of methanol-water solution of known composition and pour it into the
equipment from top.
(iii) We started the water flow through condenser.
(iv) We switched ON the heater and adjusted the heating rate with the help of the variac.
(v) We allowed the heating to proceed till the temperature in the thermometer reaches to 80
o
C in thermocouple 1, which indicates the initiation of vaporization of liquid mixture.
(vi) We maintained 70 0C temperature at thermocouple 2, wait about 2 – 3 minutes after the
temperature has stabilized.
(vii) We collected vapor and liquid samples and cool them to room temperature, and find out
their refractive indices using Abbe refractometer.
(viii) We repeated the steps 4 to 6 for new temperatures, i.e. 75, 80, 85 and 90 oC until
sufficient data was obtained to determine the VLE.
(ix) We took refractive index of all samples and report in the observation table.
5. Observations
a. Data
Total pressure = 101, 325 Pa
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b. Observation table
6. Calculation
(i) Calculate top and bottom product volume fractions into mole percent.
Table 2 Top and bottom product volume fraction from mole fraction
(ii) Calculate activity coefficient (γi) with the help of following equation.
y i P=γ i x i P si
Let a and b represent methanol and water, respectively. Total pressure, P =101.32 kPa
(a) Compare the values of the experimentally determined vapor–liquid composition with those
given in the literature.
(b) Calculate the vapor pressures of methanol and water at the observed temperatures using
Antoine equation.
(c) Calculate the activity coefficient of methanol and water for the two compositions taken using
modified Roult’s law.
(d) Evaluate the Van Laar constants from the azeotropic data and then calculate the activity
coefficients of methanol and water for the two compositions taken from equations mentioned
below:
−2
A' x
(
ln γ 1= A ' 12 1+ A ' 12 x 1
21 2
)
' −2
A 21 x 2
(
ln γ 2= A '21 1+
A ' 12 x 1 )
2 Department of Chemical Engineering Date:
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no.:___________
γ (Methanol) (Water)
S. Temperature PaS PbS
xa ya xb yb (Exp. (Exp
No. (0C) (KPa) (KPa) (Theor.) (Theor.)
) )
1
2
3
4
10. Nomenclature
ai Activity
T Temperature
P Pressure
γi Activity Coefficient of component i
11. Precautions
12. References
1. Smith, J.M., Van Ness, H.C., Abbott, M.M., “Introduction to Chemical Engineering
Thermodynamics”, VII ed., McGraw–Hills International Edition, pp. 223-225
26 Department of Chemical Engineering Date : _____________
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1. Objective
(i) To determine the partial molar volumes of water and of methyl alcohol as a function of
concentration at fixed temperature and pressure.
(ii) To determine the partial molar volumes of water and methyl alcohol, respectively, at their
infinite dilutions.
(iii) To verify the Gibbs-Duhem equation applied to partial molar volumes of a binary
solution.
3. Chemicals required
1. Distilled water
2. Methanol
4. Theory
The properties of a solution are not the additive properties of their constituents, i.e. when a
substance becomes a part of the solution it loses its identity. The term partial molar volume is
used to designate the property of a component when it is in a mixture with one or many
components. Partial molar also referred as the “intrinsic volume” of the solution. For a two
component system composed of A and B, the partial molar volumes are defined as:
∂M
( )
Ḿ A = ∂ n
A P ,T ,nB
(1)
∂M
( )
Ḿ B = ∂ n
B P ,T ,n
A
(2)
In general, the partial molar volume of any substance (A or B) in a mixture is the change in
volume per mole of (A or B) added to the mixture. The partial molar volume varies with the
composition of the mixture.
The equation used to relate the partial molar volume of one component of the mixture to the
others is the Gibbs-Duhem equation. It is given as:
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( ∂∂MP ) T,x
dP+( ∂∂MT )
P,x
dT −∑ x i d Ḿ i=0
i
(3)
This equation must be satisfied for all changes in P,T and Ḿ i caused by changes in state in a
homogeneous phase. For constant temperature and pressure equation (3) becomes
∑i x i d Ḿ i=0 (4)
Other form of the Gibbs-Duhem equation is:
∂M´ ∂M´
x A ∂ x A =x B ∂ x B (5)
A B
where
∂M ∂M
Ḿ A =M + x B ∂ x ∧ Ḿ B=M −x A ∂ x (6)
A A
5. Procedure
(i) We prepared solutions of different known compositions of methyl alcohol and water.
Suggested mole fractions of methyl alcohol are: 0.02, 0.05, 0.10, 0.20, 0.30, 0.40, 0.50,
0.60, 0.70, 0.80, 0.90, and 1.00.
(ii) We noted down the temperature of pure water and methyl alcohol.
(iii) We determine the densities of pure components and different solutions prepared
using density bottle.
6. Observations
(a) Data:
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28 Department of Chemical Engineering Date : _____________
Indian Institute of Technology Roorkee Page no.: __________
2 0.05
3 0.1
~ ~ ~ ~ ~ ~ ~ ~
11 0.9
12 1.0
(c) Calculations:
(i) Calculate the required volume of each component (methyl alcohol and water) to make
a particular amount of solution of known composition.
(ii) Measure the weight of solution and calculate the densities of solutions.
(iii) Calculate the average molecular weight of each solution using the following equation:
M = MAxA + MBxB
(iv) Calculate molar volume of each solution prepared, including pure components using
density and average molecular weights, i.e.
Volume occupied
Molar volume= Number of moles
(v) Plot a graph of the molar volume as a function of mole fraction of water, covering the
entire range from 0 to 1.0 mole fractions.
(vi) Determine the values of partial molar volumes of methyl alcohol and water at
different mole fractions of water (0.25, 0.50, 0.75) by drawing tangents at these
points.
(vii) Plot partial molar volume of methyl alcohol and water respectively as a function of
mole fraction of water.
(viii) At typical values of mole fraction of water, 0.3 and 0.6, test whether the experimental
results are consistent with the Gibbs-Duhem equation mentioned below:
∂V ∂V
(
xA ∂x A )
A T ,P
(
=x B ∂ x B )
B T ,P
8. Nomenclature
M Molar volume
X Mole fraction
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29 Department of Chemical Engineering Date : _____________
Indian Institute of Technology Roorkee Page no.: __________
Subscripts:
T Temperature
P Pressure
9. Precaution
10. References
(i) Smith, J.M., Van Ness, H.C., Abbott, M.M. Introduction to Chemical Engineering
Thermodynamics, Seventh Edition, McGraw-Hill, Chemical Engineering Series, 2005.
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