CH2016: Chemical Engineering Thermodynamics Laboratory

Experiment: Vapour-Liquid Equilibrium

Experiment Date: 13th March, 2024
Report Submission Date: 27th March, 2024

Lab Group Details

Group: W1-2 : Wednesday Batch (3 - 5pm)

SaiShiva Charan (CH22B005)
Deepanjhan Das (CH22B020)
Chinmay Kumar (CH22B034)
Charmika P (CH22B060)

1
CONTENTS CONTENTS

Contents
1 Introduction & Background Theory 3

2 Aim 3

3 Modelling of VLE and Activity Coefficient 4

3.1 To calculate the Activity Coefficient value : . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2 To calculate the liquid & vapour mixture compositions : . . . . . . . . . . . . . . . . . . 4
3.3 Redlich-Kister Equation : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.4 Van Laar Equation : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

4 Experimental Details 7
4.1 Materials Required . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1.1 Chemicals: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1.2 Apparatus: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2 Apparatus Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.3 Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.4 Precautions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

5 Experimental Data & Observations 8

5.1 Tabulated Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.2 Sample Calculations (shown for reading 5): . . . . . . . . . . . . . . . . . . . . . . . . . . 8

6 Results and Discussions 10

6.1 Plots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

7 Conclusions 14

8 Part-wise Codes 14
8.1 Azeotropic Analysis : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
8.2 Calculation of liquid-mixture composition : . . . . . . . . . . . . . . . . . . . . . . . . . . 15
8.2.1 Matlab Code to obtain the Rdlich-Kister Coefficients : . . . . . . . . . . . . . . . 15
8.2.2 Python code to evaluate the xW & xE values : . . . . . . . . . . . . . . . . . . . . 16
8.3 Code to obtain the linear regression line for the plot in figure 5 . . . . . . . . . . . . . . . 16
8.4 Code to run the Thermodynamic-Consistency test : . . . . . . . . . . . . . . . . . . . . . 17

9 Suggestions 17

References 18

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 2 AIM

1 Introduction & Background Theory

Vapour-liquid equilibrium (VLE) refers to the state of coexistence between a vapour phase and a
liquid phase in a system at a specific temperature and pressure, where the composition of each phase
remains constant. In a binary mixture, there are two components involved. Rate of liquid evaporating
into vapour is equal to the rate of vapour condensing into liquid. In the case of a pure substance, this
would just be the boiling point of the liquid.

When dealing with a binary mixture, such as a mixture of two liquids or a liquid and its vapor, several
factors come into play:

1. Raoult’s Law: It states that for an ideal solution, the partial pressure of each component of the
mixture in the vapour phase is directly proportional to its mole fraction in the liquid phase, at a
given temperature. Mathematically, for component i Raoult’s Law can be expressed as:

Pi = xi Pisat (1)

Where,

• Pi is the partial pressure of component i in vapour phase.

• xi is the mole fraction of component i in liquid phase.
• Pisat is the saturation vapour pressure of pure component i at the given temperature.

A modified version of Raoult’s law is discussed below (eq 4) to include the real scenario also.

2. Relative volatility: It, often denoted as α, is a measure of the difference in vapour pressures
of the two components in a mixture. It is defined as the ratio of the vapour pressures of the two
components. Mathematically, for components 1 and 2, relative volatility(α) is given by:

P1sat
α= (2)
P2sat

3. Bubble Point & Dew Point: The bubble point is the temperature at which the first bubble
of vapour forms when a liquid-vapour mixture is heated at constant pressure. The dew point is
the temperature at which the first drop of liquid forms when a vapour-liquid mixture is cooled at
constant pressure.

2 Aim
• Obtain experimental data: Temperature, liquid and vapour composition for different cases of
vapour liquid equilibrium of ethanol and water.

• Calculate γ1 , γ2 for each run: Equate fugacities in vapour and liquid phase for each species.
Assume mixture of ideal gases.

3
 3 MODELLING OF VLE AND ACTIVITY COEFFICIENT

• Check thermodynamic consistency by checking (as described in Koretky’s book [1]),

Z 1
γ1
ln( )dx1 = 0 (3)
0 γ2

• Plot (RT lnγE ) vs (RT lnγW ) and find Van Laar constants.
p p

• Calculate γ1 , γ2 from Van Laar equation using the fitted constants. For different temperatures,
calculate the liquid and vapour phase composition. Plot experimental and predicted γ1 , γ2 and
Txy . Compare with the literature data.

3 Modelling of VLE and Activity Coefficient

3.1 To calculate the Activity Coefficient value :
⇒Raoult’s Law works well at low to moderate pressures for mixtures comprising of chemically similar
species. For chemically different species at low to moderate pressures, results of Raoult’s Law begin to
deviate from experimental data. A modified version of the Raoult’s Law, considering the vapour phase
as ideal but the liquid phase as real, gives more realistic results.
yi P
sat
yi P = xi γi Pi,vap ⇒ γi = sat
(4)
xi Pi,vap

Here, Fi = 1, P = 1.01325 bar;

γi : Activity Coefficient for the species i; it represents the non idealities in the phase;
yi & xi : mole fractions of i-th component in vapour and liquid phase respectively;
sat
Pi,vap : is the saturation vapour pressure of pure species.

⇒Antoine’s equation is used to calculate Pi,vap

sat
, which is expressed as :
B 
sat
log10 (Pi,vap ) =A− (5)
T +C
Where Pi,vap
sat
is in bar and T is temperature in K.
A, B & C are coefficients of Atoine’s equation.

If the compositions of vapour and liquid phases are known, then activity coefficients at different
equilibrium conditions for each species can be calculated.

3.2 To calculate the liquid & vapour mixture compositions :

We can calculate the composition in liquid and vapour phases using the following set of relations :
⇒Relating Equations: The multiplicative fractions, considered here are mass(in g).
In liquid phase (neglected, not used in latter calculations):

ρliq = (ρE,liq )(mE,liq ) + (ρW,liq )(mW,liq ) (6)

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3.3 Redlich-Kister Equation : 3 MODELLING OF VLE AND ACTIVITY COEFFICIENT

mW,liq + mE,liq = 1 (7)

In vapour phase (used in sample calculation):

ρvap = (ρE,vap )(mE,vap ) + (ρW,vap )(mW,vap ) (8)

mW,vap + mE,vap = 1 (9)

But this assumes no change in volume when mixture is formed, which doesn’t consider the real scenario
for liquid phase. So this approach can be used to calculate yW & yE and is neglected for calculations in
liquid phase and instead more empirical formula is used to calculate the xW & xE .

Considering the volume change of mixing,

VT = VW + VE + ∆Vmix (10)
Which will turn out to be as expressed in the following,
M x + M x  M x ME xE 
W W E E W W
nT = nT + + ∆Vmix (11)
ρliq ρW,liq ρE,liq
The expression for the ∆Vmix is given by one of the empirical equations, Redlich-Kister equa-
tion(described in details in the paper [3]).

3.3 Redlich-Kister Equation :

(using the identity: xW + xE = 1)
n
X  n
X 
∆Vmix = nT xW xE Ap (xE − xW ) p
= nT (xE − x2E ) p
Ap (2xE − 1) (12)
p=0 p=0

The final equation to solve for xW & xE hence is as shown below:

 M (1 − x ) + M x   M (1 − x ) M x  Xn 
W E E E W E E E
H(xE ) = − + + + (xE − x2E ) Ap (2xE − 1)p (13)
ρliq ρW,liq ρE,liq p=0

Here, n = 5 is used to get more accurate values.

Solve for H(xE ) = 0 to find xE and find xW = (1 − xE ).
Using the experimental data collected in the ∆Vmix experiment in CH2016 course, a "Non-
Linear Regression" is applied on the Redlich-Kister equation form to obtain the regression coefficients,
i.e. Ai ’s (The fitted plot is shown in the figure 1), which yields in the values tabulated below (the
method is described in the codes’ section):

A0 A1 A2 A3 A4 A5

-3.550934 1.034918 1.384338 3.830211 -7.441973 -11.440259

Table 1: Redlich-Kister Coefficients

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3.4 Van Laar Equation : 3 MODELLING OF VLE AND ACTIVITY COEFFICIENT

Figure 1: The fitted polynomial from the ∆Vmix data

3.4 Van Laar Equation :

The Van Laar equation is a thermodynamic activity model, which was developed to describe phase
equilibria of liquid mixtures. The equation was derived from the Van der Waals equation.
 Bx2 2  Ax1 2
RT ln(γ1 ) = A ; RT ln(γ2 ) = B (14)
Ax1 + Bx2 Ax1 + Bx2
Where,
√ √ 2 √ √ 2
b 1  a1 a2 b 2  a1 a2
A= − &B= −
RT b1 b2 RT b1 b2

Above equations are the Van-Laar Equations, which relate the activity coefficient to temperature,composition
and properties of the pure components i.e., (a1 ,b1 ) and (a2 ,b2 ). Here a and b are Van Der Waals Con-
stants.
√ √
In order to obtain a fitting regression line after plotting the data between RT lnγW vs RT lnγE , a
linear approximation can be made, (as discussed in the paper [2]), which is of the form discussed below,

√
r
Bp
(15)
p
ln(γW ) = B − ln(γE )
A

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 4 EXPERIMENTAL DETAILS

4 Experimental Details
4.1 Materials Required
4.1.1 Chemicals:
Water(H2 O), Ethanol(ET OH).

4.1.2 Apparatus:
Heater, Condenser, Sampling Vials, Beakers, Mercury Thermometer, Measuring cylinders, Densit-
ometer, three-neck Round-Bottom Flask, Chiller, corks.

4.2 Apparatus Setup

The experimental arrangement comprises a 3-neck round-bottom flask on a heater for continuous
heating. One flask opening is linked to a condenser, where the vapour condenses and accumulates at
the base for sample retrieval and subsequent calculations. Other openings are closed with rubber corks.

4.3 Procedure
1. Add 300 mL of water to the flask. Start heating the flask. When it reaches equilibrium, note down
the temperature.

2. Collect 15 mL of the condensed vapour from the condenser’s base and 15 mL from the flask’s base.
Add 30 mL of ethanol to the flask. Repeat the same process, i.e. collect samples from respective
sites.

3. Repeat the above process six times.

4. Clean the flask and add 300 mL of ethanol. Repeat the same process as above by adding 30 mL
of water each time and collecting samples from respective sites.

4.4 Precautions
• Be careful when handling liquid at high temperature.

• Clean the apparatus properly before use.

• Always check and rectify leaks. The valves and flask openings should be properly closed before
heating.

• Turn off the heater every time after noting down the temperature.

• While adding water/ethanol to the flask, pour it slowly to avoid splashes.

• Do not inhale ethanol vapours; it can cause respiratory irritation.

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 5 EXPERIMENTAL DATA & OBSERVATIONS

5 Experimental Data & Observations

The experimentally observed data are tabulated below(Table 2 & 3) :

5.1 Tabulated Data

Volume of Liquid Density Vapour Density

Sl. No. Temperature(◦ C)
Ethanol(mL) (g/cm3 ) (g/cm3 )
1 0 100.2 0.997 0.997

2 30 92.5 0.987 0.892

3 60 87.7 0.979 0.860

4 90 84.2 0.974 0.847

5 120 81.2 0.966 0.843

6 150 80.7 0.959 0.839

Table 2: Data when ETOH was poured in succession

Volume of Liquid Density Vapour Density

Sl. No. Temperature(◦ C)
Water(mL) (g/cm3 ) (g/cm3 )
7 0 78.6 0.797 0.812
8 30 78.8 0.822 0.830
9 60 79.5 0.866 0.833
10 90 80.1 0.902 0.836
11 120 80.8 0.908 0.839
12 150 81.2 0.909 0.841

Table 3: Data when H2 O was poured in succession

5.2 Sample Calculations (shown for reading 5):

Molecular weight of Water(MW ) = 18.01528 g/mol.
Molecular weight of Ethanol(ME ) = 46.068 g/mol.

The equilibrium temperature is = 81.2 ◦ C = 354.35 K.

The Density of Liquid is (ρliq ) = 0.966 g/cm3 .

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5.2 Sample Calculations (shown for reading 5): 5 EXPERIMENTAL DATA & OBSERVATIONS

The Density of Vapour is (ρvap ) = 0.843 g/cm3 .

The Density of Pure Ethanol(liquid) is (ρE,liq ) = 0.797 g/cm3 .
The Density of Pure Water(liquid) is (ρW,liq ) = 0.997 g/cm3 .
The Density of Pure Ethanol(vapour) is (ρE,vap ) = 0.812 g/cm3 .
The Density of Pure Water(vapour) is (ρW,vap ) = 0.997 g/cm3 .

• To find the Mole Fractions (xW , xE , yW , yE ) :

⇒ Substituting the values of densities in vapour phases and solving the equations(8 & 9), we get :
mW,vap = 0.16756757g ; mE,vap = 0.83243243g.
Mole fractions of components in vapour mixture:
(m /MW )
yW = (mW,vap /MW,vap
W )+(mE,vap /ME )
= 0.339827 ; yE = (1 - yW ) = 0.660173.

⇒ Solving the equation(13) for H(xE ) = 0 we get,

Mole fractions of components in liquid mixture:
xE = 0.090444 ; xW = (1 - xE ) = 0.909556.

• We now use the Antoine’s Equation(eq 5) to calculate the saturation vapour pressures of Ethanol
and Water at the given temperature.

Antoine’s Coefficients for Ethanol and Water are :

Antoine’s Coefficients A B C

Ethanol 5.24677 1598.673 -46.424

Water 5.08354 1663.125 -45.622

Table 4: Data from NIST Chemistry WebBook [4] & [5]

1663.125

(5.08354− )
sat
PW,vap = 10 354.35 − 45.622 = 0.49722 bar.
1598.673

(5.24677− )
sat
PE,vap = 10 354.35 − 46.424 = 1.13508 bar.
√ √
Now from the fitted plot between RT lnγW vs RT lnγE , the values of Van Laar constants are
coming out to be, A = 7200.4939 & B = 610.5398.

From A & B, predicted values of activity coefficients are (at this specific temperature),
γW,predicted = 1.06223;
γE,predicted = 1.67822.

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 6 RESULTS AND DISCUSSIONS

6 Results and Discussions

• The composition of vapour mixture is obtained considering the mixture to be ideal.

• The composition of liquid mixture is obtained including the real scenario considering the change
in volume of mixture (by the empirical formula discussed in eq 12) ans so the follwoing result is
obtained :
Vapor composition of Vapor composition of Liquid composition of Liquid composition of
Sl. No.
Water(yW ) Ethanol(yE ) Water(xW ) Ethanol(xE )
1 1.0000 0.0000 1.0000 0.0000
2 0.6608 0.3392 0.9761 0.0239
3 0.4726 0.5274 0.9528 0.0472
4 0.3737 0.6263 0.9368 0.0632
5 0.3398 0.6602 0.9096 0.0904
6 0.3041 0.6959 0.8852 0.1148

7 0.0000 1.0000 0.0000 1.0000

8 0.2161 0.7839 0.2151 0.7849
9 0.2467 0.7533 0.5061 0.4938
10 0.2759 0.7241 0.6792 0.3208
11 0.3041 0.6959 0.7033 0.2967
12 0.3222 0.6778 0.7072 0.2927

Table 5: Liquid & Vapour compositions of Water & ETOH

• Using assumptions of ideal gas, the fugacities are equalted to calculate γ values. For that saturation
vapour pressure is also calculated using Antoine’s equation and as at the pressure at which our
experiment was carried out, the assumption ϕ = 1 is valid, γ(activity coefficient) values are
calculated using modified Rault’s law.
√ √
• Then from the fitted plot between RT lnγW vs RT lnγE (shown in figure 5), the values of Van
Laar constants are coming out to be, A = 7200.4939 & B = 610.5398, which are further used to
predict the values of activity coefficients, which are approcimately in the same nature of change
to the calculated values. They are tabulated below in table 6,

• The thermodynamic consistency test was carried out and The value of the integral is obtained to
be 0.29789 (using simpson’s formula in Python), which is pretty close to zero implying that the
test is satisfied approximately (code for the same is provided in the codes’ section in figure 12).
The error occurs due to change in temperature as the thermodynamic consistency is perfectly valid
only at constant temperature and the graph obtained is shown in figure 2.

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 6 RESULTS AND DISCUSSIONS

Calculated value of Calculated value of Predicted value of Predicted value of

Sl. No.
γW γE γW γE
1 2.03783 - 1.078842 10.17286

2 1.37967 12.64872 1.06223 4.15803

3 1.01066 9.98179 1.04121 2.60327

4 0.81294 8.84034 1.02804 2.11951

5 0.76137 6.51581 1.01016 1.67822

6 0.70008 5.41039 0.80123 1.46587

7 - 0.89267 1.23216 1.00000

8 2.04791 0.89146 1.22053 1.00127

9 0.99309 1.36176 1.19276 1.01587

10 0.82809 2.01445 1.16117 1.05842

11 0.88109 2.09391 1.15469 1.07095

12 0.92838 2.06675 1.15345 1.07321

Table 6: Calculated & Predicted Activity Coefficient Values

Figure 2: Thermodynamic Consistency test

11
 6 RESULTS AND DISCUSSIONS

• Studying the Txy versus xE and yE graph, we might obtain an azeotrope at temperatures lower
than 80◦ C, the plot is shown below in figure 3 and code for the same is also provided at the "codes"
section(figure 7).

Figure 3: From experimentally calculated data

Which is also satisfying the literature data (Azeotropic composition is achieved at a temperature
lower than 80◦ C.), shown in figure 4 below.

Figure 4: Comparing with lietrature data

12
6.1 Plots 6 RESULTS AND DISCUSSIONS

6.1 Plots

Figure 5: In order to obtain the Van Laar coefficients

Figure 6: Comparing the activity coefficient values

13
 8 PART-WISE CODES

7 Conclusions
◦ At the given conditions the gases can be approximated to behave ideally and follow Raoult’s law
for fugacity.

◦ At the given conditions, the liquids follow the simplified expression for fugacity after neglecting
the Poynting correction factor.

◦ At equilibrium, the fugacities are equal and using this the activity coefficients are calculated.

◦ From the calculated activity coefficients, the parameters of Van Laar expression are calculated and
they are close to the theoretical values.

◦ All quantities were back calculated and were found to match the original values approximately.

◦ Results obtained are comparable to those mentioned in literature.

8 Part-wise Codes
8.1 Azeotropic Analysis :

Figure 7: To obtain the azetropic analysis from the experimental data

14
8.2 Calculation of liquid-mixture composition : 8 PART-WISE CODES

8.2 Calculation of liquid-mixture composition :

8.2.1 Matlab Code to obtain the Rdlich-Kister Coefficients :

Figure 8: Experimental Data and Further Calculations from ∆Vmix experimental data

Figure 9: Multilinear Regression Applied to obtain the coefficients

15
8.3 Code to obtain the linear regression line for the plot in figure 5 8 PART-WISE CODES

8.2.2 Python code to evaluate the xW & xE values :

Figure 10: Solving upto x5 to obtain more accurate results

8.3 Code to obtain the linear regression line for the plot in figure 5

Figure 11: Applying TLS regression to obtain the A & B values

16
8.4 Code to run the Thermodynamic-Consistency test : 9 SUGGESTIONS

8.4 Code to run the Thermodynamic-Consistency test :

Figure 12: The integral value is pretty close to zero

9 Suggestions
• As soon as the liquid and vapour extracts are removed the mixture moves towards equilibrium.
This causes vapours to condense. This vapour has to be removed and added back to the condenser
before the next measurement.

• The extraction of liquid and condensed vapour must be done as quickly as possible to avoid change
in vapour composition due to reaction progress towards equilibrium before the addition of water.

• Due to the shape of the condenser, some condensed vapour may reside in the column from previous
experiments. This has to be washed with alcohol before the start of the experiment. Similarly, it
has to be washed with water when the mixture inside the flask is changed to pure water.

• It must be ensured that the vapours do not reach the top half of the condenser.

• The analysis assumes linear interpolation of density of a mixture. This is an approximation that
causes errors in mole fraction calculation.

• The fugacity of the vapour mixture is calculated by assuming the fugacity coefficient to be 1, i.e.
ideal gas assumption. To improve accuracy the entire equation must be used by calculating ϕsat .

17
REFERENCES REFERENCES

• Since the Pvap for both water and alcohol

 l at the given temperature range is around P, the Poynt-
RP v
ing correction factor "exp{ P sat ln RTi dx}" has been neglected without much error while cal-
i
culating the liquid phase fugacity.

• The density of the solutions has to be measured only after they have reached room temperature
as the density measurements depend on temperature.

• The sample bottles must be labelled properly to ensure quick recognition.

• Sources of errors are human errors and instrumentation and least count errors. Due to these errors;
inaccurate values of density and temperature may be obtained.

• These values provide values of activity coefficient less than 1, which gives us complex numbers in
further calculations; especially at conditions when x1 is almost equal to 1 or 0. We ignore the
imaginary part of these results.

References
[1] M. D. Koretsky. 8.1 - Vapor–Liquid Equilibrium (VLE). Ed. by M. D. Koretsky. 2012. url: https:
//students.aiu.edu/submissions/profiles/resources/onlineBook/X2r3k2_0470259612_
Thermodynamics.pdf.
[2] Professors M.A. Matthews and J.A. Ritter. ETHANOL/WATER VAPOR-LIQUID EQUILIBRIUM.
url: https://cse.sc.edu/~gatzke/460/C-VLE.
[3] N. O. Alzamel N. Ouerfelli. “THE REDUCED REDLICH-KISTER EQUATIONS FOR CORRE-
LATING EXCESS PROPERTIES OF 1,2-DIMETHOXYETHANE + WATER BINARY MIX-
TURES AT TEMPERATURES FROM 303.15 K TO 323.15 K.” In: Vol-9 (2016). url: https:
//rasayanjournal.co.in/admin/php/upload/99_pdf.pdf.
[4] SRD 69 - Ethanol - NIST Chemistry WebBook, ed. url: https://webbook.nist.gov/cgi/cbook.
cgi?ID=C64175&Mask=4&Type=ANTOINE&Plot=on.
[5] SRD 69 - Water - NIST Chemistry WebBook, ed. url: https://webbook.nist.gov/cgi/cbook.
cgi?ID=C7732185&Mask=4&Type=ANTOINE&Plot=on.

18