CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

Volume change of mixing(1)

Marks:
Experiment done on:11 /03/2020

100
Report submitted on: dd/mm/2020

For Instructors use only:

No Section Max. Marks Marks

1 Introduction / Background Theory -

2 Experimental Details: Materials and Methods -

3 Experimental Observations & Raw Data 20

4 Sample Calculations 20

5 Results, Discussion and Conclusions 40

7 Suggestions for Improvement 10

8 Overall Formatting & References 10

Total 100

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

1. INTRODUCTION / BACKGROUND THEORY

Ideal Solutions

For ideal solutions the volume of the mixing is equal to zero that is, ΔVmix = 0. This means that total
volume of solution is exactly same as the sum of the volume of solute and solution. Adding further,
it also signifies that there will be contraction or expansion of the volume while the mixing of two
components is taking place.

Non-Ideal Solutions

For non-ideal solutions the volume of mixing that is, ΔVmix ≠ 0, which depicts that there will be some
expansion or contraction in the dissolution of liquids.

Non-ideal solutions are of two types:

• Non-ideal solutions showing positive deviation
→ The volume of mixing is positive that is, ΔV mix > 0 as the volume expands on the
dissolution of components
• Non-ideal solutions showing negative deviation
→ The volume of mixing is negative that is, ΔV mix < 0 as the volume decreases on the
dissolution of components

For the ideal solution,

V = V1+V2 (assuming we are mixing two solutions)
For the non-ideal solution,
V = V1+V2+ ΔVmix (assuming we are mixing two solutions)

Property Changes of Mixing

We use the symbol K to represent any possible extensive thermodynamic

property, that is, K = V, H, U, S, G, and so on. Partial molar properties are represented as

A property change of mixing, ΔKmix , describes how much a given property changes as a result of the
mixing process. It is defined as the difference between the total solution property in the mixture and
the sum of the pure species properties of its constituents, each in proportion to how much is present
in the mixture. Mathematically, the property change of mixing is given by:

We know that,

therefore,

Analogously for intensive properties, we get:

Ethanol-Water mixture will have a negative volume change in mixing because of the favourable
intermolecular hydrogen bonding interactions.

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

1.1 Aim

• Experimental data: Density of the mixture for different composition.

• Calculate molar volume of mixture and volume change of mixing.
• Fit Δ𝑣𝑚𝑖𝑥/(𝑥1𝑥2) vs 𝑥1 as a polynomial.
• Calculate Δ𝑣𝑚𝑖𝑥 using the fitted coefficients and compare with experimental data.
• Compare Δ𝑣𝑚𝑖𝑥 with literature data.
• Calculate partial molar volume 𝑣̅1 analytically using the equation
𝑣̅1−𝑣1=Δ𝑣𝑚𝑖𝑥−𝑥2*(dΔ𝑣𝑚𝑖𝑥 / d𝑥2). Similarly, for 𝑣̅2.

2. EXPERIMENTAL DETAILS

2.1 Materials
Chemicals: Pure ethanol, Distilled Water
Apparatus: Magnetic Stirrer, Digital Weighing Machine, Densitometer, Beaker(s), Dropper

2.2 Experimental Setup & Procedure

• Prepare ethanol-water solutions of 50 grams with varying mass-fractions of ethanol (0.0, 0.1,
0.2, 0.3, …....., 0.9, 1.0).
• Take an empty beaker in order to make ethanol-water solution, and keep it on a weighing
balance and calibrate the device.
• Pour the required amount of ethanol in the beaker, and then pour water so as to make the total
weight of the solution as 50 grams.
• Now put the beaker over a magnetic stirrer and leave it for around a minute so that the solution
mixes thoroughly.
• Calculate the density of the resulting solution using a densitometer and note it down.
• Repeat the above steps for different mass-fractions of ethanol and calculate the density using
a densitometer.
2.3 Precautions
• Wash and dry beaker(s) properly after measuring the density of solution with specific mass-
fraction.
• Rinse the densitometer after each measurement.
• Make sure that chemicals with pouring into the beaker does not spill on the digital weighing
machine.
• The solution should be mixed properly to avoid getting false results.
• While calculating density with densitometer make sure that there are no air bubbles in the
tube.
• Wear chemical-resistant gloves, and goggles.
• Do not touch any part of the face if your hand is exposed to ethanol, in case of contact
remember to wash your hands.

3. EXPERIMENTAL OBSERVATIONS & DATA

Density of pure water = 0.998 g/cc

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

Density of pure ethanol = 0.789 g/cc

S.No Mass of water (H2O)(g) Mass of Ethanol Density of

mixture(g/cm3)

1. 50 0 0.998

2. 45 5 0.980

3. 40 10 0.9645

4. 35 15 0.9450

5. 30 20 0.9273

6. 25 25 0.9055

7. 20 30 0.8834

8. 15 35 0.8589

9. 10 40 0.8363

10. 5 45 0.8117

11. 0 50 0.7833

4. SAMPLE CALCULATIONS

Calculation (calculation done for x1 = 0.0417)

MW1 = Molecular weight of ethanol = 46 g/mol

MW2 = Molecular weight of water =18 g/mol

m1 = mass of water = 45.0g

m2 = mass of IPA = 5.0 g

m = mass of mixture = m1 + m2 = 50.00g

Calculation for ∆Vmix

d1 = density of pure ethanol =0.789g/cc

d2 = density of pure water = 0.998 g/cc

D = Density of mixture measured using densitometer = 0.980g/cc

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

n1 = moles of ethanol = m1/ MW1 = 0.1087

n2 = moles of water = m2/MW2 = 2.5

n = number of moles in mixture = n1 + n2 = 2.6087

V = volume of mixture = m/D = 51.020cc

v = molar volume of mixture = V/n = 19.558 cc/mol

v1 = Molar volume of pure ethanol = MW1/d1 = 58.726cc/mol

v2 = molar volume of pure water = MW2/d2 = 18.036 cc/mol

videal = ideal molar volume of mixture = x1 × v1 + x2 × v 2 = 19.733 cc/mol

∆vmix = v- videal = -0.175cc/mol .

Density of V(ml n1 n2 n v(ml/mo x1 x2 videal Δvmix

mixture(g/cm3 ) l) (ml/mo (ml/mo
x) l) l)

( m1, m2)

0.998 (0, 50) 50.10 0 2.77 2.778 18.036 0 1.00 18.036 0.00
0 8

0.980 (5,45) 51.02 0.108 2.5 2.608 19.558 0.041 0.958 19.733 -0.175
0 7 7 7 3

0.9645 ( 10,40) 51.84 0.217 2.22 2.440 21.246 0.089 0.911 21.657 -0.411
4 3 0 0

0.9450 (15,35) 52.91 0.326 1.94 2.270 23.308 0.143 0.856 23.886 -0.578
0 5 6 8

0.9273 (20,30) 53.92 0.434 1.66 2.101 25.654 0.206 0.793 26.453 -0.799
8 7 8 9

0.9055 (25,25) 55.22 0.543 1.38 1.932 28.574 0.281 0.719 29.482 -0.908
5 9 5 2

0.8834 (30,20) 56.60 0.652 1.11 1.764 32.082 0.369 0.630 33.079 -0.996
2 2 2 7 3

0.8589 (35,15) 58.21 0.760 0.83 1.594 36.50 0.477 0.522 37.58 -1.08
4 9 4 9 1 9

0.8363 (40,10) 59.79 0.869 0.55 1.425 41.940 0.610 0.390 42.86 -0.917
6 6 6 0 0

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

0.8117 (45,5) 61.60 0.978 0.27 1.256 49.033 0.779 0.221 49.734 -0.701
3 8 3

0.7833 (50,0) 63.83 1.087 0 1.087 58.726 1.00 0 58.73 0.00

Total mass m = 50 g

Δvmix,experimental (ml/mol) Δvmix,fit (ml/mol) Δvmix,literature (ml/mol)

-0.175 -0.1839 -0.2063

-0.411 -0.3829 -0.6688

-0.578 -0.5881 -0.6614

-0.799 -0.7813 -0.7980

-0.908 -0.9390 -0.8852

-0.996 -1.0317 -0.9363

-1.08 -1.0312 -0.9333

-0.917 -0.9246 -0.8588

-0.701 -0.7024 -0.6092

Then partial molar volumes were estimated using the expression:

𝑑∆𝑣𝑚𝑖𝑥
𝑣1 = 𝑣1 + ∆𝑣𝑚𝑖𝑥 − 𝑥2
𝑑𝑥2
Similarly for partial molar value for water:

𝑑∆𝑣𝑚𝑖𝑥
𝑣2 = 𝑣2 + ∆𝑣𝑚𝑖𝑥 + 𝑥1
𝑑𝑥1
The values were estimated in MATLAB by applying the polyder() function to evaluate the
derivative with respect to x1 and the 2 derivatives were subsequently related using the Gibbs-
Duhem relationship.

X1 0.0417 0.089 0.1436 0.2069 0.2812 0.3697 0.4771 0.6100 0.7790

𝑣1(mL/ 57.658 57.095 56.785 56.655 56.914 57.484 58.255 59.082 58.546
mol)
𝑣2(mL/ 18.182 17.971 17.695 17.220 16.727 16.212 15.916 16.764 20.326
mol)
At x1 =1, 𝑣1=v1 and at x1=0, 𝑣2=v2

MATLAB code:

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

5. RESULTS, DISCUSSION & CONCLUSION

The fit values seem to agree overall with the literature values.

Cubic fit seems to be the best fit. From the plot we can see that it can’t be linear or quadratic
because it has at least two extrema. And as we increase the degree of the polynomial, more weightage
seems to be given to outlier points like the second point from left. The outlier could have occurred
because of incorrect density measurements due to presence of gas bubbles in the densitometer

Fit equation: −15.3498𝑥1 3 + 18.703𝑥12 − 4.805𝑥1 − 4.4321

We can see that the volume change in mixing of ethanol + water is negative which substantiates the
fact that the intermolecular attraction between the 2 molecules is high because of hydrogen bonding.
This high attraction causes the molecules to come closer resulting in a decrease in volume.

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 CH 2016: Chemical Engineering Thermodynamics Laboratory, January-May 2020

The partial molar volume of water is close to its molar volume when x1 →0 and similar behavior is
observed for ethanol when x1→1. This is because when one component is in excess, inter-molecular
interactions are low, A-A interactions dominate. This is also reflected in Δvmix which peaks at a value
of about 0.85 mole fraction of ethanol and falls off to zero when the mole fractions tend to zero or
one.

Also each component has a non-zero partial molar volume not equal to their free state molar volume
when their mole fractions are itself zero. This value is called partial molar volume at infinite
dilution. This is the molar volume to be expected when for e.g. A-A interactions die out and A
molecules can see only B molecules. (Note that B-B interactions would still be present).

There is a reasonable agreement between the literature and experimentally obtained values for the
volume change in mixing.

5.1 Conclusions

• Because of strong intermolecular forces we encounter a negative volume change in

mixing of ethanol-water mixture.
• The Δvmix/(x1x2) graph follows a cubic equation more or less.
• Partial molar volumes approach the actual molar volumes when the respective mole
fraction =1 and to infinite partial molar volume when the respective mole fraction = 0.
• Literature values agree very well because mixing was done on the basis of the more
accurate mass measurements (rather than volume measurement).

6. SUGGESTIONS

• Use a proper measuring cylinder and dropper for pouring the liquids.
• Wash the beaker carefully and use a tissue to dry it.
• Ethanol vapourises easily, so make sure that the measurements are done quickly.
• Calibrate the digital weighing balance before every measurement. This will also ensure
that there are no big errors due to earlier spillages.
7. REFERENCES
1. M. D. Koretsky, Engineering and Chemical Thermodynamics; 2nd Edition, Wiley: New York,
2012; Chapter 6.
2. https://www.toppr.com/guides/chemistry/solutions/ideal-and-non-ideal-
solutions/
3. Ethanol MSDS sheet(Fischer Scientific).