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CH116L: PHYSICAL CHEMISTRY 1(LABORATORY)

1ST Quarter SY 2019-2020

B. Molar volumes of ethanol-water mixture at different concentrations


Measurement of Density and Determination of Partial Molar Volume of Ethanol-Water
System (Experiment Number 4)

Portus, Hannah Mae S.A.

Michelle Almendrala, School of Chemical, Biological, and Materials Engineering and Sciences, Mapúa University; CH116L/B2

B. Molar volumes of ethanol-water mixture at different concentrations


V1, V2, n1 n2 x1 Mavg ρmix, V, cm3/mol ∆Vmix,
3 3 3
cm cm g/cm cm3/mol
0 30 0 0.65 0 46.07 1.8428 25.0000 -21.1538
3 27 0.17 0.59 0.22 39.8946 1.5958 24.9997 -14.4790
6 24 0.33 0.52 0.39 35.1227 1.4049 25.0001 -10.2940
9 21 0.50 0.46 0.55 30.6315 1.2253 24.9992 -6.2508
12 18 0.67 0.39 0.63 28.2859 1.1354 25.0008 -3.3011
15 15 0.83 0.33 0.72 25.8596 1.0334 24.9996 -0.8625
18 12 1.00 0.26 0.79 23.8947 0.9558 24.9997 1.1902
21 9 1.17 0.195 0.86 21.9298 0.8772 24.9998 3.0218
24 6 1.33 0.13 0.91 20.9870 0.8395 24.9994 4.4515
27 3 1.50 0.07 0.96 19.1228 0.7649 25.0004 5.8920
30 0 1.67 0 1.00 18 0.7200 25.0000 7.0369
V1 - volume of distilled water n1 – moles of distilled water x1 – mole fraction of water pmix – density of mixture
V2 – volume of ethanol n2 – moles of ethanol V – volume of mixture ∆V – molar change in volume due to mixing
Mavg – average molecular weight of mixture

Density of pure ethanol: 1.8428 g/cm3 (at 30°C)


Density of distilled water: 0.7200 g/cm3 (at 25°C)

Different parameters were determined through the experiment. The molar volumes were
only about 25 cm3/mol, whereas the original liquid used 30 cm3. This is due to the amount the
pycnometer could handle. Even though that was the case, the concentration of the mixture stayed
the same since nothing was added to the mixture. It could be seen from the table above that some
values of molar volume were negative. This meant that the liquid phase contracted as solute was
added. Its value became positive when less amount of ethanol were used and high amount of
water were used.

C. Plot of molar volume vs. molar fraction


CH116L: PHYSICAL CHEMISTRY 1(LABORATORY)
1ST Quarter SY 2019-2020

∆Vmix vs. x1
10
y = -0.2453x2 + 5.5769x - 25.338
5 R² = 0.9951

0
0 2 4 6 8 10 12
-5
∆Vmix

-10

-15

-20

-25
x1

The graph had showed that the molar change in volume of the mixture was directly proportional
to the mole fraction of water. By plotting the change in molar volume and the mole fraction of
water, the resulting equation of the line was used to help determine the values of the partial molar
volumes of water and ethanol.

Partial molar volumes of ethanol-water system


x1 1-x1 𝑽𝟏 − 𝑽, 𝑽𝟏 , cm3mol-1 𝑽𝟐 − 𝑽, cm3mol- 𝑽𝟐 , cm3mol-1
3 -1 1
cm mol
0 1 0.0000 25.0000 5.0863 30.0863
0.22 0.78 -1.20316 23.79654 4.051476 29.05118
0.39 0.61 -2.10038 22.89972 3.219336 28.21944
0.55 0.45 -2.91891 22.0803 2.388195 27.3874
0.63 0.37 -3.31871 21.68209 2.12645 27.12725
0.72 0.28 -3.76106 21.23854 1.52306 26.52266
0.79 0.21 -4.09955 20.90015 1.149498 26.1492
0.86 0.14 -4.4333 20.5665 0.771148 25.77095
0.91 0.09 -4.66876 20.33065 0.497943 25.49734
0.96 0.04 -4.90166 20.09874 0.222292 25.22269
1 0 -5.0863 19.9137 0 25

The partial molar volumes of ethanol and water were obtained through
𝑑𝑉 𝑑𝑉
𝑉1 = 𝑉 − (𝑥1 ) 𝑑𝑥 for water, and 𝑉2 = 𝑉 + (1 − 𝑥1 ) 𝑑𝑥 for ethanol. It could be seen at the table
1 1
above that as the mole fraction of ethanol increased, the partial molar volume of ethanol also
increased, and almost approached the original volume used for the pure liquid (30 cm3). For water,
as the mole fraction of water increased in amount. The molar volumes and partial molar volumes
of each component differs with each other because the molecular interaction of the between water
and ethanol were no longer an individual property. As the components were combined, the
volume of the mixture changed itself as to how its particles existed.

Sample Computation:
CH116L: PHYSICAL CHEMISTRY 1(LABORATORY)
1ST Quarter SY 2019-2020

For the first ethanol-water mixture made by the group:

V1 = 0 cm3 V2 = 30 cm3
1 1
𝑛1 = (𝑝𝑤𝑎𝑡𝑒𝑟 )(𝑉𝑤𝑎𝑡𝑒𝑟 )( ) 𝑛2 = (𝑝𝐸𝑡𝑂𝐻 )(𝑉𝐸𝑡𝑂𝐻 )( )
𝑀𝑊𝑤𝑎𝑡𝑒𝑟 𝑀𝑊𝐸𝑡𝑂𝐻

𝑔 1 𝑔 1
𝑛1 = (1.0 3
) (0 𝑐𝑚3 ) ( 𝑔 ) 𝑛2 = (0.789 3
)(30 𝑐𝑚3 )( 𝑔 )
𝑐𝑚 18 𝑐𝑚 46.07
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑛1 = 0 𝑚𝑜𝑙 𝑛2 = 0.65 𝑚𝑜𝑙

0 𝑚𝑜𝑙
𝑥1 = = 0 𝑚𝑜𝑙
0 𝑚𝑜𝑙 + 0.65 𝑚𝑜𝑙

𝑀𝑎𝑣𝑔 = 𝑋𝑤𝑎𝑡𝑒𝑟 𝑀𝑀𝑤𝑎𝑡𝑒𝑟 + 𝑋𝐸𝑡𝑂𝐻 𝑀𝑀𝐸𝑡𝑂𝐻


(0 𝑚𝑜𝑙)(18 𝑔/𝑚𝑜𝑙) (0.65 𝑚𝑜𝑙)(46.07 𝑔/𝑚𝑜𝑙)
𝑀𝑎𝑣𝑔 = +
0 𝑚𝑜𝑙 + 65 𝑚𝑜𝑙 0 𝑚𝑜𝑙 + 0.65 𝑚𝑜𝑙
𝑔
𝑀𝑎𝑣𝑔 = 46.07
𝑚𝑜𝑙
𝑀𝑎𝑣𝑔 46.07 𝑔/𝑚𝑜𝑙
𝑉= = = 25.0000 𝑐𝑚3 /𝑚𝑜𝑙
𝜌𝑚𝑖𝑥 1.8408 𝑐𝑚3 /𝑚𝑜𝑙

𝑀𝑎𝑣𝑔 46.07 𝑔/𝑚𝑜𝑙


𝜌𝑚𝑖𝑥 = = = 25.0000 𝑔/𝑐𝑚3
𝑉 1.8408 𝑐𝑚3 /𝑚𝑜𝑙

𝑉𝑡
∆𝑉 = 𝑉 −
𝑛𝑡
𝑐𝑚3 30 𝑐𝑚3
∆𝑉 = 25.000 −
𝑚𝑜𝑙 0.65 𝑚𝑜𝑙
𝑐𝑚3
∆𝑉 = −21.1538
𝑚𝑜𝑙

For water:

𝑑𝑉
𝑉1 = 𝑉 − (𝑥1 )
𝑑𝑥1
cm3
= 25.0000 mol − (0 𝑚𝑜𝑙)(0 𝑐𝑚3 /𝑚𝑜𝑙2 )
= 25.0000 cm3/mol

For ethanol:
𝑑𝑉
𝑉2 = 𝑉 + (1 − 𝑥1 )
𝑑𝑥1
= 25.0000 + (1 − 0)(5.0863)
= 30.0863 cm3/mol

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