University of San Carlos Department of Chemical Engineering

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University of San Carlos

Department of Chemical Engineering
Talamban, Cebu City, Philippines 6000

Data Processing and Analysis Report

Laboratory Course: ChE412L
Experiment Title: Partial Molar Volume
Students Name and Signature: Comendador, Marvin John
Go, James Nevin
Variacion, Manuel Jr.
Scheduled Date: July 5, 2017
Date Performed: July 5, 2017 and July 7, 2017
Date Submitted:
Submission Number: 1
Instructor: Engr. May V. Tampus
Term and Academic Year: 1st semester 2017-2018

Data Processing and Results Grade

Data Processing (x0.40)
Data Presentation (x 0.20)
Data Analysis and Interpretation (x 0.40)
Grade

Assessed and Graded By: ENGR. MAY V. TAMPUS

(Signature over printed name)
Date and Time
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University of San Carlos

Department of Chemical Engineering
Talamban, Cebu City, Philippines 6000

Partial Molar Volume

Objectives of the Experiment

1. To measure the densities of ethanol-water solutions using a pycnometer and a
densitometer.
2. To determine the partial molar volumes of ethanol and water in the ethanol-water solutions
as a function of mole fraction

Results & Discussion

Objective 1:
Mixtures are composed of two or more pure substance that is mixed together. In a mixture,
the components behave differently compared when it is alone. For components a and b, there will
be a-a interaction, b-b interaction and a-b interaction. The volume is not additive because there
will be contraction or expansion of the volume as you mix different species.
The contribution of a component to the volume of the mixture is called partial molar volume.
Partial molar volume can be determined through density measurements of mixtures. In this
experiment, the densities of ethanol-water solutions at different concentrations were determined
using the pycnometer (50-mL) and the densitometer.

Table 1. Density of water-ethanol solutions using Densitometer @ =

Actual xethanol (g/mL) Average Standard

(mole/mole) Trial 1 Trial 2 () Deviation ( )

0.0000 0.9983 0.9973 0.9978 0.0007
0.0347 0.9874 0.9872 0.9873 0.0001
0.0599 0.9732 0.9730 0.9731 0.0001
0.0902 0.9632 0.9645 0.9639 0.0009
0.1202 0.9532 0.9534 0.9533 0.0001
0.1498 0.9433 0.9424 0.9429 0.0006
0.1806 0.9352 0.9354 0.9353 0.0001
0.2109 0.9251 0.9251 0.9251 0.0000
0.2412 0.9191 0.9192 0.9192 0.0001
0.3018 0.9040 0.9043 0.9042 0.0002
0.4029 0.8774 0.8772 0.8773 0.0001
0.5032 0.8571 0.8570 0.8571 0.0001
0.6049 0.8401 0.8398 0.8400 0.0002
0.7080 0.8247 0.8248 0.8248 0.0001
0.8098 0.8071 0.8084 0.8078 0.0009
0.9137 0.7963 0.7958 0.7961 0.0004
1.0000 0.7845 0.7834 0.7840 0.0008

In getting the density using the densitometer, we are able to get directly the density by
multiplying -1 to the reading and moving the decimal once to the left or by using the following
formula.

= 10 Equation (1)
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Table 2. Density of water-ethanol solutions using Pycnometer @ =

Actual xethanol (g/mL) Average Standard

(mole/mole) Trial 1 Trial 2 () Deviation ( )

0.0000 1.0003 1.0002 1.0002 0.0001
0.0347 0.9865 0.9865 0.9865 0.0000
0.0599 0.9765 0.9765 0.9765 0.0000
0.0902 0.9680 0.9681 0.9680 0.0000
0.1202 0.9591 0.9590 0.9591 0.0001
0.1498 0.9503 0.9506 0.9504 0.0002
0.1806 0.9408 0.9409 0.9408 0.0001
0.2109 0.9291 0.9295 0.9293 0.0003
0.2412 0.9223 0.9224 0.9224 0.0001
0.3018 0.9057 0.9060 0.9058 0.0002
0.4029 0.8807 0.8806 0.8806 0.0001
0.5032 0.8593 0.8590 0.8591 0.0002
0.6049 0.8412 0.8402 0.8407 0.0007
0.7080 0.8251 0.8250 0.8251 0.0000
0.8098 0.8125 0.8124 0.8125 0.0001
0.9137 0.7978 0.7983 0.7980 0.0004
1.0000 0.7863 0.7865 0.7864 0.0002

In getting the density using the pycnometer, we use the following equation,
+
= Equation (2)

where m refers to mass and V refers to volume which is equivalent to 50mL.
The density decreases since the volume contributed by the ethanol to the over-all mixture is
lesser than that of water. As a result, at constant temperature equal to 26 the density of the
solution decreases as the ethanol concentration increases.
Comparing the densities determined using pycnometer and densitometer by the literature
value as shown in Table 3.

Table 3. Density @ = in g/mL

Densitometer Pycnometer
Water Ethanol Water Ethanol
Literature Value1 0.9983 0.7829 0.9983 0.7829
Experimental Value 0.9978 0.7840 1.0002 0.7864
Percent Error 0.0501% 0.1405% 0.3706% 0.4471%

% = | | 100% Equation (3)

Using equation 3 to solve for the percent error of the experimental value. The percent error of
the density of ethanol in both densitometer and pycnometer is just estimation since the ethanol in
the experiment is 99.99% (vol/vol) and there is no literature data for the density of 99.99% (vol/vol)
ethanol.
Based from the result, densitometer gives accurate measurements than the pycnometer.

1Data taken from Langes Handbook of Chemistry by Lange and Dean, 1973.
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Objective 2:
Determination of partial molar volume was done using three methods which are direct
graphical method, indirect graphical method and analytical method.

Analytical Method (Redlich-Kister Expansion)

From the densities gathered and known molar mass and concentration, we solve for volume
of the mixture using the following formula.
(1 )( )+(11 )( )
= = Equation (4)

Table 4. Computed in both densitometer and pycnometer

Densitometer Pycnometer
Molar Mass ( ) Average Average
xethanol
(g/mol) solution (g/ml) (ml/mol) solution (g/ml) (ml/mol)
0.0000
18.0200 0.9978 18.0597 1.0002 18.0157
0.0347
18.9943 0.9873 19.2386 0.9865 19.2542
0.0599
19.7020 0.9731 20.2467 0.9765 20.1768
0.0902
20.5516 0.96385 21.3224 0.9680 21.2299
0.1202
21.3940 0.9533 22.4421 0.9591 22.3072
0.1498
22.2231 0.94285 23.5702 0.9504 23.3822
0.1806
23.0882 0.9353 24.6853 0.9408 24.5401
0.2109
23.9365 0.9251 25.8745 0.9293 25.7564
0.2412
24.7867 0.91915 26.9670 0.9224 26.8733
0.3018
26.4875 0.90415 29.2955 0.9058 29.2412
0.4029
29.3267 0.8773 33.4283 0.8806 33.3023
0.5032
32.1403 0.85705 37.5011 0.8591 37.4104
0.6049
34.9931 0.83995 41.6610 0.8407 41.6238
0.7080
37.8852 0.82475 45.9354 0.8251 45.9186
0.8098
40.7442 0.80775 50.4416 0.8125 50.1485
0.9137
43.6579 0.79605 54.8432 0.7980 54.3707
1.0000
46.0800 0.78395 58.7793 0.7864 58.5958

We use the computed molar volume of mixture to Equation 5 to get the .

= (1 1 + 2 2 ) Equation (5)

where 1 is the molar fraction of ethanol and 2 is the molar fraction of water. 2 is the molar
volume of pure water or the molar volume when 1 is zero. From Table 4, the molar volume 2 of
3
water is 18.0597
. And for the molar volume of pure ethanol 1 from the literature data is
3
58.760 . We cant use the experimental data molar volume above for ethanol since the ethanol
that was used was not pure.
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Then, we solve for excess molar volume analytically, using Redlich-Kister equation:

= 1 2 (1 2 ) Equation (6)
=0

where is the excess molar volume, 1 is the molar fraction of ethanol and 2 is the
molar fraction of water. By differentiating equation 6, we obtain the
following:
Equation (7)

= (21 1)+1 + 21 (1 1 ) (21 1)1
1
=0 =0

We solve then for the square of the residuals and do some iterations using solver function
in excel to find the values of excess molar volumes that will result to the least sum of the squares
of the residual.

2 = [( ) ( ) ]2 Equation (8)

Table 5. Calculated data from Redlich-Kister equation using the densitometer density values.
mixV (xe-xw) RK St Sr r2
0.0000 -1.0000 0.0000 0.3854 0.0000 1.0000
-0.2350 -0.9306 -0.1835 0.1489 0.0026 0.9822
-0.2540 -0.8801 -0.3004 0.1345 0.0022 0.9840
-0.4111 -0.8196 -0.4254 0.0440 0.0002 0.9953
-0.5139 -0.7595 -0.5351 0.0114 0.0004 0.9607
-0.5890 -0.7004 -0.6308 0.0010 0.0018 -0.7339
-0.7291 -0.6388 -0.7192 0.0117 0.0001 0.9916
-0.7710 -0.5783 -0.7955 0.0226 0.0006 0.9735
-0.9123 -0.5177 -0.8622 0.0850 0.0025 0.9705
-1.0520 -0.3965 -0.9688 0.1859 0.0069 0.9628
-1.0392 -0.1941 -1.0726 0.1751 0.0011 0.9936
-1.0495 0.0064 -1.0917 0.1838 0.0018 0.9903
-1.0295 0.2098 -1.0330 0.1670 0.0000 0.9999
-0.9519 0.4159 -0.8952 0.1097 0.0032 0.9707
-0.5946 0.6197 -0.6748 0.0007 0.0064 -8.3755
-0.4212 0.8274 -0.3501 0.0398 0.0051 0.8728
0.0000 1.0000 0.0000 0.3854 0.0000 1.0000
-0.620775621 -0.619902817 2.091788617 0.034958659 0.983287671
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Table 6. Calculated data from Redlich-Kister equation using the pycnometer density values.
(RK) R2
xethanol
0.0000 0.0000 0.3946 0.0000 1.0000
0.0000
-0.1705 -0.2045 0.2095 0.0012 0.9945
0.0347
-0.2714 -0.3340 0.1273 0.0039 0.9692
0.0599
-0.4469 -0.4704 0.0329 0.0006 0.9831
0.0902
-0.5880 -0.5870 0.0016 0.0000 0.9994
0.1202
-0.7120 -0.6854 0.0070 0.0007 0.8993
0.1498
-0.8051 -0.7727 0.0313 0.0011 0.9664
0.1806
-0.8156 -0.8446 0.0351 0.0008 0.9761
0.2109
-0.9283 -0.9047 0.0901 0.0006 0.9938
0.2412
-1.0201 -0.9931 0.1536 0.0007 0.9953
0.3018
-1.0650 -1.0626 0.1908 0.0000 1.0000
0.4029
-1.0260 -1.0513 0.1582 0.0006 0.9959
0.5032
-0.9383 -0.9709 0.0962 0.0011 0.9889
0.6049
-0.8260 -0.8311 0.0391 0.0000 0.9993
0.7080
-0.7307 -0.6426 0.0105 0.0078 0.2612
0.8098
-0.3352 -0.4025 0.0858 0.0045 0.9472
0.9137
0.0000 0.0000 0.3946 0.0000 1.0000
1.0000

The figures below illustrate the deviation of the experimental or the actual to the
using the Redlich-Kister equation from both densitometer and pycnometer density values.

Change in Volume due to mixing vs. Mole Fraction of

Ethanol
0.0
0 0.2 0.4 0.6 0.8 1
-0.2

-0.4
Actual
mixV

Volume
-0.6 Mix
Analytical
Volume
-0.8 Mix

-1.0

-1.2

Mole Fraction of Ethanol

Figure 1. Volume Change of ethanol-water solution
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Change in Volume due to mixing vs. Mole Fraction of

Ethanol
0.0
0 0.2 0.4 0.6 0.8 1
-0.2

-0.4
Actual
mixV

Volume
-0.6 Mix
Analytical
Volume
-0.8 Mix

-1.0

-1.2

Mole Fraction of Ethanol

Figure 2. Volume Change of Ethanol-Water solution using the pycnometer density values

As observed, the volume change of mixing is negative. This means that the actual volume of
the solution is smaller compared to the weighted summation of the molar volumes of the pure
components. This is due to the different interactions between water-ethanol molecules, water-
water molecules and ethanol-ethanol molecules.

Table 6. Partial molar volumes using Analytical method from densitometer density values

Xethanol 1 1 2 2 1 2
0.0000 -6.9003 0.0000 51.6955 18.0157
0.0347 -5.6819 0.0051 52.9139 18.0434
0.0599 -4.9658 0.0114 53.6300 18.0436
0.0902 -4.2573 0.0166 54.3385 17.9467
0.1202 -3.6861 0.0156 54.9098 17.8511
0.1498 -3.2249 0.0062 55.3710 17.7464
0.1806 -2.8272 -0.0141 55.7686 17.6563
0.2109 -2.5015 -0.0451 56.0943 17.6505
0.2412 -2.2242 -0.0871 56.3716 17.4991
0.3018 -1.7745 -0.2024 56.8213 17.3216
0.4029 -1.2178 -0.4764 57.3780 17.0538
0.5032 -0.8186 -0.8428 57.7773 16.7796
0.6049 -0.5380 -1.3391 58.0578 16.4646
0.7080 -0.3522 -2.0354 58.2436 16.0414
0.8098 -0.2123 -2.9729 58.3836 15.0768
0.9137 -0.0831 -4.0392 58.5127 15.3030
1.0000 0.0000 -5.1377 58.5958 14.8762
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Table 7. Partial molar volumes using analytical method from pycnometer density values

Xethanol 1 1 2 2 1 2
0.0000 -5.7083 0.0000 52.8875 18.0157
0.0347 -4.9038 0.0051 53.6920 18.0154
0.0599 -4.4299 0.0114 54.1659 18.0094
0.0902 -3.9540 0.0166 54.6418 17.9166
0.1202 -3.5586 0.0156 55.0372 17.8337
0.1498 -3.2252 0.0062 55.3706 17.7465
0.1806 -2.9217 -0.0141 55.6741 17.6771
0.2109 -2.6574 -0.0451 55.9385 17.6921
0.2412 -2.4180 -0.0871 56.1778 17.5607
0.3018 -1.9975 -0.2024 56.5983 17.4180
0.4029 -1.4266 -0.4764 57.1692 17.1947
0.5032 -0.9924 -0.8428 57.6034 16.9557
0.6049 -0.6571 -1.3391 57.9387 16.6470
0.7080 -0.3892 -2.0354 58.2067 16.1309
0.8098 -0.1769 -2.9729 58.4190 14.9261
0.9137 -0.0440 -4.0392 58.5518 14.9339
1.0000 0.0000 -5.1377 58.5958 14.1289

The following graphs show the trend of the calculated values of the partial molar volume of
ethanol and water with respect to the molar concentration of ethanol using the Redlich-Kister
expansion.

PMV (Densitometer) vs. Mole Fraction of Ethanol

59 20

18
58
16
57
14
56
12
PMV

PMV of
55 10 Ethanol

8 PMV of
54
Water
6
53
4
52
2

51 0
0 0.2 0.4 0.6 0.8 1
Mole Fraction of Ethanol

Figure 3. Partial molar volume of ethanol and water with respect to x ethanol (Densitometer) Using
Redlich-Kister Expansion
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PMV (Pycnometer) vs. Mole Fraction of Ethanol

59 20

18
58
16
57 14

12
PMV

56 PMV of
10 Ethanol
55
8 PMV of
Water
54 6

4
53
2

52 0
0 0.2 0.4 0.6 0.8 1
Mole Fraction of Ethanol
Figure 4. Partial molar volume of ethanol and water with respect to x ethanol (pycnometer) Using
Redlich-Kister Expansion

From these graphs, it can be inferred that the partial molar volume varies with concentration
for the reason that any substance, when placed in a mixture, the behavior of the substance
changes upon interaction with unlike substance. As the mole fraction approaches to zero, the
partial molar volume of the mixture is most different from the pure component since the dilute
species is forced to interact with the concentrated species thus having a partial molar volume very
different from that of the pure component.

Direct Graphical Method

Using the values of mixV obtained from regression (refer to table 5) using the density
measured directly from the pycnometer which was then used in computing for the molar volume
of the solution, we are able to establish 2 graphs:

0.0000
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000 1.0000

-0.2000
y = -11.785x6 + 42.69x5 - 55.474x4 + 30.549x3 - 1.6944x2 - 4.2709x - 0.0242
R = 0.9854
-0.4000
mix V

-0.6000

-0.8000

-1.0000

-1.2000
Mole fraction of Ethanol

Figure 5. mixV of Ethanol-Water Mixture with respect to the change in mole fraction of ethanol
(Densitometer)
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0.0000
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000 1.0000

-0.2000

-0.4000
y = 6.2232x5 - 8.8237x4 - 1.6658x3 + 10.51x2 - 6.2511x + 0.025
R = 0.9919
mix V

-0.6000

-0.8000

-1.0000

-1.2000
xe

Figure 6. mixV of Ethanol-Water Mixture with respect to the change in mole fraction of ethanol
(Pycnometer)

We take the derivative of the equation of the curve to determine the slope of a tangent line.
Equation of Graph 1:

= 6.2232 5 8.8237 4 1.6658 3 + 10.51 2 6.2511 + 0.025 Eq. (9)

Deriving the equation

= 31.1161 4 35.29481 3 4.99741 2 + 21.021 6.2511 Eq. (10)
1
To solve for the partial molar volume, we use these equations:

= 1 = 2 2 Eq. (11)
1

= + 2 = 1 1 Eq. (12)
1
where A and B are the ordinates of the tangent lines drawn in the graph (used in indirect
method).
We can solve for the partial molar volumes using equations (3) and (4). Results from
calculations are tabulated in tables 8 and 9. Same process is done in getting the partial molar
volume with the data using density from densitometer measurements and pycnometer
measurements.

Table 8. Data results for Direct graphical method (Densitometer)

X1
- - 1 2
(actual)
0.0000 0.0000 -4.2709 -4.2709 0.0000 0.0000 54.4891 18.0597
0.0347 -0.2350 -4.1382 -4.3732 -0.1489 -0.0861 54.3868 17.9736
0.0599 -0.2540 -3.9387 -4.1926 -0.2512 -0.0028 54.5674 18.0569
0.0902 -0.4111 -3.6208 -4.0319 -0.3591 -0.0520 54.7281 18.0077
0.1202 -0.5139 -3.2518 -3.7657 -0.4445 -0.0695 54.9943 17.9903
0.1498 -0.5890 -2.8617 -3.4507 -0.5042 -0.0848 55.3093 17.9749
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0.1806 -0.7291 -2.4476 -3.1768 -0.5395 -0.1896 55.5832 17.8701

0.2109 -0.7710 -2.0508 -2.8218 -0.5480 -0.2231 55.9382 17.8367
0.2412 -0.9123 -1.6744 -2.5867 -0.5321 -0.3802 56.1733 17.6795
0.3018 -1.0520 -1.0148 -2.0668 -0.4386 -0.6134 56.6932 17.4464
0.4029 -1.0392 -0.2398 -1.2790 -0.1619 -0.8773 57.4810 17.1824
0.5032 -1.0495 0.1731 -0.8763 0.1754 -1.2248 57.8837 16.8349
0.6049 -1.0295 0.3633 -0.6662 0.5562 -1.5856 58.0938 16.4741
0.7080 -0.9519 0.4390 -0.5129 1.0643 -2.0162 58.2471 16.0435
0.8098 -0.5946 0.4335 -0.1610 1.8464 -2.4410 58.5990 15.6188
0.9041 -0.4212 0.2911 -0.1302 3.0808 -3.5020 58.6298 14.5577
1.0000 0.0000 0.0000 0.0000 4.4413 -4.4413 58.7600 13.6184

Table 8. Data results for Direct graphical method (Pycnometer)

X1
- -
(actual)
0.0000 0.0000 -6.2511 -6.2511 0 0.0000 52.3447 18.0157
0.0347 -0.1705 -5.3367 -5.5072 -0.1920 0.0215 53.0886 18.0371
0.0599 -0.2714 -4.7155 -4.9869 -0.3007 0.0293 53.6089 18.0449
0.0902 -0.4469 -4.0205 -4.4674 -0.3987 -0.0482 54.1285 17.9675
0.1202 -0.5880 -3.3877 -3.9757 -0.4630 -0.1250 54.6202 17.8907
0.1498 -0.7120 -2.8206 -3.5326 -0.4970 -0.2150 55.0632 17.8006
0.1806 -0.8051 -2.2880 -3.0931 -0.5044 -0.3007 55.5027 17.7149
0.2109 -0.8156 -1.8233 -2.6390 -0.4872 -0.3285 55.9569 17.6872
0.2412 -0.9283 -1.4133 -2.3417 -0.4491 -0.4792 56.2542 17.5364
0.3018 -1.0201 -0.7506 -1.7707 -0.3244 -0.6957 56.8252 17.3199
0.4029 -1.0650 -0.0486 -1.1136 -0.03281 -1.0322 57.4822 16.9835
0.5032 -1.0260 0.2776 -0.7484 0.2812 -1.3071 57.8475 16.7085
0.6049 -0.9383 0.3909 -0.5474 0.5984 -1.5367 58.0484 16.4790
0.7080 -0.8260 0.4142 -0.4118 1.0041 -1.8300 58.1841 16.1857
0.8098 -0.7307 0.4054 -0.3253 1.7267 -2.4574 58.2705 15.5582
0.9041 -0.3352 0.3236 -0.0116 3.0519 -3.3872 58.5842 14.6285
1.0000 0.0000 0.0000 0.0000 5.5927 -5.5927 58.5958 12.4230

Solving for partial molar volumes using equation (11) and (12):

2 = 1 + 2
1

1 = + 2 + 1
1
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70.0000

60.0000 y = 6.2232x5 - 8.8237x4 - 1.6658x3 + 10.51x2 + 34.329x + 18.041

R = 1
50.0000
Molar Vsolution

40.0000

30.0000

20.0000

10.0000

0.0000
0.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000 1.0000
xe

Figure 7. Molar Volume of Ethanol-Water Mixture as a function of mole fraction of ethanol

Graph 2 shows the behavior of ethanol in the ethanol-water mixture. It is observed that there is a
steady increase of the molar volume of the mixture as we increase the mole fraction of ethanol.

Indirect Graphical Method

To solve for partial molar volume, we create a tangent line in the curve. The ordinate at = 0
is labeled A while the ordinate at = 1 is labeled B. Using equations (11) and (12), we can solve
for partial molar volume.

= 2 2

= 1 1

Creating tangent lines at every xethanol in the graph as illustrated below:

0.0
0 0.2 0.4 0.6 0.8 1
-0.2

-0.4
mixV

-0.6

-0.8

-1.0

-1.2

Mole Fraction of Ethanol

Figure 8. Change in Volume due to mixing vs. Mole Fraction of Ethanol (Pycnometer)
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Change in Volume due to mixing vs. Mole Fraction of Ethanol

0.0
0 0.2 0.4 0.6 0.8 1

-0.2

-0.4
mixV

-0.6

-0.8

-1.0

-1.2

Mole Fraction of Ethanol

Figure 9. Change in Volume due to mixing vs. Mole Fraction of Ethanol (Densitometer)

Tables below are the results of solving partial molar volumes of water and ethanol using indirect
graphical method. (see appendix 2 for sample calculations).

Table 1. Data Results for Indirect Graphical Method of solving Partial Molar Volumes (Pycnometer)

A B ( ) ()

0 -4.5691 18.0304 54.2742
-0.0315 -3.4901 17.9988 55.3532
0.0759 -4.8255 18.1064 54.0179
-0.0228 -3.5471 18.0076 55.2962
-0.0833 -2.8561 17.9470 55.9873
-0.2595 -1.6696 17.7708 57.1737
-0.7420 0.5404 17.2883 59.3837
-0.0313 -1.8943 17.9990 56.9491
-0.5633 -0.0369 17.4671 58.8065
-0.8862 0.8001 17.1442 59.6435
-1.2218 1.2193 16.8086 60.0627
-1.4599 1.2790 16.5705 60.1224
-1.5975 1.1442 16.4329 59.9876
-1.4874 0.9084 16.5430 59.7518
-3.4126 0.6727 14.6178 59.5161
-4.4820 0.0000 13.5484 58.8434
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Table 10. Data Results for Indirect Graphical Method of solving Partial Molar Volumes
(Densitometer)

3 3 3 3
A ( ) B ( ) 2 ( ) 1 ( )

0 -6.2971 18.0304 52.5463
-0.2088 -0.4543 17.8216 58.3891
0.0570 -4.3099 18.0875 54.5335
-0.1020 -2.4997 17.9284 56.3436
-0.2084 -1.5710 17.8220 57.2724
0.0920 -2.9962 18.1224 55.8472
-0.4789 -0.3222 17.5515 58.5212
0.2122 -2.6264 18.2427 56.2169
-0.3567 -0.5566 17.6736 58.2868
-1.0900 1.1145 16.9404 59.9579
-0.9979 0.9986 17.0325 59.8419
-1.1483 1.1071 16.8821 59.9505
-1.484 1.1717 16.5457 60.0151
-3.4348 1.2615 14.5956 60.1048
-1.9464 0.5653 16.0840 59.4087
-4.8800 0.0000 13.1503 58.8434

Comparing the results of all the three methods used to solve the partial molar volumes of
ethanol and water at different concentrations.

3
Table 2. Comparison of results for partial molar volumes ( ) of ethanol using the different

methods
Densitometer Pycnometer
Standard Standard
Direct Indirect Analytical Direct Indirect Analytical
deviation deviation
0.0000 54.4891 52.5463 51.6955 52.3447 54.2742 52.8875
0.0347 54.3868 58.3891 52.9139 53.0886 55.3532 53.6920
0.0599 54.5674 54.5335 53.6300 53.6089 54.0179 54.1659
0.0902 54.7281 56.3436 54.3385 54.1285 55.2962 54.6418
0.1202 54.9943 57.2724 54.9098 54.6202 55.9873 55.0372
0.1498 55.3093 55.8472 55.3710 55.0632 57.1737 55.3706
0.1806 55.5832 58.5212 55.7686 55.5027 59.3837 55.6741
0.2109 55.9382 56.2169 56.0943 55.9569 56.9491 55.9385
0.2412 56.1733 58.2868 56.3716 56.2542 58.8065 56.1778
0.3018 56.6932 59.9579 56.8213 56.8252 59.6435 56.5983
0.4029 57.4810 59.8419 57.3780 57.4822 60.0627 57.1692
0.5032 57.8837 59.9505 57.7773 57.8475 60.1224 57.6034
0.6049 58.0938 60.0151 58.0578 58.0484 59.9876 57.9387
0.7080 58.2471 60.1048 58.2436 58.1841 59.7518 58.2067
0.8098 58.5990 59.4087 58.3836 58.2705 59.5161 58.4190
0.9137 58.6298 58.8434 58.5127 58.5842 58.8434 58.5518
1.0000 58.7600 52.5463 58.5958 58.5958 54.2742 58.5958
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Densitometer Pycnometer
Standard Standard
Direct Indirect Analytical Direct Indirect Analytical
deviation deviation
1.0000 18.0597 18.0304 18.0157 18.0157 18.0304 18.0157
0.9653 17.9736 17.8216 18.0434 18.0371 17.9988 18.0154
0.9401 18.0569 18.0875 18.0436 18.0449 18.1064 18.0094
0.9098 18.0077 17.9284 17.9467 17.9675 18.0076 17.9166
0.8798 17.9903 17.8220 17.8511 17.8907 17.9470 17.8337
0.8502 17.9749 18.1224 17.7464 17.8006 17.7708 17.7465
0.8194 17.8701 17.5515 17.6563 17.7149 17.2883 17.6771
0.7891 17.8367 18.2427 17.6505 17.6872 17.9990 17.6921
0.7588 17.6795 17.6736 17.4991 17.5364 17.4671 17.5607
0.6982 17.4464 16.9404 17.3216 17.3199 17.1442 17.4180
0.5971 17.1824 17.0325 17.0538 16.9835 16.8086 17.1947
0.4968 16.8349 16.8821 16.7796 16.7085 16.5705 16.9557
0.3951 16.4741 16.5457 16.4646 16.4790 16.4329 16.6470
0.2920 16.0435 14.5956 16.0414 16.1857 16.5430 16.1309
0.1902 15.6188 16.0840 15.0768 15.5582 14.6178 14.9261
0.0863 14.5577 13.1503 15.3030 14.6285 13.5484 14.9339
0.0000 13.6184 18.0304 14.8762 12.4230 18.0304 14.1289

Conclusions

Given the results and your discussion of the results, what conclusion/s can be made regarding each objective of the
experiment?
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APPENDIX 1: Raw Data

To be found here should be your raw data sheets or a photocopy of the raw data page(s) from your
laboratory journal.
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APPENDIX 2: Processing of Data and Sample Calculations

Table 5. Raw Data Table for Densitometer

T= 26C TRIAL 1 TRIAL 2 Average
xethanol xwater Buoyancy (g) solution (g/ml) Buoyancy (g) solution (g/ml) solution (g/ml)
0.0000 1.0000 -9.9830 0.9983 -9.9730 0.9973 0.9978
0.0347 0.9653 -9.8740 0.9874 -9.8720 0.9872 0.9873
0.0599 0.9401 -9.7320 0.9732 -9.7300 0.9730 0.9731
0.0902 0.9098 -9.6320 0.9632 -9.6450 0.9645 0.9639
0.1202 0.8798 -9.5320 0.9532 -9.5340 0.9534 0.9533
0.1498 0.8502 -9.4330 0.9433 -9.4240 0.9424 0.9429
0.1806 0.8194 -9.3520 0.9352 -9.3540 0.9354 0.9353
0.2109 0.7891 -9.2510 0.9251 -9.2510 0.9251 0.9251
0.2412 0.7588 -9.1910 0.9191 -9.1920 0.9192 0.9192
0.3018 0.6982 -9.0400 0.9040 -9.0430 0.9043 0.9042
0.4029 0.5971 -8.7740 0.8774 -8.7720 0.8772 0.8773
0.5032 0.4968 -8.5710 0.8571 -8.5700 0.8570 0.8571
0.6049 0.3951 -8.4010 0.8401 -8.3980 0.8398 0.8400
0.7080 0.2920 -8.2470 0.8247 -8.2480 0.8248 0.8248
0.8098 0.1902 -8.0710 0.8071 -8.0840 0.8084 0.8078
0.9137 0.0863 -7.9630 0.7963 -7.9580 0.7958 0.7961
1.0000 0.0000 -7.8450 0.7845 -7.8340 0.7834 0.7840

Table 6. Raw Data Table for Pycnometer

mpyncometer +msolution (g) msolution (g) solution (g/ml) solution (g/ml) Average
xethanol Trial 1 Trial 2 Trial 1 Trial 2 Trial 1 Trial 2 solution (g/ml)
0.0000 82.2077 82.2030 50.0144 50.0097 1.0003 1.0002 1.0002
0.0347 81.5198 81.5170 49.3265 49.3237 0.9865 0.9865 0.9865
0.0599 81.0173 81.0163 48.8240 48.8230 0.9765 0.9765 0.9765
0.0902 80.5949 80.5964 48.4016 48.4031 0.9680 0.9681 0.9680
0.1202 80.1502 80.1429 47.9569 47.9496 0.9591 0.9590 0.9591
0.1498 79.7082 79.7213 47.5149 47.5280 0.9503 0.9506 0.9504
0.1806 79.2316 79.2384 47.0383 47.0451 0.9408 0.9409 0.9408
0.2109 78.6503 78.6704 46.4570 46.4771 0.9291 0.9295 0.9293
0.2412 78.3090 78.3131 46.1157 46.1198 0.9223 0.9224 0.9224
0.3018 77.4759 77.4935 45.2826 45.3002 0.9057 0.9060 0.9058
0.4029 76.2275 76.2211 44.0342 44.0278 0.8807 0.8806 0.8806
0.5032 75.1560 75.1434 42.9627 42.9501 0.8593 0.8590 0.8591
0.6049 74.7889 74.7850 42.5956 42.5917 0.8412 0.8402 0.8407
0.7080 73.4470 73.4447 41.2537 41.2514 0.8251 0.8250 0.8251
0.8098 72.7187 72.7150 40.5254 40.5217 0.8125 0.8124 0.8125
0.9041 72.0820 72.1090 39.8887 39.9157 0.7978 0.7983 0.7980
1.0000 71.5070 71.5200 39.3137 39.3267 0.7863 0.7865 0.7864

In the determination of the partial molar volumes of the components ethanol and water in the
solution, the density of the solution at different concentrations were measured using a
pycnometer (50mL) and densitometer
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From the densities gathered and known molar mass and concentration, we solve for volume
of the mixture using the following formula.
(1 )( )+(11 )( )
= Equation (4)

Partial molar volume is determined using three methods the direct graphical method, indirect graphical method and
the analytical method or using the Redlich-Kister Expansion.

Analytical Method (Redlich-Kister Expansion)

Redlich-Kistler Expansion for any change in thermodynamic property upon mixing.

Equation (5)
= 1 2 (1 2 )
=0

Since i = 5;
= 1 2 (0 + 1 (1 2 )1 + 2 (1 2 )2 + 3 (1 2 )3 + 4 (1 2 )4 +5 (1 2 )5 )
Sample Calculations:
= (0)2 (0 + 1 (2(0) 1)1 + 2 (2(0) 1)2 + 3 (2(0) 1)3 + 4 (2(0) 1)4 +5 (2(0) 1)5

Since i = 5;

Equation (6)
= (21 1)+1 + 21 (1 1 ) (21 1)1
1
=0 =0

= ( )2
Sample Calculations
= (0 (0.6282)2 = 0.3946
= ( )2

2 =

All calculations are tabulated (Pycnometer):
mixV (xe-xw) RK St Sr r2
0.0000 -1.0000 0.0000 0.3946 0.0000 1.0000
-0.1705 -0.9306 -0.2045 0.2095 0.0012 0.9945
-0.2714 -0.8801 -0.3340 0.1273 0.0039 0.9692
-0.4469 -0.8196 -0.4704 0.0329 0.0006 0.9831
-0.5880 -0.7595 -0.5870 0.0016 0.0000 0.9994
-0.7120 -0.7004 -0.6854 0.0070 0.0007 0.8993
-0.8051 -0.6388 -0.7727 0.0313 0.0011 0.9664
-0.8156 -0.5783 -0.8446 0.0351 0.0008 0.9761
-0.9283 -0.5177 -0.9047 0.0901 0.0006 0.9938
-1.0201 -0.3965 -0.9931 0.1536 0.0007 0.9953
-1.0650 -0.1941 -1.0626 0.1908 0.0000 1.0000
-1.0260 0.0064 -1.0513 0.1582 0.0006 0.9959
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-0.9383 0.2098 -0.9709 0.0962 0.0011 0.9889

-0.8260 0.4159 -0.8311 0.0391 0.0000 0.9993
-0.7307 0.6197 -0.6426 0.0105 0.0078 0.2612
-0.3352 0.8083 -0.4025 0.0858 0.0045 0.9472
0.0000 1.0000 0.0000 0.3946 0.0000 1.0000
Ave: -0.6282 Sum: -0.6328 2.0583 0.0236 0.9886

All calculations are tabulated (Densitometer):

mixV (xe-xw) RK St Sr r2
0.0000 -1.0000 0.0000 0.3854 0.0000 1.0000
-0.2350 -0.9306 -0.1835 0.1489 0.0026 0.9822
-0.2540 -0.8801 -0.3004 0.1345 0.0022 0.9840
-0.4111 -0.8196 -0.4254 0.0440 0.0002 0.9953
-0.5139 -0.7595 -0.5351 0.0114 0.0004 0.9607
-0.5890 -0.7004 -0.6308 0.0010 0.0018 -0.7339
-0.7291 -0.6388 -0.7192 0.0117 0.0001 0.9916
-0.7710 -0.5783 -0.7955 0.0226 0.0006 0.9735
-0.9123 -0.5177 -0.8622 0.0850 0.0025 0.9705
-1.0520 -0.3965 -0.9688 0.1859 0.0069 0.9628
-1.0392 -0.1941 -1.0726 0.1751 0.0011 0.9936
-1.0495 0.0064 -1.0917 0.1838 0.0018 0.9903
-1.0295 0.2098 -1.0330 0.1670 0.0000 0.9999
-0.9519 0.4159 -0.8952 0.1097 0.0032 0.9707
-0.5946 0.6197 -0.6748 0.0007 0.0064 -8.3755
-0.4212 0.8274 -0.3501 0.0398 0.0051 0.8728
0.0000 1.0000 0.0000 0.3854 0.0000 1.0000
-0.620775621 -0.619902817 2.091788617 0.034958659 0.983287671

By Data Regression parameter values was obtained.

Parameters of Pycnometer
0 1 2 3 4 5
-4.3692 0.3508 -0.5739 -0.1240 -0.1234 0.4150

Parameters of Densotimer
0 1 2 3 4 5
-4.2112 0.8936 -0.8267 -0.0123 -0.9812 -0.5500
( )
1 1
| = (2 2 ) Substitute Eq. 1 and Eq. 2 .
,

( )
+ 1
| = (1 1 ) Substitute Eq. 1 and Eq. 2.
,
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The following data for the partial molar volume of the two components was obtained and tabulated.

Densitometer: Pycnometer:
pve pmvw-pure pvw
51.69555 0 18.01566
52.9139 0.005129 18.04342
53.63001 0.011406 18.04359
54.33851 0.016627 17.94666
54.90976 0.015644 17.85111
55.37096 0.006202 17.74639
55.76861 -0.01412 17.65631
56.09434 -0.04508 17.65046
56.37165 -0.08708 17.49911
56.8213 -0.20235 17.32162
57.37802 -0.47641 17.05381
57.77728 -0.84278 16.77961
58.0578 -1.33913 16.46462
58.24359 -2.03542 16.04139
58.38357 -2.97288 15.07677
58.51271 -4.03924 15.303
58.59584 -5.13775 14.8762

By Direct Graphical Method

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Sample calculations for Indirect Graphical Method.

At 1 = 0.1498, the y-intercept which is also A is about .
Therefore,
3
2 ( @ 26 = 18.03039925
3
= 2 2 = -0.208801532

3
2 = 0.208801532 +18.03039925
3
= 17.8216

Using similar triangles, we B.

Solving for B:
0.5890 0.208801532
=
0.1498 1 0.1498
3
=2.159943513
3
= ( 0.5890) = -1.5710
3
1 = + 1 =-1.5710 +58.84336451 = 57.2724

Same calculations are done and tabulated insert table name

3 3 3 3
A B 2 1

0 -6.2971 18.0304 52.5463
-0.208801532 -0.4543 17.8216 58.3891
0.057092457 -4.3099 18.0875 54.5335
-0.102013411 -2.4997 17.9284 56.3436
-0.208439075 -1.5710 17.8220 57.2724
0.092050438 -2.9962 18.1224 55.8472
-0.478935896 -0.3222 17.5515 58.5212
0.212252862 -2.6264 18.2427 56.2169
-0.356769635 -0.5566 17.6736 58.2868
-1.090031228 1.1145 16.9404 59.9579
-0.99791794 0.9986 17.0325 59.8419
-1.148313829 1.1071 16.8821 59.9505
-1.484672635 1.1717 16.5457 60.0151
-3.434829372 1.2615 14.5956 60.1048
-1.946412257 0.5653 16.0840 59.4087
-4.880098563 0.0000 13.1503 58.8434
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As you can see from the graph, there are variations. The probable cause of error was in the preparation of the solutions. Also
ethanol is very volatile, and the experiment must be carried out in a fast phase manner, prolonging the solutions in the weighing
instrument would cause a change in the composition due to volatilization.