Lim, Shaneeka Elise P.

Problem Set 1 BSChE – 4

Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

Problem 8.20
The molar property of a component in a mixture may be either greater than or less than the corresponding
pure-component molar property. Furthermore, the partial molar property, may vary with composition in a
complicated way. Show this to be the case by computing (a) the partial molar volumes and (b) the partial
molar enthalpies of ethanol and water in an ethanol-water mixture. (The data that follow are from Volumes 3
and 5 of the International Critical Tables, McGraw Hill, New York, 1929.)

Heat Evolved on Mixing at 17.33 °C

Alcohol wt % Density at 20 °C (kg m-3) ×10-3 mol % water
(kJ/ mol of Ethanol)

0 0.9982
5 0.9894 5 0.042
10 0.9819 10 0.092
15 0.9751 15 0.167
20 0.9686 20 0.251
25 0.9617 25 0.335
30 0.9538 30 0.423
35 0.9449 35 0.519
40 0.9352 40 0.636
45 0.9247 45 0.757
50 0.9138 50 0.946
55 0.9026 55 1.201
60 0.8911 60 1.507
65 0.8795 65 1.925
70 0.8677 70 2.478
75 0.8556 75 3.218
80 0.8434 80 4.269
85 0.831 85 5.821
90 0.818 90 7.801
95 0.8042 95 9.818
100 0.7893

Required:

Partial molar volumes of ethanol and water, 𝑉1 and 𝑉2 respectively

Partial molar enthalpies of ethanol and water, 𝐻1 and 𝐻2 respectively

Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

Solution:
𝜕(∆𝑚𝑖𝑥 𝑉)
𝑉1 = ∆𝑚𝑖𝑥 𝑉 + 𝑥2 + 𝑉1
𝜕𝑥1
𝜕(∆𝑚𝑖𝑥 𝑉)
𝑉2 = ∆𝑚𝑖𝑥 𝑉 − 𝑥2 + 𝑉2
𝜕𝑥1

1. Calculate for ∆𝑚𝑖𝑥 𝑉 = 𝑉𝑚𝑖𝑥 − 𝑥1 𝑉1 − 𝑥2 𝑉2

Molar volume of pure ethanol 58.37788532 cm3/mol

Molar volume of pure water 18.05195195 cm3/mol
MW of pure ethanol 46.08 g/mol
MW of pure water 18.02 g/mol
Density of pure ethanol 0.78934 g/cm3
Density of pure water 0.99823 g/cm3

Alcohol wt % 𝒙𝟏 𝒙𝟐 𝑴𝑾𝒎𝒊𝒙 [g/mol] 𝝆𝒎𝒊𝒙 [g/cm3] 𝑽𝒎𝒊𝒙 [cm3/mol] ∆𝒎𝒊𝒙 𝑽

0 0.0000 1.0000 18.0200 0.9982 18.0525 0.0005
5 0.0202 0.9798 18.5859 0.9894 18.7850 -0.0802
10 0.0416 0.9584 19.1885 0.9819 19.5422 -0.1890
15 0.0646 0.9354 19.8314 0.9751 20.3378 -0.3174
20 0.0891 0.9109 20.5190 0.9686 21.1842 -0.4591
25 0.1153 0.8847 21.2559 0.9617 22.1024 -0.5999
30 0.1435 0.8565 22.0477 0.9538 23.1157 -0.7247
35 0.1739 0.8261 22.9008 0.9449 24.2363 -0.8301
40 0.2068 0.7932 23.8226 0.9352 25.4733 -0.9178
45 0.2424 0.7576 24.8217 0.9247 26.8430 -0.9839
50 0.2811 0.7189 25.9083 0.9138 28.3523 -1.0362
55 0.3234 0.6766 27.0944 0.9026 30.0182 -1.0749
60 0.3697 0.6303 28.3943 0.8911 31.8643 -1.0969
65 0.4207 0.5793 29.8251 0.8795 33.9115 -1.1060
70 0.4771 0.5229 31.4079 0.8677 36.1967 -1.0954
75 0.5398 0.4602 33.1680 0.8556 38.7658 -1.0559
80 0.6100 0.3900 35.1372 0.8434 41.6613 -0.9903
85 0.6891 0.3109 37.3549 0.8310 44.9517 -0.8870
90 0.7787 0.2213 39.8714 0.8180 48.7425 -0.7128
95 0.8814 0.1186 42.7515 0.8042 53.1602 -0.4341
100 1.0000 0.0000 46.0800 0.7893 58.3808 0.0030
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

2. Using Redlich-Kister form, calculate for ∆𝑚𝑖𝑥 𝑉𝑚𝑜𝑑𝑒𝑙 = 𝑥1 𝑥2 {𝑎0 + [𝑎1 (𝑥1 − 𝑥2 )1 ] + [𝑎2 (𝑥1 −
𝑥2 )2 ] + [𝑎3 (𝑥1 − 𝑥2 )3 ]}

𝒙𝟏 𝒙𝟐 ∆𝒎𝒊𝒙 𝑽 ∆𝒎𝒊𝒙 𝑽𝒎𝒐𝒅𝒆𝒍 Res2 with model Res2 with mean

0.0000 1.0000 0.0005 0.0000 0.0000 0.4886
0.0202 0.9798 -0.0802 -0.1198 0.0016 0.4908
0.0416 0.9584 -0.1890 -0.2396 0.0026 0.4921
0.0646 0.9354 -0.3174 -0.3584 0.0017 0.4909
0.0891 0.9109 -0.4591 -0.4752 0.0003 0.4889
0.1153 0.8847 -0.5999 -0.5886 0.0001 0.4887
0.1435 0.8565 -0.7247 -0.6970 0.0008 0.4896
0.1739 0.8261 -0.8301 -0.7985 0.0010 0.4900
0.2068 0.7932 -0.9178 -0.8910 0.0007 0.4896
0.2424 0.7576 -0.9839 -0.9719 0.0001 0.4888
0.2811 0.7189 -1.0362 -1.0386 0.0000 0.4886
0.3234 0.6766 -1.0749 -1.0881 0.0002 0.4888
0.3697 0.6303 -1.0969 -1.1174 0.0004 0.4892
0.4207 0.5793 -1.1060 -1.1236 0.0003 0.4890
0.4771 0.5229 -1.0954 -1.1041 0.0001 0.4887
0.5398 0.4602 -1.0559 -1.0565 0.0000 0.4886
0.6100 0.3900 -0.9903 -0.9788 0.0001 0.4887
0.6891 0.3109 -0.8870 -0.8666 0.0004 0.4891
0.7787 0.2213 -0.7128 -0.7067 0.0000 0.4886
0.8814 0.1186 -0.4341 -0.4581 0.0006 0.4894
1.0000 0.0000 0.0030 0.0000
AVERAGE -0.6990
SUM 0.0110 9.7866
R2 0.9989

𝒂𝟎 𝒂𝟏 𝒂𝟐 𝒂𝟑
-4.3581 1.4190 -1.2236 -0.8885

∆𝑚𝑖𝑥 𝑉𝑚𝑜𝑑𝑒𝑙 = 𝑥1 𝑥2 {−4.3581 + [1.4190 (𝑥1 − 𝑥2 ) ] + [−1.2236 (𝑥1 − 𝑥2 )2 ]

+ [−0.8885 (𝑥1 − 𝑥2 )3 ]}
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

𝜕(∆𝑚𝑖𝑥 𝑉)
3. Calculate for = −[𝑎0 (2𝑥1 − 1) + 𝑎1 (2𝑥1 − 1)2 + 𝑎2 (2𝑥1 − 1)3 + 𝑎3 (2𝑥1 − 1)4 ] +
𝜕𝑥1

2𝑥1 (1 − 𝑥1 )[𝑎1 + 2𝑎2 (2𝑥1 − 1) + 3𝑎3 (2𝑥1 − 1)2 ] and 𝑉1 and 𝑉2

𝝏(∆𝒎𝒊𝒙 𝑽)
𝒙𝟏 𝒙𝟐 ∆𝒎𝒊𝒙 𝑽 𝑽𝟏 𝑽𝟐
𝝏𝒙𝟏
0.0000 1.0000 0.0005 -6.1122 52.2662 18.0525

0.0202 0.9798 -0.0802 -5.7651 52.6489 18.0880

0.0416 0.9584 -0.1890 -5.3892 53.0241 18.0874

0.0646 0.9354 -0.3174 -4.9841 53.3982 18.0563

0.0891 0.9109 -0.4591 -4.5498 53.7741 17.9980

0.1153 0.8847 -0.5999 -4.0870 54.1623 17.9233

0.1435 0.8565 -0.7247 -3.5972 54.5723 17.8436

0.1739 0.8261 -0.8301 -3.0834 55.0007 17.7582

0.2068 0.7932 -0.9178 -2.5496 55.4377 17.6614

0.2424 0.7576 -0.9839 -2.0022 55.8771 17.5534

0.2811 0.7189 -1.0362 -1.4496 56.2996 17.4232

0.3234 0.6766 -1.0749 -0.9027 56.6922 17.2690

0.3697 0.6303 -1.0969 -0.3753 57.0445 17.0939

0.4207 0.5793 -1.1060 0.1170 57.3397 16.8967

0.4771 0.5229 -1.0954 0.5585 57.5745 16.6901

0.5398 0.4602 -1.0559 0.9386 57.7539 16.4894

0.6100 0.3900 -0.9903 1.2629 57.8801 16.2913

0.6891 0.3109 -0.8870 1.5775 57.9814 16.0780

0.7787 0.2213 -0.7128 2.0197 58.1120 15.7664

0.8814 0.1186 -0.4341 2.9245 58.2907 15.0403

1.0000 0.0000 0.0030 5.0512 58.3808 13.0037

Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.0

-0.2

-0.4
∆mixV

-0.6

-0.8

-1.0

-1.2
Ethanol composition (wt/wt)

Data Model

59.0 19.0

58.0 18.0
Partial Molar Volume of ethanol

Partial Molar Volume of water

57.0
17.0
56.0
16.0
55.0
15.0
54.0
14.0
53.0

52.0 13.0

51.0 12.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ethanol Composition (wt/wt)

Ethanol Water
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

For partial molar enthalpies, still use the same procedures as getting the partial molar volumes. Substitute
variable V with H

𝒙𝟏 𝒙𝟐 ∆𝒎𝒊𝒙 𝑯 ∆𝒎𝒊𝒙 𝑯𝒎𝒐𝒅𝒆𝒍 Res2 with model Res2 with mean

0.95 0.05 0.040 0.021 0.000 0.222
0.9 0.1 0.083 0.075 0.000 0.222
0.85 0.15 0.142 0.140 0.000 0.222
0.8 0.2 0.201 0.204 0.000 0.222
0.75 0.25 0.251 0.260 0.000 0.222
0.7 0.3 0.296 0.307 0.000 0.222
0.65 0.35 0.337 0.345 0.000 0.222
0.6 0.4 0.382 0.381 0.000 0.222
0.55 0.45 0.416 0.418 0.000 0.222
0.5 0.5 0.473 0.462 0.000 0.222
0.45 0.55 0.540 0.519 0.000 0.222
0.4 0.6 0.603 0.589 0.000 0.222
0.35 0.65 0.674 0.671 0.000 0.222
0.3 0.7 0.743 0.756 0.000 0.222
0.25 0.75 0.805 0.832 0.001 0.221
0.2 0.8 0.854 0.878 0.001 0.222
0.15 0.85 0.873 0.864 0.000 0.222
0.1 0.9 0.780 0.749 0.001 0.221
0.05 0.95 0.491 0.482 0.000 0.222

AVERAGE 0.471
SUM 0.004 4.215

R2 0.999

𝒂𝟎 𝒂𝟏 𝒂𝟐 𝒂𝟑
1.850 -2.006 4.258 -4.178
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

∆𝑚𝑖𝑥 𝑉𝑚𝑜𝑑𝑒𝑙 = 𝑥1 𝑥2 {1.850 + [−2.006(𝑥1 − 𝑥2 ) ] + [4.258 (𝑥1 − 𝑥2 )2 ]

+ [−4.178 (𝑥1 − 𝑥2 )3 ]}

𝜕(∆𝑚𝑖𝑥 𝐻)
𝒙𝟏 𝒙𝟐 ∆𝒎𝒊𝒙 𝑯 𝐻1 [kJ/mol] 𝐻2 [kJ/mol]
𝜕𝑥1
0.95 0.05 0.040 -0.8300 31.857 21.962

0.9 0.1 0.083 -1.2436 31.848 22.087

0.85 0.15 0.142 -1.3269 31.830 22.221

0.8 0.2 0.201 -1.2167 31.810 22.324

0.75 0.25 0.251 -1.0250 31.794 22.388

0.7 0.3 0.296 -0.8385 31.784 22.428

0.65 0.35 0.337 -0.7190 31.774 22.469

0.6 0.4 0.382 -0.7029 31.751 22.543

0.55 0.45 0.416 -0.8020 31.708 22.657

0.5 0.5 0.473 -1.0028 31.621 22.855

0.45 0.55 0.540 -1.2666 31.482 23.117

0.4 0.6 0.603 -1.5299 31.305 23.401

0.35 0.65 0.674 -1.7039 31.112 23.661

0.3 0.7 0.743 -1.6749 30.987 23.796

0.25 0.75 0.805 -1.3041 31.072 23.663

0.2 0.8 0.854 -0.4276 31.566 23.076

0.15 0.85 0.873 1.1436 32.707 21.781

0.1 0.9 0.780 3.6235 34.402 19.399

0.05 0.95 0.491 7.2512 35.240 15.482

Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0
0.9
0.8
0.7
0.6
∆mixV

0.5
0.4
0.3
0.2
0.1
0.0
Ethanol Composition (wt/wt)

Data Model

35.5 25.0
35.0
Partial Molar Enthalpy of ethanol

34.5 20.0

Partial Molar Enthalpy of water

34.0
33.5 15.0
33.0
32.5 10.0
32.0
31.5 5.0
31.0
30.5 0.0
0 0.2 0.4 0.6 0.8 1
Ethanol Composition (wt/wt)

Ethanol Water
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

Problem 8.27
When water and n-propanol are isothermally mixed, heat may either be absorbed (Q > 0) or evolved (Q < 0),
depending on the final composition of the mixture. Volume 5 of the International Critical Tables gives the
following data:

mol % water Q (kJ/mol) of NP

5 0.042
10 0.084
15 0.121
20 0.159
25 0.197
30 0.23
35 0.243
40 0.243
45 0.209
50 0.167
55 0.084
60 -0.038
65 -0.201
70 -0.431
75 -0.778
80 -1.335
85 -2.264
90 -4.11
95 -7.985

Required: Plot (𝐻𝑤 − 𝐻𝑤 ) and (𝐻𝑛𝑝 − 𝐻𝑛𝑝 ) over the whole composition range.
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

Solution:
𝜕(∆𝑚𝑖𝑥 𝐻)
𝐻𝑤 − 𝐻𝑤 = ∆𝑚𝑖𝑥 𝐻 + 𝑥𝑛𝑝
𝜕𝑥𝑤
𝜕(∆𝑚𝑖𝑥 𝐻)
𝐻𝑛𝑝 −𝐻𝑛𝑝 = ∆𝑚𝑖𝑥 𝐻 − 𝑥𝑛𝑝
𝜕𝑥𝑤

1. Calculate for ∆𝑚𝑖𝑥 𝐻 = 𝑥𝑛𝑝 𝑄

𝒙𝒏𝒑 𝒙𝒘 Q (kJ/mol) of NP ∆𝒎𝒊𝒙 𝑯 [kJ/mol]

0.95 0.05 0.042 0.04
0.9 0.1 0.084 0.08
0.85 0.15 0.121 0.10
0.8 0.2 0.159 0.13
0.75 0.25 0.197 0.15
0.7 0.3 0.23 0.16
0.65 0.35 0.243 0.16
0.6 0.4 0.243 0.15
0.55 0.45 0.209 0.11
0.5 0.5 0.167 0.08
0.45 0.55 0.084 0.04
0.4 0.6 -0.038 -0.02
0.35 0.65 -0.201 -0.07
0.3 0.7 -0.431 -0.13
0.25 0.75 -0.778 -0.19
0.2 0.8 -1.335 -0.27
0.15 0.85 -2.264 -0.34
0.1 0.9 -4.11 -0.41
0.05 0.95 -7.985 -0.40
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00
1
2. Using Redlich-Kister form, calculate for ∆𝑚𝑖𝑥 𝐻𝑚𝑜𝑑𝑒𝑙 = 𝑥𝑤 𝑥𝑛𝑝 {𝑎0 + [𝑎1 (𝑥𝑤 − 𝑥𝑛𝑝 ) ] +
2 3
[𝑎2 (𝑥𝑤 − 𝑥𝑛𝑝 ) ] + [𝑎3 (𝑥𝑤 − 𝑥𝑛𝑝 ) ]}

𝒙𝒏𝒑 𝒙𝒘 ∆𝒎𝒊𝒙 𝑯 ∆𝒎𝒊𝒙 𝑯𝒎𝒐𝒅𝒆𝒍 Res2 with model Res2 with mean
0.95 0.05 0.04 0.07 0.00 0.01
0.9 0.1 0.08 0.10 0.00 0.02
0.85 0.15 0.10 0.12 0.00 0.02
0.8 0.2 0.13 0.12 0.00 0.02
0.75 0.25 0.15 0.12 0.00 0.02
0.7 0.3 0.16 0.13 0.00 0.02
0.65 0.35 0.16 0.13 0.00 0.03
0.6 0.4 0.15 0.14 0.00 0.03
0.55 0.45 0.11 0.13 0.00 0.02
0.5 0.5 0.08 0.11 0.00 0.02
0.45 0.55 0.04 0.08 0.00 0.01
0.4 0.6 -0.02 0.02 0.00 0.00
0.35 0.65 -0.07 -0.06 0.00 0.00
0.3 0.7 -0.13 -0.15 0.00 0.01
0.25 0.75 -0.19 -0.24 0.00 0.05
0.2 0.8 -0.27 -0.33 0.00 0.09
0.15 0.85 -0.34 -0.38 0.00 0.12
0.1 0.9 -0.41 -0.37 0.00 0.12
0.05 0.95 -0.40 -0.26 0.02 0.06

AVERAGE -0.03

SUM 0.04 0.67

R2 0.95

𝒂𝟎 𝒂𝟏 𝒂𝟐 𝒂𝟑
0.44 -1.07 -3.03 -3.48
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00
1 2
∆𝑚𝑖𝑥 𝐻𝑚𝑜𝑑𝑒𝑙 = 𝑥𝑤 𝑥𝑛𝑝 {0.44 + [−1.07(𝑥𝑤 − 𝑥𝑛𝑝 ) ] + [−3.03(𝑥𝑤 − 𝑥𝑛𝑝 ) ]
3
+ [−3.48(𝑥𝑤 − 𝑥𝑛𝑝 ) ]}
𝜕(∆𝑚𝑖𝑥 𝐻)
3. Calculate for = −[𝑎0 (2𝑥𝑤 − 1) + 𝑎1 (2𝑥𝑤 − 1)2 + 𝑎2 (2𝑥𝑤 − 1)3 + 𝑎3 (2𝑥𝑤 −
𝜕𝑥𝑤

1)4 ] + 2𝑥𝑤 (1 − 𝑥𝑤 )[𝑎1 + 2𝑎2 (2𝑥𝑤 − 1) + 3𝑎3 (2𝑥𝑤 − 1)2 ] and 𝐻𝑤 − 𝐻𝑤 , 𝐻𝑛𝑝 − 𝐻𝑛𝑝

𝜕(∆𝑚𝑖𝑥 𝐻)
𝒙𝒏𝒑 𝒙𝒘 ∆𝒎𝒊𝒙 𝑯 𝐻𝑤 − 𝐻𝑤 𝐻𝑛𝑝 − 𝐻𝑛𝑝
𝜕𝑥𝑤
0.95 0.05 0.04 0.961 -0.873 0.953
0.9 0.1 0.08 0.395 -0.280 0.431
0.85 0.15 0.10 0.136 -0.013 0.219
0.8 0.2 0.13 0.065 0.075 0.180
0.75 0.25 0.15 0.082 0.086 0.209
0.7 0.3 0.16 0.108 0.085 0.237
0.65 0.35 0.16 0.086 0.102 0.214
0.6 0.4 0.15 -0.022 0.159 0.132
0.55 0.45 0.11 -0.232 0.242 -0.012
0.5 0.5 0.08 -0.537 0.352 -0.185
0.45 0.55 0.04 -0.913 0.449 -0.373
0.4 0.6 -0.02 -1.313 0.510 -0.541
0.35 0.65 -0.07 -1.670 0.514 -0.655
0.3 0.7 -0.13 -1.893 0.439 -0.697
0.25 0.75 -0.19 -1.875 0.274 -0.663
0.2 0.8 -0.27 -1.484 0.030 -0.564
0.15 0.85 -0.34 -0.570 -0.254 -0.425
0.1 0.9 -0.41 1.040 -0.515 -0.307
0.05 0.95 -0.40 3.538 -0.576 -0.222
Lim, Shaneeka Elise P. Problem Set 1 BSChE – 4
Mangubat, Robin Geiger B. (Sept. 20, 2018) TTH 10:30-12:00

0.6 1.2
0.4 1.0
0.8
0.2
0.6

𝐻𝑛𝑝 − 𝐻𝑛𝑝
0.0
𝐻𝑤 − 𝐻𝑤

0.4
-0.2 0.2
-0.4 0.0
-0.2
-0.6
-0.4
-0.8 -0.6
-1.0 -0.8
0.0 0.2 0.4 0.6 0.8 1.0
n-Propanol Composition (mol/mol)

Water n-Propanol