8.

15
N2

MIHS
0.25
1.00
1.50
2.33
4.00
5.44
9.00
10.10
19.00
20.00

molar integral heat

8242
28200
34980
44690
54440
58370
62800
64850
70710
71970

80000
70000
60000
50000
40000
Molar Integral Heat of Solutions
30000
20000
10000
0
0.00

8.16
x CCl4
Cp
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

Cp(CCl4)
1.7655
1.6300
1.4930
1.3580
1.2220
1.1000
1.0040
0.9270
0.8580
0.8160
0.8070

Cp(Benz)
-1.722
2.2842
-1.57822
2.0842
-1.43444
1.8842
-1.29066
1.6842
-1.14688
1.4842
-1.0031
1.2842
-0.85932
1.0842
-0.71554
0.8842
-0.57176
0.6842
-0.42798
0.4842
-0.2842
0.2842

8.20
Alcohol wt% x EtOH
0
5
10
15
20
25
30
35
40
45
50
55

0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55

Ave.(mol wgt)
Density (x1 Density (kg
18.00
0.9982
998.2
18.57
0.9894
989.4
19.17
0.9819
981.9
19.81
0.9751
975.1
20.50
0.9686
968.6
21.23
0.9617
961.7
22.02
0.9538
953.8
22.87
0.9449
944.9
23.79
0.9352
935.2
24.79
0.9247
924.7
25.88
0.9138
913.8
27.06
0.9026
902.6

5.00

10.00
15.00
x H2O

60
65
70
75
80
85
90
95
100
Alcohol wt% x EtOH
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100

0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1

28.36
29.78
31.36
33.12
35.08
37.30
39.81
42.68
46.00

891.1
879.5
867.7
855.6
843.4
831.0
818.0
804.2
789.3

Heat evolved on Ave Cp (kJ/delta mix H

0
0
0.0000
-1.3040
0.05
0.042
0.0001
-1.2902
0.1
0.092
0.0003
-1.2684
0.15
0.167
0.0006
-1.2216
0.2
0.251
0.0009
-1.1658
0.25
0.335
0.0012
-1.1100
0.3
0.423
0.0015
-1.0502
0.35
0.519
0.0018
-0.9824
0.4
0.636
0.0022
-0.8936
0.45
0.757
0.0026
-0.8008
0.5
0.946
0.0033
-0.6400
0.55
1.201
0.0041
-0.4132
0.6
1.507
0.0052
-0.1354
0.65
1.925
0.0066
0.2544
0.7
2.478
0.0085
0.7792
0.75
3.218
0.0111
1.4910
0.8
4.269
0.0147
2.5138
0.85
5.821
0.0200
4.0376
0.9
7.801
0.0269
5.9894
0.95
9.818
0.0338
7.9782
1
0
0.0000
-1.8680

USING THE TRENDLINE FEATUR

IN THE PLOT

Problem 8.27

mol % H2OQ, kJ/mol of nmol fraction H2O

5
10
15
20
25
30
35
40
45
50
55
60
65
70
75

0.8911
0.8795
0.8677
0.8556
0.8434
0.8310
0.8180
0.8042
0.7893

0.042
0.082
0.121
0.159
0.197
0.23
0.243
0.243
0.209
0.167
0.084
-0.038
-0.201
-0.431
-0.778

0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75

d(delta
Q = delta mimix h)/dx
H2O
0.95
0.040 0.201811
0.9
0.074 0.634243
0.85
0.103 0.693453
0.8
0.127 0.541553
0.75
0.148 0.293644
0.7
0.161 0.024949
0.65
0.158 -0.222051
0.6
0.146 -0.430486
0.55
0.115 -0.601958
0.5
0.084 -0.749413
0.45
0.038
-0.89
0.4
-0.015 -1.037946
0.35
-0.070 -1.197412
0.3
-0.129 -1.355366
0.25
-0.195 -1.474446

mol fraction npropanol

80
85
90
95

-1.335
-2.264
-4.11
-7.985

0.8
0.85
0.9
0.95

0.2
0.15
0.1
0.05

-0.267 -1.485825
-0.340 -1.282082
-0.411 -0.71006
-0.399 0.43626

USING THE REDLICH KESTER EQ

Q = delta
mix H
kJ/mol
sol'n
a0
a1
a2
a3
a4
St
Q mean

0.28801
-1.07650
-0.20566
-3.47327
-5.18651

-0.033

0.040
0.074
0.103
0.127
0.148
0.161
0.158
0.146
0.115
0.084
0.038
-0.015
-0.070
-0.129
-0.195
-0.267
-0.340
-0.411
-0.399

Q = delta
mix H
kJ/mol
sol'n (RK)
0.0104
0.0604
0.1131
0.1501
0.1659
0.1628
0.1466
0.1235
0.0981
0.0720
0.0431
0.0068
-0.0431
-0.1114
-0.1987
-0.2967
-0.3829
-0.4147
-0.3222
SUM

8.34
Given:
a0
a1
a2
a3
-500.0616 4995.30891 893.3083367298 2018.5632753

Find: Partial molar enthalpies of

_ =_1 _2 (2
General Equation for
Expansion

Isothermal heat of mixing of trichloromethane (1) and ethanol (2) at 30 C. Compute the partial molar entha
((_
_
_
_1
))/

from
x1
(J/mol)
n = 3 RK
R sqrd
_1 )
0.01
-68.80 -75.8929346212 50.30972154(-5424.933
5291.034
0.02
-101.30 -112.9711768922 136.21637005 -5222.562 5025.689
0.03
-179.10 -197.5199943703 339.2961926 -4729.249 4389.354
0.05
-244.40 -264.8788572008 419.38359225 -4296.598 3845.102
0.07
-344.60 -365.6198155953 441.83264766 -3554.756 2948.526
0.11
-451.10 -465.0732411591 195.25146849 -2628.726 1895.038
0.17
-565.30 -563.4517697048 3.4159552241 -1093.453 341.2816
0.19
-581.00 -575.5226530934 30.001329136 -641.4082 -62.67806
0.23
-585.00 -576.4115340761 73.761746926 108.8124 -668.7747

0.26
0.27
0.27
0.31
0.32
0.35
0.37
0.40
0.46
0.49
0.51
0.54
0.59
0.62
0.65
0.70
0.75
0.78
0.80
0.82
0.85
0.88
0.90
0.93
0.95
0.98
0.99
1.00

-566.10
-561.90
-557.80
-519.60
-508.00
-468.50
-424.40
-369.10
-197.10
-135.40
-66.10
-1.90
117.10
186.50
266.90
360.30
436.60
470.50
495.90
510.00
515.80
505.30
486.00
420.50
329.20
184.70
123.30
25.10

-558.1768062966
-554.5469253879
-551.1026939538
-512.6085343673
-492.4320831894
-451.1534682632
-409.8051511933
-358.559644069
-221.3750038004
-161.1657745369
-90.5514612693
-25.5926256681
95.5117028502
176.233373324
269.1990479622
380.2617552977
466.6321213277
500.0636071392
520.4101861839
530.9538666382
525.023148208
498.4964217173
467.1015707229
380.9628867156
279.4686687857
148.7081787338
97.360569494
21.2037232302
SUM

62.776998461
54.067706251
44.853908277
48.880591693
242.36003382
300.9021633
213.00961169
111.09910315
589.27580951
663.87513749
597.8739582
561.34051105
466.05457383
105.40362331
5.2856215325
398.47167457
901.92831144
874.00686708
600.74922677
439.06452709
85.066462866
46.288677448
357.15062914
1563.1833269
2473.2053043
1295.4111981
672.85405498
15.180972667
15479.089609

690.1806
762.8252
826.3147
1341.048
1533.887
1844.293
2081.176
2305.76
2661.102
2734.759
2770.069
2758.291
2629.332
2464.469
2185.238
1680.587
1044.213
648.4479
265.7832
-189.2313
-760.2586
-1342.593
-1762.704
-2554.203
-3233.781
-3933.676
-4175.546
-4509.783

-1074.349
-1120.212
-1159.274
-1448.544
-1547.822
-1669.873
-1731.379
-1756.476
-1633.031
-1542.707
-1413.184
-1273.196
-971.9694
-756.8989
-487.6625
-136.9857
177.5308
326.0258
442.6105
543.3236
628.3183
668.5593
668.7924
604.658
480.5409
272.0276
181.7576
38.17837

molar integral heat of solution for H2SO4-H2O solutions

80000

70000

60000
molar integral heat of
solution for H2SO4-H2O
solutions

50000

40000
r Integral Heat of Solutions
30000

20000

10000
0
0.00

5.00

10.00
15.00
x H2O

20.00

25.00

Constant pressure heat capacity of a benzene-CCl4 mixture at 20 C

2.5
2

2.0000

1.5

1.8000

f(x) = 0.7189393939x^2 - 1.7219848485x + 1.7894090909

1.6000
R = 0.9979510968
1.4000

0.5
0

1.2000
1.0000
Cp (J/g C)
0.8000
0.6000
0.4000
0.2000
0.0000

-0.5

Constant
pressure heat
capacity of a
benzene-CCl4
mixture at 20
C

-1
-1.5
-2

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

wt % CCl4

Molar Volum
Delta V mixt d(Delta V mA
PMV H2O
0.01803
2.46E-06
-0.0297
0
0.018
0.01876 -1.28E-03 -0.027212 0.001361
0.018
0.01952 -2.54E-03
-0.0251 0.00251
0.018
0.02031 -3.75E-03 -0.02326 0.003489
0.018
0.02116 -4.92E-03 -0.02159 0.004318
0.017
0.02208 -6.02E-03 -0.019988 0.004997
0.017
0.02309 -7.02E-03 -0.018349 0.005505
0.017
0.02421 -7.91E-03 -0.016571
0.0058
0.016
0.02544 -8.69E-03 -0.014551 0.00582
0.015
0.02681 -9.33E-03 -0.012187 0.005484
0.014
0.02832 -9.84E-03 -0.009375 0.004688
0.013
0.02998 -1.02E-02 -0.006013 0.003307
0.011

B
-0.0297
-0.025851
-0.02259
-0.019771
-0.017272
-0.014991
-0.012844
-0.010771
-0.008731
-0.006703
-0.004688
-0.002706

PMV EtOH
2.86E-02
3.11E-02
3.32E-02
3.48E-02
3.61E-02
3.73E-02
3.84E-02
3.96E-02
4.09E-02
4.22E-02
4.38E-02
4.54E-02

0.2

0.03182
0.03386
0.03615
0.03871
0.04160
0.04488
0.04866
0.05307
0.05828

-1.04E-02
-1.03E-02
-1.01E-02
-9.51E-03
-8.63E-03
-7.36E-03
-5.59E-03
-3.20E-03
-5.12E-07

d(delta mix A
-2.4961
0
-0.769609 -0.0384804
0.356262 0.0356262
1.008106 0.1512158
1.312516 0.2625032
1.396088 0.3490219
1.385414 0.4156242
1.40709 0.4924813
1.587708 0.6350832
2.053864 0.9242386
2.93215 1.466075
4.349162 2.3920388
6.431492 3.8588952
9.305736 6.0487281
13.09849 9.1689402
17.93634 13.452253
23.94588 19.156707
31.25372 26.565662
39.98644 35.987794
50.27063 47.757102
62.2329
62.2329

-0.001997
0.002775
0.008407
0.015
0.022658
0.031485
0.041582
0.053053
0.066

0.001198
-0.001804
-0.005885
-0.01125
-0.018127
-0.026762
-0.037424
-0.0504
-0.066

0.009
0.006
0.002
(0.003)
(0.009)
(0.016)
(0.025)
(0.036)
(0.048)

-0.000799
0.000971
0.002522
0.00375
0.004532
0.004723
0.004158
0.002653
0

4.71E-02
4.89E-02
5.07E-02
5.25E-02
5.42E-02
5.56E-02
5.68E-02
5.77E-02
5.83E-02

B
-2.4961

-2.4961
-0.731128
0.320636
0.85689
1.050013
1.047066
0.96979
0.914608
10.0000
0.952625
1.129625
8.0000
f(x) = 42.1975713522x^4 - 48.4814860137x^3 + 20.8686797644x^2 - 2.4961412639x - 1.
1.466075
deta mix H vs. x
R = 0.99945272246.0000
1.957123
2.572597
Polynomial (deta mix H
Delta mix H 4.0000
vs. x)
3.257007
2.0000
3.929546
4.484084
0.0000
4.789177
0 0.2 0.4 0.6 0.8 1
-2.0000
4.688058
3.998644
x EtOH
2.513532
0

deta mix H vs. x

USING THE TRENDLINE FEATURE

IN THE PLOT
_1
_1
0.231621
0.644619
0.692285
0.560443
0.367983
0.178464
0.013617
-0.112492
-0.216127
-0.291206
-0.3627
-0.430378
-0.489444
-0.53591
-0.563111

_2
_2
0.0298094
0.0103757
-0.001168
0.0188893
0.074339
0.1535153
0.235668
0.3179944
0.3858311
0.4582063
0.5273003
0.6075676
0.7079679
0.8194562
0.9113343

Enthalpy of mixture vs. mole fraction of H2O

0.200

f(x) = 31.7070818564x^6 - 91.2180284471x^5 + 103.3213686604x^4 - 57.4209526242x^3 + 14.0368811818x^2 - 0.8200667779x +

0.100
R = 0.9991215265
0.000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-0.100
-0.200
-0.300
-0.400
-0.500

Enthalpy of mixture vs. mole

fraction of H2O
Polynomial (Enthalpy of
mixture vs. mole fraction of
H2O)

-0.200
-0.300

-0.564165
-0.531912
-0.482006
-0.377437

0.9216604
0.7501697
0.2280544
-0.813697

-0.400
-0.500

USING THE REDLICH KESTER EQUATION n=4

d(delta mix
R(squared) h)/dx H2O _1
_1
0.0009 0.7653381
0.0002 1.1142546
0.0001 0.9322916
0.0005 0.5308496
0.0003 0.1114685
0.0000 -0.2155007
0.0001 -0.4122244
0.0005 -0.494715
0.0003 -0.5141598
0.0001 -0.5382491
0.0000 -0.6325049
0.0005 -0.8416099
0.0007 -1.1707355
0.0003 -1.5668706
0.0000 -1.9001502
0.0009 -1.9451839
0.0019 -1.3623847
0.0000 0.3207027
0.0059 3.7280734
0.013356

0.737494
1.063265
0.905519
0.574747
0.249509
0.011944
-0.121387
-0.173333
-0.184641
-0.197123
-0.241486
-0.329829
-0.45281
-0.58148
-0.673783
-0.685729
-0.587231
-0.382607
-0.135756

_2
_2

Q - Qmean

-0.027845
-0.05099
-0.026773
0.043898
0.138041
0.227445
0.290837
0.321382
0.329519
0.341126
0.391019
0.511781
0.717925
0.985391
1.226367
1.259454
0.775153
-0.70331
-3.863829

0
0
-1
H excess
-2
-3
-4
-5

Isothermal heat of mixing of trichloromethane (1) and ethanol (2) at 30 C. Compute the partial molar
enthalpies of trichloromethane and ethanol in their mixtures at 30 C
ind: Partial molar enthalpies of mixing of trichloromethane and ethanol

=_1 _2 (24_(=1)^ (_1_2) ^ )

eneral Equation for the Redlich Kester
pansion

Compute the partial molar enthalpies of trichloromethane and ethanol in their mixtures at 30 C
_2

((_
))/
(_1 )

-3.700802 -6033.7125
-5.727112 -5738.6261
-18.30555 -5040.6599
-37.30399 -4453.2392
-82.96994 -3499.0025
-168.5119 -2399.6956
-378.4289 -791.55792
-457.9138 -365.89763
-610.0377 297.00087

_1

_2

5885.415
5520.638
4671.758
3973.714
2875.856
1676.655
92.8289
-279.8408
-805.0725

-3.488385
-7.95432
-26.13756
-50.23273
-108.0932
-207.106
-428.1745
-505.3069
-644.7514

_1=_ (1_1 )((_ )/(_1 ))

+_1
_2=_ (_1 )((_ )/(_1 ))
+_2

_ =_1 (1_1)(_0+_1 (2_11)+_2 (2_1

(2_11)" " ^3)

((_ ))/(_1 ) _(
(2_11))+(_3 (2_11)^3)(12_1)+((2_1+(4_
^2)(_1((_1)^2))

-748.0316 777.39482
-766.4134 835.65351
-782.6402 886.28296
-931.704 1288.3715
-1002.065 1436.2372
-1111.421 1673.5235
-1198.598 1856.626
-1287.484 2035.911
-1422.271 2359.9805
-1462.852 2453.2017
-1489.084 2532.441
-1488.895 2578.2676
-1423.163 2591.8708
-1334.57 2540.6885
-1163.775 2402.1631
-823.0013 2060.7853
-348.5438 1512.7664
-33.47374 1116.5702
283.4063 696.54594
665.9076 152.14961
1163.54 -597.34779
1684.634 -1435.0547
2065.912 -2084.1955
2790.545 -3406.8395
3411.64 -4644.3249
4031.049 -6015.4173
4240.389 -6511.7749
4521.805 -7216.5861

-1130.65
-1166.162
-1196.228
-1405.063
-1466.057
-1541.287
-1575.766
-1583.567
-1494.82
-1423.583
-1322.078
-1213.916
-978.0412
-796.3422
-560.2679
-229.5246
91.31477
251.2918
380.7527
504.1603
613.4306
672.9991
683.2326
626.596
496.8231
282.2504
188.5254
42.13182

-763.0981
-778.5856
-792.2603
-908.5251
-955.0441
-1034.544
-1100.47
-1169.463
-1307.91
-1351.95
-1391.466
-1415.537
-1422.806
-1391.88
-1303.497
-1070.737
-670.8169
-367.7348
-36.47829
405.5978
1033.963
1759.048
2335.166
3542.169
4706.439
6030.583
6517.971
7216.862

((_ ))/(_1 ) _(
(2_11))+(_3 (2_11)^3)(12_1)+((2_1+(4_
^2)(_1((_1)^2))
((_ ))/(_1 ) _(
)=31869
_1 ^2+33088_15817.4

600.00
400.00

f(x) = - 10623.0906964252
R = 0.9950051256

200.00
0.00
Delta mix H (kJ/mol)
0.00
-200.00
-400.00
-600.00
-800.00
x

2.5
2
1.5
1
Partial Molar Heat
Capacities

0.5
0
-0.5

0.2

0.4

0.6

0.8

1.2

Partial Molar Heat

Capacities of Benzene

-1
-1.5
-2

Delta V mixture
2.00E-03
0.00E+00
f(x) = 0.0343349494x^4 - 0.031939676x^3
0.0270601486x^2
0 0.2 0.4 +0.6
0.8 1 1.2 - 0.0296996516x + 0.0001032844
R = 0.9995252089 -2.00E-03
-4.00E-03
Delta V mixture
-6.00E-03
-8.00E-03
-1.00E-02

Delta V mixture
Polynomial (Delta V mixture)

Delta V mixture

-4.00E-03
Delta V mixture

Polynomial (Delta V mixture)

-6.00E-03
-8.00E-03
-1.00E-02
-1.20E-02
x EtOH

PMV EtOH
7.00E-02
6.00E-02
5.00E-02
4.00E-02
PMV EtOH

PMV EtOH

3.00E-02
2.00E-02
1.00E-02
0.00E+00

7644x^2 - 2.4961412639x - 1.1947719298

mix H vs. x

nomial (deta mix H

x)

2O

14.0368811818x^2 - 0.8200667779x + 0.0560645769

0.2

0.4

0.6

x EtOH

0.8

1.2

H1 Excess and H2 excess vs. x H2O

2
1
0
0

0.1

0.2

0.3

0.4

0.5

-1

0.6

0.7

0.8

0.9

H1 excess from

H excess

H2 from RK
-2
-3
-4
-5
x H2O

e the partial molar

C

)/(_1 ))

)/(_1 ))

(2_11)+_2 (2_11)" " ^2+_3

)=((_0+(_1 (2_11))+(_2
12_1)+((2_1+(4_2 (2_11))+(6_3 ( (2_11)

 )=((_0+(_1 (2_11))+(_2
12_1)+((2_1+(4_2 (2_11))+(6_3 ( (2_11)

33088_15817.4

= - 10623.0906964252x^3 + 16543.6122321554x^2 - 5817.3674382998x

0.9950051256

0.50

x CHCl3

1.00

Change of heat of mixing

Polynomial (Change of
heat of mixing)

0.0001032844

re

elta V mixture)

re

elta V mixture)

1
H1 excess from RK
H2 from RK

8.7a
x MF

Factor
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

a0
a1
a2

0.6875
0.8125
0.5625
0.9375
0.1250
0.0000
0.5000
0.6875
0.5625

((_
Delta mix V
))/
(RK)
(_ )
(cm3/mol) (cm3/mol) R sqrd
0.0844
0.08233
4.2E-06
0.7688
0.1406
0.14051
1.4E-08
0.5782
0.1781
0.17863
2.6E-07
0.3886
0.1969
0.19971
8.1E-06
0.1999
0.2063
0.20568
3.3E-07
0.0122
0.2000
0.19737
6.9E-06
-0.1745
0.1750
0.17452
2.3E-07
-0.3602
0.1344
0.13581
2.1E-06
-0.5449
0.0781
0.07881
4.6E-07
-0.7287
SUM 2.25E-005
Delta mix V

_
((_
))/(_
)
0.0769

0.1156
0.1166
0.0800
0.0061
-0.1047
-0.2521
-0.4360
-0.6558

0.8227
(0.0245)
0.1132
_ =_ (1_)
(0.82270.0245(2_1)+0.1132(2_1)^2)

x MF

((_
Delta mix V
_
))/
(RK)
((_
(_ )
))/(_
(cm3/mol) (cm3/mol) R sqrd
0.4242
-0.0212
-0.03355 0.000152
-0.2946 )-0.029462773
0.3125
-0.0656
-0.05995 3.22E-005
-0.2250 -0.04500689
0.65625
-0.0828
-0.07822 2.11E-005
-0.1579 -0.047382566
0.78125
-0.0891
-0.08788 1.40E-006
-0.0934 -0.037340014
0.75
-0.0875
-0.08893 2.04E-006
-0.0313 -0.015629447
0.5625
-0.0781
-0.08188 1.41E-005
0.0283 0.0169989207
0.3125
-0.0656
-0.06772 4.38E-006
0.0854 0.0597948764
0
-0.0500
-0.04795 4.22E-006
0.1400 0.1120082063
0.5625
-0.0281
-0.02455 1.28E-005
0.1921 0.1728886969
SUM
0.000244

Factor
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

a0 -0.355715
a1 0.062518
a2 0.051511

Delta mix V

_ =_ (1_)
(0.35572+0.062518(2_1)+0.051511(2_1)^2)

(cm3/mol)
58.69
58.70
58.74
58.80
58.88
58.98
59.11
59.25
59.41

_
(cm3/mol)
62.17243
62.45806
62.68612
62.85693
62.98013
63.04979
63.06306
63.02336
62.931

0.2500
0.2000
0.1500
0.1000
0.0500

-0.0500

-0.1500

2_1)^2)

Delta mix V of methyl

formate + ethanol

0.0000

-0.1000

_
_

(cm3/mol)
(cm3/mol)
40.738
63.024
40.709
62.894
40.695
62.808
40.678
62.747
40.658
62.708
40.635
62.691
40.605
62.689
40.568
62.702
40.529
62.733

Delta mix V of methyl

formate + methanol

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Delta mix V of methyl

formate + methanol
Delta mix V of methyl
formate + ethanol