SOLID – LIQUID

EQUILIBRIUM OF A
BINARY SYSTEM
GROUP 2 (MONDAY GROUP)
 ABSTRACT
The eutectic composition, eutectic temperature, enthalpy of fusion and normal freezing points of the components of the
binary system naphthalene-paradichlorobenzene were determined. The eutectic point of the phase diagram of the binary system
naphthalene – paradichlorobenzene was obtained through polynomial technique wherein it contained 0.3393 ± 0.0026 mole fraction
naphthalene and 0.6607 ± 0.0026 mole fraction paradichlorobenzene with a percent error of 5.7361 ± 0.7200% and 3.2266 ± 0.4050%,
respectively. Also, the obtained eutectic temperature was 311.796 ± 0.6659 with a percent error of 2.9452 ± 0.2199%. The enthalpy of
fusion and normal freezing point of the components were obtained from the experimental value of the eutectic point of the binary
system. The enthalpy of fusion of naphthalene was 19.2527 ± 0.1554 kJ/mol and of paradichlorobenzene was 20.8512 ± 1.8864 kJ/mol
with a percent error of 7.5571 ± 0.8621% and 11.2984 ± 9.3688%, respectively. The normal freezing point obtained for naphthalene was
74.7628 ± 1.2846 °C and for paradichlorobenzene was 51.5130 ± 1.3891 °C with a percent error of 5.3635 ± 1.2621% and 2.2513 ±
0.9213%, respectively. It was shown that the results obtained from the method improvement were generally accurate and precise.
 INTRODUCTION
• Two substances were used; naphthalene (C10H8) and p-dichlorobenzene (C6H4Cl2).
• Naphthalene is a polycyclic aromatic compound known as being the main ingredient in
mothballs. The pungent substance has a melting temperature of 80 degrees Celsius.
• Paradichlorobenzene is a colorless solid that has a strong odor. The molecule consists of
a benzene ring with two chlorine atoms on opposing sites of the ring. It is used as a
disinfectant, pesticide, and deodorant, most familiarly in mothballs in which it is a
replacement for the more traditional naphthalene because of naphthalene's greater
flammability.
 INTRODUCTION
• By exploiting the temperature as well as investigating the mole fractions, a phase diagram
of the two substances can be constructed.
• Phase diagrams are graphs of either a mixture of materials, or of a pure substance under
different thermodynamic conditions. These two phase diagrams (mixture, compared to an
isolated material) differ in that for a pure substances, the graph shows the different states
for a single substance in relation to pressure and temperature.
• For a mixture of materials, the phase diagram is constructed based on temperature and
mole fraction values of one of the substances at a constant pressure.
 INTRODUCTION
• Binary system, which relies on more than one substance. This means that in the phase diagram
there are where one substance is a solid while the other is not, or vice versa.
• When a substance’s temperature increases or decreases, it will do so at a constant
temperature. This is true until it has gotten high or low enough to transition into a new phase.
When this occurs, the substance goes into thermal arrest, and the temperature remains
constant for a given period of time.
• In a mixture however, one substance may be in thermal arrest while the other has a thermal
break and the temperature continues to rise, or decrease if a liquid. This causes the actual
melting point of the system to be lower than expected, or the boiling point higher than
expected.
• This experiment will cover the solid-liquid binary phase, and thus will focus on.
 OBJECTIVES
• To familiarize and understand concept of a binary system;
• To determine the break point (if any) and the plateau temperature from each of the
cooling curves obtained;
• To estimate the eutectic mixture composition by the intersection of lines represented by
equation 5 and 6;
• To prepare the eutectic mixture according to the estimate;
 OBJECTIVES
• To construct a binary solid-liquid phase diagram of the p-dichlorobenzene-napththalene
system and to label all regions and pertinent points of the diagram;
• To calculate the enthalpies of fusion and the normal freezing points of each of the two
compounds based on the equation of the lines from plot of lnx aginst 1/T;
• To compare estimates if the enthalpies of fusion and freezing points w/ the literature
values;
• To determine the enthalpies of fusion of the components of a binary system.
SCHEMATIC DIAGRAM
 DATA AND RESULTS
Test tube A (Trial 2)
58
57
56
Temperature (◦C)

55
54
53
Trial 2
52
51
50
49
0 50 100 150 200 250 300
Time (sec)

Figure 1.1 Cooling curve of 0% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube B (Trial 2)
60

50
Temperature (◦C)

40

30
Trial 2
20

10

0
0 200 400 600 800 1000 1200
Time (sec)

Figure 1.2 Cooling curve of 10% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube C (Trial 2)
70

60

50
Temperature (◦C)

40

30 Trial 2

20

10

0
0 200 400 600 800 1000 1200
Time (sec)

Figure 1.3 Cooling curve of 20% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube D (Trial 2)
70

60

50
Temperature (◦C)

40

30 Trial 2

20

10

0
0 100 200 300 400 500 600 700 800
Time (sec)

Figure 1.4 Cooling curve of 30% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube E (Trial 2)
70

60

50
Temperature (◦C)

40

30 Trial 2

20

10

0
0 100 200 300 400 500 600 700 800 900 1000
Time (sec)

Figure 1.5 Cooling curve of 40% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube F (Trial 2)
60

50

40
Temperature (◦C)

30
Trial 2
20

10

0
0 100 200 300 400 500 600 700
Time (sec)

Figure 1.6 Cooling curve of 50% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube G (Trial 2)
70

60

50
Temperature (◦C)

40

30 Trial 2

20

10

0
0 100 200 300 400 500 600 700 800 900
Time (sec)

Figure 1.7 Cooling curve of 60% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube H (Trial 2)
70

60

50
Temperature (◦C)

40

30 Trial 2

20

10

0
0 100 200 300 400 500 600 700 800
Time (sec)

Figure 1.8 Cooling curve of 70% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube I (Trial 2)
80

70

60
Temperature (◦C)

50

40
Trial 2
30

20

10

0
0 200 400 600 800 1000 1200
Time (sec)

Figure 1.9 Cooling curve of 80% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Test tube J (Trial 2)
90

80

70
Temperature (◦C)

60

50

40
Trial 2
30

20

10

0
0 100 200 300 400 500 600 700 800
Time (sec)

Figure 1.10 Cooling curve of 100% naphthalene in naphthalene paradichlorobenzene mixture

 DATA AND RESULTS
Table 1.1 Break points and plateaus of different compositions for trial 2
Trial 2
Weight Molar mass Mole Mole fraction lnX
Test % Break in
tube Naph Naph PDB Naph PDB Naph PDB Naph PDB Naph PDB Break Plateau K 1/T
A 0 0 5.0208 128.1705 147 0 0.0342 0 1 51

B 10 0.5052 4.5133 128.1705 147 0.0039 0.0307 0.1138 0.8862 -2.1735 -0.1208 47.9 28.5 321.05 0.0031

C 20 1.0075 4.0078 128.1705 147 0.0079 0.0273 0.2238 0.7762 -1.4970 -0.2533 39 28.5 312.15 0.0032

D 30 1.5105 3.5009 128.1705 147 0.0118 0.0238 0.3310 0.6690 -1.1055 -0.4020 37 28.9 310.15 0.0032

E 40 2.0043 3.0126 128.1705 147 0.0156 0.0205 0.4328 0.5672 -0.8375 -0.5670 35 29 308.15 0.0032

F 50 2.5131 2.5023 128.1705 147 0.0196 0.0170 0.5353 0.4647 -0.6250 -0.7663 48 29 321.15 0.0031

G 60 3.0072 2.0636 128.1705 147 0.0235 0.0140 0.6257 0.3743 -0.4690 -0.9826 54 30 327.15 0.0031

H 70 3.5003 1.5389 128.1705 147 0.0273 0.0105 0.7229 0.2771 -0.3245 -1.2833 55.5 29 328.65 0.0030

I 80 4.0371 1.0111 128.1705 147 0.0315 0.0069 0.8208 0.1792 -0.1975 -1.7191 65 29.5 338.15 0.0030
J 100 5.0606 0 128.1705 147 0.0395 0 1 0 0 28
 DATA AND RESULTS
Phase diagram (Trial 2)
100

90
Break and Plateau Temperature (◦C)

80
y = 121.17x2 - 82.474x + 53.074
70 R² = 0.8797

60

50 Break in C vs mole fraction

Plateau in C vs mole fraction
40
Poly. (Break in C vs mole fraction)
30

20

10

0
0 0 0 1 1 1 1
Naph mole fraction

Figure 1.11 Phase diagram of naphthalene – paradichlorobenzene system for trial 2

 DATA AND RESULTS
Table 1.2 Eutectic point naphthalene – paradichlorobenzene system
Trial 1 Trial 2 Trial 3 Average
Equation y = 120.83x2 - 82.482x + y = 121.17x2 - 82.474x + y = 123.97x2 - 83.41x + -
51.928 53.074 52.997
Variables
a 120.83 121.17 123.97 -
b 82.482 82.474 83.41 -
c 51.928 53.074 52.997 -
(h,k) Naph PDB Naph PDB Naph PDB Naph PDB
0.3393 ± 0.6607 ±
h=b/2a 0.3413 0.6587 0.3403 0.6597 0.3364 0.6636 0.0026 0.0026
38.6196 ± 311.7696 ±
k=(4ac-b2)/4a 37.8519 311.0019 39.0401 312.1901 38.9669 312.1169 0.6659 0.6659
theoretical mole
fraction 0.36 0.64 0.36 0.64 0.36 0.64 0.36 0.64
5.7361 ± 3.2266 ±
percent error 5.1905 2.9196 5.4657 3.0745 6.5522 3.6856 0.7200% 0.4050%
theoretical
temperature 302.85 302.85 302.85 302.85
 DATA AND RESULTS
Eutectic mixture (Trial 2)
70

60

50
Temperature (◦C)

40

30 Trial 2

20

10

0
0 50 100 150 200 250 300 350 400 450 500
Time (sec)

Figure 1.12 Cooling curve for eutectic mixture for trial 2

 DATA AND RESULTS
Table 1.3 Break points and plateaus of different compositions for trial 2
Mole
Weight Molar mass Mole fraction lnX Brea
Test Bre Plat k in
tube Naph PDB Naph PDB Naph PDB Naph PDB Naph PDB ak eau K 1/T
- -
1.70 128.17 0.013 0.022 0.371 0.628 0.989 0.464 328.1 0.00
1 64 3.3096 05 147 3 5 6 4 9 6 55 29 5 30
- -
1.70 128.17 0.013 0.022 0.371 0.628 0.990 0.464 324.3 0.00
2 15 3.3039 05 147 3 5 3 7 7 1 51.2 29 5 31
- -
1.72 128.17 0.013 0.022 0.374 0.625 0.981 0.469 326.1 0.00
3 68 3.3042 05 147 5 5 8 2 5 6 53 29 5 31
 DATA AND RESULTS
Table 1.4 lnX and 1/T in K of the break temperature for napthalene richer side
lnX 1/T
Trial 1 Trial 2 Trial 3 Trial 1 Trial 2 Trial 3
-0.8393 -0.8375 -0.8475 0.0033 0.0032 0.0032
-0.6270 -0.6250 -0.6271 0.0031 0.0031 0.0031
-0.4611 -0.4690 -0.4538 0.0031 0.0031 0.0030
-0.3211 -0.3245 -0.3213 0.0030 0.0030 0.0030
-0.1995 -0.1975 -0.1982 0.0030 0.0030 0.0030
 DATA AND RESULTS
Naph - richer side (Trial 2)
0.00000000
0.00290000 0.00295000 0.00300000 0.00305000 0.00310000 0.00315000 0.00320000 0.00325000 0.00330000
-0.10000000

-0.20000000

-0.30000000

-0.40000000
lnX

-0.50000000 Trial 2
Linear (Trial 2)
-0.60000000

-0.70000000

-0.80000000

-0.90000000 y = -2303.3x + 6.6107

R² = 0.953
-1.00000000
1/T

Figure 1.13 Plot of lnX versus 1/T in K of the break temperature of naphthalene richer side for trial 2
 DATA AND RESULTS
Table 1.5 lnX and 1/T in K of the break temperature for paradichlorobenzene richer side
lnX 1/T

Trial 1 Trial 2 Trial 3 Trial 1 Trial 2 Trial 3

-0.1204 -0.1208 -0.1199 0.0031 0.0031 0.0031

-0.2526 -0.2533 -0.2546 0.0032 0.0032 0.0032

-0.4000 -0.4020 -0.4005 0.0032 0.0032 0.0032

 DATA AND RESULTS
PDB - richer side (Trial 2)
0.00000000
0.00310000 0.00312000 0.00314000 0.00316000 0.00318000 0.00320000 0.00322000 0.00324000
-0.05000000

-0.10000000

-0.15000000

-0.20000000
lnX

Trial 2
-0.25000000 Linear (Trial 2)

-0.30000000

-0.35000000 y = -2248.1x + 6.8923

R² = 0.8637
-0.40000000

-0.45000000
1/T

Figure 1.14 Plot of lnX versus 1/T in K of the break temperature of paradichlorobenzene richer side for trial 2
 DATA AND RESULTS
Table 1.6 Enthalpy of fusion from the equation of the lines
Trial 1 Trial 2 Trial 3 Average
Variables PDB Naph PDB Naph PDB Naph PDB Naph
equation of y = -2609x + y = -2337.2x + y = -2248.1x + y = -2303.3x + y = -2666.8x + y = -2306.6x +
the line 8.0663 6.7461 6.8923 6.6107 8.2215 6.6117 - -
slope -2609 -2337.2 -2248.1 -2303.3 -2666.8 -2306.6 - -
enthalpy of
fusion 21691.2260 19431.4808 18690.7034 19149.6362 22171.7752 19177.0724 - -
20.8512 ± 19.2527 ±
EOF KJ/MOL 21.6912 19.4315 18.6907 19.1496 22.1718 19.1771 1.8864 0.1554
literature
values 18.8 17.9 18.8 17.9 18.8 17.9 - -
percent 11.2984 ± 7.5571 ±
error 15.3789 8.5558 0.5814 6.9812 17.9350 7.1345 9.3688% 0.8682%
 DATA AND RESULTS
Table 1.7 Normal freezing point from the equation of the lines
Trial 1 Trial 2 Trial 3 Average
Variables PDB Naph PDB Naph PDB Naph PDB Naph
equation of y = -2609x + y = -2337.2x + y = -2248.1x + y = -2303.3x + y = -2666.8x + y = -2306.6x +
the line 8.0663 6.7461 6.8923 6.6107 8.2215 6.6117 - -
slope 2609 2337.2 2248.1 2303.3 2666.8 2306.6 - -
b 8.0663 6.7461 6.8923 6.6107 8.2215 6.6117 - -
b/slope 0.0031 0.0029 0.0031 0.0029 0.0031 0.0029 - -
1/(b/slope) 323.4445 346.4520 326.1756 348.4200 324.3690 348.8664 - -
51.5130 ± 74.7628 ±
NFP 50.2945 73.3020 53.0256 75.2700 51.2190 75.7164 1.3891 1.2846
lit values 52 79 52 79 52 79 - -
2.2513 ± 5.3635 ±
% error 3.2799 7.2126 1.9723 4.7215 1.5019 4.1565 0.9213% 1.2621%
 CONCLUSION
This experiment determined the eutectic composition, eutectic temperature, enthalpy of fusion and normal freezing points
of the components of the binary system naphthalene-paradichlorobenzene. A solid-liquid equilibrium of a binary system is composed
of 2 components wherein both are completely miscible in liquid phase but immiscible in solid phase. Eutectic composition is obtained
when the liquid phase solidifies without change of composition. The eutectic point of the phase diagram of the binary system
naphthalene – paradichlorobenzene was obtained through polynomial technique wherein it contained 0.3393 ± 0.0026 mole fraction
naphthalene and 0.6607 ± 0.0026 mole fraction paradichlorobenzene with a percent error of 5.7361 ± 0.7200% and 3.2266 ±
0.4050%, respectively. Also, the eutectic temperature was obtained which was 311.796 ± 0.6659 with a percent error of 2.9452 ±
0.2199%. All the phases of the binary system coexist at this point of mixture. The enthalpy of fusion and normal freezing point of
the components were obtained from the experimental value of the eutectic point of the binary system. Enthalpy of fusion is the
enthalpy change accompanying the conversion of a solid to liquid while normal freezing point is equal to the melting point of the solid
to a given pressure. Based on the results, the enthalpy of fusion of naphthalene was 19.2527 ± 0.1554 kJ/mol and of
paradichlorobenzene was 20.8512 ± 1.8864 kJ/mol with a percent error of 7.5571 ± 0.8621% and 11.2984 ± 9.3688%, respectively.
The normal freezing point obtained for naphthalene was 74.7628 ± 1.2846 °C and for paradichlorobenzene was 51.5130 ± 1.3891
°C with a percent error of 5.3635 ± 1.2621% and 2.2513 ± 0.9213%, respectively. Generally, accurate and precise results were
obtained from the method improvement. It was suggested to pick or detect better break points in order to obtain more accurate
and precise results.
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