CHEM 254

Number of the experiment : 8

Name of the experiment : Phase Diagrams, Solid-Liquid Phase Equilibrium for

Two Component System and Missibility Gap

Date of the experiment : 24.03.2017

Asistant name : Seza Göker

Group number : 7

Name of the student : Berfin ŞAK

Name of the partner : Başak Coşkun

CALCULATIONS :
- Mole fraction of Naphthalene
5.0 g
nN = = 39.01 mmol
128.1705 g /mol

0.5 g
nN(0.5 g) = = 3.901 mmol
128.1705 g /mol

1.5 g
nN(1.5 g) = = 11.70 mmol
128.1705 g /mol

2.5 g
nN(2.5 g) = = 19.51 mmol
128.1705 g /mol

5.0 g
nDPA = = 29.55 mmol
169.23 g /mol

0.5 g
nDPA(0.5 g) = = 2.955 mmol
169.23 g /mol

1.5 g
nDPA(1.5 g) = = 8.864 mmol
169.23 g /mol

2.5 g
nDPA(2.5 g) = = 14.77 mmol
169.23 g /mol

39.01 mmol
xN (N + 0.5 g DPA) = ( 39.01+ 2.955 ) mmol = 0.9296
 39.01 mmol
xN (N + 1.5 g DPA) = ( 39.01+ 8.864 ) mmol = 0.8148

39.01 mmol
xN (N + 2.5 g DPA) = ( 39.01+ 14.77 ) mmol = 0.7254

19.51 mmol
xN (DPA + 0.5 g N) = ( 29.55+19.51 ) mmol = 0.3977

11.70 mmol
xN (DPA + 1.5 g N) = ( 29.55+11.70 ) mmol = 0.2836

3.901 mmol
xN (DPA + 2.5 g N) = ( 29.55+3.901 ) mmol = 0.1160

0 mmol
xN (DPA) = ( 29.55+0 ) mmol = 0

- Cooling curves
 pure naphthalene
90
80
70
temperature (oC)

60
50
40
30
20
10
0
0 20 40 60 80 100 120 140
time (s)

Freezing point : 79.6 oC

N + 0.5 g DPA
76
75
74
temperature (oC)

73
72
71
70
69
68
0 20 40 60 80 100 120 140
time (s)

Freezing point : 74.8 oC

 N + 1.5 g DPA
80
70
60
temperature (oC)

50
40
30
20
10
0
0 20 40 60 80 100 120 140
time (s)

Freezing point : 68.8 oC

N + 2.5 g DPA
70

60

50
temperature (oC)

40

30

20

10

0
0 20 40 60 80 100 120 140
time (s)

Freezing point : 64.5 oC

 pure DPA
80
70
60
temperatıre (oC)

50
40
30
20
10
0
0 50 100 150 200 250 300 350 400 450 500
time (s)

Freezing point : 51.8 oC

DPA + 0.5 g N
80
70
60
temperature (oC)

50
40
30
20
10
0
0 50 100 150 200 250 300 350 400 450 500
time (s)

Freezing point : 46.3 oC

 DPA + 1.5 g N
70

60

50
temperature (oC)

40

30

20

10

0
0 50 100 150 200 250 300 350 400
time (s)

Freezing point : 39.6

DPA + 2.5 g N
70

60

50
temperature (oC)

40

30

20

10

0
0 50 100 150 200 250 300 350 400
time (s)

Freezing point : 32.4 oC

- Comparison of freezing points of pure naphthalene and pure diphenyl amine

Theoretical value for N : 80.26 oC

Experimental value for N : 79.6 oC

(79.6−80.26)
% Error = x 100 = -0.82 %
80.26

Theoretical value for DPA : 53.0 oC

Experimental value for DPA : 51.8 oC
(51.8−53.0)
% Error = x 100 = -2.26 %
53.0

- Wphenol %
solution 1 : 0.5 g /5.00 g x 100 = 10%
solution 2 : 1.0 g /5.00 g x 100 = 20%

solution 3 : 1.5 g /5.00 g x 100 =30%

solution 4 : 2.0 g /5.00 g x 100 =40%

solution 5: 2.5 g /5.00 g x 100 = 50%

solution 6 : 3.0 g /5.00 g x 100 = 60%

solution 7 : 3.5 g /5.00 g x 100 = 70%

From the phase diagram the eutectic point is found as 29 oC at 0.424 mol fraction.

From the solubility diagram the upper critical point is found as 75.5 oC.

QUESTIONS :
1) ‘A liquid with the eutectic composition freezes at a single temperature, without
previously depositing solid A or B. Solid with the eutectic composition melts, without
change of composition, at the lowest temperature of any mixture’; which is named as
eutectic point. (Atkins & de Paula,2010,p.186)
2) ‘ The upper critical solution temperature is the highest temperature at which phase
separation occurs. Above the upper critical point the two components are fully
miscible while below the two components are fully immiscible.’(Atkins & de
Paula,2010,p.183)

DISCUSSION:
In this experiment , solid- liquid phase equilibrium for two component system and missibility
gap was studied. First, the temperature measurements was done with diffirent solid- liquid
phase systems (liquid naphthalene + solid diphenyl amine at different portions and the
reverse). Then, the cooling curves was sketched to find freezing points. Experimentally,
freezing point of pure napthalene is found as 79.6 oC while theoretically it should be 80.26
o
C. There is approximately -0.82 % error. This is very low ; even, it can be said that the
freezing point of naphthalene is found with only random error which could be interested
with the atmospheric pressure of laboratory. The laboratory is present above the see level.
Therefore, the atmospheric pressure should be less than 1 atm (∽0.9997 atm). As the
atmospheric pressure is lower, and while naphthalene freezes its volume decreases, the
freezing point decreases,too. Apart from this, as the napthalene sublimates in atmospheric
pressure, this could also cause the detection of freezing to be lower than it should be. In the
case of diphenyl amine, freezing point was found as 51.8 oC while theoretically it sould be
53.0 oC. There is approximately – 2.26 % error. This is also a random error,and the source
could be interested with atmospheric pressure,too. In the temperature-composition
diagram, the eutectic point was found as 29 oC at 0.424 mol fraction of naphthalene.
According to Go, Manaloto and Reyes; ‘comparing it with the values taken by other studies,
it was found that the eutectic point is around 0.36-0.38 mole fraction of naphthalene, and
the temperature roughly 31⁰C.’( Go et al.,n.d.) As the freezing points was found
lower,consequently, eutectic point also is in low temperature. If more measurements could
be done, more accurate values can be found.

Secondly, to obtain solubility diagram of phenol water mixture (missibility gap),the phenol-
water mixtures,at diffrerent weight percent of phenol, was prepared, and their temperature
measurements was done with thermocouple. From the missibility gap, the upper critical
point was found as 75.5 oC.

REFERENCES :
1. Retrieved from http://www.sigmaaldrich.com/catalog/product/aldrich/147141?
lang=en&region=TR
2. Retrieved from http://www.sigmaaldrich.com/catalog/product/sial/45456?
lang=en&region=TR
3. Atkins, P., & de Paula, J. (2010). Critical solution temperature: Physical Chemistry (9th
ed.). (p.183). New York , NY: W.H. Freeman and Company
4. Atkins, P., & de Paula, J. (2010). Eutectics: Physical Chemistry (9th ed.). (p.186). New
York , NY: W.H. Freeman and Company
5. Go, M., Manaloto, N., & Reyes, R. (n.d) Solid-Liquid Phase Diagramof Naphthalene-
Diphenylamine Two-Component System. Retrieved from
https://tr.scribd.com/doc/62776289/Solid-Liquid-Phase-Diagram