Monday, 8 December 2014

 

PRACTICAL 3:PHASE DIAGRAM


PART B

TITLE:

Mutual solubility curve for phenol and water



DATE OF EXPERIMENT:


3rd   November 2014


OBJECTIVES:

                              *            To measure the miscibility temperatures of several water-phenol mixtures of known   composition
                              *            To construct and understand the
                              *            To determine upper consolute/critical temperature of water-phenol mixtures


INTRODUCTION:

       A phenol – water solution was used to determine the solubility of two partially miscible liquids.  The group calculated the volume of water required to prepare the following mixtures with volume percentage ranging from 5% to 95% sample at 5% increment using 10mL phenol sample.  The different volume ratios of mixtures prepared were subjected to constant heating and cooling in order to gather the needed temperature necessary for the construction of the mutual solubility curve of Phenol- Water solution.

        Mutual solubility of the components in a liquid-liquid system may results complete miscibility or partial miscibility. Complete miscibility can be defined as particles involves are well distributed or fully mixed (mix in all proportions; “like dissolve like”). Meanwhile, partial miscibility is the formation of two layers when certain amounts of liquids are mixed. Two liquids are “partially miscible” if shaking equal volumes of the liquids together results in a meniscus visible between two layers of liquid, but the volumes of the layers are not identical to the volumes of the liquids originally mixed. In the experiment, we used water and phenol to discuss the idea of this mutual solubility. Phenol-water binary system is a system that shows the nature of the mutual solubility between phenol and water at a certain temperature and fixed pressure. According to the theory, water and phenol have the property of partial miscibility when it is initially mixed. As we learnt, mutual solubility of partially miscible mixture is influenced by temperature.
   As the temperature of the water-phenol mixture is increased, it will reach a critical point or we called it as upper consolute temperature where the homogenous mixture will form. Thus, under or beyond this critical point temperature, it will become heterogeneous or 2 layers of mixture will form back. In this phase, the compositions for two liquid phases in equilibrium are constant and are not affected by the relative amount of these two phases. These phases are termed conjugate phases. The relative amounts of the two phases vary. The miscibility between two partial miscible liquids is normally affected by the existence of third component. For more understanding of this mutual solubility of phenol-water mixture, the plot of mutual solubility curve for phenol and water(temperature measured versus phenol composition) is needed. By doing so, we can easily know the critical point temperature, temperature for each phenol composition for the mixture to change to the phase required and many more.

APPARATUS:

                                                                    Thermometer


                                                                       Test tubes


                                                                         Parafilm



                                                                   Measuring cylinder




                                                                       Test tube holder




                                                                         Water bath


MATERIALS:

Phenol,Water



EXPERIMENTAL PROCEDURES:



1)  Students were given tightly sealed tubes containing amounts of phenol concentration scaled between 8% to 80%.
2)    In order to increase the temperature through heating, students were about to heat the tubes in the beaker containing water.
3)  The water was stirred and the tubes were shaken as well. The temperature for each of the tube at which the turbid liquid becomes clear were observed and recorded.
4)  The tubes were removed from the hot water and the temperature was allowed to reduce gradually, the temperature at which the liquid becomes turbid and two layers were separated.
5)  The average temperature for each tube at which two phases were no longer seen or at which two phases exists were determined.
6)  Part of the tubes was to be cooled besides being heated as instructed above.



RESULTS:

Tabulation of data

PERCENTAGE OF PHENOL (%)
VOLUME OF PHENOL (mL)
VOLUME OF DISTILLED WATER (mL)
AVERAGE TEMPERATURE AT WHICH THE TURBID LIQUID BECOMES CLEAR (°C)
AVERAGE TEMPERATURE AT WHICH THE LIQUID BECOME TURBID (°C)
8
1.6
18.4
35
33
11
2.2
17.8
50
45
20
4.0
16.0
68
65
35
7.0
13.0
69
64
50
10.0
10.0
65
60
63
12.6
7.4
60
58
70
14.0
6.0
55
51
80
16.0
4.0
44
39

Graph

A graph of Composition of Phenol in water (% by volume) against Temperature at complete miscibility (°C )




                             Temperature at
                         complete miscibility
                                     ( °C )
                                                                  Composition of Phenol 
                                                                              in water  (% by volume)




 DISCUSSION:

Phase rule is a useful and may be used to determine the variance of any system at equilibrium. It is used to relate the effect of the least number of independent variables like pressure, temperature and concentration upon the various phases (solid, liquid and gaseous) that can exist in an equilibrium system containing a given number of components. There are some factors to be considered in order for the system to be in equilibrium. Those are the degree of freedom (F), the number of component making up the phases (C) and the number of phases that can coexist or the number of phases in thermodynamic equilibrium with each other (P). The number of degrees of freedom is the number of independent intensive variables.
The rule is the equality:  
 F = C – P + 2
In this experiment, the phenol and water are partially miscible. We plotted the graph of average temperature against percentage of phenol based on the data we obtained in the experiment. We get an n-shaped graph after it is been plotted. The peak of the graph showed the critical temperature for the solution where critical solution temperature is the temperature at which a mixture of two liquids (Phenol and Water for this experiment), immiscible at ordinary temperatures, cease to separate into two distinct phases. The region outside the curve will have one liquid phase and the region within the curve will have two liquid phases. The first boiling tube containing 8 % of phenol and the last boiling tube containing 80% will have their mixtures exist as one liquid phase. As the percentage of phenol increases, the amount of phenol-rich phase will continuously increase and forming two phases system. Finally, the critical solution temperature for this experiment is 69 °C. In this experiment, we are measuring the temperature of the phenol-water system at miscible and temperature at which two phases separated.
There are some precautionary steps that should be taken during this experiment. Firstly, after inserting the thermometer into the test tube, the tube must be sealed immediately and tightly to prevent evaporation of phenol once it is mixed with water. This is to ensure the accuracy of the result obtained as evaporation of phenol may affect the result. Besides, this step also ensures that there will be no heat lost to the surrounding when the test tube is heated in water bath and when the temperature is measured. Parallax error also may occur when we measure the volume of phenol and water and recording of the temperature of the thermometer. The desired volume of phenol may not be obtained due to this error and thus causes deviation the result of the experiment. Lastly, we must be very careful in taking the reading of the temperature when heating and cooling the mixtures. This is to avoid the inaccuracy in the result of the experiment as the temperature will increase or decrease rapidly.
  

CONCLUSION:

The critical solution temperature peaks at 69°C. A two-component system is formed between phenol and water. In this experiment, both water and phenol are partially miscible.

QUESTIONS
Explain the effect of adding foreign substances and show the importance of this effect in pharmacy.

 The foreign substances will affect the critical solution temperature. If the foreign substance is soluble in one of the two liquids, the mutual solubility of the latter is destroyed, and the temperature at which the system becomes homogeneous is raised.This increase in temperature is due to the salting out of water. When the added substance dissolves in both the liquids, the critical solution temperature is lowered due to negative salting out effect. This effect is important to the industrial production of highly concentrated solutions of tar acids (phenols and cresols) used as disinfectants. 


REFERENCE:

3  3)     http://www.scribd.com/doc/116082090/The-Binary-System-Phenol‎















PRACTICAL 3: PHASE DIAGRAM

PART A

TITLE:

Determination of Phase Diagram for Ethanol/ Toluene/ Water System Theory
Three-Component Systems

DATE OF EXPERIMENT:
3rd November 2014


OBJECTIVES:

(i)                 To become familiar with certain ‘rules’ that relate to the use of triangular coordinates  to know the mutual solubilities of liquids in a two-phase system
(ii)               Determination of the solubility limits in a ternary system of water and two other liquids (ethanol and toluene), one of which is completely miscible (ethanol) and the other is partly miscible with water (toluene)


INTRODUCTION:

    In making pharmaceutical formulation often multiple component need to be mixed together and need to be in homogeneous form. This is usually possible by knowing the exact ratio of each component to be mixed with regard of some other condition such as temperature. In this experiment, there are three components of concern which were ethanol, toluene and water. Water is insoluble in toluene, but as it were mixed together with ethanol, all three components can achieve homogeneous solution at equilibrium if proper proportion was used.For 3 component systems at constant temperature and pressure, the compositions may be stated in the form of coordinates for a triangular diagram.



           Each side of a triangular diagram correspond one of the three component in the system and can be divided into part to produce equilateral grids as shown above. Thus any point in the diagram will show the amount of all three components while a point on the sides will show amount of any two components with each apex represent an amount of 100% of any one of the three components. In this experiment, the pressure is considered fixed at 1 atm, and so the number of degrees of freedom becomes three.

The three lines joining the corner points represent two-component mixture of the three possible combinations of A, B and C. By dividing each line into 100 equal units, the location of a point along the line can be directly related to the percent concentration of one component in a two-component system. The area within the triangle represents all the possible combinations of A, B and C to give three-component system. Line AC , opposite apex B represent system containing A and C (B=0). The horizontal lines running across the triangle parallel to AC denote increasing percentages of B from B=0 (on line AC) to B=100 (at point B). Line drawn parallel to one side of the triangle represents ternary system in which the percent by weight of one component is constant.

            Consider a three-component system consisting of liquids A, B and C. A and B are immiscible with each other while C is miscible with both. A mixture of A and B at equilibrium will exist as two physically distinct phases. The addition of C will markedly increase the mutual solubility of A and B such that at a certain concentration of C. The mixture will become homogenous. Conversely, a mixture of A and C will exist as a homogenous phase at equilibrium. The addition of the third component will markedly reduce the mutual solubility of A and C such that at a particular concentration of the third component, the mixture will separate out into two phases. Examples of three-component systems that has been studied include castor oil/ alcohol/ water; peppermint oil/ propylene glycol/ water; peppermint oil/ polyethylene glycol/ water.



APPARATUS:

Beaker, burette, pipette, conical flask, measuring cylinder,dropper,retort stand


MATERIAL:

Toluene,distilled water, ethanol


EXPERIMENTAL  PROCEDURES:

1)  Mixtures of ethanol and toluene were prepared in sealed containers measuring 100cmᵌ containing the following percentages of ethanol: 10%, 25%, 35%, 50%, 65%, 75%, 90%, 95%        
2) 20ml of each mixture was prepared by filling a certain volume using a burette.
3) Each mixture was triturated with water until cloudiness was observed due to the existence of a second phase

       

4)    A little water was added and shaken well after each addition.
 5)  Titration with water is repeated twice to get the average volume.
6)  The room temperature was measured using the thermometer.
7)   The percentage based on the volume of each component was calculated when the second phase starts to appear.
8) The points were plotted onto a triangular paper to give a triple phase diagram at the recorded temperature. One more measurement was done if necessary.

TABLE OF RESULT:


Titration with water

                  Conical flask

Volume
of water (mL)

A

B


C

D

E

F

G

H

First Titration


6.20

1.10

1.35

1.90

2.75

3.90

10.50

16.90

Second Titration

6.95

1.60

1.70

2.55

3.15

4.40

10.90

17.25

Average Volume

6.58

1.35

1.53

2.23

2.95

4.15

10.70

17.08



The percentage of each components


Conical Flask

Ethanol (%)
Total volume (water+ ethanol+ toluene)
(mL)
Ethanol
Toluene
Water
Volume
(mL)
Percentage
(%)
Volume
(mL)
Percentage
(%)
Volume
(mL)
Percentage
(%)
A
10
26.58
2.00
7.52
18.00
67.72
6.58
24.76
B
25
21.35
5.00
23.42
15.00
70.26
1.35
6.32
C
35
21.53
7.00
32.51
13.00
60.38
1.53
7.11
D
50
22.23
10.00
44.98
10.00
44.98
2.23
10.03
E
65
22.95
13.00
56.64
7.00
30.50
2.95
12.85
F
75
24.15
15.00
57.97
5.00
24.84
4.15
17.18
G
90
30.70
18.00
58.63
2.00
6.51
10.70
34.85
H
95
37.08
19.00
51.24
1.00
2.70
17.08
46.06


GRAPH:





DISCUSSION:


     The phase diagram for ternary system is usually represented in a triangular diagram. The graph plotted in the triangular diagram accounts for the fact that only two variables are required. Along the phase boundary only one variable is required. Each of the three corners or apexes of the triangle represent 100% by volume of one component (ethanol, toluene and water). So, each apex will represent 0% of the other two components. The real curve was determined in this experiment. Due to slightly miscibility, the water and toluene will form a two-phase system. For ethanol, it is completely miscible with both toluene and water. Thus, the addition of sufficient amount of ethanol to the toluene-water system would produce a single liquid phase in which all the three components are miscible and the mixture is homogenous.

      However, for this experiment we do it in another way, that is, the addition of water into toluene-ethanol system. The curve of the plotted graph is termed as binomial curve. The peak of the curve is at which the ethanol is 60% by volume. The region under the curve shows that the presence of two phases that is water and toluene whereas the region above the curve boundary which is the unbound region shows one phase of homogenous solution. The bounded region is actually between the binomial curve and the line of toluene and water mixture. Ethanol which acts as surfactant allow the two phase solution to become one phase solution.

         The points at both ends of the curve are the limits of solubility of toluene in water and water in toluene. Along the toluene-water line, which represents a binary mixture of toluene and water, the liquids are able to form a homogenous mixture as long as the first point is not exceeded. However, the second point must be exceeded for a homogenous mixture to be formed. The length of line between the two points represents the mixture of toluene and water with such composition that they cannot form a homogenous mixture. This may be due to insolubility of toluene in water or water in toluene.

         From the graph plotted, the binomial curve is incomplete as the points are deviated a bit from theoretical points and no tie line is obtained as there may be some errors during the experiment. Firstly, the glass wares are contaminated. So, the precaution step taken is we must rinse the glass wares and then wiped and dried the glass wares before used. The presence of distilled water in the glass wares when we mixed toluene and ethanol will cause the immediate of cloudiness observed and this cause the result to be inaccurate. Secondly, there is no specific range for the degree of cloudiness. This might greatly affect the volume of water added to the solution and causing the volume to be less than or more than the theoretical. As a result, the percentage by volume of each component and the curve are affected. The way to overcome this error is by fixed a consistent range of cloudiness for each set of the experiment or we use the same person to conduct the set of experiment so that he or she could compare the cloudiness he or she made before.


        Next, there is vaporization of liquid occurred. As we know that, ethanol and toluene are volatile liquid and easily vaporized. When some liquid vaporized, the measured volume will be less and affect the volume of water that needed for the titration. So, the volatile liquid must be mixed and used immediately when they are poured out from the container to avoid the loss of the measured volume. Parallax error was occurred when we measured and read the volume of the liquid from the measuring cylinder and burette. To avoid this from happening, the eye level of the observer must be in perpendicular to the meniscus of the liquids in the measuring apparatus to obtain accurate volume of the liquids. Lastly, inconsistency of room temperature during the experiment will affect the result too because temperature is one of the factor to determine graph pattern and phase diagram. Therefore, we have to conduct the experiment under the room temperature which is consistent to avoid the deviation of the final result.

PRACTICE:

1)   Does the mixture containing 70% ethanol, 20% water and 10% toluene (volume) appear clear or does it form two layer?
The mixture containing 70% ethanol, 20% water and 10% toluene (volume) is not line within the region of the graph plotted but above the graph plotted, so it appeared clear as single phase solution.
2) What will happen if you dilute 1 part of the mixture with 4 parts of (a) Water (b) toluene (c) ethanol?
1 part of the mixture:
70% ethanol = 0.7 part ethanol of whole mixture
20% water = 0.2 part water of whole mixture
10% toluene = 0.1 part toluene of whole mixture

(a)     1 part of mixture + 4 parts of water:

      Ethanol =   0.7 x 100% =14%
                            1+4

      Water =  0.2+4 x 100% = 84%
                          1+4

      Toluene = 0.1  x 100% =2%
                       1+4

For 14% ethanol, 84% water, 2% toluene, it does not lie within the area bounded by the graph, so the solution appeared clear and as single phase liquid solution.

(b)      1 part of mixture + 4 parts of toluene

  Ethanol =  0.7 x 100% =14%
                                    1+4

 Water =0.2  x 100% = 4%
                1+4

  Toluene = 0.1+4 x 100% =82%
                         1+4

For 14% ethanol, 4% water, 82% toluene, it does not lie within the area bounded by the graph, so the solution appeared clear and as single phase liquid solution.

(c)     1 part of mixture + 4 parts of ethanol

      Ethanol = 0.7+4  x 100% =94%
                           1+4

     Water = 0.2 x 100% = 4%
                     1+4

     Toluene = 0.1  x 100% =2%
            1+4

For 94% ethanol, 4% water, 2% toluene, it does not lie within the area bounded by the graph, so the solution appeared clear and as single phase liquid solution.

CONCLUSION:



The experiment of ternary system involves three different liquids which are ethanol, toluene, and water. This ternary system was representing in the form of triangular diagram. The data obtained from the experiment of mixing the ethanol and toluene and then triturated with water is the percentage of ethanol was much higher than the percentage of toluene and higher amount of water was needed to achieve cloudiness. The two phase system was established once the cloudiness was observed. The single liquid phase formed when toluene and water partially miscible and the ethanol in a sufficient amount. The presence of ethanol helps to increase the miscibility of toluene and water. Lastly, when water added exceed the theoretical percentage where the three components are partially miscible, the two phase systems occur. 

REFERENCE:

1.      Physicochemical Principles of Pharmacy , 3rd edition (1998) . A.T. Florence and D.Attwood. Macmillan Press Ltd.

2.     Physical Pharmacy: Physical Chemistry Principles in Pharmaceutical Sciences, by Martin, A.N.


4.    Phase diagram of a three-component partially immiscible liquid system : http://kimia.um.edu.my/physical/PHY_Chem_Year_3/Experiment%205.pdf

5.    Ternary Phase Diagrams : http://www.tulane.edu/~sanelson/eens212/ternaryphdiag.htm