Vous êtes sur la page 1sur 34

TABLE OF CONTENTS

CONTENT Abstract / summary Introduction PAGE 2 3

Aims / objectives

Theory

5-8

Apparatus

9-11

Experimental procedure

12-16

Result

17-19

Sample calculation

20-26

Discussion

27-28

Conclusion

29

References

30

Recommendation

31

Appendix

32-34

1.0 ABSTRACT:
Vapor-Liquid Equilibrium (VLE) unit can be used to study about the binary system. The main purpose of this experiment is to determine the composition of methanol in the vapor phase and liquid phase. In this experiment, a mixture of methanol and water is initially fed into the evaporator. The quantity of methanol is added until the volume of methanol added is equal to the volume of water which is 3.0 litres. The mixture was heated until boiled. The mixture vapor will rise up and will be cooled down by the condenser at the top of the evaporator. As the vapor starts to condense, the liquid falls back into the evaporator. When temperature remains constant, the system will stabilize and reached an equilibrium state. Finally, the samples of vapor and liquid were taken to determine their compositions by using a digital refractometer.

2.0 INTRODUCTION:
One of the most common chemical engineering operations is the separation of two or more compounds based on the differences of the boiling point. Therefore, this operation is applied in the vaporliquid equilibrium (VLE) experiment. In this experiment, vapor-liquid equilibrium unit is suitable for investigating the relationship between the vapor and liquid at equilibrium state at 1 atm (at atmospheric pressure) and at high pressure up to 2 bars. The purpose of the experiment using vapor-liquid equilibrium unit is to construct an equilibrium curve for the methanol and water system at the atmospheric pressure. The vapor-liquid equilibrium unit actually can be used to study any binary system as well as the multi component system. For example, in this experiment, the mixture of methanol and water with unknown composition is fed into an evaporator. When the heater is switched on, the mixture started to boil. The vapor will rise up and cooled down by the condenser at the top of the evaporator. As the vapor starts to condense, the liquid will fall back into the evaporator. So, the system will stabilize and finally reached at equilibrium state when the temperature is constant. Then, the samples of the vapor and liquid are taken to determine their compositions by using a refractometer to know the refractive index.

This unit must be operated under the supervision of authorized personnel who has been properly trained to handle this unit. Before attempting to start the experiment and run the unit, make sure that all operating instructions supplied with this unit carefully and have already been read. Moreover, while conducting the experiment, the students should always check and identify any leak or make sure that the level of water is enough to submerge the heater and temperature sensor. All the safety and precautions should be taken while conducting this experiment. Besides that, the students must be careful while handling the liquid at high temperature and before draining the samples, the heater must be switched off in order to cool the liquid in the evaporator.

3.0 OBJECTIVES:
The objective of this experiment is: To construct an equilibrium curve for the methanol-water system at atmospheric pressure. The Vapor-Liquid Equilibrium Unit is a bench top unit designed to investigate the relationship between vapor and liquid at equilibrium for any binary system as well as for multi component system. The system may run the unit an elevated pressure.

4.0 Theory
Vapor liquid equilibrium obeys Roults Law which give a definition law that relates the vapor pressure of an solution was dependent on the mole fraction of a solute added to solution. Roults Law only works for ideal mixture and was commonly used for predicting the vapor-liquid equilibrium for an ideal solution in equilibrium with an ideal gas mixture from the pure component vapor-pressure data. The partial vapor pressure of a component in a mixture was equal to the vapor pressure of the pure component at that temperature multiplied by its mole fraction in the mixture(Clark,2005).Roults Law can be expressed by:

Figure 4.1.1: Schematic diagram of VLE setup

Psolution = XsolventPsolvent Where Psolution=vapor pressure of the solution Xsolvent=mole fraction of the solvent Psolvent=vapor pressure of the pure solvent

(Equation 4.1)

In order to reduce VLE calculations by Roults Law were the vapor phase was an ideal gas and the liquid phase was an ideal gas solution. YiP = XiPisat P = P= (eq 4.2) (eq 4.3) (eq 4.4)

P =

(Equation 4.5)

When we discussed the phase behavior of pure fluids, we found that the temperature and pressure were constant when the two phases were in equilibrium. Thus, the saturated liquid and vapor points were both at the same temperature. When the liquid is heated it will boil at the same temperature as that at which the vapor will condense when it is cooled. Another way of saying the same thing is that the bubble point (boiling point) and dew point are the same for a pure fluid. When we have two components in both the vapor and liquid phases, the bubble point and dew points no longer coincide. There is a difference in composition between the liquid and vapor phases that are in equilibrium at the same T and P.It means that when you raise the temperature of a mixture until it boils, more of the more-volatile component ends up in the vapor phase. The liquid phase is left enriched in the less-volatile component. Thus, you can achieve a partial separation in the mixture. This is the principle behind distillation that accounts for most of the separation done in the chemical industry(Rowley,Vapor Liquid Equilibrium).By using the partial pressure calculation of Roults Law,value of compositions vapor and liquid can be findalso its boiling point.The graph from figure 4.1.1 below can be plotted when all the values were get while figure 4.1.2 was for composition of two different component when its equilibrium state achieved.

Figure 4.1.2 : Boiling Point Diagram

Figure 4.1.3: Equilibrium Diagram In other hand,Vapor Liquid Equilibrium also can be determine by other law which was Daltons Law.Daltons Law states that the total pressure exerted by the mixture of non-reactive gases is equal to the sum of the partial pressure of gases itself(Daltons Law,2013).Mathematically,the pressure of a mixture of gases can be defined as the summation, Or (Equation 4.6)

Ptotal=p1+p2+p3+...+pn

Where pn is partial pressure for each component.

5.0 Apparatus

Vapor Liquid Equilibrium Unit Refractometer Distilled water Measurement cylinder Dropper Power supply Suck pump Mask Gloves Methanol Beaker

Figure 5.19:V9

5.0 Apparatus
Figure 5.17: V14 Figure 5.18:V8

Figure 5.21: Pressure Gauge

Figure 5.20: Safety Valve

Figure 5.16: TI 02

Figure 5.14: V1

Figure 5.15: Control Panel

Figure 5.13:V5 Figure 5.11:V6 Figure 5.12: V4 Figure 5.8: Evaporator Figure 5.7:Heater Figure 5.10 Cooling Water Figure 5.9: V10

Figure 5.5: V7 Figure 5.6:V3 Figure 5.2: V13 Figure 5.1:V2 Figure 5.4:V12 Figure 5.3: V11

Figure 5.0 :- Model BP16 Vapor Liquid Equilibrium Unit

10

Figure 5.22 :- REFRACTOMETER

Figure 5.24: TIC 01

Figure 5.28:PT 1

Figure 5.25:TI 02 Figure 5.26: SUIZ HEATER Figure 5.27: MAIN SWITCH

Figure 5.23 :- Control Panel of Model BP16 VLE

11

6.0 Procedures
6.1 General start-up procedures 1. The equilibrium data for the binary system were obtain to studied from lecture. 2. A calibration curve of refractive index vs. composition plot was prepared for the particular binary system. 3. The evaporator and condenser were checked to ensure it empty with liquid. 4. All the valves were ensuring initially closed and the heater power was switched off. 5. The main power at the control panel was switched on. All sensors and indicators were checked to make sure it well functioning. 6.2 General Experiment Procedures 1. The liquid mixture of 3 to 6L at the desired composition were prepared and was poured into the evaporator through valve 1 and closed it. 2. The valve V13 and V14 were opened at the level sight tube. The liquid level has been sure that it above the safety line on the level sight tube. The valves V13 and V14 were closed back. 3. The valve V8 was opened for operation at atmospheric pressure. 4. Turn on the compressed air supply and set the desired pressure at the regulator for operation at elevated pressure. The valve V9 was opened to start pressurizing the unit, Then the valve V9 was closed when the pressure has been reached. 5. The valve V10 was opened and adjusted to allow about 5 to 10 L/min of cooling water to flow through the condenser. 6. The temperature controller TIC-01 was set to slightly above the expected boiling point of the liquid mixture. 7. The heater was switched on. 8. The temperature rise in TCI-01 was observed. When the temperature at TCI-02 started to increased sharply, the liquid in the evaporator has begun to boil. The pressure at PI-01.All the temperature and pressure were waited to stabilize at a steady state value. 9.The evaporator pressure and the liquid, vapor temperatures recorded.

12

10.A vapor and liquid sample were collected from the unit as described in section 3.4.

6.3

General Shut-Down Procedures 1. The heater was switched off. 2. The valve V10 was opened to allow cooling water flow rate through the condenser. 3. The valve V11 was opened to allow cooling water to flow through the cooling coil in the evaporator. 4. When the unit has been pressurized, valve V8 was slowly opened to depressurize the unit. 5. Temperature was waited at the unit until it drops to below 50C. 6. Valves V2 and V3 opened to drain all liquid from the evaporator. 7. Valves V5 and V7 opened to drain all liquid accumulated at the condenser. 8. All valves were closed and the main power at the control panel was switched off.

13

6.4

Sampling Procedures Both vapor and liquid samples can be taken from the unit for analysis. 1. Vapor sampling from the condenser. i. ii. The vent valve V6 was ensured opened and drain valve V7 was closed. Valve V5 was slowly opened to allow some condensed vapor from the condenser to flow into the top sample collector. Valve V5 closed. iii. iv. Valve V7 was opened to collect the sample in a sampling vial. The cap on the vial was immediately closed and was immersed in cold water.

2. Liquid sampling from the evaporator i. ii. Vent valve V4 was ensure that it opened and drain valve V3 was closed. Valve V12 was opened to allow cooling water to flow through the bottom sample collector. iii. Then, valve V2 was slowly opened to allow some liquid from the evaporator to flow into the sample collector. Valve V2 closed. iv. v. Valve V3 was opened to collect the sample in a sampling vial. The cap on the vial was immediately closed and was immersed in the cold water.

14

6.5

Experiment 1: Equilibrium Curve at Atmospheric Pressure Objective: To construct an equilibrium curve for the methanol-water system at atmospheric pressure. 1. The general start-up procedures as described in section 6.1 were performing. 2. 12-L of pure methanol and 5-L of deionized water were prepared. 3. Valve V8 was opened. 4. 0.1-L methanol and 3-L water were poured into the evaporator through valve V1.Then, V1 was closed. 5. Valves V13 and V14 were opened at the level sight tube. The liquid level was ensuring it was above the safety line on the level sight tube.V13 and V14 were closed back. 6. Valve V10 was opened and adjusted to allow about 5 L/min of cooling water to flow through the condenser. 7. The temperature controller TIC-01was set to about 100C.The heater was switched on. 8. The temperature rose in TIC-01 was observed. When the temperature at TI-02 starts to increase sharply, the liquid in the evaporator has begun to boil. The pressure at PI-01 was observed. Waited until temperatures and pressure stabilized at a steady state value. 9. The evaporator pressure and the liquid, vapor temperatures value were recorded. 10. A liquid and vapor sample were collected from the unit as described in section 6.4.The samples were analyzed to determine their compositions. 11. The heater was switched off and valve V11 opened to allow cooling water to flow through the cooling coil in the evaporator. 12. The temperature at TI-02 was waited to drop significantly to signify that boiling has stopped. Valve V11 closed. 13. Additional 0.2-L methanol was poured into the evaporator through V1.Valve V1 closed. There was now about 0.3-L methanol and 3-L water in the evaporator. Steps 5 to 12 were above repeated. 14. An additional 0.2-L methanol was poured into the evaporator through valve V1.Valve V1 was closed. There was now about 0.5-L methanol and 3-L water in the evaporator .Steps 5 to 12 above were repeated.

15

15. An additional 0.5-L methanol was poured into the evaporator through valve V1.Valve V1 was closed. There was now about 1-L methanol and 3-L water in the evaporator .Steps 5 to 12 above were repeated. 16. An additional 1-L methanol was poured into the evaporator through valve V1.Valve V1 was closed. There was now about 2-L methanol and 3-L water in the evaporator .Steps 5 to 12 above were repeated. 17. An additional 1-L methanol was poured into the evaporator through valve V1.Valve V1 was closed. There was now about 3-L methanol and 3-L water in the evaporator .Steps 5 to 12 above were repeated. 18. Valve V2 and V3 were opened to drain all liquid from the evaporator. 19. 2-L methanol and 1-L water were poured into the evaporator through V1.Valve V1 was closed. Steps 5 to 12 above were repeated. 20. An additional 1-L methanol was poured into the evaporator through valve V1.Valve V1 was closed. There was now about 5-L methanol and 1-L water in the evaporator .Steps 5 to 12 above were repeated. 21. An additional 2-L methanol was poured into the evaporator through valve V1.Valve V1 was closed. There was now about 5-L methanol and 1-L water in the evaporator .Steps 5 to 12 above were repeated. 22. The general shut-down procedures as described in section 6.3 were performed.

16

7.0 RESULT
Vapor liquid equilibrium data Water (L) Methanol (L) 3.0 3.0 3.0 3.0 3.0 3.0 0.1 0.3 0.5 1.0 2.0 3.0 Temperature (oC) Vapor 93.0 89.3 87.5 83.3 79.9 77.8 Table 7.1 Water (L) Methanol (L) 1.0 1.0 1.0 2.0 3.0 5.0 Temperature (oC) Vapor 72.7 71.0 70.1 Table 7.2 Liquid 71.6 70.1 68.6 Refractive Index (nD) Vapor 1.34187 1.33969 1.33812 Liquid 1.34246 1.34230 1.34162 Liquid 89.3 86.6 83.6 81.5 76.5 73.6 Refractive Index (nD) Vapor 1.34074 1.33895 1.33899 1.33832 1.33830 1.33798 Liquid 1.33367 1.33385 1.33384 1.33384 1.33394 1.34040

Methanol Density (g/m3) Molecular weight (g/ mol) 0.79 32.04 Table 7.3

Water 1 18

17

Temperature and mole fraction of Methanol (

Mole fraction Y (Vapor) 93.0 89.3 87.5 83.3 79.9 77.8 72.7 71.0 70.1 X (Liquid) 89.3 86.6 83.6 81.5 76.5 73.6 71.6 70.1 68.6 Y (Vapor) 0.01341 0.05356 0.09373 0.1740 0.3078 0.4148 0.6307 0.7770 0.9233 X (Liquid) 0.01333 0.05335 0.09337 0.1734 0.3068 0.4155 0.6340 0.7785 0.9257

18

T-xy diagram for methanol-water system


100 90 80 70 temperature (C) 60 50 40 30 20 10 0 0 0.2 0.4 0.6 0.8 1 Vapor/Liquid Mole Fraction (x/y)

Temperature Vapor (C) Temperature Liquid (C)

X-Y Equilibrium Graph


1 0.9 0.8 Vapor mol fraction 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.1 0.2 0.3 0.4 0.5 Liquid mol fraction 0.6 0.7 0.8 0.9 1

19

8.0 CALCULATIONS
Density of water 79

Density of methanol ( Molecular weight Molecular weight

i)

Number of moles of

VOLUME OF WATER (L) 3 1

MOLES OF WATER (MOL) 166.667 55.556

Volume

Volume

20

ii)

Number of moles

Volume of Methanol (L) 0.1 0.3 0.5 1.0 2.0 3.0 2.0 3.0 5.0

Moles of Methanol (mol) 2.4744 7.4231 12.3719 24.7438 49.4875 74.2313 49.4875 74.2313 123.7188

Table 8.1

Volume 79

79

79

Volume 79

2 7

2 7

21

Volume 79

9 9

9 9

Volume 79

79

79

Volume 79

Volume 79

2 7

2 7

22

Volume 79

Volume 79

2 7

2 7

Volume 79

9 9

9 9

23

Mole fraction of Methanol (


used (L) Volume

).
used (L) Mole (mol) Mole (mol) ( ) ( ) Mole fraction Mole fraction

Volume

3.0 3.0 3.0 3.0 3.0 3.0 1.0 1.0 1.0

0.1 0.3 0.5 1.0 2.0 3.0 2.0 3.0 5.0

7 7 7 7 7 7

2.4744 7.4231 12.3719 24.7438 49.4875 74.2313 9 7 2 2 7 7

169.1414 174.0901 179.0389 191.4108 216.1545 240.8983 105.0435 129.7873 179.2748

0.99 0.96 0.93 0.87 0.77 0.69 0.53 0.42 0.31

0.01 0.04 0.07 0.13 0.23 0.31 0.47 0.58 0.69

Table 8.2

24

Composition of Methanol (

) in mole fraction

Mole fraction Vapor Vapor

Refractive Index, RI Vapor Liquid

Mole fraction

(vapor) ( ) ( ) Y

(liquid) X

93.0 89.3 87.5 83.3 79.9 77.8 72.7 71.0 70.1

89.3 86.6 83.6 81.5 76.5 73.6 71.6 70.1 68.6

0.99 0.96 0.93 0.87 0.77 0.69 0.53 0.42 0.31

0.01 0.04 0.07 0.13 0.23 0.31 0.47 0.58 0.69

1.34074 1.33895 1.33899 1.33832 1.33830 1.33798 1.34187 1.33969 1.33812

1.33367 1.33385 1.33384 1.33384 1.33394 1.34040 1.34246 1.34230 1.34162

0.01341 0.05356 0.09373 0.1740 0.3078 0.4148 0.6307 0.7770 0.9233

0.01333 0.05335 0.09337 0.1734 0.3068 0.4155 0.6340 0.7785 0.9257

Table 8.3

25

Temperature and mole fraction of Methanol (

Mole fraction Y (Vapor) 93.0 89.3 87.5 83.3 79.9 77.8 72.7 71.0 70.1 X (Liquid) 89.3 86.6 83.6 81.5 76.5 73.6 71.6 70.1 68.6 Y (Vapor) 0.01341 0.05356 0.09373 0.1740 0.3078 0.4148 0.6307 0.7770 0.9233 X (Liquid) 0.01333 0.05335 0.09337 0.1734 0.3068 0.4155 0.6340 0.7785 0.9257

Table 8.4

26

9.0

DISCUSSION
Vapor-liquid equilibrium (VLE) undergirds the bulk of industrial separation processes,

particularly in the distillation processes. It will be consider only binary (two components) mixture for simplicity. The composition of the liquid phase will be designated by the mole fraction of the more volatile component (lower boiling point), represented by x. The mole fraction of the vapor represented by y. When the liquid is heated to its boiling point, the vapor will produce, in general, have a different composition than the liquid. Thus, boiling the mixture produces a partial separation of the component. If the vapor is collected, it can be condensed and boil again to further change the composition. T-xy Diagram (temperature x versus y) represents the data for two-component (binary) system. T-xy Diagram is convenient for analysis the binary distillation system. There are two main factors that make the vapor and liquid compositions different at equilibrium which are the pure component vapor pressures and the no idealities in the liquid phase. The refractive index for vapor and liquid is recorded. The composition of methanol in the liquid and vapor is determined based on the refractive index. The mole fraction for methanol and water are determined by calculation. The mole fraction of methanol and water can be calculated by using the density of each compound. The density of methanol is 0.7918 g/cm3 whereas the density of water is 1g/cm3. From the volume of methanol and water that we had been used, we can calculate the mass of the methanol and water by using the density of the methanol and water. For first experiment, we constant the volume of water at 3L then mixed with different amount of volume of methanol from 0.1L until 3L. The temperature of the liquid methanol is decrease from 89.3C to 73.6C. The temperature of the vapor methanol is also decrease from 93.0C to 77.8C. The refractive index for liquid methanol is increase from 1.33367 to .1.34040. The refractive index for the vapor methanol is decrease from 1.34074 to 1.33798. The mole fraction of the liquid methanol is increase from 0.01333 to 0.4155. The mole fraction for vapor methanol is increase from 0.01341 to 0.4148 For the second experiment, we constant the volume of water at 1L then mixed with different amount of volume of methanol from 2L until 5L. The temperature of liquid methanol is decrease from 71.6C to 68.6C. The temperature of vapor methanol is also decrease from 72.7C to 70.1C. The refractive index for liquid methanol is decrease from 27

1.34246 to 1.34162. The refractive index for vapor methanol is also decrease from 1.34187 to 1.33812. The mole fraction of the liquid methanol is increase from 0.6340 to 0.9257. The mole fraction of the vapor methanol is also increase from 0.6307 to 0.9233. Through the X-Y equilibrium graph, when the mole fraction of liquid methanol increase the mole fraction of vapor methanol is also increase. The mole fraction that had been used in the graph is calculated using the mole fraction formula. Methanol is a volatile liquid. During the experiment, putting the methanol in the beaker without closing the beaker can cause the half of the methanol is vaporize slowly. The methanol is added before the temperature heater is lower than 50C. All this action can cause the error for this experiment and it can give not accurate reading. The eyes are not perpendicular when the reading of methanol in the cylinder is recorded.

28

10.0 CONCLUSION
As the conclusion, this experiment was successful carried out. The relationship between the vapor and liquid at the normal pressure was successfully determined. The maximum mole fraction of methanol is 1. The objective of this experiment is to construct an equilibrium curve for the methanol-water system at atmospheric pressure. From the data of this experiment, the composition of methanol in vapor is higher than the liquid. The composition of methanol in vapor and liquid is increase when the volume of methanol is also increase. When the objective of this experiment was achieved, it can be concluded that this experiment is successfully done.

29

11.0 RECOMMENDATION
Make sure that the evaporator, condenser and tubings are cleaned properly. Flush the system with the de-ionized water. Always make sure that there is enough liquid all the time to fully submerged the heater and temperature sensor. Be extremely careful when handling the liquid at high temperature. Always switch of the heater and allow the liquid to cool before draining. Make sure that the eyes is perpendicular during the reading the methanol in the cylinder is recorded.

30

12.0 Reference
1. http://www.fpharm.uniba.sk/fileadmin/user_upload/english/Physical_Chemistry/3Liquid-vapour_equilibrium.pdf , Retrieved 25 November 2013 2. http://www.chemguide.co.uk/physical/phaseeqia/idealpd.html November 2013 3. http://chemed.chem.wisc.edu/chempaths/GenChem-Textbook/Vapor-LiquidEquilibrium-843.html Retrieved 25 November 2013 4. Manual Lab Report CPE 451 5. http://lorien.ncl.ac.uk/ming/distil/distilvle.htm Retrieved 25 November 2013 6. http://chemed.chem.wisc.edu/chempaths/GenChem-Textbook/Vapor-LiquidEquilibrium-843.html Retrieved 25 November 2013 Retrieved 25

31

13.0 Appendix

Figure 13.1 :-Distilled Water

Figure 13.2 :-Measurement Cylinder

Figure 13.3 :-Dropper

Figure 13.4 :-Power Supply

32

Figure 13.5 :-Suck Pump

Figure 13.6 :- Masks

Figure 13.7 :-Gloves

Figure 13.8 :-Methanol

33

Figure 13.9 :- Model BP16 Vapor Liquid Equilibrium Unit

34