Experiment 3: Vapour Liquid Equilibrium Abstract This experiment is carried out to investigate the vapour liquid equilibrium of methanol-water

system. The objective of this experiment is to construct an equilibrium curve for the methanol-water system at atmospheric pressure. In order to accomplish this experiment, Vapour Liquid Equilibrium Unit (Model: BP 16) is used. A known volume of methanol is mixed with a known volume of water and the refractive indices are measured to plot a standard VLE curve. Refractive index against mole fraction of methanol graph is plotting to get a standard curve. Then certain amount of methanol is heated with 3L of water where the amount of methanol is added until it reached 3L in the equilibrium unit. The refractive index of sample collected in both the vapour and liquid phase is measured. The refractive index measured indicating the amount of methanol exists in the liquid and vapour phase. The equilibrium curve is obtained by plotting two type of graph. There are vapour and liquid compositions against the vapour temperature graph and graph of vapour compositions against liquid compositions. Through these two types of graph, vapour-liquid equilibrium data can be obtained. Introduction Many processes in chemical engineering do not only involve a single phase but a combination of two immiscible liquids, or a stream containing both gas and liquid. It is very important to recognize and be able to calculate when these phases are in equilibrium with each other, and how much is in each phase. This knowledge will be especially useful when you study separation processes, for many of these processes work by somehow distorting the equilibrium so that one phase is especially rich in one component, and the other is rich in the other component. More specifically, there are three important criteria for different phases to be in equilibrium with each other: 1. The temperature of the two phases is the same at equilibrium. 2. The partial pressure of every component in the two phases is the same at equilibrium. 3. The Gibbs free energy' of every component in the two phases is the same at equilibrium. In general, chemical engineers are not dealing with single components; instead they deal with equilibrium of mixtures. When a mixture begins to boil, the vapor does not, in general, have the same composition as the liquid. Instead, the substance with the lower boiling temperature (or higher vapor pressure) will have a vapor concentration higher than that with the higher boiling temperature, thoughboth will be present in the vapor. A similar argument applies when a vapor mixture condenses.

The concentrations of the vapor and liquid when the overall concentration and one of the temperature or pressure are fixed can easily be read off of a phase diagram. In order to read and understand a phase diagram, it is necessary to understand the concepts of bubble point and dew point for a mixture. 1. The bubble point is the point at which the first drop of a liquid mixture begins to vaporize. 2. The dew point is the point at which the first drop of a gaseous mixture begins to condense. If you are able to plot both the bubble and the dew points on the same graph, you come up with what is called a Pxy or a Txy diagram, depending on whether it is graphed at constant temperature or constant pressure. The "xy" implies that the curve is able to provide information on both liquid and vapor compositions.

Aims 1. To construct an equilibrium curve for the methanol-water system at atmospheric pressure.

Theory The vapour-liquid equilibrium data is best described by the boiling point diagram. The boiling point diagram shows how the equilibrium compositions of the components in a liquid mixture vary with temperature at a fixed pressure. Consider an example of a liquid mixture containing 2 components (A and B) which is a binary mixture. This has the following boiling point diagram.

Figure 4.1: The boiling point diagram

The boiling point of A is that at which the mole fraction of A is 1. The boiling point of B is that at which the mole fraction of A is 0. In this example, A is the more volatile component and therefore has a lower boiling point than B. The upper curve in the diagram is called the dew-point curve while the lower one is called the bubble-point curve. The dew-point is the temperature at which the saturated vapour starts to condense. The bubble-point is the temperature at which the liquid starts to boil. The region above the dew-point curve shows the equilibrium composition of the superheated vapour while the region below the bubble-point curve shows the equilibrium composition of the subcooled liquid. For example, when a subcooled liquid with mole fraction of A=0.4 (point A) is heated, its concentration remains constant until it reaches the bubble-point (point B), when it starts to boil. The vapours evolved during the boiling has the equilibrium composition given by point C, approximately 0.8 mole fraction A. This is approximately 50% richer in A than the original liquid. This difference between liquid and vapour compositions is the basis for distillation operations. Distillation columns are designed based on the boiling point properties of the components in the mixtures being separated. Thus the sizes, particularly the height, of distillation columns are determined by the vapour liquid equilibrium (VLE) data for the mixtures. Vapour-liquid equilibrium (VLE) curves

Constant pressure VLE data is obtained from boiling point diagrams. VLE data of binary mixtures is often presented as a plot, as shown in the figure on the right. The VLE plot expresses the bubble-point and the dew-point of a binary mixture at constant pressure. The curved line is called the equilibrium line and describes the compositions of the liquid and vapour in equilibrium at some fixed pressure.

Figure 4.2: The curve showing equilibrium line

Figure 4.2 shows a binary mixture that has a uniform vapour-liquid equilibrium that is relatively easy to separate. Figure 4.3 below on the other hand, show non-ideal systems which will present more difficult separations. We can tell from the shapes of the curves.

Figure 4.3: The VLE curve for non-ideal system The most intriguing VLE curves are generated by azeotropic systems. An azeotrope is a liquid mixture which when vaporised, produces the same composition as the liquid. Figure 4.4 below shows two different azeotropic systems, one with a minimum boiling point and one with a maximum boiling point. In both plots, the equilibrium curves cross the diagonal lines, and this are azeotropic points where the azeotropes occur. In other words azeotropic systems give rise to VLE plots where the equilibrium curves crosses the diagonals. Note the shapes of the respective equilibrium lines in relation to the diagonal lines that bisect the VLE plots.

Figure 4.4: VLE curve showing azeotrope conditions

Material and apparatus Vapour Liquid Equilibrium Unit (Model: BP 16) Equilibrium still Refractometer 10 mL volumetric flasks Sample vials Digital thermometer Graduated cylinders Beakers Syringe Methanol Water

Procedures General start up 1. Obtain the equilibrium data for the binary system to be studied from literature. 2. Prepare a calibration curve of refractive index vs. composition plot for the particular binary system. 3. Check that the evaporator and condenser is empty of liquid. 4. Ensure all valves are initially closed and the heater power switch is turn off. 5. Switch on the main power at the control panel. Check all sensors and indicators are functioning properly.

Heating of mixture 1. The general start-up procedures were performed. 2. 12-L of pure methanol and 5-L deionized water were prepared and V8 was opened. 3. 3.0.1-L methanol and 3-L water were poured into the evaporator through V1.V1 was closed. 4. V13 and V14 were opened at the level sight tube to make sure that the liquid level is above the safety line on the level sight tube. Both valves were then closed. 5. V10 was opened and adjusted to allow 5L/min of cooling water to flow through the condenser. 6. Temperature controller TIC-01 was set to 100 C and the heater was switched on. 7. The temperature at TIC-01 and TIC-02 were observed. The pressure at PI-01 was also being observed. The readings were recorded when the temperatures and the pressure were stabilized at a steady state value. 8. A vapour and liquid sample were collected and the samples were analyzed to determine their compositions.

9. The heater was switched off and the V11 was opened to allow cooling water to flow through the cooling coil in the evaporator. 10. V11 was closed when the temperature at TI-02 dropped significantly 11. Additional 0.2L methanol was poured into the evaporator through V1.V1 was closed. There were about 0.3L methanol and 3L water in the evaporator. Steps 4-10 above were repeated. 12. Additional 0.2L methanol was poured into the evaporator through V1.V1 was closed. There were about 0.5L methanol and 3L water in the evaporator. Steps 4-10 above were repeated. 13. Additional 0.5L methanol was poured into the evaporator through V1.V1 was closed. There were about 1.0L methanol and 3L water in the evaporator. Steps 4-10 above were repeated. 14. Additional 2.0L methanol was poured into the evaporator through V1.V1 was closed. There were about 3.0L methanol and 3L water in the evaporator. Steps 4-10 above were repeated. 15. V2 and V3 were opened to drain all liquid from the evaporator. 16. 5.0L methanol and 1.0L water was poured into the evaporator through V1.V1 was closed. Steps 4-10 above were repeated. 17. The general shut down procedure were performed. Sampling procedures Both vapour and liquid samples can be taken from the unit for analysis. i. Vapour sampling from the condenser 1. Ensure that vent valve V6 is opened and drain valve V7 is closed. 2. Slowly open valve V5 to allow some condensed vapour from the condenser to flow into the top sample collector. Close valve V5. 3. Open valve V7 to collect the sample in a sampling vial. 4. Immediately close the cap on the vial and immerse it in cold water. ii. Liquid sampling from the evaporator 1. Ensure that vent valve V4 is opened and drain valve V3 is close. 2. Open valve V12 to allow cooling water to flow through the bottom sample collector. 3. Then, slowly open valve V12 to allow some liquid from the evaporator to flow into the sample collector. Close valve V2. 4. Open valve V3 to collect the sample in a sampling vial. 5. Immediately close the cap on the vial and immerse it in cold water.

Results

Volume of water (ml) 0 20 40 60 80 100

Volume of methanol(ml) 100 80 60 40 20 0

Mol fraction 1 0.002 0.0015 0.00099 0.00049 0

% weight 100 76 54 35 16.5 0

Refractive Index 1.3323 1.3390 1.3402 1.3377 1.3379 1.3325

Pressure

Volume Of methanol 100 ml 200 ml 200 ml 500 ml 1000 ml 1000 ml

1 atm 1 atm 1 atm 1 atm 1 atm 1 atm

Volum e of water 3L 3L 3L 3L 3L 3L

Temperature L 98.0 94.0 91.5 86.1 80.6 77.7 V 90.4 87.6 83.7 80.5 76.7 74.0

Mole fraction methanol L V 0.011 0.329 0.037 0.421 0.057 0.533 0.124 0.607 0.230 0.632 0.311 0.759

Refractive index L 1.3340 1.3302 1.3305 1.3322 1.3317 1.3340 V 1.3322 1.3326 1.3327 1.3316 1.3321 1.3320

Sample calculation Given Volume of methanol = 80ml Volume of water = 20ml

Mole fraction of methanol

No of mole of methanol (CH3OH)

Mass of methanol (CH3OH) Density of methanol

= = = =

Density x volume 0.7918 0.7918 7.918 x x( )3

Volume of methanol

= =

80ml = 0.08l 8.0 x

Thus; Mass of methanol

= =

7.918 x 63.344 g

8.0 x

Mole of methanol

= = 1.977mol

No of mole of water (H2O)

Mass of water (H2O) Density of water (H2O)

= = = =

Density x volume 1.0 1.0 1.0 x 20ml = 0.02l 2.0 x x( )3

Volume of water (H2O)

= =

Thus; Mass of water (H2O) = = Mole of water (H2O) = 1.0 x 20 g 2.0 x )

1.11 mol

Total mole

Mole of methanol + mole of water

= = Thus; Mole fraction of methanol

1.977mol + 1.11 mol 3.097mol

0.64

Percent weight (%wt)

= = 76%

x 100

Interpolation of mole fraction from the data given in appendix

x =

0.011

Discussion This experiment has been carried out to construct an equilibrium curve for the methanolwater system at atmospheric pressure. For the first part of this experiment, the series of mixture of methanol and water with known volume are prepared which give the mole fraction of methanol ranging from 1 to 0. Then the refractive index of each mixture is measured by using refractometer. From these data, graph of refractive index vs. mole fraction of methanol is plot. This graph is the calibration curve and acts as a standard curve. Then in the second part of this experiment, the mixture of methanol and total 3L water is heated. The methanol is added gradually until its volume is 3L. This mixture is said to be in equilibrium when the evaporation rate of both components is constant. When a binary

mixture is heated, the difference in boiling point for each component is taken into account. In this experiment, methanol-water system is studied where methanol and water have two distinct boiling points which are around 65C and 100C respectively. Theoretically the components with low boiling points will vaporise first followed by the higher boiling point components. Then the samples collected at the distillate and residue are tested. The refractive index of both samples are measured. For water and methanol, as it is binary mixture, the respective mole fractions of each component must be taken into account in a phase diagram. To plot an equilibrium curve, different approach is used. In this experiment several graph are plot. There are as follows: Graph of vapour and liquid compositions against the vapour temperature Graph of vapour compositions against liquid compositions

The refractive index measured in this experiment indicates the mole fraction of methanol exist in liquid or vapour phase. The graph of vapour and liquid compositions against the vapour temperature would give a boiling point diagram with two curves (refer graph 7.1). The lower one, representing boiling liquid mole fraction at various temperatures, is called a bubble point curve. The upper one, representing vapour mole fraction at corresponding temperatures, is called a dew point curve. In mixtures containing two or more components where their concentrations are compared in the vapour and liquid phases, mole fraction is indicating the concentrations of each component in the system. These two curves meet where the mixture becomes purely one component, where x 1 = 0 and x2 = 1 or x1 = 1 and x2 = 0. The temperatures at those two points correspond to the boiling points of the two pure components. But unfortunately, these cannot be shown in the graph plot (refer graph 12.2 in appendix). This might due to some error occurred during the experiment. For the graph of vapour compositions against liquid compositions where liquid mole fractions for components 1 and 2 can be represented as x1 and x2 respectively, and vapour mole fractions of the corresponding components are commonly represented as y1 and y2. Similarly for binary mixtures in these VLE diagrams; where x1 + x2 = 1 and y1 + y2 = 1 Such VLE diagrams are square with a diagonal line running from the (x1=0, y1=0) corner to the (x1=1, y1=1) corner for reference. These types of VLE diagrams are used in the McCabeThiele method to determine the number of theoretical stages needed to distil a given composition binary feed mixture into one distillate fraction and one bottoms fraction. Such VLE information retrieved from those two graphs are useful in designing columns for distillation, especially fractional distillation, which is a particular specialty of chemical engineers. Distillation is a process used to separate or partially separate components in a mixture by boiling followed by condensation. Distillation takes advantage of differences in concentrations of components in the liquid and vapour phases.

Conclusion At the end of this experiment, the equilibrium curve is managed to be constructed. However, several errors occurred which affects the accuracy of the result data. The errors might due to the sample at vapour and liquid phase is collected when the temperature is below the boiling point of methanol which directly affects the refractive index measured by the refractometer. Other mistakes might due to the sample taken at vapour phase is still hot and again affects the reading of refractometer. At the end of this experiment, a lot of knowledge regarding the vapour-liquid equilibrium data can be known. Last but not least, vapour liquid equilibrium data has many application and very useful to be applied in the industry. For example distillation columns in industry are designed using VLE data for the mixtures to be separated. The vapour-liquid equilibrium characteristics (indicated by the shape of the equilibrium curve) of the mixture will determine the number of stages, and hence the number of trays, required for the separation. Recommendations 1. The sample collected from vapour phase must be left cooled before the refractive index is measured. 2. Make sure the boiling point of methanol is reached before the sample at both liquid and vapour phase is taken. 3. The readings should be taken twice or three times.

References 1. Gmehling.J;Onken.U; (1977); Vapor Liquid Data Collection; DECHEMA, Chemistry Data Series,Vol. 1 Part 1;Frankfurt. 2. E. Hala, J. Pick, V. Fried, and 0. Vilim; (1958); Vapor-Liquid Equilibrium; Pergamon Press, New York. 3. K. G. Denbigh;(1966);The Principles of Chemical Equilibrium;2d ed;Cambridge University Press, New York. 4. Perry H.Robert, Don W.Green (1999); Perrys Chemical Engineers Handbook; Mc Graw Hill. Appendices

Methanol

Refractometer

Vapour Liquid Equilibrium Unit (Model: BP 16)

Graph 1: The standard curve

Refractive Index against mole fraction

1.341 1.34 1.339 1.338 1.337 1.336 1.335 1.334 1.333 1.332 1.331 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Graph 2: Temperature of vapour against liquid and vapour fraction

100 90 80 70 60 50 40 30 20 10 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Series1 Series2

Graph 3: y against x

y versus x graph
0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 V