Fall Organic Chemistry Experiment #6
Distillation and Analysis (GC-MS, IR, NMR)
Suggested Reading:
From "The Student's Lab Companion: Laboratory Techniques for Organic Chemistry”, by John W. Lehman
Operation #27 Simple Distillation p.148
Operation #29 Fractional Distillation p.174
Operation #31a Distillation Boiling Point p.194
Operation #34 Gas Chromatography p.205
Introduction
Most of us have some idea of what distillation is all about and are familiar with Jack Daniel's whiskey and other hard liquors. In fact, the process of purifying ethanol for alcoholic beverages in one of the main applications of distillation. Another common usage is in the purification of crude oil for gasoline. Notice, by the way, that both of these processes involve the purification of mixtures of LIQUIDS. As organic chemists,distillation is the method primarily used to purify mixtures of liquids.
So what underlying physical phenomena allow us to purify liquids by distillation? Actually, you should have a pretty good understanding of the process from what you learned in general chemistry with regard to vapor pressure equilibrium. However, in order to employ this technique (distillation), you will need to understand how vapor pressures of mixtures are dependent upon the structures of the components. In addition, you will need to develop an understanding of how vapor pressure affects the behavior of the components during the distillation and how it facilitates their separation.
Vapor pressure equilibrium and boiling
Imagine that you have an flask in front of you at room temperature that contains some liquid (say about 100 mL). Now, we all know that the molecules that make up the liquid are dynamic. That is, they are in constant motion and have a certain degree of kinetic energy associated with them. Some of these molecules may contain enough internal kinetic energy so that they can actually escape from the liquid phase to the gas phase. We expect that this is occurring to a certain degree at any temperature. Over time a certain amount of the liquid molecules will escape into the gas phase and exert a pressure (vapor pressure) on the liquid below. Although vapor pressure will differ according to the identity of a compound, vapor pressure always increases as the temperature rises (Figure 1).
Figure 1
As the temperature of our system increases (say, by external heating of the flask), the percentage of liquid molecules with enough energy to escape to the gas phase will increase. In addition, the vapor pressure will also increase. Ultimately, we expect that as we raise the temperature, we will be able to increase the vapor pressure of our system to the point where it equals any external pressure (atmospheric pressure at liquid surface + hydrostatic pressure) on the system. At this point (the boiling point), any trapped vapor within the liquid may expand and form bubbles that can rise to the surface of the liquid. The result is the observed phenomenon of boiling.
Simple distillation and boiling point-composition diagrams
The process of distillation consists of generating the vapor by boiling a liquid and subsequently condensing the "purified" vapor and collecting it in a separate container. The apparatus for this process can vary considerably depending upon the type of separation that you desire. There are basically two types of distillation set-ups -- simple and fractional. A representative fractional distillation set-up is shown below (Figure 2). The only difference for the simple distillation set-up is the absence of the Vigreux column (or some facsimile thereof).
Figure 2
If we were to distill a pure liquid, then we would expect that the liquid would boil at the boiling point of that pure liquid and that the temperature of the vapor above the liquid would be equal to the boiling point of the liquid. Furthermore, the temperature of the vapor should remain constant throughout the process. However, things change considerably when distilling mixtures. In this experiment, you will be distilling a mixture of two liquids in order to separate them based upon a difference in their boiling points.
Let us consider a simple mixture of toluene and carbon tetrachloride. The vapor pressure varies as a function of temperature similar to that as shown in Figure 1 (above). According to this graph, the pure liquids will boil at 110 ˚C and 77 ˚C, respectively, at standard atmospheric pressure (1 atm = 760 torr). However, if we have a mixture of the two liquids, the vapor pressure above this binary mixture will have contributions from BOTH components. As a result, the mixture will end up boiling at some intermediate temperature.
What is that intermediate temperature? In order to answer this question, chemists routinely use a boiling point-composition diagram (Figure 3). A boiling point-composition diagram enables us to interpret the behavior of a binary mixture as a function of composition and temperature.
Figure 3
The boiling point of a mixture is defined as the temperature at which the TOTAL vapor pressure of the mixture equals the atmospheric pressure on the solution. This total vapor pressure is simply the sum of the partial vapor pressures of the individual components (Dalton's Law of Partial Pressures):
Ptot = pa + pb + ......
How do we find the partial vapor pressure of each component in a mixture? The pressure and composition of vapor above a mixture at a given temperature can be calculated if: (a) the composition of the mixture and (b) the vapor pressures of the pure components are known. According to Raoult's law:
pa = pa˚Xa
wherepa is the vapor pressure of A above the mixture
pa˚ is the vapor pressure of pure A
Xa is the mole fraction of A in the mixture
Basically, Raoult's law states that the vapor pressure of any one component in a mixture is proportional to the number of molecules of that component present in the liquid solution. If we take Dalton's and Raoult's laws together, we can conclude that for an ideal mixture at any temperature, the most volatile component has a greater mole fraction in the vapor than in the solution.
If we return to the boiling point-composition diagram (Figure 3) for the mixture of toluene and carbon tetrachloride, we can look at some practical applications of Raoult's and Dalton's laws in terms of a distillation. If we start with a 50:50 mixture of the two liquids, the observed boiling point should be at some intermediate value between the boiling points of the pure substances. The boiling point is obtained by finding the appropriate binary composition on the x-axis and drawing a vertical line upwards until it intersects the liquid curve. To find the boiling point, simply draw a horizontal line until it intersects the y-axis. Therefore, from Figure 3 it can be shown that our 50:50 mixture will boil at 86 ˚C. This means that a thermometer placed in the boiling LIQUID will read 86 ˚C. However, the observed temperature for the vapors condensing in the distillation head will be different. In this case, the condensing vapors that are enriched in the lower boiling (more volatile) component will have a boiling point of 78 ˚C (Figure 3). The composition of this enriched vapor can be determined by drawing a vertical line downwards toward the x-axis from this lower boiling point. From Figure 3, we can see that the vapor generated from our original 50:50 mixture of carbon tetrachloride/toluene has been enriched to 80:20 carbon tetrachloride/toluene. This demonstrates that the original mixture has indeed been enriched in the lower boiling, more volatile component (carbon tetrachloride). Consequently, the remaining liquid gradually shifts toward a purer solution of toluene. Therefore, we expect that the observed boiling point of the remaining liquid will also rise gradually.
Azeotropes
Not all liquids conform to Raoult's law and form ideal solutions. An example is the mixture of water and ethanol. Because of certain intermolecular interactions, a unique mixture (an azeotrope) of 95.5% ethanol and 4.5% water forms that boilds below (78.1 ˚C) the boiling point of ethanol (78.3 ˚C). Thus, we say that ethanol/water mixtures form a low-boiling azeotrope because the boiling point of the azeotrope is lower than the boiling points of either single component. No matter how efficient is our distilling apparatus, pure 100% ethanol cannot be obtained by the distillation of a mixture of ethanol/water. You need to be careful when dealing with azeotropic systems, because a constant boiling point is NOT necessarily an indication of a single component system. In fact, azeotropes represent an example of a system that consists of two (or even three) components that boil at a constant temperature that is different than the boiling point of either pure component.
Fractional distillation
The methodology introduced above is for the process of simple distillation. You would start with a mixture that has each component present in a certain proportion (e.g. 50:50). You would distill the liquid and collect a fraction containing the enriched mixture (80:20). However, what would you do if you wanted to purify the 50:50 mixture to say 95:5? Well, there are actually two ways to accomplish this. To separate the mixture, a series of fractions could be collected and each of these can be distilled. Essentially, you would be performing a series of simple distillations. However, there is a better way. The series of distillations can be accomplished "automatically" in a fractional distillation. A common method of purification by fractional distillation is the refining of crude oil. Crude oil passes through a series of "bubble plates" that are placed one on top of another to heights of 150 ft. Their capacity can run up to 200,00 barrels of oil per day!! An example of a bubble plate column is shown in Figure 4. The entire set-up consists of:
(a) a series of plates that support a layer of distillate
(b) capped risers that allow for vapors to ascend
(c) overflow pipes to return excess distillate to the lower plate.
Figure 4
The bubble plate process functions in the same manner as the fractionating column that we will use in this experiment. Basically, the process involves a series of vaporizations and condensations. Each plate in the set-up corresponds to a single simple distillation. Therefore, the first plate on the column corresponds to the first fraction obtained in a simple distillation and is, thus, enriched in the lower boiling component. In an idealized situation, each plate in the column will achieve an incremental improvement in separation equivalent to one simple distillation. The separation process as achieved by fractional distillation is shown in Figure 3. If we start with our original 50:50 mixture of carbon tetrachloride/toluene and subject it to a separation by fractional distillation, we should achieve an incremental improvement in separation with each plate. Let's follow the dashed line in the diagram. If we vaporize mixture A and subsequently condense the distillate (vapor), we end up with mixture B. Mixture B is enriched in the lower boiling component (carbon tetrachloride) 80:20. Repetition of this process starting with B results in the enriched mixture C (90:10). This process continues for each successive plate. Table 1 shows the improvement in separation for three different experiments. The first (simple distillation) achieves a modest separation. The last experiment (fractional--3 plates) shows a significant improvement over the first.
TABLE 1
Experiment / Composition of liquid / Composition of vaporPre-distillation / 50:50 CT/T / 0:0 CT/T
#1 Simple distillation / 20:80 CT/T / 80:20 CT/T
#2 Fractional distillation
(2 plates) / 10:90 CT/T / 90:10 CT/T
#3 Fractional distillation
(3 plates) / 5:95 CT/T / 95:5 CT/T
Separation efficiency
Separation efficiency in fractional distillation is measured by the theoretical plate. A theoretical plate is defined as the unit of separation corresponding to the composition ratio, , for the liquid mixture and its corresponding vapor.
For example, for our original 50:50 mixture, a distillation utilizing a single theoretical plate will result in an enrichment to 71:29. Plugging into the equation, we get the following result:
This means that the first fraction of distillate is 2.5 times richer in the lower boiling component. The length of a packed fractionating column needed to obtain this degree of separation is the HETP (Height Equivalent to a Theoretical Plate). This number is used to determine the efficiency of the column. The general rule is the smaller the value of HETP, the more efficient the column. The primary variable in determining HETP is the type of packing material used for a particular liquid mixture. Representative packing materials include carborundum chips, glass beads, copper mesh, and glass helices. As an alternative, there are special columns that are available that achieve the series of vaporizations/condensations due to their construction. An example is the Vigreux column that will be on display during your lab period.
We want to have some idea of the number of theoretical plates required to efficiently separate mixtures so that we may design successful experiments. Essentially, if we know the number of theoretical plates, then we can choose appropriate packing materials, columns, etc. that will optimize the separation. For instance, an equation has been derived for 50:50 mixtures, which determines the number of theoretical plates require to achieve an enrichment in the lower boiling component to 95% for the first 40% of the mixture distilled (Form A). The usefulness is enhanced if we are able to modify the equation so that it is expressed in terms of the difference in boiling points for the two components (Form B).
Reflux ratio and holdup
The primary technique factors that influence separation efficiency are the reflux ratio and holdup. Reflux is the process of vaporizing the liquid to the top of the column and recondensing it onto the column. Takeoff is the process of vaporizing the liquid and condensing it out of the column as distillate. At the extremes we may experience total reflux (where no distillate is received) or total takeoff (where all of the vapor is immediately removed as distillate). Neither of these will produce good separation efficiency. Obviously, the best-case scenario is to have some type of compromise between these two extremes.
The other confounding factor is the total amount of vapor present in the column at an instant in time (holdup). The general rule of thumb is if there is more than 10% of our liquid mixture on the column at any time, then the separation efficiency is greatly reduced. Taken altogether, it appears that a moderately slow distillation (2-3 drops of distillate per min) will produce the best results.
Gas Chromatography
In gas chromatography, a liquid sample is injected into a port on the instrument that immediately vaporizes your sample. A carrier gas (usually helium and/or nitrogen gas) flows throughout the system in order to move your sample through the instrument. The sample quickly reaches a long metal column that is coated either with glass or some polymeric material. This column is housed within an oven whose temperature is usually 10-20 degrees less than the injection port. Once your sample reaches the column, the various components of the sample will interact with the material on the column (the stationary phase). The function of the column’s stationary phase is to provide a surface upon which your vapor may condense. The general idea here involves a solid-vapor or liquid-vapor phase separation of your material. That is, your sample will undergo a series of vaporizations and condensations (just like distillation) until it reaches the end of the column.
(a)If your sample contains a component with a high boiling point, then it will more readily condense into the liquid and adhere to the column and take a long time to get to the end. We say that components that readily condense onto the column have a high affinity for the column (stationary phase) and consequently, have a low affinity for the carrier gas (mobile phase). As a result, these components will spend a relatively longer time on the column and will have a long "retention time".
(b)If your sample has a component with a low boiling point, it is likely to remain in the vapor phase a move along with the carrier gas and spend a relatively short amount of time on the column. We say that components that readily travel through the column with the carrier gas have a low affinity for the column (stationary phase) and consequently, have a high affinity for the carrier gas (mobile phase). As a result, these components will spend a relatively short time on the column and will have a short "retention time".
The bottom-line here is that high boiling components have higher affinities for the column and longer retention times and low boiling components have lower affinities for the column and shorter retention times. Therefore, GC allows us to separate components of a mixture based upon their differences in boiling point.
Procedure
The purpose of this experiment is to illustrate the use of distillation to separate a mixture of two volatile liquids with different boiling points and to analyze the separation via gas chromatography. Each mixture will be issued to you and consist of a combination of two of the following liquids.
Componentscyclohexane
toluene
pentane
heptane
diethyl ether
1-butanol
Isobutyl alcohol
2-propanol
ethyl acetate
2-butanone
acetone
2-butanol
The liquids in the mixture will be separated by FRACTIONAL distillation. The results will be analyzed by gas chromatography-mass spectrometry (GC-MS), infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. You will also construct a graph of the distillation temperature versus the total volume of distillate collected. This graph will enable you to determine the boiling points of the two liquids and to evaluate the overall efficiency of the two methods.
Each team will acquire an unknown sample mixture. The appropriate apparatus (MACROSCALE) should be assembled according to the diagrams shown in the suggested reading. Carefully notice the position of the thermometer bulb in these diagrams. It must be positioned correctly for optimum results. Also, note that we will be packing the fractional distillation column with glass beads. For either simple or fractional distillation, add your unknown mixture to a 50 mL round bottom flask along with a stir bar.
Start circulating the cooling water in the condenser and adjust the heat so that INITIALLY the liquid boils rapidly. You will want to maintain a gentle boiling as you are heating, so be advised that you may have to adjust the setting on your hotplate. Do not heat up too quickly otherwise you will not achieve a good separation of components. We want to keep the rate to about 2-3 drops of distillate per minute. Collect the distillate in a series of vials. Be sure to record the temperature after every 3-5 drops.