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What is a phase? At its simplest, a phase can be just another term for solid, liquid or gas. If you have some ice floating in water, you have a solid phase present and a liquid phase. If there is air above the mixture, then that is another phase. But the term can be used more generally than this. For example, oil floating on water also consists of two phases - in this case, two liquid phases. If the oil and water are contained in a bucket, then the solid bucket is yet another phase. In fact, there might be more than one solid phase if the handle is attached separately to the bucket rather than moulded as a part of the bucket.
Ideal mixtures
An ideal mixture is one which obeys Raoult's Law. but I want to look at the characteristics of an ideal mixture before actually stating Raoult's Law. The page will flow better if I do it this way around. Examples of ideal mixtures There is actually no such thing as an ideal mixture! However, some liquid mixtures get fairly close to being ideal. These are mixtures of two very closely similar substances. Commonly quoted examples include: hexane and heptane benzene and methylbenzene propan-1-ol and propan-2-ol Ideal mixtures and intermolecular forces In a pure liquid, some of the more energetic molecules have enough energy to overcome the intermolecular attractions and escape from the surface to form a vapour. The smaller the intermolecular forces, the more molecules will be able to escape at any particular temperature. If you have a second liquid, the same thing is true. At any particular temperature a certain proportion of the molecules will have enough energy to leave the surface.
In an ideal mixture of these two liquids, the tendency of the two different sorts of molecules to escape is unchanged.
You might think that the diagram shows only half as many of each molecule escaping - but the proportion of each escaping is still the same. The diagram is for a 50/50 mixture of the two liquids. That means that there are only half as many of each sort of molecule on the surface as in the pure liquids. If the proportion of each escaping stays the same, obviously only half as many will escape in any given time. If the red molecules still have the same tendency to escape as before, that must mean that the intermolecular forces between two red molecules must be exactly the same as the intermolecular forces between a red and a blue molecule. If the forces were any different, the tendency to escape would change. Exactly the same thing is true of the forces between two blue molecules and the forces between a blue and a red. They must also be the same otherwise the blue ones would have a different tendency to escape than before. If you follow the logic of this through, the intermolecular attractions between two red molecules, two blue molecules or a red and a blue molecule must all be exactly the same if the mixture is to be ideal. This is why mixtures like hexane and heptane get close to ideal behaviour. They are similarly sized molecules and so have similarly sized van der Waals attractions between them. However, they obviously aren't identical - and so although they get close to being ideal, they aren't actually ideal. For the purposes of this topic, getting close to ideal is good enough! Ideal mixtures and enthalpy change of mixing When you make any mixture of liquids, you have to break the existing intermolecular attractions (which needs energy), and then remake new ones (which releases energy). If all these attractions are the same, there won't be any heat either evolved or absorbed. That means that an ideal mixture of two liquids will have zero enthalpy change of mixing. If the temperature rises or falls when you mix the two liquids, then the mixture isn't ideal.
Raoult's Law
You may have come cross a slightly simplified version of Raoult's Law if you have studied the effect of a non-volatile solute like salt on the vapour pressure of solvents like water. The definition below is the one to use if you are talking about mixtures of two volatile liquids. The partial vapour pressure of a component in a mixture is equal to the vapour pressure of the pure component at that temperature multiplied by its mole fraction in the mixture. Raoult's Law only works for ideal mixtures. In equation form, for a mixture of liquids A and B, this reads:
In this equation, PA and PB are the partial vapour pressures of the components A and B. In any mixture of gases, each gas exerts its own pressure. This is called its partial pressure and is independent of the other gases present. Even if you took all the other gases away, the remaining gas would still be exerting its own partial pressure. The total vapour pressure of the mixture is equal to the sum of the individual partial pressures.
The Po values are the vapour pressures of A and B if they were on their own as pure liquids. xA and xB are the mole fractions of A and B. That is exactly what it says it is - the fraction of the total number of moles present which is A or B. You calculate mole fraction using, for example:
Notice that the vapour pressure of pure B is higher than that of pure A. That means that molecules must break away more easily from the surface of B than of A. B is the more volatile liquid. To get the total vapour pressure of the mixture, you need to add the values for A and B together at each composition. The net effect of that is to give you a straight line as shown in the diagram.
For non-ideal mixtures, these straight lines become curves. For a nearly ideal mixture, they are near enough straight lines - that's the assumption we are working on here. The less ideal the mixture is, the more curved the lines become.
There are two ways of looking at this. Choose whichever seems easiest to you. It doesn't matter how you work this out - it is the result that is important. Either: If the molecules are escaping easily from the surface, it must mean that the intermolecular forces are relatively weak. That means that you won't have to supply so much heat to break them completely and boil the liquid. The liquid with the higher vapour pressure at a particular temperature is the one with the lower boiling point. Or:
Liquids boil when their vapour pressure becomes equal to the external pressure. If a liquid has a high vapour pressure at some temperature, you won't have to increase the temperature very much until the vapour pressure reaches the external pressure. On the other hand if the vapour pressure is low, you will have to heat it up a lot more to reach the external pressure. The liquid with the higher vapour pressure at a particular temperature is the one with the lower boiling point.
Don't go on until you are sure about this: For two liquids at the same temperature:
The one with the higher vapour pressure is the one with the lower boiling point.
Constructing a boiling point / composition diagram To remind you - we've just ended up with this vapour pressure / composition diagram:
We're going to convert this into a boiling point / composition diagram. We'll start with the boiling points of pure A and B. B has the higher vapour pressure. That means that it will have the lower boiling point. If that isn't obvious to you, go back and read the last section again! For mixtures of A and B, you might perhaps have expected that their boiling points would form a straight line joining the two points we've already got. Not so! In fact, it turns out to be a curve.
The second line C2 shows the composition of the vapour over the top of any particular boiling liquid. If you boil a liquid mixture, you would expect to find that the more volatile substance escapes to form a vapour more easily than the less volatile one. That means that in the case we've been talking about, you would expect to find a higher proportion of B (the more volatile component) in the vapour than in the liquid. You can discover this composition by condensing the vapour and analysing it. That would give you a point on the diagram. The diagram just shows what happens if you boil a particular mixture of A and B. Notice that the vapour over the top of the boiling liquid has a composition which is much richer in B - the more volatile component. If you repeat this exercise with liquid mixtures of lots of different compositions, you can plot a second curve - a vapour composition line. Using the phase diagram The diagram is used in exactly the same way as it was built up. If you boil a liquid mixture, you can find out the temperature it boils at, and the composition of the vapour over the boiling liquid. For example, in the diagram above, if you boil a liquid mixture C1, it will boil at a temperature T1 and the vapour over the top of the boiling liquid will have the composition C 2. All you have to do is to use the liquid composition curve to find the boiling point of the liquid, and then look at what the vapour composition would be at that temperature. Notice again that the vapour is much richer in the more volatile component B than the original liquid mixture was.
The beginnings of fractional distillation Suppose that you collected and condensed the vapour over the top of the boiling liquid and reboiled it. You would now be boiling a new liquid which had a composition C2. That would boil at a new temperature T2, and the vapour over the top of it would have a composition C3.
You can see that we now have a vapour which is getting quite close to being pure B. If you keep on doing this (condensing the vapour, and then reboiling the liquid produced) you will eventually get pure B. This is obviously the basis for fractional distillation. However, doing it like this would be incredibly tedious, and unless you could arrange to produce and condense huge amounts of vapour over the top of the boiling liquid, the amount of B which you would get at the end would be very small. Real fractionating columns (whether in the lab or in industry) automate this condensing and reboiling process.
If you reboil that liquid C2, it will give a vapour with composition C3. Again you can condense that to give a liquid of the same new composition (the red lines). Reboiling the liquid C3 will give a vapour still richer in the more volatile component B (the green lines). You can see that if you were to do this once or twice more, you would be able to collect a liquid which was virtually pure B. The secret of getting the more volatile component from a mixture of liquids is obviously to do a succession of boiling-condensing-reboiling operations. It isn't quite so obvious how you get a sample of pure A out of this. That will become clearer in a while.
Some notes on the apparatus The fractionating column is packed with glass beads (or something similar) to give the maximum possible surface area for vapour to condense on. You will see why this is important in a minute. Some fractionating columns have spikes of glass sticking out from the sides which serve the same purpose. The mixture is heated at such a rate that the thermometer is at the temperature of the boiling point of the more volatile component. Notice that the thermometer bulb is placed exactly at the outlet from the fractionating column.
Relating what happens in the fractionating column to the phase diagram Suppose you boil a mixture with composition C1. The vapour over the top of the boiling liquid will be richer in the more volatile component, and will have the composition C2. That vapour now starts to travel up the fractionating column. Eventually it will reach a height in the column where the temperature is low enough that it will condense to give a liquid. The composition of that liquid will, of course, still be C2.
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So what happens to that liquid now? It will start to trickle down the column where it will meet new hot vapour rising. That will cause the already condensed vapour to reboil.
Some of the liquid of composition C2 will boil to give a vapour of composition C3. Let's concentrate first on that new vapour and think about the unvaporised part of the liquid afterwards. The vapour This new vapour will again move further up the fractionating column until it gets to a temperature where it can condense. Then the whole process repeats itself. Each time the vapour condenses to a liquid, this liquid will start to trickle back down the column where it will be reboiled by up-coming hot vapour. Each time this happens the new vapour will be richer in the more volatile component. The aim is to balance the temperature of the column so that by the time vapour reaches the top after huge numbers of condensing and reboiling operations, it consists only of the more volatile component - in this case, B. Whether or not this is possible depends on the difference between the boiling points of the two liquids. The closer they are together, the longer the column has to be. The liquid So what about the liquid left behind at each reboiling? Obviously, if the vapour is richer in the more volatile component, the liquid left behind must be getting richer in the other one. As the condensed liquid trickles down the column constantly being reboiled by up-coming vapour, each reboiling makes it richer and richer in the less volatile component - in this case, A. By the time the liquid drips back into the flask, it will be very rich in A indeed. So, over time, as B passes out of the top of the column into the condenser, the liquid in the flask will become richer in A. If you are very, very careful over temperature control, eventually you will have separated the mixture into B in the collecting flask and A in the original flask. Finally, what is the point of the packing in the column? To make the boiling-condensing-reboiling process as effective as possible, it has to happen over and over again. By having a lot of surface area inside the column, you aim to have the maximum possible contact between the liquid trickling down and the hot vapour rising. If you didn't have the packing, the liquid would all be on the sides of the condenser, while most of the vapour would be going up the middle and never come into contact with it.
The column contains a number of trays that the liquid collects on as the vapour condenses. The up-coming hot vapour is forced through the liquid on the trays by passing through a number of bubble caps. This produces the maximum possible contact between the vapour and liquid. This all makes the boiling-condensing-reboiling process as efficient as possible. The overflow pipes are simply a controlled way of letting liquid trickle down the column. If you have a mixture of lots of liquids to separate (such as in petroleum fractionation), it is possible to tap off the liquids from some of the trays rather than just collecting what comes out of the top of the column. That leads to simpler mixtures such as gasoline, kerosene and so on. NON-IDEAL MIXTURES OF LIQUIDS This page looks at the phase diagrams for non-ideal mixtures of liquids, and introduces the idea of an azeotropic mixture (also known as an azeotrope or constant boiling mixture). It goes on to explain how this complicates the process of fractionally distilling such a mixture. This is the final page in a sequence of three pages.
In this case, pure A has the higher vapour pressure and so is the more volatile component. Raoult's Law only works for ideal mixtures. In these, the forces between the particles in the mixture are exactly the same as those in the pure liquids. The tendency for the particles to escape is the same in the mixture and in the pure liquids. That's not true in non-ideal mixtures. Positive deviations from Raoult's Law In mixtures showing a positive deviation from Raoult's Law, the vapour pressure of the mixture is always higher than you would expect from an ideal mixture.
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Explaining the deviations The fact that the vapour pressure is higher than ideal in these mixtures means that molecules are breaking away more easily than they do in the pure liquids. That is because the intermolecular forces between molecules of A and B are less than they are in the pure liquids. You can see this when you mix the liquids. Less heat is evolved when the new attractions are set up than was absorbed to break the original ones. Heat will therefore be absorbed when the liquids mix. The enthalpy change of mixing is endothermic. The classic example of a mixture of this kind is ethanol and water. This produces a highly distorted curve with a maximum vapour pressure for a mixture containing 95.6% of ethanol by mass. Negative deviations from Raoult's Law In exactly the same way, you can have mixtures with vapour pressures which are less than would be expected by Raoult's Law. In some cases, the deviations are small, but in others they are much greater giving a minimum value for vapour pressure lower than that of either pure component. Explaining the deviations These are cases where the molecules break away from the mixture less easily than they do from the pure liquids. New stronger forces must exist in the mixture than in the original liquids. You can recognise this happening because heat is evolved when you mix the liquids - more heat is given out when the new stronger bonds are made than was used in breaking the original weaker ones. Many (although not all) examples of this involve actual reaction between the two liquids. The example of a major negative deviation that we are going to look at is a mixture of nitric acid and water. These two covalent molecules react to give hydroxonium ions and nitrate ions.
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Using the diagram Suppose you are going to distil a mixture of ethanol and water with composition C 1 as shown on the above diagram. It will boil at a temperature given by the liquid curve and produce a vapour with composition C2. When that vapour condenses it will, of course, still have the composition C 2. If you reboil that, it will produce a new vapour with composition C3. You can see that if you carried on with this boiling-condensing-reboiling sequence, you would eventually end up with a vapour with a composition of 95.6% ethanol. If you condense that you obviously get a liquid with 95.6% ethanol. What happens if you reboil that liquid? The liquid curve and the vapour curve meet at that point. The vapour produced will have that same composition of 95.6% ethanol. If you condense it again, it will still have that same composition. You have hit a barrier. It is impossible to get pure ethanol by distiling any mixture of ethanol and water containing less than 95.6% of ethanoll. This particular mixture of ethanol and water boils as if it were a pure liquid. It has a constant boiling point, and the vapour composition is exactly the same as the liquid. It is known as a constant boiling mixture or an azeotropic mixture or an azeotrope. The implications of this for fractional distillation of dilute solutions of ethanol are obvious. The liquid collected by condensing the vapour from the top of the fractionating column can't be pure ethanol. The best you can produce by simple fractional distillation is 95.6% ethanol. What you can get (although it isn't very useful!) from the mixture is pure water. As ethanol rich vapour is given off from the liquid boiling in the distillation flask, it will eventually lose all the ethanol to leave just water. To summarise: Distilling a mixture of ethanol containing less than 95.6% of ethanol by mass lets you collect:
a distillate containing 95.6% of ethanol in the collecting flask (provided you are careful with the temperature control, and the fractionating column is long enough); pure water in the boiling flask.
What if you distil a mixture containing more than 95.6% ethanol? Work it out for yourself using the phase diagram, and starting with a composition to the right of the
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a distillate containing 95.6% of ethanol in the collecting flask (provided you are careful with the temperature control, and the fractionating column is long enough); pure ethanol in the boiling flask.
A large negative deviation from Raoult's Law: nitric acid and water mixtures Nitric acid and water form mixtures in which particles break away to form the vapour with much more difficulty than in either of the pure liquids. You can see this from the vapour pressure / composition curve discussed further up the page. That means that mixtures of nitric acid and water can have boiling points higher than either of the pure liquids because it needs extra heat to break the stronger attractions in the mixture. In the case of mixtures of nitric acid and water, there is a maximum boiling point of 120.5C when the mixture contains 68% by mass of nitric acid. That compares with the boiling point of pure nitric acid at 86C, and water at 100C. Notice the much bigger difference this time due to the presence of the new ionic interactions (see above). The phase diagram looks like this: Using the diagram Distilling dilute nitric acid Start with a dilute solution of nitric acid with a composition of C1and trace through what happens.
The vapour produced is richer in water than the original acid. If you condense the vapour and reboil it, the new vapour is even richer in water. Fractional distillation of dilute nitric acid will enable you to collect pure water from the top of the fractionating column. As the acid loses water, it becomes more concentrated. Its concentration gradually increases until it gets to 68% by mass of nitric acid. At that point, the vapour produced has exactly the same concentration as the liquid, because the two curves meet. You produce a constant boiling mixture (or azeotropic mixture or azeotrope). If you distil dilute nitric acid, that's what you will eventually be left with in the distillation flask. You can't produce pure nitric acid from the dilute acid by distilling it. Distilling nitric acid more concentrated than 68% by mass This time you are starting with a concentration C2 to the right of the azeotropic mixture.
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The vapour formed is richer in nitric acid. If you condense and reboil this, you will get a still richer vapour. If you continue to do this all the way up the fractionating column, you can get pure nitric acid out of the top. As far as the liquid in the distillation flask is concerned, it is gradually losing nitric acid. Its concentration drifts down towards the azeotropic composition. Once it reaches that, there can't be any further change, because it then boils to give a vapour with the same composition as the liquid. Distilling a nitric acid / water mixture containing more than 68% by mass of nitric acid gives you pure nitric acid from the top of the fractionating column and the azeotropic mixture left in the distillation flask.
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Total vapour pressure of the mixture Assuming that the mixture is being agitated, then both of the liquids will be in equilibrium with their vapours. The total vapour pressure is then simply the sum of the individual vapour pressures:
. . . where po refers to the saturated vapour pressure of the pure liquid. Notice that this is independent of the amount of each sort of liquid present. All you need is enough of each so that both can exist in equilibrium with their vapour. For example, phenylamine and water can be treated as if they were completely immiscible. (That isn't actually true, but they are near enough immiscible to be usable as an example.) At 98C, the saturated vapour pressures of the two pure liquids are: phenylamine water 7.07 kPa 94.30 kPa
The total vapour pressure of an agitated mixture would just be the sum of these - in other words, 101.37 kPa Boiling point of the mixture Liquids boil when their vapour pressure becomes equal to the external pressure. Normal atmospheric pressure is 101.325 kPa. Compare that with the figure we have just got for the total vapour pressure of a mixture of water and phenylamine at 98C. Its total vapour pressure is fractionally higher than the normal external pressure. This means that such a mixture would boil at a temperature just a shade less than 98C - in other words lower than the boiling point of pure water (100C) and much lower than the phenylamine (184C). Exactly the same sort of argument could be applied to any other mixture of immiscible liquids. I've chosen the phenylamine-water mixture just because I happen to have some figures for it! Important conclusion Agitated mixtures of immiscible liquids will boil at a temperature lower than the boiling point of either of the pure liquids. Their combined vapour pressures are bound to reach the external pressure before the vapour pressure of either of the individual components get there.
STEAM DISTILLATION
Notice that in the presence of water, phenylamine (or any other liquid which is immiscible with water) boils well below its normal boiling point. This has an important advantage in separating molecules like this from mixtures. Normal distillation of these liquids would need quite high temperatures. On the whole these tend to be big molecules we are talking about. Quite a lot of molecules of this sort will be broken up by heating at high temperatures. Distilling them in the presence of water avoids this by keeping the temperature low. That's what steam distillation achieves. Carrying out steam distillation We will carry on with the phenylamine example for now. During the preparation of phenylamine it is produced as a part of a mixture containing a solution of all sorts of inorganic compounds. It is
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removed from this by steam distillation. Steam is blown through the mixture and the water and phenylamine turn to vapour. This vapour can be condensed and collected.
The steam can be generated by heating water in another flask (or something similar). As the hot steam passes through the mixture it condenses, releasing heat. This will be enough to boil the mixture of water and phenylamine at 98C provided the volume of the mixture isn't too great. For large volumes, it is better to heat the flask as well to avoid having to condense too much steam and increase the volume of liquid in the flask too much. The condensed vapour will consist of both water and phenylamine. If these were truly immiscible, they would form two layers which could be separated using a separating funnel. In fact, the phenylamine has a slight solubility in water and various other techniques have to be used in this particular case to get the maximum yield of phenylamine. These aren't relevant to this topic. Some other applications of steam distillation Steam distillation can be used to extract some natural products - for example, to extract eucalyptus oil from eucalyptus, citrus oils from lemon or orange peel, and to extract oils used in perfumes from various plant materials.
Normally one of the solvents chosen is water while the second is hydrophobic such as octanol.[3] Hence both the partition and distribution coefficient are measures of how hydrophilic ("water loving") or hydrophobic ("water fearing") a chemical substance is.
Applications of distillation methods in industries Cite examples of the Applications of distillation methods used in various industries. Petroleum, rum, brewing and fragrance industries
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