AN INTRODUCTION TO SATURATED VAPOUR PRESSURE

This page looks at how the equilibrium between a liquid (or a solid) and its vapour leads to the idea of a saturated vapour pressure. It also looks at how saturated vapour pressure varies with temperature, and the relationship between saturated vapour pressure and boiling point.

The origin of saturated vapour pressure

The evaporation of a liquid The average energy of the particles in a liquid is governed by the temperature. The higher the temperature, the higher the average energy. But within that average, some particles have energies higher than the average, and others have energies lower than the average. Some of the more energetic particles on the surface of the liquid can be moving fast enough to escape from the attractive forces holding the liquid together. They evaporate. The diagram shows a small region of a liquid near its surface.

Notice that evaporation only takes place on the surface of the liquid. That's quite different from boiling which happens when there is enough energy to disrupt the attractive forces throughout the liquid. That's why, if you look at boiling water, you see bubbles of gas being formed all the way through the liquid. If you look at water which is just evaporating in the sun, you don't see

any bubbles. Water molecules are simply breaking away from the surface layer. Eventually, the water will all evaporate in this way. The energy which is lost as the particles evaporate is replaced from the surroundings. As the molecules in the water jostle with each other, new molecules will gain enough energy to escape from the surface.

The evaporation of a liquid in a closed container Now imagine what happens if the liquid is in a closed container. Common sense tells you that water in a sealed bottle doesn't seem to evaporate - or at least, it doesn't disappear over time. But there is constant evaporation from the surface. Particles continue to break away from the surface of the liquid - but this time they are trapped in the space above the liquid.

As the gaseous particles bounce around, some of them will hit the surface of the liquid again, and be trapped there. There will rapidly be an equilibrium set up in which the number of particles leaving the surface is exactly balanced by the number rejoining it.

In this equilibrium, there will be a fixed number of the gaseous particles in the space above the liquid. When these particles hit the walls of the container, they exert a pressure. This pressure is called the saturated vapour pressure(also known as saturation vapour pressure) of the liquid.

Measuring the saturated vapour pressure It isn't difficult to show the existence of this saturated vapour pressure (and to measure it) using a simple piece of apparatus.
Note: This experiment is much easier to talk about than do, given the safety problems in handling mercury because of its poisonous vapour. This is particularly going to be a problem if you want to find the saturated vapour pressure of a liquid at a higher temperature. You would have to use a more complex bit of apparatus. That isn't a problem you need to worry about for UK A level purposes.

If you have a mercury barometer tube in a trough of mercury, at 1 atmosphere pressure the column will be 760 mm tall. 1 atmosphere is sometimes quoted as 760 mmHg ("millimetres of mercury").

If you squirt a few drops of liquid into the tube, it will rise to form a thin layer floating on top of the mercury. Some of the liquid will evaporate and you will get the equilibrium we've just been talking about provided there is still some liquid on top of the mercury. It is only an equilibrium if both liquid and vapour are present.

The saturated vapour pressure of the liquid will force the mercury level down a bit. You can measure the drop - and this gives a value for the saturated vapour pressure of the liquid at this temperature. In this case, the mercury has been forced down by a distance of 760 - 630 mm. The saturated vapour pressure of this liquid at the temperature of the experiment is 130 mmHg.

You could convert this into proper SI units (pascals) if you wanted to. 760 mmHg is equivalent to 101325 Pa. A value of 130 mmHg is quite a high vapour pressure if we are talking about room temperature. Water's saturated vapour pressure is about 20 mmHg at this temperature. A high vapour pressure means that the liquid must be volatile - molecules escape from its surface relatively easily, and aren't very good at sticking back on again either. That will result in larger numbers of them in the gas state once equilibrium is reached. The liquid in the example must have significantly weaker intermolecular forces than water.

The variation of saturated vapour pressure with temperature

The effect of temperature on the equilibrium between liquid and vapour You can look at this in two ways. There is a common sense way. If you increase the temperature, you are increasing the average energy of the particles present. That means that more of them are likely to have enough energy to escape from the surface of the liquid. That will tend to increase the saturated vapour pressure. Or you can look at it in terms of Le Chatelier's Principle - which works just as well in this kind of physical situation as it does in the more familiar chemical examples.
Note: You could follow this link if you aren't sure about Le Chatelier's Principle. Use the BACK button on your browser to return to this page later.

When the space above the liquid is saturated with vapour particles, you have this equilibrium occurring on the surface of the liquid:

The forward change (liquid to vapour) is endothermic. It needs heat to convert the liquid into the vapour. According to Le Chatelier, increasing the temperature of a system in a dynamic equilibrium favours the endothermic change. That means that increasing the temperature increases the amount of vapour present, and so increases the saturated vapour pressure.

The effect of temperature on the saturated vapour pressure of water The graph shows how the saturated vapour pressure (svp) of water varies from 0C to 100 C. The pressure scale (the vertical one) is measured in kilopascals (kPa). 1 atmosphere pressure is 101.325 kPa.

Saturated vapour pressure and boiling point A liquid boils when its saturated vapour pressure becomes equal to the external pressure on the liquid. When that happens, it enables bubbles of vapour to form throughout the liquid - those are the bubbles you see when a liquid boils. If the external pressure is higher than the saturated vapour pressure, these bubbles are prevented from forming, and you just get

evaporation at the surface of the liquid. If the liquid is in an open container and exposed to normal atmospheric pressure, the liquid boils when its saturated vapour pressure becomes equal to 1 atmosphere (or 101325 Pa or 101.325 kPa or 760 mmHg). This happens with water when the temperature reaches 100C. But at different pressures, water will boil at different temperatures. For example, at the top of Mount Everest the pressure is so low that water will boil at about 70C. Depressions from the Atlantic can easily lower the atmospheric pressure in the UK enough so that water will boil at 99C - even lower with very deep depressions. Whenever we just talk about "the boiling point" of a liquid, we always assume that it is being measured at exactly 1 atmosphere pressure. In practice, of course, that is rarely exactly true.

Saturated vapour pressure and solids

Sublimation Solids can also lose particles from their surface to form a vapour, except that in this case we call the effect sublimation rather than evaporation. Sublimation is the direct change from solid to vapour (or vice versa) without going through the liquid stage. In most cases, at ordinary temperatures, the saturated vapour pressures of solids range from low to very, very, very low. The forces of attraction in many solids are too high to allow much loss of particles from the surface. However, there are some which do easily form vapours. For example, naphthalene (used in old-fashioned "moth balls" to deter clothes moths) has quite a strong smell. Molecules must be breaking away from the surface as a vapour, because otherwise you wouldn't be able to smell it. Another fairly common example (discussed in detail on another page) is solid carbon dioxide - "dry ice". This never forms a liquid at atmospheric pressure and always converts directly from solid to vapour. That's why it is known as dry ice.

PHASE DIAGRAMS OF PURE

SUBSTANCES
This page explains how to interpret the phase diagrams for simple pure substances - including a look at the special cases of the phase diagrams of water and carbon dioxide. This is going to be a long page, because I have tried to do the whole thing as gently as possible.

The basic phase diagram

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. You can recognise the presence of the different phases because there is an obvious boundary between them - a boundary between the solid ice and the liquid water, for example, or the boundary between the two liquids.

Phase diagrams A phase diagram lets you work out exactly what phases are present at any given temperature and pressure. In the cases we'll be looking at on this page, the phases will simply be the solid, liquid or vapour (gas) states of a pure substance. This is the phase diagram for a typical pure substance.

These diagrams (including this one) are nearly always drawn highly distorted in order to see what is going on more easily. There are usually two major distortions. We'll discuss these when they become relevant. If you look at the diagram, you will see that there are three lines, three areas marked "solid", "liquid" and "vapour", and two special points marked "C" and "T". The three areas These are easy! Suppose you have a pure substance at three different sets of conditions of temperature and pressure corresponding to 1, 2 and 3 in the next diagram.

Under the set of conditions at 1 in the diagram, the substance would be a solid because it falls into that area of the phase diagram. At 2, it would be a liquid; and at 3, it would be a vapour (a gas).
Note: I'm using the terms vapour and gas as if they were interchangeable. There are subtle differences between them that I'm not ready to explain for a while yet. Be patient!

Moving from solid to liquid by changing the temperature: Suppose you had a solid and increased the temperature while keeping the pressure constant - as shown in the next diagram. As the temperature increases to the point where it crosses the line, the solid will turn to liquid. In other words, it melts.

If you repeated this at a higher fixed pressure, the melting temperature would be higher because the line between the solid and liquid areas slopes slightly forward.

Note: This is one of the cases where we distort these diagrams to make them easier to discuss. This line is much more vertical in practice than we normally draw it. There would be very little change in melting point at a higher pressure. The diagram would be very difficult to follow if we didn't exaggerate it a bit.

So what actually is this line separating the solid and liquid areas of the diagram? It simply shows the effect of pressure on melting point. Anywhere on this line, there is an equilibrium between solid and liquid. You can apply Le Chatelier's Principle to this equilibrium just as if it was a chemical equilibrium. If you increase the pressure, the equilibrium will move in such a way as to counter the change you have just made.

If it converted from liquid to solid, the pressure would tend to decrease again because the solid takes up slightly less space for most substances. That means that increasing the pressure on the equilibrium mixture of solid and liquid at its original melting point will convert the mixture back into the solid again. In other words, it will no longer melt at this temperature. To make it melt at this higher pressure, you will have to increase the temperature a bit. Raising the pressure raises the melting point of most solids. That's why the melting point line slopes forward for most substances. Moving from solid to liquid by changing the pressure: You can also play around with this by looking at what happens if you decrease the pressure on a solid at constant temperature.
Note: You have got to be a bit careful about this, because exactly what happens if you decrease the pressure depends on exactly what your starting conditions are. We'll talk some more about this when we look at the line separating the solid region from the vapour region.

Moving from liquid to vapour: In the same sort of way, you can do this either by changing the temperature or the pressure.

The liquid will change to a vapour - it boils - when it crosses the boundary line between the two areas. If it is temperature that you are varying, you can easily read off the boiling temperature from the phase diagram. In the diagram above, it is the temperature where the red arrow crosses the boundary line. So, again, what is the significance of this line separating the two

areas? Anywhere along this line, there will be an equilibrium between the liquid and the vapour. The line is most easily seen as the effect of pressure on the boiling point of the liquid. As the pressure increases, so the boiling point increases.
Note: I don't want to make any very big deal over this, but this line is actually exactly the same as the graph for the effect of temperature on the saturated vapour pressure of the liquid. Saturated vapour pressure is dealt with on a separate page. A liquid will boil when its saturated vapour pressure is equal to the external pressure. Suppose you measured the saturated vapour pressure of a liquid at 50C, and it turned out to be 75 kPa. You could plot that as one point on a vapour pressure curve, and then go on to measure other saturated vapour pressures at different temperatures and plot those as well. Now, suppose that you had the liquid exposed to a total external pressure of 75 kPa, and gradually increased the temperature. The liquid would boil when its saturated vapour pressure became equal to the external pressure - in this case at 50C. If you have the complete vapour pressure curve, you could equally well find the boiling point corresponding to any other external pressure. That means that the plot of saturated vapour pressure against temperature is exactly the same as the curve relating boiling point and external pressure - they are just two ways of looking at the same thing. If all you are interested in doing is interpreting one of these phase diagrams, you probably don't have to worry too much about this.

The critical point You will have noticed that this liquid-vapour equilibrium curve has a top limit that I have labelled as C in the phase diagram. This is known as the critical point. The temperature and pressure corresponding to this are known as the critical temperature andcritical pressure. If you increase the pressure on a gas (vapour) at a temperature lower than the critical temperature, you will eventually cross the liquid-vapour equilibrium line and the vapour will condense to give a liquid.

This works fine as long as the gas is below the critical temperature. What, though, if your temperature was above the critical temperature? There wouldn't be any line to cross! That is because, above the critical temperature, it is impossible to condense a gas into a liquid just by increasing the pressure. All you get is a highly compressed gas. The particles have too much energy for the intermolecular attractions to hold them together as a liquid. The critical temperature obviously varies from substance to substance and depends on the strength of the attractions between the particles. The stronger the intermolecular attractions, the higher the critical temperature.
Note: This is now a good point for a quick comment about the use of the words "gas" and "vapour". To a large extent you just use the term which feels right. You don't usually talk about "ethanol gas", although you would say "ethanol vapour". Equally, you wouldn't talk about oxygen as being a vapour - you always call it a gas. There are various guide-lines that you can use if you want to. For example, if the substance is commonly a liquid at or around room temperature, you tend to call what comes away from it a vapour. A slightly wider use would be to call it a vapour if the substance is below its critical point, and a gas if it is above it. Certainly it would be unusual to call anything a vapour if it was above its critical point at room temperature - oxygen or nitrogen or hydrogen, for example. These would all be described as gases. This is absolutely NOT something that is at all worth getting worked up about!

Moving from solid to vapour: There's just one more line to look at on the phase diagram. This is the line in the bottom left-hand corner between the solid and vapour areas. That line represents solid-vapour equilibrium. If the conditions of temperature and pressure fell exactly on that line, there would be solid and vapour in equilibrium with each other - the solid would be subliming. (Sublimation is the change directly from solid to vapour or vice versa without going through the liquid phase.) Once again, you can cross that line by either increasing the temperature of the solid, or decreasing the pressure. The diagram shows the effect of increasing the temperature of a solid at a (probably very low) constant pressure. The pressure obviously has to be low enough that a liquid can't form - in other words, it has to happen below the point labelled as T.

You could read the sublimation temperature off the diagram. It will be the temperature at which the line is crossed.

The triple point

Point T on the diagram is called the triple point. If you think about the three lines which meet at that point, they represent conditions of:

solid-liquid equilibrium liquid-vapour equilibrium solid-vapour equilibrium

Where all three lines meet, you must have a unique combination of temperature and pressure where all three phases are in equilibrium together. That's why it is called a triple point. If you controlled the conditions of temperature and pressure in order to land on this point, you would see an equilibrium which involved the solid melting and subliming, and the liquid in contact with it boiling to produce a vapour - and all the reverse changes happening as well. If you held the temperature and pressure at those values, and kept the system closed so that nothing escaped, that's how it would stay. A strange set of affairs!

Normal melting and boiling points The normal melting and boiling points are those when the pressure is 1 atmosphere. These can be found from the phase diagram by drawing a line across at 1 atmosphere pressure.

AN INTRODUCTION TO KINETIC THEORY

This page takes a simple look at solids, liquids and gases, and changes of state such as melting and boiling, in terms of the behaviour of the particles present.

The arrangements of particles in solids, liquids and gases

A simple view of the arrangement of the particles in solids, liquids and gases looks like this:

Solids In the solid, the particles are touching, and the only motion allowed to them is vibration. The particles may be arranged regularly (in which case, the solid is crystalline), or at random (giving waxy solids like candles or some forms of polythene, for example). The particles are held in the solid by forces which depend on the actual substance - ionic bonds, covalent bonds, metallic bonds, hydrogen bonds or van der Waals attractions. Liquids In a liquid, the particles are mainly touching, but some gaps have appeared in the structure. These gaps allow the particles to move, and so the particles are arranged randomly.The forces that held the solid particles together are also present in the liquid (unless melting has broken up a substance consisting only of covalent bonds - a giant covalent structure). However, the particles in the liquid have enough energy to prevent the forces holding them in a fixed arrangement. For most liquids, the density of the liquid is slightly less than that of the solid, but there isn't much difference. That means that the particles in the liquid are almost as close together as they are in a solid. If you draw diagrams of liquids, make sure that most of the particles are touching, but at random, with a few gaps.
Note: Water is an exception to this. Ice floats on water, and so the liquid must be denser than the solid. You will find an explanation of this on a page about molecular structures. If you choose to follow this link, use the BACK button on your browser to come back here afterwards.

Gases In a gas, the particles are entirely free to move. At ordinary pressures, the distance between individual particles is of the order of ten times the diameter of the particles. At that distance, any attractions between the particles are fairly negligible at ordinary temperatures and pressures.

Changes of state
Melting and freezing If energy is supplied by heating a solid, the heat energy causes stronger vibrations until the particles eventually have enough energy to break away from the solid arrangement to form a liquid. The heat energy required to convert 1 mole of solid into a liquid at its melting point is called the enthalpy of fusion. When a liquid freezes, the reverse happens. At some temperature, the motion of the particles is slow enough for the forces of attraction to be able to hold the particles as a solid. As the new bonds are formed, heat energy is evolved. Boiling and condensing If more heat energy is supplied, the particles eventually move fast enough to break all the attractions between them, and the liquid boils. The heat energy required to convert 1 mole of liquid into a gas at its boiling point is called the enthalpy of vaporisation. If the gas is cooled, at some temperature the gas particles will slow down enough for the attractions to become effective enough to condense it back into a liquid. Again, as those forces are re-established, heat energy is released.
Remember: Breaking bonds needs energy; making bonds releases it.

The evaporation of a liquid The average energy of the particles in a liquid is governed by

the temperature. The higher the temperature, the higher the average energy. But within that average, some particles have energies higher than the average, and others have energies lower than the average. Some of the more energetic particles on the surface of the liquid can be moving fast enough to escape from the attractive forces holding the liquid together. They evaporate. The diagram shows a small region of a liquid near its surface.

Notice that evaporation only takes place on the surface of the liquid. That's quite different from boiling which happens when there is enough energy to disrupt the attractive forces throughout the liquid. That's why, if you look at boiling water, you see bubbles of gas being formed all the way through the liquid. If you look at water which is just evaporating in the sun, you don't see any bubbles. Water molecules are simply breaking away from the surface layer. Eventually, the water will all evaporate in this way. The energy which is lost as the particles evaporate is replaced from the surroundings. As the molecules in the water jostle with each other, new molecules will gain enough energy to escape from the surface.

The evaporation of a liquid in a closed container Now imagine what happens if the liquid is in a closed container. Common sense tells you that water in a sealed bottle doesn't seem to evaporate - or at least, it doesn't disappear over time. But there is constant evaporation from the surface. Particles

continue to break away from the surface of the liquid - but this time they are trapped in the space above the liquid.

As the gaseous particles bounce around, some of them will hit the surface of the liquid again, and be trapped there. There will rapidly be an equilibrium set up in which the number of particles leaving the surface is exactly balanced by the number rejoining it.

In this equilibrium, there will be a fixed number of the gaseous particles in the space above the liquid. When these particles hit the walls of the container, they exert a pressure. This pressure is called the saturated vapour pressure(also known as saturation vapour pressure) of the liquid.

Sublimation Solids can also lose particles from their surface to form a vapour, except that in this case we call the effect sublimation rather than evaporation. Sublimation is the direct change from solid to vapour (or vice versa) without going through the liquid stage. In most cases, at ordinary temperatures, the saturated vapour pressures of solids range from low to very, very, very low. The forces of attraction in many solids are too high to allow much loss of particles from the surface. However, there are some which do easily form vapours. For example, naphthalene (used in old-fashioned "moth balls" to deter clothes moths) has quite a strong smell. Molecules must be breaking away from the surface as a vapour, because otherwise you wouldn't be able to smell it. Another fairly common example (discussed in detail elsewhere on the site) is solid carbon dioxide - "dry ice". This never forms a liquid at atmospheric pressure and always converts directly from solid to vapour. That's why it is known as dry ice.

The phase diagram for water

There is only one difference between this and the phase diagram that we've looked at up to now. The solid-liquid equilibrium line (the melting point line) slopes backwards rather than forwards. In the case of water, the melting point gets lower at higher pressures. Why?

If you have this equilibrium and increase the pressure on it, according to Le Chatelier's Principle the equilibrium will move to reduce the pressure again. That means that it will move to the side with the smaller volume. Liquid water is produced. To make the liquid water freeze again at this higher pressure, you will have to reduce the temperature. Higher pressures mean lower melting (freezing) points. Now lets put some numbers on the diagram to show the exact positions of the critical point and triple point for water.

Notice that the triple point for water occurs at a very low pressure. Notice also that the critical temperature is 374C. It would be impossible to convert water from a gas to a liquid by compressing it above this temperature. The normal melting and boiling points of water are found in exactly the same way as we have already discussed - by seeing where the 1 atmosphere pressure line crosses the solid-liquid and then the liquidvapour equilibrium lines. Just one final example of using this diagram (because it appeals to me). Imagine lowering the pressure on liquid water along the line in the diagram below.

The phase diagram shows that the water would first freeze to form ice as it crossed into the solid area. When the pressure fell low enough, the ice would then sublime to give water vapour. In other words, the change is from liquid to solid to vapour. I find that satisfyingly bizarre!

The phase diagram for carbon dioxide

The only thing special about this phase diagram is the position of the triple point which is well above atmospheric pressure. It is impossible to get any liquid carbon dioxide at pressures less than 5.11

atmospheres. That means that at 1 atmosphere pressure, carbon dioxide will sublime at a temperature of -78C. This is the reason that solid carbon dioxide is often known as "dry ice". You can't get liquid carbon dioxide under normal conditions - only the solid or the vapour.

IDEAL GASES AND THE IDEAL GAS LAW

This page looks at the assumptions which are made in the Kinetic Theory about ideal gases, and takes an introductory look at the Ideal Gas Law: pV = nRT. This is intended only as an introduction suitable for chemistry students at about UK A level standard (for 16 - 18 year olds), and so there is no attempt to derive the ideal gas law using physics-style calculations.

Kinetic Theory assumptions about ideal gases

There is no such thing as an ideal gas, of course, but many gases behave approximately as if they were ideal at ordinary working temperatures and pressures. Real gases are dealt with in more detail on another page. The assumptions are:

Gases are made up of molecules which are in constant random motion in straight lines. The molecules behave as rigid spheres. Pressure is due to collisions between the molecules and the walls of the container. All collisions, both between the molecules themselves, and between the molecules and the walls of the container, are perfectly elastic. (That means that there is no loss of kinetic energy during the collision.) The temperature of the gas is proportional to the average kinetic energy of the molecules.

And then two absolutely key assumptions, because these are the

two most important ways in which real gases differ from ideal gases:

There are no (or entirely negligible) intermolecular forces between the gas molecules. The volume occupied by the molecules themselves is entirely negligible relative to the volume of the container.

The Ideal Gas Equation

The ideal gas equation is:

pV = nRT
On the whole, this is an easy equation to remember and use. The problems lie almost entirely in the units. I am assuming below that you are working in strict SI units (as you will be if you are doing a UK-based exam, for example).

Exploring the various terms Pressure, p Pressure is measured in pascals, Pa - sometimes expressed as newtons per square metre, N m-2. These mean exactly the same thing. Be careful if you are given pressures in kPa (kilopascals). For example, 150 kPa is 150,000 Pa. You must make that conversion before you use the ideal gas equation. Should you want to convert from other pressure measurements:

1 atmosphere = 101,325 Pa 1 bar = 100 kPa = 100,000 Pa

Volume, V This is the most likely place for you to go wrong when you use this

equation. That's because the SI unit of volume is the cubic metre, m3 - not cm3 or dm3. 1 m3 = 1000 dm3 = 1,000,000 cm3 So if you are inserting values of volume into the equation, you first have to convert them into cubic metres. You would have to divide a volume in dm3 by 1000, or in cm3 by a million. Similarly, if you are working out a volume using the equation, remember to covert the answer in cubic metres into dm3 or cm3 if you need to - this time by multiplying by a 1000 or a million. If you get this wrong, you are going to end up with a silly answer, out by a factor of a thousand or a million. So it is usually fairly obvious if you have done something wrong, and you can check back again.

Number of moles, n This is easy, of course - it is just a number. You already know that you work it out by dividing the mass in grams by the mass of one mole in grams. You will most often use the ideal gas equation by first making the substitution to give:

I don't recommend that you remember the ideal gas equation in this form, but you must be confident that you can convert it into this form.

The gas constant, R A value for R will be given you if you need it, or you can look it up in a data source. The SI value for R is 8.31441 J K-1 mol-1.

Note: You may come across other values for this with different units. A 3 -1 -1 commonly used one in the past was 82.053 cm atm K mol . The units tell you that the volume would be in cubic centimetres and the pressure in atmospheres. Unfortunately the units in the SI version aren't so obviously helpful.

The temperature, T The temperature has to be in kelvin. Don't forget to add 273 if you are given a temperature in degrees Celsius.

Using the ideal gas equation Calculations using the ideal gas equation are included in my calculations book (see the link at the very bottom of the page), and I can't repeat them here. There are, however, a couple of calculations that I haven't done in the book which give a reasonable idea of how the ideal gas equation works. The molar volume at stp If you have done simple calculations from equations, you have probably used the molar volume of a gas. 1 mole of any gas occupies 22.4 dm3 at stp (standard temperature and pressure, taken as 0C and 1 atmosphere pressure). You may also have used a value of 24.0 dm3 at room temperature and pressure (taken as about 20C and 1 atmosphere). These figures are actually only true for an ideal gas, and we'll have a look at where they come from.

We can use the ideal gas equation to calculate the volume of 1 mole of an ideal gas at 0C and 1 atmosphere pressure. First, we have to get the units right. 0C is 273 K. T = 273 K

1 atmosphere = 101325 Pa. p = 101325 Pa We know that n = 1, because we are trying to calculate the volume of 1 mole of gas. And, finally, R = 8.31441 J K-1 mol-1. Slotting all of this into the ideal gas equation and then rearranging it gives:

And finally, because we are interested in the volume in cubic decimetres, you have to remember to multiply this by 1000 to convert from cubic metres into cubic decimetres. The molar volume of an ideal gas is therefore 22.4 dm 3 at stp. And, of course, you could redo this calculation to find the volume of 1 mole of an ideal gas at room temperature and pressure - or any other temperature and pressure.

Finding the relative formula mass of a gas from its density This is about as tricky as it gets using the ideal gas equation. The density of ethane is 1.264 g dm-3 at 20C and 1 atmosphere. Calculate the relative formula mass of ethane. The density value means that 1 dm3 of ethane weighs 1.264 g. Again, before we do anything else, get the awkward units sorted out. A pressure of 1 atmosphere is 101325 Pa. The volume of 1 dm3 has to be converted to cubic metres, by dividing by 1000. We have a volume of 0.001 m3.

The temperature is 293 K. Now put all the numbers into the form of the ideal gas equation which lets you work with masses, and rearrange it to work out the mass of 1 mole.

The mass of 1 mole of anything is simply the relative formula mass in grams. So the relative formula mass of ethane is 30.4, to 3 sig figs.

Now, if you add up the relative formula mass of ethane, C2H6 using accurate values of relative atomic masses, you get an answer of 30.07 to 4 significant figures. Which is different from our answer so what's wrong? There are two possibilities.

The density value I have used may not be correct. I did the sum again using a slightly different value quoted at a different temperature from another source. This time I got an answer of 30.3. So the density values may not be entirely accurate, but they are both giving much the same sort of answer. Ethane isn't an ideal gas. Well, of course it isn't an ideal gas - there's no such thing! However, assuming that the density values are close to correct, the error is within 1% of what you would expect. So although ethane isn't exactly behaving like an ideal gas, it isn't far off.

If you need to know about real gases, now is a good time to read about them.

REAL GASES
This page looks at how and why real gases differ from ideal gases, and takes a brief look at the van der Waals equation. If you have come straight to this page via a search engine, it might be a good idea to read the page about ideal gases first.

Real gases v ideal gases

Real gases and the molar volume I want to use this to illustrate the slight differences between the numerical properties of real and ideal gases at normal temperatures and pressures. If you have read the page about ideal gases, you will remember that we used the ideal gas equation to work out a value for the molar volume of an ideal gas at stp (standard temperature and pressure). If you know the density of a gas at a particular temperature and pressure, it is very easy to work out its molar volume. For example, at 273 K and 1 atmosphere pressure, the density of helium is 0.1785 g dm-3. That means that 0.1785 g of helium occupies 1 dm3 at stp. It is a fairly simple sum to work out what 1 mole of helium, He, would occupy. 1 mole of He weighs 4 g, and would occupy 4 / 0.1785 dm 3 = 22.4 dm3. That's the same (at least to 3 significant figures) as the ideal gas value, suggesting that helium behaves as an ideal gas under these conditions.
Note: If your maths isn't very good, and you can't understand why I divided 4 by 0.1785 to get the answer, think of it like this:

Replace the awkward value of 0.1785 by something simple, like 2. If 2 g of 3 He occupied 1 dm , what would 4 g occupy? It is obviously twice as much, 3 2 dm - but how did you get at that mathematically? You found out how many times 2 would go into 4 - in other words, you divided 4 by 2. Do exactly the same with the more complicated number.

If you do this for a random sample of other gases, you get these values (to 3 significant figures) for the molar volume at stp (273 K and 1 atmosphere pressure). density (g dm-3) He N2 O2 CH4 CO2 C2H4 NH3 SO2 0.1785 1.2506 1.4290 0.717 1.977 1.260 0.769 2.926 molar volume at stp 22.4 22.4 22.4 22.3 22.3 22.2 22.1 21.9

So although for simple calculation purposes we use the value 22.4 dm3 for all gases, you can see that it isn't exactly true. Even at ordinary temperatures and pressures, real gases can deviate slightly from the ideal value. The effect is much greater under more extreme conditions, as we will see next.

Compression factors For an ideal gas, pV = nRT. If pV and nRT are the same, and you divide one by the other, then the answer will, of course, be 1. For real gases, pV doesn't equal nRT, and so the value will be something different. The term pV / nRT is called the compression factor. The graphs below show how this varies for nitrogen as you change the temperature and the pressure.

Note: These diagrams were generated using data produced from Patrick Barrie's program, and converted into graphs using Excel. The figures are derived from the van der Waals equation - not because it is the best source, but because it is the only one you are likely to come across at this level, and I shall mention it below. If you wanted to play around with some of the other equations, you would find that the results produce similarly shaped curves, but the absolute sizes of the deviations would vary.

If nitrogen was an ideal gas under all conditions of temperature and pressure, every one of these curves would be a horizontal

straight line showing a compression factor of 1. That's obviously not true!

Things to notice

At low pressures of about 1 bar (100 kPa - just a bit less than 1 atmosphere), the compression factor is close to 1. Nitrogen approximates to ideal behaviour at ordinary pressures. The non-ideal behaviour gets worse at lower temperatures. For temperatures of 300 or 400 K, the compression factor is close to 1 over quite a large pressure range. The nitrogen becomes more ideal over a greater pressure range as the temperature rises. The non-ideal behaviour gets worse at higher pressures. There must be at least two different effects causing these deviations. There must be at least one effect causing the pV / nRT ratio to be too low, especially at low temperatures. And there must be at least one effect causing it to get too high as pressure increases. We will explore those effects in a while.

Other gases Is the same behaviour shown by other gases? The next diagram shows how the compression factors vary with pressure for a variety of gases at a fixed temperature.

If you were to redo the set of original nitrogen graphs (at varying temperatures) for any of these other gases, you would find that each of them will produce a set of curves similar to the nitrogen ones. What varies is the temperature at which the different graph shapes occur. For example, if you look at the carbon dioxide graph at 273 K, it looks similar to the nitrogen one at 100 K from the first set of curves, although it doesn't increase so steeply at higher pressures. It is easy to say that gases become less ideal at low temperatures, but what counts as a low temperature varies from gas to gas. The closer you get to to the temperature at which the gas would turn into a liquid (or, in the case of carbon dioxide, a solid), the more non-ideal the gas becomes.

What causes non-ideal behaviour? In the compression factor expression, pV / nRT, everything on the bottom of the expression is either known or can be

measured accurately. But that's not true of pressure and volume. In the assumptions we make about ideal gases, there are two statements which say things which can't be true of a real gas, and these have an effect on both pressure and volume.

The volume problem The kinetic theory assumes that, for an ideal gas, the volume taken up by the molecules themselves is entirely negligible compared with the volume of the container. For a real gas, that assumption isn't true. The molecules themselves do take up a proportion of the space in the container. The space in the container available for things to move around in is less than the measured volume of the container.

This problem gets worse the more the gas is compressed. If the pressure is low, the volume taken up by the actual molecules isinsignificant compared with the total volume of the container. But as the gas gets more compressed, the proportion of the total volume that the molecules themselves take up gets higher and higher. You could imagine compressing it so much that the molecules were actually all touching each other. At that point the

volume available for them to move around in is zero! Suppose at some high pressure, you measure the volume of the container as, say, 1000 cm3, but suppose the molecules themselves occupy as much as 100 cm3 of it. The ideal gas equation was worked out by doing calculations based on Kinetic Theory assumptions. The V in pV is assumed to be the volume which the molecules are free to move around in - but in this case, it would only be 900 cm3, not 1000 cm3. If you worked out the compression factor, pV / nRT, by putting the total volume of the container into the formula, the answer is bound to be higher than it ought to be. It doesn't allow for the volume taken up by the molecules themselves. Let's just repeat one of the earlier diagrams so that you can see this effect in operation.

For an ideal gas, the compression factor would be 1 over the whole pressure range. For a real gas like nitrogen, notice how the compression factor tends to increase with pressure.

The value of the compression factor is too high at high pressures for a real gas. The reason for that is that the measured volume that you put into the expression is too high because you aren't allowing for the volume taken up by the molecules. That error gets relatively worse the more compressed the gas becomes.

The pressure problem Another key assumption of the Kinetic Theory for ideal gases is that there are no intermolecular forces between the molecules. That is wrong for every real gas. If there weren't any intermolecular forces then it would be impossible to condense the gas as a liquid. Even helium, with the weakest of all intermolecular forces, can be turned to a liquid if the temperature is low enough. So what effect do intermolecular forces have? For a gas molecule in the middle of the gas, there is no net effect. It will be attracted to some extent to all the other molecules around it, but, on average, those attractions will cancel each other out. Attractions from behind a molecule, tending to slow it down, will be cancelled out by attractions from in front of it, tending to speed it up.

Despite all the intermolecular forces it is experiencing, the molecule picked out in green will just continue to move in the

same direction at the same speed. That's different if the molecule is just about to hit the wall of the container.

Now there aren't any gas molecules in front of it, and the net pull is backwards into the body of the gas. The molecule will slow down just before it hits the wall. If it slows down, it will hit the wall less hard, and so exert less pressure. The overall effect of this is to make the measured pressure less than it would be if the gas was ideal. That means that if you put the measured pressure into the expression pV / nRT, the value of the compression factor will be less than it would be if the gas was ideal. This is why, under some conditions, graphs of compression factors drop below the ideal value of 1. Look yet again at the nitrogen curves:

This effect is most important at low temperatures. Why is that? At lower temperatures, the molecules are moving more slowly on average. Any pull they feel back into the gas will have relatively more effect on a slow moving particle than a faster one. At higher temperatures, where the molecules are moving a lot faster, any small pull back into the body of the gas is hardly going to be noticeable. At high temperatures, the effect of intermolecular forces is indeed negligible. And there is one final effect concerning intermolecular forces which is slightly more hidden away. As pressure increases, the molecules are forced more closely together. If they are closer, the intermolecular forces will become more important. So, as pressure increases, you would expect more lowering of the compression factor relative to the ideal case. The molecules which slow down the one just about to hit the wall will be closer to it, and so more effective.

Is that what happens? Yes, up to a point. Look again at the nitrogen curve at 100 K. As the pressure increases, at first the value of the compression factor falls. But it soon starts to rise again. Why? Because at this point, the effect of the size of the molecules starts to become more important - and as the pressure is increased even more, this other effect becomes dominant.

Which is the most ideal gas? You are looking for a gas with the smallest possible molecules, and the lowest possible intermolecular forces. That is helium. A helium molecule consists of a single small atom, and the van der Waals dispersion forces are as low as it is possible for them to be.
Note: If you aren't happy about the factors which affect the size of van der Waals dispersion forces, follow this link. Use the BACK button to come back to this page afterwards.

Other gas laws - Boyle's Law and Charles' Law

This page takes a simple look at Boyle's Law and Charles' Law, and is suitable for 16 - 18 year old chemistry students doing a course the equivalent of UK A level. The aim is simply to show how these laws relate to Kinetic Theory (in a non-mathematical way), and to the ideal gas equation. Before you waste time on this, be sure that you actually need to know about it. Certainly in the UK exam system, it is pretty rare for chemistry students to be expected to know either of these laws these days. They have been almost completely

replaced by the ideal gas equation.

Boyle's Law
Statement For a fixed mass of gas at constant temperature, the volume is inversely proportional to the pressure.
That means that, for example, if you double the pressure, you will halve the volume. If you increase the pressure 10 times, the volume will decrease 10 times.

You can express this mathematically as pV = constant

Is this consistent with pV = nRT ?

You have a fixed mass of gas, so n (the number of moles) is constant. R is always constant - it is called the gas constant. Boyle's Law demands that temperature is constant as well.

That means that everything on the right-hand side of pV = nRT is constant, and so pV is constant - which is what we have just said is a result of Boyle's Law.

Simple Kinetic Theory explanation I'm not going to try to prove the relationship between pressure and volume mathematically - I'm just showing that it is reasonable. This is easiest to see if you think about the effect of decreasing the volume of a fixed mass of gas at constant

temperature. Pressure is caused by gas molecules hitting the walls of the container. With a smaller volume, the gas molecules will hit the walls more frequently, and so the pressure increases. You might argue that this isn't actually what Boyle's Law says - it wants you to increase the pressure first and see what effect that has on the volume. But, in fact, it amounts to the same thing. If you want to increase the pressure of a fixed mass of gas without changing the temperature, the only way you can do it is to squeeze it into a smaller volume. That causes the molecules to hit the walls more often, and so the pressure increases.

Charles' Law
Statement For a fixed mass of gas at constant pressure, the volume is directly proportional to the kelvin temperature. That means, for example, that if you double the kelvin temperature from, say to 300 K to 600 K, at constant pressure, the volume of a fixed mass of the gas will double as well. You can express this mathematically as V = constant x T

Is this consistent with pV = nRT ?

You have a fixed mass of gas, so n (the number of moles) is constant.

R is the gas constant. Charles' Law demands that pressure is constant as well.

If you rearrange the pV = nRT equation by dividing both sides by p, you will get V = nR/p x T But everything in the nR/p part of this is constant. That means that V = constant x T, which is Charles' Law.

Simple Kinetic Theory explanation Again, I'm not trying to prove the relationship between pressure and volume mathematically - just that it is reasonable. Suppose you have a fixed mass of gas in a container with a moveable barrier - something like a gas syringe, for example. The barrier can move without any sort of resistance.

The barrier will settle so that the pressure inside and outside is identical. Now suppose you heat the gas, but not the air outside. The gas molecules will now be moving faster, and so will hit

the barrier more frequently, and harder. Meanwhile, the air molecules on the outside are hitting it exactly as before. Obviously, the barrier will be forced to the right, and the volume of the gas will increase. That will go on until the pressure inside and outside is the same. In other words, the pressure of the gas will be back to the same as the air again. So we have fulfilled what Charles' Law says. We have a fixed mass of gas (nothing has been added, and nothing has escaped). The pressure is the same before and after (in each case, the same as the external air pressure). And the volume increases when you increase the temperature of the gas. What we haven't shown, of course, is that there is a "directly proportional" relationship. It can be done, but it needs some maths.