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0651 - Physical Chemistry I

**Joule-Thomson Expansion
**

Professor Paul J. Gans September, 1992 Minor Revision: October, 1993

1. Introduction We are at the point where we can make our ﬁrst analysis of an actual experiment.1 The experiment will be explained ﬁrst. Then thermodynamics will be used to show that the experiment is isoenthalpic (meaning a constant enthalpy process). With this result, we can then explain the main result of the experiment in terms of the properties of the gases involved.

2. The Joule-Thomson Experiment The apparatus itself is quite simple. Imagine a tube with a porous plate separating it into two parts. The porous plate will allow a gas to go through it, but only slowly. It acts as a throttle. On each side of the plate there is a piston that ﬁts the tube tightly. Each piston can (in principle) be pushed up against the porous plate. The tube itself is insulated so that no heat can enter or leave the tube.2 The experiment is also quite simple. Imagine that some gas is placed between the porous plate and the piston on the left side of the tube. This is side 1. On the other side the piston is ﬂush against the porous plate. This is side 2. The initial volume of gas on side 1 is V 1 . The pressure is p1 and the temperature T 1 . Now during the experiment gas is pushed through the porous plate by pushing on the piston on the left side. At the same time the piston on the right side is pulled in such a way that the pressure on the right side is always p2 .3 At the end of the experiment all of the gas has been pushed through the porous plate. The volume on side 1 is zero. The ﬁnal volume on the right side (side 2) is V 2 , the pressure is p2 and the temperature T 2 . The curious result of this experiment is that careful measurement shows that T 2 is not equal to T 1 . Under some conditions it is higher, under others it is lower. The problem is to decide how to analyse this.

1 2

Although we do need to drag in one result that will not be obtained until later in the course. There is a drawing of the apparatus on page 69 of Atkins. 3 Of course, p2 must be less than p1 .

the total change in U is just the work. The work done on the right side is: W 2 = − p2 (V 2 − 0). or ∆ U = U 2 − U 1 = p1V 1 = p2V 2 U 2 + p2V 2 = U 1 + p1V 1 so that: H2 = H1 and the process is isoenthalpic. The total work done is then: w = p1V 1 − p2V 2 Since the process is adiabatic. taking into account that the process is isoenthalpic: µ JT = ∂T ∂ p H (6) All that we’ve done so far is reduced the experiment to mathematics.-2- 3. the ﬁnal temperature is lower than the initial temperature. In fact it is found that there is a certain temperature called the inversion temperature such that if the initial temperature T 1 is above the inversion temperature. experimentally. The Joule-Thomson Coefﬁcient What is measured experimentally is µ JT = lim ∆ p→0 T2 − T1 p2 − p1 (5) which becomes. The experimental result is that µ JT is sometimes positive and sometimes negative. the ﬁnal temperature is higher than the initial temperature. To understand this we need to relate µ JT to quantities that are experimentally measureable. to depend on the pressure. . (4) (2) (1) (3) 4.4 4 The ability to do this is one of the main points of thermodynamics. If the initial temperature is below the inversion temperature. The work done on the left side is: w 1 = − p1 (0 − V 1 ). It ends with volume V 1 = 0 and volume V 2 = V 2 . The inversion temperature is found. Initial Analysis The process starts with volume V 1 = V 1 and volume V 2 = 0.

so dH = 0. Perhaps the best way to think of it is to think of dp (or whatever) as actually representing a very small. This gives: 0 = ∂H ∂H dT + dp ∂T p ∂ p T (8) Now I divide through by dp at constant H to get:5 ∂H ∂T ∂H + ∂T p ∂ p H ∂ p T Note the subscript H at the appropriate point in eq. 5 This is a touchy point. right? . so: (∂T /∂ p) H = − (∂H/∂ p)T Cp (11) but we can’t make it any simpler. We need to express (∂H/∂ p)T in terms that can be measured. but ﬁnite change in pressure. We know that (∂H/∂T ) p is the heat capacity C p . (9). Lastly. But this procedure of dividing by dx (where here x = p) in thermodyanmic equations can be justiﬁed mathematically and we do it all the time. Then at the very end let all inﬁnitesimal ratios go to their limits. let us solve for (∂T /∂ p) H to get: (∂T /∂ p) H = − (∂H/∂ p)T (∂H/∂T ) p (9) (10) This result simpliﬁes a bit right away. this can be done. A result that will be proven later6 ∂H ∂V = V −T ∂ p T ∂T p which.-3- To do this we can start with the total differential of H assuming that T and p are the independent variables: dH = ∂H ∂H dT + dp ∂T p ∂ p T (7) Now our process is isoenthalpic. Pure mathematicians would perhaps object to treating an inﬁnitesimal as if it were a ﬁnite quantity. 6 They always say this. Indeed. (11) gives: µ JT = (12) T (∂V /∂T ) p − V Cp (13) a neat equation in which all of the quantities are measureable. but it requires one slight bit of magic. when used in eq.

With this available we can plug into eq. Now since Z = pV /RT . Since we can’t solve van der Waals equation for V explicitly7 we have to use an approximation. The Joule-Thomson Coefﬁcient for Model Gases If we knew the equation of state for a gas. From eq.-4- So we come to the end of the theory with a formula but no explanation. A gas obeying van der Waals equation will prove more interesting.10a in Atkins. And how do ideal gases differ from real gases? They have no interactions at all. for an ideal gas (∂V /∂T ) p = V /T . solve it for V . RT + b− + p RT (16) What we want is (∂V /∂T ) p .... A convenient one is eq 1. (13) and calculate µ JT . No attractiions and no repulsions. ∂T p p RT 2 Now this has to be multiplied by T . 5. So we conclude that the Joule-Thomson effect depends on the interactions between gas molecules. and then differentiate it to get (∂V /∂T ) p . But they have told us something. It all seems to depend on how the volume of the gas changes with temperature and on the heat capacity. This gives:8 It’s a cubic in V ... we can solve eq. For instance. Looking at some of these may tell us something.. There is no Joule-Thomson effect for an ideal gas at all. But that’s the only way in which they differ. so µ JT = 0 ideal gas (14) Ideal gases are boring. Just read it and learn where the Joule-Thomson effect comes from. we can look at model gases. RT RT (15) which is the ﬁrst two terms of the virial equation approximation for a van der Waals gas. (16) we get: R a ∂V = + + . gases for which we know the equation of state. we could calculate the Joule-Thomson coefﬁcient. 8 7 (17) . Nobody expects you to memorize this stuff. This can be written Z = 1+ 1 a b− p + . (15) for V to get: V = a . How can we learn anything more? Well. We want to take this expression. that is. remember? I’m showing all the steps.

(16) we get (after some cancellations: 2a . Let’s see what happens to the Joule-Thomson coefﬁcient when the temperature gets very low. First. If we’d carried one more term in eq.. Cp µ JT (20) OK. the Joule-Thomson coefﬁcient for a gas obeying van der Waals equation is: 2a −b = RT + . But also note that the resulting expression only contains the van der Waals a. ﬁnally. This result is quite simple since all terms containing a T in the denominator go to zero.-5RT a ∂V = + + . . as T goes to 0. Lastly. The result is: µ JT = − b Cp (very high temperature) (22) and that’s very interesting. ∂V −V = − b− + ∂T p RT T (19) and so. leaving only b. what is the limit when T goes to 0? Well. µ JT = 2a + . (20). And the b term can be neglected at very low temperatures. So the term involving 2a/RT gets much larger than b. you can’t tell much from this equation all by itself except that it certainly looks messy. all terms with T in the denominator get very large. (20) does not agree with experiment. Eq.. it agrees with experiment since it is negative.. . This agrees with experiment.. it should be pointed out that there is one way in which eq. The problem is that this inversion temperature is not a function of the pressure. A positive JouleThomson coefﬁcient means cooling. That is.. . RTC p (very low temperature) (21) which is clearly positive since every term in it is positive. (20) predicts an inversion temperature of: T inversion = 2a bR (van der Waals gas) (23) which is gotten by setting µ JT equal to zero in eq. ∂T p p RT T (18) And now subtracting V as given in eq. All of the terms involving b have gone away at low temperature. (15) we would have had a (much more messy) result that is a function of pressure. Experimentally the inversion temperature is a function of the pressure. Second. We can also look at what happens when T gets very large. meaning heating.. notice that all of the terms involving van der Waals a have now vanished. But there is a way theoreticians handle things like this: they look at the extremes.

the average distance between molecules is increased.10 So the JouleThomson effect can be explained this way: At low temperatures the intermolecular attraction is the most important interaction. it must have an inversion temperature. with the internal energy reduced.9 At high temperatures the repulsive forces predominate. Conclusions So what can we conclude? Several things. Since they attract each other this takes energy. a accounts for the attractiongs between molecules in van der Waals equation. This means that the molecules are pulled apart. the gas cools. at high enough temperatures the predominant interaction is repulsion. It wants to expand. On the other hand. This increases the internal energy of the gas. When it does expand energy is obtained as the molecules separate. The ones associated with b. And since the process is adiabatic. . The gas wants to separate. the effect seems to depend (as we expected) on the attractive and repulsive forces acting between molecules. since µ JT is positive at low temperatures and negative at high temperatures. 9 10 Remember. And the gas heats. When the cold gas is expanded. So. Second.-6- 6. the only source of energy is the internal energy of the gas itself. At low temperatures the attractive forces predominate. First.

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