Indiana U, Physics Dept (H.O.

Meyer 7/06)

Lab #23: Real Gases

Goal: observe the difference between the behavior of a real gas and the ideal gas law.
Study of the liquid-gas interface, the van-der-Waals equation of state, and the Clausius-
Clapeyron equation, measure the latent heat of vaporization.
Equipment: critical point apparatus (CENCO 32019), cylinders with sulfur hexafluoride
(SF6) and ethane (CH3CH3).

1 Physics:
The state of a given amount of gas is described by the pressure p, the temperature T and
the volume V that it occupies. The three variables are related by the state equation. The
amount of a gas may be measured by its mass, but we will use the number n of mols it
contains. One mol is the amount of material that
100
contains NA = 6.021023 atoms or molecules (NA
90
critical point is called Avogadros number).
80
The S.I. units for pressure and temperature are
70 Pa=N/m2 and K (Kelvin), respectively. The
p gas
60 volume occupied by 1 mol is called the mol-
105 Pa 50 volume and defined by VM V/n ; the unit of VM
40 is m3/mol.
30 For an ideal gas, the state equation is pVM=RT,
20 where R = 8.3143 J/K/mol is the gas constant.
10 gas and liquid This relation follows from the assumption that
0
molecules are non-interacting, point-like masses
0.1 1
that collide elastically with the walls of the
log VM (arb. units) container.
In reality, molecules are not point-like. If b is
Fig 1: Isothermes (curves of p vs VM at
constant temperature) calculated from the volume occupied by all molecules in a mol,
the van-der-Waals equation the mol-volume should be replaced by VM b.
Also, real molecules attract each other (cohesive
forces). This leads to an internal pressure, because molecules on the surface have
neighbors only on one side. This pressure is proportional to the square of the number
density of molecules (can you see why?), and thus to VM2 . This leads to a more realistic
state equation, proposed by Johannes D. van der Waals in 1873:

(VM b ) = RT .
a
p + 2 (1)
VM

Here, a and b, called van-der-Waals constants, are material constants that, for a given
gas, are determined empirically (see table 1). When T = Tk is held constant, the resulting
function p(VM) is called an isotherme. From eq. 1 follows

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 RTk a
p (VM ) = 2 . (2)
VM b VM

Fig.1 shows some isothermes for ethane. The lowest curve is for Tk=285 K. The
temperature increase from one curve to the next is 10 K. At the lower temperatures, eq.2
exhibits a wiggle. In this region, the isotherme is actually constant (as shown for the
lowest temperature in fig.1 by a dashed line), with the lobes above and below having
equal areas. In this region, the pressure depends on the temperature, but not on the
volume, and gas and liquid co-exist. The constant pressure of this mixture is the vapor
pressure p*(T). The highest temperature Tc and pressure pc for which the gas can just be
liquefied mark the critical point. From the conditions dp/dVM = 0 and d2p/dVM 2= 0, the
critical temperature and pressure can be calculated from eq. 2 as

8a a
Tc = and pc = . (3)
27 Rb 27b 2

As already pointed out, if liquid and gas coexist, the pressure of the system is the vapor
pressure p*(T). In 1834, Benoit Clapeyron (who, incidentally, also engineered the first
stretch of French railroad) formulated the following equation (later proven by Clausius):

dp* L
= . (4)
dT T (VMG VML )
.
Here, p* is the vapor pressure (in Pa), and VMG and VML are the mol-volumes (in m3/mol)
of the gas or the liquid (all three taken at the same temperature T (in K). The latent heat
of vaporization, L, is the energy it takes to vaporize 1 mol of liquid at constant
temperature. The derivation of this equation makes use of a Carnot process and the 2nd
law of thermodynamics (see, e.g., [FEY66]). We neglect VML since it is much smaller
than VMG, and express the latter by the ideal gas equation pVMG=R T. Then eq.1 becomes

1 dp d (ln( p)) L
= = . (5)
p dT dT RT 2

Integrating eq. 5 over T yields

L
ln( p) = + const. . (6)
RT

You will use eq. 6 to deduce the latent heat of vaporization L from a measurement of the
vapor pressure as a function of temperature.

2 Experiment
Chose one of the two gases and fill the apparatus as described below. Measure some
isothermes for several temperatures below and above the critical temperature, i.e., in the

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range from 0 C to 50 C (note that T(K) = T(C) + 273.2). Enter the data in a spreadsheet
and plot. Compare your measurement with eq. 2. Note, that in order to get the mol-
volume you have to convert your volume measurements (in cm3) to m3 and then divide
by the number n of moles in the system (typically, n ~ 1/250). Since you dont really
know n, you may adjust it to get the best fit to the data.
In a second experiment, determine the vapor pressure p* as a function of temperature.
Start at low temperature (ice water) and use the heater to change the temperature. Make
sure you always see some liquid in the capillary. Do this for both available gases
(CH3CH3 and SF6).
Deduce the latent heat of vaporization L, using the Clausius-Clapeyron relation, eq. 6.
Compare the experimental results with the values in table 1. Estimate the uncertainty of
your value for L. Discuss sources for possible systematic errors.

3 Gas properties

ethane sulfur hexafluoride units

chemical formula CH3CH3 SF6 --
Molecular weight 30.07 146.05 g/mol
critical temperature, Tc 305.4 (32.2) 318.7 (45.5) K (C)
critical pressure, pc 48.839105 37.59105 Pa
Boiling point @ 105 Pa 184.5 209.3 K
heat of vaporization, L 1.47105 2.37105 J/mol
Van der Waals constant a 0.557 0.788 Pa m6/mol2
Van der Waals constant b 6.5010-5 8.8110-5 m3/mol
Table 1: some properties of CH3CH3 and SF6 from ref. [AIRLI]. The van-der-Waals constants
are calculated from the critical temperature and pressure, using eq. 3; these values differ slightly
from other sources, such as ref. [REI87].

4 References:
[AIRLI] http://encyclopedia.airliquide.com/encyclopedia.asp (a very useful collection of the
properties of a large number of gases)
[FEY66] Feynman Lectures on Physics, Addison-Wesley, Reading, MA, 1966, vol.1, p.45-6.
[LAN72] Lange's Handbook of Chemistry, 13th edition, ed. J.A. Dean, McGraw-Hill, New
York, 1972. [QD65.L36]
[REI87] R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and Liquids, 4th
ed., Mc Graw-Hill, New York, 1987

5 Instructions for filling the apparatus with gas (refer to fig.2)

NEVER operate without water around the capillary!
MANIPULATE VALVES ONLY WHEN INSTRUCTOR IS PRESENT!
first thing: LOWER PISTON ALL THE WAY (counterclockwise, seen from above)

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5.1 Setting up for a given gas (say, ethane)
1. Lower piston all the way
2. Set gas switch valve N to ethane, close E1 and open E2
3. Open cylinder valve E4, adjust regulator E3 such that the gauge pEL shows 160 psi
4. Close vent valve, open pump valve, turn on pump
5. Close E2, open V, G, and E1. You are now pumping the whole system. The dial of pV
should go all the way counterclockwise (to 30 inches Hg). Do this for a few minutes.
6. Close E1 and V, open E2
7. Very carefully open E1 until pG reads 1105 Pa (one division, only!), close E1 and E2
8. open E1, then very carefully open V (pV should never go above 0). Pump for a few
minutes.
9. Repeat 6 - 8 once or twice (the system is being purged, leaving you with pure ethane)
10. Close V, close E1 and open E2
11. Carefully open E1 and Slowly bring up the system pressure until pG reads 10105 Pa
12. Close V and G. Ready. Do not touch any valves from now on.

5.2 Shut down

13. Lower piston all the way
14. Close E1 through E4
15. Turn pump off, open vent valve, close pump valve
16. Carefully open V (pV should never go above 0) until pG reads zero.
17. turn off water circulator. Done.

water out

pEL pEH
E4
E1
pV to pump
water in
ethane
E3 E2 N
G V
S4 vent valve
S1
pG
gas
S3 S2
sulfur Hg
hex near
wall
hose connections:
always pV < 0 !

Fig. 2 piston wheel

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