Fisika Termal – PAP3109

The van der Waals Gas

Jurusan Fisika, Fakultas MIPA1– Universitas Andalas

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 The van der Waals Gas
The simplest model of a liquid-gas phase transition -
the van der Waals model of “real” gases – grasps
some essential features of this phase transformation.
(Note that there is no such transformation in the
ideal gas model).

Nobel 1910This will be our attempt to take intermolecular

interactions into account.

Outline
• Thermodynamics of vdW gas
• critical point
• liquid-gas phase transition

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 van der Waals gas = ideal gas + interaction
Lennard-Jones The main reason for the transformation of gas
   
12 6
short-distance
U r       into liquid at decreasing T and (or) increasing
repulsion r r P - interaction between the molecules.
4

U(r) 3

2
Two ingredients of the model:
Energy

0 1. the weak long-range attraction:

N 2a
-1
N
-2

-3
U   N   a  
1.5 2.0 2.5
r
distance
3.0 3.5 4.0 V V
r= N 2a N 2a
U vdW  U IG   Peff  P  2
long-distance V V
attraction the constant a is a measure of the long-range
attraction
2. the strong short-range repulsion: the molecules are rigid: P   as soon as the
molecules “touch” each other.
the constant b (~ 43/3) is a measure of the short-range
Veff  V  Nb repulsion, the “excluded volume” per particle

 N 2a  N 2a
 P  2 V  Nb   Nk BT
The vdW equation Nk BT
P  2
of state
 V  V  Nb  V
Fisika
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 The van der Waals Parameters
b – roughly the volume of a molecule, (3.5·10-29 – 1.7 ·10-28) m3 ~(few Å)3
a – varies a lot [~ (8·10-51 – 3 ·10-48) J · m3] depending on the intermolecular
interactions (strongest – between polar molecules, weakest – for inert gases).
Substance a’ b’ Pc Tc
(J. m3/mol2) (x10-5 m3/mol) (MPa) (K)
Air .1358 3.64 3.77 133 K
Carbon Dioxide (CO2) .3643 4.27
N
7.39 A
2
a 
304.2 K
a' N Ab  b'
Nitrogen (N2) .1361 3.85 3.39 126.2 K  J  m3 
a' 
 J  m 3
  mol2 
Hydrogen (H2) .0247 2.65 1.30
a  33.2 K
2 
 2
Water (H2O) .5507 3.04 22.09  molecule
647.3 K   molecules 
 NA 
Ammonia (NH3) .4233 3.73 11.28 406 K  mole 
Helium (He) .00341 2.34 0.23 5.2 K
Freon (CCl2F2) 1.078 9.98 4.12 385 K

 N 2a 
When can  P  2 V  Nb   Nk BT be reduced to PV  Nk BT ?
 V 
(1) Nb  V low densities
 Na  Na
(2) PV  N  k BT   k BT  high temperatures
 V  V (kinetic energy >> interaction energy)
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 Problem
The vdW constants for N2: NA2a = 0.136 Pa·m6 ·mol-2, NAb = 3.85·10-5 m3 ·mol-1.
How accurate is the assumption that Nitrogen can be considered as an ideal gas
at normal P and T?

 N 2a 
 P  2 V  Nb   Nk BT
 V 

1 mole of N2 at T = 300K occupies V1 mol  RT/P  2.5 ·10-2 m3 ·mol-1

NAb = 3.9·10-5 m3 ·mol-1 NAb / V1 mol ~1.6%

NA2a / V2 = 0.135 Pa·m6 ·mol-2 /(2.5 ·10-2 m3 ·mol-1) 2 = 216 Pa NA2a / V2P
= 0.2%

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 Entropy of monatomic van der Waals gas
V N  2 mU 
3N / 2
1
Multiplicity of ideal gas:  IG  N ,V ,U     2p
N !  3 N / 2 !  h 2 

N 2a
van der Waals gas: Veff  V  Nb U vdW  U IG 
V
Multiplicity of monatomic van der Waals gas:

  
3N / 2
1 V  Nb   2 m U 
N N 2a

 vdW  N ,V ,U    2p
V

N !  3N / 2 !  h2 
 
Entropy of monatomic van der Waals gas:
 V  Nb  4 m U  N 2 a 3/ 2  5 
 
S vdW ( N ,V ,U )  Nk B ln   2
V
   
  N  3h N   2 

Is it correct?
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 Equations of state (vdW)
 V  Nb  4 m U  N 2 a 3/ 2  5 
 
S vdW ( N ,V ,U )  Nk B ln   2
V
   
  N  3h N   2
 
Equations of state:
1  S  3 N 2a
  U vdW  Nk BT 
T  U V , N 2 V

 S  Nk BT N 2a
P  T   P  2
 V U , N V  Nb  V
 S 
  T   
 N U ,V

V  Nb  2 mk BT 3/ 2  2 Na Nb
  k BT ln     
 N  h
2
  V V  Nb
(take home exercise: derive these results)
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 S, F, and G for the monatomic van der Waals gas
 S   S  C  P  f dT Nk B
S dS    dT    dV  V dT    dV  Nk B  dV
 T V  V T T  T V 2 T V  Nb

Nk B ln T  Nk B ln V  Nb   const
f
(see Pr. 5.12) S vdW 
2
the same “volume” in the
 Nb    V  Nb   2  m   5 
3/ 2
momentum space, smaller
S vdW  Sideal  Nk B ln 1    N k B ln   2 k BT    
 V    N  h   2  accessible volume in the
coordinate space.

3 N 2a   V  Nb   2  m   5 
3/ 2

F FvdW  U  TS  Nk BT   N k BT ln   2 k BT    
2 V   N  h   2 
 V  Nb   2  m  
3/ 2
aN 2
  N k BT ln   2 k BT    Nk BT 
 N  h   V

 Nb  N a  F 
2
 Fideal  N k BT ln 1  Nk BT aN 2
FvdW  PvdW      2
 V  V  V T V  Nb V
 V  Nb   2 m   2aN
3/ 2 2
N 2b
G GvdW  F  PV   Nk BT ln   2 k BT     k BT  N
 N  h   V V  Nb
(take home exercise: derive these results)
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Quasi-static Processes in a vdW Gas (low n, high T)
U  Q  W dU  TdS  PdV

P isochoric ( V = const )
2 W12  0

Q12  Nk B T2  T1   0  CV T 
T2 3
1 T1 2
V1,2 V dU  Q12 same as ideal gas

isobaric ( P = const )
P 2
W12    P(V , T )dV   PV2  V1   0
2 1
1 T2  U   dV 
Q12  CP T C P  CV     P  
T1  V T  dT P
V1 V2 V
dU  W12  Q12 complicated
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 Isothermal Process in a vdW Gas (low n, high T)

isothermal ( T = const ) :
P
N 2a N 2a
PV= NkBT  U T  
V1 V2
W V2

V2 V1 V W12    P(V , T )dV

V1

 Nk B T N 2a 
V2

Wi-f > 0 if Vi >Vf (compression)     2  dV

V1 
V  Nb V 
Wi-f < 0 if Vi <Vf (expansion)
V2  Nb  N 2 a N 2 a 
  Nk BT ln   
V1  Nb  V1 V2 

V2  Nb
Q12  U  W12  Nk BT ln
V1  Nb
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 Isothermal Process in a vdW Gas (low n, high T)
For N2, the vdW coefficients are N2a = 0.138 kJ·liter/mol2 and Nb = 0.0385 liter/mol.
Evaluate the work of isothermal and reversible compression of N2 (assuming it is a
vdW gas) for n=3 mol, T=310 K, V1 =3.4 liter, V2 =0.17 liter. Compare this value to
that calculated for an ideal gas. Comment on why it is easier (or harder, depending
on your result) to compress a vdW gas relative to an ideal gas under these
conditions.
WvdW T  9mol 2  0.138 kJ  l2 
1

1 
  3mol  8.3
J  0.17l  3mol  0.0385l / mol 
 310 K ln  
mol  3.4l 0.17l  K  mol  3.4l  3mol  0. 0385l / mol 
 6.94kJ  31.64kJ  24.7kJ
   0.17l 
Wideal T   Nk BT ln V2   3mol  8.3 J
 310 K  ln    23.12kJ
 V1  mol  K  3.4l 
Depending on the interplay between the 1st and 2nd terms, it’s
Upot
either harder or easier to compress the vdW gas in comparison with
an ideal gas. If both V1 and V2 >> Nb, the interactions between
r molecules are attractive, and WvdW < Wideal However, as in this
problem, if the final volume is comparable to Nb , the work against
repulsive forces at short distances overweighs that of the attractive
forces at large distances. Under these conditions, it is harder to
compress the vdW gas rather than an ideal gas.
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 Adiabatic Process in a vdW Gas
adiabatic (thermally isolated system) Q12  0  S  0 dU  W12

 V  Nb  2 mk T 3/ 2  5 
P S vdW ( N ,V , T )  Nk B ln     
B

2
  N  h   2 
2

 V  Nb  T 3/ 2  const.  T V  Nb 
T2  1
1  const.
T1
V2 V1 V
 N 2a 
 

V2   P  2 
V  Nb  const
W12    P(V , T )dV  V 
V1

recall:
3  N 2
a N 2
a
 U  Nk B T2  T1   
2
U vdW
3
 Nk BT 
N a  
2 V 2  1
V V 2 

take home exercise: Carnot engine efficiency using vdW gas

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 Problem (vdW + heat engine)
The working substance in a heat engine is the vdW gas with a known constant b and
a temperature-independent heat capacity cV (the same as for an ideal gas). The gas
goes through the cycle that consists of two isochors (V1 and V2) and two adiabats.
Find the efficiency of the heat engine.
P A  QC
  1
 QH
A-D QH  cV TA  TD 
TB  TC 
B
D
  1
B-C QC  cV TB  TC  TA  TD 
C

V2 V The relationship between TA, TB, TC, TD – from

V1
the adiabatic processes B-C and D-A
Tf V f  Nb
S vdW  Nk B ln T  Nk B ln V  Nb   const
f f
S vdW  Nk B ln  Nk B ln
2 2 Ti Vi  Nb
Tf V f  Nb f
T 2 V  Nb   const
f
Nk B ln  Nk B ln 0 adiabatic process
2 Ti Vi  Nb for the vdW gas
2/ f 2/ f
 V  Nb   V  Nb 
TA  1   TD  1   1
T  T 
2/ f
Q    V  Nb   V  Nb 
 1  2   2 
V Nb V Nb
  1 C  1 B C  1  1   1  1 
QH TA  TD  TA  TD  2
V  Nb   2
V  Nb 
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 The van der Waals Isotherms

Nk BT aN 2  Nk T  aN 2
abN 3
P  2 V 3   Nb  B  V 2  V 0
V  Nb  V  P  P P

unstable
0

N·b

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 The Critical Point
The critical point is the unique point where both
(dP/dV)T = 0 and (d2P/dV 2)T = 0 (see Pr. 5.48)

Critical parameters:
1 a 8 a
VC  3Nb PC  2
k BTC 
27 b 27 b
in terms of P,T,V normalized by the critical parameters:

Pˆ 
P
Vˆ 
V
Tˆ 
T  ˆ 3  ˆ 1  8k B Tˆ
PC VC TC  P  ˆ 2 V   
 V  3 3
the materials parameters vanish if we introduce the proper scales.
RTC 8 substance H2 He N2 CO2 H20
KC    2.67 KC 3.0 3.1 3.4 3.5 4.5
PCVC 3
TC (K) 33.2 5.2 126 304 647
the critical coefficient PC (MPa) 1.3 0.23 3.4 7.4 22.1

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 Problems
For Argon, the critical point occurs at a pressure PC = 4.83 MPa and
temperature TC = 151 K. Determine values for the vdW constants a and b for Ar
and estimate the diameter of an Ar atom.

27 k BTC 
2
1 a 8 a k T
PC  k BTC  b B C a
27 b 2 27 b 8PC 64 PC

a
27 k BTC 
2


27 1.38 10  23 J/K 151 K 
2

 3.8 10  49 J 2 /Pa

64 PC 64 4.83 106 Pa

k BTC 1.38 10 23 J/K 151 K  29

b   5.4  10 m 3

8PC 8  4.83 106 Pa

b1/ 3  3.86 10 10 m  3.86 A

Per mole: a=0.138 Pa m6 mol-2; b=3.25x10-5 m3 mol-1

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 Problem
One mole of Nitrogen (N2) has been compressed at T0=273 K to the volume
V0=1liter. The critical parameters for N2 are: VC = 3Nb = 0.12 liter/mol, TC =
(8/27)(a/kBb) = 126K. The gas goes through the free expansion process (Q = 0, W
= 0), in which the pressure drops down to the atmospheric pressure Patm=1 bar.
Assume that the gas obeys the van der Waals equation of state in the compressed
state, and that it behaves as an ideal gas at the atmospheric pressure. Find the
change in the gas entropy.
f
S vdW  R ln T  R ln V  N Ab   g ( N , m )
2
f
Sideal  R ln T  R lnV  g ( N , m )
2
5 Tf  Vf  5 T  Vf 
S  R ln  R ln    R ln f  R ln  
2 T0  0
V  Nb  2 T 0  0
V  VC / 3 
2 aN A2 9 TCVC RT f
T f  T0   T0   266.2 K Vf   2.2  102 m3
5 RV0 20 V0 Patm
5 266.2  2.2 10 2 
S  R ln  R ln  3
  5.24 10 1  26  25.5 J/K
3 
2 273  110  0.04 10 

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 Phase Separation in the vdW Model
P
T = const (< TC) The phase transformation in the vdW model is easier to analyze by
minimizing F(V) rather than G(P) (dramatic changes in the term PV
makes the dependence G(P) very complicated, see below).
At T< TC, there is a region on the F(V) curve in which F makes a
concave protrusion (2F/V 2<0) – unlike its ideal gas counterpart.
Due to this protrusion, it is possible to draw a common tangent line
V1 V2 V so that it touches the bottom of the left dip at V = V1 and the right
dip at V = V2. Since the common tangent line lies below the free
energy curve, molecules can minimize their free energy by refusing
F to be in a single homogeneous phase in the region between V1 and
V V2, and by preferring to be in two coexisting phases, gas and liquid:
F1
(liquid) N gas V  V1 N liquid V2  V
N  N gas  N liquid  
F2 N V2  V1 N V2  V1
(gas)

F1 F V  V2 V V
F N liquid  2 N gas  F1  F2 1
N N V1  V2 V1  V2
- we recognize this as the common tangent line.

As usual, the minimum free energy principle controls the

V < V1 V1 < V < V2 V2 < V way molecules are assembled together.
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 Phase Separation in the vdW Model (cont.)
P 7
T < TC
Since the tangent line F(V) maintains the same slope
3 between V1 and V2, the pressure remains constant between
6 V1 and V2:  F 
2
Pvap 4    P
 V T , N
1
5 In other words, the line connecting points on the PV plot is
horizontal and the two coexisting phases are in a mechanical
V
F equilibrium. For each temperature below TC, the phase
V transformation occurs at a well-defined pressure Pvap, the so-
Fliq called vapor pressure.

Two stable branches 1-2-3 and 5-

Fgas 6-7 correspond to different phases.
P Along branch 1-2-3 V is large, P is
P small, the density is also small –
critical
point gas. Along branch 5-6-7 V is small,
P is large, the density is large –
liquid. Between the branches – the
Pvap(T1) gas-liquid phase transformation,
which starts even before we reach
triple 3 moving along branch 1-2-3.
point

Vliq Vgas V T1 T
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 Phase Separation in the vdW Model (cont.)
 
T / TC
P / PC

n / nC

n / nC P / PC
 F    3n   3nC  1  9  n

     k BT ln  C 
 ln   1    k BTC  
 N T ,V   nQ   n  3nC / n  1 4  nC 
For T<TC, there are three values of n with the same  . The outer two values of n correspond
to two stable phases which are in equilibrium with each other.
The kink on the G(V) curve is a signature of the 1st order transition. When we move along the
gas-liquid coexistence curve towards the critical point, the transition becomes less and less
abrupt, and at the critical point, the abruptness disappears.
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 The Maxwell Construction
P 7
T < TC

3
[finding the position of line 2-6 without analyzing F(V)]
6
Pvap 2
4 On the one hand, using the dashed line on the F-V plot:
1
5

 F 
Fgas  Fliquid    V2  V6    Pvap V2  V6 
V
F
 V T , N
V
Fliq
On the other hand, the area under the vdW isoterm 2-6
on the P-V plot:
Fgas
 F 
V2 V2

V PdV  V  V T , N dV   Fgas  Fliquid 

G 3 6 6
4
7 Thus, V2

 P V dV P V  V6 
5 2,6
vdW vap 2
V6
1

the lowest branch represents P the areas 2-3-4-2 and 4-5-6-4

the stable phase, the other must be equal !
branches are unstable -Maxwell construction
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 P
T < TC
Phase Diagram in T-V Plane
At T >TC, the N molecules can exist in a single phase in any
Pvap
volume V, with any density n = N/V. Below TC, they can exist in a
homogeneous phase either in volume V < V1 or in volume V > V2.
There is a gap in the density allowed for a homogeneous phase.
V
F There are two regions within the two-phase “dome”: metastable
V (P/V< 0) and unstable (P/V>0). In the unstable region with
Fliq negative compressibility, nothing can prevent phase separation.
In two metastable regions, though the system would decrease
the free energy by phase separation, it should overcome the
Fgas potential barrier first. Indeed, when small droplets with radius R
T are initially formed, an associated with the surface energy term
Single Phase tends to increase F. The F loss (gain) per droplet:
TC

N1  4 
 F   R / V1 
3
unstable condensation:
N 3 
interface:  4 R 2

V1(T) VC V2(T) V Total balance: F RC R

P 2F N1  4 
 0, 0  F   4 R 2  F   R / V1 
3

V V 2 N 3 
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Joule-Thomson Process for the vdW Gas heating

cooling
The JT process corresponds to an isenthalpic expansion:

 H   H   H   H 
H    T    P  0    CP C P T    P
 T P  P T  T  P  P T

 H   V   H   S 
  T  V
H  TS  VP    T  V
 T   P T   T P  P T  P T
    S   V 
 P  H CP CP      (see Pr. 5.12)
 P T  T  P

This is a pretty general (model-independent) result. By applying this result to the vdW
equation, one can qualitatively describe the shape of the inversion curve (requires solving
cubic equations...).
N 2a
We’ll consider the vdW gas at low densities: P  V  Nb
V2
 N 2a  N 2a 
 P  2 V  Nb   Nk BT PV   PNb  Nk BT ...P
 V  V T

Na
 V  N 2 a  V   V  Nk B 2  Nb
P   2    Nk B     T 
  
k BT
 T P V  T P  T  P P  N a
2

 P H CP
V2
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 Joule-Thomson Process for the vdW Gas (cont.)
2a 2a
Cooling: b  0 Heating: b  0
k BT k BT
If b = 0, T always decreases in the JT process: an increase of Upot at the expense of K.
If a = 0, T always increases in the JT process (despite the work of molecular forces is 0):

PV  Nb   RT PV  RT  PNb H  U  PV  CV  R T  PNb  CPT  PNb

The upper inversion temperature:

(at low densities) TINV
Substance
heating 2a (P=1 bar)
b  0 CO2 (2050)
k BTINV
CH4 (1290)
cooling
2a 27 O2 893
TINV   TC
k Bb 4 N2 621
H2 205
(TC – the critical temperature of 4He 51
the vdW gas, see below) 3He (23)

Thus, the vdW gas can be liquefied by

compression only if its T < 27/4TC.

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 Problem
The vdW gas undergoes an isothermal expansion from volume V1 to volume V2.
Calculate the change in the Helmholtz free energy.

In the isothermal process, the change of the Helmholtz free energy is

dF T , N   SdT  PdV  dN T , N   PdV

 RT N 2a  2  1 1  V2  Nb 
V2 V2

F    PdV      2 dV N a     RT ln 
   
V1 V1 
V  Nb V   V1 V2   V1  Nb 

compare with F  U  TS  1
U vdW T  N 2 a  1   TSvdW T
 V1 V2 

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