Force between two neutral atoms

𝑟
Force between two neutral atoms

𝑟
Force between two neutral atoms

𝑟
𝑉(𝑟)

𝑟
𝑉 → (𝑉 − 𝑏)
𝑈 𝑁 𝑁 2
∝ ⇒ 𝑈 = −𝑎′
𝑁 𝑉 𝑉
 Van der Waals equation

𝑎
𝑝+ 2 𝑉 − 𝑏 = 𝑅𝑇
𝑉
Sir James Dewar FRS (1842 – 1923) Heike Kamerlingh Onnes (1853 – 1926) Johannes Diderik van der Waals (1837 – 1923)
 Isotherms for a van der waals gas
50
clear all;
45 v = 19:1:200;
t=340;
40
b=14; MATLAB code
35
a=78435;
30 for i=1:20
25 t = t-10;
p

r = 8.314;
20
p = r*t./(v-b)-(a./v.^2); a and b were chosen to
15 plot(v,p)
axis([10 200 0 50]);
give a Tc of 200 K
10
xlabel('v');
5
ylabel('p');
0
20 40 60 80 100 120 140 160 180 200
hold on;
v end

Set a = b = 0 and you get the isotherms for an ideal gas

50

45

40

35

30

25
p

20

15

10

0
20 40 60 80 100 120 140 160 180 200
v
At a particular temperature a vdw gas develops a point of inflexion.
The gas can be liquefied below this temperature.

50

45

40

35

30

25
p

20

15

10

0
20 40 60 80 100 120 140 160 180 200
v

To find the point of inflexion set:

𝜕𝑝 𝜕2𝑝
=0 and =0
𝜕𝑉 𝑇
𝜕𝑉 2 𝑇
Which gives:

𝑎
𝑝𝑐 =
27𝑏2

𝑉𝑐 = 3𝑏

8𝑎
𝑇𝑐 =
27𝑅𝑏

Define dimensionless reduced variables

𝑝
𝑝෤ =
𝑝𝑐

𝑉
𝑉෨ =
𝑉𝑐
𝑇
𝑇෨ =
𝑇𝑐
 Which gives the reduced form of the vdw equation

3
𝑝෤ + 2 3𝑉෨ − 1 = 8𝑇෨
𝑉෨

Can be applied to any gas (to some extent) since its independent of a
and b (law of corresponding states)
 Isotherms for the reduced form of the van der waals equation of state

5
MATLAB code
4.5

4 clear all;
3.5 vr = 0.5:0.01:10;
3
tr=2;
for i=1:15
2.5
tr = tr-0.1;
r
p

2 pr = (8*tr./(vr.*3-1))-(3./vr.^2);
1.5 plot(vr,pr)
axis([0.1 5 0 5]);
1
xlabel('v_r');
0.5
ylabel('p_r');
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
hold on;
vr end
Below the critical temperature Tc, the vdw equation has a few problems

2.5

1.5

Negative compressibility, unphysical

r
p

0.5

Multivaluedness, unphysical
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
vr
 Free energy considerations can remove these problems

3
𝑝෤ + 3𝑉෨ − 1 = 8𝑇෨
𝑉෨ 2
8𝑇෨ 3
⇒ 𝑝෤ = − 2 (1)
3𝑉෨ − 1 𝑉෨

𝑑𝐹 = −𝑆𝑑𝑇 − 𝑝𝑑𝑉

𝜕𝐹
⇒𝑝=− (2)
𝜕𝑉 𝑇

8 3
(1) and (2) ⇒ 𝐹 = − 𝑇෨ ln 3𝑉෨ − 1 − + 𝑓(𝑇)
෨
3 𝑉෨
8 3
⇒ 𝐺 = − 𝑇෨ ln 3𝑉෨ − 1 − + 𝑝෤𝑉෨ + 𝑓(𝑇)
෨
3 𝑉෨

8𝑇෨ 𝑉෨ 3
From (1) ⇒ 𝑝෤𝑉෨ = −
3𝑉෨ − 1 𝑉෨

8 6 8𝑇෨ 𝑉෨
⇒ 𝐺 = − 𝑇෨ ln 3𝑉෨ − 1 − + ෨
+ 𝑓(𝑇)
3 𝑉෨ ෨
3𝑉 − 1
8 2 8𝑇෨ 𝑉෨
෨ ෨
⇒ 𝐺 = − 𝑇 ln 3𝑉 − 1 − + ෨
+ 𝑓(𝑇)
9 𝑉෨ 3 3𝑉෨ − 1
 Plotting the gibbs function using matlab…

5 -1

4.5
-1.1
4

3.5
-1.2
3
v-reduced

g-reduced
2.5 -1.3

2
-1.4
1.5

1
-1.5
0.5

0 -1.6
0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4
p-reduced p-reduced

The system will choose the minimum Gibb’s free energy

 Maxwell construction

B2
clc; clear all; close all Clear command, clears the screen; clears all objects; closes
all figures etc.
Vr = linspace(0.5,3,100); Creates values of Vr from 0.5 to 3 in steps of (3-0.5)/100
figure(1); Opens a figure window
ylim([0 2]) Y axis limits
xlim([0.25 3]) X axis limits
xlabel('V_r') Labels x axis
ylabel('P_r') Labels y axis
Tr = 0.9;
Prfunc = @(Vr) 8*Tr./(3*Vr - 1) - 3./(Vr.^2); Defines the van der Waals equation as a function of Tr and
Pr = Prfunc(Vr); Vr
plot(Vr,Pr) Calculate Pr using the vdW equation
Plots Pr vs. Vr
if Tr < 1 Makes sure the temperature is below critical, Tr = T/Tc

Pr_b = 1.0; Starts with a trial value for Pr at which liquid transform to gas

vdW_Pr_b = [1 -1/3*(1+8*Tr/Pr_b) 3/Pr_b -1/Pr_b]; Defines a polynomial function to calculate the values of Vr for the
trial value of Pr (Pr_b).
8𝑇𝑟 3
⇒ − 2 = 𝑃𝑟𝑏
3𝑉𝑟 − 1 𝑉𝑟

8𝑇𝑟 3
⇒ − 2 − 𝑃𝑟𝑏 = 0
3𝑉𝑟 − 1 𝑉𝑟

⇒ 8𝑇𝑟 𝑉𝑟2 − 3 3𝑉𝑟 − 1 − 𝑃𝑟𝑏 3𝑉𝑟 − 1 𝑉𝑟2 = 0

⇒ 8𝑇𝑟 𝑉𝑟2 − 9𝑉𝑟 + 3 − 3𝑃𝑟𝑏 𝑉𝑟3 + 𝑃𝑟𝑏 𝑉𝑟2 = 0

1 8𝑇𝑟 2 3 1
⇒ 𝑉𝑟3 − 1+ 𝑉𝑟 + 𝑉𝑟 − =0
3 𝑃𝑟𝑏 𝑃𝑟𝑏 𝑃𝑟𝑏
The terms in the square brackets are the coefficients of the
polynomial.
v = sort(roots(vdW_Pr_b)); Finds the roots of the polynomial and sorts them in
increasing order: v(1), v(2), and v(3)

A1 = (v(2)-v(1))*Pr_b - integral(Prfunc,v(1),v(2));
Calculates the area enclosed by the line and the vdW
A2 = integral(Prfunc,v(2),v(3)) - (v(3)-v(2))*Pr_b; curve between v(1) and v(2) and then from v(2) and v(3).
2.5 (clearer figure later).

1.5

0.5

0
0.5 1 1.5 2 2.5 3
Z = abs(A1-A2); Calculates the difference between the two areas
while Z > 0.0001 If z > 0.0001 then this loop starts
vdW_Pr_b = [1 -1/3*(1+8*Tr/Pr_b) 3/Pr_b -1/Pr_b]; Defines the polynomial in the loop
v = sort(roots(vdW_Pr_b)); Calculates and sorts the roots
Prfunc = @(Vr) 8*Tr./(3*Vr - 1) - 3./(Vr.^2); Defines vdW equation in the loop
A1 = (v(2)-v(1))*Pr_b - integral(Prfunc,v(1),v(2)); Calculates the areas again
A2 = integral(Prfunc,v(2),v(3)) - (v(3)-v(2))*Pr_b;
Z = abs(A1 - A2); Calculates the difference
Pr_b = Pr_b - 0.00001; Lowers the test values Pr_b by 0.00001
figure(1); hold off; Chooses figure 1 window; new plot will appear, old graph is removed
plot(Vr,Pr) Plots Pr vs. Vr
figure(1); hold on; Chooses figure 1window; new plot will appear keeping the old graph
plot([0.5 3],[Pr_b Pr_b],'k--') Plots the line for Pr_b vs. Vr in a black dashed line
hold off; Next time a new graph is plotted the old plots will be removed
end Starts the loop again and checks if the difference between A1 and A2
(Z) > 0.0001 for the new value of Pr_b. Loop stops if Z < 0.0001 i.e
A1  A2
 2.5

1.5

1
v(1) v(2) v(3)

Pr_b
0.5

0
0.5 1 1.5 2 2.5 3

(v(2)-v(1))*Pr_b (v(3)-v(2))*Pr_b
 2.5

1.5

1
v(1) v(2) v(3)

Pr_b
0.5

0
0.5 1 1.5 2 2.5 3

Calculates the area under the vdW curve from

integral(Prfunc,v(1),v(2)) integral(Prfunc,v(2),v(3)) v(1) to v(2) and from v(2) to v(3).
 2.5

1.5

1
v(1) v(2) v(3)

Pr_b
0.5

0
0.5 1 1.5 2 2.5 3

Calculates the relevant area for the Maxwell

(v(2)-v(1))*Pr_b - integral(Prfunc,v(1),v(2)) constructions
integral(Prfunc,v(2),v(3)) - (v(3)-v(2))*Pr_b
end Ends the if loop
A1 Prints A1 and A2
A2
Pr_b Prints the value of pressure Pr_b which satisfies Maxwell’s condition.
 Liquefying a gas by applying pressure

T
 Liquefying a gas by applying pressure

T
 Liquefying a gas by applying pressure

T
 Liquefying a gas by applying pressure

T
 Liquefying a gas by applying pressure

T
 Liquefying a gas by applying pressure

T
 Liquefying a gas by applying pressure

T
Two phase region in the vdW gas
P (bar)
http://www.youtube.com/watch?v=GEr3Nx
sPTOA