Write the van der Waals EOS in the reduced coordinatesTr Pr
Solution
a)
Vander waals equation of state is
P = RT/V-b - a/V2 which can be reduced to
PV3 - (Pb+RT)V2 + aV-ab = 0
P(V3 - ( b+RT/P)V2 +aV/P - ab/P ) = 0
since at critical point we can write (V-Vc)3 = V3-3V2Vc+3V(Vc)2 - (Vc)3 = 0
by comparison we can write 3Vc = b+RT/P ; 3(Vc)2 = a/P : (Vc)3 = ab/P
here P and T corresponds to critical pressure and temperatures
from last 2 equations we can write Vc = 3b substitute this value in 1st equation
8b= RT/P divide this equation with 2nd equation from this we can write Tc = 8a/27Rb and Pc = a/27b2
now
P = Pr*Pc = Pr*a/27b2 , V = Vr*Vc = 3bVr , T = Tr*Tc = 8aTr/27RB , put these values in below vanderwaals equation
(P+a/V2) (V-b) = RT ( Pr*a/27b2 +a/(3bVr)^2) *( 3bVr -b) = R*8aTr/27RB
after simplication we can write
(Pr +3/Vr^2) (3Vr-1) = 8Tr
Pr = 8Tr/3Vr-1 - 3/Vr^2
B)
Vc = 3b , Tc = 8a/27Rb , Pc = a/27b2
use above equations to get
RTc/8Pc = b and 27R2(TC)2/64PC = a
