1.

How Aspen HYSYS calculates CP

In all versions of Aspen HYSYS CP is calculated rigorously from the molar enthalpy
temperature relationship. How enthalpy is calculated depends on the thermodynamic
model being used. (See the Aspen HYSYS Simulation Basis manual for a full
description of this)
1.2

How Aspen HYSYS calculates CV

Aspen HYSYS does not report CV directly; instead Gamma (CP / CV), is displayed,
although CV is calculated internally by Aspen HYSYS in order to get Gamma.
The method used for calculating CV depends on which version of Aspen HYSYS is used.
Before version 2.1.3, the Gamma value reported in Aspen HYSYS was based on a
semi-ideal CV (i.e. CV = CP - R)

From version 2.1.3 onwards Aspen HYSYS calculates CV internally using the
following equation:
V
C P CV T
T

V
P

(1)
T

where, T = Temperature, V = Molar Volume, P = Pressure. (See Appendix 2 for a

derivation of this equation from first principles.)
If this method fails then Aspen HYSYS reports the semi-ideal value. A semi-ideal value
will also be calculated when:
Stream has a solid phase
Magnitude of dV/dP < 1 10 12 (because this cannot be distinguished from round
off errors)
CP / CV < 0.1 or CP / CV > 20, since this is outside of the range of applicability
This method is considered to be the best and most rigorous way to calculate CP / CV.
1.3

Entropy Method for calculating Cv

The following relation is used in the gas properties entropy method

CV
S

T
T

(2)
V

where, S = Entropy, T = Temperature, V = Molar Volume. (See Appendix 1 for a

derivation of this equation from first principles.)
This is approximated by:
CV
S1 S 2

(3)
T1 T2 T1 T2 2
Where T1 = stream temperature (corresponding pressure = P1, molar volume = V1) and T2
= T1 + 0.01 C, with pressure P2 at T2 set to give molar volume V2 equal to V1.

[This outline as used in HYSIM Calculator program cpcv.hcl by Dain Stone / Process
Solutions (Nov 92, July 93)]

Appendix 1 Derivation of Enthalpy Method CV equation

Derivation of:
CV
S

T
T

Write
S
T

S
U

U
T

(A1-1)
V

From the definition of CV

CV

U
T

(A1-2)
V

From the First Law and the definitions of work and entropy
dU TdS PdV

Write U U S ,V and use the chain rule

dU

U
S

dS
V

U
V

dV
S

(A1-3)
(A1-4)

Comparing to (A1-3) gives

U
S

(A1-5)

Substituting (A1-2) and (A1-5) into (A1-1) gives

S
T

1
CV
T

hence
CV
S

T
T

(A1-6)

Appendix 2 Derivation of Aspen HYSYS Rigorous CV equation

Derivation of:
V
C P CV T
T

V
P

From the definition of Enthalpy

H U PV
so substituting this into the definition of CP gives
CP

H
T

U
T

P
P

V
T

(A2-1)
(A2-2)

combine with the definition of CV

CV

U
T

(A2-3)

to give
U
T

C P CV

P
P

V
T

U
T

(A2-4)

Write U U T ,V and use the chain rule

dU

U
T

dT
V

U
V

dV

(A2-5)

now differentiate with respect to T at constant P

U
T

U
T

T
T

U
V

V
T

V
T

(A2-6)
P

simplify and rearrange

U
T

U
T

Now substitute for T

U
T

U
V

(A2-7)

in (A2-4)

C P CV

Now V

U
V

U
V

V
T

V
T

P
P

V
P
T
V
T

V
T

U
T

(A2-8)

can be rewritten to eliminate the P in the bracket.

Write S S T , V and use the chain rule

dS

S
T

dT
V

From equation (A1-6)

S
V

dV
T

(A2-9)

S
T

1
CV
T

and a Maxwell equation gives

S
V

P
T

hence
dS

CV
P
dT
T
T

dV

(A2-

10)
From the First Law and the definitions of work and entropy
dU TdS PdV

(A2-

11)
and substitute for dS using (A2-10)

P
dU CV dT T

P dV

(A2-

12)
Comparing to (A2-5) gives
U
V

T
T

P
T

(A2-

13)
Substitute (A2-13) into (A2-8) to give
P
T

C P CV T

V
T

(A2P

14)
Now use the triple product relationship
P
T

V
P

T
V

(A2-

15)
rearranged to give
P
T

V
T

V
P

16)
to substitute into (A2-14) to give
V
C P CV T
T

V
P

(A2T