1.

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:
2
 V  V
C P  CV  T   (1)
 T P  P 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
 (2)
T T 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:
S1  S 2 CV
 (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 V

Write
S S U
  (A1-1)
T V U V T V

From the definition of CV

U
CV  (A1-2)
T V

From the First Law and the definitions of work and entropy
dU  TdS  PdV (A1-3)
Write U  U  S ,V  and use the chain rule
U U
dU  dS  dV (A1-4)
S V V S

Comparing to (A1-3) gives

U
T (A1-5)
S V

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

S 1
  CV (A1-6)
T V T
hence
CV S

T T V
Appendix 2 – Derivation of Aspen HYSYS Rigorous CV equation
Derivation of:
2
 V  V
C P  CV  T  
 T P  P T

From the definition of Enthalpy

H  U  PV (A2-1)
so substituting this into the definition of CP gives
H U V
CP   P (A2-2)
T P T P T P

combine with the definition of CV

U
CV  (A2-3)
T V

to give
U V U
C P  CV  P  (A2-4)
T P T P T V

Write U  U  T ,V  and use the chain rule

U U
dU  dT  dV (A2-5)
T V V T

now differentiate with respect to T at constant P

U U T U V
  (A2-6)
T P T V T P V T T P

simplify and rearrange

U U U V
  (A2-7)
T P T V V T T P

U
Now substitute for T in (A2-4)
P

U U V V U
C P  CV   P 
T V V T T P T P T V

U V V
 P (A2-8)
V T T P T P

 U  V
   P 
 V T  T P

U
Now V can be rewritten to eliminate the P in the bracket.
T

Write S  S  T , V  and use the chain rule

S S
dS  dT  dV (A2-9)
T V V T

From equation (A1-6)

 S 1
  CV
T V T
and a Maxwell equation gives
S P

V T T V

hence
CV P
dS  dT  dV (A2-
T T V

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-
 T V 
12)
Comparing to (A2-5) gives
U P
T P (A2-
V T T V

13)
Substitute (A2-13) into (A2-8) to give
P V
C P  CV  T (A2-
T V T P

14)
Now use the triple product relationship
P V T
   1 (A2-
T V P T V P

15)
rearranged to give
V
P
  T P
(A2-
T V
V
P T

16)
to substitute into (A2-14) to give
2
 V  V
C P  CV  T  
 T P  P T