Thermo Relations

Thermodynamic Relationships
D.F. Mendoza
Universidad de Antioquia
D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 1 / 112

Fundamental equations
Thermodynamic laws and associated state variables
Law Concept Primitive Derived

Zeroth Thermal equil. T –
First Energy conserv. U H
Second Spontaneity S –
First + Second Fundamental Eqn. T, U, S H, A, G
where: H ≡ U + pV A ≡ U − TS G ≡ H − TS
State functions commonly used in thermodynamics
• Measurable: T , p, V .
• Conceptual: U , S, H, A, G.

Fundamental equations for closed systems

The fundamental equation comes from combining the first and second
laws to get an equation only in terms of state functions, i.e. we don’t have
to evaluate heat and work interactions.
The first law for a closed system, neglecting changes in potential and
kinetic energy is:
dU = δQ − δW
if heat interaction is reversible
δQ = T dS
and if the only work transfer is due to a reversible expansion
δW = pdV

Fundamental equation (closed system)

Replacing δQ and δW terms in the first law expression, we obtain the
fundamental equation for a closed system.
Fundamental equation (closed system)
dU = T dS − pdV Internal energy form

1 p
dS = dU + dV Entropy form
T T
This equation involves state variables (path independent) only, therefore it

is valid for irreversible processes.
dU = dUrev = dUirrev
dUrev = δQrev − δWrev = T dS − pdV
dUirrev = δQirrev − δWirrev = T dS − pdV
note that
δQrev ≠ δQirrev
δWrev ≠ δWirrev
but
δQrev − δWrev = δQirrev − δWirrev
Therefore,
dU = T dS − pdV
Example
Fundamental equation applied to reversible and irreversible
processes Isothermal-isobaric expansion

Fundamental equation in terms of derived properties
We might express the fundamental equation in terms of derived properties

(H, A, G), applying the chain rule to express:
T dS = d(T S) − SdT, and pdV = d(pV ) − V dp.
• Enthalpy form of the fundamental equation
dU = T dS − pdV
dU = T dS − d(pV ) + V dp
dH = T dS + V dp

Fundamental equation in terms of derived properties
• Helmholtz form of the fundamental equation
dU = T dS − pdV
dU = d(T S) − SdT − pdV
dA = −SdT − pdV
• Gibbs form of the fundamental equation
dU = T dS − pdV
dU = d(T S) − SdT − d(pV ) + V dp
dG = −SdT + V dp

Diverse forms of the fundamental equations
dU = T dS − pdV Internal energy form

1 p
dS = dU + dV Entropy form
T T
dH = T dS + V dp Enthalpy form
dA = −SdT − pdV Helmholtz energy form
dG = −SdT + V dp Gibbs energy form

Mathematical properties
Thermodynamic identities
Thermodynamic state functions are mathematically defined as exact

differentials. Let F = F (x, y), then:
∂F ∂F
dF = ( ) dx + ( ) dy
∂x y ∂y x
This mathematical property allows us to relate the derivatives of different

thermodynamic properties appearing in the diverse forms of the
fundamental equation.

• U = U (S, V )
dU = T dS − pdV
∂U ∂U
dU = ( ) dS + ( ) dV
∂S V ∂V S
Therefore, we establish the following relations:
∂U ∂U
( ) = T; ( ) = −p
∂S V ∂V S

• H = H(S, p)
dH = T dS + V dp
∂H ∂H
dH = ( ) dS + ( ) dp
∂S p ∂p S

∂H ∂H
( ) = T; ( ) =V
∂S p ∂p S

• A = A(T, V )
dA = −SdT − pdV
∂A ∂A
dA = ( ) dT + ( ) dV
∂T V ∂V T
∂A ∂A
( ) = −S; ( ) = −p
∂T V ∂V T

• G = G(T, p)
dG = −SdT + V dp
∂G ∂G
dG = ( ) dT + ( ) dp
∂T p ∂p T

∂G ∂G
( ) = −S; ( ) =V
∂T p ∂p T

Summary of some thermodynamic identities
∂U ∂H
T= ( ) = ( )
∂S V ∂S p
∂U ∂A
p = −( ) = −( )
∂V S ∂V T
∂A ∂A
S = −( ) = −( )
∂T V ∂T V
∂H ∂G
V = ( ) = ( )
∂p S ∂p T

Maxwell’s relations
Maxwell’s relation are obtained from the following theorem concerning

exact differentials. Let F = F (x, y), and
dF = M dx + N dy
therefore:
∂M ∂N
( ) =( )
∂y x ∂x y

• U = U (S, V )
dU = T dS − pdV
∂T ∂p
( ) = −( )
∂V S ∂S V

• H = H(S, p)
dH = T dS + V dp
∂T ∂V
( ) =( )
∂p S ∂S p

• A = A(T, V )
dA = −SdT − pdV
∂S ∂p
( ) =( )
∂V T ∂T V

• G = G(T, p)
dG = −SdT + V dp
∂S ∂V
−( ) =( )
∂p T ∂T p

Summary of Maxwell’s relations
∂T ∂p
−( ) =( )
∂V S ∂S V
∂T ∂V
( ) =( )
∂p S ∂S p
∂S ∂p
( ) =( )
∂V T ∂T V
∂S ∂V
−( ) =( )
∂p T ∂T p

Change of variable
Transform
F (x, y) → F (x, w); y = y(x, w)
Both F and y are state variables, thus its total derivatives are:
∂F ∂F
dF (x, y) = ( ) dx + ( ) dy
∂x y ∂y x
∂y ∂y
dy = ( ) dx + ( ) dw
∂x w ∂w x
This two differentials allows us to change variables from (x, y) to (x, w)
∂F ∂F ∂y ∂y
dF (x, w) = ( ) dx + ( ) [( ) dx + ( ) dw]
∂x y ∂y x ∂x w ∂w x

Arranging terms
∂F ∂F ∂y ∂F ∂y
dF (x, w) = [( ) +( ) ( ) ] dx + ( ) ( ) dw
∂x y ∂y x ∂x w ∂y x ∂w x
Therefore:
∂F ∂F ∂F ∂y
( ) =( ) +( ) ( )
∂x w ∂x y ∂y x ∂x w
∂F ∂F ∂y
( ) =( ) ( )
∂w x ∂y x ∂w x

Example
Transform: U (S, V ) → U (T, V ).
• Step 1.
∂U ∂U
dU = ( ) dS + ( ) dV
∂S V ∂V S
∂S ∂S
dS = ( ) dT + ( ) dV
∂T V ∂V T
• Step 2.
∂U ∂S ∂S ∂U
dU = ( ) [( ) dT + ( ) dV ] + ( ) dV
∂S V ∂T V ∂V T ∂V S
∂U ∂S ∂U ∂S ∂U
dU = ( ) ( ) dT + [( ) ( ) +( ) ] dV
∂S V ∂T V ∂S V ∂V T ∂V S

Example
• Step 3.
∂U ∂U ∂S
( ) =( ) ( )
∂T V ∂S V ∂T V
∂U ∂U ∂S ∂U
( ) =( ) ( ) +( )
∂V T ∂S V ∂V T ∂V S

Triple product
Let F = F (x, y), and x = x(y, F ), thus
∂F ∂F
dF = ( ) dx + ( ) dy
∂x y ∂y x
∂x ∂x
dx = ( ) dy + ( ) dF
∂y F ∂F y
replacing dx in the first equation and grouping terms
∂F ∂x ∂F ∂x ∂F
[1 − ( ) ( ) ] dF = [( ) ( ) +( ) ] dy
∂x y ∂F y ∂x y ∂y F ∂y x

Since F and y are independent (i.e. can change independently) the only
way to fulfill this relation is that the terms in squared brackets be zero,
thus
∂F ∂x
1=( ) ( )
∂x y ∂F y
∂F ∂y ∂x
−1 = ( ) ( ) ( )
∂x y ∂F x ∂y F

Example
• Show that
∂U ∂S
( ) =T( ) −p
∂V T ∂V T
• Show that
∂U ∂U ∂U ∂V
( ) =( ) +( ) ( )
∂T p ∂T V ∂V T ∂T p
• Show that
∂U ∂V ∂T
( ) ( ) ( ) = −1
∂T V ∂U T ∂V U

Measurable thermodynamic variables
The measurable thermodynamic variables (properties) are:

1 Heat capacities
2 Compressibility and expansion coefficients
3 Enthalpies of phase change, mixing, chemical reaction and its
corresponding changes of volume
4 Equilibrium constants of reactions and e.m.f.’s of cells
5 Vapor pressures, solubilities, etc.

Heat capacities
Temperature increment of a body due to heat transfer
δQ
C≡ = Nc
dT
Constant volume heat capacity
δQ ∂U ∂S
Cv ≡ ( ) =( ) =T( ) = N cv
dT V ∂T V ∂T V
Constant presure heat capacity
δQ ∂H ∂S
Cp ≡ ( ) =( ) =T( ) = N cp
dT p ∂T p ∂T p
Notes
• c becomes infinite large at points of phase change. The term heat capacity
is usually applied only to changes of state not involving a phase change.
• cv , cp must always be positive quantities.

Thermal expansion, isothermal compressibility and pressure

coefficients
1 ∂V 1 ∂V 1 ∂p
β≡ ( ) ; κ≡− ( ) ; αp ≡ ( )
V ∂T p V ∂p T p ∂T V
Both β and κ refer to fractional changes in volume, thus are intensive
properties.
Example
Show that
β
αp =
pκ
use the transformation
∂p ∂V ∂T
( ) ( ) ( ) = −1
∂T V ∂p T ∂V p

Relation between Cp and Cv
We start by using the transformation: S(T, V ) → S(T, p); V = V (T, p)
∂S ∂S ∂S ∂V
( ) =( ) +( ) ( )
∂T p ∂T V ∂V T ∂T p
∂S ∂S ∂V
( ) =( ) ( )
∂p T ∂V T ∂p T
The first PDE is rewritten using thermodynamic relations to replace the

conceptual (S) for measurables (Cv , Cp , T , p, etc.)
Cp Cv ∂p ∂V
= +( ) ( )
T T ∂T V ∂T p

arranging terms
∂p ∂V
Cp − Cv = T ( ) ( )
∂T V ∂T p
β2
= TV
κ
where
∂p β ∂V
( ) = pαp = ; ( ) =Vβ
∂T V κ ∂T p

Relation between β and κ
We use the relation V = V (T, p)
∂V ∂V
dV = ( ) dp + ( ) dT
∂p T ∂T p
d ln V = βdT − κdp
Now ln V is a function of state, therefore:

∂κ ∂β
−( ) =( )
∂T p ∂p T

Joule-Thomson coefficient
⎧
⎪+ T decreases
∂T ⎪
⎪
⎪
µJT ≡( ) ; µJT = ⎨− T increases
∂p H ⎪
⎪
⎪
⎪
⎩0 T does not change

Variation in Cp with pressure

We start from the entropy as function of T and p
Cp ∂V
dS = dT − ( ) dp
T ∂T p
Applying the exactness test
∂ Cp ∂ ∂V
( ) =− [( ) ]
∂p T T ∂T ∂T p p
∂Cp ∂2V
( ) = −T ( 2 )
∂p T ∂T p
Integrating through an isothermal path

p2 ∂2V
Cp (T, p2 ) − Cp (T, p1 ) = −T ∫ ( ) dp
p1 ∂T 2 p

Variation in Cp with volume
∂Cp ∂2V
( ) = −T ( 2 )
∂p T ∂T p
∂Cp ∂p ∂2V ∂p
( ) ( ) = −T ( 2 ) ( )
∂p T ∂V T ∂T p ∂V T
∂Cp ∂2V ∂p
( ) = −T ( 2 ) ( )
∂V T ∂T p ∂V T

⎡ 2 ⎤
V2 ⎢ ∂ V ∂p ⎥⎥
Cp (T, V2 ) − Cp (T, V1 ) = −T ∫ ⎢( ) ( )
⎢ ∂T 2 ∂V T ⎥⎥
dp
V1 ⎢
⎣ p ⎦

Variation in Cv with volume

We start from the entropy as function of T and v
Cv ∂p
dS = dT + ( ) dV
T ∂T V
Applying the exactness test
∂ Cv ∂ ∂p
( ) = [( ) ]
∂V T T ∂T ∂T V V
∂Cv ∂2p
( ) = T ( 2)
∂V T ∂T V

V2 ∂2p
Cv (T, V2 ) − Cv (T, V1 ) = −T ∫ ( ) dV
V1 ∂T 2 V

Variation in Cv with pressure
∂Cv ∂2p
( ) = ( 2)
∂V T ∂T V
∂Cv ∂V ∂2p ∂V
( ) ( ) = ( 2) ( )
∂V T ∂p T ∂T V ∂p T
∂Cv ∂2p ∂V
( ) = ( 2) ( )
∂p T ∂T V ∂p T

p2 ∂2p ∂V
Cv (T, p2 ) − Cv (T, p1 ) = ∫ [( 2
) ( ) ] dp
p1 ∂T V ∂p T

Cp as function of p for propane

Calculation of changes in thermodynamic properties
Thermodynamic properties should be computed using experimental

(measurable) variables (T , p, V , Cp , Cv , etc.). In general, it is common
practice using (T , V ) and (T , p) pairs as independent variables.
• Accounting property changes using T and V as independent variables:
U (T ,V ), S(T ,V ), A(T , V ).
• Accounting property changes using T and p as independent variables:
H(T ,p), S(T ,p), G(T , p).

Thermodynamic properties using T and V
∂p
dU = Cv dT + [T ( ) − p] dV
∂T V
Cv ∂p
dS = dT + ( ) dV
T ∂T V
dA = −SdT − pdV
∂p ∂p
dG = [V ( ) − S] dT + V ( ) dV
∂T V ∂V T
∂p ∂V ∂p ∂V
dH = [Cp + ( ) [V − T ( ) ]] dT + ( ) [V − T ( ) ] dV
∂T V ∂T p ∂V T ∂T p

Thermodynamic properties using T and p
∂V
dH = Cp dT + [V − T ( ) ] dp
∂T p
Cp ∂V
dS = dT − ( ) dp
T ∂T p
dG = −SdT + V dp
∂V ∂p ∂V ∂p
dU = [Cv + ( ) [T ( ) − p]] dT + ( ) [T ( ) − p] dp
∂T p ∂T V ∂p T ∂T V
∂V ∂V
dA = [−S − p ( ) ] dT − p ( ) dp
∂T p ∂p T

Incompressible substance model (solids and liquids)

V does not change with T and p (i.e. V = constant).
∂V ∂V
( ) = 0; ( ) = 0; Cp = Cv = C
∂T p ∂p T
• H and S as functions of T and p
dH = Cp dT + V dp
Cp
dS = dT
T
• U and S as functions of T and V
dU = Cv dT
Cv
dS = dT
T

integrating
T2
H(T2 , p2 ) − H(T1 , p1 ) = ∫ Cp dT + V (p2 − p1 )
T1
T2 Cp
S(T2 ) − S(T1 ) = ∫ dT
T1 T
T2
U (T2 ) − U (T1 ) = ∫ Cv dT
T1
T2 Cv
S(T2 ) − S(T1 ) = ∫ dT
T1 T

p vs u diagram for propane

p vs s diagram for propane

Ideal gas model (gas and vapor)

The ideal gas model follows the pV T relation
pV = N RT
From this expression we obtain:
∂p R ∂V R
( ) = ; ( ) = ; Cp − Cv = R
∂T V V ∂T p p
• H and S as functions of T and p

dH = Cp dT
Cp R
dS = dT − dp
T p
• U and S as functions of T and V
dU = Cv dT
Cv R
dS = dT + dV
T V

integrating
T2
H(T2 ) − H(T1 ) = ∫ Cp dT
T1
T2 Cp p2
S(T2 , p2 ) − S(T1 , p1 ) = ∫ dT − R ln ( )
T1 T p1
T2
U (T2 ) − U (T1 ) = ∫ Cv dT
T1
T2 Cv V2
S(T2 , v2 ) − S(T1 , v1 ) = ∫ dT + R ln ( )
T1 T V1

Example
Find the isothermal-reversible compression work per kilogram of propane.
Assume ideal gas model. Account property changes using: (a) p and T as
independent variables (b) v and T as independent variables.

Example
Find the heat transfer rate and entropy change per kilogram of propane.
Assume ideal gas model. Account property changes using: (a) p and T as
independent variables (b) v and T as independent variables.

U and S from CEoS (gas and liquid)

The general form of a CEoS is:
RT a(T )
p= −
v − b (v + δ1 b)(v + δ2 b)
where:
R2 Tc2 RTc
a(T ) = a(Tc )f (T ); a(Tc ) = Ωa ( ); b = Ωb ( )
pc pc
√ 2
f (T ) = [1 + m(1 − Tr )]
EoS δ1 δ2 Ωa Ωb m
SRK 1√ 0√ 0.42748 0.08664 0.48 + 1.574 ω − 0.176ω 2
PR 1+ 2 1- 2 0.45724 0.0778 0.37464 + 1.54226 ω − 0.26992ω 2

The derivatives of interest are:

∂p R a′ (T )
( ) = −
∂T v v−b (v + δ1 b)(v + δ2 b)
∂p RT 2v + (δ1 + δ2 )b
( ) =− + a(T )
∂v T (v − b)2 [(v + δ1 b)(v + δ2 b)]2
∂v (∂p/∂T )v
( ) =−
∂T p (∂p/∂v)T
where, √
T a′ (T ) = −m a(Tc )a(T )Tr

replacing the derivatives in the expressions of du, ds as functions of T and v
a(T ) − T a′ (T )
du = cv dT + [ ] dv
(v + δ1 b)(v + δ2 b)
cv R a′ (T )
ds = dT + [ − ] dv
T v − b (v + δ1 b)(v + δ2 b)
integrating
u(T2 , v2 ) − u(T1 , v1 ) =
T2 a(T2 ) − T a′ (T2 ) δ 1 b + v2 δ1 b + v 1
∫ cv dT + [ln ( ) − ln ( )]
T1 (δ2 − δ1 )b δ 2 b + v2 δ 2 b + v1
s(T2 , v2 ) − s(T1 , v1 ) =
T2 cv v2 − b a′ (T2 ) δ 1 b + v2 δ1 b + v 1
∫ dT + R ln ( )− [ln ( ) − ln ( )]
T1 T v1 − b (δ2 − δ1 )b δ 2 b + v2 δ 2 b + v1

∆u vs p for propane as described by a CEoS

∆s vs p for propane as described by a CEoS

Example
Find the isothermal-reversible compression work per kilogram of propane.
Use PR EoS.

∆u, ∆h, ∆s: phase change
Heat capacities are not suitable to describe property changes during phase
change processes since its values are not defined for pure substances
during phase change.
We start using the G form of the fundamental equation for a closed
system:
dG = SdT − V dp
during phase change T = T sat and p = psat become constant, therefore,
dGT,p = 0


The Gibbs energy of a heterogeneous (closed) system is the contribution

of each phase present in the system1 ,
dG = dGπT,p
1
+ dGπT,p
2
= 0; Ô⇒ d(nπ1 g π1 ) + d(nπ2 g π2 ) = 0
Molar (or specific) Gibbs energy is constant during the phase change due
to T and p are constant,
g π1 dnπ1 + g π2 dnπ2 = 0
since the total number of moles in a closed, nonreactive system is constant
dn = dnπ1 + dnπ2 = 0; Ô⇒ dnπ1 = −dnπ2
at phase equilibrium molar (or specific) Gibbs energy is the same in each
phase,
g π1 = g π2 (T sat , psat )
1
Here we neglect surface energy effects.
further development of the phase equilibrium condition
hπ1 − T sat sπ1 = hπ2 − T sat sπ2
arranging terms
∆hphase = T sat ∆sphase
from the definition h = u + pv we obtain the following relation
∆hphase = ∆uphase + psat ∆v phase
where
∆v phase = v π2 (T sat ) − v π1 (T sat )

∆uphase = uπ2 (T sat ) − uπ1 (T sat )
∆hphase = hπ2 (T sat ) − hπ1 (T sat )
∆sphase = sπ2 (T sat ) − sπ1 (T sat )

Available phase change measurements for describing phase change process

are:
• Phase change enthalpies: ∆hphase (vaporization, melting,
sublimation).
• Saturation pressures: psat as function of T sat (vaporization, melting,
sublimation).
from these data we calculate:

• v π (T sat ) for each phase from a suitable pvT expression (e.g. CEoS
(vapor-liquid), Rackett (liquid), tables, etc.)
• ∆uphase and ∆sphase
∆uphase = ∆hphase − psat ∆v phase

∆hphase
∆sphase =
T sat

Wagner, Saul, Pruβ. International equation for the pressure along the melting and along the sublimation curve for ordinary
water substance. J. Phys. Chem. Ref. Data, 23:515-527, 1994.
T sat - psat relationship: Liquid-vapor
aτ + bτ 1.5 + cτ 2.5 + dτ 5
ln pvpr =
Tr

∆hv vs T : Watson’s correlation.
∆hV2 1 − Tr2 n
= ( )
∆hV1 1 − Tr1
Poling E., Prausnitz J., O’Conell J. The properties of gases and liquids, 5ed. McGrawHill, 2001.

Estimating ∆uV ∆sV and ∆hV using a CEoS
a(T sat ) − T a′ (T sat ) δ 1 b + vg δ 1 b + vf

∆uV = [ln ( ) − ln ( )]
(δ2 − δ1 )b δ 2 b + vg δ 2 b + vf
vg − b a′ (T sat ) δ1 b + vg δ1 b + vf
∆sV = R ln ( )− [ln ( ) − ln ( )]
vf − b (δ2 − δ1 )b δ2 b + vg δ2 b + vf
∆hV = ∆uV + psat (vg − vf )
where vg and vf are the vapor and liquid molar volumes given by the
CEoS at T sat and psat .

Hypothetical thermodynamic paths
Hypothetical thermodynamic path refers to the way we account changes in

thermodynamic properties. In general we follow a path varying one variable
at time, the order of the variation depends on the available information.
Typical available information
• Condensed phases (solid, liquid): cp (T ) and v(T ).

p (T ).
• Gas or vapor: equation of state, and cig
• Phase equilibrium: ∆hphase and T sat at normal conditions (1 atm),
psat (T )






Example
We are testing the performance of a turbine that uses propane as working fluid.
For a particular test we measured (at steady state) inlet and outlet pressures and
temperatures. From this data (see figure) find:
1 Work per kilogram of propane.
2 Entropy production per kilogram of propane.
Assumptions: adiabatic process, ∆P E and ∆KE << ∆H.
Use: (a) Ideal gas EoS. (b) PR EoS.

1. Balance equations
• Mass balance
ṁ1 = ṁ2
• Energy balance
ṁ1 h1 = ṁ2 h2 + Ẇ out Ô⇒ wout = h1 − h2
• Entropy balance
ṁ1 s1 + Ṡ gen = ṁ2 s2 Ô⇒ sgen = s2 − s1
2. Ancillary equations
• PR EoS: v and required pvT derivatives
• cp (kJ/kg-K) equation at p = 1.1 bar

3. Thermodynamic path: approach 1

Use PR EoS to calculate v1 (T1 , p1 ), vA (T1 , p2 ), v2 (T2 , p2 ) from
z 3 + d1 z 2 + d2 z + d3 = 0
where:
A
d1 = (δ1 + δ2 − 1)B − 1; d2 = −B (δ1 + δ2 + (δ1 − δ1 δ2 + δ2 )A − )
B
a(T )p bp
d3 = −B(A + B(1 + B)δ1 δ2 ); A= ; B=
(RT )2 RT

Suggested path for enthalpy:
h2 − h1 = (hA − h1 ) + (h2 − hA )
where:
hA − h1 = uA − u1 + p2 vA − p1 v1
a(T1 ) − T1 a′ (T1 ) δ1 b + vA δ 1 b + v1
uA − u1 = [ln ( ) − ln ( )]
(δ2 − δ1 )b δ2 b + vA δ 2 b + v1
T2
h2 − hA = ∫ cp dT
T1

Suggested path for entropy:
s2 − s1 = (sA − s1 ) + (s2 − sA )
where:
vA − b a′ (T1 ) δ1 b + vA δ1 b + v1
sA − s1 = R ln ( )− [ln ( ) − ln ( )]
v1 − b (δ2 − δ1 )b δ2 b + vA δ2 b + v1
T2 cp
s2 − sA = ∫ dT
T1 T

3. Thermodynamic path: approach 2

Use PR EoS to calculate v1 (T1 , p1 ), v2 (T2 , p2 ) from
z 3 + d1 z 2 + d2 z + d3 = 0
where:
A
d1 = (δ1 + δ2 − 1)B − 1; d2 = −B (δ1 + δ2 + (δ1 − δ1 δ2 + δ2 )A − )
B
a(T )p bp
d3 = −B(A + B(1 + B)δ1 δ2 ); A= ; B=
(RT )2 RT

Suggested path for enthalpy:
h2 − h1 = (uA − u1 ) + (u2 − uA ) + p2 v2 − p1 v1
where:
a(T1 ) − T1 a′ (T1 ) δ1 b + v2 δ1 b + v1
uA − u1 = [ln ( ) − ln ( )]
(δ2 − δ1 )b δ2 b + v2 δ2 b + v1
T2
u2 − uA = ∫ cv dT
T1

Suggested path for entropy:
s2 − s1 = (sA − s1 ) + (s2 − sA )
where:
v2 − b a′ (T1 ) δ1 b + v2 δ1 b + v1
sA − s1 = R ln ( )− [ln ( ) − ln ( )]
v1 − b (δ2 − δ1 )b δ2 b + v2 δ2 b + v1
T2 cv
s2 − sA = ∫ dT
T1 T

Example
We wish to design a devise to make dry ice (solid CO2 ) which could be
attached to the outlet tube of a cylinder of CO2 . Assume that the CO2 in
the cylinder consists of a liquid and gas in equilibrium at 300 K (67.01
bar), but that the outlet is connected only to the liquid phase by means of
an eductor tube.
• Suggest what you think would be a good engineering way to design
such a devise.
• How much dry ice at 1 bar do you think you could make per kilogram
of liquid CO2 drawn from the cylinder? (Use PR and IG EoS)
Data: hf g (300 K) = 103.7 kJ/kg, hcg (1 bar) = 570 kJ/kg, T sub (1 bar) =
194.7 K, cgp at 1 bar (kJ/kg K) = 26.62 + 0.0363 T (K) for 194 K ≤ T ≤
300 K.


An idea we think could work for our devise 2 . . .
2
Niu X., Yamaguchi H., Iwamoto Y., Neksa P. Experimental study on a CO2 solid-gas-flow-based ultra-low temperature
cascade.International Journal of Low-Carbon Technologies 6:93-99, 2011.
Reference states and thermodynamic tables3
The values of u, h, and s cannot be measured directly, and they are

calculated from measurable properties using the relations between
thermodynamic properties. However, those relations give the changes
in properties, not the values of properties at specified states.
Therefore, we need to choose a convenient reference state and assign a
value of zero for a convenient property or properties at that state.
Some reference states
• Water: sat. liq. at 0.01°C; uf = 0, sf = 0.

• R134a: sat. liq. at -40°C; hf = 0, sf = 0.
3
Cengel Y., Boles M. Thermodynamics an engineering approach, 8ed., McGraw-Hill, 2015.
Reference states in tables4
4
Note that5 . . .
• Some properties may have negative values as a result of the reference state
chosen.
• Sometimes different tables list different values for some properties at the
same state as a result of using a different reference state.
Let F be a state function, thus,
F 1 = F ref + [F 1 − F ref ]
F 2 = F ref + [F 2 − F ref ]
when we calculate F 2 − F 1 the reference state vanishes as long as we use the

same reference state.
5
Example
Derive a general route to compute u, h, s, g and a for propane (liquid,
liquid-vapor, and gas regions), using:
1 Reference state: Sat. liq. T = 233.15 K
• Liquid phase properties: v L (sat), cL
p
• Vapor-liquid equilibrium properties: hf g at 1 bar, pvap
• Gas(vapor) properties: IG EoS, cigp
2 Reference state: T = 298.15 K, p = 0.001 bar.
• PR EoS, cig
p , p
vap

Example
Determine the heat load to condense 10 kg/s of propane, using two approaches:
1 Incompressible liquid model and virial equation of state.
2 PR EoS to model the liquid and vapor pvT behavior of the compound, and
cig
p.
In both cases use the reference estate of propane Tables6 : -40 °C, sat. liq., h = 0
kJ/kmol-K, s = 0 kJ/kmol-K.
6
Moran M, Shapiro H, Fundamentos de termodinámica técnica, 2ed., Reverté, 2004.
1 Incompressible liquid model and virial equation of state.
f g = 18620.8 kJ/kmol, pvap = 1.11 bar, vf = 0.076 m /kmol,

Data: href ref ref 3
Tc = 369.8 K, pc = 42.5 bar, ω = 0.153, clp = 102 kJ/kmol-K,

−3
p = 68.032 × 10
cig + 22.59 × 10−5 T − 13.31 × 10−8 T 2 + 31.71 × 10−12 T 3 ,
p units are kJ/mol-K, and T in °C. R = 0.08314 bar m /kmol-K
where cig 3
Virial equation:
Bp
z =1+
RT
where:
RTc 0 0.422 0.172
B= (B + ωB 1 ); B 0 = 0.083 − ; B 1 = 0.139 −
pc T r1.6 T r4.2
Wagner equation:
−6.76368τ + 1.55481τ 1.5 − 1.5872τ 2.5 − 2.024τ 5
ln pvpr =
Tr
where,
pvap T
pvpr = ; Tr = ; τ = 1 − Tr
pc Tc
Thermodynamic path (liquid phase):
hl (T, p) = href + [h(T ref , p) − href ] + [h(T, p) − h(T ref , p)]

T
hl (T, p) = href + vfref (p − pref ) + ∫ clp dT
T ref
Stream 2: In this case T = T2 corresponds to T vap at p2 = 5 bar, since the

outlet stream is saturated liquid. T2 can be calculated solving the
following problem:
Find T2 , such that: p − pvap (T2 ) = 0
The iterative process gives us T2 = 274.87 K. Now we have all information

needed to compute hl (T2 , p2 ),
T2 kJ kJ
hl (T2 , p2 ) = href + vfref (p2 − pref ) + ∫ clp dT = 4285 or 97.39
T ref kmol kg

Thermodynamic path (gas phase):
hv (T, p) = href + href

f g + [h(T , p ) − hg ]+
ref ∗ ref
[h(T, p∗ ) − h(T ref , p∗ )] + [h(T, p) − h(T, p∗ )]
where:
p∗ ∂v
h(T ref , p∗ ) − href
g =∫ [v − T ( ) ] dp
pref ∂T p
T
h(T, p∗ ) − h(T ref , p∗ ) = ∫ cig
p dT
T ref
p ∂v
h(T, p) − h(T, p∗ ) = ∫ [v − T ( ) ] dp
p∗ ∂T p
p∗ is a low enough pressure to consider ideal gas behavior (z ≈ 1) in the

interval [T ref , T ]. In this case we set p∗ = 0.001 bar.

Using the virial EoS to evaluate the pvT behavior in the gas phase we
obtain:
RT ∂v RT dB
v= + B; and T ( ) = +T
p ∂T p p dT
where
dB RTc 0.6752 0.7224
T = [ 1.6 + ω 4.2 ]
dT pc Tr Tr
Stream 1: From these expressions we obtain the enthalpy change with
respect to the pressure in the gas phase, thus:

g =
p∗ ∂v dB
∫ [v − T ( ) ] dp = [B(T ref ) − T ref ( ) ] (p∗ − pref )
pref ∂T p dT T ref

The expression is calculated at:
T ref 233.15K
Tr = = = 0.63
Tc 369.8K
where
0.422
B 0 (T ref ) = 0.083 − = −0.80
T r1.6
0.172
B 1 (T ref ) = 0.139 − = −1.06
T r4.2
RTc 0 ref m3
B(T ref ) = (B (T ) + ωB 1 (T ref )) = −0.7
pc kmol
3
dB RTc 0.6752 0.7224 m
T ref ( ) = [ 1.6 + ω 4.2 ] = 1.58
dT T ref pc Tr Tr kmol
replacing terms we get

kJ
g = 252.43
kmol

Now, we evaluate the temperature change term at p = p∗
h(T, p∗ ) − h(T ref , p∗ ) =

T1
∫ (68.032 × 10−3 + 22.59 × 10−5 T − 13.31 × 10−8 T 2 + 31.71 × 10−12 T 3 )dT
T ref
After replacing T ref = −40°C and T1 = 30°C, we get

kJ
h(T, p∗ ) − h(T ref , p∗ ) = 4680
kmol

To evaluate the last term we need to calculate is the enthalpy change from p∗ to
p1 at T = T1 .
h(T1 , p1 ) − h(T1 , p∗ ) =
p ∂v dB
∫ [v − T ( ) ] dp = [B(T1 ) − T1 ( ) ] (p1 − p∗ )
p∗ ∂T p dT T1
The expression is calculated at:
T1 303.15K
Tr = = = 0.82
Tc 369.8K
where
0.422
B 0 (T1 ) = 0.083 − = −0.50
T r1.6
0.172
B 1 (T1 ) = 0.139 − = −0.26
T r4.2
RTc 0 m3
B(T1 ) = (B (T1 ) + ωB 1 (T1 ) = −0.39
pc kmol
dB RTc 0.6752 0.7224 m3
T1 ( ) = [ 1.6 + ω 4.2 ] = 0.84
dT T1 pc Tr Tr kmol

kJ
h(T1 , p1 ) − h(T1 , p∗ ) = −621.25
kmol
Now we add up terms in the expression
hv (T1 , p1 ) = href + href

f g + [h(T , p ) − hg ]+
ref ∗ ref
[h(T1 , p∗ ) − h(T ref , p∗ )] + [h(T1 , p1 ) − h(T1 , p∗ )]
kJ kJ
h(T1 , p) = 22931.98 or 521.18
kmol kg
The head load needed to condense the propane stream is -4238.2 kW.

2 PR EoS and cig

p
vap = 1.11 bar, Tc = 369.8 K, pc = 42.5 bar, ω = 0.153,

Data: pref
cp = 68.032 × 10−3 + 22.59 × 10−5 T − 13.31 × 10−8 T 2 + 31.71 × 10−12 T 3 ,
ig
p units are kJ/mol-K, and T in °C. R = 0.08314 bar

where cig
3
m /kmol-K
In this case both phases follow the same expression, namely:
h(T, p) = href + [h(T ref , p∗ ) − href ]+

T
p dT + [h(T, p) − h(T, p )]
cig ∗
∫
T ref

Stream 1
hv (T1 , p1 ) = href + [u(T ref , v(T ref , p∗ )) − uref ] + p∗ v(T ref , p∗ ) − pref v ref +
T1
∗ ∗ ∗
∫ p dT + [u(T1 , v1 ) − u(T1 , v(T1 , p ))] + p1 v1 − p v(T1 , p )
cig
T ref
Table: volumes for different states using PR
T (K) p (bar) pvap (bar) v (cm3 /mol ) Phase

233.15 1.110 1.110 71.29 sat. liq.
233.15 0.001 1.110 19’384672.28 vap.
303.15 5.000 10.79 4622.61 vap.
303.15 0.001 10.79 25’205041.95 vap.

Stream 2
hl (T2 , p2 ) = href + [u(T ref , v(T ref , p∗ )) − uref ] + p∗ v(T ref , p∗ ) − pref v ref +
T2
∗ ∗ ∗
∫ p dT + [u(T2 , v2 ) − u(T2 , v(T2 , p ))] + p2 v2 − p v(T2 , p )
cig
T ref
Table: volumes for different states using PR
T (K) p (bar) pvap (bar) v (cm3 /mol ) Phase

233.15 1.110 1.110 71.29 sat. liq.
233.15 0.001 1.110 19’384672.28 vap.
274.87 5.000 5.000 79.22 sat. liq.
274.87 0.001 5.000 22’853542.85 vap.

Ideal gas heat capacity
Ideal gas heat capacities cig 0

p or cp , are correlated using:
• Polynomial expression:
c0p = a + bT + cT 2 + dT 3 + ⋯
where a, b, c, . . . , are fitted constants.

• Hyperbolic functions (DIPPR7 ):
2 2
c3 /T c5 /T
c0p = c1 + c2 [ ] + c4 [ ]
sinh(c3 /T ) cosh(c5 /T )
where c1 ,. . . , c5 are fitted constants.
7
Design Institute for Physical Properties (DIPPR) - AIChE
Heat capacity correlations for liquids and solids
Condensed phase heat capacities cp or c, are correlated using polynomial

expressions8 :
cπp = a + bT ; (π = l, s)
c
cπp = a + bT + 2 ; (π = l, s)
T
where a, b, c are fitted constants.
8
Green W., Southard M. Perry’s Chemical Engineering Handbook, 9th ed.,
McGraw-Hill, 2018.
cp estimation methods
There are many methods to estimate cp . Some useful methods are

1 Joback’s method: Ideal gas heat capacity
2 Corresponding states method: Liquid heat capacity
3 Modified Kopp’s rule: solid and liquid heat capacity

Ideal gas cp estimation methods: Joback9
c0p (J/mole-K) = a + bT + cT 2 + dT 3 ; (273 K ≤ T ≤ 1000 K)

where:
a = ∑ Nk ak − 37.93
b = ∑ Nk bk + 0.210
c = ∑ Nk ck − 3.91 × 10−4
d = ∑ Nk dk + 2.06 × 10−7
Nk is the number of times a group k appears in the compound, and ak ,

bk , ck , dk are the group contributions to the terms a, b, c and d in the c0p
equation.
9
Joback K, Reid R. Estimation of pure-component from group-contributions. Chem.
Eng. Comm. 57:233-243, 1987.
Example
Use Joback’s method to estimate c0p of p-dichlorobenzene at: 298, 400,
800, and 1000 K. Compare your answer with experimental values.

The groups involved and its contributions are:
Group Type Nk ak bk ck dk
−Cl Non-ring 2 33.3 -9.63 × 10−2 1.87 × 10−4 -9.96 × 10−8
=C< Ring 2 -8.25 0.101 -1.42 × 10−4 6.78 × 10−8
= CH− Ring 4 -2.14 5.74 × 10−2 -1.64 × 10−6 -1.59 × 10−8
Summing group contributions:

−5 −7
∑ Nk ak = 41.54; ∑ Nk bk = 0.239; ∑ Nk ck = 8.42; ×10 ∑ Nk dk = −1.27×10
The estimated c0p (J/mole-K) expression as function of T is:
c0p = (41.54 − 37.93) + (0.239 + 0.21)T +

(8.42 × 10−5 − 3.91 × 10−4 )T 2 + (−1.27 × 10−7 + 2.06 × 10−7 )T 3

Liquid heat capacity estimation methods: Corresponding

states principle (CSP)10
crp cp − c0p 0.49 (1 − Tr )1/3 0.4355

= = 1.586 + + ω [4.2775 + 6.3 + ]
R R 1 − Tr Tr 1 − Tr
Of the substances in Appendix A, there are 212 that have values of clp
at 298 K. The deviation in clp was greater than 10% for 18 of the 212
substances. These 18 substances included the C1 to C4 alcohols and
acids, water, D2O, bromoethane, hydrazine, HF, SO3, N2O4, C6F14 ,
and isobutyl amine. Most of these 18 substances associate by forming
hydrogen bonds or dimers. For the other 194 substances, the average
absolute percent deviation in clp was 2.5%.
10
Poling B., Prausnitz J., O’Connell J., The properties of gases and liquids. 5th ed.,
McGraw-Hill, 2000.
Example
Use CSP correlation to estimate clp of cis-2-butene at 350 K. Compare
your answer with experimental values.
Data: Tc = 435.5 K and ω = 0.203. The ideal gas heat capacity at 350 K
is c0p = 91.21 J/mol-K.

The reduced temperature of cis-2-butene at 350 K is:

350K
Tr = = 0.804
435.5
Now we substitute the required values (Tr and ω) in the CSP correlation:
clp − c0p 0.49

= 1.586 + +
R 1 − 0.804
(1 − 0.804)1/3 0.435
0.203 [4.2775 + 6.3 + ] = 6.329
0.804 1 − 0.804
Finally, we get
J J J
clp = 8.314 6.329 + 91.21 = 143.909
mol K mol K mol K
Reported value clp = 151 J/mol-K.

Liquid and solid heat capacity estimation methods:

modified Kopp’s rules11
n
cp = ∑ ci Ni + cmisc Nmisc
i=1
where:
cp : Heat capacity at 298 K in J/mol-K

ci : Constant associated with each element i
Ni : Number of occurrences of element i
cmisc : Constant associated with elements not having a specific element
Nmisc : Number of occurrences of elements not having a specific element
n: Number of different elements in compound for which there are specific
constants
11
Hurst J., Harrison K. Estimation of liquid and solid heat capacities using modified
Kopp’s rule. Chem. Eng. Comm. 112:21-30, 1992.
Example
1 Use modified Kopp’s rule to to estimate csp of iron sulfate (F eSO4(s) )

at 298.15 K. Compare your answer with experimental values.
2 Use modified Kopp’s rule to to estimate clp of fluorobenzene
(C6 H5 F(l) ) at 298.15 K. Compare your answer with experimental
values.

• Compound: F eSO4(s)
Element Ni ci
Fe 1 29.08
S 1 12.36
O 4 13.42
csp = 1 ⋅ 29.08 + 1 ⋅ 12.36 + 4 ⋅ 13.42 = 95.12 J/mole-K. Reported value 100.7

J/mole-K.
• Compound: C6 H5 F(l)
Element Ni ci
C 6 13.08
H 5 9.2
F 1 19.47
clp = 6 ⋅ 13.08 + 5 ⋅ 9.2 + 1 ⋅ 19.47 = 144.12 J/mole-K. Reported value 146.5

J/mole-K.

Thermo Relations

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Thermodynamic Relationships

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 1 / 112

Thermodynamic laws and associated state variables

Law Concept Primitive Derived

State functions commonly used in thermodynamics

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 2 / 112

Fundamental equations for closed systems

and if the only work transfer is due to a reversible expansion

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 3 / 112

Fundamental equation (closed system)

dU = T dS − pdV Internal energy form

This equation involves state variables (path independent) only, therefore it

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 5 / 112

Fundamental equation in terms of derived properties

We might express the fundamental equation in terms of derived properties

T dS = d(T S) − SdT, and pdV = d(pV ) − V dp.

• Enthalpy form of the fundamental equation

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 6 / 112

Fundamental equation in terms of derived properties

• Helmholtz form of the fundamental equation

• Gibbs form of the fundamental equation

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 7 / 112

Diverse forms of the fundamental equations

dU = T dS − pdV Internal energy form

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 8 / 112

Thermodynamic state functions are mathematically defined as exact

This mathematical property allows us to relate the derivatives of different

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 9 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 10 / 112

Therefore, we establish the following relations:

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 11 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 12 / 112

Therefore, we establish the following relations:

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 13 / 112

Summary of some thermodynamic identities

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 14 / 112

Maxwell’s relation are obtained from the following theorem concerning

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 15 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 16 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 17 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 18 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 19 / 112

Summary of Maxwell’s relations

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 20 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 21 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 22 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 23 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 24 / 112

Let F = F (x, y), and x = x(y, F ), thus

replacing dx in the first equation and grouping terms

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 25 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 26 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 27 / 112

Measurable thermodynamic variables

The measurable thermodynamic variables (properties) are:

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 28 / 112

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 29 / 112

Thermal expansion, isothermal compressibility and pressure

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 30 / 112

Relation between Cp and Cv

We start by using the transformation: S(T, V ) → S(T, p); V = V (T, p)

The first PDE is rewritten using thermodynamic relations to replace the

D.F. Mendoza (Universidad de Antioquia) Thermodynamic Relationships 31 / 112