Thermodynamic Property Relations
Content: Mathematic Relations Maxwell Relation Clapeyron Equation General Relations for du, dh, ds cv and cp
Mathematical Relations
z = z ( x, y ) z z dz = dx + y dy x y x or dz = Mdx + Ndy z z where M = and N = y x y x Therefore, M y Then 2z 2z N = yx and x = xy y x M y N = x y x
(12-5)
Mathematical Relations
Partial Differential Relations x = x(y,z)
x x dx = y dy + z dz y z
z x z x z + dz = dy + dz z y x y x y y z y x x z z x z + dy = 1 dz z y x y x y y z y x
The variable y and z are independent. If y = const., then dy = 0 and z can be varied over a range of values (dz0) .
Mathematical Relations
The variable y and z are independent. If y = const., then dy = 0 and z can be varied over a range of values (dz0) . Reciprocity relation
1 x z x =1 = z y x y z y (z / x) y
Cyclic relation
z z x = y x y y z x x y z y = 1 z z x x y
The Tds Relations
Differential form of the conservation of energy equation for closed system (internally reversible process):
Qint rev Wint rev,out = U
But
Qint rev,out = TdS and
Wint rev,out = PdV
(12-10)
dU = TdS PdV or du = Tds Pdv
By h = u + Pv
or dh = du + Pdv + vdP
dh = Tds + vdP
(12-11)
Because these equations involve only state variables, they do not depend on path. So they must hold for both reversible and irreversible processes. These identities describe the change in one state variable in terms of changes in two other state variables.
The Maxwell Relations
Two other state variables can be defined, The Helmholtz function: The Gibbs function:
a = u Ts
(12-12)
g = h Ts = u + Pv Ts (12-13)
Use these definitions in (12-10)-(12-13),
da = sdT Pdv
(12-14) (12-15)
dg = sdT + vdP
The Maxwell Relations
Because u, h, a and g are state variables, and
u = u ( s, v), h = h( s, P), a = a(T , v), g = g (T , P)
each can be written in the form of exact differential. 1) For u, du = so 2) For h, so
u u ds + dv v s s v
but
du = Tds Pdv
u u = P =T , v s s v h h dh = ds + dP P s s P
h =T , s p h p =v s
but
dh = Tds + vdp
The Maxwell Relations
3) For a, da = so
a a dT + dv v T T v
a = P T v
but da = sdT Pdv
a = s , v T
4) For g, dg =
g g dT + dP P T T P
g p =v T
but
dg = sdT + vdP
so
g = s , T p
The Maxwell Relations
Apply Eq.(12-4) to each term:
T P = v s s v
(12-16)
Now recall that the condition for a function to be exact is,
dz = Mdx + Ndy
(12-4) (12-5)
P s = v T T v
T v = P s s p s V = P T T p
(12-17) (12-18)
M N = y x
u u du = ds + dv v s s v
u =T , s v u = P v s
(12-19)
(12-16)-(12-18) are called the Maxwell relations.
Clapeyron Equation
Clapeyron used to determine enthalpy change associated with a phase change (hfg) when P, v and T data are known. From Maxwells relations
T v = P s s P
(12-18)
During a phase change process, P = Psat = f (Tsat), therefore
P dP = T v dT sat
P = const. T sat
For an isothermal liquid-vapor phasechange process, the integration yields:
s fg dP = dT sat v fg
(12-21)
Clapeyron equation
During this process the pressure also remain constant, therefore from
dh = Tds + vdP
=0
(12-11)
dh = Tds
f f
and
h fg = Ts fg
Substituting this result into Eq. 12-21, the Clapeyron equation become
h fg dP = dT sat Tv fg
(12-22) (12-23)
and
h dP = 12 dT sat Tv12
Clapeyron-Clausius equation
To simplify the Clapeyron equation at low pressure vg>>vf and vfg vf . By treating the vapor as ideal gas
v g = RT / P
Ph fg dP = 2 dT sat RT
h fg dT dP or = R T 2 sat dT sat
ClapeyronClapeyron-Clausius equation become:
P2 h fg 1 1 ln P 1 R T1 T2 sat
Integrating this equation between two saturation state yields,
(12-24)
Internal Energy Change
Internal energy is a function of T and v, that is u = u(T,v)
u u du = dT + dv T v v T
from then
s du = cv dT + T v P dv T s P From Maxwell relations Eq.(12-17) = v T v T
P du = cv dT + T T P dv v Integrate from (T1, P1) to (T2, P2)
s s u dT + T P dv = cv and du = Tds Pdv du = T T v T v v T
Basic equation for entropy change
s T = cv T v
2 2 P u2 u1 = cv dT + T P dv T v v1 T1
Enthalpy change
Enthalpy is a function of T and P, that is h = h(T,P)
h h dh = dT + dP T P P T
h h s from = C P and dh = Tds + vdP = T + v T
P
P T
P T
then
v s From Maxwell relations Eq.(12-19) = T P
v dh = cP dT + v T T dP P Integrate from (T1, P1) to (T2, P2)
s dh = cP dT + T P + v dP T
P T
2 2 v h2 h1 = c p dT + v T dP T P T1 v1
Entropy Changes
Entropy is a function of T and v, that is s = s(T,v)
s s ds = dT + dv T v v T
First relation for entropy change:
s S from T = c v and From Maxwell relations Eq.(12-18) T v
P then ds = CV dT + dv T T v
12-38
V T P = T V
and s2 s1 =
T2
2 cv P dT + dv T v T T1 v1
Second relation for entropy change:
c s from = P T P T
= and From Maxwell relations Eq.(12-19) P T
T2
s
P2
V T p
then
C v ds = P dT dP T T P
12-40
dP and s2 s1 = T dT + T
T1 P 1 P
cp
Specific Heats cv and cp
For general pure substance, the specific heats depend on pressure, specific volume and temperature
2P cv = T T 2 v T v
and
2v cP = T T 2 P T P
The deviation of cp from cpo with increasing pressure:
P 2v (c p c po )T = T T 2 dP P 0
The integrating on the right-hand side requires a knowledge of the p-V-T behavior.
Relationship between cv and cp
From Eq. 12-38 and 12-40 solving for dT:
dT = T (P / T ) v T (v / T ) P dv + dP c p cv c p cv
From cyclic relation
P T v = 1 T v v P P T
Choosing T=T(v,P)
T T dT = dv + dP v P P v
then
P v P = T v T P v T
Substitute to Eq.12-45:
v P cP cv = T 12-46 T P v T
2
From equation coefficient:
v P cP cv = T T P v T
12-45
Relationship between cv and cp
From the volume expansivity, and the isothermal compressibility,
=
1 v v T P
and
1 v v P T
And Eq.12-46, we obtain a third general relation for cp-cv or Mayer Relation T 2 cP cv =
10
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