Universidad EAFIT

Escuela de Ingeniería

Termodinámica

Propiedades de una Sustancia Pura

I.M. Luis Santiago París Londoño

2011
 El Postulado de estado para una
sustancia pura, simple compresible

El estado de una
• Sustancia pura (no mezclada ni contaminada)
• simple compresible (solo un tipo de trabajo: el de
la deformación de los límites del sistema, es decir
en ausencia de efectos eléctricos, magnéticos, de
tensión superficial, elásticos, etc.),
• y en equilibrio termodinámico,
está completamente determinado o especificado
por dos propiedades intensivas independientes.
 Preguntas claves
• Para el estado de una sustancia pura (sistema),
cuales son las dos propiedades intensivas
independientes?
• R/: Depende si la sustancia está en una sola fase o
si coexisten varias fases.
• Como se determinan el resto de propiedades
conociendo dos propiedades intensivas
independientes?
• R/ Mediante las ecuaciones de estado, expresadas
en la forma de tablas, cartas o expresiones
matemática, o en bases de datos especializadas.
 Experimento:
Calentamiento de agua a Presión constante
P = 1atm

compressed saturated saturated

saturated superheated
liquid liquid–vapor
liquid. mixture.
vapor vapor
subcooled
liquid.
 Representación gráfica del Experimento:
Calentamiento de agua a Presión P constante
( De Líquido a vapor)

Datos y resultados del

Experimento:
• P = 101.3 kPa
• Tsat =100 C
• vf = 0.001 m3/kg
• vg = 1.67 m3/kg

vf vg
Repetición del calentamiento del agua a
diferentes Presiones.
(Proceso de cambio de fase)
Diagrama T-v de una sustancia Pura.
Identificación de regiones
Diagrama P-v de una sustancia pura.
Identificación de regiones
The 3D P-v-T surfaces present a great deal of information at once, but in a
thermodynamic analysis it is more convenient to work with 2-dimensional
diagrams, such as the P-v and T-v diagrams.

P-v-T surface of a substance that P-v-T surface of a substance that

contracts on freezing. (CO2) expands on freezing (like water). 9
 Diagrama de fases P-T

For water,
Ttp = 0.01°C
A bajas Ptp = 0.6117 kPa
presiones (por
debajo del punto At triple-point
triple), el solido pressure and
(hielo) se temperature, a
evapora sin substance
fundirse primero exists in three
(sublimación). phases in
equilibrium.
Resumen: diagramas P-v, T,v , P,T
 For water,
Ttp = 0.01°C
Extending the Ptp = 0.6117 kPa

Diagrams to Include At triple-point pressure and

temperature, a substance
the Solid Phase exists in three phases in
equilibrium.

P-v diagram of a substance that P-v diagram of a substance that expands

contracts on freezing. on freezing (such as water).
 Liquido saturado.
Vapor saturado.
• Durante los procesos de
– vaporización, evaporación o ebullición, o de
– condensación o licuefacción,
las fases líquida y gaseosa coexisten en equilibrio
termodinámico.

• En esta condiciones, el líquido se llama líquido

saturado y el vapor se llama vapor saturado.
 Temperatura y Presión de Saturación
• The temperature at which water starts boiling depends on the pressure; therefore, if the
pressure is fixed, so is the boiling temperature.
• Water boils at 100°C at 1 atm pressure.
• Saturation temperature Tsat: The temperature at which a pure substance changes
phase at a given pressure.
• Saturation pressure Psat: The pressure at which a pure substance changes phase at a
given temperature.

The liquid–
vapor
saturation
curve of a pure
substance
(numerical
values are for
water).

14
 Temperatura de saturación
Presión de saturación.
• Durante un proceso de cambio de fase de una
sustancia pura:
– P y T no son propiedades independientes,
– la presión P y la temperatura T son propiedades
dependientes,
– Es decir P = f(T)
• y por lo tanto no se pueden emplear para
identificar el estado de la sustancia segun el
postulado de estado para una sustancia pura,
simple compresible.
 Temperatura de saturación.
Presión de saturación. ( Cont.)
• Para una presión dada P, una sustancia pura
cambia de fase a una temperatura fija T
llamada temperatura de saturación
• Para una temperatura dada T, una sustancia
pura cambia de fase a una presión fija P
llamada presión de saturación
• Para el agua: Ps ≈ f EXP[g/(T+h)] con
f = 1,40974x107kPa g = -3928.5C h = 231,667C
Patm = Po EXP(-gz / RaT)

Po = 101.32 kPa
g = 9.81 m/s2
Ra = 287 J/kg-K

Tsat ≈ g/ln(Patm / f ) - h
f = 1,40974x107kPa
g = -3928.5C
h = 231,667C
 Líquido comprimido o
subenfriado
• Dependiendo del nivel de energía, una
sustancia pura puede existir en diferentes fases.
• Si una sustancia está en fase líquida y en
estados alejado de la condición de vaporización
se dice que es líquido comprimido o sub-
enfriado.
• Por ejem. Agua a Patm=86 kPa y 15°C
Vapor recalentado o sobrecalentado

• Si una sustancia está en fase gaseosa

(Vapor), y sus estados termodinámicos no
corresponden a la condición para
condensación, es un vapor recalentado
• Ej.: Vapor de agua a
– P = 101.3 kPa
– T = 150 °C
Está en fase gaseosa como vapor recalentado
 Concepto de Calidad, x
• En una mezcla saturada de líquido y vapor,
la fracción másica de vapor se llama la
calidad x, definida como:
m
x = vapor

m total 0 ≤ x ≤1 Vg , mg
m vapor
x =
m liq + m vapor
Vf , mf
• Líquido saturado: x=0
• Vapor saturado: x=1
Diagrama T- v mostrando los puntos de líquido (f)
y vapor saturado (g)
 Relaciones con el concepto de Calidad, x
V y m propiedades extensivas: aditivas
m = m f + mg V = V f + Vg

V Vf Vg mg mf
Definiciones v= vf = vg = x= (1 − x ) =
m mf mg mtotal mtotal

Desarrollo
V Vg + V f Vg V f v g m g v f m f Vg , mg
v= = = + = +
m m m m m m
V  mg   mf 
v = =  vg +  v f = xvg + (1 − x )v f Vf , mf
m  m   m 
v − vf v − vf
Relaciones v = xvg + (1 − x )v f x= =
vg − v f v fg
 Propiedades intensivas de una
mezcla saturada (de fases)
• En la región de mezclas saturadas, el valor promedio
de cualquier propiedad intensiva genérica y se puede
determinar conociendo la calidad x y los valores yf
del liquido saturado (f) y yg del vapor saturado (g)

y = xy g + (1 − x) y f
y = y f + xy fg con y fg = y g − y f
y : v, u, h, s
 Saturated Liquid–Vapor Mixture
Quality, x : The ratio of the mass of vapor to the total mass of the mixture.
Quality is between 0 and 1 0: sat. liquid, 1: sat. vapor.
The properties of the saturated liquid are the same whether it exists alone or in
a mixture with saturated vapor.
Temperature and pressure
are dependent properties
for a mixture.

The relative
amounts of
liquid and vapor
phases in a
saturated
mixture are
specified by the
quality x.
A two-phase system can be
treated as a homogeneous
mixture for convenience.
 y v, u, or h.

Quality is related
to the horizontal
distances on P-v
and T-v diagrams.

The v value of a
saturated liquid–vapor
mixture lies between
the vf and vg values at
the specified T or P.
25
 PROPERTY TABLES
• For most substances, the relationships among thermodynamic properties are too complex
to be expressed by simple equations.
• Therefore, properties are frequently presented in the form of tables.
• Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties.
• The results of these measurements and calculations are presented in tables in a
convenient format.
Enthalpy—A Combination Property

The combination
u + Pv is
frequently
encountered in
the analysis of The product pressure ×
control volumes. volume has energy units.
 Tabla de
propiedades
del agua
Saturada
 Saturated Liquid and Saturated Vapor States
• Table A–4: Saturation properties of water under temperature.
• Table A–5: Saturation properties of water under pressure.
A partial list of Table A–4.

Enthalpy of vaporization, hfg (Latent

heat of vaporization): The amount of
energy needed to vaporize a unit mass of
saturated liquid at a given temperature or
pressure.
 Tabla de
propiedades
del vapor de
agua
sobrecalentada
Ejemplo:
Para Agua:
Si T=90C determinar:
Presión de saturación,
volumen especifico del
liquido saturado (x=0) y
del vapor saturado (x=1)

"Propiedades del Agua empleando EES"

T1 = 90 [C]
P_sat = P_SAT(Water,T=T1)
v_f = VOLUME(Water,T=T1,x=0)
v_g = VOLUME(Water,T=T1,x=1)

P_sat = 70.12 [kPa]

T1 = 90 [C]
v_f = 0.001036 [m^3/kg]
v_g = 2.362 [m^3/kg]
Ejemplo:
Para Agua: "Propiedades del Agua empleando EES"
Si P = 50 PSIa determinar: {sistema unidades Ingles (E)}
Temperatura de saturación,
volumen especifico del P1 = 50 [PSI]
liquido saturado (x=0) y T_sat = T_SAT(Water,P=P1)
del vapor saturado (x=1) v_f = VOLUME(Water,P=P1,x=0)
v_g = VOLUME(Water,P=P1,x=1)
V = 2 [ft^3]
m = V/v_g

m = 0.2346 [lb_m]
P1 = 50 [PSI]
T_sat = 281 [F]
V = 2 [ft^3]
v_f = 0.01727 [ft^3/lb_m]
v_g = 8.523 [ft^3/lb_m]
Ejemplo:
Para Agua: "Propiedades del Agua empleando EES"
Si P = 100 kPa determinar: {sistema unidades SI }
Temperatura de saturación, P1 = 100 [kPa]
volumen especifico del T_sat = T_SAT(Water,P=P1)
liquido saturado (x=0) y v_f = VOLUME(Water,P=P1,x=0)
del vapor saturado (x=1) v_g = VOLUME(Water,P=P1,x=1)
rho_f = 1/v_f
rho_g = 1/v_g

P1 = 100 [kPa]
rho_f = 958.7 [kg/m^3]
rho_g = 0.5897 [kg/m^3]
T_sat = 99.61 [C]
v_f = 0.001043 [m^3/kg]
v_g = 1.696 [m^3/kg]
Ejemplo: Para Agua: "Propiedades del Agua empleando EES"
Si T = 90 C mg = 2 kg mf = 8 kg {sistema unidades SI }
determinar: m_g = 2[kg]
Presion de saturación, m_f = 8[kg]
volumen especifico del T1 = 90 [C]
liquido saturado (x=0) y P_sat = P_SAT(Water,T=T1)
del vapor saturado (x=1) v_f = VOLUME(Water,T=T1,x=0)
v_g = VOLUME(Water,T=T1,x=1)
Calidad x
x = m_g/m { def. calidad}
volumen especifico de la mezcla m = m_g+m_f { Masa total}
v = x*v_g+(1-x)*v_f { volumen esp. mezcla}

m = 10 [kg]
m_f = 8 [kg]
m_g = 2 [kg]
P_sat = 70.12 [kPa]
T1 = 90 [C]
V = 0.4732 [m^3/kg]
v_f = 0.001036 [m^3/kg]
v_g = 2.362 [m^3/kg]
x = 0.2
Ejemplo: Para R134a: "Propiedades del R134a empleando EES"
Si P = 160 kPa mg = 4 kg {sistema unidades SI }
mf = 6 kg determinar: m_g = 4[kg]
Temperatura de saturación, m_f = 6[kg]
volumen especifico del P1 = 160 [kPa]
liquido saturado (x=0) y T_sat = T_SAT(R134a,P=P1)
del vapor saturado (x=1) v_f = VOLUME(R134a,P=P1,x=0)
Calidad x v_g = VOLUME(R134a,P=P1,x=1)
volumen especifico de la mezcla x = m_g/m { def. calidad}
m = m_g+m_f { Masa total}
v = x*v_g+(1-x)*v_f { volumen esp. mezcla}
Vg = m_g*v_g
Vf = m_f*v_f
F_vol = Vg/(Vf+Vg){fraccion volum del vapor}

F_vol=0.991 x=0.4
m=10 [kg] m_f=6 [kg] m_g=4 [kg]
P1=160 [kPa] T_sat=-15.6 [C]
v=0.04984 [m^3/kg]
Vf=0.004462 [m^3] Vg=0.4939 [m^3]
v_f=0.0007437 [m^3/kg] v_g=0.1235 [m^3/kg]
In this region, In the region to the
right of the saturated vapor line
Superheated Vapor
and at temperatures above the Compared to saturated vapor, superheated
critical point temperature, a vapor is characterized by
substance exists as superheated
vapor.
temperature and pressure are
independent properties.

At a specified P,
superheated
vapor exists at a
higher h than the
saturated vapor.

A partial
listing of
Table A–6. 35
The compressed liquid properties Compressed Liquid
depend on temperature much more Compressed liquid is characterized
strongly than they do on pressure.
by
y → v, u, or
h
A more accurate relation for h

At a given P and
T, a pure
substance will
exist as a
A compressed liquid compressed
may be approximated as liquid if
a saturated liquid at the
given temperature.
36
 Reference State and Reference Values
• The values of u, h, and s cannot be measured directly, and they are calculated from measurable
properties using the relations between 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.
• The referance state for water is 0.01°C and for R-134a is -40°C in tables.
• 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.
• However, In thermodynamics we are concerned with the changes in properties, and the reference
state chosen is of no consequence in calculations.
 THE IDEAL-GAS EQUATION OF STATE
• Equation of state: Any equation that relates the pressure, temperature, and
specific volume of a substance.
• The simplest and best-known equation of state for substances in the gas phase is
the ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas
quite accurately within some properly selected region.

Ideal gas equation of state

R: gas constant
M: molar mass (kg/kmol)
Ru: universal gas constant

Different substances have different gas

constants.
Mass = Molar mass × Mole number Ideal gas equation at two
states for a fixed mass
Real gases behave as
an ideal gas at low
Various
densities (i.e., low
expressions pressure, high
of ideal gas temperature).
equation

The ideal-gas relation

Properties per often is not applicable to
unit mole are real gases; thus, care
denoted with a should be exercised
bar on the top. when using it.
 Ecuaciones de Estado
Para los gases ideales
ℜ : Constante Universal de los gases
PV = nℜT = nR T ℜ = 8.31447 kJ/kmol

PV = mRT R: Constante particular del gas

V  ℜ R
P  = RT Pv = RT R= =
m PM PM

Para los gases reales

Pv
Pv = ZRT Z= Z: Factor de compresibidad
RT
 COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
Compressibility factor Z A The farther away Z is from unity, the more the gas
factor that accounts for the deviates from ideal-gas behavior.
deviation of real gases from Gases behave as an ideal gas at low densities (i.e.,
ideal-gas behavior at a given low pressure, high temperature).
temperature and pressure. Question: What is the criteria for low pressure and
high temperature?
Answer: The pressure or temperature of a gas is high
or low relative to its critical temperature or pressure.

At very low pressures, all gases approach

The compressibility factor is
ideal-gas behavior (regardless of their
unity for ideal gases.
temperature).
 Reduced pressure Reduced temperature

Pseudo-reduced
specific volume Z can also be determined from
a knowledge of PR and vR.

Gases deviate from the

ideal-gas behavior the
most in the neighborhood
of the critical point.
Comparison of Z factors for various gases.
 Z: Factor de compresibidad

El factor de compresibidad Z para el Nitrógeno

 OTHER EQUATIONS OF
STATE
Several equations have been proposed to
represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals Equation of State

Critical isotherm
of a pure
substance has an
inflection point at
the critical state.

This model includes two effects not considered in the

ideal-gas model: the intermolecular attraction forces
and the volume occupied by the molecules
themselves. The accuracy of the van der Waals
equation of state is often inadequate.
Beattie-Bridgeman Equation of State

The constants are given in Table

3–4 for various substances. It is
known to be reasonably accurate
for densities up to about 0.8ρcr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 3–4. This equation can handle substances
at densities up to about 2.5 ρcr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are

functions of temperature alone are called virial coefficients.
 Complex equations of
state represent the P-v-T
behavior of gases more
accurately over a wider
Percentage of error involved in various equations of
range.
state for nitrogen N2
(% error = [(|vtable - vequation|)/vtable] ×100).
 Is Water Vapor an Ideal Gas?

• At pressures below 10 kPa, water

vapor can be treated as an ideal gas,
regardless of its temperature, with
negligible error (less than 0.1 percent).
• At higher pressures, however, the ideal
gas assumption yields unacceptable
errors, particularly in the vicinity of
the critical point and the saturated
vapor line.
• In air-conditioning applications, the
water vapor in the air can be treated as
an ideal gas. Why?
• In steam power plant applications,
however, the pressures involved are
usually very high; therefore, ideal-gas
relations should not be used.

Percentage of error ([|vtable - videal|/vtable] ×100) involved in assuming

steam to be an ideal gas, and the region where steam can be treated as an
ideal gas with less than 1 percent error.
 N.B.
• Latent heat: The amount of energy absorbed or released during a
phase-change process.
• Latent heat of fusion: The amount of energy absorbed during
melting. It is equivalent to the amount of energy released during
freezing.
• Latent heat of vaporization: The amount of energy absorbed during
vaporization and it is equivalent to the energy released during
condensation.
• The magnitudes of the latent heats depend on the temperature (T) or
pressure (P) at which the phase change occurs.
• At 1 atm pressure, the latent heat of fusion of water is hif = 333.7
kJ/kg and the latent heat of vaporization is hfg =2256.5 kJ/kg.
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation.
 Summary
• Pure substance
• Phases of a pure substance
• Phase-change processes of pure substances
– Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
– Saturation temperature and Saturation pressure
• Property diagrams for phase change processes
– The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface
• Property tables
– Enthalpy
– Saturated liquid, saturated vapor, Saturated liquid vapor mixture,
Superheated vapor, compressed liquid
– Reference state and reference values
• The ideal gas equation of state
– Is water vapor an ideal gas?
• Compressibility factor
• Other equations of state