Properties of Pure Substances

Reading Problems
3-1 → 3-7 3-49, 3-52, 3-57, 3-70, 3-75, 3-106,
3-9 → 3-11 3-121, 3-123

Pure Substances

• a Pure Substance is the most common material model used in thermodynamics.

– it has a fixed chemical composition throughout (chemically uniform)
– a homogeneous mixture of various chemical elements or compounds can also be con-
sidered as a pure substance (uniform chemical composition)
– a pure substance is not necessarily physically uniform (different phases)

Phases of Pure Substances

• a pure substance may exist in different phases, where a phase is considered to be a physically
uniform
• 3 principal phases:

Solids:
– strong molecular bonds
– molecules form a fixed (but vibrating) structure (lattice)
Liquids:
– molecules are no longer in a fixed position relative to one another
– molecules float about each other
Gases:
– there is no molecular order
– intermolecular forces ≈ 0

Behavior of Pure Substances (Phase Change Processes)

• Critical Point: liquid and vapor phases are not distinguishable
• Triple point: liquid, solid, and vapor phases can exist together

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 P substances that substances that
expand on freezing contract on freezing

melting condensation
freezing LIQUID critical point

mel
ting

lting
n vaporization
tio
za
ori

me
vap
SOLID
triple point
sublimation VAPOR
on
ati sublimation
b lim
su

P0
P0
P0
P0
P0

G G
L L
S L
S

dQ dQ dQ dQ dQ

T critical point
sa
tur
line

ate
iquid

d
fusion

va

P0
l

po
ated

r li
line

ne
satur

L L+G
S+L
S
triple point line

S+G

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T − v Diagram for a Simple Compressible Substance
• consider an experiment in which a substance starts as a solid and is heated up at constant
pressure until it all becomes as gas

• depending on the prevailing pressure, the matter will pass through various phase transforma-
tions. At P0 :

1. solid
2. mixed phase of liquid and solid
3. sub-cooled or compressed liquid
4. wet vapor (saturated liquid-vapor mixture)
5. superheated vapor

The Vapor Dome

• general shape of a P − v diagram for a pure substance is similar to that of a T − v diagram

P
critical point gas (vapor)
subcooled
liquid two-phase region
Tcr
T (saturated liquid &
saturated vapor)
L+G
Psat(T) T

saturated saturated
vfg vapor line
liquid line

vf vg
v

• express values of properties for conditions on the vapor dome as:

specific volume: vf , vg and vf g = vg − vf

internal energy: uf , ug and uf g = ug − uf

specific enthalpy: hf , hg and hf g = hg − hf

specific entropy: sf , sg and sf g = sg − sf

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 • in the two phase region, pressure and temperature cannot be specified independently

Psat = P (Tsat) ⇔ Tsat = T (Psat)

this only holds true under the vapor dome in the two-phase region.

The Two-Phase Region

mg mg
Quality ⇒ x= =
m mg + mf

total mass of mixture ⇒ m = mg + mf

x = mg/m G mass fraction of the gas ⇒ x = mg /m

L mass fraction of the liquid ⇒ 1 − x = mf /m

1-x = mf/m

Properties of Saturated Mixtures

• all the calculations done in the vapor dome can be performed using Tables.

– in Table A-4, the properties are listed under Temperature

– in Table A-5, the properties are listed under Pressure

• use if given mixture:

1) is saturated, 2) has a quality, 3) liquid & vapor are present

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

= vf + x vf g
v − vf
x =
vf g

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Properties of Superheated Vapor

• superheated vapor is a single phase (vapor phase only).

– T and P are independent of each other in the single-phase region

– properties are typically calculated as a function of T and P

L P = 100 kPa
o
T = 200 C P
G
L+G
Tsat(P) state: 200 oC and 100 kPa

Properties of Sub-cooled Liquid

P
G
L L+G
P = 100 kPa
Tsat(P)
o
T = 20 C

P o
state: 20 C and 100 kPa

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 • can be treated as incompressible (independent of P )

v = v(T, P ) ⇒ v ≈ v(T ) = vf (T )

u = u(T, P ) ⇒ u ≈ u(T ) = uf (T )

s = s(T, P ) ⇒ s ≈ s(T ) = sf (T )

• while property values for the sub-cooled liquids are not available as a function of temperature
and pressure, they are available as a function of temperature only.

• for enthalpy:

h(T, P ) = u(T, P ) + v(T, P )P ≈ uf (T ) + vf (T )P

= uf (T ) + vf (T )Psat(T ) +vf (T )[P − Psat(T )]

  
hf (T )

= hf (T ) + vf (T )[P − Psat(T )]

Equation of State for Gaseous Pure Substances

Thermodynamic relations are generally given in three different forms:

Tables: water (Tables A-4 → A-8), R134a (Tables A-11 → A-13)

Graphs: water (Figures A-9 & A-10), R134a (Figure A-14)

Equations: air (Tables A-2 & 3-4)

• since most gases are highly superheated at atmospheric conditions. This means we have to
use the superheat tables – but this can be very inconvenient

• a better alternative for gases: use the Equation of State which is a functional relationship
between P, v, and T (3 measurable properties)

Ideal Gases

• gases that adhere to a pressure, temperature, volume relationship

P v = RT or P V = mRT

referred to as ideal gases

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 – where R is the gas constant for the specified gas of interest (R = Ru/M̃ )
Ru = Universal gas constant, ≡ 8.314 kJ/(kmol · K)

M̃ = molecular wieght (or molar mass) of the gas (see Table A-1))

• When is the ideal gas assumption viable?

– for a low density gas where:

∗ the gas particles take up negligible volume
∗ the intermolecular potential energy between particles is small
∗ particles act independent of one another
– Under what conditions can it be used?
∗ low density
∗ high temperatures - considerably in excess of the saturation region
∗ at very low pressures

Real Gases

• experience shows that real gases obey the following equation closely:

P v = ZRT (T and P are in absolute terms)

– this equation is used to find the third quantity when two others are known
– Z is the compressibility factor
– Note: Rair = 0.287 kJ/kg · K, RH2 = 4.124 kJ/kg · K

• what is the compressibility factor (Z)?

– Z charts are available for different gases, but there are generalized Z charts that can
be used for all gases
– if we “reduce” the properties with respect to the values at the critical point, i.e.

P
reduced pressure = Pr = Pc = critical pressure
Pc

T
reduced temperature = Tr = Tc = critical temperature
Tc

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Reference Values for u, h, s
• values of enthalpy, h and entropy, s listed in the tables are with respect to a datum where we
arbitrarily assign the zero value. For instance:

Tables A-4, A-5, A-6 & A-7: saturated and superheated water - the reference for both hf
and sf is taken as 0 ◦ C. This is shown as follows:
uf (@T = 0 ◦ C) = 0 kJ/kg

hf (@T = 0 ◦ C) = 0 kJ/kg

sf (@T = 0 ◦ C) = 0 kJ/kg · K

Tables A-11, A-12 & A-13: saturated and superheated R134a - the reference for both hf
and sf is taken as −40 ◦ C. This is shown as follows:
hf (@T = −40 ◦ C) = 0 kJ/kg

hf (@T = −40 ◦ C) = 0 kJ/kg

sf (@T = −40 ◦ C) = 0 kJ/kg · K

Others: sometimes tables will use 0 K as the reference for all tables. While this standard-
izes the reference, it tends to lead to larger values of enthalpy and entropy.

Calculation of the Stored Energy

• for most of our 1st law analyses, we need to calculate ΔE

ΔE = ΔU + ΔKE + ΔP E

• for stationary systems, ΔKE = ΔP E = 0

1
• in general: ΔKE = m(V22 − V12 ) and ΔP E = mg(z2 − z1 )
2
• how do we calculate ΔU ?

1. one can often find u1 and u2 in the thermodynamic tables (like those examined for the
states of water).
2. we can also explicitly relate ΔU to ΔT (as a mathematical expression) by using the
thermodynamic properties Cp and Cv .

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Specific Heats: Ideal Gases
• for any gas whose equation of state is exactly

P v = RT

the specific internal energy depends only on temperature

u = u(T )

• the specific enthalpy is given by

h = u + Pv

where

h(T ) = u(T ) + RT

Note: Since u = u(T ), and R is a constant, enthalpy is only a function of temperature.

• for an ideal gas

du
Cv = ⇒ Cv = Cv (T ) only
dT

dh
Cp = ⇒ Cp = Cp (T ) only
dT

From the equation for enthalpy,

RT = h(T ) − u(T )

If we differentiate with respect to T

dh du
R= −
dT dT

R = Cp − Cv

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 • the calculation of Δu and Δh for an ideal gas is given as

 2
Δu = u2 − u1 = Cv (t) dT (kJ/kg)
1
 2
Δh = h2 − h1 = Cp (t) dT (kJ/kg)
1

• to carry out the above integrations, we need to know Cv (T ) and Cp (T ). These are available
from a variety of sources

Table A-2a: for various materials at a fixed temperature of T = 300 K

Table A-2b: various gases over a range of temperatures 250 K ≤ T ≤ 1000 K
Table A-2c: various common gases in the form of a third order polynomial

Specific Heats: Solids and Liquids

• solids and liquids are incompressible. (i.e., ρ = constant).

• for solids and liquids it can be shown (mathematically) that for incompressible materials:

Cp = Cv = C and dQ = mCdT

• Table A-3 gives C for incompressible materials

• as with ideal gases, for incompressible materials C = C(T )

 2
Δu = C(T ) dT ≈ Cavg ΔT
1

Δh = Δu + Δ(P v) = Δu + vΔP ≈ Cavg ΔT + vΔP

– for solids:
Δh = Δu = Cavg ΔT (vΔP is negligible)

– for liquids:

If P = const, Δh = Cavg ΔT

If T = const, Δh = vΔP (we already used this to do more accurate

calculations in the subcooled region).

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