Agus Haryanto

Agricultural Engineering Dept.

16-02-2010
 Introduce the concept of a pure substance
 Discuss the physics of phase-change processes
 Illustrate the P-v, T-v, & P-T diagrams and P-v-T
surfaces of pure substances
 Demonstrate the use of property tables
 Describe “ideal gas” and the ideal-gas EOS
 Apply the ideal-gas EOS for typical problems
 Introduce the compressibility factor
 Present some of the best-known equations of
state.
 Is a substance that has a fixed chemical
composition throughout.
 Eg.: Water, N2, He, and CO2.
 A mixture of elements can be a pure substance
if the mixture is homogeneous. (Eg.: Air)
 Mixture of oil & water is NOT a pure substance.
 Mixture of two phases is a pure substance if the
chemical composition is the same.
 Mixture of ice n water is a pure substance.
 Mixture of liquid air and gaseous air is NOT
since the composition is different.
A phase : distinct molecular arrangement that is
homogeneous throughout and separated from
the others by boundary surfaces.
 Primary: Solid, Liquid, Gas
 A substance may have several phases, each with
a different molecular structure:
* Carbon: 2 solid phases (graphite or diamond).
* Helium: 2 liquid phases
* Iron: 3 solid phases
* Ice: 7 phases at high pressures.
 The molecules are
arranged in a three-
dimensional pattern
(lattice).
 Intermolecular bonds are
so strong that molecules
are closely packed.
 The attractive forces
(turn to repulsive forces)
of molecules on each
other are large and keep
the molecules at fixed
positions.
 The molecular spacing is almost similar to solid,
they are not in fixed positions.
 Groups of molecules move about each other
 They can rotate and translate
freely.
 Intermolecular forces are
weaker than solids, but
stronger than gases.
 The distances between
molecules increase as a solid
turns liquid, except for water.
 Molecules are far apart.
 No molecular order.
 Molecules move about at
random, continually colliding
with each other and the walls.
 Intermolecular bonds are
weak (Intermolecular forces
are small)
 Interaction between the molecules are collisions
 Molecules are at a considerably higher energy
level  release a large amount of energy before
gas condense or freeze.
 There are many practical situations where
two phases of a pure substance coexist in
equilibrium.
 Water exists as a mixture of liquid and vapor
in the boiler and the condenser of a steam
power plant (PLTU).
 The refrigerant turns from liquid to vapor in
the freezer of a refrigerator.
 Our focus: the liquid and vapor phases and
their mixture.
 A piston–cylinder
containing liquid water at
20°C and 1 atm pressure
(state 1).
 Water exists in the liquid
phase, called compressed
liquid, or a subcooled
liquid, meaning that it is
not about to vaporize.
 Heat is added (to 40oC) but,
water slightly expands,
piston slightly increase, P
still 1 atm, phase State 1:
compressed liquid. compressed liquid
 More heat is added until it
reaches 100°C and 1 atm
(state 2).
 Water starts to boil
 Still a liquid, but any heat
addition will cause some of
the liquid to vaporize.
 A liquid that is about to
vaporize is called a
saturated liquid.
 A phase-change process
from liquid to vapor is State 2:
about to take place. saturated liquid
 More heat is added 
phase change occurs.
 Liquid water turn to
vapor.
 State 3: saturated
liquid – vapor mixture
(saturated liquid and
vapor coexist I
equilibrium).
 T = 100°C and 1 atm
 Gas volume increases, State 3:
liquid decrease. saturated liquid –
vapor mixture
 More heat is added all
liquid water turn to vapor.
 State 4: saturated vapor
(vapor that is about to
condense)
 T = 100°C and 1 atm
 Any heat loss from this
vapor will cause some of
the vapor to condense State 4:
(phase change from Saturated vapor
vapor to liquid).
 More heat is added  T
increases, v increases
 State 5: superheated
vapor (vapor that is NOT
about to condense)
 T = 300°C and 1 atm
 The END  P-v Diagram

State 5:
Superheated vapor
T-v Diagram
 “water boils at 100°C” (INCORECT)
 “water boils at 100°C at 1 atm” (CORECT)
 The temperature at which a pure substance
changes phase is called the saturation
temperature Tsat.
 The pressure at which a pure substance
changes phase is called the saturation
pressure Psat.
 @ 101.325 kPa, Tsat is 99.97°C.
 @ 99.97°C, Psat is 101.325 kPa.
 @ 100.00°C, Psat is 101.42 kPa.
 More: see Saturation tables
liquid–vapor saturation curve
Psat = f(Tsat)
Variation of
the standard
atmospheric
pressure and
the boiling
(saturation)
temperature
of water with
altitude
 Large energy is required to melt a solid or vaporize
a liquid.
 The amount of energy absorbed or released during
a phase-change process is called the latent heat.
 Latent heat of fusion is energy absorbed during
melting (= energy released during freezing).
 Latent heat of vaporization is energy absorbed
during vaporization (= energy released during
condensation).
 Latent heats depend on T or P of phase change.
 @ 1 atm, latent heat of fusion of water is 333.7 kJ/kg
and latent heat of vaporization is 2256.5 kJ/kg.
T-v Diagram
T-v Diagram
T-v Diagram
P-v Diagram
P-v Diagram
Including
Solid phase
P-v-T Surface
P-v Diagram
WATER
P-v-T Surface
For WATER
 Under some conditions: all three phases of a pure
substance coexist in equilibrium.
 On P-v or T-v diagrams, these triple-phase states
form a line called the triple line.
 The states on the triple line of a substance have
the same P and T but different v.
 On the P-T diagrams triple line appears as a
point, therefore, is called the triple point.
 No substance can exist in the liquid phase in
stable equilibrium at P < Ptp.
 Water: 0.01°C,
0.6117 kPa

P-T Diagram Including

Solid phase
 Two ways a substance can pass from the solid to
vapor phase:
1. it melts first into a liquid and then evaporates, or
2. it evaporates directly (called sublimation).
 The 2nd case occurs at P < Ptp value, since a pure
substance cannot exist in the liquid phase at those
pressures.
 For substances that have a Ptp > Patm such as solid
CO2 (dry ice), kapur barus, sublimation is the only
way to change from the solid to vapor phase at
atmospheric conditions.