CHE 3473

Chemical Engineering Thermodynamics

Room A-235, SEC
M, W, F, 9:30-10:20 AM

Lecture 7
Phase Diagram

From the previous lecture

a. First Law for closed system & steady-state flow
b. Phase Rule:

F = 2 +N
Non-reacting system

Q & A
1. HW 1 solution & grade available at D2L.
2. Please pick your HW1 from the same file holder.

Reversible vs. Irreversible Processes

Reversible: A process for which a system can be restored to its
initial state, without leaving a net influence on the
system or its environment.
* idealized, frictionless;
* proceeds slowly enough for the system to remain in
thermodynamic equilibrium with the surroundings.
Irreversible: Not reversible
* natural;
* proceeds freely, spontaneously;
* interacts with environment, can not be exactly reversed

Example of a Reversible Process

(I) Pendulum
No friction forces. The state of
both the pendulum and its
surroundings would be restored
at the end of each period motion.
(II) Piston
No friction between Piston
and Cylinder
Piston moves infinitesimally
Slowly so gas is always in eqbm.

Why are Reversible Processes Important?

Real processes are irreversible, not reversible. However,
reversible processes are important because:
1.We can calculate changes in properties of the system
(volume, pressure, temperature, enthalpy, heat capacity,
etc.) for reversible processes from our equation of state.
2.These changes in properties are independent of the path
taken in making the change, whether it is reversible or
irreversible. Thus the change in the property calculated for
a reversible process is the same as the change that actually
occurs for the real, irreversible process.

Phases of a Pure Substance

Solid:
-The molecules in a crystalline solid are kept at their
positions by the large spring-like intermolecular
forces.
-The attractive and repulsive forces between the
molecules tend to maintain them at relatively
constant distances from each other.
Liquid:
- Groups of molecules are close packed but move
about each other.
Gas:
- Molecules are usually far apart and move about freely.

Phase-Change Processes of Pure Substance

Compressed liquid or a subcooled liquid: A liquid
that is not about to vaporize.
Saturated liquid: A liquid that is about to vaporize, is
in equilibrium with the vapor.
Saturated vapor: A vapor that is about to condense,
is in equilibrium with the liquid.
Saturated liquid-vapor mixture: the liquid and vapor
phases coexist in equilibrium.
Superheated vapor: A vapor that is not about to
condense a vapor whose temperature is above the
condensation temperature for that pressure.

Diagram for heating process of water

T-V diagram for the heating process of water at constant pressure, P=1 atm.
From the McGraw-Hill Companies, Inc

PVT Diagram
P

L+S
L-G

B1(S)
G+L

B2(L)
S+G

V
S-G

B3(G)

L-G
Gas

PVT Diagram
Notes:
1) For P=0, PV=RT (Ideal Gas)
2) As P increases, the attractive forces produce
condensation for T<Tc
3) Phase rule says:
F=N-+2=3-
=1 phase F=2 (surface)
=2 phase F=1 (line)
4) At C, the critical point, the gas-liquid lines vanish. The G
and L phases become identical here. Discovered by Thomas
Andrews (1869)

PVT Diagram
5) B1, B2, B3 and the line connecting them
represent the triple point-G, L, S in equilibrium,
can only occur at this one point in the phase
diagram. Here F=N-+2=1-3+2=0.
For H2O:
Tt=273.16 K (0.01 )
Pt=611.73 Pa (0.0061173 bar)
6) The S-L transition does not have a critical point.

PVT Diagram
7) Because of the gas-liquid line
(a) Liquid can't exist for T>Tc
(b) Can have LG, and GL without a phase
transition - see next figure
8) Typically:
Pt 1mmHg (exception CO2 :Pt5bar)
Pc 50bar (2~200bar)

PVT Diagram Projections

Melting

Liquid

Pc

Pt

Vaporization

Solid

Gas

Sublimation

Tt

Tc

PV Diagram Projections
At Point C:

T4

S+L

T3

L+G
G

B1
A

B2

2P
(
) =0
2 T ,C
V

Tc

L
S

P
(
) T ,C = 0
V

3P
(
)
<0
3 T ,C
V

T2

S+G

T1
V

Water Phase Diagram

Water phase diagram. The dotted green line gives the anomalous behavior of water.
http://en.wikipedia.org/wiki/Phase_diagram

Tie Lines & the Lever Rule

Consider point D: this represents a 2-phase
system consisting of liquid of molar volume Vl
and gas of molar volume Vg

G+L

Vl

VD

Vg

Tie Lines & Lever Rule

Think about 1 mole: G moles of gas, L moles of liquid
Total volume/mole

VD = GVg + LVl
also G + L = 1

VD = GVg + (1 G )Vl = G (Vg Vl ) + Vl

VD Vl
G =
Vg Vl
Also VD = (1 L )Vg + LVl = L (Vl Vg ) + Vg
L =

Vg VD
Vg Vl

L V g VD

=
G
VD Vl

Lever Rule

Phase Diagram Examples

Some insight into the nature of the critical
point is gained from a description of the changes
that occur when a sealed, transparent upright tube
of constant volume containing liquid and vapor is
heated. Describe what will happen to the liquid
meniscus upon heating if we start with a saturated
liquid-vapor mixture that is: (a) at point K
(b) at point J, (c) at point M in the diagram shown.
(See the diagram in the next slide)

Phase Diagram Examples

P
C

Pc

Liquid

N
Vapor

T>Tc
Tc
T1<Tc

Liquid/vapor
Vc

T2<Tc
D
V

Phase Diagram Examples

Solution:
1.For the three cases, the tube will be filled witha
liquid-vapor mixture. Lets discuss what happen with
the meniscus and the liquid level in each one of the
paths:
(a) Path K-N: since v>vc, as T increases the meniscus
and the liquid level will decrease, and at point N the
last drop of liquid will vaporize and the tube will be
filled with saturated vapor.

Phase Diagram Examples

(b) Path J-Q: since v< vc, as T increases the meniscus
and the liquid level will increase, and at point Q the last
bubble of vapor will disappear and the tube will be filled
with saturated liquid.
(c) Path M-C: since v= vc, as T increases the meniscus
and the liquid level go down slightly. As the critical point
C is approached, the meniscus becomes indistinct, then
hazy, and finally disappears as the system changes from
two phases (T<Tc) to a single phase (at T>Tc)

Phase Diagram Examples

In a simple lab experiment, called Franklins
experiment, water is heated in an open glass container.
When water starts boiling, the container is hermetically
closed and retired from the heat source, allowing it to
cool down a little bit. If we pour liquid water at room
temperature (25) over the glass container, water
inside it starts boiling again. Explain this observation
using appropriate P-V-T diagrams.

Phase Diagram Examples

Solution

T
Critical point

Water starts boiling,

container hermetically closed

P1
System cools down a little bit

P2
Pour cold water over container,
system cools down quickly, since
V<Vc, amount of vapor increases and
water inside container boils again!