CHG 343

SECTION 2

5. THE PHASE RULE

The state of a pure homogeneous fluid is fixed when two
intensive thermodynamic properties are fixed. In contrast when
two phases in a system are in equilibrium, the state of the
system is fixed when only one of such properties is specified.
For example, a mixture of steam and water at 101.33kPa can
only exist at 100oC. It is impossible to change the temperature
without the pressure changing also (if equilibrium is to be
maintained). The number of independent variables that must be
arbitrarily fixed to establish the intensive state of any system is
called the degree of freedom (F) of the system and is given by
the Phase Rule of J.W Gibbs.
F=2+ N−π (10)
The intensive state of a system at equilibrium is established
when its T, P and compositions of all phases are fixed. These are
called phase rule variables but they are not all independent. the
PHASE RULE gives the number of variables from this set which
must be arbitrarily specified (independent) in order to fix all
remaining phase rule variables.
A phase is a homogeneous region of matter e.g. a gas or a gas
mixture, a liquid or solution or a solid crystal. A phase need not
be continuous e.g. gas bobbles in a liquid medium is a two-
phase system, oil globules dispersed in water medium is a two-

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phase system. An example of a 3-phase system in equilibrium is
a boiling saturated solution of a salt in water with solid salt
crystals present. Phase rule variables are intensive. The
compositions that are phase rule variables are only those of the
individual phases (total compositions are not phase rule
variables -for systems with more than one phase) Minimum F =
0 such that π=2+ N -like the case of triple point of water Any
change from the prevailing condition causes at least one phase to
disappear.

6. CONSTANT V-CONSTANT P- PROCESSES

Q and W represent total heat and work no matter the value of N.
U, V etc. represents molar or unit mass property.
nU or mU represent total property.
For a closed system of n Moles, equation (6) is written
d ( nU ) =dQ−dW (11)
The work of a mechanically non-flow process is given by
dW =Pd (nV ) (12)
If such a process occurs at constant volume then the work is
zero: if at constant pressure then integration yields
W =nP ∆ V (13)
So that Equation (11) becomes
d ( nU ) =dQ−Pd (nV ) (14)

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Equation (14) is the first law for a mechanically reversible non-
flow process. Also, for a constant-volume process,
dQ=d (nU ) ------------(constant V) (15)
Integration yields
Q=n ∆ U --------- (constant V) (16)
Thus, for a mechanically reversible constant-volume non-
flow process, the heat transferred is equal to the internal energy
change of the system. Equation (7) which defines the enthalpy
may be written as
nH =nU + PnV (16-b)
For an infinitesimal constant-pressure change of state.
d ( nH )=d (nU )+ Pd(nV ) (16-c)
Combining Eqn. (16-c) with Eqn. (14) yields
dQ=d (nH ) (17)
Integration yields
Q=n ∆ H (18)
Thus, for a mechanically reversible constant-pressure non-
flow process, the heat transferred is equal to the enthalpy
change of the process. Comparing Eqns. (17) and (18) with
Eqns. (15) and (16) shows that the enthalpy plays a role in
constant-pressure processes analogous to the role of internal
energy in constant-volume processes.

7. HEAT CAPACITY
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Heat is often viewed in relation to its effect on the object from
which it is transferred. This is the origin of the idea that a body
has a capacity for heat – it is really a reciprocal of a response or
a resistance to effect rather than a capacity. Thus, the smaller the
temperature change in a body caused by the transfer of a given
quantity of heat, the greater the heat capacity. A heat capacity
might be defined as
dQ
C=
dT
(19)
This wrongly suggests that C is a path function, so we define
two useful heat capacities in terms of other states functions
Heat Capacity at constant volume
C ≡(
∂T )
∂U
V (20)
V

Heat capacity at constant pressure

CP ≡ ( ∂∂ HT )
P
(21)
These definitions also accommodate molar or specific heat
capacities (or specific heats) depending on whether U and H are
molar or specific values. They also allow for the description for
the process. For a constant-volume process equation (20) is
dU =C dT V (constant V) (22)
Integration yields
∆ U =C ∆ T V (constant V) (23)
Combining Eqn. (23) with Eqn. (16), we have for a
mechanically reversible constant-volume process,
Q=n ∆ U=nC ∆ T V (constant V) (24)

For a process during which volume varies but the final volume
is the same as the initial, such a process can not rightly be called
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a constant-volume process even though Vf = Vi. But property
changes can be calculated from equations for a truly constant-
volume process (involving no volume change at all) – Eqn. (23)
since all terms involved are state functions. On the other hand,
Eqn. (24) holds for only constant volume processes, yet Q is
path-dependent. For the same reason, W is zero only for a
constant-volume process. There is therefore a careful distinction
between state functions and heat and work. Thus, for the
calculation of property changes (changes in state functions)
an actual process may be replaced by any other process which
accomplishes the same change in state. Such an alternative
process may be selected because of its simplicity.
For a constant-pressure process Eqn. (21) may be written as

dH =C P ddT (25)
From where
T2

∆ H =∫ ❑ ¿❑T (26)
T1

For a mechanically reversible constant-pressure process we may

combine Eqn.(26) with Eqn. (18) to obtain
T2

Q=n ∆ H=n ∫ ❑¿ T ❑ (27)

T1

Eqn. (27) applies just like Eqn. (24).

Example 3 – An ideal gas (one for which PV/T is a constant) has

a volume of 0.02271m3/mol at 0oC and 1 bar. Assuming air at
the given condition to be ideal with CV =5R/2 and CP = 7R/2
Where R = 8.314 J/mol.K. The initial conditions of the air are
1bar and 25oC. It is compressed to 5bar and 25oC by two
5
different mechanically reversible processes. Calculate the heat
and work requirements and ∆ U and ∆ H of the air for each path
(a) cooling at constant P followed by heating at constant V
(b) heating at constant V followed by cooling at constant P

8. STEADY STATE FLOW PROCESS

The application of Eqns. (5) and (6) is restricted to non-flow
(constant-mass) processes in which only internal energy changes
occur. In the industry we more often have cases where fluid
flows at a steady state through equipment.
We will here consider the special case of a steady-state steady-
flow process for which flow rates and conditions at all points
along the flow path are constant with time. This means no
accumulation of material or energy at any point. We shall
employ the application of Eqn. (4).

Figure 3: Steady-state Steady-flow Process

Consider the figure above. The fluid flowing through the

equipment is either a liquid or a gas. The mass flow rate is
constant over the entire flow path. The system is taken as a unit
mass of the fluid. The kinetic energy change of a un=it mass of
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fluid between sections 1 and 2 is
1 1 2 1 2
∆ E K = ∆ ( u ) = u2 − u1
2
2
2 2
(27-b)

‘u’ is the average velocity of the flowing fluid defined as the

volumetric flow rate divided by the cross-sectional area. The
potential energy change of a unit mass of fluid between sections
1 and 2 is

∆ E P =g ∆ z=g z2−g z 1 (27-c)

Eqn. (4) now becomes
2
∆u (28)
∆U= + g ∆ z=Q−W
2
W ≠ Ws

Ws represents the work which is interchanged between the

system and its surroundings through a shaft which protrudes
from an equipment and rotates or reciprocates. In addition to W ,
s

there is work interaction between the system (unit mass) and the
fluid on either side of it. The system may be imagined as a
cylindrical element of the fluid. There are pressure forces on its
ends exerted by the adjacent fluid. The forces move with the
system and do work. The force on the upstream side of the
cylinder does work on the system while the force on the
downstream side is in the opposite direction and results from
work done by the system. From section 1 to 2 these two pressure
forces follow exactly the same path and vary in exactly the same
manner. Hence, the net work which they produce between these
two sections is zero. However, the terms representing work
done by these pressure forces as the fluid enters and leaves the
apparatus do not in general cancel out.
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 In the figure, the unit mass of fluid is shown just before it
enters the apparatus. This cylinder of fluid has a volume equal
to its specific volume V . With a cross-sectional area of A then
1 1

its length is V / A 1. The force exerted on the upstream face is P A

1 1 1 1

and the work done by this force in pushing the cylinder into the
apparatus is
V
W =P A
1 1
A
=P V
1
1
1 1[−W ] 1 (28-b)
1

Eqn. (27-e) represents work done on the system by the

surroundings. At section 2, work is done by the system on the
surroundings as the fluid cylinder emerges from the apparatus.
This work is therefore given by
V2
W 2 =P 2 A2
A2
=P 2 V 2 [W ]
2 (28-c)

Since W in Eqn. (28) represents all the work done by the system,
it is equal to the sum of the shaft work and the work done at the
entrance and exit i.e.
W =W s + ∆ ( PV )

¿ W s+ P 2 V 2−P1 V 1
¿ W s+ W 2−W 1 (28-d)

In the light of Eqn. (28-d), Eqn. (28) becomes

2
∆u
∆U= +g ∆ z
2
¿ Q− [W s + ∆ ( PV ) ]
¿ Q−W s−∆ ( PV )

Or

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 2
∆u (28-e)
∆ U + ∆ ( PV )= + g ∆ z=Q−W s
2

But by Eqn. (9),

∆ U + ∆ ( PV )=∆ H ((9))
Therefore,
(29)
2
∆u
∆ H+ + g ∆ z=Q−W s
2

Eqn. (29) is the Steady Flow Energy Equation - SFEE

Eqn. (29) is the mathematical expression of the first law of

Thermodynamics for a steady state steady flow process between
a single entrance and a single exit. All terms are expressions for
energy per unit mass of fluid (SI = Joule).
In the English Engineering System of Units it must include “ g ”c

in the kinetic and potential energy terms thus;

2
∆u g
∆ H+ + ∆ z=Q−W s
2 gc gc
(29-b)
where ∆ H unit is Btu while E and E are in ft.lbf
K P

For many of the applications considered in thermodynamics, the

kinetic and potential energy terms are usually very small in
comparison with other terms and are therefore often negligible
so that Eqn. (29) reduces to

∆ H =Q−W s (30)

Eqn. (30) for a steady state steady flow process is analogous to

Eqn. (5) for a non-flow process but H (enthalpy) rather than U
(internal energy) is of importance here. Eqn. (30) requires that
values of the enthalpy must be available. Since it is a state
9
function, once it is determined it can be tabulated for later use.
Eqn. (29) applies to laboratory processes designed specifically
for the measurement of enthalpy and data generation where Eqn.
(29) reduces to
∆ H =Q (31)
So that
H =H −Q
2 1 (32)

9. IDEAL GAS BEHAVIOR

For an ideal gas there is no molecular interaction so that

PV =nRT (33)

Eqn. (33) describes the macroscopic behavior of the gas. Also,

for an ideal gas, the internal energy U (and hence Cv also) is a
function of temperature only. The ideal gas as a model fluid
with no molecular interactions is very useful because it is
described by simple equations that are frequently applicable as
good approximations for real gases. In engineering applications
(by experience) it has been found or established that pressures
up to a few atmospheres may often be considered ideal.

The Isochoric Process

Recall for a mechanically reversible constant-volume process,
we can write
dU =dQ=C dT v (34)

and for a finite change

❑
∆ U =Q=∫ ❑¿ T ❑ (35)
❑

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Since for an ideal gas, ∆ U and C are functions of temperature
v
❑

only, we may always calculate ∆ U by ∫ ❑¿ T regardless of the

❑
❑

kind of process causing the change.

Figure 4: ab , A Constant-Volume Process with variable

Temperature
From the figure above, U is independent of V at constant T.ab
represents a constant volume process for which T increases from
T1 to T2 and U changes from U1 to U2. Lines ac and ad represent
other processes not occurring at constant volume but which also
lead from temperature T1 to T2. It is clear that ∆ U for process ac
and ad is the same as that for the constant-volume process (ab )
and is therefore given by the same equation thus;
❑
∆ U =∫ ❑ ¿ T❑ (36)
❑

However, for these processes ∆ U is not equal to Q because Q

depends not only on T1 and T2 but also on the path of the
process.

The Isobaric Process

Recall for a mechanically reversible constant-pressure non-flow
process, we can write for 1 mole

dH =dQ=C p dT (37)
❑
∆ H =Q=∫ ❑¿❑ T (38)
❑

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Since for an ideal gas, U is a function of T only, then both Cp
and H also depend on T only. Afterall,
H=U + PV =U + RT (39)

Just as
❑
∆ U =∫ ❑ ¿ ❑ T (for ideal gas processes)
❑

So also,
❑
∆ H =∫ ❑ ¿ ❑ T (40)
❑

Eqn. (40) holds not only for constant-pressure processes but for
all finite processes involving an ideal gas.
There is a relationship between Cp and Cv for an ideal gas. This
stems from the expression for dH and dU
H=U + PV
¿ U + RT

for an ideal gas

Therefore,
dH =dU + RdT (41)
PV =nRT
∆ ( PV )=∆ ( nRT )
P ∆ V =nR ∆ T ¿

Eqns. (34) and (37), Eqn. (41) becomes

C p dT =C v dT + RdT C p =C v + R

(42)

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Eqn. (42) does not imply that Cp and Cv are constants for an ideal
gas rather they vary with T in such a way that their difference
is a constant and equals R.

The Isothermal Process

The internal energy of an ideal gas can not change in an
isothermal process. For one mole of an ideal gas in any non-flow
process,
dU =dQ−dW =0

Rearranging and integrating,

We have
Q=W

For a mechanically reversible non-flow process for which

P=RT /V , we have
❑
dV
Q=W =∫ ❑dV = RT
V ¿ (42-b)
❑

Integrating at constant T from V1 to V2 yields

V
Q=W =RTln
V
2
(43)
1

Since T is constant, then

PV =RT =P1 V 1=P 2 N 2=P3 V 3

Hence,
P1 V 2
=
P2 V 1

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So that
P1
Q=W =RTln
P2
(44)

The Irreversible Adiabatic (Isentropic) Process

An adiabatic process is one for which there is no heat transfer
between the system and its surroundings; that means
dQ=0 (44-b)

So applying the first law to one mole of an ideal gas in a

mechanically reversible non-flow process, we have
dU =−dQ=−PdV (45)

Since the change in U for any process involving an ideal gas

is given by equation (34), this becomes (for a unit mass or
mole,
C dT =−PdV
V (46)
Since P=RT /V , we have
dV
C V dT =−RT
V
dT −R dV
T
=
CV V
(47)
C
If CVP =γ Then Eqn. (42) yields

CV +R R
γ=
CV
=1+
CV
(48)
Or
R
=γ −1
CV
Putting this into Eqn. (47) yields
dT dV
T
=−(γ−1)
V
(48-b)
If γ is constant (which is usually the case), integration yields
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 T2 V2
ln
T1
=−( γ −1 ) ln
V1
(48-c)

So that
( )
γ−1
T2 V 1
=
T1 V 2
(49)
NOTE:
To assume that γ is constant seems tantamount to assuming
that C and C are constant. However, since both C and C
P V P V

vary with T, their ratio (γ ) is very much less sensitive to T

Illustration:
C C C
C
P
is constant V P

T1 20 70 2/7
T2 40 (=20 x 2) 140 (=70 x 2) 2/7
T3 60 (=20 x 3) 210 (= 70 x 3) 2/7

Combining Eqn. (49) and the ideal gas equation, we can get
its equivalent for T-P and P-V

Homework
Employ Eqn. (49) and the Ideal gas equation to obtain Eqns.
(50) and (51) below
( )
(γ −1 )/ γ
T P
T
2
=
P
2
(50)
1 1

( ) ( )
γ −1 (γ −1 )/ γ
V1 P2
V2
=
P1
(51)

Example 4- Air is compressed from an initial condition of 1bar

and 25oC to a final state of 5 bar and 25oC by three different
mechanically reversible processes.
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(a) heating at constant volume followed by cooling at constant
pressure
(b) isothermal compression
(c) adiabatic compression followed by isochoric cooling
At these conditions, we assume the air to be ideal with constant
heat capacities
Cv = 5R/2; Cp = 7R/2
For each process calculate the work, heat transferred and the
changes in internal energy and enthalpy.

Homework
An ideal gas undergoes the following sequence of mechanically
reversible processes
(a) from an initial state of 70oC and 1 bar it is compressed
adiabatically to 150oC
(b) it is then cooled from 150oC to 70oC isobaricaly
(c) finally it is expanded isothermally to the original state.
Sketch the 3-step process on a P-V diagram
Calculate W, Q, ∆ U and ∆ H for each of the steps and for the
entire process. Take CV = 3R/2 and CP = 5R/2
Part b (Irreversibility)
If these processes are carried out irreversibly but so as to
accomplish exactly the same changes of state (i.e., the same
changes in P, T, U and H) then the values of Q and W would be
different. Calculate values of Q and W for an efficiency of 80%
for each step.

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