DEPARTMENT OF CHEMICAL ENGINEERING

College of Engineering and Agro-Industrial Technology

University of the Philippines Los Baos
College, Laguna 4031 Philippines Telefax No. (063) 49-536-2315

ChE 142 CHEMICAL ENGINEERING THERMODYNAMICS I

Handout #5 PVT Behavior of Pure Substances
Prepared by: Prof. Myra G. Borines

A. DEFINITION OF PURE SUBSTANCE

a substance that has a fixed chemical composition throughout
Examples: water, nitrogen, helium, carbon dioxide
could be a mixture of various chemical elements or compounds as long as the
mixture is homogeneous
Example: air
could be a mixture of two or more phases of a pure substance as long as the chemical
composition of all phases is the same
Example: mixture of ice and liquid water
B. PHASE
A distinct molecular arrangement that is homogeneous throughout and is separated from
the others by easily identifiable boundary surfaces
SOLID PHASE
LIQUID PHASE
GAS PHASE
Phase Change Processes of Pure Substances
Compressed Liquid/Subcooled Liquid - liquid which is not about to vaporize
Saturated Liquid - liquid that is about to vaporize
Saturated Vapor - a vapor that is about to condense
Saturated Liquid-Vapor Mixture liquid and vapor phases coexisting in equilibrium
Superheated Vapor vapor that is not about to condense ( i.e. not a saturated vapor)

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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
For example at a pressure of 1 atm, Tsat is 100 0C and conversely at a temperature of 100 0C ,
Psat is 1 atm
Table 1. Saturation pressure of water at various temperatures
Temperature,

Saturation
Pressure , kPa

Temperature,
0
C

Saturation
Pressure , kPa

-10

0.26

25

3.17

-5

0.40

30

4.25

0.61

40

7.38

0.87

50

12.35

10

1.23

100

101.3 (1 atm)

15

1,71

200

1554

20

2.34

300

8581

Latent heat- the amount of energy absorbed or released during phase-change process
Latent heat of fusion
Latent heat of vaporization
Latent heat of sublimation

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C. PRESSURE-TEMPERATURE (PT) DIAGRAM

Figure 1. PT Diagram of Pure Substance ( Source: Van Ness et al, 2005)

Figure 2. PT Diagram of Water

Triple Point point at which three phases coexist in equilibrium

Critical Point (T and P) the highest temperature and pressure at which a pure
substance can exist in vapor-liquid equilibrium
For water, critical point is at 374.14C, 22.09 MPa, 0.003155 m/kg while the
triple point is at pressure of 0.6113 kPa and temperature of 0.01 0C.

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Gas vs. Vapor

Vapor is part of the gas region which can be condensed either by
o Compression at constant T
o Cooling at constant P

The term gas is used to refer to a substance that is normally in the gaseous state at
ordinary T&P, whereas a vapor is the gaseous form of any substance that is a liquid
or solid at normal T&P.
Thus, at 25C & 1 atm, we have water vapor & oxygen gas.

C. PRESSURE-VOLUME (PV) DIAGRAM

a diagram showing the behavior of pure substances in terms of pressure, volume
and temperature
two-phase systems coexist in equilibrium are represented as regions in PV
diagram compared to PT diagram where they are being displayed as lines or
curves separating one-phase regions

Figure 3. PV Diagram of Pure Substance( Source: Van Ness et al, 2005)

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D. IDEAL GAS
In the region of PV diagram, there is a relation connecting the pressure, volume, and
temperature. The simplest form of the equation of state relating P, V, and T is the ideal
gas equation.
This relation is given by,
PV = nRT
Where:

P absolute pressure
V volume
n number of moles

T absolute temperature
R Ideal gas constant

The assumptions of the Ideal Gas Equation are as follows:

1. The intermolecular attraction is extremely small.
2. The volume occupied by the molecules themselves is negligible, compare to
the total volume (point molecule).
The concept of an ideal gas is useful for it leads to simple equations frequently
applicable as good approximations for actual gases. Real gases behave ideally at low
P and high T.

Laws Governing Ideal Gas Behavior

1. Boyles Law
at constant T,

PV = k

2. Charles Law
at constant P,

V = kT

3. Combined Gas Law combination of the two laws

where: k = nR

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Types of Non-flow Reversible Processes for an Ideal Gas

1. Isochoric Process constant volume
Since =

then

=0
2

= =
1

=
1

Internal energy changes for an ideal gas

Figure 4. Internal energy changes for an ideal gas ( Source: Van Ness et al, 2005)
From Figure 4, the following interpretations can be made:
U is independent of V at constant T
U is the same for all processes; but Q = U for a-b (isometric)
Q is dependent on T and path, while U is dependent on T alone

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2. Isobaric Process constant pressure

2

= =
1

=
1

3. Isothermal Process constant temperature

= = 0
=
Since =

and

Then,
=

Upon integration,
=

= =

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2
1

2
2
= ln
1
1

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4. Adiabatic Process no heat transfer

= 0
2

= =
1

=
1

But T1 and T2 are not given,

=
Since =

Then,
2

=
1
1

ln

2
2
=
1
1

Define = and since = , then

T2 P2

T1 P1

T2 V1

T1 V2

P1V1 P2V2 PV

Then the work would be,

=
=

P1V1 P2

W
1 P1

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RT
P
1
2

1
1
1 P1

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Table 2. Values for

Gas

Monoatomic gas

1.67

Diatomic gas

1.4

Triatomic/polyatomic gas

1.3

R CP CV

CP
CV

5. Polytropic Process
a general case when no specific condition is given other than reversibility
means turning many ways
The applicable equations will be

U Q W
W PdV
U CV dT
H CP dT
With as constant,
= constant
T = constant
T

()

= constant

Analogously,
1 2
=
[( )
1 1

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1]

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Using 1st Law with constant capacities yield,

1

( )1
2
=
[( )
( 1)( 1) 1

1]

Values for
Isobaric Process, =

0 = , =

Isothermal Process , =

1 = , =

Adiabatic Process, =

= ,

Isochoric Process, =
Example
One hundred moles of an ideal gas with Cp= 5/2 R and Cv = 3/2 R is changed from 1 bar and 12
m3 to 12 bar and 1 m3 by the following mechanically reversible processes:
a) Isothermal compression
b) Adiabatic compression followed by cooling at constant pressure
c) Adiabatic compression followed by cooling at constant volume
d) Heating at constant volume followed by cooling at constant pressure
e) Cooling at constant pressure followed by heating at constant volume
Calculate Q, W, U and H for each of these processes.

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