Introduction to

CHEMICAL ENGINEERING
THERMODYNAMICS
PREPARED BY
A. R. CAPARANGA, PhD
FOR CH126P
 THERMODYNAMICS
• Describes macroscopic properties of
equilibrium systems
• Entirely empirical
• Built on 4 laws and ‘simple’ mathematics
VOLUME SCALES

• MACROSCOPIC
– in uniform thermodynamic state
– properties, uniform throughout the system
• MICROSCOPIC
– differential volume elements (too small)
– each volume element contains enough
molecules to be considered as continuum
– microscopic balances are performed over
differential elements which can be integrated
to describe behavior in the macroscopic world
VOLUME SCALES (con’t)

• MICROSCOPIC (con’t)
– microscopic balances are often used when
the properties over the volume of the system
change with time
• MOLECULAR
– individual atoms or molecules
– at this level, the continuum breaks
– matter can be viewed as discrete elements
4 LAWS OF THERMODYNAMICS

• ZEROTH LAW
– defines temperature (T)
• FIRST LAW
– defines internal energy (U)
• SECOND LAW
– defines entropy (S)
• THIRD LAW
– gives numerical value to entropy
Important Note:

These 4 laws of thermodynamics are

universally valid, they cannot be
circumvented.
DEFINITIONS

• SYSTEM
– part of the universe that we chose to study
• SURROUNDINGS
– the rest of the universe
• BOUNDARY
– the surface dividing the system from the
surroundings
• SYSTEMS can be
– OPEN
• Mass and energy can transfer between the system
and the surroundings.
• Control volume
– CLOSED
• Energy can transfer between the system and the
surroundings, but not mass.
• Control mass
– ISOLATED
• Neither mass nor energy can transfer between the
system and the surroundings.
• DESCRIBING SYSTEM REQUIRES THE
FOLLOWING:
– A few macroscopic properties: P, T, V, n,
mass
– Knowledge if system is homogeneous or
heterogeneous
– Knowledge if system is in equilibrium state
– Knowledge of the number of components
• TWO CLASSES OF PROPERTIES
– EXTENSIVE
• Depends on the size of the system
• V, n, mass
– INTENSIVE
• Independent of the size of the system
• T, P, v = V/n
• THE STATE OF SYSTEM AT EQUILIBRIUM
– Defined by the collection of all macroscopic
properties that are described by state
variables (P, n, T, V, …)
– Gibbs PHASE RULE: F = 2 + N - 
– For one-component system, all that is required is “n”
and 2 variables; all the other properties then follow.
– Examples:
• 3 H2 (g, 1 bar, 100oC)
• 2 Cl2 (g, 5 L, 50oC)
• 5 Ar (s, 5 bar, 50 K)
• CHANGE OF STATE (Transformations)
– Example:
3 H2 (g, 5 bar, 100oC)  3 H2 (g, 1 bar, 50oC)
initial state final state
PATH: sequence of intermediate states

i
5

P, bar
f

T, oC
50
100
PROCESS: describes the path
• REVERSIBLE
• Always in equilibrium
• IRREVERERSIBLE
• Defines direction of time
• ADIABATIC
• No heat transfer across boundary
• ISOBARIC – constant pressure
• ISOTHERMAL – constant temperature
• ISOCHORIC – constant volume
THERMAL EQUILIBRIUM

A + B A B A B

HOT Cold Heat flows Warm

• When a hot object is placed in contact with a

cold object, heat flows from the warmer to the
cooler object. This continues until they are in
thermal equilibrium (heat flow stops). At this
point, the bodies are said to be in the thermal
equilibrium (same ‘temperature’).
 ZEROTH LAW OF THERMODYNAMICS

• If A and B are in thermal equilibrium and B

and C are in thermal equilibrium, then A
and C are in thermal equilibrium.

• Consequence of zeroth law:

– B acts like a thermometer
– A, B, and C are all at the same temperature
Operational definition of TEMPERATURE

• Need:
– Substance
– Property that depends on T
– Reference points
– Interpolation scheme between reference
points
• Example: Ideal Gas Thermometer with the
Celsius scale
 The Ideal Gas Thermometer with Celsius scale

Based on Boyle’s Law:

lim  Pv  T  f (T )
P 0

The substance is a gas.

The property is f(T).
The boiling point (TB = 100oC) and freezing
point (TF = 0oC) of water are reference
points.
The interpolation is linear (see next slide).
 lim  Pv  T  f (T ) Experimental result:
P 0

A = 0.0036609
= 1/273.15

Note:
T = -273.15oC is
called the absolute
zero.

f (T )  f (0o C )(1  AT )

-273.15oC 0oC 100oC

• This suggests a new temperature scale
(KELVIN)
T (K) = T (oC) + 273.15
• Better reference points for the KELVIN
scale are T = 0 K (absolute zero) and TTP =
273.16 K (triple point of water)
 INDEPENDENT AND DEPENDENT
THERMODYNAMIC PROPERTIES
• If we have a system containing a pure
substance, its thermodynamic state and,
therefore, all its intensive properties can
be determined from two independent
intensive properties. (Recall: Gibbs Phase Rule)
Example: v = v(T,P)
V = V(T,P); (specify the size)
• Constraining single-component systems
with more than 1 phase
– For a 2-phase system, F = 2 + 1 – 2 = 1
– T and P are equal in both phases; however,
most other properties are different between
phases.
 The case of WATER

• The P (and T) in each phase of a 2-phase

system is equal; hence, if we know P (or
T), we know values of all the other
intensive properties in both phases.
• To constrain the system, the proportion of
matter in each phase must be known.
• A second independent intensive property
that is related to the mass fraction in each
phase is required.
QUALITY (x): fraction of water that is vapor

nv
x
nv  nl
Any intensive property can be found by
proportioning its value in each phase by the
fraction of the system that the phase occupies.
Example:
v  xvv  (1  x)vl
u  xuv  (1  x)ul
• PvT surface and its projections for pure
substance
• Thermodynamic properties charts and
tables
– Water
• Steam tables
• T-s diagram, P-h diagram, Mollier diagram (h-s
plot)
– Other fluids
Exercises
 1
Determine the volume change when 1 kg of
saturated water is completely vaporized
at a pressure of
a) 1 kPa
b) 100 kPa
c) 10,000 kPa
 2
Four kg of water is placed in an enclosed
volume of 1 m3. Heat is added until the
temperature is 150oC. Find
a) the pressure,
b) the mass of vapor, and
c) the volume of the vapor.
 3
Four kg of water is heated at a pressure of
220 kPa to produce a mixture with quality
x = 0.80. Determine the final volume
occupied by the mixture.
 4
Water (0.91 kg) is contained in a constant-
pressure container held at 36.73 atm.
Heat is added until the temperature
reaches 370oC. Determine the final
volume of the container.
 5
Using the steam tables, plot to scale P-v, P-
T and T-v diagrams.
 6
If the quality of each of the following
substance is 82%, calculate the specific
volume:
a) Water at 500 psia and
b) HFC-134a at 80 psia
 7
Five kg of steam occupies a volume of 10
m3. Find the quality and pressure if the
temperature is measured at
a) 40oC
b) 86oC
 8
Provide the missing information for air at an
elevation where g = 9.82 m/s2.

P, kPa T, oC v, , w,
m3/kg kg/m3 N/m3
(a) 100 20

(b) 400 20
 9
Nitrogen is contained in a 4-m3 rigid vessel
at a pressure of 4200 kPa. Determine
the mass if the temperature is
a) 30oC
b) -120oC
 10
Steam at 300oC has a density of 7 kg/m3.
Find the pressure using
a) the ideal gas equation,
b) the van der Waals equation,
c) the compressibility factor,
d) the steam tables, and
e) Mollier diagram