Thermodynamics is a funny subject.

The first
time you go through it, you don't understand it
at all. The second time you go through it, you
think you understand it, except for one or two
small points. The third time you go through it,
you know you don't understand it, but by that
time you are so used to it, it doesn't bother you
any more.
Arnold Sommerfeld
Laws of Thermodynamics

1) You cannot win, you can only break even.

2) You can only break even at absolute zero.

3) You cannot reach absolute zero.

 The 1st law and other
basic concepts

CHEMICAL ENGINEERING 122:

Chemical Engineering Thermodynamics 1
 Thermodynamics
• the science that deals with heat and work
and the properties and work of substances
that bear a relation to heat
• the principles of thermodynamics govern
the conversion of thermal energy to other,
more useful forms
• the science of energy and entropy
Let’s talk about goose bumps
The body looses heat faster
than it can internally replace it.

The body instinctively starts to

shiver
Shivering produces
mechanical energy that is
converted into heat
energy
Your skin develops “goose
bumps” to increase it's ability
as an insulator
Thermodynamics
chemical energy stored in fuel
and oxygen molecules

thermal energy by combustion

extracts part of that thermal

energy to perform the work
necessary to propel the car
forward, overcoming friction
 Energy and Entropy

• Energy is conserved: it can neither be produced

nor destroyed, although it is possible to change
its form or move it around.

• Entropy has a different character: it can't be

destroyed, but it's easy to produce more entropy
(and almost everything that happens actually
does). Like energy, entropy too can appear in
different forms and be moved around.
 Thermodynamics
• Gives information on what direction the
process proceeds

• Predicts the extent at which processes goes

• Do not establish the rates of chemical and

physical processes
 PROBLEM Energy / Heat Transport
Mass Transport/ Diffusion
Momentum Transport/ Fluid
Dynamics

MODEL Thermodynamics
/ Kinetics

Economics
PROTOTYPE

DESIGN
DESIGN AND PROCESS
IMPLEMENTATION MODEL
 Thermodynamics
Useful equations
– Calculation of heat and work
requirements for physical and chemical
processes

– Determination of equilibrium conditions

for chemical reactions
 Thermodynamics
• Thermodynamics allows
us to understand why
matter appears in different
phases (solid, liquid, or
gaseous), and under what
conditions one phase will
transform to another
Classical thermodynamics
• developed in the 19th century, before the atomic
nature of matter was accepted, and it makes no
reference to atoms
• theory which is based on a set of postulates about
how macroscopic matter behaves
• postulates (the most important of which are energy
conservation and the impossibility of complete
conversion of heat to useful work) can't be derived
within the context of classical, macroscopic
physics
 Thermodynamics

Their validity lies in the absence of contrary

experience.
– Based on primitive law.
 Thermodynamics
A theory is the more impressive the greater
the simplicity of its premises, the more
different kinds of things it relates, and the
more extended its area of applicability.
Therefore the deep impression that classical
thermodynamics made upon me. It is the
only physical theory of universal content
which I am convinced will never be
overthrown, within the framework of
applicability of its basic concepts.
A. Einstein
 Statistical Thermodynamics
• The “average” values of variables which
describe all particles under consideration
are taken to represent or describe the system
⇒ used in kinetic theory and statistical
mechanics
• Reduces the number of equations and
variables to a few that can be computed
easily
 System and Environment

“focus our attention on

only a small part of the
world at a time”

open system closed system isolated system

Both energy and matter
can be exchanged with
the environment
Energy, but not matter, Neither energy nor matter
can be exchanged with can be exchanged with the
the environment environment
{ in fact, no interactions
with the environment are
possible at all.
 Control masses and control volumes
• A control mass is a system which is
defined to consist of a specified piece or
pieces of matter.
• By definition, no matter can enter or
leave a control mass.
•If the matter of the control mass is
moving, then the system boundary moves
with it to keep it inside (and matter in the
environment outside).
•A control volume is a system which
is defined to be a particular region
of space.
•Matter and energy may freely
enter or leave a control volume, and
thus it is an open system.
 State of a Substance/System
• The condition of a substance as described
by certain observable macroscopic
parameters called properties; (examples of
properties are pressure, temperature,
specific volume, etc.)
• Each of the properties of a substance in a
given state has only one definite value
• Conversely, these properties always have
the same (or unique) value for the same
state
 Property
• Any quantity that depends only on the state of the
system
• Independent of the path by which the state is arrived
at.
– Intensive Property – independent of the mass;
e.g. pressure, temperature, density
– Extensive Property – varies directly with the
mass; e.g. mass, total volume; extensive
properties per unit mass are intensive properties,
e.g., specific volume = total volume / mass
• A property of a system has significance for
the entire system only when the system is in
EQUILIBRIUM
A Note on Units
• SI system is Simple
• Energy, no matter what its form, is
measured in Joules (1 J = 1 kg-m2/s2)
• unit of force is identical to the unit of (mass
x acceleration)
 English Units
Unit of force: 1 lbf = force that accelerates 1 pound
mass 32.1740 ft/s2

1
F = ma
gc
1 −2
1lb f = x 1(lb m ) x 32.1740 (ft)(s)
gc
−1 −2
g c = 32.1740 (lb m )( ft )(lb f ) ( s )
 Temperature
1. The degree of hotness or coldness of a
body or environment.

2. A measure of the average kinetic

energy of the particles in a sample of
matter, expressed in terms of units or
degrees designated on a standard
scale.
 Heat
• Heat always flows from a higher temperature to a
lower one.
– Temperature as the driving force for the transfer of
energy as heat.
– Heat is never regarded as being stored within a body.
Unit: Calorie- quantity of heat which when transferred to
one gram of water raised its temperature 1oC,
British thermal unit (BTU) - quantity of heat which
when transferred to one pound mass of water raised its
temperature 1oF
Joule – SI Unit equal to 1 N-m
 Pressure

F mg
P= =
A A
Some terms

Gauge Pressure
Absolute Pressure
Pressure

P = Po +ρ
ρgh

Pressure is expressed as a
head of a fluid
(e.g., 33.9 ft H2O or 76
cm Hg )
 Work
• Is performed whenever a force acts through
a distance.
dW = FdldW = Fdl
l

Fl x l

Fdl

dl
 U

u
Kinetic Energy (Ek)
uf
ui =0 uf

uf/t

½ muf2
Potential Energy (EP)

When a body of a certain

weight is lifted from z1
to z2
W=Fxd
F = ma = mg
W = mg (z2-z1) =∆(mzg)
EP = mzg
Mechanical Energy Balance

∆EK = -∆EP

∆EK + ∆EP = 0
2 2
mv2 mv 1
− + mz2 g − mz1g = 0
2 2
 Joule’s Experiments
•Placed known amounts of
water, oil and mercury
•Agitated fluid with a stirrer
•Work done on fluid by stirrer
is accurately measured
•Temperature changes of
fluid were carefully noted
•Fluid is brought back to its
original temperature by
contact with colder object

Conclusion: Heat is a form of energy

 Internal Energy(U)

•Ek and Pk are external energy

•Absolute values are unknown
•Only changes can be determined
 The 1st law of thermodynamics
• It was first a postulate. However, the
overwhelming evidence accumulated over time
has elevated it to the stature of a law of nature.
• Although energy assumes many forms, the total
quantity of energy is constant, and when energy
disappears in one form it appears simultaneously
in other forms.
∆ (energy of the system) + ∆ (energy of surroundings ) = 0
 First Law of Thermodynamics
t t t
∆ ( Energy of the sys ) = ∆Ek + ∆EP + ∆U
∆ (Energy of the surr)= -Q-W
t t t
∆Ek + ∆EP + ∆U -Q-W = 0
t t t
∆Ek + ∆EP + ∆U = Q+W
Heat effect
SYSTEM Environment/Surroundings
Work

Boundary
(1) adiabatic or diathermal
(2) permeable or impermeable
(3) rigid or movable

An isolated system: impermeable, rigid, adiabatic and independent

of events in the environment
 Example
• The driver of a 1350 kg car, coasting down
a hill sees a red light at the bottom for
which he must stop. His speed at the time
the brakes are applied is 28 m/s and he is 30
m vertically above the bottom of the hill.
How much energy as heat must be
dissipated by the brakes if wind and other
frictional effects are neglected.
 Thermodynamics
• For most chemical system: no change in
position and stationary

t
∆U = Q + W
t
dU = dQ + dW
for a closed system of n moles
∆ ( nU ) = n ∆ U = Q + W
d ( nU ) = ndU = dQ + dW
for n=1,
∆ U = Q + W and dU = dQ + dW
 ∆E = Q + W
Total internal energy of the system,
depends on the quantity of material
in a system, i.e., the extensive ∆U t = Q + W
property.

c.f. intensive property,

e.g. temperature and pressure.
e.g. specific or molar properties

• If the gas is heated or cooled, compressed or expanded, and

then returned to its initial temperature and pressure, its
intensive properties are restored to their initial values.
• Such properties do not depend on the past history of the
substance nor on the means by which it reaches a given state.
Such quantities are known as state functions.
• A state function may therefore be expressed mathematically
as a function of other thermodynamic properties. Its values
may be identified with points on a graph.
 State and Path Functions
• State functions –depend only on present
conditions reached

• Path functions – depend on the path of the

process
When a system is taken from state a to state b along path acb, 100 J of heat
flows into the system and the system does 40 J of work. (1) How much heat
flows into the system along path aeb if the work done by the system is 20J? (2)
The system returns from b to a along path bda. If the work done on the system
is 30J, does the system absorb or liberate heat? How much?

t
b ∆U ab = Q +W
c = 100 − 40 = 60 J
P d Qaeb = 80 J
= Qaeb + Waeb
e
= Qaeb − 20
a

∆U bat = − ∆U ab
t

= −60 J
V Qbda = −90 J
= Qbda + Wbda
= Qbda + 30
 Equilibrium
• In thermodynamics, equilibrium means not only
the absence of change but the absence of any
tendency toward change on a macroscopic scale.
• Different kinds of driving forces bring about
different kinds of change. For example:
– imbalance of mechanical forces tend to cause energy
transfer as a work.
– temperature differences tend to cause the flow of heat.
– Gradients in chemical potential tend to cause substance
to be transfer from one phase to another.
 Equilibrium
• A system is in equilibrium when it is in thermal,
mechanical, and chemical equilibrium
– Thermal equilibrium – uniform temperature
throughout the system.
– Mechanical equilibrium – pressure at any point
in the system does not vary
with time when system is isolated
– Chemical equilibrium – no tendency to change
composition
– Thermodynamic Equilibrium – a system
condition that precludes all possible changes of
state ⇒ all equilibrium conditions are satisfied
 Phase rule
• For any system at equilibrium, the number of independent
variables that must be arbitrarily fixed to establish its intensive
state is given by J.W. Gibbs (1875).
• The degrees of freedom of the nonreacting systems:
F = 2 −π + N
– where π is the number of phases, N is the number of chemical species
• A phase is a homogeneous region of matter. A gas or a mixture
of gases, a liquid or a liquid solution, and a crystalline solid are
examples of phases. Various phases can coexist, but they must
be in equilibrium for the phase rule to apply.
• The minimum number of degrees of freedom for any system is
zero:
F = 2 −π + N = 0
– N = 1, π = 3 (i.e. the triple point)
 PROPERTIES AND STATE OF
A SUBSTANCE
Phase
• A quantity of matter that is homogenous
throughout; solid, liquid, gas
• When more than one phase is present, each
phase is separated by phase boundaries
How many degrees of freedom has each of the following systems:
(1) Liquid water in equilibrium with its vapor.
(2) Liquid water in equilibrium with a mixture of water vapor and nitrogen.
(3) A liquid solution of alcohol in water in equilibrium with its vapor.

(1) 1 species, 2 phases

F = 2 − π + N = 2 − 2 +1 = 1
(2) 2 species, 2 phases

F = 2 −π + N = 2 − 2 + 2 = 2
(3) 2 species, 2 phases

F = 2 −π + N = 2 − 2 + 2 = 2