Chapter 1 Introductory

Material
Internal Energy: associated with
molecular motion and interactions
External Energy: associated with the
center of mass of a system
For example, the kinetic and potential
energy of throwing a ball in the air.
(Thermodynamic) State: the
properties of a system defined by
specific physical or thermodynamic
variables
Thermodynamics Basics: Energy
System: a specific volume in
space defined by user.
Surroundings: the rest of the
universe outside of a system
Boundary: the surface
separating the system from
surroundings either real or
invented
State of Agglomeration (or
Phase): the form of the material
either solid, liquid, or vapor.
Thermodynamics Basics: Systems
Heat: flow of energy due to temperature
differences on each side of a boundary
Work: flow of mechanical motion across a
boundary
Mechanical Contact: a physical boundary
that allows changes in pressure (or work) in
the system to change that in the
surroundings and vice-versa
Rigid: a boundary that does not deform with
pressure
Thermal Contact: a boundary that allows
heat to cross
Adiabatic: a system whose boundary does
not allow heat to cross
Thermodynamics Basics: Contact
Open: a system that allows
mass to cross the boundary
Closed: a system that does
Not allow mass to cross the
boundary
Isolated: a system whose
boundary does not allow any
mass, heat, or work to cross
Thermodynamics Basics: Contact
Letters: M mass; N moles; V Volume; U
Internal Energy; H Enthalpy; A
Helmholtz; G Gibbs; P Pressure; T
Temperature; t time
Underbar Molar Property
V= total volume [cm
3
]; V = molar volume [cm
3
/mol]
(V= V * N)
Hat Specific (mass) Property
is specific volume [cm
3
/g]
Overbar Partial molar property
Partial Molar Volume
Except Mixture Fugacity
Nomenclature
V

f
i
V
Extensive variables depend on size
The Volume, V, of water in a beaker
depends on how much water that you put in
it.
Intensive variable: scaled by mass or
moles,
e.g. molar volume V= V/N, as long as T & P
remain constant, V will remain the same with
either 1 ml or 1000 ml of water
T, and P are exceptions
P [Pa] : 1 Pa = 1 N/m
2
= J/m
3
= kg / m /s
2
T. I dunno
Types of Variables: Intensive/Extensive
Elements and Compounds usually have at least 3 states of
matter (aka. states of aggregation): Solid, Liquid, Vapor
Fluid is a term for a vapor/gas OR Liquid
Supercritical Fluid is a substance above its critical point
States of Matter States of Matter
P
P
c
T
c
T
Supercritical
Fluid
LIQUID
Critical Point
P
c
SOLID
VAPOR
Critical Point:
Max T & P in
which
Liquid and
Vapor can
coexist
Triple Point
Each phase has a transition
to the other:
Vaporization (Liquid-to-Vapor
; and vice-versa)
Melting (Solid-to-Liquid)
Sublimation (Solid-to-Vapor)
If you are exactly at the T & P conditions of the
transitions, then you are in 1 component phase
equilibrium (see Chapter 7 & onward) also called saturation
Each Phase Coexists and Each phase has its
own thermodynamic properties, U, H, V, etc.
In property diagrams, you will see envelopes where
each side of the envelopes represents the two phases
States of Matter: Transitions & Equilibrium
Chapter 2:
Conservation of Mass
Balances!
Material Balance:
Control
Volume
Surface
through
which
mass
passes
Multiple
entrances/exits (M can be negative if out)
What did you Learn in CPE211?
Choosing the right control volume is sometimes
more of an art than science
Actually based on experience
Sometimes multiple control volumes are correct
Some are easier to implement and use than
others.
Types:
Static (non-changing)
Volume changes from beginning to end
Constant mass/moles
Closed
Open
Etc. etc.
Be Creative
Control Volumes
In this Book, any flow (crossing
of a control volume boundary)
Entering into a system has a
POSITIVE (+) Sign.
Any Flow Exiting a system has
a NEGATIVE (-) Sign.
Thus, We will not use in minus out, but we
will sum all flows and let their signs and
magnitudes determine what the accumulation
is.
In the diagram above, M
1, 2, and k
, may be inlets and
thus positive signs, while M
3
may be an exit and
thus a negative sign.
You will see this will be consistent with the
signs of heat and work flows in Chap. 3.
Control Volume and Signs
There are two Main Types of Balance Equations:
Difference and Differential.
Difference: the change in material determined
from a subtraction of the system contents at two
different times or at two different conditions
Differential: the change of material over time
(RATE) from calculus
The difference equations are nothing more than
the differential equations integrated over a time
period.
Each Type has two sub-types based on Mass
units OR Mole units
Thus, Difference (mass or mole); & Differential
(mass or mole)
Balance Equations
For any real system, you will most often be assigning
numbers to represent certain components,
inlets/outlets, reactions, phases (CPE512), etc.
In this course,
C = total number of Components in the system
K = total number of Inlets/Outlets
M = total number of Independent Reactions
Variables will have subscripts to identify each of the
parts that combine to make C, K & M
i = the component number, with the number that represents
C as the last in the series and the total number
k = the inlet or outlet ID number with K being the last
inlet/outlet specified.
j = the reaction number, with M being the number of the last
reaction
Dots over variable indicate flow rates (d/dt)
Nomenclature for Balance Equations
Difference Material Balance: No Reaction

=
= =
K
k
k system
N N N N
1
1 2

=
= =
K
k
k t t system
M M M M
1
1 2
Mass:
Mole:
( )

=
=
C
i
k
i k
M M
1
where
( )

=
=
C
i
k
i k
N N
1
where
Differential Material Balance: No Reaction

=
=
K
k
k
system
M
dt
dM
1

Mass:
Mole:

=
=
K
k
k
system
N
dt
dN
1

( )

=
=
C
i
k
i k
M M
1

where
( )

=
=
C
i
k
i k
N N
1

where
We can write general chemical reaction balances
as:
Where the Greek letters are the Stoichiometric
coefficients (positive for products; negative for
reactants); so that:
Molar Extent of Reaction
(X, , etc.)
N
i,0
is the initial (before reaction)
amount, N
i
is at any time.
It is the same no matter what species you follow (even
if different stoich. amounts initially)
Notation for Chemical Reactions:
Note Sandlers Notation for
Molecular Weight is, m
i
.
I find this slightly confusing with
mass, molality, or even molarity,
etc.
I will use MW
i
to remove ambiguity.
Molecular Weight
Overall
Species:
Difference: Material & Species: w/Reaction
( )
( )


= = = =
= =
= + = =
= = =
C
i
k
i k
C
i
M
j
j j i
K
k
k t t system
C
i
k
i k
K
k
k t t system
N N N N N N
M M M M M M
1 1 1
,
1
1 1
1 2
1 2

( )
( )


= =
= =
+ = =
+ = =
M
j
j j i
K
k
k
i t i t i i
M
j
j j i i
K
k
k
i t i t i i
N N N N
MW M M M M
1
,
1
, ,
1
,
1
, ,
1 2
1 2

Species:
Overall:
Differential: Material & Species: w/Reaction
( )
( )

= = =
=
= =
= =
+ =
=
+ =
+ =
C
i
M
j
j j i
K
k
k
K
k
k
M
j
j j i
K
k
k
i
i
M
j
j j i i
K
k
k
i
i
N
dt
dN
M
dt
dM
N
dt
dN
MW M
dt
dM
1 1
,
1
1
1
,
1
1
,
1

( )

=
=
C
i
k i k
M M
1

( )

=
=
C
i
k i k
N N
1

Chapter 3:
The Energy Balance and
Thermodynamic Properties
The ability/capacity to do Work
Potential,
Gravitational
Chemical
Magnetic
Nuclear
Kinetic
Thermal
Electrical
Sound/Acoustic
Radiant (Electromagnetic)
What is Energy?
gz g e
gravity
= . .
Internal Energy: U
The energy associated with the motion and
interactions of Molecules
U: Microscopic Energy
as opposed to External Energy which are
the whole Objects/Systems that are in motion
or are in a potential field (electrical, magnetic,
gravitational, etc.)
Associated with the systems center of mass
Includes Kinetic and Potential
Total Energy, E, would include the effects of
the Internal and External Energy
Total Energy = Internal Energy + Kinetic Energy +
Potential Energy
Internal Energy & Total Energy
Heat
Heat may be defined as energy in transit
which flows naturally (no work) from a
higher temperature object to a lower
temperature object.
An object does not possess "heat";
the appropriate term for the microscopic
energy in an object is internal energy.
The internal energy may be increased by
transferring energy to the object from a higher
temperature (hotter) object - this is properly
called heating.
Heat
http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/
If the sets of systems A-B and A-C each
have no heat interactions when
connected across non-adiabatic
boundaries, there will be no heat
interaction if systems B and C are also
connected.
Somewhat Obvious, but you need to start
somewhere to build the laws of thermo.
Zero
th
Law of Thermodynamics
Conservation of Energy:
The total energy change of a system is composed of
internal energy (molecular behavior) and external energy
(kinetic and potential of the center of mass of the system)
changes
In addition, the system may change due to the heat flows,
work flows, and mass flows; Mass flows have with their
accompanying enthalpy, and kinetic and potential energy.
For closed System only
When kinetic and potential energy of the system are negligible:
U=E
1
st
Law of Thermodynamics
Open system bounded by a surface
1 or many Mass Entrances/Exits,
K = number of entrances/outlets
Total Work, W
There may be several sources, shaft, PV, electrical: W= W
s

PdV+
Total Heat, Q
Volume and surface area may change/deform (dV, d)
Generalized Open Systems
Q
W

dM
in
, v
in
, z
in
dM
out
, v
out
, z
out
Ws
: surface area
There are two Types of Internal Energy
that we need to keep track of:
the U of the entire system vs. the U of the
plugs of mass coming in and out
Each plug of mass has its own internal
energy, kinetic energy and potential energy
The system U is a function of the ins and
out and the remainders and/or reactions
Internal Energy: Total vs. Flows
If Work or Heat flow INTO the system then
the value is POSITIVE
If Work or Heat flow OUT the system then
the value is NEGATIVE
Work: Shaft Work & System Boundary
Work of -Surface
Shaft work : Mechanical Work, W
s
system boundary (volume) being move by
pressure aka PV-work
Work & Heat and Signs
PdV W =
To simplify the Balance, especially for what is
usually one of the dominant terms, U, we
use/define a new Thermodynamic Variable
Enthalpy: H
H = U +PV
It is similar to U, but with built in flow work
associated with it.
Do not jump to conclusions that H can only be
used with flow systems, it is a thermodynamic
property of all matter in all conditions
Enthalpy, H Enthalpy, H
Difference: mass/mole
Differential: mass/mole
1
st
Law: Energy Balance: with Enthalpy, H

=
=
(

|
|
.
|

\
|
+ + + + =
(
(

|
|
.
|

\
|
+ + =
(

+ + + + =
(
(

|
|
.
|

\
|
+ + =
K
k
k
k
k k k
system
K
k
k
k
k k
system
gz
v
MW H N W Q gz
v
MW N U
dt
d
dt
dE
gz
v
H M W Q gz
v
M U
dt
d
dt
dE
1
2
2
1
2
2
2 2
2

=
=
(

|
|
.
|

\
|
+ + + + =
(
(

|
|
.
|

\
|
+ + =
(

+ + + + =
(
(

|
|
.
|

\
|
+ + =
K
k
k
k
k k k
syst
K
k
k
k
k k
syst
gz
v
MW H N W Q gz
v
MW N U E
gz
v
H M W Q gz
v
M U E
1
2
2
1
2
2
2 2
2

2
MEB Summary: Difference:
( )

=
= =
(

|
|
.
|

\
|
+ + + + =
(

|
|
.
|

\
|
+ + =
= = =
K
k
k
k
sys
system
C
i
k i k
K
k
k system
gz
v
MW H N W Q gz
v
MW N U E
N N N N N N
1
2 2
1 1
1 2
2 2
( )

=
= =
|
|
.
|

\
|
+ + + + =
(

|
|
.
|

\
|
+ + =
= = =
K
k
k
k system
C
i
k i k
K
k
k t t system
gz
v
H M W Q gz
v
M U E
M M M M M M
1
2 2
1 1
2

2
1 2
Mass:
Mole:
Non reacting systems
MEB Summary: Differential:
( )

=
= =
|
|
.
|

\
|
+ + + + =
(

|
|
.
|

\
|
+ +
=
= =
K
k
k
k
system
C
i
k i k
K
k
k
system
gz
v
H M W Q
dt
gz
v
M U d
dt
dE
M M M
dt
dM
1
2
2
1 1
2

2


Mass:
Mole:
( )

=
= =
(

|
|
.
|

\
|
+ + + + =
(

|
|
.
|

\
|
+ +
=
= =
K
k
k
k
system
K
k
k i k
K
k
k
system
gz
v
MW H N W Q
dt
gz
v
MW N U d
dt
dE
N N N
dt
dN
1
2
2
1 1
2
2


Non reacting systems