Elementary Principles of

Elementary Principles of
Chemical Engineering
Chemical Engineering

Unit 6:
Material Balance
Energy Balances

Prepared by: Jan-Cherie

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Campbell-Fraser
 Topics

l Kinetic, Potential and Internal Energy

l Thermodynamic Data
l Energy Balance on Open & Closed Systems
l Mechanical Energy Balances

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 Energy

l There are three forms of energy

•Kinetic
•Potential
•Internal

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 Kinetic Energy

l Kinetic energy, Ek (J) or Ek (J/s) : energy due to

motion of an object or flowing stream relative to
the surface of the earth.
Body of mass m (3.00kg) moving
with a velocity u (5.00m/s)
1 2 0.5 3.00 kg (5.00)2 m2 1N 37.5 N .m
Ek mu
2 s2 1 kg. m/s2 37.5 J

1 2 0.5 3.00 kg (5.00)2 m2 1N 37.5 N.m s

Ek mu
2 s s2 1 kg. m/s2
37.5 J s

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 Potential Energy

l Potential energy, EP(J) or E P(J/s) (due to position

in a gravitational or electromagnetic potential field
or due to height of center of mass of object above a
reference height)
• Ep =mgz
m = 3.00 kg
3.00 kg 9.81 m 10.0 m 1N
Z = 10.0 m
s2 1 kg. m/s2

294 N .m s
294 J s 294 W

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 Internal Energy

l Internal energy, U (J) or U (J/s) : sum of

rotational, vibrational, and electromagnetic
energies of individual molecules, atoms, &
subatomic particles moving around in a body of
material or a flowing stream.
l Specific internal energy:
J J U J /s
Uˆ batch or continuous
mol mol n mol / s

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 Useful Definitions

l Adiabatic, Isothermal, Isobaric, and Isochoric

are useful to specify conditions that do not change
in a process.
l The concept state or point functions or variables is
important to understand.
l T, P, composition and all other intensive variables
are known as state variables because between two
states their change in value is the same no matter
what the path taken between the two states

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 Useful Definitions

l If two systems are in the state them then their state

values such temperature or internal energy must be
identical.

Fig. Values for change

2
T A in state variables are the
B same for path A and B
1
P

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 Internal Energy

l State of a species: The temperature, pressure,

and phase (solid, liquid, gas) of the species.

l State function: A property of a species that

depends only on its state, and not how it got to
that state. Û is a state function.

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 Internal Energy

l Û depends strongly :
• on the phase of a species
• on temperature
l On pressure it depends
• moderately for a real gas,
• very slightly for a liquid or solid
• not at all for an ideal gas.

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 Internal Energy

l We can never know the value of Û for a species at

a given state since we can’t measure energies of
individual molecules, atoms, and subatomic
particles & add them,
l But, we can measure the change in Û from one
state to another. For example, if we increase the
temperature of a species by five degrees, we can
determine the change in its specific internal energy
as a result of the temperature increase.

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 Energy Transfer

l Two forms of energy transfer between a system & its

surroundings

1. Heat, Q(kJ ) or Q(kJ / s) :

Energy transferred as a result of a temperature difference

between a system and its surroundings (always from
high T to low T). Define Q as positive if heat flows to
system from surroundings. (Universal convention)
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 Energy Transfer

2. Work W (kJ ) or W (kJ / s) :

Energy transferred any other way, such as by mechanical

motion or electric current. Define W as positive if work
is done by system on surroundings.

ETOT = EK + EP + U

Energy can be transferred as heat (Q) or work (W)

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 Energy Balances on Closed Systems

l Closed Systems – no mass crosses system

boundaries during process operation (batch)
l Open System – mass crosses the system
boundaries (continuous, semi-batch)

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 Energy Balances on Closed Systems
l Lets consider a non-reactive batch process, starting
at a one condition and add Q (kJ) heat to the process
and suppose the process delivers W (kJ) work.

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 Energy Balances on Closed Systems
l The process may involve heating or cooling(change
in T), compression or decompression (change in P)
and a phase change, all of which lead to change in
V.
l ΔT =T2-T1 , ΔEk =Ek2-Ek1 ,etc

l Recall :ETOT = EK + EP + U , Q & W are the only

ways energy can be transferred.
Input – Output = Accumulation

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 Energy Balances on Closed Systems
l Q-W = ΔEk + ΔEp + ΔU (The First law of thermodynamics for a closed system)

l Net energy transferred = Final system state – Initial System state

to the system
(Q-W) = (ΔEtotal )

l Simplifying the first law for specific systems:

1. System not accelerating: ΔEk = 0
2. System not moving vertically: ΔEp = 0
3. No reaction or changes in phase or temperature, pressure changes
< a few atm → ΔU ≈ 0 (For an ideal gas ΔU = 0 for P changes)
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 Energy Balances on Closed Systems
4. No temperature difference across system boundary (or perfectly
insulation) Q = 0 (adiabatic system)
5. No moving parts, electrical currents or radiation flow cross system
boundary. W = 0

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 Measuring ΔU
for a specified change in state

l Note: The true value of Û at a given state is never known

But Q & W can be measured with relation to changes between two

state for a closed stationary system.

U Q W Uˆ U ( J ) / n(mol )

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 Internal Energy Tables
l Choose a reference state (phase, T, P) for a species, at which Û is
set equal to 0. (Example: Liquid water at the triple point, used in
Tables B.5–B.7)
l Determine Û for the change from the reference state to another.
Call the result Û of the species at the second state relative to the
reference state. Repeat for many states, & tabulate
Û .
l Thereafter, calculate Û for a specified change of state
(to substitute into the energy balance equation) as Uˆ final Uˆ initial ,
substituting values from the table for both internal energies.

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 Internal Energy Tables

l Example:
l

l If you chose a different reference state, the numbers in the

table would all be different but the difference between the
values for any two states would always be the same.
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Energy Balance on Open Systems
at Steady State

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 Energy Balance on Open Systems
at Steady State

Q(kJ / s) rate of heat transfer to the system

Ws (kJ / s ) rate of shaft work done by the system on its
surroundings, which includes energy transmitted
by moving parts (pistons, propellers, turbines,...) or
electric currents that cross the system boundary.
m j(kg/s or m ol/s) flow rate of the jth stream, and the variables that
follow it are the velocity, elevation (relative to a
reference height at which Ep = 0), temperature,
pressure, and specific volume of that stream, and
the molar flow rates and specific internal energies
of the stream components.
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 Energy Balance on Open Systems
at Steady State

The first law of thermodynamics (energy balance equation) for an open steady-
state system:
Hˆ Uˆ ( PVˆ ) Uˆ final Uˆ initial PˆfinalVˆfinal Pˆinitial Vˆinitial
Ĥ is the specific enthalpy at pressure P
Û is the specific internal energy
Vˆ is the specific volume
Like Uˆ , H ˆ is
(a) a state property,
(b) immeasurable
(c) heavily dependent on phase, moderately dependent on temperature, slightly
dependent (real gases, liquids & solids) or independent (ideal gases) on pressure.
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 Energy Balance on Open Systems
at Steady State
In the same way Û can determined from one state to
another, the change in Ĥ for the same state change can be
determined.
Hˆ Uˆ ( PVˆ ) Uˆ final Uˆ initial PˆfinalVˆfinal Pˆinitial Vˆinitial

Therefore we prepared tables for specific enthalpies

relative to a reference state at which Û and Ĥ is defined to
be 0. Value of Ĥ for water found in this manner can be
found in the steam tables.(B5-B7)
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 Energy Balance on Open Systems
at Steady State
For an open System Δ denotes (out – in) for closed systems its
denoted (final-initial).

Net work done by an open system to its surroundings

W Ws Wfl
where
Ws is the shaft work or the rate of work done by the process fluid
on a moving part

Wfl is the flow work or the rate of work done by the fluid at the
system outlet minus that at the inlet
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 Energy Balance on Open Systems
at Steady State

l Therefore Wfl PoutVout PinVin

l The first law of thermodynamic for an open steady state system:

Q - Ws ( U PV ) Ek Ep
Q - Ws H Ek Ep

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 Energy Balance on Open Systems
at Steady State

Applying above equation to non-reactive systems.

• If there are no phase changes or temperature changes and
relatively small pressure changes (no more than a few
atm) from inlet to outlet, drop ΔH .
• If there are phase changes or significant temperature
changes from inlet to outlet, usually ΔEk and ΔEp are
negligible compared to ΔH – drop them.
• − If there are no significant velocity changes from inlet to
outlet, drop ΔEk . If there are no significant elevation
changes from inlet to outlet, drop ΔEp .
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 Energy Balance on Open Systems
at Steady State
• If the system and the surroundings are at the same
temperature or the system is very well insulated (adiabatic),
drop Q.
• If the system contains no moving parts or electric currents
that cross its boundary, drop Ws.
• If ΔH remains in the equation, use a table of enthalpies
(e.g., B.5–B.7 for water) to look up the values of H to
substitute into or estimate them.
• Substitute all other known values into the equation, and
solve for whichever value is unknown (usually Q in this
text).
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 Using the Steam Tables
l Table B.5: Saturated Steam Temperature Table
• Use Table B.5 to find the following properties of
saturated water (water on the vapor-liquid equilibrium
curve) at 32oC. Include units in your responses.

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 Using the Steam Tables
Vapor pressure = _______________
Specific volume of liquid water ________________ and
water vapor ______________________
Reference state used to determine internal energies and
enthalpies _________________________
Specific internal energy of liquid water ______________ and
water vapor __________________
Specific enthalpy of liquid water ___________________ and
water vapor __________________
Heat of vaporization __________________________

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 Using the Steam Tables
l Table B.6 : Saturated Steam Pressure Table
• Use Table B.6 to find the following properties of
saturated water at 4.2 bar

l Boiling point = _______________

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 Using the Steam Tables

l Table B.7: Superheated Steam Table

• If a point falls within the “stairstep box” outlined on p.
650, then water is a liquid. Outside the box, water is a
superheated vapor. Use Table B.7 to find the following
properties of water at 20 bar and 350oC.

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 Using the Steam Tables
l Phase ________________________________
l Specific internal energy relative to liquid water at the
triple point __________________
l Specific enthalpy relative to liquid water at the triple point
__________________
l Specific volume _________________
l Dew point temperature _________________
l Specific internal energy of liquid water ______________
and water vapor __________________ at the dew point
temperature
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 Using the Steam Tables
l Specific enthalpy of liquid water ___________________
and water vapor __________________ at the dew point
temperature
l Specific volume of liquid water ___________________
and water vapor __________________ at the dew point
temperature

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 Specific Properties and Enthalpies
l Properties are either intensive or extensive
l A specific property is an intensive quantity obtained by
dividing an extensive property by the of the process
material.
• E.g. if the volume of the fluid is 200 cm3 and the mass of the fluid is 200 kg,
the specific volume is 1cm3/kg.
• If the KE transported by a stream is 300 J/min and the mass flowrate of the
stream is 100kg/min, the specific kenetic energy of the stream material is 3
J/kg.
U (J ) m(kg )Uˆ ( J / kg )
U ( J / s) m(kg / s)Uˆ ( J / kg )
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 Specific Properties and Enthalpies
l A property that is frequent is its occurrence in energy
balance is specific enthalpy.
Hˆ Uˆ PVˆ
l The gas constant provides a convenient source for
conversion factors needed to evaluate Ĥ .

Example: the specific internal energy of helium at 300 K and 1 atm is 3800
J/mol, and the specific molar volume at the same T and P is 24.63 L/mol.
Calculate the specific enthalpy of helium at this T & P and the rate at which
enthalpy is transported by a stream of helium at 300 K and 1 atm with a
molar flowrate of 250 kmol/h.
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 Steady State Open-Systems Energy
Balance
Input =Output
l The ‘input’ signifies the total rate of transport of KE, PE, and IE by
all process input streams plus the rate at which energy is transferred
in a heat, and the ‘output’ is the total rate of energy transport by the
output streams plus the energy transferred out as work.

Q Ej Ej W
input output
streams streams

Ej Ej Q W
output input
streams streams

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 Steady State Open-Systems Energy
Balance
Ej Uj Ekj E pj
Uj m jUˆ j
2
Ekj m ju j / 2
E pj m j gz j
2
uj
Ej m j Uˆ j gz j
2

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 Steady State Open-Systems Energy
Balance
W Ws W fl
W fl PjV j PjV j
output input
stream stream

Vj m jVˆ j
W Ws m j PjVˆ j m j PjVˆ j
output input
stream stream

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 Steady State Open-Systems Energy
Balance
u 2j u 2j
m j Uˆ j PjVˆ j gz j m j Uˆ j PjVˆ j gz j Q Ws
output 2 input 2
stream stream

u 2j u 2j
m j Hˆ j gz j m j Hˆ j gz j Q Ws
output 2 input 2
stream stream

H Ek Ep Q Ws

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 Steady State Open-Systems Energy
Balance
• Example

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 Mechanical Energy Balance
l Units such as reactors, distillation columns, evaporators and heat
exchangers, the shaft work, the kinetic & potential energies are
negligible compared to heat flow enthalpy and internal energy
changes. Hence, Energy balances on such system have the simple
form: Q = ΔU (closed systems) or Q = ΔH (open systems)
l Another class of equipment uses the opposite phenomenon, where
the internal energy, enthalpy and heat change are negligible
compared to PE, KE and shaft work. Includes operations which
involve the flow of fluids to and from and between tanks, reservoir,
well, process unit etc. This is called The Mechanical Energy
Balance

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 Energy Balance on Reactive Systems
l Most problems in Ch. 8 have the following form:
Given:
• Feed and product states (phase, T, P), some flow rates (n’s) &
compositions (y’s)
• W (closed) or Ws (open) = zero (no moving parts or electric currents)
• Calculate other flow rates (material balances)
• Determine ΔU (closed) or ΔH(open), Ek & Ep (usually neglect the
latter two).
• If we have tables of specific internal energies and enthalpies (as we do
for water in the steam tables), calculating ΔU, ΔH is straightforward.
• If tables are not available then they have to be calculated.

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