Section 5: FR&B, Ch.

7 (Energy Balances – I)

FORMS OF ENERGY AND ENERGY TRANSFER (Sections 7.1 and 7.2)

Exercise. Brainstorm examples of “systems” that you’ve encountered recently that use energy. As an
engineer, why is energy an important consideration?

FIRST LAW OF THERMODYNAMICS (another “tattoo” equation)

Energy can neither be _____________________________.

Total Energy of System has 3 components: Kinetic Energy, Potential Energy, Internal Energy.

These components are always defined relative to something. Height is analogous: it is usually measured
relative to the floor. Consider this example of basketball players from the 1974 NCAA Championship
NC State basketball team (and the mascot):

~7 ft ~5 ft ~3 ft

Tommy Burleson Monte Towe Wolf

Once you define a consistent reference (in this case, the ground), you can calculate the relative changes in
some metric (such as height). For example:

How much taller is Monte Towe than the Wolf?

Approach 1: Use the ground as a reference. __________________________________________
Approach 2: Use the wolf as a reference. ___________________________________________
Approach 3: Use Tommy Burleson as a reference. _____________________________________

In dealing with energy, we choose references that simplify calculations, but you must be consistent in
your selection.

 Note Questions 1–6 in the introduction to Chapter 7. Answering them requires energy balances
on the processes described.

5-1
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: FR&B, Ch. 7 (Energy Balances – I)

Three forms of energy:

1. Kinetic energy, : energy due to motion of an object or flowing stream relative to the
surface of the earth.
body of mass m (3.00 kg) moving with velocity u (5.00 m/s)

stream with mass flow rate (3.00 kg/s) moving with velocity

u (5.00 m/s) [= ]

is the rate at which the stream is transporting kinetic energy.

2. Potential energy, (due to position in a gravitational or electromagnetic potential

field—in CHE 205, due to height of center of mass of object above a reference height)

m (3.00 kg)

z (= 10.0 m)

Reference height: EP = 0

(3.00 kg/s)

z (= 10.0 m)

Reference height: EP = 0

3. Internal energy, : sum of rotational, vibrational, and electromagnetic energies of

individual molecules, atoms, and subatomic particles moving around in a body of material or a
flowing stream.
Specific internal energy:

(batch) or (continuous)

 State of a species: The temperature, pressure, and phase (solid, liquid, gas) of the species.
5-2
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: FR&B, Ch. 7 (Energy Balances – I)

State function: A property of a species that depends only on its state, and not how it got to that
state. is a state function.

 depends strongly on the phase of a species (liquid molecules have more kinetic energy than
solid molecules, and vapor molecules have much more kinetic energy than liquid molecules), and
on temperature (molecules have more kinetic energy at higher temperatures). It depends on
pressure moderately for a real gas, very slightly for a liquid or solid, and not at all for an ideal
gas.

 We can never know the value of for a species at a given state since we can’t measure energies
of individual molecules, atoms, and subatomic particles & add them, but we can measure the
change in 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. (We’ll shortly find out how.)

 Calculating Ek and Ep. See Examples 7.2-1 and 7.2-2.

 Exercise: Do the Test Yourself at the end of Section 7.2

Two forms of energy transfer between a system & its surroundings

1. Heat, : 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)
+Q (heat added)

2. Work, : Energy transferred any other way, such as by mechanical motion or

electric current. Define W as positive if work is done on the system by the surroundings. (Opposite
convention sometimes used)
+ W (work done)

Summary:

ETOT = EK + EP + U
Energy can be transferred as heat (Q) or work (W)

5-3
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

ENERGY BALANCES ON CLOSED SYSTEMS (Section 7.3)

 Closed system—no mass crosses system boundaries during process operation (batch)
Open system—mass crosses system boundaries (continuous, semibatch)
 Consider a nonreactive batch process (reactive processes come in Chapter 9). Starting at one
condition, add Q (kJ) heat to process and do work on the process W (kJ)

Q (kJ) W(kJ)

n (kmol) n (kmol)
T1(K) T2(K)
P1(atm) P2(atm)
V1 (m3) V2 (m3)
U1 (kJ) U2 (kJ)
Ek1 (kJ) Ek2 (kJ)
Ep1 (kJ) Ep2 (kJ)

t=0 t = tf (s)

Sign convention:
 Heat (Q) added to the process is positive, heat (Q) withdrawn is negative
 Work (W) done on the process is positive, work (W) done by the process is negative
Process may involve heating or cooling (change in T), compression or decompression (change in P), and
phase change, all of which lead to change in V.
Say that  denotes (final – initial): T = T2 – T1 , Ek = Ek2 – Ek1 , U = U2 – U1 , etc.
Recalling that Etotal = Ek + Ep + U for a system, and Q and W are the only ways energy can be transferred,
write the law of conservation of energy (Input–Output = Accumulation) for the system between the two
given times:
Net energy transferred = Final system energy – Initial system energy (Etotal)
to the system (Q+W)

Q+W = First law of thermodynamics for a closed system

Simplifying the first law for specific systems:

 System not accelerating  Ek = 0
 System not moving vertically Ep = 0

5-4
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

 No reactions or changes in phase or temperature, pressure changes < a few atm  U  0. (For an
ideal gas, U = 0 for pressure changes.)
 No temperature difference across system boundary (or perfect insulation)  Q = 0 (“adiabatic
system”)
 No moving parts, electrical currents, radiation across system boundary  W = 0

Exercises
(a) A can of coke is taken from a refrigerator and left standing. Write energy balance on the can from the
moment it is left standing to an hour later.

(b) Example 7.3–1 (talk through it and make sure you understand it)

Measuring for a specified change in state

 We can never measure the true value of at a given state – it’s unknown and unknowable! We can,
however, measure Q (heat) and W (work) associated with the change between two states for a closed
stationary system and calculate . (We assume no changes in
kinetic and potential energy for the system; if there are any, include them in the energy balance.)

Example:

0.100 kg H2O(v)
0.100 kg H2O(l) 100oC, 1 atm
0.01oC, 0.00611 bar 167.3 L
Q = 268 kJ
0.100 L
W = -17 kJ

The system is the water within the cylinder. Neglecting the very slight change in potential energy due to
vertical expansion of the fluid, the first law yields

= (268–17) kJ = 251 kJ

We can then say that the specific internal energy of water vapor at 100C and 1 atm relative to liquid
water at the triple point (0.01C and 0.00611bar) is 2510 kJ/kg.

5-5
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

 Internal energy table

(a) Choose a reference state (phase, T, P) for a species, at which is set equal to 0. (Example:
Liquid water at the triple point, used in Tables B.5–B.7)
(b) Determine for the change from the reference state to another. Call the result of the
species at the second state relative to the reference state. Repeat for many states, & tabulate .
(c) Thereafter, calculate for a specified change of state (to substitute into the energy balance
equation) as , substituting values from the table for both internal energies.
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. The two internal energy
tables shown below for carbon dioxide at 1 atm illustrate this point.

Ref: CO2(g, 1 atm, 0oC) Ref: CO2(g, 1 atm, 100oC)

T(oC) (kJ/mol) T(oC) (kJ/mol)
0 0.00 0 –3.82
100 3.82 100 0.00
200 8.00 200 4.18
300 12.50 300 8.68

Exercise: A table of specific internal energies of nitrogen at P = 1 atm contains the following entries:

T(oC) (kJ/mol)
0 – 0.73
25 0.00
100 2.19
200 5.13

(a) What reference state was used to generate this table? __________________________________
(b) Q: What is the physical significance of the value 2.19 kJ/mol?

A: It is for the process N2(__, ____ atm, ____oC)  N2(__, ____ atm, ____oC)

(c) What is for the process N2(g, 1 atm, 200oC)  N2(g, 1 atm, 100oC)? ______________________
(d) Calculate the heat required to cool 2.00 mol N 2 from 200oC to 100oC.

5-6
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

ENERGY BALANCES ON OPEN SYSTEMS AT STEADY-STATE (Section 7.4)

= rate of heat transfer to the system

= rate of shaft work done on the system by its surroundings, which includes energy transmitted
by moving parts (pistons, propellers, turbines,...) or electric currents that cross the system boundary.

= flow rate of a jth component within a stream

Note: There may be one or more inlet (feed) streams and one or more outlet streams, and the same
species may enter in several streams at different states (velocity, elevation, pressure, volume). It can get
complicated fast!

Energy Balance: An energy balance on this system states that “input = output” (why no generation,
consumption, or accumulation terms?), where “input” is the total rate at which energy is transferred to the
system from the surroundings (as heat and by being transported in by the input streams) and “output” is
the total rate of energy transfer out:

or since :

5-7
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

We could use this form of the equation for all energy balance calculations; however, in an open system
there are two forms of work— flow work and shaft work — which it is convenient to separate.

= flow work (also known as “PV work”), work done to push entering fluid streams into
system minus work done by exiting fluid streams pushing back the surroundings

= shaft work, all other work transmitted across system boundary by moving parts (pistons,
turbines, rotors, propellors,...), electrical currents, radiation
 This notation is can be inserted into the energy balance. (see end of notes for full derivation)

 This equation can be simplified by defining a new term: Enthalpy

(7.4-7)

is the specific enthalpy of a species at pressure P with internal energy and specific volume .
Like , is (a) a state property, (b) unmeasurable (since it includes ), (c) heavily dependent on
phase, moderately dependent on temperature, slightly dependent (real gases, liquids & solids) or
independent (ideal gases) of pressure.

 Since the change in from one state to another ( ) can be determined, the change in for the
same state change ( ) can be determined as

We can therefore prepare a table of specific enthalpies relative to a reference state at which or
is defined to be 0. Values of for water determined in this manner can be found in the steam tables,
B.5–B.7. (See Example 7.5-1 and Section 7.5b.)

5-8
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

7.4-15

First law of thermodynamics for an

open system at steady state

Applying the open system balance equation (we will discuss reactive systems in Ch. 9):
 Drop unimportant terms in (7.4-15):
 If there are no phase changes, reactions, or temperature changes and relatively small pressure
changes (no more than a few atm) from inlet to outlet, drop .
 If there are phase changes, reactions or significant temperature changes from inlet to outlet,

usually and are negligible compared to — drop them.

 If there are no significant velocity changes from inlet to outlet, drop . If there are no

significant elevation changes from inlet to outlet, drop .

 If the system and the surroundings are at the same temperature or the system is very well
insulated (adiabatic), drop .
 If the system contains no moving parts or electric currents that cross its boundary, drop .
 If remains in the equation, use a table of enthalpies (e.g., B.5–B.7 for water) to look up the

values of to substitute into Eq. (7.4-14a), or wait until Chapter 8 to learn how to estimate those
values.
 Substitute all other known values into the equation, and solve for whichever value is unknown
(usually in this text).

Example 1: Example 7.4-2

5-9
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

Example 2. Pump 10 kg H2O(l)/s through a 5-cm ID pipe to a point 125 meters above the pipe inlet.
How much shaft work must the pump deliver to the water? Assume Tin = Tout and neglect any heat
transferred to or from the water in the pipe between inlet & outlet. (Note: the “system” is defined as the
water in the pipe).

(kg H2O(l)/s)
uout (m/s)
125 m

10 kg H2O(l)/s
uin (m/s)
Pump
Solution: First, prove that the inlet and outlet fluid velocities (uin and uout) must be the same.

Next, cross out negligible terms in the balance equation:

Finally, substitute what you know to determine all terms in the equation but and solve the equation to
prove that —that is, the pump must deliver 12.3 kW of power to the water.

Q: More electrical power than 12.3 kW must be delivered to run the pump. Why?
A:

Example 3. Example 7.5-3

5-10
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.
 Section 5: F&R, Ch. 7 (Energy Balances – I)

STEAM TABLES (Sect. 7.5b)

So, where do you start to find values of and other values that appear in the energy balance? If
the species is water, you’re in luck – the steam tables in Tables B.5, B.6, and B.7 have tabulated values.
For other species, we’ll cover that in Chapter 8.
 Table B.5: Saturated Steam Temperature Table
Find the following properties of saturated water (water on the vapor-liquid equilibrium curve) at
32oC. Include units in your responses.
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 __________________________
 Table B.6 : Saturated Steam Pressure Table
Find the following properties of saturated water at 4.2 bar
Boiling point = _______________
 Table B.7: Superheated Steam Table
If a point falls within the “stairstep box” outlined on Table B.7, 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.
Phase ___________________________
Specific internal energy relative to liquid water at the triple point __________________
Specific enthalpy relative to liquid water at the triple point __________________
Specific volume _________________
Dew point temperature _________________
Specific internal energy of liquid water ______________ and water vapor __________________
at the dew point temperature
Specific enthalpy of liquid water ___________________ and water vapor __________________
at the dew point temperature
Specific volume of liquid water ___________________ and water vapor __________________
at the dew point temperature

Also note that the following APEx functions can be used to retrieve these values. This is
especially handy if interpolation is required for values which are in between listed values on
the steam table:

 SteamSatT - returns values from the saturated steam temperature table (Table B.5)
 SteamSatP - returns values from the saturated steam pressure table (Table B.6)
 SteamSH - returns values from the superheated steam table (Table B.7)
5-11
Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes.
Copyright ©John Wiley & Sons, Inc.