Energy Balances.

F&R Chapter 8

How do we calculate enthalpy (and internal energy) changes when we

don’t have tabulated data (e.g., steam tables) for the process species?
Basic procedures to calculate enthalpy (and internal energy changes)
associated with the following processes are covered in Chapter 8 (no
Reaction): Remember, 3 pieces of information set the thermodynamic
state of matter: P, T and Phase.

• Ĥ with change in P (at constant T and phase) (F&R 8.2)

• Ĥ with change in T (at constant P and phase) (F&R 8.3)

• Ĥ with change in phase (at constant T and P) (F&R 8.4)

To keep track of our calculations, we will summarize enthalpies in

an Inlet-Outlet Enthalpy Table. Sections not covered in Ch 8
include 8.3c, 8.3e, 8.4b, 8.4d, 8.4e, 8.5

CHEE 221 1
Hypothetical Process Paths

 To calculate enthalpy changes, we need to construct a hypothetical

process path, with:
– A starting point: your defined reference state (phase, T and P)
– An end point: the conditions of the stream of interest (inlet or
outlet)

 Since Û and Ĥ are state properties (values are dependent only on

the state of the species (phase, T and P) and not how they got
there), any convenient process path from a reference state to
a process state can be chosen

 The ideal process path will allow you to make use of:
– sensible heats  heat capacities
– phase transition temperatures  Tm, Tb (at which data are often
listed, e.g. latent heats)
– latent heats  heat of vapourization, heat of melting
CHEE 221 2
Hypothetical Process Paths

Calculate the enthalpy change as 1 kg of ice at 0C is transformed to

superheated steam at 400C at 10 bar.

H 2O(s) Hˆ  ? H2O(v)

400C, 10 atm
0C, 1 atm

We could use the steam tables and find (Remember: final-initial):

Ĥ  3264  ( 334)  3612 kJ/kg  - 334 kJ/kg is the enthalpy of ice

How would we calculate the enthalpy change if we didn’t have the

steam tables?

CHEE 221 3
 Hypothetical Process Path

reference H2O(s) Hˆ  ? H2O(v)

state (0C, 1 atm) true path (400C, 10 atm)
Hˆ 1  Hˆ m at the
normal melting point Ĥ1 Ĥ 5 Hˆ 5  0
(Tm ) of H2O (Table B.1) ( A reasonable assumption
for small changes in P)
H2O(l) H2O(v)
(0C, 1 atm) (400C, 1 atm)
100 400

 
H O
Hˆ 2  C p 2 ( l ) dT Hˆ 4 
H O( v )

0
Ĥ 2 Ĥ 4 100
Cp 2 dT

(C p expressions are (C p expressions are

found in Table B.2) Ĥ 3 found in Table B.2)
H2O(l) H2O(v)
(100C, 1 atm) (100C, 1 atm)
Hˆ 3  Hˆ v at the
normal boiling point
(Tb ) of H2O (Table B.1)

Hˆ  Hˆ final  0  Hˆ 1  Hˆ 2  Hˆ 3  Hˆ 4  Hˆ 5

CHEE 221 4
Changes in H and U with P (constant T, phase)

Ideal Gases:
– By definition, Uˆ  0 (molecules don’t interact, so changing P
doesn’t change the internal energy)
– H = U + PV but PV = nRT = 0 (constant T)  Hˆ  0

Non-Ideal Gases:
– Changes in internal energy and enthalpy are small, provided P
is small (< 5 atm)  Uˆ  Hˆ  0
– For steam, use tabulated values
In a problem, state
that changes in U and
Liquids and Solids: H with respect to
– Uˆ  0 pressure are small
– Hˆ  PVˆ (but still very small) and will be neglected
(except for steam
tables).
CHEE 221 5
Changes in U and H with T (constant P, phase)-
Sensible Heat
Sensible heat refers to heat that must be transferred to raise or lower
the temperature of a substance without change in phase.

1) Sensible heat of solid,

H (Tinitial Tmelting)
Hvapourization

2) Sensible heat of liquid,

H (Tmelting  Tvapourization)
Hmelting  3) Sensible heat of gas, H
 (Tvapourization  Tfinal)


Tinitial Tfinal

CHEE 221 6
Changes in U and H with T (constant P, phase)-Sensible
Heat
Closed System--Find  U . The quantity of sensible heat required to
produce a temperature change in a system can be determined from the
appropriate form of the first law of thermodynamics:
Q =  U (closed system;
must be kept at constant
volume)

 Uˆ   Uˆ 
Cv (T )   lim  
T 0 T   T 
V
T2


Uˆ  C v (T )dT
T1

Ideal gas: exact

Solid or liquid: good approximation
Slope = Cv = heat capacity at
Nonideal gas: valid only if V constant
constant volume
CHEE 221 7
Changes in U and H with T (constant P, phase)-Sensible Heat

Open System--Find  H. Enthalpy, like internal energy, also depends

strongly on temperature.
˙ =  H˙
Q (open system; calculate at constant pressure)
Ideal gas: exact
 Hˆ   Hˆ 
C p (T )   lim   Solid or liquid: good approximation
T 0 T   T 
P Nonideal gas: exact only if P constant
T2


Hˆ  C p (T )dT
T1
Cp = heat capacity at constant pressure

Liquids and Solids: Cp  Cv

Ideal Gases: Cp = Cv + R

CHEE 221 8
Heat Capacity Formulas

Heat capacity – the amount of heat required to raise the temperature of

one mole or one gram of a substance by one degree Celsius without
change in phase
– units: J cal
or
mol K g C
If Cp were constant, our job would be easy: H = CP (T2-T1)
But, heat capacities are functions of temperature and are expressed in
polynomial form:
Cp = a + bT + cT2 + dT3 (Form “1”)
or,
Cp = a + bT+ cT-2 (Form “2”)

Values of coefficients a, b, c, and d are given in Table B.2.

CHEE 221 9
Notes Regarding Table B.2

 Be sure you use the correct functional form

– Cp = a + bT + cT2 + dT3 (Form 1) or Cp = a + bT+ cT-2 (Form 2)

 Temperature units are sometimes K and sometimes C

 Positive exponent in table heading means you use negative

exponent in the expression
– E.g., if a x 103 = 123.0  a = 123.0 x 10-3

 Be careful when you integrate! (T22 – T12)  (T2 – T1)2

CHEE 221 10
Heat Capacity Calculations – Integration

Cp molkJC  a  bT  cT 2  dT 3

T2

 
 kJ 
Ĥ    a  bT  cT 2
 dT 3
dT
 mol  T
1
b c d
 a( T2  T1 )  ( T2 2  T12 )  ( T2 3  T13 )  ( T2 4  T14 )
2 3 4

CHEE 221 11
Specific Enthalpies of Gases – Table B.8
Table B.8 lists specific enthalpies (kJ/mol) of selected gases (mainly
combustion products, i.e. this table might be useful when solving energy
balances for combustion problems) as a function of temperature.

• Can be used to estimate H changes as an alternative to integrating the Cp

equation.

• Interpolation may be required.

• The reference state of these gases is: 1 atm and 25C.

• Use this table as you would for the steam tables, however, note that for H2O,
the units and reference state are different than the steam tables.

CHEE 221 12
Phase Changes (at constant T and P) – Latent Heat

Phase changes occur from the solid to the liquid phase, and from the
liquid to the gas phase, and the reverse. The specific enthalpy change
(heat) associated with the phase change at constant T and P is known
as the latent heat of the phase change (i.e., latent heat of vapourization
or simply heat of vapourization).

Hˆ v (T , P ) : liquid  gas

Hvapourization Hˆ m (T , P ) : solid  liquid

Table B.1 reports these

Hmelting two latent heats for
substances at their
normal melting and
boiling points (i.e., at a
pressure of 1 atm).
CHEE 221 13
 Hypothetical Process Path

reference H2O(s) Hˆ  ? H2O(v)

state (0C, 1 atm) true path (400C, 10 atm)
Hˆ 1  Hˆ m at the
normal melting point Ĥ1 Ĥ 5 Hˆ 5  0
(Tm ) of H2O (Table B.1) ( A reasonable assumption
for small changes in P)
H2O(l) H2O(v)
(0C, 1 atm) (400C, 1 atm)
100 400

 
H O
Hˆ 2  C p 2 ( l ) dT Hˆ 4 
H O( v )

0
Ĥ 2 Ĥ 4 100
Cp 2 dT

(C p expressions are (C p expressions are

found in Table B.2) Ĥ 3 found in Table B.2)
H2O(l) H2O(v)
(100C, 1 atm) (100C, 1 atm)
Hˆ 3  Hˆ v at the
normal boiling point
(Tb ) of H2O (Table B.1)

Hˆ  Hˆ final  0  Hˆ 1  Hˆ 2  Hˆ 3  Hˆ 4  Hˆ 5

CHEE 221 14
Examples Week 9

– Calculate the increase in specific enthalpy that occurs when

acetone(v) is heated from 25 C to 100 C.
– A stream of nitrogen flowing at a rate of 1kg/min is heated from
50C to 200C. Calculate the heat that must be transferred.
– Fifteen kg/min of air is cooled from 400C to 30C. Calculate the
required heat removal rate.
– Estimate the increase in specific enthalpy when H2O(v) is heated
from 300 C to 450 C.

CHEE 221 15
Example 8.4-2

One hundred moles per second of liquid hexane at 25 ºC and 7 bars

pressure is vaporized and heated to 300 ºC at constant pressure.
Estimate the rate at which that must be supplied.

CHEE 221 16
Procedure for Energy Balance Calculations

1.Draw and completely label a process flow diagram

2.Perform all material balance calculations
3.Choose a reference state (phase, T, P) for each species involved
– If using enthalpy tables, use reference state used to generate
table
– If no tables are available, choose one inlet or outlet condition as
the reference state for the species
4.Construct an inlet-outlet enthalpy table
– Columns for inlet and outlet amounts of each species along with
their corresponding Ûi or Ĥi values
– Use a separate row for each phase of a species
– Identify unknowns with variables (e.g., Ĥ1, Ĥ2, etc.)

CHEE 221 17
Procedure for Energy Balance Calculations

6.Calculate all required values of Ûi or Ĥi and insert values into table

7.Calculate U or H (e.g., H=miĤi- miĤi)
8.Write the appropriate form of the energy balance equation, remove
any negligible term, and calculate any other terms in the energy balance
equation (i.e., W, Ek, Ep)
9.Solve for the unknown quantity in the energy balance equation
– Typically solve for Q but sometimes asked to solve for a mass
(mole) flow or occasionally a T.

CHEE 221 18
Example 1 F&R 8.3-5

A stream containing 10% CH4 and 90% air by volume is to be heated

from 20C to 300C. Calculate the required rate of heat input in
kilowatts if the flow rate of the gas is 2.00 x 103 litres (STP)/min.

CHEE 221 19
Example 2 F&R 8.1-1

Acetone (denoted as Ac) is partially condensed out of a gas stream

containing 66.9 mole% acetone vapour and the balance nitrogen.
Process specifications and material balance calculations lead to the
flowchart shown below.

The process operates at steady-state. Calculate the required cooling

rate.
CHEE 221 20
 Example: Final Exam 2006

In the following process for condensing methanol vapour from air most of
the entering methanol is liquefied in this steady-state process, with the
remaining fraction exiting with the air stream. Both exit streams are at 0
°C and 5 atm. Shaft work is delivered to the system at a rate of 30 kW
to achieve the compression.
5.184 mol air/s
0.058 mol MeOH(v) /s
150 °C 1 atm
5.760 mol/s 0 °C 5 atm
0.10 mol MeOH(v) /mol
0.90 mol air/mol 0 °C 5 atm

0.518 mol MeOH(l) / s

Q Ws

Construct an inlet-outlet enthalpy table for the process, and calculate all
unknown enthalpies. Identify the reference states selected for the
components, and state all assumptions. What is the rate (kW) at which
heat must be removed from the condenser?
CHEE 221 21
Interactive Tutorial

Now is a good time to try Interactive Tutorial 5…

CHEE 221 22