CHEE 221: Chemical Processes and Systems

Module 4. 
Energy Balances without Reaction 

Part c: Calculating Changes in Enthalpy
(Felder & Rousseau Ch 8)
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 2
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 (Table B2)
– phase transition temperatures  Tm, Tb (at which data are often listed, 
e.g. latent heats) (Table B1)
– latent heats  heat of vapourization, heat of melting (Table B1)

CHEE 221 F&R Ch 8.1b 3

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 4
 Construction of the Hypothetical Process Path

Our chosen  H2O(s) Hˆ  ? H2O(v)

reference 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 5
Changes in H and U with P (constant T, phase)
Ideal Gases:
Uˆ  0
– By definition,                (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 H with 
Liquids and Solids:   respect to pressure are 
– Uˆ  0 small and will be 
– Hˆ  PVˆ (but still very small) neglected (except for 
steam tables).  

CHEE 221 F&R Ch 8.2 6

 Does H change with P? Steam Enthalpy Diagram

Use the steam tables to

determine the state (liquid,
vapour or mixture of the two;
saturated or supersaturated) and
approximate temperature (no
need to use extrapolate) of 1 kg
of water at 1 bar with the
following enthalpies (relative to
liquid water at the triple point)

a) 100 kJ
b) 419 kJ
c) 1500 kJ
d) 2676 kJ
e) 3000 kJ

Conclusion: Enthalpy is not a strong function of pressure below 10 bar

CHEE 221 7
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 two 
Hmelting latent heats for substances 
at their normal melting and 
boiling points (i.e., at a 
pressure of 1 atm).

CHEE 221 F&R Ch 8.4a 8

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 F&R Ch 8.3a 9

Changes 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 constant 
volume Nonideal gas: valid only if V constant
CHEE 221 10
Changes 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 11
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 F&R Ch 8.3b 12

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 13
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 14
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 F&R Ch 8.3b 15

 Putting it all together: 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 16
Calculating enthalpy changes: Examples

1. Calculate the increase in specific enthalpy that occurs when

acetone(v) is heated from 25 C to 100 C.
2. 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.
3. Fifteen kg/min of air is cooled from 400C to 30C. Calculate
the required heat removal rate.
4. Estimate the increase in specific enthalpy when H2O(v) is
heated from 300 C to 450 C.

CHEE 221 17
Constructing a Process Pathway: 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 18
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 F&R Ch 8.1c, 8.3d, 8.4c 19

Procedure for Energy Balance Calculations (cont’d)

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 F&R Ch 8.1c, 8.3d, 8.4c 20

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 21
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 22
 Example 3: 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 ºC 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 23